JPH01149043A - Photosensitive planographic printing plate without wetting water - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a positive type photosensitive lithographic printing plate that does not require dampening water and has a silicone rubber layer as an ink repellent layer. The present invention relates to a positive type photosensitive lithographic printing plate that does not require dampening water and can be developed using an aqueous solution.

[Conventional technology]

Conventionally, various photosensitive lithographic printing plates that do not require dampening water have been proposed, which are comprised of a substrate, a silicone rubber layer provided on the substrate, and a photosensitive layer provided on the silicone rubber layer.

Among these known techniques, regarding a positive type photosensitive lithographic printing plate that does not require dampening water and uses a photosensitive layer containing an orthoquinone diazide compound together with a novolac resin, an epoxy resin, etc., Japanese Patent Publication No. 73t3, Japanese Patent Publication No. A/-
It is described in Publication A/J, Japanese Unexamined Patent Publication No. 74-2J Near 1fiO, etc.

[Problem that the invention seeks to solve]

However, the printing plates shown in these cannot be said to be practically sufficient.

For example, in general, as a developer for photosensitive planographic printing plates,
Although solutions using organic solvents have been used, it has become desirable to use an alkaline aqueous solution as a developer without using organic solvents due to the deterioration of the working environment caused by organic solvents and the complexity of work associated with solvent recovery. Ta. However, special public official Akijj −
A dampening water-free photosensitive lithographic printing plate using a photosensitive layer containing an orthoquinone diazide resin and an epoxy resin prepared based on Example Hiroshi of Publication ψ73t3 was developed using an alkaline aqueous solution containing no organic solvent. However, a good image cannot be obtained.

In addition, when a lithographic printing plate that does not require dampening water is produced using a photosensitive layer containing orthoquinone diazides and novolak resin, cracks occur in the photosensitive layer during or after production, and in addition, cracks occur in the photosensitive layer between the silicone rubber layer and the photosensitive layer. There is a problem in that it is difficult to obtain good images because the adhesion force with the film is not sufficient.

As a photosensitive printing plate that has improved this point, the present inventor first created a photosensitive printing plate that can be developed using an alkaline aqueous solution that does not contain an organic solvent by using an orthoquinone diazide compound and a polymer compound with a specific structure in the photosensitive layer. Proposed a positive-type photosensitive lithographic printing plate that does not require dampening water (Patent application 1982-23/
J-Taco). However, it has been observed that in the photosensitive lithographic printing plate, redness may occur in halftone areas during development, and if this redness remains in the image area, cracks are likely to occur in this area.

It is an object of the present invention to provide a photosensitive lithographic printing plate that does not require dampening water and that solves the above problems and further improves the adhesive strength between the photosensitive layer and the silicone rubber layer.

[Means for solving problems]

As a result of various studies to achieve the above object, the inventor
The present invention was achieved based on the knowledge that an excellent photosensitive lithographic printing plate can be obtained by including an orthoquinonediazide compound, a novolak resin, and a polymer compound with a specific structure in the photosensitive layer.

That is, the gist of the present invention is to provide a positive type photosensitive lithographic printing plate that does not require dampening water and includes a substrate, a silicone rubber layer provided on the substrate, and a photosensitive layer provided on the silicone rubber layer. (a) an orthoquinone diazide compound, (b) j to 30 mol% of the structural unit represented by the following general formula (1), and O1.1 to 30 mol% of the structural unit formed from acrylic acid and/or methacrylic acid. 5 mol %, and a polymer compound having 6 to 4 mol of structural units formed from esters of α-methylene aliphatic monocarboxylic acid, and having a weight average molecular weight within the range of 10,000 to 150,000, and (C) A photosensitive lithographic printing plate that does not require dampening water and is characterized by containing an alkali-soluble novolac resin.

C0NR4- + It can be a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, Y is an aromatic group which may have a substituent, and X is a divalent group connecting the nitrogen atom and the carbon atom of the aromatic group. It is an organic group, and n is the number of O or l.

) The present invention will be explained in detail below.

The photosensitive lithographic printing plate which does not require dampening water of the present invention has a silicone rubber layer serving as an ink repelling layer and a photosensitive layer serving as an ink receiving layer on a substrate in this order.

The substrate used is not particularly limited as long as it is flexible enough to be set in a normal lithographic printing machine and can withstand the load applied during printing. Examples include papers such as coated paper, metal plates such as aluminum plates, and plastic films such as polyethylene terephthalate. Halesh on the surface of these boards! ! It is also useful to provide a /prevention layer.

The silicone rubber layer used in the present invention is usually formed by thermosetting a thermosetting silicone rubber according to a conventional method.

Examples of such thermosetting silicone rubber include addition polymerization type silicone rubber and condensation polymerization type silicone rubber.

Examples of the addition polymerization type silicone rubber include those having the following repeating units.

Here, n is an integer of 2 or more. R represents an alkyl group having 7 to IO carbon atoms, an aryl group, a cyanoalkyl group, a cyanoaryl group, a vinyl group, an alkyl group having a vinyl group, or an aryl group having a vinyl group. However, l-≠0 in the molecule represents a vinyl group, an alkyl group having a vinyl group, or an aryl group.

Such silicone rubbers can be crosslinked by the addition of organic peroxides such as be/diyl peroxide and perbenzoic acid.

The weight average molecular weight of addition polymerization type silicone rubber is /,
000 to so o, o o o, preferably 3,
It is preferable to use those within the range of o o o to zooo, ooo.

Specifically, such addition polymerization type silicone rubber includes, for example, silicone gum S manufactured by Toshi Silicone ■.
H,? jU, SR dato, Bhir san O, etc. can be used.

Examples of polycondensation type silicone rubbers include those having the following repeating units.

R' where n' is an integer of 2 or more. R' is carbon number l~I
It is preferable that Q is an alkyl group or an aryl group, and 60% or more of R' is a methyl group. Usually, the terminal end is a hydroxyl group or an amino group, a crosslinking agent and/or a catalyst is added, and if necessary, heat treatment is performed to harden.

A specific example of the polycondensation silicone rubber having a hydroxyl group at the end is dimethylpolysiloxane BYI&-40/ manufactured by Toshi Silicone ■.

BY/J-1/7, PRX Hiro 13, alcohol-modified silicone BY/4-1441, BX manufactured by Toshi Silicone■
l&-411IB, BX16-00/, f3X/&-0
02, BXl&-003, BX/4-001, f3X/
6-01011f3X/&-0/2, SF half, etc. can be used.

As a condensation type silicone rubber with an amino group at the end,
Specifically, for example, amino-modified silicone BXlt-1' manufactured by Toshi Silicone ■! J, BX/A-413B, etc. can be used.

In addition, silicone rubber having a hydroxyl group or an amino group in the side chain can also be used. Specifically, for example, alcohol-modified silicone manufactured by Toshi Silicone ■ = r-7f3pr
4Ljl, 5HJ77/.

BY//-ta j3, BY//-ta! ≠, BX/+7-ta/I(J), BXIO-ta/r(#), BX/g-0/
r.

Amino-modified silicone f3FII manufactured by Toshi Silicone■
I/7, BYI&-1211I BY#-1110°f3X/&-119, BX/1-rto, etc. can be used.

The weight average molecular weight of the condensation type silicone rubber is /,
000 to 700,000 is suitable, especially λ, o o
It is preferable to use those within the range of o, t o o, and o o o.

Examples of crosslinking agents include acetoxysilane, ketoximesilane, alkoxysilane, aminosilane, and amidosilane.

Preferred examples of the catalyst to be added include titanium carboxylates such as tetramethyl orthotitanate and tetraethylorthotitanate; tin carboxylates such as di-n-butyltin diacetate, tri-n-butyltin acetate, and di-n-butyltin dilaurate. can be mentioned.

In addition, nickel carboxylates, zinc carboxylates, etc. can also be used.

The curing catalyst is 0,0
/-6% by weight is preferable, and it is particularly preferable to use within the range of 0.02 to 3% by weight.

In the present invention, the addition polymerization type silicone rubber and the condensation polymerization type silicone rubber may be used alone, but they can also be used in combination. At that time, the addition polymerization type silicone rubber is preferably ≠0 to ta weight % in the silicone rubber layer. It is preferable to use 5% by weight of O to 5% by weight, and 5 to 72% by weight of the polycondensation silicone rubber, preferably 5% by weight of io to 5% by weight.

A silicone solution prepared by dissolving these thermosetting silicone rubbers in an appropriate solvent is applied according to a conventional method, and is heated and dried at a temperature of usually ≠0 to 100°C for 7 to 20 minutes to form an uncured state. A silicone rubber layer is provided. Solvents for silicone rubber include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, cyclohexane, n-,
Hesensan, n-hebutane, methylcyclohexane, λ-
Aliphatic hydrocarbon solvents such as methylhexane can be suitably used.

In order to cure the obtained uncured silicone rubber layer, the temperature is usually ≠0 to 200°C for /-#0 hours,
Heat treatment. Curing at high temperatures is not preferred as it tends to deteriorate the photosensitive layer, so by adding a curing catalyst to the silicone rubber layer, l-μO
Preferably, heat treatment is performed for a period of time.

The thickness of the silicone rubber layer of the present invention is 0. l~200p
rn, preferably in the range of /-100 pm.

Any orthoquinone diazide compound to be contained in the photosensitive layer used in the present invention can be used as long as it meets the purpose. For example, ortho-naphthoquino/diazide sulfonic acid ester of polycondensate of pyrogallol and acetone, which is described in Japanese Patent Publication No. 4C3-CO-R4C03,
A polycondensation resin of a mixture of pyrogallol and resorcin and acetone, phenols such as orthonaphthoquinonediazide sulfonic acid ester, and aldehyde or ketone as described in JP-A-1-763≠2. Examples include orthonaphthoquinone diazide sulfonic acid esters.

The esterification rate of the orthonaphthoquinonediazide group to the hydroxyl group of phenols is /! -10- is preferred.

Further, as the orthoquinonediazide compound used in the present invention, a condensation product of orthobenzoquinonediazide or orthonaphthoquinonediazide sulfonyl chloride and para-substituted phenol/formalin resin described in Japanese Patent Publication No. Shoj O-1013 can also be used.

This para-substituted phenol/formalin resin, para-cresol/formalin resin, para-butylphenol/formalin resin, para-ethylphenol/formalin resin, para-propylphenol/formalin resin, para-n-propylphenol/formalin resin, para-n-
Butylphenol/formalin resin, paraoctylphenol/formalin resin, parabenzylphenol/formalin resin, rose phenyl phenol/formalin resin, rose methoxyphenol/formalin resin, rose benzyloxyphenol/formalin resin, rose carbogyethylphenol/formalin resin, rose Examples include hydroxybenzenesulfonic acid ethylphenol formalin resin, paraacetophenol formalin resin, and the like.

Furthermore, examples of the orthoquinonediazide compound used in the present invention include orthoquinonediazide sulfonic acid esters of polyhydroxybenzophenone.

This polyhydroxybenzophenone is a compound formed by substituting two or more hydrogen atoms of benzophenone with hydroxyl groups, such as dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxybenzophenone, or derivatives thereof (such as halogen substituents of atoms, alkyl groups, aryl groups, aralkyl groups, and carboxyl groups). Preferred is trihydroxybenzophenone or tetrahydroxybenzophenone, more preferred. 't-trihydroxybenzophenone, 3. Examples include φ, φ'-tetrahydroxybenzophenol.

This orthonaphthoquinonediazide sulfonic acid ester of polyhydroxybenzophenone is a combination of the polyhydroxypendophenone, J-naphthoquino/-1-diazide, monosulfonic acid chloride, l,2-naphthoquinone-
2-diazide-V-sulfonic acid chloride or ll, 2
It is synthesized by a known method using -naphthoquinone-2-diazide-6-sulfonic acid chloride or the like and an alkali carbonate or triethylamine as a catalyst. This esterification rate is preferably 30 to 00%.

Furthermore, as the orthoquinone diazide compound used in the present invention, the following compounds described in Japanese Patent Application Laid-Open No. 1997-3-3'Aj can also be used. That is, for example, known /, J-quinonediazide compounds such as /, 2-benzoquinonediazide sulfonic acid ester, /, 2-naphthoquinonediazide sulfonic acid ester, /, 2-benzoquinonediazide sulfonic acid amide, /12-naphthoquinonediazide sulfonic acid amide, etc. , and more specifically G. Kosar (
"Light Sensitive System J (Light-8ens65ive Sys.
(1961) / John Wiley and Sons
& 5ons) (New York) and F.Bliny Varnish Day Forest (W, S, D, For
Photoresist J (Photoresist J)
ist) Volume to (117J) Z McGraw-Hill (M
/, -1penzoquinone diazido≠-sulfonic acid phenyl ester %'/12,7',2'-di(
benzoquinonediazide-ψ-sulfonyl)-dihydroxybiphenyl, l,2-benzoquinonediazide-ψ-(
N-ethyl-N-β-naphthyl)-sulfonamide, l
, 2-naphthoquinonediazide-3-sulfonic acid cyclohexyl ester, /-(/, J-naphthoquinonediazide-y-sulfonyl)-3,j-dimethylpyrazole,
/,2-naphthoquinonediazide-yo-sulfonic acid-vl
-Hydroxydiphenyl-V"-azo-β-naphthol ester, N,N-di(/,J-naphthoquinone di7
shi)'-3-sulfonyl)-7ni/,λ'-(l
, 2-naphthoquinonediazide-y-sulfonyloxy)
-1-Hydroxy-anthraquinone, /, 2-naphthoquinonediazide-! -Sulfonic acid-+2. μm dihydroxybenzophenone ester, /, 2-naphthoquinone diazide-y-sulfonic acid-2,3,II-to-17-hydroxybenzophenone ester, /, J-naphthoquinone diazide! -Condensation product of 2 moles of sulfonic acid chloride and 1 mole of φ,μ'-diaminobenzophenone, l,2-naphthoquinonediazide -2 moles of sulfonic acid chloride and l,l
I-dihydroxy-/, /'I-diphenylsulfone condensate of 1 mol, l,2-naphthoquinonediazide-y-sulfonic acid chloride 1 mol and purprogalin 1 mol, 1,2-naphthoquinonediazide-t-( Examples include 2-quinonediazide compounds such as N-dihydroabethyl)-sulfonamide. Also, Special Publications No. 37-/953, No. 37-3427, No. 37-
/3109, 11O-26126, tio-3
rO1, 11j-jtOu, pt-27JII
J issue, J/-/30/3 issue, Tokukai Sho ar-Taro! 7j
No., same≠r-6JIO2, same ttr-tzros No./,! -Quinonediazide compounds may also be mentioned.

As the orthoquinone diazide compound used in the present invention, each of the above compounds may be used alone, or two or more thereof may be used in combination. The content of the orthoquinonediazide compound in the photosensitive layer is preferably j-60% by weight, particularly preferably 10-10% by weight. If the content or amount is too large, the sensitivity tends to decrease too much. On the other hand, if the amount is too small, it tends to be difficult to obtain sufficient developability.

The polymer compound contained in the photosensitive layer used in the present invention is a monomer represented by the following general formula (n), acrylic acid and/or methacrylic acid, and seven or more α
- Copolymers of esters of methylene aliphatic monocarboxylic acids.

Furthermore, a copolymer obtained by combining other seven or two or more types of copolymerizable monomers may be used as required.

(In the formula, R1, R2, R3, R4, An alkyl group or a carboxyl group such as the like is preferable, and a hydrogen atom is more preferable. R3 is preferably a hydrogen atom, a halogen atom such as bromine or chlorine, or an alkyl group such as a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group. Y is preferably a phenylene group or a naphthylene group which may have a substituent, and examples of the substituent include alkyl such as methyl group and ethyl group, halogen atoms such as bromine and chlorine, carboxyl group, methoxy group, and ethoxy group. Examples include alkoxy groups, hydroxyl groups, sulfonic acid groups, cyano groups, nitro groups, and acyl groups. More preferably, Y is an unsubstituted phenylene group or a naphthylene group having a methyl group. X is a covalent organic group that connects a nitrogen atom and an aromatic carbon, and n is preferably O, and when n is l, an alkylene group having 3 or less carbon atoms is preferable.

Monomers represented by the above general formula (II) -r, e.g., t, N-(4'-hydroxyphenyl)methacrylamide, N-(≠-hydroxyphenyl)acrylamide, N-(J-methyl -≠-hydroxyphenyl) methacrylamide, N-(j-hydroxynaphthyl)
methacrylamide)”, N-(J-chloro-≠-hydro-hydro-7-enyl)acrylamide, N-(3,dihydroxyphenyl)methacrylamide, N-(2-hydroxy-gucyanophenyl)methacrylamide , N-methyl-N-(<c-hydroxyphenyl)acrylamide, N-(≠-hydroxyphenylethyl)methacrylamide, etc. Particularly preferred among these is N-(<=-hydroxyphenyl) It is methacrylamide.

Specific examples of the above α-methylene aliphatic monocarboxylic acid esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate,
Examples include phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate.

Among these, methyl acrylate, ethyl acrylate,
Methyl methacrylate and ethyl methacrylate are preferable because they exhibit excellent performance overall.

In addition, the above-mentioned copolymerizable monomers include ethylene,
Ethylenically unsaturated olefins such as propylene, isobutylene, butadiene, and isoprene; Styrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene; Nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate; methyl vinyl ether, ethyl Vinyl ethers such as vinyl ether, inphthyl vinyl ether, β-chloroethyl vinyl ether; vinyl chloride, vinylidene chloride, vinylidene cyanide, /-methyl-7'-methoxyethylene, /, l/-dimethoxyethylene, l, 2-
Ethylene derivatives such as dimethoxyethylene, l,l'-dimethoxycarbonylethylene, l-methyl-7'-ditroethylene; N-vinylpyrrole, N-vinylcarbasol, N-vinylindole, N-vinylpyrolidene, N- There are N-vinyl compounds such as vinylpyrrolidone and other vinyl monomers. These copolymerizable monomers exist in a polymer compound with a structure in which unsaturated double bonds are cleaved.

Among the above copolymerizable monomers, nitriles, especially
Acrylonitrile and methacrylonitrile are preferred in terms of improving wear resistance.

The copolymerizable monomers are preferably copolymerized at θ to 30 moles.

These monomers may be bound in a block or random manner in the polymer compound.

The polymer compound used in the present invention can be synthesized according to a known method as follows. In other words, the general formula (
II) A monomer having the structural unit represented by acrylic acid and/or methacrylic acid and esters of at least seven kinds of α-methylene aliphatic monocarboxylic acids, and further, if necessary, other copolymerizable monomers. The polymer compound of the present invention can be obtained by copolymerizing with. At this time, by varying the charging molar ratio of each monomer and the polymerization conditions, the molecular weight of the polymer compound and the molar ratio of each structural unit can be set over a wide range.

However, in order to effectively serve the purpose of the present invention, the weight average molecular weight is set to 10,000 to izo, ooo. If the weight average molecular weight is too small, the developability is good, but the adhesiveness is weak and the reproducibility of small dots tends to be poor. or,
If it is too large, redness in halftone areas, fine lines, and highlight areas will be significant, and the development speed will also tend to be slow. The molar content of the structural unit represented by the general formula (n) is j ~
Make it 30 morti. If it is too small, the developability with an alkaline aqueous solution containing no organic solvent will be reduced, and if it is too large, redness will tend to occur during development. Furthermore, in order to effectively serve the purpose of the present invention, the amount of acrylic acid and/or methacrylic acid must be 0.7~! Morti copolymerize. If it is too small, the development speed will be slow and the adhesive force between the photosensitive layer and the silicone layer will also be reduced. If the amount is too large, the development speed will be high, but the image area will tend to become weak against the developer.

Esters of α-methylene aliphatic monocarboxylic acids are 6j
~the law of nature! It is preferable to carry out molti copolymerization.

The proportion of the polymer compound used in the present invention in the photosensitive layer is preferably 4% to 5% by weight, particularly preferably! θ~ri is 0% by weight.

By further containing a novolak resin in the photosensitive layer of the present invention, the strength of the image area against the developer and the adhesion between the photosensitive layer and the silicone rubber layer can be improved.

The novolak resin used is an alkaline aqueous solution-soluble novolak resin. It is usually obtained by condensing phenols and formalin in the presence of an acidic catalyst, and uses a resin that is soluble in an alkaline developer. Examples of such novolac resins include phenol-formalin resin, cresol-formalin resin, phenol-cresol-formalin resin, and the like.

The weight average molecular weight of the novolac resin used is 2,00
0 to ko o, o o o are preferable.

The proportion of the novolac resin in the photosensitive layer is j-'70
Preferably 70% by weight, particularly preferably io to 30% by weight
It is.

It is advantageous to include known exposure-visible image-imparting agents and dyes in the photosensitive layer. As the exposure visible image imparting agent, a substance that generates an acid upon exposure to light is generally used, and as the dye, a compound that forms a salt with this acid is generally used.

As a compound that generates an acid upon exposure to light, a trihaloalkyl compound represented by the following general formula is preferred.

(However, Xa is a trihaloalkyl group having 1 to 3 carbon atoms, W is N or P, 2 is 0, S or Se, and Y cyclizes W and 2 and has a chromophore. ) Specific compounds include oxadiazole compounds having a benzofuran ring such as \1,
Tokukai Akira! Quattrichloromethyl-t-(p-methoxystyryl)- described in Gu 7ψ721 publication
/, 3. Examples include II-oxadiazole compounds.

In addition, ≠-(co, ≠-dimethoxy≠-styryl)-trichloromethyl-2-pyrone compound, λ, l-bis-(
trichloromethyl)-6-p-methoxystyryl-8-
Examples include triazine compounds, 2, goobis-(trichloromethyl)-p-dimethylaminostyryl-8-triazine compounds, and the like.

The amount of exposure visible image imparting agent added is 0.0/-20 in the photosensitive layer.
% by weight, more preferably 0. /-1
It is 0% by weight.

On the other hand, as the dye, any compound that generally forms an acid salt can be used, such as triphenylmethane dyes, cyanine dyes, diazo dyes, and stinyl dyes.

Specifically, Victoria Pea Blue BOH.

Ethyl violet, crystal violet, brilliant green, pacific tuxin, eosin, phenolphthalein, xylenol blue, Congo red, malachite IJ-n, oil blue #l, 03
, oil pink #31.2, cresol red, auramine, ≠-p-diethylaminophenylimino naphthoquinone, leucomalachite green, leuco crystal violet, and the like. The amount of dye added is 0 in the photosensitive layer.
0O7 to 10% by weight is preferable, more preferably 0.0
2-g% by weight.

The photosensitive layer of the present invention may contain various other additives depending on the purpose. For example, surfactants to improve coating properties, various sensitizers to improve sensitivity,
Plasticizers are used to improve the physical properties of coatings, and various additives with hydrophobic groups are used to improve the adhesion of printing inks to images, such as p-octylphenol/formalin novolacs with alkyl groups having carbon atoms or more. resin, pt-
Butylphenol/formalin novolac resin, pt
-Butylphenol/benzaldehyde resin etc. can be added.

The content of these additives varies depending on their type and purpose, but is generally preferably o, oi-, or zo% by weight in the photosensitive layer, particularly preferably from 0.02 to 10% by weight.

The photosensitive layer of the present invention comprises the orthoquinone diazide compound,
The above-mentioned polymer compound, alkali-soluble novolak resin, and if necessary, an exposure visible image imparting agent, a dye, and other various additives are mixed in various solvents such as methyl (ethyl).
Cellosolve, methyl (ethyl) cellosolve acetate and other cellosolves; dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone,
It is formed by dissolving it in a coating solvent such as trichlorethylene, coating it, and drying it.

The thickness of the photosensitive layer of the present invention is preferably selected from the range of 0.2 to 100 μm, and particularly preferably from the range of /−20 μm.

The method for producing a photosensitive lithographic printing plate that does not require dampening water of the present invention usually involves the following steps: It is manufactured according to the following method (1) or (2).

(1) A photosensitive layer and a silicone rubber layer are coated on a polymer film in this order, and the substrate and silicone rubber layer are pressed together so that they are in close contact with each other.

(2) The silicone rubber layer provided on the substrate and the photosensitive layer provided on the polymer film are pressed together so that the silicone rubber layer and the photosensitive layer are in close contact with each other.

Examples of the polymer film include polyethylene, polypropylene, acrylonitrile-butadiene-styrene copolymer, polystyrene, acrylonitrile-styrene copolymer, polymethyl methacrylate, Nylo/6, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, etc. An example is film. For polyolefin films having relatively low surface tension, the surface may be subjected to treatments such as discharge treatment and surface roughening treatment to improve wettability.

The thickness of the polymer film is 0. /-j 00 prn is preferable, and those of O0j to vOOμm are particularly preferable.

In the method (1) above, the photosensitive layer and the silicone rubber layer are relatively easily brought into close contact, and good adhesion can be obtained. Above (1
) As shown in Japanese Patent Application No. 1.2-22523, the substrate and the silicone rubber layer are pressed together so that they are in close contact with each other, and then the silicone rubber layer is heated as it is or after the polymer film is peeled off. , a method of curing the silicone rubber layer is advantageous.

In addition, in order to improve the adhesion between the photosensitive layer and the silicone rubber layer, a silane cuff agent, a silicone primer, etc. may be coated on the photosensitive layer, or a silane cup may be applied to the photosensitive layer or the silicone rubber layer. ring agent,
A silicone primer or the like may also be added. Similarly, in order to improve the adhesion between the silicone rubber layer and the substrate, a silane coupling agent, silicone primer, etc. may be applied to the substrate, or a silane coupling agent, silicone primer, etc. may be applied to the silicone rubber layer. may be added.

A dampening water-less lithographic printing plate can be obtained from the dampening water-less photosensitive lithographic printing plate of the present invention obtained as described above in the following manner.

That is, a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, or an argon lamp is applied to the photosensitive layer from above the polymer film of the photosensitive lithographic printing plate of the present invention or after the polymer film is peeled off. After image exposure is performed using a general-purpose light source that includes ultraviolet rays and visible light of / r Onm or more, such as ion laser, helium cadmium laser, krypton laser, etc., an alkaline aqueous solution containing no organic solvent is used as a developer. When the polymer film is dissolved in these developing solutions, it is developed either on top of it or after peeling off the polymer film, and an ink-receptive silicone rubber layer is formed on the ink-repellent silicone rubber layer provided on the substrate. A printing plate can be obtained by forming an image.

Suitable alkaline agents used in the developer include inorganic agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, and sodium bicarbonate. Examples include alkaline agents and organic amine compounds such as trimethylamine, diethylamine, monoisopropylamine, n-butylamine, monoethanolamine, jetanolamine, and triethanolamine, which can be used alone or in combination, and when the pH is f-/j , preferably pH ~
12 is preferred. Further, the developer may contain a surfactant as necessary. Suitable surfactants include, for example, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfones; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids can be used; ~30% by weight
It is appropriate to contain it within the range of .

Furthermore, the developer solution may contain a known buffering agent, if necessary.
Other additives such as dyes, pigments, etc. may also be added.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to synthesis examples and examples of the polymer compound of the present invention, but the present invention is not limited by the following examples unless the gist thereof is exceeded.

Note that all "parts" used below indicate "parts by weight."

(Synthesis Example 1) N-(≠-hydroxyphenyl) methacrylamide (hereinafter abbreviated as HPMA) lr, rit, acrylonitrile (
Hereinafter abbreviated as AN. )! , 7F, methyl acrylate (hereinafter abbreviated as MA) J r, r fl.

Ethyl acrylate (hereinafter abbreviated as EA) z, or.

Acrylic acid (hereinafter abbreviated as AA) /, /f, and α, α
'-Azobisisobutyronitrile (hereinafter abbreviated as AIBN)/j? was dissolved in a mixed solvent of some ethanol and acetone jOMl, and heated at reflux temperature for 4 hours under a nitrogen atmosphere to carry out a polymerization reaction.

Hydroquinone was added to stop the reaction, then ethyl cellosolve≠Oml was added and the reaction solvent and unreacted monomers were removed by vacuum distillation.

to decompose unreacted AIBN.

After heat treatment for 3 hours, ethyl cellosolve was further added to obtain a 23% by weight solution of polymer compound-7 in ethyl cellosolve. When the molecular weight distribution was measured by gel permeation chromatography under the following conditions, the weight average molecular weight (hereinafter abbreviated as Mw) was 72. ooo, thousands □ average molecular weight (
Hereinafter abbreviated as Mn. ) 22,000.

Molecular weight measurement conditions (same method below) Column: Toyo Soda Kogyo ■TSK-GELGMH&
2 mobile phases: Tetrahydrofuran flow rate: 2 l waste l/min Detection: ■ Shimadzu UV-visible spectrophotometer 5PD-
Detected using AAV at a wavelength of jφnm.

Calibration curve: Prepared using standard polystyrene manufactured by Toyo Soda Kogyo ■.

(Synthesis Example 2) HPMA /7.79%AN 2.7f, MA 2! ,
Hirot%EkJ, Of%AA O,≠? , and AIBN/
,,4F was dissolved in a mixed solvent of 10ml of methanol and 30.1ml of acetone, and in the same manner as in Synthesis Example 1, a 25% by weight ethyl cellosolve solution of polymer compound-2 was obtained.

Mw was 103,000, Mn /3,000.

(Comparative Synthesis Example 1) Ethanol, the reaction solvent of Synthesis Example 1! 0. l and acetone jO
A mixed solvent of methanol 3jtnl and acetone 33ml
In the same manner as in Synthesis Example 1, except for replacing the mixed solvent of 1 with
A 23% by weight ethyl cellosolve solution of comparative polymer compound-7 was obtained. Mw320.0001Mn III, 000
Met.

(Comparative Synthesis Example 2) Reaction solvent of Synthesis Example 1 ethanol jOgo and acetone 30@
A 23% by weight ethyl cellosolve solution of Comparative Polymer Compound-2 was obtained in the same manner as in Synthesis Example/, except that 1 liter of the mixed solvent was replaced with a mixed solvent of 111 liters of methanol and 1 liter of acetone.

Mw l&0,000. MH! /, 000 hz.

(Comparative synthesis example 3) HPMA /7.7 t%AN2.7? , MA 2j,
Irf.

EAz, or, AIBN /, A P with ethanol jO
Synthesis Example 1 by dissolving in a mixed solvent of me and some acetone.
In the same manner as above, a 2j Shigei thiethyl cellosolve solution of comparative polymer compound-3 was obtained.

Mw was 6, ooo% Mn was 65, ooo.

(Example 1) The following photosensitive liquid (A) was applied to a 10 μm thick polypropylene film (manufactured by Honshu Paper Corporation) using a bar coater, and dried at to° C. for 3 minutes.

A 58 m photosensitive layer was provided.

Photosensitive liquid (A) (a) High molecular compound -/ (HPMA/AN/MA
/EA/AA=to7/lo/b7/10/3 molar ratio)
2j weight% ethyl cellosolve solution 2≠θ parts (b)
Phenol/m-cresol/p-cresol/formalin novolak resin (phenol/m-cresol/p-cresol=co
/p♂/32 molar ratio, MW=lI,! 00)
20 parts (c) pyrogallol/acetone polycondensate/J-su7toquinone diazido monosulfonic acid ester (esterification rate 30%, MW=/,!00)/
0 parts (d) 2+ 3+≠-trihydroxybenzophenone/2-naphthoquinonediazide-yo-sulfonic acid ester (esterification rate 3%) 70 parts (
c) p-octylphenol formalin novolac resin (MW=l, 300) /, 2-naphthoquinonediazide-! -Sulfonic acid ester (esterification rate -t
o%) 2 parts (f) 2-)lichloromethyl-s-(
β-(2'-benzofuryl)vinyl) -1,3,II
- 2 parts of oxadiazole)
Part 2 to Victoria Beer Blue BOX (
h) Ethyl cellosolve 1la
Part O Next, the following silicone solution (L) was applied onto the photosensitive layer using a percoater, and dried at 60°C for 3 minutes.
An uncured silicone rubber layer with a thickness of 10 μm was provided.

Silicone solution (L) (a) Silicone rubber 5I (-
71/ Part 10 (b) Dimethylpolysilaxane BY/&-1 made by Toshi Silicone ■
01zO part (C) Dibutyltin diacetate 0.2 part (d)
Toshi silicone primer PRX-30≠
3 parts (c) Methylcyclohexane 100 parts (f) Toluene
Next, use a laminator to cut the io part to a thickness of 0.
．． A polypropylene film 1 in which the photosensitive layer and silicone rubber layer are laminated on a 2-wall aluminum plate.
7. Rubber roll temperature≠0℃, jkf/I-FA, linear speed 60cm so that the cone rubber layer and aluminum surface are in contact.
It was crimped in 1 minute. Peel off the polypropylene film and
The silicone rubber layer was cured by heat treatment at 35° C. for 3 hours to obtain a photosensitive lithographic printing plate that did not require dampening water.

Pass this tile through Bon's original film according to the usual method.
With a high-pressure mercury lamp (UMH1Ooo manufactured by Ushio Inc.),
Image exposure was carried out for 3 minutes from a distance of 700 m.

This was developed using a 21-fold dilution of a positive PS plate developer DP-≠ (manufactured by Fuji Photo Film ■) at 2J°C for 1 minute.

During the development process, redness appeared in the midtone areas, fine lines, and highlights, but all redness was removed by rubbing lightly with a sponge.

By the development treatment, the photosensitive layer in the exposed area was dissolved and removed, the underlying silicone rubber layer was exposed, and a lithographic printing plate with good image reproducibility and no dampening water was obtained.

Using this plate, too many sheets were printed using Toyo King Ultra TKU Aquares G ink manufactured by Toyo Ink Mfg., without supplying dampening water, on a Sun Offset 220E press manufactured by San Printing Machinery. After doing so, the board still had no damage whatsoever.

Furthermore, when printing was carried out and a total of rooo sheets were printed, some so-called "print removal", in which the image portion disappeared, was observed.

(Example 2) Component (b) of the photosensitive solution (A) of Example 1 was mixed with phenol.
-Cresol-p-cresol/formalin/novolak resin (phenol/m-Fre7'-ni/p-riL/
7”-# = 170/3 t/21% Le ratio, Mw
A photosensitive lithographic printing plate which did not require dampening water was obtained in the same manner as in Example 1, except for changing the etchant to 7,100).

This plate was imagewise exposed and developed in the same manner as in Example 1 to obtain a lithographic printing plate that did not require any dampening water and had no redness and good image reproducibility.

When this was printed under the same conditions as Example 1, joo
After printing o sheets, the plate was not damaged in any way.

(Example 3) After imagewise exposing the photosensitive lithographic printing plate that did not require dampening water obtained in Example 1, it was developed using the following developer (1). Although redness occurred, the sponge When rubbed lightly, all redness was removed, and a lithographic printing plate with good image reproducibility and no need for dampening water was obtained.

Developer (1) (Example ≠) After imagewise exposing the dampening water-free photosensitive lithographic printing plate obtained in Example 1, development was performed using the following developer (2), and the redness was reduced. However, by rubbing lightly with a ζ sponge, all redness was removed, and a photosensitive lithographic printing plate with good image reproducibility and no need for dampening water was obtained.

Developer (2) (Comparative Example 1) A dampening water-free photosensitive lithographic printing plate was prepared in the same manner as in Example 1, except that the photosensitive liquid (A) in Example 1 was replaced with the following photosensitive liquid (B). Obtained.

Photosensitive solution (B) (a) 320 parts of 2% by weight ethyl cellosolve solution of polymer compound-7 (b) 2-naphthoquinonediazide-sulfonic acid ester of pyrogallol/acetone polycondensate (esterification rate: 30 %, MW=/, 100) 10 parts (
c) 2+ 3+ψ-trihydroxybenzophenone/2-naphthoquinonediazide-! -Sulfonic acid ester (esterification rate j%) 10 parts (d
) p-octylphenol formalin novolac resin (MW=1.300) /, 2-naphthoquinonediazide-! -Sulfonic acid ester (esterification rate jQ %) 2 parts (c) J-)
Lichloromethyl-yo-[β-(2'-benzofuryl)vinyl)'+3*≠-oxadiazole
2 parts (f) Victoria Pure Blue BOH/, 2 parts (g) Ethyl cellosolve
100 copies of this plate were subjected to image exposure and development in the same manner as in Example 1. The redness that occurred in the midtone areas, fine lines, and /% illite areas was completely removed by rubbing lightly with a sponge.

2000 sheets of the obtained lithographic printing plate that did not require dampening water were printed under the same conditions as in Example 1. Although the plate was not damaged in any way, further printing was carried out, and the total ≠ After printing 000 sheets, plate removal was observed.

(Comparative Example C) Component (a) of the photosensitive solution (B) of Comparative Example/ was used as a comparative polymer compound -/ (HPMA/AN/MA/EA/AA: 10/
The same procedure as in Comparative Example 1 was carried out, except that the solution was changed to a 2j wt% ethyl cellosolve solution (10/67/10/3 molar ratio).
A photosensitive lithographic printing plate requiring no dampening water was obtained.

After this plate was exposed imagewise in the same manner as in Comparative Example 1, it was developed using a 2-part diluted solution of the developer DP-4' at 21°C for 3 minutes, but the development speed was very low. The redness that appeared in mid-tone areas, fine lines and highlights could not be completely removed even after rubbing with a sponge. Further, in the area where the redness was removed, there was no image, and the image reproducibility was poor.

(Comparative Example 3) A dampening solution was prepared in the same manner as in Example 1, except that component (a) of the photosensitive liquid (A) in Example 1 was changed to a 2J 11% ethyl cellosolve solution of comparative polymer compound -/. A water-free photosensitive lithographic printing plate was obtained.

After imagewise exposing this plate in the same manner as in Example 1, development was performed at 26°C for 3 minutes using a 21-fold dilution of the developer DP-μ, but the development speed was very slow, and the intermediate The redness that appeared in tonal areas, fine lines, and highlights could not be completely removed even when rubbed with a sponge.

(Comparative example≠) Comparison of component (a) of photosensitive solution (A) of Example 1.

Child compound-2 (HPMA/AN/MA/EA/AA=
/ 0 / / 0 / A 7 / / 0 / 3
A dampening water-free photosensitive lithographic printing plate was obtained in the same manner as in Example 1, except that the solution was changed to a 25% by weight ethyl cellosolve solution (molar ratio).

This plate was subjected to image exposure in the same manner as in Example 1, and then developed!
A development process was performed using a 21-fold dilution of ff1DP-≠ at 0°C for - minutes. Redness that appeared in midtone areas, fine lines, and highlights remained without being completely removed, even when rubbed with a sponge. Therefore, image reproducibility was poor.

(Example) A dampening water-free photosensitive lithographic printing plate was obtained in the same manner as in Example 1, except that the photosensitive liquid (A) in Example 1 was replaced with the following photosensitive liquid (C).

Photosensitive liquid (C) (a) Polymer compound-2 (HPMA/AN/MA/
EA/AA==20/10/jri//0/1 molar ratio)+7)-2jffi-flft thiethyl cellosolve solution 211-0 parts (b) Phenol/formalin/novolac resin (Mw -/≠, 000)
20 parts (C) 1,2-naphthoquinone diazide of pyrogallol/acetone polycondensate! -Sulfonic acid ester (esterification rate 30%, MW=/, 300) 20 parts (d
) p-octylphenol formalin novolak resin (MW=l, 300)/2-naphthoquinonediazide-yosulfonic acid ester (esterification rate jO%) 2 parts (c) 2-
) Lichloromethyl-s-(β-(,2'-benzofuryl)vinyl)'+3+≠-oxadiazole
Part 2 (f) Glutaric anhydride
3 parts (g) Victoria Pure Blue BOX /, 2 parts (h) Ethyl Cellosolve / 1.0 parts This plate was imagewise exposed and developed in the same manner as in Example 1. Any redness that appeared in the midtone areas, fine lines, and highlights during the development process was completely removed by rubbing lightly with a sponge.

The resulting lithographic printing plate, which does not require dampening water, was used to print a large number of sheets under the same conditions as in Example 1, but the plate was still free from any damage.

Further printing was performed, and plate removal was observed after a total of 7,000 sheets had been printed.

(Comparative example) Example! Compare component (a) of photosensitive solution (C) of polymer compound-3 (HPMA/AN/MA/EA=2°7107
Image exposure and development were carried out in the same manner as in Example except that the solution was changed to a 2j'wt% ethyl cellosolve solution (60,710 molar ratio) to obtain a lithographic printing plate that did not require dampening water.

When this plate was used to print 2000 sheets under the same conditions as in Example 1, plate removal was observed.

〔Effect of the invention〕

The photosensitive lithographic printing plate of the present invention that does not require dampening water is organic.

You can use an alkaline aqueous solution as a developer without using a solvent.
The adhesive strength between the silicone rubber layer and the photosensitive layer is strong, and good images can be obtained. Therefore, the present invention is extremely useful industrially.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - 1 other person

Claims (1)

[Claims] (1) In a positive type photosensitive lithographic printing plate that does not require dampening water and comprises a substrate, a silicone rubber layer provided on the substrate, and a photosensitive layer provided on the silicone rubber layer, the photosensitive layer is (a ) an orthoquinone diazide compound, (b) 5 to 30 mol% of a structural unit represented by the following general formula [I], 0.1 to 5 mol% of a structural unit formed from acrylic acid and/or methacrylic acid, and α - A polymer compound having 65 to 95 mol% of structural units formed from esters of methylene aliphatic monocarboxylic acids and having a weight average molecular weight within the range of 10,000 to 150,000, and (c) an alkali-soluble novolak A photosensitive lithographic printing plate that does not require dampening water and is characterized by containing a resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I
] (In the formula, R^1 and R^2 are hydrogen atoms, halogen atoms,
is an alkyl group, aryl group or carboxyl group, R
^3 is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, R^4 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and Y is an aromatic group that may have a substituent. , X is a divalent organic group that connects the nitrogen atom and the carbon atom of the aromatic group, and n is a number of 0 or 1. )