JPH07120913A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. capable of application in a uniform film thickness. CONSTITUTION:A polyester having mol.wt. of 7.000 is produced by dehydrating and condensing 0.5mol perfluorooctanesulfonic acid diethanolamide, polyethylene glycol having mol.wt. of 200 and 1mol succinic anhydride. This polyester is added to a compsn. prepd. by dissolving an ester compd. of 1,2-naphthoquinone-2- diazido-5-sulfonyl chloride with pyrogallol-acetone resin, cresol-formaldehyde resin and a dye in an org. solvent to obtain the objective photo-sensitive compsn. This compsn. can be applied in a uniform film thickness without pinholes or unevenness and a printing plate having satisfactory ink receptivity is obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition containing a novel fluorine-containing surfactant, more specifically, the photosensitive composition is dissolved in an organic solvent together with the fluorine-containing surfactant. Alternatively, the present invention relates to a photosensitive composition which can be dispersed, coated on a support, and then dried to obtain a uniform film thickness.

[0002]

2. Description of the Related Art Fluorine-based surfactants are
It has the property of significantly changing the properties of the gas-liquid, liquid-liquid or solid-liquid interface. Among them, the fluorine-based surfactant is a very special and high detergency unique to the fluorine atom, which the conventional hydrocarbon-based surfactant does not have.
It has properties such as wetting power.

Various types of such fluorine-containing surfactants are known. JP-A-62-36657 discloses that
A copolymer of a fluorinated aliphatic group-containing mono (meth) acrylate and a polyoxyalkylene mono (meth) acrylate is described, and JP-A-57-40249 discloses that a perfluoromonocarboxylic acid and a polyfluoromonocarboxylic acid should be used. A diester type nonionic fluorosurfactant obtained by reaction with an alkylene glycol is described.

In the field of photosensitive compositions, it is essential to coat the support with a photosensitive composition to form a uniform photosensitive layer in order to exert the performance of the photosensitive composition. At this time, if a non-uniform photosensitive layer having so-called streaky unevenness, pinholes, wrinkle unevenness, wavy unevenness, etc. is formed, it not only impairs the value as a product in terms of appearance, but also sensitivity, halftone dot reproducibility, This causes instability in characteristics such as printing durability.

To solve such a problem, Japanese Patent Laid-Open No. 57-178242
The publication describes that the streak-like unevenness is improved by adding a relatively low concentration of a fluorosurfactant to a specific coating solvent and coating. However, the above technique is effective for the stripe unevenness, but is not effective for improving the wavy unevenness.

Japanese Patent Laid-Open No. 60-24545 discloses that a streak-like unevenness is improved by using a mixed solvent of two kinds of solvents having different boiling points as a coating solvent. However, this technique was also not effective at all in improving the above-mentioned wavy unevenness in shade.

Further, JP-A-62-36657 describes that the streak-like unevenness is improved by adding a fluorine-based surfactant to a specific coating solvent and coating. However, this technique was also ineffective in the wavy unevenness.

Further, the diester type nonionic fluorosurfactant described in JP-A-57-40249 is not sufficiently effective for the uniformity of the coating film in comparison with the addition amount.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photosensitive composition capable of obtaining a uniform film thickness by coating on a support and then drying.

[0010]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of the above situation. As a surfactant made of a polyester compound, a fluorine-based polyester having 3 or more ester bonds is a diester-type fluorine compound. It has been found that, when used in a photosensitive composition, it exhibits an excellent effect as compared with a surfactant.

That is, when the polyester was applied to a photosensitive composition and applied, it was found that a coating film having a uniform film thickness which could not be obtained by a conventional fluorine-containing surfactant was obtained, and the present invention was made. It came to completion.

The present invention provides a photosensitive composition containing a fluorosurfactant, wherein the fluorosurfactant is a fluoroaliphatic group (a) and a polyoxyalkylene group (b).
And / or an anionic group (c), which is a polyester having 3 or more ester bonds. Hereinafter, the present invention will be described in detail.

The surfactant used in the present invention is a fluoroaliphatic group (a), a polyoxyalkylene group (b) and / or
Alternatively, it comprises a polyester having an anionic group (c) and having 3 or more ester bonds. The polyester must be at least oil soluble. The oil solubility in the present invention means a property of being soluble in an organic solvent. The surfactant used in the present invention may further have water solubility.

The fluoroaliphatic group (a) is, for example, a perfluoroalkyl group, and the polyoxyalkylene group (b) is, for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene group). -Oxypropylene) random copolymerization group, poly (oxyethylene / oxypropylene) block copolymerization group, etc., and as the anionic group (c), for example, sulfonic acid group, carboxylic acid group, etc. are neutralized with a base. And a base such as sodium hydroxide, potassium hydroxide, an inorganic base such as ammonia, triethylamine,
Examples thereof include organic bases such as diethylamine and diethanolamine.

At least one of the polyoxyalkylene group (b) which is a lipophilic group and the anionic group (c) is
It is only necessary to have one group in the polyester, two different
You may have one group at the same time.

The fluoroaliphatic group (hereinafter abbreviated as Rf group) in the polyester used in the present invention is a saturated and generally monovalent or divalent aliphatic group.
It is straight-chain, branched and, if sufficiently large, cyclic or combinations thereof (eg alkylcycloaliphatic radicals). The fluoroaliphatic backbone chain can contain chain oxygen and / or trivalent nitrogen heteroatoms bonded only to carbon atoms. This heteroatom provides a stable bond between the fluorocarbon groups and does not interfere with the inert character of the Rf group.

The Rf group is 3 to 20, preferably 6 to 12, in order to exert a sufficient effect for the purpose of the present invention.
40% by weight or more, preferably 50
It has a weight percentage of fluorine bonded to a carbon atom. At least three carbon atoms of the Rf group should be fully fluorinated. Examples of the Rf group include CF
₃ CF ₂ CF ₂ —, suitable Rf groups are substantially completely or fully fluorinated alkyl groups such as C _n F _{2n + 1} (n is an integer of 3 or more).

Even if the Rf group has 2 or less carbon atoms, the fluorine content can be increased, but the total amount of fluorine atoms becomes insufficient and the effect tends to be weakened. Even if the fluorine content in the polyester is increased by increasing the ratio of the fully fluorinated Rf group-containing diol having 2 or less carbon atoms or the dicarboxylic acid or its derivative to the polyester, the fluorine atom is localized. Since it has not been realized, it tends to be difficult to obtain a sufficient effect.

On the other hand, when the number of carbon atoms of the Rf group is 21 or more, when the fluorine content is high, the solubility of the obtained polyester in a solvent tends to be low, and when the fluorine content is low, the fluorine atom locality is high. Localization becomes insufficient, and it tends to be difficult to obtain sufficient effects.

The molecular weight of the poly (oxyalkylene) group of the polyester of the present invention is usually 100 to 5,000, preferably 200 to 1,000. The poly (oxyalkylene) group unit preferably contains 10% by weight or more of one molecular weight. When the content of the poly (oxyalkylene) group unit is less than 10% by weight, the surface active property represented by wettability and leveling property is insufficient, and when the photosensitive composition is prepared, pinholes are generated in the coating film. It will be easier.

The polyester used in the present invention preferably contains the fluoroaliphatic group-containing unit in an amount of 20 to 80% by weight based on the weight of the polyester. If the amount of the fluoroaliphatic group-containing unit is less than 20% by weight, the effect is insufficient, and if it is more than 80% by weight, the solubility in the solvent is too low, which is not preferable.

The polyester used in the present invention preferably has a molecular weight of 2,000 to 100,000, preferably 2,000.
If it is smaller than this, the effect is not sufficient, and if it is larger than 100,000, the solubility in a solvent decreases, which is not preferable. The number of ester bonds in polyester is 10 to
It is preferably 500.

The group (a) is oleophobic and the groups (b) and (c) are lipophilic as compared with the group (a). The lipophilicity of group (b) or group (c) renders this polyester oil soluble. Thus, this polyester has the group (a)
And the group (b) and / or the group (c) differ in the degree of lipophilicity, thereby exhibiting the surfactant activity. In addition, in the present invention, the anionic group (c) refers to a functional group charged with an anion.

The polyester used in the present invention can be prepared by any means known in the art, such as "Lecture Polymerization Reaction Theory 9, Polycondensation", Ogata, Kagaku Dojinsha, or JP-A-60-165,646. It can be easily produced by the method described in the publication and U.S. Pat. No. 3,622,320.

Specifically, the polyester used in the present invention includes, for example, a fluoroaliphatic group (a) -containing diol, a polyoxyalkylene group (b) -containing diol, an anionic group (c) -containing diol, and an anion by neutralization. A diol component such as a diol containing a group (d) capable of becoming acidic, a dicarboxylic acid containing a fluoroaliphatic group (a), a dicarboxylic acid containing a polyoxyalkylene group (b), a dicarboxylic acid having an anionic group (b), and neutralization Can be easily produced by combining with a dicarboxylic acid component such as a dicarboxylic acid having a group (d) capable of becoming anionic by a dehydration condensation reaction or a transesterification reaction. A polyester having a structure having at least one of the groups (c) and the group (a) can be used. Of course, the diol compound and the dicarboxylic acid may be derivatives thereof.

In producing the polyester used as the surfactant in the present invention, a trifunctional or higher functional alcohol component, a trifunctional or higher functional carboxylic acid component, a monoalcohol or a monocarboxylic acid may be used in combination, if necessary.

Examples of the diol compound having a fluoroaliphatic group used in the present invention include those having the following structures.

[0028]

[Chemical 1]

[0029]

[Chemical 2]

[0030]

[Chemical 3]

Examples of the diol compound having a nonionic group used in the present invention include a diol compound having a poly (oxyalkylene) group. The poly (oxyalkylene) group is represented by the general formula — (OR) _n —, R is an alkylene group having 2 to 4 carbon atoms,
For example _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH
(CH ₃₎ CH-, or -CH (CH ₃₎ CH (C
H ₃₎ - is preferably.

The oxyalkylene units in the above poly (oxyalkylene) groups may be repeats of the same oxyalkylene, such as in poly (oxypropylene), or two or more different oxyalkylene units may be irregular. May be a linear or branched oxypropylene and oxyethylene unit, or a linear or branched oxypropylene unit block and an oxyethylene unit block. May be present in.

The poly (oxyalkylene) chain may be mediated by or may include one or more chain bonds. Examples of the chain bond include the following structures.

[0034]

[Chemical 4]

If the linkage of the chain has a valency of three or more, this provides a means for obtaining branched oxyalkylene units. When the polyester is added to the photosensitive composition, the molecular weight of the poly (oxyalkylene) group moiety is 5 in order to obtain the desired solubility.
0 to 1,000 is suitable.

The diol compound having an anionic group or a group capable of becoming anionic by neutralization used in the present invention is, for example, a diol compound having a --SO ₃ M group or a --COOM group, and is as follows. It can be represented by a general formula.

[0037]

[Chemical 5]

In the formula, R ₁ is a hydrogen atom or a substituent [for example,
Cyano, nitro, -F, -Cl, -Br, -I, -CO
_{NH 2, -COOR 5, -OR 5} , -NHCONHR 5, -
NHCOOR ₅ , -NHCOR ₅ , -OCONHR ₅ ,-
Each group such as CONHR ₅ (wherein R ₅ represents an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 15 carbon atoms) is included. ] The alkyl, aralkyl, aryl, alkoxy, and aryloxy group which may have are shown, Preferably it is a hydrogen atom, a C1-C8 alkyl, and a C6-C15 aryl group are shown.

R ₂ , R ₃ and R ₄ may be the same or different and each represents a single bond, an alkyl group, an aralkyl group,
A divalent aliphatic or aromatic hydrocarbon group which may have a substituent such as an aryl group, an alkoxy group and a halogeno group is shown. It is preferably an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms.

Examples of M include sodium, potassium and quaternary ammonium.

Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, and is preferably an aromatic group having 6 to 15 carbon atoms. Specific examples of the above compound include 2,2-bis (hydroxymethyl) propionic acid, 2,2
2-bis (2-hydroxyethyl) propionic acid, 2,
2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, etc. and sodium, potassium, etc. Examples thereof include salts with metals or amines.

The dicarboxylic acid having an anionic group or a group capable of becoming anionic by neutralization used in the present invention and a derivative thereof include, for example, a dicarboxylic acid having a —SO ₃ M group and a derivative thereof. For example, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 3-sodium sulfophthalic acid,
3-potassium sulfophthalic acid, 4-sodium sulfophthalic acid, 4-potassium sulfophthalic acid, α-sodium sulfosuccinic acid, α-potassium sulfosuccinic acid, β-sodium sulfoadipic acid, 2,5-disodium sulfoadipic acid, Such as 5- (γ-sodium sulfopropoxy) isophthalic acid, 5- (γ-potassium sulfopropoxy) isophthalic acid, 5- (p-sodium sulfophenoxy) isophthalic acid, 5- (p-potassium sulfophenoxy) isophthalic acid and the like. Dicarboxylic acids; dialkyl esters such as dimethyl esters and diethyl esters of the above dicarboxylic acids; di (alkylene glycol) esters such as di (ethylene glycol) esters and di (propylene glycol) esters of the above dicarboxylic acids.

The present invention will be described in detail by taking a printing plate coating material as an example. The printing plate coating material is a photosensitive composition composed of a photosensitive compound and a synthetic resin that is insoluble in water and soluble in an alkaline aqueous 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-mentioned surfactant of the present invention to the photosensitive composition.

The preferred range of use of the fluorosurfactant used in the composition of the present invention is 0.01 to 5% by weight based on the photosensitive composition (coating component excluding the organic solvent). Yes, the more preferable range of use is 0.05 to 3% by weight. When the amount of the fluorine-based surfactant used is within the above range, there is a concern that the effect will be sufficient, the coating film will not be dried sufficiently, and the performance as a photosensitive material (eg, developability) will be adversely affected. Also few.

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

As the positive photosensitive composition, any composition can be used as long as the solubility or swelling property in a developing solution changes before and after exposure. For example, in the case of a positive photosensitive composition containing an alkali-soluble resin and an o-quinonediazide compound, at least one o-quinonediazide compound is used.
-A compound having a quinonediazide group, which increases the solubility in an alkaline aqueous solution by actinic rays and is known to have various structures. For example, see J. KOSAR, "Li.
ght-Sensitive Systems "(John Wiley & Sons, Inc, 1
Issued in 965) P336 to P352 are described in detail.
Particularly, sulfonic acid esters of various hydroxyl compounds and o-benzoquinone diazide or o-naphthoquinone diazide are preferable.

Examples of the o-quinonediazide compound as described above include 1,2-naphthoquinone-2diazide-
Ester of 5-sulfonyl chloride with phenol-formaldehyde resin or cresol-formaldehyde resin; 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin described in US Pat. No. 3,635,709. Ester of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and resorcin-benzaldehyde resin described in JP-B-63-13,528; described in JP-B-62-44,257. 1,
Ester of 2-naphthoquinone-2-diazide-5-sulfonyl chloride and resorcinol-pyrogallol-acetone co-condensation resin; 1,2-naphthoquinone in polyester having hydroxyl group at the end described in JP-B-56-45,127 -2-diazide-5-sulfonyl chloride esterified; Japanese Patent Publication No. 50-24,64
1,2-naphthoquinone-containing N- (4-hydroxyphenyl) methacrylamide homopolymers or copolymers with other copolymerizable monomers described in JP-A-1
An esterification product of 2-diazide-5-sulfonyl chloride; an ester of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and a bisphenol-formaldehyde resin described in JP-B-54-29922. Esterification of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride on a homopolymer of p-hydroxystyrene or a copolymer with other copolymerizable monomers described in JP-B-52-36,043. There is an ester of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and polyhydroxybenzophenone. Other known o-quinonediazide compounds usable in the present invention include those disclosed in
63-80,254, JP-A-58-5,737, JP-A-57-111,
530, JP-A-57-111,531, JP-A-57-114,138
JP, 57-142,635, JP 51-36,129,
Japanese Patent Sho 62-3,411, Japanese Patent Sho 62-51,459, Japanese Sho
Items described in each specification such as No. 51-483 can be cited.

The content of the o-quinonediazide compound in the previous period is 5 to 60% by weight based on the total solid content of the photosensitive composition.
And more preferably 10 to 40% by weight.

Examples of the synthetic resin which is insoluble in water and soluble in an alkaline aqueous solution (hereinafter referred to as an alkali-soluble resin) include, for example, phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde co-condensation resin, phenol-modified xylene resin,
Examples thereof include polyhydroxystyrene, polyhalogenated hydroxystyrene, N- (4-hydroxyphenyl) methacrylamide copolymer, and hydroquinone monomethacrylate copolymer. Such an alkali-soluble resin is used in an amount of 90% by weight or less based on the total composition.

In the photosensitive composition, if necessary, further,
A cyclic acid anhydride for increasing sensitivity, a printout agent for obtaining a visible image immediately after exposure, a dye as an image colorant, and other fillers can be added.

Examples of cyclic acid anhydrides include succinic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride,
Examples thereof include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, chloromaleic anhydride, and pyromellitic dianhydride. These cyclic acid anhydrides can be contained in 1 to 15% by weight of the total 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 the color tone. it can.

Examples of the photosensitive compound which releases an acid upon exposure are, for example, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36,209; JP-A-53-36,223. Trihalomethyl-2-pyrone and trihalomethyl-s-triazine described; various o-naphthoquinonediazide compounds described in JP-A-55-62,444; JP-A-55-77,
2-trihalomethyl-5 described in Japanese Patent No. 742
Aryl-1,3,4-oxadiazole compounds; diazonium salts and the like can be mentioned. These compounds can be used alone or as a mixture, and the addition amount thereof is preferably in the range of 0.3 to 15% by weight based on the total composition.

Examples of organic dyes capable of forming salts include triphenylmethane dyes, cyanine dyes, diazo dyes and styryl dyes. Specific examples include
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 amount added is preferably in the range of 0.3 to 15% by weight based on the total composition.

Others In the composition of the present invention, various resins having a hydrophobic group, such as octylphenol / formaldehyde resin, t-butylphenol / formaldehyde resin, t, for improving the ink receptivity of an image are included.
-Butylphenol / benzaldehyde resin, rosin-modified novolak resin, and o of these modified novolak resins
-Naphthoquinone diazide sulfonate, etc .; plasticizers for improving the flexibility of the coating film, such as dibutyl phthalate, dioctyl phthalate, butyl glycolate, tricresyl phosphate, dioctyl adipate, etc., depending on various purposes. Various additives can be added. The content of these additives is preferably 0.01 to 30% by weight based on the total composition.

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

Examples of the diazo resin in the case of the negative photosensitive composition include a diazo resin represented by a salt of a condensation product of a diazodiarylamine and an active carbonyl compound, which is photosensitive, water-insoluble and soluble in an organic solvent. Those are preferable.

A particularly suitable diazo resin is, 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, etc. and formaldehyde, paraformaldehyde, acetaldehyde,
It is an organic acid salt or an inorganic acid salt of a condensate with benzaldehyde, 4,4′-bis-methoxymethyldiphenyl ether and the like.

As the organic acid, 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-methoxybenzophenone-5
-Sulfonic acid and the like can be mentioned, and as the inorganic acid, hexafluorophosphoric acid, tetrafluoroboric acid, thiocyanic acid and the like can be mentioned.

Further, a diazo resin whose main chain is a polyester group described in JP-A-54-30,121; JP-A-61-2
73,538, a diazo resin obtained by reacting a polymer having a carboxylic acid anhydride residue 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 be used.

The amount of these diazo resins used is preferably in the range of 0 to 40% by weight based on the solid content of the composition, and if necessary, two or more kinds of diazo resins may be used in combination.

When preparing the negative photosensitive composition, an organic polymer binder is usually used together. Examples of such organic polymer binders include acrylic resins, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polystyrene resins and novolac resins.

Further, in order to improve the performance, known additives,
For example, a thermal polymerization inhibitor, dye, pigment, plasticizer, stability improver, etc. can be added.

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

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 be used together.

The addition amount of these various additives varies depending on the purpose, but generally, the solid content of the photosensitive composition is 0%.
The range of ˜30 wt% is preferred.

In the case of a photosensitive composition containing an addition polymerizable unsaturated compound and a photopolymerization initiator, for example, US Pat. No. 2,760,
No. 863, No. 3,060,023, JP-A No. 62-121,448 and the like, there are compositions comprising an addition-polymerizable unsaturated compound having two or more terminal ethylene groups and a photopolymerization initiator.

Further, as the binder resin, for example, (meth) acrylic acid "hereinafter, acrylic acid and methacrylic acid are generically referred to as (meth) acrylic acid", (meth) acrylic acid ester copolymer, US Pat. Hydroxyalkyl (meth) acrylate and (meth) acrylonitrile-containing copolymers having an acid value of 10 to 100 described in Japanese Patent No. 4,123,276, and copolymers having an aromatic hydroxyl group described in Japanese Patent Publication No. 57-43,890. Copolymers such as polymers having a 2-hydroxy-3-phenoxypropyl (meth) acrylate unit described in JP-B No. 57-51,656; epoxy resins; polyamide resins; vinyl halides, particularly polyvinyl chloride, polyvinylidene chloride; Polyvinyl acetate; Polyester; Acetal resin such as formal resin and butyral resin; Trade name of Estan Soluble polyurethane resin sold by Goodrich Co., Ltd .; polystyrene; styrene-maleic anhydride copolymer or its half ester; fibrin derivative; shellac; rosin or its modified product, described in JP-A-61-285,449. A copolymer having an unsaturated group in its side chain can be used.

The above-mentioned photosensitive composition is further dissolved in a suitable solvent, if necessary, with addition of dyes, pigments, stabilizers, fillers, crosslinking agents and the like.

In the case of a photosensitive composition containing a photocrosslinkable resin,
As the photocrosslinkable resin, a photocrosslinkable resin having an affinity for an aqueous alkaline developer is preferable.
54-15,711, a cinnamic acid group- and carboxyl group-containing copolymer; JP-A-60-165,646, a phenylenediacrylic acid residue- and carboxyl group-containing polyester resin; JP-A-60-203,630 A polyester resin having a phenylenediacrylic acid residue and a phenolic hydroxyl group described in JP-A-59-208,552; a polyester resin having a phenylenediacrylic acid residue and a sodium iminodisulfonyl group described in JP-B-57-42,858; Polymers having an azide group and a carboxyl group in the side chain described in JP-A No. 1994-2000 can be used.

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

When the photosensitive composition containing the fluorine-containing surfactant of the present invention is used as a paint, it is provided on a support. The photosensitive composition containing the fluorine-containing surfactant of the present invention is dissolved or dispersed in one or a mixture of the following organic solvents, coated on 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 coated with synthetic resin solution, metal layer is vacuum-deposited and laminated on plastic film And other materials used as a support for the printing plate. Further, in the case of a support having a surface of metal, particularly aluminum, it is preferable that surface treatment such as graining treatment, anodic oxidation treatment and hydrophilic treatment is performed. The coating amount is usually about 0.5 to about 5 g / m ² on a dry weight basis.

The organic solvent used may be any of those known and commonly used, but the boiling point is 40 ° C. to 200 ° C., especially 6
Those in the range of 0 ° C. to 160 ° C. are selected due to their advantages in drying. Of course, it is preferable to select one in which the surfactant of the present invention can be dissolved.

Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n- or iso-propyl alcohol, n- or iso-butyl alcohol and 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,
Acetate esters such as n- or iso-propyl acetate, n- or iso-butyl acetate, ethylbutyl acetate, hexyl acetate, halides such as methylene dichloride, ethylene dichloride, monochlorobenzene, isopropyl ether, n-butyl ether, dioxane, Dimethyldioxane, ethers such as 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 Jiechi 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, and 3-methyl-3-methoxybutanol, and their derivatives, dimethyl sulfoxide, N A special solvent such as N, N-dimethylformamide or the like is preferably used alone or as a mixture. And
The concentration of solid content in the composition to be applied is suitably 2 to 50% by weight.

As the coating method, for example, 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, and particularly 10 ml / m ² to A composition coverage of 100 ml / m ² is preferred.

The photosensitive composition coated on the support is dried by heated air. Heating is from 30 ℃
200 ° C. Particularly, the range of 40 ° C. to 140 ° C. is suitable.
The drying temperature is not only a constant method during drying,
A method of increasing gradually can also be carried out.

In some cases, good results may be obtained by dehumidifying the dry air. The heated air is 0.1 m / sec to 30 m / sec, especially 0.5 m / sec to 20 m on the coated surface.
It is preferable to supply at a rate of / sec.

The photosensitive composition of the present invention contains a surfactant composed of a fluorinated polyester having 3 or more ester bonds and having a surface activity superior to that of the conventional surfactants. Therefore, the unevenness of the film thickness of the photosensitive layer, which has been conventionally generated in the drying process, is eliminated and the performance as a printing plate is made uniform, and the photosensitive layer having a uniform film thickness is applied under an extremely wide range of drying conditions. Therefore, 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 coating a photosensitive composition dissolved or dispersed in an organic solvent, and drying. Remarkably recognized.

[0081]

EXAMPLES The present invention will now be described in more detail based on examples. However, the present invention is not limited to these examples. In the examples,% means% by weight.

Polyester used in the present invention was obtained by using the raw materials shown in Table 1 at a predetermined ratio.

[0083]

[Table 1]

[0084]

[Table 2]

Synthesis Example 6 2 mol of C ₈ F ₁₇ COOH and poly (oxyethylene.
A dehydration condensation reaction is carried out using 1 mol (molecular weight 1000) of oxypropylene) block copolymer diol,
A diester having two ester bonds having perfluorooctyl groups at both ends of a poly (oxyethylene / oxypropylene) random copolymer was obtained.

Synthesis Example 7 80 parts by weight of N-butyl perfluorooctane sulfonamide ethyl acrylate and CH ₃ O (CH ₂ CH ₂ O)
₂₀ parts by weight of ₂₀ COCH = CH ₂ was copolymerized to obtain an acrylic resin having a molecular weight of 15,000.

Then, the following photosensitive compositions were prepared, respectively.

[Table 3]

Note 1 What is described in Example 1 in US Pat. No. 3,635,709 Note 2 What is described in US Pat. No. 4,123,279 Note 3 Base manufactured by Hodogaya Chemical Co., Ltd. Oil-soluble dye

Examples 1 to 6 An aluminum plate having a thickness of 0.30 mm was degreased with an aqueous sodium hydroxide solution, and this was electrolytically polished in a 2% hydrochloric acid bath to have a center line average roughness (Ra) of 0.6 μm. I got a grain board. Then, in a 20% sulfuric acid bath, anodize at a current density of 2 A / dm ² to form an oxide film of 2.7 g / m ² , wash with water and dry,
Led to the coating process. In the coating step, the coating liquids of the photosensitive composition prepared in Table 2 above were used.

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

After exposing each of the obtained photosensitive lithographic printing plates through an image film, an automatic developing machine PD-911 manufactured by Dainippon Screen Co., Ltd., an automatic developing solution manufactured by Dainippon Ink and Chemicals Co., Ltd.
Using PD-1 (1: 8), develop at 30 ℃ for 12 seconds,
Printing was performed by applying the company's gum PF-2. The results are summarized below.

[0092]

[Table 4]

In Table 3, the results are evaluated on a scale of 5 from A to D. The closer to A, the better the result, and the closer to D, the poorer the result.

Comparative Example 1 Using the photosensitive composition containing the diester type fluorine-based surfactant of Synthesis Example 6, a printing plate was obtained in the same manner as in Example 1 above, and the same evaluation was performed. As a result, the coating film was significantly more uneven than that of the example.

Comparative Example 2 A printing plate was obtained in the same manner as in Example 1 using the photosensitive composition using the acrylic resin type fluorine-containing surfactant of Synthesis Example 7, and the same evaluation was performed. As a result, the wavy unevenness of the printing plate, which did not occur in the examples, occurred.

From Table 3 and Comparative Examples, the printing plate obtained from the photosensitive composition of the present invention using the specific fluorine-containing surfactant was more uniform in the film thickness of the photosensitive layer than the conventional printing plate. Is significantly improved, there is no pinhole, and the ink receptivity is excellent.

When the photosensitive lithographic printing plates obtained in Examples 1 to 5 were contact-exposed to the original film and then developed with a positive developer, they were excellent in sensitivity and reproducibility of the original pattern. I understood. When printing was carried out using this, it was also found that it had excellent printing durability and uniform image strength.

Examples 6 to 10 The following photosensitive compositions were prepared, respectively. In Example 6, the polyester of Synthesis Example 1 was used, in Example 7, the polyester of Synthesis Example 2 was used, in Example 8, the polyester of Synthesis Example 3 was used, and in Example 9, the polyester of Synthesis Example 4 was used.
In No. 0, the polyester of Synthesis Example 5 was used.

[0099]

[Table 5]

The strip-shaped aluminum support provided with the anodized film in Example 1 was passed through a 2.5% aqueous solution of sodium silicate at 70 ° C. for 30 seconds, washed with water and dried, and led to the coating step. In the coating process, the coating liquid of each of the photosensitive compositions described above was used.

After the above coating solution was continuously applied to the strip-shaped aluminum at a rate of 40 g / m ² , the drying zone in which hot air of 80 ° C. was supplied was supplied with hot air of 100 ° C. for 1 minute. It was dried by passing through the drying zone for 1 minute to form a photosensitive layer.

The printing plates obtained in Examples 6 to 10 were free from pinholes and had no unevenness, and a photosensitive layer having a uniform film thickness could be obtained. The photosensitive lithographic printing plate, which was cut into a sheet after drying, had excellent sensitivity and reproducibility as a negative printing plate, and the printing plate obtained from this had a uniform and excellent printing durability and image strength. there were.

Comparative Example 3 Using the photosensitive composition containing the diester type fluorine-based surfactant of Synthesis Example 6, a printing plate was obtained in the same manner as in Example 6 and the same evaluation was performed. As a result, the coating film was significantly more uneven than that of the example.

Comparative Example 4 A printing plate was obtained in the same manner as in Example 6 using the photosensitive composition using the acrylic resin type fluorine-containing surfactant of Synthesis Example 7, and the same evaluation was performed. As a result, the wavy unevenness of the printing plate, which did not occur in the examples, occurred.

[0105]

In the present invention, the fluoroaliphatic group (a) is used.
And a polyoxyalkylene group (b) or an anionic group (c), and a surfactant composed of polyester having 3 or more ester bonds is added to the photosensitive composition for use. A particularly remarkable effect that a photosensitive coating film having a uniform film thickness, which cannot be solved by a photosensitive composition containing an activator, can be easily obtained.

Claims (5)

[Claims] 1. A photosensitive composition containing a fluorosurfactant, wherein the fluorosurfactant comprises a fluoroaliphatic group (a), a polyoxyalkylene group (b) and / or an anionic group ( and c), which is a polyester having 3 or more ester bonds. 2. A polyester having 10 to 5 ester bonds.
The composition of claim 1 which is a 00 polyester. 3. The polyester has a fluoroaliphatic group (a).
The composition according to claim 1, which is a polyester having a polyoxyalkylene group (b) in the molecular main chain or an anionic group (c) in the molecular side chain. 4. The polyester is a polyester obtained by reacting a fluoroaliphatic group-containing diol, a polyalkylene glycol and a dicarboxylic acid, or a fluoroaliphatic group-containing diol is reacted with an anionic group-containing dicarboxylic acid. The composition of claim 1 which is a wrought polyester. 5. A surfactant comprising a polyester having a fluoroaliphatic group (a) and a polyoxyalkylene group (b) and / or anionic group (c) and having 3 or more ester bonds, and a photosensitive material. A photosensitive composition containing, as essential components, a polymerizable compound and a synthetic resin insoluble in water and soluble or swellable in an alkaline aqueous solution.