JPS61217035A - Production of printing plate - Google Patents

Abstract

PURPOSE:To obtain a printing plate causing no printing stain and having superior printing resistance by subjecting a photosensitive material using a photosensitive composition contg. resol type phenol resin having a specified percentage or more of dibenzilic ether bonds to exposure, development and curing by heating to a specified temp. or above. 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. A soln. of a photosensitive composition contg. diazo resin as well as the resol type phenol resin is applied to an Al plate and dried to produce a photosensitive material. This material is exposed, developed with an alkaline aqueous developer, and heated to >=140 deg.C. Thus, a printing plate causing no printing stain and having high printing resistance is obtd. by using the photosensitive material having superior developability and aging stability and curable at such a low temp.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing copying materials or printing plates by exposing, developing and then heat-treating a photosensitive material.

[Prior art]

In order to improve the printing durability of a printing plate obtained by exposing and developing a photosensitive material, a method of further heat-treating the plate to harden the image area is described, for example, in British Patent No. 1.151.19.
It is disclosed in the specification No. 9 and the specification No. 1.154.749. This heat treatment is performed at 180°C or higher, usually at 220°C.
The heating is carried out at a temperature of .degree. C. to 260.degree. C. for about 5 minutes to 60 minutes. However, when such high-temperature heat treatment is applied to a photosensitive material formed by coating a photosensitive composition containing a photosensitive compound and a novolac type phenolic resin or a resol type phenolic resin as a binder on a support, A drawback is that the composition in the image area thermally decomposes, staining the non-image area and causing stains on the printed matter.

Staining in non-image areas is more serious in the case of photosensitive materials using novolac type phenolic resins, which require relatively high temperature heating for curing of image areas. Although a method using an active solution has been proposed to remove stains from the non-image area, there is a risk that the stain may attack the image area. For this reason, as described in JP-A-51-34001 and JP-A-52-6205, it is possible to remove the image by coating it with a layer of water-soluble organic compounds or water-soluble inorganic salts before heat treatment. Methods have also been proposed to prevent soiling of the parts or to easily wash away adhering thermal decomposition products with water.

However, if the heat treatment temperature is high, the commonly used aluminum support may undergo thermal deformation and become unusable. In order to prevent such deformation of the support, it is desirable to perform the heat treatment at a low temperature.

Therefore, a method has also been proposed in which the heating temperature is lowered to below 200°C by adding a certain type of compound to the photosensitive composition. For example, West German Patent Publication No. 3.
No. 039.926 discloses a photosensitive composition containing a phenol derivative having 2 to 4 hydroxymethyl groups, and JP-A-59-113435 discloses a photosensitive composition containing a cyclic acid amide. Each of these compositions is disclosed. However, the addition of these compounds has the disadvantage that developability is impaired.

On the other hand, photosensitive materials using resol type phenolic resins have the disadvantage that developability deteriorates over time.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a method for manufacturing printing plates with no printing stains and high printing durability using photosensitive materials that have excellent developability and stability over time and can be cured by heating at low temperatures or in a short time. It is to provide.

[Structure of the invention]

The present inventors have discovered that the above object can be achieved by using a specific 17-sol type phenolic resin as a binder, and have completed the present invention.

The present invention is based on the general formula (I) R1 [wherein R1, R2 and R3 may be the same or different, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an alkyl group having 1 to 20 carbon atoms, alkoxy group,
They are 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 a method for producing a copying material or a printing plate, which is characterized in that a photosensitive material using a photosensitive composition containing the resol type phenolic resin as described above is exposed and developed, and then heated to a temperature of 140 t: or more.

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 (I) that can be used in the present invention include phenol, cresol,
Ethylphenol, chlorophenol, m-nitrophenol, p-acetylphenol, p-propionylphenol, p-butyrylphenol, methoxyphenol, phenylphenol, p-1 ruylphenol, cyclohexylphenol, isopropylphenol, t
ert-butylphenol, n-butylphenol, t
ert-amylphenol, n-amylphenol, t
art-octylphenol, nonylphenol, dodecylphenol, hexylphenol, resorcin, methylresorcin, ethylresorcin, chlorresorcin, methoxyresorcin, phenylresorcin, cyclohexylresorcin, isopropylresorcin, tert
-butylresorcin, n-butylresorcin, tart
-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, tart-amylhydroquinone, n-amylhydroquinone, tart-octylhydroquinone, nonylhydroquinone, dodecylhydroquinone, hexylhydroquinone, pyrogallol, methylpyrogallol, chlorpyrogallol, methoxypyrogallol, ethylpyrogallol, phenylpyrogallol,
Cyclohexylpyrogallol, isopropylpyrogallol, tert-butylpyrogallol, n-butylpyrogallol, tert-amylpyrogallol, n-amylpyrogallol, tert-octylpyrogallol, nonylpyrogallol, dodecylpyrogallol, hexylpyrogallol, 41-dihydroxydiphenylmethane, 4'-
Examples include isopropylidene diphenyl.

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, methylbenzophenone, 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.

'Catalysts to make the reaction system neutral or weakly acidic include naphthenic acid metal salts such as lead naphthenate, manganese naphthenate, and zinc naphthenate; acetate metal salts such as lead acetate and zinc acetate; and lead borate. , metal borates such as zinc oxalate and magnesium oxalate. 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 dibenzylic ether (dimethylene ether) bonds, methylene bonds, and methylol groups, but the resin has only a small proportion of dipendylic ether bonds in the total number of these bonds. It is a resol type phenolic resin in which the proportion of is 15 mol 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 to an internal temperature of 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 balacresol 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 t under a reduced pressure of r to obtain a resol type phenol resin having dibenzylic ether bonds.

Synthesis Example 3 In a reactor of the same type as Synthesis Example 1, 750 parts by weight of phenol was added.
60% meta-cresol (contains 40% vala-cresol) 250 parts, 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 dipendylic ether bonds was obtained.

Synthesis Example 4 60% metacresol 10 was placed in the same reactor as Synthesis Example 1.
00 weight IN, 520 parts by weight of 80% paraformaldehyde was charged. 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. Furthermore, under reduced pressure of 30 to 45 Torr, the internal temperature was 123
The temperature was raised to 0.degree. 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, 70 parts by weight of para-cresol, 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 and reduce the internal temperature to 118℃.
heated until. Further, under 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 with dibenzylic ether bonds was developed.

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 pu of the reaction system to 6.0 by adding zinc naphthenate, the temperature was raised to 4.
．． It was refluxed for 5 hours. Subsequently, it was dehydrated under normal pressure and heated until the internal temperature reached 115°C. Furthermore, 30 to 45 Torr
The water was removed by raising the temperature to an internal temperature of 123° C. under reduced pressure of r to obtain a resol type phenol resin having dibensilic ether bonds.

Comparative Example 1 1000 parts by weight of phenol and 950 parts by weight of 37% formalin were charged into a reaction apparatus of the same type as in Synthesis Example 1, 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 In the same type of reaction apparatus as Synthesis Example 1, Phenosif 00 was added.
300 parts by weight of 60% metacresol and 1240 parts by weight of 37% formalin were charged.

25% caustic soda 40% and 25% ammonia water 30%
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 until the internal temperature reached 180° C., and moisture was removed to obtain a novolac type cresol resin.

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 the 150° C. hot plate method using K6909. 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.

(I) Composition made of diazo resin Diazo resins, typified by the condensate of p-diazophenylamine and paraformaldehyde, may be water-soluble or
It may be water-insoluble, but preferably it is water-insoluble and soluble in common organic solvents. Particularly preferred diazo compounds include salts of condensates of p-diazophenylamine and formaldehyde or acetaldehyde, such as phenol salts, fluorocaprates, and triisopropylnaphthalenesulfonic acid, 4,4-biphenyldisulfonic acid, 5-nitroortho -Toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-
Chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, 2
-Salts of sulfonic acids such as -fluorocaprylnaphthalenesulfonic acid, -su7to-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid and para-toluenesulfonic acid, etc. It is a compound having two or more diazo groups. Other desirable diazo resins include 2.5-
Included are condensates of diazomethoxy-4-p-)lylmerkabutobenzenediasonium and formaldehyde, and condensates of 2,5-dimethoxy-4-morpholinobenzenediazonium and formaldehyde or acetaldehyde.

Also preferred are the diazo resins described in GB 1.312.925.

The diazo resin can be used alone as a photoresist for making a resist, but is preferably used in conjunction with a binder.

Various polymeric compounds can be used as such binders, but those containing groups such as hydroxy, amino, carboxylic acid, amide, sulfonamide, active methylene, thioalcohol, and epoxy are preferred. Such preferred binders include Shera ivy, described in GB 1.350.521, GB jK 1.46;
．． No. 0.978 and U.S. Pat. No. 4.123.276; No. 257, the polyamide resin described in British Patent No. 1. -074.392 and polyvinyl acecool resins such as polyvinyl formal resins, polyvinyl butyral resins, linear resins as described in U.S. Pat. No. 3,660,097, Polyurethane resin, polyvinyl alcohol phthalate resin, epoxy resin condensed from bisphenol A and epichlorohydrin, polymers containing amino groups such as polyaminostyrene and polyalkylamino(meth)acrylate, cellulose acetate, cellulose alkyl ether, cellulose acetate phthalate, etc. This includes celluloses and the like.

The content of the binder is suitably such that the total content of the binder together with the resol type phenolic resin according to the present invention is 30 to 95% by weight based on the total weight of the photosensitive composition. A more preferred amount of binder is about 40-90% by weight.

Compositions comprising diazo resins are further described in U.S. Patent No. 3.
236.646, phosphoric acid, dyes,
Additives such as pigments can be added.

(2) Composition consisting of an 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, in particular, 0-naphthoquinonediazide sulfonic acid ester or 0-naphthoquinonediazidocarboxylic acid ester of aromatic hydroxy compounds, and 0-naphthoquinonediazide sulfonic acid amide or 0-naphthoquinonediazidecarboxylic acid amide of aromatic amino compound. are preferred, particularly those prepared by esterifying a condensate of pyrogallol and acetone described in U.S. Pat. No. 3.635.709 and 0-naphthoquinonediazide sulfonic acid, and U.S. Pat. No. 4.028.111. British Patent No. 1.49, which is obtained by ester-reacting a polyester having a hydroxyl group at the end described in the specification with 0-naphthoquinonediazide sulfonic acid or O-naphthoquinonediazidecarboxylic acid.
0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid is added to a homopolymer of p-hydroxystyrene or a copolymer of this with other copolymerizable monomers as described in No. 4.043. Those subjected to ester reaction are very good.

Although these O-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
, 279, in addition to the above-mentioned phenol resins, phenol substituted with an alkyl group having 3 to 8 carbon atoms such as 1-butylphenol formaldehyde resin or a condensation product of cresol and formaldehyde can be used. It is even more preferable to use them 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.

(3) Composition Comprising a Photosensitive Azide Compound Suitable photosensitive azide compounds include aromatic azide compounds in which the azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group. In these, the azide group is decomposed by light to produce nitrene, which undergoes various reactions and becomes insolubilized. Preferred aromatic azide compounds include compounds containing one or more groups such as azidophenyl, azidostyryl, azidobenzal, azidobenzoyl and azidocinnamoyl, e.g.
．． 4'-Diazidochalcone, 4-azido-4'-(4
-azidobenzoylethoxy)chalcone, N, N-bis-p-azidobenzal-p-phenylenediamine, 1
,2.6-)li(4'-azidobenzoxy)hexane, 2-azido-3-chloro-henzquinone, 2.4-
Diazide-4'-ethoxyazobenzene, 2,6-di(
4°-azidobenzal)-4-methylcyclohexanone, 4.4′-diazidobenzophenone, 2.5-diazido-3,6-cyclopenzoquinone, 2°5-bis(4
-azidostyryl)-1,3,4-oxadiazole,
2-(4-azidocinnamoyl)thiophene, 2.5-
Di(4″-azidobenzal)cyclohexanone, 4,4
°-Diazidiphenylmethane, 1-(4-azidophenyl)-5-furyl-2-penta-2,4-diene-1
-one, 1-(4-acidophenyl)-5-(4-methoxyphenyl)-penta-1°4-dien-3-one,
1-(4-azidophenyl)-3-(I-naphthyl)propen-1-one, 1-(azidophenyl)-3-(4
-dimethylaminophenyl)-propan-1-one, 1
-(4-azidophenyl)5-phenyl-1゜4-pentadien-3-one, 1-(4-azidophenyl)-3
-(4-nitrophenyl)-2-propen-1-one,
1-(azidophenyl)-3-(2-furyl)-2-propen-1-one, 1,2.6-)su(4°-azidobenzoxy)hexane, 2,6-bis-(4-azidobenzoxy) lysine-pt-butyl)cyclohexanone, 4,4
゛-Diazidobenzalacetone, 4-4''-diazidostilbene-2,2°-disulfonic acid, 4''-azidopendelacetophenone-2-sulfonic acid, 4,4''-diazidostilbene-α-carboxylic acid , G (4-azido-
2°-hydroxybenzal)acetone-2-sulfonic acid, 4-azidopendelacetophenone-2-sulfonic acid, 2-azido-1,4-dibenzenesulfonylaminonaphthalene, 4,4°-diazide-stilbene-2, 2'
-Disulfonic acid nilide, etc. can be mentioned.

In addition to these low molecular weight aromatic azide compounds, Japanese Patent Publications No. 44-9047, No. 44-31837, No. 45-
No. 9613, No. 45-24915, No. 45-2571
Also suitable are the azide group-containing polymers described in JP-A-50-5102, JP-A-50-84302, JP-A-50-84303, and JP-A-53-12984.

These photosensitive azide compounds are preferably used together with a polymer compound as a binder. Preferred binders include alkali-soluble resins, such as natural resins such as shellac and rosin, novolac type phenolic resins such as phenol formaldehyde resin and m-cresol formaldehyde resin, and polyacrylic acid, polymethacrylic acid, and methacrylic acid-styrene resins. Polymers, homopolymers of unsaturated carboxylic acids such as methacrylic acid-methyl acrylate copolymers, styrene-maleic anhydride copolymers, or copolymers of these with other copolymerizable monomers, polyacetic acid Included are resins obtained by partially or completely saponified vinyl partially acetalized with aldehydes such as acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and carboxybenzaldehyde, and polyhydroxystyrene. Furthermore, organic solvent soluble resins including cellulose alkyl ethers such as cellulose methyl ether and cellulose ethyl ether can also be used as binders.

The binder is preferably contained in such a manner that the total amount together with the resol type phenolic resin according to the present invention is in the range of about 10% by weight to about 90% by weight based on the total weight of the composition comprising the photosensitive azide compound.

The composition comprising the photosensitive azide compound may further contain dyes and pigments, plasticizers such as phthalates, phosphoric esters, aliphatic carboxylic esters, glycols, and sulfonamides, such as Ebamichler ketone and 9-fluorenone. , 1-ditropylene, 1,8-dinitropyrene, 2-
Chloro-1,2-benzanthraquinone, 2-bromo-
Additives such as sensitizers such as 1,2-benzanthraquinone, pyrene-1,6-quinone, 2-chloro-1,8-phthaloylnaphthalene, and cyanoacridine can be added.

○ Those whose main component is a photosensitive polymer such as polyesters, bohelamides, and polycarbonates containing -CH=CH-C- as a photosensitive group in the polymer main chain or side chain (for example, U.S. Patent No. 3.030.2
No. 08, No. 3.707.373 and No. 3.453
．． Compounds as described in each specification of No. 237)
; Those whose main components are photosensitive polyesters derived from (2-properidene) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols (for example, U.S. Pat. No. 2.956.878 and U.S. Pat. 3.173.78
Photosensitive polymers as described in each specification of No. 7)
; cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose and their analogs (
For example, U.S. Patent No. 2,690.966, U.S. Pat.
2.372, 2.732.301, etc.). These compositions may also contain sensitizers, stabilizers, plasticizers, pigments, dyes, and the like.

(5) Photopolymerizable composition comprising an addition polymerizable unsaturated compound This composition preferably comprises (a) a vinyl monomer having at least two terminal vinyl groups, (b) a photopolymerization initiator and (C) Consists of a polymer compound as a binder.

As the vinyl monomer of component (a), Japanese Patent Publication No. 35-50
No. 93, Special Publication No. 35-14719, Special Publication No. 44-28
Acrylic or methacrylic acid esters of polyols, namely diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, as described in each publication No. 727. ) acrylates, etc., or bis(meth)acrylamides such as methylene bis(meth)acrylamide and ethylene bis(meth)acrylamide, or unsaturated monomers containing urethane groups, such as di(2°~ methacryloxyethyl)- 2,4-) Relene diurethane,
Examples include reaction products of diol mono(meth)acrylate and diisocyanate such as di(2'-acryloxyethyl)trimethylene diurethane.

Examples of the photopolymerization initiator of component (b) include J.

"Light Sensitive Systems" by Kosar, No. 5
Examples include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes as described in Chapter 1. More specifically, it is disclosed in British Patent No. 1,459,563.

On the other hand, various known polymers can be used as the binder for component (C). Details of specific binders are provided in US Pat. No. 4,072,527. Furthermore, the chlorinated polyolefins described in GB 1.459.563 are particularly preferred binders.

Component (a) and component (C) containing the resol type phenolic resin according to the present invention are contained in combination in a weight ratio of 1=9 to 6=4. In addition, component (a) is contained in an amount of 0.5 to 10% by weight based on component (a).

The photopolymerizable composition can further contain a thermal polymerization inhibitor, a plasticizer, a dye, and a pigment.

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

(a) Compounds that generate acid upon irradiation with actinic rays include diazonium, phosphonium, sulfonium, and iodonium BF, -, pps-, 5bFs-,
S+Fs-, CI! 0. Salts such as -, organohalogen compounds, orthoquinonediazide sulfonyl chloride 1, organometallic/organohalogen compound combinations, U.S. Patent 3.77
No. 9.778 and West German Patent No. 2.610,842
Examples include compounds that generate acids upon photolysis and are described in the specification of No.

(b) Compounds decomposed by acids include acetals or O,N-acetal compounds (Japanese Patent Application Laid-Open No. 48-8900
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 novolak-type phenolic resins, and specifically include phenol formaldehyde m IIL O-cresol formaldehyde resin, m-9 resol formaldehyde resin, and the like. Furthermore, as described in U.S. Pat. No. 4,123,279, along with the above-mentioned phenolic resins,
It is even more preferable to use 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 in combination. 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 II resin, polyvinyl acecool 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 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 9130, 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.)
, crystal violet (CI42555), methyl violet ((, I42535), rhodamine B (C
I45170B), malachite green (CI4200
0), 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-55-62444, Various 0-naphthoquinonediazide compounds, 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 coating the photosensitive composition of the present invention include aluminum, paper, plastic films, and laminates thereof that have been subjected to appropriate surface treatment. can be given.

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:
Examples include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc 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 a helium-neon laser, an argon laser, a krypton ion laser, and a helium-cadmium laser.

As the developer for the photosensitive composition of the present invention, for example, Japanese Patent Publication No. 56-42860, Japanese Patent Application Laid-Open No. 50-26601
No., U.S. Patent No. 3.669.660, ○L33.10
0.259A 1, JP-A-57-136647, Special M
No. 56-153341, 0L32.809,774,
DA Sl, 447.946, U.S. Patent No. 3.707
．． 373, British Patent No. 1.322.325, Japanese Patent Publication No. 49-14681, DASl, 622.297, Japanese Patent Publication No. 47-39895, Japanese Patent Publication No. 47-32682, U.S. Patent No. 3.645.732, Japanese Patent Publication No. 52-1430
No. 19, JP-A-55-59459, JP-A-58-25
2064 and the like can be used. More specifically, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate,
・Ammonium triphosphate, ammonium diphosphate,
Aqueous solutions of inorganic alkaline agents such as sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic alkaline agents such as monoethanolamine or jetanolamine are suitable, and their concentrations are 0.1 to 10% by weight. , preferably in an amount of 0.5 to 5% by weight.

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

(Heat curing treatment of photosensitive material) Heat curing treatment is performed to further improve the printing durability and the like of the developed photosensitive material. This heat treatment can be performed by various known methods such as those described in Japanese Patent Publication No. 47-44045. A photosensitive material using a photosensitive composition containing a resol type phenolic resin of the present invention can be heat-cured more easily than conventional materials, and can improve printing durability and the like. For example, a printing plate using a photosensitive composition containing a resol-type phenolic resin of the present invention can be heated at a lower temperature than before, or at the same temperature for a shorter time than before, to produce a printing plate that is equivalent to or equal to a conventional product. This results in a printing plate with longer printing durability.

Generally, the imaging materials of the present invention are prepared at 140°C to 260°C.
, especially at temperatures in the range of 150°C to 210°C, for 20 seconds to 2
The purpose can be achieved by heat treatment for 0 minutes, especially 1 to 7 minutes. If a support material that is stable even at a temperature higher than the upper limit of this temperature range is used, the heat treatment can be performed at a temperature higher than this upper limit. Therefore, in this case, the heating time can be further shortened.

However, in general, when the heat treatment temperature is high, non-image areas tend to become dirty. For this reason, pretreatment with a water-soluble compound and the like have conventionally been performed before this heat treatment. Although such pretreatment can be carried out when heat-treating the photosensitive material of the present invention, it is usually not necessary. Particularly when heat treatment is carried out at a low temperature, for example, 140 DEG C. to 180 DEG C., contaminants hardly adhere to non-image areas, and even if they do, they can be easily removed. Therefore, for the photosensitive material of the present invention, such treatment before heat treatment can usually be omitted.

The photosensitive material of the present invention heat-treated in this way is
Various organic solvents, printing inks, plate cleaners, PI
It is insoluble in ink and other chemicals used in plate-making and printing processes, and there are concerns about its chemical resistance.

〔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 nylon black 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
It was treated with a 2.degree. C. 5% aqueous sodium silicate solution for 1 minute, washed with water and dried. Subsequently, the following photosensitive solution was applied using a wheeler and dried at 100° C. for 2 minutes.

The membrane weight after drying was 2.5 g/m2.

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].

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 (Touhou Metal Halide Lamp M).
Exposure was carried out for 30 seconds using a U2000-2-OL model (model U2000-2-OL, equipped with a 3 kW light source, 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
180mj! sample[
Similar to sample [B), in A), the exposed areas were dissolved and the unexposed areas were not dissolved, forming an image.

After washing samples [A] and [B] with water, a gum arabic solution of 14@Be was applied to the plate surface and puff-dried. After storing the completed printing plate for 7 days, Heidelberg G, T
,0. Printed by attaching it to a mold printing machine.

The printing durability is 100,000 sheets for sample [A], and 100,000 sheets for sample [B].
) was 80,000 pieces. Next, in order to increase the printing ability, samples [A] and [B] after the development treatment were placed in a heating furnace for 4 hours.
After heating at 200°C for minutes, a 14°B6 gum arabic solution was applied to the printing plate and puff-dried. After storing the thus completed printing plates [A]' and [B]° for 7 days, they were transferred to Heidelberg G and T.

○: Printed by attaching it to a mold printing machine. The number of printing sheets of sample [A]° according to the present invention was 250,000 sheets, which was significantly increased compared to 100,000 sheets of sample [B]°, which is a comparative example.

In addition, this sample [A] becomes insoluble in organic solvents such as methyl ethyl ketone, acetone, and alcohol.
Chemical resistance was significantly increased.

Example 2.3.4 The following photosensitive solution was applied to the support used in Example 1 using a wheeler and dried at 100° C. for 2 minutes.

Methyl ethyl ketone 75g cyclohexanone 60g After drying, the film weight is 2.7
g/m". This is referred to as sample (C). For comparison, instead of the resol type phenol resin described in Synthesis Example 3 used in the photosensitive liquid, the usual resol type phenol resin described in Comparative Example 2 was used. The same amount of resin was applied and dried in the same manner.The film weight after drying was 2.7 g/m'.

This is called a sample CD).

Samples [C], [D] and comparative sample CB of Example 1 prepared in this manner were heated at a temperature of 45°C and a humidity of 75°C.
% in an air constant temperature bath for 2 weeks.

The photosensitive lithographic printing plate made in this way was placed in a vacuum printing frame through a transparent positive film from a distance of 1 m using Fuji Film PS Light (Touhou Metal Halide Lamp M).
Exposure was carried out for 30 seconds using a U2000-2-OL type (model U2000-2-OL, equipped with a 3KH 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
After washing each 180 mA lithographic printing plate with water, a 14°B6 gum arabic solution was applied to the plate surface and puff-dried.

The printing plate thus completed was stored for 3 days and then mounted on a Heidelberg G, T, O, type printing machine and printed.

When Comparative Example Sample CD using a normal resol type phenolic resin was used, the printed matter was stained, but
In sample [C], a stain-free printed matter similar to that of comparative sample [B] using a novolak type phenolic resin was obtained. Thus, sample [C] has excellent stability over time.

Above samples [A), [C] and comparative sample CB)
After development, heat treatment is performed under the following conditions, and Heidelberg G
, T, O, type printing machine was installed and printed, and its printing durability was evaluated. The results are shown in Table 3.

Table 3 The printing durability of samples (A) and [C] according to the present invention was significantly increased by heating.

Example 5 A substrate was produced by the method disclosed in Japanese Patent Application Laid-Open No. 56-28893. That is, the surface of an aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and a 400 mesh water suspension of pumice stone, and then thoroughly washed with water. Then add 6% to 10% sodium hydroxide at 70°C.
After immersion for 0 seconds and etching, after washing with running water, 20%
It was neutralized and washed with HNO, and then washed with water. This was converted to 1% by using a sinusoidal alternating waveform current under the conditions that the anode voltage was 12.7μ and the ratio of the cathode special charge to the anode special charge was 0.8.
Electrolytic surface roughening treatment was carried out in an aqueous nitric acid solution with an electrical charge of 160 corons/dm''.The surface roughness at this time was measured to be 0.6 μm (indicated by Ra).

Subsequently, it was immersed in 30% sulfuric acid and desmutted at 55°C for 2 minutes, followed by a current density of 2 A/d in 20% sulfuric acid.
Anodizing was carried out for 2 minutes at m2. Then 70℃
After being immersed in a 2.5% aqueous solution of sodium silicate for 1 minute, it was washed with water and dried. The following photosensitive liquid was applied to the thus prepared substrate using a wheeler and dried at 100° C. for 2 minutes.

Resol type phenolic resin of Synthesis Example 3 004g
Oil Blue #603 (manufactured by Orient Chemical Industry ■) 0.03 g2
-Methoxyethanol 6g methanol
6g ethylene dichloride
After drying 6g, the membrane weight is 2.3 g/m2
Met. This is called sample [E].

For comparison, a photosensitive solution obtained by removing the resol type phenolic resin of Synthesis Example 3 from the above photosensitive solution and adding 0.6 g of 2-hydroxyethyl methacrylate copolymer was coated and dried in the same manner. The membrane weight after drying was 2.3 g/m'. This is referred to as sample [FI.

Furthermore, for comparison, a photosensitive solution using 0.4 g of the resol type phenolic resin of Comparative Example 2 instead of the resol type phenolic resin of Synthesis Example 3 was coated and dried in the same manner. The membrane weight after drying was 2.3 g/m2. This is designated as sample [G).

Samples [E], [F], and [G] were heated at a temperature of 45℃ and a humidity of 7.
It was left in a 5% air constant temperature bath for 5 days.

The photosensitive lithographic printing plate made in this way was exposed in a vacuum printing frame through a transparent negative film for 70 seconds using Fuji Film PS Light (using Toho metal halide lamp ML12000-2-OL type 3kW) from a distance of 1 m. After immersing it in the following developer at 25° C. for 1 minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed areas to obtain a lithographic printing plate.

Sodium sulfite 3g Benzyl alcohol 30g Triethanolamine 20g Monoethanolamine
After washing each 5g lithographic printing plate with water, 14°8
The gum arabic solution No. 6 was applied to the plate surface and puff-dried.

The thus completed printing plate was stored for 3 days and then mounted on a Heidelberg G, T, O, type printing machine and printed. Samples [E] and [F] produced clean prints, but
Staining occurred in sample [G].

The print life is 50,000 sheets for sample [E] and 50,000 sheets for sample [F].
It also sold 50,000 copies. In order to increase the printing ability, samples [E] and [F] were heated in a heating oven for 5 minutes after the development process.
After heating to 10° C., a 14@Be gum arabic solution was applied to the printing plate and puff-dried. After storing the thus completed printing plates [E]” and [F]° for three days, the Heidelberg G
,T.

0. Printing was carried out by attaching it to a mold printing machine. Sample [E)'' according to the present invention had a printing durability of 1 g, 10,000 sheets, which was significantly increased compared to 55,000 sheets of sample [F]'', which was a comparative example.

Moreover, this sample [E] became insoluble in organic solvents such as methyl ethyl ketone, acetone, and alcohol, and its chemical resistance was significantly increased.

Example 6 The following photosensitive solution was applied to the support used in Example 5 using a wheeler and dried at 100° C. for 2 minutes.

1.3.4-Oxadiazole 2 g Oil-soluble acute dye (C, 1,42595) 0.8 g
Ethylene dichloride 150g Methyl ethyl ketone 150g Film weight after drying is 2.2
g/m'. This is referred to as sample CHI.

For comparison, the resol type phenolic resin of Synthesis Example 2 was removed from the above photosensitive solution, and 32% of poly(allyl methacrylate)/methacrylic acid (copolymerization molar ratio 85/15) was used.
．． A photosensitive solution weighing 5 g was applied and dried in the same manner. The weight of the membrane after drying was 2.2 g/m''.
1).

Furthermore, for comparison, a photosensitive solution using 12.5 g of the resol type phenolic resin of Comparative Example 2 instead of the resol type phenolic resin of Synthesis Example 2 was coated and dried in the same manner. The membrane weight after drying was 2.2 g/m2.

This is designated as sample [J].

Samples [H), [■], and [J) were heated at a temperature of 45°C and a humidity of 7.
It was left in a 5% air constant temperature bath for 5 days.

Samples [H], (I), [J
] Layer a negative image film on top of the Berkey printer manufactured by Berkey Technical Co., Ltd. (Icor Addalux 2).
KW), immersed in the following developer for 50 seconds at room temperature, and developed by lightly rubbing the surface with absorbent cotton to obtain a printing plate.

Sodium sulfite 5g Benzyl alcohol 30g Sodium carbonate
5g sodium inpropyl naphthalene sulfonate 12g water
1000g
After storing the printed version for 3 days, Heidelberg G, T, O.

When installed on a mold printing machine and printed, samples [H], [
A clean printing plate was obtained with sample [I], but with sample [J
] stains occurred.

The printing durability was 70,000 sheets for both samples [H] and [■].

In order to increase printing capacity, samples after processing [
H] and [I] were heated at 220 t: for 3 minutes in a heating furnace, and a 14°Be gum arabic solution was applied to the plate surface.
It was puff dry. The completed printing version [H]゛, [
I]° was stored for 3 days, then attached to a Heidelberg G, T, O, type printing machine and printed. Sample [H] according to the present invention has a printing durability of 150,000 sheets, and sample [H] which is a comparative example has a printing durability of 150,000 sheets.
This was a significant increase compared to 75,000 sheets for I].

Showa year, month, day, 2, title of the invention, method for manufacturing printing plates, 3, relationship with the case of the person making the amendment, applicant (520) Fuji Photo Film Co., Ltd., 4, agent, 5, date of the amendment order, voluntarily corrected. .

Claims (1)

[Claims] General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1, R_2 and R_3 may be the same or different, and include hydrogen atoms, halogen atoms, group, nitro group, alkyl group having 1 to 20 carbon atoms, alkoxy group, acyl group, phenyl group, 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 method for producing a copying material or a printing plate, which comprises exposing and developing a photosensitive material using a photosensitive composition containing 15 mol% or more of a resol type phenolic resin, and then heating it to a temperature of 140° C. or more.