CH691775A5 - Photopolymerisable composition - Google Patents

Abstract

A composition comprises: (a) polymerisable ethylenically unsaturated compound(s); and (b) compound(s) of formula (I) or (I') as unimolecular photoinitiator. - In the formulae, R1, R2 and R3 = phenyl or other aromatic hydrocarbon (optionally with heteroatom) optionally substituted 1-5 times by 1-20C alkyl (optionally substituted by OR6 or R7R8N), 2-20C alkyl which is interrupted by O, S(O)p or NR5, or are substituted by OR6, R6S(O)p, R6S(O)2O, R7R8N, R6OC(O), R7R8NC(O), R9C(O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P(O)q, CN and/or a group of formula (i)-(iv), or the R2 and R3 form bridges to produce structures of formula (II), (IIa) or (IIb) in which the aromatic rings are optionally substituted by 1-20C alkyl, 2-20C alkyl which is interrupted by O, S(O)p or NR5, or are substituted by OR6, R6S(O)p, R6S(O)2O, R7R8N, R6OC(O), R7R8NC(O), R9C(O), R9R10R11Si, halogen, R9R10P(O)q and/or R9R10R11Sn, provided that not more than two of R1, R2 and R3 are identical and either at least two of them are aromatic hydrocarbon radicals or phenyl radicals which are substituted in both ortho-positions or at least one of them is a sterically bulky aryl radical and the remainder are aromatic hydrocarbon radicals or phenyl radicals which are substituted in ortho-position(s); R1a = divalent aromatic hydrocarbon radical (optionally substituted by 1-6C alkyl, OR6, S(O)pR6, OS(O)2R6, NR8R7, C(O)OR6, C(O)NR8R7, C(O)R9, SiR9R10R11 or halogen) or phenyl-1-6C alkylene; R4 = phenyl or other aromatic hydrocarbon (optionally with heteroatom) optionally substituted 1-5 times by 1-20C alkyl (optionally substituted by OR6 or R7R8N), 2-20C alkyl which is interrupted by O, S(O)p or NR5, or are substituted by OR6, R6S(O)p, R6S(O)2O, R7R8N, R6OC(O), R7R8NC(O), R9C(O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P(O)q, CN and/or a group of formula (i)-(iv), or R4 = 1-20C alkyl, 2-20C alkyl which is interrupted by O, S(O)p or NR5, or is 2-20C alkyl which is interrupted by O, S(O)p and/or NR5 or is phenyl, other aromatic hydrocarbon, 1-20C alkyl, 3-12C cycloalkyl, 2-8C alkenyl, phenyl-1-6C alkyl or naphthyl-1-3C alkyl optionally substituted by OR6, R6S(O)p, R6S(O)2O, R7R8N, R6OC(O), R7R8NC(O), R9C(O), R9R10R11Si, R9R10R11Sn, R12R13B, halogen, R9R10P(O)q and/or CN; Y = (CH2)n, CH=CH, C(O), NR5, O, S(O)p or a group of formula (v); n = 0, 1 or 2, m = 2 or 3; p = 0, 1 or 2; q = 0 or 1; E = R21R22R23P, R7R7aR8N or R6R6aS; R5 = H, 1-12C alkyl or phenyl-1-6C alkyl or phenyl which are optionally substituted 1-5 times by 1-6C alkyl, 1-12C alkoxy and/or halogen; R6 and R6a = as R5 except H; R7, R7a and R8 = 1-12C alkyl (optionally substituted with 1-12C alkoxy, halogen, OH, COOR6 or CN) or 3-12C cycloalkyl or phenyl-1-6C alkyl or phenyl (optionally substituted 1-5 times with 1-6C alkyl, 1-12C alkoxy and/or halogen) or R7 and R8, together with the N to which they are attached, form a 5- or 6-membered ring which may additionally contain O or S atoms; R9, R10 and R11 = 1-12C alkyl, 3-12C cycloalkyl or phenyl-1-6C alkyl or phenyl which are optionally substituted 1-5 times by 1-6C alkyl, 1-12C alkoxy and/or halogen; R12-R15 = H, 1-12C alkyl (optionally substituted by 1-12C alkoxy), phenyl-1-6C alkyl (optionally substituted by mono- to penta-1-6C alkyl, -1-12C alkoxy or -halogen) or phenyl (optionally substituted by mono- to penta-1-6C alkyl, -1-12C alkoxy or -halogen), or R12-R15 together form an aromatic ring to which further aromatic rings may be fused; R16-R20 and R18a = H, 1-12C alkyl (optionally substituted by 1-12C alkoxy, OH or halogen) or phenyl (optionally substituted by 1-12C alkoxy, OH or halogen); R21, R22 and R23 = 1-12C alkyl, 2-12C alkenyl or 3-12C cycloalkyl (optionally substituted by R6OCO or CN) or they are phenyl-1-6C alkyl (optionally substituted by mono- to penta-1-6C alkyl, -1-12C alkoxy or -halogen) or phenyl (optionally substituted by mono- to penta-1-6C alkyl, -1-12C alkoxy or -halogen); X = N, S or O; and G = a radical which is able to form positive ions. - Also claimed are: (i) a compound of formula (I) or (I'); (ii) a process for the photopolymerisation of non-volatile monomeric, oligomeric or polymeric compounds containing ethylenically unsaturated double bond(s); (iii) a substrate which is coated on its surface(s) with a composition as above; (iv) a process for the photographic production of relief images which comprises subjecting a coated substrate as in (iii) to imagewise exposure and removing the unexposed areas with a solvent; (v) a process for producing relief images which comprises exposing a coated substrate as in (iii) by means of a movable laser beam (without mask) and subsequently removing the unexposed areas with a solvent; and (vi) a process for the thermal polymerisation of compounds containing ethylenically unsaturated double bonds, which comprises using (I) or (I') as an initiator.

Description

       

  



  The invention relates to photopolymerizable compositions which contain borate photoinitiators, in particular also unimolecular borate photoinitiators.



  The use of borates as photoinitiators in combination with coinitiators is known in the prior art. For example, U.S. Patents 4,772,530, 4,772,541 and 5,151,520 triarylalkyl borate anions with cationic dyes such as e.g. Cyanines, rhodamines, etc., as counterions. These compounds are used as photoinitiators. In U.S. Patent 4,954,414, cationic transition metal complexes are used together with triarylalkyl borate anions in photopolymerizable compositions. It is also known from U.S. Patent 5,055,372 the use of quaternary ammonium compounds such as e.g. Tetramethylammonium, pyridinium, cetylpyridinium etc., as cationic counterions to the triarylalkyl borate.

   In this publication, the borates are used in conjunction with aromatic ketone initiator compounds as coinitiators in photocurable materials.



  There is a need in the art for the extensive field of application of photoinitiators for stable reactive compounds which can be used as initiators in photopolymerizable compositions.



  The borate compounds described in the publications mentioned above are always used in combination with coinitiators as photoinitiators. It is interesting in the art to provide photopolymerizable compositions which contain photoinitiators which, even without the addition of coinitiators, are reactive enough to initiate the photopolymerization. Surprisingly, it has now been found that borates with certain substitution patterns have these properties.



  The invention relates to a photopolymerizable composition containing



  a) at least one polymerizable ethylenically unsaturated compound and



  b) at least one compound of formula I or 1 min as a unimolecular photoinitiator
EMI2.1
 
 
 



  wherein R1, R2 and R3 independently of one another represent phenyl or another aromatic hydrocarbon, with or without a hetero atom, these radicals being unsubstituted or 1- to 5-fold with C1-C20-alkyl which is unsubstituted or substituted by OR6 or R7R8N, with one or more Residues O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q, CN or / and
EMI2.2
 



   
EMI2.3
 
 
 are substituted,
 or the radicals R2 and R3 form bridges, structures of the formulas II, IIa or IIb
EMI2.4
 
 
 



  arise, the aromatic rings in the formula II, IIa or Ibb being unsubstituted or with C1-C20-alkyl, with one or more residues O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O ) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, halogen, R9R10P (O) q or / and R9R10R11Sn;
 with the provisos that at most two of the radicals R1, R2 and R3 are the same and either at least two of the radicals R1, R2 and R3 are phenyl radicals substituted in both ortho positions or aromatic hydrocarbon radicals
 or at least one radical R1, R2 or R3 is a bulky aryl radical and the remaining radicals R1, R2 or R3 are at least one ortho-substituted phenyl radicals or aromatic hydrocarbon radicals;

  
 R1a represents a divalent aromatic hydrocarbon radical, this radical being unsubstituted or with C1-C6-alkyl, OR6, S (O) pR6, OS (O) 2R6, NR8R7, C (O) OR6, C (O) NR8R7, C ( O) R9, SiR9R10R11 or halogen is substituted or R1a is phenyl-C1-C6-alkylene;
 R4 represents phenyl or another aromatic hydrocarbon radical, with or without a hetero atom, these radicals being unsubstituted or 1- to 5-fold with C1-C20-alkyl which is unsubstituted or substituted by OR6 or R7R8N, with one or more radicals O, S (O) p or NR5 interrupted C2-C20 alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O ) q, CN or / and
EMI3.1
 
 
 



  are substituted, or R4 C1-C20-alkyl, with one or more residues O, S (O) p or NR5 interrupted C2-C20-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6- alkyl or naphthyl-C1-C3-alkyl, where the radicals C1-C20-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or naphthyl-C1-C3-alkyl are unsubstituted or are substituted by OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q, or / and CN ;
 Y for (CH2) n, CH = CH, C (O), NR5, O, S (O) p or
EMI3.2
 stands;
 n represents 0, 1 or 2;
 m is 2 or 3;
 p represents 0, 1 or 2;
 q is 0 or 1;
 E represents R21R22R23P, R7R7aR8N or R6R6aS;

   
 R5 is hydrogen, C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, where the radicals phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12-alkoxy or / and halogen are substituted;
 R6 and R6a are unsubstituted or halogen-substituted C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, where the radicals phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12-alkoxy or / and halogen are substituted;

  
 R7, R7a and R8 independently of one another are unsubstituted or C1-C12-alkoxy, halogen, OH, COOR6 or CN-substituted C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals Phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold substituted with C1-C6-alkyl, C1-C12-alkoxy or / and halogen, or R7 and R8 together with the N atom to which they are attached , form a 5- or 6-membered ring, which may additionally contain O or S atoms;
 R9, R10 and R11 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold with C1 -C6 alkyl, C1-C12 alkoxy or / and halogen are substituted;

  
 R12, R13, R14 and R15 independently of one another are hydrogen, unsubstituted or C1-C12-alkoxy-substituted C1-C12-alkyl, unsubstituted or one to five times with C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl-C1 -C6-alkyl or unsubstituted or one to five times with C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl, or the radicals R12, R13, R14 and R15 together form an aromatic ring on which further aromatic rings can be fused;
 R16, R17, R18, R18a, R19 and R20 independently of one another are hydrogen, unsubstituted or C1-C12-alkoxy, OH or halogen-substituted C1-C12-alkyl or unsubstituted or C1-C12-alkyl, C1-C12-alkoxy, OH or halogen substituted phenyl;

  
 R21, R22 and R23 independently of one another C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, where the residues C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl are unsubstituted or with R6OCO or CN are substituted, or R21, R22 and R23 are unsubstituted or mono- to pentasubstituted with C1-C6-alkyl, C1-C12-alkoxy or halogen-phenyl-C1-C6-alkyl or unsubstituted or mono- to pentasubstituted with C1-C6- Alkyl, C1-C12-alkoxy or halogen-substituted phenyl;
 X is N, S or O, and
 G represents a residue which can form positive ions.



  Even without the addition of coinitiators, the compounds of the formulas I and I min are reactive initiators for the photopolymerization of ethylenically unsaturated compounds.



  The compounds are characterized in that firstly at most two of the radicals R1, R2 and R3 are the same and secondly
 either at least two of the radicals R1, R2 and R3 are phenyl radicals substituted in both ortho positions or aromatic hydrocarbon radicals
 or at least one radical R1, R2 or R3 is a sterically bulky aryl radical and the remaining radicals R1, R2 or R3 are at least one ortho-substituted phenyl radicals or aromatic hydrocarbon radicals.



  Aromatic hydrocarbons, as they can be contained in the compounds according to the invention, can e.g. contain one or more, in particular 1 or 2, heteroatoms. As heteroatoms, e.g. N, O, P or S, preferably N or O, in question. Examples of aromatic hydrocarbons are: phenyl, 1- and 2-naphthyl, stilbenyl, biphenyl, o-, m-, p-terphenyl, triphenylphenyl, fluorenyl, binaphthyl, anthracyl, phenanthryl, ferrocenyl, pyrenyl, furan-2-yl or furan -3-yl, thiophene-2-yl or thiophene-3-yl, pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, pyrimidinyl, quinolyl or isoquinolyl. Aromatic hydrocarbon radicals of the formula are also suitable
EMI5.1
 ,
 wherein A and Z are independently - (CH2) n -, -C (O) -, N, S (O) p; n and p have the meanings given above. Examples of this are e.g.

   Anthracyl, fluorenyl, thianthryl, xanthyl, acridinyl, phenazinyl, phenothiazinyl, phenoxathiinyl, phenoxazinyl.



  Is stilbenyl
EMI5.2
 Biphenyl means
EMI5.3
 
 are o-, m- or p-terphenyl
EMI6.1
 
 
EMI6.2
 
 
EMI6.3
 
 



  Triphenylphenyl means
EMI6.4
 
 



  Is binaphthyl
EMI6.5
 
 



  Anthracyl means
EMI6.6
 
 



  Phenanthryl stands for
EMI7.1
 
 



  Pyrenyl means
EMI7.2
 
 



  Quinolinyl means
EMI7.3
 
 



  Isoquinolinyl means
EMI7.4
 
 



  Furanyl is furan-2-yl or furan-3-yl. Thiophenyl means thiophene-2-yl or thiophene-3-yl. Pyridinyl stands for pyridin-2-yl, pyridin-3-yl or pyridin-4-yl.



  If the radicals phenyl, stilbenyl, biphenyl, o-, m- or p-terphenyl, triphenylphenyl, naphthyl, binaphthyl, anthracyl, phenanthryl, pyrenyl, ferrocenyl, furanyl, thiophenyl, pyridinyl, quinolinyl or isoquinolinyl are substituted, they are one to one fourfold, e.g. mono-, di- or trisubstituted, in particular mono- or disubstituted. Substituents on the phenyl ring are preferably in the 2-, 4-, 6-, 2,6- or 2,4,6-position of the phenyl ring.



  The term "bulky aryl radical" as used in this application includes e.g. Polycycles, i.e. understand multinuclear aryl residues. These are, for example, fused hydrocarbon rings, with or without a hetero atom, preferably S, O or N, such as e.g. 1- and 2-naphthyl, binaphthyl, anthracyl, phenanthryl, pyrenyl, quinolyl or isoquinolyl.



  However, the term "sterically bulky aryl radical" also includes ring sequences, i.e. aryl rings linked by single bonds. Examples include biphenyl, o-, m- and p-terphenyl or triphenylphenyl.



  C1-C20 alkyl is linear or branched and is, for example, C1-C12, C1-C8, C1-C6 or C1-C4 alkyl. Examples are 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, octadecyl, nonadecyl or icosyl. For example, R4 is C1-C8-alkyl, especially C1-C6-alkyl, preferably C1-C4-alkyl, e.g. Methyl or butyl. If R1, R2, R3 and R4 are C1-C20-alkyl substituted with R9R10R11Si, the alkyl radical is e.g. C1-C12, especially C1-C8, preferably C1-C4 alkyl. Methyl is particularly preferred.



  C1-C12 alkyl and C1-C6 alkyl are also linear or branched and have e.g. the meanings given above up to the corresponding number of carbon atoms. R5, R6, R7, R8, R9, R10, R11, R12, R13, R6a and R7a are e.g. C1-C8, especially C1-C6, preferably C1-C4 alkyl, e.g. Methyl or butyl. C1-C6-alkyl substituents for phenyl-C1-C6-alkyl or phenyl, especially C1-C4-alkyl, e.g. Methyl or butyl.



  C2-C20 alkyl which is interrupted one or more times by -O-, -S (O) p- or -NR5- is, for example, 1-9, e.g. 1-7 or 1 or 2 times interrupted by -O-, -S (O) p- or -NR5-. For example, Structural units such as -CH2-O-CH3, -CH2CH2-O-CH2CH3, - [CH2CH2O] y-CH3, with y = 1-9, - (CH2CH2O) 7CH2CH3, -CH2-CH (CH3) -O-CH2-CH2CH3 , -CH2-CH (CH3) -O-CH2-CH3, -CH2SCH3 or -CH2-N (CH3) 2.



  C3-C12 cycloalkyl means e.g. Cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, especially cyclopentyl and cyclohexyl, preferably cyclohexyl.



  C2-C8-alkenyl radicals can be mono- or polyunsaturated and are, for example, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl or 7 -Octenyl, especially allyl. R4 as C2-C8 alkenyl is e.g. C2-C6, especially C2-C4 alkenyl.



  Phenyl-C1-C6-alkyl means e.g. Benzyl, phenylethyl, alpha-methylbenzyl, phenylpentyl, phenylhexyl or alpha, alpha-dimethylbenzyl, especially benzyl. Phenyl-C1-C4-alkyl, in particular phenyl-C1-C2-alkyl, is preferred. Substituted phenyl-C1-C6-alkyl is one to four times, e.g. substituted once, twice or three times, in particular once or twice on the phenyl ring.



  Phenyl-C1-C6-alkylene has two free bonds, one on the phenylene ring and the other in the alkylene radical:
EMI9.1
 with x = 1 to 6.



  Substituted phenyl is one to five times, e.g. substituted once, twice or three times, in particular once or twice on the phenyl ring. The substituents are e.g. in the 2- / 6-, 2- / 4- or 2- / 4- / 6-position of the phenyl ring, preferably in the 2- / 6- or 2- / 4- / 6-position.



  Naphthyl-C1-C3-alkyl is, for example, naphthylmethyl, naphthylethyl, naphthylpropyl or naphthyl-1-methylethyl, especially naphthylmethyl. The alkyl unit can be in the 1- or 2-position of the naphthyl ring. Substituted naphthyl-C1-C3-alkyl is one to four times, e.g. substituted once, twice or three times, in particular once or twice, on the aromatic rings.



  C1-C12-alkoxy stands for linear or branched radicals and means e.g. Methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy or dodecyloxy, in particular methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, preferably methoxy.



  Halogen means fluorine, chlorine, bromine and iodine, in particular chlorine, fluorine and bromine, preferably chlorine and fluorine.



  If C1-C20-alkyl is substituted one or more times with halogen, e.g. 1 to 3 or 1 or 2 halogen substituents on the alkyl radical.



  If R7 and R8 together with the N atom to which they are attached form a 5- or 6-membered ring which may also contain O or S atoms, these are e.g. saturated or unsaturated rings, for example aziridine, pyrrole, pyrrolidine, oxazole, thiazole, pyridine, 1,3-diazine, 1,2-diazine, piperidine or morpholine.



  Divalent aromatic hydrocarbon residues are e.g. Phenylene, stilbenylene, biphenylene, o-, m- or p-terphenylene, triphenylphenylene, naphthylene, binaphthylene, anthracenylene, phenanthrylene, pyrenylene, ferrocenylene, furanylene, thiophenylene, pyridinylene, quinolinylene or isoquinolinylene.



  Naphthylene stands for
EMI10.1
 , especially for
EMI10.2
 



  . Is stilbenylene
EMI10.3
 
 or
EMI10.4
 . Biphenylene means
EMI10.5
 
 



  are o-, m- or p-terphenylene
EMI10.6
 
 
EMI10.7
 
 



  Triphenylphenylene means
EMI10.8
 
 



  Is binaphthylene
EMI11.1
 
 
 in particular
EMI11.2
 
 



  Anthracylene means
EMI11.3
 
 
EMI11.4
 
 



  Phenanthrylene stands for
EMI11.5
 
 or
EMI11.6
 Pyrenylene means
EMI11.7
 
 
EMI11.8
 
 



  Furanylene is
EMI12.1
 
 



  Thiophenylene means
EMI12.2
 
EMI12.3
 
 



  Pyridinylene stands for
EMI12.4
 
 



  Quinolinylene means
EMI12.5
 
 



  Isoquinolinylene means
EMI12.6
 
EMI12.7
 
 



  1,4-Duryl
EMI12.8
 



  If the radicals are phenylene, stilbenylene, biphenylene, o-, m- or p-terphenylene, triphenylphenylene, naphthylene, binaphthylene, anthracylene, phenanthrylene, pyrenylene, ferrocenylene, furanylene, thiophenylene, pyridinylene, quinolinylene or isoquinolinylene, they are mono- to substituted fourfold, e.g. mono-, di- or trisubstituted, in particular mono- or disubstituted. Substituents on the 1,4-phenylene ring are in the 2-, 3-, 5- or 6-position, in particular in the 2- or 3-position of the phenyl ring. Substituents on the 1,3-phenylene ring are in the 2-, 4-, 5- or 6-position, in particular in the 4- or 5-position of the phenyl ring.



  As counterion G Residues which can form positive ions are generally suitable for the negative borate in formula I.



  These are, for example, alkali metals, in particular lithium or sodium, quaternary ammonium compounds, sulfonium and phosphonium compounds, cationic transition metal complex compounds or dyes. For the unimolecular borate compounds of the formula I, G is preferably ammonium or tetraalkylammonium.



  Examples of tetraalkylammonium are in particular tetramethylammonium or tetrabutylammonium. Trisalkylammonium ions are also suitable, e.g. Trimethylammonium. Other interesting quaternary ammonium compounds are e.g. Trimethylcetylammonium or cetylpyridinium. Phosphonium and ammonium counterions of the formulas are suitable <+> PRwRxRyRz and <+> NRwRxRyRz, where Rw, Rx, Ry, Rz independently of one another represent hydrogen, unsubstituted or substituted alkyl, cycloalkyl, alkenyl, phenyl or arylalkyl. Substituents for these alkyl, cycloalkyl, alkenyl, phenyl or arylalkyl radicals are e.g. Halide, hydroxy, heterocycloalkyl (e.g. epoxy, aziridyl, oxetanyl, furanyl, pyrrolidinyl, pyrrolyl, thiophenyl, tetrahydrofuranyl, etc.), dialkylamino, amino, carboxy, alkyl and arylcarbonyl, and aryloxy and alkoxycarbonyl.

   The tetravalent nitrogen can also be a member of a 5- or 6-membered ring, which ring can in turn be fused to other ring systems. These systems can also contain additional heteroatoms, e.g. S, N, O.



  The tetravalent nitrogen can also be a member of a polycyclic ring system, e.g. Azonia propellan. These systems can also contain other heteroatoms, e.g. S, N, O.



  Also suitable are polyammonium and polyphosphonium salts, in particular the bite salts, where the same substituents as described above for the "mono" compounds may be present.



  The ammonium and phosphonium salts can also be substituted with neutral dyes (e.g. thioxanthenes, thioxanthones, coumarins, ketocoumarins, etc.). Such salts are obtained from the reaction of the ammonium and phosphonium salts substituted with reactive groups (e.g. epoxy, amino, hydroxy, etc.) with suitable derivatives of neutral dyes. Corresponding examples are described in EP-A 224 967 (Quantacure QTX).



  Likewise, ammonium and phosphonium salts can also be substituted with colorless electron acceptors (e.g. benzophenones):



  Examples of this are Quantacure ABQ
EMI14.1
 
 



  Quantacure BPQ
EMI14.2
 and Quantacure BTC
EMI14.3
 
 
 from International Bio-Synthetics.



  The compounds of formula I are reactive even if they do not contain any dye or cationic transition metal complex as the counter ion, i.e. they can also be used unimolecularly.



  The invention therefore relates in particular to compounds in which G in particular for a metal from group I of the periodic table in the first oxidation stage, in particular Na <+>, K <+> or Li <+>, or where G MgZ1 <+> or CaZ1 <+>, wherein Z1 represents a halogen or C1-C4-alkoxy, means or G represents an ammonium, phosphonium or sulfonium salt.



  An ammonium or phosphonium salt is e.g. RaRbRcRdN <+> or RaRbRcRdP <+>, where Ra, Rb, Rc and Rd independently of one another are C1-C20-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl, naphthyl-C1-C3-alkyl or phenyl .



  The reactivity of the unimolecular photoinitiator compounds can of course be increased by adding coinitiators, e.g. Dyes, increase.



  Dye cations or cationic transition metal coordination complex compounds can therefore also serve as counterions. These residues then act as a coinitiator for the borate.



  As positive counterions G <+> in the compound of formula I are e.g. also use the following ions:
EMI14.4
 



   
EMI15.1
 
 
 wherein Z is P, S or N and R is an alkyl or aryl radical. Connections such as e.g.
EMI15.2
 
EMI 15.3
 (described by Yagci et al. in J. Polym. Sci. Part A: Polymer Chem. 1992, 30, 1987 and Polymer 1993, 34 (6), 1130), or as e.g.
EMI 15.4
 



   
EMI15.5
 with R min = unsubstituted or substituted benzyl or phenacyl (described in JP-A Hei 770 221). In these compounds, the aromatic rings in the pyridinium can also be substituted.



  Tetraalkylammonium is e.g. (C1-C10 alkyl) 4N <+>, e.g. Tetrahexylammonium, tetraoctylammonium, tetradecylammonium, tetrabutylammonium or tetramethylammonium. Tetra (C1-C4-alkyl) ammonium, N (C1-C4-alkyl) 4 is preferred <+>, where C1-C4-alkyl may have the meanings given above up to the corresponding number of carbon atoms. Examples of corresponding ammonium compounds are tetramethylammonium, tetraethylammonium, tetrapropylammonium or tetrabutylammonium, in particular tetramethylammonium and tetrabutylammonium. Benzyl-tri (C1-C4-alkyl) ammonium means C6H4-CH2-N (C1-C4-alkyl) 3 <+>, where C1-C4-alkyl may have the meanings given above up to the corresponding number of carbon atoms.

   Examples of such radicals are benzyltrimethylammonium, benzyltriethylammonium, benzyltripropylammonium and benzyltributylammonium, especially benzyltrimethylammonium and benyzltributylammonium.



  As positive counterions G Other onium ions, such as e.g. Iodonium or sulfonium ions can be used.



  Examples of such counterions to the borate are residues of the formula
EMI16.1
 as described, for example, in EP-A 555 058 and EP-A 690 074. Also interesting as counterions
EMI16.2
 
 
EMI 16.3
 
 



  Further suitable counterions for the borates according to the invention are cations of the formula
EMI 16.4
 wherein R9 represents an alkyl radical, in particular ethyl, or benzyl and the aromatic ring can carry further substituents.



  Other suitable counterions are halonium ions, especially diaryliodonium ions, e.g. in EP-A 334 056 and EP-A 562 897.



  However, cations of ferrocenium salts, such as described in EP-A 94 915 and EP-A 109 851, for example
EMI 16.5
 
 



  Other suitable "onium" cations such as ammonium, phosphonium, sulfonium, iodonium, selonium, arsonium, tellonium, bismuthonium are e.g. in Japanese Patent Application Hei 6 266 102.



  Examples of cationic transition metal complex compounds which are useful as counterions are described in U.S. Patent 4,954,414. Bis (2.2 min -bipyridine) (4.4 min -dimethyl-2.2 min -bipyridine) -ruthenium, Tris (4.4 min -dimethyl-2.2 min -bipyridine) -ruthenium, Tris are particularly interesting (4.4 min -dimethyl-2.2 min -bipyridine) -iron, tris (2.2 min, 2 min -terpyridine) ruthenium, tris (2.2 min -bipyridine) ruthenium and bis (2, 2 min -bipyridine) (5-chloro-1,10-phenanthroline) ruthenium.



  Dyes suitable as counterions are, for example, cations of triarylmethanes, e.g. Malachite green, indolines, thiazines, e.g. Methylene blue, xanthones, thioxanthones, oxazines, acridines, cyanines, rhodamines, phenazines, e.g. Safranin, preferably cyanines and thioxanthones.



  Compounds of the formula I and I min are preferred in which R1 and R2 are identical.



  Other interesting compositions are those in which the compounds of the formula I R1, R2 and R3 independently of one another are phenyl or another aromatic hydrocarbon, with or without a hetero atom, these radicals being unsubstituted or 1- to 5-fold with unsubstituted or with OR6 or R7R8N substituted C1-C6-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, halogen or / and
EMI17.1
 are substituted,
 or the radicals R2 and R3 form bridges, structures of the formulas II, Ila or lIb being formed,
 R4 is phenyl, C1-C20-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or naphthyl-C1-C3-alkyl;
 R12, R13, R14 and R15 independently of one another are H, C1-C12-alkyl or phenyl, or the radicals R12, R13, R14 and R15 together form an aromatic ring to which further aromatic rings can be fused; and
 X is N or O.



  To be emphasized are compositions in which in the compound of the formula I or 1 min R4 is C1-C12-alkyl, allyl, cyclopentyl, cyclohexyl, benzyl or naphthylmethyl.



  In particular, those compositions are preferred in which, in the compound of the formula I and 1 min, R6 is C1-C4-alkyl, trifluoromethyl or unsubstituted or 1- to 5-fold substituted by C1-C6-alkyl, C1-C12-alkoxy or / and halogen .



  Interesting compositions are those in which, in the compound of the formula I and l, R7 and R8 are C1-C4-alkyl, phenyl, phenyl-C1-C6-alkyl, or pyrrolidino together with the N atom to which they are attached , Piperidino or Morpholino mean.



  Also preferred are compositions in which in the compound of the formula I R1 and R2 2,6-di (C1-C6-alkyl) phenyl, 2,6-di (C1-C6) alkoxyphenyl, 2,6-bis (trifluoromethyl) phenyl , 2,6-di (halogen) phenyl, 2,4,6-tri (C1-C6-alkyl) phenyl, 2,4,6-tri (C1-C6) alkoxyphenyl, 2,4,6-tris (trifluoromethyl ) phenyl or 2,4,6-tri (halogen) phenyl.



  Also preferred are compositions in which R1 and R2 in the compound of the formula I are mesityl.



  Further preferred compositions are those in which R1 in the compound of the formula I denotes 1-naphthyl, 2- (C1-C6-alkyl) naphth-1-yl, 1-anthracyl, 9-anthracyl or ferrocenyl.



  Also of interest are compositions in which in the compound of the formula I R1 and R2 are o- (C1-C6-alkyl) phenyl, o- (halogen) phenyl, o- (C1-C6-alkoxy) phenyl or o-trifluoromethylphenyl.



  Also preferred are compositions in which R1 and R2 are the same in the compound of the formula I and are phenyl, naphthyl or anthracyl which are mono- to pentasubstituted by C1-C4-alkyl and / or halogen, R3 is unsubstituted or halogen or C1-C4- Represents alkyl substituted phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-anthracyl, 9-phenanthryl or 1-pyrenyl, R4 means phenyl or C1-C4-alkyl or R2 and R3 form a bridge and a structure of formula II is formed , wherein Y represents a bond, and G for tetramethylammonium, safranin O cation
EMI18.1
 

 
EMI18.2
 
 
  <+> N (CH3) 3 (n-C16H33),
EMI18.3
 
EMI19.1
   <+> N (CH3) 3 (CH2OH),
 (CH3) 3N <+> (CH2) 6N <+> (CH3) 3, <+> N (C2H5) 3 ([CH2] 3Br),
EMI19.2
 
 
 (Phenyl) 3P = N <+> = P (phenyl) 3,
EMI 19.3
 
 
EMI 19.4
 



   (Phenyl) 3S <+>,
EMI19.5
 
 
EMI19.6
 



   stands or a compound of formula l min, wherein R1a is naphthylene and E represents trimethylammonium or dimethyl-benzyl-ammonium.



  The compounds of formula I can e.g. by reacting triorganylboranes (A) with organometallic reagents, e.g. Alkyl lithium compounds or Grignard reagents are obtained:
EMI19.7
 
 
 



  M is e.g. an alkali metal, such as Li or Na, or MgX, where X represents a halogen atom, in particular Br.



  Another possibility for the preparation of the compounds of formula I is, for example, the reaction of alkyldihaloboranes or alkyldialkoxy- or alkyldiaryloxyboranes (B) with organometallic compounds such as e.g. Grignard reagents or lithium organyl compounds:
EMI20.1
 
 
 



  X stands for halogen, in particular Br, X min means halogen, alkoxy or aryloxy. The meanings of the other radicals are as stated above.



  In the event that G in the formula I given above represents a positive radical other than lithium or magnesium, these compounds can e.g. can be obtained by cation exchange reactions.



  The reaction conditions when working with organometallic reagents are generally familiar to the person skilled in the art. For example, the reaction is conveniently carried out in an inert organic solvent, for example an ether or aliphatic hydrocarbon, e.g. Diethyl ether, tetrahydrofuran or hexane.



  The organometallic reagents for the preparation of the polyborates according to the invention are, for example, the lithium compounds of the corresponding aliphatic and aromatic hydrocarbon radicals. The production of Grignard reagents is familiar to the person skilled in the art and is described in various ways in textbooks and other publications.



  The reaction with the organometallic reagent is conveniently carried out in the absence of air in an inert gas atmosphere, e.g. carried out under nitrogen. The reaction is usually carried out with cooling to 0 ° C. or below and then heating to room temperature.



  It is advisable to stir the reaction mixture. The isolation and cleaning of the products is also carried out according to methods generally known to the person skilled in the art, e.g. Chromatography, recrystallization, etc.



  If the compounds of the formula I according to the invention contain a dye residue as a cation, these compounds are prepared by cation exchange reaction of a corresponding borate salt with a dye. The borate salts suitable for exchange are e.g. the lithium, magnesium, sodium, ammonium or tetraalkylammonium salts.



  If the compounds of the formula I contain a transition metal complex as a cation, these compounds are prepared analogously to the method described in US Pat. No. 4,954,414, column 7, section 2.



  Production of triorganylboranes (A): The production of some alkyl-diarylboranes is e.g. by A. Pelter et al. in Tetrahedron 1993, 49, 2965. The synthesis of some triarylboranes is by Doty et al. in J. Organomet. Chem. 1972, 38, 229, by Brown et al. in J. Organomet. Chem. 1981, 209, 1, Brown et al. in J. Amer. Chem. Soc. 1957, 79, 2302, and by Wittig et al. in Chem. Ber. 1955, 88, 962.



  Production of aryldihaloboranes (B): access to some alkyldihaloboranes (B) is e.g. by Brown et al. in JACS 1977, 99, 7097, and U.S. Patent 3,083,288. Mikailov et al. in Zh. Obshch. Khim. 1959, 29, 3405, and Tuchagues et al. in Bull. Chim. Soc. France, 1967, 11, 4160, describe the preparation of such compounds. The production of phenyldifluoroborane is described by Nahm et al. in J. Organomet. Chem. 1972, 35, 9.



  The alkyl dialkoxy and alkyl diaryloxy boranes can e.g. manufactured according to various published regulations; e.g. Brown et al. Organometallics 1983, 2, 1316; Brown et al. Organometallics 1992, 11 3094; Brown et al. J. Org. Chem. 1980, 2, 1316.



  The boranes required as starting materials for the compounds according to the invention can be obtained, for example, in accordance with one of the published methods mentioned above.



  According to the invention, compounds of the formula la and la min
EMI21.1
 
 
 



  wherein R1 min and R2 min independently of one another for at least one o-position for bonding to the boron atom with C1-C20-alkyl, with one or more radicals O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q, CN,
EMI22.1
 
EMI22.2
 or and
EMI22.3
 
 
 substituted phenyl;
 R3 min represents phenyl or another aromatic hydrocarbon, with or without a hetero atom, these radicals being unsubstituted or 1- to 5-fold with C1-C20-alkyl which is unsubstituted or substituted by OR6 or R7R8N, with one or more radicals O, S (O ) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P ( O) q, CN
EMI22.4
 
EMI22.5
 or and
EMI22.6
 are substituted;

  
 or the residues R2 min and R3 min form bridges, structures of the formulas II, Ila or IIb
EMI22.7
 
 
 



  arise, the aromatic rings in formula II are unsubstituted or with C1-C20-alkyl, with one or more radicals O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, halogen, R9R10P (O) q or / and R9R10R11Sn;
 R1a min is a divalent aromatic hydrocarbon radical, this radical being unsubstituted or with C1-C6-alkyl, OR6, S (O) pR6, OS (O) 2R6, NR8R7, C (O) OR6, C (O) NR8R7, C (O) R9, SiR9R10R11 or halogen is substituted or R1a is phenyl-C1-C6-alkylene;

   
 R4 is phenyl, C1-C20-alkyl, C2-C20-alkyl interrupted by one or more radicals O, S (O) p or NR5, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or Naphthyl-C1-C3-alkyl means, where the residues C1-C20-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or naphthyl-C1-C3-alkyl are unsubstituted or with OR6 , R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q, or / and CN;

   
 Y for (CH2) n, CH = CH, C (O), NR5, O, S (O) p or
EMI24.1
 stands;
 n represents 0, 1 or 2;
 m is 2 or 3;
 p represents 0, 1 or 2;
 q is 0 or 1;
 E represents R21R22R23P, R7R7aR8N or R6R6aS;
 R5 is hydrogen, C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, where the radicals phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12-alkoxy or / and halogen are substituted;
 R6 and R6a independently of one another are C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12 Alkoxy or / and halogen are substituted;

  
 R7, R7a and R8 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold with C1 -C6-alkyl, C1-C12-alkoxy or / and halogen are substituted, or R7 and R8 together with the N atom to which they are attached form a 5- or 6-membered ring which additionally contains O or S - can contain atoms;
 R9, R10 and R11 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold with C1 -C6 alkyl, C1-C12 alkoxy or / and halogen are substituted;

  
 R12, R13, R14 and R15 independently of one another are hydrogen, unsubstituted or C1-C12-alkoxy-substituted C1-C12-alkyl, unsubstituted or one to five times with C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl-C1 -C6-alkyl or unsubstituted or one to five times with C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl, or the radicals R12, R13, R14 and R15 together form an aromatic ring on which further aromatic rings can be fused;

  
 R21, R22 and R23 independently of one another C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, where the residues C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl are unsubstituted or with R6OCO or CN are substituted, or R21, R22 and R23 unsubstituted or mono- to pentasubstituted by C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl-C1-C6-alkyl or unsubstituted or mono- or pentasubstituted by C1-C6 Alkyl, C1-C12-alkoxy or halogen-substituted phenyl; and
 G represents a residue which can form positive ions.



  Compounds are preferred in which R3 is 1- or 2-naphthyl, binaphthyl, anthracyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, biphenyl, o-, m- or p-terphenyl or triphenylphenyl.



  The meanings of the residues R1 min, R2 min and R3 min are given exactly like those for R1, R2 and R3.



  According to the invention, the compounds of the formula Ia can be used as photoinitiators for the photopolymerization of ethylenically unsaturated compounds or mixtures which contain such compounds.



  Compounds of the formula Ia which do not contain any dye residue as a counterion can be used as unimolecular photoinitiators.



  According to the invention there are therefore in particular those compounds of the formula Ia in which G for a metal from Group I of the periodic table in the first oxidation stage, in particular Na <+>, K <+> or Li <+>, stands, or G MgZ1 <+> or CaZ1 <+> means in which Z1 represents a halogen or C1-C4-alkoxy, or G represents an ammonium, phosphonium or sulfonium salt.



  To increase the reactivity, it can of course also be used in combination with at least one coinitiator or electron acceptor (c).



  It can also be used in combination with another photoinitiator and / or other additives.



  In addition to components (a) and (b), the composition according to the invention can also contain other photoinitiators (d) and / or other additives, and also at least one coinitiator or electron acceptor (c).



  Dyes suitable as electron acceptors which can be added as coinitiators are e.g. in U.S. Patent 5,151,520. For example, triarylmethanes, e.g. Malachite green, indolines, thiazines, e.g. Methylene blue, xanthones, thioxanthones, oxazines, acridines or phenazines, e.g. Saffron.



  The transition metal complex compounds or onium ion compounds described above can also be used as coinitiators.



  Cationic, neutral or anionic dyes can be used as coinitiators for the compounds according to the invention.



  Particularly suitable cationic dyes are malachite green, methylene blue, safranine O, rhodamines of the formula III
EMI26.1
 
 
 



  where R and R min are alkyl or aryl, e.g. Rhodamine B, Rhodamine 6G or Violamin R, also Sulforhodamine B or Sulforhodamine G.



  Other suitable dyes are fluorones, e.g. by Neckers et al. in J. Polym. Sci., Part A, Poly. Chem, 1995, 33, 1691-1703. Is particularly interesting
EMI26.2
 
 



  Examples of other suitable dyes are cyanines of the formula IV
EMI26.3
 
 
 



  where R = alkyl; n = 0, 1, 2, 3 or 4 and Y1 = CH = CH, N-CH3, C (CH3) 2, O, S or Se. Preferred are cyanines, wherein Y1 in formula IV is C (CH3) 2 or S.



  The following dye compounds are also suitable as coinitiators:
EMI27.1
 
 
 



  wherein Z is P, S or N and R is an alkyl or aryl radical. Preferred compounds of the above formulas are those in which ZR3 is N (CH3) 3, N (C2H5) 3 or P (C6H5) 3.



  Connections such as e.g.
EMI27.2
 as e.g. by Yagci et al. in J. Polym. Sci. Part A: Polymer Chem. 1992, 30, 1987, and Polymer 1993, 34 (6), 1130, or as e.g.
EMI27.3
 or
EMI27.4
 with R min = unsubstituted or substituted benzyl or phenacyl, described in JP-A Hei 770 221. The above-mentioned pyridinium compounds can also be substituted in the aromatic pyridinium ring.



  Other suitable dyes can be found, for example, in US Pat. No. 4,902,604. They are azulene dyes. Of particular interest as coinitiators for the compounds according to the invention are the compounds 1-18 given in columns 10 and 11 of this patent in the table.



  Other suitable dyes are e.g. Merocyanine dyes as described in U.S. Patent 4,950,581 from column 6, line 20 to column 9, line 57.



  Coumarin compounds can also be used as coinitiators for the compounds and compositions according to the invention. Examples of this are given in U.S. Patent 4,950,581 in columns 11, line 20 through column 12, line 42.



  Other suitable coinitiators are xanthones or thioxanthones, e.g. in U.S. Patent 4,950,581, column 12, line 44 to column 13, line 15.



  Anionic dye compounds, for example, can also be used as coinitiators. For example, Rose Bengal, Eosin or Fluorescein are also suitable as coinitiators. Other suitable dyes, such as from the triarylmethane or azo class, e.g. in U.S. Patent 5,143,818.



  Further suitable coinitiators or electron acceptors (c) are benzopteridinediones (described in JP Hei 02 113 002), substituted benzophenones (e.g. Michler's Keton, Quantacure ABQ, Quantacure BPQ and Quantacure BTC from International Biosynthetics), trichloromethyltriazines (described in JP Hei 01 033 548), metal complexes (described in JP Hei 04 261 405), porphyrins (described in JP Hei 06 202 548 and JP Hei 06 195 014), coumarins and ketocoumarins (described in US 4 950 581 and JP Hei 06 175 557), p -Aminophenyl compounds (described in EP-A 475 153), xanthenes (described in JP Hei 06 175 566) or pyrilium, thiopyrilium and selenopyrilium dyes (described in JP Hei 06 175 563).



  Other suitable electron acceptor compounds or coinitiators are given below.



  Also of interest are compositions in which an easily reducible compound, in particular a halogenated hydrocarbon, is used as a further additive.



  Halogenated hydrocarbons are suitable as easily reducible compounds.



  Examples of this are particular
EMI28.1
 
 
EMI28.2
 
 



  In this context, an easily reducible compound is also understood to mean compounds as described in US Pat. No. 4,950,581, for example also iodonium salts, sulfonium salts, organic peroxides, compounds with carbon-halide bonds (trichloromethyltriazines), heterocyclic sulfur compounds and others Photoinitiators (alpha aminoketones). Other additives include heterocylene, as described in patents and patent applications US 5 168 032, JP 02 244 050, JP 02 054 268, JP 01 017 048 and DE 383 308.



  Other additives are e.g. aromatic lmine, described in US 5,079,126 and aromatic diazo compounds, described in US 5,200,292 (eg iminoquinonediazides), thiols described in US 4,937,159, and thiols and N, N-dialkylanilines, described in US 4,874,685 several of the coinitiators or electron acceptors and additives listed can also be used in combination.



  The invention also relates to a composition comprising, in addition to components (a) and (b), at least one compound of the formula XI
EMI29.1
 
 
 



  wherein Ra, Rb, Rc and Rd independently of one another for C1-C12-alkyl, trimethylsilylmethyl, phenyl, another aromatic hydrocarbon, C1-C6-alkylphenyl, allyl, phenyl-C1-C6-alkyl, C2-C8-alkenyl, C2- C8-alkynyl, C3-C12-cycloalkyl or saturated or unsaturated heterocyclic radicals, where the radicals phenyl, other aromatic hydrocarbon, phenyl-C1-C6-alkyl and saturated or unsaturated heterocyclic radical are unsubstituted or 1- to 5-fold with unsubstituted or with OR6 or R7R8N substituted C1-C20-alkyl, with one or more residues O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O) , R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q or / and CN;
 p represents 0, 1 or 2;
 q is 0 or 1;

  
 R5 is hydrogen, C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, where the radicals phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12-alkoxy or / and halogen are substituted;
 R6 is unsubstituted or halogen-substituted C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1- C12 alkoxy or / and halogen are substituted;

  
 R7 and R8 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl which are unsubstituted or substituted by C1-C12-alkoxy, halogen, OH, COOR6 or CN, the radicals being phenyl- C1-C6-alkyl or phenyl unsubstituted or 1- to 5-fold substituted with C1-C6-alkyl, C1-C12-alkoxy or / and halogen, or R7 and R8 together with the N atom to which they are attached, one Form 5- or 6-membered ring, which can additionally contain O or S atoms;
 R9, R10 and R11 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold with C1 -C6 alkyl, C1-C12 alkoxy or / and halogen are substituted;

   and
 Z represents a radical which can form positive ions, in particular alkali metals, ammonium, tetraalkylammonium, phosphonium or sulfonium compounds.



  The meanings for C1-C12-alkyl, aromatic hydrocarbon, C1-C6-alkylphenyl, allyl, phenyl-C1-C6-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C12-cycloalkyl, saturated or unsaturated heterocyclic The rest, which can form positive ions, alkali metal, tetraalkylammonium, and R5 to R11 are as given above for the formulas I, l min, la or la min.



  According to the invention is also a composition containing at least one borate of the formula I, l min, la or la min and at least one dye which changes or loses its color during or after the irradiation, this dye also being a component of the compound of the formula I , l min, la or la min. Examples of such dyes are cyanine or pyrilium dyes.



  As already mentioned, the combination of the borate compounds according to the invention with coinitiators, e.g. even those that act as sensitizers (= energy transfer) are possible. Combinations with several different sensitizers, such as e.g. Mixtures of the borate compounds according to the invention with "onium" salts and thioxanthones or coumarins or dyes, very effectively. Preferred "onium" salts in these mixtures are diphenyliodonium hexafluorophosphate, (p-octyloxyphenyl) (phenyl) iodonium hexafluorophosphate or corresponding other anions of these compounds, e.g. the halides; but also sulfonium salts, e.g. Triarylsulfonium salts (Cyracure <TM> UVI 6990, Cyracure Union Carbide's UVI-6974; Degacure <TM> KI 85 from Degussa or SP-150 and SP-170 from Asahi Denka).

   For example, a mixture of the borate compounds according to the invention with diphenyliodonium hexafluorophosphate and isopropylthioxanthone, a mixture of the borate compounds according to the invention with (p-octyloxyphenyl) (phenyl) iodonium hexafluorophosphate and isopropylthioxanthone, and a mixture of the borate compounds according to the invention are preferred
EMI31.1
 
EMI31.2
 



    (= Cyracure <TM> UVI-6974) and isopropylthioxanthone.



  However, it is also particularly advantageous to add a further photoinitiator of the alpha-aminoketone type to the mixtures mentioned above. For example, mixtures of the borates according to the invention with "onium" salts and thioxanthones or dyes and alpha-aminoketones are very effective. A preferred example is the mixture of the borate compounds according to the invention with diphenyliodonium hexafluorophosphate or (p-octyloxyphenyl) (phenyl) iodonium hexafluorophosphate, isopropythioxanthone and (4-methylthiobenzoyl) methyl-1-morpholino-ethane. Tetramethylammonium-methyl-dimesityl- (1-naphthyl) borate is particularly suitable as a borate compound in these mixtures.



  The invention therefore also includes compositions comprising, in addition to components (a) and (b), at least one neutral, anionic or cationic dye or a thioxanthone and an onium compound, and also compositions comprising an additional free radical photoinitiator, in particular an alpha-aminoketone compound.



  The unsaturated compounds of component (a) can contain one or more olefinic double bonds. They can be low molecular weight (monomeric) or higher molecular weight (oligomeric). Examples of monomers with a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, e.g. Methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate, methyl or ethyl methacrylate. Silicone acrylates are also interesting. Further examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylic amides, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl and halostyrenes, N-vinyl pyrrolidone, vinyl chloride or vinylidene chloride.



  Examples of monomers with multiple double bonds are ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or bisphenol A diacrylate, 4.4 min bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or vinytetracrylate or vinylacetate Divinylbenzene, divinylsuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2-acryloylethyl) isocyanurate.



  Examples of higher molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated or vinyl ether or epoxy group-containing polyesters, polyurethanes and polyethers. Further examples of unsaturated oligomers are unsaturated polyester resins, which are usually produced from maleic acid, phthalic acid and one or more diols and have molecular weights of approximately 500 to 3000. In addition, vinyl ether monomers and oligomers as well as maleate-terminated oligomers with polyester, polyurethane, polyether, polyvinyl ether and epoxy main chains can also be used. Combinations of vinyl ether group-bearing oligomers and polymers, as described in WO90 / 01 512, are particularly suitable. Copolymers of vinyl ether and maleic acid functionalized monomers are also suitable.

   Such unsaturated oligomers can also be referred to as prepolymers.



  For example, Esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers with ethylenically unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers with (meth) acrylic groups in side chains, and also mixtures of one or more such polymers.



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



  Aromatic and particularly aliphatic and cycloaliphatic polyols are suitable as polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) propane, and novolaks and resols. Examples of polyepoxides are those based on the polyols mentioned, especially the aromatic polyols and epichlorohydrin. Polymers and copolymers which contain hydroxyl groups in the polymer chain or in side groups, such as e.g. Polyvinyl alcohol and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof, are suitable as polyols. Other suitable polyols are oligoesters with hydroxyl end groups.



  Examples of aliphatic and cycloaliphatic polyols are alkylene diols with preferably 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol , Octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols with molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris (beta-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.



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



  Examples of esters are:



  Trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Tripentaerythritoctaacrylat, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, Dipentaerythrittetramethacrylat, Tripentaerythritoctamethacrylat, pentaerythritol, Dipentaerythrittrisitaconat, dipentaerythritol, dipentaerythritol hexaitaconate, Ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate,

   Pentaerythritol-modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol di- and triacrylate, 1,4-cyclohexane diacrylate, bisacrylates and bismethacrylates of polyethylene glycol with a molecular weight of 200 to 1500, or a molecular weight of 200 to 1500 thereof.



  Also suitable as component (a) are the amides of identical or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines with preferably 2 to 6, particularly 2 to 4, amino groups. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-beta-aminoethyl ether, diethylene triamine, triethylene tetramine, di (beta-aminoethoxy) - or di (beta-aminopropoxy) ethane. Other suitable polyamines are polymers and copolymers with optionally additional amino groups in the side chain and oligoamides with amino end groups.

   Examples of such unsaturated amides are: methylene-bis-acrylamide, 1,6-hexamethylenebis-acrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamidopropoxy) ethane, beta-methacrylamidoethyl methacrylate, N [(beta-hydroxyethoxy) ethyl] acrylamide.



  Suitable unsaturated polyesters and polyamides are derived e.g. on maleic acid and diols or diamines. Maleic acid can be partially replaced by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, e.g. Styrene. The polyesters and polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from long-chain ones with e.g. 6 to 20 carbon atoms. Examples of polyurethanes are those which are composed of saturated or unsaturated diisocyanates and unsaturated or saturated diols.



  Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers are e.g. Olefins such as ethylene, propene, butene, hexene, (meth) acrylates, acrylonitrile, styrene or vinyl chloride. Polymers with (meth) acrylate groups in the side chain are also known. For example, are reaction products of novolak-based epoxy resins with (meth) -acrylic acid, homo- or copolymers of vinyl alcohol or their hydroxyalkyl derivatives which are esterified with (meth) -acrylic acid, or homo- and copolymers of (meth) -acrylates with Hydroxyalkyl (meth) acrylates are esterified.



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



  Binders can also be added to the compositions according to the invention, which is particularly expedient if the photopolymerizable compounds are liquid or viscous substances. The amount of binder can e.g. 5-95, preferably 10-90 and particularly 40-90 wt .-%, based on the total solids. The choice of binder depends on the field of application and the properties required for this, such as developability in aqueous and organic solvent systems, adhesion to substrates and sensitivity to oxygen.



  Suitable binders are e.g. Polymers with a molecular weight of about 5000-2,000,000, preferably 10,000-1,000,000. Examples are: homo- and copolymers acrylates and methacrylates, e.g. Copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (methacrylic acid alkyl ester), poly (acrylic acid alkyl ester); Cellulose esters and ethers such as cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; Polyvinyl butyral, polyvinyl formal, cyclized rubber, polyethers 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 (ethylene / vinyl acetate), polymers such as polycaprolactam and poly (hexamethylene adipamide), polyesters such as poly (ethylene glycol) ) and poly (hexamethylene glycol succinate).



  The unsaturated compounds can also be used in a mixture with non-photopolymerizable film-forming components. These can e.g. physically drying polymers or their solutions in organic solvents, e.g. Nitrocellulose or cellulose acetobutyrate. However, these can also be chemically or thermally curable resins, such as Polyisocyanates, polyepoxides or melamine resins. The use of thermally curable resins is important for use in so-called hybrid systems, which are photopolymerized in a first stage and crosslinked by thermal aftertreatment in a second stage.



  Compositions are also according to the invention in which, in addition to components (a) and (b), at least one coinitiator or electron acceptor (c), such as e.g. a neutral, cationic or anionic dye or a UV absorber is included.



  Suitable dyes (c) are described above. Also suitable are e.g. Benzoxanthene, benzothioxanthene, pyronine or porphyrin dyes.



  Compositions with cyanine derivatives as the dye are particularly preferred. Particularly preferred are cyanines of the formula IV, in which n = 1-4, Y1 = C (CH3) 2 or S and R = C1-C10-alkyl.



  UV absorbers suitable as coinitiators or electron acceptors (c) are e.g. Thioxanthone derivatives, coumarins, benzophenone, benzophenone derivatives or hexaarylbisimidazole derivatives.



  Suitable hexaarylbisimidazole derivatives are e.g. in U.S. Patents 3,784,557, 4,252,887, 4,311,783, 4,459,349, 4,410,621 and 4,622,286. Of particular interest are 2-o-chlorophenyl-substituted derivatives such as e.g. 2.2 min -bis (o-chlorophenyl) -4.4 min, 5.5 min -tetraphenyl-1.1 min -bisimidazole. Other suitable UV absorbers in this context are e.g. polycyclic aromatic hydrocarbons, e.g. Anthracene or pyrene, as well as the triazines described in EP-A-137 452, DE-A-2 718 254 and DE-A-2 243 621. Further suitable triazines can be found in US Pat. No. 4,950,581 column 14, line 60 to column 18, line 44. Trihalomethyltriazines, e.g. 2,4-bis (trichloromethyl) -6- (4-styrenephenyl) -s-triazine.



  In addition to the photoinitiator, the photopolymerizable mixtures can contain various additives. Examples of this are thermal inhibitors which are intended to prevent premature polymerization, e.g. Hydroquinone, hydroquinone derivatives, p-methoxyphenol, beta-naphthol or sterically hindered phenols such as e.g. 2,6-di (tert-butyl) -p-cresol. To increase dark storage stability, e.g. Copper compounds such as copper naphthenate, stearate or octate, phosphorus compounds such as e.g. Triphenylphosphine, tributylphosphine, triethylphosphite, triphenylphosphite or tribenzylphosphite, quaternary ammonium compounds such as e.g. Tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives such as e.g. N-diethyl-hydroxylamine can be used.

   In order to exclude atmospheric oxygen during the polymerization, paraffin or similar wax-like substances can be added, which migrate to the surface at the beginning of the polymerization due to the lack of solubility in the polymer and form a transparent surface layer which prevents the entry of air. An oxygen-impermeable layer can also be applied. Small amounts of UV absorbers such as e.g. those of the hydroxyphenyl-benzotriazole, hydroxyphenyl-benzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type, who added. Individual or mixtures of these compounds with or without the use of sterically hindered amines (HALS) can be used.



  Examples of such UV absorbers and light stabilizers are



  1. 2- (2 min -hydroxyphenyl) benzotriazoles, e.g. 2- (2 min -hydroxy-5 min -methylphenyl) -benzotriazole, 2- (3 min, 5 min -di-tert-butyl-2 min -hydroxyphenyl) -benzotriazole, 2- (5 min -tert-butyl-2 min -hydroxyphenyl) -benzotriazole, 2- (2 min -hydroxy-5 min - (1,1,3,3-tetramethylbutyl) phenyl) -benzotriazole, 2- (3 min, 5 min -Di-tert-butyl-2 min -hydroxyphenyl) -5-chloro-benzotriazole, 2- (3 min-tert-butyl-2 min -hydroxy-5 min -methylphenyl) -5-chlorobenzotriazole, 2- (3 min -sec-butyl-5 min -tert -butyl-2 min -hydroxyphenyl) -benzotrizole, 2- (2 min -hydroxy-4 min -octoxyphenyl) -benzotriazole, 2- (3 min, 5 min -Di-tert-amyl-2 min -hydroxyphenyl) -benzotriazole, 2- (3 min, 5 min-bis-alpha, alpha -dimethylbenzyl) -2 min -hydroxyphenyl) -benzotriazole, mixture of 2- (3 min-tert-butyl-2 min -hydroxy-5 min - (2-octyloxycarbonylethyl ) phenyl) -5-chloro-benzotriazole, 2- (3 min-tert-butyl-5 min - [2- (2-ethylhexyloxy)

  -carbonylethyl] -2 min -hydroxyphenyl) -5-chloro-benzotriazole, 2- (3 min-tert-butyl-2 min -hydroxy-5 min - (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3 min-tert-butyl-2 min -hydroxy-5 min - (2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3 min-tert-butyl-2 min -hydroxy-5 min - (2-octyloxycarbonylethyl) phenyl ) -benzotriazole, 2- (3 min -tert-butyl-5 min - [2- (2-ethylhexyloxy) carbonylethyl] -2 min -hydroxyphenyl) -benzotriazole, 2- (3 min -dodecyl-2 min -hydroxy-5 min -methylphenyl) benzotriazole, and 2- (3 min-tert-butyl-2 min -hydroxy-5 min - (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, 2.2 min -methylene-bis [4- (1.1 , 3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol];

   Transesterification product of 2- [3 min-tert-butyl-5 min - (2-methoxycarbonylethyl) -2 min-hydroxy-phenyl] -benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO (CH2) 3] 2- with R = 3 min-tert-butyl-4 min -hydroxy-5 min -2H-benzotriazol-2-yl-phenyl.



  2. 2-hydroxybenzophenones, e.g. the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4.2 min, 4 min tri-hydroxy, 2 min hydroxy-4,4 min -dimethoxy derivative.



  3. Esters of optionally substituted benzoic acids, e.g. 4-tert-butylphenyl 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-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2- methyl 4,6-di-tert-butylphenyl ester.



  4. Acrylates, e.g. alpha-cyano-beta, beta -diphenylacrylic acid ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, alpha-carbomethoxy-p-methoxy-cinnamic acid- methyl ester, N- (beta-carbomethoxy-beta-cyanovinyl) -2-methyl-indoline.



  5. Sterically hindered amines, e.g. Bis (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-butyl-4-hydroxybenzyl-malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2, 6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N, N min-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine 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-butanetetraoate, 1.1 min - (1,2-ethanediyl) -bis- (3,3,5,5-tetramethyl-piperazinone), 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 tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,

  9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2 , 2,6,6-tetramethylpiperidyl) succinate, condensation product of N, N min-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-morpholino-2,6-dichloro-1 , 3,5-triazine, condensation product of 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis - (3-aminopropylamino) ethane, condensation product of 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3- 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. oxalic acid diamides such as e.g. 4.4 min -di-octyloxy-oxanilide, 2.2 min -diethoxy-oxanilide, 2.2 min -di-octyloxy-5.5 min -di-tert-butyl-oxanilide, 2.2 min -di-dodecyloxy -5.5 min -di-tert-butyl-oxanilide, 2-ethoxy-2 min -ethyloxanilide, N, N min-bis (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2 min -ethyloxanilide and its mixture with 2-ethoxy-2 min -ethyl-5.4 min -di-tert-butyl-oxanilide, mixtures of o- and p-methoxy- and of o- and p-ethoxy-di-substituted oxanilides .



  7. 2- (2-hydroxyphenyl) -1,3,5-triazines, e.g. 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-dimethylphenyl) 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy- 3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyl / tridecyl-oxy- (2-hydroxypropyl) oxy-2-hydroxyphenyl] -4.6 -bis (2,4-dimethylphenyl) -1,3,5-triazine.



  8. Phosphites and phosphonites, e.g. Triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodhritol (diisithritol) bisphite tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ) -pentaerythritol diphosphite, bis- (2,4,6-tri-tert-butylphenyl) -pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4.4 min -biphenylene-diphosphonite , 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra- tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis- (2,

  4-di-tert-butyl-6-methylphenyl) ethyl phosphite.



  Amines can be added to accelerate the photopolymerization, e.g. Triethanolamine, N-methyl-diethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone. The effect of the amines can be enhanced by adding aromatic ketones of the benzophenone type. Amines which can be used as oxygen scavengers are, for example, substituted N, N-dialkylanilines, as described in EP-A-339 841. Further accelerators, coinitiators and autoxidizers are thiols, thioethers, disulfides or phosphines, phosphonium salts or phosphine oxides as described in EP-A-438 123, GB 2 180 358 and JP Hei 06 268 309.



  The photopolymerization can also be accelerated by adding further photosensitizers which shift or broaden the spectral sensitivity. These are especially aromatic carbonyl compounds such as Benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives as well as 3- (aroylmethylene) thiazolines, but also eosin, rhodamine and erythrosine dyes.



  The curing process can be supported, in particular, by compositions pigmented (e.g. with titanium dioxide), also by adding a component which forms free radicals under thermal conditions, e.g. an azo compound such as 2.2 min azobis (4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazosulfide, pentazadiene or a peroxy compound such as hydroperoxide or peroxycarbonate, e.g. t-butyl hydroperoxide, e.g. described in EP-A 245 639.



  Other common additives are - depending on the intended use - optical brighteners, fillers, pigments, dyes, wetting agents or leveling agents.



  For the hardening of thick and pigmented coatings, the addition of micro glass balls or powdered glass fibers, e.g. in US-A-5 013 768.



  The invention also relates to compositions comprising, as component (a), at least one ethylenically unsaturated photopolymerizable compound dissolved or emulsified in water.



  Such radiation-curable aqueous prepolymer dispersions are commercially available in many variations. This is understood to mean a dispersion of water and at least one prepolymer dispersed therein. The concentration of water in these systems is e.g. at 5 to 80, in particular 30 to 60 wt .-%. The radiation-curable prepolymer or prepolymer mixture is contained, for example, in concentrations of 95 to 20, in particular 70 to 40,% by weight. In these compositions, the sum of the percentages given for water and prepolymers is 100 in each case, and the auxiliaries and additives are added in different amounts, depending on the intended use.



  The radiation-curable, water-dispersed, and often also dissolved, film-forming prepolymers are mono-or polyfunctional ethylenically unsaturated prepolymers which are known per se and which can be initiated by free radicals for aqueous prepolymer dispersions and contain, for example, a content of 0.01 to 1.0 mol per 100 g prepolymer of polymerizable double bonds, and an average molecular weight of, for example have at least 400, in particular from 500 to 10,000. Depending on the application, prepolymers with higher molecular weights can also be used.

   For example, polymerizable CC double bonds containing polyesters with an acid number of at most 10, polymerizable CC double bonds containing polyethers, hydroxyl group-containing reaction products of a polyepoxide containing at least two epoxy groups per molecule with at least one alpha, beta-ethylenically unsaturated carboxylic acid, polyurethane (meth) Acrylates and alpha, beta-ethylenically unsaturated acrylic copolymers containing acrylic copolymers are used, as are 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 with an average molecular weight of at least 600, a carboxyl group content of 0.2 to 15% and a content of 0.01 up to 0.8 mol of polymerizable CC double bonds per 100 g of prepolymer. Other suitable aqueous dispersions based on special (meth) acrylic acid alkyl ester polymers are described in EP-A-41 125; suitable water-dispersible, radiation-curable prepolymers made from urethane acrylates can be found in DE-A-2 936 039.



  As further additives, these radiation-curable aqueous prepolymer dispersions can include dispersing aids, emulsifiers, antioxidants, light stabilizers, dyes, pigments, fillers, e.g. Talc, gypsum, silica, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, leveling agents, lubricants, wetting agents, thickeners, matting agents, defoamers and other auxiliaries customary in coating technology. Water-soluble high-molecular organic compounds with polar groups, such as e.g. Polyvinyl alcohols, polyvinyl pyrrolidone or cellulose ether in question. Non-ionic, optionally also ionic emulsifiers can be used as emulsifiers.



  In certain cases it may be advantageous to use mixtures of two or more of the photoinitiators according to the invention. Of course, mixtures with known photoinitiators can also be used, e.g. Mixtures with benzophenone, acetophenone derivatives, such as, for example, alpha-hydroxycycloalkylphenyl ketones, dialkoxyacetophenones, alpha-hydroxy or alpha-aminoacetophenones, 4-aroyl-1,3-dioxolanes, benzoinalkyl ethers and benzil ketals, monoacylphosphinophene phenin, antioxidants, antioxidants, antioxidants, xenoxylacidophosphinoxinophene, or titanocenes.



  Examples of particularly suitable additional photoinitiators are: 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl-1- hydroxy-1-methylethane, 1- [4 (2-hydroxyethoxy) benzoyl] -1-hydroxy-1-methylethane, 1- [4 (acryloyloxyethoxy) benzoyl] -1-hydroxy-1-methylethane , Diphenyl ketone, phenyl-1-hydroxycyclohexyl ketone, (4-morpholinobenzoyl) -1-benzyl-1-dimethylamino-propane, 1- (3,4-dimethoxyphenyl) -2-benzyl-2-dimethylamino-butanone-1, (4- Methylthiobenzoyl) -1-methyl-1-morpholino-ethane, benzil dimethyl ketal, bis (cyclopentadienyl) bis (2,6-difluoro-3-pyrrylphenyl) titanium, cyclopentadienyl-arene-iron (II) complex salts, e.g.

   (eta <6> -isopropylbenzene) (eta <5> -cyclopentadien-yl) -iron-II-hexafluorophosphate, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy-benzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6- trimethylbenzoyl) -2,4-dipentoxyphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. Further suitable additional photoinitiators can be found in US Pat. No. 4,950,581 column 20, line 35 to column 21, line 35.



  Triazine compounds, such as e.g. the triazines described in EP-A-137 452, DE-A-2 718 254 and DE-A-2 243 621. Further suitable triazines can be found in US Pat. No. 4,950,581, column 14, line 60 to column 18, line 44. Trihalomethyltriazines, e.g. 2,4-bis (trichloromethyl) -6- (4-styryl-phenyl) -s-triazine.



  If the photoinitiators according to the invention are used in hybrid systems, in addition to the radical hardeners according to the invention, cationic photoinitiators such as e.g. Peroxide compounds, e.g. Benzoyl peroxide (other suitable peroxides are described in US Pat. No. 4,950,581, column 19, lines 17-25), aromatic sulfonium or iodonium salts, such as, for example, US Pat. No. 4,950,581 column 18, line 60 to column 19, Line 10, or cyclopentadienyl-arene-iron (II) complex salts, for example (eta <6> -isopropylbenzene) (eta <5> -cyclopentadien-yl) -iron-II-hexafluorophosphate, used.



  The invention therefore also relates, as already mentioned above, to compositions which, in addition to the photon initiator (b), also comprise at least one further photoinitiator (d) and / or other additives.



  The photopolymerizable compositions advantageously contain the photoinitiator (b) or the components (b) + (d) in an amount of 0.05 to 15% by weight, preferably 0.1 to 5% by weight, based on the composition .



  (The quantity refers to the total amount of photoinitiator in the composition)



  Particularly preferred are compositions containing as photoinitiator (d) a titanocene, a ferrocene, a benzophenone, a benzoin alkyl ether, a benzil ketal, a 4-aroyl-1,3-dioxolane, a dialkoxyacetophenone, an alpha-hydroxy or alpha-aminoacetophenone alpha-Hydroxycycloalkyl-phenyl ketone, a xanthone, a thioxanthone, an anthraquinone or a mono- or bisacylphosphine oxide or mixtures thereof as an additional photoinitiator.



  The photopolymerizable compositions can be used for various purposes, for example as a printing ink, as a clear lacquer, as a white lacquer, e.g. for wood or metal, as paint, etc. for paper, wood, metal or plastic, as daylight-curable coating for building and street marking, for photographic reproduction processes, for holographic recording materials, for image recording processes or for the production of printing plates that can be developed with organic solvents or aqueous-alkaline, for the production of masks for screen printing, as dental filling compounds, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etching or permanent resists and as solder masks for electronic circuits, for the production of three-dimensional objects by mass hardening (UV hardening in transparent forms)

   or by the stereolithography method, e.g. in U.S. Patent No. 4,575,330, for the manufacture of composite materials (e.g. styrenic polyesters, which may or may not contain glass fibers and other auxiliaries) and other thick-film compositions, for coating or sealing electronic parts or as coatings for optical fibers.



  The compounds according to the invention can furthermore be used as initiators for emulsion polymerizations, as initiators of a polymerization for fixing order states of liquid-crystalline mono- and oligomers, as initiators for fixing dyes on organic materials.



  Mixtures of a prepolymer with polyunsaturated monomers, which also contain a monounsaturated monomer, are often used in paints. The prepolymer is primarily decisive for the properties of the lacquer film; through its variation, the person skilled in the art can influence the properties of the hardened film. The polyunsaturated monomer acts as a crosslinker, which makes the paint film insoluble. The monounsaturated monomer acts as a reactive diluent that lowers viscosity without the need to use a solvent.



  Unsaturated polyester resins are mostly used in two-component systems together with a monounsaturated monomer, preferably with styrene. Specific one-component systems are often used for photoresists, e.g. Polymaleimides, polychalkones or polyimides, as described in DE-OS 2 308 830.



  The compounds according to the invention and mixtures thereof can furthermore be used as radical photoinitiators or photoinitiating systems for radiation-curable powder coatings. The powder coatings can be based on solid resins and monomers containing reactive double bonds, e.g. Maleates, vinyl ethers, acrylates, acrylamides and mixtures thereof. A free-radically UV-curable powder coating can be prepared by mixing unsaturated polyester resins with solid acrylamides (for example methyl acrylamidoglycolate methyl ester) and a radical photoinitiator according to the invention, as described, for example, in the lecture "Radiation Curing of Powder Coating", Conference Proceedings, Radtech Europe 1993 by M. Wittig and Th. Gohmann described, can be formulated. The powder coatings can also contain binders, such as those e.g. in DE-A-4 228 514 and EP-A-636 669.

   Radically UV-curable powder coatings can also be formulated by mixing unsaturated polyester resins with solid acrylates, methacrylates or vinyl ethers and a photoinitiator (or photoinitiator mixture) according to the invention. The powder coatings can also contain binders, such as those e.g. in DE-A-4 228 514 and EP-A-636 669. The UV-curable powder coatings can also contain white or colored pigments. For example, preferably rutile titanium dioxide can be used up to concentrations of 50% by weight in order to obtain a hardened powder coating with good covering properties. The method usually involves electrostatically or tribostatically spraying the powder onto the substrate, e.g.

   Metal or wood, melting the powder by heating and, after a smooth film has formed, radiation curing the coating with ultraviolet and / or visible light, e.g. with medium pressure mercury lamps, metal halide lamps or xenon lamps. A particular advantage of the radiation-curable powder coatings in comparison to the corresponding thermally curable ones is that the flow time after the powder particles have melted can optionally be delayed to ensure the formation of a smooth, high-gloss coating. In contrast to thermally curable systems, radiation-curable powder coatings can be formulated in such a way that they melt at lower temperatures without the undesirable effect of shortening the service life. For this reason, they are also suitable as coatings for heat-sensitive substrates, e.g.

   Wood or plastics.



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



  The photocurable compositions according to the invention are suitable e.g. as coating materials for all types of substrates, e.g. Wood, textiles, paper, ceramics, glass, plastics such as polyester, polyethylene terephthalate, polyolefins or cellulose acetate, in particular in the form of films, and metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO2 to which a protective layer or an image is to be applied by image-wise exposure.



  The substrates can be coated by applying a liquid composition, a solution or suspension to the substrate. The choice of solvent and the concentration depend mainly on the type of composition and the coating process. The solvent should be inert, i.e. there should be no chemical reaction with the components and it should be possible to remove them again after drying after coating. Suitable solvents are e.g. Ketones, ethers and esters such as 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, acetic acid n-acetate -butyl ester and 3-ethoxy-propionic acid ethyl ester.

   The solution is applied uniformly to a substrate, e.g. by spinning, dipping, knife coating, curtain casting, brushing, spraying, especially by electrostatic spraying and reverse roll coating, and by electrophoretic deposition. It is also possible to place the light-sensitive layer on a temporary, flexible support and then to transfer the final substrate, e.g. a copper-clad printed circuit board.



  The application quantity (layer thickness) and type of substrate (layer carrier) depend on the desired application area. The layer thickness range generally comprises values from approx. 0.1 μm to more than 100 μm.



  The radiation-sensitive compositions according to the invention are used as negative resists which have a very high sensitivity to light and can be developed without swelling in an aqueous alkaline medium. They are suitable as photoresists for electronics (galvanoresist, etching resist, solder resist), the production of printing plates such as offset printing plates or screen printing forms, the use in molded part etching or the use as micro-resist in the production of integrated circuits. The possible layer supports and the processing conditions of the coated substrates are correspondingly different.



  The compounds according to the invention are also used for the production of single- or multi-layer materials for image recording or image multiplication (copies, reprography), which can be single or multi-colored. Furthermore, these materials can also be used in color inspection systems. This technology can also use formulations containing microcapsules, and a thermal step can be added after the exposure step to form the image. Such systems and technologies are e.g. in US 5,376,459.



  * For photographic information records e.g. Foils made of polyester, cellulose acetate or paper coated with plastic; Specially treated aluminum for offset printing forms, copper-clad laminates for the production of printed circuits and silicon wafers for the production of integrated circuits. The layer thicknesses for photographic materials and offset printing forms are generally approximately 0.5 .mu.m to 10 .mu.m, for printed circuits 1 .mu.m to approximately 100 .mu.m.



  After the substrates have been coated, the solvent is generally removed by drying and a layer of the photoresist on the support results.



  The term “image-wise” exposure includes both exposure through a photomask that contains a predetermined pattern, for example a slide, exposure through a laser beam that is moved, for example, computer-controlled, over the surface of the coated substrate and in this way forms an image, and irradiation with computer-controlled electron beams.



  After the imagewise exposure of the material and before development, it can be advantageous to carry out a thermal treatment for a shorter time. Only the exposed parts are thermally hardened. The temperatures used are generally 50-150 ° C., preferably 80-130 ° C .; the time for the thermal treatment is usually between 0.25 and 10 minutes.



  The photocurable composition can also be used in a process for the production of printing forms or photoresists, e.g. in DE-A-4 013 358 is used. In it, the composition is exposed to visible light of a wavelength of at least 400 nm without a mask for a short time before, simultaneously with or after the image-wise irradiation.



  After the exposure and, if appropriate, thermal treatment, the unexposed areas of the photoresist are removed in a manner known per se using a developer.



  As already mentioned, the compositions according to the invention can be developed in an alkaline aqueous medium. Suitable aqueous-alkaline developer solutions are, in particular, aqueous solutions of tetraalkylammonium hydroxides or of alkali metal silicates, phosphates, hydroxides and carbonates. Smaller amounts of wetting agents and / or organic solvents can optionally be added to these solutions. Typical organic solvents that can be added to the developer liquids in small amounts are, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of such solvents.



  Photocuring is of great importance for printing inks, since the drying time of the binder is a decisive factor for the production speed of graphic products and should be on the order of fractions of a second. UV-curable inks are particularly important for screen printing.



  As already mentioned above, the mixtures according to the invention are also very suitable for the production of printing plates. Here, e.g. Mixtures of soluble linear polyamides or styrene / butadiene or styrene / isoprene rubber, polyacrylates or polymethyl methacrylates with carboxyl groups, polyvinyl alcohols or urethane acrylates with photopolymerizable monomers, for example acrylic or methacrylamides or acrylic or methacrylic esters, and a photoinitiator. Films and plates from these systems (wet or dry) are exposed via the negative (or positive) of the print template and the uncured parts are then eluted with a suitable solvent.



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



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



  It is also interesting to use the compounds according to the invention for curing molded parts made of composite materials. The composite mass consists of a self-supporting matrix material, e.g. a glass fiber fabric, or for example plant fibers [cf. K.-P. Mieck, T. Reussmann in Kunststoffe 85 (1995), 366-370], which is soaked in the light-curing formulation. Shaped parts made of composite materials produced with the connections according to the invention achieve high mechanical stability and resistance. The compounds according to the invention can also be used as photo hardeners in molding, impregnating and coating compositions, as are described, for example, in EP-A-7086.

   Such compositions are, for example, fine-layer resins, where A N = 64>
 <tb> <TABLE> Columns = 2
 <tb> <SEP> 10.0 g <SEP> dipentaerythritol monohydroxy pentaacrylate, <TM> SR399, Sartomer (Craynor, France)
 <tb> <CEL AL = L> 15.0 g <SEP> tripropylene glycol diacrylate
 <tb> <SEP> 15.0 g <SEP> N-vinyl pyrrolidone, Fluka
 <tb> <SEP> 10.0 g <CEL AL = L> trismethylolpropane triacrylate, Degussa
 <tb> <SEP> 50.0 g <SEP> urethane acrylate <TM> Actilan AJ20, Société Nationale des Poudres et Explosifs
 <tb> <SEP> 0.3 g <SEP> flow aid Byk 300, Byk-Mallinckrodt.
 <tb> </TABLE>



  Portions of this composition are heated to 40 ° C. and 1.6% of the borate photoinitiator to be tested, based on the total amount of the formulation, are dissolved in the formulation at this temperature. All operations are carried out under red light. The samples mixed with initiator are applied to a 300 μm aluminum foil. The thickness of the dry layer is approx. 60-70 µm. A 76 µm thick polyester film is applied to this film and a standardized test negative with 21 levels of different optical density (Stouffer wedge) is placed on it. The sample is covered with a second UV-transparent film and pressed onto a metal plate using a vacuum. The exposure is carried out for 20 seconds at a distance of 30 cm using a 5 kW MO61 lamp.

   After the exposure, the films and the mask are removed and the exposed layer is developed in an ultrasound bath at 23 ° C. in ethanol for 10 seconds. Drying takes place at 40 ° C. for 5 minutes in a forced air oven. The sensitivity of the initiator system used is characterized by the indication of the last wedge step shown without sticking. The higher the number of levels, the more sensitive the system tested.

   The results are summarized in Tables 4a to 4g.
 <tb> <TABLE> Columns = 2 Table 4a
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 1a <SEP> 11
 <tb> <SEP> 6a <SEP> 12
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 4b
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 2a <SEP> 3
 <tb> <SEP> 4b <SEP> 5
 <tb> <SEP> 4a <SEP> 6
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 4c
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 2b <SEP> 8
 <tb> <SEP> 3b <SEP> 7
 <tb> <SEP> 7a <CEL AL = L> 10
 <tb> <CEL AL = L> 8a <SEP> 10
 <tb> <SEP> 9a <SEP> 13
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 4d
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 14a <SEP> 9
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 4e
 <tb> Head Col 1: connection
 <tb> Head Col 2:

   Number of hardened stages
 <tb> <SEP> 11a <SEP> 6
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 4f
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 13a <SEP> 8
 <tb> <SEP> 16a <SEP> 6
 <tb> <SEP> 19a <CEL AL = L> 7
 <tb> <CEL AL = L> 20a <SEP> 10
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 4g
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 22b <SEP> 6
 <tb> </TABLE>


 Example 27:
 



  0.4% of the borate photoinitiator to be tested and 0.3% (N, N min -dibutyl) dimethylindocarbocyanine chloride are incorporated into a formulation as described in Example 26. The preparation of the film, the curing and the determination of the reactivity are also carried out as described in Example 25.

   The results are shown in Tables 5 to 5f.
 <tb> <TABLE> Columns = 3 Table 5
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> Head Col 3: bleaching behavior *
 <tb> <SEP> 1a <SEP> 19 <SEP> b
 <tb> <SEP> 6a <SEP> 18 <SEP> b
 <tb>
 * b = formulation fades (visual inspection)
  
 <tb> </TABLE>
 <tb> <TABLE> Columns = 3 Table 5a
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> Head Col 3: bleaching behavior *
 <tb> <SEP> 2a <SEP> 18 <SEP> b
 <tb> <SEP> 4b <SEP> 20 <SEP> b
 <tb> <CEL AL = L> 4a <CEL AL = L> 17 (SEP) <-> (TB>
 * b = formulation fades (visual inspection)
 - = visually there is no fading
  
 <tb> </TABLE>
 <tb> <TABLE> Columns = 3 Table 5b
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> Head Col 3:

   Bleaching behavior *
 <tb> <SEP> 2b <SEP> 18 <SEP> b
 <tb> <SEP> 3b <SEP> 20 <SEP> b
 <tb> <CEL AL = L> 7a <CEL AL = L> 17 (SEP) <-> (TB> <SEP> 8a <SEP> 15 (SEP) <-> (TB> <SEP> 9a <SEP> 18 <SEP> b
 <tb>
 * b = formulation fades (visual inspection)
 - = visually there is no fading
  
 <tb> </TABLE>
 <tb> <TABLE> Columns = 3 Table 5c
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> Head Col 3: bleaching behavior *
 <tb> <SEP> 14a <SEP> 16 <SEP> b
 <tb>
 * b = formulation fades (visual inspection)
  
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 5d
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 11a <SEP> 14
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 5e
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 2f <SEP> 15
 <tb> </TABLE>
 <tb> <TABLE> Columns = 3 Table 5f
 <tb> Head Col 1: connection
 <tb> Head Col 2:

   Number of hardened stages
 <tb> Head Col 3: bleaching behavior
 <tb> <SEP> 13a <SEP> 11 (SEP) <-> (TB> <SEP> 16a <SEP> 14 (SEP) <-> (TB> <CEL AL = L> 19a <CEL AL = L> 9 (SEP) <-> (TB> <SEP> 20a <SEP> 12 <SEP> b
 <tb>
 * b = formulation fades (visual inspection)
 - = visually there is no fading
  
 <tb> </TABLE>


 Example 28: Photocuring of a monomer-polymer mixture
 



  A photocurable composition is made by mixing
 <tb> <TABLE> Columns = 2
 <tb> <SEP> 37.64 g <SEP> <TM> Sartomer SR 444, pentaerythritol triacrylate, (Sartomer Company, Westchester)
 <tb> <SEP> 10.76 g <SEP> <TM> Cymel 301, hexamethoxymethylmelamine (American Cyanamid, USA)
 <tb> <CEL AL = L> 47.30 g <SEP> <TM> Carboset 525, thermoplastic polyacrylate with carboxyl groups (B. F. Goodrich)
 <tb> <SEP> 4.30 g <SEP> polyvinylpyrrolidone PVP (GAF, USA)
 <tb> <SEP> 319.00 g <SEP> methylene chloride and
 <tb> <SEP> 30.00 g <SEP> methanol
 <tb> </TABLE>



  Portions of this composition are mixed with 1.6% of a borate according to the invention, based on the solids content, by stirring for one hour at room temperature. All operations are carried out under red light. The samples mixed with initiator are applied to a 300 μm aluminum foil (10 × 15 cm). The solvent is first removed by drying at room temperature for 5 minutes and then heating to 60 ° C. for 15 minutes in a forced air oven. A 76 μm thick polyester film is placed on the approx. 30-35 μm layer and a standardized test negative with 21 levels of different optical density (Stouffer wedge) is applied to it. The sample is covered with a second UV-transparent film and pressed onto a metal plate using a vacuum.

   The sample is then exposed to a 4 kW xenon lamp at a distance of 30 cm for 40 seconds. After exposure, the films and the mask are removed and the exposed layer is developed in an ultrasonic bath for 240 seconds with a 0.85% solution of sodium carbonate in water. The drying is then carried out at 60 ° C. for 15 minutes in a forced air oven. The sensitivity of the initiator system used is characterized by the indication of the last wedge step shown without sticking. The higher the number of levels, the more sensitive the system is. An increase by two steps means a doubling of the hardening speed.

   The results are shown in Tables 6 and 6a.
 <tb> <TABLE> Columns = 2 Table 6
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 2a <SEP> 6
 <tb> <SEP> 4a <SEP> 5
 <tb> <SEP> 4b <SEP> 7
 <tb> </TABLE>
 <tb> <TABLE> Columns = 2 Table 6a
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 7a <SEP> 10
 <tb> <SEP> 8a <SEP> 8
 <tb> <SEP> 3b <CEL AL = L> 5
 <tb> <CEL AL = L> 2b <SEP> 9
 <tb> <SEP> 14a <SEP> 6
 <tb> <SEP> 13a <SEP> 5
 <tb> <SEP> 19a <SEP> 5
 <tb> <SEP> 20a <SEP> 6
 <tb> <SEP> 16a <SEP> 6
 <tb> </TABLE>


 Example 29:
 



  0.3% of a borate photoinitiator with dye cation is incorporated into a formulation as described in Example 28. The preparation of the film, the curing and the determination of the reactivity are also carried out as described in Example 28. The results are shown in Tables 7 and 7a.
 <tb> <TABLE> Columns = 2 Table 7
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 2c <SEP> 19
 <tb> <SEP> 2d <SEP> 10
 <tb> </TABLE>
 <tb> <TABLE> Columns = 3 Table 7a
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> Head Col 3: bleaching behavior *
 <tb> <SEP> 3c <SEP> 10 (SEP) <-> (TB> <SEP> 3d <SEP> 18 <SEP> b
 <tb> <CEL AL = L> 2e <CEL AL = L> 16 (SEP) <-> (TB>
 * b = formulation fades (visual inspection)
 - = visually there is no fading
  
 <tb> </TABLE>


 Example 30:
 



  A photocurable composition is made by mixing
 <tb> <TABLE> Columns = 2
 <tb> <SEP> 37.64 g <SEP> <TM> Sartomer SR 444, pentaerythritol triacrylate, (Sartomer Company, Westchester)
 <tb> <SEP> 10.76 g <SEP> <TM> Cymel 301, hexamethoxymethylmelamine (American Cyanamid, USA)
 <tb> <CEL AL = L> 47.30 g <SEP> <TM> Carboset 525, thermoplastic polyacrylate with carboxyl groups (B. F. Goodrich)
 <tb> <SEP> 4.30 g <SEP> polyvinylpyrrolidone PVP (GAF, USA)
 <tb> <SEP> 319.00 g <SEP> methylene chloride and
 <tb> <SEP> 30.00 g <SEP> methanol
 <tb> </TABLE>



  Portions of this composition are mixed with 0.4% of the borate from Example 2a, 0.4% isopropylthioxanthone and 0.4% (4-methylthiobenzoyl) methyl-1-morpholino-ethane, based on the solids content, by stirring at room temperature for one hour. All operations are carried out under red light. The samples mixed with initiator are applied to a 200 μm aluminum foil (10 × 15 cm). The solvent is first removed by drying at room temperature for 5 minutes and then heating to 60 ° C. for 15 minutes in a forced air oven. A 76 μm thick polyester film is placed on the approx. 30-35 μm layer and a standardized test negative with 21 levels of different optical density (Stouffer wedge) is applied to it.

   The sample is covered with a second UV-transparent film and pressed onto a metal plate using a vacuum. The sample is then exposed to an SMX-3000 metal halide doped high pressure mercury lamp at a distance of 30 cm for 40 seconds. After the exposure, the films and the mask are removed and the exposed layer is developed in an ultrasound bath for 180 seconds with a 1% strength solution of sodium carbonate in water. The drying is then carried out at 60 ° C. for 15 minutes in a forced air oven. The sensitivity of the initiator system used is characterized by the indication of the last wedge step shown without sticking. The higher the number of levels, the more sensitive the system is. An increase by two steps means a doubling of the hardening speed.

   The results are listed in Table 8.
 <tb> <TABLE> Columns = 3 Table 8
 <tb> Head Col 1 to 3 AL = L: Number of levels shown after
 <tb> Head Col 1:10 s
 <tb> Head Col 2: 20 s
 <tb> Head Col 3: 40 s
 <tb> <SEP> 10 <SEP> 12 <SEP> 14
 <tb> </TABLE>


 Example 31:
 



  A composition as described in Example 27 contains 0.6% of the borate from Example 2a, 0.4% isopropylthioxanthone and 1.2% Cyracure <TM> UVI-6974 (UnionCarbide) =
EMI70.1
 
 
 



  incorporated as a 50% solution in propylene carbonate, based on the solids content. The tests are also carried out and evaluated as described in Example 30. The results are shown in Table 9.
 <tb> <TABLE> Columns = 3 Table 9
 <tb> Head Col 1 to 3 AL = L: Number of levels shown after
 <tb> Head Col 1:10 s
 <tb> Head Col 2: 20 s
 <tb> Head Col 3: 40 s
 <tb> <SEP> 9 <SEP> 12 <SEP> 14
 <tb> </TABLE>


 Example 32:
 



  0.4% of the borate from example 2a, 0.4% isopropylthioxanthone, 0.8% cyracure are incorporated into a composition as described in example 30 <TM> UVI-6974 (UnionCarbide) =
EMI71.1
 
 
 



  incorporated as a 50% solution in propylene carbonate and 0.4% (4-methylthiobenzoyl) methyl-1-morpholino-ethane, based on the solids content. The tests are also carried out and evaluated as described in Example 30. The results are shown in Table 10.
 <tb> <TABLE> Columns = 3 Table 10
 <tb> Head Col 1 to 3 AL = L: Number of levels shown after
 <tb> Head Col 1:10 s
 <tb> Head Col 2: 20 s
 <tb> Head Col 3: 40 s
 <tb> <SEP> 11 <SEP> 13 <SEP> 15
 <tb> </TABLE>


 Example 33:
 



  0.4% of a borate photoinitiator and 0.3% of the safranin O dye are incorporated into a formulation as described in Example 28. The preparation of the film, the curing and the determination of the reactivity are also carried out as described in Example 28. The results are shown in Table 11.
 <tb> <TABLE> Columns = 2 Table 11
 <tb> Head Col 1: connection
 <tb> Head Col 2: number of hardened stages
 <tb> <SEP> 2g <SEP> 16
 <tb> <SEP> 2h <SEP> 16
 <tb> <SEP> 2i <CEL AL = L> 3
 <tb> <CEL AL = L> 2y <SEP> 17
 <tb> <SEP> 2k <SEP> 18
 <tb> <SEP> 2m <SEP> 17
 <tb> <SEP> 2o <SEP> 13
 <tb> <SEP> 2p <CEL AL = L> 15
 <tb> <SEP> 2q <SEP> 15
 <tb> <SEP> 2r <SEP> 15
 <tb> <SEP> 2s <SEP> 15
 <tb> </TABLE>


 Example 34:
 



  0.4% of compound 2a and 0.3% of a dye are incorporated into a formulation as described in Example 28. In addition, instead of the xenon lamp, a frequency-doubled Nd / YAG laser (COHERENT DPSS 532-50, beam diameter 0.7 mm, divergence <1.3 mrad) with monochromatic light with a wavelength of 532 nm and a power of 50 mW. The laser beam with a diameter of approx. 3.3 mm is moved at a speed of 6 mm / s over a Stouffer wedge fixed on the sample with 21 steps. After development, a line of different widths and lengths remains. For the evaluation, the number of stages is indicated at which a hardened line can still be seen. The preparation of the film, the curing and the determination of the reactivity are also carried out as described in Example 28.

   The results are shown in Table 12.


 Table 12
 
EMI73.1
 
 
EMI74.1
 
 
EMI75.1
 
 


 Example 35:
 



  The same formulations as in Example 28 are used and portions of this composition are mixed with 0.4%, based on the total amount of the formulation, of compound 5 and 0.3% of a dye. All operations are carried out under red light. The samples are filled into pill jars approx. 3 cm in diameter. These formulations are used in the glasses with a frequency-doubled Nd / YAG laser (COHERENT DPSS 532-50, beam diameter 0.7 mm, divergence <1.3 mrad) with monochromatic light of wavelength 532 nm and a power of 50 mW at a distance of 30 cm for 10 seconds. After exposure, the uncured formulation is poured out and the remaining, hardened layer is developed in an ultrasound bath at 23 ° C. in ethanol for 10 seconds. Drying takes place at 40 ° C. for 5 minutes in a forced air oven.

   After development, a needle-like figure of different lengths remains. The length of the figure is given for evaluation and this is a measure of the hardening capacity. The dyes and results used are shown in Table 13:


 Table 13
 
EMI75.2
 



   
EMI75.3
 
 


 Example 36:
 



  The procedure is as in Example 28, but using 0.4% of the dye borate salts. In addition, instead of the xenon lamp, a frequency-doubled Nd / YAG laser (COHERENT DPSS 532-100, beam diameter 0.7 mm, divergence <1.3 mrad) with monochromatic light of the wavelength 532 nm and a power of 100 mW. The laser beam with a diameter of approx. 3.3 mm is moved at a speed of 6 mm / s over a Stouffer wedge fixed on the sample with 21 steps. After development, a line of different widths and lengths remains. For the evaluation, the number of stages is indicated at which a hardened line can still be seen.

   The dyes and results used are listed in Table 14.
 <tb> <TABLE> Columns = 2 Table 14:
 <tb> Head Col 1: connection
 <tb> Head Col 2: Number of stages shown
 <tb> <SEP> 2e <SEP> 11
 <tb> </TABLE>


 Example 37:
 



  The procedure is as in Example 35, but dye borate salts are used in such concentrations, since the optical density of a layer of 2 mm for the wavelength of 532 nm is 0.5 and additional compound 2a is used. In contrast to Example 34, a frequency-doubled Nd / YAG laser (COHERENT DPSS 532-100, beam diameter 0.7 mm, divergence <1.3 mrad) with monochromatic light of the wavelength 532 nm and a power of 100 mW and exposed at a distance of 30 cm for 5 seconds.

   The results are shown in Table 15.
 <tb> <TABLE> Columns = 4 Table 15:
 <tb> Head Col 1: connection
 <tb> Head Col 2: concentration
 Compound 2a
 <tb> Head Col 3: Length of the figure formed in mm
 <tb> Head Col 4: bleaching behavior *
 <tb> <SEP> 0.03% 2e <SEP> 0 <SEP> 5 (SEP) <-> (TB> <SEP> 0.03% 2e <CEL AL = L> 0.3% <CEL AL = L> 14 <SEP> b
 <tb> <SEP> 0.03% 2e <SEP> 0.6% <SEP> 17 <SEP> b
 <tb>
 * b = formulation fades (visual inspection)
 - = visually there is no fading
  
 <tb> </TABLE>


 Example 38:
 



  The same formulations as in Example 26 are used and portions of this composition are mixed with 0.4%, based on the total amount of the formulation, of the compound 2a and 0.3% of a dye. All operations are carried out under red light. The samples are filled into black plastic lids with a diameter of approx. 1.5 cm and a height of approx. 12 mm and covered with a Mylar film. These samples are taken with daylight and a dose of 1200 mJ / cm <2> exposed. After exposure, the uncured formulation is poured out and the remaining, hardened layer is developed in an ultrasound bath at 23 ° C. in ethanol for 1 minute. Drying takes place at 40 ° C. for 5 minutes in a forced air oven. For the evaluation, the thickness of the hardened layer is measured and this is a measure of the hardening capacity.

   The dyes and results used are shown in Table 16:
 <tb> <TABLE> Columns = 2 Table 16:
 <tb> Head Col 1: dye
 <tb> Head Col 2: Thickness of the hardened layer in mm
 <tb> <SEP> Safranin O <SEP> 1.45
 <tb> <SEP> Methylene blue <CEL AL = L> 2.94
 <tb> </TABLE>


 Example 39:
 



  The procedure is as in Example 38, but instead of mixtures of borates and dyes, 0.4% of the dye borate salts according to the invention and additionally of compound 2a are used. The results are shown in Table 17:
 <tb> <TABLE> Columns = 3 Table 17:
 <tb> Head Col 1: connection
 <tb> Head Col 2: concentration
 the connection 2a
 <tb> Head Col 3: Thickness of the hardened layer in µm
 <tb> <SEP> 2e <SEP> 0 <SEP> 1140
 <tb> <SEP> 2e <CEL AL = L> 0.3% <CEL AL = L> 1440
 <tb> <SEP> 2e <SEP> 0.6% <SEP> 1880
 <tb> </TABLE>


 Example 40:
 



  The procedure is as in Example 26, but 0.4% of a cationic photoinitiator is added together with 0.4% of compound 2a. The results are described in Table 18.


 Table 18
 
EMI78.1
 
 


 Example 41:
 



  The procedure is as in Example 26, but 0.4% of a cationic photoinitiator is added together with 0.4% of compound 2a and 0.3% of a dye. The results are described in Table 19.


 Table 19
 
EMI79.1
 
 


 Example 42:
 



  The procedure is as in Example 26, but 0.4% of compound 2a and 0.3% of a dye or electron acceptor are added in each case. The results are described in Table 20.


 Table 20
 
EMI80.1
 
 
 



  * b = formulation fades (visual inspection)
 - = visually there is no fading


 Example 43:
 



  The procedure is as in Example 26, but 2% of compound 2a and 2% of an electron acceptor are added in each case. The results are described in Table 21.


 Table 21
 
EMI81.1
 
 


 Example 44:
 



  The procedure is as in Example 26, but 0.4% of compound 2a and 0.3% of an electron acceptor and 0.3% of a dye are added in each case. The results are described in Table 22.
 <tb> <TABLE> Columns = 3 Table 22
 <tb> Head Col 1: electron acceptance
 <tb> Head Col 2: dye
 <tb> Head Col 3: Number of hardened stages
 <tb> <SEP> Quantacure ITX <SEP> Safranin O <SEP> 13
 <tb> </TABLE>


    

Claims (18)

  1. Containing composition    a) at least one polymerizable ethylenically unsaturated compound and    b) at least one compound of formula I or 1 min as a unimolecular photoinitiator EMI82.1          wherein R1, R2 and R3 independently of one another represent phenyl or another aromatic hydrocarbon, with or without a hetero atom, these radicals being unsubstituted or 1- to 5-fold with C1-C20-alkyl which is unsubstituted or substituted by OR6 or R7R8N, with one or more Residues O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q, CN or / and EMI82.2       EMI82.3    are substituted,  or the radicals R2 and R3 form bridges, structures of the formulas II, Ila or lIb EMI82.4          arise, the aromatic rings in formula II,  lIa or lIb are unsubstituted or with C1-C20-alkyl, with one or more radicals O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, halogen, R9R10P (O) q or / and R9R10R11Sn are substituted;  with the provisos that at most two of the radicals R1, R2 and R3 are the same and either at least two of the radicals R1, R2 and R3 are phenyl radicals substituted in both ortho positions or aromatic hydrocarbon radicals  or at least one radical R1, R2 or R3 is a bulky aryl radical and the remaining radicals R1, R2 or R3 are at least one ortho-substituted phenyl radicals or aromatic hydrocarbon radicals;  R1a represents a divalent aromatic hydrocarbon radical, this radical being unsubstituted or with C1-C6-alkyl, OR6, S (O) pR6, OS (O) 2R6, NR8R7, C (O) OR6, C (O) NR8R7, C ( O) R9, SiR9R10R11 or halogen is substituted or R1a is phenyl-C1-C6-alkylene;  R4 represents phenyl or another aromatic hydrocarbon radical, with or without a hetero atom, these radicals being unsubstituted or 1- to 5-fold with C1-C20-alkyl which is unsubstituted or substituted by OR6 or R7R8N, with one or more radicals O, S (O) p or NR5 interrupted C2-C20 alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O ) q, CN or / and EMI83.1          are substituted, or R4 C1-C20-alkyl, C2-C20-alkyl interrupted by one or more radicals O, S (O) p or NR5, C3-C12-cycloalkyl, C2-C8-alkenyl,  Phenyl-C1-C6-alkyl or naphthyl-C1-C3-alkyl, where the residues C1-C20-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or naphthyl-C1- C3-alkyl are unsubstituted or with OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q, or / and CN are substituted;  Y for (CH2) n, CH = CH, C (O), NR5, O, S (O) p or EMI83.2  stands;  n represents 0, 1 or 2;    m is 2 or 3;  p represents 0, 1 or 2;  q is 0 or 1;  E represents R21R22R23P, R7R7aR8N or R6R6aS;  R5 is hydrogen, C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, where the radicals phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12-alkoxy or / and halogen are substituted;  R6 and R6a are unsubstituted or halogen-substituted C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, where the radicals phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12-alkoxy or / and halogen are substituted;  R7, R7a and R8 independently of one another are unsubstituted or C1-C12-alkoxy, halogen, OH, COOR6 or CN-substituted C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals Phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold substituted with C1-C6-alkyl, C1-C12-alkoxy or / and halogen, or R7 and R8 together with the N atom to which they are attached , form a 5- or 6-membered ring, which may additionally contain O or S atoms;  R9, R10 and R11 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold are substituted with C1-C6-alkyl, C1-C12-alkoxy or / and halogen;  R12, R13, R14 and R15 independently of one another are hydrogen, unsubstituted or C1-C12-alkoxy-substituted C1-C12-alkyl, unsubstituted or one to five times with C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl-C1 -C6-alkyl or unsubstituted or one to five times with C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl, or the radicals R12, R13, R14 and R15, together form an aromatic ring, on which further aromatic Rings can be fused;  R16, R17, R18, R18a, R19 and R20 independently of one another are hydrogen, unsubstituted or C1-C12-alkoxy, OH or halogen-substituted C1-C12-alkyl or unsubstituted or C1-C12-alkyl, C1-C12-alkoxy, OH or halogen substituted phenyl;  R21, R22 and R23 independently of one another C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, where the residues C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl are unsubstituted or with R6OCO or CN are substituted, or R21, R22 and R23 unsubstituted or mono- to pentasubstituted by C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl-C1-C6-alkyl or unsubstituted or mono- or pentasubstituted by C1-C6 Alkyl, C1-C12-alkoxy or halogen-substituted phenyl;  X is N, S or O; and  G represents a residue which can form positive ions. 2nd  Compositions according to Claim 1, in which in the compound of the formula I R1 and R2 are identical and are phenyl, naphthyl or anthracyl which are mono- to pentasubstituted by C1-C4-alkyl and / or halogen, R3 is unsubstituted or by halogen or C1-C4- Represents alkyl substituted phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-anthracyl, 9-phenanthryl or 1-pyrenyl, R4 means phenyl or C1-C4-alkyl or R2 and R3 form a bridge and a structure of formula II is formed , wherein Y represents a bond, and G for tetramethylammonium, safranin O cation EMI85.1       EMI85.2      <+> N (CH3) 3 (n-C16H33), EMI85.3  , EMI85.4  , <+> N (CH3) 3 (CH2OH), (CH3) 3N <+> (CH2) 6N <+> (CH3) 3, <+> N (C2H5) 3 ([CH2] 3Br), EMI85.5  , (Phenyl) 3P = N <+> = P (phenyl) 3, EMI85.6     EMI85.7       (Phenyl) 3S <+>, EMI85.8     EMI85.9       stands or a compound of formula I min,  wherein R1a is naphthylene and E represents trimethylammonium or dimethylbenzylammonium. 3. Composition according to one of claims 1 or 2 containing in addition to components a) and b) at least one coinitiator (c). 4. The composition according to claim 1, comprising in addition to components (a) and (b) at least one compound of formula XI EMI86.1          wherein Ra, Rb, Rc and Rd independently of one another for C1-C12-alkyl, trimethylsilylmethyl, phenyl, another aromatic hydrocarbon, C1-C6-alkylphenyl, allyl, phenyl-C1-C6-alkyl, C2-C8-alkenyl, C2- C8-alkynyl, C3-C12-cycloalkyl or saturated or unsaturated heterocyclic radicals, where the radicals are phenyl, another aromatic hydrocarbon,  Phenyl-C1-C6-alkyl and saturated or unsaturated heterocyclic radical unsubstituted or 1- to 5-fold with C1-C20-alkyl which is unsubstituted or substituted with OR6 or R7R8N, with one or more radicals O, S (O) p or NR5 interrupted C2- C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q or / and CN are substituted;  p represents 0, 1 or 2;  q is 0 or 1;  R5 is hydrogen, C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, where the radicals phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12-alkoxy or / and halogen are substituted;  R6 is unsubstituted or halogen-substituted C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1- C12 alkoxy or / and halogen are substituted;  R7 and R8 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl which are unsubstituted or substituted by C1-C12-alkoxy, halogen, OH, COOR6 or CN, the radicals being phenyl- C1-C6-alkyl or phenyl unsubstituted or 1- to 5-fold substituted with C1-C6-alkyl, C1-C12-alkoxy or / and halogen, or R7 and R8 together with the N atom to which they are attached, one Form 5- or 6-membered ring, which can additionally contain O or S atoms;  R9, R10 and R11 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold are substituted with C1-C6-alkyl, C1-C12-alkoxy or / and halogen; and  Z stands for a residue which can form positive ions. 5. The composition of claim 1, containing at least one borate of the formula I or 1 min and at least one dye which changes or loses its color during or after the irradiation, which dye can also be a component of the compound of the formula I as a cation. 6. Composition according to one of claims 1-5, characterized in that it contains, in addition to the photoinitiator (b), at least one further photoinitiator (d) and / or other additives. 7.  Composition according to Claim 6, in which an easily reducible compound, in particular a halogenated hydrocarbon, is used as a further additive. 8. The composition according to claim 1, comprising in addition to components (a) and (b) at least one neutral, anionic or cationic dye and an onium compound. 9. The composition according to claim 8, additionally containing a radical photoinitiator, in particular an alpha-aminoketone compound. 10. The composition according to any one of claims 1-9, containing 0.05 to 15, in particular 0.2 to 5 wt .-%, of component (b), or components (b) + (d), based on the Composition. 11.  Connection of the formula la and la min EMI87.1          wherein R1 min and R2 min independently of one another for at least one o-position for bonding to the boron atom with C1-C20-alkyl, with one or more radicals O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q, CN, EMI88.1   EMI88.2  or and EMI88.3       substituted phenyl;  R3 min represents phenyl or another aromatic hydrocarbon, with or without a hetero atom, these radicals being unsubstituted or 1- to 5-fold with C1-C20-alkyl which is unsubstituted or substituted by OR6 or R7R8N, with one or more radicals O, S (O ) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P ( O) q, CN EMI88.4   EMI88.5  or and EMI88.6       are substituted;  or the residues R2 min and R3 min form bridges, structures of the formulas II, Ila or Ilb EMI88.7          arise, the aromatic rings in formula II are unsubstituted or with C1-C20-alkyl, with one or more radicals O, S (O) p or NR5 interrupted C2-C20-alkyl, OR6, R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, halogen, R9R10P (O) q or / and R9R10R11Sn;  R1a min is a divalent aromatic hydrocarbon radical, this radical being unsubstituted or with C1-C6-alkyl, OR6, S (O) pR6, OS (O) 2R6, NR8R7, C (O) OR6, C (O) NR8R7, C (O) R9, SiR9R10R11 or halogen is substituted or R1a is phenyl-C1-C6-alkylene;  R4 is phenyl, C1-C20-alkyl, C2-C20-alkyl interrupted by one or more radicals O, S (O) p or NR5, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or Naphthyl-C1-C3-alkyl means, where the residues C1-C20-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or naphthyl-C1-C3-alkyl are unsubstituted or with OR6 , R6S (O) p, R6S (O) 2O, R7R8N, R6OC (O), R7R8NC (O), R9C (O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P (O) q, or / and CN;  Y for (CH2) n, CH = CH, C (O), NR5, O, S (O) p or EMI89.1  stands;  n represents 0, 1 or 2;  m is 2 or 3;  p represents 0, 1 or 2;  q is 0 or 1;  E represents R21R22R23P, R7R7aR8N or R6R6aS;  R5 is hydrogen, C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, where the radicals phenyl-C1-C6-alkyl or phenyl are unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12-alkoxy or / and halogen are substituted;  R6 and R6a independently of one another are C1-C12-alkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold with C1-C6-alkyl, C1-C12 Alkoxy or / and halogen are substituted;  R7, R7a and R8 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold with C1 -C6-alkyl, C1-C12-alkoxy or / and halogen are substituted, or R7 and R8 together with the N atom to which they are attached form a 5- or 6-membered ring which additionally contains O or S - can contain atoms;  R9, R10 and R11 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, phenyl-C1-C6-alkyl or phenyl, the radicals phenyl-C1-C6-alkyl or phenyl being unsubstituted or 1- to 5-fold with C1 -C6 alkyl, C1-C12 alkoxy or / and halogen are substituted;  R12, R13, R14 and R15 independently of one another are hydrogen, unsubstituted or C1-C12-alkoxy-substituted C1-C12-alkyl, unsubstituted or one to five times with C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl-C1 -C6-alkyl or unsubstituted or one to five times with C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl, or the radicals R12, R13, R14 and R15 together form an aromatic ring on which further aromatic rings can be fused;  R21, R22 and R23 independently of one another C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, where the residues C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl are unsubstituted or with R6OCO or CN are substituted, or R21, R22 and R23 unsubstituted or mono- to pentasubstituted by C1-C6-alkyl, C1-C12-alkoxy or halogen-substituted phenyl-C1-C6-alkyl or unsubstituted or mono- or pentasubstituted by C1-C6 Alkyl, C1-C12-alkoxy or halogen-substituted phenyl; and  G represents a residue which can form positive ions. 12. Compounds according to claim 11, in which G represents a metal from group I of the periodic table in the first oxidation stage, in particular Na +, K + or Li +, or G MgZ1 + or CaZ1 < +> means in which Z1 represents a halogen or C1-C4-alkoxy, or G represents an ammonium, phosphonium or sulfonium salt. 13.  Compounds according to claim 11, wherein R3 min is 1- or 2-naphthyl, binaphthyl, anthracyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, biphenyl, o-, m- or p-terphenyl or triphenylphenyl. 14. Use of compounds defined in claims 1 and 11 as unimolecular photoinitiators for the photopolymerization of ethylenically unsaturated compounds. 15. A process for the photopolymerization of non-volatile monomeric, oligomeric or polymeric compounds having at least one ethylenically unsaturated double bond, characterized in that these compounds have at least one compound of the formula I or 1 min according to Claim 1 or a compound of the formula Ia according to Claim II as a unimolecular photoinitiator is added and irradiated with light from the infrared range over the UV range up to the wavelength of 200 nm. 16.  Use of a composition according to any one of claims 1-10 for the production of pigmented and non-pigmented lacquers, powder coatings, printing inks, printing plates, adhesives, dental materials, optical fibers, optical switches, color testing systems, glass fiber cable coatings, screen printing stencils, resist materials, for encapsulating electrical and electronic components, for production of composite materials, for the production of magnetic recording materials, for the production of three-dimensional objects by means of stereolithography, for photographic reproduction and as image recording material, in particular for holographic recordings. 17. Coated substrate which is coated on at least one surface with a composition according to any one of claims 1-10. 18th  Use of the compounds of the formula I or l min or la or la min as an initiator for the thermal polymerization of compounds having ethylenically unsaturated double bonds.