JPH10319582A - Photosensitive composition and lithographic printing plate made from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the lithographic printing plate superior in uniformity of a coat film and ink receptivity and to provide the photosensitive composition for producing this printing plate. SOLUTION: This photosensitive composition comprises a photosensitive compound and a surfactant having a maleimide skeleton, especially, a fluorinated surfactant, having 3-20 C and at least 2 of the 2 H atoms at the end are substituted for F atoms and the surfactant comprises this fluoroaliphatic group and the above maleimide skeleton.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive composition,
The present invention relates to a photosensitive lithographic printing plate using the same, and more specifically, a photosensitive composition capable of obtaining a uniform film thickness after coating and drying a photosensitive composition dissolved or dispersed in a solvent on a support. The present invention relates to a photosensitive composition for producing a photosensitive lithographic printing plate having a photosensitive layer having a uniform coating film, and a photosensitive lithographic printing plate. is there.

[0002]

2. Description of the Related Art In general, a photosensitive lithographic printing plate is obtained by applying a solution obtained by dissolving or dispersing a photosensitive composition in an organic solvent to the surface of a support such as aluminum, paper or plastic which has been subjected to an appropriate surface treatment. It is manufactured by drying. When applying and drying this photosensitive composition, it is important to provide a uniform photosensitive layer on the support in order to exhibit the performance of the photosensitive composition.

In order to achieve such an object, Japanese Patent Laid-Open Publication No. Sho 62-170950 and Japanese Patent Laid-Open Publication No. Sho 62-2261 have been disclosed.
As described in JP-A-43-43, it has been proposed to include a specific fluorine-based surfactant in a photosensitive composition. However, although these techniques improve the non-uniformity of coating, they are not always sufficient.
Further, when used in a photosensitive lithographic printing plate, there is a problem that one of its important properties, such as insufficient ink deposition, is required.

A method of adding a polymer compound as described in Japanese Patent Application Laid-Open No. 55-527 has been proposed to improve the ink inking property, but it is still insufficient. . Examples of the fluorine-based surfactant include JP-A-1-18142 and JP-A-3-17284.
Although a method of adding a compound as described in JP-A No. 9 has been proposed, although the ink inking property is improved, it is not always sufficient, and the uniformity of coating is still insufficient. Was enough.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photosensitive lithographic printing plate which is further excellent in ink inking property and coating film uniformity, and a photosensitive composition for producing the same. And

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have used a surfactant having a maleimide skeleton as a surfactant contained in a photosensitive composition. As a result, it has been found that a photosensitive lithographic printing plate excellent in ink inking property and uniformity of a coating film and a photosensitive composition for producing the same can be obtained, and the present invention has been completed.

That is, a first structure of the present invention relates to a photosensitive composition containing a surfactant having a maleimide skeleton.

The present invention further relates to a fluorine-containing surfactant (A)
And a photosensitive compound (B) as an essential component, the fluorine-containing surfactant (A)
It is characterized by using a fluorosurfactant having 3 to 20 carbon atoms and having a fluoroaliphatic group in which at least two of the three terminal hydrogen atoms are substituted with a fluorine atom, and a maleimide skeleton. To a photosensitive composition.

The present invention also relates to a photosensitive composition characterized by further comprising a binder resin as a component contained in the above-mentioned photosensitive composition.

Further, the present invention relates to a photosensitive composition wherein the maleimide skeleton is an N-substituted maleimide skeleton.

Further, the present invention relates to a photosensitive composition wherein the maleimide skeleton is an N-cyclic hydrocarbon-substituted maleimide skeleton.

Further, the present invention provides a fluoroaliphatic surfactant (A) wherein the fluorosurfactant (A) has 3 to 20 carbon atoms and at least two of the three terminal hydrogen atoms are substituted with fluorine atoms. The present invention relates to a photosensitive composition which is a fluorine-containing surfactant having a group, a maleimide skeleton, and a poly (oxyalkylene) group.

Further, the present invention provides a fluoroaliphatic surfactant (A) wherein the fluorosurfactant (A) has 3 to 20 carbon atoms and at least two of the terminal three hydrogen atoms are substituted with fluorine atoms. The present invention relates to a photosensitive composition which is an acrylic polymer obtained by polymerizing a group-containing fluoro (meth) acrylate and an N-substituted maleimide as essential components.

In the present invention, the fluorine-containing surfactant (A) preferably has 3 to 20 carbon atoms and at least two of the terminal three hydrogen atoms are substituted with fluorine atoms. The present invention relates to a photosensitive composition which is an acrylic polymer obtained by polymerizing acrylate, N-substituted maleimide, and poly (oxyalkylene) (meth) acrylate as essential components.

According to a second aspect of the present invention, there is provided a photosensitive lithographic printing plate characterized in that the above-mentioned photosensitive composition is provided on a metal support, and further, the above-mentioned photosensitive composition becomes negative. Working negative working lithographic printing plates.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The surfactant having a maleimide skeleton used in the photosensitive composition of the present invention is an anionic surfactant.
Any type of surfactants such as cationic, nonionic, fluorine-based, and silicon-based surfactants may be used and can be suitably used. In particular, a fluorine-based surfactant has a large effect of lowering the surface tension and can be cited as a typical system that can be suitably used in the present invention. Therefore, the fluorine-based surfactant will be described below in detail taking a fluorine-based surfactant as an example.

The fluorosurfactant used in the present invention is a fluoroaliphatic group having 3 to 20 carbon atoms in which at least two of the three terminal hydrogen atoms are substituted with fluorine atoms (hereinafter referred to as a fluoroaliphatic group). , Rf group) and a maleimide skeleton. The Rf group is usually a saturated and generally a monovalent or divalent aliphatic group. It can be linear, branched and, if large enough, cyclic or a combination thereof (eg, an alkylcycloaliphatic group). The fluoroaliphatic backbone can include linked oxygen and / or trivalent nitrogen heteroatoms attached only to carbon atoms. This heteroatom provides a stable bond between the fluorocarbon groups and does not interfere with the inert nature of the Rf group.

The Rf group preferably has 3 to 20, more preferably 6 to 12, carbon atoms and 30% by weight.
Those having at least 40% by weight or more of fluorine bonded to a carbon atom are particularly preferred. The Rf group preferably has at least two of the three terminal hydrogen atoms replaced with fluorine atoms. Such an Rf group is, for example, CF ₃ CF ₂ CF ₂ —
The group is a perfluoroalkyl group, which is a substantially completely or fully fluorinated alkyl group such as C _n F _{2n + 1} (n is an integer of 3 or more).

When the fluorine content of the Rf group is 30% or more, the effect as a surfactant is remarkably exhibited, and the effect is more enhanced when the fluorine atom is localized at the terminal of the Rf group. Further, even when the number of carbon atoms of the Rf group is 2 or less, the fluorine content can be increased, but the total amount of fluorine atoms is insufficient and the effect is small. When the fluorine content in the copolymer is increased by increasing the ratio of the fully fluorinated Rf group-containing monomer having 2 or less carbon atoms to the copolymer, the fluorine atoms are localized. The effect is small because it is not converted.

On the other hand, when the number of carbon atoms in the Rf group is 21 or more, the solubility of the obtained copolymer in a solvent is low when the fluorine content is high, and when the fluorine content is low, the localization of fluorine atoms is low. Is not sufficient, and the effect as a surfactant is reduced.

Surfactants preferably used in the present invention include:
Those containing a fluoroaliphatic group-containing unit in an amount of from 20 to 80% by weight based on the surfactant are preferable because of good solubility in a solvent and sufficient effects.

The maleimide skeleton can be incorporated into the structure of the surfactant by various methods. For example, a method in which an amine compound is added to a maleic anhydride-containing polymer (imidation), a compound having a maleimide skeleton is used as a monomer. And a surfactant obtained by polymerization. Such a synthesis method is described in, for example,
No. 24844, JP-A-61-34046, JP-A-61-61946
-128243, JP-A-61-162039, JP-A-61-250048, JP-A-62-94840,
JP-A-62-153305, JP-A-62-28310
No. 8, for example. A typical example of the maleic anhydride-containing polymer is a styrene-maleic anhydride resin.

Examples of the compound having a maleimide skeleton include N-phenylmaleimide, N-phenylmethylmaleimide, N-chlorophenylmaleimide, and N-phenylmaleimide.
Methoxyphenylmaleimide, N-methylphenylmaleimide, N-dimethylphenylmaleimide, N-ethylphenylmaleimide, N-diethylphenylmaleimide, N-nitrophenylmaleimide, N-phenoxyphenylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenyl Maleimide, N-phenylcarbonylphenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-vinylmaleimide, N
-Allyl maleimide, N-cyclohexyl maleimide,
N-substituted maleimides such as N-lauryl maleimide,
Non-N-substituted maleimides such as maleimide can be mentioned.

However, in the substituted phenyl group bonded to the maleimides, the substituent may be bonded to any other carbon atom not bonded to an N atom in the phenyl group.

When the surfactant of the present invention is used in a lithographic printing plate, a fluorine-based surfactant having an N-substituted maleimide skeleton has a large effect of improving ink inking property. Can be used. Further, a fluorine-based surfactant having an N-cyclic hydrocarbon-substituted maleimide skeleton,
The effect of improving the ink inking property is even greater and can be mentioned as a particularly preferred example.

The maleimide skeleton-containing surfactant of the present invention more preferably has a polyoxyalkylene group. The polyoxyalkylene group in the surfactant suitably used in the present invention includes, for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene / oxypropylene) random copolymer group, and a polyoxyalkylene group. (Oxyethylene / oxypropylene) block copolymer groups and the like.

The oxyalkylene unit in the poly (oxyalkylene) group may be the same oxyalkylene as in poly (oxypropylene), or two or more different oxyalkylenes may be irregular. Such as linear or branched oxypropylene and oxyethylene units, or linear or branched oxypropylene unit blocks and oxyethylene unit blocks. May exist. The polyoxyalkylene chain may be mediated or include one or more chain bonds. If the linkage in the chain has three or more valencies, this provides a means for obtaining branched oxyalkylene units.

The molecular weight of the polyoxyalkylene group is usually from 100 to 5,000, preferably from 200 to 1,000. The polyoxyalkylene group unit preferably contains 10% by weight or more of one molecular weight of the synthetic resin. When the amount of the polyoxyalkylene group unit is 10% by weight or more, when a photosensitive composition is prepared, a pinhole is hardly generated in the coating film.

Surfactants having a maleimide skeleton and having a fluoroaliphatic group and a poly (oxyalkylene) group have various structures. In the case of an acrylic resin, the raw materials are abundant. Therefore, it is convenient for controlling various characteristics of the photosensitive composition, and the system can be suitably used in the present invention. Hereinafter, an acrylic resin system will be described as an example in detail.

The acrylic resin used as a surfactant in the present invention can be produced by a known and commonly used method. For example, a polymerizable compound having a maleimide skeleton, a (meth) acrylate having a fluoroaliphatic group, a (meth) acrylate having a polyoxyalkylene group, and optionally an addition-polymerizable unsaturated compound having an anionic group, The addition-polymerizable unsaturated compound having a substituent having an acidic hydrogen atom and other addition-polymerizable unsaturated compounds can be produced by thermal polymerization in an organic solvent with addition of a conventional radical polymerization initiator.

In the present invention, (meth) acrylate is a general term for acrylate and methacrylate.

(Meth) acryl having a fluoroaliphatic group
As the rate, for example, Rf-R ₁-OCO-C
(R_Two) = CH_Two (Where R₁Is, for example, a single bond,
Alkylene, sulfonamidoalkylene, or carboxyl
A midalkylene, R_TwoIs a hydrogen atom or a methyl group
It is. )).

As a specific example, for example, US Pat.
No. 3615, No. 2642416, No. 282656
No. 4, No. 3,102,103, No. 3,282,905 and No. 3,334,278.

(Meth) having a polyoxyalkylene group
Examples of the acrylate include those having a structure in which hydroxypoly (oxyalkylene) is reacted with (meth) acrylic acid, (meth) acryloyl chloride, or (meth) acrylic anhydride by a known method.

Examples of the hydroxy poly (oxyalkylene) material in this case include “Pluronic” and “Adeka polyether” (trade names, manufactured by Asahi Denka Kogyo KK) and “Tint” (Rohm & Hass).
Co. "Carbowax" (Glyco Pro
ducts Co. ), P. E. FIG. G. FIG. [Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.].

Examples of the addition-polymerizable unsaturated compound having an anionic group include a —SO ₃ M group and a —COOM
There are addition-polymerizable unsaturated compounds having a group, and specific examples thereof include p-styrenesulfonic acid and 2-acrylamide-
2-methylpropanesulfonic acid, ethylenesulfonic acid,
2-chloroethylenesulfonic acid, ethylenedisulfonic acid, 1-propene-1-sulfonic acid, 1-propene-2
-Sulfonic acid, 2-methyl-1,3-propenedisulfonic acid, 1-butene-1-sulfonic acid, 1-pentene-1
-Sulfonic acid, 1-hexene-1-sulfonic acid, 2-phenylethylenesulfonic acid, 1-methyl-2-phenylethylenesulfonic acid, 3-chloroallylsulfonic acid, allylsulfonic acid, 3-chloro-2-butenesulfone acid,
3-chloromethallylsulfonic acid, methallylsulfonic acid, 3-methyl-2-butene-2-sulfonic acid, 3-phenylallylsulfonic acid, 3-phenylmethallylsulfonic acid, 2-benzylallylsulfonic acid, Chloro-
4-styrenesulfonic acid, vinyltoluenesulfonic acid,
α-methylstyrenesulfonic acid, (meth) acrylic acid,
Salts of maleic anhydride, fumaric acid, crotonic acid, itaconic acid and the like with sodium, potassium, amines and the like can be mentioned.

Examples of the addition-polymerizable unsaturated compound having a substituent having an acidic hydrogen atom include (meth) acrylic acid and CH ₂ ＣC (R ₂ ) —CO—X ₁ —R ₃ —SO ₂ NH—.
_{R 4, CH 2 = C (} R 2) -CO-X 2 -R 5 -NHSO 2
And compounds such as —R ₆ .

Where X₁, X_TwoIs -O- or
-NR₇-And R_Three, R_FiveHas a substituent
May be C₁-C₁₂Alkylene group, cycloalkylene
Group, an arylene group or an aralkylene group,_FourIs the water
An elemental atom and optionally substituted C₁-C₁₂The alkyl of
Group, cycloalkyl group, aryl group, aralkyl group
R₆Is an optionally substituted C₁-C₁₂The alkyl of
Group, cycloalkyl group, aryl group, aralkyl group
R₇Is a hydrogen atom, C which may have a substituent ₁-C
₁₂Alkyl group, cycloalkyl group, aryl group,
Aralkyl group.

Examples of other addition-polymerizable unsaturated compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. ) Acrylate, octyl (meth) acrylate, 2-chloroethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) Acrylate, diethylaminoethyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, phenyl (meth) acrylate, hydroxyphenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth)
(Meth) acrylates such as acrylate, benzyl (meth) acrylate, and methoxybenzyl (meth) acrylate;

(Meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N- Cyclohexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl (meth) acrylamide, N Such as -tolyl (meth) acrylamide, N-hydroxyphenyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dicyclohexyl (meth) acrylamide; ) Acrylamides: N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-pentylmaleimide, Nn-hexylmaleimide, N-laurylmaleimide, N-stearylmaleimide, N-cyclohexylmaleimide N-substituted maleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-tolylmaleimide, N-hydroxymaleimide, N-benzylmaleimide;

Allyl compounds such as allyl acetate, allyl caproate, allyl stearate and allyloxyethanol; ethyl vinyl ether, propyl vinyl ether,
Vinyl ethers such as 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, and diethylaminoethyl vinyl ether; vinyl acetate, vinyl Vinyl esters such as butyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl benzoate, vinyl chlorobenzoate;
Styrenes such as styrene, α-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, ethoxymethylstyrene, hydroxystyrene, chlorostyrene and bromostyrene; methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, etc. Olefins such as isobutylene, butadiene, and isoprene; and butyl crotonate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl fumarate, N-vinylpyrrolidone, N-vinylpyridine, acrylonitrile, and the like. Can be

The photosensitive composition of the present invention can be prepared by using the above-mentioned surfactant having a maleimide skeleton and a photosensitive compound as essential components. In general, a photosensitizer and a binder resin are used in combination with the photosensitive compound. Here, the surfactant having a maleimide skeleton of the present invention is:
It is fundamentally different from a sensitizing agent added to improve the ink inking property in a photosensitive lithographic printing plate in that it also has an excellent surfactant function.

Taking the photosensitive composition for a lithographic printing plate as an example,
The constitution of the photosensitive composition of the present invention will be described in more detail. The photosensitive composition for a lithographic printing plate is a photosensitive composition comprising a photosensitive compound and a synthetic resin which is water-insoluble and soluble or swellable in an aqueous alkaline solution as essential components. Usually, the composition contains an organic solvent. The photosensitive composition of the present invention can be prepared by adding the above-described surfactant of the present invention to the photosensitive composition.

The preferred range of use of the fluorosurfactant used in the present invention is in the range of 0.01 to 5% by weight based on the photosensitive composition (the coating component excluding the solvent).
A more preferred use range is the range of 0.05 to 3% by weight. When the amount of the fluorosurfactant is within the above range, the effect is sufficient, and there is little fear that the drying of the coating film becomes insufficient or the performance (for example, developability) as a photosensitive material is adversely affected.

In preparing the composition of the present invention, either a negative photosensitive compound or a positive photosensitive compound can be used as the photosensitive compound, and a negative photosensitive composition and a positive photosensitive compound can be used, respectively. It can be used as a composition.

As the positive type photosensitive composition, any one can be used as long as its solubility or swelling in a developer changes before and after exposure. Examples of such a photosensitive composition include various known photosensitive compositions such as a positive photosensitive composition containing an alkali-soluble resin and an o-quinonediazide compound, and a three-component chemically amplified positive photosensitive composition. The system can be mentioned. In the case of a positive photosensitive composition containing an alkali-soluble resin and an o-quinonediazide compound, it can be mentioned as a system that can be particularly preferably used in the present invention. explain.

The o-quinonediazide compound is preferably a compound having at least one o-quinonediazide group, which increases the solubility in an aqueous alkali solution by actinic rays. As such a thing, those having various structures are known. KOSAR "Light-
Sensitive Systems "(John Wi
ley & Sons, Inc. 1965). 33
6-352.

As the positive photosensitive composition, sulfonic acid esters of various hydroxyl compounds and o-benzoquinonediazide or o-naphthoquinonediazide are particularly preferable.

The o-quinonediazide compound as described above includes, for example, 1,2-naphthoquinone-2diazide-
Ester of 5-sulfonyl chloride with phenol-formaldehyde resin or cresol-formaldehyde resin; 1,2-naphthoquinone-2-diazide-5 described in U.S. Pat. No. 3,635,709.
Esters of sulfonyl chloride with pyrogallol acetone resin;

Esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and resorcin-benzaldehyde resin described in JP-B-63-13528; described in JP-B-62-44257. Ester of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride with resorcinol-pyrogallol-acetone co-condensation resin;
1,2-naphthoquinone-2-diazide-
5-sulfonyl chloride esterified;

1,2-Naphthoquinone-2-polymer can be added to a homopolymer of N- (4-hydroxyphenyl) methacrylamide or a copolymer with another copolymerizable monomer described in JP-B-50-24641. Diazide-5
Esterified sulfonyl chloride; ester of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and bisphenol-formaldehyde resin described in JP-B-54-29922;
Japanese Patent Publication No. 52-36043 discloses 1,2-naphthoquinone-2-polymer with a homopolymer of p-hydroxystyrene or a copolymer with another copolymerizable monomer.
Esterified diazide-5-sulfonyl chloride; esters of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride with polyhydroxybenzophenone.

Other known o-quinonediazide compounds usable in the present invention include JP-A-63-80254.
JP-A-58-5737 and JP-A-57-11153.
0, JP-A-57-111531, and JP-A-57-11
No. 4138, JP-A-57-142635, JP-A-Sho 51
-36129, JP-B-62-3411, JP-B-62
-51459, JP-B-51-483, and the like.

The content of the above-mentioned o-quinonediazide compound is usually 5 to 60 with respect to the total solid content of the photosensitive composition.
%, More preferably 10 to 40% by weight.

In the photosensitive composition of the present invention, a resin insoluble in water and soluble in an alkaline aqueous solution (hereinafter referred to as an alkali-soluble resin) can be used as a binder resin.
Characteristics such as development characteristics, printing durability, solvent resistance, and chemical resistance can be improved.

Examples of the alkali-soluble resin include novolak resins or resol resins such as phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde cocondensation resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, (4-hydroxyphenyl) methacrylamide, hydroquinone monomethacrylate, N
-(Sulfamoylphenyl) methacrylamide, N-
Acrylic resin containing at least one monomer having an acidic group such as phenylsulfonylmethacrylamide, N-phenylsulfonylmaleimide, acrylic acid and methacrylic acid; active methylene group-containing resin described in JP-A-63-127237; Vinyl polymer-based resins such as urea bond-containing resins described in Japanese Patent Application No. 8-19912;
No. 61350, N-sulfonylamido group, N-
Polyurethane resins having a sulfonylureido group and an N-aminosulfonylamide group, polyurethane resins such as an active imide group-containing polyurethane resin described in JP-A-2-77748, and polyamides such as a polyhydroxypolyamide described in JP-A-1-6947. Resins, JP-A-6
And polyester resins such as polyester resins having a phenolic hydroxyl group described in JP-A-236029. Such alkali-soluble resins may be used alone or in combination of two or more kinds.
It is used at a content of not more than% by weight.

In the photosensitive 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, Other fillers and the like can be added.

Examples of the cyclic acid anhydride include succinic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride,
Examples thereof include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, chloromaleic anhydride, and pyromellitic anhydride. These cyclic acid anhydrides can be contained in an amount of 1 to 15% by weight of the whole composition.

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 to change color. I can do it.

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. The described trihalomethyl-2-pyrone and trihalomethyl-
s-triazine; various o-naphthoquinonediazide compounds described in JP-A-55-62444; 2-trihalomethyl-5-aryl-1,3 described in JP-A-55-77742. And 4-oxadiazole compounds; diazonium salts and the like.
These compounds can be used alone or as a mixture, and the added amount thereof is 0.3 to 15 with respect to the total weight of the composition.
A range of weight% is preferred.

Examples of the organic dye capable of forming a salt include triphenylmethane dyes, cyanine dyes, diazo dyes, styryl dyes, and the like.
Crystal violet, ethyl violet, methyl violet, methylene blue Victoria blue B
H, Victoria Pure Blue BOH, Malachite Green, Oil Blue # 603, Oil Green BG,
Brilliant green, fuchsin, eosin, rhodamine B, oil pink # 312, oil red 5B, oil black BS, oil yellow # 101, phenolphthalein, cresol red, auramine, leuco crystal violet, leucomalachite green and the like can be mentioned. . The addition amount is preferably in the range of 0.3 to 15% by weight based on the total weight of the composition.

In the composition of the present invention, various resins having a hydrophobic group, for example, 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.

The photosensitive compound used in the negative photosensitive composition includes (1) a photosensitive diazonium compound,
(2) Combination of an addition-polymerizable unsaturated group-containing compound and a photopolymerization initiator, and (3) a combination of a photosensitive diazonium compound, an addition-polymerizable unsaturated group-containing compound, and a photopolymerization initiator are preferably used. I can do it.

As the photosensitive diazonium compound, for example, there is a diazo resin typified by a salt of a condensate of a diazodiarylamine and an active carbonyl compound, and a photosensitive, water-insoluble and organic solvent-soluble compound is preferable.

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, paraformaldehyde, acetaldehyde,
Organic or inorganic acid salts of condensates with benzaldehyde, 4,4'-bis-methoxymethyldiphenyl ether and the like.

As the organic acid at this time, for example, 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, diazo resins having a main chain of a polyester group described in JP-A-54-30121;
A diazo resin obtained by reacting a polymer having a carboxylic anhydride residue described in JP-A 1-273538 with a diazo compound having a hydroxyl group; a diazo resin obtained by reacting a polyisocyanate compound with a diazo compound having a hydroxyl group Etc. 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. If necessary, two or more diazo resins may be used in combination.

In preparing a negative photosensitive 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 the performance, known additives,
For example, a thermal polymerization inhibitor, a dye, a pigment, a plasticizer, a stability improver, 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”.
[Orient Chemical Industry Co., Ltd.] and the like. 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 amounts of these various additives vary depending on the purpose, but generally, the amount of the solid content of the photosensitive composition is 0%.
The range is preferably from 30 to 30% by weight.

In the case of a photosensitive composition containing an addition-polymerizable unsaturated group-containing compound and a photopolymerization initiator, for example, US Pat. Nos. 2,760,863 and 3,060,023; There is a composition comprising an addition-polymerizable unsaturated group-containing compound having two or more terminal ethylene groups and a photopolymerization initiator described in JP-A-112448.

The compound having an addition-polymerizable unsaturated group is a compound having a boiling point of 100 ° C. or more at normal pressure and having at least one, preferably two or more addition-polymerizable ethylenically unsaturated groups in one molecule. Monomer or oligomer.
Examples of such a monomer or oligomer include, for example,
Polyethylene glycol mono (meth) acrylate [Hereinafter, methacrylate and acrylate are collectively referred to as (meth) acrylate. Monofunctional (meth) acrylates such as polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, tri (acryloyloxyethyl) isocyanurate (Meth) acrylates of polyhydric alcohol / alkylene oxide adducts and (meth) acrylates of polyhydric phenol / alkylene oxide adducts Relate, JP-B-48-41708, JP-B-50-603
4, urethane acrylates described in JP-B-51-37193 and JP-A-48-64183.
No., JP-B-49-43191, JP-B-52-3049
Polyfunctional (meth) acrylates such as polyester acrylates and epoxy acrylates obtained by adding an epoxy resin and (meth) acrylic acid described in each of JP-A No. 0 can be mentioned.

The amount of the compound having an ethylenically unsaturated group capable of undergoing addition polymerization is preferably in the range of 5 to 70% by weight based on the solid content of the composition.

Examples of the photopolymerization initiator include α-carbonyl compounds described in US Pat. No. 2,367,661, acyloin ethers described in US Pat. No. 2,448,828, and US Pat. No. 27225.
No. 12, α-hydrocarbon-substituted aromatic acyloin compounds, polycyclic quinone compounds described in U.S. Pat. No. 3,046,127, and U.S. Pat. No. 3,549,367. A combination of triarylbiimidazole / p-aminophenyl ketone,
Trihalomethyl-s-triazine compounds described in U.S. Pat. No. 4,239,850, U.S. Pat.
Oxadiazole compounds described in U.S. Pat. No. 221970, acridine and phenazine compounds described in U.S. Pat. No. 3,751,259,
Examples thereof include benzothiazole compounds described in JP-A-1-48516, and the amount thereof is preferably in the range of 0.5 to 20% by weight based on the solid content of the composition.

The characteristics of the above-mentioned negative type photosensitive compound are as follows: (1) When a photosensitive diazonium compound is used, the adhesion between the photosensitive layer and the substrate is good; When a combination of a photopolymerization initiator is used, a tough coating film is obtained by exposure. (3) In the case of a combination of a photosensitive diazonium compound, an addition-polymerizable unsaturated group-containing compound, and a photopolymerization initiator, the characteristics of both are obtained. Can be obtained.

Further, as the binder resin, for example, a (meth) acrylic acid- (meth) acrylate copolymer, an acid value of 10 described in US Pat. No. 4,123,276.
A hydroxyalkyl (meth) acrylate and (meth) acrylonitrile-containing copolymer having from 100 to 100;
The copolymer having an aromatic hydroxyl group described in JP-B-57-43890 and the copolymer described in JP-B-57-51656.
Copolymers such as polymers having hydroxy-3-phenoxypropyl (meth) acrylate units; Epoxy resins; Polyamide resins; Vinyl halides, especially polyvinyl chloride, polyvinylidene chloride; Polyvinyl acetate; Polyester; Formal resins, Butyral Acetal resins such as resins; Soluble polyurethane resins sold by Goodrich, USA under the trade name of Estan; Polystyrene;
Styrene-maleic anhydride copolymer or half ester thereof; fibrin derivative; shellac; rosin or a modified product thereof, and a copolymer having an unsaturated group in a side chain described in JP-A-61-285449. I can do it.

The negative photosensitive composition may further contain a dye, a pigment, a stabilizer, a filler, a crosslinking agent, and the like, if necessary.
Dissolved in a suitable solvent.

In the case of a photosensitive composition containing a photocrosslinkable resin,
As the photocrosslinkable resin, a photocrosslinkable resin having an affinity for an aqueous alkali developer is preferable.
A copolymer having a cinnamic acid group and a carboxyl group described in JP-A-4-15711; a polyester resin having a phenylenediacrylic acid residue and a carboxyl group described in JP-A-60-165646; JP-A-60-203630 A polyester resin having a phenylenediacrylic acid residue and a phenolic hydroxyl group described in JP-A-57-42858; a 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 -208552 can be used.

The above-mentioned photosensitive composition is further dissolved in an appropriate solvent, if necessary, by adding a dye, a pigment, a stabilizer, a filler, a crosslinking agent and the like.

When a lithographic printing plate photosensitive material is obtained from the photosensitive composition containing a fluorine-containing surfactant of the present invention, it is first provided on a suitable support. The photosensitive composition containing the fluorinated surfactant of the present invention is dissolved or dispersed in the following organic solvents alone or as a mixture, applied to a support, and dried.

As the support, for example, aluminum,
Metal plate of zinc, copper, stainless steel, iron, etc .; plastic film of polyethylene terephthalate, polycarbonate, polyvinyl acetal, polyethylene, etc .; paper on which synthetic resin is melt-coated or synthetic resin solution coated, vacuum-depositing and laminating metal layer on plastic film And other materials used as a support for a printing plate.

In the case of a support having a metal surface, particularly an aluminum surface, it is preferable that a surface treatment such as a graining treatment, an anodic oxidation treatment and a hydrophilic treatment is performed.
The coating amount of the composition is usually about 0.5 to about 5 by dry weight.
g / m ² .

As the organic solvent, any known organic solvents can be used, but the boiling point is 40 ° C. to 200 ° C., especially 60 ° C.
Those in the range of -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 dissolves.

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, 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 Dieci Ether, propylene glycol,
Polyhydric alcohols such as propylene glycol monomethyl ether, propylene glycol monomethyl ether 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-dimethylformamide and the like are preferably used alone or in combination. And
The concentration of the solid content in the composition to be applied is suitably 2 to 50% by weight.

As a method for 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. Especially 10ml / m
A composition coverage of ^{2 to} 100 ml / m ² is preferred.

The drying of the photosensitive composition applied on the support is usually performed with heated air. Heating is 30
C. to 200.degree. C., particularly preferably 40 to 140.degree. 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.

In some cases, good results can be obtained by dehumidifying the dry air. The heated air is applied at a rate of 0.1 m / sec to 30 m / sec, particularly 0.5 m / sec to 2
It is preferable to supply at a rate of 0 m / sec.

According to the present invention, the unevenness of the thickness of the photosensitive layer which has conventionally occurred in the drying step is eliminated, the performance as a printing plate is made uniform, and the uniform thickness is obtained under a wide range of drying conditions. Can be applied, and the drying equipment can be simplified.

Further, the present invention is particularly effective in a photosensitive lithographic printing plate obtained by transporting a belt-shaped support, continuously applying a photosensitive composition dissolved or dispersed in an organic solvent, and drying. Notably recognized.

[0093]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail based on embodiments. However, the present invention is not limited by these examples. Incidentally,% in the examples is% by weight.
It shows.

<Synthesis of Fluorinated Surfactant> Resins used in the present invention were obtained by using the raw materials shown in Table 1 at predetermined ratios.

[0095]

[Table 1]

Note that (Note 1) and (Note 2) in Table 1 represent the following. (Note _{1) C 8 F 17 SO 2} N (C 3 H 7) CH 2 CH 2 OCOC
H = CH ₂ (Note 2) HO (C ₂ H ₄ O) ₈ COC (CH ₃ ) = CH ₂

(Synthesis Example 6) N-propylperfluorooctylsulfonylaminoethyl acrylate (Note 1)
Using 37% by weight and 63% by weight of polyoxyethylene methacrylate (Note 2), acrylic resin (Synthesis Example-
6) was obtained.

(Synthesis Example 7) N-propylperfluorooctylsulfonylaminoethyl acrylate (Note 1)
An acrylic resin (Synthesis Example-7) was obtained using 37% by weight, 19% by weight of polyoxyethylene methacrylate (Note 2), and 44% by weight of butyl acrylate.

(Preparation of Photosensitive Composition) The following photosensitive compositions shown in Table 2 were prepared using the surfactants of Synthesis Examples 1 to 7, respectively.

[0100]

[Table 2]

(Preparation of 2-Hydroxyethyl Methacrylate Copolymer) 300 g of dioxane was added to 10
The mixture was heated to 0 ° C., and a mixture of 150 g of 2-hydroxyethyl methacrylate, 60 g of acrylonitrile, 79.5 g of methyl methacrylate, 10.5 g of methacrylic acid and 1.2 g of benzoyl peroxide was added dropwise over 2 hours. Fifteen minutes after the completion of the dropwise addition, 300 g of dioxane and 0.3 g of benzoyl peroxide were added, and the mixture was allowed to react for 4 hours. After completion of the reaction, the reaction mixture was diluted with methanol and poured into water to precipitate a copolymer, which was dried at 70 ° C. under vacuum.
A 2-hydroxyethyl methacrylate copolymer described in JP-A-118802 was obtained. The acid value was 20.

(Examples 1 to 5 and Comparative Examples 1 and 2) In Examples 1 to 5, the compositions using the resins of Synthesis Examples 1 to 5, respectively, were used. The composition using the acrylic resin of No. 7 was used.

An aluminum plate having a thickness of 0.30 mm was degreased with an aqueous solution of sodium hydroxide and subjected to electrolytic polishing in a 2% hydrochloric acid bath to obtain a center line average roughness (Ra) of 0.6 μm.
m was obtained. Then, in a 20% sulfuric acid bath, anodizing treatment was performed at a current density of 2 A / dm ² to form an oxide film of 2.7 g / m ^2.
%, Passed through a 30% aqueous solution for 30 seconds, washed with water and dried, and led to a coating process. In the coating process, the coating solutions of the respective photosensitive compositions prepared in Table 2 above were used.

The coating solution was applied to a support at a low speed with a roll coater and dried at 100 ° C. for 3 minutes to obtain a photosensitive lithographic printing plate. At this time, the amount of the dried coating film was 2.0 g / m ² .

Each of the resulting photosensitive lithographic printing plates was prepared using an automatic developing machine PD-912 manufactured by Dainippon Screen Co., Ltd. and a developing solution ND-1 (1: 3) manufactured by Polychrome Japan Co., Ltd.
Development was performed at 30 ° C. for 20 seconds, and printing was performed by applying gum NF-2 manufactured by the company. In addition, the ink inking property was determined by examining the number of printed sheets until the ink was completely transferred to printing paper at the time of actual printing. The results are shown below.

[0106]

[Table 3]

In Table 3, the uniformity of the coating film was visually evaluated with respect to unevenness of density due to drying air and the like, and unevenness of stripes generated during coating and drying, and evaluated on a scale of A to E.
In this case, the result is better when the value is closer to A, and the result is worse when the value is closer to E. As is clear from these examples, the ink inking property and the uniformity of the coating film of a lithographic printing plate using the photosensitive solution composition of the present invention were determined by conventional techniques (Comparative Example 1,
Very superior to 2). In addition, the ink inking property of Examples 2 to 5 using the N-cyclic hydrocarbon-substituted maleimide was higher than that of Example 1 using N-laurylmaleimide, which is an N-acyclic hydrocarbon-substituted maleimide. And a good printed matter is obtained with a small number of printed sheets.
-It was also found that the use of a cyclic hydrocarbon-substituted maleimide further improved the ink inking property.

[0108]

The present invention is characterized in that a surfactant having a maleimide skeleton is used as the surfactant contained in the photosensitive composition, whereby the ink is excellent in the ink adhesion property and the uniformity of the coating film. It has a particularly remarkable effect.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Eiji Hayakawa 15-1 Sumiyoshicho, Utsunomiya City, Tochigi Prefecture (72) Koji Oe 5-90 Higashima, Kitamoto City, Saitama Prefecture 2-505 Kitamoto Kitamoto

Claims (10)

[Claims] 1. A photosensitive composition comprising a surfactant having a maleimide skeleton. 2. In a photosensitive composition containing a fluorine-based surfactant (A) and a photosensitive compound (B) as essential components, the fluorine-based surfactant (A) has 3 to 3 carbon atoms.
20, a fluoroaliphatic group in which at least two of the terminal three hydrogen atoms are substituted with a fluorine atom,
A photosensitive composition using a fluorine-based surfactant having a maleimide skeleton. 3. The photosensitive composition according to claim 1, further comprising a binder resin as a component contained in the photosensitive composition. 4. The photosensitive composition according to claim 1, wherein the maleimide skeleton is an N-substituted maleimide skeleton. 5. The photosensitive composition according to claim 1, wherein the maleimide skeleton is an N-cyclic hydrocarbon-substituted maleimide skeleton. 6. The fluorinated surfactant (A) has 3 carbon atoms.
-20, a fluoroaliphatic group in which at least two of the terminal three hydrogen atoms are substituted with a fluorine atom, a maleimide skeleton, and a poly (oxyalkylene)
6. A fluorosurfactant also having a group.
The photosensitive composition according to any one of the above. 7. The fluorinated surfactant (A) has 3 carbon atoms.
An acrylic polymer obtained by polymerizing a fluoro (meth) acrylate containing a fluoroaliphatic group in which at least two of the three terminal hydrogen atoms are substituted with a fluorine atom, and an N-substituted maleimide as essential components The photosensitive composition according to any one of claims 1 to 6, which is a system polymer. 8. The fluorosurfactant (A) having 3 carbon atoms
-20, wherein at least two of the terminal three hydrogen atoms are substituted with a fluorine atom, and a fluoro (meth) acrylate, an N-substituted maleimide, and a poly (oxyalkylene) (meth) acrylate are essential components. The photosensitive composition according to any one of claims 1 to 7, wherein the photosensitive composition is an acrylic polymer polymerized as a polymer. 9. A photosensitive lithographic printing plate comprising the photosensitive composition according to claim 1 provided on a metal support. 10. The photosensitive lithographic printing plate according to claim 9, wherein the photosensitive composition acts negatively.