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United States Patent (19) 11) 4,442,022 Van Der Hauw Et Al

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United States Patent (19) 11) 4,442,022 Van Der Hauw Et Al United States Patent (19) 11) 4,442,022 van der Hauw et al. 45) Apr. 10, 1984 (54) PHOTOPOLYMERIZABLE COMPOSITION, 4,054,721 10/1977 Cordes ............ 252/426 PHOTONTIATOR MIXTURE AND CURNG PROCESS FOREIGN PATENT DOCUMENTS 75) Inventors: Tjerk van der Hauw, Diepenveen; 1408265 10/1975 United Kingdom. Hans Jaspers, Putten, both of Primary Examiner-Allan Lieberman Netherlands Attorney, Agent, or Firm-Francis W. Young; Daniel N. 73) Assignee: Akzona, Inc., Asheville, N.C. Christus (21) Appl. No.: 315,799 57 ABSTRACT The present invention relates to a photopolymerizable 22 Filed: Oct. 28, 1981 composition comprising a polymerizable, polyethyleni (30) Foreign Application Priority Data cally unsaturated compound, benzil and/or fluorenone, a specific biphenyl ketone such as para-phenyl benzo Nov. 5, 1980 NL Netherlands ......................... 8006035 phenone, and a reducing agent such as a tertiary amine. 51) Int, C. ............................ C08F 2/46; C08F 4/00 The present composition permits rapid and complete 52 U.S. C. ............................... 502/150; 204/159.23; curing. Moreover, in the photopolymerization of com 502/167 pounds sensitive to air inhibition non-tacky surfaces are 58) Field of Search ................... 204/159.23; 252/426, obtained. The effect observed is based on a synergism 252/438 between the present photoinitiators. The advantages of (56) References Cited the invention are most manifest in curing relatively U.S. PATENT DOCUMENTS thick layers of materials. 4,024,297 5/1977 Gruber ................................ 252/426 3 Claims, No Drawings 4,442,022 1. 2 cally unsaturated compound. In the photopolymeriza PHOTOPOLYMERIZABLE COMPOSITION, tion of compounds sensitive to air inhibition it is possi PHOTOINITIATOR MIXTURE AND CURING ble, moreover, to obtain non-tacky surfaces. The use of PROCESS only benzil and/or fluorenone generally leads to better BACKGROUND OF THE INVENTION curing but to a lower surface hardness than the sole use Prior art photoinitiator systems comprising an aro of a corresponding amount of the present biphenylyl matic carbonyl compound and a reducing agent are ketones. known from U.S. Pat. No. 3,759,807. In it are enumer As far as these aspects are concerned, it was found ated a great many aromatic carbonyl compounds, in 10 that a corresponding amount of a mixture of these aro cluding acetophenone, 4-tolyl acetophenone, benzophe matic carbonyl compounds results in both rapid curing none, 3-tolyl benzophenone, fluorenone, antraquinone, and high surface hardness of the polymerizable com xanthone and thioxanthone. Reducing agents men pound. Moreover, it has been surprisingly found that tioned includes amines, viz. tertiary amines such as the result is not merely cumulative but is synergistic, triethanolamine and methyldiethanolamine. Photopo 15 lymerizable compositions are also known from British and that this synergistic effect is not produced by other Patent Specification No. 1,408,265, which also mentions combinations of the above-mentioned initiators. a great many aromatic carbonyl compounds, including The present composition contains a polymerizable, benzil, benzil derivatives, naphthyl, phenanthraqui polyethylenically unsaturated compound. Examples none, benzophenone, benzoin, benzoin ethers and fluo 20 thereof include polymethacrylates and polyacrylates, Teone, the acryl being built in as reactive end group in a poly Although these prior art photoinitiator systems may mer chain, via hydroxy, amino, carboxy, isocyano or be satisfactorily applied for various purposes, a particu lar problem exists in completely and rapidly curing epoxy groups. Examples of this last mentioned type of material having a thickness of 1-20 mm. Moreover, in 25 compound include polyacryl-modified polyesters, poly the case of polymerizable, polyethylenically unsatu amides, polyethers, polyurethanes and polyvinyl resins. rated compounds such as methacrylate resins that are Optionally, the polyethylenically unsaturated com sensitive to air inhibition, there is the problem of insuffi pound may be mixed with a co-polymerizable unsatu cient surface hardening, which manifests itself in a rated monomer such as acrylic esters and methacrylic tacky surface. For optimum properties, there are two 30 esters, acrylic and methacrylic amides and acrylic and requirements: the material should be both thoroughly methacrylic nitriles, for instance acrylonitrile, methyl cured and of a good surface hardness, Often the known photoinitiator systems satisfy only methacrylate and 2-ethylhexyl acrylate. To that end, one of the two requirements. In actual practice, it has use may further be made of vinyl esters and vinylidene therefore often been found necessary to isolate the sur 35 esters, vinyl ethers and vinyl ketones, such as vinyl face to be cured from the ambient air by covering it acetate, vinyl propionate, N-vinyl-pyrrolidone and with a transparent film to obtain a satisfactory surface vinylbutyl ether. hardness and/or to use prolonged exposure times for Moreover, monomers may be added that have more thorough curing. than one unsaturated terminal group. Examples thereof SUMMARY OF THE INVENTION 40 include diallyl phthalate, diallyl fumarate, ethylene The photopolymerizable composition according to glycol dimethacrylate, pentaerythritol triacrylate, tri the invention is non-tacky, rapid setting, and hard cur methylol propane triacrylate, neopentylglycol dimeth ing, and comprises: acrylate and polyethylene glycol diacrylate. The mono a. a polymerizable, polyethylenically unsaturated 45 mers that may be used include suitable copolymerizable compound; hydrocarbons, such as styrene, vinyl toluene and divi b. benzil and/or fluorenone; nyl benzene. c. A biphenylyl ketone of the formula: The present composition also may contain a mixture of an unsaturated polyester resin and a monomeric com 50 polymerizable compound, such as styrene. The unsatu rated polyester resins may be prepared in a known man ner from unsaturated polycarboxylic acids or their an hydrides, such as maleic anhydride or fumaric acid, and wherein: 55 generally in the presence of aromatic and/or saturated R1=hydrogen, an alkyl group having 1-8 carbon aliphatic dicarboxylic acids such as phthalic anhydride, atoms, an alkoxy group having 1-10 carbon tetrahydrophthalic anhydride, adipic acid and the like atoms, an alkyl carbonyl group having 2-12 car and polyols, such as ethylene glycol, diethylene glycol, bon atoms or a halogen atom; and propylene glycol and the like, and after the polyester R2=an alkyl group having 1-12 carbon atoms, preparation the terminal carboxylic groups may be fur phenyl, naphthyl, furyl or thiophenyl, which ther reacted to completion with reactive epoxides, such groups may be substituted or not; and as phenylglycidyl ether. d. a reducing agent capable of reducing the aromatic carbonyl compounds when they are in the excited The present photoinitiator mixture contains a mixture State. 65 of aromatic carbonyl compounds which at least consists It has been found that the use of the above-mentioned of: composition permits rapid and complete curing of rela a benzil and/or fluorenone; and tively thick layers of the polymerizable polyethyleni b. a biphenylketone of the formula: 4,442,022 4. group attached to M. It is preferred that as reducing agent there should be O used an amine, more particularly a tertiary amine. Ex R C-R2 amples of suitable amines include triethanolamine, tri isopropanolamine, N-methyl diethanolamine, N,N- dimethyl ethanolamine, N,N-dimethyl isopropanola mine, N-hydroxyethyl piperidine, N-hydroxyethyl mor wherein: pholine, bis(2-hydroxymethyl) oleylamine, N,N,N',N'- R1=hydrogen, an alkyl group having 1-8 carbon tetramethyl-1,3-diaminopropane, N,N-dimethylbenzyl atoms, an alkoxy group having 1-10 carbon 10 amine, N,N-dimethyl aniline, 4-dimethyl aminobenzo atoms, an alkyl carbonyl group having 2-12 car ate, dimethyl aminoethyl acrylate and dimethyl amino bon atoms or a halogen atom; and ethyl methacrylate. R2 = an alkyl group having 1-12 carbon atoms, The present composition generally contains 0.1-4.5% phenyl, naphthyl, furyl or thiophenyl, which ... by weight, preferably 0.25-2.0% by weight of reducing groups may be substituted or not. 5 agent. The weight ratio between the mixture of aro The group R2 may be substituted, for instance with the matic ketones and the reducing agent is generally in the groups denoted by R1. range of 1:3 to 3:1, preferably 2:1 to 1:2. Examples of suitable biphenylyl ketones include: The present compositions are cured by exposure to para-phenyl acetophenone, para-phenyl benzophenone, radiation in a known manner. To that end use is gener para-tolyl benzophenone, para, para'-diacetyl biphenyl, 20 ally made of a radiation source emitting radiation hav para-(para-chlorophenyl)-benzophenone, para-(para ing a wave length in the range of 200 to 500 nm. Suit methoxyphenyl)-benzophenone, a-furyl biphenylyl ke able radiation sources include medium-pressure mer tone, a-naphthylbiphenylyl ketone, para-tertiary butyl cury lamps. w phenyl biphenylyl ketone, para-methoxyphenyl biphe The invention also relates to the curing of relatively nylyl ketone and 2,4-dichlorophenyl biphenylyl ketone. 25 thick layers of material (i.e., having a thickness of 1-20 As biphenylyl ketone the composition preferably mm, more particularly 4-10 mm) based on the present contains para-phenyl benzophenone. As regards benzil st photopolymerizable compositions. When the photopo and fluorenone it should be noted that both have a lymerizable
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