DE19907957A1 - Pigmented photopolymerizable compositions based on ethylenically unsaturated compounds - Google Patents

Abstract

Photopolymerizable compositions contain: (a) ethylenically unsaturated photopolymerizable compound(s); (b) mono-, bis- and/or tris-acylphosphine oxide(s) or a mixture with an alpha -hydroxyketone, alpha -aminoketone or/and benzoin derivative as photoinitiator; and (c) optical brightener(s) and (d) pigment(s). Independent claims are also included for: (a) a photopolymerization process; (b) a substrate with at least one surface coated with the cured composition; and (c) the cured compositions.

Description

The invention relates to pigmented photocurable compositions which acylphos contain phinoxidphotoinitiatoren and optical brighteners and especially as white find paint formulations.

Mono-, bis- and trisacylphosphine oxides are used as photoinitiators, especially for Hardening thick pigmented coatings, known in the literature. So at for example in US patent 4298738 monoacylphosphine oxides, in US patents 4737593 and 4792632 and in US 5399770 bisacylphosphine oxides. Also photoinitiatorge mix from mono- and bisacylphosphine oxides with α-hydroxyketones and benzophenones are known from this publication. The description of Trisacylphosphinoxidverbin can be found in WO 96/07662. EP 741333 describes a combination of acyl phosphine oxide compound with an optical brightener compound in unpigmented photo polymerizable compositions described, the reactivity of the particular re composition used in imaging systems is increased.

In technology, especially in the production of pigmented paints, there is a Be may be used on photocurable formulations which, despite the high pigment content, are quick and easy show complete hardening.

It has now been found that by adding optical brighteners to connections pigmented photocurable formulations containing acylphosphine oxide photoinitiators the brightener compounds act as a kind of sensitizer and the hardening of such Wording is unexpectedly improved.

The invention therefore relates to photopolymerizable compositions comprising

• (a) at least one ethylenically unsaturated photopolymerizable compound and
• (b) at least one mono-, bis- or trisacylphosphine oxide compound as photoinitiator or a mixture of such compounds with an α-hydroxyketone, α-aminoketone or / and Benzoin derivative compound
• (c) at least one optical brightener, and
• (d) at least one pigment.

The mono-, bis- or trisacylphosphine oxide compounds are, for example, compounds of the formula I.

wherein
R ₁ and R ₂ are independently C ₁ -C ₁₈ alkyl substituted by one or several non-successive O atoms interrupted C ₂ -C ₁₈ alkyl, phenyl-substituted C ₁ - C ₄ alkyl, C ₂ -C ₈ - Represent alkenyl, phenyl, naphthyl, biphenyl or C ₅ -C ₁₂ cycloalkyl, where the radicals phenyl, naphthyl, biphenyl and C ₅ -C ₁₂ cycloalkyl are unsubstituted or mono- to pentas with halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkylthio and / or C ₁ -C ₈ alkoxy are substituted or R ₁ and R _{2 are} -COR ₃ ;
R _{3 is} unsubstituted or mono- or pentasubstituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkylthio and / or halogen.

The α-hydroxyketone, α-aminoketone and benzoin derivative compounds are compounds of the formula II

wherein
R _{4 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, -OCH ₂ CH ₂ -OR ₈ , morpholino, SCH ₃ , a group

or a group

stands;
n has a value from 2 to 10;
G for the rest

stands;
R _{5 is} hydroxy, C ₁ -C ₁₆ alkoxy, morpholino, dimethylamino or -O (CH ₂ CH ₂ O) _m -C ₁ -C ₁₆ alkyl;
R ₆ and R ₇ independently of one another are hydrogen, C ₁ -C ₆ -alkyl, phenyl, benzyl, C ₁ -C ₆ -alkoxy or -O (CH ₂ CH ₂ O) _m -C ₁ -C ₁₆ -alkyl, or R ₆ and R ₇ together with the carbon atom to which they are attached form a cyclohexyl ring;
m represents a number from 1-20;
wherein R ₅ , R ₆ and R _{7 are} not all C ₁ -C ₁₆ alkoxy or -O (CH ₂ CH ₂ O) _m -C ₁ -C ₁₆ alkyl at the same time; and
R _{8 is} hydrogen,

is; is.

C ₁ -C ₁₈ alkyl is linear or branched and is, for example, C ₁ -C ₁₂ , C ₁ -C ₈ , C ₁ -C ₆ or C ₁ -C ₄ alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl , Decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

C ₁ -C ₁₂ alkyl, C ₁ -C ₈ alkyl and C ₁ -C ₆ alkyl are also linear or branched and have, for. B. the meanings given above up to the corresponding number of carbon atoms.

C ₂ -C ₁₈ alkyl which is interrupted one or more times by non-successive O atoms is interrupted, for example, 1-7 or 1 or 2 times by -O-. The O atoms are separated by at least one methylene group. There are z. B. Structural units such as -CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , - [CH ₂ CH ₂ O] _y -CH ₃ , with y = 1-8, - (CH ₂ CH ₂ O) ₇ CH ₂ CH ₃ , -CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH ₂ CH ₃ or -CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH ₃ .

C ₁ -C ₁₈ alkoxy represents linear or branched radicals and is, for example, C ₁ -C ₁₂ -, C ₁ -C ₈ -, C ₁ -C ₆ - or C ₁ -C ₄ alkoxy. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy , Dodecyloxy, hexadecyloxy or octadecyloxy, in particular methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, preferably methoxy.

C ₁ -C ₁₂ alkoxy, C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkoxy and C ₁ -C ₄ alkoxy are also linear or ver branched and have, for. B. the meanings given above up to the corresponding number of carbon atoms.

C ₁ -C ₁₂ alkylthio represents linear or branched radicals and is, for example, C ₁ -C ₈ -, C ₁ -C ₆ - or C ₁ -C ₄ -alkylthio and means, for. B. methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, heptylthio, 2,4,4-tri methylpentylthio, 2-ethylhexylthio, octylthio, nonylthio, Decylthio or dodecylthio, in particular methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, preferably methylthio. C ₁ -C ₈ alkylthio is also linear or ver branched and has z. B. the meanings given above up to the corresponding number of carbon atoms.

C ₅ -C ₁₂ cycloalkyl means e.g. B. cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, in particular cyclopentyl and cyclohexyl, preferably cyclohexyl.

C ₂ -C ₈ alkenyl radicals can be mono- or polyunsaturated and linear or branched and are, for example, C ₂ -C ₆ or C ₂ -C ₄ alkenyl. Examples are allyl, methallyl, 1,1-dimethyllallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl or 1-octenyl, especially allyl. C ₁ -C ₄ alkyl substituted with phenyl is in particular benzyl.

Substituted phenyl, naphthyl or biphenyl is one to five times, e.g. B. one, two or three times, in particular mono- or disubstituted on the phenyl ring. R ₃ as substituted phenyl is in particular substituted twice or three times.

Preferred substituents for R ₁ , R ₂ and R ₃ , as phenyl, naphthyl and biphenyl are C ₁ -C ₄ alkyl, especially methyl, C ₁ -C ₄ alkoxy, especially methoxy, and chlorine. Especially before is R ₃ z. B. 2,4,6-trimethylphenyl, 2,6-dimethylphenyl or 2,6-dimethoxyphenyl.

Halogen is preferably fluorine, chlorine, bromine and iodine, especially chlorine and bromine Chlorine.

The preparation of the compounds of the formula I is known to the person skilled in the art and is exemplary as in US 4298738, 47 37 593 and 47 92 632, GB 2259704 and in WO 96/07662 be wrote. Some of these compounds are commercially available.

Some compounds of formula II are also commercially available. They are manufactured according to known methods and z. B. EP 3002, EP 284561 and EP 805152. The preparation of oligomeric compounds of the formula II is described, for example, in EP 161 463 described.

Preference is given to compositions wherein, independently in the compounds of formula IR ₁ and R ₂ of each other C ₁ -C ₁₈ alkyl substituted by one or several non-successive O atoms interrupted C ₂ -C ₁₈ alkyl, or phenyl-substituted C ₁ -C _4- Alkyl, C ₂ -C ₈ alkenyl, phenyl, naphthyl, biphenyl or C ₅ -C ₁₂ cycloalkyl, the radicals phenyl, naphthyl, biphenyl and C ₅ -C ₁₂ cycloalkyl being unsubstituted or one to five times with Halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkylthio and / or C ₁ -C ₈ alkoxy are substituted; and
R _{3 is} unsubstituted or mono- or pentasubstituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkylthio and / or halogen.

The compounds are in further preferred compositions according to the invention of the formula I monoacylphosphine oxides.

In other preferred compositions in the compounds of the formula IR ₁ and R _{2 are,} independently of one another, C ₁ -C ₁₈ -alkyl, unsubstituted or mono- to pentafixed with halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkylthio and / or C ₁ -C ₈ alkoxy substituted phenyl.

Also of interest are compositions in which the compounds of the formula IR _{3 are} phenyl which is substituted twice or three times by C ₁ -C ₁₂ -alkyl or C ₁ -C ₁₂ -alkoxy.

Further preferred compositions are those in which the compounds of formula II R _{4 are} hydrogen, -OCH ₂ CH ₂ -OR ₈ , morpholino or SCH ₃ ;
R _{5 is} hydroxy, C ₁ -C ₁₆ alkoxy, morpholino or dimethylamino;
R ₆ and R ₇ independently of one another are C ₁ -C ₆ alkyl, benzyl or C ₁ -C ₁₆ alkoxy, or R ₆ and R ₇ together with the carbon atom to which they are attached form a cyclohexyl ring;
wherein R ₅ , R ₆ and R _{7 are} not all C ₁ -C ₁₆ alkoxy at the same time; and
R _{8 is} hydrogen.

Compositions in which the compound of the formula II is an α-hydroxy ketone.

Preferred compounds of the formula II are α-hydroxycyclohexylphenyl ketone or 2-Hy droxy-2-methyl-1-phenyl-propanone, (4-methylthiobenzoyl) -1-methyl-1-morpholino-ethane, (4- Morpholino-benzoyl) -1-benzyl-1-dimethylamino-propane or benzil dimethyl ketal.

Preferred compounds of the formula I are (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, Bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethyl-pent-1-yl) phosphine oxide, bis (2,4,6-trimethyl  benzoyl) phenyl phosphine oxide or bis (2,4,6-trimethylbenzoyl) - (2,4-dipentoxyphenyl) phos phinoxide.

Also preferred are compositions in which in the formula II R ₆ and R ₇ independently of one another are C ₁ -C ₆ -alkyl, or together with the carbon atom to which they are attached form a cyclohexyl ring and R _{5 is} hydroxyl.

Also important are compositions in which R ₆ and R _{7 are the} same in the compounds of the formula II and are methyl and R _{5 is} hydroxy or i-propoxy.

The proportion of compounds of the formula I in a mixture with compounds of the formulas II is 5 to 99%, e.g. B. 20-80%, preferably 25 to 75%.

Also of interest are compositions as described above, which photoinitiator contain mixtures of formulas I and II which are liquid at room temperature.

The compositions according to the invention contain at least one optical opening brighter, d. H. but you can also use several, e.g. B. one or two such connections contain.

Those to be used as component (c) in the composition according to the invention Optical brighteners can come from a wide variety of classes known in the art come.

So z. B. those from the groups of pyrazolines, stilbenes, z. B. 4,4'-bis (diphenyltriazine yl) -stilbene, triazines, thiazoles, benzoxazoles, xanthones, triazoles, e.g. B. stilbenyl-naphthotriazole, Oxazoles, e.g. B. bis (benzoxazol-2-yl) derivatives, thiophenes, e.g. B. bisbenzoxazolyl-thiophenes and Suitable for coumarins.

Further examples can be found in US Patents 2,784,183 and 3,644,394. Examples are also in R.L. Allen, Color Chemistry, pp. 278-286, Nelson, 1971.

2,2 '- (Thiophendiyl) -bis- (t-butyl-benzoxazole), 2- (stilbyl-4' ') - (naphtho-1', 2 ', 4,5) - are preferred 1,2,3-triazol-2 '' - sulfonic acid phenyl ester, 7- (4'-chloro-6 '' - diethylamino-1 ', 3', 5'-triazin-4'-yl) ami no-3-phenyl-coumarin and 2,5-bis (6,6'-bis (t-butyl) benzoxazol-2-yl) thiophene.

The optical brighteners are in particular compounds of the formula III

wherein
X for the group

stands; and
R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of one another are hydrogen, C ₁ -C ₈ -alkyl, through -COO-C ₁ -C ₈ -alkyl, in particular -COOCH ₃ and -COOCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ , substituted C ₁ -C ₈ alkyl, -COO-C ₁ -C ₂₀ alkyl or α, α-dimethylbenzyl.

Compounds of the formula III are preferred in which
X for a group

stands; and
R ₉ , R ₁₀ , R ₁₁ and R _{12 are} independently hydrogen, methyl, tert-butyl, -COO-C ₁ -C ₂₀ -alkyl or α, α-dimethylbenzyl.

Are particularly preferred

wherein R _{15 is} either CH ₃ or CH ₂ CH (CH ₃ ) CH ₂ CH ₃ .

Other preferred optical brightener compounds are

Optical brightener compounds are known to the person skilled in the art and are widely available commercially, e.g. B. available under the "UVITEX" brand from Ciba Specialty Chemicals, Switzerland.

®UVITEX OB (Ciba Specialty Chemicals, Switzerland) is particularly preferred.

The optical brighteners (c) are used in the compositions according to the invention moderately in an amount of 0.05% to 2.0%, preferably from 0.2% to 1.0% puts.  

Preferred are compositions containing as component (b) a compound of formula I, wherein R ₁ and R _{2 are} phenyl and R ₃ is phenyl substituted with C ₁ -C ₄ alkyl, or containing as component (b) a mixture of a compound of the formula I in which R ₁ and R _{2 are} phenyl and R ₃ is phenyl substituted by C ₁ -C ₄ alkyl, and a compound of the formula II in which R _{4 is} hydrogen, R _{5 is} hydroxy and R ₆ and R _{7 are} C. ₁ -C ₄ alkyl or together form a cyclohexyl ring; as component (c) a compound of formula III, wherein X is a radical

R ₁₀ and R _{12 are} hydrogen and R ₉ and R _{11 are} each tert-butyl; and as component (d) a titanium dioxide pigment.

Compositions are particularly preferred

and a 1: 1 mixture of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propanone;
®UVITEX OB and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide;
®UVITEX OB and a 1: 1 mixture of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide and (1-hydroxycyclohexyl) phenyl ketone;
®UVITEX OB and a 1: 1 mixture of (2,4,6-trimethylbenzoyl) -ethoxy-phenyl-phosphine oxide and (1-hydroxy-cyclohexyl) -phenyl-ketone; and
®UVITEX OB and a 1: 1 mixture of

and (1-hydroxy-cyclo hexyl) phenyl ketone.

The unsaturated compounds (a) can have one or more olefinic double bonds contain. They can be low molecular weight (monomeric) or higher molecular weight (oligomeric). Examples of monomers with a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as. B. methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, iso bornyl acrylate, methyl or ethyl methacrylate. Silicone acrylates are also interesting.  

Further examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acryla mide, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl and halo genstyrole, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.

Examples of monomers with several double bonds are ethylene glycol, propylene gly col, neopentyl glycol, hexamethylene glycol or bisphenol A diacrylate, 4,4'-bis (2-acryloyl oxyethoxy) diphenylpropane, trimethylolpropane triacrylate, tripropylene glycol diacrylate, penta erythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinylsuccinate, diallyl phtha lat, triallyl phosphate, triallyl isocyanurate or tris (2-acryloylethyl) isocyanurate.

Examples of higher molecular weight (oligomeric) polyunsaturated compounds are acry gelled epoxy resins, acrylated or vinyl ether or epoxy group-containing polyesters, Polyurethanes and polyethers. Other examples of unsaturated oligomers are unsaturated Polyester resins, which mostly consist of maleic acid, phthalic acid and one or more diols are produced and have molecular weights of about 500 to 3000. In addition, also vinyl ether monomers and oligomers, and maleate-terminated oligomers with Po main chains of polyester, polyurethane, polyether, polyvinyl ether and epoxy are used. In particular combinations of oligomers and polymers bearing vinyl ether groups, as described in WO 90/01512 are well suited. But also copolymers Monomers functionalized from vinyl ether and maleic acid are suitable. Such un saturated oligomers can also be referred to as prepolymers.

Z are particularly suitable. B. esters of ethylenically unsaturated carboxylic acids and polyol s or polyepoxides, and polymers with ethylenically unsaturated groups in the chain or in page groups, such as B. unsaturated polyesters, polyamides and polyurethanes and Co polymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and iso pren copolymers, polymers and copolymers with (meth) acrylic groups in side chains, and Mixtures of one or more such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, ita cons acid, cinnamic acid, unsaturated fatty acids such as linolenic acid or oleic acid. Prefers are acrylic and methacrylic acid.  

Aromatic and especially aliphatic and cycloaliphatic polyols are ge as polyols is suitable. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl 2,2-di- (4-hydroxyphenyl) propane, as well as novolaks and resols. Examples of polyepoxides are sol che based on the polyols mentioned, especially the aromatic polyols and epichlor hydrine. Furthermore, there are also polymers and copolymers that contain hydroxyl groups in the polymer chain or contained in page groups, such as. B. polyvinyl alcohol and copolymers thereof or Hydroxyalkyl polymethacrylic acid or copolymers thereof, suitable as polyols. Further suitable polyols are oligoesters with hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols are alkylene diols with preferably 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, Pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene englycols with molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerin, tris (β-hydroxy-eth yl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.

The polyols can be partially or completely with one or different unsaturated Carboxylic acids may be esterified, with the free hydroxyl groups modified in partial esters, e.g. B. can be etherified or esterified with other carboxylic acids.

Examples of esters are:
Trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, tri propylene glycol, thrittriacrylat trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, Pentaery, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, di, dipentaerythritol hexaacrylate, ythritoctaacrylat dipentaerythritol pentaacrylate Tripentaer, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, methacrylate dipentaerythritol, Dipentaerythrittetramethacrylat, Tripentaerythritoctamethacrylat, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaita conat, ethylene glycol diacrylate, 1,3-butane diol diacrylate, 1,3-butane diol dimethacrylate, 1,4-butane diol diacrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylate, sorbitol triacrylate acrylic, t, oligoester acrylates and methacrylic late, glycerol and tri-acrylate, 1,4-cyclohexane diacrylate, bisacrylates and bis methacrylates of polyethylene glycol with a molecular weight of 200 to 1500, or mixtures thereof.

As component (a) are also the amides of the same or different unsaturated carbon acids of aromatic, cycloaliphatic and aliphatic polyamines with preferably 2 to 6, especially 2 to 4 amino groups suitable. Examples of such polyamines are Ethy lendiamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine amine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diamino-cyclohexane, iso phorondiamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, Triethylenetetramine, di (β-aminoethoxy) - or di (β-aminopropoxy) ethane. More suitable Polyamines are polymers and copolymers with optionally additional amino groups in the side chain and oligoamides with amino end groups. Examples of such unsaturated Amides are: methylene-bis-acrylamide, 1,6-hexamethylene-bis-acrylic amide, diethylenetriamine-tris methacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylic amidoethyl methacrylate, N [(β-hydroxyethoxy) ethyl] acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for. B. of maleic acid and diols or diamines. Maleic acid can be partially replaced by other dicarboxylic acids be. You can together with ethylenically unsaturated comonomers, for. B. styrene be set. The polyesters and polyamides can also differ from dicarboxylic acids and derive ethylenically unsaturated diols or diamines, especially those with longer chains e.g. B. 6 to 20 carbon atoms. Examples of polyurethanes are those that consist of saturated or un saturated diisocyanates and unsaturated or saturated diols are built up.

Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomes re are z. B. olefins such as ethylene, propene, butene, hexene, (meth) acrylates, acrylonitrile, styrene or vinyl chloride. Polymers with (meth) acrylate groups in the side chain are also be knows. It can e.g. B. with reaction products of epoxy resins based on novolak (Meth) acrylic acid act to homo- or copolymers of vinyl alcohol or their Hy droxyalkyl derivatives which are esterified with (meth) acrylic acid, or around homo- and copoly mers of (meth) acrylates esterified with hydroxyalkyl (meth) acrylates.

The photopolymerizable compounds can be used alone or in any mixtures be used. Mixtures of polyol (meth) acrylates are preferably used.  

Binders can also be added to the compositions according to the invention, which is particularly useful if it is the photopolymerizable compound en is liquid or viscous substances. The amount of binder can e.g. B. 5-95% by weight, preferably 10-90% by weight and particularly 40-90% by weight on the total solid. The choice of binder depends on the application offers and required properties such as adhesion to substrates and oxygen sensitivity.

Suitable binders are e.g. B. Polymers with a molecular weight of about 5000-2,000,000, preferably 10,000-1,000,000. Examples are: homo- and copolymers, acrylates and Methacrylates, e.g. B. Copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (methacrylic acid alkyl ester), poly (acrylic acid alkyl ester); Cellulose esters and ethers such as Cellu loose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; Polyvinyl butyral, Polyvi nyl formal, cyclized rubber, polyethers such as polyethylene oxide, polypropylene oxide, polyte trahydrofuran; Polystyrene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, Copolymers of vinyl chloride / vinylidene chloride, copolymers of vinylidene chloride with Acrylni tril, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly (ethylene / vinyl acetate), poly mers such as polycaprolactam and poly (hexamethylene adipamide), polyesters such as poly (ethylene glycol kolterephtalat) and poly (hexamethylene glycol succinate).

The unsaturated compounds can also be mixed with non-photopolymerizable film-forming components are used. These can e.g. B. physically drying Polymers or their solutions in organic solvents, such as. B. nitrocellulose or Cellulose acetobutyrate. However, these can also be chemically or thermally curable resins be like B. polyisocyanates, polyepoxides or melamine resins. The use of ther mix-curable resins is for use in so-called hybrid systems from Be interpretation, which are photopolymerized in a first stage and in a second stage can be crosslinked by thermal aftertreatment.

Compositions which contain no binder are preferred.

The compositions according to the invention are also suitable in oxidative drying Systems such as z. B. in the textbook of paints and coatings Volume III, 296-328, Ver  W.A. Colomb in Heenemann GmbH, Berlin-Oberschwandorf (1976) are.

The compositions according to the invention contain at least one pigment (d), d. H. they contain one or more different pigments, e.g. B. one to three or one or two Pigments. The compositions according to the invention can be inorganic act or organic pigments. Black, white or colored pigments can ver be applied. Examples of pigments are white pigments of the rutile type such as ®RTC-2 from Tioxide, carbon black, such as ®Special Black 250 from Degussa, diketopyrrolo-pyrrole, such as ®Ir gazin DPP Red Bo from Ciba Specialty Chemicals, Isoindolinone, such as ®Irgazin Yellow 3RLTN from Ciba Specialty Chemicals, arylamides such as ®Irgalite Yellwo Gu from Ciba specialties chemistry, Cu phthalocyanines, such as ®Irgalite Blue GLNF from Ciba Specialty Chemicals or Cu Phthalocyanines (halogenated) such as ®Irgalite Green GLNnew from Ciba Specialty Chemicals.

A white pigment, e.g. B. of the titanium dioxide type, in the invention compositions used as component (d).

The photopolymerizable compositions according to the invention contain the or the pigments (d) usually in amounts of 5% to 50%, e.g. B. from 10% to 50%.

In addition to the photoinitiator, the photopolymerizable mixtures can contain various additives. Examples of this are thermal inhibitors which are intended to prevent premature poly merization, such as. As hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol or sterically hindered phenols such as. B. 2,6-di (tert-butyl) -p-cresol. To increase the dark storage stability z. B. copper compounds, such as copper naphthenate, arate or octoate, phosphorus compounds, such as. B. triphenylphosphine, tributylphosphine, triethylphosphite, triphenylphosphite or tribenzylphosphite, quaternary ammonium compounds, such as. B. tetramethylammonium chloride or trimethyl-benzylammonium chloride, or Hy droxylamine derivatives, such as. B. N-diethylhydroxylamine can be used. In order to exclude atmospheric oxygen during the polymerization, paraffin or similar wax-like substances can be added, which migrate to the surface at the beginning of the polymerization due to the lack of solubility in the polymer and form a transparent surface layer which prevents the entry of air. An oxygen-impermeable layer can also be applied. UV absorbers, such as. B. those of the hydroxy phenyl-benzotriazole, hydroxyphenyl-benzophenone, oxalic acid or hydroxyphenyl-s triazine-type can be added. Individual or mixtures of these compounds with or without the use of sterically hindered amines (HALS) can be used. Examples of such UV absorbers and light stabilizers are

• 1. 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl -2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert- butyl- 2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl- 5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl ) -benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole, mixture of 2- (3'-tert-butyl-2'-hydroxy xy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethyl-hex yloxy) carbonylethyl] -2'-hydroxyphenyl) - 5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2' -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonyleth yl) p henyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy -5'-methylphenyl) tenzotriazole, and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, 2,2'-methylene-bis [4- (1, 1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; Transesterification product of 2- [3'-tert-butyl-5- (2-methoxycarbonylethyl) -2'-hydroxy-phenyl] tenzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO (CH ₂ ) ₃ ] ₂ - with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.
• 2. 2-hydroxybenzophenones, such as. B. 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4- Dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivative.
• 3. Esters of optionally substituted benzoic acids, such as. B. 4-tert-butylphenylsali cylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -re sorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2-methyl-4,6-di-tert-butylphe nyl ester.
• 4. Acrylates, such as. B. α-cyan-β, β-diphenylacrylate or isooctyl ester, α-carbo methoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- (β-carbomethoxy-β-cy anovinyl) -2-methyl-indoline.  
• 5. Sterically hindered amines, such as. B. bis- (2,2,6,6-tetramethyl-piperidyl) sebacate, bis- (2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-Bu tyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonic acid bis (1,2,2,6,6-pentamethylpipendyl) ester, Condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and Bern succinic acid, condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa-meth ylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris- (2,2,6,6-tetramethyl-4-piper idyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetraoate, 1,1 '- (1,2- Ethanediyl) -bis- (3,3,5,5-tetramethyl-piperazinone), 4-benzoyl-2,2,6,6-tetramethyl-piperidine, 4- Stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2- hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro- [4.5] decane-2,4-dione, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis- (1-octyloxy- 2,2,6,6-tetramethylpiperidyl) succinate, condensation product from N, N'-bis (2,2,6,6-tetra methyl-4-piperidyl) hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensates tion product from 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, condensation product from 2-chloro-4,6-di- (4-n-bu tylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) - ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-Do decyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-penta methyl-4-piperidyl) pyrrolidine-2,5-dione.
• 6. oxalic acid diamides, such as. B. 4,4'-di-octyloxy oxanilide, 2,2'-diethoxy oxanilide, 2,2'-di-octyl oxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p- Methoxy- and of o- and p-ethoxy-di-substituted oxanilides.
• 7. 2- (2-hydroxyphenyl) -1,3,5-triazines such as e.g. B. 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5- triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-di hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxy phenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-me thylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-di methylphenyl) -1,3,5-triazine, 2- [4-dodecyl / tridecyl-oxy- (2-hydroxypropyl) oxy-2-hydroxy-phen yl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.  
• 8. Phosphites and phosphonites, such as. B. triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, diste aryl-pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpenta-erythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-tert-butyl-4-meth ylphenyl) pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis- (2,4-di-tert butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol di phosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocin, bis- (2,4-di tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphos phit.

Furthermore, additives customary in the art, such as flow control agents and Adhesion improvers are used.

To accelerate the photopolymerization, amines can be added as further additives (e) be set, such as B. triethanolamine, N-methyl-diethanolamine, p-dimethylaminobenzoe acid ethyl ester or Michler's ketone. The effect of the amines can be enhanced by the addition of aromatic ketones of the benzophenone type. As an oxygen scavenger usable amines are, for example, substituted N, N-dialkylanilines, as described in US Pat EP 339841 are described. Other accelerators, coinitiators and autoxidizers are thiols, Thioethers, disulfides and phosphines, such as. B. in EP 438123 and GB 2180358 ben.

It is also possible to make the compositions according to the invention customary in the art Add chain transfer reagents. Examples are mercaptans, amines and Benzthi azole.

An acceleration of the photopolymerization can also be done by adding photosensi bilisators happen as further additives (e), which ver the spectral sensitivity push or widen. These are especially aromatic carbonyl compounds such as e.g. B. benzophenone, thioxanthone, especially isopropylthioxanthone, anthraquinone and 3-acylcoumarin derivatives, terphenyls, styryl ketones, and 3- (aroylmethylene) thiazolines, Camphorquinone, but also eosin, rhodamine and erythrosine dyes.  

For example, the amines given above can also be used as photosensitizers to be sought.

The hardening process can be supported in particular by (e.g. with titanium dioxide) pig mented compositions, also by adding as an additional additive (s) one under thermal conditions radical-forming component such. B. an azo compound such as about 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazo sulfide, pen tazadiens or a peroxy compound such as hydroperoxide or peroxycarbonate, e.g. B. t- Butyl hydroperoxide, e.g. B. described in EP 245639.

The compositions according to the invention can also be used as further additives (e) photoreducible dye, such as. B. xanthene, benzoxanthene, benzothioxanthene, thia tin, pyronine, porphyrin or acridine dyes, and / or a tri-cleavable by radiation contain halogen methyl compound. Similar compositions are for example in described in EP 445624.

Other common additives (e) - depending on the intended use - are fillers, dyes, mesh medium or flow aid.

For the hardening of thick and pigmented coatings, the addition of micro- Glass balls or powdered glass fibers, such as. B. described in US 5013768.

The choice of additives (e) depends on the respective area of application and for desired properties in this area. The additives (e) described above are the skilled worker familiar and are in the compositions according to the invention in in the usual amounts used in technology.

The invention also relates to compositions comprising as component (a) at least one ethylenically unsaturated photopolymer dissolved or emulsified in water connectable connection.

Such radiation-curable aqueous prepolymer dispersions are available in many variations Available commercially. This means a dispersion of water and at least one egg dispersed therein. The concentration of water in these systems lies z. B. at 5 to 80, in particular 30 to 60 wt .-%. The radiation-curable prepoly mere or prepolymer mixture is, for example, in concentrations of 95 to 20, in particular  contain special 70 to 40 wt .-%. In these compositions, the sum is for Percentages of water and prepolymers each named 100, the auxiliaries and additives come in different amounts depending on the intended use.

With the radiation-curable, water-dispersed, often also dissolved film-forming pre polymers are known per se for aqueous prepolymer dispersions mono- or polyfunctional ethylenically unsaturated prepolymers which can be initiated by free radicals, which, for example, contains from 0.01 to 1.0 mol of polymeri per 100 g of prepolymer sizable double bonds, and an average molecular weight of z. B. at least 400, in particular from 500 to 10,000. Depending on the application, however, come prepolymers with higher molecular weights are also possible.

There are, for example, polymerizable polyesters containing C-C double bonds an acid number of at most 10, Po containing polymerizable C-C double bonds lyether, hydroxyl-containing reaction products from at least two epoxies Groups per molecule containing polyepoxide with at least one α, β-ethylenically saturated carboxylic acid, polyurethane (meth) acrylates and α, β-ethylenically unsaturated Acrylic copolymers containing acrylic residues are used, as described in EP 12339. Mixtures of these prepolymers can also be used. Come into question also the polymerizable prepolymers described in EP 33896, in which it are thioether adducts of polymerizable prepolymers with a medium molecule lar weight of at least 600, a carboxyl group content of 0.2 to 15% and a Content of 0.01 to 0.8 mol of polymerizable C-C double bonds per 100 g of prepolymer acts. Other suitable aqueous dispersions based on special (meth) acrylic acid Realkylester polymers are described in EP 41125, suitable in water disper gable, radiation-curable prepolymers made from urethane acrylates are in DE 29 36 039 remove.

These radiation-curable aqueous prepolymer dispersions can be used as further additives Dispersing agents, emulsifiers, antioxidants, light stabilizers, dyes, fillers, e.g. B. talc, gypsum, silica, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, Leveling agents, lubricants, wetting agents, thickeners, matting agents, defoamers and other auxiliaries common in paint technology. As a dispersing aid come water-soluble high molecular organic compounds with polar groups, such as e.g. B. polyvinyl alcohols, polyvinyl pyrrolidone or cellulose ether in question. As emulsifiers can be used non-ionic, optionally also ionic emulsifiers.  

In certain cases it may be advantageous to use mixtures of two or more photoinitiators of the formula I and II. Of course, mixtures with other known photoinitiators can also be used, for. B. mixtures with other benzophe derivatives, acetophenone derivatives, dialkoxyacetophenones, α-hydroxy or α-amino cetophenones, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, such as. B. Ben zildimethylketal, phenylglyoxalates and derivatives thereof, dimeric phenylglyoxalates, ferro cenium compounds or titanocenes, such as dicyclopentadienyl bis (2,6-difluoro or 3-pyrrolo-phenyl) titanium, benzoyl peroxides (suitable peroxides are in US 4950581, column 19, lines 17-25) or cyclopentadienylarene-iron (II) complex salts, e.g. B. (η ⁶ - iso-propylbenzene) (η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate.

If the photoinitiators are used in hybrid systems, in addition to the ra dical hardeners cationic photoinitiators such. B. aromatic sulfonium, phosphone ium or iodonium salts such as z. B. in US 4950581, column 18, line 60 to column 19, Line 10 are used.

The photopolymerizable compositions contain the photoinitiator or the pho to initiator mixtures (b) advantageously in an amount of 0.05 to 15% by weight, preferably 0.1 to 5 wt .-%, based on the composition. The specified amount of photoiniti ator refers to the sum of all added photoinitiators when mixtures of same can be used.

The photopolymerizable compositions can be used for various purposes are used, for example as a printing ink, as a clear lacquer, as a white lacquer, for. B. for wood or metal, as a powder coating, as a paint, u. a. for paper, wood, metal or plastic, as a daylight-curable coating for building and road marking, as dental filling compounds, as Adhesives, as pressure-sensitive adhesives, as laminating resins, for the production of three dimensions sional objects by mass hardening (UV hardening in transparent forms) or after the stereolithography process, as it is e.g. B. is described in US 4575330 for Manufacture of composite materials (e.g. styrenic polyesters, possibly glass fibers and / or other fibers and other auxiliaries, may contain) and other thick layered masses, for coating or sealing electronic parts or as Coatings for optical fibers. The compositions according to the invention are suitable continue to manufacture medical devices, aids such. B. contact lenses, or Implants.  

The compositions according to the invention can also be used to prepare gels thermotropic properties are used, as z. B. in DE 197 00 064 and EP 678534 are described.

The photoinitiators can be used as initiators for emulsion, bead or suspension polymers sations or as initiators of a polymerization for the fixation of order states of liquid crystalline monomers and oligomers, as initiators for the fixation of dye fen can be used on organic materials.

The compositions according to the invention are preferred for the production of Paints used.

The invention therefore also relates to a pigmented lacquer containing one as before the composition described above, in particular a white pigmented composition setting, as well as the use of a composition as described above as a coating or varnish, especially white varnish.

Mixtures of a prepolymer with polyunsaturated mono are often used in paints mers, which also contain a monounsaturated monomer. The Prepolymers is primarily decisive for the properties of the paint film, the person skilled in the art can influence the properties of the hardened film through its variation rivers. The polyunsaturated monomer acts as a crosslinker, which unifies the paint film makes soluble. The monounsaturated monomer acts as a reactive diluent with which The viscosity is reduced without using a solvent got to.

Unsaturated polyester resins are usually used in two-component systems together with egg nem monounsaturated monomer, preferably with styrene.

The compositions according to the invention can also be used for radiation-curable pulp varnish can be used. The powder coatings can be on solid resins and monomers containing reactive double bonds based, such. B. maleates, vinyl ethers, acrylates, Acrylamides and mixtures thereof. A radically UV-curable powder coating can Mixing unsaturated polyester resins with solid acrylamides (e.g. methyl acrylamido glycolate methyl ester) and a radical photoinitiator, such as in the lecture "Radiation Curing of Powder Coating", Conference Proceedings, Radtech Europe 1993 by  M. Wittig and Th. Gohmann. Likewise, radical UV-curable powder coatings by mixing unsaturated polyester resins with solid acrylic aten, methacrylates or vinyl ethers and a photoinitiator (or photoinitiator mixture) be formulated. The powder coatings can also contain binders, such as those used for. B. in the DE 42 28 514 and EP 636669 are described. The UV-curable powder coatings can also contain white or colored pigments. So z. B. preferably rutile titanium di oxide up to concentrations of 50 wt .-% can be used to make a hardened powder obtain paint with good covering ability. The process usually involves electrostatic or tribostatic spraying of the powder onto the substrate, such as. B. Metal or wood, melt the powder by heating and after a smooth film radiation hardening of the coating with ultraviolet and / or visible light, e.g. B. with medium pressure mercury lamps, metal halide lamps or xenon lamps. A be special advantage of radiation-curable powder coatings in comparison to the corresponding ones thermally curable is that the flow time after melting the powder batch can optionally be delayed to form a smooth high-gloss finish To ensure coating. In contrast to thermally curable systems, it can be blasted oil-curable powder coatings without the undesirable effect of shortening the lifespan be mulated that they melt at lower temperatures. Because of this, are they are also suitable as coatings for heat-sensitive substrates, such as. B. wood or art fabrics.

In addition to the photoinitiators, the powder coating formulations can also contain UV absorbers hold. Corresponding examples are given above under items 1-8. listed.

The photocurable compositions according to the invention are suitable, for. B. as loading coating materials for substrates of all kinds, for. B. wood, textiles, paper, ceramics, glass, plastics such as polyester, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO ₂ , on which a protective layer is to be applied.

The substrates can be coated by a liquid composition, a Solution or suspension is applied to the substrate. The choice of the solvent and the concentration depends mainly on the type of composition and after the coating process. The solvent should be inert, i. H. it should with the Components do not undergo a chemical reaction and it is said to dry after drying  Coating can be removed again. Suitable solvents are e.g. B. ketones, Ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methox y-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and 3-eth oxy-propionic acid ethyl ester.

The formulation is applied uniformly to a sub using known coating methods applied strat, z. B. by spinning, dipping, knife coating, curtain casting driving, brushing, spraying, especially by electrostatic spraying and reverse roll-loading layering, as well as by electrophoretic deposition. It is also possible to use the light Apply sensitive layer on a temporary, flexible support and then through Layer transfer via lamination to coat the final substrate.

The application quantity (layer thickness) and type of substrate (layer carrier) are dependent from the desired application area. The layer thickness range generally includes Values from approx. 0.1 µm to more than 100 µm, e.g. B. 20 mm or 0.02 to 10 cm, preferably 0.02 up to 2 cm.

Photocuring is of great importance for printing inks, the manufacture of which is invented Compositions according to the invention can also be used because the dry time of the binder is a decisive factor for the production speed graphic products and is on the order of fractions of a second should. UV-curable inks are particularly important for screen printing.

Another area of application for photocuring is metal coating, for example at the painting of sheets and tubes, cans or bottle closures, as well as the Pho curing on plastic coatings, for example of floor or wall coverings PVC-based or for painting automobiles.

Examples of the photocuring of paper coatings are the coating of labels, Record sleeves or book covers.

It is also interesting to use the compositions according to the invention for Manufacture of molded parts from composite materials. The composite mass consists of a self-supporting matrix material, e.g. B. a glass fiber fabric, or for example Vegetable fibers [cf. K.-P. Mieck, T. Reussmann in Kunststoffe 85 (1995), 366-370 or V.  Narayanan, A.B. Scranton, Trends in Polymer Science 1997 (5), 12, 415] using light curing formulation is soaked. With the composition according to the invention Molded parts made from composite materials achieve high mechanical stability lity and resilience. The compositions according to the invention are also in Molding, impregnating and coating compositions, as described for example in EP 7086 are usable. Such compositions are, for example, fine-layer resins to which high demands are made changes in hardening activity and resistance to yellowing, fiber reinforced molded materials, such as. B. flat, longitudinally or cross-corrugated light panels. Procedure for Production of such molded materials, such as. B. hand laying process, fiber spraying, sluice der- or winding process, z. B. by P.H. Selden in "Glass fiber reinforced plastics", Page 610, Springer Verlag Berlin-Heidelberg-New York 1967. Utility objects that can be produced using this method, for example Boats, chipboard or carpentry board coated on both sides with glass fiber reinforced plastic ten, pipes, sports equipment, roof coatings, containers, etc. Further examples of form, Impregnating and coating compounds are UP resin fine layers for glass fiber-containing molding materials (GRP), e.g. B. corrugated sheets and paper laminates. Paper laminates can be based on urea or Me based on laminate resins. The fine layer is placed on a support before the laminate is produced (e.g. a slide). The photocurable compositions according to the invention can also be used for casting resins or for embedding objects, e.g. B. of electronics len etc. can be used. In addition, they can also be used to line cavities men and pipes are used. Medium pressure mercury lamps are used for curing used as they are common in UV curing. But are of particular interest even less intense lamps, e.g. B. of the type TL 40W / 03 or TL 40W / 05. The intensity these lamps correspond approximately to the sunlight. There can also be direct sunlight Hardening can be used. Another advantage is that the composite is in one hardened, plastic state can be removed from the light source and deformed.

Then complete curing takes place by further exposure.

The photosensitivity of the compositions according to the invention is usually sufficient from approx. 200 nm to approx. 600 nm (UV range). Suitable radiation contains e.g. B. Sunlight or light from artificial light sources. A large number therefore come as light sources of various types for use. There are both point sources and areas shaped spotlights (lamp carpets) suitable. Examples are: carbon arc lamps, Xen on-arc lamps, medium-pressure, high-pressure and low-pressure mercury lamps, ge  optionally doped with metal halides (metal halogen lamps), microwave-excited Metal halide lamps, excimer lamps, superactin fluorescent tubes, fluorescence lamps, argon bulbs, flash lamps, photographic floodlights, light emitting Diodes (LED), electron beams and X-rays. The distance between lamp and substrate to be exposed according to the invention can, depending on the application and Lam pen type or strength vary, e.g. B. between 2 cm to 150 cm. Lasers are particularly suitable light sources, e.g. B. excimer lasers, such as krypton-F lasers for exposure at 248 nm. Also Lasers in the visible range can be used. According to this method, e.g. B. lithographic offset printing plates or relief printing plates can be produced.

The photocurable compositions according to the invention have surprisingly good ones Through hardening properties.

The invention also relates to a process for the photopolymerization of non-volatile monomeric, oligomeric or polymeric compounds with at least one ethylenically unsaturated double bond, characterized in that a be written composition is irradiated with light in the range of 200 to 600 nm.

The subject of the invention is also the use of the composition described above for the production of pigmented and unpigmented paints, printing inks, powders varnishes, printing plates, adhesives, dental materials, compound materials, glass fiber cable coating s, screen printing stencils, for the production of three-dimensional objects using stereoli thography, or corresponding methods of manufacture.

The subject of the invention is also the use of a composition according to claim 1 as a coating or varnish, in particular white varnish, and screen printing ink, in particular white screen printing ink.

The invention also relates to a coated substrate which has at least one egg ner surface is coated with a composition as described above, and the cured composition as such.

The following examples further illustrate the invention. Figures in parts or percentages ten relate, just like in the rest of the description and in the patent claims,  by weight unless otherwise stated. If alkyl or alkoxy with more than three carbon atoms are given without reference to their isomeric form, so rel the information on the respective n-isomers.

The following photoinitiators are used in the examples:
P1 is a 1: 1 mixture of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propanone
P2 is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
P3 is a 1: 1 mixture of (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide and (1-hydroxy-cyclohexyl) phenyl ketone
P4 is a 1: 1 mixture of (2,4,6-trimethylbenzoyl) ethoxy-phenyl-phosphine oxide and (1-hydroxy-cyclohexyl) -phenyl-ketone
P5 is a 1: 1 mixture of

and (1-hydroxy cyclohexyl) phenyl ketone.

The following optical brighteners are used in the examples

example 1 Curing an epoxy acrylate white lacquer

A white lacquer of the following composition is produced
65% epoxy acrylate (®Ebecryl 604, from UCB, Belgium)
10% hexanediol diacrylate
25% titanium dioxide (rutile type, ®RTC-2, from Tioxide, France).

3% photoinitiator and 0.5% optical brightener (®UVI TEX OB, Ciba Specialty Chemicals, Switzerland). With a 150 µm splitting knife layers are applied to lightly primed chipboard. The exposure takes place with two 80 W / cm medium pressure mercury lamps (UV processor from AETEK, USA) on a conveyor belt speeds of 10 m / min and 20 m / min. After exposure, be scratched solid and fully hardened layers the pendulum hardness (PH) according to König (DIN 53 157) in [s] and the Yellowness Indices (ASTMD 1925-88). The layer is cured through viewed when the underside of the detached from the substrate after irradiation Layer is dry. The higher the values of the pendulum hardness, the better hardened the be beamed coating. The lower the Yellowness Index (YI) value, the lower the Yellowing of the hardened layer. The results are summarized in Table 1 below quantified.

Table 1

Example 2 Hardening of a polyester acrylate white lacquer

A white lacquer of the following composition is produced
67.5% polyester acrylate (®Ebecryl 830, from UCB, Belgium)
5.0% hexanediol diacrylate
2.5% trimethylolpropane triacrylate
25.0% titanium dioxide (rutile type, ®RTC-2, from Tioxide, France).

Application, curing and measurement are carried out as described in Example 1. The used Photoinitiators, optical brighteners and measurement results are listed in Table 2.  

Table 2

Example 3 Hardening of a polyester acrylate white lacquer

A white lacquer of the composition described in Example 2 is produced. Application and curing take place as described in Example 1. Be determined in each case the yellowness index and the pendulum hardness after curing at a belt speed of 5 m / min. In addition to the yellowness index and the pendulum hardness, however maximum curable free layer depth (FS) determined. For this, a drop of the to be hardened Formulation applied to a substrate and at a belt speed of Irradiated at 3 m / min. Then the hardened layer is separated from the substrate and the Layer thickness of the hardened layer (in µm) determined. The thicker this layer, the more the hardening of the tested formulation is better. In addition, the number of Runs determined at 10 m / min, which is required to create a smudge-proof hardened layer to be obtained (indicated as WF n × 10 m / min). The photoinitiators used, optical Brighteners and measurement results are listed in Table 3.

Table 3

Example 4 Hardening of a polyester acrylate white lacquer

A white lacquer of the composition described in Example 2 is produced. As The initiator P3 is used as a photoinitiator.

Application and curing take place as described in Example 1. The is determined in each case Pendulum hardness after hardening at a belt speed of 3 m / min. In addition to Pendulum hardness becomes the maximum hardenable free layer depth (FS) as described in Example 3, certainly. The optical brighteners used and the measurement results are in the table 4 listed.

Table 4

Claims (16)

1. Containing photopolymerizable composition

• (a) at least one ethylenically unsaturated photopolymerizable compound and
• (b) as a photoinitiator at least one mono-, bis- or trisacylphosphine oxide compound or a mixture of such compounds with an α-hydroxyketone, α-aminoketone or / and benzoin derivative compound
• (c) at least one optical brightener, and
• (d) at least one pigment.

2. The composition of claim 1, wherein the mono-, bis- or trisacylphosphine oxide compound is a compound of formula I.
wherein
R ₁ and R ₂ independently of one another C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkyl interrupted by one or more non-successive O atoms, C ₁ -C ₄ alkyl substituted by phenyl, C ₂ -C ₈ - Represent alkenyl, phenyl, naphthyl, biphenyl or C ₅ -C ₁₂ cycloalkyl, where the radicals phenyl, naphthyl, biphenyl and C ₅ -C ₁₂ cycloalkyl are unsubstituted or mono- to pentas with halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkylthio and / or C ₁ -C ₈ alkoxy are substituted or R ₁ and R _{2 are} -COR ₃ ;
R _{3 is} unsubstituted or mono- or pentasubstituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkylthio and / or halogen; is. 3. The composition of claim 1, wherein the α-hydroxyketone, α-aminoketone or benzoin derivative compound is a compound of formula II
is what
R _{4 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, -OCH ₂ CH ₂ -OR ₈ , morpholino, SCH ₃ , a group
or a group
stands;
n has a value from 2 to 10;
G for the rest
stands;
R _{5 is} hydroxy, C ₁ -C ₁₆ alkoxy, morpholino, dimethylamino or -O (CH ₂ CH ₂ O) _m -C ₁ -C ₁₆ alkyl;
R ₆ and R ₇ independently of one another are hydrogen, C ₁ -C ₆ -alkyl, phenyl, benzyl, C ₁ -C ₆ -alkoxy or -O (CH ₂ CH ₂ O) _m -C ₁ -C ₁₆ -alkyl, or R ₆ and R ₇ together with the carbon atom to which they are attached form a cyclohexyl ring;
m represents a number from 1-20;
wherein R ₅ , R ₆ and R _{7 are} not all C ₁ -C ₁₆ alkoxy or O (CH ₂ CH ₂ O) _m -C ₁ -C ₁₆ alkyl at the same time; and
R _{8 is} hydrogen,
is. 4. The composition of claim 1, wherein in the compounds of formula I
R ₁ and R ₂ independently of one another are C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkyl interrupted by one or more non-consecutive O atoms, C ₁ -C ₄ alkyl substituted by phenyl, C ₂ -C ₈ Represent alkenyl, phenyl, naphthyl, biphenyl or C ₅ -C ₁₂ cycloalkyl, where the radicals phenyl, naphthyl, biphenyl and C ₅ -C ₁₂ cycloalkyl are unsubstituted or mono- to pentas with halogen, C ₁ -C ₈ alkyl , C ₁ -C ₈ alkylthio and / or C ₁ -C ₈ alkoxy are substituted; and
R _{3 is} unsubstituted or mono- or pentasubstituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkylthio and / or halogen. 5. The composition according to claim 1, wherein in the compounds of the formula IR ₁ and R ₂ independently of one another are C ₁ -C ₁₈ -alkyl, unsubstituted or mono- to pentafixed with halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -Alkylthio and / or C ₁ -C ₈ -alkoxy substituted phenyl. 6. The composition according to claim 1, wherein in the compounds of the formula IR ₃ is phenyl which is substituted twice or three times with C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ alkoxy. 7. The composition of claim 1, wherein in the compounds of formula II R _{4 is} hydrogen, -OCH ₂ CH ₂ -OR ₈ , morpholino or SCH ₃ ;
R _{5 is} hydroxy, C ₁ -C ₁₆ alkoxy, morpholino or dimethylamino;
R ₆ and R ₇ independently of one another are C ₁ -C ₆ alkyl, benzyl or C ₁ -C ₁₆ alkoxy, or R ₆ and R ₇ together with the carbon atom to which they are attached form a cyclohexyl ring;
however, R ₅ , R ₆ and R _{7 are} not all simultaneously C ₁ -C ₁₆ alkoxy; and
R _{8 is} hydrogen. 8. The composition according to claim 1, wherein the pigment (d) is a white pigment, especially titanium dioxide. 9. The composition of claim 1, wherein the optical brightener (c) is a compound selected from the group of pyrazolines, stilbenes, triazines, thiazoles, benzoxazoles It is xanthones, triazoles, oxazoles, thiophenes and coumarins. 10. The composition of claim 1, wherein component (c) is a compound of formula III
wherein
X for a group
stands; and
R _9, R _10, R ₁₁ and R ₁₂ are independently hydrogen, C ₁ -C ₈ alkyl, by -COO-C ₁ -C ₈ - alkyl substituted C ₁ -C ₈ alkyl, -COO-C ₁ -C ₂₀ alkyl or α, α-dimethylbenzyl. 11. The composition of claim 1, containing as component (b) a compound of formula I, wherein R ₁ and R _{2 are} phenyl and R ₃ is phenyl substituted with C ₁ -C ₄ alkyl, or containing as component (b) Mixture of a compound of the formula I in which R ₁ and R _{2 are} phenyl and R ₃ is phenyl substituted by C ₁ -C ₄ alkyl, and a compound of the formula II in which R _{4 is} hydrogen, R _{5 is} hydroxy and R ₆ and R _{7 is} C ₁ -C ₄ alkyl or together form a cyclohexyl ring; as component (c) a compound of formula III, wherein X is a radical
R ₁₀ and R _{12 are} hydrogen and R ₉ and R _{11 are} each tert-butyl; and as component (d) a titanium dioxide pigment. 12. Pigmented lacquer containing a composition according to claim 1. 13. Use of a composition according to claim 1 as a coating or lacquer, especially white lacquer, and screen printing ink, especially white screen printing ink. 14. Process for the photopolymerization of non-volatile monomers, oligomers or polymeric compounds with at least one ethylenically unsaturated double bond, characterized in that a composition according to claim 1 with light in Range from 200 to 600 nm is irradiated. 15. Coated substrate that has at least one surface with a Composition according to claim 1 is coated. 16. The cured composition of claim 1.