JPH11184079A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To highly maintain the balance of developability to an aq. alkali developer and printing resistance by incorporating two specified diazo resins and the reaction product of isocyanates including a specified diisocyanate with alcohols including a specified diol. SOLUTION: The photosensitive compsn. contains a diazo resin in which counter anions are inorg. acid anions or <=3C aliphatic org. acid anions, a diazo resin in which counter anions are >=6C aliphatic or arom. org. acid anions and a polyurethane resin which is the reaction product of isocyanates including 40-90 mol.%, based on the total isocyanate components, diisocyanate represented by formula I with alcohols including 30-90 mol.%, based on the total alcohol components, diol represented by formula II. In the formula I, R1 -R4 may be the same or different and are each H, 1-4C alkyl, 1-6C alkoxy or halogen. In the formula II, R5 is H or 1-8C alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit and a photomask. More specifically, the present invention relates to a photosensitive composition comprising a negative-working photosensitive compound and a polymer compound having excellent abrasion resistance.

[0002]

2. Description of the Related Art The majority of compounds used as a photosensitive substance in a photosensitive composition acting negatively are diazonium compounds.
-There is a diazo resin represented by a formaldehyde condensate of diazodiphenylamine. The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin is described, for example, in US Pat.
No. 2,714,066, a diazo resin alone, that is, one without a binder, and a binder and a diazo resin as described in, for example, JP-A-50-30604. Although it can be classified into those in which the resin is mixed, in recent years many of the photosensitive lithographic printing plates using diazonium compounds are made from a diazonium compound and a polymer serving as a binder in order to impart high printing durability. Has become.

[0003] Such a photosensitive layer is disclosed in
As described in Japanese Patent Application Laid-Open No. 0604/1985, a so-called alkali developing type in which unexposed portions are removed (developed) with an aqueous alkali developing solution is known.
The polymer obtained by copolymerizing a carboxylic acid-containing monomer as described in JP-A-04-2004 has a poor abrasion resistance due to its structure, and is obtained from a photosensitive lithographic printing plate containing such a binder and a diazo resin in a photosensitive layer. Gave only a lithographic printing plate with low printing durability. Further, as a known polymer having excellent abrasion resistance, there is a polyurethane resin. Further, for the purpose of imparting aqueous alkali developability, JP-A Nos. 62-123452 and 62
2-123453, 63-287946, JP-A-1-134354, 1-255854, 1-2
Nos. 71741, 1-293336, and 2-24
In publications such as 656, a combination system of a polyurethane resin having a carboxyl group introduced therein and a diazo resin is disclosed.

However, when a photosensitive lithographic printing plate is aged in a high-temperature, high-humidity environment, the developability and the printing durability of lithographic direct printing (daily lithographic printing), which is more severe printing than normal lithographic printing, are not sufficient. Further improvement was desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive composition which overcomes the above-mentioned drawbacks and has a high balance between developability with an aqueous alkaline developer and printing durability. More specifically, an object of the present invention is to provide a photosensitive lithographic printing plate excellent in developability and printing durability of dilitho printing even when stored in a high-temperature, high-humidity environment.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, by combining the components of two types of diazo resins and polyurethane resins having different counter anions and their contents, in combination with these components, It has been found that the object of the present invention is achieved, and the present invention has been achieved. That is, the present invention, as a diazo resin to be combined with an alkali-soluble polyurethane resin, by using two or more diazo resins having different polarities in combination, during exposure, the entire photosensitive layer can be photocured without causing uneven portions. In addition, there is an effect that the stability is improved even under high temperature and high humidity. More specifically, a diazo resin a whose counter anion is an inorganic acid anion or an aliphatic organic acid anion having 3 or less carbon atoms, and a diazo resin whose counter anion is an aliphatic or aromatic organic acid anion having 6 or more carbon atoms b and isocyanate in which the diisocyanate represented by the general formula (I) is contained in an amount of 40 to 90 mol% in all isocyanate components, and 30 to 90 mol% in the total alcohol component is a diol represented by the general formula (II). An object of the present invention is to provide a photosensitive composition comprising a polyurethane resin which is a reaction product with an alcohol.

[0007]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and each represents a hydrogen atom, a carbon atom having 1 to 4 carbon atoms.
, An alkyl group, an alkoxy group having 1 to 6 carbon atoms or a halogen atom. Preferably, a hydrogen atom, a methyl group,
An ethyl group or a chlorine atom, more preferably a hydrogen atom or a methyl group. R ₅ is a hydrogen atom or a carbon number of 1 to 8
Alkyl groups. It is preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group, and more preferably a hydrogen atom or a methyl group. Hereinafter, components used in the photosensitive composition of the present invention, and methods for producing and using the photosensitive composition of the present invention will be described in detail. (1) Diazo resin The diazo resin used in the present invention is a diazo resin represented by a condensate of an aromatic diazonium salt and an active carbonyl group-containing compound, for example, formaldehyde, or a carboxyl group, a sulfonic acid group, a sulfinic acid group. An oxygen acid group of phosphorus, a co-condensed diazo resin containing an aromatic compound having at least one hydroxyl group and an aromatic diazonium compound as constituent units, or an aromatic amine, phenol,
A co-condensed diazo resin containing, as constituent units, an aromatic compound having a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound, an organic acid amide, and an aromatic diazonium compound. Examples of the inorganic acid or an aliphatic organic acid having 3 or less carbon atoms that form a counter anion of the diazo resin a include hexafluorophosphoric acid, tetrafluoroboric acid, phosphoric acid, phosphotungstic acid, thiocyanic acid, methanesulfonic acid, and ethanesulfonic acid. Acids, propanesulfonic acid, trifluoromethanesulfonic acid or mixtures thereof. Particularly preferred of these are:
Hexafluorophosphoric acid and tetrafluoroboric acid.

On the other hand, aliphatic or aromatic organic acids having 6 or more carbon atoms forming a counter anion of the diazo resin b include:
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 5-sulfosalicylic acid, paratoluenesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy -3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3
-Propanesulfonic acid, diamylphenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, mesitylenesulfone Acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3 -Chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2
-Chloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5- Benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic Acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene-1-sulfonic acid, naphthalene- -Sulfonic acid, 1,8-dinitronaphthalene-3,6-disulfonic acid, 4,4'-diazido-stilbene-3,3'-disulfonic acid, 1,2-naphthoquinone-2-diazido-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-
Naphthoquinone-1-diazide-4-sulfonic acid or a mixture thereof. Among them, particularly preferred are dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, and octylnaphthalenesulfonic acid.

In the present invention, a diazo resin a whose counter anion is an inorganic acid anion or an aliphatic organic acid anion having 3 or less carbon atoms, and an aliphatic or aromatic organic acid anion whose counter anion has 6 or more carbon atoms. The weight ratio with a certain diazo resin b is preferably in the range of 0.1: 0.9 to 0.9: 0.1, more preferably 0.2: 0.8 to 0.8: 0.2. Range. When the ratio of the diazo resin a is smaller than 0.1 (when the ratio of the diazo resin b is larger than 0.9), the adhesion to the support is poor and the printing durability is reduced. On the other hand, when the ratio of the diazo resin a is larger than 0.9 (when the ratio of the diazo resin b is smaller than 0.1), the wear resistance of the photosensitive layer is inferior and the printing durability is reduced. (2) Polyurethane resin The polyurethane resin suitably used in the present invention has a structure represented by a reaction product of a diisocyanate compound represented by the following general formula (I) and a diol compound represented by the general formula (II). It is a polyurethane resin having a basic skeleton.

[0011]

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(In the formula, R _{1 to} R ₅ have the same meanings as described above.) As typical examples of the diisocyanate compound represented by the general formula (I), 4,4′-diphenylmethane diisocyanate, 4,4′- (2,2-diphenylpropane) diisocyanate. Further, if necessary, in addition to the diisocyanate compound represented by the general formula (I), the following diisocyanate compounds are used in combination within the preferable composition range of the present invention. That is, 2,4-tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p
-Xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3 '
Aromatic diisocyanate compounds such as -dimethylbiphenyl-4,4'-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylene bis (Cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3
An alicyclic diisocyanate compound such as-(isocyanatomethyl) cyclohexane; a diisocyanate compound which is a reaction product of a diol and a diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate; Can be

As the diisocyanate compound used in combination with the diisocyanate compound of the general formula (I), among the above, hexamethylene diisocyanate, isophorone diisocyanate and m-xylylene diisocyanate are particularly preferred. Further, two or more of the above diisocyanate compounds may be used in combination with the diisocyanate of the general formula (I). Representative diol compounds having a carboxyl group represented by the general formula (II) include 2,2-bis (hydroxymethyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid, and 2,2-bis (hydroxymethyl) propionic acid. Bis (hydroxymethyl) butyric acid is mentioned, among which 2,2-
Bis (hydroxymethyl) propionic acid is preferred. Furthermore, specific examples of the diol compound used in combination with the diol compound of the general formula (II) include the following. That is, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,2-dipropylene glycol, 1,2-tripropylene glycol, 1,2-tetrapropylene glycol, 1,3-dipropylene glycol, 1,3 -Dibutylene glycol and the like. Of these, preferred are diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-tripropylene glycol, and 1,2-tetrapropylene glycol, and particularly preferred are triethylene glycol and tetraethylene glycol.

In the polyurethane resin suitably used in the present invention, the content of the diisocyanate compound represented by the above general formula (I) is 40 to 90 in all the diisocyanate components.
Mol%, preferably 50 to 85 mol%, more preferably 60 to 80 mol%. As the remaining components, the above-mentioned diisocyanate compound used in combination with the diisocyanate compound of the general formula (I) is used. The content of the diol compound represented by the general formula (II) is 3% of the total diol component.
0-90 mol%, preferably 40-80 mol%,
More preferably, it is 50 to 70 mol%. The remaining part uses the diol compound used in combination with the diol compound of the general formula (II). Further, two or more of the above diol compounds may be used in combination with the diol compound of the general formula (II).

The molecular weight of the polyurethane resin preferably used in the present invention is a weight average (polystyrene standard).
It is preferably 40,000 or more. In general, when the molecular weight is high, printing durability is excellent, but developability is reduced. Conversely, when the molecular weight is low, the developability is improved, but the printing durability is reduced. When the weight average molecular weight of the polyurethane resin having the composition of the present invention is smaller than 40,000, printing durability and deterioration are not preferred. Preferred weight average molecular weight is 50,000-
500,000, and more preferably 70,000 to 200,000. At this time, the degree of dispersion (Mw / Mn) is 20 or less, preferably 16 or less, more preferably 14 or less. When it is 20 or more, a significant amount of a low molecular weight component having a weight average molecular weight of less than 40,000 is mixed, which causes a problem of deterioration in printing durability.

The content of the polyurethane resin of the present invention in the photosensitive composition is 50 to 97% by weight, preferably 70 to 95% by weight in terms of solids. The polyurethane resin of the present invention is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent, adding a known catalyst having an activity corresponding to the respective reactivity, and heating. The molar ratio of the diisocyanate and the diol compound to be used is preferably 0.8: 1 to 1.2: 1. When the isocyanate group remains at the polymer terminal, it is treated with alcohols or amines to obtain the final compound. Is synthesized in such a manner that no isocyanate group remains. The ratio of the diazo resin to the polyurethane resin is preferably 3:97 to 3 by weight.
0:70, more preferably from 5:95 to 2
The range is 5:75.

(3) Other components In the composition of the present invention, in addition to the above-mentioned polyurethane resin, phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene and carboxyl group A known alkali-soluble polymer compound such as an epoxy resin, a polyacetal resin, an acrylic resin, and a methacrylic resin can be contained. Such an alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition. In the composition of the present invention,
Dyes, pigments, stabilizers, surfactants, plasticizers, sensitizers and other fillers can be added as a printing-out agent and an image coloring agent for obtaining a visible image immediately after exposure. As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be exemplified. Specifically, JP-A-50-36209 and JP-A-53-8
Combinations of o-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dyes described in JP-A-128, JP-A-53-36223 and JP-A-54-74.
No. 728, a combination of a trihalomethyl compound and a salt-forming organic dye. Dyes other than the salt-forming organic dyes described above can also be used as colorants for the image. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603,
Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl violet (CI42)
535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (C
I52015) and the like.

Further, as a stabilizer, phosphoric acid, phosphorous acid,
Oxalic acid, p-toluenesulfonic acid, dipicolinic acid, malic acid, tartaric acid, 2-methoxy-4-hydroxy-5-
Examples thereof include benzoyl-benzenesulfonic acid, butylnaphthalenesulfonic acid, p-hydroxybenzenesulfonic acid, 4-sulfophthalic acid, tricarballylic acid, and phenylphosphonic acid. As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable. Examples of the plasticizer include tricresyl phosphate, dihexyl phthalate, dioctyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, and polypropylene glycol. Further, as the sensitizer, those described in JP-B-62-60701 and JP-A-63-262624 are preferable. Further, development accelerators (eg, higher alcohols, acid anhydrides, etc.) are preferably used. The amount of these additives varies depending on the object and purpose of use, but is generally 0.01 to 30% by weight based on the solid content of the photosensitive composition.

The composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied on a support. Examples of the solvent used herein include methanol, ethanol, isopropanol, n-butanol, t-butanol, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, -Methoxy-2-propanol, 1-methoxy-2-propyl acetate, methyl lactate, ethyl lactate, N, N-dimethylformamide, N,
N-dimethylacetamide, γ-butyrolactone, N-
There are methylpyrrolidone, tetramethylurea, tetrahydrofuran, dioxane, dimethylsulfoxide, sulfolane, toluene, ethyl acetate and the like, and these solvents are used alone or as a mixture. The concentration (solid content) of the above components is 2 to 50% by weight. Although the amount of application varies depending on the application, for example, in the case of a photosensitive lithographic printing plate, it is generally preferred that the solid content be 0.5 to 3.0 g / m ² . The photosensitivity increases as the coating amount decreases, but the physical properties of the photosensitive film deteriorate.

As the support on which the photosensitive composition of the present invention is applied, for example, paper, paper laminated with plastics (for example, polyethylene, polypropylene, polystyrene, etc.), for example, aluminum (including aluminum alloy), Plates of metals such as zinc, copper, etc., for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene,
Examples include plastic films such as polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and paper or plastic films on which a metal as described above is laminated or deposited. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

The surface of the aluminum material is desirably surface-treated for the purpose of increasing water retention and improving adhesion to the photosensitive layer. For example, as a roughening method,
Commonly known brush polishing methods, ball polishing methods, electrolytic etching, chemical etching, liquid honing, methods such as sand blasting and combinations thereof, preferably include brush polishing methods, electrolytic etching, chemical etching and liquid honing. Among them, a surface roughening method including the use of electrolytic etching is particularly preferable.
Further, as described in JP-A-54-63902, a method of performing brush polishing followed by electrolytic etching is also preferable. Further, as the electrolytic bath used in the case of electrolytic etching, an aqueous solution containing an acid, an alkali or a salt thereof or an aqueous solution containing an organic solvent is used, and among these, particularly, hydrochloric acid, nitric acid or a salt thereof is included. Electrolytes are preferred. Further, the roughened aluminum plate is desmutted with an acid or alkali aqueous solution as required.

The aluminum plate thus obtained is desirably subjected to anodic oxidation treatment, particularly preferably a method of treating it with a bath containing sulfuric acid or phosphoric acid. Further, if necessary, silicate (sodium silicate, sodium silicate) treatment described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461,
Potassium fluorozirconate treatment described in U.S. Pat. No. 2,946,638; U.S. Pat. No. 3,201,2
No. 47, phosphomolybdate treatment, British Patent 1,108,559, alkyl titanate treatment, and German Patent No. 1,091,433. Acrylic acid treatment, German patent No. 1,
No. 134,093 and British Patent No. 1,230,447, polyvinylphosphonic acid treatment, Japanese Patent Publication No. 44-6409, phosphonic acid treatment, U.S. Pat. , Phytic acid treatment described in JP-A-58-951, and the reaction between a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-16893 and JP-A-58-18291. A treatment with a salt, which has been subjected to a hydrophilizing treatment by undercoating a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651, and described in JP-A-60-64352 Those colored with an acid dye are particularly preferred. Another hydrophilic treatment method is disclosed in U.S. Pat.
The silicate electrodeposition described in the specification of Japanese Patent No. 8,662 can also be mentioned. Further, after graining treatment and anodic oxidation, sealing treatment is preferable. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

More specifically about the support suitable for use in the present invention, 0.1 to 0.5% iron and silicon
A 1S aluminum plate containing 0.03% to 0.3%, 0.001% to 0.03% of copper, and 0.002% to 0.1% of titanium is alkali-preferably 1% to 30% of sodium hydroxide. And immersion in an aqueous solution of potassium hydroxide, sodium carbonate, sodium silicate or the like at a temperature of 20 to 80 ° C. for 5 seconds to 250 seconds for etching. Aluminum ions may be added to the etching bath in an amount of about one-fifth of alkali. Then
It is immersed in a 10 to 30% nitric acid or sulfuric acid aqueous solution at a temperature of 20 to 70 ° C. for 5 to 250 seconds to neutralize and remove smut after alkali etching. After the surface of the aluminum alloy plate is cleaned, a surface roughening process is performed. As the roughening treatment, brush polishing and / or electrolytic etching treatment is suitable. For brush polishing, it is preferable to use a pumistone-water suspension and a nylon brush, and it is preferable to set the average surface roughness to 0.25 to 0.9 μ. The electrolytic solution used for the electrolytic etching treatment is an aqueous solution of hydrochloric acid or nitric acid, and the concentration is preferably used in the range of 0.01 to 3% by weight, and more preferably 0.05 to 2.5% by weight. preferable. The electrolyte may contain a corrosion inhibitor (or stabilizer) such as nitrate, chloride, monoamines, diamines, aldehydes, phosphoric acid, chromic acid, boric acid, and ammonium oxalate, as necessary. A graining agent and the like can be added. Also, an appropriate amount (1 to 1)
0 g / liter) of aluminum ions.

The electrolytic etching process is usually performed at 10 to 60 ° C.
At the temperature of the electrolyte. If the alternating current used at this time is one in which the positive and negative polarities are alternately exchanged,
Any of a rectangular wave, a trapezoidal wave, and a sine wave can be used, and normal commercial AC single-phase and three-phase AC currents can be used. The current density is 5 to 100 A / dm ² ,
It is desirable to process for 10 to 300 seconds. The surface roughness of the aluminum alloy support according to the present invention is adjusted to 0.2 to 0.8 μm by adjusting the quantity of electricity. The grained aluminum alloy is removed and etched (preferably 0.1%) of the smut attached to the surface with 10 to 50% hot sulfuric acid (40 to 60 ° C.) or a dilute alkali (such as sodium hydroxide). (In the range of from 0.01 to 2.0 g / m ² ). If the smut has been removed and etched with an alkali, it is subsequently neutralized by immersion in an acid (nitric acid or sulfuric acid) for cleaning. After de-smutting the surface, an anodic oxide coating is provided. As the anodic oxidation method, a conventionally well-known method can be used, but sulfuric acid is used as the most useful electrolytic solution. Then,
Phosphoric acid is also a useful electrolyte. Further, JP-A-55-
The mixed acid of sulfuric acid and phosphoric acid disclosed in JP 28400 is also useful.

In the sulfuric acid method, the treatment is usually performed with a direct current, but an alternating current can also be used. Sulfuric acid concentration 5-3
It is electrolyzed at 0% in a temperature range of 20 to 60 ° C. for 5 to 250 seconds to provide an oxide film of 1 to 10 g / m ^{2 on} the surface. The electrolyte preferably contains aluminum ions. Further, the current density at this time is 1-2.
0 A / dm ² is preferred. In the case of the phosphoric acid method, 5 to 50
% Phosphoric acid concentration, at a temperature of 30-60 ° C, 10-300
It is processed at a current density of 1 to 15 A / dm ^{2 for} a ^second . The aluminum support thus treated is preferably further subjected to a surface treatment with silicates as described in U.S. Pat. No. 2,714,066. Further, the aluminum support may be subbed. Examples of the compound used for the undercoat include carboxymethylcellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid optionally having a substituent, naphthylphosphonic acid, and alkylphosphonic acid. Acids, organic phosphonic acids such as glycerophosphonic acid, methylene diphosphonic acid and ethylene diphosphonic acid, organic phosphoric acids such as phenylphosphoric acid, naphthyl phosphoric acid, alkyl phosphoric acid and glycerophosphoric acid which may have a substituent, substituents Having organic groups such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydroxyl groups such as triethanolamine hydrochloride. Hydrochloride salt of Min, JP-A-59-101
Water-soluble polymers having a sulfonic acid group described in JP-A-651 and acid dyes described in JP-A-60-64352 are preferably used. This undercoat layer can be provided by dissolving the above compound in water, methanol, ethanol, methyl ethyl ketone, or the like, or a mixed solvent thereof, coating the support on a support, and drying.
Further, a yellow dye can be added for improving the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the undercoat layer after drying is suitably from ² to 200 mg / m ² , preferably from 5 to 200 mg / m ^2.
100 mg / m ² .

It is preferable to provide a mat layer composed of protrusions provided independently of each other on the photosensitive layer. The purpose of the mat layer is to improve the vacuum adhesion between the negative image film and the photosensitive lithographic printing plate in contact exposure, thereby shortening the evacuation time and preventing minute dots during exposure due to poor adhesion. That is. As a method for applying the mat layer, a method for thermally fusing powdered solid powder described in JP-B-62-62337, JP-A-50-125805, and JP-B-57-65 can be used.
No. 82, No. 61-28986, Tokuhei 3-21902
The method includes spraying and drying the polymer-containing water described in the above item, and any method can be used. The mat layer is desirably composed of a substance which is dissolved in an aqueous developer substantially free of an organic solvent or which can be removed thereby.

A photosensitive lithographic printing plate having a photosensitive composition layer coated and dried on a roughened aluminum plate is exposed to an image and then developed with an aqueous alkali solution-based developer to give a negative image to the original image. A relief image is obtained. Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, laser beams and the like. Examples of the alkaline aqueous solution-based developer used for developing the photosensitive lithographic printing plate include JP-A-51-77401 and JP-A-51-80228.
And JP-A-53-44202 and JP-A-55-52054, each having a pH of 8 to 1.
3. Preferably, water contains 75% by weight or more. If necessary, an organic solvent (benzyl alcohol, ethylene glycol monophenyl ether) having a solubility in water of 10% by weight or less at room temperature, an alkali agent (triethanolamine, diethanolamine, monoethanolamine, sodium phosphate, sodium carbonate), anionic surface activity Agents (aromatic sulfonate, dialkyl sulfosuccinate,
Alkyl naphthalene sulfonate, fatty acid salt, alkyl sulfate ester salt), nonionic surfactant (polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block polymer), antifouling agent (sodium sulfite, Sulfopyrazolone sodium salt) or water softener (ethylenediaminetetraacetic acid tetrasodium salt, nitrilotriacetic acid trisodium salt) can be added.

The photosensitive lithographic printing plate using the photosensitive composition of the present invention is disclosed in JP-A-54-8002 and JP-A-55-1150.
Needless to say, the plate-making process may be performed by the methods described in JP-A No. 45 and JP-A-59-58431. That is, after the development processing, dewatering treatment after washing with water, or desensitization treatment as it is, treatment with an aqueous solution containing an acid, or desensitization treatment after treatment with an aqueous solution containing an acid may be performed. . Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. The processing capacity is reduced. At this time, a fresh and unused developer (replenisher) is added, or a process is disclosed in JP-A-54-62004.
The processing capacity may be restored by using a highly alkaline replenisher as described in the above item. In this case, it is preferable to replenish by a method of adding a replenisher in an amount proportional to the length of one piece of the PS plate to be processed or a method described in US Pat. No. 4,882,246.

The plate making process described above is disclosed in
It is preferably carried out using an automatic developing machine as described in JP-A-7054 and JP-A-2-32357. Examples of the desensitized gum which is applied as required in the final step of the plate making process include JP-B-62-16834 and JP-B-62-251.
No. 18, No. 63-52600, JP-A-62-7595
And those described in JP-A-62-11693 and JP-A-62-83194 are preferred.

[0030]

The photosensitive composition of the present invention is excellent in developability when developing with an aqueous alkaline developer. The resulting relief image has good abrasion resistance and good adhesion to a support, and when used as a printing plate, many good printed matter can be obtained. Especially,
Excellent developability after storage under high temperature and high humidity, and excellent printing durability of dilitho printing.

[0031]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples, which should not be construed as limiting the scope of the present invention. Synthesis Example 1 In a 500 ml three-necked round bottom flask equipped with a condenser and a stirrer, 17.4 g (0.13 mol) of 2,2-bis (hydroxymethyl) propionic acid and 13.6 g (0.070 mol) of tetraethylene glycol were added. ) Was added and dissolved in 120 ml of N, N-dimethylacetamide. To this, 37.5 g (0.15 mol) of 4,4'-diphenylmethane diisocyanate and 8.4 g (0.05 mol) of hexamethylene diisocyanate were added.
0 mol), and the mixture was heated and stirred at 100 ° C. for 8 hours. Thereafter, the mixture was diluted with 120 ml of N, N-dimethylformamide and 60 ml of methanol. The reaction solution was poured into 4 liters of water while stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 73 g of a polymer.

The molecular weight was measured by gel permeation chromatography (GPC). As a result, the weight average (polystyrene standard) was 85,000, and the degree of dispersion was 4.1. Further, the carboxyl group content (acid value) was measured by titration and found to be 1.64 meq / g (polyurethane resin of the present invention). Synthesis Examples 2 to 11 In the same manner as in Synthesis Example 1, the polyurethane resin of the present invention was synthesized using the diisocyanate compound and the diol compound shown in Table 1. Further, the molecular weight was measured by GPC, and the acid value was measured by titration. Table 1 shows the measured acid value, molecular weight, and degree of dispersion. All molecular weights are indicated by weight average (polystyrene standard).

[0033]

[Table 1] ───────────────────────────────────Polyurethane diisocyanate used diacid value molecular weight dispersion Degree ethane anate compound urea compound (meq / g) (× 10 ⁴ ) resin (mol%) (mol%) 2 ++ 1.61 9.3 4.5 (70) (30) (60) (40) 3 ++ 1.60 9.5 4.0 (80) (20) (65) (35) 4 + 1.51 8.2 3.8 (75) (25) (60) (40) 5 + + 1.77 7.3 3.6 (80) (20) (70) (30) 6 + ＋ 1.64 9.2 4.4 (80) (20) (65) (35) 7 ＋ 1.79 8.9 4.2 (80) (20) (70) (30) 8 ＋ +1.93 10.4 5.2 (70) (30) (70) ( 30) 9 + + 1.88 7.2 3.6 (75) (25) (70) (30) 10 + + 1.79 8.5 4.3 (75) (25) (65) (35) ──────────── ───────────────────────

[0034]

Embedded image

[0035]

Embedded image

Examples 1 to 5 An aluminum plate having a thickness of 0.24 mm was coated with a nylon brush and
The surface was sand-grained with an aqueous suspension of 0-mesh pamistone, and then thoroughly washed with water. This was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, neutralized and washed with 20% nitric acid, and then subjected to electrochemical roughing described in JP-A-53-67507. Surface roughening, that is, electrolytic surface roughening treatment using a sinusoidal alternating current of V _A = 12.7 V and V _C = 9.1 V in a 1% nitric acid aqueous solution at an anode electricity of 160 coulomb / dm ^2. went. Subsequently, after immersion in a 30% aqueous sulfuric acid solution and desmutting at 55 ° C. for 2 minutes, anodizing treatment was performed in a 7% aqueous sulfuric acid solution so that the coating amount of aluminum oxide was 2.0 g / m ² . Then 1% aqueous solution of sodium silicate at 70 ° C
It was immersed for a minute, washed with water and dried. The following photosensitive solution was applied to the aluminum plate obtained as described above using a wheeler and dried at 80 ° C. for 2 minutes. 1.6 g dry weight
/ M ² . Photosensitive composition 0.35 g of diazo resin-1 0.15 g of diazo resin-2 5.00 g of the polyurethane resin of Synthesis Example-1 5.00 g of Stylite HS-2 (manufactured by Daido Kogyo Co., Ltd.) 0.10 g of Victoria Pure Blue BOH 0.15 g Tricresyl phosphate 0.50 g Dipicolinic acid 0.20 g FC-430 (surfactant manufactured by 3M) 0.05 g Solvent 1-methoxy-2-propanol 25.00 g Methyl lactate 12.00 g Methanol 30.00 g Methyl ethyl ketone 30.00 g Water 3.00 g Diazo resin-1 is a hexafluorophosphate salt of a condensate of p-diazodiphenylamine and paraformaldehyde described in Synthesis Example 1 of JP-A-59-78340. Diazo resin-2 is a dodecylbenzene sulfonate of a condensate of p-diazodiphenylamine and paraformaldehyde. Stylite HS-2 (manufactured by Daido Kogyo Co., Ltd.) is a polymer compound having higher oil sensitivity than a binder, and is styrene / mono-4-methyl-2-maleate maleate.
It is a copolymer of pentyl ester = 50/50 (molar ratio) and has an average molecular weight of about 100,000. This photosensitive lithographic printing plate was placed in a high-temperature, high-humidity thermostat at 45 ° C. and 75% for 3 days, image-exposed, and 800H (Fuji Photo Film Co., Ltd. automatic developing machine), DN-3C (Fuji Photo Film). Developed with a 1: 1 diluted aqueous solution of an aqueous alkali solution (manufactured by Film Co., Ltd.), and immediately diluted 1: 1 with FN-2 (a gum solution manufactured by Fuji Photo Film Co., Ltd.) with water. Apply the liquid,
Dried.

A lithographic printing plate having a bright and clear blue image without any residual film of diazo resin and dye and no residual color was obtained at the portion corresponding to the non-image portion. In the following Examples and Comparative Examples, this degree of developability is evaluated as “「 ”. Thereafter, this plate was cut into two pieces with a guillotine cutter, and one sheet was attached to a printing machine of a non-offset type, die litho system (manufactured by Tabitson), and a commercially available ink (Toyo Ink Co., Ltd. Web King) and a commercially available wet 4,000 sheets / water using Shimizu (Alky 1: 200 dilution, Toyo Ink Co., Ltd.)
When printing was carried out at the speed of the time, 60,000 sheets of printed matter having a sufficient ink density were obtained. In the following Examples and Comparative Examples,
This is referred to as "Dailyso printing durability: 60,000 sheets". The remaining one sheet was mounted on a Harris Aurelia printing machine (manufactured by Harris Corporation) and printing was performed at a speed of 6,000 sheets / hour. In addition, 150,000 sheets of printed matter having a sufficient ink density were obtained. In the following examples and comparative examples, this is referred to as “offset printing press life 150,000 sheets”. Examples 2 to 12 Printing plates were prepared in the same manner as in Example 1 using the polyurethane resin of Example 1 and various diazo resins. The developability of high temperature and high humidity thermostats and the printing durability of dilitho printing and offset printing were examined. The results are shown in Tables 2 and 3.

[0038]

[Table 2] Example Diazo resin a Diazo resin b Polyurethane resin Type Amount (g) Type Amount (g) Type Amount (g) ────────────────────────────────── 2-1 0.05 -2 0.45 -1 5.00 3-1 0.25 -2 0.25 -1 5.00 4 -1 0.40 -2 0.10 -1 5.00 5 -1 0.45 -2 0.05 -15.00 6 -1 0.35 -3 0.15 -15.00 7-1 0.35 -4 0.15 -1 5.00 8 -5 0.35 -4 0.15 -1 5.00 9 -1 0.35 -6 0.15 -1 5.00 10 -7 0.35 -6 0.15 -1 5.00 11 -1 0.35 -8 0.15 -1 5.00 12 -9 0.35 -8 0.15 -1 5.00 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0039]

[Table 3] 実 施 Example Developability Dairizo printing Offset printing Printing durability ( 10,000 sheets) Printing durability (10,000 sheets) ────────────────────────────────── 2 ○ 514 3 ○ 61 54 ○ 61 55 ○ 51 46 ○ 61 57 ○ 61 58 ○ 61 59 ○ 615 10 ○ 615 11 ○ 615 12 ○ 615 ━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━ The diazo resin-3 is a dibutylnaphthalene sulfonate of a condensate of p-diazodiphenylamine and formaldehyde. Diazo resin-4 is an octylnaphthalene sulfonate of a condensate of p-diazodiphenylamine and formaldehyde. The diazo resin-5 is a tetrafluoroborate salt of a condensate of p-diazodiphenylamine and formaldehyde. Diazo resin-6 is phenoxy resin / p-diazodiphenylamine (cocondensation ratio 5
0/50) and dodecylbenzenesulfonate of a condensate of formaldehyde. The diazo resin-7 was prepared from phenoxyacetic acid / p-diazodiphenylamine (cocondensation ratio 50
/ 50) and a formaldehyde condensate of hexafluorophosphate. Diazo resin-8 is 4,4'-bis (methoxy) diphenyl ether / 3-methoxydiphenylamine-4-diazonium (cocondensation ratio 50/50)
Mesitylene sulfonate. Diazo resin-9 is
4,4'-bis (methoxy) diphenyl ether / 3-
Sulfate of methoxydiphenylamine-4-diazonium (cocondensation ratio 50/50). Examples 13 to 21 Printing plates were prepared in the same manner as in Example 1 using the diazo resin of Example 1 and the polyurethane resin of Synthesis Examples 2 to 12. high temperature·
The developability of the high humidity thermostat and the printing durability of dilitho printing and offset printing were examined. The results are shown in Tables 4 and 5.

[0040]

[Table 4] Example Diazo resin a Diazo resin b Polyurethane resin Type Amount (g) Type Amount (g) Type Amount (g) ────────────────────────────────── 13 −1 0.35 −2 0.15 −2 5.00 14 −1 0.35 −2 0.15 −3 5.00 15 −1 0.35 −2 0.15 −4 5.00 16 −1 0.35 −2 0.15 −5 5.00 17 −1 0.35 −2 0.15 −6 5.00 18 −1 0.35 −2 0.15 −7 5.00 19 −1 0.35 −2 0.15 −8 5.00 20 −1 0.35 −2 0.15 −9 5.00 21 −1 0.35 −2 0.15 −10 5.00 ────────── ────────────────────────

[0041]

[Table 5] Example Developability Dairizo printing Offset printing Printing durability ( (10,000 sheets) Printing durability (10,000 sheets) ────────────────────────────────── 13 ○ 615 14 ○ 615 15 615 16 615 17 615 18 615 19 615 20 615 21 615 ━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━ Synthesis examples 12 to 14 (polyurethane of comparative example) Hereinafter, in the same manner as in Synthesis example 1, the diisocyanate compound and the diol compound shown in Table 6 were used for comparative examples. Polyurethane resin was synthesized. The molecular weight and the acid value were determined in Synthesis Examples 1 to
Performed similarly to 11. Table 6 shows the results.

[0042]

[Table 6] ───────────────────────────────────Polyurethane used Diisocyanate used diacid value molecular weight dispersion Degree ethane anate compound urea compound (meq / g) (× 10 ⁴ ) resin (mol%) (mol%) 11 ++ 1.59 6.4 4.2 (30) (70) (60) (40) 12 ++ 1.61 7.3 4.0 (100) (0) (60) (40) 13 + + 1.15 7.5 4.6 (70) (30) (20) (80) 14 + + 1.75 7.3 4.5 (70) (30) (100) (0) ── ───────────────────────────────── Synthesis Example 15 (JP-A-62-123453, polyurethane of Example 1) Resin) 125 g (0.50 mole) of 4,4'-diphenylmethane diisocyanate and 67 g (0.50 mole) of 2,2-bis (hydroxymethyl) propionic acid were added to a 500 ml three-necked round bottom flask equipped with a condenser and a stirrer. ,
Dissolved in 290 ml of dioxane. 1 g of N, N-diethylaniline was added as a catalyst, and the mixture was heated and refluxed for 6 hours with stirring. Thereafter, the reaction solution was poured into a solution of 4 liters of water and 40 ml of acetic acid with stirring to precipitate a white polymer. The polymer was separated by filtration, washed with water, and dried under vacuum to obtain 185 g of a polymer.

The molecular weight measured by gel permeation chromatography (GPC) was 28,000 in weight average (polystyrene standard). Further, the content of the carboxyl group was measured by titration and found to be 2.47 meq / g. Further, 40 g of this polymer was placed in a 300 ml three-necked round-bottom flask equipped with a condenser and a stirrer.
F was dissolved in 200 ml. Add triethylamine to this solution
6.3 g (0.062 mole) was added, and after heating to 80 ° C., 7.7 g (0.062 mole) of ethylene bromohydrin was added under stirring to 1 g.
It was added dropwise over 0 minutes. Thereafter, stirring was continued for 2 hours. After completion of the reaction, the reaction solution was poured into a solution of 4 liters of water and 200 ml of acetic acid with stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 42 g of a polymer.

It was confirmed by NMR measurement that the hydroxyethyl group had been introduced into the carboxyl group, and the residual carboxyl group content was measured by titration to be 1.21 meq / g. Comparative Examples 1 to 9 Printing plates were prepared in the same manner as in Example 1 using a diazo resin other than the present invention and the polyurethane resin of Example 1. high temperature·
The developability of the high humidity thermostat and the printing durability of dilitho printing and offset printing were examined. The results are shown in Tables 7 and 8.

[0045]

[Table 7] Comparative Example Diazo resin a Diazo resin b Polyurethane resin Amount (g) Type Amount (g) Type Amount (g) ────────────────────────────────── 1 -1 0.50--1 5.00 2 -5 0.50--1 5.00 3 -7 0.50--1 5.00 4 -9 0.50--1 5.00 5--2 0.50 -1 5.00 6--3 0.50 -1 5.00 7- -4 0.50 -1 5.00 8--6 0.50 -1 5.00 9--8 0.50 -1 5.00 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━

[0046]

[Table 8] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Comparative example Developability Dairizo printing Offset printing Printing durability ( 10,000 sheets) Printing durability (10,000 sheets) ────────────────────────────────── 1 △ 25 2 △ 2 5 3 △ 2 5 4 △ 2 5 5 ○ 18 6 ○ 18 7 ○ 18 8 ○ 16 9 ○ 16 ○ ━━━━━━━━━━━━━━ Developability “△” indicates that the diazo resin remained in the non-image area and became yellow. Comparative Examples 10 to 15 Printing plates were prepared in the same manner as in Example 1 using the diazo resin of the present invention and a polyurethane resin or a binder other than the present invention. The developability of high temperature and high humidity thermostats and the printing durability of dilitho printing and offset printing were examined. The results are shown in Tables 9 and 10.

[0047]

[Table 9] Comparative Example Diazo resin a Diazo resin b Polyurethane resin Binder Type Amount (g) Type Amount (g) Type Amount (g) Type Amount (g) ────────────────────────────── ───── 10 −1 0.35 −2 0.15 −11 5.00 − − 11 −1 0.35 −2 0.15 −12 5.00 − − 12 −1 0.35 −2 0.15 −13 5.00 − − 13 −1 0.35 −2 0.15 −14 5.00 − − 14 −1 0.35 −2 0.15 − − −1 5.00 15 −1 0.35 −2 0.15 − − −2 5.00 ━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━

[0048]

[Table 10] ━━━━━━━━━━━━━━━━━━━━━━━━━━━ Comparative example Developability Dairizo printing Offset printing Printing durability (10,000 sheets) Printing durability (万 10 ○ 13 11 × 63 12 × 48 13 ○ 12 14 ○ 25 15 ○ 26 ━━━━━━━━━━━━━━━━━━━━━━━━━━━ The developability “x” indicates that the binder and dye remain blue in the non-image area and become blue. Indicates that

Binder-1 was 2-hydroxyethyl methacrylate / acrylonitrile / methyl methacrylate / methacrylic acid copolymer (weight ratio 50/20/26 /
4, average molecular weight 75,000, acid value 0.4 meq / g) Binder-2 was 2-hydroxyethyl methacrylate /
Acrylonitrile / ethyl methacrylate / methacrylic acid copolymer (weight ratio 45/15/36/4, average molecular weight
120000, acid value 0.4 meq / g)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/30 502R

Claims (1)

[Claims] 1. A diazo resin a wherein the counter anion is an inorganic acid anion or an aliphatic organic acid anion having 3 or less carbon atoms,
The diazo resin b whose counter anion is an aliphatic or aromatic organic acid anion having 6 or more carbon atoms, and 40% of the diisocyanate represented by the general formula (I) among all isocyanate components
And the diol represented by the general formula (II) in the total alcohol component is 30 to 90 mol%.
A photosensitive composition containing a polyurethane resin which is a reaction product with an alcohol contained in mol%. Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom. Is shown. R ₅ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.