JPH01270048A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To optimize development by incorporating a compd. contg. >=1 thiol or thioether groups and >=1 alcohol or ether groups in the molecule into the negative type photosensitive compsn. contg. a diazonium compd. and a high- polymer compd. which is soluble in an aq. alkaline soln. CONSTITUTION:The compd. having the >=1 thiol and/or thioether groups and >=1 alcohol and/or ether groups in the molecule refers to the compd. having the HS- and/or -S- group (including -S-S-) or HO- and/or -O- groups in the molecule and is, for example, 2-mercaptoethanol, 3-mercapto-2-butanol, 2- mercapto ethyl ether, etc. The correct developing characteristic is obtd. at the time of executing development after exposing and the generation of stain, etc., in the non-image part is obviated if the compsn. is formed in such a manner.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, IC circuits, photomasks, and the like. More specifically, the present invention relates to a photosensitive composition comprising a diazonium compound, a polymer compound having excellent abrasion resistance and solubility in an alkaline aqueous solution, and an additive for improving developability.

[Conventional technology]

The majority of materials used as photosensitive substances in negative-acting photosensitive compositions are diazonium compounds, and the most commonly used ones include diazo resins such as formaldehyde condensates of p-diazodiphenylamine. be.

The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin may be a diazo resin alone, i.e. without a binder, as described, for example, in U.S. Pat. No. 2,714,066. For example, JP-A-50-3060
As described in Publication No. 4, it can be classified as a mixture of binder and diazo resin, but in recent years many photosensitive planographic printing plates using diazonium compounds have high rigidity resistance. It consists of a diazonium compound and a polymer as a binder.

As described in Japanese Patent Application Laid-Open No. 50-30604, such an intense light layer is of the so-called alkaline development type in which the unexposed area is removed (developed) with an aqueous alkaline developer, and an organic solvent developer. The so-called solvent-developed type is known, but from the viewpoint of occupational safety and health, the alkali-developed type is attracting attention, and this is mainly determined by the properties of the binder. A method for imparting alkaline developability to the binder is to copolymerize a carboxylic acid-containing monomer as described in JP-A-50-30604, or as described in U.S. Pat. No. 2,861,058. For example, there is a method of introducing a carboxylic acid into a polymer by reacting a hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride.

On the other hand, when developing these negative photosensitive lithographic printing plates after exposure, the aqueous alkaline developer compositions used are, for example, those disclosed in JP-A-51-77401.
Developing solution composition consisting of benzyl alcohol, anionic surfactant, alkaline agent and water, JP-A-53-4420
A developing solution composition consisting of an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite is described in No. 2, and a developer composition that has a solubility in water at room temperature is described in JP-A-55-155355. Examples include developer compositions containing an organic solvent, an alkaline agent, and water in an amount of 10% by weight or less.

All of these contain organic substances such as organic solvents and surfactants in their developing/liquid compositions. However, organic solvents have many drawbacks, such as being generally toxic and odorous, and pose a risk of fire, and are subject to BOD regulations even in waste liquid, and are also expensive.

Furthermore, surfactants have the problem of generating bubbles during development, and it is desirable to use a developer composition that does not substantially contain these organic substances.

On the other hand, examples of developer compositions that do not substantially contain these organic substances include the developer composition described in JP-A-59-84241. However, these developer compositions are used when developing positive-working photosensitive lithographic printing plates containing O-naphthoquinonediazide compounds as photosensitive compounds, and these developer compositions that are substantially free of organic matter are When the above-mentioned negative photosensitive lithographic printing plate is developed using the above-mentioned photosensitive lithographic printing plate, it cannot be developed without leaving a residual film, and furthermore, unexposed areas turn yellow, and proper developability cannot be obtained. Even when apparently appropriate developability is obtained, there is a problem in that stains occur in non-image areas when printed.

In the present invention, "substantially free of organic substances" means that the proportion of the substance in the composition is 3% by weight or less, preferably 1% by weight, from the above-mentioned safety point of view. It is as follows.

[Problem to be solved by the invention]

Therefore, the object of the present invention is to achieve excellent solubility in an alkaline aqueous solution by using appropriate additives, and to provide an appropriate level of solubility when developed after exposure using an aqueous alkaline developer containing organic substances such as organic solvents and/or surfactants. Proper developability is obtained even when developed after exposure using an aqueous alkaline developer that does not substantially destroy these organic substances, and furthermore, no stains are produced in non-image areas when printed. An object of the present invention is to provide a photosensitive composition that provides a lithographic printing plate.

[Means to solve the problem]

As a result of intensive study by the present inventors to achieve the above object,
It has been discovered that these objects can be achieved by using a novel photosensitive composition, and the present invention has been achieved.

That is, the present invention provides a negative photosensitive composition containing a diazonium compound and a polymer compound that is insoluble in water and soluble in an alkaline aqueous solution, which contains one or more thiol and/or thioether groups and one or more alcohol in the molecule. The present invention provides a photosensitive composition further containing a compound having an ether group and/or an ether group.

Hereinafter, each component used in the present invention and the method for producing and using the photosensitive composition of the present invention will be explained in detail.

(1) Compounds having one or more thiol and/or thioether groups and one or more alcohol and/or ether groups in the molecule; Compounds having one or more thiol and/or thioether groups and one or more alcohol and/or ether groups in the molecule A compound having an alcohol and/or ether group is a compound having an R5- and/or -S- group (including -3-8-) and a HO- and/or -0- group in the molecule.

Such compounds preferably used in the present invention include compounds represented by general formula (I).

R'-5-R''-0-(CHzCIIO)fi-R'
-(1) (wherein R1 is -H or an alkyl group of 01 to C1□ which may have a substituent, a cycloalkyl group of 03 to C1□, an aryl group of C6''CIz, C?
7 La/L of CI 2 indicates a kill group, R2 is C, H
,N,O.

Represents a divalent linking group consisting of S, R3 is -H or -C
I+3, R4 has -H or a substituent.''
C8~CI that can be used! Alkyl group, C1-C+Z
cycloalkyl group, C1 to C+Z aryl group, 07
~CI□ represents an aralkyl group, which may form a ring together with R2, and n represents an integer of θ~20. ) Examples of the compound represented by the general formula (1) suitably used in the present invention include 2-mercaptoethanol, 3-mercapto-2-butanol, 2-mercaptoethyl ether, 3-mercapto-1,2- Propanediol, 2,3-dimercapto-1-propatol, 2-
(2-mercaptoethylthio)ethanol, 1,4-
Dimercapto-2,3-butanediol, 6-mercaptopurine riboside, 2-thiopheneethanol, 3-thiopheneethanol, 2-thiophenemethanol, thiochroman-4-ol, 2,2'-thiodietanol,
3.3'-thiodibrobanol, 5-thio D-glucose, l-hydroxymethyl-2-mercaptoimidazole, 1-(2-hydroxyethyl)-2-mercaptobenzimidazole, 1-(p-(2- hydroxyethoxy)phenyl)-5-mercaptotetrazole,
triethylene glycol methyl 2-mercapto-4
-methylphenyl ether, 2-mercaptohydroquinone di(methoxyethoxyethoxy)ether, and the like.

Generally, compounds having a divalent sulfur atom have a bad odor, so in the present invention, it is preferable to use compounds having a boiling point of 100° C. or higher at normal pressure.

The molecular weight is preferably 80 or more, more preferably 1
00-1000.

The compounds having a thiol and/or thioether group and an alcohol and/or ether group used in the present invention can be used alone or in combination of two or more,
The proportion in the photosensitive composition is preferably 0.1 to
The content is 30% by weight, more preferably 0.2 to 20% by weight.

(2) Negative-acting diazonium compound The negative-acting diazonium compound used in the present invention is disclosed in U.S. Pat.
Examples include the diazonium compounds described in US Pat. No. 867,147 and the diazonium compounds described in US Pat.
Diazo resins represented by condensates with are useful. Preferred diazo resins include, for example, hexafluorophosphates, tetrafluoroborates, and phosphates of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, sulfonates of condensates of p-diazodiphenylamine and formaldehyde as described in U.S. Pat. No. 3,300,309 (e.g.
p-) luenesulfonate, dodecylbenzenesulfonate, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonate, etc.), phosphinate (e.g. benzenephosphinate, etc.), hydroxy group-containing compound salt ( For example, 2,4-dihydroxybenzophenone salts, etc.), organic carboxylic acid salts, etc. are also preferred.

Furthermore, 3-methoxy-4-diazo-diphenylamine as shown in JP-A No. 58-27141 is added to 4,4
Mesitylene sulfonate obtained by condensation with '-bis-methoxy-methyl-diphenyl ether is also suitable.

The content of these diazonium compounds in the photosensitive composition is 1 to 50% by weight, preferably 3 to 20% by weight.

Moreover, two or more types of diazonium compounds may be used in combination, if necessary.

(3) Polymer compounds that are water-insoluble and soluble in alkaline aqueous solutions Examples of water-insoluble and alkaline aqueous-soluble polymer compounds used in the present invention include phenol formaldehyde resins, cresol formaldehyde resins, and phenol-modified xylene resins. , polyhydroxystyrene, polyhalogenated hydroxystyrene, carboxyl group-containing epoxy resin, polyacecool resin, acrylic resin, methacrylic resin, carboxyl group-containing polyurethane resin, etc., one or more types of known alkali-soluble polymer compounds can be used. .

Among these, preferred are the following general formulas (II) to
It is a polymer compound containing one or more types of structural units represented by (V).

Okisen CH, -C1Go-Y'-R'``-5OzNH-R''' ・
・・・・・・(II)I4 +CII□−C÷ Co−Y”−R”−NH3O,−R” ・・・・・・
・(I[[)R1F+CH,-C÷Co-Y'-R'”-OH...(IV')■ (In the formula, R1, RI4, and R17 are each -H or -
C1 (represents s, R12 and RIS are C1 to C+z alkylene groups which may each have a substituent, C3 to C
At represents a cycloalkylene group, C1 to C+z arylene group, and C7 to C+Z aralkylene group, and R11l is C1 to C1! which may have a substituent. represents an arylene group, and R13 is C which may have a -H1 substituent.
I"' Ct□ alkyl group, C1~CI! cycloalkyl group% Ch'wc, □ aryl group, C9~Ct
Z represents an aralkyl group, R1& is a C1-Cat alkyl group which may have a substituent, a C2-C+Z cycloalkyl group, C6-C1! aryl group, C1-C1
t represents an aralkyl group.

Moreover, Yl, Yl, Y:l are respectively -0- or -
Indicates NH-. ) In the present invention, the polymer compound more preferably used is a polymerized metal compound consisting of structural units represented by general formulas (n) to (V) and other structural units. Such a polymer compound includes one or more of the low molecular weight compounds having a polymerizable unsaturated bond represented by the following formulas (Vl) to (IX) and another low molecular weight compound having a polymerizable unsaturated bond. It can be obtained by polymerizing one or more molecular compounds in a suitable solvent using a known polymerization initiator.

CIl□=C C0-Y'-R"-5O□NH-RI3030.-0-
(V[)CH,,C ■ Co-Y"-R15-NHSOz-R"...
... (■) R heavy CF! ! =C C0-Y”-R”-OR,,,,,,,i1)■ (wherein, R1-R11 and y + , y 3 are the formula
II) to (V)) Other low molecular weight compounds having polymerizable unsaturated bonds used in the present invention include acrylic acid, methacrylic acid, acrylic esters, methacrylic esters,
Examples include acrylonitrile, metacyclonitrile, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and crotonic acid esters. Among these low molecular weight compounds having polymerizable unsaturated bonds, those preferably used are methacrylic acid esters, acrylic acid esters, methacrylamides, acrylamides, acrylonitrile,
These are metacyclonitrile, methacrylic acid, and acrylic acid.

One or more of such polymerizable compounds and general formula (Vl)
In the present invention, a polymer obtained by copolymerizing one or more of the compounds represented by (IX) is used, but as a polymer,
Block bodies, random bodies, graft bodies, etc. can all be used.

In these copolymers, it is preferable that the structural units represented by general formulas (II) to (V) be contained in an amount of 5 mol% or more, and 10 to 9% by mole, based on all the structural units constituting the copolymer.
It is more preferable to contain 0 mol%.

Further, the molecular weight of the polymer compound of the present invention is preferably 2. OO0 or more, more preferably 5.0
The range is from 00 to 300.000.

Examples of solvents used in synthesizing such polymers include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, Examples include 2-propatol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, toluene, ethyl acetate, methyl lactate, and ethyl lactate.

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

In the present invention, particularly preferably used polymer compounds are polymer compounds obtained by selecting one or more types from the compound groups described in the following groups (A) to (D), respectively, and copolymerizing them.

(A) Group - C Compounds represented by formulas (Vl) to (IX) Group (B) Acrylonitrile, metacyclonitrile and - General formula (X
) Compound R2' / (wherein, R"J:!-H or bar CII t-L, R"
4;! H, -CHI, -CI2Cl, -CIIZC
H3 is shown, and n is an integer of 1 to 10. ) Group (C) compound represented by the general formula (XI) t2 / cut:c \ C0OR'' (wherein, Rzx represents -H or -CH, and Rz4 is
C2 to C12 alkyl group which may have a substituent,
It shows a cycloalkyl M of C1 to C1□, an aryl group of cb to C+Z, and an aralkyl group of C1 to C1□. ) (Group D) Acrylic acid, methacrylic acid and a compound represented by the general formula (X n') H2S / (wherein, R2% represents -H or -0113, R26
represents -H1-CH or halogen. ) The content of these polymers contained in the photosensitive composition is about 5 to 9
5% by weight, preferably about 10-85% by weight.

Further, U.S. Pat. No. 4,179,531 and the like disclose a photocurable composition comprising a monoalkenyl aromatic diene copolymer resin, a crosslinkable carbon-carbon double bond-containing monomeric polythiol, and a photoinitiator; , JP-A-57-176035, etc., describe a positive photosensitive composition comprising a high molecular weight polyene containing a reactive unsaturated carbon-carbon group, a reactive mercapto acid, and a radiation-sensitive radical-generating system. The present invention is a negative photosensitive composition that uses a diazonium compound as a photosensitizer, and is essentially different from these known examples. It is not necessary to contain a crosslinkable carbon-carbon unsaturated bond, and rather it is preferable not to contain such an unsaturated bond.

(4) Other additives In the composition of the present invention, print-out agents for obtaining a visible image immediately after exposure, dyes as image coloring agents, pigments, stabilizers,
Additives such as surfactants, plasticizers and other fillers can be added.

Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-8
The combination of 0-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 128, JP-A-53-36223, JP-A-54-7
Examples include the combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 4728. Dyes other than the above-mentioned salt-forming organic dyes can also be used as image colorants. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic 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 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI
42555), methyl violet (C142535)
), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue (C15
2015).

In addition, as stabilizers for diazonium compounds, phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, boric acid, p-toluenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy- 5-benzoyl-benzenesulfonic acid, malic acid, tartaric acid, dipicolinic acid, polyacrylic acid and its copolymers, polyvinylphosphonic acid and its copolymers, polyvinylsulfonic acid and its copolymers, 5-nitronaphthalene-1- Phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, 2-
Examples include phosphonobutanetricarboxylic acid-1,2,4,1-phosphonoethanetricarboxylic acid-1,2,2,1-hydroxyethane-1°1-disulfonic acid.

In addition, alkyl ethers (e.g. ethyl cellulose, methyl cellulose), surfactants (e.g. fluorine surfactants), film flexibility,
Plasticizers (for example, tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added to impart wear resistance. The amount of these additives added varies depending on the purpose for which they are used, but
Generally 0.5 to 30% by weight based on the total solid content of the photosensitive layer
It is.

The photosensitive composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. Solvents used here include methanol, ethanol, isopropanol, n
-butanol, t-butanol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone,
Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-
Methoxyethyl acetate, ■-methoxy 2-propanol, 1-methoxy-2-propyl acetate, N,
Examples include N-dimethylformamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, ethyl acetate, methyl lactate, and ethyl lactate, and these solvents may be used alone or in combination.

Also suitable are mixed solvents in which a small amount of water or a solvent such as toluene that does not dissolve the diazo resin or polymer compound is added to these solvents or mixed solvents. The concentration (solid content) of the above components is 1 to 50% by weight.

When applying and drying a photosensitive liquid dissolved in these solvents, it is desirable to dry at 50°C to 120°C. The drying method may be performed by starting at a low temperature and drying at a high temperature after preliminary drying, or by selecting an appropriate solvent and concentration, it may be directly dried at a high temperature.

The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.5 to 3.
．． 0g1rd is preferred. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

Examples of the support to which the photosensitive composition of the present invention is applied include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), aluminum (including aluminum alloys), etc.
Plates of metals such as zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include paper or plastic films laminated with or vapor-deposited with metals such as those mentioned above. Among these supports, aluminum plates are significantly more dimensionally stable;
Moreover, it is particularly preferable because it is inexpensive. In addition, the special public
A composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent No. 18327 is also preferred.

Further, in the case of a support having a surface of metal, particularly aluminum, it is desirable to perform an appropriate hydrophilic treatment.

Such hydrophilic treatment includes, for example, mechanical methods such as wire brush graining, ball graining, which roughens the aluminum surface with a nylon brush while pouring slurry of abrasive particles, and mechanical methods such as HF and A.
After the surface is grained by chemical graining using lC1x, HClt as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolyte, or composite graining performed by combining these roughening methods, roughening is performed as necessary. etching treatment with acid or alkali, followed by sulfuric acid,
Preferably, the aluminum surface is anodized in phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid thereof using a direct current or alternating current power source to form a strong passive film on the aluminum surface. Such a passive film itself makes the aluminum surface hydrophilic, but if necessary, silicate treatment (sodium silicate, sodium silicate,
Potassium silicate), potassium fluorozirconate treatment as described in U.S. Pat. No. 2,946,638, phosphomolipdate treatment as described in U.S. Pat. No. 3,201,247, alkyl as described in British Patent No. 1,108,559 Titanate treatment, German patent 10914
Polyacrylic acid treatment described in Specification No. 33, German Patent No. 1134093 and British Patent No. 123044
Polyvinylphosphonic acid treatment described in the specification of No. 7, phosphonic acid treatment described in Japanese Patent Publication No. 44-6409, phytic acid treatment described in U.S. Pat. No. 3,307,951, JP-A-58 -16893 and JP-A-58-18291, a composite treatment consisting of a hydrophilic organic polymer compound and a divalent metal;
Particularly preferred are those subjected to hydrophilic treatment by undercoating with a water-soluble polymer having sulfonic acid groups as described in JP-A-59-101651. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,658,662.

The photosensitive composition of the present invention coated on a support can form a line image,
Exposure through a transparent original having a halftone image or the like, followed by development with an aqueous alkaline developer, provides a negative relief image on the original.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, and laser beams.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent coating properties when applied onto a support. In addition, after coating, drying, and image exposure, it has excellent developability when developed with an aqueous alkaline developer, and has appropriate developability when developed with an aqueous alkaline developer containing organic substances such as organic solvents and/or surfactants. is obtained, and appropriate developability is obtained even when developed with an aqueous alkaline developer that is substantially free of these organic substances.

Furthermore, when used as a printing plate, there is no staining in non-image areas, and a large number of good prints can be produced.

Therefore, it is now possible to develop negative-working planographic printing plates using an aqueous alkaline developer known as a developer for positive-working planographic printing plates, and both positive-working planographic printing plates and negative-working planographic printing plates can be processed. In this case, it is possible to save the trouble of adjusting the developer composition to suit each, changing the developer composition, and preparing two types of developer compositions and development processing equipment in advance. This makes it possible to significantly improve work efficiency, equipment costs, installation space, etc.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the content of the present invention is not limited thereto.

According to the method described in JP-A No. 61-275838, polymer compounds (a) to (C1) shown in Table 1 were converted to
According to the method described in No. 890, the polymer compound-(d) was
Polymer compound (e) was synthesized according to the method described in JP-A-60-115932.

The weight average molecular weight (polystyrene standard) of these polymer compounds is 20.000 to 100.000.
Met.

Next, the surface of a JIS 1050A aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and an aqueous suspension of 400 mesh pumice stone, and then thoroughly washed with water. Add this to 10% sodium hydroxide aqueous solution.
After etching by dipping at 0°C for 60 seconds, washing with running water and neutralizing with 20% nitric acid, the surface was roughened using the electrochemical surface roughening method described in JP-A-53-67507, that is, a sinusoidal alternating waveform current. 160 clones/dts in 1% sulfuric acid aqueous solution
Electrolytic surface roughening treatment was carried out with a special electric charge of 2.5%.Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55°C for 2 minutes, and then the coating amount of aluminum oxide was 2.0g/ rrr.Then, it was immersed in a 3% aqueous solution of JISa sodium silicate at 70°C for 1 minute, washed with water, and dried.The aluminum plate obtained in the above manner was subjected to the following photosensitive Liquid (E)-
Apply 1 to [E]-5 using a wheeler and heat 2 at 80℃.
Dry for a minute. The dry weight was 2.0g1rd.

The polymer compounds used in the present invention in photosensitive solutions (E)-1 to (E)-5 are shown in Table 2.

Photosensitive liquid (E) Next, as a comparative example, 3-mercapto-
Photosensitive liquid (F)-1~ excluding 1,2-propanediol
CF)-5 was similarly applied and dried.

Photosensitive liquids (E)-1 to (E)-5 and (F)-1 to [F)
-5 Each photosensitive planographic printing plate (E)-1~ obtained using
(E)-5 and (F)-1 to (F)-5 were image-exposed for 1 minute from a distance of 1 m using Fuji Photo Film ■ PS Light, and then the following developers (S) and (T) were applied. After each sample was immersed for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton.

Developer [S] Developer (T) Each of the printing plates thus obtained was attached to a GTO type printing machine manufactured by Heidelberg, and printed on high-quality paper using commercially available ink.

At this time, stains occurring on the paper in non-image areas were visually determined. (O: No stain, △: Slight stain, ×: Stain) The results are shown in Table 2. When developer (S) was used, lithographic printing plates (E)-1 to (E)-5 and (F)-1~(F)
-5 did not cause any stains, but when using a developer (T) that does not contain organic matter, lithographic printing plates (E) -1 to
(E)-5 did not cause staining, but (F)-1
-(F)-5, staining occurred.

Next, the following photosensitive liquid CG was applied to the aluminum plate mentioned above.
)-1 to (G)-3 using a wheeler and heated at 80°C.
and dried for 2 minutes. The dry weight was 2.0 g/I.

The compounds (P) having a thiol and/or thioether group and an alcohol and/or ether group used in the photosensitive solutions (G)-1 to CG)-3 are shown in Table 3.

Photosensitive liquid (G) Each of the photosensitive planographic printing plates (G)-1 to CG)-3 obtained using photosensitive liquids (G)-1 to (G)-3 was coated with PS Light manufactured by Fuji Photo Film ■. After imagewise exposure for 1 minute from a distance of 1 m, and immersion in the developer (T) shown above for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton. Each of the obtained printing plates was mounted on a Heidelberg GTO type printing machine and printed on high-quality paper using commercially available ink. On this occasion,
The stains occurring on the paper in the non-image areas were visually determined. (
(○: No stain, Δ: Slight stain, ×: No stain) The results are shown in Table 3. None of these produced stains. On the other hand, these comparative examples are based on the aforementioned printed version CF)-
However, when printing plate CF)-1 was used, stains occurred as described above.

Showa year month day 1. Description of the case Patent Application No. 99552 of 1988 2, Title of the invention Photosensitive composition 3, Person making the amendment Relationship to the case Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Order for amendment Date Initiation 6, Subject of amendment Detailed explanation of the invention in the specification (1) “may be or n” in line 8 on page 8 of the specification
Correct it to "It's okay. Also, n is."

(2) "Hydroxy group" on page 10, line 20 of the same book is corrected to "hydroxyl group."

(3) The same book, page 18, line 4 “...(XI) Insert J.

(4) Same book, page 18, line 12 2S / “...Insert (Xll)J.

Claims (1)

[Claims] In a negative photosensitive composition containing a diazonium compound and a polymer compound that is insoluble in water and soluble in an alkaline aqueous solution, one or more thiol and/or thioether groups and one or more alcohol and/or ether groups in the molecule. A photosensitive composition further comprising a compound having the following.