JPH0443359A - Production of planographic printing plate - Google Patents

Abstract

PURPOSE:To produce the planographic printing plate which has the high adhesiveness of image parts and a base and the excellent image part strength and printability at the time of development and is free from the generation of surface stains by incorporating silicate into a developer used for development. CONSTITUTION:The silicate is incorporated into the developer used at the time of exposing and developing the photosensitive planographic printing plate which is formed by applying a liquid compsn. contg. an inorg. high polymer obtd. by subjected an org. metal compd. having an org. functional group and a group to be polycondensed in succession to hydrolysis to the hydrolysis and polycondensation in a liquid on a metallic surface and providing a photosensitive resin layer thereon. The planographic printing plate which has high adhesiveness of the image parts and the base and the excellent image part strength and printability at the time of development and is free from the generation of surface stains is produced in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a printing plate, and more particularly to a method for manufacturing a lithographic printing plate that has excellent strength in the image area during development, printing durability, and resistance to staining. .

[Conventional technology]

Lithographic printing is a printing method that uses water and ink on a planographic printing plate, supplying ink to the image area and water to the non-image area, increasing the strength of the image area during development and making it possible to obtain a large number of prints.・In order to ensure that the image area adheres to the support, it is necessary to strengthen the adhesion between the image area and the support. On the other hand, in the non-image area, it is necessary that sufficient hydrophilicity is maintained after development and that no staining occurs during the printing process.

In this way, as an attempt to strengthen the adhesion between the image area and the support, for example, Japanese Patent Application Laid-Open Nos. 59-192250 and 1997-1922,
As seen in No. 4250 and JP-A No. 2-4259,
It has been proposed to provide a non-photosensitive intermediate layer containing a silane coupling agent and/or a titanium coupling agent between the support and the photosensitive layer, but not only is the adhesion insufficient, but the silane cup Microscopically, the areas where the ring agent and the titanium coupling agent adhered to the surface of the support were found to have an excess of organic matter, and were unsatisfactory in terms of staining. Furthermore, JP-A-2-23347 and JP-A-2-23348 disclose that a photosensitive resin composition layer is provided on a support whose surface has been treated with a sol of a metal compound; When an iron material is used as a substrate, the purpose is to improve the hydrophilicity of its surface, and as in the present invention, organic functional groups are included to actively improve the adhesion between the image area and the support. Not only is this method ineffective, but it also has the problem that adhesion between the sol and the base material can only be obtained under specific electrolytic deposition conditions.

[Problem to be solved by the invention]

An object of the present invention is to provide a method for producing a lithographic printing plate that has strong adhesion between the image area and the support, and therefore has excellent image area strength and printability during development, and does not cause scumming. It is in.

[Means to solve the problem]

As a result of intensive studies, the present inventors have discovered a liquid composition containing an inorganic polymer obtained by hydrolyzing and polycondensing an organometallic compound having an organic functional group and a group that undergoes polycondensation following hydrolysis in a liquid. A method for manufacturing a lithographic printing plate in which a photosensitive lithographic printing plate having a photosensitive resin layer provided thereon is exposed and developed after coating a material on a metal surface, the developer used for the development is a silicate It has been found that the above object can be achieved by a method for producing a lithographic printing plate characterized by containing.

The present invention will be explained in detail below.

A specific example of the organometallic compound that can be used in the present invention is represented by the following general formula (1).

AyoM(OR), (1) In the formula, M represents a metal, A represents an organic functional group, and R represents hydrogen, an alkyl group, or a functional group that can be substituted for an alkyl group in a liquid, preferably an organic solvent. mSn is a positive integer and represents 2≦m+n≦6, and when mXn is 2 or more, A and R may be of the same type or a mixture of different types. can.

- Only one type of organometallic compound represented by (1) may be used, or several types may be used in combination). In addition, the following formula (2) which does not have an organic functional group A
may be mixed with other organometallic compounds.

M(OR) , (2) In the formula, M and R have the same meaning as in formula (1), and n is a positive integer satisfying 1≦n≦6.

Formulas (1) and (2) in which part or all of OR is replaced with halogen atoms can also be suitably used as organometallic compounds for preparing the composition according to the present invention. More specifically, by the action of water, alcohol, etc. - installation (1) and (2)
Any precursor organometallic compound capable of producing the compound represented by can also be used. Typical examples of halogen atoms are F, CA,
Br and I.

In addition, in -Installation (1) and (2), organometallic compounds in which part or all of OR undergoes hydrolysis and polycondensation reactions and have a metal-oxygen-metal bond in the molecule are also included. , can be used in the present invention.

Mixing organometallic compounds of general formulas (1) and (2),
When hydrolysis and polycondensation reactions are carried out to form a polymer or colloidal polymer containing a metal-oxygen-metal bond, and a metal surface is treated with this liquid composition, the compound (1 ) In addition to the functional group A derived from compound (2)
or optionally OH group derived from compound (1)
The group and the OH group derived from compound (2) are implanted on the metal surface. This OH group is present during -installation (2) or during -installation (
It is nothing but the one in which the OR group in 1) and -installation (2) is hydrolyzed to become an OH group.

The density of organic functional groups A on the treated surface changes the concentration of the liquid composition according to the invention as well as the concentration of compounds (1) and (
It can also be controlled by changing the relative amount of 2).

In general formulas (1) and (2), metal M is Ll, N
a.

K, Rb, Cs, Be, Mg, Ca, Sr
, Ba, Sc, Y, rare earth metal, Ti, V
, Cr, Mn, Fe, [:o, Ni
, mouth u, 2n.

Zr, Nb, Mo, Hf, Ta5WSRuSR
hSPdSIr, Pt.

BS AI, Ga, In5T1%5iSGeSSn
SPbSP.

^s, Sb, Bi, AI, 5iST
i is preferable from the viewpoint of raw material availability.

Further, A is a functional group covalently fixed to the treated surface, and may be any functional group as long as it exists stably in the form of formula (1). The chemical reactivity of the treated surface can be controlled by the type and amount of A.

Typical examples of A include alkyl groups, aryl groups, groups, alkenyl groups, propargyl groups, alkoxy groups, and epoxyalkyl groups. may be substituted with a functional group. Halogen group, alkyl group, aryl group, hydroxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, acyloxy group, acyl group, alkoxycarbonyl group, carbamoyl group, carboxy group, alkenyl group, Propargyl group, amino group, alkylamino group, acylamino group, ureido group, carbamate group, diazonio group, diazo group, azo group, mercapto group, alkylthio group, sulfonyl group, sulfo group, cyano group, isocyanato group, thioisocyanato group, sulfamoyl group group, nitro group, silyl group, siloxy group.

A more specific example of A is shown below.

CH3-1C2H5-1n-CJt, 1-Ca)h
, n-CeH+ to -n-C+J2S-1n-Cl
s H37-1CH, CA-1CFfCF soup CL"C
(CL)CD[H-CLh, CH2=CHC=CL
, ■ H3CL-1)IS-(-CHrh-, ll2N[:H
2-112N+CII#r-1H2to1CHTh-1H
,N-(CH meter NH+CH dancho, doCiCH dancho, NC
+CH r10CN+CHrh-1OCN+CH=-)
y, HD-CH2-C= C-1CH3CO-3-CH
2-1CH3CO-0-CI12-1(CHT+TC-
1 mouth f CH2CH25CH, -, (mouth II-) 2CH
O-1HD[:H2C112S[l:H2-, H2NC
II, Mouth H2NHCH2NC3CH23+CI(Soup", CH,=CIICH,0→CHr)y S C) I 2
-1NC3CH2CH2CH, -5(CH5)2N-C
3-5CL-1(CH3) 2CHNHCH2-1C)
1. CH2C0-C= C-1 CF+CD-TOCHdy, NC3C) I2- CHz=CH3+CHyh-.

CH, NHCO-0+ CHrh-1 HOOC-+CH ``.

(C2H5) aPSCl(aCH2-HJ-←CHf
+rS+ CH7 squares, (C7H6O) 2P-CH2
Cl2. -5-CH.

H, N-←CHTh-NH-+ CRT)7 NH-←
C1 (→Go rρ ([)13) 30-C1-[, To N soup Iro H Ding nako,
(CH. Represents a functional group that can be substituted, and may be a single group or several groups coexisting.Alkyl groups can be straight, branched, or cyclic, and typical examples are , CH3-, C2
Examples of the functional group R that can be substituted with an alkyl group in H5-, n-CJl, 1-CJt, and an organic solvent include halogen atoms such as CA and Br, and organic acid residues. As the organic acid residue, -C[1CH3 is easily used, but those having a large number of carbon atoms can also be used. The substitution of the functional group R with an alkyl group includes not only the substitution of R and an alkyl group as they are, but also the substitution of -OR with a 10-alkyl group.

Moreover, -OR is not limited to a monodentate type, and can also be a polydentate alkoxide such as a diol or triol, or a polydentate organic acid residue such as oxalic acid or succinic acid.

Specific examples of the compound represented by general formula (1) include the following.

82N ((1:H-) 2NH(C)I2) 3-5
l (OCH3) 3CH2=C)I-3i (OC
OCH3) 3CH2=CH-3i (OC2L) 3
HJ(CL)s-3i(OC2Hs)30CNCH,C
H2CH,-3i (OCL) 5CH3SiH(OC
H, ) 2 Hsl (OCH3) 2 CLCA Sl (OCH3) 3 CH3S+ (O[:I3) ! H3CH23i (DC)13) 3 CL-CH5+ (CH3) 20CH3CH2=CH
3i (OCH3) = CL=CHCH,Si (0[1:2H5) 3) IS
CH2CH2CH2Si (OCH3)3CH, ・CH
-3+ ([1:I3) (OCOCH3) 20H2
=CH-5+ (CH3)(DC2Hs)-(CH2=
CH) 2Sl (QC2Hs) 2H2N(CH2)
3SI (mouth H3) (OC2H5) 282N (CH2
) 3NH(CH2) 3S1 (CH:l) (O[
I3) 2NC(CH2) 2Sl (mouth C2H1)3
CH7-CHCH20CJsS1 ([]CH3) -
\. /cH2=CIICH,NH(CH2),Si(OC
H3)3(C,H5謬昌CH2)2S,(OCH3).

CH2=C(CH-)CO[l([:L)-3l(DC
)l->3[:L”[: ([:)I-) COD
(CH2) psi (CH3) (OCH3) 2C
L: CHCOO (CH2) 3Sl (OCH3) 3
CH2=CHCOO(CH=) 3Si (CH3)
(OCH3) 2NH,'JNH(CH2)ssi (
OC2H5) 3(:H= C5i (OC2H5) 3
CH2=CH3l (OCOCH3) 3(C5H70
2) 2Tl (0”3+(7) 2(C5H702)
2V (QC3H,).

(Cs8.02) 2 days a (OC211s) Specific examples of the compound represented by 2-incorporation (2) include the following.

Si (OCH3) 4 S+ ([]C2Hs) 4 Si (O[:OCH,) 4 S+ (0[:scd- 3+ (QC4Cs) 4 Tl (OC3H7) 4 Ti(OC,H=)= 2r (mouth C3L).

V(QC, H5).

W(DCJsL Examples of organic solvents for hydrolyzing and polycondensing the organometallic compounds represented by general formulas (1) and [2] are as follows.

methanol, ethanol, n- and]-propertools,
1- and 2-butanol, isobutyl alcohol, amyl alcohol, pentanol, fusel oil, hexanol, heptatool, octatool, cyclohexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, hexane, heptane, octane, decane, Petroleum ether, petroleum benzine, ligroin, gasoline, solvent oil, cyclohexane, benzene, toluene, o-lm- and p-xylene, styrene, cresol, tetralin, decalin, turpentine, chloroform, carbon tetrachloride, methylene chloride, ethylene chloride , ethylidene chloride, trichloroethane, tetrachloroethane,
Trichlorethylene, tetrachlorethylene, trichloropropane, isopropyl chloride, dichloropropane, chloride fJLi, amyl chloride, hexyl chloride, ethylene bromide, tetrabromoethane, chlorobenzene, 0-dichlorobenzene, trichlorobenzene, bromobenzene, Chlortoluene, diethyl ether, isopropyl ether, dibutyl ether, diisoamyl ether, hexyl ether, methylphenyl ether, ethylphenyl ether, butylphenyl ether, ethylbenzyl ether, 1,4-dioxane, 2-methylfuran, tetrahydrofuran, tetrahydropyran , 2-ethoxytetrahydropyran, cineole, acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl hexyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, dipropyl ketone, diacetone alcohol, holone, isophorone, cyclohexanone,
Methylcyclohexanone, acetophenone, ethyl formate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, nibutyl acetate, amyl acetate, isoamyl acetate, acetic acid Methylisoamyl, methoxybutyl acetate, 2-ethylbutyl acetate, hexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, amyl propionate, methyl butyrate, ethyl butyrate,
Butyl butyrate, amyl butyrate, isoamyl butyrate, methyl acetoacetate, ethyl acetoacetate, isoamyl isovalerate, methyl lactate, ethyl lactate, butyl lactate, amyl lactate, methyl benzoate, diethyl oxalate, ethylene glycol,
Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether,
Ethylene glycol monobutyl ether acetate, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monophenyl ether acetate, ethylene glycol benzyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene Glycol butyric acid monoester, ethylene glycol propionic acid diester, ethylene glycol butyric acid diester, diethylene glycol, diethylene glycol methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether , diethylene glycol monoisobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol acetate, diethylene glycol dibutyl ether, buapyrene glycol,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol probyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether,
Dipropylene glycol diethyl ether, trimethylene glycol, triethylene glycol dimethyl ether, butanediol, bentanediol, hexylene glycol, 3-methoxy-3-methoxybutanol, formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, Valeric acid, lactic acid, pyridine, picoline, quinoline, isoquinoline, dimethyl sulfoxide, triethyl phosphate, dimethylformamide, γ-butyrolactone, T
- Valerolactone, 6-hexanolactone, methyl salicylate, ethyl salicylate, butyl salicylate, diethyl adipate, ethyl carbonate, butyl sulfide, acetylacetone, acetonylacetone, mono-, di- and triethanolamine, N,N-dimethylformamide , Grise Lin.

Particularly preferred are methanol, ethanol, i-propertool, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, tetrahydrofuran, methyl ethyl ketone, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether. , acetylacetone, N,N-dimethylformamide and monoethanolamine.

The organic solvents may be used alone or in combination of two or more.

When the organometallic compounds represented by general formulas (1) and (2) are hydrolyzed in an organic solvent, it is possible to use the water remaining in the organic solvent as it is as a hydrolyzing agent. In order to control the preparation of the liquid composition according to the present invention to be completed within a certain time, it is generally preferable to add 0.5 to 1.000 mol of water per 1 mol of the organometallic compound. When the amount of water is less than this range, the progress of hydrolysis and subsequent polycondensation reaction becomes very slow, and it may take several days before metal surface treatment becomes possible. On the other hand, if the amount of water is too much than this range, it will not only cause poor adhesion even when the resulting composition is applied to the metal surface, but also the stability of the composition over time will be poor and it will often gel quickly. t. It becomes difficult to perform the coating operation stably.

In addition to acting as a reactant for hydrolysis, water can also serve as a solvent for the treatment liquid of the present invention. A liquid composition according to the method of the present invention can be prepared in an aqueous medium under conditions where the hydrolysis rate of the compounds represented by general formulas (1) and (2) is sufficiently slow to prevent easy gelation.

The reaction temperature is usually from room temperature to about 100°C, but by adding a reflux condenser, the reaction can be carried out at a temperature higher than the boiling point of the solvent.

The reaction temperature determines the time required for the hydrolysis and polycondensation reactions. If the reaction takes several days at room temperature, it will be completed in several hours at 80°C, so the reaction time should be set appropriately depending on the purpose.

As the catalyst used as necessary, acids such as hydrochloric acid and acetic acid, or bases such as ammonia and tetramethylammonium hydroxide can be used.

The amount of the catalyst added is generally from 0.01 mol to 0.01 mol per mol of the organometallic compound represented by general formulas (1) and (2).
．． It is about 1 mole. However, in some cases, 0.1 mol or more is preferable. The appropriate amount of catalyst to be added is 1 mole at most, and it is possible to avoid wasting the catalyst by adding too much.

The catalyst can be added not only by adding the catalyst itself, but also by adding a catalyst solution. For example, instead of adding hydrochloric acid as it is, a solution of hydrochloric acid in anhydrous methanol may be added. Tetramethylammonium hydroxide can also be used, for example, in the form of an aqueous solution or an ethanol solution.

A composition consisting of one or more organometallic compounds represented by general formula (1) and optionally (2), an organic solvent, water, and optionally a catalyst is heated at an appropriate reaction temperature, reaction time, and optionally. If the appropriate stirring conditions are selected and the reaction is carried out, a polycondensation reaction will occur along with hydrolysis, and the metal-
A polymer or colloidal polymer containing an oxygen-metal bond is generated, the viscosity of the liquid composition increases, and the liquid composition becomes a sol.

When the sol or liquid composition used in the present invention is applied to a metal surface and then air-dried or heated, the inorganic polymer consisting of metal-oxygen-metal bonds gels and simultaneously adheres to the metal surface.

Drying is performed to volatilize the solvent, residual water, and optionally the catalyst, but depending on the case, this step can be omitted. In order to increase the adhesion between the inorganic polymer portion in the liquid composition according to the present invention and the surface of the metal to be treated, it is also possible to actively apply temperature. The drying process in this case is
The process can be continued even after the solvent, water, etc. have been volatilized. The maximum drying temperature is the organic functional group planted on the metal surface ((1)
It must be lower than the decomposition temperature of formula A). Usually temperatures from room temperature to 200°C are used, preferably from room temperature to 150°C.

The liquid composition (sol solution) used in the present invention can be applied by any method such as brush coating, dip coating, atomizing, spin coating, doctor blade coating, bar coater coating, etc. It is determined by taking into consideration the processing film thickness, etc.

The coating amount of the liquid composition (sol solution) of the present invention is 0.01 mg/m' to 1 g/m', preferably 0.1 mg/m'' to 500 mg/m', more preferably 0. .5 mg/m' to 100 mg/m''. If the amount applied is too small or too large, the adhesion will decrease, and if the amount applied is too large, scumming may easily occur.

The liquid composition used according to the invention comprises: -Installation (1)
and optionally one or more organometallic compounds represented by formula (2), an organic solvent, water, and optionally one catalyst used at an appropriate reaction temperature.
It is obtained by selecting appropriate reaction time and stirring conditions in some cases, and when applied to a metal surface, the inorganic polymer adheres to the metal surface and the organic functional group is fixed. Any liquid composition may be used as long as the hydrolysis and polycondensation reactions have progressed to a state where the effect can be achieved.

Whether or not the liquid composition achieves the object of the present invention can be determined by actually coating the liquid composition on a metal surface and measuring the reflection infrared absorption spectrum, Raman spectrum, etc. This can be determined by confirming its presence and checking the adhesion between the inorganic polymer layer and the metal surface using a tape peel test after drying.

It is also possible to accurately monitor the hydrolysis reaction and polycondensation reaction spectroscopically to determine the degree of progress of the reaction. Regarding the progress of hydrolysis, for example, when using infrared absorption spectroscopy, the vibrational absorption spectrum based on -OR in - installation (1) decreases, and the vibrational absorption spectrum based on -OH becomes stronger. I can judge.

The subsequent polycondensation reaction can be confirmed, for example, by the appearance of a vibrational absorption peak derived from the metal-oxygen-metal bond in the infrared absorption spectrum, which gradually becomes stronger.
When measuring the MR spectrum, it is observed that the spectral width of A in general formula (1) widens as the polycondensation progresses,
This also allows confirmation of the reaction.

If any one of such spectral information is confirmed, the liquid composition used in the present invention can be suitably used to achieve the object of the present invention.

More conveniently, the viscosity of the liquid composition at the time of preparation is measured, and if a significant increase in viscosity is observed compared to the viscosity before the start of the reaction, it is determined that the liquid composition according to the present invention has been prepared at that point. can.

Although it varies depending on the composition and reaction conditions, the viscosity at the time of liquid preparation (2
5°C) is preferably about 0.2 centipoise to 10 poise. If the viscosity is too low, it will be difficult to monitor the progress of polymerization, and if the viscosity is too high, it will not only be difficult to coat on metal, but also the film may peel off after drying, which is not preferable. When applying the liquid composition to the surface of the metal to be treated, it can be used after being diluted with a suitable solvent or liquid such as water. Alternatively, it is also possible to volatilize a part of the solvent used during liquid preparation and use the concentrated solution. The viscosity of the liquid during application varies depending on the application method, desired coating thickness, etc.
It is easy to use a range from about 0.2 centipoise to about 10 poise.

If the molecular weight of the inorganic polymer in the liquid composition is to be determined, there is a method in which the liquid composition whose reaction has been stopped by trimethylsilylation treatment is made into a benzene solution and the number average molecular weight is determined from the freezing point depression, and the result is 1,000. All you have to do is confirm that it is on the order of tens of thousands.

As the photosensitive resin layer used in the present invention, any material can be used as long as its solubility or swelling property in a developer changes before and after exposure.

Representative examples are listed below.

(1) Photosensitive resin layer consisting of diazo resin and binder: As a negative-acting photosensitive diazo compound, US Pat.
Diphenylamine, which is a reaction product of the diazonium salt disclosed in No. 063.631 and No. 2.667, 415, and an organic condensing agent containing a reactive carbonyl group such as aldol or acetal. Condensation product of p-diazonium salt and formaldehyde (so-called
A photosensitive diazo resin) is preferably used. Other useful condensed diazo compounds are Japanese Patent Publication No. 49-48001, No. 4
It is disclosed in each publication such as No. 9-45322 and No. 49-45323. These types of photosensitive diazo compounds are usually obtained in the form of water-soluble inorganic salts and can therefore be coated from aqueous solution. Further, these water-soluble diazo compounds are reacted with an aromatic or aliphatic compound having one or more phenolic hydroxyl groups, sulfonic acid groups, or both by the method disclosed in Japanese Patent Publication No. 47-1167,
The reaction product, a substantially water-insoluble photosensitive diazo resin, can also be used.

It can also be used as a reaction product with hexafluorophosphate or tetrafluoroborate as described in JP-A-56-121031.

Examples of reactants with phenolic hydroxyl groups include diphenolic acids such as hydroxybenzophenone, 4,4-bis(4'-hydroxyphenyl)pentanoic acid, resorcinol, or diresorcinol, which may further contain substituents. It may have. Hydroxybenzophenone includes 2゜4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2.2'-
Dihydroxy-4,4'-dimethoxybenzophenone or 2,2',4,4'-tetrahydroxybenzophenone is included. Preferred sulfonic acids include aromatic sulfonic acids such as sulfonic acids such as benzene, toluene, xylene, naphthalene, phenol, naphthol and benzophenone, or soluble salts thereof, such as ammonium and alkali metal salts. The sulfonic acid group-containing compound may generally be substituted with a lower alkyl group, a nitro group, a halogen, and/or another sulfonic acid group. Preferred such compounds include benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, sodium mesitylenesulfonate, naphthalene-2-sulfonic acid, l
-Naphthol-2 (or 4)-sulfonic acid, 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid
Examples thereof include sodium m(p/-anilinophenylazo)benzenesulfonate, f'Jsulfonic acid, o-toluidine-m-sulfonic acid, ethanesulfonic acid, and their ammonium salts and alkali metal salts. Sulfonic esters of alcohols and their salts are also useful. Such compounds are usually readily available as anionic surfactants. Examples include ammonium or alkali metal salts such as lauryl sulfate, alkylaryl sulfate), p-nonylphenyl sulfate, 2-phenylethyl sulfate, and isooctylphenoxyjethoxyethyl sulfate.

These substantially water-insoluble photosensitive diazo resins can be precipitated by mixing the water-soluble photosensitive diazo resin and the water-soluble aromatic or aliphatic compound, preferably in approximately equal amounts. be separated.

Also preferred are the diazo resins described in GB 1.312.925.

In addition, JP-A-1-102456, JP-A-1102457
Diazo resins such as those disclosed in Japanese Patent No. 1-254949, No. 1-255246, No. 2-66, and No. 229650 can also be used.

The most preferred diazo resins are 2methoxy-4-hydroxy-5-benzoylbenzene sulfonate, hexafluorophosphate, and dodecylbenzene sulfonate, which are condensates of p-diazodiphenylamine and formaldehyde.

The appropriate content of the diazo resin in the photosensitive resin layer is 3 to 50% by weight, preferably 5 to 20% by weight. As the amount of diazo resin decreases, photosensitivity naturally increases, but stability over time decreases. The optimum amount of diazo resin is about 8-20% by weight.

On the other hand, various polymer compounds can be used as the binder, but in the present invention, hydroxy, amino,
Carboxylic acids, amides, sulfonamides, activated methylene,
Those containing groups such as thioalcohol and epoxy are desirable. Such preferred binders include those described in British Patent No. 1.
350.521, British Pat. No. 1, 460.978 and U.S. Pat. No. 4.12.
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit as described in U.S. Pat. No. 3,751,257; mido resins, phenolic resins as described in British Patent No. 1.074.392 and polyvinyl acetal resins such as polyvinyl formal resins, polyvinyl butyral resins, U.S. Pat. No. 3,660.0
Linear polyurethane resins, phthalated polyvinyl alcohol resins, epoxy resins condensed from bisphenol A and epichlorohydrin, polyaminostyrene and polyalkylamino (meth) described in the specification of No. 97
Included are polymers containing amino groups such as acrylates, cellulose derivatives such as cellulose acetate, cellulose alkyl ethers, and cellulose acetate phthalate.

Also, JP-A-54-98614, JP-A No. 61-26704
2, No. 62-58242, No. 61-128123, No. 62-123452, No. 62-123453, and No. 63-113450 are also preferably used.

The composition comprising a diazo resin and a binder further includes:
Additives such as pH indicators as described in GB 1.041.463, phosphoric acid and dyes as described in US 3.236.646 can be added.

(2) Photosensitive resin layer consisting of O-quinonediazide compound: A particularly preferred O-quinonediazide compound is O-naphthoquinonediazide compound, for example, U.S. Patent No. 2.76
6, 118, 2.767, 092, 2.7
No. 72.972, No. 2.859.112, No. 2.
No. 907.665, No. 3.046.110, No. 3
．． 046.111, 3.046.115, 3.046.118, 3.046.119, 3.046.120, 3.046.121,
Same No. 3.046.122, Same No. 3.046.123, Same No. 3.061.430, Same No. 3.102.809
No. 3.106.465, No. 3.635.
No. 709 and No. 3.647.443, and many other publications, which can be suitably used. Among these, in particular, 0-naphthoquinonediazide sulfonic acid ester or O-naphthoquinonediazide sulfonic acid ester of an aromatic hydroxy compound, and ○-naphthoquinonediazide sulfonic acid amide or O-naphthoquinonediazide sulfonic acid ester of an aromatic amino compound. -Naphthoquinonediazidecarboxylic acid amides are preferred, especially those described in US Pat. No. 3,635.
No. 709, a condensate of pyrogallol and acetone subjected to an ester reaction with ○-naphthoquinonediazide sulfonic acid, U.S. Patent No. 4.028.111
British Patent No. 1.494.043 describes a polyester having a hydroxyl group at the end described in the specification, which is obtained by ester-reacting O-naphthoquinonediazide sulfonic acid or O-naphthoquinonediazidecarboxylic acid. A homopolymer of p-hydroxystyrene or a copolymer of p-hydroxystyrene with other copolymerizable polymers as described above is subjected to an ester reaction with O-naphthoquinone diazide sulfonic acid or O-naphthoquinone dioxycytocarboxylic acid. ,
Copolymers of p-aminostyrene and other copolymerizable monomers as described in British Patent No. 3,759,711 include 0-naphthoquinonediazide sulfonic acid or The amide reaction of quinonediazidecarboxylic acid is very good.

Furthermore, 0-naphthoquinonediazide-4-sulfonic acid esters as described in JP-A-2-96758 and JP-A-2-96761 are also preferred.

Although these 0-quinonediazide compounds can be used alone, it is preferable to use them in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolak-type phenolic resins, and specifically include phenol formaldehyde resins, 0-cresol formaldehyde iMB'ti, m-cresol formaldehyde resins, and the like. Additionally, U.S. Patent No. 4.123.279
As stated in the specification, the above-mentioned phenol resin is used in combination with a phenol substituted with an alkyl group having 3 to 8 carbon atoms, such as t-butylphenol formaldehyde resin, or a condensate of cresol and formaldehyde. Then, - layer is preferable. Alkali soluble resin is
It is contained in an amount of about 50 to about 85% by weight, more preferably 60 to 80% by weight, based on the total weight of the composition constituting the photosensitive resin layer.

A photosensitive composition comprising an 0-quinonediazide compound includes
If necessary, further dyes, plasticizers, such as those described in British Patent No. 1.
No. 401.463, No. 1.039.475, No. 2
．． 192.729, U.S. Pat. No. 3.969.118, and Japanese Patent Application Laid-Open No. 63-58440)! Additives can be added, such as ingredients that provide performance.

(3) Photosensitive resin layer consisting of an azide compound and a binder (polymer compound): For example, British Patent No. 1.235.281, British Patent No. 1.4
Specifications of No. 95.861 and JP-A-51-32331
In addition to the compositions comprising an azide compound and a water-soluble or alkali-soluble polymer compound described in JP-A No. 51-36128, JP-A No. 50-5102 and JP-A-50-50-
No. 84302, No. 50-84303, No. 53-129
Included are compositions comprising a polymer containing an azide group and a polymer compound as a binder, as described in each publication of No. 84.

Also, Japanese Patent Publication No. 49-44601, Japanese Patent Publication No. 52-899
It is also possible to use compositions containing polyvinyl acecool resins having azide groups, which are described in Patent Publications No. 14 and No. 59-208552.

(4) Photopolymerizable photopolymer resin layer: A photosensitive composition containing an ethylenically unsaturated addition polymerization compound, a polymer soluble in an organic solvent and capable of forming a film, and a photopolymerization initiator is a typical example. Can be mentioned. Specific examples of these are described in JP-A-61-282836.

(5) Photo-crosslinkable funatopolymer resin layer: For example, the polyester compound disclosed in JP-A-52-96696, British Patent No. 1.112.277, i! 1,
No. 313,390, No. 1.341.004, No. 1
, 377, 747, and the like.

A particularly preferred composition is a photosensitive composition containing a photocrosslinkable polymer having a maleimide group in its side chain. The details are described in JP-A-62-78544.

(6) Electrophotographic photosensitive resin layer: The electrophotographic photosensitive resin mainly consists of a photoconductive compound and a binder, but may be added as necessary for the purpose of improving sensitivity or obtaining a desired photosensitive wavelength range. Well-known pigments, dyes, chemical sensitizers, other additives, etc. can be used. The photosensitive resin layer can be composed of a single layer or a plurality of layers in which charge generation and charge transport functions are separated. A lithographic printing plate can be obtained by forming a toner image on a photosensitive resin layer by a known electrophotographic process, and using this as a resist layer, decoding the non-image area. For example, Special Publication No. 37-17162, No. 3
No. 8-6961, JP-A-56-107246, JP-A No. 60
-254142, Special Publication No. 59-36259, 59
-25217, JP 56-146145, JP 62-194257, JP 57-147656, JP 58-1
It is described in many publications including No. 00862 and No. 57-161863, and any of these can be suitably used.

The thickness of the photosensitive resin layer may be 0.1 to 30 μm, preferably 0.5 to 10 μm.

The amount of photosensitive resin layer provided on the metal surface is about 0.1 to
about 7 g/m's, preferably 0.5-4 g/m''.

Further, the surface of the photosensitive layer provided as described above is preferably matte in order to shorten the evacuation time during contact exposure using a vacuum printing frame and to prevent printing blur. Specifically, Japanese Patent Publication No. 50-125805,
7-6582 and 61-28986, a method of providing a matte layer, Japanese Patent Publication No. 1983-
Examples include a method of heat-sealing solid powders as described in Japanese Patent No. 62337.

The silicates used in the developer of the present invention include sodium silicate [crystalline sodium silicates such as sodium orthosilicate, sodium sesquisilicate, and sodium metasilicate, sodium silicate No. 1, and sodium silicate No. 2]. , Sodium silicate solutions such as Sodium silicate No. 3 and Sodium silicate No. 4, Sodium silicate powder, etc.], Potassium silicate [A Potassium silicate, IK
Potassium silicate, potassium silicate, etc.], lithium silicate,
Examples include ammonium silicate. Sodium silicate and potassium silicate are particularly preferred.

These silicates may be used alone or in combination of two or more, and the appropriate content in the developer composition is 0.05 to 10% by weight, preferably 0.1 to 7% by weight. It is.

Moreover, in addition to the above-mentioned silicate, various alkaline agents can be used in combination with the developer of the present invention.

Such alkaline agents include potassium hydroxide, sodium hydroxide, lithium hydroxide, tertiary sodium phosphate,
Inorganic alkaline agents such as dibasic sodium phosphate, tertiary ammonium phosphate, dibasic ammonium phosphate, sodium bicarbonate, sodium borate, ammonium borate, ammonia, etc., and monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine,
There are organic amine compounds such as jetanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, etc., which can be used alone or in combination.

Further, an anionic surfactant may be added to the developer composition as necessary. Furthermore, organic solvents can be added. Examples of anionic surfactants include higher alcohol sulfate ester salts having 8 to 22 carbon atoms, such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, and disodium alkyl sulfate. Aliphatic alcohol phosphate ester salts such as the sodium salt of heptyl alcohol phosphate ester, etc., alkylaryl sulfones such as the sodium salt of dodecylbenzenesulfonic acid, the sodium salt of isopropylnaphthalenesulfonic acid, the sodium salt of metanitrobenzenesulfonic acid, etc. Acid salts, e.g. aryloxypolyethyleneoxysulfate ester salts, such as sodium naphthyloxypolyethyleneoxysulfate, e.g. sodium 4-n-butylbenzoate;
Alkylarylcarboxylate salts such as potassium 4-t-butylbenzoate, e.g. C+J3:+C[]N(CHs
) Sulfonates of alkylamides such as CHzCHzSO3Na, etc. Sulfonates of dibasic fatty acid esters such as sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, for example 8-(2-naphthyloxy) These include aryloxyalkylene sulfate ester salts such as -3,6-thioxaoctyl dipotassium nisulfate.

It is appropriate that the anionic surfactant is contained in an amount of 0.1 to 5% by weight based on the total weight of the developer at the time of use. If it is less than 0.1% by weight, the effectiveness of its use will be lowered, and if it is more than 5% by weight, for example, the dye contained in the photocurable photosensitive liquid may elute excessively (color loss). This results in disadvantages such as deterioration of mechanical and chemical strength such as abrasion resistance of photocured images.

Suitable organic solvents are those having a solubility in water of about 10% by weight or less, preferably 5% by weight or less. For example, 1-phenylethanol, 2-
Phenylethanol, 3-phenylpropanol-1,
4-phenylbutanol-1,4-phenylbutanol-2,2-phenylphtanol-1,2-phenoxyethanol, 2-benzyloxyethanol, 0-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, Examples include benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, and 3-methylcyclohexanol.

The content of organic solvent is 1% based on the total weight of the developer when used.
~5% by weight is preferred. The amount used is closely related to the amount of surfactant used, and as the amount of organic solvent increases, it is preferable to increase the amount of anionic surfactant. This is because if the amount of anionic surfactant is small and the amount of organic solvent is large, the organic solvent will not dissolve, and therefore good developability cannot be expected to be ensured.

Furthermore, additives such as an antifoaming agent and a water softener can be added as required. Examples of water softeners include Na-P2O7, Na, P, 0. , Na, P
3011, Na2O<P(NaO+P)POJa2, polyphosphates such as carvone (sodium polymetaphosphate),
For example, ethylenediaminetetraacetic acid, its potassium salt,
Its sodium salt; diethylenetriaminepentaacetic acid,
Its potassium salt, sodium salt; Triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt; Hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; Nitrilotriacetic acid, its potassium salt, its sodium salt; 1.2- Diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; Aminopolycarboxylic acids such as 1,3-diamino-2-propatoltetraacetic acid, its potassium salt, its sodium salt, etc., ethylenediaminetetraacetic acid (methylenephosphonic acid) , l-hydroxyethane-1°l-diphosphonic acid, and alkali metal salts thereof. The optimal amount of such water softeners varies depending on the hardness of the hard water used and the amount used, but if the amount used is 0.01 to 5 weight by weight in the developer solution at the time of use, %, more preferably 0.
It is contained in a range of 0.01 to 0.5% by weight. If necessary, desensitization treatment may be applied after development, washing with water, desensitization treatment as is, treatment with an aqueous solution containing an acid, or desensitization treatment after treatment with an aqueous solution containing an acid. Also good. Regarding such post-development processing, Japanese Patent Application Laid-Open Nos. 54-8002, 55-115045, and 57-
No. 158643, No. 59-57242, No. 59-58
431 and Japanese Unexamined Patent Application Publication No. 2-32357, which are described in detail, and may be used for other purposes. Furthermore, in the development process of this type of photosensitive planographic printing plate, the alkaline aqueous solution is consumed depending on the processing amount, and the alkaline concentration decreases.
Alternatively, when an automatic processor is operated for a long period of time, the alkali concentration is reduced by the air, resulting in a decrease in processing capacity, but in this case, even if the processing capacity is restored using a replenisher as described in JP-A-5462004, good.

EXAMPLES Hereinafter, the present invention will be explained in more detail using examples.

Examples 1 to 5 A solution having the composition shown in Table 1 was placed in a beaker and stirred at room temperature to form a uniform solution. Next, these solutions were transferred to a three-hole flask equipped with a stirrer and a reflux condenser, immersed in an oil path, and reacted for 8 hours without stirring while keeping the bath temperature at 70°C. ) ■～■ were obtained.

On the other hand, the surface of an aluminum plate having a thickness of O13 was grained using a nylon brush and an aqueous suspension of 400 mesh bumiston, and then thoroughly washed with water. This is 10
% sodium hydroxide aqueous solution at 70° C. for 60 seconds, washed with running water, and neutralized with 20% nitric acid, VA=12.7V, V,=9. Using a sinusoidal alternating waveform current of IV, 160 corons per liter in a 1% nitric acid solution
Electrolytic surface roughening treatment was carried out using an anode special electricity amount of dm2. Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55°C for 2 minutes, and then immersed in a 7% sulfuric acid aqueous solution to a thickness of 2.0 g/m.
Anodic oxidation treatment was carried out so that it became 1.

After diluting the sol solutions ■ to [F] with methanol on this substrate, they were applied using a wheeler so that the dry coating amount was 10 mg/m'', and dried at 80°C for 30 seconds. Apply the following photosensitive liquid 1 with a wheeler, and
It was dried at 0° C. for 2 minutes to obtain photosensitive planographic printing plates A to E.

Photosensitive liquid 1 /35 (!Gravity ratio) co-combination bg・Sensitizer represented by the following structural formula・Methyl ethyl ketone 0g・Copper phthalocyanine i material (CL 1. OgP
These photosensitive lithographic printing plates A-E were imagewise exposed using a negative film from a distance of 1 m using a PS light (manufactured by Fuji Photo Film Co., Ltd.), and the following steps were carried out. After being immersed in Developer 1 having the composition shown for 5 minutes, the surface of the photosensitive resin layer of the image was rubbed with a microscope, and almost no scratches were observed in all cases.

In addition, these photosensitive planographic printing plates A-E were heated at 40°C and 80°C.
After storage for 5 days under high temperature and high humidity conditions of 100% L 'l', the image was exposed in the same manner as above, developed using the above developer in an automatic developing machine 800U manufactured by Fuji Photo Film Company, and a printing test was performed. As a result, clear printed matter was obtained without any background smearing up to 100,000 sheets.

Developer l S+L/10%tvkti'''1°2(7)'7[t
filJ,.

3% by weight aqueous solution Ll'') ■ = → Toro Toro O Sodium ethylenediaminetetraacetate・48.0 0.1g Examples 6 to 12 Sol solutions ■ to O were obtained in the same manner as in Example 1.These sol solutions were On a substrate prepared in the same manner as in Example 1, and further immersed in a 3% aqueous solution of IJum for 1 minute in a 3% aqueous solution of IJum, washed and dried, the sol solutions ■ to ■ were applied in the same manner as in Example 1,
Dry. Apply the following photosensitive liquid 2 to these aluminum plates.
was coated with a wheeler and dried at 80° C. for 2 minutes to obtain photosensitive planographic printing plates F to L.

Photosensitive solution 2 2-methoxyethanol 100 g Developed in the same manner as in Example 1, except that developer 2 having the composition shown below was used as a developer using these photosensitive lithographic printing plates F-L.
When a printing test was conducted, clear prints were obtained without any background smearing up to 100,000 sheets.

Developer 2 Sodium sulfite 5g Benzyl alcohol 30g Isopropylnaphthalene sulfonic acid 12g Sodium malate Victoria Pure Blue BOH 0.05g 0.1g Megafac F-1770.03g (Dainippon Ink ■, fluorine-based surfactant) Example 13
~16 A photosensitive lithographic printing plate M was obtained in the same manner as in Example 6. However, the photosensitive liquid 3 having the composition shown below was used, and the dry coating amount of the photosensitive layer was 1.5 g/m'.

Photosensitive liquid 3 Polyurethane resin with the following composition (molar ratio 25/25/30/20, weight average molecular weight 70.000) phenylphosphonic acid
0.1 g Victoria Pure Blue BOH 0.1 g Megafac F-1770.05 g (Fluorine surfactant manufactured by Dainippon Ink ■) 2-methoxyethanol 20 g Propylene glycol monomethyl 30 g Ether methyl ethyl ketone 30 g Methanol 20 g This photosensitive lithographic printing plate M When development and printing tests were conducted in the same manner as in Example 1 using Developers 3 to 6 having the compositions shown below, 100,000 sheets of clear printed matter without background smudge were obtained in all cases.

Developer 3 Sodium sulfite developer 4 g Phenyl cellosolve 0 g Sodium sulfite developer 5 g Triethanolamine 5 g Benzyl alcohol 2-methylresorcin 0 g Developer 6 SI [+2/2] Potassium silicate at a molar ratio of about 2 1
Sodium silicate with a molar ratio of 0g5i02/NazO about 2 1
0g benzyl alcohol 40g triethanolamine 10g 2-methylresorcinol 5g water
11 As a comparative example, the photosensitive lithographic printing plates of Examples 13 to 16 were treated with the following developer 7.
The printing plate developed with the above-mentioned printing plate showed significant background smearing from the beginning of printing.

Developer 7 Triethanolamine 15g Benzyl alcohol 30g 2-methylresorcinol 8g Water [Effects of the invention] According to the present invention, the adhesiveness between the image area and the support is strong, and the image area strength and printing durability during development are excellent. , it is possible to produce a lithographic printing plate that does not cause scumming.

Claims (1)

[Claims] After coating a metal surface with a liquid composition containing an inorganic polymer obtained by hydrolyzing and polycondensing an organometallic compound having an organic functional group and a group that undergoes polycondensation following hydrolysis in a liquid, A method for producing a lithographic printing plate comprising exposing and developing a photosensitive lithographic printing plate having a photosensitive resin layer thereon, characterized in that the developer used for said development contains a silicate. How to make the plate.