JPH11292910A - Colored photocurable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocurable prescribed composition expressing complete and sufficient curing irrespective of its high pigment content in preparing especially a colored surface coating. SOLUTION: This colored photocurable composition comprises (a) at least one ethylenic unsaturated photopolymerizable compound, (b), as a photopolymerization initiator, at least one of mono-, bis- or tris-acylphosphine oxide compound or a mixture of the compound with α-hydroxyketone, α-amino ketone and/or a benzoin derivative compound, (c) at least one fluorescent whitener and (d) at least one pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a colored photocurable composition containing an acylphosphine oxide photoinitiator and an optical brightener, particularly for use as a white surface coating formulation.

[0002]

BACKGROUND OF THE INVENTION Mono-, bis-, and tris-acylphosphine oxides are known in the literature as photoinitiators, especially for curing deeply colored coatings. For example, US Pat. No. 4,298,738 discloses monoacylphosphine oxides and US Pat.
3 and US4792632, and US5399770
Discloses bisacylphosphine oxides. The latter reference also discloses photoinitiators which are mixtures of mono- and bis-acylphosphine oxides with α-hydroxy ketones and benzophenone. Tris-acyl phosphine oxide compounds are described in WO 96/07662.
It is also described in EP 714333 describes the combination of an acylphosphine oxide compound and an optical brightener compound in an uncolored photopolymerizable composition, wherein the reactivity of the composition, especially used in an imaging system, is enhanced. ing.

[0003]

There is a need in the art for photocurable formulations that exhibit rapid and complete cure despite high pigment content, especially in the preparation of pigmented surface coatings. .

[0004] When a fluorescent brightener compound is added to a colored photocurable formulation containing an acylphosphine oxide photopolymerization initiator, the brightener compound acts as a kind of sensitizer. It has now been found that the curability of the article is unexpectedly improved.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention provides
(A) at least one ethylenically unsaturated photopolymerizable compound; (b) as photopolymerization initiator, at least one mono-, bis-, or tris-acylphosphine oxide compound, or such a compound, and α-hydroxy A photopolymerizable composition comprising: a mixture with a ketone, an α-aminoketone and / or a benzoin derivative compound; (c) at least one optical brightener; and (d) at least one pigment.

[0006]

DETAILED DESCRIPTION OF THE INVENTION Mono-, bis-, or tris-acyl phosphine oxide compounds are, for example, of the formula (I):

[0007]

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Wherein R ₁ and R ₂ are, independently of each other,
C ₁ -C _{1 8} alkyl; one or more C by oxygen is interrupted discontinuously in ₂ -C _{1 8} alkyl; C ₁ -C substituted with phenyl ₄ alkyl; C ₂ -C ₈ alkenyl ,
Phenyl, naphthyl, biphenyl, or C ₅ -C _{1 2} cycloalkyl (of which phenyl, naphthyl, biphenyl, and C ₅ -C _{1 2} cycloalkyl group, which is unsubstituted or halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkylthio, and / or C ₁ -C ₈ alkoxy mono- to penta-substituted), or R ₁ and R ₂ are
It is -COR _3; R ₃ is phenyl (which is unsubstituted or C ₁ -C _{1 2} alkyl, C ₁ -C _{1 2} alkoxy, C ₁ -C _{1 2} alkylthio, and / or halogen Is mono- or penta-substituted).

The α-hydroxyketone, α-aminoketone, and benzoin derivative compound have the formula (II):

[0010]

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[0011] wherein, R ₄ is hydrogen, C ₁ -C _{1 8} alkyl, C ₁ -C _{1 8} alkoxy, -OCH ₂ CH ₂ -OR _8, morpholino, -SCH _3, wherein:

[0012]

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Or a group represented by the formula:

[0014]

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N has a value of 2 to 10; G is a group represented by the formula:

[0016]

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A group represented by [0017]; R ₅ is hydroxy, C ₁ -C _{1 6} alkoxy, morpholino, dimethylamino, or a _{-O (CH 2 CH 2 O)} m -C 1 -C 1 6 alkyl R ₆ and R ₇ independently of one another are hydrogen, C ₁ -C ₆
Alkyl, phenyl, benzyl, C ₁ -C _{1 6} alkoxy, or _{-O (CH 2 CH 2 O)} m -C 1 -C 1 6 alkyl Oh there, or R ₆ and R _7, and they are attached Taken together with the carbon atom to form a cyclohexyl ring;
m is a number from 1 to 20; where R ₅ , R ₆ , and R
_7, all at the same time C ₁ -C _{1 6} alkoxy, or -O (C
H ₂ CH ₂ O) not be _m -C ₁ -C _{1 6} alkyl;
R ₈ is hydrogen, formula:

[0018]

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Or a group represented by the formula:

[0020]

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Which is a group represented by the formula:

[0022] C ₁ -C _{1 8} alkyl is a straight or branched chain, for example, _{C 1 -C 1 2 -, C} 1 -C 8 -, C 1 -C
₆ -, or C ₁ -C ₄ - alkyl. Examples include methyl, ethyl, propyl, isopropyl, n-butyl,
sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl No. C ₁ -C _{1 2} - alkyl, C ₁ -C ₈ - alkyl, and C ₁ -C ₆ - alkyl is likewise linear or branched chain, for example, the above-mentioned meanings up to the corresponding number of carbon atoms Have.

[0023] One or C ₂ -C _{1 8} alkyl in more oxygen atoms is interrupted discontinuously is, -O-, for example, by 1-7 times, or is interrupted once or twice.
Oxygen atom and the other oxygen atoms are separated from each other via at least one methylene group, a structural unit, such as the _{following: -CH 2 -O-CH 3,} -CH 2 CH 2 -
O-CH ₂ CH _3, - [CH ₂ CH ₂ O] _y -CH ₃ (where, y is _{1~8), - (CH 2 CH} 2 O) 7 -CH
_{2 CH 3, -CH 2 -CH (} CH 3) -O-CH 2 -CH 2 C
H _3, or _{-CH 2 -CH (CH 3) -O} -CH 2 -C
H _3.

[0024] C ₁ -C _{1 8} alkoxy is a straight or branched chain groups, for example _{C 1 -C 1 2 -, C} 1 -C 8 -, C 1 -
C ₆ -, or C ₁ -C ₄ - alkoxy. Examples include methoxy, ethoxy, propoxy, isopropoxy, b-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethyl -Hexyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, hexadecyloxy and octadecyloxy, especially methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy and tert-butyloxy. And preferably methoxy. C ₁ -C _{1 2} alkoxy, C ₁ -C ₈ alkoxy, C ₁ -C ₆ alkoxy, and C ₁ -C ₄ alkoxy are likewise linear or branched chain, for example, up to the corresponding number of carbon atoms Has the above-mentioned meaning.

C₁-C_{1 Two}Alkylthio is linear or
A branched group such as C₁-C ₈-, C₁-C₆−,
Or C₁-C_Four-Alkylthio, for example methylthio
E, ethylthio, propylthio, isopropylthio, n
-Butylthio, sec-butylthio, isobutylthio, ter
t-butylthio, pentylthio, hexylthio, hepti
Luthio, 2,4,4-trimethylpentylthio, 2-e
Tylhexylthio, octylthio, nonylthio, decyl
Thio or dodecylthio, especially methylthio, ethyl
Luthio, propylthio, isopropylthio, n-butyl
Thio, sec-butylthio, isobutylthio, or tert-
Butylthio, and preferably methylthio. C₁
-C₈Alkylthio is also straight-chain or branched
Yes, for example with the above meaning up to the number of corresponding carbon atoms
Have.

[0026] C ₅ -C _{1 2} cycloalkyl, such as cyclopentyl, cyclohexyl, cyclooctyl, or cyclododecyl, in particular cyclopentyl or cyclohexyl, preferably cyclohexyl.

The C ₂ -C ₈ alkenyl group can be mono- or poly-unsaturated, linear or branched, for example C ₂ -C ₆ -or C ₂ -C ₄ -alkenyl. . Examples include allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, and 1-octenyl, especially allyl.

As C ₁ -C ₄ alkyl substituted by phenyl, mention may in particular be made of benzyl.

The substituted phenyl, naphthyl or biphenyl is mono- to penta-substituted on the phenyl ring;
For example mono-, di- or tri-substituted, especially mono- or di-substituted. R ₃ , which is defined as substituted phenyl, is especially di- or tri-substituted.

Preferred substituents for R ₁ , R ₂ and R ₃ defined as phenyl, naphthyl or biphenyl are
C ₁ -C ₄ alkyl (especially methyl), C ₁ -C ₄ alkoxy (especially methoxy), and chloro. A particularly preferred definition of R _3, for example 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, or 2,6-dimethoxyphenyl.

Halogen is fluorine, chlorine, bromine or iodine, especially chlorine or bromine, preferably chlorine.

The preparation of the compounds of the formula (I) is known to the person skilled in the art and is described, for example, in US Pat. No. 4,298,738, 4,737,593.
And 4792632, GB2259704, and WO
96/07662. Some of these compounds are commercially available. Some compounds of formula (II) are also commercially available. The preparation can be performed by a known method, and for example, EP3002, EP
284561 and EP805152.
The preparation of the oligomeric compound of formula (II) is described, for example, in EP
1463.

In the compounds of formula (I), R ₁ and R
_2, independently of one another, C ₁ -C _{1 8} alkyl; one or C ₂ -C ₁ which in more oxygen atoms is interrupted discontinuously
₈ alkyl; C ₁ -C ₄ alkyl substituted with phenyl;
C ₂ -C ₈ alkenyl, phenyl, naphthyl, biphenyl, or C ₅ -C _{1 2} cycloalkyl (of which phenyl, naphthyl, biphenyl, and either C ₅ -C _{1 2} cycloalkyl is unsubstituted, or Halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkylthio, and / or C ₁ -C ₈
Mono- to penta-substituted with alkoxy);
₃ is phenyl (which is unsubstituted or C ₁ -C
_{1 2} alkyl, C ₁ -C _{1 2} alkoxy, C ₁ -C _{1 2} alkylthio, and / or composition is a halogen are mono- to pentasubstituted in) are preferred.

In a further preferred composition of the present invention,
The compound of formula (I) is a monoacylphosphine oxide.

In another preferred composition, the compound of formula (I)
R ₁ and R ₂ are independently of each other C
₁ -C _{1 8} alkyl, or phenyl (which is unsubstituted or halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkylthio, and / or mono- to in C ₁ -C ₈ alkoxy
Penta-substituted).

[0036] In compounds of formula (I), is R _3, phenyl (which is, C ₁ -C _{1 2} alkyl, or C ₁ -C _{1 2}
Compositions which are di- or tri-substituted with alkoxy) are also of interest.

Further preferred compositions are those in which R ₄ is hydrogen, —OCH ₂ CH ₂ —OR ₈ , morpholino, or —SCH ₃ in the compound of formula (II); R ₅ is hydroxy, C ₁
-C _{1 6} alkoxy, morpholino, or a dimethylamino; R ₆ and R ₇ are, independently of one another, C ₁ -C ₆ alkyl, benzyl, or a C ₁ -C _{1 6} alkoxy, or R ₆ And R ₇ together with the carbon atom to which they are attached form a cyclohexyl ring;
_5, R ₆ and R ₇ are, that they are not C ₁ -C _{1 6} alkoxy at the same time all, R ₈ is hydrogen, is a composition.

Compositions in which the compound of formula (II) is an α-hydroxy ketone are also particularly preferred.

Preferred compounds of formula (II) are α-hydroxycyclohexylphenyl-ketone and 2-hydroxy-2-methyl-1-phenyl-propanone, (4-methylthiobenzoyl) -1-methyl-1-morpholino-
Ethane, (4-morpholino-benzoyl) -1-benzyl-1-dimethylamino-propane, and benzyldimethyl ketal.

Preferred compounds of formula (I) are (2,4,
6-trimethylbenzoyl) -diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl)-
(2,4,4-trimethylpent-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide, and bis (2,4
4,6-trimethylbenzoyl)-(2,4-dipentyloxyphenyl) phosphine oxide.

In the compound of formula (II), R ₆ and R
₇ is independently C ₁ -C ₆ alkyl, or together with the carbon atom to which they are attached, forming a cyclohexyl ring; and compositions wherein R ₅ is hydroxy preferable.

In the compound of formula (II), R ₆ and R
Also of interest are compositions wherein ₇ is the same, methyl, and R ₅ is hydroxy or isopropoxy.

The proportion of the compound of the formula (I) to be mixed with the compound of the formula (II) is 5 to 99%, for example, 20 to 80%, preferably 25 to 75%.

Also of interest are the compositions described above, which comprise the photoinitiator mixtures of the formulas (I) and (II) and are liquid at room temperature.

The compositions according to the invention contain at least one optical brightener, ie they can contain one or more, for example one or two, such compounds. The optical brighteners used as component (c) in the compositions according to the invention can be derived from a wide range of types known in the art. Pyrazoline, stilbene (e.g. 4,4'-bis (diphenyltriazinyl) stilbene), triazine, thiazole, benzoxazole, xanthone, triazole (e.g. stilbenyl-naphthotriazole), oxazole (e.g. bis (benzoxazol-2-yl)
Derivatives), thiophenes (eg bisbenzooxazolyl-thiophene), and those from the group of the coumarins are suitable. Examples of these include US Pat. No. 2,784,183.
And US Pat. No. 3,644,394. Also RL Allen, Color Chemistry, pages 278-286, Nel
son, 1971. 2,2 '-(thiophenediyl) -bis (tert-butyl-benzoxazole), 2- (stilbill-4 ")-(naphtho-
1 ', 2', 4,5) -1,2,3-triazole-
2 "-sulfonic acid phenyl ester, 7- (4'-chloro-6" -diethylamino-1 ', 3', 5'-triazin-4'-yl) -amino-3-phenyl-coumarin, and 2,5 -Bis (6,6'-bis (tert-butyl) -benzoxazol-2-yl) -thiophene is preferred.

The optical brightener is preferably of the formula (III):

[0047]

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[Wherein X is a formula:

[0049]

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[0050] a group represented by; and R _9, R _{1 0,}
R _{1 1,} and R _{1 2} are independently of each other hydrogen, C ₁ -C ₈ alkyl; by -COO-C ₁ -C ₈ alkyl, especially -C
OOCH _3, or _{-COOCH 2 CH (C 2 H 5} ) C substituted by C ₄ H _{9 1} -C ₈ alkyl; -COO-C ₁ -C _2
0 alkyl or α, α-dimethylbenzyl].

X is the formula:

[0052]

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[0053] a group represented by; and R _9, R _{1 0,}
R _{1 1,} and R _{1 2} are, independently of one another, hydrogen, methyl, te
rt- butyl, -COO-C ₁ -C _{2 0} alkyl, or alpha,
Compounds of formula (III) which are α-dimethylbenzyl are preferred.

Formula:

[0055]

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And a compound represented by the formula:

[0057]

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[0058] wherein, R _{1 5} is, CH ₃ or CH ₂ CH (C
H ₃ ) CH ₂ CH ₃ ] are particularly preferred.

Further preferred optical brightener compounds have the formula:

[0060]

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Is a compound represented by the formula:

Optical brightener compounds are known to those skilled in the art and are widely marketed, for example, under the trademark “UVITEX” of Ciba Spezialitaetenchemie, Switzerland. "U
VITEX OB ”(Ciba Spezialitaetenchemie, Swi
tzerland) is particularly preferred.

An optical brightener (c) is added to the composition of the present invention.
Conveniently 0.05-2.0%, preferably 0.2%
Add in an amount of ~ 1.0%.

As component (b), a compound of formula (I) wherein R ₁ and R ₂ are phenyl and R ₃ is C ₁ -C ₄
Alkyl-substituted phenyl) or compounds of formula (I) as component (b), wherein R ₁ and R
₂ is phenyl, R ₃ is phenyl substituted with C ₁ -C ₄ alkyl) and a compound of formula (II) wherein R ₄ is hydrogen and R ₅ is hydroxy And R ₆ and R ₇ are each C ₁ -C ₄ alkyl, or together form a cyclohexyl ring); as component (c), a compound of formula (III) X is the formula:

[0065]

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[0066] a group represented by, R _{1 0} and R _{1 2} is hydrogen and R ₉ and R _{1 1} are each a tert- butyl); and titanium dioxide pigment as the component (d) Compositions containing are preferred.

Particular preference is given to the formula:

[0068]

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UVITEX OB®, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 2-hydroxy-2-
A 1: 1 mixture of methyl-1-phenyl-propanone; U
VITEX OB® and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; U
VITEX OB® and (2,4,6-
1: 1 mixture of trimethylbenzoyl) -diphenyl-phosphine oxide and (1-hydroxy-cyclohexyl) -phenyl-ketone; UVITEX OB®, and (2,4,6-trimethylbenzoyl)
-Ethoxy-phenyl-phosphine oxide and (1-
A 1: 1 mixture of (hydroxy-cyclohexyl) -phenyl-ketone; or UVITEX OB®, and the formula:

[0070]

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And a compound represented by the formula (1)
1: 1 mixture of cyclohexyl) -phenyl-ketone;
It is a composition containing.

The unsaturated compounds (a) can contain one or more olefinic double bonds and can be of low (monomeric) or high (oligomeric) molecular weight. Examples of monomers having a double bond include alkyl and hydroxyalkyl acrylates and methacrylates (eg, methyl, ethyl, butyl, 2-ethylhexyl, and 2-hydroxyethyl acrylate; isobornyl acrylate; and methyl and ethyl (Methacrylate). Silicone acrylates are also interesting. Examples further include acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl esters (such as vinyl acetate), vinyl ethers (such as isobutyl vinyl ether), styrene, alkyl and halo-styrene, N-vinyl pyrrolidone, vinyl chloride, And vinylidene chloride.

Examples of monomers having several double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4 '-
Bis (2-acryloyloxyethoxy) -diphenylpropane, trimethylolpropane triacrylate,
Tripropylene glycol diacrylate, pentaerythritol triacrylate and tetraacrylate,
Vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, and tris (2-acryloylethyl) isocyanurate.

Examples of high molecular weight (oligomeric) polyunsaturated compounds include acrylated epoxy resins,
Acrylic esterified or vinyl ether group containing or epoxy group containing polyesters, polyurethanes, and polyethers. Further examples of unsaturated oligomers include unsaturated polyester resins, usually prepared from maleic acid, phthalic acid, and one or more diols, having a molecular weight of about 500-3,000. Vinyl ether monomers and oligomers, and polyesters,
Polyurethanes, polyethers, polyvinyl ethers, and maleic acid terminated oligomers having an epoxide backbone can also be used. Combinations of oligomers and polymers containing vinyl ether groups as described in WO 90/01512 are particularly suitable. However, copolymers of monomers functionalized with vinyl ether or maleic acid are also suitable. Such unsaturated oligomers are also described as prepolymers.

For example, esters of ethylenically unsaturated carboxylic acids with polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the chain or side chain groups (eg, unsaturated polyesters, polyamides and polyurethanes, and copolymers thereof), Alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth) acrylic groups in the side chains, and mixtures of one or more of these polymers are particularly suitable.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids (such as linolenic acid or oleic acid). Acrylic acid and methacrylic acid are preferred.

Suitable polyols are aromatic, and especially aliphatic and cycloaliphatic polyols. Examples of aromatic polyols include hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl)
-Propane, and novolaks and resols. Examples of polyepoxides include the above polyols,
In particular, mention may be made of those based on aromatic polyols and epichlorohydrin. Polymers and copolymers having hydroxy groups in the polymer chains or side groups (eg, polyvinyl alcohol and its copolymers, polyalkyl methacrylate hydroxyalkyl esters and its copolymers) are also suitable as polyols. Further suitable polyols are oligoesters having terminal hydroxy groups.

Examples of aliphatic and cycloaliphatic polyols include alkylene diols, preferably having 2 to 12 carbon atoms, ethylene glycol, 1,2- and 1,3
-Propanediol, 1,2-, 1,3- and 1,4-
Butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycol (preferably having a molecular weight of 2,000 to 1,500), 1,3-cyclopentanediol, 1,2
-, 1,3- and 1,4-cyclohexanediol,
Examples thereof include 1,4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.

The polyols can be partially or completely esterified by one or various unsaturated carboxylic acids, wherein the free hydroxyl groups in the partially esterified esters are, for example, ethers It can also be modified, such as by esterification or esterification with another carboxylic acid.

The following are examples of esters: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, trimethylolethane trimethacrylate, tetramethylene glycol diacrylate. Methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaac Relate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol di-itaconate, dipenta Erythritol trisitaconate, dipentaerythritol pentitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butane Diol di-itaconate,
Sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester methacrylate and acrylate,
Glycerol di- and tri-acrylate, molecular weight 20
1,4-cyclohexanediacrylate, bisacrylate and bismethacrylate of polyethylene glycol from 0 to 1,500.

Suitable as component (a) are the same or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines having preferably 2 to 6, especially 2 to 4, amino groups. Is an amide. Examples of such polyamines are ethylenediamine, 1,2- and 1,3-
Propylenediamine, 1,2-, 1,3- and 1,4-
Butylenediamine, 1,5-pentylenediamine, 1,
6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diamino-cyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetraamine, and diethylenediamine (Β-aminoethoxy)-and di (β-aminopropoxy) -ethane. Further suitable polyamines are polymers and copolymers which may have additional amino groups in the side chain, and oligoamides having terminal amino groups. Examples of such unsaturated amides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriamine trismethacrylamide, bis (methacrylamidopropoxy) ethane, β-
Methacryl-amidoethyl methacrylate, and N-
[(Β-hydroxyethoxy) ethyl] acrylamide.

[0082] Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines. Maleic acid may be partially replaced by other dicarboxylic acids. These may be used with ethylenically unsaturated comonomers, such as styrene. Polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially those having a long chain of, for example, 6 to 20 carbon atoms. Examples of polyurethanes include those composed of saturated or unsaturated diisocyanates and unsaturated or saturated diols.

[0083] Polybutadienes and polyisoprenes and their copolymers are known. Suitable comonomers include, for example, ethylene, propene, butene, hexene,
(Meth) acrylate, acrylonitrile, styrene,
And olefins such as vinyl chloride. Polymers having (meth) acrylate groups in the side chains are likewise known. Examples are the reaction products of epoxy resins based on novolaks with (meth) acrylic acid: homo- or co-polymers of vinyl alcohol or its hydroxyalkyl derivatives [esterified with (meth) acrylic acid]; Mention may be made of homo- or co-polymers of (meth) acrylate esterified with hydroxyalkyl (meth) acrylate.

The photopolymerizable compounds can be used alone or in any desired mixtures. Preferably, a mixture of polyol (meth) acrylates is used.

A binder may also be added to the composition according to the invention, which is particularly advantageous when the photopolymerizable compound is a liquid or viscous substance. The amount of binder is, for example, from 5 to 95% by weight, preferably from 10 to 90% by weight and especially from 40 to 90% by weight, based on the total solids. The binder is selected according to the field of application and the properties required for it, the adhesion to the support and the sensitivity to oxygen.

Suitable binders are, for example, from about 5,000 to
2,000,000, preferably 10,000 to 1,0
It is a polymer having a molecular weight of 00,000. Examples are homo- and co-polymers of acrylates and methacrylates, such as copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (alkyl methacrylates), poly (alkyl acrylates); cellulose esters and Ether (cellulose acetate, cellulose acetate butyrate, methylcellulose, ethylcellulose, etc.); polyvinyl butyral, polyvinyl formal, cyclized natural rubber, polyether (polyethylene oxide, polypropylene oxide, polytetrahydrofuran, etc.); polystyrene, polycarbonate, polyurethane , Chlorinated polyolefin, polyvinyl chloride, copolymer of vinyl chloride / vinyldenchloride, vinylidene chloride and acrylonitrile Polymers, copolymers of methyl methacrylate and vinyl acetate, polyvinyl acetate,
Polymers such as copoly (ethylene / vinyl acetate), polycaprolactam and poly (hexamethylene adipamide), and polyesters such as poly (ethylene glycol terephthalate) and poly (hexamethylene glycol succinate).

The unsaturated compounds can also be used as a mixture with a non-photopolymerizable film-forming component. These are, for example, polymers that can be physically dried,
Or its solution in an organic solvent (eg, nitrocellulose, or cellulose acetobutyrate, etc.). However, it can alternatively be a chemically or thermosetting resin such as a polyisocyanate, polyepoxide or melamine resin. The combined use with a thermosetting resin is important for use in a so-called hybrid system in which photopolymerization is performed in the first step and crosslinking is performed by a thermal post-treatment in the second step.

Compositions that do not contain a binder are preferred.

The compositions according to the invention are, for example, Lehrbuch d.
er Lacke und Beschichtungen, Volume III, 296-328,
WA Colomb of Heenemann GmbH, Berlin-Oberschwando
It is also suitable in oxidative drying systems, as described in rf (1976).

The composition according to the invention contains at least one pigment (d), ie the composition comprises one pigment or two or more different pigments, for example 1
Contains ~ 3, or 1 or 2 pigments. In the composition according to the invention, the pigment can be inorganic or organic. Black, white, or colored pigments can be used. Examples of pigments include Tioxide RTC-
Rutile-type white pigments such as Degussa S 2
carbon black, such as pecial Black 250®, IRGAZIN DPP Red Bo from Ciba Specialty Chemicals
Diketopyrrolopyrrole, Ciba Speci
isoindolinones such as IRGAZIN Yellow 3RLTN® from alty Chemicals, IR from Ciba Specialty Chemicals
Allylamides such as GALITE YellowGu®, Cib
Copper phthalocyanines, such as IRGALITE Blue GLNF® from Specialty Chemicals, and Ciba Specialty Che
Copper phthalocyanines (halogenated) such as IRGALITE Green GLNnew® from Micals can be mentioned.

In the composition of the present invention, it is preferable to use a white pigment, for example, of the titanium dioxide type as the component (d).

The photopolymerizable composition according to the present invention usually contains the pigment (d) in an amount of 5 to 50%, for example, 10 to 50%.

The photopolymerizable mixture can contain various additives (e) in addition to the photopolymerization initiator. Examples of additives include temperature inhibitors aimed at preventing incomplete polymerization (eg, hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol, or sterically hindered phenols, such as 2,6-diphenol). -(Tert-butyl) -p-cresol and the like). In order to enhance the storage stability in a dark place, for example, a copper compound (such as copper naphthenate, stearate, or octoate), a phosphorus compound (eg, triphenylphosphine, tributylphosphine, triethylphosphite, triphenylphosphite, Or a quaternary ammonium compound (such as tetramethylammonium chloride or trimethylbenzylammonium chloride), or a hydroxylamine derivative (such as N-diethylhydroxylamine). During the polymerization, for the purpose of excluding atmospheric oxygen, it is insoluble in the polymer and migrates to the surface at the beginning of the polymerization, forming a transparent surface layer that prevents air from entering. Substances can be added. Similarly, it is possible to apply a layer that does not transmit oxygen. Ultraviolet absorbers, such as those of the hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone, oxalic amide or hydroxyphenyl-s-triazine type, can also be added as light stabilizers. Such compounds can be used alone or in mixtures, with or without sterically hindered amines (HALS).

The following are examples of such UV absorbers and light stabilizers: 1.2- (2'-hydroxyphenyl) -benzotriazole. For example, 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-chlorobenzotriazole, 2- (3'
-Tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-
sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) -benzotriazole, 2- (3 ', 5'-di -Tert-amyl-2'-
(Hydroxyphenyl) -benzotriazole, 2-
(3 ', 5'-bis (α, α-dimethylbenzyl)-
2'-hydroxyphenyl) -benzotriazole; 2
-(3'-tert-butyl-2'-hydroxy-5'-
(2-octyloxycarbonylethyl) phenyl)-
5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5
Chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole,
2- (3'-tert-butyl-2'-hydroxy-5'-
(2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -benzotriazole, 2- (3' −te
rt-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl)
-Benzotriazole, 2- (3'-dodecyl-2'-
Hydroxy-5'-methylphenyl) -benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl)
A mixture of phenyl) -benzotriazole, 2,2′-
Methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; 2- [3'-tert-butyl-5 '-(2-methoxycarbonyl Ethyl) -2'-hydroxyphenyl]
-Polyethylene glycol 300 of benzotriazole
A transesterification product with [R-CH ₂ CH ₂ -C
OO (CH _{2) 3] 2} - (wherein, R represents, 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl - phenyl).

2. 2-Hydroxybenzophenone. For example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, or 2'-hydroxy-4,4'- Dimethoxy derivatives,

3. Esters of unsubstituted or substituted benzoic acids:
For example, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate,
Dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, 3,5
Hexadecyl di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, and 3,5-di-
tert-butyl-4-hydroxybenzoate 2-methyl-
4,6-di-tert-butylphenyl ester.

4. Acrylate. For example, α-cyano-
β, β-diphenylacrylic acid ethyl ester or isooctyl ester, α-methoxycarbonylcinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, α-methoxycarbonyl- p-methoxy-cinnamic acid methyl ester, and N- (β-methoxycarbonyl-
β-cyanovinyl) -2-methyl-indole.

5. Sterically hindered amines. For example, screw (2,
2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl- 3,5-di-tert-
Bis butyl-4-hydroxybenzylmalonate (1,
2,2,6,6-pentamethylpiperidyl) ester,
A condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid,
N, N'-bis (2,2,6,6-tetramethyl-4-
Piperidyl) condensation product of hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) Nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetraoate,
1,1 '-(1,2-ethanediyl) -bis (3,3
5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2 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, N, N'-bis (2 , 2,6,6-tetramethyl-4-piperidyl) condensation product of hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-di ( 4-n-butylamino-2,2,6,6-tetramethylpiperidyl)
Condensation product of -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 2-chloro 4,
6-di (4-n-butylamino-1,2,2,6,6-
Condensation product of (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-dodecyl-1-
(2,2,6,6-tetramethyl-4-piperidyl)-
Pyrrolidine-2,5-dione, 3-dodecyl-1-
(1,2,2,6,6-pentamethyl-4-piperidyl) -pyrrolidine-2,5-dione.

6. Diamine oxalate. For example, 4,4 '
-Dioctyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-
5,5'-di-tert-butyloxanilide, 2,2'-
Didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide,
N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its 2-ethoxy-2'-ethyl-5,4'-di- Mixtures with tert-butyl oxanilide, mixtures of o- and p-methoxy and o- and p-ethoxy-disubstituted oxanilides.

7.2- (2-hydroxyphenyl)-
1,3,5-triazine. For example, 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-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6 (2,4-dimethylphenyl)-
1,3,5-triazine, 2- (2-hydroxy-4-
Octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl Phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3
-Butyloxy-propyloxy) phenyl] -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl]
-4,6-bis (2,4-dimethylphenyl) -1,
3,5-triazine and 2- [4-dodecyloxy /
Tridecyloxy- (2-hydroxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4-
Dimethylphenyl) -1,3,5-triazine.

8. Phosphites and phosphonites. For example, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4
-Di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2
4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4)
-Methylphenyl) pentaerythritol diphosphite, bisisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6 -Tri-tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-te
rt-butylphenyl) -4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10
-Tetra-tert-butyl-12H-dibenzo [d, g]
-1,3,2-dioxaphosphosine, 6-fluoro-
2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6- Methylphenyl) methyl phosphite, and bis (2,4-di-
(tert-butyl-6-methylphenyl) ethyl phosphite.

Additives commonly used in the art, such as flow control agents and adhesion improvers, can also be used.

To promote photopolymerization, further additives (e) such as amines such as triethanolamine, N
-Methyl-diethanolamine, p-dimethylaminobenzoic acid ethyl ester or Michler's ketone can also be added. The action of the amine is enhanced by the addition of aromatic ketones of the benzophenone type. Amines that can be used as oxygen scavengers include, for example, EP3
Substituted N, N-dialkylanilines as described in 39841. Further accelerators, co-initiators, and autoxidants are, for example, EP43
Thiols, thioethers, disulfides and phosphines as described in 8123 and GB2180358.

The compositions according to the invention can also contain chain transfer reagents commonly used in the art.
Examples include mercaptans, amines and benzothiazole.

The photopolymerization can be promoted by adding, as a further additive (e), a photosensitizer which shifts or broadens the spectral sensitivity. These include, in particular, aromatic carbonyl compounds, such as benzophenone and thioxanthone derivatives, and especially isopropylthioxanthone, anthraquinone and 3-acylcoumarin derivatives, terphenyl, styryl ketone, and 3
-(Aroylmethylene) -thiazoline, camphorquinone, and also eosin, rhodamine and erythrosine dyes. For example, the amines described above can be considered as photosensitizers.

Particularly in the case of colored compositions (for example, compositions colored with titanium dioxide), additional additives (e)
As a component that generates free radicals under temperature conditions, for example, an azo compound (eg, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), triazene, diazosulfide, or pentazadiene); or The addition of a peroxy compound (such as a hydroperoxide or a peroxycarbonate such as tert-butyl hydroperoxide) (eg as described in EP 245639) can also assist in the curing process.

The compositions according to the invention may comprise, as further additives (e), photoreducible dyes (eg xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronin, porphyrin or acridine dyes) and / or
Alternatively, it can contain a trihalomethyl compound that can be removed by radiation. Similar substances are, for example, E
P445624.

Depending on the intended use of the composition, further commonly used additives (e) include fillers, colorants, wetting agents and flow control agents. For example, US
Addition of glass microbeads, or ground glass fibers, as described in 5013768, is suitable for curing thick, pigmented coatings.

The additives (e) can be selected according to the field to be used and the properties required in the field. The abovementioned additives (e) are well known to the person skilled in the art and are used in the compositions according to the invention in amounts customary in the art.

The present invention also relates to a composition containing as component (a) at least one ethylenically unsaturated photopolymerizable compound dissolved or emulsified in water. Such aqueous radiation-curable prepolymer dispersions are widely available commercially and are understood to be dispersions consisting of water and at least one prepolymer dispersed therein. The concentration of water in such a system is, for example, 5 to 80% by weight, in particular 30%.
６０60% by weight. The radiation-curable prepolymer or mixture of prepolymers is, for example, 95 to 20% by weight, in particular 7%.
It is present at a concentration of 0-40% by weight. In such compositions, the sum of the proportions mentioned above for water and the prepolymer is in each case 100, with the addition of auxiliaries and additives present in different amounts depending on the intended use.
Irradiation-curable film-forming prepolymers, which are dispersed or sometimes dissolved in water, are mono- or poly-functional ethylenically unsaturated prepolymers, which are initiated by free radicals, which are aqueous prepolymers. Polymer dispersions are known per se, for example having from 0.01 to 1.0 mol of polymerizable double bonds per 100 g of prepolymer and having an average molecular weight of, for example, at least 40
0, especially 500 to 10,000. However, prepolymers having a high molecular weight could be considered depending on the intended use.

For example, a polymerizable CC double bond-containing polyester having a maximum acid value of 10, a polymerizable CC double bond-containing polyether, a hydroxy group-containing reaction product (containing at least two epoxy groups per molecule) Polyepoxide and at least one α, β-ethylenically unsaturated carboxylic acid), polyurethane (meth) acrylate, and α,
Acrylic acid copolymers containing β-ethylenically unsaturated acrylic acid radicals (as described in EP 12339) can be used. Mixtures of these prepolymers can also be used. Also suitable are the polymerizable prepolymers described in EP 33896, which have an average molecular weight of at least 600, a carboxyl group content of 0.2 to 15%, and a content of 0.1 to 100 g of prepolymer per 100 g. It is a thioether adduct of a polymerizable prepolymer containing from 0.1 to 0.8 mol of a polymerizable CC double bond. Other suitable aqueous dispersions based on certain alkyl (meth) acrylate polymers are described in EP 41125, and suitable water-dispersible, radiation-curable prepolymers of urethane acrylate are
It is described in DE 2936039.

Such radiation-curable aqueous prepolymer dispersions may contain, as further additives, dispersants, emulsifiers, antioxidants, light stabilizers, colorants, fillers such as talc, gypsum, silicic acid, Rutile, carbon black, zinc oxide,
Iron oxides, accelerators, flow regulators, lubricants (glidan
t), wetting agents, thickeners, matting agents, defoamers, and other adjuvants commonly used in surface coating technology can be included. Suitable dispersants include water-soluble, high molecular weight organic compounds having a polar group, such as polyvinyl alcohol, polyvinylpyrrolidone, and cellulose ether. As the emulsifier, a nonionic emulsifier can be used, and if appropriate, an ionic emulsifier can also be used.

In some cases, it may be advantageous to use a mixture of two or more photoinitiators of the formulas (I) and (II). Mixtures with further known photoinitiators can also be used, for example further benzophenone derivatives, acetophenone derivatives, dialkoxyacetophenone, α-hydroxy- or α-amino-acetophenone, 4-aroyl-1 , 3-dioxolane, benzoin alkyl ethers and benzyl ketals (such as benzyl dimethyl ketal), phenylglyoxalate and its derivatives, dimeric phenylglyoxalate,
Ferrocenium compounds or titanocenes such as dicyclopentadienyl-bis (2,6-difluoro-3-pyrrolo-phenyl) -titanium and the like, benzoyl peroxide (a suitable peroxide is US Pat.
1, column 19, lines 17-25), or a cyclopentadienylene-iron (II) complex salt (eg (η ⁶ -iso-propylbenzene) (η ⁵ -cyclopentadienyl) And mixtures with iron (II) hexafluorophosphate.

When a photopolymerization initiator is used in the hybrid system, a cationic photopolymerization initiator (for example, an aromatic sulfonium, phosphonium or iodonium salt) (for example, US Pat. No. 4,950,581, columns 18, 60)
Row to column 19, lines 10) are used in addition to the free radical curing agent.

The photopolymerizable composition is advantageously present in an amount of from 0.05 to 15% by weight, preferably from 0.1 to 5% by weight, of the photopolymerization initiator or the photopolymerization initiator mixture (based on the composition). b)
It contains. The amounts of photoinitiator indicated are relative to the sum of all photoinitiators added when the mixture is used.

The photopolymerizable compositions can be used for various purposes, for example for printing inks, clear lacquers, white surface coating compositions (for example for wood or metal), powder coating compositions, especially for paper, wood, metal or plastic. Bulk curing (ultraviolet curing in transparent molds) as a coating material, sun-curable paints for marking buildings and roads, dental filling compositions, adhesives, pressure sensitive adhesives, laminating resins Or 3 by the step of stereolithography described, for example, in US Pat.
In the manufacture of three-dimensional articles, in the manufacture of composite materials (e.g., styrene polyester, which may contain glass fibers and / or other fibers, and other adjuvants where appropriate) and other thick layer compositions, It can be used in coating or sealing electronic components or as a coating for optical fibers. The compositions according to the invention are furthermore suitable for the production of medical devices, auxiliary devices, such as contact lenses, or implants.
The compositions according to the invention can also be used for the production of gels having thermotropic properties, as described, for example, in DE1976004 and EP678534. The photopolymerization initiator is used as an initiator for emulsion polymerization, granular polymerization, or suspension polymerization, as an initiator for a polymerization step for fixing the alignment state of liquid crystal monomers and oligomers, or fixing a dye on an organic material. Can be used as an initiator for

The compositions according to the invention are preferably used for preparing surface coatings.

The present invention therefore relates to a colored surface coating comprising a composition as described above, especially a white-colored composition, and the use of the above-described composition as a coating or surface coating, especially a white surface coating. About.

Mixtures of prepolymers with polyunsaturated monomers, further containing monounsaturated monomers, are often used in surface coatings. The person skilled in the art can influence the properties of the cured film by changing the prepolymer, especially since the choice of the prepolymer determines the properties of the surface coating film. The polyunsaturated monomer functions as a crosslinking agent,
This makes the surface coating film insoluble.
Monounsaturated monomers function as reactive diluents, which reduce viscosity without the use of solvents.

Unsaturated polyester resins are generally used in a two-compartment system with a monounsaturated monomer, preferably styrene.

The compositions according to the invention can furthermore be used for radiation-curable powder coating compositions. Powder coating compositions may be based on solid resins and monomers containing reactive double bonds, such as maleate, vinyl ether, acrylate, acrylamide, and mixtures thereof. Free radical UV curable powder coating compositions can be formulated by mixing the unsaturated polyester resin with a solid acrylamide (eg, methyl acrylamide glycolate methyl ester) and a free radical polymerization initiator (eg, “ Radiation Curing of Powder Coa
ting ”, Conference Proceedings, Radtech Europe 199
3 by M. Wittig and Th. Gohmann in a presentation). Similarly, free radical UV curable powder coating compositions can be formulated by mixing the unsaturated polyester resin with a solid acrylate, methacrylate, or vinyl ether and a photoinitiator (or a photoinitiator mixture). it can. The powder coating compositions can also include a binder, for example, as described in DE 4228514 and EP 636669. UV curable powder coatings can also contain white or colored pigments.
For example, especially rutile / titanium dioxide can be used at a concentration of up to 50% by weight to obtain a cured powder coating composition with good covering power. This method
Usually, the powder is sprayed electrostatically or tribostatically on a support such as metal or wood,
Once the powder is melted by heating and a smooth film is formed, the method may include irradiating the coating with ultraviolet and / or visible light, for example, using a medium pressure mercury lamp, metal halide lamp or xenon lamp. The particular advantage of the radiation curable powder coating composition over the corresponding temperature curable composition is that the flow time after the powder particles have melted is required to ensure the formation of a smooth, glossy coating. It can be extended as much as Unlike thermosetting systems,
The radiation curable powder coating composition can be formulated to melt at relatively low temperatures without the undesirable effect of shortening its shelf life.
For this reason, they are also suitable as coatings for heat-sensitive supports such as, for example, wood or plastic.

In addition to the photoinitiator, the powder coating formulation can also contain an ultraviolet absorber.
Suitable examples have been described above as 1-8.

The photocurable compositions according to the invention include, for example, wood, textiles, paper, ceramics, glass, plastics (such as polyester, polyethylene terephthalate, polyolefin or cellulose acetate) (especially in the form of a film), and Al. , Cu, Ni, Fe, Zn, Mg
Or as a coating material for any kind of support on which a protective layer is formed, such as Co and metals such as GaAs, Si or SiO ₂ .

The support can be coated by applying a liquid composition, solution or suspension to the support. The solvent and its concentration are selected mainly depending on the nature of the composition and the coating method. The solvent must be inert, meaning that it must not undergo any chemical reaction with the components and must be able to be removed again by drying after the coating step. Suitable solvents include, for example, ketone ethers and esters (methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-
Methylpyrrolidone, dioxane, tetrahydrofuran,
2-methoxyethanol, 2-ethoxyethanol, 1
-Methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate, and ethyl 3-ethoxypropionate).

The formulation may be coated by known coating methods such as spin coating, dipping, knife coating, flow coating (cu
The composition is uniformly applied to the support by a method such as coating with a brush, or spraying (especially electrostatic spraying), and reverse roll coating, or electrophoretic coating.
It is also possible to coat the final support by applying a photosensitive layer to the primary flexible support and then transferring the layers by lamination.

The amount applied (layer thickness) and the nature of the support (layer support) depend on the desired field of application. The thickness range of the layer is generally from about 0.1 μm to 100 μm or more,
For example, 20 mm, 0.02 cm to 10 cm, preferably 0.0
Includes values between 2 cm and 2 cm.

Photocuring is very important for printing inks (the compositions according to the invention can also be used for the preparation of such inks). The drying time of the binder is the rate-limiting factor in the production of graphic products and is a fraction of a second
Because it must be in the order of UV curable inks are particularly important for screen printing.

Other areas of application of light curing include, for example, metal coatings in the application of sheet or tube finishes, can or bottle seals, and light curing of, for example, PVC-based floor or wall coatings to plastic coatings, Or application of a finishing agent to an automobile.

Examples of photocuring of a paper coating include the application of a finish to a label, record sleeve, or book cover.

The use of the compositions according to the invention in the production of moldings from composite materials is also of interest. Composite materials are self-supporting matrix materials, such as woven glass fibers,
Alternatively, for example, plant fibers impregnated with a photocurable formulation (K.-P. Mieck, T. Reussmann in Kunststoffe 85
(1995), 366-370 or V. Narayanan, AB Scranton, Tre
nds in Polymer Science 1997 (5), 12, 415). Composite moldings prepared using the composition according to the invention have a high degree of mechanical stability and resistance. The compositions according to the invention can also be used for shaping, impregnating and coating materials, for example as described in EP 7086. Such materials include, for example, thin-layer resins for which curing activity and yellowing resistance are highly required, and fiber-reinforced molding materials (eg, flat or vertical or horizontal corrugated lightweight panels). Methods for preparing such molding materials, such as hand lay-up, fiber spraying,
Spinning or winding methods are described, for example, by PH Selden in "Gla
sfaserverstaerkte Kunststoffe ”, page 610, Springe
r Verlag Berlin-Heidelberg-New York 1967. Articles that can be prepared by the present method include, for example, boats, chipboards, or plywood, pipes, coated with glass fiber reinforced plastic on both sides.
Sports equipment, roof coatings, containers, etc. Further examples of molding, impregnating and coating materials are
UP resin thin layer (GRP) for molding materials containing glass fiber,
For example, corrugated panels and laminated paper. Laminated paper can be based on urea or melamine resins. The lamina is produced on a support (for example a foil) before the production of the laminate. The photocurable composition according to the present invention can be used for injection molding of a resin or potting of an article, for example, an electronic component. They can also be used for lining cavities and pipes. In the curing process, as is usual with UV curing,
A lamp that uses a medium-pressure mercury lamp but is not so intense,
Of particular interest, for example, of the TL40W / 03 or TL40W / 05 type. The intensity of these lights roughly corresponds to that of sunlight. Direct sunlight can also be used for curing. A further advantage is that the composite material can be partially cured, in a plasticized state, removed from the light source and subjected to molding, and then fully cured by further exposure to light. is there.

The photosensitivity of the composition according to the invention is usually
The range is from about 200 nm to about 600 nm (ultraviolet region).
For example, suitable illumination exists for sunlight or light from artificial light sources. Thus, a very wide variety of light sources can be used. Both point sources and planar radiators (lamp carpets) can be used. Examples include carbon arc lamps, xenon arc lamps, medium-pressure, high-pressure and low-pressure mercury arc radiators (doped with metal halides where appropriate) (metal halide lamps), microwave-excited metal vapor lamps, Excimer lamps, higher order actinide fluorescent tubes, fluorescent lamps, argon incandescent lamps, flashlights, photographic floodlights, light emitting diodes (LEDs), electron beams, and X-rays. The distance between the lamp and the substrate according to the invention to be exposed can vary depending on the intended use and the type and intensity of the lamp, for example from 2 cm to 150 cm. Particularly suitable is a laser light source, for example, for exposure at 248 nm, an excimer laser such as a krypton F laser. Visible lasers can also be used. For example, a lithographic offset plate or letterpress printing plate can be manufactured by the present method.

The photocurable compositions according to the invention have surprisingly good sufficient curing properties.

The present invention is a method for photopolymerizing a non-volatile monomer, oligomer or polymer compound having at least one ethylenically unsaturated double bond, wherein the composition as described above has a composition in the range from 200 to 600 nm. It also relates to a method comprising irradiating a light beam.

The invention also relates to colored and uncolored surface coatings, printing inks, powder coatings, printing plates, adhesives, dental materials, composites, fiberglass cable coatings, and screen printing stencils ( Use of the above-described composition for the preparation of three-dimensional objects by stereolithography) and colored and uncolored surface coatings, printing inks, powder coatings, printing plates, adhesives, dental The invention also relates to a method for producing materials, composites, fiberglass cable coatings and screen printing stencils (in the production of three-dimensional objects by stereolithography).

The present invention also relates to the composition of claim 1
It also relates to the use as a coating or surface coating, especially a white surface coating, and as a screen printing ink, especially a white screen printing ink.

The invention likewise relates to a support coated on at least one surface with a composition as defined above, and to the cured composition thereof.

[0137]

The following examples further illustrate the present invention.
In the remainder of the description and in the claims, parts and percentages are by weight unless otherwise indicated. When an alkyl or alkoxy group having more than 3 carbon atoms is mentioned without reference to its isomeric form,
Each n-isomer is intended.

In the examples, the following photopolymerization initiators were used. P1 is 2,4,6-trimethylbenzoyl-
Diphenyl-phosphine oxide and 2-hydroxy-
It is a 1: 1 mixture of 2-methyl-1-phenyl-propanone. P2 is 2,4,6-trimethylbenzoyl-
Diphenyl-phosphine oxide. P3 is
(2,4,6-trimethylbenzoyl) -diphenyl-
It is a 1: 1 mixture of 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 has the formula:

[0140]

Embedded image

And a compound represented by the formula (1-hydroxy-
1: 1 mixture of (cyclohexyl) -phenyl-ketone.

In the examples, the following optical brighteners were used. The formula of Ciba Spezialitaetenchemie:

[0143]

Embedded image

UVITEX OB (registered trademark) represented by formula:

[0145]

Embedded image

[0146] wherein, R _{1 5} = a CH _3] represented by A1. formula:

[0147]

Embedded image

[0148] _{wherein, R 1 5 = CH 2 CH} (CH 3) CH 2
A2 represented by CH ₃ a is].

Example 1 Curing of Epoxy Acrylate White Surface Coating A white surface coating of the following composition was prepared: 65%
Epoxy acrylate (EBECRYL®604, UCB,
Belgium) 10% hexanediol diacrylate 25% titanium dioxide (rutile form, RTC-2 (registered trademark), T
ioxide, France) 3% photoinitiator and optical brightener (UVITEX OB®, Ciba Spezialitaetenchemie, Switzerland)
5% was incorporated into the above formulation. The layers were applied to the lightly primed chipboard using a 150 μm slotted knife. Belt speed 10 m using two 80 W / cm medium pressure mercury lamps (UV equipment from AETEK, USA)
Exposure was performed at 20 m / min and 20 m / min. After exposure, the scratch resistance and the pendulum hardness,
PH) is determined according to Koenig (DIN 53157),
The yellowing index was confirmed (ASTM D1925- 8).
8). After irradiation, the underside of the layer separated from the support dried and the layer was considered fully cured. The higher the pendulum hardness value, the harder the irradiated coating. The lower the Yellowness Index (YI), the less the cured layer was yellowed. The results are shown in Table 1 below.

[0150]

[Table 1]

UVITEX OB (registered trademark): Ciba Spezialita
etenchemie

Example 2 Curing of a Polyester Acrylate White Surface Coating A white surface coating having the following composition was prepared. 67.5% polyester acrylate (EBECRYL (registered trademark) 830, UCB, Belgium) 5.0% hexanediol diacrylate 2.5% trimethylolpropane triacrylate 25.0% titanium dioxide (rutile type, RTC- 2 (registered trademark), Tioxide, France) Coating, curing and measurement were performed in the same manner as in Example 1. Table 2 shows the photopolymerization initiator and the fluorescent brightener used, and the measurement results.

[0153]

[Table 2]

Example 3 Curing of a Polyester Acrylate White Surface Coating A white surface coating of the composition described in Example 2 was prepared. Coating and curing were performed as described in Example 1. In each case, after curing, the yellowing index and the pendulum hardness were measured at a belt speed of 5 m / min. However, in addition to the yellowing index and pendulum hardness, the maximum curable free layer depth (F
L) was confirmed. For this purpose, one drop of the formulation to be cured was applied to the support and irradiated at a belt speed of 3 m / min. Next, the cured layer was separated from the support, and the thickness (μm) of the cured layer was confirmed. If the layer is thick, the tested formulation is fully cured. Further, the number of runs and runs at 10 m / min required to obtain a non-tacky cured layer was confirmed (quoted as the number of runs n × 10 m / min). Table 3 shows the photopolymerization initiator and the fluorescent brightener used, and the measurement results.

[0155]

[Table 3]

* Unmeasurable value UVITEX OB (registered trademark): Ciba Spezialitaetenchemie

Example 4 Curing of a Polyester Acrylate White Surface Coating A white surface coating of the composition described in Example 2 was prepared. Polymerization initiator P3 was used as a photopolymerization initiator.
Coating and curing were performed as described in Example 1.
In each case, the pendulum hardness after hardening was measured at belt speed 3
It was measured in m / min. In addition to pendulum hardness, the maximum curable free layer depth (FL) was determined as described in Example 3. Table 4 shows the optical brighteners used and the measurement results.

[0158]

[Table 4]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 299/02 C08F 299/02 299/04 299/04 (72) Inventor Patrick Contig Switzerland 4147 Esch St. Jakobstrasse 38 ( 72) Inventor David George Leppard Switzerland 1723 Marly Route de Pourguillon 6

Claims (5)

[Claims] (1) at least one ethylenically unsaturated photopolymerizable compound; (b) as a photopolymerization initiator, at least one mono-,
A bis- or tris-acylphosphine oxide compound or a mixture of such a compound with an α-hydroxyketone, α-aminoketone and / or benzoin derivative compound; (c) at least one optical brightener; A) a photopolymerizable composition comprising at least one pigment; 2. A mono-, bis-, or tris-acylphosphine oxide compound having the formula (I): Wherein, R ₁ and R ₂ independently of one another, C ₁ -C _{1 8} alkyl; phenyl; one or C ₂ -C _{1 8} alkyl in more oxygen atoms is interrupted discontinuously substituted C ₁ -C ₄ alkyl; C ₂ -C ₈ alkenyl, phenyl, naphthyl, biphenyl, or C ₅ -C _{1 2} cycloalkyl (of which phenyl, naphthyl, biphenyl, and C
₅ -C _{1 2} cycloalkyl group, unsubstituted or halogen, is mono- to penta-substituted by C ₁ -C ₈ alkyl, C ₁ -C ₈ alkylthio and / or C ₁ -C ₈ alkoxy ) Or R ₁ and R ₂ are -COR ₃
R ₃ is phenyl (which is unsubstituted or
Or C ₁ -C _{1 2} alkyl, C ₁ -C _{1 2} alkoxy, C ₁ -
C _{1 2} alkylthio and / or halogen are mono- to penta-substituted)]. 3. An α-hydroxyketone, α-aminoketone, or benzoin derivative compound represented by the formula (II): Wherein, R ₄ is hydrogen, C ₁ -C _{1 8} alkyl, C ₁ -C _{1 8}
Alkoxy, -OCH ₂ CH ₂ -OR _8, morpholino, -
SCH ₃ , formula: embedded image Or a group represented by the formula: N has a value of 2 to 10;
Has the formula: Be a group represented by; R ₅ is hydroxy, C ₁ -C _{1 6} alkoxy, morpholino, dimethylamino, or -O (C
H ₂ CH ₂ O) be _m -C ₁ -C _{1 6} alkyl; R ₆ and R ₇
Independently of one another, hydrogen, C ₁ -C ₆ alkyl, phenyl, benzyl, C ₁ -C _{1 6} alkoxy, or -O (CH _{2
CH 2 O) m -C 1 -C} 1 6 alkyl Oh there, or R ₆
And R ₇ together with the carbon atom to which they are attached form a cyclohexyl ring; m is a number from 1 to 20; wherein R ₅ , R ₆ , and R ₇ are all at the same time C ₁ -C _{1 6} alkoxy, or _{-O (CH 2 CH 2 O)} m -C 1
Not be -C _{1 6} alkyl; R ₈ is hydrogen, the formula: embedded image Or a group represented by the formula: The compound according to claim 1, which is a compound represented by the formula: 4. The optical brightener (c) is a compound selected from the group consisting of pyrazoline, stilbene, triazine, thiazole, benzoxazole, xanthone, triazole, oxazole, thiophene, and coumarin.
The composition of claim 1. 5. A method for photopolymerizing a non-volatile monomer, oligomer or polymer compound having at least one ethylenically unsaturated double bond, wherein the composition according to claim 1 comprises 200. A method comprising irradiating a light beam in the range of -600 nm.