CA2022587C - Mono- and di-acylphosphine oxides - Google Patents

Mono- and di-acylphosphine oxides Download PDF

Info

Publication number
CA2022587C
CA2022587C CA002022587A CA2022587A CA2022587C CA 2022587 C CA2022587 C CA 2022587C CA 002022587 A CA002022587 A CA 002022587A CA 2022587 A CA2022587 A CA 2022587A CA 2022587 C CA2022587 C CA 2022587C
Authority
CA
Canada
Prior art keywords
phenyl
substituted
c4alkyl
c4alkoxy
unsubstituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA002022587A
Other languages
French (fr)
Other versions
CA2022587A1 (en
Inventor
Werner Rutsch
Kurt Dietliker
Roger Graham Hall
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Publication of CA2022587A1 publication Critical patent/CA2022587A1/en
Application granted granted Critical
Publication of CA2022587C publication Critical patent/CA2022587C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3247—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
    • C07F9/3252—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se) containing the structure -C(=X)-P(=X)(R)(XR), (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)

Abstract

Compounds of the formula I
(see formula I) in which at least one of the radicals R1, R2 and R3 is a substituted alkyl radical or cycloalkyl radical, or R1 and R2 together with the phosphorus atom form a monocyclic or tricyclic ring, are effective photoinitiators for the photopolymerization of ethylenically unsaturated compounds.

Description

20225$

A-17681/+
Mono- and di-acylphosphine oxides The invention relates to special mono- and di-acylphosphine oxides and to their use as photoinitiators for the photopolymerization of eth.ylenically unsaturated compounds.
Monoacylphosphine oxides are known as photoinitiators from EP-A-7,508.
Bisacylphosphine oxides and their use as photoinitiators are known from EP-A-184,095.
Novel mono- and bis-acylphosphine oxides have now been found which differ from the known compounds by the presence of certain substituents. These are compounds of the formula I

ii Rt~PiC' R3 R / v0 in which Rt is Ct-Ctsalkyl, C2-CtBalkenyl, Ct-CBalkyl which is monosubstituted or polysubstituted by phenyl, (Ct-Ct2alkyl)-phenyl, halogenophenyl, (Ct-Ct2alkoxy)-phenyl, cyano, C2-Csalkoxycarbonyl, Ct-Ct2alkoxy or/and halogen, C5-CBCycloalkyl, C6-Ct2aryl, which is unsubstituted or mono- or poly-substituted by halogen, Ct-Ct2alkyl or/and Ct-Ct2alkoxy, a 5-membered or 6-membered heterocyclic monovalent radical which contains one or more O, S or/and N atoms and which may contain a fused benzo radical or/and which is unsubstituted or substituted by Ct-C4alkyl, Ct-C,~alkoxy or/and halogen, or is a radical of the formula o !I
!!/C-R3 R P~

in which X is phenylene, xylylene, cyclohexylene or Ct-Cbalkylene which may be unsubstituted or monosubstituted or polysubstituted by halogen, Ct-C4alkyl, Ct-C4alkoxy or phenyl" R2 is Ci-Clgalkyl, Cl,-CtBalkenyl, Ct-CBalkyl which is monosubstituted or 202258' polysubstituted by phenyl, (C1-Cl2alkyl)-phenyl, halogenophenyl, (CI-Cl2alkoxy)-phenyl, cyano, C2-Csalkoxycarbonyl, Ci-Cl2alkoxy or/and halogen, CS-CBCycloalkyl, C6-Ct2ary1 which is unsubstituted or mono- or poly-substituted by halogen, Ct-Cl2alkyl or/and Cl-Cl2alkoxy, a 5-membered or 6-membered heterocyclic monovalent radical which contains one or more O, S or N atoms and which may contain a fused benzo radical or/and is unsubstituted or substituted by Ci-C4alkyl, Cl-C4alkoxy or/and halogen, or is a radical -CO-R3 or -OR4, or Rt and RZ or Rl and Ra together with the phosphorus atom form a monocyclic or bicyclic or tricyclic ring having 4-15 C atoms, R3 is Cl-Ctsalkyl, C2-C6alkenyl, phenylvinyl, Ct-Csalkyl which is mono- or poly-substituted by phenyl, CZ-Csalkoxycarbonyl, halogen, Cl-Ct2alkoxy, phenoxy, Ct-Cl2alkylthio or/and phenylthio, CS-Ctpcycloalkyl which is unsubstituted or substituted by Cl-Ct2alkyl, phenyl, phenoxy, Ct-Ct2alkoxy, Ci-Csalkoxycarbonyl, Cl-C4alkylthio or/and halogen, C6-C12ary1 which is unsubstituted or mono- or poly-substituted by Cl-CIZallcyl, Cl-Ct2alkoxy, Ct-Ct2alkoxyalkyl, Ct-C4alkylthio or/and halogen, or a monovalent 5-membered or 6-membered heterocyclic radical containing one or more O, S or N atoms, which radical can be mono- or poly-substituted by halogen, Ct-C4alkyl or Cl-C4alkoxy, and R4 is Ct-Ctsalkyl, phenyl-Ct-C4alkyl, CS-C8cycloalkyl or C6-Ctoaryl, with the proviso that at least one of the radicals Rt, R2 and R3 is a substituted alkyl radical or that R1 and RZ
together with the phosphorus atom form a bicyclic or tricyclic ring, or that R3 is a substituted cycloalkyl radical which, however, cannot contain alkyl radicals as the only substituents.
Ct-CtsAlkyl Rt, R2, R3 and R4 can be branched or unbranched alkyl and can, for example, be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tent-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trirnethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl or octadecyl.
Alkyl R3 is preferably tertiary alkyl, for example tent-butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl or 1,1,3,3-tetramethylbutyl.
C2-CtsAlkenyl Rt and R2 can, for example be vinyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl or octadecenyl.
Furthermore, C2-Clgalkenyl R4 can also be vinyl.
C2-C6Alkenyl R3 can, for example, be vinyl, propenyl or butenyl.
Ct-CBAIky1 Rt and R2, which is monosubstituted or polysubstituted, for example monosubstituted to trisubstituted, especially monosubstituted or disubstituted, can, for example, be benzyl, 1-phenylethyl, 2-phenylethyl, a,a-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1-(p-butylphenyl)-ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di-(methoxycarbonyl)-ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl or trifluoromethyl, preferably benzyl.
Ct-C8Alkyl R3, which is mono- or poly-substituted, for example mono- to tri-substituted, especially mono- or di-substituted, can, for example, be benzyl, phenylethyl, a,a-dimethylbenzyl, benzhydryl, 1,1-dichloroethyl, trichloromethyl, trifluoromethyl, l, l-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl or 2-phenylthioethyl.
Ct-CgAlkyl R4 which is mono- or poly-substituted, for example mono- to tri-substituted, especially mono- or di-substituted, can, for example, be benzyl, 2-phenylethyl, 3-phenylpropyl, 2-methoxyethyl, 2-butoxyethyl, 2-hexyloxyethyl, 2-isopropoxypropyl, 2-chloroethyl or 2,2,2-trifluoroethyl.
CS-CBCycloalkyl Rt, R2, R3 and R4 can, for example, be cyclopentyl, cyclohexyl or cyclooctyl. Cg-CloCycloalkyl R3 which is, for example, mono- to tetra-substituted, can, for example, be methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl or dichlorocyclopentyl or a saturated or unsaturated bicyclic system, for example norbornyl or norbornenyl.
C6-Ct2Ary1 Rt, R2, R3 and R4 can, for example, be phenyl, a-naphthyl, ~-naphthyl or 4-diphenylyl, especially phenyl. Substituted C6-Ct2aryl Rt, R2 and R3 can, for example, be chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, tolyl, ethylphenyl, tent-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl or ethoxynaphthyl.

202258' Furthermore, substituted aryl R3 can also, for example, be methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
Substituted aryl also is preferably substituted phenyl.
A heterocyclic radical Rl, R2 and R3 can, for example, be furyl, thienyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl or benzothiazolyl.
Preferably, such a heterocyclic radical contains 3-12 C atoms, especially 3-5 C atoms.
Substituted heterocylic radicals (for example mono- to tri-substituted and especially mono-or di-substituted heterocyclic radicals) can, for example, be dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
Cl-C6Alkylene X can, for example, be methylene, 1,2-ethylene, 2,2-dimethyl-1,3-propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene or phenylmethylene.
A monocyclic ring formed by Rl and R2 together with the P atom is preferably a phosphacyclopentane ring.
A bicyclic ring formed by Rt and R2 together 'with the P atom is preferably a phosphabicyclohexane or phosphabicyclononane ring.
A tricyclic ring formed by Rt and R4 together with the P atom is preferably a (6H)-dibenzo[c,e][1,2]oxaphosphorine ring.
Those compounds of the formula I are preferred in which RI is Ct-Ct2alkyl, Ct-C4alkyl which is mono- to tri-substituted by phenyl, (Ct-C4alkyl)-phenyl, chlorophenyl, (Cl-C4alkoxy)-phenyl or/and Ct-C4alkoxy, cyclohexyl, C6-Ctoaryl which is unsubstituted or mono- to tri-substituted by chlorine, Ct-Ct2alkyl or/and Ct-C4alkoxy, or is a 5-membered or 6-membered heterocyclic monovalent radical which contains one or more O, S or N atoms, R2 is as defined for Rt or a radical -CO-R3 or -OR4, or Rt and R2 or Rt and R4 together with the P atom form a monocyclic or bicyclic radical having 4-atoms, R3 is Ct-CBalkyl, Cl-C6alkyl which is mono- or di-substituted by phenyl, Ct-C4alkoxy, C2-Csalkoxycarbonyl or/and chlorine, CS-C6cycloalkyl which is unsubstituted or substituted by phenyl, Ct-C4alkoxy, C2-Csalkoxycarbonyl or/and chlorine, or C6-Ctparyl which is unsubstituted or mono- to tri-substituted by Cl-Cl2alkyl, Cl-C4alkoxy or/and chlorine, and R4 is Cl-C8alkyl, cyclohexyl, benzyl or phenyl, and 20~258'~

especially those in which Rl is Cl-CBalkyl, Cl-C4alkyl which is mono- or di-substituted by phenyl, (Ct-Cqalkyl)-phenyl or Cl-C4alkoxy, cyclohexyl or phenyl which is unsubstituted or mono- to tri-substituted by Cl-C4alkyl or Cl-C4alkoxy, R2 is as defined for Rl or is a radical -CO-R3 or -OR4, or Rl and R2 or Rl and R4 together with the P atom form a monocyclic or bicyclic ring, R3 is Ci-Cbalkyl which is unsubstituted or substituted by phenyl, chlorine or/and Cl-C4alkoxy, CS-Cbcycloalkyl which is unsubstituted or substituted by phenyl, Cl-C4alkoxy, C2-Csalkoxycarbonyl or/and chlorine, or phenyl which is unsubstituted or mono- to tri-substituted by Ct-C4alkyl, Cl-C4alkoxy or/and chlorine, and R4 is Cl-C4alkyl, cyclohexyl or phenyl.
Preferably, Rl is a substituted alkyl radical as defined above, especially Ct-C4alkyl which is mono- to di-substituted by phenyl, (Cl-C4alkyl)-phenyl or Ct-C4alkoxy and with particular preference is benzyl.
R3 is especially a phenyl radical which is substituted in both ortho-positions by Ct-C4alkyl, Ct-C4alkoxy or chlorine.
Moreover, bicyclic compounds of the formula II or III

ii /C'R3 ~ ~ C-R3 PLO (cH2> n PLO
II III
are preferred, in which n is 1-8 and R3 is as defined above, in particular those compounds of the formula II or III in which n is 1-8, especially 1-4, and R3 is Ct-C4alkyl substituted by phenyl, C6-Ctoaxyl or phenyl which is mono- to tri-substituted by Ct-Ct2alkyl, Ct-C4alkoxy or chlorine.
Examples of individual compounds of the formula I are:
dibenzyl-(2,4,6-trimethylbenzoyl)-phosphine oxide bis(2-phenylethyl)-(2,6-dichlorobenzoyl)-phosphine oxide bis(2-phenylpropyl)-(2,6-dimethoxybenzoyl)-phosphine oxide bis(2-phenylpropyl)-(2,4,6-trimethylbenzoyl)-phosphine oxide bis(2-cyanoethyl)-(2,4,6-trimethylbenzoyl)-phosphine oxide 2U2258~
methyl 2-phenylpropyl-(2,4,6-trimethylbenzoyl)-phosphinate 6-[bis(chloromethyl)propionyl]-(6H)-dibenz[c,e][1,2]oxaphosphorine 6-oxide methyl phenyl-(2,2-dimethyl-3-phenylpropionyl)-phosphinate diphenyl-(2,2-dimethyl-3-phenylpropionyl)-phosphine oxide diphenyl-2,6-dimethoxycyclohexanoylphosphine oxide dibutyl-(2-methyl-2-phenylbutyryl)-phosphine oxide butyl-1,1-diethoxyethyl-2,4,6-trimethylbenzoyl-phosphine oxide bis(cyclohexyl)-(2-methyl-2-phenylthiopropionyl)-phosphine oxide diphenyl-(2-octyloxy-2-phenylpropionyl)-phosphine oxide 1-(2,6-dimethylbenzoyl)-phospholan 1-oxide 6-(2,6-dichlorobenzoyl)-6-phosphabicyclo[2.1.1]hexane 6-oxide 9-(2,6-dichlorobenzoyl)-9-phosphabicyclo[3.3.1]nonane 9-oxide 9-(2,4,6-trimethylbenzoyl)-9-phosphabicyclo[4.2.1]nonane 9-oxide bis(2,6-dichlorobenzoyl)-2-phenylpropylphosphine oxide bis(2,6-dimethoxybenzoyl)-benzylphosphine oxide bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide bis(2,6-dichlorobenzoyl)-benzylphosphine oxide bis(2,6-dichlorobenzoyl)-2-phenylethlphosphine oxide bis(2,4,6-trimethylbenzoyl)-benzylphosphine oxide bis(2,4,6-trimethylbenzoyl)-2-phenylpropylphosphine oxide bis(2,4,6-trimethylbenzoyl)-2-phenylethylphosphine oxide bis(2,4,6-trimethylbenzoyl)-2-cyanoethylphosphine oxide bis(2,6-dichlorobenzoyl)-2-cyanoethylphosphine oxide bis(2,6-dimethoxybenzoyl)-2-cyanoethylphosphine oxide bis(2-methylthiobenzoyl)-2-phenylpropylphosphine oxide bis(2-methyl-1-naphthoyl)-2-phenylpropylphosphine oxide bis(2-methyl-2-phenylpropionyl)-cyclohexylphosphine oxide bis(2-methyl-2-phenylbutyryl)-phenylphosphine oxide bis(2,2-dimethyl-4-phenylbutyryl)-phenylphosphine oxide bis(2-methoxy-2-phenylbutyryl)-4-propylphenylphosphine oxide bis(2-methylthio-2-phenylbutyryl)-cyclohexylphosphine oxide bis(2-methyl-2-phenylthiopropionyl)-2-phenylpropylphosphine oxide bis(2-methyl-2-phenylbutyryl)-2-phenylpropylphosphine oxide bis(2-methyl-2-phenylbutyryl)-2-cyclohexylphosphine oxide (2,6-dichlorobenzoyl)-(1,3-dioxolan-2-yl)-phenylphosphine oxide diphenyl-(3-phenyl-bicyclo[2.2.1]kept-5-en-2-ylcarbonyl)-phos phine oxide diphenyl(2-methyl-3-phenyl-bicyclo[2.2.1]heptan-2-ylcarbonyl) -phosphine oxide 2,4,6-trimethylbenzoyl-benzyl-butylphosphine oxide 2,6-dichlorobenzoyl-benzyl-butylphosphine oxide 2,6-dimethoxybenzoyl-benzyl-butylphosphine oxide 2,6-dimethoxybenzoyl-benzyl-octylphosphine oxide 2,6-dichlorobenzoyl-benzyl-octylphosphine oxide 2,4,6-trimethyIbenzoyl-benzyl-octylphosphine oxide 2,4,6-trimethylbenzoyl-benzyl-methylphosphine oxide 2,4,6-trimethylbenzoyl-benzyl-cyclohexylphosphine oxide 2,6-dichlorobenzoyl-benzyl-cyclohexylphosphine oxide 2,6-dimethoxybenzoyl-benzyl-cyclohexylphosphine oxide The compounds of the formula I, in which RZ is a radical -OR4, can be prepared by an Arbusow-Michaelis reaction of the corresponding phosphonite N with a carboxylic acid chloride V according to the equation:
Rt-P(OR4)2 + R3COCl ---~ R~ ~O-Rg + R4C

N V
The reaction can take place with or without a solvent. If the components IV
and V are liquid, it is preferable to work without a solvent. Suitable solvents are especially hydrocarbons such as alkanes and alkane mixtures, benzene, toluene or xylene.
The reaction is preferably carried out at 20-120°C. The R4C1 being formed is preferably distilled off continuously during the reaction. If a solvent is used, this is dissolved off at the end of the reaction. The crude reaction product can be purified, for example, by distillation, crystallization or chromatography.
The phosphonites N can be prepared in a known manner by reacting a dichlorophosphine Rt-PCl2 with at least 2 mol of R4OH in the presence of an HCl acceptor (in this connection, see Houben-Weyl, Methoden d. Org. Chemie [Methods of Organic Chemistry) XII/1, 324-327 (1963), G. Thieme-Verlag, Stuttgart).

20258'7 _g_ The compounds of the formula I in which R2 is a radical -COR3 can be prepared by double acylation of a primary phosphine VI with at least 2 equivalents of an acid chloride V in the presence of at least 2 equivalents of a base and subsequent oxidation of the resulting diacylphosphine VII to the phosphine oxide according to the equation:
R-PH2 + 2 R3COCl Base ~ Rt-P(CORg)2 VII

R ~ (COR ) Examples of suitable bases are tertiary amines, alkali metals, lithium diisopropylamide, alkali metal alcoholates or alkali metal hydrides. The first reaction stage preferably takes place in solution. Suitable solvents are especially hydrocarbons, for example alkanes, benzene, toluene or xylene. After the resulting chloride of the base has been separated off, the phosphine VII can be isolated by evaporation, or the second reaction stage is carried out with the solution of the crude product, without isolation of VII.
Oxidizing agents suitable for the second stage are especially hydrogen peroxide and organic peroxy compounds, for example peractic acid.
The primary phosphines VI used as the starting material are known compounds or can be prepared analogously to known compounds (in this connection, see Houben-Weyl, Methoden der Org. Chemie [Methods of Organic Chemistry] XII/1, 60-63 (1963), G.
Thieme-Verlag, Stuttgart).
The compounds of the formula I in which R2 is neither a radical -OR4 nor a radical -COR3 can be prepared by acylation of secondary phosphines VIII and subsequent oxidation according to the equation:
R KPH + RgCOCI Bate R /P-COR3 R
~OR3 The same comments as above apply to these reactions. The starting phosphines VIII can be obtained by known methods, for example by reduction of monochlorophosphines (Rt)(R2)PCl by means of LiAlH4 (in this connection, see Houben-Weyl, Methoden der Org. Chemie [Methods of Organic Chemistry] XII/1, 60-63 (1963), G. Thieme-Verlag, Stuttgart).
An alternative possibility for the preparation is the Arbusow-Michaelis reaction of phosphinites IX with V according to the equation:
Rt jP-ORS + R3COC1 --~ R~ ~ + RSCI
R2 ~ ~COR3 IX V
in which RS is an alkyl radical.
The starting materials IX can be prepared by known methods, for example by alcoholysis of monochlorophosphines (Rt)(R2)PCl with RSOI-I in the presence of bases (in this connection, see Houben-Weyl, Methoden der Org. Chemie [Methods of Organic Chemistry] XII/1, 208-210, 1963), G. Thieme-Verlag, Stuttgart).
According to the invention, the compounds of the formula I can be used as photoinitiators for the photopolymerization of ethylenically unsaturated compounds or of mixtures containing such compounds. The unsaturated compounds can contain one or more olefinic double bonds. They can be low-molecular (monomeric) or higher-molecular (oligomeric).
Examples of monomers having one double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate and methyl or ethyl methacrylate. Further examples thereof are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkylstyrenes and halogenostyrenes, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.
Examples of monomers having more than one double bond are the diacrylates of ethylene 202258'7 - to -glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or bisphenol A, 4,4'-bis-(2-acryloyloxyethoxy)-diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris-(2-acryloylethyl) isocyanurate.
Examples of higher-molecular (oligomeric) polyunsaturated compounds are acrylated epoxide resins, acrylated polyethers, acrylated polyurethanes or acrylated polyesters.
Further examples of unsaturated oligomers are unsaturated polyester resins which are in most cases prepared from malefic acid, phthalic acid and one or more diols, and have molecular weights of about 500 to 3000. Such unsaturated oligomers can also be described as prepolymers.
Frequently, two-component mixtures of a prepolymer with a polyunsaturated monomer or three-component mixtures additionally also containing a monounsaturated monomer are used. In this case, the prepolymer is mainly responsible for the properties of the paint film, and those skilled in the art can influence the properties of the cured film by varying this prepolymer. The polyunsaturated monomer functions as a crosslinking agent which renders the paint film insoluble. The monounsaturated monomer functions as a reactive diluent, by means of which the viscosity is reduced without a solvent having to be used.
Such two- and three-component systems based on a prepolymer are used both for printing inks and for paint, photoresists or other photocurable compositions. One-component systems based on photocurable prepolymers are frequently also used as binders for printing inks.
Unsaturated polyester resins are in most cases used in two-component systems together with a monounsaturated monomer, preferably with styrene. Specific one-component systems, for example polymaleimides, polychalkones or polyimides, such as are described in German Offenlegungsschriften 2,308,830, are frequently used for photoresists.
The unsaturated compounds can also be used in a mixture with non-photopolymerizable film-forming components. These can be, for example, physically drying polymers or solutions thereof in organic solvents, for example nitrocellulose or cellulose acetobutyrate.
However, these can also be chemically or thermally curable resins, such as polyisocyanates, polyepoxides or melamine resins. The additional use of thermally curable 202258' resins is of importance for the use in so-called hybrid systems, which are photopolymerized in a first stage and crosslinked by thermal afterneatment in a second stage.
In addition to the photoinitiator, the phatopolymerizable mixtures can contain diverse additives. Examples of these are thermal inhibitors which are intended to prevent premature polymerization, for example hydroquinone or sterically hindered phenals. Far example copper compounds, phosphorus compounds, quaternary ammonium compounds ar hydroxylamine derivatives can be used for improving the storage stability in the dark.
In order to exclude atmospheric oxygen during the polymerization, paraffin or similar waxy substances can be added, which migrate to the surface at the start of the polymerization. Small quantities of UV absorbers, for example those of the benzotriazole, benzophenone or oxanilide type, can be added as light stabilizers. Even better is the addition of light stabilizers which do not absorb UV light, such as sterically hindered amines (HALS).
In certain cases, it can be of advantage to use mixtures of two or more of the photoinitiators according to the invention. Of course, mixtures with known photoinitiators can also be used, for example mixtures with benzophenone, acetophenone derivatives, benzoin ethers or benzil ketals.
To accelerate the photopolymerization, amines can be added, such as triethanolamine, N-methyl-diethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone.
The effect of the amines can be intensified by the addition of aromatic ketones of the benzophenone type.
An acceleration of the photopolymerization can also be effected by an addition of photosensitizers, which shift or broaden the spectral sensitivity. These are especially aromatic carbonyl compounds, for example derivatives of benzophenane, thioxanthone, anthraquinone and 3-acylcoumarin, and also 3-(aroylmethylene)-thiazolines.
Further conventional additives - depending on the intended use - are fillers, pigments, dyes, wetting agents or levelling agents.
The invention therefore also relates to photopolymerizable compositions which contain 2022~8'~

a) at least one ethylenically unsaturated photopolymerizable compound and b) at least one compound of the formula I as a photoinitiator, it being possible for the composition in addition to contain also another photoinitiator and/or other additives.
The photopolymerizable compositions contain the photoinitiator (b) advantageously in a quantity from 0.05 to 15 % by weight, preferably 0.2 to 5 % by weight, relative to the composition.
The photopolymerizable compositions can be used for various purposes, for example as a printing ink, as a white enamel, as a paint, as a paint for exterior coatings, for photographic reproduction processes, for image recording processes or for the production of printing plates, as dental filling compositions, as adhesives, as coatings for optical fibres, for printed circuits or for coating electronic components.
The polymerization is carried out by the known methods of photopolymerization by means of irradiation with sunlight or with light rich in shortwave radiation.
Suitable light sources are, for example, mercury medium-pressure, high-pressure and low-pressure radiators, superactinic fluorescent tubes, metal halide lamps or lasers, whose emission maxima are in the range between 250 and 450 nm. In the case of a combination with photosensitizers, longer-wave light or laser beams up to 600 nm can also be used.
The examples which follow explain the invention in more detail. In the same way as in the rest of the description and in the patent claims, data in parts or percent relate to the weight, unless otherwise stated.
Example 1: Preparation of bis-(2-phenylpropyl)-(2,6-dimethoxybenzoyl)-phosphine oxide.
6.9 ml (0.011 mol, 1.6 M) of butyllithium are added dropwise under argon at 0°C in the course of 10 minutes to a solution of 1.1 g (0.011 mol) of diisopropylamine in 10 ml of absolute tetrahydrofuran (THF).
This solution is added dropwise at -20 to -30°C in the course of about 40 minutes to a solution of 2.2 g (0.011 mol) of 2,6-dimethoxybenzoyl chloride and 2.7 g (0.01 mol) of bis-(2-phenylpropyl)-phosphine in 20 ml of absolute THF.

2o~~~s7 After stirnng at -30°C for 2 hours, the yellow solution is allowed to warm to room temperature, diluted with 100 ml of toluene and washed once with water and once with saturated bicarbonate solution. The organic phase is dried with magnesium sulfate, filtered and concentrated in a rotary evaporator. The residue is dissolved in 40 ml of acetonitrile, and 1.1 g (0.01 mol) of 30 % hydrogen peroxide are added.
After stirring for 1 hour at 50°C, the mixture is diluted with toluene, washed with brine and saturated sodium carbonate solution, dried with magnesium sulfate and evaporated in a rotary evaporator. After purification by means of chromatography (solvent:
hexane/ethyl acetate 1:1), this gives 3.1 g, i.e. 68.9 % of theory, of the abovementioned title compound as a yellow oil.
Elemental analysis calc. C 71.98 % H 6.94 %
found C 71.45 % H 7.05 %
Example 2: Preparation of bis-(2-phenylpropyl)-(2,4,6-trimethylbenzoyl)-phosphine oxide.
The phosphine oxide named above is prepared analogously to the method described in Example 1:
Elemental analysis calc. C 77.75 % H 7.69 %
found C 77.24 % H 7.72 %
Example 3: Preparation of diphenyl-[2,2-bis-(chloromethyl)-propionyl]-phosphine oxide.
3.8 g (0.02 mol) of dichloropivaloyl chloride are introduced into 20 ml of toluene and heated to 80°C. 4.3 g (0.02 mol) of methoxydiphenylphosphine are added dropwise in the course of about 5 minutes to this solution, methyl chloride escaping. After stirring for 1 hour at 80°C, the slightly yellow solution is cooled to room temperature and evaporated in a rotary evaporator. After purification by means of chromatography (solvent:
hexane/ethyl acetate 3:1), this gives 1.6 g, i.e. 22.8 % of theory, of the abovementioned compound as a yellow resin.
Elemental analysis calc. C 57.48 % H 4.82 % Cl 19.96 %
found G 57.37 % H 5.16 % Cl 18.84 %

Example 4: Preparation of ethoxy-(2,6-dimethoxybenzoyl)-(diethoxymethyl)-phosphine oxide.
The preparation is carried out analogously to the method described in Example 3. This gives the compound having a melting point of 81°C.
Elemental analysis calc. C 53.33 % H 6.99 % P 8.60 %
found C 53.15 % H 6.94 % P 9.24 %
Example 5: Preparation of diphenyl-[(1,2,2-trimethyl-3-methoxycarbonyl)-cyclopent-1 -yl]-phosphine oxide.
The preparation is carried out analogously to the method described in Example 3. This gives the compound as an oil in a yield of 28.2 % of theory.
Elemental analysis calc. C 69.33 % H 6.83 %
found C 68.75 % H 6.87 %
Examyle 6: Initiator reactivity in a white enamel topcoat A white enamel is prepared from 30 parts of ~Ebecryl 608 (epoxyacrylate from UCB, Belgium) 15 parts of trimethylolpropane trisacrylate parts of N-vinylpyrrolidone 50 parts of titanium dioxide (rutile).
Two per cent by weight of the photoinitiator to be tested are incorporated into the white enamel and the formulation is applied in a layer thickness of 100 ~.m to aluminium sheets which have been primed with a white coil coat. The samples are fully cured under an Hg medium-pressure lamp (Hanovia, 80 W/cm). Full curing has taken place when the underside of a paint film which has been separated off is dry. To measure the reactivity, the number of passes under the lamp at a defined belt speed is determined. In addition, the reactivity is measured after a pre-exposure of one minute under 5 40 W lamps (Philips TL03). The pendulum hardness (according to KOnig, DIN 53157), the yellowing (Yellowness Index, ASTM D 1925-70) and the gloss at 20° and 60°
(mufti-gloss apparatus, ASTM D 523) are measured directly after curing and after additional irradiation for 15 minutes or 16 hours (gloss) under 5 40 W lamps (Philips TL03).
The results are reproduced in Tables 1 and 2.

Table 1: White enamel topcoat without pre-exposure CompoundWipinPendulum Yellowness Gloss hard- Index (20/60) accordingresist-ness [sec]

t0 Example~ce* immeai- tee- immedi-after ~~r after ately lately ately minutes minutes hours 2 6 43 70 1.2 0.8 78/9077/90 1 7 36 90 1.1 0.8 81/9179/92 * as the number of passes at 20 m/minute Table 2: White enamel topcoat with pre-exposure CompoundWipinPendulum Yellowness Gloss hard- Index (20/60) accordingresist-ness [sec]

to Exampleance*immeai- tee- immedi-after after after ately lately ately minutes minutes hours 1 7 35 76 1.6 1.2 81/9180/91 2 8 38 56 1.8 1.4 59/8958/89 * as the number of passes at 20 m/minute Example 7: Initiator reactivity in a clearcoat A clearcoat is prepared from 99.5 parts of ~Roskydal UV 502 A (solution of an unsaturated polyester in styrene, from BAYER, Federal Republic of Germany) 0.5 part of ~Byk 300 (additive).
Two per cent by weight of the photoiniator to be tested are mixed in, and the formulation is applied in a coating thickness of 100 wm to chipboard coated with a white synthetic resin.
The samples are irradiated in a PPG irradiation apparatus with Hg medium-pressure lamps (2 x 80 W/cm). The belt speed in m/minute is then determined which is necessary to obtain a wiping-resistant paint surface. The hardness is determined by measuring the Konig pendulum hardness (DIN 53157) and the yellowing is measured as the yellowness index (ASTM D 1925-70).

202258' The results are reproduced in Table 3.
Table 3:
CompoundWiping resistancePendulumYellowness Index according[number of passeshardness to Exampleat 20 m/min] [seconds]

3 5 82 6.6 6 83 6.7

Claims (21)

1. A compound of the formula I
in which R1 is C1-C18alkyl, C2-C18alkenyl, C1-C8alkyl which is monosubstituted or polysubstituted by phenyl, (C1-C12alkyl)-phenyl, halogenophenyl, (C1-C12alkoxy)-phenyl, cyano, C2-C5alkoxycarbonyl, C1-C12alkoxy or halogen, C5-C8cycloalkyl, C6-C12aryl, which is unsubstituted or mono- or poly-substituted by halogen, C1-C12alkyl or C1-C12alkoxy, a 5-membered or 6-membered heterocyclic monovalent radical which contains one or more O, S or N atoms and which may contain a fused benzo radical or which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy or halogen, or is a radical of the formula in which X is phenylene, xylylene, cyclohexylene or C1-C6alkylene which may be unsubstituted or monosubstituted or polysubstituted by halogen, C1-C4alkyl, C1-C4alkoxy or phenyl, R2 is C1-C18alkyl, C2-C18alkenyl, C1-C8alkyl which is monosubstituted or polysubstituted by phenyl, (C1-C12alkyl)-phenyl, halogenophenyl, (C1-C12alkoxy)-phenyl, cyano, C2-C5alkoxycarbonyl, C1-C12alkoxy or halogen, C5-C8cycloalkyl, C6-C12aryl which is unsubstituted or mono- or poly-substituted by halogen, C1-C12alkyl or C1-C12alkoxy, a 5-membered or 6-membered heterocyclic monovalent radical which contains one or more O, S or N atoms and which may contain a fused benzo radical or is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy or halogen, or is a radical -CO-R3 or -OR4, or R1 and R2 or R1 and R4 together with the phosphorus atom form a monocyclic or bicyclic or tricyclic ring having 4-15 C atoms, R3 is C1-C18alkyl, C2-C6alkenyl, phenylvinyl, C1-C8alkyl which is mono- or poly-substituted by phenyl, C2-C5alkoxycarbonyl, halogen, C1-C12alkoxy, phenoxy, C1-C12alkylthio or phenylthio, C5-C10cycloalkyl which is unsubstituted or substituted by C1-C12alkyl, phenyl, phenoxy, C1-C12alkoxy, C2-C5alkoxycarbonyl, C1-C4alkylthio or halogen, C6-C12aryl which is unsubstituted or mono- or poly-substituted by C1-C12alkyl, C1-C12alkoxy, C1-C12alkoxyalkyl, C1-C4alkylthio or halogen, or a monovalent 5-membered or 6-membered heterocyclic radical containing one or more O, S or N atoms, which radical can be mono- or poly-substituted by halogen, C1-C4alkyl or C1-C4alkoxy, and R4 is C1-C18alkyl, phenyl-C1-C4alkyl, C5-C8cycloalkyl or C6-C10aryl, with the proviso that at least one of the radicals R1, R2 and R3 is a substituted alkyl radical or that R1 and R2 together with the phosphorus atom form a bicyclic or tricyclic ring, or that R3 is a substituted cycloalkyl radical which, however, cannot contain alkyl radicals as the only substituents.
2. A compound according to claim 1 of the formula I, in which R1 is C1-C12alkyl, C1-C4alkyl which is mono- to tri-substituted by phenyl, (C1-C4alkyl)-phenyl, chlorophenyl, (C1-C4alkoxy)-phenyl or C1-C4alkoxy, cyclohexyl, C6-C10aryl which is unsubstituted or mono- to tri-substituted by chlorine, C1-C12alkyl or C1-C4alkoxy, or is a 5-membered or 6-membered heterocyclic monovalent radical which contains one or more O, S or N atoms, R2 is as defined for R1 or a radical -CO-R3 or -OR4, or R1 and R2 or R1 and R4 together with the P atom form a monocyclic or bicyclic radical having 4-8 C
atoms, R3 is C1-C8alkyl, C1-C6alkyl which is mono- or di-substituted by phenyl, C1-C4alkoxy, C2-C5alkoxycarbonyl or chlorine, C5-C6cycloalkyl which is unsubstituted or substituted by phenyl, C1-C4alkoxy, C2-C5alkoxycarbonyl or chlorine, or C6-C10aryl which is unsubstituted or mono- to tri-substituted by C1-C12alkyl, C1-C4alkoxy or chlorine, and R4 is C1-C8alkyl, cyclohexyl, benzyl or phenyl.
3. A compound according to claim 1 of the formula I, in which R1 is C1-C8alkyl, C1-C4alkyl which is mono- or di-substituted by phenyl (C1-C4alkyl)-phenyl or C1-C1alkoxy, cyclohexyl or phenyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl or C1-C4alkoxy, R2 is as defined for R1 or is a radical -CO-R3 or -OR4, or R1 and R2 or R1 and R4 together with the P atom form a monocyclic or bicyclic ring, R3 is C1-C6alkyl which is unsubstituted or substituted by phenyl, chlorine or C1-C4alkoxy, C5-C6cycloalkyl which is unsubstituted or substituted by phenyl, C1-C4alkoxy, C2-C5alkoxycarbonyl or chlorine, or phenyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4alkoxy or chlorine, and R4 is C1-C4alkyl, cyclohexyl or phenyl.
4. A compound according to claim 1 of the formula I, in which R1 is a substituted alkyl radical as defined in claim 1.
5. A compound according to claim 4, in which R1 is C1-C4alkyl which is substituted by phenyl, (C1-C4alkyl)-phenyl, chlorophenyl, Ct-C4alkoxy or cyano.
6. A compound according to claim 1 of the formula I, in which R1 is benzyl.
7. A compound according to claim 1 of the formula I, in which R2 is C1-C4alkyl which is unsubstituted or substituted by phenyl, (C1-C4alkyl)-phenyl, chlorophenyl, C1-C4alkoxy or cyano, or is phenyl or cycloalkyl.
8. A compound according to claim 1 of the formula I, in which R3 is phenyl which is substituted by C1-C4alkyl, C1-C4alkoxy or chlorine.
9. A compound according to claim 1 of the formula I, in which R3 is C1-C8alkyl which is mono- to tri-substituted by phenyl, C2-C5alkoxycarbonyl, halogen or C1-C12alkoxy.
10. A compound according to claim 1 of the formula I, in which R3 is C5-C10cycloalkyl which is unsubstituted or substituted by C1-C4alkyl, phenyl, phenoxy, C1-C12alkoxy, C2-C5alkoxycarbonyl or halogen.
11. A compound according to claim 1 of the formula II or III
in which n is 1-8 and R3 is as defined in claim 1.
12. A compound according to claim 11 of the formula II or III, in which n is 1-8 and R3 is phenyl-substituted C1-C4alkyl, C6-C10aryl or phenyl which is mono- to tri-substituted by C1-C12alkyl, C1-C4alkoxy or chlorine.
13. A compound according to claim 1 of the formula I, in which R2 is a radical -CO-R3.
14. A compound according to claim 1 of the formula I, in which R1 is C1-C4alkyl which is unsubstituted or substituted by phenyl, C1-C4alkoxy or chlorine, phenyl or (C1-C4alkyl)-phenyl, R2 is as defined for R1 or is -O-(C1-C4alkyl) and R3 is phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy or chlorine, C1-C4alkyl which is unsubstituted or substituted by chlorine, C1-C4alkoxy or phenyl, or C5-C6cycloalkyl which is unsubstituted or substituted by C1-C4alkyl or C2-C5alkoxycarbonyl.
15. A compound according to claim 1 of the formula I, in which R1 is C1-C4alkyl substituted by phenyl or C1-C4alkoxy, or phenyl, R2 is as defined for R1 or is -O-(C1-C4alkyl) and R3 is phenyl substituted by C1-C4alkyl or C1-C4alkoxy, C1-C4alkyl substituted by chlorine or cyclopentyl substituted by C1-C4alkyl or C2-C5alkoxycarbonyl.
16. A photopolymerizable composition, containing a) at least one ethylenically unsaturated photopolymerizable compound and b) at least one compound of the formula I as defined in claim 1 as a photoinitiator.
17. A composition according to claim 16, which contains, in addition to the photoinitiator (b) also another photoinitiator or other additives.
18. A composition according to claim 16, containing 0.05 to 15 % by weight of component (b), relative to the composition.
19. A composition according to claim 16, containing 0.2 to 5 % by weight of component (b), relative to the composition.
20. A composition according to claim 16, which contains at least one further photoinitiator.
21. A process for photopolymerizing non-volatile monomeric, oligomeric or polymeric compounds having at least one ethylenically unsaturated double bond, which comprises adding a compound of the formula I according to claim 1 to the said compounds alone or in combination with another photoinitiator or other additives and irradiating with light in the range from 200 to 600 nm.
CA002022587A 1989-08-04 1990-08-02 Mono- and di-acylphosphine oxides Expired - Fee Related CA2022587C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH289789 1989-08-04
CH2897/89-8 1989-08-04

Publications (2)

Publication Number Publication Date
CA2022587A1 CA2022587A1 (en) 1991-02-05
CA2022587C true CA2022587C (en) 2000-12-05

Family

ID=4244067

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002022587A Expired - Fee Related CA2022587C (en) 1989-08-04 1990-08-02 Mono- and di-acylphosphine oxides

Country Status (8)

Country Link
EP (2) EP0736540A3 (en)
JP (1) JP2973130B2 (en)
KR (1) KR0168328B1 (en)
CA (1) CA2022587C (en)
DD (1) DD298405A5 (en)
DE (1) DE59010615D1 (en)
ES (1) ES2098260T3 (en)
RU (2) RU2071610C1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8770880B2 (en) 2008-12-19 2014-07-08 Stabilo International Gmbh Pen or pencil

Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4115950A1 (en) * 1991-05-16 1992-11-19 Herberts Gmbh Liquid mixtures of photoinitiators, process for their preparation and their use
RU2091385C1 (en) * 1991-09-23 1997-09-27 Циба-Гейги АГ Bisacylphosphine oxides, composition and method of application of coatings
DE59307404D1 (en) * 1992-03-11 1997-10-30 Ciba Geigy Ag Benzoyl substituted phosphabicycloalkanes and sulfides as photoinitiators
ES2059261B1 (en) * 1992-10-08 1995-11-16 Ciba Geigy Ag ALKYL-BISACILPHOSPHINOXIDES.
DE4302123A1 (en) * 1993-01-27 1994-07-28 Herberts Gmbh Printing glass hollow-ware esp. bottle with ink contg. organic binder
CA2134156A1 (en) * 1993-11-22 1995-05-23 Thomas P. Klun Coatable compositions, abrasive articles made therefrom, and methods of making and using same
JPH08171209A (en) * 1994-12-15 1996-07-02 Japan Synthetic Rubber Co Ltd Radiation curable composition
US5707781A (en) * 1995-05-05 1998-01-13 Bayer Corporation Photopolymerizable compositions having acyl or diacyl phosphine oxide and a fluorescent optical brightner
DE69710657T3 (en) * 1996-08-23 2007-07-05 Showa Denko K.K. Photohardenable composition and curing process
SG53043A1 (en) * 1996-08-28 1998-09-28 Ciba Geigy Ag Molecular complex compounds as photoinitiators
HUP0101680A3 (en) 1998-03-13 2005-09-28 Akzo Nobel Nv Non-aqueous coating compositions based on an oxidatively drying alkyd resins and process for producing this alkyd resins
GB2360283B (en) * 2000-02-08 2002-08-21 Ciba Sc Holding Ag Monoacylarylphosphines and acylphosphine oxides and sulphides
GB2365430B (en) * 2000-06-08 2002-08-28 Ciba Sc Holding Ag Acylphosphine photoinitiators and intermediates
CA2467576A1 (en) 2001-11-20 2003-05-30 Jean-Pierre Wolf Multimer forms of acylphosphines and their derivatives
DE10205191C1 (en) * 2002-02-08 2003-10-09 Hobas Engineering Gmbh Klagenf Multi-layer plastic tube manufactured using the centrifugal process
EP1511754B1 (en) 2002-06-11 2008-07-23 Ciba Holding Inc. Multimer forms of mono- and bis-acylphosphine oxides
DE602005025217D1 (en) * 2004-04-15 2011-01-20 Basf Se PROCESS FOR PHOTO-PAINTING WITH LIGHT-EMITTING DIODES
US20090137771A1 (en) * 2005-08-11 2009-05-28 Satoshi Moriyama Resin composition
US7465819B2 (en) 2006-01-24 2008-12-16 Chung Shan Institute Of Science And Technology Bisbiphenylacylphosphine oxide and preparation method therefore
JP4824460B2 (en) * 2006-04-28 2011-11-30 ゼブラ株式会社 Writing instrument
TWI357536B (en) * 2006-10-24 2012-02-01 Taiyo Ink Mfg Co Ltd Photosetting and thermosetting solder resist ink c
EP1958994B1 (en) 2007-01-31 2010-12-08 FUJIFILM Corporation Ink set for inkjet recording and inkjet recording method
JP5227521B2 (en) 2007-02-26 2013-07-03 富士フイルム株式会社 Ink composition, ink jet recording method, printed matter, and ink set
JP4601009B2 (en) 2007-03-30 2010-12-22 富士フイルム株式会社 Ink set for inkjet recording and inkjet recording method
JP5243072B2 (en) 2007-03-30 2013-07-24 富士フイルム株式会社 Ink composition, and image recording method and image recorded material using the same
JP5306681B2 (en) 2007-03-30 2013-10-02 富士フイルム株式会社 Polymerizable compound, polymer, ink composition, printed matter, and inkjet recording method
US8076393B2 (en) 2007-09-26 2011-12-13 Fujifilm Corporation Ink composition, inkjet recording method, and printed material
JP5148235B2 (en) 2007-09-28 2013-02-20 富士フイルム株式会社 Ink composition
JP5236238B2 (en) 2007-09-28 2013-07-17 富士フイルム株式会社 White ink composition for inkjet recording
JP5227560B2 (en) 2007-09-28 2013-07-03 富士フイルム株式会社 Ink composition, inkjet recording method, printed matter, and method for producing molded printed matter
JP5457636B2 (en) 2008-01-22 2014-04-02 富士フイルム株式会社 Photocurable composition, photocurable ink composition, method for producing photocured product, and inkjet recording method
JP5254632B2 (en) 2008-02-07 2013-08-07 富士フイルム株式会社 Ink composition, inkjet recording method, printed matter, and molded printed matter
JP4914862B2 (en) 2008-03-26 2012-04-11 富士フイルム株式会社 Inkjet recording method and inkjet recording apparatus
JP5414367B2 (en) 2008-06-02 2014-02-12 富士フイルム株式会社 Pigment dispersion and ink composition using the same
JP2010180330A (en) 2009-02-05 2010-08-19 Fujifilm Corp Non-aqueous ink, ink set, method for recording image, device for recording image, and recorded matter
JP5350827B2 (en) 2009-02-09 2013-11-27 富士フイルム株式会社 Ink composition and inkjet recording method
JP5349097B2 (en) 2009-03-19 2013-11-20 富士フイルム株式会社 Ink composition, inkjet recording method, printed matter, and method for producing molded printed matter
JP2010229284A (en) 2009-03-27 2010-10-14 Fujifilm Corp Photocurable composition
JP5424764B2 (en) 2009-07-28 2014-02-26 富士フイルム株式会社 Pigment dispersion, ink composition, and ink jet recording method
JP2011068783A (en) 2009-09-25 2011-04-07 Fujifilm Corp Ink composition and inkjet recording method
JP5530141B2 (en) 2009-09-29 2014-06-25 富士フイルム株式会社 Ink composition and inkjet recording method
JP5437824B2 (en) 2010-01-14 2014-03-12 富士フイルム株式会社 Inkjet ink composition and inkjet recording method
KR101523421B1 (en) * 2010-06-30 2015-05-27 디에스엠 아이피 어셋츠 비.브이. D1492 liquid bapo photoinitiator and its use in radiation curable compositions
JP5687964B2 (en) 2010-07-27 2015-03-25 富士フイルム株式会社 Ink jet ink composition, ink jet recording method, and printed matter
JP5240799B2 (en) 2010-11-25 2013-07-17 富士フイルム株式会社 Ink set, ink jet recording method, and ink jet recording apparatus
JP5349543B2 (en) 2011-02-03 2013-11-20 富士フイルム株式会社 Ink jet ink composition, ink set, ink jet recording method, and printed matter
JP5351293B2 (en) 2011-02-16 2013-11-27 富士フイルム株式会社 Ink jet ink composition, method for producing the same, and ink jet recording method
JP5419934B2 (en) 2011-07-12 2014-02-19 富士フイルム株式会社 Inkjet ink composition and inkjet recording method
JP5474882B2 (en) 2011-07-12 2014-04-16 富士フイルム株式会社 Inkjet ink composition and inkjet recording method
JP5566979B2 (en) 2011-09-22 2014-08-06 富士フイルム株式会社 Ink composition for ink jet recording, ink pack, and ink jet recording method
JP2013193349A (en) 2012-03-21 2013-09-30 Fujifilm Corp Inkjet recording apparatus and inkjet recording method
JP5958803B2 (en) 2012-03-28 2016-08-02 富士フイルム株式会社 Actinic ray curable ink jet ink composition, method for producing the same, ink jet recording method, and printed matter
JP5718845B2 (en) 2012-03-30 2015-05-13 富士フイルム株式会社 Inkjet recording method and printed matter
JP5758832B2 (en) 2012-03-30 2015-08-05 富士フイルム株式会社 Actinic radiation curable inkjet ink composition, inkjet recording method, and printed matter
DE102012212429A1 (en) 2012-07-16 2014-01-16 Voco Gmbh Dental handset unit i.e. polymerization lamp, for invasive curing of light-curable material in e.g. dental cavity in mouth of human patient, has removable body separable together with control unit from non-destructive autoclavable handgrip
GB201213163D0 (en) 2012-07-24 2012-09-05 Lambson Ltd Photopolymerisation processes and novel compounds therefor
JP5642125B2 (en) 2012-08-24 2014-12-17 富士フイルム株式会社 Inkjet recording method
JP5752652B2 (en) 2012-08-29 2015-07-22 富士フイルム株式会社 Ink jet ink composition and method for producing the same, ink jet recording method, and pigment dispersion and method for producing the same
JP5788918B2 (en) 2013-02-19 2015-10-07 富士フイルム株式会社 Inkjet recording method and inkjet recording apparatus
JP5980702B2 (en) 2013-03-07 2016-08-31 富士フイルム株式会社 INKJET INK COMPOSITION, INKJET RECORDING METHOD, AND MOLDED PRINTED PRODUCTION METHOD
JP5939640B2 (en) 2013-03-08 2016-06-22 富士フイルム株式会社 MULTILAYER COMPOSITION AND METHOD FOR PRODUCING MULTILAYER COMPOSITION
JP5939644B2 (en) 2013-08-30 2016-06-22 富士フイルム株式会社 Image forming method, in-mold molded product manufacturing method, and ink set
JP6887484B2 (en) 2017-02-28 2021-06-16 富士フイルム株式会社 Liquid composition for inkjet and inkjet recording method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2909994A1 (en) * 1979-03-14 1980-10-02 Basf Ag ACYLPHOSPHINOXIDE COMPOUNDS, THEIR PRODUCTION AND USE
EP0007508B1 (en) * 1978-07-14 1983-06-01 BASF Aktiengesellschaft Acylphosphinoxide compounds, their preparation and their use
DE3133419A1 (en) * 1981-08-24 1983-03-10 Basf Ag, 6700 Ludwigshafen ACYLPHOSPHINOXIDE COMPOUNDS AND THEIR USE
DE3245297A1 (en) * 1982-12-08 1984-06-14 Basf Ag, 6700 Ludwigshafen Isocyanate group-containing copolymer
DE3443221A1 (en) * 1984-11-27 1986-06-05 ESPE Fabrik pharmazeutischer Präparate GmbH, 8031 Seefeld BISACYLPHOSPHINOXIDE, THEIR PRODUCTION AND USE

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8770880B2 (en) 2008-12-19 2014-07-08 Stabilo International Gmbh Pen or pencil

Also Published As

Publication number Publication date
JP2973130B2 (en) 1999-11-08
RU2071610C1 (en) 1997-01-10
RU2057759C1 (en) 1996-04-10
EP0413657B1 (en) 1996-12-27
EP0736540A2 (en) 1996-10-09
KR0168328B1 (en) 1999-03-20
EP0736540A3 (en) 1997-06-18
JPH03101686A (en) 1991-04-26
DE59010615D1 (en) 1997-02-06
ES2098260T3 (en) 1997-05-01
EP0413657A2 (en) 1991-02-20
DD298405A5 (en) 1992-02-20
CA2022587A1 (en) 1991-02-05
EP0413657A3 (en) 1992-03-18
KR910004641A (en) 1991-03-29

Similar Documents

Publication Publication Date Title
CA2022587C (en) Mono- and di-acylphosphine oxides
US5218009A (en) Mono- and di-acylphosphine oxides
US5399770A (en) Alkylbisacylphosphine oxides
KR100363978B1 (en) Alkoxyphenyl-substituted bisacylphosphine oxides
US4522693A (en) Photopolymerizable composition with acylphosphine sulfide photoinitiator and method
KR100903939B1 (en) Long-wavelength mono- and bis-acylphosphine oxides and sulfides as photoinitiators
KR100829076B1 (en) Organometallic monoacylalkylphosphines
CA1129422A (en) Acylphosphine oxide compounds, their preparation and use
US5723512A (en) Dimeric bisacylphosphines, oxides and sulfides
CA2037769A1 (en) Photoinitiator mixtures
US7511084B2 (en) Acyl- and bisacylphosphine derivatives
KR100363977B1 (en) Acylphosphine oxide
CA2059144C (en) Bisacylphosphine sulfides
KR0168316B1 (en) Mono- and di-acylphosphine oxides
US5210110A (en) Silylated acylphosphine oxides
JP2005225793A (en) Phosphine oxide compound
US5368985A (en) Bisacylphosphine sulfides
CA2175302A1 (en) Bis(alk or arylsulphonyl) alkyl phosphine oxides

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed