JP2000250211A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable composition capable of giving a photosensitive planographic printing plate having high sensitivity and excellent in mechanical strength by incorporating an addition polymerizable compound having a urethane bond group and an alkylene oxide group having an ethylenically unsaturated double bond group and a photopolymerization initiator. SOLUTION: The photopolymerizable composition contains an addition polymerizable compound having a urethane bond group and an alkylene oxide group having an ethylenically unsaturated double bond group and a photopolymerization initiator. The photopolymerization initiator may be a titanocene compound and the addition polymerizable compound may be a reaction product of an isocyanate compound and an alcohol of formula I, wherein R1-R12 are each H, 1-10C alkyl or phenyl, Y is H or a group of formula II, X is alkyl or a group of the formula II or the like, R13 is H or methyl and (n) and (a) to (f) are each 0 or a positive integer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition,
And a photosensitive lithographic printing plate using the same. In particular, it relates to a photosensitive lithographic printing plate that is highly sensitive to light in the visible light range and has excellent printing durability and a photopolymerizable composition suitable for the photosensitive layer. The present invention relates to a lithographic printing plate and a photopolymerizable composition suitable for the photosensitive layer.

[0002]

2. Description of the Related Art Conventionally, photopolymerizable compositions and negative-working photosensitive lithographic printing plates using the same have been widely known and have various photosensitive layers. In order to prepare such a photosensitive lithographic printing plate, it is common to place a transparent negative film original (lith film) on these photosensitive lithographic printing plates and to perform image exposure using ultraviolet light or the like. Therefore, the work was very time-consuming. In recent years, with the development of image forming technology, a photopolymer having high photosensitivity to light in the visible region has been demanded. It is a photosensitive material suitable for, for example, non-contact type projection exposure plate making and visible light laser plate making, and a photopolymer system is the most sensitive and promising. As the visible light laser, an Ar laser of 488, 514.5 nm is used.
Light, second harmonic light of a semiconductor laser (SHG-LD, 3
50-600 nm), 532 of SHG-YAG laser
nm light is promising. Therefore, by using a kind of high-sensitivity photopolymerizable photosensitive layer in the photosensitive layer, a laser beam with a narrow beam is scanned over the plate surface, and character documents, image documents, etc. are formed directly on the plate surface, Plate making can be performed directly without using a manuscript. For example, JP-A-9-
No. 143142 has attempted to use a photopolymerizable monomer having a urethane compound. However,
With the technology described in Japanese Patent Application Laid-Open No. 9-143142, sufficient printing durability cannot be obtained.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photopolymerizable composition which can be used as a photosensitive lithographic printing plate having high sensitivity and excellent mechanical strength.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that the following photopolymerizable compositions (1) to (6) can be used without deteriorating other properties. A photosensitive lithographic printing plate having high sensitivity and excellent mechanical strength was obtained. That is, the present invention is as follows. (1) a photopolymerizable composition comprising: i) an addition-polymerizable compound having an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bond group; and ii) a photopolymerization initiator. object. (2) The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator is a titanocene compound. (3) The photopolymerizable composition according to claim 1, wherein the addition-polymerizable compound is a reaction product of an isocyanate compound and an alcohol represented by the following general formula (I).

[0005]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group;
Is a hydrogen atom or a group represented by the following general formula (II)

[0007]

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And at least one of them is a hydrogen atom, and X is an alkyl group, an aryl group, an alkoxy group, -OH or a group represented by the following general formula (II)

[0009]

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Wherein at least one (more preferably at least two) of all X and Y is the above-mentioned general formula (I)
A group represented by I), wherein n, a, b, c, d, e, f
Represents 0 or a positive number)

(4) The photopolymerizable composition according to claim 1, which contains an alkali water-soluble polymer having an acid in at least one of a main chain and a side chain. (5) The photopolymerizable composition according to (4), wherein the alkali water-soluble polymer is a copolymer of at least one of an acrylic ester and a methacrylic ester. (6) The photopolymerizable composition according to (4), wherein the alkali water-soluble polymer is a polyurethane resin having a carboxyl group of 0.4 meq / g or more.

It is considered that the photosensitive composition of the present invention is provided with the tonicity of urethane bonds and the flexibility of alkylene oxide bonds of the addition polymerizable compound contained therein. As a result, when the photosensitive layer of a photosensitive lithographic printing plate is used, the compatibility with the binder is good due to the flexibility, and the mechanical strength is excellent and the sensitivity is high due to the tonicity. It is assumed that a lithographic printing plate can be obtained.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Among the components contained in the photopolymerizable composition, compounds capable of addition polymerization, which are features of the present invention, include an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bond group. The reaction product is not particularly limited as long as it has the following. Specific examples thereof include a reaction product of an isocyanate compound and an alcohol represented by the following general formula (I).

[0014]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group;
Is a hydrogen atom or a group represented by the following general formula (II)

[0016]

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And at least one of them is a hydrogen atom, and X is an alkyl group, an aryl group, an alkoxy group, -OH or a group represented by the following general formula (II).

[0018]

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Wherein at least one (more preferably at least two) of all X and Y is represented by the general formula (I)
A group represented by I), wherein n, a, b, c, d, e, f
Represents 0 or a positive number)

The following are specific examples of the isocyanate compound.

[0021]

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[0022]

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[0023]

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[0024]

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Specific examples of the alcohol represented by the general formula (I) include the following.

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The amount of i) the addition-polymerizable compound having an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bonding group depends on the total amount of the components of the photopolymerizable composition of the present invention. 5 to 95% by weight (hereinafter abbreviated as%), preferably 10 to 90%.

In addition to the above "i) an addition-polymerizable compound having an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bond group," The compound having a heavy bond group can be arbitrarily selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated double bond groups. For example, those having 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 unsaturated carboxylic acids (eg, acrylic acid,
Esters of methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with aliphatic 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 pentaacrylate, dipentaerythritol hexaacrylate, sorbitol Triacry Over DOO, sorbitol tetraacrylate, sorbitol pentaacrylate, 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, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate , Bis [p- (3--methacryloxy-2-hydroxypropoxy) 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, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. And sorbitol tetritaconate.

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. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, 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 methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Another example is JP-B-48-417.
08 polyisocyanate compound having two or more isocyanate groups in one molecule described in
A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl group-containing vinyl monomer represented by the following general formula (A) is added is exemplified. CH ₂ = C (Q ¹ ) COOCH ₂ CH (Q ² ) OH (A) (However, Q ¹ and Q ² independently represent H or CH _3. )

Also, urethane acrylates 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. Furthermore, Japan Adhesion Association Journal Vol.20, No.7, 300-308
Those introduced as photocurable monomers and oligomers on page (1984) can also be used. Incidentally, in addition to these i) an addition-polymerizable compound having an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bonding group, an addition-polymerizable ethylenically unsaturated double bond which may be contained The amount of the compound having a bonding group to be used is 5 to 90% by weight (hereinafter abbreviated as%), preferably 1 based on all components of the photopolymerizable composition of the present invention.
0 to 80%.

Component ii) As the photopolymerization initiator, various photopolymerization initiators known in patents and literatures, or a combination system of two or more photopolymerization initiators (photopolymerization, depending on the wavelength of the light source used) Initiation system) can be appropriately selected and used. In the present invention, a photopolymerization initiator used alone and a system using two or more photopolymerization initiators are collectively referred to simply as a photopolymerization initiator or a photoinitiator. For example, 400
When light near nm is used as a light source, benzyl, benzoyl ether, Michler's ketone, anthraquinone,
Thioxanthone, acridine, phenazine, benzophenone and the like are widely used.

In addition, visible light of 400 nm or more, an Ar laser, a second harmonic of a semiconductor laser, SHG-YAG
When a laser is used as a light source, various photoinitiators have been proposed, for example, certain photoreducing dyes described in U.S. Pat. No. 2,850,445, for example, rose bengal, eosin, erythrosine. Or a combination system of a dye and an initiator, for example, a complex initiation system of a dye and an amine (Japanese Patent Publication No. 44-20189), and a combination system of a hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. -37377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528, JP-A-54-15529).
No. 2), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a cyclic triazine and a merocyanine dye (JP-A-54-151024),
A system of ketocoumarin and an activator (JP-A-52-11268)
No. 1, JP-A-58-15503), biimidazole,
Styrene derivative, thiol system (JP-A-59-1402)
No. 03), a system of an organic peroxide and a dye (JP-A-59-15)
04, JP-A-59-140203, JP-A-59-1
No. 89340, JP-A-62-174203, JP-B-6-6
No. 2,1641, U.S. Pat. No. 4,766,055),
System of dye and active halogen compound (JP-A-63-1781)
No. 05, JP-A-63-258903, JP-A-2-63
No. 054), a system of a dye and a borate compound (JP-A-6
2-143044, JP-A-62-150242, JP-A-64-13140, JP-A-64-13141,
JP-A-64-13142, JP-A-64-13143
JP-A-64-13144, JP-A-64-1704
8, JP-A-1-229003, JP-A-1-2983
No. 48, JP-A-1-138204, etc., and a system of a dye having a rhodanine ring and a radical generator (JP-A No. 2-17)
No. 9643, JP-A-2-244050), a system of titanocene and a 3-ketocoumarin dye (JP-A-63-22111).
No. 0), a system comprising a combination of titanocene and a xanthene dye, and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group (JP-A-4-221958).
JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061),
A dye system having a titanocene and a benzopyran ring (Japanese Patent Application No. 7-164585) can be used.

Preferred photoinitiators are combinations using cyanine, merocyanine, xanthene, ketocoumarin and benzopyran dyes as dyes and titanocene compounds and triazine compounds as initiators. Preferable examples of the cyanine dye include those having the following structures, but are not particularly limited.

[0036]

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(Wherein, Z ¹ and Z ² represent a group of non-metallic atoms necessary for forming a benzimidazole or naphthoimidazole ring and may be the same or different.
¹ , R ² , R ³ and R ⁴ each represent an optionally substituted alkyl group. X ⁻ represents a counter anion, and n is 0 or 1. )

Table 1 below shows specific examples of cyanine dyes.

[0039]

[Table 1]

The merocyanine dye preferably has the following structure, but is not particularly limited.

[0041]

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[0042] (wherein, Z ^1, .R ¹ Z ² are each represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic 5-membered ring and / or 6-membered ring usually used in cyanine dyes, R ²
Each represents an alkyl group. Q ¹ and Q ² combine to form a 4-thiazolidinone ring, a 5-thiazolidinone ring, a 4-imidazolidinone ring, a 4-oxazolidinone ring, a 5-oxazolidinone ring, a 5-imidazolidinone ring or a 4-dithiolanone ring. Represents the group of atoms required to perform L ¹ , L ² , L ³ , L ⁴ and L ⁵ each represent a methine group. m represents 1 or 2. i and h each represent 0 or 1. l represents 1 or 2. j and k represent 0, 1, 2 or 3, respectively. X ^- represents a counter anion. )

[0043]

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(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group Or A represents an aralkyl group, wherein A is an oxygen atom, a sulfur atom,
Represents a selenium atom, tellurium atom, alkyl or aryl substituted nitrogen atom, or dialkyl substituted carbon atom. X represents a nonmetallic atom group necessary to form a nitrogen-containing hetero five-membered ring. Y represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z represents 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; To form a ring. )

Specific examples of the merocyanine dyes are shown below.

[0046]

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[0047]

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Examples of xanthene dyes include rhodamine B, rhodamine 6G, ethyl eosin, alcohol-soluble eosin, pyronin Y and pyronin B.

The ketocoumarin dyes preferably include those having the following structures, but are not particularly limited.

[0050]

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(Wherein R ¹ , R ² and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ³ and R ⁴ each represent an alkyl group, at least one of which has 4 carbon atoms. Represents up to 16 alkyl groups, R ⁶ is a hydrogen atom, an alkyl group, an alkoxy group,
R ⁷ represents an acyl group, a cyano group, a carboxyl group, or an ester derivative or an amide derivative thereof;
Is a heterocyclic residue having a total number of carbon atoms of 3 to 17 -CO-R
It represents ^8, R ² and R ^3, R ⁴ and R ⁵ may be bonded to each other to form a ring. Here, R ⁸ is a group shown below. )

[0052]

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Specific examples of the ketocoumarin-based dye are shown below.

[0054]

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The benzopyran-based dyes preferably include those having the following structures, but are not particularly limited.

[0056]

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[0057] (wherein, R ³ to R ⁵ are independently of each other, represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. Further, R ³ ~
R ⁵ may form a ring consisting of a non-metallic atom together with the carbon atoms to which they can each be attached. R ⁷ 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 ⁵ is a radical or -Z-R ⁷ is represented by R ^7, Z represents a carbonyl group, a sulfonyl group, a sulfinyl group or arylene dicarbonyl group. R ⁷ and R ⁸ may together form a ring composed of a nonmetallic atom.
A represents O, S, NH or a nitrogen atom having a substituent. B is a group

[0058]

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And G ₁ and G ₂ may be the same or different and each 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. Group, arylsulfonyl group or 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. )

The following are specific examples of the benzopyran dye.

[0061]

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Examples of the triazine compound as a photopolymerization initiator include the following compounds.

[0063]

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Wherein Hal represents a halogen atom.
Y ² is _{-C (Hal) 3, -NH 2} , -NHR 21, -NR
²¹ ₂ , represents -OR ²¹ . Here, R ²¹ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.
R ²⁰ represents —C (Hal) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ).

Specific examples of the triazine compound are shown below.

[0066]

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Preferred photopolymerization initiators include titanocene compounds. Examples of titanocene compounds include, for example, JP-A-59-152396 and JP-A-61-61396.
Known compounds described in JP-A-151197 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-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-tetra Fluorophenyl-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 are listed. be able to.

The content of these photopolymerization initiators 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 in the present invention is 0.01% based on the total of the compound having a photopolymerizable ethylenically unsaturated double bond group and the organic polymer described below which is added as necessary. Preferably, it is used in the range of from 70% by weight to 70% by weight. More preferably, 1% to 50% by weight gives good results.

Further, an auxiliary such as an amine compound or a thiol compound may be added to the initiator. Particularly preferred are an amine compound and an amino acid represented by the following general formula.

[0071]

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(In the formula, R ^{8 to} R ¹⁸ each represent an alkyl group.)

[0073]

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(Wherein, R ^{19 to} R ²² represent alkyl or alkoxy, R ²¹ and R ²² may form a ring, and R ²³ represents a heterocyclic ring or alkylthio).

[0075]

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(Wherein R ²⁸ and R ²⁹ are the same or different,
It represents a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a heterocyclic group. R ²⁶ , R ²⁷
Are the same or different, a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group,
Represents a substituted thio group. R ²⁶ and R ²⁷ are bonded to each other to form a ring, and —O—, —NR ²⁴ —, —O—CO—, and —
NH-CO -, - S-, and / or, -SO ₂ - represents an alkylene group having from 2 carbon atoms which may contain a linking backbone of the ring 8. R ²⁴ and R ^{25 each} represent a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. )

Further, dialkyl benzoates such as ethyl p-diethylaminobenzoate, bisaminobenzophenones such as 4,4'-bis (dimethylamino) benzophenone, and bisaminobenzyls such as 4,4'-bis (diethylamino) benzyl ,

[0078]

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N-phenylgulin and N-phenylglycine sodium salt are exemplified.

The photopolymerizable composition of the present invention comprises the aforementioned component i) an addition-polymerizable compound having an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bonding group, and component ii) photopolymerization initiation In addition to the ingredients, if necessary, ingredients
and iii) containing a binder. Component ii
As the binder of i), an organic high molecular polymer can be mentioned, and such an organic high molecular polymer is an organic high molecular polymer that is compatible with a photopolymerizable ethylenically unsaturated compound. Any may be used as long as there is. Preferably, an organic high molecular polymer which is soluble or swellable in water or weakly alkaline water which enables water development or weakly alkaline water development is selected. The organic high molecular polymer is selected and used not only as a film-forming agent of the composition but also as a developer for water, weakly alkaline water or an organic solvent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such organic high-molecular polymers include addition polymers having a carboxylic acid group in a side chain, for example, JP-A-59-1984.
44615, JP-B-54-34327, JP-B-58
-12577, JP-B-54-25957, JP-A-5
4-92723, JP-A-59-53836, JP-A-59-71048, that is,
Examples include methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer.

In these carboxylic acid group-containing copolymers, various (meth) acrylic acid esterified products, that is, methyl (meth) acrylate, Ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyacrylate, etc., and various (meth) acrylamide compounds, that is, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) Acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide,

[0082]

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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 / optionally And other addition-polymerizable vinyl monomers] copolymers.
In addition, polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, an alcohol-soluble polyamide, a polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. Further, a polyurethane resin can be used.

Of these, particularly preferred are (meth) acrylic acid ester copolymers and carboxyl groups having a content of 0.1%.
It is a polyurethane resin containing 4 meq / g or more. Examples of such a polyurethane resin include a diisocyanate compound represented by the following formula (1) and formulas (2), (3),
A structural unit represented by a reaction product of at least one of the diol compounds (4) and / or a structural unit derived from a compound obtained by ring opening tetracarboxylic dianhydride with a diol compound is defined as a basic skeleton. Polyurethane resin.

[0086]

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[0087] (wherein, L ₈ substituent shows also be a divalent aliphatic or aromatic hydrocarbon group optionally having. If necessary, other functional group which does not react with the isocyanate group in L ₈ For example, it may have an ester, urethane, amide, or ureido group.

R ₁ is a hydrogen atom, a substituent (eg, cyano, nitro, halogen atom (—F, —Cl, —Br, —
_{I), - CONH 2, -COOR} 113, -OR 113, -N
HCONHR ₁₁₃ , -NHCOOR ₁₁₃ , -NHCOR
₁₁₃ , —OCONHR ₁₁₃ (where R ₁₁₃ has 1 to 1 carbon atoms)
10 represents an alkyl group and an aralkyl group having 7 to 15 carbon atoms. )). A) alkyl, aralkyl, aryl, alkoxy, aryloxy groups, and preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms.
L ₁₀ , L ₁₁ , and L ₁₂ may be the same or different, and include a single bond, a substituent (eg, alkyl, aralkyl,
Aryl, alkoxy and halogeno groups are preferred. )
A divalent aliphatic or aromatic hydrocarbon group which may have It preferably represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. If necessary, L ₁₀ , L ₁₁ , and L ₁₂ may have other functional groups that do not react with an isocyanate group, such as carbonyl, ester, urethane, amide, ureide, and ether groups. Note that two or three of R ₁ , L ₁₀ , L ₁₁ , and L ₁₂ may form a ring. Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, and preferably has 6 carbon atoms.
Represents up to 15 aromatic groups. )

A) Diisocyanate Compound Specific examples of the diisocyanate compound represented by the formula (1) include the following. That is, 2,4
-Tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5- Aromatic diisocyanate compounds such as naphthylene diisocyanate, 3,3'-dimethylhiphenyl-4,4'-diisocyanate;
Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc .; isophorone diisocyanate, 4,4 '
Alicyclic diisocyanate compounds such as methylene bis (cyclohexyl isocyanate), methylcyclohexacy-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane and the like;
Examples thereof include a diisocyanate compound which is a reaction product of a diol and a diisocyanate, such as an adduct of 1 mol of 3-butylene glycol and 2 mol of tolylene diisocyanate.

B) Carboxyl-Containing Diol Compound The carboxyl-containing diol compound represented by the formula (2), (3) or (4) specifically includes the following compounds. That is, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, Bis (hydroxymethyl) acetic acid, bis (4-
(Hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl ) -3
-Carboxy-propionamide and the like.

In the present invention, preferred tetracarboxylic dianhydrides used for synthesizing a polyurethane resin include those represented by formulas (5), (6) and (7).

[0092]

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(Wherein L ₂₁ is a single bond, a divalent aliphatic group which may have a substituent (for example, preferably an alkyl, aralkyl, aryl, alkoxy, halogeno, ester, or amide group) or Aromatic hydrocarbon group, -CO
—, —SO—, —SO ₂ —, —O— or —S—. Preferably a single bond, a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, -CO -, - SO ₂ -, - O-or -
S- is shown. R ₂ and R ₃ may be the same or different,
It represents a hydrogen atom, an alkyl, an aralkyl, an aryl, an alkoxy, or a halogeno group. Preferably, a hydrogen atom,
It represents an alkyl having 1 to 8 carbons, an aryl having 6 to 15 carbons, an alkoxy having 1 to 8 carbons, or a halogeno group. Also, _{two of} L ₂₁ , R ₂ and R ₃ may combine to form a ring. R ₄ and R ₅ may be the same or different and represent a hydrogen atom, an alkyl, an aralkyl, an aryl or a halogeno group. Preferably a hydrogen atom, carbon number 1-8
Alkyl or an aryl group having 6 to 15 carbon atoms. Also, two of L ₂₁ , R ₄ and R ₅ may combine to form a ring. L ₂₂ and L ₂₃ may be the same or different and represent a single bond, a double bond, or a divalent aliphatic hydrocarbon group. It preferably represents a single bond, a double bond, or a methylene group. A represents a mononuclear or polynuclear aromatic ring. It preferably represents an aromatic ring having 6 to 18 carbon atoms. )

The compounds represented by the formulas (5), (6) and (7) specifically include the following compounds. That is, pyromellitic dianhydride, 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride,
3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride,
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ′-[3,3 ′-(alkylphosphoryldiphenylene) ) -Bis (iminocarbonyl)]
Examples include diphthalic dianhydride, adducts of hydroquinone diacetate and trimellitic anhydride.

A method for introducing a structural unit derived from a compound obtained by ring-opening these tetracarboxylic dianhydrides with a diol compound into a polyurethane resin includes, for example, the following method. a) A method in which an alcohol-terminated compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound is reacted with a diisocyanate compound. b) A method in which a diisocyanate compound is reacted under the condition of an excess of a diol compound to react an alcohol-terminated urethane compound obtained with tetracarboxylic dianhydride.

The diol compound used at this time specifically includes the following compounds. That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6
-Hexanediol, 2-butene-1,4-diol,
2,2,4-trimethyl-1,3-pentanediol,
1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A,
A propylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol F, a propylene oxide adduct of bisphenol F, an ethylene oxide adduct of hydrogenated bisphenol A, and a propene oxide adduct of hydrogenated bisphenol A.

C) Other diol compounds The polyurethane resin used in the present invention is more preferably represented by a reaction product with at least one of a polyether diol compound, a polyester diol compound and a polycarbonate diol compound. It is a polyurethane resin having a structure. Examples of the polyether diol compound include compounds represented by formulas (A), (B), (C), (D),
The compound represented by (E) and a random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at a terminal are exemplified.

[0098]

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(Wherein R ₆ is a hydrogen atom or a methyl group,
X represents the following groups. )

[0100]

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A, b, c, d, e, f, and g each represent 2
The following integers are shown. Preferably it is an integer of 2 to 100.

Specific examples of the polyether diol compounds represented by the formulas (A) and (B) include the following. That is, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-
1,2-propylene glycol, tri-1,2-propylene glycol, tetra-1,2-propylene glycol, hexa-1,2-propylene glycol, di-1,
3-propylene glycol, tri-1,3-propylene glycol, tetra-1,3-propylene glycol,
Di-1,3-butylene glycol, tri-1,3-butylene glycol, hexa-1,3-butylene glycol, polyethylene glycol with an average molecular weight of 1,000, polyethylene glycol with an average molecular weight of 1500, polyethylene glycol with an average molecular weight of 2,000, average molecular weight 30
00 polyethylene glycol, polyethylene glycol having an average molecular weight of 7,500, polypropylene glycol having an average molecular weight of 400, polypropylene glycol having an average molecular weight of 700, polypropylene glycol having an average molecular weight of 1,000, polypropylene glycol having an average molecular weight of 2,000, polypropylene glycol having an average molecular weight of 3,000,
Polypropylene glycol having an average molecular weight of 4000.

Specific examples of the polyether diol compound represented by the formula (C) include the following. PTMG650, PTMG1 manufactured by Sanyo Chemical Industries, Ltd.
000, PTMG20000, PTMG3000 and the like.

As the polyether diol compound represented by the formula (D), the following compounds are specifically mentioned. New Pole PE-61, New Pole PE-62, New Pole PE-64, New Pole PE-68, New Pole PE-71, New Pole PE-74, New Pole PE-75, New Pole manufactured by Sanyo Chemical Industries, Ltd. Pole PE-78, New Pole PE-108, New Pole PE-128, New Pole PE-61 and the like.

Specific examples of the polyether diol compound represented by the formula (E) include the following. New pole BPE-20 manufactured by Sanyo Chemical Industry Co., Ltd.
New Pole BPE-20F, New Pole BPE-2
0NK, New Pole BPE-20T, New Pole B
PE-20G, New Pole BPE-40, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180, New Pole BP-2P, New Pole BPE-23P, New Pole BPE-3P,
New Paul BPE-5P etc.

Specific examples of the random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at the terminal include the following. New Pole 50HB-100, New Pole 50HB-260, New Pole 50HB-400, New Pole 50HB-660, New Pole 50HB- manufactured by Sanyo Chemical Industries, Ltd.
2000, Newpole 50HB-5100, etc.

Examples of the polyester diol compound include compounds represented by formulas (8) and (9).

[0108]

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In the formula, L ₁ , L ₂ and L ₃ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group, and L ₄ represents a divalent aliphatic hydrocarbon group. . Preferably, L ₁ , L ₂ and L ₃ each represent an alkylene group, alkenylene group, alkynylene group or arylene group;
₄ represents an alkylene group. In L ₁ , L ₂ , L ₃ and L ₄ , other functional groups which do not react with an isocyanate group, such as ether, carbonyl, ester, cyano, olefin,
Urethane, amide, ureido groups or halogen atoms may be present. n1 and n2 are each an integer of 2 or more, and preferably an integer of 2 to 100.

As the polycarbonate diol compound, there is a compound represented by the formula (10).

[0111]

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(In the formula, L ₅ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ₅ is an alkylene group, an alkenylene group, an alkynylene group or an arylene group. shown. the L _5, another functional group which does not react with the isocyanate group, such as an ether, carbonyl, ester, cyano, olefin, urethane, amide, good .n ₃ be a ureido group or a halogen atom is Each is an integer of 2 or more,
It preferably represents an integer of 2 to 100. )

Specific examples of the diol compound represented by the formula (8), (9) or (10) include the following. N in a specific example is an integer of 2 or more.

[0114]

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[0115]

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Further, a diol compound having no carboxyl group and optionally having another substituent which does not react with isocyanate can be used in combination. Such diol compounds include those shown below. _{HO-L 6 -O-CO-} L 7 -CO-O-L 6 -OH (11) HO-L 7 -CO-O-L 6 -OH (12)

(Wherein L ₆ and L ₇ may be the same or different and each has a substituent (for example, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (—F, —Cl, —Br, -I), a divalent aliphatic hydrocarbon group optionally having:
It represents an aromatic hydrocarbon group or a heterocyclic group. As needed,
Other functional groups which do not react with isocyanate groups in L ₆ and L ₇ , such as carbonyl, ester, urethane, amide,
It may have a ureido group or the like. Note that L ₆ and L ₇ may form a ring. )

Specific examples of the compound represented by the formula (11) or (12) include the following.

[0119]

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[0120]

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[0121]

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The diol compounds shown below can also be used preferably.

[0123]

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(In the formula, R ₇ and R ₈ may be the same or different, and may be an alkyl group which may have a substituent;
Represents an integer of 2 or more, preferably 2 to 100
Is an integer. )

Specific examples of the diol compound represented by the formula (13), (14), (15) or (16) include the following.

That is, as formula (13), ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Formula (14) such as 1,8-octanediol includes the following compounds.

[0127]

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Formula (15) is given by 2-butene-1,4
-Diol, cis-2-butene-1,4-diol, trans-2-butene-1,4 as formula (16)
-Diols and the like. Also, the following diol compounds can be suitably used. _{HO-L 6 -NH-CO-} L 7 -CO-NH-L 6 -OH (17) HO-L 7 -CO-NH-L 6 -OH (18)

(Wherein L ₆ and L ₇ may be the same or different and each has a substituent (for example, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (—F, —Cl, —Br, -I), a divalent aliphatic hydrocarbon group optionally having:
It represents an aromatic hydrocarbon group or a heterocyclic group. As needed,
Other functional groups which do not react with isocyanate groups in L ₆ and L ₇ , such as carbonyl, ester, urethane, amide,
It may have a ureido group or the like. Note that L ₆ and L ₇ may form a ring. )

Specific examples of the compound represented by the formula (17) or (18) include the following.

[0131]

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Further, the following diol compounds can also be suitably used. _{HO-Ar 2 - (L 16} -Ar 3) n -OH (19) HO-Ar 2 -L 16 -OH (20)

(In the formula, L ₁₆ represents a divalent aliphatic hydrocarbon group which may have a substituent (for example, alkyl, aralkyl, aryl, alkoxy, aryloxy, and halogeno are preferable). If necessary, L ₁₆ may have another functional group which does not react with an isocyanate group, for example, an ester, urethane, amide, or ureide group, and Ar ₂ and Ar ₃ may be the same or different. A bivalent aromatic hydrocarbon group which may have a substituent;
It preferably represents an aromatic group having 6 to 15 carbon atoms. n is 0
And an integer of 10 to 10. )

The diol compound represented by the formula (19) or (20) specifically includes the following. That is, catechol, resorcin, hydroquinone, 4-methylcatechol, 4-t-butylcatechol, 4-acetylcatechol, 3-methoxycatechol, 4-phenylcatechol, 4-methylresorcinol,
4-ethyl resorcinol, 4-t-butyl resorcinol, 4
-Hexylresorcin, 4-chlororesorcin, 4-benzylresorcin, 4-acetylresorcin and the like. The following diol compounds can also be suitably used.

[0135]

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(Wherein R₁Is a hydrogen atom, a substituent (eg,
For example, cyano, nitro, halogen atoms (-F, -Cl,-
Br, -I), -CONH_Two, -COOR₁₁₃, -OR
₁₁₃, -NHCONHR₁₁₃, -NHCOOR₁₁₃, -N
HCOR₁₁₃, -OCONHR₁₁₃, -CONHR
₁₁₃(Where R₁₁₃Is an alkyl group having 1 to 10 carbon atoms,
It represents an aralkyl group having a prime number of 7 to 15. ))
I will. Alkyl), aralkyl,
Represents an aryl, alkoxy, or aryloxy group and is preferred
A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, 6 carbon atoms
Represents up to 15 aryl groups. L_Ten, L₁₁, L₁₂Is it
Each may be the same or different, and include a single bond, a substituent (eg,
For example, alkyl, aralkyl, aryl, alkoxy,
Halogen groups are preferred. 2) which may have
Represents an aliphatic or aromatic hydrocarbon group. Preferably charcoal
An alkylene group having a prime number of 1 to 20, an alkylene group having a carbon number of 6 to 15
Rylene group, more preferably alkyl having 1 to 8 carbon atoms
Represents a len group. L if necessary_Ten, L ₁₁, L₁₂Inside
Other functional groups that do not react with the socyanate group, such as carbohydrate
Nil, ester, urethane, amide, ureido, ethe
It may have a hydroxyl group. Note that R₁, L_Ten, L₁₁, L
₁₂And two or three of them may form a ring. Ar is
Represents a trivalent aromatic hydrocarbon group which may have a substituent
And preferably represents an aromatic group having 6 to 15 carbon atoms. Z
₀Represents the following groups.

[0137]

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Here, R ₁₀₇ and R ₁₀₈ may be the same or different and each represent a hydrogen atom, sodium, potassium, an alkyl group or an aryl group, preferably a hydrogen atom, an alkyl having 1 to 8 carbon atoms. And an aryl group having 6 to 15 carbon atoms. )

The diol compound having a phosphonic acid, a phosphoric acid and / or an ester group thereof represented by the formula (21), (22) or (23) is synthesized, for example, by the following method.

That is, the following equations (24), (25),
After protecting the hydroxy group of the halogen compound represented by (26) as required, the Michaeli represented by the formula (27)
Synthesis is carried out by phosphonate esterification by the s-Arbuzov reaction and, if necessary, hydrolysis with hydrogen bromide or the like.

[0141]

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(Wherein R ₁ , L ₁₀ , L ₁₁ , L ₁₂ and A
r has the same meaning as in formulas (21), (22) and (23). R ₁₀₉ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R ₁₁₀ is _calculated by the formulas (24), (25), (2)
6) a group given by removing X ₀₁ of, X ₀₁ is a halogen atom,
It preferably represents Cl, Br, or I. )

After the reaction with phosphorus oxychloride represented by the formula (28), the synthesis is carried out by a hydrolysis method.

[0144]

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(Wherein, R ₁₁₀ has the same meaning as in formula (27), and M represents a hydrogen atom, sodium or potassium.)

When the polyurethane resin of the present invention has a phosphonate group, a diisocyanate compound represented by the formula (1) and a diol compound having a phosphonate ester group represented by the formula (21), (22) or (23) May be reacted to form a polyurethane resin, and then hydrolyzed with hydrogen bromide or the like.

Further, similarly to the diol compound, the following amino group-containing compound may be reacted with the diisocyanate compound represented by the formula (1) to form a urea structure and incorporated into the structure of the polyurethane resin.

[0148]

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(In the formula, R ₁₀₆ and R ₁₀₈ may be the same or different and each represents a hydrogen atom, a substituent (for example, an alkoxy, a halogen atom (—F, —Cl, —Br, —I),
Each group such as an ester and a carboxyl group is included. Represents an alkyl group, an aralkyl group or an aryl group which may have a hydrogen atom, an alkyl having 1 to 8 carbon atoms which may have a carboxyl group as a substituent, and an alkyl group having 6 to 15 carbon atoms. Indicates an aryl group. L ₁₇ represents a substituent (eg, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (—F, —Cl, —Br, —
I) and carboxyl groups. A) a divalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have If necessary, L ₁₇ may have another functional group which does not react with an isocyanate group, for example, a carbonyl, ester, urethane, amide group and the like. Two of R ₁₀₆ , L ₁₇ and R ₁₀₈ may form a ring. )

Specific examples of the compounds represented by the formulas (29) and (30) include the following. That is, aliphatic diamine compounds such as ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, L-cystine, and isophoronediamine; o-phenylenediamine;
m-phenylenediamine, p-phenylenediamine,
Aromatic diamine compounds such as 2,4-tolylenediamine and 1,8-naphthalenediamine; 2-aminoimidazole, 3-aminotriazole, 5-amino-1H-
Tetrazole, 4-aminopyrazole, 2-aminobenzimidazole, 2-amino-5-carboxy-triazole, 2,4-diamino-6-methyl-S-triazine, 2,6-diaminopyridine, L-histidine, DL
-Heterocyclic amine compounds such as tryptophan, adenine and the like; ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1-amino-2-propanol, 1-amino-3-propanol, 2-aminoethoxyethanol, 2-aminothioethoxyethanol, 2-carboxy-5-amino-1-naphthol,
Amino alcohol or aminophenol compounds such as L-tyrosine and the like.

The polyurethane resin of the present invention is synthesized by adding the above-mentioned isocyanate compound and diol compound in an aprotic solvent to a known catalyst having an activity corresponding to the respective reactivity, and heating the mixture. The molar ratio of the diisocyanate and the diol compound used is preferably 0.8: 1 to 1.2: 1. When the isocyanate group remains at the polymer terminal, the polymer is treated with alcohols or amines to obtain the final Is synthesized in such a manner that no isocyanate group remains.

The polyurethane resin of the present invention needs to contain a carboxyl group in an amount of 0.4 meq / g or more, particularly preferably in the range of 0.4 to 3.5 meq / g.

The molecular weight of the polyurethane resin of the present invention is preferably at least 1,000 by weight, more preferably in the range of 5,000 to 500,000.

Any of these organic high molecular weight polymers can be mixed with the photopolymerizable composition of the present invention in an optional amount based on the weight of all components. However, when the content exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 10 to 90%, more preferably 30 to 8
0%. Further, the weight ratio of the photopolymerizable ethylenically unsaturated compound and the organic polymer is preferably in the range of 1/9 to 9/1. A more preferred range is 2/8 to 8 /
2, more preferably 3/7 to 7/3.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization is inhibited to prevent unnecessary thermal polymerization of a polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add an agent. 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-nitrosophenylhydroxylamine, aluminum aluminum N-nitrosophenylhydroxylamine and the like.
The addition amount of the thermal polymerization inhibitor is preferably from about 0.01% to about 5% based on the weight of all components of the photopolymerizable composition of the present invention.
Further, 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 higher fatty acid derivative is added in an amount of about 0.5% to about 0.5% by weight of all components of the photopolymerizable composition of the present invention.
About 10% is preferred.

A coloring agent may be added for the purpose of coloring the photosensitive layer. Examples of the coloring agent include phthalocyanine pigments (CI Pigment Blue 15: 3, 15: 4, 15
: 6), azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of the dye or pigment added is about 0.5% to about 5% based on the weight of all the components of the photopolymerizable composition of the present invention.
Is preferred. In addition, additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film. The amount of these additives is preferably 10% or less based on the weight of all components of the photopolymerizable composition of the present invention.
A surfactant can be added to the photopolymerizable composition of the present invention in order to improve the quality of the coated surface.

When the photopolymerizable composition of the present invention is applied 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, methoxymethoxy Ethanol, 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, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. The concentration of the solid content in the coating solution is suitably from 1 to 50% by weight. In the present invention, the coating amount of the photopolymerizable composition is about 0.1 g / m2 by weight after drying.
The range of ² to about 10 g / m ² are suitable. It is more preferably 0.3 to 5 g / m ² , and still more preferably 0.5 to 3 g / m ^2.
g / m ² .

As the support used in the present invention, a dimensionally stable plate is used. Examples of the dimensionally stable plate include paper, plastic (eg, polyethylene,
Paper laminated with polypropylene, polystyrene, etc.), or a metal plate such as aluminum (including aluminum alloy), zinc, copper, etc., and further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, butyric acid Cellulose, cellulose acetate butyrate,
Examples include plastic films such as cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, and the like, and paper or plastic films on which a metal is laminated or vapor-deposited as described above. 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 treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or separation oxidation treatment Preferably, the treatment has been performed. Further, an aluminum plate that is grained and then immersed in an aqueous solution of sodium silicate can be preferably used. After anodizing the aluminum plate as described in JP-B-47-5125,
Those immersed in an aqueous solution of an alkali metal silicate are 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 U.S. Pat. No. 3,658,662 is effective. Furthermore, the above-mentioned anodizing treatment and sodium silicate treatment are combined with a support having been subjected to electrolytic graining as disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503. Surface-treated ones are also useful. Further, those obtained by sequentially performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

Further, after these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable. Furthermore,
A sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in JP-A-7-159983 is also preferably used. 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 improve the adhesion of the photosensitive layer. Etc. On the layer of the photopolymerizable composition provided on the support, in order to prevent polymerization inhibition due to oxygen in the air, for example, polyvinyl alcohol, polyvinylpyrrolidone, oxygen barrier properties such as acidic celluloses A protective layer made of an excellent polymer may be provided. The method of applying such a protective layer is described in detail in, for example, U.S. Pat. No. 3,458,3111 and JP-A-55-49729.

The photosensitive material (for example, a photosensitive lithographic printing plate precursor) obtained by coating the above-mentioned photosensitive layer on the above-mentioned support was subjected to Ar laser, YAG-SHG laser or the like as described above. Directly exposed. After performing image exposure, development processing is performed. As a developing solution used for such a developing process, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium And inorganic alkali agents such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine,
Organic alkaline agents such as diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used. These alkali agents are used alone or in combination of two or more.

Among the above alkaline aqueous solutions, the developer in which the effect of the present invention is further exhibited is an aqueous solution containing an alkali metal silicate and having a pH of 12 or more. The aqueous solution of alkali metal silicate is silicon oxide Si which is a component of silicate
Ratio of O ₂ and alkali metal oxide M ₂ O (generally [SiO ₂ ] /
[Expressed in the molar ratio of [M ₂ O]) and the concentration can be adjusted. For example, the molar ratio of SiO ₂ / Na ₂ O as disclosed in JP-A-54-62004 can be adjusted. Is 1.0
1.5 (that is, [SiO _2] / [Na ₂ O] is 1.0 to 1.5)
And an aqueous solution of sodium silicate having a content of SiO ₂ of 1 to 4% by weight or [SiO ₂ ] / [M] of 0.5 as described in JP-B-57-7427. ~ 0.75
(That is, [SiO ₂ ] / [M ₂ O] is 1.0 to 1.5), the concentration of SiO ₂ is 1 to 4% by weight, and the developer contains Aqueous solutions of alkali metal silicates containing at least 20% potassium, based on gram atoms of metal, are preferably used.

Further, the photosensitive material was prepared using an automatic developing machine.
(For example, a photosensitive lithographic printing plate)
Use an aqueous solution (replenisher) with a higher alkali strength than the developer
The developer in the developing tank for a long time.
A large amount of photosensitive material can be processed without replacement
It is known that This replenishment method is also used in the present invention.
Is preferably applied. For example, JP-A-54-6200
No. 4 discloses a developing solution of SiO._Two/ Na_TwoOmo
Is 1.0 to 1.5 (that is, [SiO_Two] / [Na_TwoO] is 1.
0 to 1.5), wherein SiO_TwoContent of 1 to 4% by weight
Uses an aqueous solution of sodium silicate and has a positive photosensitive
Continuous or intermittent depending on the throughput of the lithographic printing plate precursor
SiO_Two/ Na_TwoWhen the molar ratio of O is 0.5 to 1.5 (that is, [Si
O_Two] / [Na_TwoO] is 0.5 to 1.5) sodium silicate
A method of adding an aqueous solution (replenisher) to a developer,
JP-A-57-7427 discloses [SiO_Two] /
[M] is 0.5 to 0.75 (that is, [SiO_Two] / [M_TwoO]
1.0 to 1.5), wherein SiO _TwoConcentration of 1 to 4% by weight
Aqueous solution of alkali metal silicate
The alkali metal silicate used as a replenisher (Si
O_Two] / [M] is 0.25 to 0.75 (that is, [SiO_Two] /
[M_TwoO] is from 0.5 to 1.5), and the developer and
And any of the replenishers contained therein
At least 20% potassium based on gram atoms of the genus
Development method characterized by containing
Can be.

The lithographic printing plate thus developed is described in JP-A-54-8002, JP-A-55-115045,
As described in JP-A Nos. 59-58431 and the like, treatment is carried out with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and starch derivatives.
In the post-processing of the lithographic printing plate of the present invention, these processes can be used in various combinations.

After development or, optionally, post-treatments such as the desensitization treatment described above, the entire surface is exposed by the method described above, and the lithographic printing plate thus obtained is subjected to an offset printing machine. Multiplied and used for printing many sheets.
At the time of printing, a conventionally known plate cleaner for a PS plate is used as a plate cleaner used for removing stains on a plate. For example, CL-1, CL-2, CP, CN-
4, CN, CG-1, PC-1, SR, IC (Fuji Photo Film Co., Ltd.) and the like. Preferably, CP and CN-4 are mentioned.

[0166]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Preparation of Sensitive Material) An aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and a 400 mesh aqueous suspension of pumicestone, and then washed thoroughly with water.
After being immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, neutralized and washed with a 20% aqueous nitric acid solution, and then washed with water. This is represented by V _A = 12.7
Under a condition of V, an electrolytic surface roughening treatment was performed with a 1% nitric acid aqueous solution at an anode electricity of 160 coulomb / dm ² using a sinusoidal alternating current. When the surface roughness was measured, it was found to be 0.
It was 6 μ (Ra indication). Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55 ° C. for 2 minutes.
Anodizing treatment was performed in a 2% aqueous sulfuric acid solution at a current density of 2 A / dm ² for 2 minutes so that the thickness of the anodized film became 2.7 g / m ² . Next, a liquid composition (sol solution) of the SG method was prepared by the following procedure.

[Sol Solution] Unichemical Co., Ltd .: Phosmer PE 24 parts by weight Methanol 130 parts by weight Water 20 parts by weight 85% phosphoric acid 16 parts by weight Tetraethoxysilane 50 parts by weight 3-methacryloxypropyltrimethoxysilane 48 parts by weight Were mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the content was transferred to another container and 3,000 parts by weight of methanol was added to obtain a sol solution. This sol solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio), applied with a wheeler so that the amount of Si on the substrate was 3 mg / m ^2, and dried at 100 ° C. for 1 minute. On the substrate thus treated, a photopolymerizable composition having the following composition was applied so as to have a dry application weight of 1.4 g / m ² ,
After drying at 80 ° C. for 2 minutes, a photopolymerizable photosensitive layer was formed.

[Photosensitive solution] Monomer (Used monomers and amounts are described in Tables 2 and 3 below) Binder (Used binders and amounts are described in Tables 2 and 3 below) Compound 1 0.15 g Compound 2 0.20 g Compound 30 .50 g Copper phthalocyanine Pigment Blue 15: 6 / (A) = 3/2 dispersion 0.5 g Megafac F-177 (Dainippon Ink and Chemicals) 0.02 g N-nitrosophenyl Hydroxylamine aluminum salt 0.015 g (Wako Pure Chemical Industries) Propylene glycol monomethyl ether 27.5 g Methyl ethyl ketone 19.0 g

The structural formulas of Compounds 1 to 3 are shown below.

[0170]

Embedded image

On this photopolymerizable photosensitive layer, a water-soluble protective layer having the following composition was applied so as to have a dry coating weight of 2.5 g / m ^2, and dried at 100 ° C. for 3 minutes. Polyvinyl alcohol (degree of saponification 98.5 mol%, degree of polymerization 550) 22 g Nonionic surfactant (BMALBX NP-10, 0.5 g manufactured by Nippon Emulsion Co., Ltd.)

The light-sensitive material thus obtained was used as a Gutenberg plate setter (SHG-YAG, Rhinotype Hell).
532 nm), the number of lines is 175 lpi, and the resolution is 254.
Image exposure was performed at various energies at 0 dpi. The temperature was then raised to 110 ° C to increase the degree of film curing.
A post-heating treatment was applied for seconds.

The development was carried out by Fuji Photo Film Co., Ltd. DP-4.
Using a solution obtained by diluting a developer 18-fold with water, 85
The immersion was carried out at 30 ° C. for 15 seconds using a 0NX automatic developing machine. FUJIFILM Corporation FP-2W gum solution with water 1:
It was gummed with the solution diluted to 1. The printing plate thus obtained was evaluated as follows. The plate energy at which 2% halftone dots were reproduced was determined as the sensitivity of the sample in the unit of mJ / cm ² . For the printing durability evaluation, SOR-KZ manufactured by Heidelberg was used as a printing machine, emerald premium MXE 2% diluted solution of Anchor Co., Ltd. was used as a fountain solution, and GEOS-G manufactured by Dainippon Ink was used as an ink.
(N) was used. The solid printing durability refers to the number of sheets that can be printed normally without any solid omission in the solid printing portion. Highlight printing durability indicates the number of prints at which 2% halftone dots of 175 lpi are reproduced on printed matter. The results are shown in Tables 2 and 3.

[0174]

[Table 2]

[0175]

[Table 3]

The structural formulas of the monomers M-1 to M-8 and the structural formulas of the binders B-1 to B-3 are shown below.

[0177]

Embedded image

[0178]

Embedded image

[0179]

Embedded image

As described above, by using an addition-polymerizable compound having an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bond group, the sensitivity can be increased and the printing durability can be greatly improved. did. In order to examine the compatibility between the monomer and the binder, the photosensitive solutions of Examples 1 to 9 were coated on a polyethylene terephthalate film and dried to prepare 1.5 g / m ² at 60 ° C. After a lapse of 3 days, no change was observed, and it was considered that the compatibility was good in each case. As described above, the photopolymerizable composition of the present invention and the photosensitive lithographic printing plate using the same can increase the sensitivity and improve the printing durability.

[0181]

The photopolymerizable composition of the present invention has an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bond group as a compound capable of addition polymerization, so that it can be used for an SHG-YAG laser or the like. It has sufficient sensitivity to scanning exposure by visible light laser, and has excellent mechanical strength, and has excellent printing durability when used as a photosensitive layer of a photosensitive composition and a photosensitive lithographic printing plate using the same. It will be. Further, since the compound capable of addition polymerization, which is a feature of the present invention, has good compatibility with a binder, the photosensitive composition and a photosensitive lithographic printing plate using the same are very storage-stable. It was excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/029 G03F 7/029 F-term (Reference) 2H025 AA01 AA12 AA13 AB03 AC01 AC08 AD01 BC13 BC42 BC45 BC65 BC82 BC83 CA00 CA39 FA10 FA17 2H096 AA06 BA05 EA04 4J011 AA05 AC04 QB23 SA86 TA03 UA02 WA01 4J027 AA01 AB03 AC03 AC06 AE01 AG04 AG12 AG15 AG23 AG24 AG25 AG27 AG28 AG33 AJ02 AJ08 AJ09 BA03 BA24 BA27 BA30 BA30 CA09 CA12 CA14 CA24 CA25 CA27 CA29 CA34 CB10 CC07 CD10 4J034 BA02 BA03 CA02 CA03 CA04 CA13 CA15 CA17 CA22 CB03 CB04 CB05 CB07 CB08 CC03 CC08 CC12 CC13 CC23 CC26 CC28 CC29 CC30 CC33 CC34 CC35 CC44 CC45 CC52 DA01 DB03 DC02 DC43 DF01 DF02 DF16 DF17 DF20 DF29 DG03 DG04 DG08 DG09 GA55 GA62 GA74 HA01 HA07 HC02 HC03 HC12 HC1 7 HC18 HC22 HC46 HC52 HC61 HC64 HC67 HC71 HC73

Claims (3)

[Claims] 1. A photopolymerization comprising: i) an addition-polymerizable compound having an alkylene oxide group having an ethylenically unsaturated double bond group and a urethane bonding group; and ii) a photopolymerization initiator. Composition. 2. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator is a titanocene compound. 3. The photopolymerizable composition according to claim 1, wherein the addition-polymerizable compound is a reaction product of an isocyanate compound and an alcohol represented by the following general formula (I). Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
⁹ , R ¹⁰ , R ¹¹ , and R ¹² each represent a hydrogen atom and a carbon number of 1 to 10;
Y represents a hydrogen atom or a group represented by the following general formula (II): And at least one of them is a hydrogen atom, and X
Is an alkyl group, an aryl group, an alkoxy group, -OH or a group represented by the following general formula (II): Wherein at least one of X and Y is a group represented by the general formula (II), and n, a, b, c, d,
e and f represent 0 or a positive number)