MXPA97001638A - Oxides of alkylphenilbisacilphosphine and mixtures defotoinicia - Google Patents

Abstract

The present invention relates to: Compounds of the formula I, wherein R 1 is alkyl of 1 to 4 carbon atoms, R 2 is hydrogen alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms and R 3, R 4, R 5, R 6 , and R7, independently of one another are hydrogen, halogen, alkyl of 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, alkenyl of 2 to 12 carbon atoms, alkyl of 2 to 18 carbon atoms, which is interrupted by one or more atoms of oxygen, or are alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 carbon atoms, with the proviso that at least one of the radicals R3, R4, R5, R6 and R7 are different from hydrogen and so that, if R1 and R2 are methyl, R3 and R6 are not methyl, and mixtures of such compounds with alpha-hydroxy ketones, benzophenones and alpha-amino ketones, are suitable as photoinitiators

Description

OXIDES OF ALQÜILFENILBISACILFOSFINA AND PHOTOINICIZER MIXTURES The invention relates to alkylphenylbisacylphosphine oxides and to specific mixtures of bisacylphosphine oxide compounds with other photoinitiators. For example, bisacylphosphine oxide compounds are known as photoinitiators from EP-A-184095. They are described in GB-A-2259704, alkyl bisacylphosphine oxides and also mixtures of these compounds with alpha-hydroxyketones or benzophenone compounds. EP-A-446175 describes mixtures of three components, namely mono- or bisacylphosphine oxide, alpha-idroxyketone and benzophenone. In the industry there is a need for effective photoinitiators and mixtures of photoinitiators that are capable of curing photopolymerizable compositions efficiently and without the phenomenon of extreme yellowing. It has now been found that the compounds of the formula I wherein RL is alkyl of 1 to 4 carbon atoms, R2 is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms and R3, R4, R5, Rg and R7 independently of each other are hydrogen , halogen, alkyl of 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, alkenyl of 2 to 12 carbon atoms, alkyl of 2 to 18 carbon atoms which is interrupted by one or more oxygen atoms, or is alkyl of 1 to 20 carbon atoms. at 4 carbon atoms substituted with phenyl, or are phenyl unsubstituted or mono- or disubstituted with alkyl of 1 to 4 carbon atoms, with the proviso that at least one of the radicals R3, R4, R5, Rg and R7 is different from hydrogen and so that if R ^ and R2 are methyl, R3 and Rg are not methyl, they are suitable as very good photoinitiators. It has also been found that photoinitiators of the formula can be combined with compounds of formula II, III and / or IV to give initiator mixtures (combinations) having good curing properties, especially with respect to the required curing surface and through the curing of the polymerizable compositions. In addition, the cured compositions exhibit highly advantageous properties in the context of arillation.

Therefore, this application provides a photoinitiator mixture comprising at least one compound of, the formula (la) wherein R 1 is alkyl of 1 to 4 carbon atoms; R2 is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, and R3, R4, R5, Rg and R independently of one another are hydrogen, halogen, alkyl of 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, alkenyl of 2 to 12 carbon atoms, alkyl of 2 to 18 carbon atoms which is interrupted by one or more oxygen atoms, or are alkyl of 1 to 4 carbon atoms substituted with phenyl, or are phenyl unsubstituted or mono- or disubstituted with alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 carbon atoms mono- or disubstituted; and at least one compound of the formula (II) wherein R3 is hydrogen, alkyl of 1 to 18 carbon atoms, alkoxy from 1 to 18 át or a group and A is a radical R9 v R10 independently of one another are hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, alkoxy of 1 to 16 carbon atoms, OSiR ^ R ^ R ^ ao -0 (CH2CH2?) Q-alkyl of 1 to 16 carbon atoms, where q is a number from 1 to 20, or Rg and Ri0 'together with the carbon atom to which, they join, form a cyclohexyl ring; R <1> is hydroxyl, alkoxy of 1 to 16 carbon atoms or -0 (CH2CH20) q-alkyl of 1 to 16 carbon atoms; when Rg, R10 and Rll are not all simultaneously alkoxy of 1 to 16 carbon atoms or -0 (CH2Ci-2?) Q-alkyl of 1 to 16 carbon atoms, R ^ 2 is hydrogen, alkyl of 1 to 8 carbon atoms, -, and R13 'R14a and R14 independently of one another are alkyl of 1 to 4 carbon atoms or phenyl; and / or at least one compound of the formula (III) wherein R15 'R15a' R16 and R17 independently of one another are hydrogen, methyl, phenyl, methoxy, -COOH, or alkyl of 1 to 4 carbon atoms substituted or unsubstituted with phenyl, or a group -OCH2CH2ORi2 or -SCH2CH2OR12 wherein R12 is as defined in formula II; and / or at least one compound of the formula (IV) wherein R- ^ 8 is hydrogen / alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, halogen or a group N (R 2) 2? R ^ g is as defined for R ^ g or is the group wherein in the case of the radical R ^ g of Formula IV and the radical R ^ g of this group (IVa) together have a direct ligation, and the other radicals are as defined above; R20 is alkyl of 1 to 8 carbon atoms; R21 is hydrogen, -CH = CHR24, or phenyl which is substituted or unsubstituted one to three times by alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen; or R20 and R21 'Together with the carbon atom to which they are attached, they form a cyclohexyl ring; R22 and R23 independently of one another are alkyl of 1 to 4 carbon atoms, or R22 and R23 'together with the nitrogen atom to which they are attached, form a saturated or unsaturated ring of five or six members which can be interrupted by - O-, -NH- or -N (CH3), R24 is hydrogen or alkyl of 1 to 4 carbon atoms; and R25 is hydrogen or alkyl of 1 to 12 carbon atoms. The alkyl of 1 to 20 carbon atoms may be straight or branched and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertbutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl or eicosyl. Preferably, alkyl of 1 to 18 carbon atoms is provided, e.g. alkyl of 1 to 8 carbon atoms or of 1 to 12 carbon atoms, especially alkyl of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, alkyl of 1 to 6 carbon atoms, and alkyl from 1 to 18 carbon atoms may have the same meaning as given above that corresponds to the number of carbon atoms. The alkyl of 1 to 18 carbon atoms interrupted by one or more oxygen atoms is, for example, interrupted by 1-5, e.g. 1-3 or 1 or 2 times by -0-. This produces the structural units such as -0- (CH2) 2? H, -0 (CH2) 2? CH3, -0- (CH2CH2?) 2CH2CH3, -CH2-0-CH3, -CH2CH2-0-CH2CH3, - [CH2CH2?] And -CH3i where y = 1-5, - (C ^ C ^ O ^ C ^ C ^, -CH2-CH (CH3) -0-CH2-CH2CH3 or -CH2-CH (CH3) - 0-CH2-CH3 The radical -0- (CH2CH20) q-alkyl of 1 to 16 carbon atoms represents from 1 to 20 successive ethylene oxide units, whose chain ends in an alkyl of 1 to 16 carbon atoms, q is preferably q from 1 to 10, e.g., from 1 to 8, especially from 1 to 6. The chain of the ethylene oxide units ends in an alkyl of 1 to 12 carbon atoms, e.g. from 1 to 8 carbon atoms, in particular in an alkyl of 1 to 4 carbon atoms Here, alkyl of 1 to 16 carbon atoms can have the meanings given above which correspond to the number of carbon atoms. At 12 carbon atoms it can be linear or branched and it can have more than one unsaturated ligature in the molecule. allyl, methylvinyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl. The alkoxy of 1 to 18 carbon atoms can be linear or branched and is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentoxy, isopyloxy, hexyloxy, heptyloxy, octyloxy, Nonyloxy, decyloxy, dodecyloxy or octadecyloxy. Further examples are alkoxy of 1 to 12 carbon atoms or alkoxy of 1 to 8 carbon atoms, especially alkoxy of 1 to 4 carbon atoms. The alkoxy of 1 to 6 carbon atoms and the alkoxy of 1 to 4 carbon atoms can have the same meaning given before the correpondendiente number of carbon atoms. The alkylthio having 1 to 4 carbon atoms can be linear or branched and is, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio or tertiary butylthio, especially methylthio. The phenyl-substituted alkyl of 1 to 4 carbon atoms is, for example, benzyl, 2-phenylethyl, 3-phenylpropyl, alpha-methylbenzyl or alpha, alpha-dimethylbenzyl, especially benzyl. Substituted phenyl is substituted one to five times, for example once, twice or three times, especially once or twice, in the phenyl ring. The substitution pattern in the phenyl ring is, for example, 2-, 3-, 4-, 5-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- , 2,4,6-or 3,4,5-. Alkyl substituents of 1 to 4 carbon atoms and alkoxy of 1 to 4 carbon atoms can have the meanings given above. Examples of substituted phenyl are tolyl, xylyl, 4-methoxyphenyl, 2,4- and 2,5-dimethoxyphenyl, ethylphenyl and 4-alkoxy-2-methylphenyl. The halogen is, for example, chlorine, bromine or iodine, especially chlorine.

Yes (Way) wherein the radical R g of formula IV and the radical R ^ g of this group together has a direct ligation, then results in the structures of formula IVb.

If R22 and R23 'together with the nitrogen atom to which they are attached, form a ring which can be further interrupted by -O-, -NH- or -N (CH3) -, then the ring formed is, for example, a ring morpholino, piperidino or methylpiperidino. The novel compounds of the formula I (and the) can be prepared, for example, by double acylation of a primary phosphine (V) with at least two equivalents of an acid chloride (VI) in the presence of at least two equivalents of a base and subsequent oxidation of the resulting diacylphosphine (VII) in accordance with the equations: 2 (VI) (V) (VII) Oxidaci / S > n (I) Rj_, R2, R3, R4, R5, Rg and R7, are as defined in claim 8. Examples of suitable bases are tertiary amines, pyridine, alkali metals, lithium diisopropylamide, butyllithium, alkali metal carbonates. earth, alkali metal alcoholates and alkali metal hydrides. The first reaction stage preferably takes place in solution. Particularly, suitable solvents are hydrocarbons, such as alkanes and mixtures of alkane, cyclohexane, benzene, toluene and xylene. The reaction is carried out at various temperatures depending on the solvent and the starting materials used. In the case of using bases such as lithium diisopropylamide or butyllithium, it is convenient to operate, for example, at -40 to 0 ° C. Reactions using tertiary amines, alkali metals or alkali metal hydrides as a base are conveniently carried out, for example, at 10 to 120 ° C, preferably 20 to 80 ° C. After the formed chloride base has been separated, the phosphine (VII) can be isolated by concentration by evaporation. The crude reaction product can also be used without purification or can be purified, for example, by crystallization. However, the second reaction stage can also be carried out without isolation (VII), using the solution of the crude product.

Oxidation agents particularly suitable for the second stage in the preparation of oxides are hydrogen peroxide and organic peroxy compounds, examples being peracetic acid, air and pure oxygen. The reaction products can be purified by conventional methods, for example by crystallization or chromatography. The phosphines of the formula (V) can be prepared, for example, by reducing the corresponding chlorides (VIII), phosphonic esters (IX) or phosphonous esters (X): (X) R is, for example, methyl or ethyl. The reductions are usually carried out with LiAlH4; SiHCl3; Ph2SiH2; a) LiH b) H20; a) Li / tetrahydrofuran b) H2O or a) Na / toluene b) H2O.

The hydrogenation used by LÍAIH4, for example, can also be found in Helv. Chim. Acta 1966, No. 96, page 842. The dichlorophosphine compounds of formula VIII can be obtained, for example, by reacting a corresponding aromatic compound with phosphorus trichloride and aluminum chloride.

(VIII) The dichlorides (VIII) can also be obtained, for example, by Grignard reaction of the corresponding brominated aromatic compounds (IX) with PCI3 (see, for example, Helv. Chim. Acta 1952, No. 35, page 1412): (XI) (VIII) R-L, R2, R3, R4, R5, Rg and R7 are as defined in claim 8.

The diesters of the formula (IX) can be prepared, for example, by reacting the brominated aromatic compounds (IX) with a triphosphorous ester (XII). Reactions of this type are described, for example, in DE-C-1810431.

The phosphonous esters (X) can be obtained, for example, by reacting a phosphorus dichloride (VIII) with an alcohol: The brominated aromatic compounds (XI) are obtained by the bromination reactions of the prior art, for example, by reacting alkoxylated aromatic compounds with N-bromosuccinimide or bromine / acetic acid.

The acid chlorides of the formula (VI) are generally prepared by methods known from the prior art. The preparation of the compounds of the formulas II and III are generally known, and some of the compounds are commercially available. The preparation of the oligomeric compounds of the formula II, for example, is described in EP-A-161 463. A description of the preparation of the compounds of the formula III can be found, for example, in EP-A-209 831. The preparation of the compounds of the formula IV is given, for example, in EP-A-3002 or EP-A-284 561. In addition, some compounds of the formula IV are commercially available. Examples of novel compounds are: bis (2,4,6-trimethylbenzoyl) -2,5-disopropylphenylphosphine oxide; bis (2,4,6-trimethylbenzoyl) -2-methylphenylphosphine oxide; bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine oxide; bis (2,4,6-trimethylbenzoyl) -2,5-diethylphenylphosphine oxide; bis (2,4,6-trimethylbenzoyl) -2,3,5,6-tetramethylphenylphosphine oxide.

Novel photoinitiator mixtures were prepared, for example, by mixing, milling, melting or dissolving the individual components, making possible the use of liquid components as solvents for the respective combination standards. It is also possible, however, to combine the components in an inert solvent. Photoinitiator mixtures comprise, for example, from 2 to 90%, e.g. from 5 to 50%, from 5 to 40%, especially from 5 to 25%, of the compounds of the formula la and from 98 to 50%, v.gr. from 95 to 60%, especially from 95 to 75%, of the compounds of the formulas II, III and / or IV. Other mixtures which are of interest are those in which the proportion of compounds of the formula la in the mixture with the compounds of the formulas II and III and / or IV is from 30 to 70%. Preferred examples of compounds of the formulas II and III are 1-benzoylcyclohexanol, 2,2-dimethoxy, 1,2-diphenylethan-1-one and 1-benzoyl-1-hydroxy-1-methylethane. Examples of novel photoinitiator mixtures (combinations) are examples. 5% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 95% of 1-benzoyl-1-hydroxy-1-methylethane; 5% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 95% of 1-benzoylcyclohexanol; % bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 75% of 1-benzoylcyclohexanol; 25% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 75% of 1-benzoyl-1-hydroxy-1-methylethane; 25% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 75% 2,2-dimethoxy-1,2-diphenyletan-1-one oxide; 5% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 95% 2,2-dimethoxy-1,2-diphenyletan-1-one oxide; 25% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 75% of 4- (2-hydroxyethoxy) benzoyl-1-hydroxy-1-methylethane; 5% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 95% of 4- (2-hydroxyethoxy) benzoyl-l-hydroxy-l-m-ethylethane; 5% bis (2,4,6-trimethylbenzoyl) -2-5-diisopropylphenylphosphine oxide and 95% of 1-benzoylcyclohexanol; 5% bis (2,4,6-trimethylbenzoyl) -2-5-diisopropylphenylphosphine oxide and 95% of 1-benzoyl-1-hydroxy-1-ethylethane; 25% bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide and 75% of 1-benzoylcyclohexanol; % bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide and 75% 1-benzoyl-1-hydroxy-1-methylethane oxide; 5% bis (2,4,6-trimethylbenzoyl) -4-tert-butyl-2,6-dimethylphenylphosphine oxide and 95% of 1-benzoylcyclohexanol; 5% bis (2,4,6-trimethylbenzoyl) -4-tert-butyl-2,6-dimethylphenylphosphine oxide and 95% of 1-benzoyl-l-hydroxy-1-methylethane; 25% bis (2, 4,6-trimethylbenzoyl) -4-tert-butyl-2,6-dimethylphenylphosphine oxide and 75% of 1-benzoylcyclohexanol; 25% bis (2,4,6-trimethylbenzoyl) -4-tert-butyl-2,6-dimethylphenylphosphine oxide and 75% of 1-benzoyl-1-hydroxy-1-methylethane; 5% bis (2,6-dimethylbenzoyl) phenylphosphine oxide and 95% of 1-benzoyl-1-hydroxy-1-methylethane; 5% bis (2,6-dimethylbenzoyl) phenylphosphine oxide and 95% of 1-benzoylcyclohexanol; 25% bis (2,6-dimethylbenzoyl) phenylphosphine oxide and 75% of 1-benzoyl-1-hydroxy-1-methylethane; 25% bis (2,6-dimethylbenzoyl) phenylphosphine oxide and 75% of 1-benzoylcyclohexanol; 5% bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide and 95% 1-benzoylcyclohexanol oxide; % bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide and 95% 1-benzoyl-1-hydroxy-1-methylethane oxide; 25% bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide and 75% 1-benzoylcyclohexanol oxide; 25% bis (2,4,6-trimethylbenzoyl) -2,5-di-ethylphenylphosphine oxide and 75% of 1-benzoyl-1-hydroxy-1-ethylethane oxide; 25% bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide and 75% 2,2-dimethoxy-1,2-diphenyletan-1-one oxide; 25% bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphelosphine oxide and 75% of 4- (2-hydroxyethoxy) benzoyl-l-hydroxy-1-methylethane. Photoinitiator mixtures of particular interest are those obtained by dissolving bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide in a liquid hydroxy ketone compound. Preferably more than two components, especially 3 are used in the mixture. The three component mixture is conveniently prepared by mixing the respective constituents and heating the mixture slightly, for example at 50-60 ° C. The invention further provides mixtures of photoinitiators comprising at least one compound of the formula la and two compounds of the formula II.

Preferably, for example, mixtures of 3 components comprising 25% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide are provided; 70% of 1-benzoylcyclohexanol and 5% of 1-benzoyl-l-hydroxy-1-methylethane; or 25% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 60% 1-benzoylcyclohexanol and 15% 1-benzoyl-1-hydroxy-1-methylethane; or 25% of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 50% of 1-benzoylcyclohexanol and 25% of 1-benzoyl-1-hydroxy-1-methylethane. Preferably, the compounds of the formula I are provided in which R3, R4, R5, Rg and R7 are hydrogen, alkyl of 1 to 8 carbon atoms, phenyl, allyl, benzyl, cyclohexyl or chloro. In addition, the advantageous compounds of formula I and A are those in which R 3, R 4, R 5 are hydrogen, alkyl of 1 to 4 carbon atoms, especially methyl or phenyl. The compounds of the formula I and that wherein Rg and R7 are hydrogen or alkyl of 1 to 4 carbon atoms, especially methyl, are carefully extracted.

Preferably, in particular those compounds of the formula I and wherein R2 is hydrogen or alkyl of 1 to 4 carbon atoms are provided. Preferably, the compounds of the formula I and the one in which R ^ is methyl are extended. Preferably, in a similar manner, compounds of the formula I and wherein R1 and R2 are the same are provided. Also of interest are the compounds of Formulas I and wherein Rj and R2 are alkyl of 1 to 4 carbon atoms, especially methyl. In novel photoinitiator mixtures, preference is given to the use of compounds of the formula la, wherein R3, R4, R5, Rg and R7 are hydrogen. Additional compounds of the formula that are preferably used are those in which R3 and Rg are methyl. Other mixtures of photoinitiators of interest are those in which the compounds of the formula la, R3, R4, R5, Rg and R7 are hydrogen. Additional preferred photoinitiator mixtures are those comprising compounds of formula la and compounds of formula II wherein Rg is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, -OCH2CH2OR12 'a group independently one of the other are hydrogen, alkyl of 1 to 3 carbon atoms, phenyl, alkoxy of 1 to 12 carbon atoms or -0- (CH2CH2?) g-alkyl of 1 to 8 carbon atoms, where q is a number from 1 to 10 or Rg and RiO 'Together with the carbon atom to which they are attached, they form a cyclohexyl ring; R ^ is hydroxyl, alkoxy of 1 to 4 carbon atoms -0- (CH2-CH2?) Q-alkyl of 1 to 8 carbon atoms; and / or compounds of the formula III and / or compounds of the formula IV wherein R ^ is hydrogen or methoxy; R ^ g is methoxy, methylthio, morpholino or a group of the formula IVa, R20 is methyl or ethyl; R22 and R23 are the same and are methyl or, together with the nitrogen atom to which they are bound, they form a saturated five or six membered ring which can be interrupted by -0-; and R25 is hydrogen or alkyl of 1 to 8 carbon atoms. Similarly, there is interest in a photoinitiator mixture comprising compounds of the formula II wherein Rg is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or -0CH2CH20Ri2; Rg and Ri0 'independently of one another are hydrogen, phenyl, methyl, or methoxy, or Rg and R ^ Q together with the carbon atom to which they are attached, form a cyclohexyl ring; and R- ^ is hydroxyl or methoxy. Other preferred photoinitiator mixtures are those wherein the compound of the formula III is benzophenone, 2,4,6-trimethylphenyl phenyl ketone, 4-methylphenyl phenyl ketone, (3-methyl-4-methoxyphenyl 3-methylphenyl ketone, 4- ( 4-methylphenylthio) phenyl phenyl ketone, 2-carboxyphenyl phenyl ketone or 4- (2-hydroxyethoxy) phenyl phenyl ketone are also preferred photoinitiator mixtures wherein the compound of formula II is 1-benzoyl-1-hydroxy-1-phenyl. Methylethane, 1-benzoylcyclohexanol, 4- [(2-hydroxyethoxy) benzoyl] -l-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -l-hydroxy-1-methylethane or 2, 2-dimethoxy-2, -difeniletan-1-one The preference is extended to photoinitiator mixtures wherein the compound of the formula IV is l- (3,4-dimethoxybenzoyl) -l-benzyl-l-morpholinopropane, 1- (4-methylthiobenzoyl) - 1-methyl-1-morpholinoethane, 1- (4-morpholinobenzoyl) -l-benzyl-1-dimethylaminopropane or 3,6-bis (2-methyl-2-morpholinopropan-1-one) -9-octylcarbazole. are the photoinitiator mixtures where the c The compound of the formula is bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide, bis [2,6-dimethyl-4- (2-methylpropyl) -benzoyl] -phenylphosphine oxide, bis (2,6-dimethylbenzoyl) phenylphosphine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide. The novel photoinitiator mixtures comprise, as the compound of the formula, preferably the bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. Mixtures of benzophenone are preferably provided. Preferably, mixtures comprising compounds of the formula II are provided. Also of interest are the photoinitiator mixtures comprising, as the compound of the formula, bis (2,4,6-trimethylbenzoyl) -2,5-diisopropyl-phenylphosphine oxide; bis (2,4,6-trimethylbenzoyl) -2-methylphenylphosphine oxide; bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine oxide; bis (2,4,6-trimethylbenzoyl) -2,5-diethylphenylphosphine oxide; and / or bis (2,4,6-trimethylbenzoyl) -2,3,5,6-tetramethylphenylphosphine oxide. Particular preference is given to a photoinitiator mixture comprising 25% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 75% 1-benzoylcyclohexanol oxide. Similarly, a photoinitiator mixture comprising 25% of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 75% of 1-benzoyl-1-hydroxy-1-methylethane is preferred. Also of interest are the photoinitiator mixtures comprising two or more compounds of the formula la or mixtures of compounds of the formula la with other bisacylphosphine oxides and / or monoacylphosphine oxide and compounds of the formula II and / or III, for example a combination of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (1,4,4-trimethylpentyl) phosphine oxide, 1-benzoylcyclohexanol or, for example, bis (2,4,6-trimethylbenzoyl) phenylphosphine, bis (2,6-dimethoxybenzoyl) (1,4,4-trimethylpentyl) phosphine oxide and 1-benzoyl-1-hydroxy-1-methylethane or, for example, oxide of bis (2,4,6-trimethylbenzoyl) -phenylphosphine, bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide, 1-benzoyl-l-hydroxy-1-methylethane and / or 1-benzoyl -l-hydroxy-1-methylethane, of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-benzoyl-1-hydroxyl-1-methylethane and / or 1 -benzoyl-l-hydroxy-l-methylethane, or bis (2,4,6) oxide -trimethylbenzoyl) -2,4-dipentaxyphenylphosphine, 1-benzoyl-1-hydroxy-1-methylethane and / or 1-benzoyl-1-hydroxy-1-ethylethane. According to the invention, the compounds of the formula I and the mixtures (combinations) of the compounds of the formula la with the compounds of the formula II and / or III and / or IV can be used as photoinitiators for the photopolymerization of compounds ethylenically unsaturated and mixtures including such compounds.

This use can also be practiced in combination with other additives. Therefore, the invention also provides photopolymerizable compositions comprising (a) at least one ethylenically unsaturated photopolymerizable compound and (b) as photoinitiator, at least one compound of formula I or a photoinitiator mixture as described above. , it being possible for the composition to contain not only component (b) but also other additives. The unsaturated compounds may contain one or more double olefinic ligatures. They may be of lower molecular mass (monomeric) or of relatively high molecular mass (oligomeric). Examples of monomers containing a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl- or 2-hydroxyethyl acrylate, isobornyl acrylate, or methyl or ethyl methacrylate. Silicone acrylates are also of interest. Additional examples include acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamides, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl and halo-styrenes, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride. . Examples of monomers containing two or more double bonds are the diacrylates of ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol and bisphenol-A, 4,4'-bis (2-acryloyloxyethoxy) diphenylpropane, tri-ethylolpropane triacrylate, triacrylate or pentaerythritol tetracrylate , vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate and tris (2-acryloylethyl) isocyanurate. Examples of polyunsaturated (oligomeric) compounds of relatively high molecular weight are acrylic epoxy resins and polyethers, polyurethanes and polyesters which are acrylated or which contain vinyl ether groups or epoxy groups. Additional examples of unsaturated oligomers are unsaturated polyester resins which are generally prepared from maleic acid, phthalic acid, and one or more diols and have molecular weights from about 500 to 3000. In addition: it is also possible to use vinyl ether monomers and ether oligomers vinyl and also maleate-terminated oligomers that have main chains of polyester, polyurethane, polyether, polyvinyl ether and epoxy. The combinations of oligomers carrying vinyl ether groups and polymers as described in WO 90/01512 are particularly suitable. However, vinyl ether copolymers and functionalized maleic acid monomers are also suitable. Said unsaturated oligomers can also be referred to as prepolymers. Examples of particularly suitable compounds are esters of ethylenically unsaturated carboxylic acids and polyols of polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups, for example. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, copolymers of butadiene and polybutadiene, copolymers of isoprene and polyisoprene, polymers and copolymers containing (meth) acrylic groups in the side chains, and mixtures of one or more of said polymers. Examples of unsaturated carboxylic acids are acrylic, methacrylic, crotonic, itaconic and cinnamic acids, and unsaturated fatty acids such as linolenic acid and oleic acid. Acrylic acid and methacrylic acid are preferred. Suitable polyols are aromatic polyols and, in particular, aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) propane, and also novolacs and resoles. Examples of polyepoxides are those based on the aforementioned polyols, especially on the aromatic polyols and epichlorohydrin. Other suitable polyols include polymers and copolymers containing hydroxyl groups in the polymer chain or in the side groups, for example polyvinyl alcohol and copolymers thereof, or hydroxyalkyl polymethacrylates or their copolymers. Additional suitable polyols are oligoesters containing hydroxyl-terminated groups. Examples of aliphatic and cycloaliphatic polyols are alkylene diols, preferably they are of 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 glycols with molecular weights preferably from 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol , tris (ß-hydroxyethyl) amine, trimethylolethane, tri-ethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. The polyols can be partially or completely esterified by means of one or more unsaturated carboxylic acids, wherein the free hydroxyl groups in the partial esters can be modified, for example etherified or esterified with other carboxylic acids. Examples of esters are: Trimethylolpropane triacrylate, triacrylate etiloletano tri, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, dimethacrylate tetrametilengliclol, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, diacrylate pentaerititol, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, octaacrylate tripentaerythritol, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octametracrilato, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, butanediol diacrylate, 1,3- , 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol tetramethyl methacrylate itol, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol di- and triacrylate, 1,4-cyclohexane diacrylate, bisacrylates and polyethylene glycol bis methacrylates of molecular weight 200 to 1500, or mixtures of equals . The additional suitable components (a) are the amides of identical or different unsaturated carboxylic acids, aliphatic and cycloaliphatic, aromatic polyamides, preferably having from 2 to 6, in particular from 2 to 4, amino groups. Examples of such polyamines are ethylene diamine, 1,2- or 1,3-propylene diamine, 1,2-, 1,3-, or 1,4-butylene diamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine. , 1,4-diaminocyclohexane, isophorone diamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di (β-aminoethoxy) - or di- (β-aminopropoxy) ethane. Suitable additional polyamides are polymers and copolymers which may contain additional amino groups in the side chain, and oligoamides containing amino end groups. Examples of unsaturated amines of this type are: methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminotrismethacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylamidoethyl methacrylate and N - [(β-hydroxyethoxy) ethyl] acrylamide. Suitable polyesters and unsaturated polyamides are derivatives, for example, of maleic acid and diols or diamines. Some of the maleic acids can be replaced by other dicarboxylic acids. These can be used together with ethylenically unsaturated comonomers, for example styrene. Polyesters and polyamides can also be derived from dicarboxylic acids and from ethylenically unsaturated diols or diamines, especially from relatively long chain compounds containing, for example, from 6 to 20 carbon atoms. Examples of polyurethanes are those constructed of saturated or unsaturated diisocyanates and saturated and / or unsaturated diols. The polybutadiene and the polyisoprene as well as the copolymers thereof are known. Examples of suitable comonomers are: olefins such as ethylene, propene, butene, hexene, (meth) acrylates, acrylonitrile, styrene and vinyl chloride. Polymers containing (meth) acrylate groups in the side chain are also known. These may be, for example, products of the reaction of epoxy resins based on novolac with (meth) acrylic acid, homopolymers or copolymers of vinyl alcohol or hydroxyalkyl derivatives thereof which have been esterified using (et) acrylic acid, or homopolymers and copolymers of (meth) acrylates which have been esterified using hydroxyalkyl (meth) acrylates. The photopolymerizable compounds can be used alone or in any of the desired mixtures. They are preferably provided to mixtures of polyol (meth) acrylates. It is also possible to add binders to novel compositions, which is particularly convenient if the photopolymerizable compounds are liquid or viscous substances. The amount of binder can be, for example, from 5 to 95% by weight, preferably from 10 to 90% by weight and, in particular, from 40 to 90% by weight, based on the total solids content. The binder is selected depending on the field of use and the properties required therefor, such as ease of development in aqueous and organic solvent systems, adhesion of substrates, and sensitivity to oxygen. Examples of suitable binders are polymers having a molecular weight of about 5,000 to 2,000,000, preferably 10,000 to 1,000,000. Examples of homo and copolymer acrylates and methacrylates are, for example, copolymers of methacrylic acid / ethyl acrylate / methyl methacrylate, poly (alkyl methacrylate), poly (alkyl acrylates); cellulose esters and cellulose ethers, such as cellulose acetate, cellulose acetate butyrate, methylcellulose, ethylcellulose, polyvinylbutyral, polyvinylformal, cyclized rubber, polyether such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, copolymers of vinyl chloride / vinylidene chloride, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly (vinyl acetate / ethylene ), polymers such as 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 in admixture with non-photopolymerizable film-forming components. These can be, for example, physically dried polymers or their solutions in organic solvents, for example cellulose acetobutyrate or nitrocellulose. However, they can also be chemically curable or heat-curable resins, for example polyisocyanates, polyepoxides or melamine resins. The additional use of heat-curable resins is important for use in so-called hybrid systems, which are light-cured in a first stage and are interlaced by subsequent heat treatment in a second stage. Photopolymerizable mixtures may contain various additives in addition to the photoinitiator. Examples of these are thermal inhibitors, with which it is intended to avoid premature polymerization, examples being hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol or sterically hindered phenols, such as 2,6 (di (tert-butyl) - p-cresol The shelf life in the dark can be increased, for example, by using copper compounds, such as copper naphthenate, copper stearate or copper octoate, phosphorus compounds, for example triphenylphosphine, tributylphosphine, triethyl phosphite , triphenyl phosphite or tribenzyl phosphite, quaternary ammonium compounds, such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, such as N-diethylhydroxylamine, so that no atmospheric oxygen enters the polymerization can be added substances similar to wax like paraffin, these migrate to the surface at the beginning of the polymerization due to their low solubility in the polymer, and form a transparent surface layer that prevents the entry of air. In a similar way it is possible to apply an oxygen barrier layer. The light stabilizers that can be added are ultraviolet ray absorbers, for example those of the hydroxyl nylbenzotriazole, hydroxy-phenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type. It is possible to use such compounds or their mixtures individually, with or without the use of spherically hindered amines (HALS). Examples of such light stabilizers and ultraviolet ray absorbers are 1. 2- (2'-hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5 '-di-butyl tertiary 2' -hydroxyphenyl) benzotriazole, 2- (5'-tertiary butyl 2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1, 1,3, 3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-tertiary dibutyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tertiary butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-secondary butyl-5 '-butyl tertiary-2'-hydroxy-5'-phenyl) -5-benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) -benzotriazole, 2- (3 ', 5', -di-tertiary amyl-2 '-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole, a mixture of 2- ( 3 '-tertiary butyl-2' -hydroxy-5 '- (2-octyloxycarbonyl-ethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tertiary butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] - '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tertiary butyl-2 '-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tertiary butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) ) phenyl) -benzotriazole, 2- (3 '-butyl tertiary-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3 '-butyl tertiary-5' - [2- (2- ethylhexyloxy) carbonylethyl] -2 '-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl)) benzotriazole, and 2- (3'-tertiary butyl-2'-hydroxy-5') - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the transesterification product of 2- [3'-tertiary butyl-5 '- (2-methoxy-carbonylethyl) -2'-hydroxyphenyl] -benzotriazole with polyethylene glycol 300; [R-CH2CH2 ~ C00 (CH2) 3] 2 wherein R = 3 '-butyl tertiary-4' -hydroxy-5'-2H-benzotriazol-2-yl-phenyl. 2 _.__ .. 2-Hydr xibenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2' derivatives. -hydroxy '4,4'-dimethoxy. 3_ .. Acid esters. "Substituted or unsubstituted benzoic acid, for example tertiary phenyl-4-butyl phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl-resorcinol, bis (4-butylbenzoyl-tertiary) -resorcinol, benzoylresorcinol, , Tertiary 2,4-di-butylphenyl-tert-butyl-4-hydroxybenzoate, tertiary 3,5-di-butyl-4-hydroxybenzoate hexadecyl, tert-3,5-di-tertiary butyl-octadecyl-4-hydroxybenzoate , Tertiary 3,5-di-butyl-4-hydroxybenzoate of 2-methyl-4,6-di-tertiary butylphenyl. 4. Acrylates, for example ac: iano-β, ethyl β-diphenylacrylate or α-cyano-β, isooctyl β-diphenylacrylate, methyl a-carbomethoxycinnamate, α-cyano-β-methyl-p-methoxy-cinnamate methyl or α-cyano-β-methyl-p-methoxycinnamate, butyl, methyl a-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline. 5. Sterically hindered amines, for example bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2, 2,6,6-tetramethylpiperidyl succinate, bis (l, 2,2,6,6-sebacate. -pentamethylpiperidyl), n-butyl 3,5-di-butyl-tertiary-4-hydroxybenzymalonate of bis (1,2,6,6-pentamethylpiperidyl), the condensate of l-hydroxyethyl-2,2,6,6 -tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-octyl tertiary-2,6-dichloro-l, 3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrile triacetate, tetrakis (2,2,6,6-tetramethyl) 1,2,3,4-butanetetraoate -4-piperidyl), 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, 2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-butylbenzyl tertiary) malonate, 3 -n-oct L-7,7,9,9-tetramethyl-l, 3,8-triazaspiro [4.5] decan-2,4-dione, bis (l-octyloxy-2,2,6-sebacate , 6-tetramethylpiperidyl, bis (l-octyloxy-2,2,6,6-tetramethylpiperidyl succinate, the condensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidii) hexamethylenediamine and -morpholino-2,6-dichloro-l, 3,5-triaz.Lna, the condensate of 2-chloro-, 6- (di) 4-n-butylamino-2, 2,6,6-tetramethylpiperidyl) -1 , 3,5-triazine yl, 2-bis (3-aminopropylamino) ethane, the condensate of 2-chloro-4,6-di (4-n-butylamino-l, 2,2,6,6-pentamethylpiperidyl) - l, 3,5-triazine yl, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-l, 3,8-triazaspirot4.5; 2,4-dione, 3-dodecyl-l- (2, 2, 6, 6-tetramethi-4-piperidi1) pyrrolidin-2, 5-dione, 3-dodecyl-1- (1,2,2,6, 6-pentamethi-4-piperidi1) pyrrolidin-2, 5-dione. 6. Oxala idas, for example 4,4-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2 '-dioctyloxy-5,5' -di-butyloxyanilide tertiary, 2,2'-didodecyloxy-5, 5-di-tertiary- tertiary butyloxyanilide, 2-ethoxy-2'-ethyloxyanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tertiary butyl-2'-ethyloxyanilide and its mixture with 2-ethoxy-2'-ethyl -5, tertiary-butyl-tertiary butyloxyanilide and mixtures of o- and p-methoxy and o-and disubstituted p-ethoxy-oxanilides. 7. 2- (2-Hydroxyphenyl) -l, 3, 5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -l, 3,5-triazine, 2- (2- hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -l, 3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -l, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -l, 3,5-triazine, 2- (2-hydroxy-4) -octyloxyphenyl) -4,6-bis (4-methylphenyl) -l, 3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -l, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4, 6-bis (2,4-dimethylphenyl) -l, 3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) -phenyl] -4,6-bis (2, 4-dimethylphenyl) -l, 3,5-triazine, 2- [4-dodecyl / tridecyloxy- (2-hydroxypropyl) -oxy-2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine. 8. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-dihydro) phosphite. tertiary butylphenyl), diisodecyl pentaerythritol diphosphite, bis (2,4-di-butylphenyl tertiary pentaerythritol) diphosphite, bis (2,6-di-tertiary butyl-4-methylphenyl) pentaerythritol diphosphite, bisisodecyloxypentaerythritol diphosphite, diphosphite bis (2,4-di-tertiary butyl-6-methylphenyl) pentaerythritol, bis (2,4,6-tri-tertiary butylphenyl) pentaerythritol diphosphite, tristearyl sulfite triphosphite, tetra-4,4'-diphenylene diphosphonate (2) , Tertiary 4-di-butylphenyl), 6-isooctyloxy-2,4,8,10-tert-butyl-tertiary-12H-dibenzo [d, g] -1,3, 2-dioxaphosphocin, 6-fluoro-2,4 , 8,10-tert-butyl-tertiary-12-methyl-dibenzo [g, d] -l, 3,2-dioxaphosphocin, bis (2,4-di-tertiary butyl-6-methylphenyl) methylphosphite, bis ethylphosphite (2,4-di- tertiary butyl-6-methylphenyl). Therefore, the invention also provides photopolymerizable compositions comprising as initiator at least one compound of formula I, or a mixture of photoinitiator as described above, and an ultraviolet light absorber of the hydroxyphenyl-s class. triazines and / or hydroxyphenylbenzotriazoles and / or sterically hindered amines based on 2,2,6,6-tetramethylpiperidines. Preferably, a composition comprising a mixture of photoinitiating compounds of the formulas la, especially bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and compounds of the formula II, especially 1-benzoylcyclohexanol and 1-benzoyl-1 is provided. -hydroxy-methylethane, and a mixture of 85% of 4,6-di (2,4-dimethylphenyl) -2- [2-hydroxy-4- (mixture of dodecyloxy and tridecyloxy) (2-hydroxy) propyl-3- oxyphenyl-1, 3,5-triazine and 15% l-mey-2-propanol as an ultraviolet light absorber. To accelerate the photopolymerization it is possible to add amines, for example triethanolamine, N-methyldiethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone. The action of the amines can be enhanced by the addition of aromatic ketones of the benzophenone type. If novel mixtures comprising the compounds of the formula II are used, the reactivity can be improved by the addition of amines. Examples of amines which can be used as oxygen scavengers are substituted N, N-dialkylanilines as described in EP-A-339 841. Additional accelerators, coinitiators and autooxidants are thiols, thioethers, disulfides and phosphines, as described by example in EP-A-438 123 and GB-A-2 180 358. The photopolymerization can also be accelerated by the addition of photosensitizers, which change or amplify the spectral sensitivity. These are, in particular, aromatic carbonyl compounds, such as benzophenone derivatives, thioxane derivatives, anthraquinone derivatives and 3-acylcoumarin derivatives, and also 3- (aroyl ethylene) thiazolines, as well as eosin dyes, and erythrosine. The curing process can be assisted, in particular, by the compositions that are pigmented (for example with titanium dioxide), and also by adding a component that forms free radicals under thermal conditions, for example an azo compound such as 2,2 '. azobis (4-mey-2,4-dimethylvaleronitrile) untriazene, a diazoic sulphide, a pentazadiene or a peroxy compound, such as a hydroperoxide or peroxycarbonate, for example t-butyl hydroperoxide, as described in EP-A 245 639 The novel compositions may also include a photon-reducing dye, for example dyes xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin or acridine, and / or a trihalogenomethyl compound that can be dissociated by radiation. Similar compositions are described, for example in EP-A-445 624. Other conventional additives are - depending on the intended application - fluorescent whitening agents, fillers, pigments, dyes, wetting agents or leveling aids. The pigmented and thickened coatings can be adequately cured by the addition of glass microbeads or powdered glass fibers, as described for example in US-A-5, 013, 768. The invention also provides compositions that include as the component (a ) at least one photopolymerizable ethylenically unsaturated compound which is emulsified or dissolved in water. Dispersions of this type of aqueous curable radiation prepolymer are commercially available in various varieties. This term is taken to mean a dispersion of water and at least one prepolymer dispersed therein. The concentration of water in these systems is, for example, from 5 to 80% by weight, in particular from 30 to 60% by weight. The radiation-curable prepolymer or prepolymer mixture is present, for example, in concentrations from 95 to 20% by weight, in particular from 70 to 40% by weight. The total of the percentages indicated for the water and the prepolymers in these compositions is in each case 100, to which the auxiliaries and additives in various amounts are added depending on the intended application. The film-forming prepolymers, dispersed in water, curable with radiation, which are often also dissolved, are aqueous prepolymer dispersions, mono- or polyfunctional ethylenically unsaturated prepolymers which are known per se, can be initiated by means of free radicals and contain, for example from 0.01 to 1.0 moles of polymerizable double bonds per 100 g. of prepolymer, and have an average molecular weight of, for example, at least 400, in particular from 500 to 10,000. Depending on the intended application, however, prepolymers having high molecular weights may also be suitable. For example, use is made of polyesters containing polymerizable CC double bonds and having a maximum acid number of 10, polyethers containing polymerizable CC double bonds, hydroxyl-containing products of the reaction of a polyepoxide containing at least two groups epoxide per molecule with at least one α, β-ethylenically unsaturated carboxylic acid, polyurethane (meth) acrylates, and α, β-ethylenically unsaturated acrylic copolymers containing acrylic radicals are as described in EP-A-12 339 Mixtures of these prepolymers can also be used. Also suitable are the polymerizable prepolymers described in EP-A-33 896, which are thioether adducts of polymerizable prepolymers having an average molecular 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 CC polymerizable double bonds per 100 g of prepolymer. Other suitable aqueous dispersions based on specific alkyl (meth) acrylate prepolymers are described in EP-A-41 125; suitable water-dispersible, radiation-curable prepolymers made of urethane acrylates are described in DE-A-2 936 039. These dispersions of aqueous, radiation-curable prepolymers can include, as additional additives, dispersion aids, emulsifiers, antioxidants, light stabilizers, colorants, pigments, fillers, for example talc, gypsum, silica, rutile, carbon black, zinc oxide and iron oxides, reaction accelerators, leveling agents, lubricants, wetting agents, thickeners, tarnish agents, defoamers and other auxiliaries that are used in coating technology. Suitable auxiliaries of the dispersion are water-soluble organic compounds of high molecular mass containing polar groups, examples being polyvinyl alcohols, polyvinylpyrrolidone and cellulose ethers. The emulsifiers that can be used are nonionic emulsifiers and possibly also ionic emulsifiers. The photopolymerizable compositions comprise the photoinitiator or the photoinitiator mixture (b) advantageously in an amount of 0.05 to 15% by weight, preferably 0.1 to 5% by weight, based on the composition. When the novel f ininitiators are used in hybrid systems, use is made - in addition to the novel free radical hardeners - of cationic photoinitiators, for example benzoyl peroxide, iodinium or aromatic sulfonium salts, or iron (II) complex salts of cyclopentadienylarene . In certain cases it may be an advantage to use additional initiators in addition to novel compounds or photoinitiator mixtures. For example, the phosphine or phosphonium salts or, for example, compounds of the formula can be used as additives. (described in US-A-5,436,280 or JP-A-Hei 6 263809) where Q is S or O and Ri ', R2' R3 'and 4' are, for example, alkyl, alkenyl or aryl, and phosphites. Various photopolymerizable compositions, for example as printing inks, as clear coatings, as white paint, for example for wood or metal, as coating materials for substrates including paper, wood, metal and plastic, as curable coatings can be used for various purposes. daylight to mark buildings and roads, for photographic reproduction techniques, for holographic engraving materials, for the image engraving process or for the production of printing plates that can be developed using organic solvents or aqueous alkaline media, for the masking production for screen printing, as dental fill materials, as adhesives, as pressure sensitive adhesives, as laminating resins, as etching or permanent protection protectors, and as welding masking for electronic circuits, for production of three-dimensional items med uring block curing (ultraviolet cure of transparent molds) or by the stereolithographic process, as described, for example in US-A-4,575,330, for the preparation of mixed materials (e.g. styrenic polyesters, which may, if appropriate, contain glass fibers and other auxiliaries) and other thick-film compositions, for the coating or encapsulation of electronic components, or as coatings for optical fibers. The novel compounds and the photoinitiator mixtures can be used additionally as initiators of the emulsion polymerizations, as initiators of a polymerization for the fixation of ordered states of liquid crystalline monomers and oligomers, and as initiators for the fixation of dyes on organic materials.

Frequently, mixtures of a prepolymer with polyunsaturated monomers which also include an unsaturated monomer are used in the surface coatings. Here the prepolymer is mainly responsible for the properties of the coating film, and its variation allows the person skilled in the art to influence the properties of the cured film. The polyunsaturated monomeric functions having an entanglement agent render the coating film insoluble. The monounsaturated monomer acts as a reactive diluent by means of which the viscosity is reduced without the need to use a solvent. Unsaturated polyester resins are usually used in two component systems together with a monounsaturated monomer, preferably with styrene. For systems of a single photoprotective specific component, polymaleimides, polycalcones or polyimides are often used, as described in DE-A-2 308 830. Mixtures and novel compounds can also be used, for example , in coating materials which are organic and / or aqueous solvents or are solvent-free. The novel compounds and their mixtures can also be used as photoinitiating systems or free radical photoinitiators for coatings in radiation curable powders. The powder coatings can be based on resins and solid monomers containing reactive double bonds, for example maleates, vinyl ethers, acrylates, acrylamides and mixtures are the same. A radically free ultraviolet curable powder coating can be formulated by mixing unsaturated polyester resins with solid acrylamides (e.g. methyl methylacrylamidoglycolate) and a novel free radical photoinitiator, such formulations being as described, for example, in the document "Radiation Curing of Powder Coating "Conference Proceedings, Radtech Europe 1993 by M.Wittig and Th. Gohmann. Radically curable ultraviolet curable powder coatings can also be formulated, by mixing unsaturated polyester resins with solid acrylates, methacrylates or vinyl ethers and with a novel photoinitiator (or photoinitiator mixture). The powder coatings may also comprise binders as described, for example, in DE-A-42 28 514 and in EP-A-636 669. The ultraviolet curable powder coatings may additionally comprise white or colored pigments. For example, rutilotitanium dioxide can preferably be employed in concentrations of up to 50% by weight in order to give a cured powder coating with good hiding power. Normally the process comprises the electrostatic or tribostatic spraying of the powder onto the substrate, for example metal or wood, melting of the powder by heating and, after a uniform film has been formed, the radiation coating of the coating with visible light and / or ultraviolet, which is used, for example, in medium pressure mercury lamps, halide metal lamps or xenon lamps. A particular advantage of radiation-curable powder coatings over their heat-curable counterparts is that the time to flow after the melting of the powder particles can be retarded if desired in order to ensure the formation of a high-gloss coating. , uniform. In contrast to heat curable systems, radiation curable powder coatings can be formulated to melt at lower temperatures without the undesired effect of shortening their life time. For this reason, they are also suitable as coatings for heat sensitive substrates, for example wood or plastics. In addition to novel photoinitiators, powder coating formulations may also include ultraviolet light absorbers. Appropriate examples are listed on sections 1-8. The novel photocurable compositions are suitable, for example, as coating materials for substrates of all kinds, for example wood, textiles, paper, ceramics, glass, plastics such as polyesters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO2 for which it is intended to apply a protective layer or, by means of exposure of the image, to generate a reproduced image. The coating of the substrates can be carried out by applying a liquid composition, a solution or a suspension to the substrate. The selection of solvents and the concentration depend mainly on the type of composition and on the coating technique. The solvent must be inert, that is, it must not undergo any chemical reaction with the components and must be capable of being removed again, after coating, during drying. Examples of suitable solvents are ketones, ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, l-methoxy-2-propanol, 1,2- dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate. The solution is applied uniformly to a substrate by means of known coating techniques, for example by centrifugal coating, dip coating, knife coating, curtain coating, brushing, spraying, especially by electrostatic spraying, and reverse roller coating. It is also possible to apply the photosensitive layer to a flexible, temporary support and then coat the final substrate, for example a circuit board coated with copper, by transferring the layer through the lamination. The amount applied (thickness of the layer) and the nature of the substrate (layer support) are dependent on the desired field of application. The thickness range of the layer generally comprises values of about 0.1 μm to more than 100 μm. The novel radiation-sensitive compositions find application as negative protectors, which have very high sensitivity to light and are capable of being developed in an aqueous alkaline medium without swelling. They are suitable as photoprotectors for electronic articles (electroplating protectors, etching protectors, welding protectors), the production of printing plates, such as offset printing plates or forms of screen printing and / or the production of dyes , for use in chemical laminates or as microprotectors in the production of integrated circuits. The layer supports, and the processing conditions of the coated substrates, are justified as they vary.

The substrates used to record the photographic information include, for example, polyester films, polymer coated papers or cellulose acetate; the forms of offset printing substrates are specially treated with aluminum, the substrates for producing printed circuits are copper-clad laminates, and substrates for producing integrated circuits are silicon wafers. The thickness of the layer for photographic materials and forms for offset printing is generally from about 0.5 μm to 10 μm, while for printed circuits it is from 0.4 μm to about 2 μm. After coating the substrates, the solvent is removed, generally by drying, to leave a light-resistant coating on the substrate. The term "image" exposure includes both exposure through a photo masking comprising a predetermined pattern, for example a glide, exposure by means of a laser beam, which for example is moved under the control of the computer over the surface of the coated substrate and in this form produces an image, and irradiation with the electron beam controlled by computer. After the exposure of the image of the material and before the development, it may be advantageous to carry out the heat treatment for a short time. In this case only the exposed sections are thermally cured. The temperatures employed are generally 50-150 ° C, preferably 8 to 130 ° C; The period of thermal treatment is usually between 0.25 and 10 minutes. The photocurable composition can be further used in a process for producing printing plates or photoresists as described, for example, in DE-A-40 13 358. In said process, the composition is exposed for a short time to visible light with a length of wavelength of at least 400 nm, without masking, before the image is irradiated simultaneously or later. After the exposure and, if implemented, the heat treatment, the unexposed areas of the photosensitive coating are removed with a developer in a manner known per se. As already mentioned, the novel compositions can be developed with aqueous alkalies. Particularly suitable aqueous-alkaline developer solutions are aqueous solutions of tetraalkylammonium hydroxides or alkali metal silicates, phosphates, hydroxides and carbonates. If desired, minor amounts of wetting agents and / or organic solvents can be added to these solutions. Examples of typical organic solvents, which can be added to the developer liquids in small amounts, are cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of such solvents. Photo curing is of great importance for printing inks, since the drying time of the binder is a critical factor for the production regime of graphic products, and must be in the order of fractions of a second. Ultraviolet-curable inks are particularly important for screen printing. As mentioned previously, novel mixtures are also highly suitable for producing printing plates. This application uses, for example, mixtures of soluble linear polyamides or styrene / butadiene rubber and / or styrene / isoprene, polyacrylates or polymethylmethacrylates containing carboxyl groups, polyvinyl alcohols or urethane acrylates with photopolymerizable monomers, for example acrylamides and / or methacrylamides. , or acrylates and / or methacrylates, and a photoinitiator. The films and plates of these systems (wet or dry) are exposed on the negative (or positive) of the printed original, and the uncured parts are subsequently washed using an appropriate solvent. Another field where photocuring is used is the coating of metals, in the case, for example, of the coating of metal plates and tubes, cans or bottle caps, and the photocuring of polymeric coatings, for example of floor or wall coatings based on polyvinyl chloride. Examples of the photocuring of paper coatings are colorless label varnishes, engraved covers and book covers. Also of interest is the use of novel compounds for the curing of shaped articles made of composite compositions. The composite composition consists of a self-supporting matrix material, for example a fiberglass cloth, or alternatively, for example, plant fibers [see K.-P. Mieck, T. Reussmann in Kunststoffe 85 (1995), 366-370], which is impregnated with the photocuring formulation. The shaped parts comprise mixed compositions, when they are produced using the novel compounds, they obtain a high level of stability and mechanical strength. The novel compounds can also be used as photo-curing agents in molding, impregnation and coating compositions as described, for example, in EP-A-7086. Examples of such compositions are gel-coated resins, which are subject to stringent requirements with respect to cure activity and resistance to yellowing, and fiber-reinforced molding, for example light diffusion panels that are flat or have longitudinal or transverse corrugation . Techniques for producing such slurries, such as hand placement, sprinkling, centrifugal casting or filament winding, are described, for example, by PH Selden in "Glasfaservestárkte Kunststoffe", page 610, Springer Verlag Berlin-Heidelberg-New York 1967. Examples of articles that can be produced by these techniques are boats, fiber boards or agglomerated wood panels with a double-sided coating of fiberglass-reinforced plastic, tubes, containers, etc. Further examples of molding, impregnation and coating compositions are UP resin gel coatings for blends containing glass fibers (GRP), such as corrugated sheets and paper sheets. The paper sheets may be based on urea resins or melamine resins. Prior to the production of the laminate, the gel coating is produced on a support (for example a film). The novel photocurable compositions can also be used for resins for castings or for incrustation articles, for example electronic components, etc. The cure is carried out using mercury lamps of medium pressure as they are conventional in curing with ultraviolet rays. However, it is also of particular interest in lamps of less intensity, for example of type TL 40W / 03 or TL40W / 05. The intensity of these lamps corresponds approximately to that of sunlight. It is also possible to use direct sunlight for healing. An additional advantage is that the mixed composition can be removed from the light source within a partial cure, plastic state and can be shaped, with a total cure taking place subsequently. The use of photocurable compositions for Image formation and for the optical production of information carriers is also important. In such applications, as described previously, the layer (wet or dry) applied to the support is irradiated through photo-masking with ultraviolet or visible light, and the unexposed areas of the layer are removed by treatment with a solvent ( = developer). The application of the photocurable layer to the metal can be carried out by electrodeposition. The exposed areas are polymeric through the interlacing and therefore insoluble and remain on the support. Proper coloration produces visible images. When the support is a metallized layer, the metal can, after exposure and development, be etched away from non-exposed areas or reinforced by electroplating. In this way it is possible to produce printed and photo-protective electronic circuits. The photosensitivity of the novel compositions generally extends from the ultraviolet ray region (approximately 200 nm) to approximately 600 nm and therefore covers a very wide range. Adequate radiation is present, for example, in sunlight or in light from artificial light sources. Consequently, a large number of very different types of light sources are employed. Both points of sources and arrangements are adequate ("lamp coating"). Examples of carbon arc lamps, xenon arc lamps, mercury pressure lamps, low, medium and high, possibly doped with metal halide (metal-halogen lamps), metal stimulated microwave vapor lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, incandescent argon lamps, electronic flashes, photographic lamps, electron beams and X-rays, produced by means of synchrotrons or laser plasma. The distance between the lamp and the substrate that will be exposed according to the invention may vary depending on the intended application and the type and output of the lamp, and may be, for example, 2 cm to 150 cm. Laser light sources, for example, excimer lasers are especially suitable, such as krypton F-laser beams for exposure at 248 nm. Laser beams can also be used in the visible region. In this case, the sensitivity to light of novel materials is very advantageous. By means of this method it is possible to produce printed circuits in the electronics industry, lithographic offset printing plates or relief printing plates, and also materials for recording the photographic image. The invention further provides for the use of the composition described above the preparation of coating materials, printing inks, printing plates, dental compositions, protective materials and as material for recording the image, especially for holographic recordings. The invention further provides a coated substrate which is coated on at least one surface, with a composition as described above, and provides a process for the photographic production of relief images, wherein a coated substrate is subjected to image exposure and then the unexposed portions are removed with a solvent. The exposure of the image in this case can take place through a masking or using a controlled laser beam (without a masking). Therefore the invention also provides a process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises the irradiation of a composition as described above, with light in the range of 200 to 600 nm. The compounds of formulas I and II are photosensitive solids, which are generally yellow, and which are soluble, for example, in esters, aromatics, alcohols and chlorinated hydrocarbons. Mixtures of the novel photoinitiator (combinations) are of good solubility in the substrate that is going to be cured. In this context, the solubility of the mixtures in the substrate to be cured is generally better than the solubility of the individual components. In the mixture, any component acts as a solubilizer for the others. When curing is carried out with novel mixtures, an optimum ratio can be obtained between curing the substrate surface and curing it. The photoinitiator mixtures are reactive, and the lower yellowing values can be achieved during the course of the cure. The following examples illustrate the invention in more detail. The parts and percentages, as in the remainder of the description and in the claims are given by weight unless othee indicated. Example 1: Preparation of bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine (a) 4-methylphenylethylphosphonate oxide in a Hickraann apparatus, 51.3 g of 4-bromotoluene were heated with 3.9 g. of nickel (II) chloride at 160 ° C. 74.8 g of triethyl phosphite were added dropwise over the course of one hour.The reaction mixture was then heated to 160 ° C. for 2 hours. 22 g of ethyl bromide, distillation at 90'C / IO "2 mbar gave 38.6 g. of 4-methylphenyldiethylphosphonate. (b) 4-Methylphenylphosphine were placed in 180 ml. of dry diethyl ether 8.23 g. of lithium aluminum hydride, and 16.43 g were added at 10 ° C. of 4-methylphenyldiethylphosphonate. The suspension was stirred at room temperature for 13 hours and then carefully washed with 8 ml. of water at 0 * C and 5ßC, and hydrolyzed with 8 g. of a 15% NaOH solution and 24 ml. of water, to give a thick white precipitate. This precipitate was filtered under argon and washed with 50 ml. of ether, and the solvent was distilled under argon, to give 9.0 g. of 4-methylphenylphosphine which was used without further purification for the preparation of the next step. (c) Bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine It was cooled to -10 ° C. a solution of 16.2 g. of diisopropylamine in 50 ml. of tetrahydrofuran (THF). 100 ml were added dropwise. of butyl lithium in hexane (1.6 M). Then, 9.0 g were added at -40 ° C. of 4-ethylphenylphosphine and, subsequently, a solution of 29.22 g of 2, 6-trimethylbenzoyl chloride in 150 ml. of tetrahydrofuran. The solution was stirred for 1.5 hours and then the solvent was removed under reduced pressure, to give 28.0 g. of bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine as a yellow powder. (d) Bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine oxide 28.0 g was dissolved. of bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine in 100 ml. of toluene and the solution was heated to 50 ° C. 8.2 g were added dropwise over the course of one hour. of 30% hydrogen peroxide. The reaction mixture was then allowed to cool to room temperature, and the phases that were carried out were separated. The organic phase was washed with 30 ml. of water, 30 ml. of 10% sodium bicarbonate solution and water until neutral, then dried over magnesium sulfate, filtered and concentrated in vacuo to give 24.5 g. of a yellow oil. Recrystallization and column chromatography of petroleum ether gave 12 g. of the title product as yellow crystals with a melting point of 151-152ßC. Elemental analysis: calculated: C. 74.98% found: C: 74.90% H: 6.76% H: 6.75% Examples 2-9: The compounds of Examples 2 to 9 were obtained following the method described in Example 1 and using the appropriately substituted starting materials. The compounds and their physical data are given in the following Table 1. Table 1 * The variation d in the 31P-NMR spectrum is 7.50 ppm ** The variation 6 in the 31P-NMR spectrum is 14.95 ppm Example 10: Preparation and curing of a transparent coating A transparent coating curable with ultraviolet rays was prepared by mixing 99.5 Parts of RRoskydal 502 (= 66% unsaturated polyester resin and 34% styrene; Bayer) 0.5 parts of RByk 300 (= auxiliary leveling, Byk-Mallinckrodt). Two parts of a mixture of 95% of 1-benzoyl-1-hydroxy-1-methylethane and 5% of the photoinitiator of Example 8 were incorporated into this formulation. The coating material was applied to an agglomerated wood panel using a scalpel with a space of 200 μm and then cured. The curing was carried out by passing the sample on a conveyor belt moving at a speed of 5 m / min, below two medium pressure mercury lamps of the Fusion H type of 120 W / cm (Fusion Systems, USA) and Hanovia type 80 W / cm (Canrad-Hanovia, USA). The hardness of the Konig pendulum (DIN 53157) of the stain-proof coating is 52 seconds. Ejepp_lo_ll: Preparation and healing of a white paint A white paint curable with ultraviolet rays was prepared by mixing 67.5 parts of REbecryl 830 (Polyester acrylate from UCB, Belgium) 5.0 parts of 1,6-hexanediol diacrylate 2.5 parts of trimethylolpropane triacrylate and 25.0 parts of RR-TC2 (dioxide rutilotitanium, by Tioxide) Three parts of a 75% photoinitiator mixture of 1-benzoyl-1-hydroxy-1-methylethane and 25% of the photoinitiator of Example 8 were incorporated into this paint formulation. The paint was applied to a rolled panel coated with aluminum using a scalpel with a space of 100 μm, and exposed on a conveyor belt to a medium pressure mercury lamp of 80W / cm (Canrad-Hanovia, USA). The maximum speed of the web in which the fully cured and stain-proof coating was obtained is a measure of the reactivity of the photoinitiator mixture. A cured coating at a belt speed of 3 m / min has a Kónig pendulum hardness (DIN 53157) of 159 seconds. Example 12: Preparation and curing of a white paint Similarly, in each case, in the formulation described in Example 11, 3 parts of a 75% photoinitiator mixture of 1-benzoyl-1-hydroxy-cyclohexane were tested in each case. % of the photoinitiators of Examples 2, 4 and 7. The corresponding white paint coatings are similar to those cured at a band speed of 15 m / min. Example _ 13: Preparation and curing of a highly pigmented white paint. A white paint curable with ultraviolet rays was prepared by mixing 45 parts of REbecryl 830 3 parts of 1,6-hexanediol diacrylate 2 parts of trimethylolpropane triacrylate 50 parts of RR-TC2 (rutile titanium dioxide) Incorporated in this paint formulation 4 parts of a 75% photoinitiator mixture of 1-benzoyl-l-hydroxycyclohexane and 25% of the photoinitiator of Example 8. The paint was applied to rolled panels coated with aluminum using a scalpel with 150 μm of space and cured on a conveyor belt under two medium pressure mercury lamps of 80 W / cm (Aetek, USA). At a band speed of 10 m / min, a completely cured and stain-proof coating was obtained whose Kónig pendulum hardness (DIN 53157) is 85 seconds. 4 parts of a 75% photoinitiator mixture of 1-benzoyl-1-hydroxycyclohexane and 25% of the photoinitiator of Example 3 similarly provided a completely cured coating with a spot-proof surface at a band speed of 10 m / min, with a pendulum hardness of 79 seconds. Example 14: Curing of a laminar compound A formulation of 99 parts of RVestopal X7231 (unsaturated polyester from Hüls, Germany) and 1 part of a 75% photoinitiator mixture of benzyl dimethylketal and 25% of the photoinitiator of Example 8 was prepared. 4-layer sheet of a fiberglass mat (cut fiber material) and the above formulation were covered with a transparent Mylar film and subjected to firm compression. This assembly was then irradiated under 5 lamps of type TL40W / 03 (Philips) at a distance of 15 cm for 10 minutes. A stable mixed layer was obtained which had a Shore D hardness (according to DIN 53505, determined with a hardness tester by Otto Wolpert Werke, Ludwigshafen, Germany) of 65. Example 15: Preparation and curing of a clear coating containing Not me. They were mixed with 98 parts of an amino-containing polyether acrylate (RLaromer P084 F, BASF), 2 parts of a 45% benzophenone photoinitiator mixture, 45% of 1-benzoyl-1-hydroxy-cyclohexane and 10% of the Photoinitiator of Example 8. The coating material is applied to pressed wood panels using a scalpel with a 100 μm gap and cured * at a band speed of 10 m / min using two mercury lamps of medium pressure of 80 W / cm (Aetek, USA). The stain-proof coating has a Kónig pendulum hardness (DIN 53157) of 65 seconds. Example 16: Preparation and curing of a powder coating An ultraviolet curable powder coating was prepared from 56.0 parts of RZA 3125 (DSM, Holland) 11.0 parts of RZA 3126 (DSM, The Netherlands) 33.0 parts of RR-TC2 (rutile titanium dioxide) 1.0 parts of RResiflow PV5 (EHWorlee, Germany) 0.5 part of RWorlee Add 900 (EH Worlee, Germany) 3.0 parts of a 75% photoinitiator mixture of 4 (2-hydroxyethoxy) -benzoyl-1-hydroxy-1-methylethane and 25% of the photoinitiator of Example 8. All the components were mixed in an extruder at 80 ° C, to give a homogeneous white paint. After cooling, the solid mass was milled and sieved. The powder with a particle size of <90 μm was applied in a film thickness of 60-90 μm to an aluminum panel using an electrostatic spray method. The coated panel was heated at 125 ° C in an oven for 3 minutes. During this period, the powder melted and a homogeneous film formed. The film was irradiated while still hot, at a band speed of 7.5 m / min, under two mercury lamps of medium pressure of 80 W / cm. After irradiation for 30 minutes, a pendulum hardness K nig of 105 seconds was measured. Example ^ 17: A pastel colored paint was prepared by mixing 75.5 parts of Ebecryl® 830 (polyester acrylate oligomer) 9.0 parts of 1,6-hexanediol diacrylate (HDODA) 4.5 parts of trimethylolpropane triacrylate (TMPTA) To this paint were added 3% (3 parts) of a 75% photoinitiator mixture of benzyldimethyl ketal and 25% of the photoinitiator of Example 1. A 100 μm paint film was applied to a wooden panel and exposed, at a band speed of 3. m / min, under two medium pressure mercury lamps of ElOW / cm (Aetek, USA). A completely cured and stain-proof coating was obtained whose Kónig pendulum hardness (DIN 53157) is 115 seconds. EXAMPLE__18: A yellow paint was prepared from 83.0 parts of Ebecryl® 830 (polyester acrylate oligomer) 9.5 parts of 1,6-hexanediol diacrylate (HDODA) 4.0 parts of trimethylolpropane triacrylate (TMPTA) 3.0 parts of Irgazin® Gelb GLTN (yellow pigment). Three parts of the photoinitiator mixture of Example 17 were added to this paint. The paint was applied as described in Example 17 and exposed, at a band speed of 3 m / min, with a medium pressure mercury lamp. of 80 W / cm (Canrad-Hanovia, USA). The pendulum hardness of the complete and waterproof cured coating is 142 seconds. Example .19: Ultraviolet stabilization of a transparent coating: A transparent coating was prepared by mixing 99.5 parts of Roskydal® 502 (= 66% unsaturated polyester with 34% styrene, BAYER), and 0.5 part of BykR 300 (auxiliary leveling, Byk-Mallinckrodt) A mixture of three liquid components was prepared by heating a 75% photoinitiator mixture of 1-benzoyl-1-hydroxycyclohexane and 25% of the photoinitiator of Example 1 at 50 ° C and adding the same amount by weight of a mixture. 85% of 4,6-di (2,4-dimethyphenyl) -2- [2-hydroxy-4- (mixture of dodecyloxy and tridecyloxy) (2-hydroxy) propyl-3-oxyphenyl], 3,5- triazine and 15% l-methoxy-2-propanol. 4 parts of this liquid mixture were incorporated into the transparent coating. The coating was applied to wood (clear substrate) using a scalpel with a space of 150 μm and exposed at a band speed of 3 m / min, using two medium pressure mercury lamps of 80 W / cm. The hardness of the pendulum (PH) and the arousal indexes (YL) (in accordance with ASTMD 1925) were measured directly after curing and after 4 hours of subsequent exposure under TL fluorescent lamps of 20W / 05 (Philips) . The sample with the mixture of three liquid components can be easily cured and provides an adequate photoprotective action (UV stabilization), as shown by the data in Table 2.

Table 2 after healing 4 hours TL 20W / 05 Additives PH Yl PH Yl 4 mixing parts of 3 liquid components 88 9.8 134 9.5 Example 20: Incorporation of a liquid mixture into an aqueous pigmented formulation: A pigmented aqueous formulation was prepared by mixing the following components: 50 parts of Roskydal® 850 W (unsaturated polyester, BAYER) 50 parts of Laromer® PE 55 W (emulsion of an acrylate of polyester in water, BASF) 10 parts of titanium dioxide R-TC2 (rutile type) parts water The photoinitiator mixture of 75% of 1-benzoyl-l-hydroxycyclohexane and 25% of photoinitiator of Example 1 was liquefied at 50 ° C, and 3 parts of it were incorporated at room temperature in the above formulation, with agitation. The 150 μm thick coatings were applied to wood, dried at 80 ° C for 4 minutes and then exposed to 3 m / min under two medium pressure mercury lamps of 80 W / cm. The coating with the liquefied photoinitiator mixture gave a pendulum hess of 50 seconds, a yellowness index of 4.3 and brightness values (the measurement at angles of 20"and 60 °) of 75/87.

Claims (18)

1. CLAIMS l.A compound of formula I wherein R ^ is alkyl of 1 to 4 carbon atoms, R2 is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, and R3, R4, R5, R5 and R independently of each other are hydrogen, halogen, alkyl of 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, alkenyl of 2 to 12 carbon atoms, alkyl of 2 to 18 carbon atoms, which is interrupted by one or more oxygen atoms, or are alkyl of 1 to 4 carbon atoms substituted with phenyl, or are phenyl which is unsubstituted or is mono- or disubstituted by alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 carbon atoms, with the proviso that at least one of the radicals R3, R4, R5, R, and R7 is different from hydrogen and so that if R and R2 are methyl R3 and R6 is not methyl.
2. 2. A compound according to claim 1, wherein R3, R4, R5, Rg, and R7 are hydrogen, alkyl of 1 to 8 carbon atoms, phenyl, allyl, benzyl, cyclohexyl or chloro.
3. 3. A compound according to claim 1, wherein R3, R4, and R5 are hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
4. 4. A compound according to claim 1, wherein R ^ is methyl.
5. 5. A compound according to claim 1, wherein R ^ and R2 are the same.
6. 6. A photoinitiator mixture comprising at least one compound of the formula (Ia) wherein R is alkyl of 1 to 4 carbon atoms; R 2 is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; R3, R4 > R6 and R7 independently of one another are hydrogen, halogen, alkyl of 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, alkenyl of 2 to 12 carbon atoms, alkyl of 2 to 18 carbon atoms, which is interrupted by one or more oxygen atoms, or are alkyl of 1 to 4 carbon atoms substituted with phenyl, or are phenyl which is unsubstituted or is mono- or disubstituted by alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 atoms of carbon; and at least one compound of the formula (II). wherein R3 is hydrogen, alkyl of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, -OCH2CH2-OR12 'a group CH2 = where I is a number from 2 to 10 and A is a radical, R9 and R10 independently of one another are hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, alkoxy of 1 to 16 carbon atoms, OSiR 3R 4Ri4a or -0- (CH2CH2? ) q alkyl of 1 to 16 carbon atoms, where q is a number from 1 to 20, or R9 and R10 Together with the carbon atom to which they are attached form a cyclohexyl ring; ll is hydroxyl, alkoxy of 1 to 16 carbon atoms or -0 (CH2CH2?) qalkyl of 1 to 16 carbon atoms. where Rg RIQ and R ^ are not all simultaneously alkoxy 1 to 16 carbon atoms or -0 (CH2CH2?) Alkyl of 1 to 16 carbon atoms, Rl2 is hydrogen, alkyl of 1 to 8 carbon atoms O 0 -C-CH = CH2, -C-alkyl of 1 to 8 carbon atoms or and R13 'R14a and R14 independently of one another are alkyl of 1 to 4 carbon atoms or phenyl; and / or at least one compound of the formula (III) wherein R15 R15a 'R16 and R17 independently of one another are hydrogen, methyl, phenyl, methoxy, -COOH, phenyl substituted with alkyl of 1 to 4 carbon atoms or unsubstituted, or a group -OCH2CH2OR12 or -SCH2CH2OR2 wherein i2 it is as defined for formula II; and / or at least one compound of the formula (IV) wherein R13 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, halogen or a group N (R22Í2 'R9 is as defined for R13 or it's the group wherein in each case the radical R s of formula IV and the radical R 3 of this group (IVa), together are a direct ligation, and the other radicals are as defined above; R20 is alkyl of 1 to 8 carbon atoms; R2? is hydrogen, -CH =: CHR24 or phenyl which is substituted or unsubstituted one to three times by alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen; or R20 and R21 together with the carbon atom to which they are attached form a cyclohexyl ring; R22 and R23 independently of one another are alkyl of 1 to 4 carbon atoms, or R22 and R23 together with the nitrogen atom to which they are bound form a saturated or unsaturated ring of 5 or 6 members which can be interrupted by -O- , -NH- or -N (CH3); R 24 is hydrogen or alkyl of 1 to 4 carbon atoms; and 25 is hydrogen or alkyl of 1 to 12 carbon atoms.
7. 7. A photoinitiator mixture according to claim 6, comprising compounds of the formula la and compounds of the formula II wherein R3 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, -OCH2CH2OR12 a group Rg and Rio independently of one another are hydrogen, alkyl of 1 to 3 carbon atoms, phenyl, alkoxy of 1 to 12 carbon atoms, or -0 (CH2CH2?) Q alkyl of 1 to 8 carbon atoms , where q is a number from 1 to 10, or Rg and Rig together with the carbon atom to which they are attached form a cyclohexyl ring; R ^ is hydroxy, alkoxy of 1 to 4 carbon atoms or -0 (CH2CH2O) q-alkyl of 1 to 8 carbon atoms; and / or compounds of the formula III, and / or compounds of the formula IV wherein R13 is hydrogen or methoxy, Rig is methoxy, methylthio, morpholino or a group of the formula IVa; R20 is methyl or ethyl, R22 and R23 are the same and are methyl or together with the nitrogen atom to which they join they form a saturated ring of 5 or 6 members which can be interrupted by -0-; and R25 is hydrogen or alkyl of 1 to 8 carbon atoms.
8. 8. A photoinitiator mixture according to claim 6, wherein the compound of formula III is benzophenone, 2,4-r6-trimethylphenyl phenyl ketone, 4-methylphenyl phenyl ketone, 3-methyl-4-methoxyphenyl 3-methylphenyl ketone. 4- (4-methylphenylthio) phenyl phenyl ketone, 2-carboxyphenyl phenyl ketone or 4- (2-hydroxyethoxy) phenyl phenyl ketone; the compound of formula II is 1-benzoyl-1-hydroxy-1-methylethane, 1-benzoylcyclohexanol, 4 - [(2-hydroethoxy) benzoyl] -l-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) 1 -hydroxy-1-methylethane or 2,2-dimethoxy-1, 2-diphenyletan-1-one; the compound of formula IV is l- (3,4-dimethoxybenzoyl) -1-benzyl-1-morpholinopropane, 1- (4-methylthiobenzoyl) -l-methyl-l-morpholinoethane, 1- (4-morpholinobenzoyl) -l -benzyl-1-dimethylaminopropane or 3,6-bis (2-methyl-2-morpholinopropan-1-one) -9-octylcarbazole; and the compound of the formula la is bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide, bis [2,6-dimethyl-4- (2-methylpropyl) benzoyl] phenylphosphine oxide, bis (2,6-dimethylbenzoyl) phenylphosphine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or bis (2,4,6-trimethylbenzoyl) -2,5-di-ethylphenylphosphine oxide.
9. 9. A photoinitiator mixture according to claim 6, comprising at least one compound of the formula la and two compounds of the formula II.
10. 10. A photoinitiator mixture comprising 25% bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 75% 1-benzoylcyclohexanol.
11. 11. A photopolymerizable composition comprising: (a) at least one photopolymerizable ethylenically unsaturated compound and (b) as photoinitiator, at least one compound of formula I according to claim 1, or a photoinitiator mixture in accordance with claim 6.
12. 12. A photopolymerizable composition according to claim 11, comprising as a photoinitiator at least one compound of the formula I according to claim 1 or a photoinitiator mixture according to any of claims 6-10. , and an ultraviolet light absorber of the class of hydroxyphenyl-s-triazine and / or sterically hindered hydroxyphenylbenzotriazoles and / or amines based on 2,2,6,6-tetramethylpiperidines.
13. 13. A process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, comprising the irradiation of a composition according to claim 11 with light in the range of 200 to 600 nm.
14. 14. The use of the compound of the formula I or a mixture of photoinitiator in accordance with the claim 6 for the photopolymerization of compounds containing ethylenically unsaturated double bonds.
15. 15. The use of a composition according to claim 11 for producing coating materials, printing inks, printing plates, dental compositions, protective materials and as material for image engraving, especially for holographic recordings.
16. 16. A process according to claim 13, for producing coating materials, printing inks, printing plates, dental compositions, protective materials and as material for image engraving especially for holographic recordings.
17. 17. A coated substrate which is coated on at least one surface with a composition according to claim 11.
18. 18. A method for the photographic production of relief images, wherein a substrate coated in accordance with claim 17, it is subjected to image exposure and then the unexposed areas are removed with a solvent. SUMMARY OXIDES OF ALKYLPHENYLBISACILPHOSPHINE AND MIXTURES OF PHOTOINICITER Compounds of the formula I wherein Ri is alkyl of 1 to 4 carbon atoms, R2 is hydrogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms and R3, R4, R5, R6, and R7, independently of another is hydrogen, halogen, alkyl of 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, alkenyl of 2 to 12 carbon atoms, alkyl of 2 to 18 carbon atoms, which is interrupted by one or more oxygen atoms, or are alkyl of 1 to 4 carbon atoms substituted with phenyl, or are phenyl which is unsubstituted or is mono- or disubstituted by alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 carbon atoms, with the proviso that at least one of the radicals R3, R4, R5, Rs and R7 are different from hydrogen and so, if R1 and R2 are methyl, R3 and R5 are not methyl, and mixtures of such compounds with α-hydroxyketones, benzophenones and a-amino ketones are suitable as photoinitiators.