DE2749263A1 - RELEASE FILM - Google Patents

Description

26 Ο76

Formica Corporation, Cincinnati, Ohio, V. St. A.

Release film

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In the production of those with a special surface Decorative laminates under high pressure have so far been carried out as follows:

A stack of the following components was placed in a hydraulic flat bed press and then placed under Pressed by the effect of heat:

Iron paper pad

Stainless steel plate

Polishing material laminated from aluminum and paper

Upper film decorative film

Layers of phenolic resin / kraft paper core material

- release film (center line)

The stack is constructed symmetrically around the center line, which is why only the upper half is shown in the illustration above is.

The aluminum and paper polishing material currently in use is alloy No. 1100, usually in a fully tempered state (-0 temper), but often also in a harder state, such as in condition H-18 or H-19 (full hardness). The one from the aluminum foil existing portion can have a matt, polished or corrugated surface on the free side. That Aluminum is attached to 18.1 kg / ream (40 pounds / ream) of paper using casein glue.

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When a # 1100 fully tempered alloy material is 0.013 mm (0.0005 inch) thick with the The matt side is laminated outwards to a machine-calendered natural kraft paper of 18.1 kg / ream, is obtained a laminate often referred to as # 6 buff. Will this material in the above compilation If used, a high pressure laminate with a finely crimped surface is obtained.

Its gloss is 5 to 10 °, measured with a 60 "gloss meter according to Gardner and depends on the particular type of polishing material selected. Most rollers make laminates with about 6 to 8 ° gloss, but others with up to 10 ° or more.

Because of these differences in gloss, it is common to dull rubbing these laminates with their final finish To provide surface quality. In this procedure the laminate is passed through a machine in which its decorative surface is made up of a number of rotating cylindrical brushes Nylon fiber is processed. The brushes are soaked in an aqueous pumice stone slurry that rubs off the laminate surface and its luster by about 1 to 5 degrees, depending on the force used to apply the brush to the surface press decreases. Typically, a laminate that emerges from the press with a gloss of 6.5 ° will be replaced by light Contact printing rubbed matt to a gloss of about 5.5 °. However, a laminate with a gloss of 10 ° requires an essential one greater force to bring the brush into very firm contact with the laminate. Even then, however, there is a reduction in gloss only about 3 °, so that a product with about 7 ° gloss is obtained.

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If the aluminum foil polishing material were more uniform, it would produce laminates having a gloss within the 6-2 ^β range, which is technically desirable. The matt rubbing could then be dispensed with, which would save manufacturing costs. In addition, the microscratches that the laminate receives during the matt rubbing make the laminate less resistant to contamination.

This disadvantage arises from the fact that thousands of microcracks are created in the surface, in the very small particles of coloring or polluting materials can penetrate and stay there for a long time.

The finely curled texture has proven to be particularly important, because it feels good and yet telegraphing connections, glue traces, coarse grain and other discontinuities that occur in modern furniture structures can, especially in those made using a frame construction instead of solid panels are largely suppressed, for example in a table top. Telegraphing is intended to describe the ability of a film to reproduce the texture of the film on its outer surface To reproduce the substrate on which it is grown. This was the best method of manufacture during those years of high pressure larainats in using plywood with hardwood on the outside, usually Birch or maple. With the advent of hardboard (reconstructed wood particleboard) as a laminate substrate, it has become common to use a three-layer construction in which a layer of fine particles was applied to the adhesive surfaces to match the expression with the underlying Turn off structure.

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The furniture manufacturers noticed that the finely curled surface is poorly textured and the furniture user does not unduly notice the depth of the texture. For example such a textured laminate provides a suitable writing surface when used as a tabletop.

Because of this unique dimensioning of the texture, i.e., that it is coarse enough to show the expression of the underlying To conceal structures, and yet is smooth enough to be viewed as flat, this "mini texture" enjoys great popularity and now makes up over 50% of the textures of all in the United States of America made of laminates.

The amount of aluminum foil used in laminate production is very considerable, so that the total value of the film consumed annually is very large. Therefore, the laminate manufacturers Looked out for materials that have lower unit costs than those that can be achieved annually Savings are of a significant order of magnitude. One way in which such savings can be achieved is in replacing the aluminum polishing material with a sheet of paper coated with a material that fills surface voids and the surface of a decorative laminate a texture of sufficient smoothness and gives sufficient shine. Textured laminates can usefully have gloss values from about 6 to about 25 to 30 units exhibit.

It is necessary for the texturing film that they

can be easily detached after use on the laminate,

why often a release agent in a very thin layer over the

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texturing coating is applied. From the U.S. PS Such a release paper is known from 3,946,135. Such release or release papers contain a first coating a clay / adhesive base and a second coating made of a thermosetting resin.

Release films with a single coating can be made by including an additive in the texturing coating which makes them easily removable after drying. Such a material is called "internal release agent" called because it is in the texturizing coating when it is applied. Release agents that are considered discrete second coating are applied, "external release agents" called because they never penetrate the inside of the texturing coating.

Demoulding breeds have now been found that can be used for the production of Release films for the production of laminates by consolidating resin-impregnated paper films with the aid of Heat and pressure can be used. These new masses result in separating films with the surface structure as used by the Manufacturers are required that are much cheaper than separating films made of aluminum.

The invention relates to a self-demolding coating compound from a solution of about 0.5 to about 80.0% on the total weight of the mass, of a mixture in an organic solvent, the mixture of

1.) about 75 to about 99% (based on the total weight of ingredients 1 and 3, of an oil-modified alkyd resin;

2.) from about 30 to about 70%, based on the total weight of component 1, on a polyalkylether of a PolymethyLolmeLamins and

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3.) from about 1 to about 25%, based on the total weight of components 1 and 3, consists of a copolymer, that is about 15 to about 85 mole percent of repeating units of the formula

(I) -CH-CH-

f I

C = O C = O ■>

I I

R R

in which each radical R taken individually has the meaning OR and R is a hydrogen atom or an alkyl group with 1 denotes up to 22 carbon atoms and contains the remaining units of recurring units of the formula

R ² (ID I.

- CH - CH ₂ -

XR ³

2

where R is hydrogen or a methyl group, R is a hydrocarbon radical having 9 to 30 carbon atoms and X is oxygen or a CH ₂ group.

The invention also relates to the application of separating films which impart a texture and which are either simple represent coated paper film or a paper film which is provided with a double deforming layer.

The separating film with the simple »coating consists of

a l'apierfoL Le au «Ce · ILuLose, which) coated with a mass Li; t that out

8 Ü 9 H I U / 0 8 6 8

A) about 75 to about 99%, based on the total weight

of components (A) and (B), on an oil-modified alkyd resin, that with about 30 to about 70%, based on the total weight of component (A), of a polyalkyl ether Polymethylolmelamine is crosslinked, and

B) about 1 to about 25%, based on the total weight of the Components (A) and (B) in a copolymer containing about 15 to about 85 mol percent of repeating units of the formula

(I) - CH r CH -

C «o C-O j R R

in which R has the meaning given above, and in which the remaining units contain recurring units of the formula

(ID

CH

I.
XR ³

2 3

are, in which R, R and X also have the meaning given above,

consists.

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The release film with the double coating consists of

a cellulose paper film covered with a first coating the end

A) an oil modified alkyd resin with about 30 to about 70%, based on the total weight of the alkyd resin, of a polyalkylether of a polymethylolmelamine crosslinked

is, and with a second coating over the coating (A)

B) a copolymer containing about 15 to about 85 mol percent of recurring units of the formula

(I) -CH-CH-

! I.

C = O C = O »

I I

R R

in which R has the meaning given above and contains the remaining units of recurring units of the formula

(II)

- CH - CH ₂

2 3

are, in which R, R "and X also have the meaning given above

own,
is provided.

For the production of the release films from the inventive, The substrates used in the masses described above can all

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IT possible cellulose films, such as, for example, bleaching sulfate paper, Kraft paper, Kraft paper coated with clay, parchment, parchment coated with clay, greaseproof paper, glassine paper, publication paper coated with clay and the like. Greaseproof paper is known to the person skilled in the art, as is glassine paper, but a complete description of both types of paper is to be found in Second Edition, Volume III, of Papermaking and Paperboard Making, McGraw-Hill Book Company, 1969, p. 182, Pulp and Paper Manufacture, Ronald G. McDonald, ed.

The oil modified alkyd resins which, as described above, are known and commonly disclosed in U.S. Patents 2,579,980, 2,600,623, 2,618,617, 2,648,642 and 2,649,423 described.

When producing the oil-modified alkyd resins, the amount of oil present as a modifier in the range of from about 5 to about 50 percent based on the total weight of the modified Alkyd resin. The alkyd resins can be prepared from saturated or unsaturated polycarboxylic acids, wherein however, the saturated acids are preferred. Suitable acids are phthalic, isophthalic, terephthalic, amber, oxalic, Malon, glutar, sebacin, adipin, pimeline, suberin, azelaic, lemon, tricarballyl, wine, apple, maleic, Fumaric, itaconic acid and the like.

Suitable polyhydric alcohols are ethylene glycol, propylene glycol, Diethylene glycol, dipropylene glycol, trimethylene glycol, Pinacol, trimethylol propane, neopentyl glycol, arabinol, sorbitol, glycerin, pentaerythritol and the like.

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The reaction conditions already known can be used, with a slight excess of alcohol being used to ensure the full implementation process. Among the oils used for the iodification of the alkyd resin wood oil, tall oil, perilla oil, linseed oil, hempseed oil, castor oil, cottonseed oil, Corn oil, olive oil, peanut oil, cod liver oil, candle nut oil and the like.

The oil-modified alkyd resins of the masses used to manufacture of the mold release compositions according to the invention are used with a suitable polyalkylether of a polymethylolmelamine networked. Examples of these melamine materials are the dimethyl, diethyl, dipropyl, dibutyl, etc. ethers, the trimethyl, Triethyl, tripropyl, tributyl ethers, the tetramethyl, tetraethyl, tetrapropyl, tetrabutyl etc. ethers, the pentamethyl, Pentaethyl, pentapropyl, pentabutyl etc. ethers and the hexamethyl, hexaethyl, hexapropyl, hexabutyl etc. ethers or Dimethylol, trimethylol, tetramethylol, pentamethylol or hexamethylol melamines. Of course, mixed ones can also be used Polyalkyl ethers such as the dimethyl, tetraethyl, etc. ethers of polymethylol melamines can be used. The preferred one Melamine material is the hexakismethoxymethyl melamine. A suitable molar ratio of melamine to aldehyde, preferably paraldehyde, is 1: 3 to 1: 6, and the alcohol that is used to introduce the alkyl ether component into the melamine material is preferably an alcohol having 1 to 4 carbon atoms. The amount of melamine material used to crosslink the oil-modified alkyd resin is used must be in the range of about 30 to about 70%, based on the total weight of oil-modified alkyd resin and melamine material.

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The copolymer of vinyl ether or unsaturated alkyl monomer, which represents the other component of the mold release agents according to the invention is also known and described in U.S. Patent 3,770,687; its production can be according to the process also described there or according to from US Pat. No. 3,047,398.

The copolymer of vinyl ether or unsaturated alkyl monomer can be prepared by copolymerizing about 15 to 85 mole percent of the vinyl ether or unsaturated alkyl monomer with about 85 to 15 mole percent maleic acid, maleic acid ester or maleic anhydride under conditions under which copolymers with a relative viscosity of at least about 0.1 arise. The preferred comonomers are maleic anhydride and a co ~ ^A l ^{k v} yl ynyl ether or octadecene -1.

The compositions according to the invention are generally in the form of solutions of from about 0.5 to about 80.0 percent by weight based on the total weight of the mass, prepared in an organic solvent and applied to the substrates either applied in the form of a solution of both components of the mass or in the form of a solution of a mixture of the components. Usable solvents are, for example, aromatic hydrocarbons such as benzene, toluene, xylene, etc .; aliphatic hydrocarbons such as hexane, heptane, etc .; Dimethylformamide, Butyrolactone, tetrahydrofuran, isopropanol, dimethyl sulfoxide, dioxane or mixtures thereof.

The masses can be made by making the oil-modified Alkyd resin, the polyalkylether of polymethylol melamine

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and the copolymer dissolves individually in its own solvents and then the resulting solutions to the mass mixed, or the components can be added to a single solvent in the correct proportions, so that in this way the masses are preserved. If a release film with a double layer is produced, the Solutions of the alkyd resin and melamine are mixed before they are applied to the substrate, after which the solution of the mixed polymer! sate applied as a second layer will.

The individual coatings can be applied to the paper substrate by any convenient method, such as with the help of a reversing roller, a slot nozzle application machine, a rotogravure roller, etc., to a total thickness of up to about 2.5µ to about 7.6µ (0.1 to 0.3 mil), corresponding to 0.24

2 to 0.81 kg per 100 qm ream dry (1.5-5.0 lbs / 3000 ft. Ream dry). . When two coatings are applied, the crosslinked alkyd resin coating makes at least about 75% of the total coating thickness.

An acid catalyst is preferably added to the mold release coating before it is applied to the substrate, to ensure that the me] amine compound modified the oil Completely crosslinked alkyd resin. This requires about 1.0 to about 10.0%, based on the total weight of oil-modified Alkyd resin and melamine material, with p-toluenesulfonic acid being preferred. However, you can also xylene sulfonic acid, o- and m-toluenesulfonic acid, more acidic Phosphoric acid ethyl ester, n-butyl phosphoric acid, phosphoric acid, Hydrochloric acid and the like can be used. If double coatings are used, the acid catalyst must be the Coating consisting of alkyd resin and melamine can be added.

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If desired, conventional thickening or leveling agents can be used etc. are added to the coating compositions in order to adapt their viscosity to the requirements of the coating equipment and regulate the intake, etc.

The coated paper substrate is then cured, the release film being heated so that the alkyd resin crosslinks with the melamine compound. For this purpose, a temperature of about 93 to about 232 ^° C. (200 to 450 ^° F.) can be selected, the crosslinking generally being complete within 5 minutes to 15 seconds. If double coatings are used, the crosslinking can be carried out before or after application of the coating consisting of the copolymer.

The release films produced from the compositions according to the invention are, as mentioned above, extremely suitable for production of decorative laminates, as they take the heat and pressure required to produce the decorative foils, withstand without deterioration and completely and quickly from the resin-impregnated surfaces the laminates separate after they are off the laminating press have been removed. They can be used for the production of so-called high pressure laminates, with one Row from 3 to 12 impregnated with phenol / formaldehyde resin Kraft foils are used as core material on which a decorative surface impregnated with melamine resin of certain Patterns, such as imitation wood grain, as well as an upper film can be applied, which are also with a Melamine resin is impregnated, or used for the production of so-called low-pressure laminates or panels made of a self-supporting substrate such as hardboard or plywood, etc. with the help of heat and pressure a melamine

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Sä

resin-impregnated decorative film is applied as described above. The amount of heat required to manufacture each type of product is about the same, that is, the temperature is about 37 to 121 ^° C (100 to 250 ^° F.), however the high pressure laminates will be at pressures in excess of 63 atmospheres (900 psi) and usually made at 77 to 105 atmospheres (1100 to 1500 psi) while the low pressure plates are made below 63 atmospheres (900 psi) and usually 17.5 to 52.5 atmospheres (250 to 750 psi).

The following examples illustrate the invention. All details about parts and percentages relate to the weight, unless otherwise stated.

Example A Comparative Example

92.5 parts of an alkyd resin solution which had been prepared from 39.7 parts of soybean oil, 41.3 parts of isophthalic acid and 19 parts of glycerol and had a solids content of about 62%, a viscosity of 23 to 29 seconds (No. 2 Zohn cup.) at 25 ⁰ C (77.0 ⁰ F.) and a density of 1.01 to 1.04 g / ccin (8.4 to 8.7 pounds per gallon) in isopropanol / xylene (67/33), further 50% Hexakismethoxymethylmelamxn contained, was added with 7.5 parts of a catalyst solution consisting of 50% p-toluene · sulfonic acid and 50% isopropanol. Using a gravure roller with a square cell pattern with a diagonal count of 47 per cm (120 per inch) and a cell depth of 0.08 mm (0.0032 inch), which is serrated evenly over its entire surface, the mixture of alkyd resin and catalyst on a bleached, greaseproof Kraft paper of 5.7 kg per 100 qm ream (35 Ib./30OO ft. ream) with a

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Thickness of 5.1 μ (0.2 rail) applied. The coated paper is then crosslinked in a high-speed hot air oven at 138 ^° C. (280 ^° F.) for 30 seconds. The weight of the top sheet after crosslinking was 0.57 kg per 100 square meters of ream (3.5 lbs./30OO ft, ² reams).

To show that the top sheet is crosslinked, two pieces of coated paper were placed so that the coated sides touched. The whole was placed in a high speed press with a platen ^{temperature of 232 °} C (450 ^° F.) and held under a pressure of 2.8 atmospheres (40 psi) for 6 seconds. The paper sheets were then removed, cooled to room temperature and peeled from one another by hand. The two sheets separated easily, with no signs of sticking, tearing of paper fiber or other signs of insufficient curing being discernible.

The coated paper was then in sheets of 1.2 χ 2.4 m (4 χ 8 feet) cut and arranged in a press pile from top to bottom as follows:

A. Stainless steel pressure plate with the polished surface facing down.

B. Sheet of coated paper with the coated surface downward.

C. Conventional 28 lbs./3000 ft. ² ream alpha cellulose paper top sheet impregnated with about 64 percent by weight of a conventional melamine / formaldehyde / laminating resin. Content of

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volatile constituents equal to about 5%.

D. Conventional, pigmented decorative paper with a wood fiber print facing upwards and with about 40 weight percent of a conventional laminating resin that that is similar to the one in the overlay, impregnated. Volatile content equals about 5%.

E. 5 layers of kraft saturating paper

ο of 18.7 kg per 100 qm ream (115 Ib./3000 ft. ream), that with 25 percent by weight of a conventional phenol / formaldehyde laminating resin is impregnated. Volatile content equals about 5%.

F. A layer of glassine paper as a release liner.

The entire arrangement is then repeated in reverse to create a so-called back-to-back press stack which is provided with conventional layers of cushioning paper on the outside of the stainless steel printing plates. The whole thing is then placed between suitable cold-rolled steel plates and then placed in a conventional high-pressure laminating press. It is compressed at 98 atmospheres (1400 psi). The whole is ^{heated to 142 °} C. within 25 minutes and held at this temperature for 12 minutes. The pressed material is then cooled to room temperature and removed from the press, after which the laminates are recovered.

It was found that the coated paper used as a release film should serve, was firmly bound to the decorative surface of the laminate and that only small parts are removed could. Numerous scraps of white paper fiber remained firmly bound even where pieces of the release liner were removed could.

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example 1

According to the procedure of Example A, solutions of alkyd resin, melamine and catalyst were combined to form 100 parts of mixture. This mixture was mixed with 5 parts of a 40 percent solution of a copolymer of alkyl vinyl ether and maleic anhydride in toluene, in which the mixture of alkyl vinyl ethers (96% C ^ alkyl, 2% C ^ alkyl and 2% C ₁₀ ~ C ₁₄ alkyl vinyl ether) was copolymerized with the equimolar amount of maleic anhydride.

The paper was then coated in the same way as before and as a texturing release film on a laminate used.

It was found that the coated paper now separated easily from the laminate, with no particles coming out Paper, resin, or other waste material was left behind. To determine the ease with which such paper of peeled off the laminate, the following experiment was carried out.

Using a sharp knife was taken from the top (uncoated) surface of the release film when it was still connected to the pressed laminate and before attempting had to separate it from the laminate created a slit. The slot was along a straight line for a distance 25.4 cm (10 in) using a metal ruler. From one end of this slot it became vertical A second slot, also 25.4 cm (10 inches) long, was cut to the first slot. At the intersection of the slots a small rag was lifted up by inserting the knife edge and then the paper along the length of the laminate Bisector between the two slots, along a line drawn with respect to the original slots in one Direction of 45 °, deducted. When about 3.8 cm (1.5 inches) was peeled off this way, it became a

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Feather clip attached to the paper flap so that it held the paper in place. A spring scale was attached to the file clip attached to a scale up to 50 g and the peeling of the paper continued along the bisector. if the paper is peeled off, the line along which the peeling takes place runs approximately perpendicular to the bisector and becomes longer and longer as the removal progresses. At the point where this line of contact between The paper and laminate is 12.7 cm (5 inches) long, the force required to continue peeling will be on the Read the spring balance. It is about 25 g. The test was repeated several times, with forces of about 15 to about 40 g measured along the 12.7 cm (5 inch) contact line. The numerical value of the force measured in this way becomes Called adhesive strength.

The laminate made as described above had a roughness (AA) of about 2.3 µ (90 microinches) and a 60 ° gloss of 5.5.

Examples BJ Comparative Examples

The following materials were added to the alkyd resin, melamine and catalyst solution of Example A in amounts of 1, 5 and 10 parts added,

B. paraffin wax

C. stearic acid

D. oleic acid

E. Sodium stearate

F. methyl stearate

G. petrolatum

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H. polyethylene

I. Lecithin

J. Pentaerythritol tetrastearate

Each material was used in each of the stated amounts in the resin-catalyst solution as a coating for the used texturing paper. Thereafter, each coated paper was used as a release film during the manufacture of a Laminate used.

None of the films obtained had any release properties. The adhesive strength is more than 500 g in all cases. In most cases, paper particles will stick to the laminate. In some cases, the paper can be removed from the laminate at all cannot be removed.

Adhesive strength

It was found that with a bond strength of 60 g / 12.7 cm (5 inches) the release paper can be peeled from the laminate without tearing paper fibers or other debris. However, well above this value, it is difficult to remove the entire sheet of release paper from the laminate surface remove. Traditional laminates are made 5 by 12 feet (1.52 by 3.66 m). It is appropriate that the person peeling off the release liner to discard it can do so with ease, usually with one light roving pull from one end of the sheet. if If the paper does not peel off easily from each part of the laminate, it will be necessary to pull several times or even pull it out walking around the sheet to peel off the more adhesive areas. This takes time, which is why either the assembly line, that the laminates to be freed from the paper must be conveyed, run more slowly or additional workers must be used. Each of these solutions naturally increases

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the operating costs. Thus, the most suitable adhesiveness lies below about 60 grams per 12.7 mm (5 inches), with values in the range of 15 to 40 grams per 12.7 mm (5 inches) being preferred.

Examples K and L Comp eichsbe i le spat

Conventional release agents that are found to be highly effective at demoulding of melamine / formaldehyde materials from metal molds and from laminates of printing plates are known in Procured aerosol cans. The first agent (Example K) is called non-silicone, so that later painting or Spraying the part is not affected. The second (Example L) is also an aerosol and consists of fluorocarbon -Telomers.

Each of these compounds is obtained from the aerosol by that the drift is allowed to flow out. The connection according to Example K is an alkyd resin / melamine / catalyst solution according to Example A in an amount of 1, 5 and 10 parts each 100 parts of the solution according to Example A were added.

In an analogous manner, the compound according to Example L

in an amount of 10 parts per 100 parts alkyd resin / melamine /

Catalyst solution added.

The alkyd resins, which contain the above additives, are used to coat greaseproof papers, and the coated papers obtained are in turn used as release films in the manufacture of high pressure laminates used. Upon removal from the press, it was found that the papers did not separate from the laminate surfaces left, i.e. they both had an indefinitely high adhesive strength.

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example

As in Example 1, release films were produced which were large enough to accommodate printing plates of 1.2 3.0 m (4 χ 10 feet) to cover. The release films were between brought the polished printing plates and vorimprägnier.ten forming the surface of a low-pressure board (hard fiber substrate) Glass fiber materials arranged with the coated side of the release film to the glass fiber material.

When opening the press and ejecting the hot pressed material after lamination, the release liner remains on the laminate and can be peeled cleanly from the polished panels. When it is still hot, the separating film can be removed from the decorative plate with an adhesive strength of about 20 g per 12.7 cm (5 inch). The surface of the plate has a roughness (AA) of about 2.5 μ (100 microinches) and a 60 ° Gloss of 6.

Examples MO ( comparative examples)

The mixed polymer of alkyl vinyl ether and maleic anhydride according to Example 1 becomes a solution with a solids content of 20% reduced in toluene and the alkyd resin component omitted. This solution is (Example M) by gravure coating in an amount of 1.6 kg (3.5 pounds) per ream (dry) Commercially available greaseproof paper applied. Similarly, a glassine paper weighing 15.9 kg (35 pounds) per ream is used (Example N) and a clay coated printing paper of 24.9 kg (55 pounds) per ream (Example 0) at 1.6 kg (3.5 pounds) coated per ream (dry) of the copolymer. Each

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these sheets are then used for separating purposes as indicated in Example A.

In the case of the coated, greaseproof paper, the peeling took place with an adhesive strength of about 25 g. The shine of the Laminate was only one unit at 60 °. This shows that the copolymer is too soft to be used as the only release coating could be used. Typically produce materials that soften under the lamination conditions and easy to flow, only low gloss surfaces. A well-known example is the polypropylene film.

In the case of the glassine paper and the printing paper, it was found that paper fiber tearing out and / or the clay coating took place. The bond strengths were 100 to 250 grams per 12.7 cm (5 inches). It turns out that that Mixed polymer cannot be removed from all types of surfaces when used alone.

Example 3

Example 1 was repeated with the difference that the copolymer from alkyl vinyl ether and maleic anhydride by an equimolar copolymer of maleic anhydride and Octadecene-1 has been replaced, i.e. that in the above formula I the

two groups R form an oxa group and in the above formula

2 3

mel II R is hydrogen, X is a CH ₂ group and R is an alkyl

mean group with 15 carbon atoms. The adhesive strength is 8 to 16 grams per 12.7 cm (5 inches).

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Example 4

100 parts of the copolymer of maleic anhydride and alkyl vinyl ether in accordance with Example 1 are heated η with 50 parts of 1N sulfuric acid for 7 hours at reflux temperature of 110 ⁰ C, in order to convert the anhydride to the acid, that is a product of the above formula I wherein R Means hydrogen. A white, solid, waxy solid can be separated off and obtained by decanting; it is washed in cold water until free of sulfuric acid and dissolved in a mixture of equal parts of isopropanol and toluene to give a solution with a solids content of 40%. This solution is used in the same way as the maleic anhydride copolymer according to Example 1. The adhesive strength of the texture release film obtained is 57 g per 12.7 cm (5 inches). A portion of the mixed polymer solutions with the free carboxyl groups is subjected to analysis by infrared spectroscopy, which shows that 90 to 100% of the mixed polymer is in the form of the free acid.

Examples 5-7

The alkyd resin / maleic anhydride copolymer mixture according to Example 1 is applied to a number of different cellulose sheets applied at a rate of 1.6 kg (3.5 pounds) per ream as described in the above example. The results are summarized in Table I below. In example 5 a sheet of kraft paper, in example 6 a sheet of printing paper, which is coated with clay on one side, and in Example 7 a sheet of printing paper coated on both sides, used. The printing paper is a fine paper material usually used for printing high quality magazines

will.

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Table I.

example

Base weight, kg / ream (lbs./ream) 18.1 (40) 20.9 (46) 14.5 (32)

Gurley densometer (sec.) 13 1860 10 200

Apparent density (g / cm ³ ) 0.74 1.22 1.02

Adhesion strength (g / 12.7 cm,

5 inch) 14 21 17

Laminate gloss (60 °) 5.0 14.0 8.0

AA roughness,

μ (microinches) 2 _f 5 (100) 0.9 (35) 2.16 (85)

Examples 8-16

The procedure according to Example 1 is repeated with the difference, that the alkyd resin used and the copolymer mixed with it can be varied. The copolymer is defined in Table II below with reference to formulas I and II. In either case, results are observed that those of Example 1 are practically equivalent. The materials are given in Table II below.

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Table II example

Alkyd resin

Mixed polymer

Soy fatty acids
Benzoic acid
Isophthalic acid
Glycerin

40%

2%

38%

20%

OR " ¹

both C ₄ alkyl

O
CD
CO
_ *

9 *

10

Coconut oil - 31% isophthalic acid - 40% Trimethylolethane - 29%

Soy Fatty Acids - 53% Phthalic Anhydride - 27.8% 98% Glycerin - 19.2%

both

OR " ¹

OR " ¹ hydrogen and C ₁₂ alkyl

CH,

C ₁₈ AlHyI

Mixture of C -C alkyl j

C 1-4 alkyl

11

Soybean oil - 45.5% dehydrated RiCi-

nut oil - 15.0%

Phthalic anhydride - 23.5%

Pentaerythritol - 16.0%

Hydrogen and mixture of

^C 18- ^C 16 alkyl

C _g alkyl

CD

cn

Table II

(Continuation)

Mixed polymer example

co cx>

co cr>

Alkyd resin

12th Soybean oil 45.1 Isophthalic acid anhydride 38.3 Pentaerythritol 5.6 Ethylene glycol 11.0 13 ** Tall oil fatty acids 40.4 Adipic acid 10.5 Trimellitic acid anhydride 41.5 Propylene glycol 38.3 14th Tall oil fatty acids 44.7 Phthalic anhydride 32.6 Pentaerythritol 15.9 Ethylene glycol 6.8 15th Soybean oil 57.0 Cod liver oil 14.2 Phthalic anhydride 19.5 Glycerin 9.3

Oxa

Oxa

Oxa

Oxa

CH ₃ 0 C ₁₂ alkyl -J he 'CJ H CH C -C alkyl U)

CH,

C _g alkyl

C ₁₃ alkyl

Table II

(Continuation)

example

Alkyd resin

Mixed polymer

16

O CO OO

Tall oil fatty acids 27.0% Phthalic anhydride 38.0% Trimethylolpropane 35.0%

Oxa

C ₁₅ alkyl

♦ mixed melamine-MF-. Me., (Medium methylolation and methylation) used for the crosslinking of the alkyl resin ** Bexabutylated bexamethylmelamine for crosslinking the alkyl resin;

CD ro

CT;

■ ** "27492b3

■ 34 ·

Examples 17-21

92.5 parts of an alkyd resin solution which had been prepared from 39.7 parts of soybean oil, 41.3 parts of isophthalic acid and 19 parts of glycerol and had a solids content of about 62%, a viscosity of 23 to 29 seconds (No. 2 Zohn cup.) at 25 ⁰ C (77.0 ⁰ F.) and a density of 1.01 to 1.04 g / ccm (8.4 to 8.7 pounds per gallon) in isopropanol / xylene (67/33), which also contained 50% hexakismethoxymethylmelamine, 7.5 parts of a catalyst solution of 50% p-toluenesulfonic acid and 50% isopropanol were added. The mixture of alkyd resin is formed using a gravure roller with a square cell pattern with a diagonal count of 47 per cm (120 per inch) and a cell depth of 0.08 mm (0.0032 inch), which is serrated evenly over its entire surface

it,

and catalyst applied to a ³ "bleached greaseproof Kraft paper weighing 5.7 kg per 100 square meters (35 lb./3000 ft. ream) with a thickness of 2.5 µ (0.1 mil). The coated paper is then dried and in a high speed hot air oven for 30 seconds at 138 ⁰ C (280 ⁰ F) crosslinked. the Oberzugsgewicht after crosslinking was 0.29 kg (1.8 ft Ib./3000. ² ream) per 1000 sq.

Various amounts of a solution of an equimolar copolymer were then applied to the coated sheet obtained Maleic anhydride and octadecene-1 in methyl isobutyl ketone applied (for the copolymer it applies that in the above formula I the two groups R form an oxa group and in the

2 3

above formula II R is hydrogen, X is a CH ₂ group and R

mean an alkyl group having 15 carbon atoms). the second coating is done using a 150Q quad rotogravure cylinder applied on a Geiger laboratory printing press. The cylinder brings 0.5 to 0.6 parts of wet coating on the substrate. The double-coated paper obtained

8098 1 9/0868

is then dried for 10 minutes at 125 ^° C. in order to remove the ketone used as solvent.

Then the coated paper is cut into sheets of 1.2 χ 2.4 m (4x8 feet), put together to form a print pile, and, as described in Example A, pressed, with the difference that the double-coated paper is used as component B will.

It has been found that the double-coated paper can be easily separated from the laminate, with no paper, Resin or other debris remained. To measure the ease with which this paper peeled off the laminate the adhesion test described above is carried out. The results are summarized in Table III below .

Table III example

Example 22

The process according to Example 17 is repeated with the difference that the second coating is in the form of a 40 percent solution of an equimolar copolymer of alkyl vinyl ether and maleic anhydride, in which the alkyl vinyl ether is a mixture of 96% C ^ -alkyl, 2% C ^ - Alkyl and 2% C _{1Q to} C ₁₄ alkyl vinyl ether is applied in toluene.

809819/0868

Concentration of
* Mixed polymer
in the ketone Adhesive
ability, g / 12.7 cm
(5 in.) 2.0% 23 1.0% 36 0.5% 34 0.2% 37 0.1% 40

The adhesive strength is similar to that measured in Example 17.

Example 23

Release films are produced as described in Example 17, large enough to cover 1.2 3.0 m (4 10 foot) printing plates. The release liners were placed between the polished pressure plates and which form the surface of a low-pressure board (hard fiber substrate) Pre-impregnated fiberglass materials arranged with the coated side of the release film to the fiberglass material.

When opening the press and ejecting the hot pressed material after lamination, the release liner remains on the laminate and can be peeled cleanly from the polished panels. Im still When hot, the separating film can easily be removed from the decorative panel. An excellent decorative panel is obtained.

Example 24

100 parts of the copolymer of maleic anhydride and alkyl vinyl ether in accordance with Example 23 are heated η with 50 parts of 1N sulfuric acid for 7 hours at reflux temperature of 110 ⁰ C, in order to convert the anhydride to the acid, that is a product of the above formula I wherein R Means hydrogen. A white, solid, waxy solid can be separated off and obtained by decanting; it is washed in cold water until free of sulfuric acid and dissolved in a mixture of equal parts of isopropanol and toluene to give a solution with a solids content of 40%. This solution is used in the same way as the maleic anhydride copolymer according to Example 17. The texture release film obtained can easily be removed from the laminate. Infrared spectrographic analysis

809819/0868

the solution of the copolymer with the free carboxyl groups showed that 90 to 100% of the copolymer was in the form the acid is present.

Examples 25-27

The coatings according to Example 17 are applied to a number of different Cellulose sheets applied as described in this example. In either case, the results are with comparable to those of example 17. In example 25 a sheet of kraft paper, in example 26 a sheet of printing paper, which is coated with clay on one side and, in Example 27, a sheet of printing paper coated on both sides used.

Example 28-36

The procedure of Example 17 is followed, with the exception that the alkyd resin is used as the first coating is used, as well as the copolymer used as the second coating can be varied. The alkyd resin / melamine coatings and the copolymer coatings are prepared using the methods described in Examples 8 to 16 in individual specified components manufactured. In each case the results are as given in Example 17 practically equivalent.

809819/0868

Claims (26)

1. Self-demoulding topping compound from a solution of about 0.5 to about 80.0 percent by weight, based on the total weight the top coating, in a mixture dissolved in an organic solvent (1) about 75 to about 99 percent based on total weight of components 1 and 3, on an oil-modified alkyd resin, (2) about 30 to about 70 percent based on total weight of component 1 on a polyalkyl ether of a polymethylolmelamine and (3) about 1 to about 25%, based on the total weight of ingredients 1 and 3, of a mixed polymer, that is about 15 to about 85 mole percent of repeating units of the formula I, CH - CH .r I. C = O 0 * 0 I. I. Ä R. wherein each radical R individually denotes the group OR and R denotes hydrogen or an alkyl group having 1 to 22 carbon atoms is, or the two groups R taken together form an oxa group and contains the remainder Units Repeating units of the formula R ^a
I.
- CH - CHa - II XR ^a 809819/0868 2 3 are where R is hydrogen or a methyl group, R is an alkyl group having 9 to 30 carbon atoms and X is the group 0 or CH ₂ . 2. Composition according to claim 1, characterized in that the recurring units of component 3 are derived from maleic anhydride and a C ₁ , .- alkyl vinyl ether. 3. Composition according to claim 1, characterized in that the two groups R taken together form an oxa group " 4. mass according to claim 1, characterized indicates that both groups R are hydrogen. 5. mass according to claim 1 or 3, characterized ge-- 2
indicates that R is hydrogen, X is a CH ₀ - 3
Group and R a C. ₅ ~ alkyl group. 6. mass according to claim 1, characterized draws that the polyalkylether of a polymethylolmelamine Is hexakismethoxymethylmelamine. 7. Composition according to claim 1 or 2, characterized in that the alkyd resin of soybean oil, isophthalic acid and glycol is derived. 809819/0868 8. Composition according to claim 1, characterized that the alkyd resin is made up of soybean oil, isophthalic acid and glycerine and the copolymer Maleic anhydride and octadecene-1 are derived. 9. Release film for use in the manufacture of laminates, consisting of a sheet of cellulose paper coated with a first coating A) an oil-modified alkyd resin with about 30 to about 70%, based on the total weight of the component (A), of a polyalkylether of a polymethylolmelamine is crosslinked, and over the layer (A) with a second layer B) is coated with a copolymer containing about 15 to 85 mol percent of recurring units of the formula -CH-CH- I, I. I. C = O C-O r I. R. R. in which each radical R for itself denotes the group OR in which R is hydrogen or an alkyl group having 1 to 22 carbon atoms is, or both radicals R taken together form an oxa group, contains, and the remaining units of which are recurring Units of the formula 809819/0868 27492b3 R ² CH-XR » 2 3 are, wherein R is hydrogen or a methyl group, R is a Alkyl group with 9 to 30 carbon atoms and X denotes the group 0 or CH-. 10. Release film according to claim 9, characterized in that the cellulose paper is a greaseproof paper, a glassine paper or a coated with clay Printing paper is. 11. Release film according to claim 9, characterized ge denotes that the repeating units of component (B) are derived from maleic anhydride and a C ₁ "-alky! vinyl ether. 12. Separating film according to claim 9, characterized in that the two groups R taken together form an oxa group. 13. Separating film according to claim 9, characterized that both groups R are hydrogen. 14. Release film according to claim 9 or 12, characterized 2 characterized in that R is hydrogen, X is a CH ₂ group and R is a C ₁ - alkyl group. 809819/0868 15. Separating film according to claim 9, characterized in that the polyalkyl ether of a polymethylolmelamine Is hexakismethoxymethylmelamine. 16. Release film according to claim 9 or 11, characterized characterized in that the alkyd resin is derived from soybean oil, isophthalic acid and glycerin. 17. Release film according to claim 9, characterized in that the alkyd resin of soybean oil, isophthalic acid and glycerol and the copolymer are derived from maleic anhydride and octadecene-1. 18. Release film for use in the manufacture of laminates, consisting of a sheet of cellulose paper coated with a composition consisting of a mixture of A) about 75 to about 99%, based on the total weight of components (A) and (B), of an oil-modified alkyd resin, that with about 30 to about 70%, based on the total weight of component A, is crosslinked on a polyalkylether of a polymethylolmelamine, and B) there is about 1 to about 25%, based on the total weight of components (A) and (B), of a copolymer, that is about 15 to about 85 mole percent of repeating units of the formula -CH- CH I. I. C = O C = O I. I. R. R. I, 809819/0868 in which each radical R, taken by itself, denotes the group OR, where R is hydrogen or an alkyl group having 1 to 22 carbon atoms, or the two radicals R taken together form an oxa group, and its remaining units contain recurring units of the formula R ² - CH- CH ₂ - n, XR ^S 2 3 are, wherein R is hydrogen or a methyl group, R is an alkyl group having 9 to 30 carbon atoms and X is the group 0 or CH-. 19. Separating film according to claim 18, characterized that the cellulose paper made of greaseproof paper, glassine paper or coated with clay Printing paper is made. 20. Separating film according to claim 18, characterized in that the recurring units of component B of maleic anhydride and a C ₁ οι O Alky! Vinyl ethers are derived. 21. Separating film according to claim 18, characterized in that the two groups R taken together form an oxa group. 809819/0868 22. Separating film according spoke 18, characterized in that both groups R are hydrogen mean. 23. Separating film according to claim 18 or 21, characterized 2 characterized in that R is hydrogen, X is a CHj group and R a C.g "" Alky! Group. 24. Separating film according to claim 18, characterized in that the polyalkyl ether of a poly methylol melamine is hexakismethoxymethyl melamine. 25. Separating film according to claim 18 or 20, characterized characterized that the alkyd resin of soybean oil, Isophthalic acid and glycerin is derived. 26. Separating film according to claim 18, characterized in that the alkyd resin is derived from soybean oil, isophthalic acid and glycerol and the copolymer is derived from maleic anhydride and 1-octadecene. £ ■ 038 19/086 *