DE2951214A1 - HEAT-CURABLE PAINTS BASED ON AN AQUEOUS DISPERSION AND THEIR USE - Google Patents

Description

Due to the demand for paints and application methods, which do not cause any environmental problems, the use of powder paints and aqueous paints has more recently Time steadily increased. These paints have important advantages, but still have various disadvantages

¹⁰ afflicted.

For powder coatings, for example, special coating devices are required, so that the adaptability of the powder coatings the application process is far less than with conventional solvent-based paints. Besides, they are coatings made from powder paints are less than satisfactory in terms of smoothness and appearance, and it is difficult to to obtain thin coatings with a thickness of less than 50 μπ ».

In the field of aqueous, water-soluble paints, it is impossible to use high-solid-concentration compositions produced so that no thick coatings can be obtained by simple coating. Because of the hydrophilic Groups that are introduced into the base resin to make it water soluble own the coatings made from it also poor durability.

Aqueous latex paints or emulsion paints have long been known, for example, from US Patents 2,904,523, 2,994,676, 3,002,940, 3,025,252, 3,170,888, 3,244,542, 3,657,175, 3,687,885, 3,839,254 and 3,926,874 are known. Since these aqueous latex or However, emulsion paints contain large amounts of wetting agents, the coatings produced from them show poor results

Water resistance, chemical resistance etc.

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To remedy these deficiencies, aqueous emulsion paints have been developed which are produced by suspending a powder resin can be obtained in water and how aqueous paints can be used. Paints of this type contain one aqueous dispersion medium and a particulate resin having a size of about 0.5 to 80 µm which is contained in the aqueous medium is dispersed in a solids concentration of 20 to 70 percent by weight.

Suitable application methods for these emulsion paints are, for example, a method in which the paint is sprayed onto the surface of the object to be coated, the water evaporates and the synthetic resin component cures to form a coating (US Pat. No. 3,787,230), and a method in which spraying an aqueous dispersion of nylon resin particles to an article, which is maintained at a temperature above 100 ⁰ C, to form a coating (U.S. Patent No. 2,972,552). Suitable paints for these application methods are, for example, (i) an agent which contains particles of a chlorinated polyester resin with a size of less than 200 mesh dispersed in water (US Pat. No. 3,089,783), (ii) an agent which contains particles of a chlorinated polyester resin Contains polyester dispersed in water, which contains a wetting agent, an ester of a polyhydric alcohol and a lower aliphatic

table contains monocarboxylic acid, an alkaline water softener and a lower aliphatic alcohol (US-PS 3,446,652),
(iii) an emulsion paint containing particles of an acrylic resin, epoxy resin, polyester resin, amino resin or polyurethane

contains resin and a water-soluble thickener (US Pat. No. 3,907,737),

(iv) an emulsion paint containing a powdery, contains thermosetting acrylic resin (US Pat. No. 3,904,795),

(v) an emulsion paint that has a reactive flow regulator of specific structure

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¹ (U.S. Patent 4,122,055), and

(vi) a dispersion paint which, in an aqueous medium, contains synthetic resin particles with a size of 0.5 to 80 µm and contains an aluminum pigment (GB-PS 1 517 834).

A process in which a synthetic resin is mixed in a water-soluble one is suitable for the production of these emulsion paints Solvent dissolves, e.g. an alcohol such as methanol or ethanol, a ketone such as acetone or diacetone alcohol, an ester such as ethyl lactate or ethylene glycol monomethyl ether acetate, or an ether, such as ethylene glycol monoethyl ether, and the resulting solution in water introduces that with high speed stirring, causing the resin particles precipitate in water (US Pat. No. 3,737,401), and a method

^t5 in which a solid synthetic resin is pulverized in the usual way and the pulverized synthetic resin is dispersed in water.

Emulsion paints produced by this process are distinguished by the fact that they have a solids concentration ^ Up to about 40 to 60 percent by weight can be applied using conventional coating equipment Can be carried out for solvent-based paints and the only volatile component of the emulsion paint is the water used as the dispersion medium. In addition, since the aqueous dispersion medium does not have a soluble component contains no recovery or environmental problems. Because of these advantages, it is expected that the demand after such paints continues to increase.

Acrylic resins, polyester resins, epoxy resins and alkyd resins, for example, are suitable as synthetic resin components for these emulsion paints. For reasons of the storage stability of the color and the smoothness and appearance of the coatings obtained Acrylic resins and polyester resins are particularly preferred. Depending on the

In the case of these synthetic resins, a distinction is made between self-hardening synthetic resins and synthetic resins with

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Crosslinkable with the help of crosslinking agents or hardeners are. Melamine resins and blocked isocyanates have hitherto been used as crosslinking or hardening agents. Also epoxy resins are sometimes used in combination with such crosslinking or hardening agents to improve corrosion resistance.

In the case of "D * -n" which contain a Melau.xnharz as a crosslinking agent, it occurs during the production of Thick layers cause the coatings to pop off in the firing stage and to adapt to the processability of the coatings is bad. The coating should therefore be repeated several times in order to obtain a coating of the desired thickness. To prevent jumping off, the com-

* ⁵ suggested use of a melamine resin and a urethane (capped isocyanate). However, this has the disadvantage that a yellow coloration can occur during subsequent firing at high temperature (JA-OSen 112 428/75 and

108 433/77). 20th

Since emulsion paints contain water as a dispersion medium, when applied directly to an iron plate, e.g. a mild steel plate, in the case of conventional aqueous systems, leads to an undesirable appearance of rust, which is the case with solvent-based systems Varnish does not occur. To avoid this undesirable phenomenon, emulsion paints are often used a rust preventive agent or the like added. These rust preventives however affect the storage stability,

so their use is not preferred. 30th

The object of the invention is to provide new thermosetting paints based on aqueous emulsion paints, which have excellent storage stability and yellowing resistance and give coatings which have excellent Properties in terms of gloss, smoothness, rust formation,

Have corrosion resistance and water resistance

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and when fired within a relatively wide temperature range don't jump off.

The invention relates to thermosetting paints based on an aqueous dispersion containing fine thermosetting paints Synthetic resin particles

(A) a polyester-modified vinyl resin having a specific hydroxyl number obtained by graft copolymerization of (i) an unsaturated polyester resin with W (Li.) An α, ß-monoethylenically unsaturated monomer and

possibly
(iii) an a, ß- containing a phosphoric acid group

monoethylenically unsaturated monomer has been obtained, and

f (B) a crosslinkable copolymer that is different from a mixture derives which

(iv) an N-alkoxymethylated monomer of an α, ß-monoethylene contains unsaturated carboxamide, these fine synthetic resin particles in the presence ^ (C) a wetting agent and / or a thickening agent in (D) the required amount of water are dispersed.

In another embodiment, the invention relates to thermosetting agents Paints based on an aqueous dispersion containing fine thermosetting synthetic resin particles

(A) a polyester-modified vinyl resin with a specific Hydroxyl number obtained by graft copolymerization of (i) an unsaturated polyester resin with a Monomergemi sch, that

(iv) an N-alkoxymethylated monomer of an α, ß-monoethylene contains unsaturated carboxamide, and

(B) a copolymer containing a phosphoric acid group,

which is derived from a monomer mixture which

(iii) an α, ß-monoethylenic containing a phosphoric acid group contains unsaturated monomer.

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these synthetic resin particles in the presence of

(C) a wetting agent and / or a thickening agent in

(D) the required amount of water are dispersed.

The invention relates in particular to an aqueous, thermosetting emulsion paint (I) containing fine thermosetting paints Synthetic resin particles

(A) 5 to 90 percent by weight of a polyester-modified vinyl resin having a hydroxyl number of 30 to 200, the by graft copolymerization of

(i) 5 to 50 weight percent of an unsaturated polyester resin with

(ii) 95 to 50 percent by weight of at least one α, ßmonoäthylenisch unsaturated monomer has been obtained, and

(B) 95 to 10 percent by weight of a crosslinkable copolymer, which is derived from a monomer mixture which

(iv) an N-alkoxymethylated monomer of a, ß-monoethylene unsaturated carboxamides and

(ii) at least one α, β-monoethylenically unsaturated Contains monomer,

(C) a wetting agent and / or a thickening agent in an amount of 0.01 to 1.0 percent by weight, based on the Resin particles, and

(D) the amount of water required.

The invention also relates to an aqueous, thermosetting emulsion paint (II) containing thermosetting resin fine particles

(A) 5 to 90 percent by weight of a polyester modified vinyl resin with a hydroxyl number of 30 to 200, which is obtained by graft copolymerization of

(i) 2 to 50 weight percent of an unsaturated polyester resin with

(ii) 95 to 40 percent by weight of at least one α, β-monoethylene unsaturated monomer and

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(iii) 0.01 to 10 percent by weight of an α, β-monoethylenically unsaturated one containing a phosphoric acid group Monomer has been obtained, and

(B) 95 to 10 percent by weight of a crosslinkable copolymer, which is derived from a monomer mixture which

(iv) an N-alkoxymethylated monomer of an α, β-monoethylene unsaturated carboxamides and (ii) at least one α, ß-ethylenically unsaturated monomer

contains,

(C) a wetting agent and / or a thickening agent in an amount of 0.01 to 1.0 percent by weight based on the synthetic resin particles, and
(D) the amount of water required.

^iS Furthermore, the invention relates to an aqueous thermosetting emulsion paint (III) containing fine particles of thermosetting resin

(A) 15 to 95 percent by weight of a polyester modified Vinyl resin with a hydroxyl number of 10 to 150,

20 that by graft copolymerization of

(i) 2 to 40 percent by weight of an unsaturated polyester resin with 98 to 60 percent by weight of one Monomer mixture that

(iv) an N-alkoxymethylated monomer of an α, ß-monoethylenically unsaturated carboxamide and

(ii) at least one α, β-monoethylenically unsaturated Monomer contains, has been obtained, and

(B) 85 to 5 percent by weight of a phosphoric acid group-containing Copolymers that differ from a monomer

³⁰ mix derives which

(iii) an α, β-monoethylenic containing a phosphoric acid group unsaturated monomer and (ii) at least one α, β-monoethylenically unsaturated one

Contains monomer,

(C) a wetting agent and / or a thickening agent in one Amount of 0.01 to 1.0 percent by weight, based on the

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1 resin particles, and

(D) the amount of water required.

The polyester-modified vinyl resin (component IA) used according to the invention is formed in the graft copolymerization of an unsaturated polyester resin as component (i) with an ^{α, β-if ~~ s} - '* - hvlenisch unsaturated''n monomer as component .i. - ^ -ster-modified vinyl resin is characterized in that it gives the vinyl resin by graft copolymerization the advantageous properties of the polyester resin, such as good flexibility, good pigment dispersibility and good appearance of the coating. An α,-unsaturated dicarboxylic acid is used as the starting compound for the production of the unsaturated polyester resin.

15 This unsaturated dicarboxylic acid is made up to a proportion

from 1 to 10 percent by weight, preferably 3 to 7 percent by weight, of the unsaturated polyester resin implemented.

If less than 1 percent by weight of unsaturated dicarboxylic acid is used, this amount is for the α, β-monoethylenically unsaturated Monomer for the production of the polyester-modified vinyl resin is insufficient because the modification with the Polyester resin is not sufficient and only a mixture of the unsaturated polyester resin and a copolymer of the α, β-monoethylenically unsaturated monomer is obtained. at When this polymer mixture is used, the resulting coating becomes cloudy and, because of its low reactivity, with it the crosslinkable copolymer (I B), the coating properties, e.g. its adhesion, are impaired. It is therefore not preferred to use the unsaturated dicarboxylic acid in such a small amount.

On the other hand, if the amount of unsaturated dicarboxylic acid is more than 10 percent by weight, gelation occurs during the reaction with the α, β-monoethylenically unsaturated Monomer, so that unsatisfactory results are obtained.

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Suitable α, B-unsaturated dicarboxylic acids are e.g. fumaric acid, Maleic acid and its anhydride, itaconic acid, glutaconic acid and citraconic acid and their anhydride. It can too Mixtures of two or more acids can be used.

To produce the unsaturated polyester resin used according to the invention, in addition to the aforementioned α, ß-unsaturated Dicarboxylic acid implemented a further carboxylic acid component in an amount of 29 to 69 percent by weight. As such Carboxylic acid components are e.g. phthalic acid and its anhydride, isophthalic acid, trimellitic acid and its anhydride, Pyromellitic acid and its anhydride, tetrahydrophthalic acid and its anhydride, hexahydrophthalic acid and its anhydride, Methylhexahydrophthalic acid and its anhydride, 3,6-endomethylenetetrahydrophthalic acid anhydride, succinic acid and their anhydride, adipic acid, sebacic acid, benzoic acid and p-tert-butybenzoic acid. Mixtures of two can also be used or more of these acids can be used.

For the production of the unsaturated used according to the invention Polyester resin, a polyhydric alcohol component is preferably reacted in an amount of 30 to 70 percent by weight. Suitable polyhydric alcohols are e.g. ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, dipropylene glycol, Glycerine, trimethylolethane, trimethylolpropane, pentaerythritol, Dipentaerythritol, butanediol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol and bisphenol A (hydrogenated bisphenol A). Mixtures of two or more of these alcohols can also be used. In combination with the multi-valued The alcohol component may optionally be a glycidyl ester of a synthetic tertiary fatty acid (e.g. "Cardura E" from the Shell Chemicals Co.) can be used.

In addition to the above components, modifiers can also be used for the unsaturated polyester resin, if necessary e.g. animal or vegetable oils, their fatty acids,

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- 16 1 Petroleum resins, synthetic resins, phenolic resins and epoxy resins.

The unsaturated polyester resin used in the present invention
can be produced in a known manner in a single or multi-stage process. Optionally, one of the polymerization solvents described below can be used as
Use thinner.

The unsaturated polyester resin used in the present invention has preferably an acid number of less than 50 (always based on the solid synthetic resin), a hydroxyl number of 50 to 250 (always based on the solid synthetic resin) and a molecular weight (weight average) of 2000 to 20,000. The weight mean the molecular weight is determined by gel permeation chromatography using a chromatograph Model A 801 from Tokyo Soda Co., Ltd. certainly.

If the acid number of the unsaturated polyester resin (i)
is more than 50, the properties of coatings

that from the paint which is a graft copolymerized of the unsaturated polyester with the α, ß-monoethylenically unsaturated monomer obtained polyester-modified Vinyl resin (I A) containing, have been produced, impaired, especially with regard to alkali resistance.

If the hydroxyl number is less than 50, the polyester-modified one has Vinyl resin (I A) obtained by graft copolymerization of the unsaturated polyester with the α, ß-monoethylenically unsaturated Monomer has been obtained, insufficient crosslinkability with the crosslinkable copolymer (IB). At a

³⁰ hydroxyl number greater than 250 decreases the water resistance

of the coatings obtained due to the increase in polar groups away. If the weight average molecular weight is less than 2,000, the polyester resin cannot maintain its properties fully unfold, while at a molecular weight of more

³⁵ than 20,000 the viscosity when modifying with the α, ß-monoethylenically unsaturated monomer due to the excessively high MoIe-

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The molecular weight of the polyester resin increases sharply and the processability the coating is made more difficult.

The polyester-modified vinyl resin of the present invention is by graft copolymerizing the above unsaturated polyester resin (i) with the α, β-monoethylenically unsaturated one Monomer (ii) produced. At least one compound from the group of α, β-monoäthylenlsch is used as monomer (ii) unsaturated carboxylic acids, hydroxyalkyl esters of these α, ß-monoethylene unsaturated acids and alkyl esters of acrylic acid or methacrylic acid.

The polyester-modified vinyl resin (I A) should have a hydroxyl group in the molecule for the crosslinking reaction with the crosslinkable Have copolymer (I B). If, therefore, the hydroxyl number of the above-mentioned unsaturated polyester resin is relatively small, a hydroxyalkyl ester of an α, ß-monoethylenically unsaturated carboxylic acid is preferably used as one of the α, ß-monoethylenically unsaturated monomers. Of the Hydroxyalkyl ester is in the α, ß-monoethylenically unsaturated Monomers in an amount of 5 to 50 percent by weight, preferably

^ Zugsweisä 8 to 30 percent by weight, applied so that the Hydroxyl number of polyester-modified vinyl resin (I A) 30 to 200. If more than 50 percent by weight of hydroxyalkyl esters are used, the viscosity of the polyester obtained will be modified icated vinyl resin (I A) and the crosslinkability of the resin (I A) with the crosslinkable copolymer (I B) large, so that the flexibility and water resistance of the obtained Coating are impaired.

Examples of suitable hydroxyalkyl esters are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl

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acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, neopentyl glycol monoacrylate, neopentyl glycol monomethacrylate, 3-butoxy-2-hydroxypropyl acrylate, S-butoxy ^ -hydroxypropyl methacrylate, 2-hydroxy-methacrylate-1-phenyl methacrylate, 2-hydroxy-hydroxy-1-acrylate, 2-hydroxy-methacrylate-1-phenyl methacrylate, 2-hydroxy-methacrylate-1-phenyl-phenyl-acrylate , Polypropylene glycol monoacrylate, propylene glycol monomethacrylate, glycerin monoacrylate and glycerin monomethacrylate. These monomers can either be made up of two or more ver

bindings are used. 10

The other monomer, in addition to the hydroxyalkyl ester of α, ß-monoethylenically unsaturated carboxylic acid, forms the graft copolymer isation is applied with the unsaturated polyester resin, can in an amount of 50 to 95% of the monomer mixture,

15 can be used. Suitable monomers of this type are e.g.

α, ß-monoethylenically unsaturated carboxylic acids, such as acrylic acid, Methacrylic acid, itaconic acid, maleic acid and fumaric acid, alkyl esters of acrylic acid and methacrylic acid, such as methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, Lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, Stearyl acrylate and stearyl methacrylate; N, N'-dimethylaminoethyl acrylate, N, N'-dimethylaminoethyl methacrylate, Glycidyl acrylate, glycidyl methacrylate, cyclohexyl

³⁰ acrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl

methacrylate, dialkyl esters of fumaric acid such as dimethyl fumarate, styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methacrylonitrile and vinyl acetate. These monomers are selected according to the purpose of the paint and can be used alone or as mixtures of two or more compounds.

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In the first embodiment (I) according to the invention, the polyester-modified vinyl resin (I A) consists of a graft copolymer from 5 to 50 percent by weight of the above unsaturated polyester resin (i) and 50 to 95 percent by weight

⁵ cent at least one of the aforementioned <x, ß-mono-

ethylenically unsaturated monomers (ii). The modification amount of the unsaturated polyester resin is thus 5 to 50 percent by weight, preferably 10 to 40 percent by weight. With a modification amount of less than 5 weight per - "* The advantageous properties of the polyester resin, such as good flexibility and good pigment dispersibility, can be achieved and good appearance of the coating, do not develop sufficiently, while at a modification amount of more than 5O weight percent the valuable properties of the vinyl resin, such as high hardness and good corrosion resistance.

In the second embodiment (II) according to the invention an α, ß-monoethylenic containing a phosphoric acid group unsaturated monomer introduced as component (iii) in the polyester-modified vinyl resin (II A). As monomers (iii) Primary phosphoric acid esters containing hydroxyl groups are suitable, for example of acrylic acid and methacrylic acid, such as acid phosphoxyethyl acrylate, acid phosphoxyethyl methacrylate, acid phosphoxypropyl acrylate, acid phosphoxypropyl methacrylate and 3-chloro-2-acid phosphoxypropyl methacrylate, bisacryloxyethyl phosphate, Bismethacryloxyethyl phosphate, acrylic alcohol acid phosphate, Vinyl phosphate, mono- (2-hydroxyethy1-acrylate) acid phosphite. Mono- (2-hydroxyethyl methacrylate) -

acid phosphite and their salts and esters. These monomers can be used alone or as mixtures of two or more compounds can be used. The monomers are prepared by adding a hydroxyl-containing α, ß-monoethylenically unsaturated one Reacts monomer with phosphoric anhydride and hydrolyzed the product obtained. You can also use of orthophosphoric acid, metaphosphoric acid, phosphorus

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¹ oxychloride, phosphorus trichloride or phosphorus pentachloride can be produced.

In embodiment (II) / in which an α, β-monoethylenically unsaturated monomer containing phosphoric acid groups (iii) is used, component (i) is used in an amount of 2 to 50 percent by weight, component (ii) in an amount from 95 to 40 percent by weight and component (iii) in an amount from 0.01 to 10.0 percent by weight, preferably 0.5 to 6.0 weight percent is used.

When using less than 0.01 percent by weight of the component (iii) the effects according to the invention, namely the prevention of rust attack and the improvement the shelf life and corrosion resistance, do not achieve. On the other hand, when using more than 10 percent by weight of component (iii) come to gelation during the graft copolymerization and are satisfactory there Results are obtained using up to 10 weight percent, it is for economic reasons not preferred to use the component (iii) in an amount of more than 10% by weight.

As mentioned above, the amount of modification is des unsaturated polyester resin, 2 to 50 percent by weight, preferably 10 to 40 percent by weight. With a modification amount of less than 2 percent by weight, the unsaturated Polyester resin has excellent properties, such as high flexibility, good pigment dispersibility and good deformation see the coating, do not unfold sufficiently, while with a modification amount of more than 50 percent by weight the characteristic properties of the vinyl resin, such as high hardness and good corrosion resistance, are impaired.

³⁵ The polyester-modified vinyl resin (II A) should have a hydroxyl group in the molecule for the crosslinking reaction with the

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contain crosslinkable copolymer (II B). Therefore, if the When the hydroxyl number of the unsaturated polyester resin is relatively small, a hydroxyalkyl ester is preferably used α, β-monoethylenically unsaturated carboxylic acid as one of the α, ß-monoethylenically unsaturated monomers. The hydroxyalkyl ester is in an amount of 1 to 40 percent by weight, preferably 5 to 20 percent by weight, in the α, β-monoethylenically unsaturated Monomers are used so that the hydroxyl number of the polyester-modified vinyl resin is 30-200. at Using this monomer in an amount greater than 40 percent by weight will modify the viscosity of the resulting polyester Vinyl resin (II A) and the degree of crosslinking with the crosslinked copolymer (II B) too high, so that the flexibility and water resistance of the coating obtained

Take 15.

The monomers mentioned above for the preparation of the polyester-modified vinyl resin can also be used in the second Embodiment for producing the polyester-modified vinyl resin (II A) can be used as a hydroxyalkyl ester.

The other monomer, besides the one containing phosphoric acid groups a, ß-monoethylene unsaturated monomer and the hydroxyalkyl ester of α, Β-monoethylene unsaturated carboxylic acid for graft copolymerization with the unsaturated polyester resin is used, in an amount of 60 to 99 percent by weight, preferably 80 to 95 percent by weight, of the Monomergemi see s, be applied.

The monomers mentioned above for the preparation of the polyester-modified vinyl resin (I A) can also be used for the preparation of the polyester-modified vinyl resin (II A) can be used.

By introducing the phosphoric acid group-containing α, ß-monoethylene unsaturated monomer into the polyester-modified

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te vinyl resin (II A) succeeds in rusting even when the paint is applied directly to an iron plate prevent and significantly improve the storage stability of the paint. It also increases the adhesion of the coating on the metal surface is further improved, and it becomes excellent in corrosion resistance and water resistance achieved.

The polyester-modified vinyl resin (I A) or (II A) can be prepared by conventional solution polymerization methods will. For example, a method can be used in which a mixture of the unsaturated polyester resin is used and making some monomer (or part of the monomer mixture) in a polymerization solvent and the remainder Monomer (or monomer mixture) and a polymerization initiator are added dropwise to the mixture to conduct polymerization. Another method is to drop the unsaturated polyester resin, monomers (or the monomer mixture) and one Polymerization initiator into a polymerization solvent to carry out polymerization. The solution polymerization process used is not critical to the invention.

The polymerization temperature is usually about 50 to 150 ° C and the polymerization time is usually in the range from about 4 to 12 hours, although the polymerization time is somewhat dependent on the temperature.

In the above solution polymerization process, a water-soluble or water-miscible solvent is used. Specific examples are alcohols such as methanol, Ethanol, isopropanol and n-propanol, ethylene glycol derivatives, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Xethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate, diethylene glycol derivatives such as diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, Esters such as methyl acetate, ethyl acetate and

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Butyl acetate, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. These polymerization solvents can be used individually or used as mixtures of two or more solvents. Solvent with a water solubility of about 10 to 30 percent by weight, determined at 20 ° C., are particularly preferred.

In the preparation of the polyester-modified vinyl resin (I A), the polymerization solvent is preferably used in is used in an amount that the nonvolatile component content of the synthetic resin is 10 to 80 percent by weight, preferably 35 to 75 percent by weight. In the production of the polyester-modified vinyl resin (II A), the polymerization solvent is used preferably used in an amount such that the non-volatile component content of the resin is 10 to 80 percent by weight, preferably 20 to 70 percent by weight. In the second embodiment (II), the content is of non-volatile components, preferably with increasing amounts of α, ß-monoethylenically unsound containing phosphoric acid groups

²⁰ saturated monomer.

As polymerization initiators for the solution polymerization, for example, organic peroxides are suitable, such as benzoyl peroxide, tert-butyl perbenzoate, tert-butyl-hydroperoxide Cumolhydroper- ^ oxide, di-tert-butyl peroxide and tert-butyl peroctoate, and azo compounds such as azobisisobutyronitrile and azodiisobutyronitrile . These polymerization initiators can be used singly or as mixtures of two or more. The polymerization initiator is used in an amount of about 0.1 to 15 percent by weight, based on the non-volatile components, in the production of the polyester-modified vinyl resin.

If necessary, a chain transfer agent can also be used to adjust the molecular weight, e.g. dodecyl mercaptan, 2-ethylhexyl thioglycolate or carbon tetrachloride.

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1 The chain transmitter is used in an amount of up to about

5 percent by weight based on the non-volatile components used in the manufacture of the polyester-modified vinyl resin.
5

The polyester-modified vinyl resin used in the present invention (I A) or (II A) has a hydroxyl number of 3O to 2OO, preferably 50 to 150 / and an acid number of 5 to 30, preferably 7 to 27. If the acid number is less than 5, a coating is used due to the inadequate heat curability obtained from poor hardness, water resistance, corrosion resistance and durability. On the other hand, with a Acid number of more than 30 affects the properties of the coating and the storage stability of the paint.

When the hydroxyl number is less than 30, the degree of crosslinking and the solvent resistance of the resulting coating is impaired. On the other hand, at a hydroxyl number of more than 200 gives poor flexibility and water resistance of the coating.

The weight average molecular weight of that used in the present invention Polyester-modified vinyl resin (I A) is preferably from 10,000 to 80,000, in particular from 20,000 to 60,000. With a molecular weight of less than 10,000

Inadequate coating properties are obtained, while with a molecular weight of more than 80,000, the coating properties are not smooth coating is created.

The weight average molecular weight of the polyester raodifi-30 Decorated vinyl resin (II A) is preferably from 20,000 to

100,000, in particular 30,000 to 80,000. With a molecular weight less than 20,000, insufficient coating properties are obtained, while at a molecular weight more than 100,000 do not produce a smooth coating. 35

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Since the polyester-modified vinyl resin (II A) used according to the invention is highly reactive, the viscosity increases at high temperatures, for example in summer. In this case, in order to improve the storage stability, the acid group introduced into the polyester-modified vinyl resin can be neutralized with a basic compound. Suitable basic compounds are, for example, alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, water-soluble amines, such as ammonia, monomethylamine, dimethylamine, trimethylamine, triethylamine, monoethylamine, mono-n-propylamine and dimethyl-npropylamine, and water-soluble hydroxylamines, such as monoethanolamine, triethanolamine, triethanolamine, N-methylethanolamine _f N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, tripropanolamine and hydroxylamine.

These basic compounds can be used singly or as mixtures of two or more. According to the invention includes this neutralization with the basic compound both partial and complete neutralization of the acid groups the polyester-modified vinyl resin (II A). In view of the stability of the polyester-modified vinyl resin (II A) and the properties of the coating obtained, an excess of the basic compound can also be used will.

According to the invention, an N-alkoxymethylated monomer becomes one α, β-monoethylenically unsaturated carboxamide as mandatory component (iv) used. This component (iv) is for the crosslinking of the crosslinkable copolymer (I B) or (II B) with the polyester-modified vinyl resin (I A) or (II A) required. Component (iv) is in an amount of 5 to 30 percent by weight, preferably 10 to 25 percent by weight, in the crosslinkable copolymer (I B) or (II B) copolymerized. If less than 5 percent by weight of component (iv) is used, the crosslinking is with the polyester-modified vinyl resin is insufficient and the solvent resistance the coating obtained is affected

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ORIGINAL INSPECTED

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'pregnant. On the other hand, it happens when using more than 30 percent by weight leads to gelation during the preparation of the crosslinkable copolymer and it cannot produce good results can be obtained.

For example, N-alkoxymethylated compounds are suitable as component (iv) Products of α, β-monoethylenically unsaturated carboxamides, such as N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-Äthoxymethylacrylamid, N-Äthoxyraethy! Methacrylamid, N-n-Propoxymethylacrylamid, N-n-Propoxymethy! Methacrylamid, N-isopropoxymethylacrylamide, N-I sopropoxymethy! Methacrylamide, N-n-Butoxymethylacrylamid, N-n-Butoxymethy! Methacrylamid, N sec. -Butoxymethy lacry lamid, N-sec-Butoxyme thylmethacry 1-amid, N-tert-butoxymethyl acrylamide, N-tert-butoxymethyl methacrylamide, N-isobutoxymethyl acrylamide and N-isobutoxymethyl methacrylamide and their N-methylolated products. These connections can be used individually or as a mixture of two or more.

According to the invention, an α, ß-monoethylenically unsaturated Carboxylic acid in an amount of 0.5 to 10 percent by weight as a component of the crosslinkable copolymer (I B) or (II B) can be used. This monomer improves the compatibility of the crosslinkable copolymer with the poly

ester-modified vinyl resin and promotes crosslinking between them. If less than 0.5 percent by weight of the monomer is used, little effect is achieved and if the amount exceeds 10 percent by weight, the properties of the cured coating will be impaired.

Specific examples of these monomers are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and Fumaric acid. These acids can be used singly or as mixtures of two or more.

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In the preparation of the crosslinkable copolymer (I B) or (II B), a copolymerizable ß, ß-ethylenically unsaturated one Monomers other than those mentioned above, preferably in an amount of from 60 to 90 percent by weight implemented. Suitable copolymerizable monomers are, for example, alkyl esters of acrylic acid and methacrylic acid, such as Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, Isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, . 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, Lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, Stearyl acrylate and stearyl methacrylate, hydroxyalkyl esters of a, ß-ethylenically unsaturated carboxylic acids, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, Neopentyl glycol monoacrylate, neopentyl glycol monomethacrylate, 3-butoxy-2-hydroxypropyl acrylate, 3-butoxy-2-hydroxypropyl methacrylate, 2-hydroxy-1-phenylethyl acrylate, 2-hydroxy-phenylethyl methacrylate, Polypropylene glycol monoacrylate, propylene glycol monomethacrylate, glycerol monoacrylate and Glycerol monomethacrylate and other monomers, such as N'-dimethylaminoethyl acrylate, N'-dimethylaminoethyl methacrylate, glycidyl acrylate, Glycidyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, Phenyl methacrylate, benzyl methacrylate, alkyl esters of fumaric acid, such as dibutyl fumarate, styrene, vinyl toluene, α-methylstyrene, acrylonitrile, methacrylonitrile and vinyl acetate.

These monomers are used according to the purpose of the Selected paint and can be used individually or as a mixture

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- 28 ¹ see of two or more can be used.

The crosslinkable copolymer (IB) or (II B) can be prepared by conventional solution polymerization processes. For the solution polymerization, one of the abovementioned water-soluble or water-miscible solvents and the abovementioned organic peroxides or azo compounds can be used as polymerization initiators. Furthermore, one of the chain transfer agents mentioned above can be used as a molecular weight regulator. To produce the crosslinkable copolymer, the polymerization is carried out for about 4 to M hours at a temperature of about 50 to 150.degree. The amount of the polymerization solvent is chosen so that the concentration of the non-volatile components in the preparation of the copolymer is 10 to 80 percent by weight, preferably 35 to 75 percent by weight. The polymerization initiator is used in an amount of about 0.1 to 15 percent by weight, and the chain transfer agent in an amount of up to about 5 percent by weight, based in each case on the non-volatile components in the preparation of the crosslinkable copolymer.

In the first embodiment (I) the molecular weight is ² ^ (weight average) of the crosslinkable copolymer is preferably from 10,000 to 70,000, especially from 20,000 to 60 000. At molecular weights of less than 10 000 is ungenü- ,. Low coating properties achieved, while at molecular weights of more than 70,000 the smoothness of the coating is impaired.

In the second embodiment (II), the molecular weight (weight average) of the crosslinkable copolymer is preferably 10,000 to 100,000, in particular 20,000 to 80,000.

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According to the invention, (A) the above-mentioned polyester-modified Vinyl resin (I A) or (II A) with (B) the above-mentioned crosslinkable copolymer (I B) or (II B) mixed. The weight ratio of polyester-modified vinyl resin to crosslinkable copolymer is in the range from 5:95 to 90:10, preferably 10:90 to 70: when using less than 10 percent by weight of crosslinkable Copolymer, the degree of crosslinking of the coating obtained is low and the solvent resistance and chemical resistance of the coating are impaired. On the other hand, if more than 95 percent by weight is used crosslinkable copolymer the amount of polyester-modified Vinyl resin and the properties characteristic of the polyester resin / such as excellent flexibility

^ Iitat, good pigment dispersibility and good appearance of the Coating do not come into play.

The synthetic resin particles consisting of the polyester-modified vinyl resin (IA) or (II A) and the crosslinkable copolymer (IB) or (II B) should have a softening point of 30 to 100.degree. C., in particular 40 to 80.degree. At a softening point of less than 30 C, the paint has poor storage stability and the Uberzugseigenschaf- be at a softening point of more than 100 ⁰ C.

²⁵ th, for example the surface smoothness, impaired.

To promote crosslinking between the polyester-modified Vinyl resin and the crosslinkable copolymer can be used according to the invention known acidic catalysts. In addition, in combination with the above synthetic resin components, film-forming resins such as epoxy resins, Cellulose or amino resins.

The following is a third embodiment of the present invention (III). In this embodiment, a monomer mixture that (iv) is an N-alkoxymethylated monomer

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1 of an α, ß ~ monoethylenically unsaturated carboxamides

contains, for the production of the polyester-modified vinyl resin used and a copolymer containing phosphoric acid groups is used as crosslinkable copolymer (B),

⁵ which is derived from a monomer mixture which (iii)

an α, Β-monoethylenically unsaturated one containing phosphoric acid groups Contains monomer.

In this third embodiment of the invention (III) the polyester-modified vinyl resin to be used becomes one of the above unsaturated ones by graft copolymerization Polyester resins prepared with a monomer mixture, the at least (iv) an N-alkoxymethylated monomer α, β-monoethylenically unsaturated carboxamides and a other common α, β-monoethylenically unsaturated carboxamide as well as another common α, β-monoethylenically unsaturated monomer such as any of the above said α, β-monoethylenically unsaturated carboxylic acids, their hydroxyalkyl esters or an alkyl ester of acrylic acid or methacrylic acid.

In this embodiment (III), the polyester-modified vinyl resin (III A) should contain a hydroxyl group in the molecule, not only for the crosslinking with the phosphoric acid group-containing copolymer (III B) but also for the Self-networking.

Therefore, if the hydroxyl number of the unsaturated polyester resin is relatively small, it is preferable to use a hydroxyl ** alkyl ester of an α, β-monoethylenically unsaturated carboxylic acid as one of the α, ß-monoethylenically unsaturated monomers. The hydroxyalkyl ester is used in an amount of 1 to 30 percent by weight, preferably 3 to 20 percent by weight, used in the monomer mixture used, so that the

The hydroxyl value of the polyester-modified vinyl resin is 10 to 150.

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If more than 30 percent by weight of the hydroxyalkyl ester is used, the polyester-modified vinyl resin (III A) is highly viscous and the degree of crosslinking is with the heat curing the phosphoric acid group-containing copolymer! sat (III B) resulting Product is too high. As a result, the properties of the coating obtained, such as flexibility and Water resistance, impaired.

The ones used in the manufacture of polyester-modified vinyl resins Hydroxyalkyl esters mentioned (I A) and (II A) can also be used in this embodiment (III).

That for the graft copolymerization with the unsaturated polyester resin used N-alkoxymethylated monomer of the polymerizable α, β-monoethylenically unsaturated carboxamide is the α, β-monoethylene for crosslinking with the hydroxyalkyl ester unsaturated carboxylic acid and the polyester resin component are absolutely necessary. The at the production of the polyester-modified vinyl resins (I A) and (II A) mentioned monomers can be used. These Monomer component is in an amount of 5 to 30 percent by weight, preferably 10 to 20 percent by weight, based on the α, β-monoethylenically unsaturated monomer mixture, graft copolymerized. If less than 5 weight percent is used, the crosslinking reactivity of the polyester-modified one Vinyl resin (III A) is insufficient and the solvent resistance of the resulting coating decreases. Using of more than 30 percent by weight, gelation takes place during the graft copolymerization and there are no good results.

³⁰ nits received.

In the embodiment (III), in combination with these Monomers an α, β-monoäthylenisch unsaturated monomer are used, that of the hydroxyalkyl ester of a, ß-monoäthylenisch unsaturated carboxylic acid and the N-alkoxymethylated monomer of α, β-monoethylenically unsaturated carboxamide is different. As such α, β-monoethylene

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1 unsaturated monomers can be used in the production of

Polyester-modified vinyl resin (I A) called monomers are used in an amount of preferably 60 to 90 percent by weight of the monomer mixture used. 5

In the embodiment (III) the polyester is modified Vinyl resin (IHA) by graft copolymerization of 2 to 40 percent by weight of the above-mentioned unsaturated polyester resin with 60 to 98 percent by weight of the above

called monomer mixture. The amount of modification of the unsaturated polyester resin is 2 to 40 percent by weight, preferably 5 to 30 percent by weight. With a modification amount of less than 2 percent by weight come the excellent properties of the polyester resin, such as good flexibility, good pigment dispersibility and excellent appearance of the coating do not show their full advantage. On the other hand, when the modification amount of the polyester resin is more than 40% by weight, the characteristic ones become Properties of vinyl resin, such as high hardness and good

20 Corrosion resistance, impaired.

The polyester-modified vinyl resin (III A) is made by solution polymerization prepared in the same manner as the polyester-modified vinyl resin (I A). 25th

The hydroxyl number of the polyester-modified vinyl resin (III A) is 10 to 150, preferably 20 to 100, and the acid number is 3 to 40, preferably 5 to 25. In the case of an acid number less than 3 becomes insufficient thermosetting properties and poor hardness, water resistance, corrosion resistance and durability of the coating obtained. On the other hand, if the acid number is more than 40 adversely affects the coating properties and the storage stability of the paint. When the hydroxyl number is less than 10, the degree of crosslinking decreases and the solvent resistance of the resulting coating is deteriorated.

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On the other hand, when the hydroxyl value is more than 150, both flexibility and water resistance become effective of the coating obtained impaired.

In the embodiment (III), the molecular weight is (Weight average) of the polyester-modified vinyl resin (III A) is preferably 40,000 to 200,000, particularly 50,000 up to 150,000. If the molecular weight is less than 40,000, the properties of the coating are unsatisfactory, while with a molecular weight of more than 200,000 no smooth coating is formed.

The one used in embodiment (III) containing phosphoric acid groups Copolymer (III B) is made by copolymerization of the phosphoric acid group-containing α, ß-monoethylene unsaturated monomer as a mandatory component with other α, ß-monoethylenically unsaturated monomers. By introducing the α, β-monoethylenically unsaturated monomer containing phosphoric acid groups into the copolymer (III B), even when the paint is applied directly to an iron plate, rust formation is reduced and the adhesion to the metal surface is greatly improved. In addition, there is an increased storage stability of the paint and excellent corrosion resistance

²⁵ speed and water resistance of the coating achieved.

The above-mentioned α, β-monoethylenic containing phosphoric acid groups unsaturated monomer is used in an amount of 0.01 to 10.0 percent by weight, preferably 0.5 to 5.0 weight percent, used in the monomer mixture. If less than 0.01 percent by weight is used, the according to the invention desired effects, namely a prevention of rust formation and an improvement in storage stability and corrosion resistance, not preserved. When using

If more than 10 percent by weight of this monomer is used, gelation will occur during the polymerization and none will occur

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get good results. Since in addition, with amounts of up to 10 percent by weight achieves satisfactory results it is not preferable, for economic reasons, to use this monomer in an amount of more than 10% by weight

⁵ to be used.

As α, ß-monoethylenically unsaturated ones containing phosphoric acid groups The monomers mentioned in the production of the polyester-modified vinyl resin (II A) can be used will.

As an α, ß-monoethylenically unsaturated monomer that is derived from the Phosphoric acid groups containing α, ß-monoethylenically unsaturated Monomer is different as an obligatory component and which in combination with this obligatory monomer for Preparation of the polymer (III B) containing phosphoric acid groups is used, customary α, ß-monoethylene are suitable unsaturated monomers, for example the abovementioned α, ß-monoethylenically unsaturated carboxylic acids, their hydroxyalkyl esters and alkyl esters of acrylic acid and methacrylic acid. These monomers can be used individually or as a mixture of two or several can be used.

The copolymer (III B) containing phosphoric acid groups should have a hydroxyl group in the molecule for crosslinking with the Polyester-modified vinyl resin (III A) contain. Therefore, a good balance between the components (III A) and (III B) to adjust with respect to the hydroxyl groups contained, a suitable amount of one is preferably used Hydroxyalkyl ester of an α, ß-monoethylenically unsaturated Carboxylic acid as one of the α, ß-monoethylenically unsaturated monomers in the preparation of the phosphoric acid group-containing Copolymer! Sates (III B).

The hydroxyalkyl ester is used in an amount of 1 to 30 percent by weight, preferably 2 to 15 percent by weight, in which

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«- w ν: t ,: rf

- 35 -

used to prepare the copolymer (III B) containing phosphoric acid groups. Using of more than 30% by weight, gelation easily occurs during the copolymerization and the resultant Copolymer (III B) containing phosphoric acid groups is highly viscous and so is the degree of crosslinking with the polyester-modified one Vinyl resin (III A) is too high, so that the flexibility and water resistance of the coating obtained be affected. It is therefore not preferable to use the hydroxyalkyl ester in such a large amount. as Hydroxyalkyl esters, the monomers mentioned above can be used.

In embodiment (III), an α, β-monoethylenically unsaturated carboxylic acid is preferably used in an amount from 0.5 to 10 percent by weight as a component of the copolymer containing phosphoric acid groups (III B). This Monomer improves the compatibility of the copolymer (III B) containing phosphoric acid groups with the polyester-modified one Vinyl resin (III A) and also the crosslinking between them is promoted. When using less than 0.5 percent by weight of this monomer, the effects are not very pronounced. On the other hand, if more than 10% by weight adversely affects the properties of the cured coating and good results are not obtained.

Suitable monomers of this type are, for example, acrylic acid, methacrylic acid, Crotonic acid, itaconic acid, maleic acid and fumaric acid. These acids can be used singly or as a mixture of two or more.

In embodiment (III), it is preferred to use a copolymerizable α, ß-monoethylenically unsaturated monomer, other than the above-mentioned monomers in an amount of 70 to 90% by weight as one of the Starting monomers in the production of the phosphoric acid group

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Γ ~ 1

containing copolymer (III B). As such, copolymerizable α, β-monoethylenically unsaturated monomers can be used in the preparation of the crosslinkable copolymer (I B) or (II B) mentioned monomers can be used.

The one used in embodiment (III) containing phosphoric acid groups Copolymer (III B) is produced by conventional solution polymerization manufactured. For this solution polymerization, the abovementioned water-soluble or with Water-miscible solvents and the aforementioned organic peroxides or azo compounds as polymerization initiators be used. In addition, one of the chain transfer agents mentioned above can be used as a molecular weight regulator will. For the production of the phosphoric acid group-containing Copolymer (III B), the polymerization is usually carried out for about 4 to 12 hours at a temperature of about 50 to 150 C through. The solvent is preferably used in an amount that the content of non-volatile components in the reaction mixture for the preparation of the copolymer (III B) 10 to 80 percent by weight, preferably 20 to 70 percent by weight, amounts to. The content of non-volatile components is preferably reduced with an increasing amount of Phosphoric acid group-containing α, ß-monoethylenically unsaturated Monomer. In addition, it is preferred to use the polymerization initiator in an amount of about 0.1 to 15 percent by weight and the Chain transfer agents in an amount of up to about 5 percent by weight, based in each case on the non-volatile components the preparation of the copolymer (III B) to be used.

³⁰ In the embodiment (III), the molecular weight

(Weight average) of the copolymer containing phosphoric acid groups (III B) preferably 8,000 to 70,000, in particular 20,000 to 50,000. With a molecular weight of less than 8,000 insufficient coating properties are obtained while if the molecular weight is more than 70,000, the smoothness of the coating obtained is impaired.

030026/0835

The hydroxyl number of the copolymer (III B) containing phosphoric acid groups is preferably in the range from 3 to 150.

Since the copolymer containing phosphoric acid groups (III B) is highly reactive, its viscosity increases at high temperatures, e.g. in summer. In order to therefore increase the storage stability improve, you can use a basic compound to neutralize the in the phosphoric acid group-containing copolymer! sat Mix in (III B) introduced acid groups. Suitable basic compounds of this type are those for neutralizing the Acid groups of the polyester-modified vinyl resin (II A) proposed connections. The neutralization with the basic compound includes both partial and partial complete neutralization of the phosphoric acid groups contained in the copolymer (III B). In terms of stability of the paint obtained and the properties of the coating, the basic compound can also be used in excess will.

In the embodiment (III), the polyester-modified Vinyl resin (III A) and the copolymer (III B) containing phosphoric acid groups in a weight ratio of from 15:85 to 95: 5, preferably 30:70 to 90:10, is used.

When using less than 15 percent by weight of the polyester modif ized vinyl resin (III A), the excellent properties of the polyester resin, such as good flexibility, good pigment dispersibility and good appearance of the coating, not fully shown. On the other hand, when using of more than 95 percent by weight of the polyester-modified vinyl resin (III A), the amount of phosphoric acid group-containing Copolymer (III B) inevitably reduced and the effects intended according to the invention, in particular the reduction rust formation and improvement in corrosion resistance and water resistance are not achieved.

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In the embodiment (III), the softening point is the synthetic resin particles made from the modified polyester Vinyl resin (III A) and the copolymer (III B) containing phosphoric acid groups, preferably from 30 to 100 ° C., in particular 40 to 80 ° C. At a softening point of less than 30 ° C, the storage stability of the paint decreases and if the softening point is higher than 100 ° C, the coating smoothness deteriorates and the results are not good obtain.

In embodiment (III), known acidic catalysts can be used to reduce the crosslinking between the polyester modif icated vinyl resin (III A) and the phosphoric acid group-containing copolymer (III B) to promote. aside from that can optionally be a film-forming synthetic resin in combination with the synthetic resin components (III A) and (III B) mentioned can be used, e.g., an epoxy resin, a cellulose resin or an amino resin.

The following is the preparation of the thermosetting according to the invention Paint based on an aqueous dispersion described. It can be used for the production of conventional powder coatings and emulsion paints, conventional mechanical pulverization methods can be used, although at lower levels Softening point of the synthetic resin mixture used, pulverization according to these mechanical pulverization methods is difficult because the resin mixture has too high a stickiness. For the production of the thermosetting according to the invention The following special process is therefore preferably used for paints based on an aqueous dispersion .

First, certain amounts of the polyester are modified Vinyl resin (I A), (II A) or (III A) and the crosslinkable copolymer (I B), (II B) or (III B) optionally together with a basic compound in a sufficient

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- 39 -

Amount to some or all of the acid groups of the polyester-modified To neutralize vinyl resin (II A) or the copolymer containing phosphoric acid groups (III B), a curing catalyst and another film-forming synthetic resin in any of the above-mentioned water-soluble ones or dissolved with water-miscible solvents to form a synthetic resin solution. If necessary, a pigment can be added to the solution add and knead to form a pigment dispersion.

Suitable solvents are the solvents mentioned for the solution polymerization, the amount of which is chosen so that that the content of the solution or dispersion of non-volatile components is 30 to 80 percent by weight.

The resulting synthetic resin solution or pigment dispersion is then dissolved in water in an amount sufficient to absorb all of it to dissolve water-soluble or water-miscible solvents contained in the synthetic resin solution or pigment dispersion, dispersed in a finely divided state. The amount of water, based on weight, is at least 6 times the amount the synthetic resin solution or pigment dispersion and with a view to the subsequent filtering of the mixture obtained preferably up to about 40 times the amount of water used.

The dispersion of the synthetic resin solution or pigment dispersion can be carried out by a method in which the solution or pigment dispersion is dripped into vigorously stirred water and poured, or by a method in which the solution or pigment dispersion is mixed with water in a pipe mixer. When the temperature of the liquid mixture rises by the stirring and the synthetic resin particles aggregate or coalesce by softening the resin, the liquid mixture is preferably cooled and at a temperature below

Maintained 30 ° C to avoid the formation of coarse particles.

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¹ Stirring or mixing with the in-line mixer is carried out until the solvent in the emulsified fine particles has passed into the water and synthetic resin particles have formed. That in the dispersed fine particles

^{Solvent contained in 5} is thus extracted into the water to obtain the desired synthetic resin particles.

The synthetic resin particles are separated from the water / solvent mixture by filtration or centrifugation, whereby

1 ° if necessary, washing with water and separating several times repeatedly to obtain synthetic resin particles in the form of a slurry or a water-containing cake. The resin particles preferably have an average particle size of about 1 to 200 µm. Each of the obtained synthetic resin parts

15 chen contains both the polyester-modified vinyl resin as also the crosslinkable copolymer. The resin particles contain in other words, groups which react with each other when heated, i.e. hydroxyl and amide groups. When heated the paints according to the invention are therefore carried out

^ O crosslinking both within and between the synthetic resin particles, so that a coating with excellent properties is obtained.

Then, a wetting agent and / or a thickening agent and water are added to the synthetic resin particles in the form of a slurry or a water-containing cake and then carried out
a fine pulverization of the synthetic resin particles in an apparatus, as is commonly used for the production of
Paints is used, for example a sand mill, a ball mill, a disperser, a Süssmeyer mill or

wherein the average particle size to about 1 to 50 to set a Centri-mill.

The thermosetting paints of the present invention based on an aqueous dispersion preferably contain the synthetic resin particles in the form of finely dispersed particles with a

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Γ "I.

- 41 -

average size from 1 to 50 μΐη. With an average The tendency to agglomerate decreases with a size of less than 1 μm of the particles to and in the film-forming heating stage it can easily jump off. The properties of the paint thus, they are similar to those of a water-soluble paint and good results are not obtained. With an average With a size of more than 50 μm, sedimentation or cohesion of the synthetic resin particles can occur during storage come and the production of coatings with a smooth surface is made more difficult. Such a large particle size is therefore not preferred. In contrast, when using synthetic resin particles with an average particle size of 5 to 30 µm paint with excellent storage stability / the smooth and bubble-free coatings result, so that such

* ⁵ resin particles are particularly preferred.

The paints according to the invention also optionally contain Curing catalysts, organic or inorganic coloring or extending pigments, such as are usually used for paints rust preventives, flow regulators, defoamers, anti-precipitation agents, antiseptic agents, mold inhibitors and other additives, and film-forming synthetic resins such as water-soluble synthetic resins, hydrosols and emulsion resins. Since the softening point of the * Resin particles is preferably 30 to 100 ° C the total amount of additive components that do not melt at the film-forming temperature, preferably less than 50 percent by weight the end.

According to the invention, known non-ionic, anionic, cationic and amphoteric wetting agents can be used as component (C).

Suitable non-ionic wetting agents are, for example, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Polyoxyethylene fatty acid ester,

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Polyoxyethylene alcohol ether, glycerol fatty acid ester, propylene glycol fatty acid ester, Polyoxyethylene ricinus oil derivatives, polyoxyethylene alkyl phenyl ethers, alkyl phosphates and polyoxyethylene phosphates. Suitable anionic wetting agents are e.g.

Salts of alkyl sulfates, salts of polyoxyethylene alkyl ether sulfates, Salts of alkyl sulfosuccinates and N-acyl sarcosine salts. Suitable cationic wetting agents are, for example, quaternary ammonium salts and pyridinium salts.

Used in view of the dispersion stability of the synthetic resin particles and the properties of the obtained coating a nonionic wetting agent, in particular with an HLB value of 8 to 18, is preferred.

Any thickening agents such as those used for conventional aqueous synthetic resin paints can be used in place of or in Combination with the wetting agent can be used as component (C). Suitable thickeners are, for example, water-soluble ones Cellulose resins such as methyl cellulose, ethyl cellulose and hydroxyethyl cellulose, polyvinyl alcohol, water-soluble polyethylene resins, such as polyethylene glycol ether and polyethylene oxide, water-soluble maleic anhydride copolymers, such as methyl vinyl ether-maleic anhydride copolymers, Ethylene-maleic anhydride copolymers and styrene maleic anhydride

25 copolymers, ammonium, amine and sodium salts of acrylic acid polymers, bentonite, polyvinylpyrrolidone, alginic acid salts, polyacrylamide and its partial hydrolysis products and natural water-soluble resins such as casein and
Gelatin.

The wetting agent and / or the thickening agent are used in an amount of 0.01 to 1.0 percent by weight based on the fine Synthetic resin particles mixed in. When using less than 0.01 weight percent wetting agent and / or thickening agent the storage stability and the adaptability to the processability of the mass are impaired. Using

030026/0835

of more than 1.0 percent by weight of wetting agents and / or thickening agents the obtained coating has poor smoothness and water resistance.

Among the thickeners mentioned above, amine salts of acrylic copolymers containing carboxylic acid groups are particular preferred because the synthetic resin is rendered water-insoluble by splitting off the amine upon heating in the film-forming step and this resin does not impair the water resistance of the resulting coating in any way.

In the paints of the present invention, the weight ratio is from water to fine synthetic resin particles, preferably 90:10 to 30:70. If less is used Resin particles outside this range will be due the low solids concentration of the paint achieved insufficient viscosity, so that when applying the Paint in the usual thickness. e.g. 20 to 80 μια, in the coating show depressions in one application run

^ O can. To avoid this, it should be applied several times be repeated. In this case, the adaptability to the coating processability is drastically reduced.

On the other hand, if the resin particles are used in one larger amount outside the above-mentioned range, so can be in the paint production by stirring or Kneading hardly achieves homogenization and the viscosity is outside the range that is required for various coating processes, such as spraying and electrostatic coating is suitable. The adaptability to the order process is therefore deteriorated and the practical use of the paint is limited.

"^ To apply the paint according to the invention you can various known coating methods are used

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e.g. brushing, dipping, spraying, electrostatic Coating, curtain coating, spraying and rolling.

5 The conditions for heating and curing the inventive Paint after application depends somewhat on the content of crosslinkable functional groups in the paint, the desired coating thickness and other factors, but a cured coating is usually obtained 10 by heat treatment for 10 to 40 minutes at one temperature from 120 to 200 ° C.

The hardened coating has both the good properties of Polyester resin, such as good flexibility, good pigment dispersion

15 greedability and good looks, as well as the good properties of the vinyl copolymer, such as high hardness and good corrosion resistance. It also happens when burning high temperature, no yellowing and no chipping, but a hardened coating with excellent

ten properties.

The examples illustrate the invention. All parts and percentages are based on weight.

The following first describes the preparation of the solutions of unsaturated polyester resins, polyester-modified vinyl resins and crosslinkable copolymers! Examples are used.

Solutions of unsaturated polyester resins

(1) Unsaturated polyester resin No. 1 (hereinafter: PE-1)

One with stirrer, thermometer, cooling tube and nitrogen inlet tube equipped reaction vessel is filled with 32.6 parts of isophthalic acid, 18.7 parts of adipic acid, 3.0 parts of fumaric acid

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I L

acid, 29.0 parts of neopentyl glycol and 16.7 parts of trimethylolpropane loaded. A synthetic resin is obtained by reacting for about 8 hours in a nitrogen atmosphere at 225 ° C with an acid number of 15.1, a hydroxyl number of 155 and a weight average molecular weight of 6,700. The synthetic resin is diluted with methyl ethyl ketone to a content of non-volatile components of 60% to form a solution of the unsaturated polyester resin PE-1.

(2) Unsaturated polyester resin No. 2 (hereinafter: PE-2):

The reaction vessel used to prepare PE-1 is filled with 32.3 parts of isophthalic acid, 15.1 parts of adipic acid, 3.0 parts of fumaric acid, 22.9 parts of neopentyl glycol, 17.4 parts of trimethylolpropane and 9.3 parts of a glycidyl ether a synthetic tertiary saturated fatty acid ("Cardura E" from Shell Chemicals Co., Ltd.). By about 8 hours of reaction in a nitrogen atmosphere at 225 ° C gives a synthetic resin with an acid number of 16.2, a Hydroxyl number of 166 and a weight average molecular weight of 4200. The synthetic resin is treated with methyl ethyl ketone diluted to a content of non-volatile components of 60% to form a solution of the unsaturated polyester resin PE-2 to obtain.

(3) Unsaturated polyester resin No. 3 (hereinafter: PE-3):

The reaction is carried out for about 6 hours in a nitrogen atmosphere at 225 ° C as in the production of PE-1, however, 32.6 parts of o-phthalic anhydride are used instead of 32.6 parts of isophthalic acid. This gives a synthetic resin with an acid number of 45, a hydroxyl number of 158 and a weight average molecular weight of 2450. The synthetic resin is mixed with methyl ethyl ketone to a content diluted 60% of non-volatile components to obtain a solution of the unsaturated polyester resin PE-3.

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- 46 ¹ Solutions of polyester modified vinyl resins

(1) A reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and nitrogen inlet tube is charged with 270 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 200 parts of methyl methacrylate, 150 parts of ethyl acrylate, 45 parts of 2-hydroxyethyl methacrylate is added , 5 parts of acrylic acid, 100 parts of the polyester resin PE-1 obtained above and 6 parts of azobisisobutyronitrile are added dropwise over 3 hours. When the addition is complete, more azobisisobutyronitrile (1 part) is added and the reaction ^{temperature is} increased to 87 ° C. After 4 hours of reaction, a synthetic resin solution with a non-volatile component content of 62.0% is obtained.

The synthetic resin has an acid number of 11.6, a hydroxyl number of 110, a weight average molecular weight of 31,000 and a softening point of about 66 to 68 ^° C. The synthetic resin solution obtained is referred to as PE-V-1.

(2) The reaction is carried out as in the preparation of the polyester-modified vinyl resin solution PE-V-1, but the polyester resin PE-3 is used instead of the polyester resin PE-1. This gives a synthetic resin solution with a non-volatile component content of 59.8%. The synthetic resin has an acid number of 14.9, a hydroxyl number of 118, a weight average molecular weight of 33,000 and a softening point of about 69 to 72 ^° C. The synthetic resin solution obtained is referred to as PE-V-2.

(3) The reaction vessel used to prepare the synthetic resin solution PE-V-1 is charged with 200 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 125 parts of methyl methacrylate, 10 parts 2-ethylhexyl acrylate, 110 parts of 2-ethylhexyl methacrylate,

45 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 1OO parts of the polyester resin PE-2 and 6 parts of azobisiso

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\ butyronitrile is added dropwise within 3 hours. When the addition is complete, more azobisisobutyronitrile (1 part) is added and the reaction temperature is increased to 87.degree. After 4 hours of reaction, a synthetic resin solution with a non-volatile component content of 63.1% is obtained. The synthetic resin has an acid number of 11.3, a hydroxyl number of 125, a weight average molecular weight of 27,000 and a softening point of about 70 to 73 ° C. The synthetic resin solution is called PE-V-3.
10

(4) The reaction is the same as for the polyester-modified ones Vinylharζlösung PE-V-2 carried out, but used the polyester resin PE-2 instead of the polyester resin PE-3 and the amount of polyester resin is 200 parts. Here a synthetic resin solution with a non-volatile component content of 60.5% is obtained. The synthetic resin has an acid number of 12.4, a hydroxyl number of 96, one weight average molecular weight of 49,000 and a softening point of about 65 to 68 ° C. The synthetic resin solution obtained is called PE-V-4

20 draws.

(5) The reaction is carried out as in the preparation of the polyester-modified Vinylharζlösung PE-V-1, but using 200 parts of styrene instead of methyl methacrylate and 100 parts of the polyester resin PE-2 instead of the polyester resin PE-1. This gives a synthetic resin solution with a non-volatile component content of 58.1%. The synthetic resin has an acid number of 9.1, a hydroxyl number of 115, a weight average molecular weight of 30,000 and a softening point of about 69 to 72 ^° C. The synthetic resin solution is designated as PE-V-5.

(6) One with stirrer, thermometer, dropping funnel, cooling tube and Nitrogen inlet tube equipped reaction vessel is charged with 265 parts of methyl ethyl ketone, whereupon the temperature is adjusted increased to 80 ° C and a liquid mixture of 175 parts

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Methyl methacrylate, 35 parts of styrene, 145 parts of ethyl acrylate, 35 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 5 parts of acidic phosphoxyethyl methacrylate, 100 parts of the polyester resin PE-2 and 6 parts of azobisisobutyronitrile are added dropwise within 3 hours. After completion of the addition is added with further azobisisobutyronitrile (1 part) and increases the reaction temperature to 87 ⁰ C. After 4 hours reaction to obtain a resin solution having a content of non-volatile components of 62.1%. The synthetic resin has an acid number of 15.3, a hydroxyl number of 119, a weight average molecular weight of δ3,000 and a softening point of about 79 to 81 ^° C. The resin solution obtained is then treated with triethylamine in an amount of 2/3 mol per acid number of the synthetic resin added to carry out a neutralization. the

¹⁵ obtained synthetic resin solution is referred to as PE-PV-1.

(7) The reaction is the same as in the preparation of the resin solution PE-PV-1 carried out, but using 200 parts of methyl ethyl ketone, 133 parts of methyl methacrylate, 25.5 parts Styrene, 109 parts of ethyl acrylate, 26 parts of 2-hydroxyethyl methacrylate, 4 parts of acrylic acid, 2.5 parts of acidic phosphoxymethyl methacrylate and 200 parts of the polyester resin PE-2. It becomes a synthetic resin solution with a non-volatile content Components received by 61.9%. The synthetic resin has an acid

²⁵ number of 15.0, a hydroxyl number of 93, a weight average molecular weight of 70,200 and a softening point of about 71 to 74 ⁰ C. The synthetic resin solution is designated PE-PV-2.

(8) The one used to prepare the resin solution PE-PV-1 The reaction vessel is charged with 430 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 157.5 parts of methyl methacrylate, 15 parts of styrene, 12.5 parts of 2-ethylhexyl acrylate, 180 parts

2-ethylhexyl methacrylate, 45 parts of 2-hydroxyethyl methacrylate,

5 parts of acrylic acid, 5 parts of acidic phosphoxyethyl methacrylate,

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5 parts of S-chloro ^ -saurem-phosphoxypropyl methacrylate, 75 parts of polyester resin PE-3 and 6 parts of azobisisobutyronitrile are added dropwise over the course of 3 hours. After the addition has ended, further azobisisobutyronitrile (1 part) is added, the reaction ^{temperature is increased to 87 °} C. and the reaction is carried out for 4 hours, a synthetic resin solution with a non-volatile component content of 50.5% being obtained. The synthetic resin has an acid number of 20.6, a hydroxyl number of 103, a weight average molecular weight of 65,000 and a ¹ ^ softening point of about 69 to 73 ° C-The resin solution obtained is with triethylamine in an amount of 2/3 mol per The acid number of the synthetic resin is neutralized. The solution obtained is called PE-PV-3.

^ (9) The one used to make the resin solution PE-PV-1 The reaction vessel is charged with 250 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid one Mixture of 157 parts of methyl methacrylate, 12.5 parts of 2-ethylhexyl acrylate, 138 parts of 2-ethylhexyl methacrylate, 56.5 parts of 2-hydroxyethyl methacrylate, 6 parts of acrylic acid, 5 parts of acid phosphoxyethyl methacrylate, 125 parts of polyester resin PE-1 and 7.5 parts of azobisisobutyronitrile within 3 hours added dropwise. When the addition is complete, more azobisisobutyronitrile (1.2 parts) is added, the reactivity is increased

"Tion temperature to 87 ⁰ C and the reaction results in 4 hours to obtain a resin solution is obtained having a content of non-volatile component of 61.5%. The resin has an acid number of 17.7, a hydroxyl value of 115, a weight average molecular weight of 32 100 and a softening point of about 67 to 69 ^° C. The synthetic resin solution obtained is neutralized with triethylamine in an amount of 2/3 mol per acid number of the synthetic resin. The synthetic resin solution obtained is designated PE-PV-4.

(10) The reaction is the same as in the preparation of the resin solution PE-PV-1 carried out, but 750 parts are used

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Methyl ethyl ketone, 190 parts of methyl methacrylate, 50 parts of styrene, 180 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 25 parts of acid phosphoxyethyl methacrylate and 40 parts of polyester resin PE-2. This gives a synthetic resin solution with a non-volatile component content of 39.8%. The resin has an acid number of 23.1, a hydroxyl number of 35, a weight average moles kulargewichts of 34 200 and a softening point of about 71 to 74 ⁰ C. The resin solution obtained is treated with triethyl amine in an amount of 3/4 mole neutralized per acid number of the synthetic resin. The solution obtained is called PE-PV-5.

(11) The reaction is the same as in the preparation of the resin solution PE-PV-1 carried out, but using 5 parts of acid phosphoxyethyl acrylate instead of 5 parts of acid Phosphoxyethyl methacrylate, a synthetic resin solution with a non-volatile component content of 61.6% being obtained will. The synthetic resin has an acid number of 14.8, a hydroxyl number of 110, a weight average molecular weight of 80,500 and a softening point of about 78 to 80 ° C. The synthetic resin solution obtained is neutralized with diethylamine in an amount of 2/3 mol / acid number of the synthetic resin.

The solution obtained is called PE-PV-6. 25th

(12) A reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and nitrogen inlet tube is charged with 300 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 75 parts of methyl methacrylate, 140 parts of styrene, 165 parts of ethyl acrylate, 10 Parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 50 parts of Nn-butoxymethylacrylamide, 50 parts of polyester resin PE-1 and 6 parts of azobisisobutyronitrile are added dropwise over the course of 3 hours. After the addition has ended, the mixture is added

*> with more azobisisobutyronitrile (1 part), increases the reaction ^{temperature to 87 e} C and carries out the reaction for 4 hours

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to obtain a synthetic resin solution having a non-volatile component content of 57.5%. The synthetic resin has an acid number of 16.2, a hydroxyl number of 40.5, a weight average molecular weight of 61,500 and a softening point of about 66 to 68 ^° C. The solution obtained is designated PE-AV-1.

(13) The reaction vessel used to prepare the synthetic resin solution PE-AV-1 is charged with 280 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 60 parts of methyl methacrylate, 145 parts of styrene, 155 parts of ethyl acrylate, 5 parts 2-Hydroxyethyl methacrylate, 10 parts of acrylic acid, 50 parts of Nn-butoxymethylacrylamide, 75 parts of polyester resin PE-2 and 6 parts of azobisisobutyronitrile are added dropwise over the course of 3 hours. After the addition has ended, further azobisisobutyronitrile (1 part) is added, the reaction ^{temperature is increased to 87 °} C. and the reaction is carried out for 4 hours, a synthetic resin solution with a non-volatile component content of 58.1% being obtained.

The synthetic resin has an acid number of 17.4, a hydroxyl number of 67.0, a weight average molecular weight of 135,100 and a softening point of about 67 to 69 ° C. the obtained solution is designated PE-AV-2.

^ (14) The implementation is the same as for the preparation of the synthetic resin solution PE-AV-2 carried out, but 300 parts are used Methyl ethyl ketone, 150 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 75 parts of N-n-butoxymethylacrylamide and 50 parts Polyester resin PE-2. A synthetic resin solution is obtained here with a non-volatile component content of 57.3%. The synthetic resin has an acid number of 16.8, a hydroxyl number of 42.5, a weight average molecular weight of 72,100 and a softening point of about 64 to 67 ° C. the

obtained solution is designated PE-AV-3. 35

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(15) The reaction vessel used to prepare the synthetic resin solution PE-AV-1 is charged with 280 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 50 parts of methyl methacrylate, 135 parts of styrene, 145 parts of ethyl acrylate, 10 parts 2-Hydroxyethyl methacrylate, 10 parts of acrylic acid, 75 parts of Nn-butoxymethylacrylamide, 75 parts of polyester resin PE-3 and 6 parts of azobisisobutyronitrile are added dropwise over the course of 3 hours. When the addition is complete, more azobisisobutyronitrile (1 part) is added, the reaction ^{temperature is increased to 87 °} C. and the reaction is carried out for 4 hours, a synthetic resin solution with a non-volatile component content of 58.2% being obtained. The synthetic resin has an acid number of 15.1, a hydroxyl number of 61.0, a weight average molecular weight of 97,500 and a softening point of about 63 to 65 ° C. The solution obtained is called PE-AV-4.

Solutions of crosslinkable copolymers 20

(1) One with stirrer, thermometer, dropping funnel, cooling tube Reaction vessel equipped and nitrogen inlet tube is charged with 340 parts of methyl ethyl ketone, whereupon the Temperature increased to 80 ° C and a liquid mixture of 50 parts of methyl methacrylate, 150 parts of styrene, 165 parts Xthylacrylate, 125 parts of N-n-butoxymethylacrylamide, 10 parts of acrylic acid and 10 parts of azobisisobutyronitrile within 3 hours added dropwise. When the addition is complete, a further 1.5 parts of azobisisobutyronitrile are added and the reaction temperature is increased to 87 ° C. and carry out the reaction for 4 hours, a synthetic resin solution having a nonvolatile component content of 58.4% being obtained. The synthetic resin has an acid number of 12.0, a weight average molecular weight of 38,000, and a softening point of about 73 to 75 ° C. The synthetic resin solution obtained is referred to as V-1.

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(2) The reaction vessel used to prepare the synthetic resin solution V-1 is charged with 340 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 150 parts of methyl methacrylate, 65 parts of styrene / 175 parts of ethyl acrylate, 100 parts of Nn- Butoxymethylacrylamide, 10 parts of acrylic acid and 10 parts of azobisisobutyronitrile are added dropwise within 3 hours. When the addition is complete, a further 1.5 parts of azobisisobutyronitrile are added, the reaction ^{temperature is increased to 87 °} C. and the reaction is carried out for 4 hours, a synthetic resin solution with a non-volatile component content of 59.0% being obtained. The synthetic resin has an acid number of 13.9, a weight average molecular weight of 42,000 and a softening point of about 72 to 75 ° C. The synthetic resin solution obtained is V-2

15 designated.

(3) A with stirrer, thermometer, dropping funnel, cooling tube and nitrogen inlet tube equipped reaction vessel is charged methyl ethyl ketone with 340 parts, followed by increasing the temperature to 80 ⁰ C and a liquid mixture of 190 parts of methyl methacrylate, 80 parts of styrene, 210 parts of ethyl acrylate, 10 Parts of 2-hydroxyethyl methacrylate, 5 parts of acidic .Phosphoxyäthylmethacrylat, 5 parts of acrylic acid and 10 parts of azobisisobutyronitrile are added dropwise over 3 hours. After loading

^ Complete addition, it is mixed with a further 1.5 parts of azobisisobutyronitrile, the reaction temperature was raised to 87 ⁰ C and the reaction results in 4 hours to obtain a resin solution is obtained having a content of non-volatile components of 59.0%. The synthetic resin has an acid number of 11.4, a weight average molecular weight of 25,000 and a softening point of about 71 to 73 ^° C. The synthetic resin solution is neutralized with triethylamine in an amount of 2/3 mol per acid number of the synthetic resin. The synthetic resin solution obtained

is referred to as PV-1. 35

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(4) The reaction vessel used to prepare the synthetic resin solution PV-1 is charged with 340 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 190 parts of methyl methacrylate, 70 parts of styrene, 215 parts of ethyl acrylate, 10 parts of 2- Hydroxyethyl methacrylate, 10 parts of acid phosphoxymethyl acrylate, 5 parts of acrylic acid and 10 parts of azobisisobutyronitrile are added dropwise over the course of 3 hours. When the addition is complete, a further 1.5 parts of azobisisobutyronitrile are added, the reaction ^{temperature is increased to 87 °} C. and the reaction is carried out for 4 hours, a synthetic resin solution with a non-volatile component content of 59.0% being obtained. The resin has an acid number of 13.7, a weight average molecular weight of 30 800 and a softening point of about 72 to 75 ^e C.

The synthetic resin solution obtained is with triethylamine in a Amount of 2/3 mol per acid number of the synthetic resin neutralized. The solution obtained is called PV-2.

(5) The reaction is carried out as in the preparation of the synthetic resin solution PV-2, except that 200 parts of ethyl acrylate and 25 parts of acid phosphoxyethyl methacrylate are used, a synthetic resin solution with a non-volatile component content of 60.1% being obtained. The synthetic resin has an acid number of 28.8, a weight average molecular weight of 31,100 and a softening point of about 73 to 76 ^° C. The solution is neutralized with triethylamine in an amount of 3/4 mol per acid number of the synthetic resin. The resin solution obtained is called PV-3.

(6) The one used to prepare the resin solution PV-1 The reaction vessel is charged with 750 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture is formed from 190 parts of methyl methacrylate, 55 parts of styrene, 195 parts of ethyl acrylate, 15 parts of 2-hydroxyethyl methacrylate, 40 parts of acid phosphoxyethyl methacrylate, 5 parts of acrylic acid and 10 parts of azobisisobutyronitrile within 3 hours

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drips. When the addition is complete, a further 1.5 parts of azobisisobutyronitrile are added, the reaction ^{temperature is increased to 87 °} C. and the reaction is carried out for 4 hours, a synthetic resin solution with a non-volatile component content of 39.5% being obtained. The synthetic resin has an acid number of 31.6, a weight average molecular weight of 22,500 and a softening point of about 73 to 76 ^° C. The synthetic resin solution is neutralized with triethylamine in an amount of 3/4 mol per acid number of the synthetic resin. Which he-

^{Resin solution holding 10 is} designated PV-4.

(7) The one used to prepare the resin solution PV-1 The reaction vessel is charged with 340 parts of methyl ethyl ketone, whereupon the temperature is increased to 80 ° C. and a liquid mixture of 19O parts of methyl methacrylate, 70 parts of styrene, 215 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 5 parts of acid phosphoxyethyl methacrylate, 5 parts of 3-chloro-2-acid phosphoxypropyl methacrylate, 5 parts of acrylic acid and 10 parts of azobisisobutyronitrile are added dropwise over the course of 3 hours. When the addition is complete, more are added 1.5 parts of azobisisobutyronitrile, increases the reaction temperature to 87 ° C and carries out the reaction for 4 hours, whereby a synthetic resin solution having a non-volatile component content of 59.3% is obtained. The resin has a Acid number of 14.5, a weight average molecular weight of 33,100 and a softening point of about 73 to 75 ° C. The synthetic resin solution obtained is neutralized with triethylamine in an amount of 2/3 mol per acid number of the synthetic resin.

The resin solution obtained is called PV-5. 30th

(8) The reaction is the same as in the preparation of the resin solution PV-1 carried out, but using 5 parts of acidic phosphoxyethyl acrylate instead of 5 parts of acidic phosphoxyethyl methacrylate, whereby a synthetic resin solution with a

retention of non-volatile components of 58.9% is obtained. The synthetic resin has an acid number of 11.9, which is a weight average

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1 with a molecular weight of 28,900 and a softening point of about 72 to 74 ^° C. The solution obtained is neutralized with triethylarain in an amount of 3/4 mol per acid number of the synthetic resin. The resin solution obtained is treated with PV-6

5 designated.

example 1

24 parts of the synthetic resin solution PE-V-1 are mixed with 12 parts of titanium dioxide and 4/5 parts of methyl ethyl ketone are added, whereupon the mixture is dispersed with a sand mill so that the dispersed Particle size is less than 10 µm (measured according to the grinding gauge). This is followed by the dispersed mixture mixed with stirring with 56 parts of the synthetic resin solution V-1 and 3.5 parts of methyl ethyl ketone to form a homogeneous pigment dispersion. The dispersion is in 2,000 parts of water at 15 ° C, which is stirred at high speed, dropped to emulsify the pigment dispersion, the solvent in water to extract and form resin particles. The filtering and washing with water are repeated, one containing water Cake of synthetic resin particles having an average size of about 100 µm. The water content of the cake is about 50%. 100 parts of the water-containing cake are mixed with 0.3 part of a 40 percent aqueous solution of a nonionic Wetting agent ("Emalgen 930" by Kao Atlas Co. Ltd.)

²⁵ with an HLB value of 15.1 and 2 parts of 10 percent

aqueous solution of a thickening agent consisting of an alkali metal salt an acrylic acid copolymer is added, whereupon the mixture is dispersed with a sand mill and knead to finely pulverize the resin particles. The received Emulsion paint contains synthetic resin particles with an average Size of 15 µm and has a pH of 7.5.

Example 2

According to Example 1, using the synthetic resin solution PE-V-2 use an emulsion paint instead of the synthetic resin solution PE-V-1 containing synthetic resin particles an average size of 15 µm and having a pH of 7.2.

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¹ example 3

24 parts of the synthetic resin solution PE-V-3 are mixed with 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone are added, whereupon the mixture is dispersed with a sand mill so that the dispersed Particle size is less than 10 µm. The dispersed Mixture is stirred with 16 parts of the synthetic resin solution PE-V-3, 40 parts of the synthetic resin solution V-1 and 3.5 parts Methyl ethyl ketone mixed to form a homogeneous pigment dispersion. The dispersion is in 3,000 parts of water at 20 ° C sprayed, which is stirred at high speed to emulsify the pigment dispersion, the solvent in water to extract and form synthetic resin parts. The filtering and washing with water are repeated, one containing water Cake of resin particles with an average Size of 150 µm is obtained. The water content of the cake is about 50%. 100 parts of the cake are made with 0.4 part of a 40 percent aqueous solution of a non-ionic wetting agent ("Emalgen 910" from Kao Atlas Co. Ltd.) with an HLB value of 12.2 and 4 parts of a 5 percent aqueous

² ^ gene solution of a thickener (hydroxyethyl cellulose) added, whereupon the mixture is dispersed with a ball mill to finely pulverize the synthetic resin particles. A dispersion paint containing synthetic resin particles having an average size of 15 µm and a

^{25 has a} pH of 7.6.

Example 4

According to Example 3, using the synthetic resin solution PE-V-4 instead of the synthetic resin solution PE-V-3, a dispersion "" paint containing synthetic resin particles an average size of 15 µm and having a pH of 7.5.

Example 5

According to Example 1, using 40 parts instead

of 24 parts of the synthetic resin solution PE-V-1 and of 40 parts Instead of 56 parts of the synthetic resin solution V-1, a Dlsper-

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1 produced sion paint , the synthetic resin particles with an average size of 15 μΐη contains and has a pH of 7.3.

5 Example 6

According to Example 3, using 8 parts instead of 40 parts of the synthetic resin solution PE-V-3 and 72 parts instead of 40 parts of the synthetic resin solution V-1, a dispersion paint is produced which contains synthetic resin particles with an average size of 15 μm and having a pH of 7.5.

Example 7
24 parts of the synthetic resin solution PE-V-5 are mixed with 12 parts of titanium dioxide, 0.5 part of a flow regulator ("Modaflow" from Monsanto Chemical Co. Ltd.) and 4.0 parts of methyl ethyl ketone, whereupon the mixture is mixed with dispersed a sand mill, so that the dispersed particle size is smaller than 10 μΐη . 56 parts of synthetic resin solution V-2 and 3.5 parts of methyl ethyl ketone are then added to the dispersed mixture, and the resulting mixture is mixed with stirring to form a pigment dispersion. The dispersion is added dropwise to 2000 parts of water at 15 ^° C. and stirred at high speed in order to emulsify the pigment dispersion, the solvent in

25 to extract water and form synthetic resin particles. That

Filtering and washing with water are repeated, a water-containing cake of synthetic resin particles with an average size of about 100 μm being obtained. The water content of the cake is about 50%. 100 parts of the water-containing cake are mixed with 0.2 part of a 50 percent aqueous solution of a non-ionic wetting agent ("Emalgen 935" from Kao Atlas Co. Ltd.) with an HLB value of 17.5 and 2 parts of a 10 percent aqueous solution of a thickener consisting of an alkali metal salt of an acrylic acid copolymer isate, and then the mixture is dispersed with a sand mill to finely pulverize the synthetic resin particles. This gives an emulsion paint,

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which contains synthetic resin particles with an average size of 13 μπ »and has a pH of 7.3.

Comparative example 1

The reaction is as in the preparation of the polyester-modified vinyl resin solution PE-V-1 used in Example 1 carried out, but no modifying polyester resin is used PE-1. A synthetic resin solution is obtained here a content of non-volatile components of 60.2%.

The synthetic resin has an acid of 11.3, a hydroxyl number of 53 and a weight average molecular weight of 11,500. 24 parts of the synthetic resin solution obtained are mixed with 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone, whereupon the mixture is dispersed so that the dispersed particle

* ⁵ size is smaller than 10 μm. The dispersed mixture is then mixed with 36 parts of the above synthetic resin solution, 20 parts of a 60 percent methyl ethyl ketone solution of a butylated methylol melamine resin with an average degree of condensation of 2.5, a degree of etherification of 2.5 and a content of water-soluble components of less than 1%, as well 3.5 parts of methyl ethyl ketone are mixed, whereupon the resulting mixture is mixed with stirring to form a homogeneous pigment dispersion. The dispersion is then processed further according to Example 1, a dispersion paint being obtained which

^ Contains synthetic resin particles with an average size of 15 μια and has a pH of 7.7.

Comparative example 2
The reaction is carried out as in the preparation of the polyester-modified vinyl resin solution PE-V-3 used in Example 3, but no polyester resin PE-2 is used. This gives a synthetic resin solution with a non-volatile component content of 59.8%. The synthetic resin has an acid number of 11.9, a hydroxyl number of 55 and a weight average molecular weight of 13,100. 24 parts of the synthetic resin solution obtained are mixed with 12 parts of titanium dioxide

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- 60 -

and 4.5 parts of methyl ethyl ketone are added, whereupon the mixture dispersed with a ball mill so that the dispersed particle size is smaller than 10 μΐη. The dispersed mixture is mixed with 41 parts of the above synthetic resin solution, 15 parts of a blocked isocyanate resin ("Crelan Ue 6109" from Bayer AG), added 0.5 part of dibutyltin dilaurate (dissociation catalyst) and 3 parts of methyl ethyl ketone, whereupon the mixture obtained is mixed with stirring to form a homogeneous pigment dispersion. The dispersion is then measured Example 3 processed further to obtain a dispersion paint containing synthetic resin particles with an average Contains size of 15 µm and has a pH of 7.5.

Comparative example 3

15 According to Example 3, using that in Comparative Example 2 vinyl resin solution used instead of the synthetic resin solution PE-V-3 from Example 3, an emulsion paint is produced, the resin particles with an average

Contains size of 15 µm and has a pH of 7.3. 20th

The emulsion paints obtained in Examples 1 to 7 and Comparative Examples 1 to 3 are independent of one another sprayed onto polished mild steel plates, preheated to 90 ° C. for 10 minutes and then heated to a certain temperature and dried to give coatings about 35 µm thick. The firing conditions and the physical Properties of the coatings obtained are given in Table I.

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Γ $ S example
1 no 88 8th? 87 8th no 89 example
4th 87 Vl example
5 89 O 87 cn 90 Well Well Firing conditions 160 2H
100/100 example
2 3H
100/100 Table Σ 2H
100/100 150 H
100/100 170 2H
100/100 example
6th H
100/100 example
7th 2H
100/100 Temperature, ⁰ C 20th 7 < 7 < Example.
3 K 20th 7 < 20th 7 <■ 7 < 7 < Duration, min 50 200 > 50 > 50 4O 50 170 40 190 50 Appearance of the coating © 20th © 180 © no O no O 20th © 20th © Jump off 20th Well Well Yellowing resistance ²⁾ no no no shine Well Well Well Physical properties
teb of the coating O
Cdi
O Pencil hardness ⁴⁾
Liability ⁵⁾ 026, Erichsen test ο Impact resistance » Solvent
persistence <η

Adhesion after the moisture resistance test '

lsi (D

οί ο cn

Table I - continued

Comparative Example Comparative Example Comparative Example 1 2 3

O OO CO

160 170 H 180 F. 20th 20th 95/100 20th 80/100 Yes no 3.5 no 5.0 Well bad 10 bad 20th 86 88 O 86 X 3H O X 60/100 2.0 IO © X

1), 2): visual evaluation;

3): 60 ° / 60 ° mirror gloss;

4): The pencil tip (Mitsubishi Uni) is placed on the coating at an angle of 45 ° and slightly pressed forward; the pencil hardness is expressed as the hardness of the hardest pencil, which leaves no trace on the coating;

5) cut adhesive tape peel test after the crosswise inputs W;

6): Measured with an Erichsen tester;

7): According to method 3B of JIS K -5400, 6-13;

8): The rubbing test with ethyl acetate is passed 50 times

and the matting is evaluated as follows (S): no change

ο: low matting

X: considerable matting

9): Adhesive strip peel test after 200 hours of damp

durability test (50 ° C,> 97% r.h.) 20

©: 100/100 - 90/100

ο: 89/100 - 60/100 X: 59/100 - 0/100

²⁵ Example 8

24 parts of the synthetic resin solution PE-PV-1 are mixed with 12 parts Titanium dioxide and 4.5 parts of methyl ethyl ketone are added, whereupon the mixture is dispersed so that the dispersed particle size is smaller than 10 μπι (measured according to the grinding gauge).

The dispersed mixture is made with 16 parts of the synthetic resin solution PE-PV-1, 40 parts of the synthetic resin solution V-1 and 3.5 parts Methyl ethyl ketone is added, whereupon the mixture is mixed with stirring to form a homogeneous pigment dispersion. The dispersion is dropped into 2000 parts of water at 15 ° C and with

stirred at high speed to emulsify the pigment dispersion, extract the solvent in water and

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To form synthetic resin particles. The filtering and washing with hater are repeated, leaving a water-containing cake of Resin particles having an average size of about 100 µm is obtained. The water content of the cake is about 50%. 100 parts of the cake obtained are mixed with 0.3 part of a 40 percent aqueous solution of a non-ionic Wetting agent ("Emalgen 930" by Kao Atlas Co. Ltd.) an HLB value of 15.1 and 2 parts of a 10 percent aqueous solution of a thickener composed of an alkali metal salt an acrylic acid copolymer is added, whereupon the mixture is dispersed with a sand mill to to finely pulverize the resin particles. Here receives a dispersion paint containing synthetic resin particles with an average size of 16 µm and a pH of 7.8.

Example 9

According to Example 8, using the synthetic resin solution PE-PV-2 instead of the synthetic resin solution PE-PV-1, a dispersion paint is prepared which has synthetic resin particles with an average Contains size of 16 μπ and has a pH of 7.6.

Example 10

24 parts of the synthetic resin solution PE-PV-3 are mixed with 12 parts

Titanium dioxide and 4.5 parts of methyl ethyl ketone are added, whereupon

the mixture is dispersed so that the dispersed particle size is smaller than 10 μm. The dispersed mixture becomes then with 56 parts of the synthetic resin solution V-2 and 3.5 parts

Methyl ethyl ketone mixed, whereupon the resulting mixture

mixed with stirring to form a homogeneous pigment dispersion. The dispersion is sprayed into 3000 parts of water that at 20 ° C and stirred at high speed in order to emulsify the pigment dispersion, the solvent in

Extract water and form resin particles. 35

The filtering and washing with water are repeated, whereby

a water-containing cake of synthetic resin particles with a

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average size of 150 μΐη is obtained. The water content of the cake is about 50%. 100 parts of the cake are mixed with 0.4 part of a 40 percent aqueous solution non-ionic wetting agent ("Emalgen 910" from Kao Atlas Co. Ltd.) with an HLB value of 12.2 and 4 parts of a 5 percent strength aqueous solution of a thickener (hydroxyethyl cellulose) added, whereupon the mixture with a Ball mill disperses and kneads to finely pulverize the synthetic resin particles. This gives an emulsion paint, contains the synthetic resin particles with an average size of 14 μm and has a pH of 7.9.

Example 11
24 parts of the synthetic resin solution PE-PV-4 are mixed with 12 parts

¹⁵ titanium dioxide, 0.5 part of a flow regulator

("Modaflow" from Monsanto Chemical Co. Ltd.) and 4.0 parts Methyl ethyl ketone is added, whereupon the mixture is dispersed with a sand mill so that the dispersed particle size is smaller than 10 µm. The dispersed mixture becomes then mixed with 24 parts of the synthetic resin solution PE-PV-4, 32 parts of the synthetic resin solution V-1 and 3.5 parts of methyl ethyl ketone, whereupon the mixture obtained is mixed with stirring to form a homogeneous pigment dispersion. In the subsequent Processing according to Example 8 gives an emulsion paint containing synthetic resin particles with an average size of 15 μπι contains and has a pH of 7.7.

Example 12
40 parts of the synthetic resin solution PE-PV-5 are mixed with 10 parts

³⁰ titanium dioxide and 0.5 part of a flow regulator

{"Modaflow" from Monsanto Chemical Co., Ltd.) added, whereupon the mixture is dispersed with a sand mill so that the dispersed particle size is smaller than 10 μm. The dispersed mixture is then mixed with 30 parts of the plastic

resin solution PE-PV-5, 12 parts of resin solution V-2 and 7.5 parts of methyl ethyl ketone are added, whereupon the resulting mixture is stirred into a homogeneous pigment dispersion

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Γ Π

- 66 -

mixed up. In the subsequent further processing according to Example 8, an emulsion paint, the synthetic resin particles, is obtained with an average size of 14 μπι contains and has a pH of 7.8.

Example 13

24 parts of the synthetic resin solution PE-PV-6 are mixed with 12 parts of titanium dioxide, 0.5 parts of a flow regulator ("Modaflow" from Monsanto Chemical Co. Ltd.) and 4.0 parts of methyl

Ό ethyl ketone added, whereupon the mixture with a sand mill dispersed so that the dispersed particle size is smaller than 10 µm. The dispersed mixture is with 8 parts of the synthetic resin solution PE-PV-6, 48 parts of the synthetic resin solution V-1 and 3.5 parts of methyl ethyl ketone mixed, whereupon

15 the mixture obtained with stirring to a homogeneous

Pigment dispersion mixed. In the subsequent processing according to Example 8, an emulsion paint is obtained which Resin particles with an average size of

15 µm and has a pH of 7.6. 20th

Comparative example 4

The implementation is as in the production of the polyester modified Vinyl resin solution PE-PV-1 carried out from Example 8, but no modifying polyester

^ ⁵ resin PE-2 and does not add any acid phosphoxyethyl methacrylate. This gives a synthetic resin solution with a non-volatile component content of 58.9%. The synthetic resin has an acid number of 11.9, a hydroxyl number of 49 and a weight average molecular weight of 12,200. 24 parts

^ the synthetic resin solution obtained are mixed with 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone are added, whereupon the mixture is dispersed with a sand mill so that the dispersed Particle size is less than 10 µm. The dispersed Mixture is with 36 parts of the above synthetic resin solution, 20 parts of a 60 percent methyl ethyl ketone solution butylated methylol melamine resin with a medium condensation

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1 degree of sation of 2.5, a degree of etherification of 2.5 and

a content of water-soluble components of less than 1% and 3.5 parts of methyl ethyl ketone mixed, whereupon one the resulting mixture with stirring to form a homogeneous pigment dispersion mixed up. In the subsequent processing according to Example 8, an emulsion paint, the synthetic resin particles, is obtained with an average size of 15 µm and has a pH of 7.4.

10 Comparative Example 5

The reaction is the same as for the preparation of the polyester-modified vinyl resin solution PE-PV-3 used in the example carried out, but no polyester resin PE-3 is used and no acidic phosphoxyethyl methacrylate and 3-chloro

15 2-acid phosphoxypropyl methacrylate to. Here receives

one is a synthetic resin solution with a content of non-volatile Components of 59.2%. The synthetic resin has an acid number of 11.3, a hydroxyl number of 51 and a weight average des Molecular weight of 18,500. 24 parts of the synthetic resin solution obtained are mixed with 12 parts of titanium dioxide and 4.5 parts Methyl ethyl ketone is added, whereupon the mixture is dispersed with a ball mill so that the dispersed particle size is smaller than 10 μπι. The dispersed mixture is made with 41 parts of the above resin solution, 15 parts a blocked isocyanate resin ("Crelan Ue 6109" from the Bayer AG), 0.5 part of dibutyltin dilaurate (dissociation catalyst) and 3 parts of methyl ethyl ketone mixed, whereupon one the mixture obtained is mixed with stirring to form a homogeneous pigment dispersion. In the subsequent processing according to In Example 10, an emulsion paint containing synthetic resin particles is obtained with an average size of 15 pm and has a pH of 7.4.

Comparative example 6

According to Example 10, using the vinyl resin solution used in Comparative Example 5 instead of the synthetic resin

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29512U

solution PE-PV-3 made an emulsion paint / the synthetic resin particles with an average size of 15 μπ and has a pH of 7.4.

Those in Examples 8 to 13 and Comparative Examples

4 to 6 emulsion paints produced are sprayed independently of one another onto polished mild steel plates,

Set for 5 minutes, preheated to 90 ° C for 10 minutes and then heated to a certain temperature and dried, coatings with a thickness of about 35 μm being obtained. The firing conditions and the physical properties of the coatings are given in Table II.

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Firing conditions Temperature, ⁰ C

Duration, min. Appearance of the coating

Rust formation Jump off Resistance to yellowing

shine

Physical properties of the coating Pencil hardness liability Erichsen test impact resistance

Solvent resistance

Adhesion after the moisture resistance test

Adhesion after the salt

sprayed

2)

Storage stability of the paint

8th? example
9 no 88 Table IZ 86 cn 89 example
12th O 190 no 3H example
10 H 3H 180 example
8th 20th Well 100/100 150 100/100 example
11 100/100 20th example
13th 160 K 20th 7 < 200 7 < no 180 20th > 50 no > 50 20th 40 no 20th no © no O no © Well no no Well no 86 no Well Well H Well 86 100/100 87 2H 7 < 2H 100/100 30th loo / ioo 7 < 0 7 < > 50 > 50 Θ ©

3)

10 <

10 <

10 <

10 <

O ti » OO fS>

CO Ui (Jl

Comparison 86 Comparison Comparison example 4 3H example 5 example 6 160 60/100 170 180 20th 2.0 2O 20th Yes 10 Yes Yes Yes ® no no Well bad Well 88 86 H F. 90/100 8O / 10O 3.0 4.0 10 20th O X

-J O

N) CO

cn

—J *

NJ

- 71 j note;

1): visual assessment during setting;

2): The sample cut crosswise down to the substrate is subjected to a salt spray test for 100 hours

(JIS Z-2371), whereupon the cross-cut area is subjected to an adhesive tape peeling test and the peeling width (on one side) is measured:
: 0 - 1.0 mm

: 1.1-2.0 mm

: 2.1-3.0mm X: 3.1mm and more.

3): The sample is ^{stored in an air bath kept at 50 °} C. and the stability is expressed by the number of days during which no gelation or precipitation occurs.

The other parameters are the same as in Table I.

Example 14

24 parts of the synthetic resin solution PE-AV-1 are mixed with 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone, whereupon the mixture is dispersed with a pot mill so that the dispersed particle size is less than 10 μm (measured according to the grinding gauge). The dispersed mixture is mixed with 51 parts of the synthetic resin solution PE-AV-1, 10 parts of the synthetic resin solution PV-4 and 3.5 parts of methyl ethyl ketone, whereupon the mixture obtained is mixed with stirring to form a homogeneous pigment dispersion. The pigment dispersion is in 20OO parts of water, maintained at 15 ⁰ C and stirred at high speed, added dropwise to emulsify the pigment dispersion to extract the solvent in water and form resinous particles. The filtering and washing with water are repeated, leaving a water-containing cake of synthetic resin particles with an average size of

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about 100 μπι is obtained. The water content of the cake is about 50%. 100 parts of the cake are made with 0.3 part a 40 percent aqueous solution of a non-ionic wetting agent ("Emalgen 930" from Kao Atlas Co. Ltd.) and 2 parts of a 10 percent aqueous solution of a thickener added, which consists of an alkali metal salt of an acrylic acid copolymer, whereupon the mixture dispersed with a sand mill to finely pulverize the synthetic resin particles. This gives an emulsion paint, contains the synthetic resin particles with an average size of 15 μm and has a pH of 7.7.

Example 15

24 parts of the synthetic resin solution PE-AV-2 are mixed with 12 parts of titanium dioxide, 0.5 part of a flow regulator

("Modaflow" by Monsanto Chemical Co. Ltd.) and 4.0 parts of methyl ethyl ketone are added, and the mixture is dispersed with a sand mill so that the dispersed particle size is less than 10 µm. The dispersed mixture is mixed PV-3 and 3.5 parts methyl ethyl ketone ²⁰ with 40 parts of the resin solution PE-AV-2, 16 parts of the resin solution, followed by blended the mixture with stirring to form a homogeneous pigment dispersion. The dispersion is added dropwise to 2000 parts of water, which is kept at 15 ^° C. and stirred at high speed in order to emulsify the pigment dispersion, to extract the solvent in water and to form synthetic resin particles. The filtering and washing with water are repeated to obtain a water-containing cake of synthetic resin particles having an average size of about 100 µm. The water content of the cake is about 50%. 100 parts of the water-containing cake are mixed with 0.3 part of a 40 percent strength aqueous solution of a nonionic wetting agent ("Emalgen 930" from Kao Atlas Co. Ltd.) with an HLB value of 15.1 and 2 parts of a 10 percent strength aqueous solution a thickener added, which consists of an alkali metal salt

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j acrylic acid copolymer, whereupon the mixture dispersed with a sand mill to finely pulverize the synthetic resin particles. This gives a dispersion paint, the synthetic resin particles with an average Contains size of 15 µm and has a pH of 7.5.

Example 16

24 parts of the synthetic resin solution PE-AV-3 are mixed with 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone, whereupon the mixture is dispersed with a ball mill so that the dispersed particle size is smaller than 10 μm. The dispersed mixture is mixed with 32 parts of the synthetic resin solution PE-AV-3, 24 parts of the synthetic resin solution PV-2 and 3.5 parts of methyl ethyl ketone, whereupon the mixture obtained is mixed with stirring to form a homogeneous pigment dispersion. The pigment dispersion is sprayed into 3000 parts of water, which is kept at 20 ^° C. and stirred at high speed in order to emulsify the pigment dispersion, extract the solvent in water and form synthetic resin particles. The filtering and washing with water are repeated to obtain a hydrous cake of synthetic resin particles having an average size of 150 µm. The water content of the cake is about 50%. 100 parts of the water-containing cake are mixed with 0.4 part of a 40 percent strength aqueous solution of a nonionic wetting agent ("Emalgen 910" from Kao Atlas Co. Ltd.) with an HLB value of 12.2 and 4 parts of a 5 percent strength aqueous solution a thickener (hydroxyethyl cellulose) is added, and the mixture is dispersed with a ball mill and kneaded to finely pulverize the synthetic resin particles. As a result, a dispersion paint containing synthetic resin particles having an average size of 16 µm and a pH of 7.8 is obtained.

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1 example 17

24 parts of the synthetic resin solution PE-AV-4 are mixed with 12 parts of titanium dioxide, 0.5 part of a flow regulator ("Modaflow" from Monsanto Chemical Co. Ltd.) and 4.0 parts MethyläthyIketon added, whereupon the mixture with dispersed a sand mill, so that the dispersed particle size is smaller than IO μπι. The dispersed mixture is mixed with 8 parts of the synthetic resin solution PE-AV-4, 48 parts of the synthetic resin solution PV-1 and 3.5 parts of methyl ethyl ketone

10 mixes, whereupon the mixture obtained is added with stirring

mixed into a homogeneous pigment dispersion. The pigment dispersion is added dropwise in 2000 parts of water maintained at 15 ° C and stirred at high speed to emulsify the pigment dispersion _to extract the solvent in water and form resinous particles. The filtering and washing with water are repeated to obtain a hydrous cake of synthetic resin particles having an average size of about 100 µm. The water content of the cake is about 50%. 100 parts of the resulting water-containing cake are mixed with 0.2 part of a 50 percent aqueous solution of a nonionic wetting agent ("Emalgen 935" from Kao Atlas Co. Ltd.) having an HLB value of 17.5 and 2 parts of a 10 percent aqueous solution A solution of a thickener consisting of an alkali metal salt of an acrylic acid copolymer is added, and the resulting mixture is dispersed with a sand mill to finely pulverize the synthetic resin particles. As a result, a dispersion paint containing synthetic resin particles having an average size of 14 µm and a

^{30 has a} pH of 7.7.

Example 18

According to Example 17, using a total amount of the synthetic resin solution PE-AV-4 of 40 parts instead of 32 parts and using 40 parts of the synthetic resin solution PV-2 instead of 48 parts of the synthetic resin solution PV-1

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prepared a dispersion paint containing synthetic resin particles with an average size of 15 μΐη and a
has a pH of 7.6.

5 Example 19

24 parts of the synthetic resin solution PE-AV-3 are mixed with 12 parts
Titanium dioxide, 0.5 part of a flow regulator ("Modaflow" from Monsanto Chemical Co. Ltd.) and 4.0 parts of methyl ethyl ketone are added, and the mixture is dispersed with a sand mill so that the dispersed particle size is obtained
is smaller than 10 μm. The dispersed mixture is with
32 parts of the synthetic resin solution PE-AV-3, 24 parts of the synthetic resin solution PV-5 and 3.5 parts of methyl ethyl ketone mixed,
whereupon the resulting mixture with stirring to a homo-

^ 5 mixed pigment dispersion. The pigment dispersion

is added dropwise to 2000 parts of water which is kept at 15 ^° C
and stirring at high speed to emulsify the pigment dispersion, the solvent in water
extract and form resin particles. The filtering and washing with water are repeated to obtain a hydrous cake of synthetic resin particles having an average size of about 100 µm. The water content of the cake is about 50%. 100 parts of the water-containing cake are mixed with 0.25 part of a 40 percent strength aqueous solution of a non-ionic wetting agent ("Emalgen 930" from Kao Atlas Co. Ltd.) with an HLB value of 15.1 and 1.5 parts of a 10 percent strength aqueous solution of a thickener, which consists of an alkali metal salt
an acrylic acid copolymer, whereupon the mixture is dispersed with a sand mill to finely pulverize the synthetic resin particles. This gives a dispersion paint which contains synthetic resin particles with an average size of 15 μm and has a pH of 7.7.

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Example 20

24 parts of the synthetic resin solution PE-AV-4 are mixed with 12 parts Titanium dioxide, 0.5 part of a flow regulator ("Modaflow" from Monsanto Chemical Co. Ltd.) and 4.0 parts Methyl ethyl ketone is added, whereupon the mixture is mixed with

a sand mill so that the dispersed particle size is smaller than 10 μπι. The dispersed mixture becomes with 24 parts of the synthetic resin solution PE-AV-4, 32 parts of the Synthetic resin solution PV-6 and 3.5 parts of methyl ethyl ketone

W mixes, whereupon the mixture is stirred to a homogeneous one Pigment dispersion mixed. The dispersion is added dropwise to 2000 parts of water, which is kept at 15 ° C and with high speed stirring to emulsify the pigment dispersion, extract the solvent in water and to form synthetic resin particles. The filtering and

Washes with water are repeated, leaving a water-containing cake of resin particles with an average Size of about 100 µm is obtained. The water content of the Cake is about 50%. 100 parts of the obtained water-containing

term cake with 0.2 part of a 40 percent aqueous Solution of a non-ionic wetting agent ("Emalgen 930" from Kao Atlas Co. Ltd.) with an HLB value of 15.1 and 1.5 parts of a 10 percent aqueous solution of a thickener, that from an alkali metal salt of an acrylic acid copolymer is added, followed by dispersing the mixture with a sand mill to remove the resin particles to be finely pulverized. This gives a dispersion paint, the synthetic resin particles with an average

Contains size of 16 µm and has a pH of 7.5. 30th

Comparative example 7

The reaction is as in the preparation of the polyester-modified vinyl resin solution PE-AV-1 used in Example 14 carried out, but no modifying polyester resin PE-1 is used and no N-n-butoxymethylacrylamide is used to. This gives a synthetic resin solution with a content

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29512U γ π

of non-volatile components of 58.4%. The synthetic resin has an acid number of 12.3, a hydroxyl number of 27 and a weight average molecular weight of 17,500. 24 parts of the synthetic resin solution obtained are mixed with 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone, whereupon the mixture is dispersed with a sand mill, so that the dispersed particle size is less than 10 µm . The dispersed mixture is mixed with 44 parts of the above synthetic resin solution, 12 parts of a 60 percent methyl ethyl ketone solution of a butylated methylol melamine resin with an average degree of condensation of 2.5, a degree of etherification of 2.5 and a content of water-soluble components of less than 1% and 3, 5 parts of methyl ethyl ketone are mixed, whereupon the resulting mixture is mixed with stirring to form a homogeneous pigment dispersion.

In the subsequent processing according to Example 14, an emulsion paint containing synthetic resin particles is obtained an average size of 15 µm and contains one

has a pH of 7.5. 20th

Comparative example 8

The reaction is the same as for the preparation of the polyester-modified vinyl resin solution PE-AV-3 used in the example carried out, but no polyester resin PE-2 is used and no N-n-butoxymethylacrylamide is added. Here receives a synthetic resin solution with a non-volatile component content of 59.1%. The resin has a Acid number of 12.2, a hydroxyl number of 33 and a weight average molecular weight of 16,200. 24 parts of the obtained Tenen synthetic resin solution are with 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone are added, whereupon the mixture is dispersed with a ball mill so that the dispersed Particle size is less than 10 µm. The dispersed mixture is mixed with 48 parts of the above synthetic resin solution,

° ^ 8 parts of a blocked isocyanate resin ("Crelan Ue 6109" from Bayer AG), 0.5 part of dibutyltin dilaurate, (dissociation catalyst) and 3 parts of methyl ethyl ketone mixed,

L J

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- 78 -

whereupon the mixture obtained is mixed with stirring to form a homogeneous pigment dispersion. In the subsequent Processing according to Example 16 gives an emulsion paint which has synthetic resin particles with an average Contains size of 15 μπι and has a pH of 7.3.

Comparative example 9

The reaction is as in the preparation of the polyester-modified vinyl resin solution PE-AV-1 used in Example 14

10, but no modifying polyester resin is used PE-1. This gives a synthetic resin solution with a non-volatile component content of 58.7%. The synthetic resin has an acid number of 13.6, a hydroxyl number of 30.5 and a weight average molecular weight of

41,000. 24 parts of the synthetic resin solution obtained are mixed with 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone. whereupon the mixture is dispersed with a ball mill so that the dispersed particle size is smaller than 10 μπ> is. The dispersed mixture is 56 parts of the

20 of the above synthetic resin solution and 3.5 parts of methyl ethyl ketone are mixed, whereupon the resulting mixture is added with stirring mixed into a homogeneous pigment dispersion. In the subsequent processing according to Example 14, an emulsion paint is obtained the synthetic resin particles with an average

Lent size of 15 μΐη contains and has a pH of 7.4.

The emulsion paints prepared in Examples 14 to 20 and Comparative Examples 7 to 9 become independent

30 of each other sprayed onto polished mild steel plates, set for 5 minutes, preheated to 90 ° C for 10 minutes and then on heated to a certain temperature and dried to obtain coatings with a thickness of about 35 µm. the Firing conditions and the physical properties of the

coatings are given in Table III.

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σ> - ^. σ αο co trt

OO CO
cn ο FVJ
cn 88 NJ
O example
16 cn O cn example
20th 88 Firing conditions example
14th 2H Table III 170 example
17th example
18th example
19th 190 2H Temperature, ⁰ C 100/100 example
15th 20th 20th 100/100 Duration, min 170 5 < 200 180 190 5 < Appearance of the coating 20th 50 160 no 20th 20th 20th no 50 Rust formation O 20th no no © Jump off no Well no no no Well Resistance to yellowing no no 89 no no no shine Well no Well Well Well Physical Properties
of the coating Well 2H 88 89 89 Pencil hardness 86 100/100 liability 5 < 3H 2H 3H Erichsen test 2H 50 100/100 100/100 100/100 Impact resistance 100/100 © 5 < 5 < 5 < Solvent resistance 5 < 4 0 50 50 50 © © © O

Adhesion after the moisture resistance test

Adhesion after the salt spray test

Storage stability of the paint

10 <

10 <

10 <

10 <

10 <

Note: The terms correspond to those in Tables I and II.

«N

Table III - continued

ο co OO IO σ>

OO U) cn

Comparison Comparison Comparison example 7 example 8 example 9 160 170 18O 20th 20th 2O Yes Yes Yes Yes no no Well bad Well 88 88 87 3H H H 40/1OO 65/100 70/100 2.0 3.0 3.5 10 10 10> © O X X O X X X X 6th 5 5

Claims (14)

V'OSSIUS · VOSSIUS TAUCHNER · H F. UN F. M AK N RAUH PATENTANWÄLTE SIEBERTSTRASSE 4 · βΟΟΟ MÜNCHEN 86 · PHONE! (Οββ) 47 4O CABLEi BENZOLPATENT MÖNCHEN · TELEX 8-3β483νθΡΑΤ Ο 29512U December 19, 1979 5 C.E .: PCase: OP 79 126-03 DAI NIPPON TORYO CO., LTD. Osaka, Japan 10 "Thermosetting paints based on an aqueous dispersion and their use" Priority: December 19, 1978, Japan, No. 156 653/78 December 26, 1978, Japan, No. 164 179/78 claims20 1. Thermosetting paints based on an aqueous
Dispersion containing fine thermosetting resin particles (A) a polyester-modified vinyl resin having a hydro- ²⁵ xylzahl of 30 to 200 obtained by graft copolymerization of from (i) an unsaturated polyester resin with
(ii) at least one α, ß-monoethylenically unsaturated monomer and optionally a phosphoric acid regruppe-containing α, ß-monoethylenically unsaturated Monomer has been obtained, and (B) a crosslinkable copolymer, which is derived from a monomer mixture derives which (iv) an N-alkoxymethylated monomer of a, ß-mono- Ethylenically unsaturated carboxamide and 030026/0835 ORIGINAL INSPECTED 29512H (ii) contains at least one α, β-monoethylenically unsaturated monomer, (C) a wetting agent and / or a thickening agent and (D) the required amount of water. S. 2. Paint according to claim 1, characterized in that there are fine thermosetting synthetic resin particles ~ us (A) 5 to QO o «-" 'a polyester-modified Vinyl resin having a hydroxyl number of 30 to 200, the,. ¹⁰ by graft copolymerization of (i) 5 to 50 weight percent of an unsaturated polyester resin with (ii) 95 to 50 percent by weight of at least one α, β-monoethylene unsaturated monomer has been obtained, and (B) 95 to 10 percent by weight of a crosslinkable copolymer, which is derived from a monomer mixture which (iv) an N-alkoxymethylated monomer of an α, β-monoethylene unsaturated carboxamides and (ii) at least one α, β-monoethylenically unsaturated monomer contains, (C) a wetting agent and / or a thickening agent in one Amount of 0.1 to 1.0 percent by weight based on the resin particles, and (D) contains the required amount of water. 3. Paint according to claim 2, characterized in that the unsaturated polyester resin is 1 to 10 percent by weight at least one α, ß-unsaturated dicarboxylic acid as a component ³⁰ te contains. 4. Paint according to claim 2, characterized in that that for graft copolymerization with the unsaturated polyester Resin-used α, β-mono-ethylenically unsaturated monomer Monomer mixture is that (ii) 5 to 50 weight percent of a hydroxyalkyl ester of a 030026/0835 α, β-monoethylenically unsaturated carboxylic acid and
(ii) "contains 95 to 50 percent by weight of a copolymerizable α, β-monoethylenically unsaturated monomer other than the monomer (ii) '. 5. Paint according to claim 2, characterized in that the cross-linkable copolymer derived from a monomer mixture comprising (iv) 5 to 30 percent by weight of an N-alkoxymethylated JO monomer of an α, Β-monoethylenically unsaturated carboxamide,
(ii) '"0.5 to 10 percent by weight of an α, Β-monoethylene unsaturated carboxylic acid and (ii) "" contains from 60 to 90 percent by weight of a copolymerizable α, β-monoethylenically unsaturated monomer other than monomers (iv) and (ii) " ¹ . 6. Paint according to claim 1, characterized in that it consists of fine thermosetting synthetic resin particles (A) 5 to 90 percent by weight of a polyester modified Vinyl resin with a hydroxyl number of 30 to 200, which is formed by graft copolymerization of (i) 2 to 50 weight percent of an unsaturated polyester resin with (ii) 95 to 40 percent by weight of at least one α, β-monoethylene unsaturated monomer and (iii) 0.01 to 10 percent by weight of an α, β-monoethylenically unsaturated one containing a phosphoric acid group Monomer has been obtained, and (B) 95 to 10 percent by weight of a crosslinkable copolymer which is derived from a monomer mixture which (iv) an N-alkoxymethylated monomer of an α, β-monoethylenically unsaturated carboxamide and
(ii) contains at least one α, β-monoethylenically unsaturated monomer, (C) a wetting agent and / or a thickening agent in one 030026/0835 29S12U Amount of 0.01 to 1.0 percent by weight, based on the Resin particles, and
(D) contains the required amount of water. ⁵ 7. Paint according to claim 6, characterized in that that the unsaturated polyester resin has 1 to 10 percent by weight of at least one α, ß-unsaturated dicarboxylic acid as a constituent contains. ¹⁰ 8. Coating material according to claim 6, characterized in that that the a, ß-monoethylenically unsaturated monomer used for the graft copolymerization with the unsaturated polyester resin is a monomer mixture that (ii) '1 to 40 percent by weight of a hydroxyalkyl ^{ester of a 15} α, β-monoethylenically unsaturated carboxylic acid and (ii)' 99 to 60 percent by weight of a copolymerizable α, β-monoethylenically unsaturated monomer which is different from the monomer (ii) ' . ^ 9. A paint according to claim 6, characterized in that the crosslinkable copolymer is derived from a monomer mixture which
(iv) 5 to 30 percent by weight of an N-alkoxymethylated one Monomers of an α, β-monoethylenically unsaturated carboxylic acid, (ii) "'0.5 to 10 percent by weight of an α, β-monoethylene unsaturated carboxylic acid and includes, (ii) ^"11 60 to 90 weight percent of a copolymerizable α, β-monoethylenically unsaturated monomer, the monomers (iv) and (ii) ³⁰ 'is different. ¹ 10. A paint according to claim 1, characterized in that it consists of fine, thermosetting synthetic resin particles (A) 15 to 95 percent by weight of a polyester modified Vinyl resin having a hydroxyl number of 10 to 150 obtained by graft copolymerization of (i) 2 to 40 percent by weight of an unsaturated poly ^L 030026/0835 \ i ester resin with 98 to 60 percent by weight of a monomer mixture, the
(iv) an N-alkoxymethylated monomer of an α, β-monoethylenically unsaturated carboxamide and (ii) at least one α, β-monoethylenically unsaturated monomer has been obtained, and (B) 85 to 5 weight percent of a phosphoric acid group containing copolymers, which is derived from a monomer mixture which (iii) an α, Β-monoethylenic containing a phosphoric acid group unsaturated monomer and (ii) at least one α, β-monoethylenically unsaturated Contains monomer, (C) a wetting agent and / or a thickening agent in one Amount of 0.01 to 1.0 percent by weight based on the synthetic resin particles, and (D) contains the required amount of water. 11. Paint according to claim 10, characterized in that the unsaturated polyester resin is 1 to 10 percent by weight at least one α, ß-unsaturated dicarboxylic acid as a component contains. 12. Paint according to claim 10, characterized in that that the α, β-monoethylenically unsaturated Monomergemi used for the graft copolymerization with the unsaturated polyester resin
(ii) 1 to 30 weight percent of a hydroxyalkyl ester of a α, β-monoethylenically unsaturated carboxylic acid, 30 (iv) 5 to 30 percent by weight of an N-alkoxymethylated one Monomers of an α, β-monoethylenically unsaturated carboxamide and
(ii) "60 to 90 weight percent of a copolymerizable α, β-monoethylenically unsaturated monomer, which is used by the 35 Monomers (iv) and (ii) 'is different, contains. 030026 / 083S 69V I 6 IW 13. A paint according to claim 10, characterized in that the copolymer containing a phosphoric acid group derived from a monomer mixture containing (iii) 0.01 to 10 weight percent of a phosphoric acid group containing <x, ß-monoethylenically unsaturated Monomers,
(ii) " ¹ 0.5 to 10 Ge * '* ~ ** - percent of an a, ß-m ^ o-ethylenic uns "t <ire, (ii) 1 to 30 percent by weight of a hydroxyalkyl ester of an α, β-monoethylenically unsaturated carboxylic acid and (ii) "70 to 90 percent by weight of a copolymerizable α, β-monoethylenically unsaturated monomer derived from the monomers (iii), (ii) " ¹ and (ii) 'is different.
15th 14. Use of the paints according to Claims 1 to 13 for coating substrates. 030026/0835