JPH10246954A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition high in sensitivity and superior in storage stability, by incorporating a compound having an additionally polymerizable ethylenically unsaturated bond, a titanocene compound a spectral sensitizing dye, such as a merocyanine dye or benzopyrane dye, and a specified aminoacid salt. SOLUTION: This photopolymerizable composition contains at least i) a compound having the additionally polymerizable ethylenically unsaturated bond, ii) the titanocene compound, iii) the merocyanine or bezopyrane dye as the speciftral sensitizing dye, and iv) the aminoacid salt represented by the formula, in which each of R<1> -R<3> is H atom or the like; Ar is an aryl group; (n) is 1, 2, 3, or 4, and when n=1, M<+> is an alkali metal ion or a quaternary ammonium ion represented by [R<4> to R<7> ]N<+> , and when n=2, 3, or 4, M<n+> is [(R<4> ) to (R<6> )N<+> ]n -r, each of R<4> -R<7> is a specified hydrocarbon group, r is an n-valent hydrocarbon group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition. More specifically, it relates to a photopolymerizable composition containing at least a polymerizable compound having an ethylenically unsaturated bond capable of addition polymerization, a titanocene compound, a spectral sensitizing dye, and a salt of an amino acid.

[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).
No. 28, JP-A-54-155292), cyclic cis-α
A system of a dicarbonyl compound and a dye (JP-A-54-841)
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).
No. 9-189340), and a system of a dye having a rhodanine skeleton and a radical generator (JP-A-2-244050).

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. Examples of use as a combined system include titanocene and 3-ketocoumarin dyes (JP-A-63-221).
No. 110), a system in which a titanocene is combined with a xanthene dye and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group (JP-A-4-22195).
No. 8, JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061,
JP-A-8-220758 and JP-A-8-262714
Or a system of titanocene and a specific benzopyran-based dye (Japanese Patent Application No. 7-1645).
No. 83) and the like. Further, a dye in which an amino acid or a derivative thereof is further combined as a co-sensitizer with a titanocene compound system (JP-A-5-1325)
No. 07, W09509383, JP-A-4-19485
7, JP-A-7-267907) and the like.

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. In particular, 400
It is an object of the present invention to provide a photopolymerizable composition having high sensitivity and excellent storage stability 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. .

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that titanocene capable of generating an active radical upon irradiation with light in the presence of a dye having a specific structure and a salt of an amino acid. The present inventors have found that a combined system of compounds has extremely high sensitivity to visible light of 400 nm or more and excellent storage stability, and has arrived at the present invention.

That is, the present invention provides the following (1). (1) at least i) a compound having an ethylenically unsaturated bond capable of addition polymerization, ii) a titanocene compound, iii) a merocyanine dye or a benzopyran dye as a spectral sensitizing dye, and iv) a compound represented by the following general formula (I). A photopolymerizable composition comprising a salt of an amino acid.

[0011]

Embedded image

[In the general formula (I), R ¹ , R ² and R ³ each represent a hydrogen atom or a hydrocarbon group which may contain an unsaturated bond. Ar represents an aryl group. n is an integer of 1 to 4. When n = 1, M ⁺ represents an alkali metal ion or a quaternary ammonium ion represented by (R ⁴ ) (R ⁵ ) (R ⁶ ) (R ⁷ ) N ⁺ . When n = 2, 3 or 4, M ^{n +} represents [(R ⁴ ) (R ⁵ ) (R ⁶ ) N ⁺ ] _n -r. Here, R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a hydrocarbon group which may contain an unsaturated bond, and r represents an n-valent hydrocarbon group. ]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The photopolymerizable composition of the present invention comprises: i) a compound having an ethylenically unsaturated bond capable of addition polymerization, ii) a titanocene compound, and iii) a merocyanine dye and / or a benzopyran dye as a spectral sensitizing dye. iv) a salt of the amino acid represented by the general formula (I).

As described above, by using a titanocene compound, a spectral sensitizing dye selected from merocyanine dyes and benzopyran dyes, and a salt of the above-mentioned amino acid as a photopolymerizable initiation system, visible light of 400 nm or more can be obtained. A photopolymerizable composition having high sensitivity to laser light and excellent storage stability can be obtained. Such an effect is presumed to be obtained by the interaction between the titanocene compound sensitized by the spectral sensitizing dye and an amino acid salt.In such a system, the merocyanine dye and the benzopyran dye are extremely effective. It is thought to act on. On the other hand, if the salt of the above-mentioned amino acid is not contained, the sensitivity is lowered. If an amino acid which is a similar compound is used, the storage stability is deteriorated.

Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail.

The polymerizable compound having an addition-polymerizable unsaturated bond of the component i) used in the present invention is selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated bonds.

Examples of the monomer include an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and an aliphatic polyhydric alcohol compound, and an unsaturated carboxylic acid and an fatty acid. And amides with group-III polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates 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.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 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.

Examples of itaconic acid esters include 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.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like.

Examples of the isocrotonic acid ester 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.

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

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

As another example, see JP-B-48-417.
JP-A-08-208, in which a hydroxyl group-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, two or more in one molecule: And a vinyl urethane compound containing a polymerizable vinyl group.

CH ₂ CC (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ represent H or CH ₃ )

Further, urethane acrylates as described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And 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. In the present invention, these monomers may be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

The amount of these used is 5 to 70% by weight (hereinafter abbreviated as%), preferably 10 to 60% with respect to all components of the photopolymerizable composition. If the amount used is large, it is easy to cause poor coating formation (stickiness), and if the amount used is small, curing failure tends to occur, which is not preferable.

Next, the titanocene compound of the component ii) will be described in detail.

As the titanocene compound of the component ii), known titanocene compounds can be mentioned. That is, as an example of the titanocene compound, JP-A-59-15239
6, JP-A-61-151197, JP-A-63-41
No. 484, JP-A-2-249 and JP-A-2-4705. Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-
Ti-bis-phenyl, di-cyclopentadienyl-T
i-bis-2,3,4,5,6-pentafluorophenyl-1-yl, 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, di-methylcyclopentadienyl-Ti-bis -2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-T
i-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) phenyl) titanium (described in Examples below) A-1), bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-butylbiaroyl-amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N-methylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-Ethylpropionylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-ethyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl-
(2,2-Dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-pentyl- (2,2-dimethylbutanoyl) amino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
Hexyl)-(2,2-dimethylbutanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-methylbutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylpentanoylamino) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-ethylisobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (2,2,5,5-tetramethyl-
1,2,5-azadisirolidin-1-yl) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (octylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (4-tolylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-dodecylphenylsulfonylamido) phenyl] titanium, bis (cyclopentadiene) Dienyl) bis [2,6-difluoro-3- (4-
(1-pentylheptyl) phenylsulfonylamide)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (ethylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3-((4-bromophenyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(2-naphthylsulfonylamido) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (hexadecylsulfonylamido) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N-methyl- (4-dodecylphenyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-methyl-4- (1-pentylheptyl) phenyl) sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-hexyl- (4-tolyl) -sulfonylamide)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pyrrolidin-2,5-dion-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (3,4
-Dimethyl-3-pyrrolidin-2,5-dion-1-yl) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (phthalimido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-isobutoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (ethoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((2-chloroethoxy) -carbonylamino) phenyl] titanium ,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylthioureido) Phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (3-butylthioureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylureido)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-butylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N , N-Diacetylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (3,3-dimethylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (acetylamino) phenyl] titanium, bis (cyclo Pentadienyl)
Bis [2,6-difluoro-3- (butyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (decanoylamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (octadecanoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (2-ethylhexanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-methylbutanoylamino) phenyl] titanium , Bis (cyclopentadienyl) bis [2,6-difluoro-3- (pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-
Dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (2-ethyl-2-methylheptanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (cyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (2,2-dimethyl-3-chloropropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenyl) Propanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chloromethyl-2-
Methyl-3-chloropropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-xyloylamino) phenyl] titanium, bis (cyclopentadienyl) Screw [2
6-difluoro-3- (4-ethylbenzoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4,6-mesitylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Difluoro-3- (benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-
Phenylpropyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-
Dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-isobutyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutylbenzoylamino) phenyl] titanium, bis (cyclopentadiene) Dienyl) bis [2,6-difluoro-3- (N-cyclohexylmethylpivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolani- 2-ylmethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylbutanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [ 2,6-difluoro-3- (N- (oxolani-2-ylmethyl)-(4-
Toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
(4-Toluylmethyl) benzoylamino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N- (4-toluylmethyl)-(4
-Toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(Butylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N- (butyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (hexyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,
4-dimethylpentyl) -2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4-dimethylpentyl) -2,2-dimethyl Pentanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2
2-dimethyl-3-ethoxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-)
Allyloxypropanolamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-allylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (2-ethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-cyclohexylmethylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (4-toluyl) amino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-2-ethylhexyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropylbenzoylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-
3- (N- (3-phenylpropyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-hexylbenzoylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3-
(N-butylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -2,2-dimethylpentanoylamino) phenyl] titanium, Bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-isopropyl-
2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) pivaloylamino) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (N-butyl-
2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) benzoylamino) phenyl] titanium, bis (cyclopentane Dienyl) bis [2,6-difluoro-3- (N-benzylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl- (4-toluyl) ) Amino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl)-(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N- (4-
Methylphenylmethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) -2,2-dimethyl Pentanoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2-ethyl-2-methylheptanoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-butyl- (4-
Chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-hexyl- (2-ethyl-2-methylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl-2,2-dimethyl) Pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolani-2-
Ylmethyl) -2,2-dimethylpentanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl-
(4-chlorobenzoyl) amino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (2-chlorobenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,3-dimethyl-2,2-azetidinon-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis (2,6-difluoro-3-isocyanatophenyl) titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-
3- (N-ethyl- (4-tolylsulfonyl) amino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3-
(N-butyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-
Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(3-phenylpropyl) -2,2-dimethyl-3-
Chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- ( 2,2-dimethyl-
3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-butyl- (2-chloromethyl-2-methyl-3-
Chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (butylthiocarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthiocarbonylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2 , 6-Difluoro-3- (N-hexyl-2,2-
Dimethylbutanoylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (methylcyclopenta Dienyl) bis [2,6-difluoro-3- (N-
Ethylacetylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-
3- (N-ethylpropionylamino) phenyl] titanium, bis (trimethylsilylpentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpropanoylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-
3- (N- (2-methoxyethyl) -trimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylhexyldimethylsilylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-
3- (N-ethyl- (1,1,2-tolylmethylpropyl) dimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (3-ethoxymethyl-3-methyl-2-azethiodinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-
Allyloxymethyl-3-methyl-2-azetidinoni-
1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-chloromethyl-3-methyl-2-azetidinoni-1-yl) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-
Dimethylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (5,5-dimethyl-2-pyrrolidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (6,6-diphenyl-2-piperidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-2) , 3-Dihydro-1,2-benzenethiazolo-3-one (1,1-dioxide) -2-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( N-hexyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-hexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl- (4
-Chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N- (4-methylphenylmethyl)-(4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N- (4-methylphenylmethyl)-(2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
Butyl- (4-chlorobenzoyl) amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N-benzyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
(2-ethylhexyl) -4-tolyl-sulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium , Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(Trifluoroacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2 6-difluoro-3- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) -2,2- Dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,
6-difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium, and the like.

Components used in the photopolymerizable composition of the present invention
The titanocene compounds of ii) can be used alone or in combination of two or more.

Next, the spectral sensitizing dye of the component iii) will be described in detail.

In the present invention, a merocyanine dye and / or a benzopyran dye are used as the spectral sensitizing dye. As these dyes, known dyes can be mentioned, and those having an absorption maximum at 450 to 600 nm are preferable.

Preferred examples of the merocyanine dye include the following general formulas [1] to [8] described in JP-B-61-9621.
There is a merocyanine dye represented by

[0037]

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In the general formulas [3] to [8], X ⁸ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group,
Represents an aryl group, a substituted aryl group, an aryloxy group, an aralkyl group or a halogen atom. In the general formula [2], Ph represents a phenyl group. In the general formulas [1] to [8], R ⁴⁸ , R ⁴⁹ and R ⁵⁰ are each an alkyl group,
Represents a substituted alkyl group, an alkenyl group, an aryl group, a substituted aryl group or an aralkyl group, which may be the same or different.

Further, as the merocyanine dye, JP-A No.
The following general formulas [9] to [11] described in -179643
There is a dye represented by

[0040]

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In the general formulas [9] to [11], A represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl or aryl substituted nitrogen atom, or a dialkyl substituted carbon atom.

Y ³ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group, or a substituted alkoxycarbonyl group.

R ⁵¹ and R ⁵² are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a halogen atom (F,
Cl, Br, I), R 53 O -, - (CH 2 CH 2 O) x -
R ⁵³ represents a substituted alkyl group having 1 to 18 carbon atoms having the following groups.

[0044]

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However, R ⁵³ is a hydrogen atom or a group having 1 to 1 carbon atoms.
Represents an alkyl group of 0, and B represents a dialkylamino group, a hydroxyl group, an acyloxy group, a halogen atom, or a nitro group.

W represents an integer of 0 to 4, and x represents an integer of 1 to 20.

Further, there is a merocyanine dye represented by the following general formula [12] described in JP-A-2-244050.

[0048]

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In the general formula [12], R ⁵⁴ and R ⁵⁵
Each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. A ² represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl or aryl substituted nitrogen atom, or a dialkyl substituted carbon atom. X ⁹ represents a nonmetallic atom group necessary for forming a nitrogen-containing 5-membered heterocyclic ring.

Y ⁴ represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic hydrocarbon ring group, or an unsubstituted or substituted heteroaromatic ring group. Z ³ is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group or an alkoxycarbonyl group, together with Y ⁴ They may combine to form a ring.

Preferred specific examples of the merocyanine dye represented by the general formula [12] include the following.

[0052]

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Further, there is a merocyanine dye represented by the following general formula [13] described in JP-B-59-28326.

[0054]

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In the general formula [13], R ⁵⁶ and R ⁵⁷
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl or an aralkyl group, which may be the same or different. X ¹⁰ is Hammett
(Hammett) represents a substituent having a sigma (σ) value in the range of -0.9 to +0.5.

Further, there is a merocyanine dye represented by the following general formula [14] described in JP-A-59-89303.

[0057]

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In the general formula [14], R ⁵⁸ and R ⁵⁹
Each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group. X ¹¹ has a Hammett's sigma (σ) value of −11.
Represents a substituent in the range from 0.9 to +0.5. Y ⁵
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group or an alkoxycarbonyl group.

Preferred specific examples of the merocyanine dye represented by the general formula [14] include the following.

[0060]

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Further, there is a merocyanine dye represented by the following general formula [15] described in Japanese Patent Application No. 6-269047.

[0062]

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In the general formula [15], R ⁶⁰ , R ⁶¹ , R
⁶² , R ⁶³ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group,
Substituted oxy group, mercapto group, substituted thio group, amino group,
Represents a substituted amino group, a substituted carbonyl group, a sulfo group, a sulfonato group, a substituted sulfinyl group, a substituted sulfonyl group, a phosphono group, a substituted phosphono group, a phosphonate group, a substituted phosphonate group, a cyano group or a nitro group. R ⁶⁰ and R
⁶¹ , ^R61 and ^R62 , ^R62 and ^R63 , ^R68 and ^R69 , ^R69 and ^R70 , ^R70 and ^R71 may be bonded to each other to form an aliphatic or aromatic ring. . R ⁶⁴ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group,, R ⁶⁵ represents a substituted or unsubstituted alkenyl group or a substituted or unsubstituted alkynyl group,, R ^66, R ⁶⁷ is each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group,
Represents an aryl group, a substituted aryl group, or a substituted carbonyl group.

Preferred specific examples of the merocyanine dye represented by the general formula [15] include the following.
Some are used as B-1 in the examples described later.

[0065]

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There is also a benzopyran dye represented by the following general formula [16] described in Japanese Patent Application No. 7-164585.

[0067]

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In the general formula [16], R ^{72 to} R ⁷⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. R ^{72 to} R ⁷⁵ may form a ring composed of a nonmetal atom together with the carbon atoms to which they can be respectively bonded.

R ⁷⁶ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group. R ⁷⁷ is a group represented by R ⁷⁶ or —ZR ⁷⁶ , and Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or an arylenedicarbonyl group. R ⁷⁶ and R ⁷⁷ may together form a ring composed of a nonmetallic atom.

A ¹ represents an O atom, an S atom, an NH or an N atom having a substituent.

B ¹ represents an O atom or the following group.

[0072]

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G ¹ and G ² may be the same or different.
Represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group. However, G ¹ and G ² are not simultaneously hydrogen atoms. G ¹ and G ² may form a ring composed of a non-metal atom together with a carbon atom.

Specific examples of the benzopyran dye represented by the general formula [16] include B-2 used in Examples described later.

Of the above-mentioned spectral sensitizing dyes, more preferred are merocyanine dyes described in JP-B-61-9621.
Examples include the merocyanine dyes described in Japanese Patent Application No. 6-269047 and the benzopyran dyes described in Japanese Patent Application No. 7-164584. Benzopyran dyes.

These spectral sensitizing dyes can be used alone or
More than one species may be used in combination.

Next, the amino acid salt represented by the general formula (I) of the component iv) will be described in detail.

In the general formula (I), R ^{1 to} R ³ each represent a hydrogen atom or a hydrocarbon group which may contain an unsaturated bond. Such a hydrocarbon group may have a substituent. Good.

The hydrocarbon group which may have a substituent represented by R ^{1 to} R ³ and may contain an unsaturated bond includes an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. No.

Examples of the alkyl group represented by R ^{1 to} R ³ include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, Examples include a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among these, a straight-chain having 1 to 12 carbon atoms, and 3 to 3 carbon atoms.
Twelve branched and C5 to C10 cyclic alkyl groups are more preferred.

As the substituent bonded to the alkylene group of the substituted alkyl group represented by R ^{1 to} R ³ , a monovalent nonmetallic atomic group other than hydrogen is used, and a preferable example is a halogen atom (—F , -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group,
Alkylthio group, arylthio group, alkyldithio group,
Aryldithio group, amino group, N-alkylamino group,
N, N-dialkylamino group, N-arylamino group,
N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group , N '
An alkylureido group, an N ′, N′-dialkylureido group, an N′-arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N ′
-Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N
-Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N '-Aryl-N-alkylureido groups, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl-N-
Alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group,
Carboxyl group and its conjugate base (hereinafter referred to as carboxylate; also including metal salt), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-
Alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl Group, sulfo group (—SO ₃ H) and its conjugate base group (also referred to as sulfonato group, including metal salt), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N -Dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-
Alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N -Alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (alkyl): a
lkyl = alkyl group, hereinafter the same) and its conjugate base group, N
-Arylsulfonylsulfamoyl group (—SO ₂ NH
SO ₂ (aryl): aryl = aryl group, the same applies hereinafter, and its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alkyl)) and its conjugate base group, N
-Arylsulfonylcarbamoyl group (-CONHSO
₂ (aryl)) and its conjugate base group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—S
i (Oaryl) ₃ ), hydroxysilyl group (-Si (O
H) ₃ ) and its conjugate base group, phosphono group (—PO ₃
H ₂ ) and its conjugated base group (referred to as a phosphonate group; also including a metal salt), a dialkylphosphono group (—PO ₃ (alky
l) _2), diarylphosphono group (-PO ₃ (aryl)
₂ , alkyl aryl phosphono group (-PO ₃ (alkyl)
(Aryl)), a monoalkylphosphono group (—PO ₃ H (al
kyl)) and its conjugate base group (also referred to as alkylphosphonato group, including metal salts), monoarylphosphono group (-
PO ₃ H (aryl) and its conjugate base group (referred to as arylphosphonato group; also includes metal salt), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group, including metal salt) ), dialkylphosphono group _{(-OPO 3 (alkyl) 2)} , diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group (-OPO ₃ (alkyl) (ary
l)), a monoalkylphosphonooxy group (—OPO ₃ H
(Alkyl) and its conjugated base group (referred to as alkylphosphonato group. Including metal salts), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (aryl phosphite Hona preparative group Metal salt), cyano group, nitro group, aryl group, alkenyl group, alkynyl group and the like.

Specific examples of the alkyl group as the substituent in these substituted alkyl groups include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, and xylyl. Group, mesityl group, cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group,
Hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, Carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonate A phenyl group and the like can be mentioned.

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, a 2-chloro-1-ethenyl group, and the like. Group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, phenylethynyl group and the like.

As the above-mentioned acyl group (R ⁸ CO-),
R ⁸ is a hydrogen atom or the above alkyl group, aryl group,
Alkenyl groups and alkynyl groups can be mentioned.

On the other hand, examples of the alkylene group in the substituted alkyl group include those obtained by removing any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to obtain a divalent organic residue. And preferably a C1-C12 linear, C3-C12 branched and C5-C10 cyclic alkylene group. Specific examples of the substituted alkyl group represented by R ^{1 to} R ³ obtained by combining such a substituent with an alkylene group include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, and hydroxy. Methyl group, 2-hydroxyethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyl An oxymethyl group,
Benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group,
Butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl Group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, the following groups,

[0086]

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Phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxy group Propyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p
-Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

The aryl group represented by R ^{1 to} R ³ is derived from a group in which one to three benzene rings form a condensed ring, or a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Groups that can be mentioned. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

The substituted aryl group represented by R ^{1 to} R ³ is ^one in which a substituent is bonded to an aryl group, and a monovalent group other than hydrogen is substituted as a substituent on a ring-forming carbon atom of the aforementioned aryl group. Having a non-metallic atomic group is used.
Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group. Preferred specific examples of such a substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a trifluorophenyl group, a chloromethylphenyl group, Trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, trimethoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group,
Tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetyl Aminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group,
Carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group,
N- (methoxyphenyl) carbamoylphenyl group, N
-Methyl-N- (sulfophenyl) carbamoylphenyl group, methylsulfonylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoyl Phenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group A methylphosphonophenyl group, a methylphosphonatophenyl group, a tolylphosphonophenyl group, a tolylphosphonatophenyl group, an allylphenyl group, a 1-propenylmethylphenyl group, a 2-butenylphenyl group, a 2-methylallylphenyl group, 2-methylpropenylphenyl , 2-propynyl phenyl group, 2-butylphenyl group, 3-butynyl phenyl group,
And a cyanophenyl group.

In the general formula (I), Ar represents an aryl group, which may have a substituent.

As the aryl group and substituted aryl group represented by Ar, those having the same meanings as the aryl group and substituted aryl group described above for R ^{1 to} R ³ can be mentioned.

N = 1 is an integer of 1 to 4.

In the general formula (I), when n = 1, M ⁺ is an alkali metal ion (preferably Li ⁺ , Na ⁺ , K ⁺ , R ⁺
b ⁺ ) or (R ⁴ ) (R ⁵ ) (R ⁶ ) (R ⁷ ) N ⁺ represents a quaternary ammonium ion. When n = 2-4,
M ^{n +} represents a ^{[(R 4) (R 5} ) (R 6) N +] n -r. Here, R ^{4 to} R ⁷ each represent a hydrocarbon group which may contain an unsaturated bond, and may further have a substituent. r
Represents an n-valent hydrocarbon group, and may further have a substituent.

Examples of the hydrocarbon group which may have a substituent represented by R ^{4 to} R ⁷ and may contain an unsaturated bond include an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. Groups.

Such an alkyl group, a substituted alkyl group,
As the aryl group and the substituted aryl group, the above R ¹
To R ³ in said alkyl group, a substituted alkyl group include those aryl groups and substituted aryl groups as defined, preferably a methyl group, an ethyl group, a benzyl group, a phenyl group.

Examples of the n-valent hydrocarbon group represented by r include an alkylene group having 1 to 10 carbon atoms, an alkanetriyl group or an alkanetetrayl group, an arylene group having 6 to 20 carbon atoms, arenetriyl group or Arenetetrayl group and the like, preferably a hexamethylene group,
Phenylene group, pentanetriyl group, pentanetetrayl group and the like.

The following are specific examples of the salt of the amino acid represented by the general formula (I), but the present invention is not limited thereto.

[0098]

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[0099]

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[0100]

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[0101]

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Among the salts of the amino acid represented by the general formula (I), those having, for example, n = 1 are generally prepared by converting the amino acid with an organic alkali or an inorganic alkali according to the scheme shown in the following method 1, for example. It can be easily synthesized by neutralization.

[0103]

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[0104] an organic alkali referred to herein, the inorganic alkali M ⁺ OH ^- it is that of, Ar in the scheme of Method 1,
R ^{1 to} R ³ and M ⁺ are the same as those in the general formula (I).

As the starting amino acid, for example, a commercially available amino acid may be used or published by Maruzen, edited by The Chemical Society of Japan, “New Experimental Chemistry Course” (Synthesis and Reaction of Organic Compounds [III]) 1672 Pp. 1692 (197
It can be easily synthesized by the method for synthesizing various α-amino acids described in 8) or a method analogous thereto.

Incidentally, those having n = 2 to 4 can also be synthesized according to the above.

The obtained compound can be identified by a mass spectrum, ¹ H nuclear magnetic resonance spectrum ( ¹ H NMR) or the like.

An example of synthesis will be described below.

Synthesis Example 1 Synthesis of Compound I-1 Commercially available N-phenylglycine (7.56 g) and methanol (100 ml) were placed in a flask, and 1.0 M NaOH was added.
An aqueous solution (50.0 ml) was added dropwise, and after 30 minutes, the solvent was removed under reduced pressure. The concentrate was put in acetone (200 ml) and stirred for 1 hour to obtain white crystals. The white crystals were collected by filtration and dried in vacuo to give the desired product I-1 (6.10 g) in a yield of 70.
%. The structure was confirmed by ¹ HNMR and mass spectrum.

Synthesis Example 2 Synthesis of Compound I-7 Commercially available N-phenylglycine (7.56 g) and methanol (100 ml) were charged into a flask, and a methanol solution of tetrabutylammonium hydroxide adjusted to 1.0 M ( 50 ml) was added dropwise. After 30 minutes, the solvent was removed under reduced pressure. The concentrate was added to ethyl acidate (200 ml) and stirred for 1 hour to obtain white crystals. The white crystals were collected by filtration and dried in vacuo to give the desired product I-7 (11.8 g) in a yield of 6
Obtained at 0%. The structure was confirmed by ¹ HNMR and mass spectrum.

Synthesis Example 3 Synthesis of Compound I-16 Commercially available hydroxyethylaniline (13.7 g), methyl chloroacetate (10.9 g), methanol (100 ml)
Was placed in a flask, and a 28% methanol solution of NaOMe (19.3 g) was slowly added dropwise, and the mixture was stirred for 3 hours after the addition. Thereafter, 200 ml of water was added, extracted with ethyl acetate, dried over Na ₂ SO ₄ , and the ethyl acetate was removed under reduced pressure. Subsequently, a 1.0 M aqueous KOH solution (50 ml) was added, followed by stirring. After stirring for 1 hour, the solvent was removed under reduced pressure, and acetone (20
0 ml) and stirred for 1 hour to give a viscous oil. Take this out and dry it in a vacuum,
The target product I-16 (12.1 g) was obtained in a yield of 52%. The structure was confirmed by ¹ HNMR and mass spectrum.

The compounds I-1 and I- in the present invention
Compounds represented by the general formula (I) other than 7 and I-16 can be easily synthesized by the same method.

The amino acid salt represented by the general formula (I) used in the photopolymerizable composition of the present invention may be used alone or
More than one species may be used in combination.

The compound of the general formula (I) is used in an amount of usually 0.05 to 50% by weight, preferably 0.5 to 35% by weight, more preferably 1 to 50% by weight, based on all components of the photopolymerizable composition.
An amount of 25% by weight is used. If the amount is too large, poor coating formation (crack) tends to occur, and if too small, poor curing tends to occur, which is not preferable.

Further, to the photopolymerizable composition of the present invention, a known compound having an effect of further improving sensitivity or suppressing polymerization inhibition by oxygen may be added as a co-sensitizer.

Examples of such co-sensitizers include amines, for example, “Journal of Polymer Socie” by MRSander et al.
ty ", Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-2
0189, JP-A-51-82102, JP-A-52-102
No. 134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 3382
No. 5, and the like, and specific examples thereof include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

Other examples of the co-sensitizer include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, and JP-A-5-142772; No. 75643, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. Is mentioned.

Another example is disclosed in JP-B-48-429.
No. 65, organometallic compounds (eg, tributyltin acetate, etc.), hydrogen donors described in JP-B-55-34414, sulfur compounds described in JP-A-5-91089 (eg,
Trithiane, etc.), phosphorus compounds described in Japanese Patent Application No. 5-32147 (diethyl phosphite, etc.), and Japanese Patent Application No. 6-1916.
Si-H and Ge-H compounds described in No. 05 are exemplified.

The components ii) and iii) in the composition according to the present invention.
And the amount of iv) is 0.01 to 6 with respect to the total amount of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer as a binder which is optionally added.
0 wt%, more preferably in the range of 1 to 30 wt%.

The ratio of component iv) to component iii) used in the present invention is based on 1 part by weight of the amino acid salt of component iv),
Is suitably used in an amount of 0.01 to 50 parts by weight, more preferably 0.02 to 20 parts by weight, and most preferably 0.05 to 10 parts by weight. Ingredients used in the present invention
The ratio of iv) to component ii) is suitably from 0.01 to 50 parts by weight, more preferably from 0.02 to 20 parts by weight of component ii) per 1 part by weight of the salt of the amino acid of component iv). Parts, most preferably 0.05 to 10 parts by weight.

When the above-mentioned co-sensitizer is used, component i
It is appropriate to use 0.01 to 50 parts by weight, more preferably 0.02 parts by weight, per part by weight of the salt of the amino acid of v).
-20 parts by weight, most preferably 0.05-10 parts by weight.

The photopolymerizable composition of the present invention preferably contains a linear organic high molecular polymer as a binder. Such a “linear organic high molecular polymer” includes
Any linear organic high molecular polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. Preferably, a water-soluble or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic polymer is appropriately selected and used depending on whether water, weakly alkaline water or an organic solvent is used as a developer as well as a film-forming agent of the photopolymerizable composition. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such linear organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, for example, JP-A-59-44615 and JP-B-54-34327.
No., JP-B-58-12577, JP-B-54-2595
7, JP-A-54-92723, JP-A-59-538.
36, JP-A-59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, There are esterified maleic acid copolymers and the like. 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 / Other addition-polymerizable vinyl monomers] copolymers are suitable, if necessary. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These linear organic high molecular polymers can be incorporated in any amount into the entire 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 30 to 85
% By weight. 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 order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond which can be polymerized during the production or storage of the photosensitive composition in addition to the above basic components, It is desirable to add a small amount of a 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, and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% by weight 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 added amount of the higher fatty acid derivative is preferably about 0.5% by weight to about 10% by weight of the whole composition. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. The amount of the dye or pigment added is preferably about 0.5% to about 5% by weight of the total composition. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

The photopolymerizable composition of the present invention is usually used after being coated on a support. When the photopolymerizable composition of the present invention is coated on a support, it is used after being dissolved in various organic solvents. 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 ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene 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, methyl lactic acid And ethyl. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50% by weight. The coating amount is about 0.1 g / m ² to about 10 g by weight after drying.
A range of g / m ² is appropriate. More preferably 0.5 to 5 g /
a m ^2.

A dimensionally stable plate is used as the support. Dimensionally stable plate-like objects include paper,
Plastics (eg polyethylene, polypropylene,
Paper laminated with polystyrene, etc., for example, aluminum (including aluminum alloy), zinc,
Plates of metal such as copper, further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate,
Examples include plastic films such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and paper or plastic films on which the above-described 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 a metal, particularly aluminum, a surface treatment such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodic oxidation. Is preferably performed.

Further, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate 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 a non-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 in which two or more kinds are combined. It is carried out by passing a current through an aluminum plate as an anode.

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

Further, a surface obtained by combining the electrolytic grains disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503 with the above-described anodic oxidation treatment and sodium silicate treatment. Processing is also useful.

[0131] It is also preferable to sequentially perform mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893.

Further, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, and water-soluble metal salts (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to adhere the photosensitive layer. This is performed for the purpose of improving the performance.

On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, in particular, having a saponification degree of 95, in order to prevent the polymerization inhibition effect by 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. For the method of applying such a protective layer, see, for example, U.S. Pat. No. 3,458,311;
No. 49729.

Further, the photopolymerizable composition of the present invention can be used for a usual photopolymerization reaction. 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.

Since the photopolymerizable composition of the present invention has high sensitivity and is sensitive to visible light, it can be particularly advantageously used for an image forming system using microcapsules.

For use in an image forming system using microcapsules, see, for example, JP-A-57-197538.
No. 61-130945, No. 58-88739,
No. 58-88740, EP 223,587 A1
References can be referred to. In this image forming method, for example, a photopolymerization initiator composition comprising an ethylenic vinyl compound and a photopolymerization initiator and a microcapsule containing a dye precursor are coated on a support, and the photosensitive sheet is exposed by imagewise exposure. After curing some of the microcapsules,
By overlapping the developer sheet and pressing the entire surface, the microcapsules in the unexposed areas are destroyed, and the color image forming substance (for example, a dye precursor) is transferred to an image receiving element (for example, a developer layer) to form a color. is there.

The photosensitive material using the photopolymerizable composition of the present invention is subjected to image exposure, and the unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. Preferred developers when these photopolymerizable compositions are used 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. Such an alkali agent has a solution concentration of 0.1 to
It is added so as to be 10% by weight, preferably 0.5 to 5% by weight.

Also, such an alkaline aqueous solution includes:
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, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. Further, Japanese Unexamined Patent Publication No.
No. 0-26601, No. 58-54341, Tokubo Sho56
The developing solutions described in JP-A-39464 and JP-A-56-42860 are also excellent.

The actinic ray used in the present invention may be in a wide range from ultraviolet light to visible light.

[0141]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

Example 1 An aluminum plate having a thickness of 0.30 mm and a nylon brush
The surface was sand-grained with an aqueous suspension of pumicestone of 00 mesh, and then thoroughly washed with water. After etching by immersion in 10% by weight sodium hydroxide at 70 ° C. for 60 seconds, the plate was washed with running water, neutralized and washed with 20% by weight nitric acid, and then washed with water. This was converted to 160% in a 1% by weight aqueous nitric acid solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
Electrolytic surface-roughening treatment was performed with an amount of electricity at the anode of Coulomb / dm ² . When the surface roughness was measured, it was 0.6 μm ( _Ra display). Subsequently, after immersing in a 30% by weight aqueous sulfuric acid solution and desmutting at 55 ° C. for 2 minutes, the thickness of the anodic oxide film was increased to 2.7 g / m ² at a current density of 2 A / dm ² in a 20% by weight aqueous sulfuric acid solution. Anodizing treatment was performed for 2 minutes.

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

[Composition] Pentaerythritol tetraacrylate 2.0 g Allyl methacrylate / methacrylic acid copolymer 2.0 g (copolymer molar ratio 85/15) Component ii) Xg (Tables 1 and 2) Component iii) Yg (Table 1, 2) Component iv) Zg (Tables 1 and 2) 20 g of methyl ethyl ketone 20 g of propylene glycol monomethyl ether acetate 20 g of a 3% by weight aqueous solution of polyvinyl alcohol (a saponification degree of 98 mol% and a polymerization degree of 1000) was dried and applied onto the photosensitive layer. Coating was performed so that the weight was 2 g / m ^2, and the coating was dried at 100 ° C. for 2 minutes to prepare a sample of a photosensitive material (Tables 1 and 2).
The following photosensitivity test was performed on a sample of this light-sensitive material.

In the photosensitivity test, each monochromatic light of visible light and Ar ⁺ laser light (wavelength = 488 nm) was used. Visible light was obtained through a kenko optical filter BP-49 using a tungsten lamp as a light source. Sensitivity was measured using a Fuji PS step guide (a step tablet having a transmission optical density of 0.05 at the first stage and increasing by 0.15 to 15 stages sequentially, manufactured by Fuji Photo Film Co., Ltd.). Sensitivity is determined by the P at the time of exposure such that the exposure energy at the photosensitive material film surface is 0.25 mJ.
It is indicated by the number of clear steps in the S step guide. The higher the value of the number of stages, the higher the sensitivity.

The development was carried out by immersion in the following developer at 25 ° C. for 1 minute.

[0147] [developer] 1K potassium silicate 30g potassium hydroxide _{15g C 12 H 25 -C 6 H} 4 -O-C 6 H 4 -SO 3 Na 3g water 1000g was also subjected to a storage stability test at the same time . In the model test of storage stability, the unexposed photosensitive material (coated plate) prepared as described above was forcibly aged (left at a temperature of 60 ° C. and a humidity of 75% RH for 3 days), and then exposed and developed in the same manner as described above. The sensitivity was evaluated by examining the sensitivity, and the evaluation was made based on the difference in sensitivity (△ clear stage number) from the case where such forced aging was not performed. The smaller the number of clear stages is, the better the storage stability is, and the better the number of clear stages is 0.5 or less in production.

Tables 1 and 2 show the results. The structures of compounds A-1, B-1, C-1 to C-7, and X-1 in Tables 1 and 2 will be described later.

[0149]

[Table 1]

[0150]

[Table 2]

As is clear from Tables 1 and 2, high sensitivity and excellent storage stability can be obtained by using the amino acid salt represented by the general formula (I) of the present invention.

Example 2 A sample of a photosensitive material was prepared in the same manner as in Example 1 except that the photopolymerizable composition was changed to the following composition in the sample of the photosensitive material of Example 1 (Table 3). The test was performed. However, the same visible light as in Example 1 and each monochromatic light of YAG-SHG laser light (wavelength = 532 nm) were used for the sensitivity measurement.

[Composition] Pentaerythritol tetraacrylate 2.0 g Ethyl methacrylate / allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 20/60/20) 2.0 g Component ii) Xg (Table 3) Component iii ) Yg (Table 3) Component iv) Zg (Table 3) Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g The results are shown in Table 3.

[0154]

[Table 3]

As is clear from Table 3, high sensitivity and excellent storage stability can be obtained by using the salt of the amino acid represented by the general formula (I) of the present invention.

Compounds A-1 and B- in Tables 1 to 3
The structures of 1, B-2, C-1 to C-10, and X-1 are as shown below.

[0157]

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[0158]

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[0159]

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[0160]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet to visible light and has excellent storage stability. Therefore, the photosensitive material obtained by using this has high sensitivity and good storage stability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 502 G03F 7/027 502 7/031 7/031

Claims (1)

[Claims] 1. A compound having at least i) an addition-polymerizable ethylenically unsaturated bond; ii) a titanocene compound;
A photopolymerizable composition comprising: i) a merocyanine dye or a benzopyran dye as a spectral sensitizing dye; and iv) a salt of an amino acid represented by the following general formula (I). Embedded image [In the general formula (I), R ¹ , R ² and R ³ each represent a hydrogen atom or a hydrocarbon group which may contain an unsaturated bond. Ar represents an aryl group. n is an integer of 1 to 4. When n = 1, M ⁺ represents an alkali metal ion or a quaternary ammonium ion represented by (R ⁴ ) (R ⁵ ) (R ⁶ ) (R ⁷ ) N ⁺ . When n = 2, 3 or 4, M
^{n +} represents a ^{[(R 4) (R 5} ) (R 6) N +] n -r. Here, R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a hydrocarbon group which may contain an unsaturated bond, and r represents an n-valent hydrocarbon group. ]