Claims
- 1. A liquid photoinitiator mixture, comprising
- (A) 70-99.9% by weight of at least one liquid photoinitiator of the formula I or of a liquid mixture of metal-free photoinitiators containing at least one compound of the formula I ##STR13## in which Ar is a phenyl group which is unsubstituted or is monosubstituted or polysubstituted by halogen, C.sub.1 -C.sub.18 -alkyl, C.sub.3 -C.sub.12 -alkenyl, C.sub.1 -C.sub.12 -alkoxy, allyloxy, phenoxy, C.sub.1 -C.sub.18 -alkylthio, allylthio, 2-hydroxyethylthio, phenylthio, tolylthio, C.sub.1 -C.sub.12 -alkylamino, C.sub.2 -C.sub.24 -dialkylamino, C.sub.4 -C.sub.8 -bis(hydroxyalkyl)-amino, diallylamino, bis-(2-methoxyethyl)amino, morpholino, piperidino or pyrrolidino, R.sup.1 and R.sup.2 independently of one another are C.sub.1 -C.sub.8 -alkyl or C.sub.1 -C.sub.4 -alkyl which is substituted by --OH, C.sub.1 -C.sub.4 -alkoxy, benzyloxy, --CN, --COO(C.sub.1 -C.sub.8 -alkyl), (C.sub.1 -C.sub.4 -alkyl)--COO--, C.sub.2 -C.sub.8 -dialkylamino or morpholino, or R.sup.1 and R.sup.2 together are C.sub.3 -C.sub.9 -alkanediyl, C.sub.3 -C.sub.9 -oxa- or -aza-alkanediyl or C.sub.5 -C.sub.9 -alkenediyl, X is a group --OR.sup.3 or , in which R.sup.3 is hydrogen, C.sub.1 -C.sub.8 -alkyl, C.sub.2 -C.sub.4 -alkyl which is substituted by halogen, --OH or C.sub.1 -C.sub.4 -alkoxy, allyl, benzyl, 2-tetrahydropyranyl, trimethylsilyl or phenyl-dimethylsilyl, R.sup.4 and R.sup.5 independently of one another are hydrogen, C.sub.1 -C.sub.12 -alkyl, C.sub.2 -C.sub.4 -alkyl which is substituted by --OH, C.sub.1 -C.sub.4 -alkoxy, --CN or --COO(C.sub.1 -C.sub.4 -alkyl), allyl, benzyl or cyclohexyl, or R.sup.4 and R.sup.5 together are C.sub.3 -C.sub.7 -alkylene which can be interrupted by --O--or --N(R.sup.6)--, R.sup.6 being hydrogen, C.sub.1 -C.sub.4 -alkyl, allyl, benzyl or C.sub.2 -C.sub.4 -hydroxyalkyl, and
- (B) 0.5-20% by weight of at least one titanocene photoinitiator, selected from
- (B.sub.1) compounds of the formula II ##STR14## in which R.sup.7 and R.sup.8 independently of one another are a cyclopentadienyl or indenyl anion which is unsubstituted or is substituted by C.sub.1 -C.sub.4 -alkyl, chlorine, phenyl or cyclohexyl, or R.sup.7 and R.sup.8 together are a divalent bis-cyclopentadienyl anion of the formula III ##STR15## in which Z is methylene, dimethylene or trimethylene, C.sub.2 -C.sub.12 -alkylidene, C.sub.5 -C.sub.7 -C -cycloalkylidene, --Si(R.sup.11)(R.sup.12)-- or --Sn(R.sup.11).sub.2- and R.sup.11 and are C.sub.1 -C.sub.12 -alkyl, phenyl or benzyl, R.sup.9 is the monovalent radical of a 6-membered carbocyclic or 5-membered or 6-membered heterocyclic aromatic ring which is substituted by fluorine in at least one ortho-position relative to the bond to the Ti atom and can also be monosubstituted or polysubstituted by halogen, C.sub.1 -C.sub.12 -alkyl, C.sub.1 -C.sub.14 -alkoxy, --O(CH.sub.2 CH.sub.2 O).sub.1-20 -C.sub.1 -C.sub.14 -alkyl, C.sub.2 -C.sub.10 -alkoxycarbonyl, aminocarbonyl having up to 12 C atoms or by a primary, secondary or tertiary amino or aminoalkyl group having up to 20 C atoms or a quaternary ammonium or ammonium alkyl group having up to 30 C atoms, R.sup.10 is as defined for R.sup.9 or is C.sub.2 -C.sub.12 -alkynyl, phenylalkynyl which has 2-5 C atoms in the alkyne radical and is unsubstituted or substituted in the phenyl radical by halogen or C.sub.1 -C.sub.14 -alkyl, or is halogen or a group --Si(R.sup.11).sub.3, --Si(R.sup.11).sub.2 (R.sup.12), --Sn(R.sup.11).sub.3, --OH, C.sub.1 -C.sub.10 -alkox C.sub.6 -C.sub.10 -aryloxy, unsubstituted or halogen-substituted C.sub.2 -C.sub.6 -acyloxy, -N.sub.3, --CN, --NCO or --NCS, or R.sup.9 and R.sup.10 together are a radical of the formula --Q--Y--Q--, in which Q is a carbocyclic or 5-membered or 6-membered heterocyclic aromatic ring which is bonded to the titanium atom in the 2-position relative to the Y group and is substituted by fluorine in the 3-position and, as further substituents, can contain C.sub.1 -C.sub.4 alkyl, halogen, C.sub.1 -C.sub.4 -alkoxy, di-(C.sub.1 -C.sub.4 -alkyl)-amino or a quaternary C.sub.3 -C.sub.20 -ammonium group, Y is methylene, C.sub.2 -C.sub.12 -alkylidene, C.sub.5 -C.sub.7 -cycloalkylidene, a direct bond or a group --NR.sup.13 --, --O--, --S--, --SO--, --SO.sub.2 --, --CO--, --Si(R.sup.11)(R.sup.12)-- or --Sn(R.sup.11).sub.2 - and R.sup.13 is hydrogen, C.sub.1 -C.sub.12 -alkyl, cyclohexyl, phenyl, tolyl or benzyl, or
- (B.sub.2) compounds of the formula IV ##STR16## in which R.sup.7 and R.sup.8 are as defined above, R.sup.14 is the monovalent radical of a 6-membered carbocyclic or 5-membered or 6-membered heterocyclic aromatic ring which is substituted by --CF.sub.3 in at least one ortho-position relative to the bond to the Ti atom and can also be monosubstituted or polysubstituted by halogen, C.sub.1 -C.sub.12 -alkyl, C.sub.1 -C.sub.14 -alkoxy, -O(CH.sub.2 CH.sub.2 O).sub.1-20 -C.sub.1 -C.sub.14 -alkyl, C.sub.2 -C.sub.10 -alkoxycarbonyl or aminocarbonyl or by a primary, secondary or tertiary amino or aminoalkyl group having up to 20 C atoms or a quaternary ammonium or ammonium alkyl group having up to 30 C atoms, and R.sup.15 is as defined for R.sup.14 or is C.sub.2 -C.sub.12 -alkynyl, phenylalkynyl which has 2-5 C atoms in the alkyne radical and is unsubstituted or substituted in the phenyl radical by halogen or C.sub.1 -C.sub.4 -alkyl, or is halogen or a group --Si(R.sup.11).sub.3, --Si(R.sup. 11).sub.2 (R.sub.12), --Sn(R.sup.11).sub.3,-OH, C.sub.1 -C.sub.10 alkoxy, C.sub.6 -C.sub.10 -aryloxy, unsubstituted or halogen-substituted C.sub.2 -C.sub.6 -acyloxy, --N.sub.3, --CN, --NCO or --NCS.
- 2. A liquid initiator mixture according to claim 1, comprising
- A) 80-99.5% by weight of a liquid photoinitiator or photoinitiator mixture containing at least one compound of the formula I, in which Ar is a phenyl group which is unsubstituted or is monosubstituted or disubstituted by halogen, C.sub.1 -C.sub.12 -alkyl, C.sub.1 -C.sub.8 -alkoxy, allyloxy, phenoxy, C.sub.1 -C.sub.8 -alkylthio, 2-hydroxyethylthio, allylthio, phenylthio, C.sub.1 -C.sub.8 -alkylamino, C.sub.2 -C.sub.16 -dialkylamino, diallylamino, C.sub.4 -C.sub.6 -bis-(hydroxyalkyl)-amino, bis-(2-methoxyethyl)-amino, morpholino, piperidino or pyrrolidino, R.sup.1 and R.sup.2 independently of one another are C.sub.1 -C.sub.6 -alkyl or C.sub.1 -C.sub.4 -alkyl which is substituted by --OH, C.sub.1 -C.sub.4 -alkoxy, benzyloxy, --COO(C.sub.1 -C.sub.4 -alkyl), C.sub.2 -C.sub.4 -dialkylamino or morpholino or R.sup.1 and R.sup.2 together are C.sub.3 -C.sub.6 -alkanediyl or C.sub.5 -C.sub.7 -alkenediyl, X is a group --OR.sup.3 or -NR.sup.4 R.sup.5, in which R.sup.3 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.2 -C.sub.4 -alkyl which is substituted by --OH or C.sub.1 -C.sub.4 -alkoxy, allyl, benzyl, 2-tetrahydropyranyl or trimethylsilyl, and R.sup.4 and R.sup.5 independently of one another are hydrogen, C.sub.1 -C.sub.8 -alkyl, C.sub.2 -C.sub.4 -alkyl which is substituted by --OH or C.sub.1 -C.sub.4 -alkoxy, allyl, benzyl or cyclohexyl, or R.sup.4 and R.sup.5 together are C.sub.3 -C.sub.7 -alkylene which can be interrupted by --O-- or --N(R.sup.6)--, R.sup.6 being hydrogen, methyl or C.sub.2 -C.sub.4 -hydroxyalkyl, and
- (B) 0.5-20% by weight of a compound of the formula II, in which R.sup.7 and R.sup.8 are a cyclopentadienyl anion which is unsubstituted or substituted by C.sub.1 -C.sub.4 -alkyl and R.sup.9 and R.sup.10 are a group of the formula V ##STR17## in which R.sup.16, R.sup.17 and R.sup.18 independently of one another are hydrogen, F, Cl, Br, C.sub.1 -C.sub.14 -alkoxy, --O--(CH.sub.2 CH.sub.2 O).sub.1-8 -C.sub.1 -C.sub.14 alkyl, a tertiary amino group or aminomethyl group having 2-20 C atoms or a quaternary ammonium or ammonium-methyl group having 3-24 C atoms, or R.sup.9 and R.sup.10 together are a divalent group of the formula ##STR18## in which Y is as defined in claim 1, or 0.5-20% by weight of a compound of the formula IV, in which R.sup.7 and R.sup.8 are a cyclopentadienyl anion which is unsubstituted or substituted by C.sub.1 -C.sub.4 -alkyl and R.sup.14 is a group of the formula VI ##STR19## in which R.sup.19, R.sup.20, R.sup.21 and R.sup.22 independently of one another are hydrogen, F, Cl, Br or C.sub.1 -C.sub.14 -alkoxy, and R.sup.15 is as defined for R.sup.14 or is F, Cl, Br, CN, --O--CO--CH.sub.3, --O--CO--CF.sub.3, N.sub.3, --NCO or --NCS.
- 3. A liquid initiator mixture according to claim 1, wherein component A is a liquid mixture of a compound of the formula I and a compound of the formula VII ##STR20## in which and R.sup.24 independently of one another are hydrogen, C.sub.1 -C.sub.12 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.2 -C.sub.4 -hydroxyalkyloxy, C.sub.2 -C.sub.4 -hydroxyalkylthio, halogen, C.sub.2 -C.sub.10 -alkoxycarbonyl or C.sub.2 -C.sub.8 -dialkylamino.
- 4. A liquid initiator mixture according to claim 3, wherein the compounds of the formula I and of the formula VII are present in a weight ratio of 0.8:1 to 1:0.8.
- 5. A liquid initiator mixture according to claim 1, wherein the component A is a liquid mixture of a compound of the formula I and a 2,4,6-tri-(C.sub.1 -C.sub.4 -alkyl)-benzophenone.
- 6. A liquid initiator mixture according to claim 1, wherein component A is a liquid mixture of a compound of the formula I and a compound of the formula VIII ##STR21## in which R.sup.25 is halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy, R.sup.26 and R.sup.27 are C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.4 -alkenyl, C.sub.7 -C.sub.10 -phenylalkyl or C.sub.2 -C.sub.4 -alkyl which is substituted by halogen, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.8 -dialkylamino, morpholino or piperidino, or R.sup.26 and R.sup.27 together are C.sub.2 -C.sub.12 -alkanediyl or 2-butene-1,4-diyl and R.sup.28 is hydrogen, C.sub.1 -C.sub.8 -alkyl, C.sub.5 -C8-cycloalkyl, phenyl or phenyl which is substituted by halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy.
- 7. A liquid initiator mixture according to claim 6, wherein the compounds of the formula I and of the formula VIII are present in a weight ratio of 2:1 to 1:2.
- 8. A liquid initiator mixture according to claim 1, wherein component A is a liquid mixture of one compound of the formula I, one compound of the formula VII and one compound of the formula VIII.
- 9. A liquid initiator mixture according to claim 1, wherein component A contains a compound of the formula I in which Ar is phenyl or phenyl which is substituted by chlorine, fluorine, C.sub.1 -C.sub.12 -alkyl, methoxy, methylthio, dimethylamino, diethylamino, bis-(2-methoxyethyl)-amino, morpholino, piperidino or pyrrolidino, R.sup.1 and R.sup.2 independently of one another are C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkyl which is substituted by --OH or C.sub.1 -C.sub.4 -alkoxy, or R.sup.1 and R.sup.2 together are C.sub.4 -C.sub.6 -alkanediyl or C.sub.5 -C.sub.7 -alkenediyl and X is --OH or -NR.sup.4 R.sup.5, R.sup.4 and R.sup.5 being C.sub.1 -C.sub.4 -alkyl, allyl or 2-methoxyethyl or R.sup.4 and R.sup.5,together with the nitrogen atom, being pyrrolidino, piperidino, morpholino, piperazino or 4-methylpiperazino.
- 10. A liquid initiator mixture according to claim 1, wherein component A contains a compound of the formula I, in which Ar is phenyl, p-tolyl, p-cumyl, 4-dodecylphenyl, 4chlorophenyl or 4-methoxyphenyl, R.sup.1 and R.sup.2 independently of one another are C.sub.1 -C.sub.4 -alkyl or R.sup.1 and R.sup.2 together are tetramethylene or pentamethylene and X is a hydroxyl group.
- 11. A liquid initiator mixture according to claim 1, wherein component A contains a compound of the formula I, in which Ar is phenyl, p-tolyl, p-cumyl, 4-chlorophenyl, 4methoxyphenyl, 4-methylthiophenyl, 4-dimethylaminophenyl, 4-diethylaminophenyl, 4-bis-(2-methoxyethyl)-aminophenyl, 4morpholinophenyl or 4-piperidinophenyl, R.sup.1 and R.sup.2 independently of one another are C.sub.1 -C.sub.4 -alkyl and X is methylamino, dimethylamino, ethylamino, diethylamino, bis-(2-methoxyethyl)amino, piperidino, pyrrolidino, morpholino, piperazino or 4methylpiperazino.
- 12. A liquid initiator mixture according to claim 1, wherein component B is either a compound of the formula II, in which R.sup.7 and R.sup.8 are a cyclopentadienyl anion or methylcyclopentadienyl anion and R.sup.9 and R.sup.10 are a group of the formula V, in which either a) R.sup.16 is H, F, Cl or Br, R.sup.17 is fluorine, C.sub.1 -C.sub.14 -alkoxy or --O--(CH.sub.2 CH.sub.2 O).sub.1-6 C.sub.1 -C.sub.14 -alkyl and R.sup.18 is H, Cl or Br or (b) R.sup.18 is H, F, Cl or Br and R.sup.16 and R.sup.17 are H, Cl, Br, C.sub.1 -C.sub.14 -alkoxy, --O--(CH.sub.2 CH.sub.2 O).sub.1-6 -C.sub.1 -C.sub.14 -alkyl, a tertiary amino or aminomethyl group or a quaternary ammomium or ammonium-methyl group, or B is a compound of the formula IV, in which R.sup.7 and R.sup.8 are a cyclopentadienyl anion or methylcyclopentadienyl anion, R.sup.14 is 2-(trifluoromethyl)phenyl or 6-fluoro-2-(trifluoromethyl)-phenyl and R.sup.15 is as defined for R.sup.14 or is F, Cl, Br, CN, N.sub.3, --O--CO--CH.sub.3, --O--CO--CF.sub.3, --NCO or --NCS.
- 13. A liquid initiator mixture according to claim 3, wherein component A is a liquid mixture of a compound of the formula I and benzophenone.
- 14. A liquid initiator mixture according to claim 1, wherein component A is a liquid mixture of a compound of the formula I and 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxy-2-phenylacetophenone.
- 15. A liquid initiator mixture according to claim 1, comprising 40-50% by weight of 1-hydroxycyclohexyl phenyl ketone, 40-50% by weight of benzophenone and 2-20% by weight of a compound of the formula II or IV.
- 16. A liquid initiator mixture according to claim 15, comprising 40-50% by weight of 1-hydroxycyclohexyl phenyl ketone, 40-50% by weight of benzophenone and 2-20% by weight of bis-(cyclopentadienyl)-bis-(4-decyloxy)-tetrafluorophenyl)titanium.
- 17. A liquid initiator mixture according to claim 1, comprising 25-30% by weight of 1-hydroxycyclohexyl phenyl ketone, 25-30% by weight of benzophenone, 35-40% by weight of 2,2-dimethoxy-2-phenylacetophenone and 2-15% by weight of a compound of the formula II or IV.
Priority Claims (2)
Number |
Date |
Country |
Kind |
4734/86 |
Nov 1986 |
CHX |
|
416/87 |
Feb 1987 |
CHX |
|
Parent Case Info
This is a continuation of application Ser. No. 122,816, filed Nov. 19, 1987, now abandoned.
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Continuations (1)
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Number |
Date |
Country |
Parent |
122816 |
Nov 1987 |
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