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WO1995003337A1 - Photoinitiator compositions - Google Patents

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Publication number
WO1995003337A1
WO1995003337A1 PCT/GB1994/001550 GB9401550W WO9503337A1 WO 1995003337 A1 WO1995003337 A1 WO 1995003337A1 GB 9401550 W GB9401550 W GB 9401550W WO 9503337 A1 WO9503337 A1 WO 9503337A1
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WO
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Prior art keywords
photoinitiator
hydrogen
optionally substituted
composition
olefinically unsaturated
Prior art date
Application number
PCT/GB1994/001550
Other languages
French (fr)
Inventor
Norman Sidney Allen
Iain Andrew Weddell
John Edward Yates
Original Assignee
Zeneca Limited
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Publication date
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Publication of WO1995003337A1 publication Critical patent/WO1995003337A1/en

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    • 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
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • This invention relates to photoinitiator compositions and photopolymerisable compositions derived therefrom and to their use in the production of polymeric materials.
  • One known class of photoinitiators comprises ketones which are generally used in conjunction with a hydrogen donor such as an amine from which the photoinitiator, when subjected to and excited by radiation of appropriate wavelength, abstracts a hydrogen atom and so forms radicals.
  • a hydrogen donor such as an amine from which the photoinitiator, when subjected to and excited by radiation of appropriate wavelength, abstracts a hydrogen atom and so forms radicals.
  • Certain ketone photoinitiators are described in United Kingdom Patent No 1408255, particular emphasis being placed on ⁇ -diketones one of which, camphorquinone, has achieved considerable commercial success as a component of visible light curable compositions.
  • Another class of ketone type photoinitiators comprises anthraquinone compounds having in the 2-position a substituent of the formula:
  • R 1 represents an optionally substituted hydrocarbyl radical and X represents 0, S or NR 2 wherein R 2 represents hydrogen or an optionally substituted hydrocarbyl radical.
  • Optionally substituted hydrocarbyl radicals which may be represented by R 1 and R 2 include optionally substituted alkenyl radicals and 2-acryloylamino anthraquinone is mentioned as a preferred compound.
  • polymers of 2-acryloylamino anthraquinone and related polymerisable 2-substituted anthraquinones are extremely effective photoinitiators and have the advantage over the corresponding non-polymeric photoinitiators of being more soluble in the olefinically unsaturated monomers and/or oligomers with which they are used. Furthermore, compared with the non-polymeric initiators, the polymeric initiators exhibit a reduce tendency to migrate from the resulting polymeric material to adjacent materials.
  • the invention provides a photoinitiator composition
  • a photoinitiator composition comprising: (a) a photoinitiator comprising a polymer obtainable by the polymerisation of an anthraquinone compound having in the 2-position an olefinically unsaturated group capable of taking part in addition polymerisation, and (b) a hydrogen donor capable of reducing the photoinitiator when the latter is in an excited state.
  • X represents an atom or group linking the olefinic group to the carbon atom at the 2-position of the anthraquinone nucleus
  • n has the value 0 or 1 and each of R 1 , R 2 and R 3 independently represents a hydrogen or halogen atom or a hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, cycloalkyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, nitro, cyano, acyloxy or alkoxycarbonyl group.
  • Alkyl groups mentioned herein either as such or as components of larger groups such as alkoxycarbonyl, particularly include lower alkyl groups having one to four carbon atoms but larger alkyl groups, for example those linear or branched groups having up to 10 carbon atoms, may be present if desired.
  • the preferred polymerisable groups are those in which each of R 2 and R 3 is hydrogen and R 1 is hydrogen, halogen, lower alkyl, cyano or alkoxycarbonyl.
  • Particular preferred groups are those in which each of R 2 and R 3 is hydrogen and R 1 is hydrogen, halogen (especially chlorine) or lower alkyl (especially methyl) .
  • linkages which may be represented by X
  • linkages there may be mentioned -0-, -S-, -CO-, -CS-, -NR 4 -CO- in which R 4 is hydrogen or alkyl, -0-CO-, -S-CO-, -CO-0-, -CO-S-, -SO-, -S0 2 -, -NR 4 -S0 2 -, -S0 2 -NR 4 -, -CH 2 -, -0-CH 2 -, -S-CH 2 -, -S0 2 -CH 2 -, -COCH 2 -, -0-CO-CH 2 -, -NR 4 -CH 2 - and -NR 4 - .
  • R s represents hydrogen or lower alkyl, for example methyl.
  • the positions of the anthraquinone nucleus other than the 2-position may be unsubstituted or, alternatively, one or more of said positions may be substituted.
  • Polymerisation of the 2-substituted anthraquinone to form the photoinitiator may be effected using conventional conditions for the polymerisation of such compounds, such conditions having been fully described in the prior art.
  • the 2- substituted anthraquinone may be dissolved or dispersed in a suitable liquid organic medium, optionally with the addition of one or more other olefinically unsaturated compounds, and subjected to the action of a free radical polymerisation initiator such as a peroxide, preferably at an elevated temperature.
  • a free radical polymerisation initiator such as a peroxide
  • Preferred photoinitiators for use in the photoinitiator compositions of the invention include homopolymers obtained by the homopolymerisation of 2-acryloylaminoanthraquinone and copolymers obtained by the copolymerisation of 2-acryloylaminoanthraquinone with at least one other polymerisable olefinically unsaturated compound. These photoinitiators may optionally be used in conjunction with one or more other photoinitiator materials.
  • Hydrogen donors which may be present in the photoinitiator composition include primary, secondary or tertiary amines in which at least one hydrogen atom is directly attached to a saturated carbon atom adjacent to the amino nitrogen.
  • Suitable amines are well known in the art and include, for example, propylamine, diethylamine, triethylamine, benzyldimethylamine, N- phenylglycine, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine and, especially, dimethylaminoethyl methacrylate or ethyl p-dimethylaminobenzoate.
  • Mixtures of hydrogen donors for example mixtures of amines, may be used.
  • the photoinitiator compositions of the invention may be used in conjunction with polymerisable olefinic compounds in the preparation of photopolymerisable compositions.
  • the invention provides a photopolymerisable composition comprising a polymerisable olefinically unsaturated compound and a photoinitiator composition as hereinbefore defined.
  • the polymerisable olefinically unsaturated compound present in the photopolymerisable composition of the invention will generally be a monomer, oligomer or polymer having at least one olefinically unsaturated double bond per molecule. Mixtures of two or more such compounds may be used if desired, for example a mixture comprising one or more monofunctional polymerisable compound and one or more polyfunctional polymerisable compound.
  • Suitable polymerisable olefinic monomers have been fully described in the prior art and include, for example, alpha-beta- unsaturated carboxylic acids, for example acrylic and methacrylic acids and the nitriles, amides and esters thereof, for example acrylonitrile, ethyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, acrylamide and methylene bis-acrylamide, vinyl aromatic compounds, for example styrene, alpha-methylstyrene and vinyltoluene, dienes, for example butadiene and isoprene, vinyl chloride, vinylidene chloride, vinyl carbazole, vinyl ketones and vinyl esters, for example vinyl acetate. Oligomers derived from these monomers may also be used. Olefinically unsaturated polymers which may be present in the
  • the photoinitiator is suitably present in the photopolymerisable compositions of the invention in an amount of from 0.01 to 5%, preferably from 0.05 to 2%, on a weight basis.
  • the hydrogen donor may be present in an amount of from 0.01 to 5%, preferably from 0.5 to 1%, on a weight basis.
  • the photopolymerisable compositions of the invention may be prepared by incorporating the photoinitiator composition or each of the separate components thereof into the polymerisable olefinically unsaturated compound or compounds in any convenient manner.
  • the photopolymerisable compositions will be prepared in a sequence of steps comprising:
  • photopolymerisable composition if desired, for example peroxides such as benzoyl peroxide, peroxyesters such as tert-butyl perbenzoate, colouring agents, plasticisers, fillers, thermal polymerisation inhibitors and the like.
  • peroxides such as benzoyl peroxide, peroxyesters such as tert-butyl perbenzoate, colouring agents, plasticisers, fillers, thermal polymerisation inhibitors and the like.
  • Photopolymerisation of the photopolymerisable compositions of the invention may be effected by subjecting said compositions, preferably in the form of films, to radiation from sources which have emission maxima in the range from 200 to 500nm and especially in the range 400 to 500nm.
  • Suitable radiation sources are known in the art and include actinic or superactinic fluorescent tubes, low pressure, medium pressure and high pressure mercury vapour lamps and xenon lamps as well as tungsten halogen and blue phosphor- fluorescent lamps.
  • a method for the preparation of a polymeric material which comprises irradiating a photopolymerisable composition of the invention with radiation having a wavelength which is capable of being absorbed by the photoinitiator so as to convert it to an excited state.
  • compositions of the invention are useful in the production of light-curable adhesives, coatings, inks and the like.
  • the invention is illustrated but not limited by the following Example.
  • 2-Acryloylaminoanthraquinone (lg) was dissolved in dimethylformamide (100cm 3 ) in a three necked flask which was immersed in a constant temperature bath (70°C) and the solution deoxygenated with pure nitrogen ( ⁇ 5ppm 0 2 ) for 20 minutes. Lauryl peroxide (0.3g) was then added to commence the polymerisation which was continued for a period of 45 minutes with constant stirring. The yellow-orange polymer (0.7g) was then precipitated by the addition of 1M hydrochloric acid solution followed by washing with distilled water. The polymer was then filtered and washed several times with acetone to remove low molecular weight material and monomer.
  • the poly(2-acryloylaminoanthraquinone) unlike the monomer, dissolved easily in chloroform and could be cast from chloroform solution into clear films.
  • the absorption spectrum of the polymer was similar to that of the of the monomer being only blue shifted by 2nm due to loss of the acrylic unsaturation.
  • the corresponding extinction coefficients were also similar to that of the monomer being reduced by only O ⁇ ftnole" 1 at each maximum.
  • Gel permeation chromatography using polystyrene as a standard gave a main number average molecular weight value for the polymer of 3,230 with a small shoulder at 1,600.
  • Differential thermal analysis of the polymer gave a glass transition temperature of 128°C and a very weak broad melting point peak over the region 180-200°C. The latter was also confirmed by visual observation in a melting point apparatus.
  • Photocurin ⁇ Poly(2-acryloylaminoanthraquinone) was dissolved (0.001 mole%) in a 50/50 (by volume) vinyl urethane/triethylene glycol dimethacrylate resin together with p-dimethylaminobenzoate (0.005 mole%) .
  • a small sample of the prepared resin was then spread between two sheets of clear polyethylene to give a film thickness of 50 ⁇ m which was controlled by a PTFE spacer and the resulting assembly was clamped between two salt flats and mounted in the sample holder of a Perkin-Elmer model 842 spectrometer.
  • the sample was then irradiated with visible light (115mW/cm 2 ) (ILC 302UV) via a light guide and the decrease in double bond absorption (1638cm "1 ) was monitored with time. The percentage conversion was measured by ratioing the decreased absorption with that for the original unirradiated sample. All measured peaks were normalised to the baseline of the final infra-red spectrum.
  • the rate of conversion of vinyl groups using the three photoinitiators is shown in the accompanying graph from which it can be seen that the polymer (2-acrylamido-AQP) is as effective as the monomer in the initial stages but becomes slightly less effective in the later stages.
  • Camphorquinone is seen to be the least effective visible photoinitiator particularly during the early stages of irradiation.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

A photoinitiator composition comprising: (a) a photoinitiator comprising a polymer obtainable by the polymerisation of an anthraquinone compound having in the 2-position an olefinically unsaturated group capable of taking part in addition polymerisation, and (b) a hydrogen donor capable of reducing the photoinitiator when the latter is in an excited state.

Description

PHOTOINITIATOR COMPOSITIONS
This invention relates to photoinitiator compositions and photopolymerisable compositions derived therefrom and to their use in the production of polymeric materials.
It is known to polymerise olefinically unsaturated compounds by exposing such compounds to electromagnetic radiation such as visible or ultraviolet light in the presence of a photoinitiator which is capable of absorbing the radiation and thereby generating free radicals.
One known class of photoinitiators comprises ketones which are generally used in conjunction with a hydrogen donor such as an amine from which the photoinitiator, when subjected to and excited by radiation of appropriate wavelength, abstracts a hydrogen atom and so forms radicals. Certain ketone photoinitiators are described in United Kingdom Patent No 1408255, particular emphasis being placed on α-diketones one of which, camphorquinone, has achieved considerable commercial success as a component of visible light curable compositions.
Another class of ketone type photoinitiators, described in our EP-A-0542439, comprises anthraquinone compounds having in the 2-position a substituent of the formula:
-XCOR1 wherein R1 represents an optionally substituted hydrocarbyl radical and X represents 0, S or NR2 wherein R2 represents hydrogen or an optionally substituted hydrocarbyl radical. Optionally substituted hydrocarbyl radicals which may be represented by R1 and R2 include optionally substituted alkenyl radicals and 2-acryloylamino anthraquinone is mentioned as a preferred compound.
It has now been found that polymers of 2-acryloylamino anthraquinone and related polymerisable 2-substituted anthraquinones are extremely effective photoinitiators and have the advantage over the corresponding non-polymeric photoinitiators of being more soluble in the olefinically unsaturated monomers and/or oligomers with which they are used. Furthermore, compared with the non-polymeric initiators, the polymeric initiators exhibit a reduce tendency to migrate from the resulting polymeric material to adjacent materials.
Accordingly, the invention provides a photoinitiator composition comprising: (a) a photoinitiator comprising a polymer obtainable by the polymerisation of an anthraquinone compound having in the 2-position an olefinically unsaturated group capable of taking part in addition polymerisation, and (b) a hydrogen donor capable of reducing the photoinitiator when the latter is in an excited state.
As examples of olefinically unsaturated groups which may be present in the 2-position of the anthraquinone compound there may be mentioned groups of the general formula:
Figure imgf000004_0001
wherein X represents an atom or group linking the olefinic group to the carbon atom at the 2-position of the anthraquinone nucleus, n has the value 0 or 1 and each of R1, R2 and R3 independently represents a hydrogen or halogen atom or a hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, cycloalkyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, nitro, cyano, acyloxy or alkoxycarbonyl group.
Alkyl groups mentioned herein, either as such or as components of larger groups such as alkoxycarbonyl, particularly include lower alkyl groups having one to four carbon atoms but larger alkyl groups, for example those linear or branched groups having up to 10 carbon atoms, may be present if desired.
The preferred polymerisable groups are those in which each of R2 and R3 is hydrogen and R1 is hydrogen, halogen, lower alkyl, cyano or alkoxycarbonyl. Especially preferred groups are those in which each of R2 and R3 is hydrogen and R1 is hydrogen, halogen (especially chlorine) or lower alkyl (especially methyl) .
As examples of linkages which may be represented by X, there may be mentioned -0-, -S-, -CO-, -CS-, -NR4-CO- in which R4 is hydrogen or alkyl, -0-CO-, -S-CO-, -CO-0-, -CO-S-, -SO-, -S02-, -NR4-S02-, -S02-NR4-, -CH2-, -0-CH2-, -S-CH2-, -S02-CH2-, -COCH2-, -0-CO-CH2-, -NR4-CH2- and -NR4- .
As examples of especially preferred polymerisable groups there may be mentioned groups of the formula:
-NH-C0-CRs=CH2 (2)
in which Rs represents hydrogen or lower alkyl, for example methyl. The positions of the anthraquinone nucleus other than the 2-position may be unsubstituted or, alternatively, one or more of said positions may be substituted.
Polymerisation of the 2-substituted anthraquinone to form the photoinitiator may be effected using conventional conditions for the polymerisation of such compounds, such conditions having been fully described in the prior art. Thus, for example, the 2- substituted anthraquinone may be dissolved or dispersed in a suitable liquid organic medium, optionally with the addition of one or more other olefinically unsaturated compounds, and subjected to the action of a free radical polymerisation initiator such as a peroxide, preferably at an elevated temperature. The degree of polymerisation may vary over a wide range.
Preferred photoinitiators for use in the photoinitiator compositions of the invention include homopolymers obtained by the homopolymerisation of 2-acryloylaminoanthraquinone and copolymers obtained by the copolymerisation of 2-acryloylaminoanthraquinone with at least one other polymerisable olefinically unsaturated compound. These photoinitiators may optionally be used in conjunction with one or more other photoinitiator materials.
Hydrogen donors which may be present in the photoinitiator composition include primary, secondary or tertiary amines in which at least one hydrogen atom is directly attached to a saturated carbon atom adjacent to the amino nitrogen. Suitable amines are well known in the art and include, for example, propylamine, diethylamine, triethylamine, benzyldimethylamine, N- phenylglycine, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine and, especially, dimethylaminoethyl methacrylate or ethyl p-dimethylaminobenzoate. Mixtures of hydrogen donors, for example mixtures of amines, may be used.
The photoinitiator compositions of the invention may be used in conjunction with polymerisable olefinic compounds in the preparation of photopolymerisable compositions.
Accordingly, in a further aspect, the invention provides a photopolymerisable composition comprising a polymerisable olefinically unsaturated compound and a photoinitiator composition as hereinbefore defined.
The polymerisable olefinically unsaturated compound present in the photopolymerisable composition of the invention will generally be a monomer, oligomer or polymer having at least one olefinically unsaturated double bond per molecule. Mixtures of two or more such compounds may be used if desired, for example a mixture comprising one or more monofunctional polymerisable compound and one or more polyfunctional polymerisable compound. Suitable polymerisable olefinic monomers have been fully described in the prior art and include, for example, alpha-beta- unsaturated carboxylic acids, for example acrylic and methacrylic acids and the nitriles, amides and esters thereof, for example acrylonitrile, ethyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, acrylamide and methylene bis-acrylamide, vinyl aromatic compounds, for example styrene, alpha-methylstyrene and vinyltoluene, dienes, for example butadiene and isoprene, vinyl chloride, vinylidene chloride, vinyl carbazole, vinyl ketones and vinyl esters, for example vinyl acetate. Oligomers derived from these monomers may also be used. Olefinically unsaturated polymers which may be present in the compositions of the invention include unsaturated polyesters derived, for example, from unsaturated dicarboxylic acids.
The photoinitiator is suitably present in the photopolymerisable compositions of the invention in an amount of from 0.01 to 5%, preferably from 0.05 to 2%, on a weight basis. The hydrogen donor may be present in an amount of from 0.01 to 5%, preferably from 0.5 to 1%, on a weight basis.
The photopolymerisable compositions of the invention may be prepared by incorporating the photoinitiator composition or each of the separate components thereof into the polymerisable olefinically unsaturated compound or compounds in any convenient manner.
Generally, the photopolymerisable compositions will be prepared in a sequence of steps comprising:
1) polymerising the anthraquinone compound, and then
2) contacting the polymerised anthraquinone compound so obtained and the hydrogen donor with the polymerisable olefinically unsaturated compound.
Other conventional additives may also be incorporated in the photopolymerisable composition if desired, for example peroxides such as benzoyl peroxide, peroxyesters such as tert-butyl perbenzoate, colouring agents, plasticisers, fillers, thermal polymerisation inhibitors and the like.
Photopolymerisation of the photopolymerisable compositions of the invention may be effected by subjecting said compositions, preferably in the form of films, to radiation from sources which have emission maxima in the range from 200 to 500nm and especially in the range 400 to 500nm. Suitable radiation sources are known in the art and include actinic or superactinic fluorescent tubes, low pressure, medium pressure and high pressure mercury vapour lamps and xenon lamps as well as tungsten halogen and blue phosphor- fluorescent lamps.
Thus, according to a still further aspect of the invention, there is provided a method for the preparation of a polymeric material which comprises irradiating a photopolymerisable composition of the invention with radiation having a wavelength which is capable of being absorbed by the photoinitiator so as to convert it to an excited state.
The compositions of the invention are useful in the production of light-curable adhesives, coatings, inks and the like.
The invention is illustrated but not limited by the following Example.
Example Preparation of Polymer
2-Acryloylaminoanthraquinone (lg) was dissolved in dimethylformamide (100cm3) in a three necked flask which was immersed in a constant temperature bath (70°C) and the solution deoxygenated with pure nitrogen (<5ppm 02) for 20 minutes. Lauryl peroxide (0.3g) was then added to commence the polymerisation which was continued for a period of 45 minutes with constant stirring. The yellow-orange polymer (0.7g) was then precipitated by the addition of 1M hydrochloric acid solution followed by washing with distilled water. The polymer was then filtered and washed several times with acetone to remove low molecular weight material and monomer. Precipitation was also undertaken with pure methanol only, for comparison purposes. Evidence for polymer formation was obtained from the FT- IR spectrum which showed, for example, that the N-H and Ar-H stretching frequencies at 3390 and 3150cm"1 remained unchanged after polymerisation whilst, for the polymer samples, two new methylene stretching bands appeared at 2900 and 2850cm"1 associated with the polymer backbone structure. Polymer formation was also confirmed by FT-NMR data.
The poly(2-acryloylaminoanthraquinone) , unlike the monomer, dissolved easily in chloroform and could be cast from chloroform solution into clear films. The absorption spectrum of the polymer was similar to that of the of the monomer being only blue shifted by 2nm due to loss of the acrylic unsaturation. The corresponding extinction coefficients were also similar to that of the monomer being reduced by only O^πftnole"1 at each maximum. Gel permeation chromatography using polystyrene as a standard gave a main number average molecular weight value for the polymer of 3,230 with a small shoulder at 1,600. Differential thermal analysis of the polymer gave a glass transition temperature of 128°C and a very weak broad melting point peak over the region 180-200°C. The latter was also confirmed by visual observation in a melting point apparatus.
Photocurinα Poly(2-acryloylaminoanthraquinone) was dissolved (0.001 mole%) in a 50/50 (by volume) vinyl urethane/triethylene glycol dimethacrylate resin together with p-dimethylaminobenzoate (0.005 mole%) . A small sample of the prepared resin was then spread between two sheets of clear polyethylene to give a film thickness of 50μm which was controlled by a PTFE spacer and the resulting assembly was clamped between two salt flats and mounted in the sample holder of a Perkin-Elmer model 842 spectrometer. The sample was then irradiated with visible light (115mW/cm2) (ILC 302UV) via a light guide and the decrease in double bond absorption (1638cm"1) was monitored with time. The percentage conversion was measured by ratioing the decreased absorption with that for the original unirradiated sample. All measured peaks were normalised to the baseline of the final infra-red spectrum.
This procedure was then repeated replacing the poly(2- acryloylaminoanthraquinone) by, first, monomeric 2-acryloylamino anthraquinone and then camphorquinone at the same concentrations (0.001 mole%) .
The rate of conversion of vinyl groups using the three photoinitiators is shown in the accompanying graph from which it can be seen that the polymer (2-acrylamido-AQP) is as effective as the monomer in the initial stages but becomes slightly less effective in the later stages. Camphorquinone is seen to be the least effective visible photoinitiator particularly during the early stages of irradiation.

Claims

1. A photoinitiator composition comprising:
(a) a photoinitiator comprising a polymer obtainable by the polymerisation of an anthraquinone compound having in the 2-position an olefinically unsaturated group capable of taking part in addition polymerisation, and
(b) a hydrogen donor capable of reducing the photoinitiator when the latter is in an excited state.
2. A composition according to Claim 1 wherein the olefinically unsaturated group present in the 2-position of the anthraquinone compound has the formula:
Figure imgf000009_0001
wherein X represents an atom or group linking the olefinic group to the carbon atom at the 2-position of the anthraquinone nucleus, n has the value 0 or 1 and each of R1, R2 and R3 independently represents a hydrogen or halogen atom or a hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, cycloalkyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, nitro, cyano, acyloxy or alkoxycarbonyl group.
3. A composition according to Claim 2 wherein each of R2 and R3 is hydrogen and R1 is hydrogen, halogen, lower alkyl, cyano or alkoxycarbonyl.
4. A composition according to Claim 2 wherein the unsaturated group has the formula:
-NH-CO-CR5=CH2
in which R5 represents hydrogen or lower alkyl.
5. A composition according to any one of Claims 1 to 4 wherein the hydrogen donor is a primary, secondary or tertiary amine in which at least one hydrogen atom is directly attached to a saturated carbon atom adjacent to the amino nitrogen.
6. A photopolymerisable composition comprising a polymerisable olefinically unsaturated compound and a photoinitiator composition as defined in any one of Claims 1 to 5.
7. A method for the preparation of a polymeric material which comprises irradiating a photopolymerisable composition as defined in Claim 6 with radiation having a wavelength which is capable of being absorbed by the photoinitiator so as to convert it to an excited state.
8. A method according to Claim 7 wherein the applied radiation comprises visible light.
PCT/GB1994/001550 1993-07-21 1994-07-18 Photoinitiator compositions WO1995003337A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004738A (en) * 2019-12-19 2021-06-22 常州强力电子新材料股份有限公司 Photo-curable composition and photo-curable ink

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993009471A1 (en) * 1991-10-30 1993-05-13 Imperial Chemical Industries Plc Polyamide materials
EP0542439A1 (en) * 1991-11-11 1993-05-19 Zeneca Limited Polymerisable compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993009471A1 (en) * 1991-10-30 1993-05-13 Imperial Chemical Industries Plc Polyamide materials
EP0542439A1 (en) * 1991-11-11 1993-05-19 Zeneca Limited Polymerisable compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004738A (en) * 2019-12-19 2021-06-22 常州强力电子新材料股份有限公司 Photo-curable composition and photo-curable ink
CN113004738B (en) * 2019-12-19 2022-04-22 常州强力电子新材料股份有限公司 Photo-curable composition and photo-curable ink

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