JPH10282680A - Negative type photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high sensitivity to Ar<+> laser or YAG laser light and to improve the adhesiveness of a protective layer to a photopolymerizable layer without deteriorating developability and ink receptivity by forming a protective layer contg. a water-soluble vinyl polymer and a polymer having specified repeating units on a specified photopolymerizable layer. SOLUTION: This negative type photosensitive material has a photopolymerizable layer contg. an addition polymerizable compd. having at least one ethylenic unsatd. double bond, a photopolymn. initiator and a polymer binder and a protective layer contg. a water-soluble vinyl polymer and a polymer having repeating units represented by formula I or II on the photopolymerizable layer. In the formula I, II, each of R<1> and R<2> is H or alkyl, each of R<11> and R<12> is H, an aliphatic or arom. group, R<11> and R<12> may bond to each other to form a 5- or 6-membered N-contg. hetero ring, each of R<21> and R<22> is H, an aliphatic or arom. group, R<21> and R<22> may bond to each other to form a 5- or 6-membered N-contg. hetero ring and R<23> is alkylene or arylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative type photosensitive material, and particularly to an extremely high sensitivity to light rays in the visible light region, for example, Ar laser, YAG-SH.
Shows good adaptability to G laser light source, printing plate, printed circuit, paint, ink, hologram recording, 3
The present invention relates to a negative photosensitive material used in a wide field such as three-dimensional molding.

[0002]

2. Description of the Related Art Conventionally, many image forming methods utilizing a photopolymerization system are known. For example, an addition polymerizable compound containing an ethylenic double bond, a photopolymerization initiator, and an organic polymer used if desired. A negative photosensitive material comprising a molecular binder and a thermal polymerization inhibitor is provided as a coating layer on a support,
A method of forming a cured relief image by image-exposing a desired image to polymerize and cure an exposed portion and dissolving and removing an unexposed portion, wherein the above-mentioned negative photosensitive material is sandwiched between two support members, at least one of which is transparent. The method of forming an image by peeling off the support, after exposing the image by exposure to light from the transparent support side and inducing a change in the adhesive strength, and providing a color material such as a photopolymerizable composition and a leuco dye. A photosensitive material provided with a microcapsule layer having contents is prepared, the photosensitive material is image-exposed, the exposed portion capsules are photo-cured, and the unexposed portion capsules are destroyed by a pressure treatment or a heat treatment to obtain a color. A method of forming a colored image by contacting with a material developer to form a colored image, or an image forming method utilizing a change in toner adhesion of a photopolymerizable composition due to light, a photopolymerizable composition The image forming method utilizing the change in refractive index due to light is known.

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 as a photosensitive material suitable for, for example, non-contact type projection exposure plate making and visible light laser plate making. I have. Here, as the visible light laser, 488 nm light of Ar + laser, YAG
-532 nm light of SHG laser and the like are promising.

In such a photopolymer polymerization system, high sensitivity is an important factor, and many photosensitive systems utilizing radical polymerization which are advantageous for high sensitivity have been studied and developed. However, radical polymerization systems are susceptible to polymerization inhibition by oxygen, and various measures have been taken, such as providing a protective layer having excellent oxygen barrier properties on the polymerized layer. US Pat. No. 3,458,311; No. 55-49729. Water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone and acidic celluloses are known as such materials having excellent oxygen barrier properties.

However, when a hydrophilic layer made of such a water-soluble polymer is laminated on a lipophilic polymer layer, film peeling is likely to occur due to insufficient adhesive force, and the peeling portion is inferior in film hardening due to inhibition of oxygen polymerization. Cause defects. For this reason, it is important to make the adhesive strength between these two layers sufficient, and various proposals have been made to improve the adhesiveness. For example, U.S. Pat. No. 292,501, U.S. Pat.
No. 563, by mixing 20 to 60% by weight of an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer in a hydrophilic polymer mainly composed of polyvinyl alcohol, and laminating the mixture on a polymer layer. It is described that sufficient adhesiveness can be obtained.
However, in these methods, in order to obtain sufficient adhesiveness, the copolymer and the like must be added to polyvinyl alcohol in a considerably large amount. No sensitivity is obtained. In addition, when developing with water or alkaline water after exposure, under appropriate developing conditions, the water-soluble polymer may not completely fall off, which may cause problems such as poor ink deposition. there were.

[0006]

SUMMARY OF THE INVENTION The present invention is directed to a high-sensitivity negative photosensitive material suitable for an Ar @ + laser and a YAG-SHG laser which does not have such a problem. It is an object of the present invention to provide a negative photosensitive material having practically sufficient adhesiveness without deteriorating the image quality.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a hydrophilic polymer mainly composed of polyvinyl alcohol is suitable for a photopolymerizable layer and a water-soluble vinyl polymer. By adding a specific polymer having affinity, the adhesion between the protective layer and the photopolymer layer is practically sufficient without deteriorating the sensitivity, ink inking property, development processing property, and image resolution. The present invention has been achieved based on the finding that performance can be achieved. That is, the object of the present invention is to provide: 1) (a) a photopolymerizable layer containing an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator and a polymer binder, and the above polymerizable layer And a protective layer containing (b) (1) a water-soluble vinyl polymer and (2) a polymer having a repeating unit represented by the following general formula (I) or (II). Negative photosensitive material,

[0008]

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[0009] In the formula, R ¹ and R ² are each a hydrogen atom or an alkyl group; R ¹¹ and R ¹² are each a hydrogen atom, or an aliphatic group or an aromatic group, or a R ¹¹ R ¹² is linked together to form a 5- or 6-membered nitrogen-containing heterocycle; R ²¹ and R ²² are each
Is a hydrogen atom, an aliphatic group or an aromatic group, or R ²¹ and R ²² combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring; and R ²³ is an alkylene group or an arylene group. Is achieved by

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [(B) (1) Water-soluble vinyl polymer] Examples of (b) (1) water-soluble vinyl polymer contained in the protective layer of the present invention include polyvinyl alcohol, its partial ester or ether, and polyvinyl acetal. Can be Further, as another useful polymer polyvinylpyrrolidone,
Examples thereof include gelatin and gum arabic, and these may be used alone or in combination. Still further, there may be mentioned copolymers of the above polymers containing an unsubstituted vinyl alcohol unit in an amount substantially necessary for imparting water solubility.
Polyvinyl alcohol which is hydrolyzed by 71 to 100% and has a polymerization degree of 300 to 2400 is preferable. Specifically, Kuraray's PVA-105, PVA-110, PV
A-117, PVA-117H PVA-120, PVA-124, PVA-124H, PVA-CS, PV
A-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-
217, PVA-220, PVA-224, PVA-217EE, PVA-220, PVA-224, PVA
-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420,
PVA-613, L-8 and the like. Examples of the copolymer include 88-100% hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal, and copolymers thereof. In the photosensitive material of the present invention,
In the protective layer, these water-soluble vinyl polymers are used in a proportion of 30 to 99%, preferably 50 to 99%, based on the total solid content.
%.

Next, (b) contained in the protective layer of the present invention.
(2) The polymer represented by the general formula (I) or (II) will be described.

[(B) (2) Polymer] The (b) (2) polymer has a repeating unit represented by the above general formula (I) or (II). In the general formula (I), R ¹ is a hydrogen atom or an alkyl group. In the general formula (I),
R ¹¹ and R ¹² are each a hydrogen atom, an aliphatic group or an aromatic group, or R ¹¹ and R ¹² are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. R ¹¹
And at least one of R ¹² is preferably an aliphatic group or an aromatic group, or forms the above-mentioned nitrogen-containing heterocyclic ring, and at least one of R ¹¹ and R ¹² is an aliphatic group, or More preferably, at least one of R ¹¹ and R ¹² is an aliphatic group, one of R ¹¹ and R ¹² is an aliphatic group, and the other is a hydrogen atom Is most preferred.

The aliphatic group includes an alkyl group, an alkenyl group,
It means an alkynyl group and an aralkyl group, both of which include those having a substituent. Of these, an alkyl group, an alkenyl group and an aralkyl group are preferred, an alkyl group and an alkenyl group are more preferred, an alkyl group is still more preferred, and an alkyl group having a substituent is most preferred. The total number of carbon atoms including the substituent of the aliphatic group is preferably 11 to 40, and 1 to 20.
Is more preferable, 1 to 15 is more preferable, and 1 to 10 is most preferable. The number of carbon atoms of the aliphatic group excluding the substituent is preferably 1 to 20, more preferably 1 to 15, and 1
It is more preferably from 10 to 10, and most preferably from 1 to 6. As the aliphatic group, a chain aliphatic group is more preferable than a cyclic aliphatic group. The chain aliphatic group may have a branch.

The aromatic group means an aryl group and includes those having a substituent. . The total number of carbon atoms including the substituent of the aromatic group is preferably 6 to 60, and 6 to 4
0, more preferably 6 to 30, still more preferably 6 to 20, and 6 to 1
Most preferably, it is 2. Examples of the substituent for the aliphatic group and the aromatic group include a hydroxyl group, a halogen atom (for example, a chlorine atom), an amino group (including those having a substituent), a heterocyclic group (for example, a morpholino group) and Includes cyano groups. The substituent that can be substituted for the amino group is the above-mentioned aliphatic group or aromatic group. Examples of the substituent of the aromatic group further include the above-mentioned aliphatic group. R
^{Heterocycle 11} and R ¹² are bonded to each other to form is preferably a 6-membered ring. The heterocycle is preferably a saturated heterocycle. Examples of the repeating unit represented by the general formula (I) are shown below. In the following examples, the names of the compounds of the monomers used as the raw materials of the repeating units are also described.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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In the general formula (II), R ² is a hydrogen atom or an alkyl group. In the general formula (II), R ²¹
And R ²² are each a hydrogen atom, an aliphatic group or an aromatic group, or R ²¹ and R ²² are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. It is preferred that at least one of R ²¹ and R ²² is an aliphatic group or an aromatic group, or that the above-mentioned nitrogen-containing heterocycle is formed, and at least one of R ²¹ and R ²² is an aliphatic group, or it is more preferable to form the above-mentioned nitrogen-containing heterocyclic ring, more preferably at least one of R ²¹ and R ²² is an aliphatic group, that both R ²¹ and R ²² is an aliphatic group most preferable. The definition of the aliphatic group, the aromatic group and the 5- or 6-membered nitrogen-containing heterocycle and the substituents thereof are the same as those in the general formula (I).

In the general formula (II), R ²³ is an alkylene group or an arylene group. The alkylene group and the arylene group may have a substituent. The total number of carbon atoms including the substituent of the alkylene group is preferably 1 to 20, more preferably 1 to 15, and 11 to 1
It is more preferably 0 and most preferably 11 to 6. The alkylene group may have a branch. The total number of carbon atoms including the substituent of the arylene group is 6 to
It is preferably 60, more preferably 6 to 40, more preferably 6 to 30, further preferably 6 to 20, and most preferably 6 to 10. Examples of the substituent of the alkylene group and the arylene group include a hydroxyl group, a halogen atom (for example, a chlorine atom), an amino group (including those having a substituent),
Heterocyclic groups (eg, morpholino groups) and cyano groups are included. Examples of the substituent of the amino group include the above-described aliphatic group and aromatic group. Examples of the substituent of the arylene group further include the above-described aliphatic group. General formula (I
Examples of the repeating unit represented by I) are shown below. In the following examples, the names of the compounds of the monomers used as the raw materials of the repeating units are also described.

[0022]

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[0023]

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[0024]

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The polymer of the present invention may be a homopolymer composed of only the repeating unit represented by the general formula (I) or (II), or a homopolymer composed of the repeating units represented by the general formulas (I) and (II). Copolymers can be used. Further, as a copolymer combined with another repeating unit, the properties (eg, water solubility) of the polymer can be adjusted. When the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) are used in a copolymer, the total of both is preferably 50 mol% or more. Formula (I) in the copolymer
Alternatively, the proportion of the repeating unit represented by (II) is preferably at least 70 mol%, more preferably at least 80 mol%, further preferably at least 90 mol%, and more preferably at least 95 mol%. It is most preferred that this is the case.

The repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) each have 5 mol% or more (50 mol% or more in total).
Copolymers are particularly preferred. The following are examples of copolymers.

Copolymer Mole% of Formula (I) Mole% of Formula (II) Repeat Unit Repeat Unit CP-1 I-190 II-16 10 CP-2 I-290 II-16 10 CP-3 I-11 90 II-16 10 CP-4 I-3 90 II-16 10 CP-5 I-28 90 II-16 10 CP-6 I-8 90 II-16 10 CP-7 I-10 50 II-16 50 CP -8 I-29 20 II-16 80 CP-9 I-16 90 II-16 10 CP-10 I-16 50 II-2 50 CP-11 I-30 10 II-2 90 CP-12 I-19 80 II-16 20 CP-13 I-1 100 CP-14 I-190 II-18 10 CP-15 I-190 II-19 10 CP-16 I-190 II-20 10

In the polymer used in the present invention, the ethylenically unsaturated group of the monomer shown as an example of the repeating unit can be synthesized by radical polymerization using a polymerization initiator as a catalyst. The polymer used in the present invention may be synthesized by synthesizing polyacrylamide, polymethacrylamide, polyacrylate, polymethacrylate, or a copolymer thereof, and then modifying the side chain. When forming a copolymer containing a repeating unit other than the repeating unit represented by formula (I) or (II), the other repeating units can be derived from various ethylenically unsaturated polymerizable compounds. As the ethylenically unsaturated polymerizable compound, the same compounds as the examples of the ethylenically unsaturated polymerizable compound which is a component of the curable layer described later can be used. The molecular weight of the polymer (b) (2) used in the present invention is preferably in the range of 2,000 to 500,000,
More preferably in the range of 3000 to 300,000,
The range is more preferably from 4,000 to 200,000, and most preferably from 5,000 to 150,000.

In the negative-working light-sensitive material of the present invention, the polymer (b) (2) is used in the protective layer in an amount of usually 2 to 50% by weight, more preferably 3 to 20% by weight of the total solids.
Contained in the range. As the amount of addition increases, the adhesive strength between the polymer layer and the protective layer improves, but there is a concern that the ink inking property and the image quality deteriorate. The dry coating weight of the protective layer is usually 0.5 to 10 g / m ² , preferably 1.0 to 5.0 g / m ^2.
g / m ² .

In the present invention, the layer containing the polymer (b) (2) may be separately provided as an adhesive layer between the photopolymerized layer and the protective layer excluding the polymer.

The dry coating weight of the adhesive layer is usually
It is 0.1 to 10 g / m ² , preferably 0.1 to 2.0 g / m ² .

The method of applying the protective layer of the present invention and, in some cases, the above-mentioned adhesive layer is not particularly limited, and the method described in US Pat. No. 3,458,311 or JP-A-55-49729 is applied. be able to. Also,
Water is used as a solvent at the time of application.

The protective layer of the present invention may further contain known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of the film. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, and sorbitol.
Further, a water-soluble (meth) acrylic polymer or the like may be added. The protective layer of the present invention has good adhesion to the photopolymerizable layer, and is water-soluble and has oxygen barrier properties.
It is transparent to actinic rays.

Next, the photopolymerized layer (a) of the present invention will be described. The main components of the photopolymerizable layer of the present invention are an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator and a polymer binder, if necessary, a thermal polymerization inhibitor, Various compounds such as a coloring agent and a plasticizer can be contained.

The compound capable of addition polymerization containing an ethylenically unsaturated double bond can be arbitrarily selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated bonds. These compounds include:
For example, those having a chemical form such as a monomer, a prepolymer such as a dimer or a trimer, and an oligomer, or a mixture thereof are included. Examples of these include esters of unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and those unsaturated carboxylic acids. Examples include amides 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 hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , So Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomers and the like.

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, and the like.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
Examples thereof include 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate. The crotonic acid ester includes ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate and the like. As isocrotonic acid esters, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate,
And sorbitol tetraisocrotonate.

Examples of maleic acid esters include 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. Further, 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, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like. Other examples include a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708, and the following general formula (A)
And a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl-containing vinyl monomer is added. General formula CH ₂ = C (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ 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. 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 addition, the amount of these used is 5-7 with respect to the total solid content.
0% by weight (hereinafter abbreviated as%), preferably 10 to 5%
0%.

As the photopolymerization initiator, various photoinitiators known in patents, literatures, etc., depending on the wavelength of the light source used,
Alternatively, a combination system (photoinitiating system) of two or more photoinitiators can be appropriately selected and used. For example, when ultraviolet light of 400 nm or less is used as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone and the like are widely used. Also, when using visible light of 400 nm or less, an argon laser, and a YAG-SHG laser as a light source,
Various photoinitiating systems have been proposed, for example, U.S. Pat.
Certain photosensitive dyes described in Japanese Patent No. 2,850,445, complex initiation system of dye and amine (Japanese Patent Publication No. 44-20189), combination system of hexaarylbiimidazole, radical generator and dye (Japanese Patent Publication No. 45-37777) Of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528, JP-A-54-155)
No. 292), 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).
No.), a system of 3-ketocoumarin and an activator (JP-A-52-1)
No. 12681, JP-A-58-15503), a system of biimidazole, a styrene derivative and a thiol (JP-A-59-15503).
140203), a system of an organic peroxide and a dye (JP-A-5
9-140203, JP-A-59-189340),
System of a dye having a rhodanine skeleton and a radical generator
No. 244050), a system of titanocene and a 3-ketocoumarin dye (JP-A-63-221110), and a system of 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-4-2197
No. 56) and a system of titanocene and a specific merocyanine dye (JP-A-6-295061). The amount of the photopolymerization initiator used is 0.05 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound,
Preferably 0.1 to 70 parts by weight, more preferably 0.2 to 5 parts by weight.
It can be used in the range of 0 parts by weight.

The light-sensitive material of the present invention usually contains a linear organic high molecular polymer as a binder, and such a linear organic high molecular polymer is compatible with a photopolymerizable ethylenically unsaturated compound. Any one may be used as long as it is a linear organic high molecular polymer having solubility. 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 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 a linear organic high-molecular polymer include addition polymers having a carboxylic acid group in a side chain, for example, JP-A-59-44615, JP-B-54-34327,
JP-B-58-12577, JP-B-54-25957
JP-A-54-92723 and JP-A-59-5383.
No. 6, 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 / optionally Other addition-polymerizable vinyl monomers] copolymers are preferred. 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 polyamides and polyethers of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These linear organic high molecular polymers can be mixed in any amount with the total solid content. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably it is 30 to 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 2/8 to 6/4.

In the present invention, in addition to the above basic components, a small amount of a thermal polymerization inhibitor is used in order to prevent unnecessary thermal polymerization of a polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive material. It is desirable to add. 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), N-nitrosophenylhydroxylamine cerium salt and the like. The addition amount of the thermal polymerization inhibitor is about 0.01% to about 5% based on the weight of the total solids.
% Is preferred. 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 photopolymerization layer in a drying process after coating. Good. The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

Further, a coloring agent may be added for the purpose of coloring the photopolymerizable layer. Examples of the coloring agent include phthalocyanine pigments, azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of dye and pigment added is about
0.5% to about 5% is preferred. In addition, to improve the physical properties of the cured film, inorganic fillers and dioctyl phthalate,
Additives such as plasticizers such as dimethyl phthalate and tricresyl phosphate may be added. These addition amounts are preferably 10% or less of the total solids.

The light-sensitive material of the present invention is usually used after being coated on a support. When coating on a support, various organic solvents can be used. As the organic solvent used herein, 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 , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,
N-dimethylformamide, dimethyl sulfoxide, γ
-Butyrolactone, methyl lactate, ethyl lactate and the like. These solvents can be used alone or as a mixture. And the concentration of solids in the coating solution is 2
~ 50% by weight is preferred.

In the present invention, a surfactant may be added to the photopolymerizable layer in order to improve the quality of the coated surface. The coating amount is about 0.1 g / m ² to about 10 g / m ² after drying.
preferably in the range of m ^2, 0.5~5g / m ² is more preferable.

A dimensionally stable plate is used as the support. As the dimensionally stable plate,
Paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper,
For example, aluminum (including aluminum alloys), metal plates such as zinc and copper, and further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, Examples include plastic films such as 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. Furthermore,
A composite sheet in which an aluminum sheet is bonded to 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 anodizing. Is preferably 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.

Electrodeposition of a silicate as described in US Pat. No. 3,658,662 is also effective. Further, Japanese Patent Publication No. 46-27481 and Japanese Patent Application Laid-Open No. 52-5860
No. 2, Japanese Patent Application Laid-Open No. 52-30503, and a surface treatment obtained by combining the support subjected to electrolytic graining with the above anodic oxidation treatment and sodium silicate treatment are also useful.

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 performing these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer and a copolymer having a sulfonic acid group in a side chain, polyacrylic acid, a water-soluble metal salt (eg, zinc borate) or Those coated with a yellow dye, an amine salt or the like are also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in Japanese Patent Application No. 5-304358 is preferably used.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions in the photopolymer layer provided thereon and to improve the adhesiveness of the photopolymer layer. It is performed for the purpose of improving the quality.

The photosensitive material thus obtained can be used as a photosensitive lithographic printing plate. The photosensitive lithographic printing plate can be subjected to development processing after being directly exposed by an Ar laser or a YAG-SHG laser. Further, after the transparent original is exposed to actinic rays using a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, or the like as a light source, development processing can be 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, potassium, ammonium, sodium carbonate,
Inorganic alkali agents such as potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine,
Diisopropylamine, triisopropylamine, n-
Organic alkali agents such as butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneamine, ethylenediamine, and pyridine are also used.

These alkaline agents are used alone or in combination of two or more. Among the above alkaline aqueous solutions, a 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 the alkali metal silicate depends on the ratio (generally represented by the molar ratio of [SiO ₂ ] / [M ₂ O]) of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O, and the concentration. Developability can be adjusted.
SiO ₂ / Na ₂ as disclosed in US Pat.
When the molar ratio of O is 1.0 to 1.5 (that is, [SiO ₂ ] / [Na ₂ O] is 1.0.
A 0-1.5, the content of SiO ₂ is and an aqueous solution of 1-4 wt% of sodium silicate, as described in JP-B-57-7427, [SiO _2] / [M Is 0.5 to 0.5.
75 (that is, [SiO _2] / [M ₂ O] is 1.0 to 1.5) a, the concentration of SiO ₂ is from 1 to 4 wt%, and the total developing solution is present therein Alkali metal silicates comprising at least 20% potassium, based on gram atoms of alkali metal, are preferably used.

In general, when developing a photosensitive lithographic printing plate using an automatic developing machine, an aqueous solution (replenisher) having an alkali strength higher than that of the developing solution is added to the developing solution so that the developing tank can be kept in the developing tank for a long time. It is known that a large amount of photosensitive lithographic printing plates can be processed without replacing the developer. This replenishment system is preferably applied even when the photopolymerizable composition of the present invention is used. For example, as disclosed in JP-A-54-62004, the molar ratio of SiO ₂ / Na ₂ O in the developer is 1.0 to 1.5 (that is, [SiO ₂ ]).
/ [Na ₂ O] is 1.0 to 1.5) and the content of SiO ₂ is 1
Using 4% aqueous solution of sodium silicate, yet continuously or intermittently molar ratio of SiO ₂ / Na ₂ O in accordance with the processing amount of the positive photosensitive lithographic printing plate is 0.5 to 1. 5 (ie, [SiO
₂ ] / [Na ₂ O] of 0.5 to 1.5) by adding an aqueous solution of sodium silicate (replenisher) to the developing solution.
[SiO ₂ ] /
[M] is 0.5 to 0.75 (that is, [SiO ₂ ] / [M ₂ O] is 1.
0 to 1.5), wherein an alkali metal silicate developer having a SiO ₂ concentration of 1 to 4% by weight is used, and [SiO ₂ ] / [M Is 0.25
00.75 (ie, [SiO ₂ ] / [M ₂ O] is 0.5-1.5), and both the developer and the replenisher are grams of total alkali metal present therein. A development method comprising at least 20% potassium based on atoms is preferably used.

The photosensitive lithographic printing plate thus developed is described in JP-A-54-8002 and JP-A-55-1504.
No. 5, No. 59-58431, etc., a rinsing solution containing washing water, a surfactant and the like,
It is post-treated with a desensitizing solution containing gum arabic and starch derivatives. For the post-processing of the photosensitive lithographic printing plate of the present invention, these processings can be used in various combinations. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets. At the time of printing, as a plate cleaner used for removing stains on the plate, a conventionally known plate cleaner for PS plate is used, 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.

[0057]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 An aluminum plate having a thickness of 0.30 mm was coated with a nylon brush and
The surface was sand-grained with a 0-mesh pumistone aqueous suspension, and then thoroughly washed with water. After immersing in 10% sodium hydroxide at 70 ° C for 60 seconds and etching,
After washing with running water, it was neutralized and washed with 20% nitric acid, and then washed with water. This was converted to 160 coulombs / dm ^{2 in} a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of VA = 12.7V.
The electrolytic surface roughening treatment was performed with the amount of electricity at the time of anode. When the surface roughness was measured, it was 0.6 μ (Ra indication). Subsequently, it was immersed in a 30% aqueous sulfuric acid solution and desmutted at 55 ° C. for 2 minutes.
Anodizing treatment was performed for 2 minutes so that the thickness of the anodic oxide film became 2.7 g / m ² at / dm ² .

On the thus treated aluminum plate, a photosensitive material having the following composition was coated so as to have a dry coating weight of 1.4 g / m ² and dried at 80 ° C. for 2 minutes to form a photopolymerized layer. .

Photosensitive solution Pentaerythritol tetraacrylate 1.5 g Allyl methacrylate / methacrylic acid 2.0 g (80/20 weight ratio) copolymer, molecular weight 30,000 (A) Compound 1 (sensitizing infection) below 0.15 g Compound 2 (photopolymerization initiator, CGI784, manufactured by Ciba-Gaigy) 0.20 g Compound 3 (photopolymerization initiator) 0.40 g ε-phthalocyanine / (A) dispersion 0.20 g Megafac F-177 (Dainippon Ink Chemical industry 0.02 g Fluorosurfactant manufactured by Co., Ltd. Cuperon AL (nitroso compound, manufactured by Wako Pure Chemical) 0.015 g Propylene glycol monomethyl ether 7.5 g Methyl ethyl ketone 9.0 g

[0061]

Embedded image

A protective layer having the following composition was applied on the photopolymerized layer so that the dry coating weight was 2.5 g / m ² ,
Dry at 100 ° C. for 3 minutes. Polyvinyl alcohol (degree of saponification 98.5 mol%, degree of polymerization 500) 22 g 10% by weight aqueous solution of copolymer (CP-1) 10 g Nonionic surfactant (EMALEX NP-10, manufactured by Nippon Emulsion Co., Ltd.) 0.5 g 450 g of distilled water

The photosensitivity test was performed with visible light. As the visible light, a monochromatic light obtained through a Kenko optical filter BP-49 using a xenon lamp as a light source was used. The photosensitivity was measured using a Fuji PS step guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet having a transmission optical density of 0.05 at the first stage and increasing by 0.15 sequentially to 15 stages). The illuminance on the surface of the photosensitive film is 0.0132 mW / cm ²
And the number of clear steps of the PS step guide at the time of exposure for 24 seconds.

Thereafter, the film was heated at 100 ° C. for 1 minute, and immersed in the following developer at 25 ° C. for 20 seconds for development. Potassium 30g potassium hydroxide 1K silicate _{15g C 12 H 25 -C 6 H} 4 -OC 6 H 4 -SO 3 Na 3g Water 1000g

For estimating the adhesion between the photopolymerization layer and the oxygen-barrier protective layer, the peeling force was measured using a Tensilon universal tensile tester (manufactured by Toyo Holdwin Co., Ltd.). When measuring, apply an adhesive tape (width 20 mm) on the protective layer of the unexposed plate material and use a Tensilon universal tensile tester to measure 40 mm.
The protective layer was peeled from the polymer layer together with the tape at a rate of / min, and the peeling force (g) required at that time was measured. In order to measure the printing inking property, the plate material was developed, the plate surface was treated with a two-fold diluted solution of FP2W (a gum solution manufactured by Fuji Photo Film Co., Ltd.), left for one day, and then printed with a printing machine (Mitsubishi Diamond 1F-2). ), And the number of sheets until printing was confirmed at the start of printing.

Examples 2 to 4 and Comparative Examples 1 to 11 The copolymer contained in the protective layer used in Example 1 (CP-
The amount of 1) was changed as shown in Table 1 below, and a light-sensitive material was prepared and evaluated in the same manner as in Example 1. Further, as Comparative Example 1, a protective layer to which no copolymer was added was prepared and similarly evaluated. The results are shown in Table 1. Further, as Comparative Examples 2 to 11, photosensitive materials in which a general-purpose adhesive polymer shown in Table 1 below was added to a protective layer were prepared and evaluated in the same manner. The results are shown in Table 1.

[0067]

[Table 1]

[0068]

Embedded image

[0069]

Embedded image

Examples 5 to 10 Photosensitive materials were prepared and evaluated in the same manner as in Example 1 except that the polymers shown in Table 2 were used instead of the polymers added to the protective layer in Example 1. The results are shown in Table 2.

[0071]

[Table 2]

The polymers used in Examples 6, 7 and 10 were each composed of repeating units I-16, I-17 and II-
8 is a homopolymer.

From the results shown in Tables 1 and 2, the sensitivity and the sensitivity of the polymer of the present invention represented by the formula (I) or (II) were improved.
It can be seen that the adhesive strength can be improved without deteriorating the inking property.

Example 11 A photosensitive material was prepared in the same manner as in Example 1 except that the degree of saponification of polyvinyl alcohol was changed to 88.0 mol% and the degree of polymerization was changed to 1700. The results are shown in Table 3.

[0075]

[Table 3]

From the results in Table 3 above, even when the degree of saponification of polyvinyl alcohol was changed to 88.0 mol% and the degree of polymerization was changed to 1700, the polymer represented by the formula (I) or (II) of the present invention was obtained. It can be seen that the addition of N can improve the adhesive strength without deteriorating the inking property. However, the sensitivity was lowered by one step because the degree of saponification of polyvinyl alcohol was lowered.

Example 12 A photographic material was prepared in the same manner as in Example 1, except that 20 g of polyvinylpyrrolidone (10% aqueous solution) (weight average molecular weight: 40,000) was further added to the water-soluble protective layer.

Example 13 Further, 1,4-cyclohexanediol was added to the water-soluble protective layer.
A light-sensitive material was prepared in the same manner as in Example 1, except that 20 g of (10% aqueous solution) was added.

Example 14 20 g of glycerin (10% aqueous solution) was further added to the water-soluble protective layer.
A light-sensitive material was prepared in the same manner as in Example 1 except that the addition was performed.

Comparative Example 12 Instead of the polymer represented by the formula (I) or (II) shown in Example 1, polyvinylpyrrolidone (10% aqueous solution) (MW4
Example 1 except that (0000) was added in the following composition.
A light-sensitive material was prepared in the same manner as described above. Polyvinyl alcohol (degree of saponification 98.5 mol%, degree of polymerization 500) 11 g polyvinylpyrrolidone 20 g nonionic surfactant (EMALEX NP-10, manufactured by Nippon Emulsion Co., Ltd.) 0.5 g distilled water 450 g

Comparative Example 13 Instead of the polymer represented by the formula (I) or (II) shown in Example 1, polyvinylpyrrolidone (10% aqueous solution) (MW4
Example 1 except that (0000) was added in the following composition.
A light-sensitive material was prepared in the same manner as described above. Polyvinyl alcohol (degree of saponification 98.5 mol%, degree of polymerization 500) 8 g polyvinylpyrrolidone 140 g nonionic surfactant (EMALEX NP-10, manufactured by Nippon Emulsion Co., Ltd.) 0.5 g distilled water 450 g

Comparative Example 14 Instead of the polymer represented by the formula (I) or (II) shown in Example 1, vinylpyrrolidone / vinyl acetate (60 /
40) A light-sensitive material was prepared in the same manner as in Example 1, except that a solution (solution b) containing a copolymer (MW 40,000) was added to the following composition (solution a).
(Liquid b) Vinylpyrrolidone / vinyl acetate copolymer 2 g Distilled water 8 g Ethanol 8 g (Liquid a) Polyvinyl alcohol (Saponification degree 98.5 mol%, polymerization degree 500) 8 g Nonionic surfactant (EMALEX NP-10, ( 0.5 g Distilled water 450 g

The results of Examples 12 to 14 and Comparative Examples 12 to 14 are shown in Table 4.

[0084]

[Table 4]

From the above results, it is possible to improve the adhesive strength by adding polyvinyl virolidone, but in this case, the sensitivity and the inking property are deteriorated, and it is not practical (Comparative Example 13). On the other hand, by adding the polymer represented by the formula (I) or (II) of the present invention, it is possible to improve the adhesive force without deteriorating the sensitivity and the inking property, and to improve the adhesion of other compounds. The performance is not deteriorated by further adding (Example 1
2-14). Further, the formula (I) of the present invention or
When the vinylpyrrolidone / vinyl acetate copolymer is used without using the polymer represented by (II), the sensitivity is deteriorated and the adhesive strength is not practically sufficient (Comparative Example 13).

Example 15 2% of the polymer shown in Example 1 was used as an adhesive layer on the polymer layer.
The aqueous solution was applied to a dry application weight of 0.5 g / m ² and dried at 100 ° C. for 3 minutes. Further, a protective layer having the following composition was further applied thereon 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 500) 22 g Nonionic surfactant (EMALEX NP-10, manufactured by Nippon Emulsion Co., Ltd.) 0.5 g distilled water 450 g The peeling force of this composition is 250 g. The sensitivity was the same as that of Example 3, and the ink inking property was 13 sheets.

[0087]

The negative photosensitive material of the present invention has high sensitivity to an Ar + laser and a YAG-SHG laser, and has a protective layer and a photopolymerizable layer without deteriorating the development processability and the ink adhesion. Excellent adhesion with

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI H05K 3/06 H05K 3/06 H

Claims (1)

[Claims] 1. A photopolymerization layer containing (a) an addition polymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator and a polymer binder, and b) A negative photosensitive material having a protective layer containing (1) a water-soluble vinyl polymer and (2) a polymer having a repeating unit represented by the following formula (I) or (II). Embedded image Wherein R ¹ and R ² are each a hydrogen atom or an alkyl group; R ¹¹ and R ¹² are each a hydrogen atom, an aliphatic group or an aromatic group, or R ¹¹ and R ¹² are R ²¹ and R ²² are each bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring;
An aliphatic group or an aromatic group, or R ²¹ and R ²²
Are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring; and R ²³ is an alkylene group or an arylene group.