JPH09297399A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high sensitivity photopolymerizable compsn. by incorporating an addition polymerizable compd. having an ethylenic unsatd. double bond, a specified compd. and a titanocene compd. SOLUTION: This photopolymerizable compd. contains an addition polymerizable compd. having at least one ethylenic unsatd. double bond, a compd. (pyrylium salt dye or thiapyrylium salt dye) represented by formula I or II and a titanocene compd. In the formulae I, II, each of X<1> and X<3> is a cation of O or S, X<2> is O or S, Y<1> -Y<3> are groups forming 6- or 10-membered hereto rings in combination with X<1> -X<3> , respectively, each of R<1> -R<3> is H, halogen, cyano, etc., each of R<4> -R<6> is H, 1-12C optionally substd. alkyl, etc., Z<-> is a counter anion and (n) is an integer of 0-3.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition. In particular, it has extremely high sensitivity to light rays in the visible light region. For example, Ar ⁺ laser light, YAG-SH
The present invention relates to a photopolymerizable composition exhibiting good sensitivity to G laser light.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerization system are known, and are used in a wide range of fields such as printing plates, printed circuits, paints, inks, hologram recording, and three-dimensional modeling. For example, a photopolymerizable composition comprising a compound containing an addition-polymerizable ethylenic double bond and a photopolymerization initiator, an organic polymer binder used as desired, a thermal polymerization inhibitor, and the like is coated on a support. A method of forming a cured relief image by providing as a layer, polymerizing and exposing an exposed portion by image exposure of a desired image, and dissolving and removing an unexposed portion,
Providing a layer of the above-described photopolymerizable composition between two supports, at least one of which is transparent, exposing the support after image exposure from the transparent support side to induce a change in adhesive strength by light; A method of forming an image by the method, a photosensitive material provided with a microcapsule layer having a color material such as a photopolymerizable composition and a leuco dye in the content is prepared, and the photosensitive material is image-exposed to expose the exposed portion capsule to light. Curing, breaking the unexposed portions of the capsules by pressure treatment or heat treatment, developing the color by contacting with a color material developer, forming a colored image, etc., by the light of the photopolymerizable composition An image forming method using a change in toner adhesion, an image forming method using a change in refractive index of a photopolymerizable composition by light, and the like are known.

In many of the photopolymerizable compositions applied to these methods, benzyl, benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone and the like have been used as photopolymerization initiators. However, these photopolymerization initiators, compared with the photopolymerization initiation ability for ultraviolet light of 400 nm or less, 400 nm
The photopolymerization initiation ability with respect to the visible light described above was remarkably low, and as a result, its application range was significantly limited.

In recent years, with the development of image forming technology, there has been a demand for a photopolymer having high sensitivity to light rays in the visible region. It is a photosensitive material suitable for non-contact type projection exposure plate making, visible light laser plate making, and the like. As such a visible light laser, Ar ⁺ laser 48
8nm light, 532nm light of YAG-SHG laser, etc.
Promising.

[0005] Many proposals have been made for photopolymerization initiation systems capable of responding to light rays in the visible light region. For example, certain sensitive dyes described in U.S. Pat. No. 2,850,445, a complex initiation system of a dye and an amine (Japanese Patent Publication No. Sho.
4-2189), a combination system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-373).
No. 77), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-25).
28, JP-A-54-155292), cyclic cis-α.
A system of a dicarbonyl compound and a dye (JP-A-48-841)
No. 83), a system of a substituted triazine and a merocyanine dye (JP-A-54-115024), a system of 3-ketocoumarin and an activator (JP-A-52-112681, JP-A-58-1).
5503), a system of biimidazole, a styrene derivative and a thiol (JP-A-59-140203), and a system of an organic peroxide and a dye (JP-A-59-140203, JP-A-5-140203).
9-189340) and the like. Also (Cheer)
The pyrylium salt dye can be applied to the initiator as a single system (Japanese Patent Publication No. 4028499), a combination system with a borate salt (JP-A-1-100536), and a combination system with triazine (Japanese Patent Publication No. 30322). Etc.

The effectiveness of titanocene as a photopolymerization initiator is disclosed in JP-A-59-152396, JP-A-61-151197, JP-A-63-10602, JP-A-63-41484, It is described in JP-A-3-12403 and JP-A-6-41170. Examples of use as a combined system include titanocene and 3-ketocoumarin dyes (JP-A-63-221110), titanocene and xanthene dyes. Further, a system in which an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group is combined (JP-A-4-221958, JP-A-4-21975)
No. 6) and a system of titanocene and a specific merocyanine dye (JP-A-6-295061).

However, although these prior arts are certainly effective for visible light, they have insufficient sensitivity or exhibit high sensitivity, but have problems such as poor storage stability and can be put to practical use. Did not.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a highly sensitive photopolymerizable composition. Especially 400
An object of the present invention is to provide a photopolymerizable composition having high sensitivity to light such as 488 nm and 532 nm corresponding to the output of visible light of at least nm, an Ar ⁺ laser, and a YAG-SHG laser. Still another object is to provide a photopolymerizable composition having excellent storage stability.

[0009]

Means for Solving the Problems The present inventors have found that a combination system of titanocene compounds capable of generating active radicals upon irradiation with light in the presence of a pyrylium salt dye or a thiapyrylium salt dye is extremely effective for visible light of 400 nm or more. The present invention has been achieved by finding that the sensitivity is high and the storage stability is excellent.

That is, the present invention is achieved by the following constitution (1). And a preferable structure is the following (2).

(1) An addition-polymerizable compound having at least one ethylenically unsaturated double bond, a compound represented by the following general formula (I) or (II) (pyrylium salt dye or thiapyrylium salt dye), and A photopolymerizable composition containing a titanocene compound.

[0012]

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In the above formula, X ¹ and X ³ each represent a cation of an oxygen atom or a sulfur atom. X ² represents an oxygen atom or a sulfur atom. Y ¹ , Y ² and Y ³ may be the same or different and each represents a group forming a 6- or 10-membered heterocycle with X ^{1 to} X ³ .

R ¹ , R ² and R ³ may be the same or different and each is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, It represents a substituted or unsubstituted aryl group.

R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group or a substituted group. Represents an alkenyl group.

[0016] Z ^- represents a counter anion. n is 0,
Represents an integer of 1, 2, and 3.

(2) The photopolymerizable initiation system containing the (thia) pyrylium salt dye and the titanocene compound further contains at least one compound selected from the group consisting of the following (a) to (h). The photopolymerizable composition according to (1) above.

(A) Compound having carbon-halogen bond (b) Ketone compound represented by the following (IX)

[0019]

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(In Chemical formula 3, Ar is selected from one of the following Chemical formulas 4.
Represents an aromatic group represented by R¹³And R ¹⁴Are hydrogen atoms or
Or an alkyl group, and R¹³And R¹⁴Is tied to each other
May combine with each other to form a carbocycle with a carbon atom.

[0021]

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In Chemical Formula 4, R ^{15 to} R ¹⁹ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, a —S—R ²¹ group, It represents a —SO—R ²¹ group or a —SO ₂ —R ²¹ group. Provided that at least one of R ¹⁵ to R ¹⁹ is -S-R ²¹
Or a —SO—R ²¹ group, wherein R ²¹ represents a hydrogen atom, an alkyl group, an acyl group, an aryl group or an alkenyl group. R ²⁰ represents a hydrogen atom, an alkyl group or an acyl group. Y ⁴ represents a hydrogen atom or a group of the following chemical formula 5.
R ¹³ and R ¹⁴ in Chemical formula 5 are the same as those in Chemical formula 3. )

[0023]

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(C) a ketoxime compound represented by the following chemical formula 6

[0025]

[Chemical 6]

(In the formula 6, R ²² and R ²³ may be the same or different from each other and each represents a hydrocarbon group or a heterocyclic group which may contain an unsaturated bond.

R ²⁴ and R ²⁵ may be the same or different from each other, and each is a hydrogen atom, a hydrocarbon group which may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group or a substituted group. Represents a thio group. Also,
R ²⁶ and R ²⁷ each represent a hydrogen atom, a hydrocarbon group which may contain an unsaturated bond, or a substituted carbonyl group. R
²⁶ and R ²⁷ are bonded to each other to form a ring, and a group selected from the following Chemical formula 7

[0028]

[Chemical 7]

May be an alkylene group having 2 to 8 carbon atoms which may be contained in the linking main chain of the ring. )

(D) Organic peroxide (e) Thio compound represented by the following chemical formula 8

[0031]

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(In Chemical Formula 8, R ²⁸ represents an alkyl group or an aryl group, and R ²⁹ represents a hydrogen atom or an alkyl group.
R ²⁸ and R ²⁹ may be bonded to each other to contain a hetero atom selected from oxygen, sulfur and nitrogen atoms.
Represents a group of non-metal atoms necessary to form a 7-membered ring.

(F) hexaarylbiimidazole (to) aromatic onium salt (h) ketoxime ester

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a specific configuration of the present invention will be described.

The photopolymerizable composition of the present invention contains a compound capable of addition polymerization and a photopolymerization initiation system.

The polymerizable compound having an addition-polymerizable unsaturated bond, which is the first essential component used in the present invention, is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Be done.

It has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and their copolymers include:
Esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated carboxylic acids with aliphatic polyhydric amine compounds Amides and the like.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate , 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , So Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

As the itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

As the crotonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.

Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned.

Specific examples of the amide monomer of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

Other examples include Japanese Examined Patent Publication No. 48-417.
JP-A-08-0838, in which a hydroxyl-containing vinyl monomer represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule. And vinyl urethane compounds containing at least two polymerizable vinyl groups.

CH ₂ ═C (R) COOCH ₂ CH (R ′) OH (A) (wherein R and R ′ represent H or CH ₃ ).

Further, urethane acrylates as described in JP-A-51-37193, JP-A-48-
64183, JP-B-49-43191, JP-B-52
Examples thereof include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. In addition, Journal of the Adhesion Society of Japan vol. 20, No. 7, 300-30
Those introduced as photocurable monomers and oligomers on page 8 (1984) can also be used. The amount of these used is 5 to 70 with respect to all components.
% By weight (hereinafter abbreviated as%), preferably 10 to 60
%.

Next, the photopolymerization initiation system which is the second essential component of the photopolymerizable composition of the present invention will be described. The photopolymerization initiation system of the present invention comprises a combination of at least two components, and the first component a) pyrylium salt dye or thiapyrylium salt dye will be described.

In a preferred embodiment of the compound represented by the general formula (I), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. A group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a heterocycle containing Y ¹ is a group represented by any one of the following general formulas (III) or (IV),
Further, the heterocycle containing Y ² is a group represented by the following general formula (V) or (VI).

[0051]

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R ¹ , R ² and R ³ are preferably hydrogen atom, halogen atom, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted group having 6 to 10 carbon atoms. It is a substituted phenyl group or an alkoxyphenyl group, more preferably H, F, Cl, Br, a methyl group, an ethyl group, a phenyl group, or a substituted phenyl group.

In a preferred embodiment of the compound represented by the general formula (II), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and a substituted or unsubstituted alkyl group. Alternatively, it is an unsubstituted aryl group or a substituted alkenyl group, and the heterocycle containing Y ³ is a group represented by the following general formula (VII) or (VIII).

[0054]

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R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group or a substituted alkenyl group. More preferably, a hydrogen atom and a carbon number of 1
To 10 substituted or unsubstituted alkyl groups, phenyl groups, phenyl groups substituted with alkyl groups, alkoxyphenyl groups, aminophenyl groups, dialkylaminophenyl groups, styryl groups substituted with alkyl groups, dialkylaminostyryl groups, alkoxy It is a styryl group.

More preferably, at least one of R ⁴ , R ⁵ and R ⁶ is a substituted or unsubstituted aryl group such as an alkoxyphenyl group or a dialkylaminophenyl group, or a substituted alkenyl group such as a styryl group.

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are
Each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group, a substituted alkenyl group, or any group bonded to an adjacent nuclear carbon atom. Together represent an atomic group necessary for forming an aryl group.

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are preferably hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, phenyl groups and alkyl groups. A phenyl group, an alkoxyphenyl group, an aminophenyl group, a dialkylaminophenyl group, a styryl group substituted with an alkyl group, a dialkylaminostyryl group, an alkoxystyryl group, or a compound represented by the general formula (XII) or (XII
I), is a group that can be represented by.

[0059]

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In the formula, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ ,
R ³⁵ , R ³⁶ , and R ³⁷ represent the same substituents as described for R ⁴ , R ⁵ , and R ⁶ .

[0061] Z ^- represents a counter anion. In particular,
Cl ⁻ , Br ⁻ , I ⁻ , CIO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , S
_{^{bF 6 -, AsF 6 -,}} SbCl 6 -, SnCl 6 -, R-
COO ⁻ , R—SO ₃ ^{− and the} like. R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Preferably, Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , R—OO ⁻ ,
R-SO ₃ ^- it is.

Specific examples of the compounds represented by the formulas (I) and (II) are shown below. The present invention is not limited to these compounds.

[0063]

[Chemical 12]

[0064]

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[0065]

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[0066]

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[0067]

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These pyrylium salt dyes or thiapyrylium salt dyes can be produced by a known method. Examples of the production method include the method described in JP-A-54-14974, U.S. Pat. No. 3,586,500, or Tetra.
hedron 29, page 795 (1973).

The pyrylium salt dye or thiapyrylium salt dye used in the photopolymerizable composition of the present invention can be preferably used alone or in combination of two or more kinds.

The b) titanocene compound which is the second component in the photoinitiating system of the present invention will be described below. The titanocene compound of the present invention may be any titanocene compound that can generate an active radical when irradiated with light in the presence of the above-described sensitizing dye. For example, Japanese Unexamined Patent Publication No.
52396, JP-A-61-151197, JP-A-6-151197
Known compounds described in JP-A-41170 can be appropriately selected and used.

Specifically, di-cyclopentadienyl-
Ti-di-chloride, di-cyclopentadienyl-T
i-bis-phenyl, di-cyclopentadienyl-Ti
-Bis-2,3,4,5,6-pentafluorophenyl-
1-yl (hereinafter referred to as A-1), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis- 2,4,6-trifluorophenyl-1-yl, di-
Cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti
-Bis-2,4-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,
5,6-pentafluorophenyl-1-yl (hereinafter A-2
Di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-
2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrid-1-yl) phenyl) titanium (hereinafter referred to as A-3) and the like Can be mentioned.

The titanocene compound used in the photopolymerizable composition of the present invention can be used alone or in combination of two or more kinds.

The amount of the sensitizing dye constituting the photopolymerization initiation system used in the photopolymerizable composition of the present invention and the titanocene compound used is 100 parts by weight of the compound having an ethylenically unsaturated double bond. , Sensitizing dye 0.05 to 3
0 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, the titanocene compound is 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably It can be used in the range of 2 to 50 parts by weight.

In the photopolymerizable composition of the present invention, in addition to the above-mentioned sensitizing dye and titanocene compound, the following compounds (a) to (h) can be added for the purpose of improving sensitivity.

As the compound (a) having a carbon-halogen bond, compounds represented by the following (XIV) to (XX) are preferable. Formula (XIV) is represented by Formula 18, formula (XV) is represented by Formula 19, XVII is represented by Formula 21, and Formula (XV) is represented by Formula 21.
For the carbonylmethylene heterocyclic compound having a trihalogenomethyl group of III), a compound of formula 22,
It is shown in Chemical formula 23 for the -halogeno-5- (halogenomethyl-phenyl) -oxazole derivative, and in Chemical formula 24 for the 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative of formula (XX).

[0076]

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In Chemical formula 17, X represents a halogen atom. Y
^{5 _{-CX 3, -NH 2, -NHR 39}} , -N (R 39) 2, -O
Represents R ³⁹ . Here, R ³⁹ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ³⁸ represents —CX ₃ (X is halogen), an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

[0078]

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Embedded image R ⁴⁰ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxy group, a nitro group or a cyano group, X is a halogen atom, and n is an integer of 1 to 3.

R ⁴¹ -E-CH _2-m X _m -R ⁴² (XVI) In the formula (XVI), R ⁴¹ is an aryl group or a substituted aryl group, and R ⁴² is -CO-NR ⁴³ = R ^44. , The following formula 19

[0081]

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Or halogen, E is --CO--,-
CS- or -SO ₂ - and is, R ^43, R ⁴⁴ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, wherein in R ⁴⁵ is of 17 (XIV) Is the same as R ³⁸ in the formula, X is halogen, and m is 1 or 2.

[0083]

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Embedded image R ⁴⁶ is an optionally substituted aryl group or heterocyclic group, and R ⁴⁷ is a carbon atom of 1 to 1
A trihaloalkyl group or a trihaloalkenyl group having 3 and p is 1, 2 or 3.

[0085]

[Chemical 21]

In formula 21, L is a hydrogen atom or a formula: CO- (R
⁴⁸ ) _n (CX ₃ ) _{m is} a substituent, M is a substituted or unsubstituted alkylene group, Q is a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group, 1, 2-phenylene group or NR ⁴⁹ group, M
+ Q together form a 3 or 4 heterocycle,
⁴⁸ is a carbocyclic or heterocyclic aromatic group, R ⁴⁹ is an alkyl group, an aralkyl group or an alkoxyalkyl group, X is a chlorine, bromine or iodine atom, and q =
0 and r = 1 or q = 1 and r = 1 or 2.

[0087]

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In Chemical Formula 22, X is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ⁵⁰ is a hydrogen atom or a CH _{3 -t} X _t group, R ⁵¹ is an s-valent optionally substituted unsaturated organic group.

[0089]

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In the chemical formula 23, X is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, R ⁵² is a hydrogen atom or a CH _3-v X _v group, R ⁵³ is a u-valent unsaturated organic group which may be substituted.

Examples of such a compound having a carbon-halogen bond include those described by Wakabayashi et al., Bull. Chem. Soc. J.
apan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl)
-S-triazine (hereinafter referred to as C-2), 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)-
S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-
Triazine, 2-methyl-4,6-his (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α,
α, β-trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine and the like. Other,
Compounds described in GB 1388492, for example 2-
Styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4, 6-bis (trichloromethyl)
-S-triazine, 2- (p-methoxystyryl) -4
-Amino-6-trichloromethyl-S-triazine and the like,
Compounds described in JP-A-53-133428, for example, 2
-(4-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S -Triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphth-5-yl)-
4,6-bis-trichloromethyl-S-triazine and the like,
The compounds described in German Patent No. 3337024, for example, the following compounds may be mentioned.

[0092]

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[0093]

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Also, J. Org. C by FC Schaefer et al.
hem., 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S
-Triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-
Examples thereof include 6-tribromomethyl-S-triazine and 2-methoxy-4-methyl-6-trichloromethyl-S-triazine.

Further, the compounds described in JP-A-62-58241, for example, the following compounds can be mentioned.

[0096]

[Chemical formula 26]

[0097]

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Further, compounds described in JP-A-5-281728, for example, compounds represented by the following chemical formula 28 can be mentioned.

[0099]

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Or even MP Hutt, EF Elsla
Ger and LM Werbel Journal of Heterocyclic
Chemistry Volume 7 (No. 3), pp. 511 et seq. (197
The following group of compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in (0).

[0101]

[Chemical 29]

[0102]

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[0103]

[Chemical 31]

[0104]

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[0105]

[Chemical 33]

[0106]

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[0107]

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[0108]

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[0109]

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Alternatively, compounds such as those described in German Patent No. 2641100, such as 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone,
Alternatively, a compound described in German Patent No. 3333450, for example, a compound represented by the following chemical formula 38:
^Examples thereof include those represented by the combination of R ^{49 of} 9 and the like.
The compound of Chemical formula 38 is included in the compound of Chemical formula 21.

[0111]

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[0112]

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Alternatively, the compound group described in German Patent No. 3021590, for example, the following may be mentioned.

[0114]

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Alternatively, the compound group described in German Patent No. 3021599, for example, the following may be mentioned.

[0116]

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Next, the ketone compound represented by (b) Formula 3 will be described. Here, Ar represents an aromatic group selected from one of Chemical formula 4, R ¹³ and R ¹⁴ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ¹³ and R ¹⁴ are bonded to each other. And C may form a carbon ring (cyclohexane, benzene ring, etc.). In Chemical formula 4, R ^{15 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 1.
2 alkyl groups, C 3-12 alkenyl groups,
An aryl group, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group,
-S-R ²¹ group, -SO-R ²¹ group represents a --SO2 -R ²¹ group, R ²¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, or an acyl group having a carbon number of 2 to 13, , Alkenyl group, aryl group (phenyl group, etc.). These alkyl group, aryl group, alkenyl group and acyl group may be further substituted with a substituent having 1 to 6 carbon atoms. R ²⁰
Represents a hydrogen atom, an alkyl group or an acyl group. Y represents a hydrogen atom or a group of Chemical formula 5, and R ¹³ and R ^{14 in} Chemical formula 5 are represented.
Are synonymous with those in Chemical formula 3, respectively.

As a concrete example, US Pat. No. 4,318,7
The following compounds described in No. 91 and European Patent No. 0284561A can be mentioned.

[0119]

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[0120]

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[0121]

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Next, the ketoxime compound represented by Chemical formula 6 will be described.

In Chemical Formula 6, R ²² and R ²³ may be the same or different, and may be a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a hetero group. Represents a ring group.

R ²⁴ and R ²⁵ may be the same or different and each is a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a heterocyclic group. ,
It represents a hydroxyl group, a substituted oxy group, a mercapto group or a substituted thio group. R ²⁶ and R ²⁷ represent a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. Further, R ²⁶ and R ²⁷ represent an alkylene group having 2 to 8 carbon atoms, which may be bonded to each other to form a ring, and the group selected from Chemical formula 7 may be contained in the linking main chain of the ring.

The following compounds can be mentioned as specific compounds, but the compounds are not limited to these.

[0126]

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[0127]

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[0128]

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[0129]

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Examples of the organic peroxide (d) include compounds having an oxygen-oxygen bond in the molecule. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1
-Bis (tert-butylperoxy) -3,3,5
-Trimethylcyclohexane, 1,1-bis (tertiarybutylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiarybutylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, Paramethane hydroperoxide, 2,5-
Dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, bis (tertiary butyl) Peroxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, acetyl per Oxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,
5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropylperoxydicarbonate, di-2
-Ethylhexyl peroxydicarbonate, di-2-
Ethoxyethyl peroxydicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butylperoxyacetate, tertiary butylperoxypivalate, tertiary butylperoxyneo Decanoate, tertiary butyl peroxyoctanoate, tertiary butyl peroxy
3,5,5-trimethylhexanoate, tertiary butyl peroxy laurate, tertiary butyl peroxy benzoate, ditertiary butyl peroxy isophthalate, 2,5-dimethyl-2,5-di (benzoyl peroxy) Hexane, tertiary butyl peroxide maleic acid, tertiary butyl peroxyisopropyl carbonate, 3,3 ', 4,4'-tetra- (t
-Butylperoxycarbonyl) benzophenone (hereinafter referred to as C-8), 3,3 ', 4,4'-tetra- (t-
Amyl peroxycarbonyl) benzophenone, 3,
3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3 ', 4,4'- Tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t- Hexyl peroxy dihydrogen diphthalate) and the like.

Among these, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone and 3,3', 4,4'-tetra- (t-amylperoxycarbonyl) Benzophenone, 3,3 ', 4,4'
-Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3',
4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone,
Peroxide ester systems such as di-t-butyldiperoxyisophthalate are preferred.

The thio compound as the component (e) used in the present invention is shown in Chemical formula 8.

The alkyl group of R ²⁸ and R ²⁹ in Chemical formula 8 is preferably one having 1 to 4 carbon atoms. Further, the aryl group of R ²⁸ is preferably one having 6 to 10 carbon atoms such as phenyl and naphthyl, and the substituted aryl group is preferably a halogen atom such as chlorine atom or a methyl group as the above aryl group. Such as an alkyl group, a methoxy group,
Those substituted with an alkoxy group such as an ethoxy group are included.

Specific examples of the thio compound represented by Chemical formula 8 include compounds having a combination of R ²⁸ and R ²⁹ as shown below in Chemical formula 8.

[0135]

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[0136]

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[0137]

[Chemical 51]

Examples of (f) hexaarylbiimidazole include 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole (hereinafter referred to as C-11), 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, , 2'-Bis (o, p-dichlorophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ',
5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole and the like.
Examples of the ketoxime ester include 3-benzoyloximinobtan-2-one and 3-acetoxyiminobutan-
2-one, 3-propionyloxy iminobutan-2-
On, 2-acetoxyiminopentan-3-one, 2-
Acetoxyimino-1-phenylpropan-1-one,
2-benzoyloxyimino-1-phenylpropane-1
-One, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-
1-phenylpropan-1-one and the like.

Further, as the (g) aromatic onium salt,
Elements of groups 15 (5B), 16 (6B), and 17 (7B) of the periodic table, specifically, N, P, As, Sb, Bi, O, S, Se,
Te or I aromatic onium salts are included. Such aromatic onium salts include the compounds disclosed in JP-B-52-14277, JP-B-52-14278, and JP-B-52-14279.

Specifically, the following compounds can be mentioned.

[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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Preferred among these are BF ₄ salts,
Or a compound of a PF ₆ salt, more preferably a BF ₄ salt of an aromatic iodonium salt, or a PF ₆ salt.

As (h) ketoxime ester, 3-
Benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one (hereinafter referred to as C-12), 3
-Bropionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1- ON, 3-
p-Toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

These additives (a) to (h) can be used alone or in combination of two or more. The amount used is 0.05 to 100 parts by weight, preferably 1 to 80 parts by weight, per 100 parts by weight of the compound having an ethylenically unsaturated double bond.
Parts by weight, more preferably in the range of 3 to 50 parts by weight.

The content concentration of these photoinitiator systems in the composition of the present invention is usually low. In addition, when the number is inappropriately large, undesired results such as blocking of the effective light beam occur. The amount of the photopolymerization initiator system in the present invention is 0.01 to the total of the compound having a photopolymerizable ethylenically unsaturated double bond and the linear organic high molecular weight polymer added as necessary. % To 60%. More preferably, good results are obtained at 1% to 30%.

The photopolymerizable composition of the present invention preferably contains a linear organic high molecular polymer as a binder. As such a "linear organic high molecular polymer",
Any linear organic high molecular polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. A linear organic polymer which is soluble or swellable in water or weak alkaline water, which enables water development or weak alkaline water development, is preferably selected. The linear organic high molecular polymer is selected and used not only as a film forming agent of the composition but also as a water, weakly alkaline water or organic solvent developing agent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include an addition polymer having a carboxylic acid group in a side chain, for example, JP-A-59-44615.
No. 54-34327, Sho 58-1257
7, JP-B-54-25957, JP-A-54-927
No. 23, JP-A-59-53836, JP-A-59-71
048, that is, methacrylic acid copolymer, alkali acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain.
In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. To increase the strength of the cured film, alcohol-soluble nylon or 2,2-bis-
Polyethers of (4-hydroxyphenyl) -propane and epichlorohydrin and the like are also useful. These linear organic high molecular polymers can be mixed in an arbitrary amount in the whole composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably it is 30 to 85%. The weight ratio of the photopolymerizable compound having an ethylenically unsaturated double bond and the linear organic high molecular weight polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 3/7 to 5/5.

In the present invention, in addition to the above basic components, in order to prevent unnecessary thermal polymerization of a compound having a polymerizable ethylenically unsaturated double bond during production or storage of the photosensitive composition. It is desirable to add a small amount of thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-
p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-
6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, ammonium N-nitrosophenylhydroxylamine, and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% based on the weight of the whole composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The amount of the higher fatty acid derivative to be added is about 0.1% of the total composition.
5% to about 10% is preferred. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer.

Examples of such colorants include phthalocyanine pigments, azo pigments, carbon black, pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes.

The amount of dye and pigment added is preferably about 0.5% to about 5% of the total composition. In addition, known additives such as inorganic fillers and other plasticizers may be added to improve the physical properties of the cured film.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adibate, dibutyl sebacate, and triacetyl glycerin. In this case, 10% or less can be added to the total weight of the compound having an ethylenically unsaturated double bond and the binder.

When the photopolymerizable composition of the present invention is coated on a support, it is dissolved in various organic solvents before use.
As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol moethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol,
Methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ -Butyrolactone, methyl lactate,
Ethyl lactate and the like. These solvents can be used alone or as a mixture. And, the concentration of the solid content in the coating solution is appropriately 2 to 50%.

The coating amount is about 0.1 g / dry weight.
range of m ² ~ about 10 g / m ² are suitable. It is more preferably 0.5 to 5 g / m ² .

As the support, a dimensionally stable plate-like material is used. As this dimensionally stable plate,
Paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper,
For example, a metal plate such as aluminum (including an aluminum alloy), zinc, copper, etc., and further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene And plastic films such as polystyrene, polypropylene, polycarbonate and polyvinyl acetal, and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a support having a surface of metal, especially aluminum, surface treatment such as graining treatment, dipping treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment. It is preferable that

Further, an aluminum plate which has been grained and then immersed in an aqueous sodium silicate solution can be preferably used. As described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment may be, for example, an aqueous solution or an aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or an electrolytic solution obtained by combining two or more types. It is carried out by passing a current through an aluminum plate as an anode.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

Further, a support which has been subjected to electrolytic graining as disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503, and the above anodizing treatment and sodium silicate Surface treatments that combine treatments are also useful.

Further, it is also preferable to use mechanical graining, chemical etching, electrolytic graining, anodic oxidation and sodium silicate treatment in that order, as disclosed in JP-A-56-28893.

Furthermore, after these treatments are carried out, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid,
A water-soluble metal salt (eg, zinc borate) or a yellow dye,
A primer coated with an amine salt or the like is also suitable.

Further, a sol-gel treated substrate to which a functional group capable of causing an addition reaction by a radical is covalently bonded, as disclosed in Japanese Patent Application No. 5-304358, is also preferably used.

These hydrophilization treatments are carried out not only to make the surface of the support hydrophilic, but also to prevent harmful reaction of the photopolymerizable composition provided thereon, and to adhere the photosensitive layer. It is given to improve the sex.

On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, particularly saponification degree of 95, is used in order to prevent the polymerization inhibiting action of oxygen in the air.
% Or more of a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol and acidic celluloses. Regarding the application method of such a protective layer,
For example, U.S. Pat. No. 3,458,311 and JP-A-55-4
9729.

The photopolymerizable composition of the present invention can be used in ordinary photopolymerization reactions. Further, the present invention can be applied to various fields such as a photoresist for producing a printing plate, a printed board, and the like. Particularly, due to the high sensitivity and the wide spectral sensitivity characteristic up to the visible light region, which are characteristics of the photopolymerizable composition of the present invention,
When applied to a photosensitive material for a visible light laser such as an Ar ⁺ laser and a YAG-SHG laser, a good effect can be obtained.

The photosensitive material using the photopolymerizable composition of the present invention is subjected to imagewise exposure, and then the unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. Preferred developers for using these photopolymerizable compositions for preparing a lithographic printing plate include those described in JP-B-57-7427, such as sodium silicate and potassium silicate. Like sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of a suitable inorganic alkali agent or an organic alkali agent such as monoethanolamine or diethanolamine is suitable. When the concentration of such an alkaline solution is 0.1 to 10
%, Preferably 0.5 to 5%.

Further, in such an alkaline aqueous solution,
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, U.S. Patent No.
Examples thereof include those described in No. 3,375,171 and No. 3,615,480.

Further, JP-A-50-26601 and 58.
No. 54341, JP-B-56-39464, 56-
The developing solutions described in JP-A-42860 are also excellent.

Examples of the light source for actinic rays used in the present invention include ultrahigh pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, and fluorescent lamps. Lamps, tungsten lamps, sunlight, etc. can be used.

[0174]

EXAMPLES Hereinafter, the present invention will be described with reference to examples shown together with comparative examples, but the present invention is not limited to these examples.

Examples 1 to 7 and Comparative Examples 1 to 8 An aluminum plate having a thickness of 0.30 mm and a nylon brush 4 were used.
The surface was sand-grained with an aqueous suspension of pumicestone of 00 mesh, and then thoroughly washed with water. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized and washed with 20% nitric acid, and then washed with water. This was subjected to 160 clones / in 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of VA = 12.7V.
The electrolytic surface-roughening treatment was performed with the amount of electricity at the anode time of dm ² . When the surface roughness was measured, it was 0.6 μm (Ra indication). Subsequent immersion in 30% sulfuric acid solution at 55 ° C
After desmutting for 2 minutes in a 20% aqueous sulfuric acid solution, the thickness of the anodic oxide film is 2.7 g at a current density of 2 A / dm ² .
/ M ² for 2 minutes.

On the aluminum plate thus treated, a photosensitive composition having the following composition was applied in a dry coating weight of 1.4 g.
/ M ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer.

Pentaerythritol tetraacrylate 1.5 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Sensitizing dye compound x g Titanocene compound y g Fluorine-based nonionic surfactant 0.03 g Methyl ethyl ketone 20g Propylene glycol monomethyl ether acetate 20g

A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 550) was coated on the photosensitive layer so that the dry coating weight was 2 g / m ^2.
Dry at 2 ° C. for 2 minutes.

The photosensitivity test was conducted with visible light. As the visible light, a monochromatic light obtained through a Kenko optical filter BP-49 using a xenon lamp as a light source was used.

Fuji PS step guide (manufactured by Fuji Photo Film Co., Ltd., the first stage had a transmission optical density of 0.
05, using a step tablet (up to 15 steps in increments of 0.15). Exposure was performed so that the energy on the PS step guide surface was 0.25 mJ / cm ² . The sensitivity was indicated by the number of clear steps of the PS step guide after development.

Thereafter, heating is performed at 120 ° C. for 20 seconds,
It was developed by immersing it in the following developer at 25 ° C. for 30 seconds.

DP-4 (manufactured by Fuji Photo Film Co., Ltd.) 66.5 g Water 881.4 g Lipomin LA (20% solution) (manufactured by Lion Corporation) 52.1 g

Tables 1 and 2 show the results of sensitivity when the following compounds were used as the photopolymerization initiator and the combinations thereof were changed.

[0184]

[Table 1]

[0185]

[Table 2]

Examples 8 to 15 and Comparative Examples 9 to 14 Samples were prepared in the same manner as in Example 1 except that the photoinitiator of Example 1 was replaced with the compounds shown in Table 3, and the same photosensitivity was obtained. The test was conducted.

Pentaerythritol tetraacrylate 1.5 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Titanocene compound y g Sensitizing dye compound x g Fluorine-based nonionic surfactant 0.03 g Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g Pigment dispersion having the following composition 2.0 g

Pigment Dispersion Composition Pigment Blue 15: 6 30 parts Allyl methacrylate / methacrylic acid copolymer 20 parts (Copolymerization ratio 83/17) Cyclohexanone 35 parts Methoxypropyl acetate 35 parts Propylene glycol monomethyl ether 80 parts

Table 3 shows the results of sensitivity when the combination of photopolymerization initiators was changed.

[0190]

[Table 3]

Examples 16 to 22 and Comparative Examples 15 to 22 Samples were prepared in the same manner as in Example 1, and a monochromatic light obtained through BP-53 instead of the Kenko optical filter BP-49 was used as a light source, and a sensitivity test was conducted. I went.

The results when changing the combination of the photopolymerization initiators are shown in Tables 4 and 5.

[0193]

[Table 4]

[0194]

[Table 5]

Examples 23 to 30 and Comparative Examples 23 to 28 Samples were prepared in the same manner as in Example 8, and a monochromatic light obtained through BP-53 instead of the Kenko optical filter BP-49 was used as a light source, and a sensitivity test was conducted. I went.

Table 6 shows the results when the combination of photopolymerization initiators was changed.

[0197]

[Table 6]

Examples 31 to 39, Comparative Example 29 A sample was prepared and a photosensitivity test was carried out in the same manner as in Example 8 except that the photoinitiating system in Example 8 was replaced with the compounds shown in Table 7. . The results are shown in Table 7.

Pentaerythritol tetraacrylate 1.5 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Sensitizing dye compound x g Titanocene compound y g (i) to (h) compounds z g Fluorine-based nonionic surfactant 0.03 g Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g Pigment dispersion of the following composition 2.0 g

Pigment Dispersion Composition Pigment Blue 15: 6 30 parts Allyl methacrylate / methacrylic acid copolymer 20 parts (Copolymerization ratio 83/17) Cyclohexanone 35 parts Methoxypropyl acetate 35 parts Propylene glycol monomethyl ether 80 parts

[0201]

[Table 7]

Examples 40 to 50, Comparative Example 30 A sample was prepared in the same manner as in Example 31, and a monochromatic light obtained through BP-53 instead of the Kenko optical filter BP-49 was used as a light source, and a sensitivity test was conducted. It was

Table 8 shows the results when the combination of photopolymerization initiators was changed.

[0204]

[Table 8]

From the results shown in Tables 1 to 8, the photopolymerizable composition of the present invention containing the sensitizing dye of the present invention and the titanocene compound as the photopolymerization initiation system has high sensitivity. It's obvious. It is also clear that it has excellent storage stability.

Further, it can be seen that by further using the compounds of (a) to (h) in combination, the sensitivity becomes higher. On the other hand, the effects of the present invention cannot be obtained if the photopolymerization initiation system contains only one of the sensitizing dye and the titanocene compound.

[0207]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet light to visible light.
Therefore, as the light source, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp,
Metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, sunlight and the like can be used.

Claims (1)

[Claims] 1. A photopolymerizable composition containing an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a compound represented by the following general formula (I) or general formula (II), and a titanocene compound. Stuff. Embedded image (In the formula, X ¹ and X ³ each represent a cation of an oxygen atom or a sulfur atom. X ² represents an oxygen atom or a sulfur atom. Y ¹ , Y ² and Y ³ may be the same or different. Well, each of the above X ^{1 to} X ^{3 is} 6 or 1
It represents a group forming a 0-membered heterocycle. R ¹ , R ² and R
³ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, or an alkyl group or aryl group having 1 to 6 carbon atoms. R ⁴ ,
R ⁵ and R ^{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkenyl group. Z ⁻ represents a counter anion. n represents an integer of 0, 1, 2, 3. )