JPS61217034A - Photosensitive composition and photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin composition and a photosensitive material giving a lithographic printing plate having a wide development latitude and superior printing resistance by using resol type phenol resin having a specified percentage or more of dibenzilic ether bonds. CONSTITUTION:Phenols represented by the formula [where each of R1, R2 and R3 is H, halogen, OH, NO2, 1-20C alkyl, alkoxy, acyl or (substituted) phenyl] are reacted with aldehyde such as H2CO or ketone to obtain resol type phenol resin having -CH2OCH2- bonded to each phenol ring by >=15mol% of the total amount of -CH2OCH2-, -CH2- and -CH2OH. The resol type phenol resin is blended with an o-quinonediazido compound, novolak type phenol resin, etc. to obtain a photosensitive composition. This composition is applied to an Al plate or the like and dried. The resulting photosensitive material is exposed through an original image and processed with an alkaline aqueous developer to dissolve and remove the exposed part. Thus, a lithographic printing plate having superior resolving power and printing resistance is obtd.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive composition and a photosensitive material containing the same, and more particularly to a lithographic printing plate, various photosensitive films, or a photosensitive material for manufacturing ICs. The present invention relates to a photosensitive composition used in a resist and a photosensitive material containing the same.

[Prior art]

A photosensitive composition comprising an 0-naphthoquinone diazide compound and a novolac type phenol resin is excellent as a photosensitive layer of a lithographic printing plate or a photoresist, and has been used industrially.

However, due to the properties of the novolak-type phenolic resin used as the main material, it has poor adhesion to the substrate, brittle film, poor coating properties, and poor abrasion resistance, resulting in poor printing durability when used in lithographic printing plates. There were some points that needed to be improved, such as insufficiency, and there were limits to its application.

In order to solve this problem, various polymer compounds have been investigated as binders. For example, special public relations
When the polyhydroxystyrene or hydroxystyrene copolymer described in Japanese Patent No. 1050 was used as a binder, film forming properties were certainly improved, but there was still a drawback of poor abrasion resistance. Furthermore, JP-A-51-34711 proposes the use of a polymer compound having a structural unit of an acrylic acid derivative in its molecular structure as a binder; The problem was that it was too narrow.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition that can be used in a wide range of appropriate development conditions and that can provide a lithographic printing plate with high stiffness resistance.

Another object of the present invention is to provide a photosensitive composition that has good adhesion to a substrate, provides a flexible film that is not brittle, and has excellent stability over time. Another object of the present invention is to provide a photosensitive material comprising such a photosensitive composition.

[Structure of the invention]

The object of the present invention is to provide compounds of the general formula (I) [wherein R,, R2 and R5 may be the same or different, hydrogen atom, halogen atom, hydroxyl group,
These include a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, a phenyl group, and a substituted phenyl group. ] The proportion of dibenzylic ether bonds (dimethylene ether bonds), methylene bonds, and methylol bonds bonded to the phenol nucleus obtained by the reaction of the phenol represented by the formula with aldehydes and/or ketones. The ratio of rick ether bonds is 15 mol%
This is achieved by a positive photosensitive composition characterized by containing the above resol type phenolic resin.

The resol type phenolic resin in the present invention is produced by subjecting phenols to aldehydes and/or ketones to a reflux reaction under neutral to weakly acidic conditions for 1 to 10 hours, followed by a reaction under normal pressure or reduced pressure at a temperature of 130°C or lower. Synthesized by removing water.

Examples of phenols represented by general formula (1) that can be used in the present invention include phenol, cresol,
Ethylphenol, chlorophenol, m-nitrophenol, p-acetylphenol, p-propionylphenol, p-butyrylphenol, methoxyphenol, phenylphenol, p-tolylphenol, cyclohexylphenol, isopropylphenol, t
ert-butylphenol, n-butylphenol, t
ert-amylphenol, n-amylphenol, t
ert-octylphenol, nonylphenol, dodecylphenol, hexylphenol, resorcin, methylresorcin, ethylresorcin, chlorresorcin, methoxyresorcin, phenylresorcin, cyclohexylresorcin, isopropylresorcin, tert
-butylresorcin, n-butylresorcin, tert
-amylresorcin, n-amylresorcin, tert
-Octylresorcinol, nonylresorcinol, dodecylresorcinol, hexylresorcinol, catechol, methylcatechol, ethylcatechol, chlorcatechol, methoxycatechol, phenylcatechol, cyclohexylcatechol, isopropylcatechol, tert-butylcatechol, n-butylcatechol, tert- Amylcatechol, n-amylcatechol, tert-octylcatechol, nonylcatechol, dodecylcatechol, hexylcatechol, hydroquinone, methylhydroquinone, ethylhydroquinone, chlorohydroquinone, methoxyhydroquinone, phenylhydroquinone, cyclohexylhydroquinone, isopropylhydroquinone, tert-butyl Hydroquinone, n-butylhydroquinone, tert-amylhydroquinone, n-amylhydroquinone, tert-octylhydroquinone, nonylhydroquinone, totylhydroquinone, hensylhydroquinone, pyrogallol, methylpyrogallol, chlorpyrogallol, methoxypyrogallol, ethylpyrogallol, phenyl pyrogallol, cyclohexylpyrogallol, isopropylpyrogallol, tart-7”-F/l/pyrogallol,
Examples include n-butylpyrogallol, tert-amylpyrogallol, n-amylpyrogallol, tert-octylpyrogallol, nonylpyrogallol, dodecylpyrogallol, hexylpyrogallol, 4'-dihydroxydiphenylmethane, 4'-isopropylidene diphenyl, and the like.

Examples of aldehydes and ketones used in the present invention include formalin, paraformaldehyde, polyoxymethylene, benzaldehyde, acetone, methyl ethyl ketone, dimethyl ketone, diethyl ketone, acetophenone, methylbenzaldehyde, ethylbenzaldehyde, and tert-butylbenzaldehyde. , methylacetophenone, benzophenone, methylbenz'phenone, dimethylbenzophenone and the like. Preferred are formalin, paraformaldehyde, and polyoxymethylene.

The resol-type phenolic resin used in the present invention is a resol-type phenolic resin obtained by condensing these phenols with aldehydes and ketones in combination with each other, or by co-condensing a mixture of two or more of these. It is a phenolic resin.

As a catalyst to make the reaction system neutral or weakly acidic,
Metal naphthenates such as lead naphthenate, manganese naphthenate, and zinc naphthenate; metal acetates such as lead acetate and zinc acetate; and metal salts of borates such as lead borate, zinc halide, and magnesium halide. Can be mentioned. These catalysts can also be used in combination with inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as benzoic acid, salicylic acid, oxalic acid, maleic acid, and p-toluenesulfonic acid, which are commonly used as catalysts.

When the molecular structure of the phenolic resin of the present invention is analyzed by 'H-NMR spectroscopy, significant characteristics are recognized in the shape of the bond of the aldehyde bonded to the phenol nucleus. The forms of bonds of aldehydes bonded to the phenol nucleus mainly consist of dipendylic ether (dimethylene ether) bonds, methylene bonds, and methylol groups, and the resin has a dibenzylic ether bond that accounts for the total number of these bonds. A resol type phenolic resin with a proportion of 15 mole percent or more.

Next, typical synthesis examples and comparative examples of the resol type phenolic resin in the present invention will be shown.

Synthesis Example 1 A reaction apparatus equipped with a stirrer, a reflux condenser, and a thermometer was charged with 1000 parts by weight of phenol and 480 parts by weight of 80% paraformaldehyde. After adjusting the pH of the reaction system to 6.0 by adding zinc naphthenate, the reaction system was heated and refluxed for 4.5 hours. Subsequently, it was dehydrated under normal pressure and heated until the internal temperature reached 115°C.

Further, under reduced pressure of 30 to 40 Torr, the temperature was raised until the internal temperature reached 123°C to remove moisture, thereby obtaining a resol type phenol resin having dibenzylic ether bonds.

Synthesis Example 2 700 parts by weight of phenol was added to the same reactor as Synthesis Example 1.
300 parts by weight of para-cresol and 580 parts by weight of 85% paraformaldehyde were charged.

After adjusting the pH of the reaction system to 6.3 by adding lead acetate, the temperature was raised and the mixture was refluxed for 3 hours. Subsequently, it was dehydrated under normal pressure and heated until the internal temperature reached 118°C. Further 35 to 55 Tor
The water was removed by raising the temperature to an internal temperature of 120° C. under reduced pressure of r, to obtain a resol type phenol resin having a dibenzylic ether bond.

Synthesis Example 3 Phenol 750 was added to the same reactor as Synthesis Example 1.
60% metacresol (contains 40% paracresol) 250 parts by weight, 88% paraformaldehyde 3
00 parts by weight, and 790 parts by weight of 37% formalin. After adjusting the pH of the reaction system to 6.5 by adding manganese naphthenate, the reaction system was heated and refluxed for 5 hours. Thereafter, in the same manner as in Synthesis Example 1, a resol type phenol resin having a dibenzylic ether bond was obtained.

Synthesis Example 4 60% 0% Metaphresy 4 in the same type of reaction apparatus as Synthesis Example 1
520 parts by weight of 000 weight 1i 1.80% paraformaldehyde was charged. By adding zinc naphthenate, the p of the reaction system
After adjusting H to 6.0, the temperature was raised and the mixture was refluxed for 4.5 hours.

Subsequently, it was dehydrated under normal pressure and heated until the internal temperature reached 115°C. Furthermore, under reduced pressure of 30 to 45 Torr, the internal temperature was 1
The temperature was raised to 23° C. to remove water, and a resol type phenol resin having dibenzylic ether bonds was obtained.

Synthesis Example 5 30 2-methylresorcinol was added to the same reactor as Synthesis Example 1.
0 parts by weight of para-cresol, 700 parts by weight of IN, and 580 parts by weight of 85% paraformaldehyde. After adjusting the pH of the reaction system to 6.3 by adding lead acetate, the temperature was raised and the mixture was refluxed for 3 hours. Next, dehydrate under normal pressure until the internal temperature reaches 118℃.
heated until. Furthermore, under a reduced pressure of 35 to 55 Torr, the temperature was raised until the internal temperature reached 120°C to remove moisture.
A resol type phenolic resin having dipendylic ether bonds was obtained.

Synthesis Example 6 In a reactor of the same type as Synthesis Example 1, 800 parts by weight of phenol,
200 parts by weight of 60% metacresol and 440 parts by weight of 80% paraformaldehyde were charged. After adjusting the pH of the reaction system to 6.0 by adding zinc naphthenate, the temperature was raised to 4.
It was refluxed for 5 hours. Next, dehydrate under normal pressure until the internal temperature reaches 1.
It was heated to 15°C. Furthermore, 30 to 45 Torr
The temperature was raised to an internal temperature of 123° C. under reduced pressure to remove moisture, thereby obtaining a resol type phenol resin having dibenzylic ether bonds.

Comparative Example 1 A reactor of the same type as Synthesis Example 1 was charged with 1,000 parts by weight of phenol and 950 parts by weight of 37% formalin, and after adding 45 parts by weight of 25% aqueous ammonia, the mixture was heated and refluxed for 1 hour. Subsequently, it was dehydrated under reduced pressure of 80 to 100 Torr and heated until the internal temperature reached 78°C. Another 30~45To
The degree of vacuum was increased to rr and dehydration was performed until the internal temperature reached 85°C to obtain a normal resol type phenol resin.

Comparative Example 2 700 parts by weight of phenol was added to the same reactor as Synthesis Example 1.
300 parts by weight of 60% metacresol and 1240 parts by weight of 37% formalin were charged.

40 parts by weight of 25% caustic soda and 30 parts by weight of 25% aqueous ammonia
After adding parts by weight, the temperature was raised and refluxed for 55 minutes. A normal resol type phenol resin was obtained in the same manner as in Comparative Example 1.

Comparative Example 3 60% metacresol 10 was added to the same reactor as Synthesis Example 1.
00 parts by weight and 560 parts by weight of 37% formalin were charged. After adding 5 parts by weight of oxalic acid, the temperature was raised and refluxed for 90 minutes. Subsequently, it was dehydrated under normal pressure and heated until the internal temperature reached 150°C. Further, the pressure was reduced to 30 to 45 Torr, and the temperature was raised to an internal temperature of 180° C., moisture was removed, and the novolac type Talesol resin was used.

These Synthesis Examples 1.2.3.4.5.6 and Comparative Example 1.
Regarding the phenolic resin obtained in 2.3, JIS
The gelation time was measured by K69090150°C hot plate method. The results are shown in Table 1.

The resol type phenolic resin having a dibenzylic ether bond obtained in Synthesis Example 1.2.3.4.5.6 has a higher level of resol type phenolic resin than the normal resol type phenolic resin obtained in Comparative Example 1.2.3. It can be seen that the gelation time is extremely long and the thermal stability is excellent.

Furthermore, regarding the phenolic resins obtained in Synthesis Example 1.2.3.4.5.6 and Comparative Example 1.2.3, 'H-
The form of bonding to the phenolic nucleus was analyzed by NMR spectroscopy. The analysis results are shown in Table 2.

The phenolic resin according to Synthesis Example 1.2.3.4.5.6 has a much higher content of dibenzylic ether bonds than the resin according to Comparative Example 1.2.3. If the dibenzilic ether bond content is less than 20%, thermal stability and stability over time will be poor, which is not preferable.

The amount of the resol type phenolic resin in the photosensitive composition according to the present invention is 2 to 98% by weight, preferably 5 to 9% by weight.
5% by weight is suitable.

(Photosensitive Composition) The photosensitive composition of the present invention in which the above resol type phenolic resin is added as a binder will be described below.

(1) Composition consisting of O-quinonediato compound This composition contains an O-quinonediazide compound and a binder as main components. Particularly preferred 0-quinonediazide compounds are 0-naphthoquinonediazide compounds, such as U.S. Pat.
No. 2, No. 2.772.972, No. 2.859.1
No. 12, No. 2.907.665, No. 3.046.
No. 110, No. 3.046.111, No. 3.046
゜No. 115, No. 3.046.118, No. 3.04
6.119, 3.046.120, 3.0
46.121, 3,046, 122, 3.
No. 046.123, No. 3.061.430, No. 3
．． No. 102.809, No. 3.106.465, No. 3,635, 709, No. 3.647.443, and many other publications. It can be suitably used. Among these, 0-naphthoquinonediazide sulfonic acid ester or 0-naphthoquinonediazidecarboxylic acid ester of an aromatic hydroxy compound, and 0-naphthoquinonediazide sulfonic acid amide or 0-naphthoquinonediazidecarboxylic acid amide of an aromatic amino compound are particularly preferred. , especially those obtained by subjecting a condensate of pyrogallol and acetone to an ester reaction with 0-naphthoquinonediazide sulfonic acid as described in U.S. Pat.
．． 028.111 to the polyester having a hydroxyl group at the end.

- naphthoquinonediazide sulfonic acid, or.

- Ester-reacted naphthoquinonediazidecarboxylic acids, homopolymers of p-hydroxystyrene as described in British Patent No. 1.494.043, or copolymerizable monomers thereof with other copolymerizable monomers. A polymer prepared by ester reaction with 0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid is very good.

Although these 0-quinonediazide compounds can be used alone, it is preferable to use them in combination with an alkali-soluble resin as a binder. Suitable alkali-soluble resins include novolak-type phenolic resins, and specifically include phenol formaldehyde resins, 0-cresol formaldehyde resins, m-cresol formaldehyde resins, and the like. Additionally, U.S. Patent No. 4,123
．． As described in the specification of No. 279, in addition to the above-mentioned phenol resin, a condensation product of phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms such as 1-butylphenol formaldehyde resin and formaldehyde. It is even more preferable to use these together.

The content of the binder is suitably 50 to 90% by weight, preferably 60 to 80% by weight, based on the total weight of the photosensitive composition.

In addition to the resol type phenolic resin according to the present invention, this composition includes polyvinyl formal resin, polyvinyl acetal resin such as polyvinyl butyral resin, linear polyurethane resin, anionic polyurethane resin, epoxy resin, nylon, polyester resin, Acrylic resins and the like can be used alone or in combination, and the appropriate amount to be added is 2 to 40% by weight. In addition, pigments, dyes, plasticizers, etc. can be added as necessary.

(2) A composition comprising a compound that is decomposed by an acid. This composition preferably includes (a) a compound that generates an acid upon irradiation with actinic rays, (a) a compound that decomposes by an acid, and (
C) Consists of a polymer compound as a binder.

(a) Compounds that generate acids upon irradiation with actinic rays include diazonium, phosphonium, sulfonium, and iodonium BF, -, PF6-. 5bFs-,5
iFs-1Cj! Salts such as 04-, organohalogen compounds, orthoquinonediazide sulfonyl chlorides 1, organometallic/organohalogen compound combinations, U.S. Patent 3.779
．． 778 and West German Patent No. 2.610.842, which generate acid upon photolysis.

(6) Compounds decomposed by acids include acetals or O,N-acetal compounds (Japanese Patent Application Laid-open No. 8900-1989)
No. 3), orthoester or amide acetal compound (
JP-A-51-120714), polymers having acetal or ketal groups in the main chain (JP-A-53-13342);
No. 9), enol ether compound (JP-A-55-129)
No. 95), N-acylimino carbonic acid compounds (Japanese Patent Application Laid-open No. 1987-
126236), polymers having an orthoester group in the main chain (Japanese Patent Application Laid-Open No. 17345-1982), and compounds having a silyl ether group (Japanese Patent Application Laid-open No. 146095-1987)
etc.

As the binder (C), an alkali-soluble resin is preferable. Suitable alkali-soluble resins include novolac type phenolic resins, and specifically include phenol formaldehyde mtlLo-cresol formaldehyde resin, m-cresol formaldehyde resin, and the like. Furthermore, as described in U.S. Pat. No. 4,123,279, t-
When used in combination with a phenol substituted with an alkyl group having 3 to 8 carbon atoms, such as butylphenol formaldehyde resin, or a condensate of cresol and formaldehyde,
Even more preferred. The total content of the binder together with the resol type phenolic resin according to the present invention is suitably about 5 to about 98% by weight, more preferably 20 to 95% by weight, based on the total weight of the photosensitive composition.

In addition to the resol type phenolic resin according to the present invention, this composition includes polyvinyl formal resin, polyvinyl acetal resin such as polyvinyl butyral resin, linear polyurethane resin, anionic polyurethane resin, epoxy resin, nylon, polyester resin, acrylic resin. These resins can be used alone or in combination, and the appropriate amount of such resins to be added is 2 to 40% by weight.

Furthermore, dyes, pigments, plasticizers, and compounds that increase the acid generation efficiency of the acid-generating compound (so-called sensitizer) can be contained.

Suitable dyes include oil-soluble dyes and basic dyes.

Specifically, oil yellow #101, oil yellow #130, oil pink #312, oil green B
G, Oil Blue BO3, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T'-505 (manufactured by Orient Chemical Industry Co., Ltd.)
, exolistal violet (CI42555), methyl violet (CI42535), rhodamine B (CI
45170B), malachite green (CI42000
), methylene blue (CI52015), etc.

These dyes are preferably added singly or in combination in an amount of 0.3 to 15% by weight based on the total photosensitive composition. Furthermore, compounds that interact with these dyes to generate photodecomposition products that change the color tone, such as JP-A-50-3620
0-naphthoquinonediazide-4-sulfonic acid halide described in JP-A-53-36223, trihalomethyl-2-pyrone and trihalomethyltriazine described in JP-A No. 55-62444, 0-Naphthoquinone diester compound, JP-A-55-777
2-trihalomethyl-5-aryl-1,3°4-oxadiazole compounds described in Japanese Patent No. 42 can be added. These compounds can be used alone or in combination, and the amount added is preferably 0.3 to 15% by weight.

The composition of the Ikemizu invention contains fillers, cellulose alkyl ethers for improving coating properties, and ethylene oxide surfactants (for example, 3M FC-
430, FC-431), and in order to improve the physical properties of the coating film, for example, dibutyl phthalate, butyl glycolate,
Various additives can be added depending on various purposes, such as plasticizers such as tricresyl phosphate and dioctyl adipate. Adding a filler not only makes it possible to further improve the physical properties of the coating film, but also makes it possible to make the surface of the photosensitive layer matte, which improves vacuum adhesion during image printing and eliminates so-called burnout blur. It can be prevented. Such fillers include talcum powder, glass powder, clay, starch, wheat flour, corn flour, Teflon powder, and the like.

(Support) Supports that can be used to produce photosensitive materials by applying the photosensitive composition of the present invention include aluminum, paper, plastic films, and laminates thereof that have been subjected to appropriate surface treatment. can give.

The material of the plastic film is, for example, polyethylene,
Polyolefins such as polypropylene, polyvinyl acetate,
Examples include vinyl polymers such as polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene-2°6-naphthalate, and cellulose acetates such as cellulose triacetate. Examples of laminates include paper coated on both sides with surface-treated aluminum, polyethylene terephthalate film coated with surface-treated aluminum on both sides or one side, and polypropylene film coated with both sides or one side coated with surface-treated aluminum. Examples include those coated with treated aluminum.

(Photosensitive material) To produce a photosensitive material using the photosensitive composition according to the present invention, the composition is dissolved in a solvent, applied to a support, and dried. As a solvent, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, n-butyl propionate, 3,3-dimethyl butyl acetate, 2-ethoxytetrahydropyran,
Ethylene glycol-mono-t-butyl ether, toluene, ethyl acetate, 2-heptanone, 2,4-pentanedione, methyl cellosolve, ethyl cellosolve, acetone, methanol, dimethylformamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, water, etc. Yes, these solvents can be used alone or in combination.

A suitable solid content concentration is 2 to 50% by weight. Coating is generally carried out using coating equipment such as gravure coat, bar code, reverse roll coat, whiler, spinner, curtain, extrusion bead, and slice bead. Further, in order to control the surface properties of the photosensitive material, a protective layer or matte layer which is soluble or permeable to developing water may be provided.

The photosensitive material prepared as described above is first exposed to actinic light. Examples of active light sources include:
There are mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon lamps. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such laser beams include helium-neon lasers, argon lasers, krypton ion lasers, helium-cadmium lasers, and the like.

Examples of the developer for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, sodium diphosphate, and tertiary phosphate. Aqueous solutions of inorganic alkaline agents such as ammonium acid, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic alkaline agents such as monoethanolamine or jetanolamine are suitable;
Their concentration is 0.1-10% by weight, preferably 0.5
It is added in an amount of ~5% by weight.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the cough alkaline aqueous solution as necessary.

〔Effect of the invention〕

According to the present invention, a photosensitive material can be obtained that has an appropriate range of development conditions, excellent stability over time, and can be heat-treated at a low temperature after development. Further, according to the present invention, a printing plate without printing stains and having high printing durability can be obtained.

〔Example〕

The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A 28 material aluminum plate with a thickness of 0.3 mm was degreased by immersing it in a 10% aqueous solution of trisodium phosphate held at 80°C for 30 seconds, while pouring pumice slurry onto the aluminum plate. It was rubbed with a nylon brush to create a grain, then etched with sodium aluminate at 60° C. for 10 seconds, and then washed with a 3% aqueous sodium hydrogen sulfate solution.

This aluminum plate was heated at a current density of 2A/d in 20% sulfuric acid.
m” for 2 minutes and then anodized at 70 m
treated with a 2.5% silicic acid (U) aqueous solution for 1 min at
Washed with water and dried. Subsequently, the following photosensitive solution was applied using a wheeler and dried at 100° C. for 2 minutes.

3 g of the novolac-type cresol resin described in Comparative Example 3 2.5 g of the resol-type phenol resin described in Synthesis Example 1 0.4 g Methyl ethyl ketone 75 g Cyclohexanone 60 g After drying, the film weight is 2.5
g 7m2.

This will be referred to as sample [A]. For comparison, a photosensitive solution obtained by removing the resol type phenol resin from the above photosensitive liquid and adding 5.5 g of the novolac type cresol resin described in Comparative Example 3 was coated and dried in the same manner. The weight of the membrane after drying is 2.
It was 5 g/m'. This is referred to as sample CB).

Furthermore, for comparison, the same amount of the ordinary resol type phenol resin described in Comparative Example 1 was used in place of the resol type phenol resin described in Synthesis Example 1 used in the photosensitive liquid, and the same amount was applied and dried in the same manner. Membrane weight after drying is 2.5 g/m
'Met. This will be referred to as sample [C].

The photosensitive lithographic printing plate made in this way was passed through a transparent positive film in a vacuum printing frame from a distance of 1 m to Fuji Film PS Light (Toshiba Metal Halide Lamp M).
Exposure was performed for 30 seconds using a U2000-2-OL model (model U2000-2-OL, equipped with a 3 kW light source and sold by Fuji Photo Film). Subsequently, the plate was immersed in a developer having the following composition for development.

JISI Sodium Silicate 10g Sodium Metasilicate 5g Pure Water
1 8 0mj! Sample [A] according to the present invention is sample [B] which is a comparative example.
Similarly, the exposed area was dissolved and the unexposed area was not dissolved and an image was formed, but in Sample C, which is a comparative example, a portion of the end exposed area was also dissolved and a complete image was not formed.

After washing samples [A] and CB] with water, a 14°Be gum arabic solution was applied to the plate surface and puff-dried. After storing the completed printing plate for 7 days, Heidelberg G, T
, printed on an O1 printing machine.

Sample [A] according to the present invention has a printing durability of 10,000 sheets,
A sample as a comparative example had a BE of 80,000 sheets. That is, sample [A] according to the present invention has excellent developability and printing durability.

Example 2 The following photosensitive solution was applied to the support used in Example 1 using a wheeler and dried at 100° C. for 2 minutes.

2.5 g of the novolak-type cresol resin described in Comparative Example 3 2.5 g of the resol-type phenol resin described in Synthesis Example 3 0.4 g Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.4 g Methyl ethyl ketone 75 g Cyclohexanone 60 g Membrane after drying Weight is 2.7g
/m". This is referred to as sample [D]. For comparison, the resol type phenolic resin described in Comparative Example 2 was replaced with the resol type phenolic resin described in Synthesis Example 3 used in the photosensitive liquid. Using the same amount, the film was applied and dried in the same manner.The film weight after drying was 2.7 g/m'.This is designated as sample [E].

Samples [D] and [E] which were removed in this way and the comparative example sample of Example 1 (BE at a temperature of 45°C and a humidity of 7
It was stored for 2 weeks in a 5% air constant temperature bath.

The photosensitive lithographic printing plate thus produced was placed in a vacuum printing frame through a transparent positive film from a distance of 1 m using Fuji Film PS Light (Toshiba Metal Halide Lamp M).
LI2000-2-OL type, equipped with a 3KW light source, sold by Fuji Photo Film)
Exposure was performed for seconds.

Subsequently, the plate was immersed in a developer having the following composition for development.

JISI Sodium Silicate 10g Sodium Metasilicate 5g Pure Water
After washing 180 ml of each lithographic printing plate with water, a 14°Be gum arabic solution was applied to the plate surface and puff-dried.

The completed printing plate was sent to Heidelberg G and T.

0. Printing was carried out by attaching it to a mold printing machine.

Sample [D] according to the present invention, sample [D] which is a comparative example
In sample [B], a print without stains was obtained both before and after storage, whereas in sample [E], which is a comparative example, a print without stains was obtained before storage, but some stains appeared after storage. Ta. On the other hand, the printing durability is 80,000 sheets for sample [D].
Sample [B] was 60,000 pieces. That is, sample CD according to the present invention] has excellent stability over time and printing durability.

Showa year, month, day I, case description 1985 patent application No. 57797 2, title of invention Photosensitive composition and photosensitive material 3
, Relationship to the case of the person making the amendment Applicant Name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Date of amendment order Voluntary

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1, R_, and R_3 may be the same or different, and include a hydrogen atom, a halogen atom, a hydroxyl group, These include a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, a phenyl group, and a substituted phenyl group. ] The ratio of dibenzylic ether bonds to the total of dibenzylic ether bonds, methylene bonds, and methylol bonds bonded to the phenol nucleus obtained by the reaction of the phenol expressed by the formula with aldehydes and/or ketones is A photosensitive composition comprising 15 mol% or more of a resol type phenolic resin. (2) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, a phenyl group, and a substituted phenyl group. ] The ratio of dibenzylic ether bonds to the total of dibenzylic ether bonds, methylene bonds, and methylol bonds bonded to the phenol nucleus obtained by the reaction of the phenol expressed by the formula with aldehydes and/or ketones is A photosensitive material comprising a photosensitive composition containing 15 mol% or more of a resol type phenolic resin.