CA1302949C - Process for the production of uv-hardened opaquely pigmented coatings - Google Patents
Process for the production of uv-hardened opaquely pigmented coatingsInfo
- Publication number
- CA1302949C CA1302949C CA000534402A CA534402A CA1302949C CA 1302949 C CA1302949 C CA 1302949C CA 000534402 A CA000534402 A CA 000534402A CA 534402 A CA534402 A CA 534402A CA 1302949 C CA1302949 C CA 1302949C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- hardened
- polyester
- cellulose nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
Abstract
Process for the production of UV-hardened opaquely pigmented coatings A b s t r a c t The invention relates to a process for the production of UV-hardened opaquely pigmented coatings, in which a polyester lacquer of 100 parts by weight of air-drying polyester, 0.1 to 10 parts by weight of cellulose nitrate, 0 to 30% by weight, based on the cellulose nitrate, of a placticizer for cellulose nitrate, 10 to 150 parts by weight of pigment, 1 to 10 parts by weight of hydroperoxide, as an initiator, 0.005 to 1 part by weight of siccative, 0.5 to 5 parts by weight of photoinitiator is applied in an amount of 60 to 150 g/m2 to the substrate and the lacquer film is pregelled for 1 to 5 minutes at a temperature of 50 to 80°C and is then hardened under UV radiation wherein the air-drying polyester is free from copolymerizable monomers and contains .beta.,.gamma.-ethylenically unsaturated ether groups. The coatings so prepared, are particularly suitable for coating wood, wood-like materials and films of plastic.
Le A 24 440
Le A 24 440
Description
~3~Z9~i ~
Process for the production of UV-hardened opaquely pigmented coatings _ The invention relates to a process for the production of UV-hardened opaquely pigmented coatings of high scratch resistance and solvent resistance based on unsaturated polyesters which are free from copolymerizable monomers (such as, for example, styrene). The process is particularly suitable for coating wood, wood-like materials and films of plastic.
The production of UV-hardened opaquely pigmented coatings has from the beginning presented serious problems which it has so far not been possible to solve, because the opaque pigment does not allow the UV radiation to penetrate into lower layers.
Compromises have therefore been sought, but these have not been able to make their mark on the market. Thus, it has already been proposed to add incompatible polymers to UV-hardenable unsaturated polyester resins in order to imitate an opaque coating with the opacity resulting from the different refractive indices (DE-OS
(German Published Specification) 2,426,602 published January 30, 1975) to achieve an opaque effect by inclusion of microbubbles in the coating (J. Paint Technol. 45, No. ~84 (1973), 73) and to use fillers with a very low covering power, instead of pigments, and thereby to enable the UV radiation to penetrate into lower layers (DE-AS (German Published Specification) 1,621,820 published March 9, 1972).
The coatings obtainable in this manner do not have a sufficient covering power or have insufficient elasticity.
1 - ~k ~3~949 23189-6495 Another problem is the frequently inadequate storage stability of the coating material.
Surprisingly, it has now been found that coating agents based on a combination of 1) so-called air-drylng polyesters which are free from copolymerizable monomers and containing ~
ethylenically unsaturated ether groups and 2) cellulose nitrate, if appropriate dissolved in an inert organic solvent, can be used for the production of UV-hardened opaquely pigmented coatings of hydroperoxides la . .
~3~Z5'~
are additionally used alongside UV initiators. Such for-mulations can have pot lives of about 5 hours at room temperature and, after an evaporation time of, for example, 2 to 3 minutes at 50 to 70C, can be hardened directly under UV radiation, for example with high pressure mercury vapour lamps.
The invention thus relates to a process for the preparation of UV-hardened opaquely pigmented coatings, in which a polyester lacquer of 100 parts by weight of air-drying polyester, 0.1 to 10, preferably 0.2 to 4, parts by weight of cellulose nitrate, O to 30% by weight, based on the cellulose nitrate, of a plasticizer for cellulose nitrate, 10 to 150 parts by weight of pigment, 1 to 10 parts by weight of hydroperoxide, as an initiator, U.005 to 1 part by weight of siccative, 0.5 to 5 parts by ~eight of photoinitiator and, if appropriate, customary additives is_applied in an amount of 60 to 150 9/m2 to the substrate and the lacquer film is pregelled for 1 to 5, preferably 2 to 3, minutes at a temperature of 50 to 80, preferably 60 to 75C and is then hardened under UV radiation.
Preferred air-drying polyesters are polyconden-sation products of at least one ~,~-ethylenically unsatu-rated dicarboxylic acid with, as a rule, 4 or 5 C atoms or ester-forming derivatives thereof (for example their anhydrides), if appropriate mixed with up to 200 mol %, based on the unsaturated acid component, of one or more aliphatic saturated dicarboxylic-acid with 4 to 10 C atoms or cycloaliphatic or aromatic dicarboxylic acid with 8 to 10 C atoms or ester-forming derivatives thereof (for example their anhydrides), with at least one hydroxy com-pound which is trihydric or polyhydric and has 3 to 8 C
atoms, in which the OH groups which are not employed for the polycondensation are at least partly etherified with ~,y-ethylenically unsaturated alcohols, if appropriate one or more dihydric hydroxy compounds with 2 to 8 Le A 24 440 C atoms and if approprlate one or more monohydric hydroxy compounds with 1 to 18 C atoms - that is to say polyesters such as are described, for example, in DE-AS (German Published 5pecification) 1, 024,654, German Patent Specification 2,221,335 published November 15, 1973 and Wagner/Sarx, "Lackkunstharze"
("Lacquer Synthetic Resins"), 5th edition, Carl Hanser Verlag, Munich 1971, pages 139 and 140.
Examples of unsaturated dicarboxylic acids which are preferably to be used, or their derivatives, are maleic acid or maleic anhydride and fumaric acid. However, it as also possible to use, for example, mesaconi.c acid, citraconic acid, itaconic acid or chloromaleic acid. Examples of the aliphatic saturated and cycloaliphatic and aromatic dicarboxyli.c acids to be used, or their derivatives, are phthalic acid and phthalic anhydride, isophthalic acid, terephthalic acid, hexa- and tetrahydrophthalic acid or anhydrides thereof, endomethylenetetrahydrophthalic acid and the anhydride thereof, succinic acid or succinic anhydride and succinic acid esters and chlorides, adipic acid and sebacic acid.
In order to prepare polyesters which are difficult to ignite, hexachloroendomethylenetetrahydrophthalic acid, tetrachlorophthalic acid or tetrabromophthalic acid, for example, can be used. Ethylene glycol, propane-1,2-diol, propane-1,3-diol, diethylene glycol, dipropylene glycol, butane-1,3-diol, butane-1,4-diol, neopentylglycol, hexane-1,6-diol, 2,2-bis(4-hydroxycyclohexyl)-propane or bis-oxyalkylated bisphenol A can be used; suitable preferred hydroxy compounds for introducing the ~,~
-ethylenically unsaturated ether groups are trimethylolpropane 13~ 9 23189-6495 mono- and diallyl ether, glycerol mono- and diallyl ether and pentaerythritol mono-, di- and triallyl ether. The polyesters to be used according to the invention preferably contain at least 10%
by weight, in parti~ular at least 20% by weight, based on the polyester, of radicals of ~,~-ethylenically unsaturated ether groups.
~ 3a -~L3~29~J
Monovalent hydroxy compounds which are preferred for the preparation of the polyester are alkanols, cyclo-alkanols and cycloalkanealkanols, for example n-hexanol, n-octanol, n-decanol, laurol, stearyl alcohol and hexa-hydrobenzyl alcohol, and preferably branched alkanols,such as 2-ethyl-1-hexanol and isononanols.
The acid numbers of the polyesters should be 1-40, preferably 10-30, the OH numbers should be 10-100, prefer-ably 20-50, and the molecular weights determined as the number-average should be 300-5,000, preferably 500-2,000.
Preferred cellulose nitrates are the customary grades of collodion cotton, for example cellulose nitrate with a nitrogen content of 10.2 to 12.4% by weight.
It is not essential to the invention whether the collodion cotton used is a butanol-, isopropanol-, ethan-ol-, methanol- or water-moist form or whether celluloid-like compositions (generally called chips), that is to say with gelatinizing plasticizers, are used~
Preferred plasticizers for cellulose nitrates are, in particular, phthalic acid esters and adipic acid esters of alcohols with 4 to 8 carbon atoms, for example dibutyl phthalate, diisobutylcarbinyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, dibutyl phthalate and di-octyl adipate, phosphoric acid esters of alcohols with 6 to 10 carbon atoms, for example tricresyl phosphate, tri-phenyl phosphate, trioctyl phosphate, cresyl phenyl phos-phate or dioctyl phenyl phosphate, and also diethylene glycol monolaurate, dipentaerythritol hexapropic,nate, 2-methoxyethyl-acetyl-tributyl aconitate, butoxy-ethyldi-glycol carbonate, acetyltributyl citrate, triethylene glycol pelargonate, butyldiglycol carbonate, polyethylene glycol di-2-ethyl-hexoate, triethylene glycol di-2-ethyl butyrate, tributyl carballylate, dibutyl sebacate and benzenesulphonic acid N-methylamide.
Pigments which can be employed are the opaque in-inorganic or organic pigments customary for unsaturated Le A 24 440 . _ 13~?2949 polyester lacquers, such as titanium dioxide, ultramarine blue, iron oxides and phthalocyanine blue.
Preferred hydroperoxides are, for example, tert.-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone hydroperoxide, dlisopropylbenzene monohydroperoxide and hydrogen peroxide.
Siccatives are, for example, iron, lead, cobalt and manganese salts of acids such as linseed oil fatty acids, tallow oil fatty acids or soya bean fatty acids,of resin acids, such as abietic acid and naphthenic acid, or of acetic acid or isooctanoic acid.
Cobalt octoate, cobalt naphthanate and cobalt acetate are preferred. Siccatives are preferably employed in the form of organic solutions.
Suitable photoinitiators are the compounds which are sufficiently known for radiation hardening, such as ketones, diketones, ~-keto-alcohols and their derivatives. Preferred photoinitiators are benzoin and its derivatives, such as, for example, benzoin ethers (German Patent Specification 1,694,149 published October 16, 1969), benzil ketals and hydroxyalkylphenones, for example benzoin isopropyl ether, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 1-hydroxycyclohexyl phenyl ketone.
The customary additives which are to be used if appropriate are, for example, fillers, thixotropic agents, smoothing agents, matting agents and flow control agents, and organic solvents, such as, for example, toluene, xylene, isopropanol and, in particular, butyl acetate. The amount of organic solvent is in general chosen ~3~29~9 such that the lacquers have a suitable processing viscosity.
The lacquers are outstandingly suitable for processing on conventional lacquering lines equipped with pouring machines.
They can also be applied by rolling and spraying.
The percentages quoted in the following examples denote percentages by weight, and parts are parts by - 5a -13~949 weight.
Examples Polyesters used Unsaturated polyesters with an acid number of 25, an OH number of 75 and a viscosity of 6,000 mPa.s, measured on an 80% strength solution in butyl acetate at 20C, prepared from 1 mol of maleic anhydride, 0.85 mol of ethylene glycol, 0.15 mol of propylene glycol and 0.3 mol of trimethylolpropane diallyl ether.
The formulations shown in the table*) were poured in an amount of 90 9/m2 onto a wood substrate prewarmed to 40C. The system was warmed at 70C for 3 minutes for evaporation of the solvent. The lacquer film was then hardened under UV radiation (2 high, pressure mercury vapour lamps each of 80 watt/cm, distance of the lamps from the lacquer 20 cm, rate of processing 3.5 m/minute).
Examples 1-3 gave colourless hard scratch-resistant lacquer-ings which were absolutely resistant towarcls water and chemicals, whilst the comparison example led to a wrinkled lacquering which was not scratch-resistant.
*) Viscosity according to DIN 53 211 tDIN cup no. 4 at 20C) corresponding to a flow time of 60 seconds Le A 24 440 ~3~ 9~9 ., ~oU~
, ~ ~ 0~ . . . .-E ~ ~ O o o O
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~ O O O `O
U) ~~O~ 0 E ~ ~ ~--~ ~ O O O
x LU
1~ ~O U~ o~
O OO `O
oJ a ~ C ~ -- ~
I ~ r~ ~ O ~o O n~ Q O _ _ ^ O ~ 1~ t~
'~ I~ Q Q vc ~, .. , c a) ~ _ ~, , Q
~_ C ~~ O
O ~ ~QJ CX
O ~ ~ ~ C :~.
a)c ~ -- Q 'C O
C ~10 ~ ~ I Q~~ ~
O ~ ~ ~ ~ u) Q
C l_ I _C~ ., _~ ., ~ _ ~O
~ ~ _ >~ x~_ ~ Q
_ ~O C
o ~v, o~s ~ ~ ~~ ~,, a~
v) D~ ~ ~ a) O-- ~ ~ L
E --O
' ~~ O O ~) I ~U) o -- ~ o Q ~ ~ >~~~ ~ --~n c 1~ 1) x --~ ~--c o a) aJ ~ u E u~ ) x x n~ r~
O ~ t~ O OO ~I~
v~U)-- ~ E ~ ~ Q
~ c ~ ~ -- ~ E ~1 0 _ l ~ ~ _ ~ ~ ~~~ C >~ O
-- U~ -- ~ I O I ~ ~ ~ ~
n~o o . o) , a~ >~~I I I o ~J o ~ o 1_0 Q ~ m x m~J ~ ~ ~ ~ ~ -Le A 24 440 __
Process for the production of UV-hardened opaquely pigmented coatings _ The invention relates to a process for the production of UV-hardened opaquely pigmented coatings of high scratch resistance and solvent resistance based on unsaturated polyesters which are free from copolymerizable monomers (such as, for example, styrene). The process is particularly suitable for coating wood, wood-like materials and films of plastic.
The production of UV-hardened opaquely pigmented coatings has from the beginning presented serious problems which it has so far not been possible to solve, because the opaque pigment does not allow the UV radiation to penetrate into lower layers.
Compromises have therefore been sought, but these have not been able to make their mark on the market. Thus, it has already been proposed to add incompatible polymers to UV-hardenable unsaturated polyester resins in order to imitate an opaque coating with the opacity resulting from the different refractive indices (DE-OS
(German Published Specification) 2,426,602 published January 30, 1975) to achieve an opaque effect by inclusion of microbubbles in the coating (J. Paint Technol. 45, No. ~84 (1973), 73) and to use fillers with a very low covering power, instead of pigments, and thereby to enable the UV radiation to penetrate into lower layers (DE-AS (German Published Specification) 1,621,820 published March 9, 1972).
The coatings obtainable in this manner do not have a sufficient covering power or have insufficient elasticity.
1 - ~k ~3~949 23189-6495 Another problem is the frequently inadequate storage stability of the coating material.
Surprisingly, it has now been found that coating agents based on a combination of 1) so-called air-drylng polyesters which are free from copolymerizable monomers and containing ~
ethylenically unsaturated ether groups and 2) cellulose nitrate, if appropriate dissolved in an inert organic solvent, can be used for the production of UV-hardened opaquely pigmented coatings of hydroperoxides la . .
~3~Z5'~
are additionally used alongside UV initiators. Such for-mulations can have pot lives of about 5 hours at room temperature and, after an evaporation time of, for example, 2 to 3 minutes at 50 to 70C, can be hardened directly under UV radiation, for example with high pressure mercury vapour lamps.
The invention thus relates to a process for the preparation of UV-hardened opaquely pigmented coatings, in which a polyester lacquer of 100 parts by weight of air-drying polyester, 0.1 to 10, preferably 0.2 to 4, parts by weight of cellulose nitrate, O to 30% by weight, based on the cellulose nitrate, of a plasticizer for cellulose nitrate, 10 to 150 parts by weight of pigment, 1 to 10 parts by weight of hydroperoxide, as an initiator, U.005 to 1 part by weight of siccative, 0.5 to 5 parts by ~eight of photoinitiator and, if appropriate, customary additives is_applied in an amount of 60 to 150 9/m2 to the substrate and the lacquer film is pregelled for 1 to 5, preferably 2 to 3, minutes at a temperature of 50 to 80, preferably 60 to 75C and is then hardened under UV radiation.
Preferred air-drying polyesters are polyconden-sation products of at least one ~,~-ethylenically unsatu-rated dicarboxylic acid with, as a rule, 4 or 5 C atoms or ester-forming derivatives thereof (for example their anhydrides), if appropriate mixed with up to 200 mol %, based on the unsaturated acid component, of one or more aliphatic saturated dicarboxylic-acid with 4 to 10 C atoms or cycloaliphatic or aromatic dicarboxylic acid with 8 to 10 C atoms or ester-forming derivatives thereof (for example their anhydrides), with at least one hydroxy com-pound which is trihydric or polyhydric and has 3 to 8 C
atoms, in which the OH groups which are not employed for the polycondensation are at least partly etherified with ~,y-ethylenically unsaturated alcohols, if appropriate one or more dihydric hydroxy compounds with 2 to 8 Le A 24 440 C atoms and if approprlate one or more monohydric hydroxy compounds with 1 to 18 C atoms - that is to say polyesters such as are described, for example, in DE-AS (German Published 5pecification) 1, 024,654, German Patent Specification 2,221,335 published November 15, 1973 and Wagner/Sarx, "Lackkunstharze"
("Lacquer Synthetic Resins"), 5th edition, Carl Hanser Verlag, Munich 1971, pages 139 and 140.
Examples of unsaturated dicarboxylic acids which are preferably to be used, or their derivatives, are maleic acid or maleic anhydride and fumaric acid. However, it as also possible to use, for example, mesaconi.c acid, citraconic acid, itaconic acid or chloromaleic acid. Examples of the aliphatic saturated and cycloaliphatic and aromatic dicarboxyli.c acids to be used, or their derivatives, are phthalic acid and phthalic anhydride, isophthalic acid, terephthalic acid, hexa- and tetrahydrophthalic acid or anhydrides thereof, endomethylenetetrahydrophthalic acid and the anhydride thereof, succinic acid or succinic anhydride and succinic acid esters and chlorides, adipic acid and sebacic acid.
In order to prepare polyesters which are difficult to ignite, hexachloroendomethylenetetrahydrophthalic acid, tetrachlorophthalic acid or tetrabromophthalic acid, for example, can be used. Ethylene glycol, propane-1,2-diol, propane-1,3-diol, diethylene glycol, dipropylene glycol, butane-1,3-diol, butane-1,4-diol, neopentylglycol, hexane-1,6-diol, 2,2-bis(4-hydroxycyclohexyl)-propane or bis-oxyalkylated bisphenol A can be used; suitable preferred hydroxy compounds for introducing the ~,~
-ethylenically unsaturated ether groups are trimethylolpropane 13~ 9 23189-6495 mono- and diallyl ether, glycerol mono- and diallyl ether and pentaerythritol mono-, di- and triallyl ether. The polyesters to be used according to the invention preferably contain at least 10%
by weight, in parti~ular at least 20% by weight, based on the polyester, of radicals of ~,~-ethylenically unsaturated ether groups.
~ 3a -~L3~29~J
Monovalent hydroxy compounds which are preferred for the preparation of the polyester are alkanols, cyclo-alkanols and cycloalkanealkanols, for example n-hexanol, n-octanol, n-decanol, laurol, stearyl alcohol and hexa-hydrobenzyl alcohol, and preferably branched alkanols,such as 2-ethyl-1-hexanol and isononanols.
The acid numbers of the polyesters should be 1-40, preferably 10-30, the OH numbers should be 10-100, prefer-ably 20-50, and the molecular weights determined as the number-average should be 300-5,000, preferably 500-2,000.
Preferred cellulose nitrates are the customary grades of collodion cotton, for example cellulose nitrate with a nitrogen content of 10.2 to 12.4% by weight.
It is not essential to the invention whether the collodion cotton used is a butanol-, isopropanol-, ethan-ol-, methanol- or water-moist form or whether celluloid-like compositions (generally called chips), that is to say with gelatinizing plasticizers, are used~
Preferred plasticizers for cellulose nitrates are, in particular, phthalic acid esters and adipic acid esters of alcohols with 4 to 8 carbon atoms, for example dibutyl phthalate, diisobutylcarbinyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, dibutyl phthalate and di-octyl adipate, phosphoric acid esters of alcohols with 6 to 10 carbon atoms, for example tricresyl phosphate, tri-phenyl phosphate, trioctyl phosphate, cresyl phenyl phos-phate or dioctyl phenyl phosphate, and also diethylene glycol monolaurate, dipentaerythritol hexapropic,nate, 2-methoxyethyl-acetyl-tributyl aconitate, butoxy-ethyldi-glycol carbonate, acetyltributyl citrate, triethylene glycol pelargonate, butyldiglycol carbonate, polyethylene glycol di-2-ethyl-hexoate, triethylene glycol di-2-ethyl butyrate, tributyl carballylate, dibutyl sebacate and benzenesulphonic acid N-methylamide.
Pigments which can be employed are the opaque in-inorganic or organic pigments customary for unsaturated Le A 24 440 . _ 13~?2949 polyester lacquers, such as titanium dioxide, ultramarine blue, iron oxides and phthalocyanine blue.
Preferred hydroperoxides are, for example, tert.-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone hydroperoxide, dlisopropylbenzene monohydroperoxide and hydrogen peroxide.
Siccatives are, for example, iron, lead, cobalt and manganese salts of acids such as linseed oil fatty acids, tallow oil fatty acids or soya bean fatty acids,of resin acids, such as abietic acid and naphthenic acid, or of acetic acid or isooctanoic acid.
Cobalt octoate, cobalt naphthanate and cobalt acetate are preferred. Siccatives are preferably employed in the form of organic solutions.
Suitable photoinitiators are the compounds which are sufficiently known for radiation hardening, such as ketones, diketones, ~-keto-alcohols and their derivatives. Preferred photoinitiators are benzoin and its derivatives, such as, for example, benzoin ethers (German Patent Specification 1,694,149 published October 16, 1969), benzil ketals and hydroxyalkylphenones, for example benzoin isopropyl ether, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 1-hydroxycyclohexyl phenyl ketone.
The customary additives which are to be used if appropriate are, for example, fillers, thixotropic agents, smoothing agents, matting agents and flow control agents, and organic solvents, such as, for example, toluene, xylene, isopropanol and, in particular, butyl acetate. The amount of organic solvent is in general chosen ~3~29~9 such that the lacquers have a suitable processing viscosity.
The lacquers are outstandingly suitable for processing on conventional lacquering lines equipped with pouring machines.
They can also be applied by rolling and spraying.
The percentages quoted in the following examples denote percentages by weight, and parts are parts by - 5a -13~949 weight.
Examples Polyesters used Unsaturated polyesters with an acid number of 25, an OH number of 75 and a viscosity of 6,000 mPa.s, measured on an 80% strength solution in butyl acetate at 20C, prepared from 1 mol of maleic anhydride, 0.85 mol of ethylene glycol, 0.15 mol of propylene glycol and 0.3 mol of trimethylolpropane diallyl ether.
The formulations shown in the table*) were poured in an amount of 90 9/m2 onto a wood substrate prewarmed to 40C. The system was warmed at 70C for 3 minutes for evaporation of the solvent. The lacquer film was then hardened under UV radiation (2 high, pressure mercury vapour lamps each of 80 watt/cm, distance of the lamps from the lacquer 20 cm, rate of processing 3.5 m/minute).
Examples 1-3 gave colourless hard scratch-resistant lacquer-ings which were absolutely resistant towarcls water and chemicals, whilst the comparison example led to a wrinkled lacquering which was not scratch-resistant.
*) Viscosity according to DIN 53 211 tDIN cup no. 4 at 20C) corresponding to a flow time of 60 seconds Le A 24 440 ~3~ 9~9 ., ~oU~
, ~ ~ 0~ . . . .-E ~ ~ O o o O
~OU~ 0 0 1 ~O`
~ O O O `O
U) ~~O~ 0 E ~ ~ ~--~ ~ O O O
x LU
1~ ~O U~ o~
O OO `O
oJ a ~ C ~ -- ~
I ~ r~ ~ O ~o O n~ Q O _ _ ^ O ~ 1~ t~
'~ I~ Q Q vc ~, .. , c a) ~ _ ~, , Q
~_ C ~~ O
O ~ ~QJ CX
O ~ ~ ~ C :~.
a)c ~ -- Q 'C O
C ~10 ~ ~ I Q~~ ~
O ~ ~ ~ ~ u) Q
C l_ I _C~ ., _~ ., ~ _ ~O
~ ~ _ >~ x~_ ~ Q
_ ~O C
o ~v, o~s ~ ~ ~~ ~,, a~
v) D~ ~ ~ a) O-- ~ ~ L
E --O
' ~~ O O ~) I ~U) o -- ~ o Q ~ ~ >~~~ ~ --~n c 1~ 1) x --~ ~--c o a) aJ ~ u E u~ ) x x n~ r~
O ~ t~ O OO ~I~
v~U)-- ~ E ~ ~ Q
~ c ~ ~ -- ~ E ~1 0 _ l ~ ~ _ ~ ~ ~~~ C >~ O
-- U~ -- ~ I O I ~ ~ ~ ~
n~o o . o) , a~ >~~I I I o ~J o ~ o 1_0 Q ~ m x m~J ~ ~ ~ ~ ~ -Le A 24 440 __
Claims (4)
1. A process for the production of UV-hardened opaquely pigmented coatings, in which a polyester lacquer of 100 parts by weight of air-drying polyester, 0.1 to 10 parts by weight of cellulose nitrate, 0 to 30% by weight, based on the cellulose nitrate, of a placticizer for cellulose nitrate, 10 to 150 parts by weight of pigment, 1 to 10 parts by weight of hydroperoxide, as an initiator, 0.005 to 1 part by weight of siccative, 0.5 to 5 parts by weight of photoinitiator is applied in an amount of 60 to 150 g/m2 to the substrate and the lacquer film is pregelled for 1 to 5 minutes at a temperature of 50 to 80°C and is then hardened under UV radiation wherein the air-drying polyester is free from copolymerizable monomers and contains .beta.,?-ethylenically unsaturated ether groups.
2. Process according to Claim 1, in which the polyester lacquer contains 0.2 to 4 parts by weight of cellulose nitrate per 100 parts by weight of polyester.
3. Process according to Claim 1, in which the lacquer film is pregelled for 2 to 3 minutes.
4. Process according to Claim 1, 2 or 3 in which the lacquer film is pregelled at 60 to 75°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19863612442 DE3612442A1 (en) | 1986-04-12 | 1986-04-12 | METHOD FOR PRODUCING UV-CURED COVERING PIGMENTED COATINGS |
DEP3612442.7 | 1986-04-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1302949C true CA1302949C (en) | 1992-06-09 |
Family
ID=6298605
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000534402A Expired - Lifetime CA1302949C (en) | 1986-04-12 | 1987-04-10 | Process for the production of uv-hardened opaquely pigmented coatings |
Country Status (7)
Country | Link |
---|---|
US (1) | US4753817A (en) |
EP (1) | EP0245639B1 (en) |
JP (1) | JPS62243657A (en) |
AT (1) | ATE64607T1 (en) |
CA (1) | CA1302949C (en) |
DE (2) | DE3612442A1 (en) |
ES (1) | ES2022190B3 (en) |
Families Citing this family (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX169697B (en) * | 1987-12-28 | 1993-07-19 | Ppg Industries Inc | IMPROVEMENTS TO RADIATION-FRAGABLE COMPOSITIONS BASED ON UNSATURATED POLYESTERS AND COMPOUNDS HAVING AT LEAST TWO GROUPS OF VINYL ETER |
BE1007373A3 (en) * | 1993-07-30 | 1995-05-30 | Dsm Nv | Radiation-curable binder composition for powder paints formulations. |
US5747115A (en) * | 1993-09-30 | 1998-05-05 | The United States Of America As Represented By The Secretary Of The Navy | UV-curable and non-volatile pigmented coatings |
BE1010713A3 (en) * | 1996-10-25 | 1998-12-01 | Ucb Sa | POWDER COMPOSITIONS BASED SEMI-CRYSTALLINE POLYESTER AND ACRYLIC COPOLYMERS; GROUP CONTAINING (METH) acrylyl. |
US5922473A (en) * | 1996-12-26 | 1999-07-13 | Morton International, Inc. | Dual thermal and ultraviolet curable powder coatings |
DE19853145A1 (en) * | 1998-11-18 | 2000-05-25 | Ostermann & Scheiwe Gmbh & Co | Coating material, especially for porous or penetrable surfaces |
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US4118366A (en) * | 1972-12-27 | 1978-10-03 | Basf Farben & Fasern Ag | Compositions for the production of opaque coatings by radiation |
DE2436614A1 (en) * | 1974-07-30 | 1976-02-19 | Basf Farben & Fasern | Opaque pigment-free covering coating prodn - from photo-polymerisable compsn contg unsatd polyester, copolymerisable monomer, opt other resin and fillers |
US4005244A (en) * | 1974-09-30 | 1977-01-25 | Ppg Industries, Inc. | Ultraviolet light curable opacifying compositions |
JPS54105774A (en) * | 1978-02-08 | 1979-08-20 | Hitachi Ltd | Method of forming pattern on thin film hybrid integrated circuit |
US4222835A (en) * | 1978-05-25 | 1980-09-16 | Westinghouse Electric Corp. | In depth curing of resins induced by UV radiation |
US4451523A (en) * | 1982-11-12 | 1984-05-29 | Loctite Corporation | Conformal coating systems |
-
1986
- 1986-04-12 DE DE19863612442 patent/DE3612442A1/en not_active Withdrawn
-
1987
- 1987-03-30 US US07/033,045 patent/US4753817A/en not_active Expired - Lifetime
- 1987-03-31 AT AT87104751T patent/ATE64607T1/en not_active IP Right Cessation
- 1987-03-31 DE DE8787104751T patent/DE3770868D1/en not_active Expired - Lifetime
- 1987-03-31 ES ES87104751T patent/ES2022190B3/en not_active Expired - Lifetime
- 1987-03-31 EP EP87104751A patent/EP0245639B1/en not_active Expired - Lifetime
- 1987-04-08 JP JP62084890A patent/JPS62243657A/en active Pending
- 1987-04-10 CA CA000534402A patent/CA1302949C/en not_active Expired - Lifetime
Also Published As
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ES2022190B3 (en) | 1991-12-01 |
EP0245639B1 (en) | 1991-06-19 |
DE3612442A1 (en) | 1987-10-22 |
EP0245639A3 (en) | 1989-09-06 |
US4753817A (en) | 1988-06-28 |
ATE64607T1 (en) | 1991-07-15 |
DE3770868D1 (en) | 1991-07-25 |
EP0245639A2 (en) | 1987-11-19 |
JPS62243657A (en) | 1987-10-24 |
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