JP2000010281A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure a high-contrast image forming property without reducing sensitivity by adding a specified fluorine-contg. polymer. SOLUTION: This photosensitive resin compsn. contains a high molecular compd. having at least fluoro-aliphatic groups and groups represented by the formula -L-P (where L is a divalent org. group bonding to the skeleton of the high molecular compd. and P is an arom. group having carboxyl groups in the ortho-positions). A fluorine-contg. (meth)acrylic resin or the like is particularly useful as the fluorine-contg. polymer. The (meth)acrylic resin has an addition polymerizable monomer having a fluoro-aliphatic group and an addition polymerizable monomer having a carboxylic acid group represented by the formula as copolymerizable components. In the formula, A is H, a halogen, or the like, X is O or the like, R1-R4 are each H, a halogen, alkyl or the like and two of R1-R4 may bond to each other to form a ring but at least one of R1-R4 is a group other than H.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive resin composition containing a fluorine-containing polymer (hereinafter also referred to as a fluorine-containing polymer), and more particularly to a photosensitive resin useful for a lithographic printing plate. The present invention relates to a composition, and more particularly, to a photosensitive resin composition which gives a hard image forming property in a lithographic printing plate.

[0002]

2. Description of the Related Art A lithographic printing plate comprising a substrate coated with a photosensitive resin composition is usually exposed, and then exposed or unexposed portions are removed by alkali development to obtain an image. Next, the image formed of the photosensitive resin composition remaining in the printing process acts as an ink receiving portion, and the substrate that appears after elution acts as a water receiving portion to obtain a printed product. At this time, in order to obtain a good printed matter, the negative type lithographic printing plate, the image obtained after exposure development regardless of the positive type lithographic printing plate, the discrimination of the image portion and the non-image portion is as high as possible,
That is, a material having a high gradation (high contrast) is preferable in terms of image reproducibility and scratch resistance, and a material having a high sensitivity is required.

[0003] The o-typical lithographic printing plate,
A photosensitive resin composition containing a quinonediazide compound has been industrially used as a lithographic printing plate as a very excellent positive photosensitive resin composition and as a photoresist. Conventionally, various proposals have been made on a method for increasing the sensitivity of the o-quinonediazide-based positive photosensitive resin composition. No product which satisfies the safety and the development tolerance has been obtained.

[0004] The high contrast, burnout, white light safety and development tolerance of an image will be described below. An image having high contrast means that the difference between the number of steps at which an image starts to remain and the number of steps at which a film completely remains when exposed and developed through a step wedge is small. Burning is caused by the fact that nitrogen produced by the decomposition of quinonediazide lifts up the lith film and makes it impossible to perform perfect contact exposure. Is easy to resolve.

[0005] The white light safety indicates the stability of image sensitivity when the printing plate is exposed to white light such as a fluorescent light, and the higher the image, the better the white light safety. This is due to the fact that quinonediazide is partially decomposed by white light, and the image with high contrast is similar to that when quinonediazide is decomposed in a small amount, the image does not elute and it was not exposed under white light. It becomes an image. The step wedge is a strip-shaped film in which the density changes by 0.15 for each step, and is used to obtain the relationship between the exposure amount and the remaining amount of the photosensitive layer after development after exposure. The clear sensitivity means the sensitivity at which an image starts to be formed after exposure and development.
The development tolerance refers to how much the image sensitivity after exposure and development changes when the concentration of the developer changes, and it is said that the smaller the sensitivity variation, the better the development tolerance.

On the other hand, a photopolymerization printing plate containing a monomer having a double bond which can be polymerized with a photopolymerization initiator represented by a negative type lithographic printing plate, particularly a laser having high sensitivity to a laser beam in a visible light region. In the case of direct exposure type printing plates, when the image is exposed by an inner drum type laser plate setter that fixes the printing plate and rotates and exposes the mirror at high speed because the gradation is soft conventionally, fogging due to scattered light and reflected light occurs It was easy. Exposure with high energy is desired to increase the printing durability of the printing plate. However, fogging due to scattered light and reflected light is getting worse, so that the exposure amount cannot be increased to increase the printing durability. In order to increase printing durability, it is necessary to prevent fogging due to scattered light and reflected light even at a high exposure amount. This can be solved by making the gradation hard. Because
Image exposure with a laser is performed for about 1 microsecond per dot, but fog due to scattered or reflected light is on the order of minutes, and extremely weak light is exposed to the photosensitive material for a long time. Is what you do.

Therefore, when the gradation of the photosensitive material becomes high, the photosensitive material is hardly photocured with weak light, and is removed by development to prevent fog. In the case of a heat-sensitive lithographic printing plate that draws using an infrared laser, etc., discrimination between the image part and the non-image part is low, that is, the gradation is low (soft tone), so that image omission may occur in the part touched by bare hands. In addition, there is a problem that stability against trauma is poor.

[0008]

Problems to be Solved by the Invention
Japanese Patent Application Laid-Open Publication No. H11-163,087 describes a fluoropolymer having a fluoroaliphatic group, a polyoxyalkylene group, and an acidic hydrogen atom group as a surfactant. However, even if a polymer described as a specific example in this publication is used, no effect was obtained with respect to burning and white light safety. An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a photosensitive resin composition exhibiting high contrast image forming properties without lowering the sensitivity. In particular, it is an object of the present invention to provide a satisfactory photosensitive resin composition having a high contrast and a wide range of satisfactory burnout, white light safety, and development tolerance.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by adding a specific fluorine-based polymer to a photosensitive resin composition. . That is, the present invention does not reduce the sensitivity when the following copolymer is added to the photosensitive resin composition as a fluorine-based polymer, without deteriorating the sensitivity, shows a high contrast image forming property, and, burnout, white light safety, It was also found that a positive photosensitive resin composition having a wide development tolerance was obtained. This method is particularly effective for increasing the contrast of a positive photosensitive resin composition which has been made highly sensitive by a conventionally known method, and by adding a fluorine-based polymer according to the present invention,
Soft images become harder, burnt, white light safety,
And the development tolerance was improved.

Further, by adding the fluoropolymer of the present invention, the gradation becomes higher in a negative type lithographic printing plate, and particularly in a laser-sensitive photopolymerization printing plate, it has high sensitivity to laser light and scattered light and It was found that a printing plate having good fogging property by reflected light and high printing durability was obtained. Further, it has been found that a heat-sensitive lithographic printing plate has a large discrimination and a high image strength, so that an image missing at a portion touched by bare hands does not occur, and a printing plate with improved stability against trauma can be obtained.

That is, the fluoropolymer contained in the photosensitive resin composition of the present invention includes at least a. A fluoroaliphatic group, b. A polymer having a group represented by the formula -LP (L represents a divalent organic group linked to a polymer compound skeleton, and P represents an aromatic group having a carboxyl group at an ortho position) (polymer compound ). The photosensitive resin composition of the present invention is characterized in that the fluorine-based polymer contained therein has an aromatic group having a carboxyl group at the ortho position, whereby the interaction between the fluorine-based polymer and the binder becomes strong, and as a result, It is considered that high contrast during development is promoted.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a fluorine-based polymer which is a feature of the present invention will be described in detail. The fluoropolymer used in the present invention may be in any polymer form as long as it has the above groups a and b. Specific examples include acrylic resin, methacrylic resin, styryl resin, polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, and the like. Among them, acrylic resin, methacrylic resin, styryl resin, polyester resin, and polyurethane resin are useful, and particularly, acrylic resin, methacrylic resin, and polyurethane resin are useful.

Among acrylic resins, methacrylic resins, and polyurethane resins, acrylic resins and methacrylic resins are particularly useful in terms of synthesis suitability. The acrylic resins and methacrylic resins are described in detail below. When the fluorine-based polymer used in the present invention is a (meth) acrylic resin, it comprises the following structural unit as a copolymer component. a. An addition-polymerizable monomer having a fluoroaliphatic group, b. An addition-polymerizable monomer having a carboxylic acid group represented by the following general formula (1) or (2):

[0014]

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(Wherein A is a hydrogen atom, a halogen atom,
Or X represents an alkyl group, and X represents an oxygen atom, NH, or
NR_Five (Where R_FiveRepresents an alkyl group),
R₁, R_Two, R_ThreeAnd R_FourAre each independently a hydrogen atom, ha
Logen atom, alkyl group, substituted alkyl group, aryl
Group, substituted aryl group, -OR₆ , -OCO-R ₇, −
NHCO-R₈ , -NHCONH-R₉, -OCONH
-R_Ten, -COO-R₁₁, -CONH-R₁₂, -CO-
R₁₃, -CON (R₁₄) (R_Fifteen), -CN or -C
Represents an HO group, or R₁, R_Two, R_ThreeAnd R_FourIs that
Two of them may combine to form a ring;₆~ R_Fifteen
Is an alkyl group, a substituted alkyl group, an aryl group or a substituted
Indicates a reel group. However, preferably R₁, R_Two, R_ThreePassing
And R_FourAt least one of them represents a group other than a hydrogen atom
You. )

[0016]

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(Where A represents a hydrogen atom, a halogen atom or an alkyl group, and X represents an oxygen atom, NH or N-
R ₅ represents (wherein R ₅ represents an alkyl group), R _1,
R _2, R ₃ and R ₄ are independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl _{group, -O-R 6, -OCO-} R 7, -NHCO
—R ₈ , —NHCONHR ₉ , —OCONH—R ₁₀ ,
_{-COO-R 11, -CONH-R} 12, -COR 13, -C
Represents an ON (R ₁₄ ) (R ₁₅ ), —CN or —CHO group, or _{two of} R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring , R _{6 to} R ₁₅ represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and preferably at least one of R ₁ , R ₂ , R ₃ and R ₄ represents a group other than a hydrogen atom , L ₁ represents a divalent organic group. )

First, a copolymer component of the fluoropolymer of the present invention a. The details of the addition-polymerizable monomer having a fluoroaliphatic group will be described. . A fluoroaliphatic group is an aliphatic group in which a hydrogen atom on a carbon atom is fluorinated, is usually saturated, and is generally monovalent or divalent. This includes straight, branched or cyclic. The fluoroaliphatic group is 3 to 20, preferably 6 to 20, in order to exert a sufficient effect for the purpose of the present invention.
It has 12 carbon atoms and has at least 40% by weight, preferably at least 50% by weight, of fluorine bonded to carbon atoms. Suitable fluoroaliphatic groups are C _n F _{2n + 1}
A substantially completely or fully fluorinated perfluoroaliphatic group (hereinafter abbreviated as Rf group), such as-(n is an integer of 1 or more, preferably 3 or more).

Component a. As the addition-polymerizable monomer part in the addition-polymerizable monomer having a fluoroaliphatic group represented by the following formula, a vinyl monomer having a radically polymerizable unsaturated group is used. Preferred among these vinyl monomers are acrylate, methacrylate, acrylamide, methacrylamide, styrene,
Vinyl based. Specific examples of acrylates and methacrylates bonded to a fluoroaliphatic group include, for example, Rf-
R'-OOC-C (R " ) = CH 2 ( wherein R ', for example, a single bond, an alkylene, a sulfonamide alkylene,
Or a carbonamidoalkylene, wherein R ″ is a hydrogen atom, a methyl group, a halogen atom, or a perfluoroaliphatic group).

Examples of these are, for example, US Pat. Nos. 2,803,615, 2,642,416, and 282.
No. 6564, No. 3102103, No. 328290
No. 5, No. 3,304,278, JP-A-6-2562.
No. 89, JP-A-62-1116, JP-A-62-487
No. 72, JP-A-63-77574, JP-A-62-36
657 and the Chemical Society of Japan 1985 (No.
10) Those described on pages 1884-1888. In addition to these fluoroaliphatic group-bonding monomers, Reports Res. Lab. Asahi Glass Co. Lld., 34
Vol. 1984, pp. 27-34, can be used to advantage. Further, as the fluoroaliphatic group-bonding monomer, a mixture having different lengths of perfluoroalkyl groups as shown in the following structural formula can be used.

[0021]

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The amount of these fluoroaliphatic group-containing vinyl monomers used in the fluoropolymer used in the present invention is 3 to 70 based on the weight of the fluoropolymer.
%, Preferably in the range of 7 to 60% by weight.

Next, a copolymer component of the fluoropolymer of the present invention, b. Will be described in detail. First, the monomer capable of addition polymerization having a carboxylic acid group represented by the following general formula (1) will be described.

[0024]

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Wherein A is a hydrogen atom, a halogen atom,
Or X represents an alkyl group, and X represents an oxygen atom, NH, or
NR_Five (Where R_FiveRepresents an alkyl group),
R₁, R_Two, R_ThreeAnd R_FourAre each independently a hydrogen atom, ha
Logen atom, alkyl group, substituted alkyl group, aryl
Group, substituted aryl group, -OR₆ , -OCO-R ₇, −
NHCO-R₈ , -NHCONH-R₉, -OCONH
-R_Ten, -COO-R₁₁, -CONH-R₁₂, -CO-
R₁₃, -CON (R₁₄) (R_Fifteen), -CN or -C
Represents an HO group, or R₁, R_Two, R_ThreeAnd R_FourIs that
Two of them may combine to form a ring;₆~ R_Fifteen
Is an alkyl group, a substituted alkyl group, an aryl group or a substituted
Indicates a reel group. However, preferably R₁, R_Two, R_ThreePassing
And R_FourAt least one of them represents a group other than a hydrogen atom
You. )

In the general formula (1), A represents a hydrogen atom, a halogen atom or an alkyl group. The halogen atom is preferably chlorine or bromine. As the alkyl group, one having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms can be used. In the above general formula (1), R ₁ , R ₂ , R
₃ and R ₄ are each independently a hydrogen atom, a halogen atom,
Alkyl group, a substituted alkyl group, an aryl group, a substituted aryl _{group, -O-R 6, -OCO-} R 7, -NHCO-R
_{8, -NHCONH-R 9, -OCONH} -R 10, -C
_{OO-R 11, -CONH-R} 12, -CO-R 13, -CO
_{N (R 14) (R 15} ), - represents CN or -CHO group. As the halogen atom, fluorine, chlorine and bromine atoms are preferred. As the alkyl group, one having 1 to 20 carbon atoms is used, and more preferably, an alkyl group having 1 to 8 carbon atoms is used. As the aryl group, one having 6 to 20 carbon atoms such as phenyl and naphthyl is used, and more preferably one having 6 to 10 carbon atoms is used. Examples of the substituent of the substituted alkyl group and the substituted aryl group include an aryl group, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, an alkoxycarbonyl group, an acyloxy group, a formyl group, and an ether group. Examples of the substituent of the substituted aryl group include an alkyl group having 1 to 10 carbon atoms in addition to those described above.

R₁, R_Two, R_ThreeAnd R_FourIs two of them
May combine with each other to form a ring. R ₁~ R_FourTwo of
Is preferably a 5- to 7-membered ring,
Cyclopentane, cyclohexane, benzene, naphthale
An aliphatic ring having 4 to 14 carbon atoms such as
Hetero such as pyridyl, furyl, pyrrole, indole
Heterocycles containing 1 to 4 atoms can be mentioned. Ma
R_FiveAs an alkyl group having 1 to 6 carbon atoms,
Preferably there may be mentioned 1 to 4 alkyl groups.
You.

R _{6 to} R ₁₅ represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. As the alkyl group, one having 1 to 20 carbon atoms is used, and more preferably, an alkyl group having 1 to 8 carbon atoms is used. Examples of the aryl group include phenyl, naphthyl and the like having 6 to 20 carbon atoms.
Are used, and more preferably 6 to 10 are used. Examples of the substituent of the substituted alkyl group and the substituted aryl group include an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and 2 carbon atoms.
Examples include 10 to 10 alkoxycarbonyl groups, 1 to 10 carbon atom acyloxy groups, and formyl groups. Examples of the substituent of the substituted aryl group include an alkyl group having 1 to 10 carbon atoms in addition to those described above.

In the above general formula (1), A is preferably a hydrogen atom or a methyl group, and X is preferably NH. R _{1 to} R _{4 each} represent a halogen atom, an alkyl group having 1 to 8 carbon atoms; an alkyl group having 1 to 15 carbon atoms substituted with a halogen atom, an aryl group or an alkoxy group; ₆ groups; -OCO-R ₇ groups; -OCO
NH-R ₁₀ group (alkyl group having wherein _{R 6, R 7, R 10} 8 pieces of carbon atoms from 1 each independently, an aryl group, a halogen atom, the total carbon substituted with an aryl group or an alkoxy group number 1 to 15 substituents alkyl group; or a halogen atom, the total carbon number of 6 preferably 15 substituted aryl group) is preferably substituted with an alkyl group or an alkoxy group, and R ₁ to R ₄ are, of which It is also preferred that the two are linked to form a ring. Specific examples of a preferable ring include naphthalene, tetralin, indene, indanone, tetralone, benzofuran, and indole when condensed with an aryl group to which a carboxyl group is bonded.

Next, specific examples of the polymerized unit represented by the above general formula (1) are shown below. However, the present invention is not limited to this specific example.

[0031]

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[0032]

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[0033]

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Next, an addition-polymerizable monomer having a carboxylic acid group represented by the following general formula (2) will be described.

[0035]

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(Where A represents a hydrogen atom, a halogen atom or an alkyl group, and X represents an oxygen atom, NH or N-
R ₅ represents (wherein R ₅ represents an alkyl group), R _1,
R _2, R ₃ and R ₄ are independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl _{group, -O-R 6, -OCO-} R 7, -NHCO
—R ₈ , —NHCONHR ₉ , —OCONH—R ₁₀ ,
_{-COO-R 11, -CONH-R} 12, -COR 13, -C
Represents an ON (R ₁₄ ) (R ₁₅ ), —CN or —CHO group, or _{two of} R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring , R _{6 to} R ₁₅ represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and preferably at least one of R ₁ , R ₂ , R ₃ and R ₄ represents a group other than a hydrogen atom. , L ₁ represents a divalent organic group. )

In the above general formula (2), A represents a hydrogen atom,
Represents a halogen atom or an alkyl group. As a halogen atom
Each atom of bromine and chlorine is preferred. As an alkyl group
Is one having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
Can be In the above general formula (2), R₁, R_Two, R_Three
And R_FourIs independently a hydrogen atom, a halogen atom,
Alkyl group, substituted alkyl group, aryl group, substituted aryl
Group, -OR₆, -OCO-R₇ , -NHCO-R
₈ , -NHCONH-R₉ , -OCONH-R_Ten, -C
OO-R₁₁, -CONH-R₁₂, -CO-R₁₃, -CO
N (R ₁₄) (R_Fifteen), -CN or -CHO group
You. Fluorine, chlorine and bromine atoms as halogen atoms
Is preferred. As the alkyl group, one having 1 to 20 carbon atoms
And more preferably 1 to 8 alkyl groups
Is used. Aryl groups include phenyl and naphthyl
C6 to C20 carbon atoms, such as
Alternatively, 6 to 10 pieces are used. Substituted alk
And the substituent of the substituted aryl group has 6 carbon atoms.
10 to 10 aryl groups, 1 to 10 carbon alkoxy
Group, halogen atom, alkoxycal having 2 to 11 carbon atoms
A bonyl group, an acyloxy group having 2 to 11 carbon atoms,
And the like. Also, a substituted aryl group
As the substituents, other than those described above, C 1 -C
Ten alkyl groups can be mentioned.

_{Two of} R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring. Examples of such a ring include cycloalkyl, phenyl, naphthyl and the like having 4 to 4 carbon atoms.
Mention may be made of 14 aliphatic rings, aryl rings and heterocycles containing 1 to 4 heteroatoms such as pyridyl, furyl, pyrrole, indole and the like. The R _5, 1 to 6 alkyl groups having a carbon number, and more preferably can be given 1-4 alkyl group.

R _{6 to} R ₁₅ represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. As the alkyl group, one having 1 to 20 carbon atoms is used, and more preferably, an alkyl group having 1 to 8 carbon atoms is used. Examples of the aryl group include phenyl, naphthyl and the like having 6 to 2 carbon atoms.
0 pieces are used, and more preferably 6 to 10 pieces are used. Examples of the substituent of the substituted alkyl group and the substituted aryl group include an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 11 carbon atoms, and 2 carbon atoms. ~ 11
Acyloxy groups and formyl groups. Examples of the substituent of the substituted aryl group include an alkyl group having 1 to 10 carbon atoms in addition to those described above.

In the general formula (2), L ₁ represents a divalent organic group. Useful divalent organic groups include, for example, alkylene groups having 1 to 20 carbon atoms such as methylene and ethylene;
For example, an arylene group having 6 to 20 carbon atoms such as phenylene and naphthylene, for example, having 2 carbon atoms such as vinylidene
The alkylene group, the arylene group, and the alkenylene group may further have a substituent. Suitable substituents include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, and the like. As described above, the alkylene group, the arylene group, and the alkenylene group, each of which may have a substituent, constitute a divalent organic group defined by L ₁ by combining two or more of the groups. You can also.

[0041] Further one end of the organic group defined by L _1, both ends, an intermediate, at one end and the intermediate or both ends and the middle, ester (-COO-), an amide group (-CONH-), carbamate group (-NHCO ₂ -), urea group (-NHCO
NH-), an ether group (-O-), an imino group (-NH
-), thioether group (-S-), sulfonamide group (-SO ₂ NH ₂ -) include, or may be interposed.
Particularly preferred L ₁ is a divalent organic group represented by the following general formula (3). _{- (L 11) a - (} L 12) b - (L 13) c -L 14 - (3) where, L ₁₁ represents a -COO- or -CONH-,
L ₁₂ is — (CH ₂ ) ₁ —O— (where 1 represents an integer of 2 to 15) or — (CH ₂ ) _m — (where m is 2 to 1)
Indicates an integer of 5. ) Wherein L ₁₃ is -CO- or = CO
— (CH ₂ ) _n —COO— (where n is an integer of 2 to 15), L ₁₄ is an arylene group having 6 to 10 carbon atoms, and — (CH ₂ ) _p — (where p Is an integer of 2 to 15) or NH, a is 0 or 1, b is 0, 1 or 2, c is 0
Or an integer of 1.

In the general formula (2), A is preferably a hydrogen atom or a methyl group, and X is preferably NH. R _{1 to} R ₄ represent a hydrogen atom, a halogen atom,
An alkyl group, an alkyl group having 1 to 8 carbon atoms;
An alkyl group having 1 to 15 carbon atoms and substituted with a halogen atom, an aryl group or an alkoxy group; -OR ₆ group;
OCO-R ₇ group; -OCONH-R ₁₀ group (where R ₆ , R
₇ and R ₁₀ each independently represent an alkyl group having 1 to 8 carbon atoms; an aryl group; a substituted alkyl group having 1 to 15 carbon atoms and substituted with a halogen atom, an aryl group or an alkoxy group; A substituted aryl group having a total of 6 to 15 carbon atoms, which is substituted by an atom, an alkyl group or an alkoxy group, is preferable), and two of R _{1 to} R ₄ may be combined with each other to form a ring. preferable.
Specific examples of a preferable ring include naphthalene, condensed with an aryl group to which a carboxyl group is bonded,
Tetralin, indene, indanone, tetralone, benzofuran, and indole.

Next, specific examples of the polymerized unit represented by the general formula (2) are shown below. However, the present invention is not limited to this specific example.

[0044]

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[0045]

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The amount of the monomer having a carboxylic acid group represented by the above general formula (1) or (2) in the side chain used in the fluoropolymer used in the present invention depends on the amount of the fluoropolymer. 5 to 80% by weight, preferably 20 to 50% by weight, based on the weight of

The fluoropolymer of the present invention can be produced by a known and commonly used method. For example, a (meth) acrylate having a fluoroaliphatic group (component a.) And a (meth) acrylate (component b.) Represented by the above general formula (1) or (2) are converted into a general-purpose radical polymerization initiator in an organic solvent. It can be produced by adding an agent and performing thermal polymerization. Alternatively, if necessary, another addition-polymerizable unsaturated compound may be added to produce the compound in the same manner as described above.

In order to achieve the object of the present invention, the fluoropolymer according to the present invention comprises the component a. And b. It is essential that the compound be composed of (meth) acrylate or (meth) acrylamide having an aliphatic group or an aromatic group as another addition-polymerized unsaturated compound. Preferred examples of the (meth) acrylate or (meth) acrylamide having an aliphatic group or an aromatic group include an aliphatic group having 4 or more carbon atoms, or a (meth) acrylate having an aromatic group or (Meth) acrylamide.

The aliphatic group having four or more carbon atoms includes a monovalent and divalent aliphatic group. The aliphatic group having 4 or more carbon atoms includes a linear, branched or cyclic aliphatic group. In order for these aliphatic groups to be more effective for the purposes of the present invention, they preferably have 6-30, preferably 8-25, carbon atoms. Specifically, n-hexyl group, cyclohexyl group,
n-octyl group, nonyl group, decyl group, undecyl group,
Dodecyl, tridecyl, tetradecyl, octadecyl and the like can be mentioned. The aromatic group preferably has 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. The aromatic group is preferably substituted with an aliphatic group having one or more carbon atoms.
Examples of the aliphatic group having one or more carbon atoms used as a substituent include those having 1 to 20, more preferably 4 to 18 carbon atoms, for example, n-butyl, t-butyl, cyclohexyl, 2-ethylhexyl and the like. A linear, branched or cyclic aliphatic group is preferred.

These aliphatic groups and aromatic groups may have other substituents, such as halogen atom, acyl, acyloxy, acylamino,
Examples include alkoxycarbonyl, cyano, and aromatic groups. Specific examples of the acrylate, methacrylate, acrylamide or methacrylamide having an aliphatic group and / or an aromatic group having 4 or more carbon atoms include the following monomers.

For example, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, pentyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, Benzyl acrylate, methyl benzyl acrylate, dimethyl benzyl acrylate,
Chlorobenzyl acrylate, bromobenzyl acrylate, ethyl benzyl acrylate, n-propylbenzyl acrylate, iso-propylbenzyl acrylate, n-butylbenzyl acrylate, iso-butylbenzyl acrylate, tert-butylbenzyl acrylate, Phenyl acrylate, naphthyl acrylate, tolyl acrylate, xylyl acrylate, chlorophenyl acrylate, bromophenyl acrylate, ethylphenyl acrylate, n-propylphenyl acrylate, i-acrylate
So-propylphenyl, n-butylphenyl acrylate, iso-butylphenyl acrylate, t-acrylate
tert-butylphenyl. Preferred are lauryl acrylate, stearyl acrylate, behenyl acrylate, tert-butylbenzyl acrylate, tert-butyl acrylate, and tert-butylphenyl acrylate.

Further, methacrylic esters can be mentioned. For example, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate,
Benzyl methacrylate, methyl benzyl methacrylate,
Dimethylbenzyl methacrylate, chlorobenzyl methacrylate, bromobenzyl methacrylate, ethylbenzyl methacrylate, n-propylbenzyl methacrylate, iso-propylbenzyl methacrylate, n-methacrylic acid
-Butylbenzyl, iso-butylbenzyl methacrylate, tert-butylbenzyl methacrylate, phenyl methacrylate, naphthyl methacrylate, tolyl methacrylate, xylyl methacrylate, chlorophenyl methacrylate, bromophenyl methacrylate, ethylphenyl methacrylate, n methacrylate -Propylphenyl, iso-propylphenyl methacrylate, n-methacrylic acid
Butylphenyl, iso-butylphenyl methacrylate, and tert-butylphenyl methacrylate. Preferred are lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, tert-butyl methacrylate, tert-butylbenzyl methacrylate, and tert-butylphenyl methacrylate.

Further, the following acrylamides and methacrylamides may be mentioned as examples. N
-Nonylacrylamide, N-decylacrylamide,
N-lauryl acrylamide, N-stearyl acrylamide, N-nonyl methacrylamide, N-decyl methacrylamide, N-lauryl methacrylamide,
N-stearyl methacrylamide and the like. The amount of the vinyl monomer bonded to the aliphatic group or aromatic group having four or more carbon atoms used in the fluoropolymer in the present invention is 5 to 70% by weight based on the weight of the fluoropolymer. %, Preferably 10 to 50% by weight
Range.

Other optionally used addition-polymerized unsaturated compounds include Polymer Handbook 2nd ed.,
J. Brandrup, Wiley Interscience (1975) Chapter 2 Pa
ge 1 to 483 can be used. Examples of these are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-chloroethyl (meth)
(Meth) acrylates such as acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-methylol ( (Meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (p-hydroxyphenyl) -methacrylamide, allyl acetate, allyl caproate, and stearin Allyl compounds such as allyl acid and allyloxyethanol;

Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, phenyl vinyl ether, tolyl vinyl ether, diethylaminoethyl Vinyl ethers such as vinyl ether; vinyl acetate, vinyl butyrate, vinyl caproate,
Vinyl chloroacetate, vinyl methoxyacetate,
Vinylphenyl acetate, vinyl acetoacetate,
Vinyl esters such as vinyl benzoate and vinyl chlorobenzoate; styrenes such as styrene, α-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, ethoxymethylstyrene, hydroxystyrene, chlorostyrene and bromostyrene;

Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; olefins such as isobutylene, butadiene, and isoprene; , Diethyl fumarate, N-vinylpyrrolidone, N-
Vinyl pyridine, acrylonitrile and the like. In addition to these monomers, JP-A-62-226143
And polyoxyalkylene (meth) acrylates described in JP-A-3-172849 can be used.

Also, when the fluorine-based polymer of the present invention is used in a form other than acrylic resin and methacrylic resin, the component a. , B. Besides the hydrophobic component c. It is more desirable to polymerize a component having an aliphatic group or an aromatic group in order to enhance the ink receptivity (inking property) of the lithographic printing plate. Particularly when used in the form of a polyurethane resin, at least one selected from an aromatic group substituted with at least 10 linear or branched aliphatic or alkylene groups and an aliphatic group having at least 4 carbon atoms. It is desirable that the polymer component has one.

Hereinafter, specific examples of the structure of the fluoropolymer according to the present invention will be described. The numbers in the formulas indicate the molar ratio of each monomer component.

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The molecular weight of the fluoropolymer used in the present invention ranges from 3,000 to 200,000 as an average molecular weight.
0, more preferably 6,000-100,
000. The range of the addition amount of the fluoropolymer in the photosensitive resin composition of the present invention is preferably from 0.001 to 10% by weight, based on the total composition except for the solvent.
More preferably, the content is from 01 to 5% by weight.

Next, other components necessary for preparing the positive photosensitive resin composition according to the present invention will be described. As the positive photosensitive resin composition, any one can be used as long as its solubility or swelling property in a developer changes before and after exposure, and an o-quinonediazide compound is preferred as a positive photosensitive resin composition. For example,
In the case of a positive photosensitive resin composition containing an alkali-soluble resin and an o-quinonediazide compound, the o-quinonediazide compound is a compound having at least one o-quinonediazide group, and increases solubility in an aqueous alkali solution by actinic light. Are preferred.

As such a structure, various structures are known. For example, “Light-Sensitive” by J. KOSAR
Systems "(John Wiley & Sons, Inc, 1965) P.33
See pages 6 to 352 for details. As the photosensitive compound of the positive photosensitive resin composition, sulfonic acid esters of various hydroxyl compounds and o-benzoquinonediazide or o-naphthoquinonediazide are particularly suitable.

Examples of the o-quinonediazide compound as described above include, for example, esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with a phenol-formaldehyde resin or a cresol-formaldehyde resin; US Pat. No. 3,635. , 709, 1,2-naphthoquinone-2-diazide-
Ester of 5-sulfonyl chloride with pyrogallol-acetone resin; 1,2-naphthoquinone-2-diazide-5 described in JP-B-63-13528.
Esters of sulfonyl chloride and resorcin-benzaldehyde resin; 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and resorcin-pyrogallol-acetone co-condensation resin described in JP-B-62-44,257. Of ester; JP-B-56-4
1,127-naphthoquinone-2-polyester having a hydroxyl group at a terminal described in US Pat.
Esterified diazide-5-sulfonyl chloride;

A homopolymer of N- (4-hydroxyphenyl) methacrylamide or a copolymer with another copolymerizable monomer described in Japanese Patent Publication No. 50-24,641 may be substituted with 1,2-naphthoquinone- 2-diazide-5
Esterified sulfonyl chloride; 1,2- described in JP-B-54-29,922
Esters of naphthoquinone-2-diazide-5-sulfonyl chloride with bisphenol-formaldehyde resins; with p-hydroxystyrene homopolymers or other copolymerizable monomers described in JP-B-52-36,043. 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride esterified to a copolymer; 1,2-naphthoquinone-2-diazide-
There are esters of 5-sulfonyl chloride with polyhydroxybenzophenone.

Other known o-quinonediazide compounds that can be used in the present invention include JP-A-63-80,2525.
4, JP-A-58-5,737, JP-A-57-11
No. 1,530, JP-A-57-111,531, JP-A-57-114,138, JP-A-57-142,635
No., JP-A-51-36,129, JP-B-62-3,4
No. 11, JP-B-62-51,459, JP-B-51-4
No. 83 and the like described in each specification can be mentioned. The content of the o-quinonediazide compound is usually 5 to 60% by weight, more preferably 10 to 40% by weight, based on the total solid content of the photosensitive resin composition.

As the photosensitive compound other than o-quinonediazide, a chemically amplified photosensitive material comprising a combination of a compound in which an alkali-soluble group is protected with an acid-decomposable group and a photoacid generator can be used. Known photoacid generators used in the chemical amplification system can be used.

For example, SI Schlesinger, Photogr. S
ci. Eng., 18, 387 (1974), TSBal etal, Polymer,
21, 423 (1980) etc., U.S. Pat.
4,069,055, 4,069,056, ammonium salts described in JP-A-3-140140, etc., DCNecker et al, Macromolecul
es, 17, 2468 (1984), CS Wen etal, Teh, Proc. Con
f. Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent Nos.
1307 (1977), Chem. & Eng. News, Nov. 28, p31 (198
8), European Patent No. 104,143, US Patent No. 339,049,
410,201, JP-A-2-150848, Iodonium salts described in JP-A-2-29514, etc., JV Crivello etal, Polymer
J. 17, 73 (1985), JV Crivello etal. J. Org. Che
m., 43, 3055 (1978), WR Wattetal, J. Polymer Sc
i., Polymer Chem.Ed., 22, 1789 (1984), JV Crive
lloetal, Polymer Bull., 14, 279 (1985), JV Criv
ello etal, Macromorecules, 14 (5), 1141 (1981), J.
V. Crivello etal, J. Polymer Sci., Polymer Chem. E
d., 17, 2877 (1979), EP 370,693, U.S. Patent 3,902,114, EP 233,567, EP 297,443,
No. 297,442, U.S. Pat.Nos. 4,933,377, 410,201,
339,049, 4,760,013, 4,734,444, 2,832
No. 3,827, Dokoku Patent No. 2,904,626, No. 3,604,580,
Sulfonium salts described in 3,604,581 and the like,

[0072] JV Crivello etal, Macromorecules, 1
0 (6), 1307 (1977), JV Crivello etal, J. Polymer
Sci., Polymer Chem. Ed., 17, 1047 (1979) and the like, CS Wen etal, Teh, Proc. Conf.R
ad. Curing ASIA, p478 Tokyo, Oct (1988) and the like, onium salts such as arsonium salts, U.S. Pat.No. 3,905,815
No., JP-B-46-4605, JP-A-48-36281, JP-A-55-32
No. 070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401
No., JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al., J. Rad.
13 (4), 26 (1986), TP Gill et al., Inorg.Chem., 1
9, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (1
2), 377 (1896), and organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer Sc
i., 25, 753 (1987); E. Reichmanis et al., J. Pholymer
Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu
etal, J. Photochem., 36, 85, 39, 317 (1987), B. Am
it etal, Tetrahedron Lett., (24), 2205 (1973), D.
HR Barton et al, J. Chem Soc., 3571 (1965), PM
Collins etal, J. Chem. SoC., Perkin I, 1695 (1975)
, M. Rudinstein etal, Tetrahedron Lett., (17), 14
45 (1975), JW Walker et al. J. Am. Chem. Soc., 11
0, 7170 (1988), SCBusman et al., J. Imaging Technol., 1
1 (4), 191 (1985), HMHoulihan et al, Macormolecules, 2
1,2001 (1988), PMCollins et al., J. Chem. Soc., Chem. Com
mun., 532 (1972), S. Hayase et al, Macromolecules, 18, 17
99 (1985), E. Reichmanis et al., J. Electrochem. Soc., Soli
d State Sci.Technol., 130 (6), FMHoulihan et al, Macr
omolcules, 21, 2001 (1988), EP 0290,750, 0
46,083, 156,535, 271,851, 0,388,343,
U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-19
No. 8538, a photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-53-133022, etc.

M. TUNOOK etal, Polymer Preprints Japa
n, 35 (8), G. Berner et al., J. Rad. Curing, 13 (4), W.
J. Mijs etal, Coating Technol., 55 (697), 45 (198
3), Akzo, H. Adachi et al, Polymer Preprints, Japa
n, 37 (3), European Patent Nos. 0199,672, 84515, 199,67
No. 2, 044,115, 0101,122, U.S. Pat.No.4,618,56
No. 4, 4,371,605, 4,431,774, JP-A-64-18143
No. 2,245,756, Japanese Patent Application No. 3-140109, etc., compounds capable of generating sulfonic acid upon photolysis represented by iminosulfonate, etc., described in JP-A-61-166544, etc. Disulfone compounds can be mentioned. The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually in the range of 0.001 to 40% by weight based on the total weight of the photosensitive resin composition (excluding the coating solvent). It is preferably used in the range of 0.01 to 20% by weight, more preferably 0.1 to 5% by weight.

Compounds in which an alkali-soluble group is protected by an acid-decomposable group include -CO-C- or -CO-Si
-A compound having a bond, and examples thereof include the following. a) at least one selected from the group consisting of orthocarboxylic acid esters and carboxylic acid amide acetals, wherein the compound can have polymerizability, said group being a crosslinking element in the main chain or a lateral substituent B) an oligomeric or polymeric compound containing in the main chain thereof a compound selected from the group consisting of repeating acetal and ketal; c) a compound containing at least one enol ester or N-acylaminocarbonate group; d. A) cyclic acetal or ketal of β-ketoester or β-ketoamide,

E) a compound containing a silyl ether group, f) a compound containing a silyl enol ether group, g) an aldehyde or ketone component
Monoacetals or monoketals having a solubility of 0.1-100 g / l, h) ethers of tertiary alcohols, and i) carboxylic esters and carbonates of tertiary allylic or benzylic alcohols.

Compounds of the type (a) which can be cleaved by acid as components of the light-sensitive mixture are described in DE-A-2,610,842 and DE-A-2,928,636. Mixtures containing compounds of type (b) are described in German Patents 2,306,248 and
718,254. Compounds of class (c) are described in EP-A-0,006,626 and EP-A-0,006,627. Compounds of class (d) are described in EP-A-0,202,
The compounds used as class (e) are described in DE 196,196 and 3,601,264. Compounds of the type (f) are described in DE-A-3,730,78.
No. 5,730,783, compounds of type (g) are described in German Offenlegungsschrift 3,731.
No. 0,783. Compounds of type (h) are described, for example, in US Pat. No. 4,603,101, and compounds of type (i) are described, for example, in US Pat.
491,628 and a paper by JM Frechet et al. (J. Im.
agingSci. 30, 59-64 (1986)). The content of the compound protected by the acid-decomposable group is usually 1 to 60% by weight, more preferably 5 to 40% by weight, based on the total solid content of the photosensitive resin composition.

Examples of the water-insoluble synthetic resin soluble in an alkaline aqueous solution (hereinafter referred to as an alkali-soluble resin) include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde co-condensation resin, phenol-modified xylene resin,
In addition to a copolymer of polyhydroxystyrene, polyhalogenated hydroxystyrene, N- (4-hydroxyphenyl) methacrylamide, a copolymer of hydroquinone monomethacrylate, a sulfonylimide polymer described in JP-A-7-28244, And carboxyl group-containing polymers described in JP-A-7-36184. Other acrylic resins containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, acrylic resins having a sulfonamide group described in JP-A-2-866, urethane-based resins, Various alkali-soluble polymer compounds can also be used. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
0 to 20,000 and number average molecular weight of 200 to 60,00
0 is preferred. These alkali-soluble polymer compounds may be used alone or in combination of two or more, and are used in an amount of 80% by weight or less of the total composition.

Further, as described in US Pat. No. 4,123,279, a compound having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a t-butylphenol formaldehyde resin and an octylphenol formaldehyde resin. It is preferable to use a condensate of phenol and formaldehyde in combination to improve the oil sensitivity of the image. Such an alkali-soluble resin is generally used in an amount of 90% by weight or less based on the total weight of the composition.

In the photosensitive resin composition, if necessary, a cyclic acid anhydride for increasing the sensitivity, a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent, and the like. Can be added.

In the photosensitive resin composition of the present invention,
It is preferable to add cyclic acid anhydrides, phenols, and organic acids to increase the sensitivity. As the cyclic acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride as described in U.S. Pat.
Hexahydrophthalic anhydride, 3,6-endooxy-Δ
⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like. As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 4,4 ', 4 "-trihydroxy-triphenylmethane, 4,4', 3", 4 "-Tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane.

As the organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphinic acids, phosphoric esters, carboxylic acids, and the like described in JP-A-2-96755 and the like. p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid,
Phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2- Examples thereof include dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The above cyclic acid anhydrides,
The proportion of phenols and organic acids in the photosensitive resin composition is preferably from 0.05 to 15% by weight, and more preferably from 0.1 to 5% by weight.

Examples of the printing-out agent for obtaining a visible image immediately after exposure include a combination of a photosensitive compound which releases an acid upon exposure and an organic dye which forms a salt with an acid and changes color. it can.

Examples of the photosensitive compound which releases an acid upon exposure include o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209; and JP-A-53-36223. Trihalomethyl-2-bilone and trihalomethyl-s-triazine described in the gazettes; various o-naphthoquinonediazide compounds described in JP-A-55-62444;
Examples thereof include 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds and diazonium salts described in JP-A-55-77742. These compounds can be used alone or as a mixture, and the amount added is 0.3% based on the total weight of the composition.
A range of １５15% by weight is preferred.

In the photosensitive resin composition of the present invention, at least one kind of organic dye which changes its color tone by interacting with a photolysis product of a compound which generates an acidic substance by photolysis is used. . Such organic dyes include diphenylmethane, triarylmethane, thiazine, oxazine, phenazine, xanthene, anthraquinone, iminonaphthoquinone,
Azomethine dyes can be used. Specifically, it is as follows.

Brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, Rose bengal, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-
Dichlorofluorescein, paramethyl red, congo red, benzopurpurine 4B, α-naphthyl red,
Nile blue 2B, Nile blue A, phenacetaline,
Methyl violet, malachite green, parafuchsin, oil blue # 603 [Orient Chemical Industry Co., Ltd.
Oil Pink # 312 [Orient Chemical Industry Co., Ltd.], Oil Red 5B [Orient Chemical Industry Co., Ltd.], Oil Scarlet # 308 [Orient Chemical Industry Co., Ltd.], Oil Red OG [Orient Chemical Co., Ltd.] Industrial Co., Ltd.), Oil Red RR (Orient Chemical Co., Ltd.), Oil Green # 502 (Orient Chemical Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), Victoria Pure Blue BOH (made by Hodogaya Chemical Industry Co., Ltd.),

Patent Pure-Blue (manufactured by Sumitomo Sangoku Chemical Co., Ltd.), Sudan Blue II (manufactured by BASF), m
-Cresol purple, cresol red, rhodamine B, rhodamine 6G, first acid violet R, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2 -Carbostearylamino-4-p-dihydroxyethyl-amino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-
o'-methylphenyliminoacetanilide, cyano-
p-diethylaminophenyliminoacetanilide, 1
-Phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-
p-diethylaminophenylimino-5-pyrazolone and the like.

Particularly preferred organic dyes are triarylmethane dyes. Triarylmethane dyes are disclosed in JP-A-62-293471 and Japanese Patent Application No. 4-1128.
Those having a sulfonic acid compound as a counter anion as shown in JP-A-44-44 are particularly useful. These dyes can be used alone or as a mixture, and the amount of addition is preferably 0.3 to 15% by weight based on the total weight of the photosensitive resin composition. If necessary, it can be used in combination with other dyes and pigments.
% By weight, more preferably 50% by weight or less.

Next, in the photosensitive resin composition of the present invention,
The photosensitive resin composition when used as a photosensitive layer of a photopolymerizable printing plate that is a negative printing plate will be described. When the photosensitive resin composition of the present invention is a photopolymerizable photosensitive resin composition, the main components thereof include, in addition to the fluorine-based polymer, a compound containing an addition-polymerizable ethylenic double bond, It is a polymerization initiator and the like, and if necessary, a compound such as a thermal polymerization inhibitor is added.

The compound containing an addition-polymerizable double bond is
The compound can be arbitrarily selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. For example, those having chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and their copolymers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated esters Examples include amides of a carboxylic acid and an aliphatic polyamine compound.

Specific examples of the monomer of the ester 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
G, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer 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, dipentaerythritol pentamethacrylate, sorbitol tri Methacrylate, 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,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonic acid esters 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 methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-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 ＣC (R ₅ ) COOCH ₂ CH (R ₆ ) OH (A) (where R ₅ and R ₆ represent H or CH ₃ )

Further, 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 5-70 with respect to all components.
% By weight (hereinafter abbreviated as%), preferably 10 to 50%
%.

The photopolymerization initiator contained in the photopolymerizable photosensitive resin composition used in the present invention may be selected from various photopolymerization initiators known in patents and literatures, depending on the wavelength of the light source used, or A combination system (photopolymerization initiation system) of two or more photopolymerization initiators can be appropriately selected and used. For example, when using light near 400 nm as a light source, benzyl, benzoin 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
Even when a laser is used as a light source, various photopolymerization initiation systems have been proposed, for example, US Pat. No. 2,850,44.
Certain photoreducing dyes described in No. 5, such as rosbengal, eosin, erythrosine, and the like, or a system based on a combination of a dye and a photopolymerization initiator, for example, a complex initiation system of a dye and an amine (Japanese Patent Publication No. Sho 44) -20189), a combination system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-37377), and a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528; 54-1 Kaisho
55292), 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
9-1504, JP-A-59-140203, JP-A-59-189340, JP-A-62-174203,
JP-B-62-1641, U.S. Pat. No. 4,766,055
No.), a system of a dye and an active halogen compound (JP-A-63-2
58903, JP-A-2-63054, etc.),

A system of a dye and a borate compound (JP-A-62-2
No. 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-64-17048,
JP-A-1-229003, JP-A-1-298348
And a system comprising a dye having a rhodanine ring and a radical generator (Japanese Patent Laid-Open No. 2-1796).
No. 43, JP-A-2-244050), titanocene and 3
-Ketocoumarin dye system (JP-A-63-221110)
), A system in which a titanocene and a xanthene dye are further combined with an ethylenically unsaturated compound capable of addition polymerization 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), and a system of titanocene and a dye having a benzopyran ring (JP-A-8-295).
No. 334897). The amount of these photopolymerization initiators used is 100 ethylenically unsaturated compounds.
It can be used in an amount of 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.2 to 50 parts by weight, based on parts by weight.

In the photopolymerizable photosensitive resin composition of the present invention, in addition to the above basic components, an unnecessary ethylenically unsaturated compound which can be polymerized during the production or storage of the photosensitive resin composition is unnecessary. It is desirable to add a small amount of a thermal polymerization inhibitor to prevent thermal polymerization. Suitable thermal polymerization inhibitors include haloquinone, p-methoxyphenol, di-tert-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 primary cerium salt, N-nitrosophenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% based on the weight of the whole composition. 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 addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

A lithographic printing plate having a photosensitive layer using a photopolymerizable resin composition according to the present invention is provided on the photopolymerizable photosensitive layer to prevent polymerization inhibition by oxygen. A barrier protective layer can be provided. Examples of the water-soluble vinyl polymer contained in the oxygen-barrier protective layer include polyvinyl alcohol, and its partial esters, ethers, and acetal, or a substantial amount of an unsubstituted vinyl alcohol unit having water solubility required for them. And copolymers thereof. Examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100% and a polymerization degree in the range of 300 to 2400.

Specifically, PVA-10 manufactured by Kuraray Co., Ltd.
5, PVA-110, PVA-117, PVA-117
H, PVA-120, PVA-124, PVA-124
H, PVA-CS, PVA-CST, PVA-HC, P
VA-203, PVA-204, PVA-205, PV
A-210, PVA-217, PVA-220, PVA
-224, PVA-217EE, PVA-217E, P
VA-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. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

The solvent used for coating the oxygen barrier protective layer of the present invention is preferably pure water, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. . The concentration of the solid content in the coating solution is suitably from 1 to 20% by weight. Known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of the film may be added to the oxygen-barrier protective layer of the present invention. 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 coating amount of the oxygen-barrier protective layer is suitably in the range of about 0.1 / m ² to about 15 / m ² by weight after drying. More preferably, it is 1.0 / m ² to about 5.0 / m ² .

The present invention provides a positive PS plate using the above-mentioned quinonediazide or a compound having an alkali-soluble group protected by an acid-decomposable group, a negative PS plate using a photopolymerization system, and the following type: The same can be used for a lithographic printing plate material. (1) Negative type lithographic printing plate material using diazo resin. (2) Negative type lithographic printing plate material using photocrosslinkable resin. (3) Negative laser direct drawing type lithographic printing material containing an alkali-soluble binder, an acid generator, and an acid (heat) crosslinkable compound. (4) A positive laser direct drawing type lithographic printing material further comprising an alkali-soluble binder, a substance which is thermally decomposable and substantially reduces the solubility of the alkali-soluble binder when not decomposed.

Hereinafter, the materials used in each example will be described in detail. The diazo resin used in (1) includes, for example, a diazo resin represented by a salt of a condensate of a diazodiarylamine and an active carbonyl compound, and is preferably photosensitive, water-insoluble, and soluble in an organic solvent. Particularly preferred diazo resins include, for example, 4-diazodiphenylamine, 4-diazo-3-methyldiphenylamine, 4-diazo-4'-
Methyldiphenylamine, 4-diazo-3'-methyldiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-diazo-3-methoxydiphenylamine and the like and formaldehyde, para Formaldehyde,
An organic acid salt or an inorganic acid salt of a condensate with acetaldehyde, benzaldehyde, 4,4'-bis-methoxymethyldiphenyl ether or the like.

In this case, examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid,
Xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy-4-methoxy Benzophenone-5-sulfonic acid and the like are mentioned, and inorganic acids include hexafluorophosphoric acid, tetrafluoroboric acid, thiocyanic acid and the like. Further, JP-A-54-301
No. 21 diazo resin having a main chain of a polyester group; diazo resin obtained by reacting a polymer having a carboxylic anhydride residue described in JP-A-61-273538 with a diazo compound having a hydroxyl group. Resin; a diazo resin obtained by reacting a polyisocyanate compound with a diazo compound having a hydroxyl group can also be used.

The use amount of these diazo resins is preferably in the range of 0 to 40% by weight based on the solid content of the composition, and if necessary, two or more diazo resins may be used in combination. In preparing the negative photosensitive resin composition, an organic polymer binder is usually used in combination. Examples of such an organic polymer binder include acrylic resin, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polystyrene resin, and novolak resin. Further, in order to improve performance, known additives, for example,
Thermal polymerization inhibitors, dyes, pigments, plasticizers, stability improvers and the like can be added.

Suitable dyes include, for example, crystal violet, maracay green, Victoria blue,
Basic oil-soluble dyes such as methylene blue, ethyl violet, and rhodamine B are included. Examples of commercially available products include “Victoria Pure Blue BOH” (manufactured by Hodogaya Chemical Industry Co., Ltd.) and “Oil Blue # 603”.
(Manufactured by Orient Chemical Industry Co., Ltd.). Examples of the pigment include phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone red, and the like.

Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, tri (2-chloroethyl) phosphate, tributyl citrate and the like. Further, as known stability improvers, for example, phosphoric acid, phosphorous acid, oxalic acid, tartaric acid, malic acid, citric acid, dipicolinic acid, polyacrylic acid, benzenesulfonic acid, toluenesulfonic acid and the like can also be used in combination. . The amount of these various additives varies depending on the purpose, but is generally preferably in the range of 0 to 30% by weight of the solid content of the photosensitive resin composition.

As the photocrosslinkable resin used in (2), a photocrosslinkable resin having an affinity for an aqueous alkaline developer is preferable. For example, a cinnamic acid group described in JP-B-54-15711 can be used. A copolymer having a carboxyl group; a phenylenediacrylic acid residue described in JP-A-60-165646 and a polyester resin having a carboxyl group; and a phenylenediacrylic acid residue described in JP-A-60-203630. Polyester resin having a phenolic hydroxyl group; polyester resin having a phenylenediacrylic acid residue and a sodium iminodisulfonyl group described in JP-B-57-42858;
Polymers having an azide group and a carboxyl group in the side chain described in JP-A-7-295212, and polymers having a maleimide group in the side chain described in JP-A-7-295212 can be used.

An alkali-soluble binder used in (3),
As the acid generator, the same materials as those described above for the positive PS plate using quinonediazide or a compound having an alkali-soluble group protected by an acid-decomposable group can be used. The acid (thermal) crosslinkable compound refers to a compound that crosslinks in the presence of an acid, and includes, for example, aromatic compounds and heterocyclic compounds that are polysubstituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. Among them, preferred examples include compounds obtained by condensing phenols and aldehydes under basic conditions. Preferred among the above compounds are, for example, compounds obtained by condensing phenol and formaldehyde under basic conditions as described above, similarly, compounds obtained from m-cresol and formaldehyde, and compounds obtained from bisphenol A and formaldehyde. Compound,
Compounds obtained from 4,4'-bisphenol and formaldehyde, and other compounds disclosed as resol resins in GB 2,082,339 are exemplified.

These acid-crosslinkable compounds have a weight average molecular weight of 500 to 100,000 and a number average molecular weight of 200 to 100.
50,000 are preferred. Other preferred examples include aromatic compounds substituted with an alkoxymethyl or oxiranylmethyl group disclosed in EP-A-0,212,482, EP-A-0,133,216, and D-A.
EA 3,634,671, DE 3,711,2
No. 64, monomer and oligomer melamine-formaldehyde condensates and urea-formaldehyde condensates, alkoxy-substituted compounds disclosed in EP-A-0,212,482. Still other preferred examples are, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl, N-alkoxymethyl or N-acyloxymethyl groups.
Of these, N-alkoxymethyl derivatives are particularly preferred.

Also, low molecular weight or oligomeric silanols can be used as silicon-containing crosslinkers. Examples of these are dimethyl- and diphenyl-silanediols and oligomers which have already been precondensed and contain these units, for example those disclosed in EP-A 0,377,155. Among aromatic compounds and heterocyclic compounds poly-substituted with an alkoxymethyl group, compounds having an alkoxymethyl group at a position adjacent to the hydroxyl group, and the alkoxy group of the alkoxymethyl group having 18 or less carbon atoms are preferable. Examples are given, and particularly preferred examples are the following general formulas (B) to (B).
The compound of (E) can be mentioned.

[0113]

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[0114]

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In the formula, L _{1 to} L ₈ may be the same or different and represent an alkoxymethyl group substituted by an alkoxy group having 18 or less carbon atoms, such as methoxymethyl, ethoxymethyl and the like. These are preferred because they have high crosslinking efficiency and can improve printing durability. The above compounds that are crosslinked by heat may be used alone,
Two or more types may be used in combination. The acid-crosslinkable compound used in the present invention is used in an amount of 5 to 80% by weight, preferably 10 to 75% by weight, particularly preferably 20 to 70% by weight, based on the total solid content of the lithographic printing plate material. .
If the amount of the acid-crosslinkable compound is less than 5% by weight, the durability of the photosensitive layer of the lithographic printing plate material obtained is deteriorated.
Exceeding 0% by weight is not preferred in terms of stability during storage.

As the alkali-soluble binder used in (4), the same materials as those used in the positive PS plate using quinonediazide described above can be used. As a substance that is thermally decomposable and substantially degrades the solubility of the alkali-soluble binder when not decomposed, various onium salts, quinonediazide compounds, etc. are excellent in lowering the solubility of the alkali-soluble binder. And is preferably used. Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and the like.

Suitable onium salts used in the present invention include, for example, S. I. Schle
singer, Photogr. Sci. Eng. , 1
8, 387 (1974); S. Bal et a
l. , Polymer, 21, 423 (1980); JP-A-5-158230; diazonium salts described in U.S. Pat.
No. 056, JP-A-3-140140 and the like. C. Necker et al. , Ma
cromolecules, 17, 2468 (198
4), C.I. S. Wen et al. , Teh, Pr
oc. Conf. Rad. Curing ASIA, p
478, Tokyo, Oct (1988), U.S. Patent Nos. 4,069,055 and 4,069,056, and the like. V. Crivello et
al. , Macromolecules, 10
(6), 1307 (1977), Chem. & En
g. News, Nov .; 28, p31 (1988), EP 104,143, US Patent 339,049.
No. 410,201, JP-A-2-150848, JP-A
2-296514 No. iodonium salt described,

JVCrivello et al., Polymer J. 17, 73
(1985), JVCrivello et al., J. Org. Chem., 43, 3055.
(1978), WRWatt et al., J. Polymer Sci., Polymer C
hem. Ed., 22, 1789 (1984), JVCrivello et al., Pol
ymer Bull., 14,279 (1985), JVCrivello et al., Mac
romolecules, 14 (5), 1141 (1981), JVCrivello et a
l., J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (197
9), EP 370,693, U.S. Patent 3,902,114,
European Patent Nos. 233,567, 297,443, 297,442,
U.S. Pat.Nos. 4,933,377, 410,201, 339,049
Nos. 4,760,013, 4,734,444, 2,833,827
Nos. 2,904,626, 3,604,580, 3,60
No. 4,581, etc., sulfonium salts, JVCrivello et
al., Macromolecules, 10 (6), 1307 (1977), JVCrivel
lo et al., J. Polymer Sci., Polymer Chem. Ed., 17,1
047 (1979) et al., CSWen et a
l., Teh, Proc. Conf. Rad. Curing ASIA, p478, Toky
o, Oct (1988) and the like.

In the present invention, among these, diazonium salts are particularly preferred. Particularly preferred diazonium salts include those described in JP-A-5-158230. Suitable quinonediazide compounds include o-quinonediazide compounds.

The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases the alkali solubility by thermal decomposition, and may be a compound having various structures. In other words, o-quinonediazide helps the solubility of the light-sensitive material system by both the effect of losing the ability to inhibit the dissolution of the alkali-soluble binder due to thermal decomposition and the effect of converting o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include, for example, J
. Writer "Light-Sensitive Systems"
(John Wiley & Sons. Inc.) The compounds described on pages 339 to 352 can be used, but in particular sulfonic esters or sulfonic acids of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. Amides are preferred. In addition, Japanese Patent Publication No. 43-2840
No. 3 benzoquinone- (1,1)
2) -Diazidesulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and an ester of pyrogallol-acetone resin, benzoquinone described in U.S. Patent Nos. 3,046,120 and 3,188,210 -(1,2) -diazidesulfonic acid chloride or naphthoquinone- (1,2) -diazide-
Esters of 5-sulfonic acid chloride with phenol-formaldehyde resin are also suitably used.

Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with phenol-formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride and pyrogallol Esters with acetone resins are likewise preferably used. Other useful o-quinonediazide compounds are reported in many patent-related documents and are known. For example, JP 47-5303, JP 48-63802, JP 48-63803,
JP-A-48-96575, JP-A-49-38701, JP-A-48-13354
No., JP-B-41-11222, JP-B-45-9610, JP-B-49-1
No. 7481, U.S. Pat.Nos. 2,797,213 and 3,454,400,
No. 3,554,323, No. 3,573,917, No. 3,674,495
No. 3,785,825; British Patent No. 1,277,602;
Nos. 1,251,345, 1,267,005, 1,329,888,
Documents such as 1,330,932 and German Patent No. 854,890
(Specification).

The amount of the o-quinonediazide compound used in the present invention is preferably from 1 to 50% by weight, more preferably from 5 to 30% by weight, particularly preferably from 10 to 50% by weight, based on the total solids of the lithographic printing plate material. -30% by weight.
These compounds can be used alone or as a mixture of several types. If the amount of the o-quinonediazide compound is less than 1% by weight, the recording properties of the image will be deteriorated, while if it exceeds 50% by weight, the durability of the image portion will be degraded or the sensitivity will be lowered.

The counter ions of the onium salt include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid,
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5- Benzoyl-benzenesulfonic acid, paratoluenesulfonic acid and the like can be mentioned. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable. The amount of the above compound other than the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 30% by weight, based on the total solid content of the lithographic printing plate material. Range.

Others In the composition of the present invention, various resins having a hydrophobic group such as octylphenol / formaldehyde resin, t-butylphenol / formaldehyde resin, t
-Butylphenol-benzaldehyde resin, rosin-modified novolak resin, and o of these modified novolak resins
-Naphthoquinonediazide sulfonic acid ester and the like; depending on various purposes, such as a plasticizer for improving the flexibility of the coating film, such as dibutyl phthalate, dioctyl phthalate, butyl glycolate, tricresyl phosphate, and dioctyl adipate. Various additives can be added. The amount of these additives is preferably in the range of 0.01 to 30% by weight based on the total weight of the composition.

Further, a known resin for further improving the abrasion resistance of the film can be added to these compositions. These resins include, for example, polyvinyl acetal resin, polyurethane resin, epoxy resin, vinyl chloride resin, nylon, polyester resin, acrylic resin and the like, and can be used alone or in combination. The addition amount is preferably in the range of 2 to 40% by weight based on the total weight of the composition.

Further, in the photosensitive resin composition of the present invention, in order to widen the development latitude, Japanese Patent Application Laid-Open No.
Non-ionic surfactants such as those described in JP-A-251740 and JP-A-4-68355, and those described in JP-A-59-121044 and JP-A-4-13149. Amphoteric surfactants can be added. Specific examples of the nonionic surfactant include:
Sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate,
Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, and Amogen K (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. N-tetradecyl-N, N-betaine type),
2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, Levon 15 (trade name, manufactured by Sanyo Chemical Co., Ltd., alkylimidazoline system) and the like. The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive resin composition is 0.05 to 1%.
It is preferably 5% by weight, more preferably 0.1 to 5% by weight.

Improvement of coating surface quality: In the photosensitive resin composition of the present invention, a surfactant for improving the coating surface quality, for example, as described in JP-A-62-170950. A fluorinated surfactant can be added. A preferable addition amount is 0.0% of the entire photosensitive resin composition.
0.01 to 1.0% by weight, more preferably 0.005 to 1.0% by weight.
~ 0.5% by weight.

The photosensitive resin composition of the present invention may contain a yellow dye, preferably a yellow dye having an absorbance at 417 nm of 70% or more of an absorbance at 436 nm.
When a lithographic printing plate photosensitive material is obtained from the photosensitive resin composition containing the fluoropolymer of the present invention, it is first provided on a suitable support. The photosensitive resin composition containing the fluoropolymer of the present invention is dissolved or dispersed in one or a mixture of the following organic solvents, applied to a support, and dried. As the organic solvent, any of known organic solvents can be used, but those having a boiling point of 40 ° C to 200 ° C, particularly 60 ° C to 160 ° C, are selected from the advantages in drying. Of course, it is better to select one in which the surfactant of the present invention is dissolved.

Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n- or iso-propyl alcohol, n- or iso-butyl alcohol, diacetone alcohol, acetone, methyl ethyl ketone, methyl propyl ketone and methyl butyl ketone. , Methyl amyl ketone, methyl hexyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone,
Ketones such as methylcyclohexanone and acetylacetone, benzene, toluene, xylene, cyclohexane,
Hydrocarbons such as methoxybenzene, ethyl acetate,
acetates such as n- or iso-propyl acetate, n- or iso-butyl acetate, ethyl butyl acetate, hexyl acetate, methylene dichloride, ethylene dichloride, halides such as monochlorobenzene, isopropyl ether, n-butyl ether, dioxane, Ethers such as dimethyldioxane and tetrahydrofuran,

Ethylene glycol, methyl cellosolve,
Methyl cellosolve acetate, ethyl cellosolve, diethyl cellosolve, cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Polyhydric alcohols such as acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, 3-methyl-3-methoxybutanol and derivatives thereof, dimethyl sulfoxide, N, N-dimethyl And special solvents such as formamide are preferably used singly or as a mixture. The concentration of the solid content in the composition to be applied is suitably 2 to 50% by weight.

As the method of applying the composition of the present invention, for example, methods such as roll coating, dip coating, air knife coating, gravure coating, gravure offset coating, hopper coating, blade coating, wire doctor coating, spray coating and the like are used. The weight after drying is preferably 0.3 to 4.0 g / m ² . As the coating amount decreases, the exposure amount for obtaining an image may be small,
The film strength decreases. As the coating amount increases, the exposure amount is required but the photosensitive film becomes strong. For example, when used as a printing plate, a printing plate having a high printable number (high printing durability) can be obtained.

The drying of the photosensitive resin composition applied on the support is usually performed with heated air. Heating is preferably performed at a temperature in the range of 30C to 200C, particularly 40C to 140C. In addition to a method in which the drying temperature is kept constant during the drying, a method in which the temperature is gradually increased may be performed. Good results may be obtained by dehumidifying the drying air. The heated air is applied at a rate of 0.1 m / sec.
It is preferable to supply at a rate of 0 m / sec, particularly 0.5 m / sec to 20 m / sec.

Matt layer: A mat layer is provided on the surface of the photosensitive layer provided as described above in order to shorten the time for evacuation and to prevent burning blur during contact exposure using a vacuum printing frame. Preferably, it is provided. More specifically,
-125805, JP-B-57-6682, and 61-
A method of providing a mat layer as described in each of JP-A-28986 and a method of heat-fusing a solid powder as described in JP-B-62-62337.

The support used for the photosensitive lithographic printing plate or the like is a plate which is dimensionally stable and includes those which have been used as the support of the printing plate. Can be. Examples of such a support include paper, paper laminated with plastics (for example, polyethylene, polypropylene, polystyrene, etc.), for example, a metal plate such as aluminum (including aluminum alloy), zinc, iron, copper, etc., for example, diacetate. Cellulose, cellulose triacetate,
Films of plastics such as cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic on which the above metals are laminated or evaporated Although a film is included, an aluminum plate is particularly preferable. The aluminum plate includes a pure aluminum plate and an aluminum alloy plate. Various aluminum alloys can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel is used. These compositions also contain some negligible amount of impurities in addition to some iron and titanium.

The support is subjected to a surface treatment as required.
For example, in the case of a photosensitive lithographic printing plate, on the surface of the support,
A hydrophilic treatment is performed. In the case of a support having a surface of metal, particularly aluminum, surface treatment such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or anodizing is performed. Preferably, it has been done. Also, as described in U.S. Pat. No. 2,714,066,
An aluminum plate which is grained and then immersed in an aqueous solution of sodium silicate, or an aqueous solution of an alkali metal silicate after anodizing the aluminum plate as described in US Pat. No. 3,181,461. What has been immersed in is preferably used. The anodizing treatment is, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or oxalic acid, an organic acid such as sulfamic acid, or an aqueous or non-aqueous solution of a salt thereof alone or in combination of two or more. It is carried out by flowing a current in an electrolytic solution using an aluminum plate as an anode.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive resin composition provided thereon, and to improve the adhesion to the photosensitive layer. It is performed in order to improve. Prior to graining the aluminum plate, if necessary, the surface may be subjected to a pretreatment to remove rolling oil on the surface and to expose a clean aluminum surface. For the former, solvents such as trichlene, surfactants and the like are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used.

As the graining method, any of mechanical, chemical and electrochemical methods is effective. Examples of the mechanical method include a ball polishing method, a blast polishing method, and a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the chemical method is disclosed in JP-A-54-31187. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the official gazette is suitable, and as an electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Is preferred. Among such surface roughening methods, in particular, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in Japanese Patent Application Laid-Open No. 55-137993 is a method for obtaining oil-sensitive images. Is preferred because of its strong adhesion to the support. The graining by the above-mentioned method has a center line surface roughness (Ra) of the surface of the aluminum plate of 0.3 to 1.0 μm.
It is preferable that the application is performed in such a range as follows. The aluminum plate thus grained is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous solutions of bases or acids that dissolve aluminum. In this case, a film different from aluminum derived from the etchant component must not be formed on the etched surface. Preferred examples of the etching agent include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate as basic substances; and sulfuric acid and persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof. Metals having a lower ionization tendency than aluminum, such as zinc, chromium, cobalt, nickel, and copper, are not preferable because they form an unnecessary film on the etched surface. In these etching agents, the dissolution rate of the aluminum or alloy to be used is determined by the immersion time 1 at the setting of the use concentration and temperature.
Most preferably, it is carried out at a rate of from 0.3 g to 40 g / m ² per minute, but it may be higher or lower.

The etching is carried out by immersing the aluminum plate in the above-mentioned etching solution, or by applying an etching solution to the aluminum plate.
The treatment is preferably performed so as to be in the range of 10 to 10 g / m ² . As the etching agent, it is desirable to use an aqueous solution of a base because of its high etching rate. In this case, since a smut is generated, a normal desmutting process is performed. The acid used for desmut treatment is
Nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. The etched aluminum plate is optionally washed with water and anodized. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, when direct current or alternating current is passed through aluminum in an aqueous solution or a non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or a combination of two or more thereof, aluminum An anodized film can be formed on the surface of the support.

The anodizing treatment conditions cannot be generally determined because they vary depending on the electrolytic solution used. However, in general, the concentration of the electrolytic solution is 1 to 80% by weight, and the liquid temperature is 5 to 70%.
° C, current density 0.5-60 amps / dm ² , voltage 1-10
0V and an electrolysis time of 30 seconds to 50 minutes are appropriate. Among these anodizing treatments, in particular, British Patent No. 1,4
Anodizing at high current density in sulfuric acid as described in U.S. Pat.
The method of anodic oxidation using phosphoric acid as an electrolytic bath described in US Pat. The aluminum plate which has been roughened and anodized as described above may be subjected to a hydrophilization treatment, if necessary. Preferred examples thereof include U.S. Pat. Nos. 2,714,066 and 3,181. , 4
No. 61, for example, an alkali metal silicate, for example, an aqueous solution of sodium silicate or JP-B-36-
There is a method of treating with potassium fluoride zirconate disclosed in 22063 and polyvinylphosphonic acid as disclosed in U.S. Pat. No. 4,153,461.

Organic undercoat layer: It is preferable to provide an organic undercoat layer on the photosensitive lithographic printing plate of the present invention before coating the photosensitive layer in order to reduce the remaining photosensitive layer in the non-image area. Examples of the organic compound used in the organic undercoat layer include carboxymethyl cellulose, dextrin, gum arabic,
-Phosphonic acids having an amino group such as -aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent,
Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid; phenylphosphoric acid which may have a substituent; naphthylphosphoric acid; Organic phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloride of triethanolamine Or a hydrochloride of an amine having a hydroxyl group, or a mixture of two or more.

In addition, at least one compound selected from a group of high molecular compounds having a structural unit represented by the following general formula (F) in the molecule, such as poly (p-vinylbenzoic acid), can be used.

[0143]

Embedded image

In the general formula (F), R₁Is hydrogen field
Represents a hydrogen atom, a halogen atom or an alkyl group, but is preferably
Is a hydrogen atom, a chlorine atom, or an alkyl having 1 to 4 carbon atoms.
Represents a kill group. Particularly preferably, a hydrogen atom or a methyl group
Represents R_TwoAnd R_ThreeAre each independently a hydrogen atom, a hydroxyl group,
Halogen atom, alkyl group, substituted alkyl group, aromatic
Group, substituted aromatic group, -OR_Four, -COOR_Five, -CONH
R ₆, -COR₇Or -CN, or R_TwoWhen
R_ThreeMay combine to form a ring. Where R_Four~ R₇Is
Each represents an alkyl group or an aromatic group. More preferred R
_TwoAnd R_ThreeAre each independently a hydrogen atom, a hydroxyl group, a chlorine atom
, A C1-C4 alkyl group, a phenyl group, -OR
_Four, -COOR_Five, -CONHR₆, -COR₇, -CN
Yes, where R_Four~ R₇Is an alkyl group having 1 to 4 carbon atoms.
Or a phenyl group. Particularly preferred R_TwoAnd R_ThreeAre each
Independently, hydrogen, hydroxyl, methyl or methoxy
Group.

X is a hydrogen atom, a metal atom, NR₈R₉R_TenR
₁₁Where R₈~ R₁₁Is each independently hydrogen
Atom, alkyl group, substituted alkyl group, aromatic group, substituted
Represents an aromatic group, or R₈And R₉Combine to form a ring
May be. X is more preferably a hydrogen atom, a monovalent metal atom.
Child, NR₈R₉R_TenR₁₁Where R₈~ R₁₁Is
Each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms
Or a phenyl group. Particularly preferred X is a hydrogen atom
Child, sodium, potassium or NR₈R₉R_TenR ₁₁The table
And where R₈~ R₁₁Is independently a hydrogen atom,
Represents a methyl group or an ethyl group. n represents an integer of 1 to 3
Preferably represents 1 or 2, more preferably 1
Represent.

The organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate and dried to form a solution. An aluminum plate is immersed in a solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof to adsorb the organic compound, and thereafter, washed with water or the like and dried to form an organic undercoat layer. Is the way. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05% by weight.
-5% by weight, the immersion temperature is 20-90 ° C., preferably 25-50 ° C., and the immersion time is 0.1 second-20 minutes,
Preferably it is 2 seconds to 1 minute.

The pH of the solution used is adjusted by a basic substance such as ammonia, triethylamine, potassium hydroxide or the like, or an acidic substance such as hydrochloric acid or phosphoric acid.
It can also be used in the range of ~ 12. Further, a yellow dye may be added for improving the tone reproducibility of the photosensitive lithographic printing plate. Further, this solution has the following general formula (a)
Can be added. Formula (a) (HO) _m -R _1- (COOH) n wherein R ₁ represents an arylene group having 14 or less carbon atoms which may have a substituent, and m and n are independently 1 to 3 Represents an integer. Specific examples of the compound represented by the general formula (a) include 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, salicylic acid, 1-hydroxy-2-naphthoic acid,
2-hydroxy-1-naphthoic acid, 2-hydroxy-3
-Naphthoic acid, 2,4-dihydroxybenzoic acid, 10-
Hydroxy-9-anthracenecarboxylic acid and the like. The coating amount of the organic undercoat layer after drying is 1 to 100 mg /
m ² is suitable, and preferably ² to 70 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 100 mg / m ² .

Back coat: A back coat is provided on the back surface of the support, if necessary. Examples of such a back coat include a coating layer comprising a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174. Is preferably used.
Among these coating layers, Si (OCH ₃ ) ₄ and Si (OC ₂ H ₅ )
₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) ₄ and other silicon alkoxy compounds are easily available at a low cost, and the metal oxide coating layer obtained therefrom has excellent developer resistance, and preferable.

The planographic printing plate prepared as described above is usually subjected to image exposure and development processing. As a light source of the active light beam used for image exposure, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp,
There are carbon arc lamps and the like. As radiation, electron beam,
X-rays, ion beams, far infrared rays, and the like. G line,
i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. Laser beams include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, KrF
Excimer laser and the like can be mentioned. In the laser direct printing plate, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser and a semiconductor laser are particularly preferable.

Preferred as a developer for a lithographic printing plate using the photosensitive resin composition of the present invention are (a) at least one saccharide selected from non-reducing sugars and (b) at least one base, and Is in the range of 9.0 to 13.5. Hereinafter, the developer will be described in detail. In the present specification, unless otherwise specified, the developing solution means a developing solution (a developing solution in a narrow sense) and a developing replenisher.

It is preferable that the main components of the developer are at least one compound selected from non-reducing sugars and at least one base, and the pH of the solution is in the range of 9.0 to 13.5. . Such non-reducing sugars are saccharides having no free aldehyde group or ketone group and exhibiting no reducing property, trehalose-type oligosaccharides in which reducing groups are bonded to each other, glycosides in which a reducing group of a saccharide is bonded to a non-saccharide. It is classified as a sugar alcohol reduced by hydrogenation of a body and a saccharide, and both are suitably used. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. As sugar alcohols, D, L-arabit,
Rebit, Xylit, D, L-Sorbit, D, L-
Mannit, D, L-idit, D, L-talit, zuricit and allozurcit. Further, maltitol obtained by hydrogenation of disaccharide and reductant (reduced starch syrup) obtained by hydrogenation of oligosaccharide are preferably used. Particularly preferred non-reducing sugars among these are sugar alcohols and saccharose, especially D-Sorbit,
Saccharose and reduced starch syrup are preferred because they have a buffering action in an appropriate pH range and are inexpensive.

These non-reducing sugars can be used alone or in combination of two or more. Their ratio in the developing solution is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. is there. Below this range, a sufficient buffering effect cannot be obtained, and at concentrations higher than this range, it is difficult to achieve high concentration and the problem of increased cost arises. When a reducing sugar is used in combination with a base, there is a problem that the color changes to brown with the lapse of time, and the pH gradually lowers, thereby deteriorating the developability.

As a base to be combined with the non-reducing sugar, a conventionally known alkali agent can be used. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, Inorganic alkali agents such as ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, and ammonium borate are exemplified. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents are used alone or in combination of two or more. Among these, sodium hydroxide and potassium hydroxide are preferred because the pH can be adjusted in a wide pH range by adjusting the amounts of these with respect to the non-reducing sugar. Also, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable since they themselves have a buffering action. These alkaline agents are added so that the pH of the developing solution is in the range of 9.0 to 13.5, and the amount of addition is determined depending on the desired pH, the type and the amount of non-reducing sugar, but more preferable pH The range is 10.0-13.
2.

Further, an alkaline buffer consisting of a weak acid other than saccharides and a strong base can be used in combination with the developer. The weak acid used as such a buffer preferably has a dissociation constant (pKa) of 10.0 to 13.2. Such weak acids include IONISATION CONSTAN published by Pergamon Press
Selected from those described in TS OF ORGANIC ACIDS IN AQUEOUS SOLUTION and the like, for example, 2,2,3,3-tetrafluoropropanol-1 (PKa 12.74),
Alcohols such as trifluoroethanol (12.37), trichloroethanol (12.24), pyridine-2-aldehyde (12.68), pyridine-4
Aldehydes such as -aldehyde (12.05), salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (12.84), catechol (12.6), and gallic acid (12.05). 4), sulfosalicylic acid (11.
7), 3,4-dihydroxysulfonic acid (12.
2), 3,4-dihydroxybenzoic acid (11.9)
4), 1,2,4-trihydroxybenzene (11.
82), hydroquinone (11.56), pyrogallol (11.34), o-cresol (10.3)
3), resorcinol (11.27), p-cresol (10.27), m-cresol (10.09)
Compounds having a phenolic hydroxyl group, such as

2-butanone oxime (12.45);
Acetoxime (12.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.37).
Oximes such as 35) and adenosine (12.5
6), inosine (12.5) and guanine (12.
3), cytosine (12.2), hypoxanthine (1)
2.1), nucleic acid-related substances such as xanthine (11.9), and diethylaminomethylphosphonic acid (12.
32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54) , 1,1-ethylidene diphosphonic acid 1
-Hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.8),
Weak acids such as picoline thioamide (12.55) and barbituric acid (12.5).

Of these weak acids, preferred are sulfosalicylic acid and salicylic acid. As the base to be combined with these weak acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.
These alkali agents are used alone or in combination of two or more. The above-mentioned various alkaline agents are used by adjusting the pH within a preferred range depending on the concentration and combination.

Various surfactants and organic solvents can be added to the developer, if necessary, for the purpose of accelerating the developability, dispersing the development residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, and glycerin fatty acid partial esters. , Sorbitan fatty acid partial esters,
Pentaerythritol fatty acid partial ester, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester , Polyoxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides,
Nonionic surfactants such as N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides;

Fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts,
Dialkyl sulfosuccinates, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl- N-oleyltaurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, Fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, Alkyl phosphate phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl phenyl ether phosphate salts, partially saponified styrene / maleic anhydride copolymers, partial olefin / maleic anhydride copolymers Saponified substances,

Anionic surfactants such as naphthalene sulfonate formalin condensates; quaternary ammonium salts such as alkylamine salts and tetrabutylammonium bromide; and cationic surfactants such as polyoxyethylene alkylamine salts and polyethylene polyamine derivatives. And amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines. Among the surfactants mentioned above, the term "polyoxyethylene" can be read as a polyoxyalkylene such as polyoxymethylene, polyoxypropylene, or polyoxybutylene, and these surfactants are also included.

More preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anionic type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine,
Cationic and perfluoroalkylamine oxides such as perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl groups and hydrophilic groups,
Non-ionic types such as oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and lipophilic groups, and urethanes containing perfluoroalkyl groups and lipophilic groups are included. The above surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

Various development stabilizers can be used in the developer. As preferred examples thereof, Japanese Patent Application Laid-Open No.
Preferred examples include polyethylene glycol adducts of sugar alcohols described in JP-A-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium salts such as diphenyliodonium chloride. Further, Japanese Patent Application Laid-Open
Anionic or amphoteric surfactants described in JP-A-51324, water-soluble cationic polymers described in JP-A-55-95946, JP-A-56-1425
And water-soluble amphoteric polymer electrolytes described in JP-A-28.

Further, an organic boron compound to which an alkylene glycol has been added described in JP-A-59-84241, and a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant described in JP-A-60-111246. Japanese Patent Application Laid-Open No. Sho 60-129750, polyoxyethylene / polyoxypropylene-substituted alkylenediamine compounds, Japanese Patent Application Laid-Open No. Sho 61-215554, polyethylene glycol having a weight average molecular weight of 300 or more, JP-A-2-39157 discloses a fluorine-containing surfactant having a cationic group, a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol, and a water-soluble polyalkylene compound. No.

An organic solvent is further added to the developer if necessary. As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1
-Propanol, 4-phenyl-1-butanol, 4-
Phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol,
-Methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanolamine, N-phenyldiethanolamine and the like can be mentioned. The content of the organic solvent is 0.1 to 5% by weight based on the total weight of the used solution. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

A reducing agent can be further added to the developer. This is to prevent stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound.Preferred organic reducing agents include thiosalicylic acid, hydroquinone, and methol. Phenol compounds such as methoxyquinone, resorcin and 2-methylresorcin; and amine compounds such as phenylenediamine and phenylhydrazine. More preferred inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, bisulfite, diphosphite, thiosulfate and dithionite. Salts and the like can be mentioned. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in a range of 0.05 to 5% by weight with respect to the developing solution at the time of use.

An organic carboxylic acid can be further added to the developer. Preferred organic carboxylic acids have 6 to 6 carbon atoms.
20 aliphatic carboxylic acids and aromatic carboxylic acids. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, a naphthalene ring, an anthracene ring, or the like.
-Chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydrobenzoic acid, 2,5-dihydroxybenzoic acid 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5
-Dihydroxybenzoic acid, gallic acid, 1-hydroxy-
2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2
-Hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-
Although there are naphthoic acid and the like, hydroxynaphthoic acid is particularly effective.

The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to increase the water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if the content is less than 0.1% by weight, the effect is not sufficient.
If it is 0% by weight or more, not only the effect cannot be further improved but also dissolution may be hindered when another additive is used in combination. Therefore, the preferred addition amount is 0.1 to 10% by weight, more preferably 0.5 to 4% by weight, based on the developer used.
% By weight.

The developing solution may further contain a preservative, if necessary.
Coloring agents, thickeners, defoamers, water softeners, and the like can be included. Examples of the water softener include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid. Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydroxy-data-ene-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.

The optimum value of such a water softener varies depending on its chelation, the hardness of the hard water used and the amount of the hard water. -5% by weight, more preferably 0.01-0.
It is in the range of 5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is larger than this range, an adverse effect on an image portion such as color omission appears. The remaining component of the developer is water. It is advantageous from the viewpoint of transportation that the developing solution is a concentrated solution having a smaller water content than at the time of use and is diluted with water at the time of use. In this case, the concentration is suitably such that the components do not separate or precipitate.

As a developer for a lithographic printing plate using the photosensitive resin composition of the present invention, a developer described in JP-A-6-282079 can also be used. This is SiO ₂ / M ₂
The molar ratio of O (M represents an alkali metal) is 0.5 to 2.
And a water-soluble ethylene oxide adduct obtained by adding 5 mol or more of ethylene oxide to a sugar alcohol having 4 or more hydroxyl groups. Sugar alcohol is a polyhydric alcohol corresponding to one obtained by reducing an aldehyde group and a ketone group of a sugar to form primary and secondary alcohol groups, respectively. Shellfish examples of sugar alcohols include D, L-trait, erythritol, D, L-arabit, ribit, xylit,
D, L-sorbit, D, L-mannit, D, L-idit, D, L-talit, dulcit, allodulcit, etc., and di, tri,
Also included are tetra, penta and hexaglycerin. The water-soluble ethylene oxide adduct is obtained by adding 5 mol or more of ethylene oxide to 1 mol of the sugar alcohol. Further, propylene oxide may be block-copolymerized with the ethylene oxide-added compound, if necessary, as long as the solubility is acceptable. These ethylene oxide addition compounds may be used alone or in combination of two or more. The addition amount of these water-soluble ethylene oxide addition compounds is suitably from 0.001 to 5% by weight, more preferably from 0.001 to 2% by weight, based on the developer (working solution).

The above-mentioned various surfactants and organic solvents can be further added to this developer, if necessary, for the purpose of accelerating the developability, dispersing the development residue and increasing the ink affinity of the printing plate image area. .

A PS developed with a developer having such a composition
The plate is subjected to post-treatment with washing water, a rinsing solution containing a surfactant or the like, a finisher containing a gum arabic or a starch derivative, or a protective gum solution. These treatments can be used in various combinations for the post-treatment of the PS plate of the present invention.

In recent years, automatic developing machines for PS plates have been widely used in the plate and printing industries in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a PS plate, each processing solution tank and a spray device, and pumps the exposed PS plate horizontally while pumping it. Each processing liquid is sprayed from a spray nozzle to perform development and post-processing. Recently, a PS plate is immersed and transported by a submerged guide roll or the like in a processing solution tank filled with a processing solution to carry out development processing, or a fixed amount of small amount of washing water is supplied to the plate surface after development for washing. A method is also known in which the waste water is reused as dilution water of a developer undiluted solution.

In such automatic processing, processing can be performed while replenishing each processing solution with a replenisher in accordance with the processing amount, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied. 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.

[0176]

The present invention will be further described below with reference to examples. However, the present invention is not limited by these examples. Synthesis Example 1 2- (perfluorooctyl) ethyl acrylate 1
5.5 g, N- (4-chloro-2-carboxyphenyl) methacrylamide 9.58 g, lauryl methacrylate 7.62 g and tetrahydrofuran 63.14
g was placed in a 300 ml three-necked flask and kept at 65 ° C. while stirring under a nitrogen stream. 1.44 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added and stirring was continued. After 4 hours, the temperature was raised to 68 ° C. and maintained for 1 hour. After the completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was poured into 400 ml of methanol. The precipitated solid was collected by filtration and dried. According to GPC (gel permeation chromatography), this solid was a high molecular compound having a weight average molecular weight of 188,000 by a yield of 22 g.

Synthesis Examples 2 to 5 Polymers shown in Table 1 were synthesized in the same manner as in Synthesis Example 1. Further, the compound (polymer) of Comparative Example was synthesized in the same manner.

[0178]

[Table 1]

[Examples 1 to 4, Comparative Examples 1 and 2] (All percentages in the following examples are% by weight unless otherwise specified.) A JIS A 1050 aluminum plate having a thickness of 0.24 mm was used. While supplying a suspension of water and pumistone having an average particle size of about 2.1 μm to the aluminum surface, brush graining was performed with a rotating nylon brush shown below. The 1st brush is 100mm bristle length, 0.95mm bristle diameter, 70 flocking density
/ cm ² , and the second brush has a hair length of 80 mm and a hair diameter of 0.295.
mm, and the flocking density was 670 fibers / cm ² . The rotation of each of the brush rolls was 250 rpm. After washing well with brush graining, the film was immersed in 10% sodium hydroxide at 60 ° C. for 25 seconds for etching, washed with running water, washed with 20% nitric acid and washed with water. These are
Electrolytic surface-roughening treatment was performed in a 1% aqueous nitric acid solution at an anode electricity of 160 clones / dm ² using a sinusoidal alternating current under the condition of _A = 12.7 V. When the surface roughness was measured, it was 0.79 μm ( _Ra display). Subsequently, after immersion in a 1% aqueous sodium hydroxide solution at 40 ° C. for 30 seconds, immersion in a 30% aqueous sulfuric acid solution at 40 ° C.
After desmutting for 2 seconds, the substrate was anodized by direct current in a 20% aqueous sulfuric acid solution at a current density of 2 A / dm ² so that the weight of the oxide film was 1.6 g / m ² .

The undercoat liquid (A) having the following composition was applied to the surface of the substrate thus treated, and dried at 80 ° C. for 30 seconds. The coated amount after drying was 10 mg / m ² . Undercoat solution (A) β-alanine 0.10 g methanol 40 g pure water 60 g Thus, substrate (I) was produced. Next, on this substrate (I), a photosensitive solution shown in the following Table 2 was applied by rod coating at 12 ml / m ^{2 and} dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. . The coating amount after drying is 1.
It was 15 g / m ² . In order to further shorten the vacuum adhesion time, a mat layer was formed as described in JP-B-61-28986.

[0181]

[Table 2]

The thus prepared photosensitive lithographic printing plate was evaluated by the following method. Sensitivity is a step wedge manufactured by Fuji Photo Film Co., Ltd. (density difference of each step is 0.15)
Through a 3 kW metal halide lamp from a distance of 1 m for 1 minute, and using a PS processor 900V manufactured by Fuji Photo Film Co., Ltd. at 30 ° C.
For 12 seconds, the molar ratio of SiO ₂ / K ₂ O is 1.16,
The film was developed with an aqueous solution having an O ₂ concentration of 1.4%, and expressed by the number of clear stages. The higher the number of stages, the higher the sensitivity.
The gradation represents the difference between the number of clear steps and the number of solid steps of the sample for which the sensitivity was evaluated. A lower value indicates a higher contrast. The development tolerance is based on the developer described above.
Exposure and development were performed in the same manner as in the above sensitivity except that a liquid whose pH was increased or decreased by 0.2 was used to show the change in the number of solid plates due to the pH. The smaller this value is, the better the development tolerance is. Table 4 shows the results.

[0183]

[Table 3]

[0184]

[Table 4]

As can be seen from Table 4, Examples 1 to 4
Has a high contrast without deteriorating the sensitivity, and has good development tolerance.

[Examples 5 to 9, Comparative Example 3] Thickness 0.30
An 1 mm aluminum plate of 1 mm was grained using a No. 8 nylon brush and an 800 mesh aqueous suspension of pumicestone, and the surface was grained, and then thoroughly washed with water. After being immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, washed neutralized with 20% HNO ₃ and washed with water. This was converted to 300 coulombs / d in a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
Electrolytic surface-roughening treatment was performed with an anode electricity amount of m ² . When the surface roughness was measured, it was 0.45 μm (Ra display). Subsequently, it was immersed in a 30% aqueous solution of H ₂ SO _{4 and} desmutted at 55 ° C. for 2 minutes.
In a H ₂ SO ₄ aqueous solution, a cathode was arranged on the grained surface, and anodized at a current density of 5 A / dm ² for 50 seconds to obtain a thickness of 2.7 g / m ² .

No. 3 sodium silicate (SiO ₂ = 28 to
(2.5% by weight of 30%, Na ₂ O = 9 to 10%, Fe = 0.02% or less), pH = 11.2, 70 ° C. for 13 seconds, followed by washing with water. The silicate amount at that time was 10 mg / m ² . For measurement, the amount of Si element was determined by fluorescent X-ray analysis. Next, a liquid composition (sol solution) of the SG method was prepared by the following procedure. The following composition was weighed into a beaker and stirred at 25 ° C. for 20 minutes. Si (OC ₂ H ₅ ) ₄ 38 g 3-methacryloxypropyltrimethoxysilane 13 g 85% phosphoric acid aqueous solution 12 g Deionized water 15 g Methanol 100 g

The solution was transferred to a three-necked flask, fitted with a reflux condenser, and immersed in the oil bath at room temperature. The contents of the three-necked flask were heated to 50 ° C. in 30 minutes while stirring with a magnetic stirrer. While maintaining the bath temperature at 50 ° C, the reaction was further performed for 1 hour to obtain a liquid composition (sol liquid). This sol solution was diluted with methanol / ethylene glycol = 20/1 (weight ratio) so as to be 0.5% by weight, applied with a wheeler to a substrate, and dried at 100 ° C. for 1 minute. The coating amount at that time was 4 mg / m ² . The amount of this coating was also determined by fluorescent X-ray analysis to determine the amount of Si element.
It was taken as the coating amount. A high-sensitivity photopolymerizable composition 1 having the following composition was applied on the aluminum plate treated in this manner so that the dry coating weight was 1.5 g / m ^2, and 100 ° C.
For 1 minute to form a photosensitive layer.

[Photopolymerizable Composition 1] Tetramethylolmethanetetraacrylate 1.5 g Linear organic high molecular polymer (B1) 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymer molar ratio 80/20) ) Sensitizer (C1) 0.15 g

[0190]

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(Λ _max THF 479 nm, ε = 6.9 × 10 ⁴ ) 0.2 g of photopolymerization initiator (D1)

[0192]

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IRGACURE907 (E1) (manufactured by Ciba-Geigy) 0.4 g Fluoropolymer (P) shown in Table 5 0.2 g ε-phthalocyanine / (B1) dispersion 0.2 g Fluorine-nonionic interface Activator Megafac F177 0.03 g (manufactured by Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone 9.0 g Propylene glycol monomethyl ether acetate 7.5 g Toluene 11.0 g

On this photosensitive layer, polyvinyl alcohol (98 mol% saponification, polymerization degree 5
00) of a 3% by weight aqueous solution having a dry coating weight of 2.5 g /
m ² and dried at 120 ° C. for 3 minutes to obtain a photopolymerizable lithographic printing plate. These plates were purchased from Optronics XLP4000 (Ar laser 75mW, 488n).
m) at 0.15 mJ / cm ² , 4000 dpi,
Under the condition of 175 lines / inch, 1% to 99% was exposed in two portions at 1% intervals. Thereafter, a post-heating treatment was performed by exposing to 120 ° C. for 20 seconds.

The development was carried out by dipping in the following developer at 25 ° C. for 30 seconds. (Developer) 1K potassium silicate 30g potassium hydroxide 15g water 1000g

Next, GU-7 (Fuji Photo Film Co., Ltd.)
) Was diluted twice with water to treat the plate surface. 400
Under the conditions of 0 dpi and 175 lines / inch, the plate energy amount reproduced by 1% was obtained as the sensitivity of the sample.
For printing durability measurement, Heidelberg SOR was used as a printing machine.
KZ was used, and Claf G (N) manufactured by Dai Nippon Ink was used as the ink. As a plate cleaner,
An acidic PS plate cleaner CL-2 (manufactured by Fuji Photo Film Co., Ltd.) was used.

Each sample was stored at 60 ° C. for 3 days, exposed and developed in the same manner and printed, and the stain resistance of the non-image area was visually evaluated to evaluate the stability over time. 5000th sheet from printing start
The S plate cleaner CL-2 was impregnated into a printing sponge, and a halftone dot portion was wiped off to wash the ink on the plate surface. After that, PS is repeated for every 10,000 sheets up to the 145,000th sheet.
Wash the ink on the plate surface with the plate cleaner CL-2,
150,000 sheets were printed. Table 5 shows the results obtained by extracting printed matter every 10,000 sheets and evaluating halftone dots obtained by washing the plate surface with PS plate cleaner CL-2 and halftone dots not washed.

The solid printing durability refers to the number of sheets that can be printed normally without any solid printing in the solid printed portion, and the highlight printing durability is such that 2% of 175 lines / inch is printed on printed matter. Indicates the number of prints to be reproduced. The gradation represents the difference between the number of clear steps and the number of solid steps of the sample for which the sensitivity was evaluated. A lower value indicates a higher contrast.

[0199]

[Table 5]

From the above results, in the photosensitive lithographic printing plate of the present invention, by using the unique fluorine-based polymer of the present invention in the photosensitive resin composition, the printing was performed while maintaining the printing durability of the printing plate. The image of the plate could be enhanced.

Next, examples of the thermal crosslinking type lithographic printing plate will be described. <Structure of crosslinking agent [KZ-1]>

[0202]

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<Structure of Crosslinking Agent [KZ-2]>

[0204]

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<Preparation of Binder Polymer [BP-1]> Poly (p-hydroxystyrene) and Marca Linker MS-4P (trade name) manufactured by Maruzen Petrochemical Co., Ltd. were obtained, and [BP-1] and did.

[Embodiments 10 to 13] The thickness of 0.30 mm
Trichlorethylene for aluminum plate (material 1050)
After washing and degreasing, nylon brush and 400 mesh
The surface of which is grained with a pumicestone-water suspension of
Washed well with water. This plate is 25% sodium hydroxide at 45 ° C
Etch by immersing in aqueous solution of lithium for 9 seconds and washing with water
Later, another 2% HNO _ThreeFor 20 seconds and washed with water.
At this time, the etching amount of the grained surface is about 3 g / m.^Twoso
there were. Next, this plate is_TwoSO_FourAs an electrolyte
Flow density 15A / dm^Two3g / m^TwoDC anodized film
And then washed with water and dried. Next on this aluminum plate
The following undercoat liquid was applied and dried at 80 ° C. for 30 seconds. Dry
10 mg / m coating amount after drying^TwoMet.

Undercoat solution β-alanine 0.1 g Phenylphosphonic acid 0.05 g Methanol 40 g Pure water 60 g

Next, the following solution [G] was prepared, and this solution was applied to the above-mentioned primed aluminum plate.
Dried at 0 ° C for 1 minute for negative type lithographic printing plate [G-1]
To [G-4]. The coated amount after drying is 1.5 g / m ²
Met.

Solution [G] Fluorine-based polymer 0.05 g Acid generator [SH-1] 0.3 g Crosslinker 0.5 g Binder polymer [BP-1] 1.5 g Infrared absorber [IK-1] 0.07 g AIZEN SPILON BLUE C-RH 0.035 g (manufactured by Hodogaya Chemical Co., Ltd.) Megafax F-177 0.01 g (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) Methyl ethyl ketone 12 g Methyl alcohol 10 g 1-methoxy-2-propanol 8 g

Table 6 shows the fluoropolymers and crosslinking agents used in Solutions [G-1] to [G-4]. The structures of the acid generator [SH-1] and the infrared absorber [IK-1] are shown below.

[0211]

[Table 6]

[0212]

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The obtained negative type lithographic printing plate material [G-1]
To [G-4] with a bare hand, and then the wavelength of 820
Scanning exposure was performed using a semiconductor laser that emits infrared light of about 850 nm. After exposure, 3 hours at 110 ° C with panel heater
After heat treatment for 0 second, development was carried out with a developing solution DP-4 (1: 8 water dilution) manufactured by Fuji Photo Film Co., Ltd. After the image formation, it was visually determined whether or not the image of the portion touched with bare hands was missing.
In [1] to [G-4], clear image omission did not occur.

Comparative Example 4 A solution was prepared in the same manner as in Example 10 except that the polymer compound [R-1] was used in place of the fluoropolymer in the solution [G] used in Example 10. Was prepared. This solution was applied to the undercoated aluminum plate used in Example 10 and was heated at 100 ° C.
For 1 minute to obtain a negative type lithographic printing plate material [Q-1]. The weight after drying was 1.5 g / m ² . An image was formed on the obtained lithographic printing plate material [Q-1] by the same operation as in Example 10. After the image formation, it was visually determined whether or not the image of the portion touched by the bare hand was missing. In the negative type lithographic printing plate material [Q-1], clear image missing occurred.

Next, examples of the thermal positive type planographic printing plate will be described. [Preparation of Copolymer 1] 4.61 g (0.6%) of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 20 ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel.
0192 mol), 2.94 g of ethyl methacrylate (0.
0258 mol), acrylonitrile 0.80 g (0.0
15 mol) and 20 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. This mixture was mixed with “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.).
0.15 g was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining at 65 ° C. N- (p-
Aminosulfonylphenyl) methacrylamide 4.61
g, 2.94 g of ethyl methacrylate, 0.80 g of acrylonitrile, N, N-dimethylacetamide and "V-
65 "and a mixture of 0.15 g was added dropwise with a dropping funnel over 2 hours. After the addition was completed, the obtained mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, methanol (40 g) was added to the mixture, and the mixture was cooled. The obtained mixture was added to 2 liters of water while stirring the water. The mixture was stirred for 30 minutes, and the precipitate was taken out by filtration and dried. 15 g of a white solid was obtained. The weight average molecular weight (polystyrene standard) of this specific copolymer 1 was determined by gel permeation chromatography to be 53,000.
It was 0.

[Preparation of Substrate] An aluminum plate (material 1050) having a thickness of 0.3 mm was washed with trichlorethylene and degreased, and then its surface was grained with a nylon brush and a 400 mesh pumicetone-water suspension. Washed well with water. This plate was etched by immersing it in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds, washed with water, further immersed in 20% nitric acid for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² .
Next, this plate was subjected to a current density of 15 A /
to provide a DC anodic oxide film of 3 g / m ² in dm ^2, washed with water, dried and further coated with the following undercoat solution, and the coating was dried for 1 minute at 90 ° C.. The coating amount after drying is 10 m
g / m ² .

Undercoating liquid β-alanine 0.5 g Methanol 95 g Water 5 g

Further, the mixture was treated with a 2.5% by weight aqueous solution of sodium silicate at 30 ° C. for 10 seconds.
The coating film was dried at 80 ° C. for 15 seconds to obtain a substrate. The coating amount of the coating film after drying was 15 mg / m ² .

Undercoat liquid 0.3 g of the following compound 100 g of methanol 1 g of water

[0220]

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Example 14 The following photosensitive solution 1 was prepared. The obtained substrate was coated with 1.8 g of this photosensitive solution 1 in an amount of 1.8 g.
/ M ² to obtain a lithographic printing plate.

Photosensitive solution 1 Fluorinated polymer P-1 0.03 g Copolymer 1 0.75 g m, p-cresol novolak (m, p ratio = 6/4, 0.25 g, weight average molecular weight 3,500, unreacted cresol 0.5% by weight) p-toluenesulfonic acid 0.003 g tetrahydrophthalic anhydride 0.03 g cyanine dye (the following structure) 0.017 g counter ion of Victoria Pure Blue BOH 0.015 g 1-naphthalenesulfonic acid anion Dye Megafac F-177 0.05 g (Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) γ-butyl lactone 10 g Methyl ethyl ketone 10 g 1-methoxy-2-propanol 1 g

[0223]

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With respect to the obtained lithographic printing plate, development stability against damage was evaluated. Table 7 shows the evaluation results.

(Development stability against damage) The obtained lithographic printing plate was exposed at a main scanning speed of 5 m / sec using a semiconductor laser having an output of 500 mW, a wavelength of 830 nm and a beam diameter of 17 μm (l / e ² ). Using a continuous load type scratch strength tester “SB62 type” (manufactured by Shinto Kagaku Co., Ltd.), “No. 5C” manufactured by Advantech Toyosha Co., Ltd. Paste the filter paper and add 10
With a load of 0 g, the film was scratched at a speed of 6 cm / sec, and developed with a developing solution DP-4 (1: 8) manufactured by Fuji Photo Film Co., Ltd. for 30 seconds. The evaluation was performed according to the following criteria. When the photosensitive film at the scratched portion is completely dissolved; × When the photosensitive film at the scratched portion is partially dissolved; 場合 When the photosensitive film at the scratched portion is not completely dissolved; ○

[0226]

[Table 7]

[Examples 15 and 16, Comparative Example 5] Instead of the fluoropolymer P-1, the fluoropolymer P
A planographic printing plate was obtained in the same manner as in Example 14 except that -2 and P-5 were used. Further, Comparative Example 5 containing no fluoropolymer of the present invention was used. The resulting lithographic printing plate was evaluated for development stability against damage in the same manner as in Example 14. Table 7 shows the evaluation results. From Table 7, it can be seen that the stability against trauma in the state before development is significantly improved by the addition of the specific fluoropolymer.

[0228]

The photosensitive resin composition of the present invention, by containing a specific fluorine-containing polymer, exhibits a high contrast image forming property without lowering its sensitivity, and is safe for burn-out and white light. The properties and the development tolerance were satisfactory.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA01 AA04 AB03 AC01 AD03 CB14 CB41 CB43 2H096 AA06 BA09 CA20 2H114 AA04 AA23 DA48 DA52 DA53 DA60

Claims (1)

[Claims] 1. At least a. A fluoroaliphatic group, b.
A polymer compound having a group represented by the formula -LP (L represents a divalent organic group linked to the polymer compound skeleton, and P represents an aromatic group having a carboxyl group at the ortho position). A photosensitive resin composition characterized in that: