JPS61203444A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To increase remarkably the rate of photopolymn. of a photopolym erizable composition by mixing an addition-polymerizable compound having at least one ethylenic unsatd. double bond with a photopolymn. initiator represented by a specified general formula to prepare the composition. CONSTITUTION:An addition-polymerizable compound having at least one ethylenic unsatd. double bond is mixed with a photopolymn. initiator represented by the formula to prepare a photopolymerizable composition. In the formula, each or R1, R2, R7 and R8 is H, alkyl, aryl or allyl, each or R3-R6 is H, alkyl, aryl, halogen carboalkoxy or alkoxy, R1 and R5, R2 and R3, R5 and R6, and R3 and R4 may form rings together with atoms to which they bond, and X is O or S.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention relates to a photopolymerizable composition, and more specifically, a polymerizable composition having an ethylenically unsaturated bond, a photopolymerization initiator, and a photopolymerization initiator. If so, it relates to a photopolymerizable composition comprising a binder, particularly a photosensitive layer of a photosensitive printing plate,
The present invention relates to a photopolymerizable composition useful for 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. A method of copying an Ili image by a photographic method is currently known.

That is, U.S. Patent 2. Octopus No. 7.022, 1°90
As described in No. 2.316 and No. 3.170 and JJl, this type of photosensitive composition hardens and becomes insolubilized by light irradiation, so this photosensitive composition is coated with a suitable film. A cured image of the desired photopolymerizable composition can be formed by irradiating light through the negative of the desired image and removing only the unexposed areas with a suitable solvent.

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. , benzoin, benzoin ethyl ether, Michler's ketone, anthranone, acridine, 7enadine, benzophenone, 2-ethyl anthranone, etc. 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 to expose one image in image formation, making it difficult to operate in the case of detailed images. If there is a slight vibration, a good quality image cannot be reproduced, and since the amount of energy radiated by the light source for exposure must be increased, it is necessary to consider the accompanying large amount of heat dissipation, and furthermore, There have been problems such as deformation and deterioration of the film of the composition due to oxidation.

In addition, these photopolymerization initiators have a significantly lower photopolymerization ability for light sources in the visible light region of %000 nm or more than for light sources in the ultraviolet region of ≠000 nm or less, and therefore, the application of photopolymerizable compositions containing them is significantly lower. The range has been severely limited.

Several proposals have been made regarding photopolymerization systems sensitive to visible light. In the old days, US Patent No. 2 RZOU HIRO! According to the publication, certain photoreducible dyes, such as rose bengal, eosin, and erythrosin, are reported to have effective visible light sensitivity. Later, improved technologies were developed such as a complex initiation system of dye and amine (Tokuko Shosan μm Co0/R Tano, a system of aryl biimidazole, radical generator, and dye (Toku Kokou Shosan 7-37377), System of imidazole and P-sialylaminobenzylidene ketone (JP-A-4C7--!Col.

Proposals have been made such as JP-A-144-111-Tacone and a system of substituted triazine and melonanine dyes (JP-A-144-111-/!t10co4c). Although these techniques are certainly effective for visible light, their photosensitive speeds are still not fully satisfactory (further improved techniques have been desired).

"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 present invention is to generally provide a photopolymerizable composition containing a photopolymerization initiator that increases the rate of photopolymerization of a photopolymerizable composition containing a polymerizable compound having an ethylenically unsaturated bond. It is.

Another object of the present invention is to provide a photopolymerizable material containing a photopolymerization initiator and a photopolymerization initiator system that is highly sensitive to visible light of uoonm or more, particularly light of around 1 rrnm corresponding to the output of an Ar laser. 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 based on the discovery that the photopolymerization rate can be significantly increased, and it also exhibits high sensitivity to visible light of more than 100 nm.

The present invention comprises a polymerizable compound having an ethylenically unsaturated bond, a binder if necessary, and the following general formula (1) (wherein R1, R2%, R7, R8 are each independently a hydrogen atom, an alkyl group, substituted alkyl group, aryl group, substituent aryl group, allyl group or substituted allyl group,
R3, Ra, Rs%R6 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a halogen atom, a carbalkoxy group, or an alkoxy group.

Or R□ and R5, R2 and R3, R5 and R6, R3 and R
4 may form a ring together with the carbon atom to which it is bonded. X represents an oxygen atom and t7'h represents a sulfur atom. The present invention relates to a photopolymerizable composition containing a photopolymerization initiator represented by 1.

The present invention will be explained in detail below.

The polymerizable compound having an ethylenically unsaturated bond in the composition of the present invention refers to a compound having at least one ethylenically unsaturated bond in its chemical structure.
compounds having ethylenically unsaturated bonds in chemical forms such as monomers, prepo-IJ-r-, λ-mers, trimers and other oligomers, mixtures thereof and copolymers thereof. It is something that has. Examples of these 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, itafonic acid, crotonic acid, inocrotonic acid,
These include maleic acid.

Salts of unsaturated carboxylic acids include sodium and potassium salts of the aforementioned acids.

A specific example of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carmenic acid is ethylene glycol diacrylate as an acrylic ester.

Triethylene glycol triacrylate %/IJ-butanediol diacrylate, tetraethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate V-), /, 4'-cyclohexanediol diacrylate, Tetraethylene glycol diacrylate, inter-taerythritol diacrylate, pentaerythritol triacrylate, inter-erythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sol Examples include bitolbentaacrylate, sorbitol hexaacrylate, and polyester acrylate oligomer. As methacrylic acid ester.

Tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpronotrimethacrylate V-t% trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol triacrylate, intererythritol trimethacrylate Cleat, dipentaerythritol dimethacrylate, nrubitol trimethacrylate, sol-
Examples include bitol tetramethacrylate, bis-(p-(J-methacrylic acid, λ-hydroxypropoxy)phenyl)dimethylmethane, bis-Cp-(acrylic acidoxy)phenylfudimethylmethane, etc.Itaconic acid esters include , ethylene glycol shiitaconate, propylene glycol shiitaconate, /,!-butanediol shiitaconate, /, 4C-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol shiitaconate, nlubitol tetra Crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetracrotonate, etc. Incrotonic acid esters include ethylene glycol dicrotonate, etc. Crotonate, interaerythritol diinocrotonate, sorbitol tetraline crotonate, etc. Maleic acid esters include ethylene glycol dimaleate, hentaerythritol simalate, sorbitol tetramaleate, etc. There is.

Furthermore, mixtures of the aforementioned esters may also be mentioned.

Examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methione bis-acrylamide, methyline bis-methacrylamide, /, 4-hexamethylene bis-acrylamide, /, 4-hexamethylene bis-methacrylamide. Construction.

Examples include diethylene triamine trisacrylamide, medium silylene bisacrylamide, and medium silylene bismethacrylamide.

As another example, a polyincanate compound having one or more incyanate groups in seven molecules described in the Bulletin of Japanese Patent Publication No. 4 At-l-1701 is represented by the following general formula (II). Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group is added.

CH2=C(R)COOCH2CH(R')0)I
CU) (R and R' represent H or CH3.) Next, the photopolymerization initiator, which is a significant feature in the photopolymerizable composition of the present invention, will be explained.

In the photopolymerization initiator represented by the general formula (I) used in the present invention, R1h R2, R?
, R, may be the same or different, and is methyl.

Ethyl, n-furovir, i-propyl, n-ethyl, t
- represents a carbon number such as methyl/-/1 alkyl group, a 1-aryl group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group, and an allyl group having 3 to 10 carbon atoms. These aryl groups, aryl groups, and allyl groups may have a substituent, and the substituent includes a methyl group, an ethyl group, etc.
-4 carbon atoms/-j alkoxy groups such as alkoxy groups, metho groups, etho groups, halogen atoms such as chlorine and hydrogen atoms, cyano groups, abano groups, dimethylamino groups, etc. An amino group substituted with an alkyl group having 7-φ carbon atoms, a carmemethoxy group, etc., a carboalkoxy group having #4L alkyl groups, phenyl 71i, diphenyl f in p-meth, p Examples include substituted or unsubstituted aryl groups having 1 to 10 carbon atoms such as -/lorophenyl group, carboxylic acid groups, sulfonic acid groups, and salts thereof.

Ra, R4, Rs % Re represents a hydrogen atom, a halogen atom such as chlorine or bromine, a carboalkoxy group having 2 to 2 carbon atoms such as carbomethoxy, methoxy,
In addition to alkoxy groups having 7 to 7 carbon atoms such as ethoxy, R,
%R2, R7, alkyl groups similar to those listed in R8,
Represents a substituted alkyl group, aryl group, or substituted aryl group.

or R, and R,, R2 and R3, R5 and R6, R3 and R
4 may form a ring with the atoms to which it is bonded. Examples of the ring include aliphatic hydrocarbon rings such as cyclohexene rings, hetero rings such as morpholino rings and diellolidino rings, aromatic rings such as benzene rings and naphthalene rings, and heteroaromatic rings such as meso-noline rings. be able to. Further, these rings may have a substituent, and as the substituent, those listed as the substituent for R1% R2% Ry s Rs can be similarly used.

The photopolymerization initiator represented by the general formula (I) used in the present invention can be easily synthesized from the compounds represented by the general formula (III) and the general formula (IV).

R,R.

Examples of the photopolymerization initiator represented by the general formula (I) used in the present invention are shown below.

The compound represented by the general formula (I) of the present invention shows a high photopolymerization initiating ability even when it is used alone, but when used in combination with a certain activator and one or more photopolymerization initiators, It becomes possible to express high photopolymerization initiation ability.

The following activators exhibit high photopolymerization initiation ability in combination with the compound of the present invention.

(1) Carzenyl compound Benzyl, benzoin, benzyl ketals.

Benzoin ethers, etc. An example of benzyl ketal is dimethoxycophenylaceto 7Znon, and other examples can be found in JP-A No. 1999-11-122, JP-A No. 2002-22230, JP-A No. 2007-22230. Are listed.

As benzoin ether, 0-methylbenzoin, 0
- Ethylbenzoin etc. Other examples are journals
Op American Chemical Society (Jou
rnal of AmerIcanChemical
5ociety3F7 volume, 1s-it page (lri7!
It is described in Year 2.

Other carbonyl compounds include acetophenone derivatives such as genoxyacetophenone, benzoyl-/-Schiff and hexanol, etc. 206
Compounds described in AI bulletin, aromatic fatty ketones such as comorpholino-2-methyl-p-methylthiopropiophenone described in U.S. Patent No. Diacetophenone derivatives etc.

(2) Examples of sulfonyl oxime compounds include JP-A-17-777447 and West German Patent C.
0LS) JailJrtAI No. 11 and US Patent No. 11! Examples include sulfonyl oxime compounds described in the specification of rlJ1.

K-form N and L”CJ-phenyl-3-phenylsulfonyl-μ(j)l)*nazolinone, caustyryl-3
- Phenylsulfonyluo middle C ≠ (3H) quinazoline,
Hydroxy/, I-naphthalimidoinzenesulfonic acid esters, and the like.

(3) Examples of compounds such as l-phenyl-/, 2-propanesion (0-ethoxycarboxylic acid), etc. Progressi/Organic Coach Inc.
n Organic Coatings J Volume 3, 17
There is a compound described on page 5 (1973).

(4) Hexaarylbiimidazole compound Specific examples of preferred hexaarylbiimidazole Toshite x, !
'-His(0-chlorophenyl)-μ, ψI,!,!'
-tetraphenylbiimidazole, co, -'-his (o
, p-')? Lolophenylin μ, μ',! ,! '-Tetraphenylbiimidazole, etc., and other examples are Tokuko Akira! It is described in the publication No.-37377.

(5) Halogen compounds British Patent No. 1.23 Da, No. 44C Jr., British Patent No. 2032
No. 0738, US Patent 3T Core J26, US Patent 3.
Ri oj, xi3, tokukai shoj! -2Viii, halogen compounds described in JP-A No. 03 in JP-A No. 1T-/J, representative examples of which include co,6-di(trichloromethyl)-
4'-(p-methodiphenyl)-/, J, j-) riazine, -trichloromethyl-! Examples include -(p-methoxystyryl)-7,3, μm oxadiazole, anthraquinone-/-sulfonyl chloride, and co-, 2-cotrichloroacetophenone.

(6) Amino Compounds “Journal of Polymer Science,” written by M.R. Sangoo et al.

[Journal of Po
lymerSocietyJ) 10th anniversary), Tokukai Shozit Jto Ko issue, Tokukai Sho! coat t3u
Compound A described in Publication No. 6y2.

Representative examples include trimethylamine, triethanolamine, p-dimethylaminobenzoic acid ethyl ester,
Examples include p-cyanodimethylaniline and p-formyldimethylaniline.

Other amino compounds include p-amino substituted benzophenone derivatives and p-amino substituted chalcone tsuba conductors.
Typical examples thereof include Michler's ketone, p-dimethylaminobenzylideneacetophenone, and dimethylaminobenzylidene/-dimethylaminochalcone.

(7) Amino acids A particularly preferred example of an amino acid is N-phenylglycine.

(8) Sulfur compound U.S. Patent No. 4cbu0101, U.S. Patent No. 77J, r
Examples include the sulfur compounds described in the Coco specification. Typical examples thereof include dibenzothiazoyl disulfide, diethyl disulfide, comelcabutobenzthiazole, comelcabutobenzimidazole%j-methylthiocomelcabutthiadiazole, and the like.

(9) Peroxide Typical peroxides include dibe/zoyl-no-hydrochloride, 31"'#"#"'-tetra(t-butylperoxycarbonylnopenzophenone, etc.).

Particularly effective among these activators are carmesyl compounds, sulfonyluosym compounds, acyloxime compounds, . . . rogen compounds, and hexaarylbiimidazole compounds.

A must-have for the polymerizable composition of the present invention! ! The binder is a polymerizable (II) polymerizable (II) ethylenically unsaturated bond compound and compatibility with the photopolymerization initiator, which leads to the preparation, application, and drying of the coating solution of the composition. The quality of the photosensitive layer or resist layer should be such that no demixing occurs during all of the manufacturing processes, and the photosensitive layer or resist layer should be capable of being developed after image exposure, whether by solution development or peeling development. It is required to have properties such as being able to form a tough film, and is usually appropriately selected from linear organic polymers.

Examples of binders include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl ester (alkyl groups include methyl group, ethyl group, n-butyl group, 1so-butyl group, n-hexyl group, 2-ethylhexyl group, etc.), acrylic acid alkyl ester (the alkyl group is the same as above) and acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, etc. Copolymer with acrylonitrile, polyvinylidene chloride, copolymer with vinylidene chloride and acrylonitrile,
Polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, copolymer of acrylonitrile and styrene,
Copolymers of acrylonitrile, butadiene and styrene, polymethacrylic acid alkyl esters (alkyl groups include methyl group, ethyl group, n-butypyl group, n
-butyl group, 1so-butyl group, n-hexyl group, cyclohexyl group, 2-ethylhexyl group], methacrylic acid alkyl ester (the alkyl group is the same as above) and acrylonitrile, vinyl chloride, vinylidene chloride, styrene,
Copolymers with at least one monomer such as butadiene, polystyrene, poly-α-methylstyrene, boria (t-nylon, etc.), methylcellulose, ethylcellulose, acetylcellulose,
Examples include polyvinyl formal, a-rivinyl butyral, and the like. 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 with 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). Copolymers, copolymers of butyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of ethyl acrylate and methacrylic acid, copolymers of methacrylic acid and styrene and methacrylic acid. polymers, etc.), acrylic acid copolymers (copolymers of ethyl acrylate and acrylic acid, copolymers of butyl acrylate and acrylic acid, copolymers of ethyl acrylate and styrene and acrylic acid, etc.) , and even itaconic acid copolymers,
These include crotonic acid copolymers, partially esterified maleic acid copolymers, and similar 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 polymer used as a binder is the species of the polymer! ljI allows for a wide range of values, but in general! A range of 1,000 to -2,000,000, more preferably 10,000 to 1,000,000 is suitable.

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-methoxydiphenol, di-thiol-p-cresol, hyrogallol, t-butylcatechol, benzoquino 7, di-ferrochloride, phenothiazine, chloranil, naphthylaquine, β-naphthol, nitrobenzene,
Examples include dinitrobenzene.

In some cases, dyes or pigments may also be used for coloring purposes, such as methylene blue, crystal violet, rhodamine B1 fuchsin, oakzine, azo dyes, anthraquinone dyes, titanium oxide, carmen 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 heptathalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diethyl phthalate, dicyclohexyl phthalate, citrizoclupthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glyplate, butylphthalyl. Glycol esters such as butyl glycolate, phosphate esters such as tricresyl phosphate and 1-phenyl phosphate, aliphatic dibasic acid esters such as diynebutyl adipate, dioctyl adipate, dibutyl sebacate, dibutyl maleate, etc. There is.

The photopolymerizable composition of the present invention is used by dissolving the above-mentioned various constituents in a solvent and coating it on 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.

Constituent component Preferred addition range (especially preferred addition interval 1!L) Photopolymerization initiator 0.01-10 parts by weight (0
, 7-10 parts by weight) Binder 0-1000' (
0~! 00 # activator o-too
(o~koQ I) Thermal polymerization inhibitor 0-/II (0
~! I) Dye or pigment 0-10 (0-2
0 # ] Plasticizer Q-200 (0-JO
#) Solvents used when applying the photopolymerizable composition of the present invention include ethylene dichloride, cyclohechugakunon, methyl ethyl ketone, methyl cellosolve, methyl cellosolve, methyl cellosolve acetate% 7-chlorobenzene, -toluene, xylene .

These include ethyl acetate and butyl acetate. These solvents may be used alone or in combination.

When manufacturing a photosensitive lithographic printing plate, the appropriate coating amount is generally 0.1-10.0 Iil in terms of solid content.
Particularly preferably 0.2 to z, op, ^2.

The photopolymerizable composition of the present invention is suitable as a photosensitive layer of a photosensitive lithographic printing plate. Suitable supports for photosensitive lithographic printing plates include hydrophilic aluminum plates, such as silicate-treated aluminum plates, anodic-modified aluminum plates, and silicate electrodeposited aluminum plates, as well as zinc plates, stainless steel plates, Examples include chromium-treated steel sheets, hydrophilized plastic films, and paper.

Further, when the composition of the present invention is used as a 7-otoresist, various materials such as a steel plate, a steel plated plate, a stainless steel plate, a glass plate, etc. can be used as a support.

"Examples" Hereinafter, examples of synthesis 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/16/f p-dimethylanobenzaldehyde'371 and tF
N-n-7'thyl-N'-phenylthiobarbic acid was heated to reflux in 14 methanol for 1 hour.

After the reaction solution was allowed to cool, the crystals formed were collected by filtration and dried. Recrystallization was performed using a mixed solvent of methanol and benzene to obtain crystals of Jcol.

Melting point Ko! P, J-col o, z”c Elemental analysis c23 Calculated value as H25N3023 C: 47.72) 11./rl N:/7.J/
Chronic measurement value c: tr, oko% H: t, o4q4 P4: to
, 5tqk electrons (cutol (tetrahydrofuran (T)
(in IFJ) 2rrlH14'r7nm log g, tj Examples 1 to 3, Comparative Examples 1 to 9 After sand-grained with a nylon brush, the coating was applied to a silicate-treated aluminum plate using a coating machine at a rotational speed of 0r, pm.
The photosensitive solution shown below using the photopolymerization initiator shown in Table 1 was coated on the film at m-, and dried for 100 eh CJ to form a photosensitive layer having a dry film thickness of about -2 mm, thereby preparing a photosensitive plate.

Benzyl methacrylate-methacrylic acid (molar ratio 73/2 7) copolymer s, op (ntaerythritol tetraacrylate 3. I photopolymerization initiator J molar ratio to monomer Methyl ethyl ketone 209 Methylcellosolve acetate 20/i exposure The tip is 1 using a vacuum baking frame device.
A step wedge (density step 0.
/J, number of density steps/! tljjl) was placed and irradiated with a JKW ultra-high pressure mercury lamp for 30 seconds, and after exposure, development was performed using a developer having the following formulation.

(Developer) Trisodium phosphate CojI phosphoric acid
Natriu A 71/Butyl Cernlube 70Il surfactant
Kod water
/11 The highest number of steps/wedges corresponding to the resulting image is shown in Table 1 as the sensitivity of the sample. The higher the number of stages, the higher the sensitivity.

For comparison, instead of the compound of the present invention as a photopolymerization initiator, the compounds shown in the comparative examples were used for each monomer! Table 2 shows the sensitivity when adding molar esff&.

As shown in Table 7, Table 1 and @Table 2, when the photopolymerization initiator of the present invention was used, higher sensitivity was exhibited compared to Comparative Examples 1 to 2, and the desired effect of the present invention was achieved. was fully recognized.

Examples 4-6 Comparative Example 10 Compound monomer of Compound Example 17 as a photopolymerization initiator of the present invention in the method of Examples 1-3! Arrogant,
Also, use the compounds shown in Table 3 below as activators! A coating solution was prepared in the same manner as in Examples 1 to 3, except that molar addition was carried out at a constant rate of 0.0 molar fractions and the exposure time was set to is seconds. A photosensitive plate was prepared using the same method, and an exposure phenomenon was performed. The highest step number of the step wedge corresponding to the image that appears is the third sensitivity of the sample.
Shown in the table. In addition, as a comparison, the sensitivity when no activator was added is shown in Comparative Example 10.

Examples 7 to 9 In the methods of Examples 1 to 3, compounds of Compound Examples 3.14 and 15 are used as the photopolymerization initiator of the present invention to monomers! Photosensitive plates were prepared in the same manner as in Examples 1 to 3, except that caustyryl-J-phenylsulfonyl-(jH)*nazolinone was added to the monomer as an activator.

Place the Step Queue on the photosensitive plate you created, and then add Fuji Filter SC4AO (filter that transmits light of 4 AOOnm or more, made by Fuji Photo Film) and Fuji Filter BPBj17 (filter that transmits light near 7001 m, half width) on top of it. $jnm, Fuji Photo Film ■Il)
The samples were overlapped and irradiated for 20 seconds using the same apparatus as in Examples 1 to 3, and the same method as in Examples 1 to 3 was performed.

The maximum step wedge number of the obtained brushes is shown in the table below.

As is clear from the results in Tables 4c and j of Table 1, the photopolymerization initiator of the present invention has a visible light rays of uoom or more and jOO1
It was clearly shown that it is highly sensitive even to light at a distance of about 1 m.

Patent applicant: Fuji Photo Film Co., Ltd. 1, Case description: 1985 Japanese Patent Application No. 4C Ko022 2, Title of the invention: Photopolymerizable composition 3, Person making the amendment Relationship with the case Patent applicant contact information: 10
6 Fuji Photo Film Co., Ltd. Tokyo Head Office, 2-26 Nishi-Azabu, Minato-ku, Tokyo Telephone: (406) 2537 Table Subject of amendment ``Detailed description of the invention'' column of the specification & Contents of the amendment The description in the "Detailed Explanation" section has been amended as follows.

Compound of Example t in Table 3 on page 32 " "of " ” and correct it.

Claims (1)

[Scope of Claims] A photopolymerizable composition comprising an addition polymerizable compound having at least one ethylenically unsaturated double bond and a photopolymerization initiator, at least one of the following general formula (I) as the photopolymerization initiator: A photopolymerizable composition containing one type of compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the formula, R_1, R_2, R_7, and R_8 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Represents a substituted aryl group, allyl group, or substituted allyl group, and R_3, R_4, R_5, and R_6 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Represents a substituted aryl group, halogen atom, carbalkoxy group or alkoxy group. or R_1 and R_5, R_2 and R_3, R_5 and 6,
Both R_3 and R_4 may form a ring with the atom to which they are bonded. X represents an oxygen atom or a sulfur atom.