EP0000705B1 - Use of esters or amides of benzoylbenzoic acids as photoinitiators and photopolymerisable composition containing them - Google Patents

Use of esters or amides of benzoylbenzoic acids as photoinitiators and photopolymerisable composition containing them Download PDF

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Publication number
EP0000705B1
EP0000705B1 EP78100370A EP78100370A EP0000705B1 EP 0000705 B1 EP0000705 B1 EP 0000705B1 EP 78100370 A EP78100370 A EP 78100370A EP 78100370 A EP78100370 A EP 78100370A EP 0000705 B1 EP0000705 B1 EP 0000705B1
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Prior art keywords
carbon atoms
composition
compounds
alkyl
benzoylbenzoate
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EP78100370A
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German (de)
English (en)
French (fr)
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EP0000705A1 (en
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James Mitchell Dr. Photis
Francis A. Dr. Via
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Stauffer Chemical Co
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Stauffer Chemical Co
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/124—Carbonyl compound containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/922—Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation

Definitions

  • This invention relates to photopolymerizable compositions and to a method employing same. More particularly, this invention relates to the use of certain benzoyl benzoates as photoinitiators for ethylenically unsaturated compounds.
  • Photopolymerization of unsaturated compositions wherein a photoinitiating compound is included in the polymerizable mass is well known in the art.
  • the process has many advantages over thermal polymerization and is particularly useful where long holding life combined with rapid hardening at low temperature is desirable.
  • Photoinitiating compounds must absorb light and utilize the energy so acquired to initiate polymerization.
  • U.S. Patent No. 3,715,293 teaches the use of acetophenone compounds such as 2,2-diethoxyacetophenone, while a series of patents including U.S. Patents 3,404,998 ; 3,926,638 ; 3,926,639; 3,926,640 ; 3,926,641 ; 4,022,674; 4,004,998 ; 4,008,138 and 4,028,204 describe complex compounds derived from benzophenone.
  • U.S. Patent No. 3,715,293 teaches the use of acetophenone compounds such as 2,2-diethoxyacetophenone
  • U.S. Patents 3,404,998 ; 3,926,638 ; 3,926,639; 3,926,640 ; 3,926,641 ; 4,022,674; 4,004,998 ; 4,008,138 and 4,028,204 describe complex compounds derived from benzophenone.
  • benzophenone-derived materials U.S.
  • Patent 3,404,998 describes photoinitiators made by reacting carboxy-substituted benzophenones with hydroxyl-containing polyethylenically unsaturated esters
  • U.S. Patent 3,404,998 describes photoinitiators made by reacting carboxy-substituted benzophenones with hydroxyl-containing polyethylenically unsaturated esters
  • U.S. Patents 3,926,639 and 4,028,204 describe a benzophenone substituted with a carboxy group and an ester group which is reacted with certain resins, such as alkyds, polyesters, polyethers, polyamides and epoxides, to provide the photoinitiator.
  • ethyl benzoylbenzoate is disclosed as a photosensitizer which must be used in connection with a photoinitiator such as a benzoin ether.
  • the photopolymerizable composition of this invention comprises an ethylenically unsaturated compound and a p-benzoyl benzoate or a p-benzoyl benzamide. After applying the compositions to the desired substrate, curing is effected by exposure to actinic radiation.
  • the photopolymerizable composition of this invention comprises an ethylenically unsaturated compound and a photoinitiating amount of a photoinitiator, characterised in that said photoinitiator is a p-benzoyl benzoate or benzamide of the formula : wherein X is OR, NHR or NRR ; R is an independently selected hydrocarbon of 1 to 30 carbon atoms, alkoxysubstituted alkyl of 2 to 12 carbon atoms or aminosubstituted alkyl of 2 to 12 carbon atoms ; R' is an independently selected halogen or X ; and n and m are independently selected integers from 0 to 3.
  • hydrocarbon of from 1 to 30 carbon atoms refers to straight and branched chain acyclic hydrocarbon groups which may contain unsaturated carbon-to-carbon bonds.
  • compositions are characterized in that X is OR and R is an alkyl of 1 to 15, especially 1 to 13 carbon atoms, an alkenyl of 3 to 5 carbon atoms, an alkoxy-substituted alkyl of 2 to 4 carbon atoms or an amino-substituted alkyl of 2 to 5 carbon atoms, or are characterized in that X is the group NHR or NRR and R is an alkyl of 1 to 4 carbon atoms.
  • Illustrative compounds I include, but are not limited to, methyl-p-benzoylbenzoate ; tridecyl-p-benzoylbenzoate ; (2-propenyl)-p-benzoylbenzoate ; (3-pentenyl)-p-benzoyl-benzoate ; methoxymethyl-p-benzoylbenzoate ; (2-ethoxyethyl)-p-benzoylbenzoate ; aminoethyl-p-benzoylbenzoate ; (2-amino-propyl)-p-benzoylbenzoate ; (dimethylaminopropyl)-p-benzoylbenzoate ; N-methyl-p-benzoylbenzamide ; N-tridecyl-p-benzoylbenzamide ; N-(2-propenyl)-p-benzoylbenzamide; N-(3-pentenyl)-p-benzoylbenzamide
  • benzoyl benzoates and benzamides I are known compounds, some of which are commercially available. Alternately, they are readily prepared by methods described in the literature. Thus, for example, they can be prepared by the techniques described in Advanced Organic Chemistry : Reactions, Mechanisms and Structure, J. March ed., McGraw Hill, New York (1968). The esters can also be prepared by the procedure of D. Bichan and M. Winnik, Tetrahedroh Letters, 3857 (1974).
  • compositions curable by actinic radiation according to the invention can contain a photopolymerizable polymer in a reactive ethylenically unsaturated monomeric medium, a reactive polymer alone, a reactive monomer alone, or any of these combined with an inert solvent. Additionally, the polymerizable composition can contain any of the pigments commonly used in photopolymerization techniques.
  • Polymerizable ethylenically unsaturated compounds which are useful in practicing the invention are acrylic, a-alkacrylic and a-chloroacrylic acid compounds such as esters, amides and nitriles. Examples of such compounds are acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, methacrylamide and methyl a-chloroacrylate. Also useful, although not preferred due to their slower rates of reactivity, are vinyl and vinylidene esters, ethers and ketones. Additionally, compounds having more than one terminal unsaturation can be used.
  • Examples of these include diallyl phthalate, diallyl maleate, diallyl fumarate, triallyl cyanurate, triallyl phosphate, ethylene glycol dimethacrylate, glycerol trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, methacrylic anhydride and allyl ethers of monohydroxy or polyhydroxy compounds such as ethylene glycol diallylether and pentaerythritol tetraallyl ether tetraallyl.
  • Nonterminally unsaturated compounds such as diethyl fumarate can similarly be used.
  • the acrylic acid derivitives are particularly well suited to the practice of the invention and are consequently preferred components as monomers in monomer-containing polymerizable systems and as reactive centers in polymerizable polymers. While monomeric styrene can be used in the practice of the invention, it is not a preferred constituent of systems polymerizable thereby due to its slow rate of reaction.
  • the photopolymerizable composition can contain a sensitizer capable of enhancing the photoinitiating reactivity of the photoinitiating compound of the invention by triplet sensitization.
  • a sensitizer capable of enhancing the photoinitiating reactivity of the photoinitiating compound of the invention by triplet sensitization.
  • sensitizers useful in the practice of the invention are such compounds as biphehyl, xanthone, thioxanthone and acetophenone. These are typically added in amounts ranging from 0,1 to 6 weight percent.
  • the techniques whereby such sensitizers are selected for use in conjunction with particular photoinitiators are well known in the art. See, for example, MUROV, Handbook of Photochemistry, Marcel Dekker, Inc., New York (1973).
  • polymerization promoters such as organic amines can be used to accelerate cure rates, either alone or in combination with a sensitizer.
  • Such amines can be primary, secondary, or preferably, tertiary, and can be represented by the general formula : wherein R' and R 2 are independently selected hydrogen, straight chain or branched alkyl having from 1 to about 12 carbon atoms, straight chain or branched alkenyl having from 2 to about 12 carbon atoms, cycloalkyl having from 3 to about 10 ring carbon atoms, cycloalkenyl having from 3 to about 10 ring atoms, aryl having from 6 to about 12 ring carbon atoms, alkaryl having 6 to about 12 ring carbon atoms ;
  • R 3 has the same meaning as R' and R 2 with the exception that it cannot be hydrogen and that it cannot be aryl when both R' and R 2 are aryl.
  • R 2 and R 3 can be divalent alkylene groups having from 2 to about 12 carbon atoms, a divalent alkenylene group having from 3 to about 10 carbon atoms, a divalent alkadienylene group having from 5 to about 10 carbon atoms, a divalent alkatrienylene group having from 5 to about 10 carbon atoms, a divalent alkyleneoxyalkylene group having a total of from 4 to about 12 carbon atoms, or a divalent alkyleneaminoalkylene group having a total of from 4 to about 12 carbon atoms.
  • the amines can be substituted with other groups ; thus, the R', R 2 and R 3 variables, whether taken singly or together, can contain one or more substituents thereon.
  • the nature of such substituents is generally not of significant importance and any substituent group can be present that does not exert a pronounced deterrent effect on the ultraviolet crosslinking reaction.
  • Exemplary suitable organic amines are methylamine, dimethylamine, triethylamine, isopropylamine, triisopropylamine, tributylamine, t-butylamine, 2-methylbutylamine, N-methyl-N-butylamine, di-2-methylbutylamine, tri-2-ethylhexylamine, dodecylamine, tri-2-chloroethylamine, di-2-bromoethylamine, metha- nolamine, triethanolamine, methyldiethanolamine, propanolamine, triisopropanolamine, butylethanolamine, dihexanolamine, 2-methoxyethylamine, 2-hydroxyethyidiisopropylamine, allylamine, cyclohexylamine, trimethylcyclohexylamine, bis-methylcyclopentylamine, tricyclohexadienylamine, N-methyl-N-cyclohexy
  • the photoinitiators of the invention can be utilized in amounts ranging from 0.01 to 30 percent by weight based on the photopolymerizable composition. However, preferable amounts of the compounds are between 1.0 and 10.0 weight percent.
  • the process can be carried out by mixing a quantity of a photoinitiating compound of the invention with a photopolymerizable composition and exposing the resultant mixture to actinic radiation.
  • a one-component system comprising the photopolymerizable composition, the photoinitiator of the invention and, if desired, pigmentation, can be stored in the dark for a prolonged period of time prior to use without fear of gelation.
  • a preferred manner of practicing the invention is by the use of photopolymerizable molding and coating compositions which consist of mixtures of unsaturated polymeric compounds and monomeric compounds copolymerizable therewith.
  • the polymeric compounds can be conventional polyesters prepared from unsaturated polycarboxylic acids such as maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid and mesaconic acid, and polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerol, propylene glycol, 1,2-butanediol, 1,4-butanediol, pentaerythritol and trimethylolpropane.
  • the carboxylic acid content can also contain saturated components.
  • a monobasic fatty acid content either as such or in the form of a triglyceride or oil
  • these resins can, in turn, be modified by silicones, epoxides or isocyanates, by known techniques.
  • compositions of the instant invention after being prepared in the ratios as set out above can be applied to the material to be coated by conventional means, including brushing, spraying, dipping, and roll coating techniques, and may, if desired, be dried under ambient or elevated conditions to provide coatings on the substrate.
  • the substrate can be of any composition, including but not limited to plastic, fiber, ceramic, glass, etc.
  • the composition After the composition is applied to the desired substrate, it is exposed to light radiation having wave lengths of above about 2 000 Angstrom units, preferably from about 2 000 up to about 8 000 Angstroms and most preferably between about 2400 Angstroms and 5400 Angstroms. Exposure should be from a source located about 2.54 to 12.70 cm from the coating for a time sufficient to cause crosslinking of the composition.
  • the light radiation can be ultraviolet light generated from low, medium, and high pressure mercury lamps. This equipement is readily available and its use is well known to those skilled in the art.
  • Other sources could include electron beam radiation, plasma arc and laser beams.
  • any of the compounds having the formula I can be used in the practice of this invention, preferred are those compounds where m and n are 0 ; R is alkyl of 1 to 12 carbon atoms, alkenyl of 3 to 5 carbon atoms, alkoxysubstituted alkyl of 2 to 4 carbon atoms or aminosubstituted alkyl of 2 to 5 carbon atoms. Particularly preferred are the p-benzoylbenzoates, i.e., compounds I where X is OR.
  • the radiation source for this apparatus consists of two high intensity medium pressure quartz mercury lamps 30.5 cm in length and each operating at a linear power density of about 200 watts per 2.54 cm or 2 400 watts per lamp.
  • the lamps are housed in an elliptical reflector above a variable speed conveyor belt and each lamp provides a 5.08 cm band of high flux actinic radiation on the conveyor. This 5.08 cm exposure area is bordered on both sides by an additional 5.08 cm area of medium flux energy for a total radiation area of 15.24 cm for each lamp.
  • cure rate of the polymerizable composition is presented in cm-per-minute- per-lamp (cm/min/lamp).
  • a conveyor belt speed of 30.5 cm/min will, with a 30.5 cm exposure area for the two lamps, provide 60 seconds of exposure or a cure rate of 15.24 cm/min/lamp.
  • a belt speed of 305 cm/min will provide 6 seconds of exposure or a rate of 15.24 cm/min/lamp while a speed of 610 cm/min will give 3 seconds exposure or a rate of 305 cm/min/lamp, etc.
  • the composition had a cure rate of 610 cm/min/lamp.
  • the amount of 4 % by weight of the n-butyl-p-benzoylbenzoate prepared in Example 2 was added to resin samples comprising 50 % by weight of EPOCYRL 8 Resin DRH-303, a diacrylate ester of Bisphenol A epoxy resin available from Shell Chemical Company, and 50 % by weight of 1,6-hexanediol diacrylate available from Celanese Corporation.
  • the ortho and meta isomers of the ester of Example 2 were prepared and tested.
  • the n-butyl-p-benzoylbenzoate was prepared by the acid-catalyzed esterification of o-benzoyl benzoic acid.
  • the n-butyl-m-benzoylbenzoate was prepared following the procedure and employing the ingredients described in Example 2 but substituting m-toluyl chloride for benzoyl chloride and benzene for toluene.
  • the cure data for 4 % by weight loading is presented below.
  • the ester (4-methyl pentyl)-p-benzoylbenzoate was prepared.
  • the structure was confirmed by the presence of carbonyl bands at 1 670 and 1 730 cm- 1 in the infrared spectrum.
  • this ester was added at a level of 4 % by weight to the test solution of Example 1, a cure rate of 457.5 cm/min/lamp was obtained.
  • n-Octyl-p-benzoylbenzoate was prepared by reacting p-benzoylbenzoic acid chloride with n-octanol. The presence of carbonyl bands at 1 725 and 1 670 cm- 1 in the infrared spectrum confirmed that the product had been obtained.
  • the test solution of Example 1 was employed and the ester was added at a level of 4 % by weight ; a cure rate of 533.8 cm/min/lamp was obtained.
  • Tridecyl-p-benzoylbenzoate was prepared from para benzoylbenzoic acid chloride and tridecanol.
  • the infrared spectrum revealed carbonyl bands at 1 725 and 1 670 cm- 1.
  • a cure rate of 457.5/min/lamp was obtained at a 4 % by weight loading in the test solution of Example 1.
  • (2-Ethoxyethyl)-p-benzoylbenzoate was prepared from para-benzoyl benzoic acid chloride and 2- ethoxyethanol. The structure of the product was confirmed by the presence of carbonyl bands in the infrared spectrum at 1 670 and 1 730 cm- 1 . When added at 4 % by weight loading to the solution described in Example 1, a cure rate of 457.5 cm/min/lamp was obtained. A sample in the same test solution was stable after three months storage following the procedure described in Example 5.
  • (2-Dimethylaminoethyl)-p-benzoylbenzoate was prepared from para-benzoylbenzoic acid chloride and 2-dimethylaminoethanol. The structure of the product was confirmed by the presence of carbonyl absorption bands in the infrared spectrum at 1 670 and 1 725 cm- 1 . When added at 4 % by weight loading to the test solution described in Example 3, a cure rate of 1 220 cm/min/lamp was observed.
  • 3-(Dimethylaminopropyl)-p-benzoylbenzoate was prepared from para-benzoylbenzoic acid chloride and 3-dimethylaminopropanol.
  • the structure of the product was confirmed by the presence of carbonyl bands in the infrared spectrum at 1 670 and 1 730 cm- 1.
  • this ester resulted in a cure rate of 457.5 cm/min/lamp in the test solution of Example 1 and a cure rate of 1 525 cm/min/lamp in the test solution of Example 3.
  • this ester exhibited a cure rate of 762.5 cm/min/lamp.
  • iso-butyl-p-benzoylbenzoate was prepared from 20 grams of p-benzoyl benzotrichloride, 50 milliliters of iso-butanol and 30 milliliters of 19 per cent by weight aqueous hydrochloric acid. When added at a loading of 4 % by weight to the test solution described in Example 3, a cure rate of 915-1 067.5 cm/min/lamp was observed for several samples.
  • Example 6 (4-pentenyl)-p-benzoylbenzoate was prepared from p-benzoylbenzoic acid chloride and 4-pentenol. The structure of the product was confirmed by the presence of carbonyl bands in the infrared spectrum at 1 670 and 1 730 cm- 1 . At a loading of 4 % by weight, a cure rate of 457.5 cm/min/lamp was obtained in the test solution described in Example 1.
  • N,N-diethyl-p-benzoyl benzamide was prepared by reacting p-benzoylbenzoic acid chloride with diethylamine. At a 4 % by weight loading in the test solution described in Example 1 a cure rate of 228.8-305 cm/min/lamp was observed for several samples.
  • N-iso-butylamine was reacted with p-benzoylbenzoic acid chloride to provide N-iso-butyl-p-benzoyl benzoic benzamide.
  • p-benzoylbenzoic acid chloride was reacted with p-benzoylbenzoic acid chloride to provide N-iso-butyl-p-benzoyl benzoic benzamide.
  • a cure rate of 228.8-305 cm/min/lamp was observed for several samples.
  • N,N-di-n-butyl-p-benzoyl benzamide was prepared from p-benzoylbenzoic acid chloride and di-n-butylamine.
  • a cure rate of 305 cm/min/lamp was observed at a 4 % by weight loading in the test solution described in Example 1.
  • a rate of 152.5 cm/min/lamp was observed at the same loading in the test solution described in Example 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)
EP78100370A 1977-07-18 1978-07-11 Use of esters or amides of benzoylbenzoic acids as photoinitiators and photopolymerisable composition containing them Expired EP0000705B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US817089 1977-07-18
US05/817,089 US4080275A (en) 1977-07-18 1977-07-18 Photopolymerizable benzoyl benzoate compositions

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EP0000705A1 EP0000705A1 (en) 1979-02-21
EP0000705B1 true EP0000705B1 (en) 1981-02-11

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US (1) US4080275A (da)
EP (1) EP0000705B1 (da)
JP (1) JPS5421480A (da)
AU (1) AU3775078A (da)
DE (1) DE2860465D1 (da)
DK (1) DK320878A (da)
IT (1) IT1105905B (da)
PH (1) PH13437A (da)
ZA (1) ZA783854B (da)

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US3926638A (en) * 1971-11-18 1975-12-16 Sun Chemical Corp Photopolymerizable compositions comprising monocarboxyl-substituted benzophenone reaction products
US3827959A (en) * 1973-01-12 1974-08-06 Scm Corp Process for photopolymerization with carbonylated phenyl nuclear sulfonyl chloride sensitizer
DE2439523C2 (de) * 1974-08-17 1979-03-22 Meto-International Gmbh, 6932 Hirschhorn Rastvorrichtung für eine Schlüsselwelle eines Druckwerks
US4017652A (en) * 1974-10-23 1977-04-12 Ppg Industries, Inc. Photocatalyst system and ultraviolet light curable coating compositions containing the same
US4024296A (en) * 1976-02-02 1977-05-17 Ppg Industries, Inc. Photocatalyst system and pigmented actinic light polymerizable coating compositions containing the same

Also Published As

Publication number Publication date
IT7850311A0 (it) 1978-07-14
EP0000705A1 (en) 1979-02-21
AU3775078A (en) 1980-01-10
US4080275A (en) 1978-03-21
DK320878A (da) 1979-01-19
PH13437A (en) 1980-04-23
JPS5421480A (en) 1979-02-17
ZA783854B (en) 1979-07-25
IT1105905B (it) 1985-11-11
DE2860465D1 (en) 1981-03-26

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