JPH0547095B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a photopolymerizable composition,
More specifically, it relates to a photopolymerizable composition comprising a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a binder if necessary,
In particular, it relates to a photopolymerizable composition useful for photosensitive layers of photosensitive printing plates, photoresists, and the like. ``Prior art'' A photosensitive composition is prepared by mixing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and, if necessary, a binder having an appropriate film-forming ability and a thermal polymerization inhibitor. Methods of copying images by photographic methods using the above methods are currently known. That is, as described in U.S. Pat. No. 2,927,022, U.S. Pat. No. 2,902,356 or U.S. Pat.
Since this type of photosensitive composition is cured and insolubilized by light irradiation, this photosensitive composition is formed into a suitable film, light is irradiated through the negative of the desired image, and only the unexposed areas are removed using an appropriate solvent. By removing it, a desired cured image of the photopolymerizable composition can be formed. It goes without saying that this type of photosensitive composition is extremely useful for making printing plates, photoresists, and the like. Conventionally, polymerizable compounds having ethylenically unsaturated bonds alone do not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to increase photosensitivity. , benzoyl, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, and the like have been used. However, when these photopolymerization initiators are used, the curing sensitivity of the photopolymerizable composition is low, so it takes a long time for image exposure during image formation. If there is, it will not be possible to reproduce images of good quality, and the amount of energy radiated by the light source for exposure must be increased, so it is necessary to consider the accompanying large amount of heat dissipation. There were problems such as deformation and deterioration of the film. "Problems to be Solved by the Invention" Therefore, an object of the present invention is to provide a highly sensitive photopolymerizable composition. Another object of the invention is generally to increase the rate of photopolymerization of photopolymerizable compositions containing polymerizable compounds having ethylenically unsaturated bonds. An object of the present invention is to provide a composition. "Means for Solving the Problems" The present inventor has made extensive research to achieve the above object, and found that a certain photopolymerization initiator is a polymerizable compound having an ethylenically unsaturated bond. The present invention was achieved by discovering that the photopolymerization rate can be significantly increased. The present invention comprises a polymerizable compound having an ethylenically unsaturated bond, an optional binder and the general formula () (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an allyl group, or a substituted allyl group, and Y is -O-, -S-, -Se-, -
2 selected from C(CH ₃ ) ₂ − and −CH=CH−
It is a valence atom or an atomic group, and X represents an oxygen atom or a sulfur atom. Further, R ₁ and R ₂ may both form a ring together with the carbon atom to which they are bonded. ) It relates to a photopolymerizable composition containing a photopolymerization initiator represented by: The present invention will be explained in detail below. The polymerizable compound having an ethylenically unsaturated bond in the composition of the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure, and is a monomer, prepolymer, or dimer. , trimers and other oligomers, mixtures thereof, and copolymers thereof. Examples thereof include unsaturated carboxylic acids and their salts, esters with aliphatic polyhydric alcohol compounds, amides with aliphatic polyhydric amine compounds, and the like. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid. Salts of unsaturated carboxylic acids include sodium and potassium salts of the aforementioned acids. Specific examples of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic esters such as ethylene glycol diacrylate, triethylene glycol triacrylate,
1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate acrylate, pentaerythritol triacrylate,
Examples include pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, and polyester acrylate oligomer. Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate,
Ethylene glycol dimethacrylate, 1,3-
Butanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-
[p-3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-
Examples include [p-acryloxyethoxy)phenyl]dimethylmethane. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. , sorbitol tetrataconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaeryloritol dicrotonate, and sorbitol tetracrotonate. Isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like. Examples of maleic esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, mixtures of the aforementioned esters may also be mentioned. Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide,
1,6-hexamethylenebis-acrylamide,
Examples include 1,6-hexamethylenebis-methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Other examples include polyisocyanate compounds having two or more isocyanate groups in one molecule described in Japanese Patent Publication No. 48-41708,
Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group represented by the following general formula () is added. CH ₂ =C(R)COOCH ₂ CH(R')OH ... () (However, R and R' represent H or CH _3. ) Next, the photopolymerizable composition of the present invention has remarkable characteristics. The photopolymerization initiator will be explained. General formula () used in the present invention In the photopolymerization initiator represented by R ₁ , R ₂ , R ₃ ,
R ₄ and R ₅ may be the same or different, and methyl,
Alkyl groups with 1 to 12 carbon atoms such as ethyl, n-propyl, i-propyl, n-butyl, and t-butyl; aryl groups with 6 to 10 carbon atoms such as phenyl and naphthyl; 3 to 10 carbon atoms; Represents 10 allyl groups. These alkyl groups, aryl groups, and allyl groups may have substituents, and the substituents include:
Alkyl groups with 1 to 6 carbon atoms such as methyl group and ethyl group, 1 to 6 carbon atoms such as methoxy group and ethoxy group
an alkoxy group, a halogen atom such as chlorine or bromine, an amino group substituted with an alkyl group having 1 to 4 carbon atoms such as a cyano group, an amino group, or a dimethylamino group, or a carbomethoxy group having 1 to 4 carbon atoms. a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, such as a carboalkoxy group, phenyl group, p-methoxyphenyl group, p-chlorophenyl group, carboxylic acid group, sulfonic acid group, or Salts thereof, etc. can be mentioned. Further, both R ₁ and R ₂ may form a ring together with the carbon atom bonded thereto. Examples of the ring include aliphatic hydrocarbon rings such as cyclohexene rings, aromatic rings such as benzene rings and naphthalene rings, and heteroaromatic rings such as quinoline rings.
Further, these rings may have a substituent, and as the substituent, those listed as the substituents for R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ can be similarly used. The photopolymerization initiator represented by the general formula () used in the present invention can be synthesized using a known method. Typical synthesis methods include T.I.
“The Theory of Photographic Process” by Etsuchi James [ed. “The Theory of Photographic Process” No. 4]
Edition, Macmillan Co., New York (1977)] and F.M. Hamer, The Cyanine Soybean.
And Relay Tide Compounds” [FM
Hamer, “The Cyanine Dyes and Related
Compounds”John Wiley & Sons Co., New
York (1964)], it can be synthesized from the general formula () and the compound represented by the general formula (). Specific examples of the photopolymerization initiator represented by the general formula () used in the present invention are shown below. The compound represented by the general formula () of the present invention shows a high photopolymerization initiating ability even when it is used alone, but when used in combination with a certain type of activator to form a combination of two or more types of photopolymerization initiators, the compound has an even higher ability to initiate photopolymerization. It becomes possible to express photopolymerization initiation ability. Examples of activators that exhibit high photopolymerization initiation ability in combination with the compound of the present invention include the following. (1) Carbonyl compounds benzyl, benzoyl, benzyl ketals,
Benzoin ethers, etc. An example of benzyl ketal is dimethoxy-2-phenylacetophenone.
No. 42653, JP-A No. 49-99147 and JP-A No. 50-
It is described in Publication No. 29930. Examples of benzoin ethers include O-methylbenzoin and O-ethylbenzoin, and other examples can be found in the Journal of American Chemical Society 97.
It is described in Volume 1519 (1975). Other carbonyl compounds include acetophenone derivatives such as diethoxyacetophenone, compounds described in European Patent No. 0125206A1 such as benzoyl-1-cyclohexanol, and 2-morpholino-2-described in U.S. Pat. No. 4,318,791.
These include aromatic aliphatic ketones such as methyl-p-methylthiopropiophenone and 2-hydroxyacetophenone derivatives such as 2-hydroxy-2-methyl-p-chloropropiophenone. (2) Sulfonyloxime compounds Examples include JP-A No. 57-53747, West German Patent (OLS) No. 3410387A1, and U.S. Patent No.
Examples include sulfonyloxime compounds described in No. 4258121. A specific example is 2-phenyl-3
-Phenylsulfonyloxy-4(3H) quinazolinone, 2-styryl-3-phenylsulfonyloxy-4(3H) quinazolinone, N-hydroxy-
Examples include 1,8-naphthalimidobenzenesulfonic acid ester. (3) Acyloxime compounds Examples include 1-phenyl-1,2-propanedione-2-(o-ethoxycarboxime), as described in Progress in Organic Coatings, Volume 3, Page 115 (1975) There are compounds of (4) Hexaarylbiimidazole compound A specific example of a preferred hexaarylbiimidazole is 2,2'-bis(o-chlorophenyl)-
4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)
-4,4',5,5'-tetraphenylbiimidazole, and other examples are described in Japanese Patent Publication No. 45-37377. (5) Halogen compounds British Patent No. 1234648, British Patent No. 2039073B, US Patent No. 3827596, US Patent No. 3905813, JP-A-55
-24113 and halogen compounds described in JP-A-58-15503. Representative examples include 2,6-di(trichloromethyl)-4-(p-methoxyphenyl)-1,3,5-triazine, 2-trichloromethyl-5-(p-methoxystyryl)-1,
3,4-oxadiazole, anthraquinone-1
-sulfonyl chloride and 2,2,2-trichloroacetophenone. (6) Amino compounds “Journal of Polymer Society” by M. R. Sander et al. [Journal of Polymer Society” by MRSander et al.] Volume 10,
3173 pages (1972), JP-A-51-82102, JP-A-52
- Amino compounds described in Publication No. 134692. Typical examples include trimethylamine, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-cyanodimethylaniline, and p-formyldimethylaniline. Other amino compounds include p-amino-substituted benzophenone derivatives and p-amino-substituted chalcone derivatives, representative examples of which include Michler's ketone, p-dimethylaminobenzylideneacetophenone, and 4,4'-dimethylaminochalcone. can. (7) Amino acids A specific example of a particularly preferred amino acid is N-phenylglycine. (8) Sulfur Compounds Examples include sulfur compounds described in US Pat. No. 2,460,105 and US Pat. No. 2,773,822. Typical examples include dibenzothiazoyl disulfide, diethylxanthogen disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 5-methylthio-2-mercaptothiadiazole, and the like. (9) Peroxide Typical peroxides include dibenzoyl peroxide and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone. Particularly effective among these activators are carbonyl compounds, sulfonyloxime compounds, acyloxime compounds, halogen compounds, and hexaarylbiimidazole compounds. A binder may be used in the polymerizable composition of the present invention if necessary. Also, the material must be so good that demixing does not occur in all of the manufacturing steps of the photosensitive material, including drying, and it is possible to develop the photosensitive layer or resist layer after image exposure, whether by solution development or peel development. In particular, it is required to have characteristics such as being able to form a tough film as a photosensitive layer or a resist layer, and is usually appropriately selected from linear organic polymers. Specific examples of binders include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl esters (alkyl groups include methyl group, ethyl group, n-butyl group, iso-butyl group, n-hexyl group, (2-ethylhexyl group, etc.), copolymers of acrylic acid alkyl esters (alkyl groups are the same as above) and at least one of monomers such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, polyvinyl chloride, vinyl chloride and acrylonitrile. copolymers of polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, copolymers of acrylonitrile and styrene, copolymers of acrylonitrile with butadiene and styrene, Methacrylic acid alkyl ester (alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, iso-butyl group, n-
hexyl group, cyclohexyl group, 2-ethylhexyl group, etc.), a copolymer of a methacrylic acid alkyl ester (the alkyl group is the same as above) and at least one monomer such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene,
Polystyrene, poly α-methylstyrene, polyamide (6-nylon, 6,6-nylon, etc.),
Examples include methyl cellulose, ethyl cellulose, acetyl cellulose, polyvinyl formal, and polyvinyl butyral. Furthermore, if a water or alkaline water soluble organic polymer is used, water or alkaline water development becomes possible. Examples of such polymers include addition polymers having carboxylic acid in the side chain, such as methacrylic acid copolymers (for example, copolymers of methyl methacrylate and methacrylic acid, and copolymers of ethyl methacrylate and methacrylic acid). polymers, copolymers of butyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of methacrylic acid with styrene and methacrylic acid, etc.), acrylic acid copolymers (acrylic acid Copolymers of ethyl and acrylic acid, copolymers of butyl acrylate and acrylic acid, copolymers of ethyl acrylate and styrene and acrylic acid, etc.), as well as itaconic acid copolymers and crotonic acid copolymers. There are polymerized and partially esterified maleic acid copolymers, as well as acidic cellulose derivatives having carboxylic acid in their side chains. These high molecular weight polymers may be used alone as a binder, but two or more types must be compatible with each other to the extent that demixing does not occur during the manufacturing process from preparation of the coating solution to application and drying. Good high molecular weight polymers can be mixed in suitable ratios and used as binders. The molecular weight of the high molecular weight polymer used as a binder can take a wide range of values depending on the type of polymer, but
Generally 5,000 to 2 million, more preferably 10,000 to 100
A range of 10,000 is preferred. Furthermore, during the production or storage of the composition of the present invention, it is desirable to add a thermal polymerization inhibitor to prevent unnecessary thermal polymerization of the polymerizable compound having an ethylenically unsaturated bond. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, cuprous chloride, phenothiazine, chloranil,
Examples include naphthylamine, β-naphthol, nitrobenzene, and dinitrobenzene. In some cases, dyes or pigments may also be used for coloring purposes, such as methylene blue, crystal violet, rhodamine B, fuchsin, auramine, azo dyes, anthraquinone dyes, titanium oxide, carbon black, iron oxide, phthalocyanine pigments, azo Pigments and the like may also be added. Furthermore, plasticity can be added to the photopolymerizable composition of the present invention, if necessary. Examples of plasticity include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. Examples include glycol esters, phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate, and aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dibutyl sebacate and dibutyl maleate. The photopolymerizable composition of the present invention is used by dissolving the above-mentioned various components in a solvent and applying the solution onto a suitable support by a known method. Next, preferred ratios of the various constituent components in this case are expressed in parts by weight based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond.

[Table] Solvents used when applying the photopolymerizable composition of the present invention include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, monochlorobenzene, toluene, xylene,
These include ethyl acetate and butyl acetate. These solvents may be used alone or in combination. The coating amount when manufacturing a photosensitive lithographic printing plate is:
Generally, a solid content of 0.1 to 10.0g/ ^m2 is appropriate;
Particularly preferred is 0.5 to 5.0 g/ ^m2 . The photopolymerizable composition of the present invention is suitable as a photosensitive layer of a photosensitive lithographic printing plate. Supports suitable for photosensitive lithographic printing plates include hydrophilic aluminum plates, such as silicate-treated aluminum plates,
Examples include anodized aluminum plates and silicate electrodeposited aluminum plates, as well as zinc plates, stainless steel plates, chromium-treated copper plates, and hydrophilized plastic films and papers. Further, when the composition of the present invention is used as a photoresist, various materials such as a copper plate, a copper plated plate, a stainless steel plate, a glass plate, etc. can be used as a support. "Examples" Hereinafter, synthesis examples of the photopolymerization initiator used in the present invention and examples of the present invention will be described, but the present invention is not limited thereto. Synthesis example Method for producing compound example 17 N-methyl-2-methylmercapto-benzo[4,5]benzothiazolium tosylate 35.4g
and 1,3-di-n-butylthiobarbituric acid
After dissolving 21.7 g in 500 ml of acetonetrile, 40 ml of triethylamine was added. The mixture was heated under reflux for 2 hours, then allowed to cool, and the precipitated crystals were collected.
It was recrystallized twice from ethyl acetate to obtain 31.0 g of crystals with a melting point of 180-182°C. Electronic spectrum (tetrahydrofuran [THF]
Medium) λmax399nm (log = 4.72) Elemental analysis value C ₂₄ H ₂₇ O ₂ N ₃ S ₂ Calculated value C; 63.55% H; 6.00% N; 9.26% Actual value C; 63.46% H; 6.14% N; 8.89 % Examples 1 to 3, Comparative Examples 1 to 9 After graining with a nylon brush, a silicate-treated aluminum plate was coated with a rotational speed using a rotary coating machine.
The following photosensitive solution using the photopolymerization initiator shown in Table 1 was applied at 200 rpm and dried at 100°C for 5 minutes to form a photosensitive layer with a dry film thickness of about 2 μm to prepare a photosensitive plate. Benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer...5.0g Pentaerythritol tetraacrylate
……3.6g Photopolymerization initiator (1 mol% based on monomer) Methyl ethyl ketone ……20g Methyl cell solve acetate 20g For exposure, a vacuum printing frame device was used, and a step wedge (density step 0.15, A 2KW ultra-high-pressure mercury lamp was used to irradiate the film for 7 seconds, and after exposure, it was developed using a developer with the following formulation. (Developer) Trisodium phosphate...25g Monosodium phosphate...5g Butyl cellosolve...70g Surfactant...2ml Water...1. The sensitivity is shown in Table 1. The higher the number of stages, the higher the sensitivity. For comparison, Table 2 shows the sensitivity when 1 mol% of each of the compounds shown in Comparative Examples was added to the monomer in place of the compound of the present invention as a photopolymerization initiator.

【table】

【table】

[Table] As shown in Tables 1 and 2, when the photopolymerization initiator of the present invention was used, higher sensitivity was exhibited compared to Comparative Examples 1 to 9, and the desired effect of the present invention was achieved. was fully recognized. Examples 4 to 6 Comparative Example 10 In the methods of Examples 1 to 3, the compound of Compound Example 17 was used as a photopolymerization initiator of the present invention at 5 mol% based on the monomer, and further as an activator shown in Table 3 below. A coating solution was prepared in the same manner as in Examples 1 to 3 except that 5 mol% of the compound was added and the exposure time was 4 seconds, and a photosensitive plate was prepared using the same method, followed by exposure and development. Ta. The highest number of step wedges corresponding to the developed image is shown in Table 3 as the sensitivity of the sample. For comparison, Table 3 shows the sensitivity of Comparative Example 10 when no activator was added.

[Table] It is clear from Table 3 that the sensitivity of the photopolymerization initiator of the present invention increases by further adding an activator. Examples 7 to 10 Comparative Examples 11 to 17 In the method of Examples 1 to 3, the compounds of Compound Examples 3, 4, 7, and 13 were added as the photopolymerization initiator of the present invention in an amount of 1 mol % based on the monomer, and also as an activator. as 2-styryl-3-phenylsulfonyloxy-
A photosensitive plate was prepared in the same manner as in Examples 1 to 3, except that 5 mol % of 4(3H) quinazolinone was added to the monomer, and then exposed and developed. Table 4 shows the number of step wedges that appeared. Table 4 shows the sensitivity obtained by carrying out the same method as in Examples 7 to 10, except that the compounds shown in Table 4 were used as comparative examples in place of Compound Examples 3, 4, 7, and 13.

【table】

【table】

[Table] It is clear from Table 4 that Examples 7 to 10 using the photopolymerization initiator of the present invention have better sensitivity than Comparative Examples 11 to 20 using known compounds.

Claims (1)

[Scope of Claims] 1. In a photopolymerizable composition containing an addition polymerizable compound having at least one ethylenically unsaturated double bond and a photopolymerization initiator, at least the following general formula ( ) A photopolymerizable composition containing one type of compound represented by: In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an allyl group, or a substituted allyl group, and Y is - O-, -S-, -Se-, -C
It is a divalent atom or atomic group selected from ( _CH3 ) _2- and -CH=CH-, and X represents an oxygen atom or a sulfur atom. Further, R ₁ and R ₂ may both form a ring together with the carbon atom to which they are bonded.