JP3378322B2 - Photosensitive composition - Google Patents

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 62-36657 A and JP 62-226143 A describe a copolymer of a fluorinated aliphatic group-containing mono (meth) acrylate and a polyoxyalkylene mono (meth) acrylate. However, JP-A-57-40249 describes a diester type nonionic fluorine-based surfactant obtained by the reaction of perfluoromonocarboxylic acid and polyalkylene glycol.

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, the diester-type nonionic fluorine-containing surfactant described in JP-A-57-40249 is not sufficiently effective for the uniformity of the coating film in comparison with the amount added.

JP-A-62-36657 discloses a fluorine-based surface active agent comprising a copolymer of a fluorinated aliphatic group-containing mono (meth) acrylate and a polyoxyalkylene mono (meth) acrylate in a specific coating solvent. It is described that the streak-like unevenness is improved by applying a photosensitive composition obtained by adding the agent to the substrate. However, this technique was also ineffective in the wavy unevenness.

JP-A-62-226143 describes a photosensitive composition containing a copolymer of a fluorinated aliphatic group-containing mono (meth) acrylate and a polyoxyalkylene mono (meth) acrylate. There is.

[0010]

However, all of the above-mentioned conventional photosensitive compositions containing a fluorine-containing surfactant can be solved by applying a high speed coating to a substrate and by using a low speed coating. There was a drawback that irregularities still occurred.

Therefore, an object of the present invention is to provide a photosensitive composition which can be coated on a support at a high speed and then dried to obtain a uniform film thickness.

[0012]

The inventors of the present invention have investigated conventional surfactants for compounds other than polyester-based and acrylic-based compounds, and as a result, the polyurethane-based surfactant has a synergistic effect with the photosensitive composition. The inventors have found that they can exert their effects and completed the present invention.

[0013] The present invention, in the photosensitive composition containing a fluorine-based surfactant, the fluorine-based surfactant,
A full Ruoro aliphatic group (a), is to provide a photosensitive composition which is a polyurethane having a neutralized anionic groups (c) with a base. Hereinafter, the present invention will be described in detail.

[0014] polyurethane used as a fluorine-based surfactant in the present invention is a polyurethane having a full Ruoro aliphatic group (a), the anionic group neutralized with a base and (c).

In the present invention, polyurethane means a compound having at least two urethane bonds, and also includes one having both urethane bonds and urea bonds. Also,
Polyurethane may have other bonds in its chain, such as ester, amide, ureido, ether bonds and the like.

The polyurethane 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). Examples of the anionic group (c) in which an oxypropylene) random copolymerization group, a poly (oxyethylene / oxypropylene) block copolymerization group and the like are neutralized with a base include a sulfonic acid group and a carboxylic acid group , a neutralized group by salt groups, Examples of the base sodium hydroxide, potassium hydroxide, ammonia or the like inorganic base,
Organic bases such as triethylamine, diethylamine, diethanolamine and the like can be mentioned.

The lipophilic group and a polyoxyalkylene group (b) is a anionic group neutralized with a base (c), which is neutralized with a base even without least an anionic group
It is only necessary to have (c) in the polyurethane, and different 2
You may have one group at the same time.

The fluoroaliphatic group (hereinafter abbreviated as Rf group) in the polyurethane 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 are fully fluorinated. An Rf group is, for example, CF ₃ CF ₂ CF ₂ —, suitable Rf groups are substantially completely or fully fluorinated, such as C _n F _{2n + 1} (n is an integer of 3 or more). It is an alkyl group.

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 polyurethane is increased by increasing the ratio of the fully fluorinated Rf group-containing diol having 2 or less carbon atoms or the diisocyanate to the polyurethane, the fluorine atom is not localized, 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 polyurethane in the 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 polyoxyalkylene group of the polyurethane used in the present invention is usually 100 to 5,000.
It is 0, preferably 200 to 1,000. The polyoxyalkylene group unit preferably contains 10% by weight or more of one molecular weight. Nonionic group unit is 10
When the content is less than wt%, pinholes are likely to occur in the coating film when the photosensitive composition is prepared.

The polyurethane used in the present invention contains a fluoroaliphatic group-containing unit in an amount of 20 to 80% by weight based on the weight of the polyurethane. 20 units containing Rf group
If the amount is less than 80% by weight, the effect is not sufficient.
If the amount is larger, the solubility in the solvent is too low, which is not preferable.

The polyurethane 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 urethane bonds in polyurethane is 10 to
It is preferably 10,000.

The group (a) is oleophobic and the group ( c) is lipophilic as compared with the group (a). The lipophilicity of the group ( c) makes the polyurethane oil soluble. Thus, this polyurethane exhibits surface-active ability due to the difference in the degree of lipophilicity between the group (a) and the group (c). Also,
In the present invention, the anionic group (c) neutralized with a base refers to a functional group neutralized with a base and charged with an anion.

The polyurethane used in the present invention can be produced by a known and commonly used method. For example, it is synthesized by adding the known diisocyanate compound and diol compound described below in an aprotic solvent with a known catalyst having an activity corresponding to each reactivity and heating.

More specific methods include, for example, the following methods. (1) Using a low molecular weight diol and a low molecular weight diisocyanate as essential components, the active hydrogen atom and the isocyanate group are reacted in an equivalent ratio. (2) The high molecular weight diol is reacted with diisocyanate as an essential component at a ratio such that active hydrogen atoms and isocyanate groups are equivalent. (3) A terminal isocyanate group-containing prepolymer obtained by reacting a diol with an isocyanate at a ratio of excess isocyanate groups is chain-extended with a low molecular weight diol or a low molecular weight diamine.

The molar ratio of the diisocyanate and the diol compound used is not particularly limited, but is preferably 0.
It is 8: 1 to 1.2: 1, and when an isocyanate group remains at the polymer terminal, it is finally synthesized in a form in which the isocyanate group does not remain by treating with an alcohol or an amine.

The above-mentioned high molecular weight diol can be obtained, for example, by subjecting a low molecular weight diol and a dicarboxylic acid to a dehydration condensation reaction. Examples of the high molecular weight diol include polyester diol, polyether diol, polyether ester diol, polycarbonate diol, polyamide ester diol and the like.

To obtain the polyurethane used in the present invention,
As the diol component and / or diisocyanate component of the polyurethane, those having an Rf group and a nonionic group and / or anionic group can be used to react with each other according to the method described above.

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

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

[0034]

[Chemical 1]

[0035]

[Chemical 2]

[0036]

[Chemical 3]

Examples of the diol compound having a nonionic group used in the present invention include a diol compound having a polyoxyalkylene group. The poly (oxyalkylene) group is represented by the general formula — (OR) _n — and R is 2 to 4
An alkylene group having carbon atoms of, for example, —CH ₂ C
_{H 2 -, - CH 2 CH} 2 CH 2 -, - CH (CH 3) CH
-, or _{-CH (CH 3) CH (CH} 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 include one or more chain bonds. Examples of the chain bond include the following structures.

[0040]

[Chemical 4]

If the linkage of the chain has a valence of 3 or more, this provides a means for obtaining branched oxyalkylene units. When the polyurethane is added to the photosensitive composition, the poly (oxyalkylene) group has a molecular weight of 5 in order to obtain a desired solubility.
0 to 1,000 is suitable.

Base neutralized for use in the present invention
Examples of the diol compound having an anionic group include a diol compound having a —SO ₃ M group or a —COOM group, which can be represented by the following general formula.

[0043]

[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 polyurethane used in the present invention is obtained, for example, by reacting a polyester polyol obtained by reacting a diol compound with a dicarboxylic acid having an anionic group neutralized with a base and a derivative thereof, and polyisocyanate. You can also

The base neutralized in the present invention
Examples of the dicarboxylic acid having a nonionic group and a derivative thereof include a dicarboxylic acid having a —SO ₃ M group and a derivative thereof, and specific examples thereof include 5-sodium sulfoisophthalic acid and 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, 5
-(Γ-sodium sulfopropoxy) isophthalic acid,
5- (γ-potassium sulfopropoxy) isophthalic acid,
Dicarboxylic acids such as 5- (p-sodium sulfophenoxy) isophthalic acid and 5- (p-potassium sulfophenoxy) isophthalic acid; dialkyl esters such as dimethyl ester and diethyl ester of the above dicarboxylic acid; di (ethylene of the above dicarboxylic acid Examples thereof include di (alkylene glycol) esters such as glycol) esters and di (propylene glycol) esters.

The above diol compounds include --SH,-
Other hydrophilic diols containing O-, etc. may be appropriately used in combination. In the present invention, a diisocyanate compound and a diol compound which do not have an Rf group, a polyoxyalkylene group, a base-neutralized anionic group may also be used in combination.

Examples of the diisocyanate compound used for obtaining the polyurethane used in the present invention include:
2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1, Aromatic diisocyanate compounds such as 5-naphthylene diisocyanate and 3,3'-dimethylbiphenyl-4,4'-diisocyanate; Aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate Compounds; isophorone diisocyanate, 4,4'-
Alicyclic diisocyanate compounds such as methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1,3-
Examples thereof include a diisocyanate compound which is a reaction product of a diol and a diisocyanate, such as an adduct of 1 mol of butylene glycol and 2 mol of tolylene diisocyanate.

Further, Rf group, polyoxyalkylene group,
Examples of the diol compound having no anionic group neutralized with a base include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4-trimethyl-
1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, and bisphenol A Propylene oxide adduct, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether p-xylylene glycol, Dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2,4-tolylene dicarbamate, 2,4-tolylene-bis (2-hydroxyethyl carbamide) Bis (2-hydroxyethyl) -m
-Xylylene dicarbamate, bis (2-hydroxyethyl) isophthalate, etc. are mentioned.

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 fluorochemical surfactant used in the present invention is 0.01 to 5% by weight based on the photosensitive composition (coating component excluding the solvent), and more preferred use. The range is 0.05 to 3% by weight. When the amount of the fluorine-based surfactant used is in the above range, the effect is sufficient, the coating film may not be sufficiently dried, and the performance (eg, developability) of the photosensitive material may 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 one 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 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 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 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 the organic dye capable of forming a salt include triphenylmethane dyes, cyanine dyes, diazo dyes and styryl dyes. Specific examples thereof 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 can 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 condensate 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 a 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 known stability improvers are, 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 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 a binder resin, for example, (meth) acrylic acid "acrylic acid and methacrylic acid are generically referred to as (meth) acrylic acid" hereinafter), (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 JP-B No. 4,123,276, copolymers having an aromatic hydroxyl group described in JP-B-57-43,890, and 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 photocrosslinking 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 photosensitive composition is further dissolved in a suitable solvent, if necessary, with addition of dyes, pigments, stabilizers, fillers, crosslinking agents and the like.

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.

As the organic solvent to be used, any known and commonly used one can be used, but the boiling point is from 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, 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, 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.

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

According to the present invention, the unevenness of the film 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 film thickness is obtained under an extremely wide range of drying conditions. It is possible to apply the photosensitive layer of, 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 coating a photosensitive composition dissolved or dispersed in an organic solvent, and drying. Remarkably recognized.

[0092]

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.

Polyurethanes used in the present invention were obtained by using the raw materials shown in Table 1 in predetermined proportions.

[0094]

[Table 1]

[0095]

Synthesis Example 2 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 3 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.

[0099]

[Table 2]

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

Example 1 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 give a grain with a center line average roughness (Ra) of 0.6 μm. I got a plate. 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 liquid of the photosensitive composition prepared in Table 2 above was 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 processor PD-911 manufactured by Dainippon Screen Co., Ltd., Polychrome Japan Co., Ltd. sold by Dainippon Ink and Chemicals Co., Ltd. Using the developer PD-1 (1: 8), perform development at 30 ° C for 12 seconds, and then use the company gum PF-2.
Was applied and printing was performed. The results are summarized below.

[0104]

[Table 3]

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. The coating speed of the photosensitive composition is 1/2
Then, the uniformity of the coating film was examined, and the evaluation of "A" was obtained for all the examples.

Comparative Example 1 Using the photosensitive composition containing the diester type fluorine-containing surfactant of Synthesis Example 2 , 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. When the coating speed of the photosensitive composition was set to 1/2 the speed of the above-mentioned examples, a printing plate without streaky unevenness was obtained as in the examples.

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 3 , and the same evaluation was performed. As a result, the wavy unevenness of the printing plate, which did not occur in the examples, occurred.
When the coating speed of the photosensitive composition was set to 1/2 of that in the above-mentioned example, a printing plate without wavy unevenness in density was obtained as in the case of the example.

As can be seen from the comparative examples, the photosensitive composition using the conventional fluorine-containing surfactant does not cause unevenness in the film thickness when it is applied at a low speed, but when it is applied at a high speed. The film thickness becomes non-uniform. However, it can be seen that the photosensitive composition of the present invention using the specific fluorine-based surfactant does not cause unevenness of the film thickness such as streaky unevenness even when applied at high speed or at low speed. .

The printing plate obtained from the photosensitive composition of the present invention has remarkably improved uniformity of the film thickness of the photosensitive layer as compared with the conventional printing plate, does not cause pinholes, and has no ink deposit. It can be seen that the meat is also excellent.

[0110] After contact exposure and original film more obtained photosensitive planographic printing plate in Example 1, was developed with a positive developing solution for sensitivity, to be excellent uniformity of reproducibility of the original pattern all right. When printing was carried out using this, it was also found that it had excellent printing durability and uniform image strength.

[0111] was made Example 2 The following sensitive optical composition adjustment. And using the polyurethane of Example 2, Synthesis Example 1.

[0112]

[Table 4]

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 to 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 plate obtained in Example 2 was free from pinholes and free from uneven mottling, 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 2 , a printing plate was obtained in the same manner as in Example 2 and the same evaluation was performed. As a result, the coating film was significantly more uneven than that of the example. When the coating speed of the photosensitive composition was set to 1/2 the speed of the above-mentioned examples, a printing plate without streaky unevenness was obtained as in the examples.

Comparative Example 4 A printing plate was obtained in the same manner as in Example 2 using the photosensitive composition using the acrylic resin type fluorine-containing surfactant of Synthesis Example 3 , and the same evaluation was performed. As a result, the wavy unevenness of the printing plate, which did not occur in the examples, occurred.
When the coating speed of the photosensitive composition was set to 1/2 of that in the above-mentioned example, a printing plate without wavy unevenness in density was obtained as in the case of the example.

The photosensitive lithographic printing plate cut into sheets after drying was excellent in sensitivity and reproducibility as a negative printing plate.
The printing plate obtained from this was uniform and excellent in printing durability and image strength.

[0119]

The photosensitive composition of the present invention exhibits, as a surfactant, a full Ruoro aliphatic group (a), since using a polyurethane having a neutralized anionic groups (c) a base, conventional In the case where the coating area per unit time is larger than that (high-speed coating), there is a particularly remarkable effect that nonuniformity of the film thickness such as pinholes and streaky unevenness does not occur.

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Claims (4)

(57) [Claims] 1. A photosensitive group containing a fluorosurfactant.
In the composition, the fluorosurfactant is a fluoro fat
Group (a) and anionic group neutralized with a base
(C) is a polyurethane having
Photosensitive composition. 2. Polyurethane has 10 or more urethane bonds.
The photosensitive composition according to claim 1, which is 10,000 polyurethane.
object. 3. A polyurethane having a number average molecular weight of 2,000 to 2.
It is a polyurethane of any one of Claim 1 or Claim 2.
Photosensitive composition. 4. A photosensitive compound, which is insoluble in water and
If it is soluble or swellable in aqueous solution of Lucari
A synthetic resin is contained in the resin composition.
The photosensitive composition according to any one of items.