JPS61117532A - Photosensitive image forming material - Google Patents

Abstract

PURPOSE:To obtain a high photosensitization effect at a broad wavelength range of from UV to a visible ray by incorporating a specific photosensitizer together with a photosensitive resin of a photocrosslinking type to a photosensitive layer of the titled material capable of developing with an aqueous developer. CONSTITUTION:The compd. A shown by the formula wherein R1 and R2 are each a halogen atom, an alkozyl, a dialkylamino, a nitro groups and a hydrogen atom, and having at least one of hydrophilic groups selected from the group comprising (a) - SO3M (M is an alkaline metal), (b) a carboxyl group and (c) a phenolic hydroxyl group as the photosensitizer is incorporated to the titled material having the photosensitive layer contg. the photosensitizer, and the prescribed photosensitive resin contg. an ethylenically unsaturated double bond. By using the compd. A as the photosensitizer, the titled material having the high sensitivity at the wavelength of from UV to >=440nm the visible range is obtd. By introducing the group (a), (b) or (c) into the prescribed compd. A, the titled material which has a high affinity against the aqueous developer is obtd. whereby the sensitizer in an unexposure pat does not remain on the substrate.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention includes a sensitizer used for photosensitizing a photocrosslinkable photosensitive resin having an ethylenically unsaturated double bond, and the sensitizer. The present invention relates to a photosensitive image forming material that has a photosensitive layer and is developable with an aqueous developer.

[Prior art] - +11 c=c-co-skeleton (hereinafter referred to as cinnamic acid skeleton) has various types in which the cinnamic acid skeleton is introduced into the side chain or main chain of the molecule in order to perform a specific photodimerization reaction. photosensitive resin, for example,
Polyvinyl alcohol and polyepichlorohydrin with a cinnamic acid skeleton in the side chain.

Some of them have been put into practical use.

For example, polyvinyl cinnamate produced by the reaction of polyvinyl alcohol and cinnamic acid chloride.

Diethyl phenylene diacrylate and 1,4-di-β-
Polyester resins produced by a combination with hydroxyethoxycyclohexane are used as image-forming materials for printing plates, LSI components, and the like.

However, since these photosensitive resins exhibit solubility only in organic solvents, organic solvents are used as developing solutions when developing photosensitive layers using these resins. When using an organic solvent as a developer, there are many problems in terms of development workability, safety and hygiene of the working environment, economic efficiency, and prevention of pollution such as air pollution.For this reason, photosensitive images that can be developed with an aqueous developer Development of forming materials is desired.

In recent years, such resins include, for example, photosensitive polyesters having -8o3M groups (Japanese Patent Application No. 58-244627).
), photosensitive polyester with Cal having a xyl group (Japanese Patent Application No. 59-20739), photosensitive polyester having a phenolic hydroxyl group (Japanese Patent Application No. 59-59591), Cal with a xyl group and a cinnamic acid group in the side chain Polymer (Unexamined Japanese Patent Publication No. 5O
-6404) etc. have been proposed.

However, when the above-mentioned photosensitive resin having a cinnamic acid skeleton is used as a photosensitive image forming material, the photosensitivity of the photosensitive resin alone is insufficient for practical use, so 5-nitroacenaphthene and 2-benzoyl Methylene-1-methyl-β-su7
Sensitizers such as tothiazoline are used together.

However, since these conventionally used sensitizers have poor affinity for water or aqueous developers, the sensitizers tend to remain on the substrate in unexposed areas during development, making it difficult to form images. When the material was used as a printing plate, there were problems such as scumming during printing.

Therefore, efforts have been made to develop sensitizers that have an affinity for water or aqueous developers.
639.4? There is 112681 of the 1970s.

In recent years, a simplified plate-making method has been proposed in which, instead of printing an image through a halftone film, a laser beam is used to print an image directly from an electrical image signal onto a photosensitive layer.

However, lasers currently available for platemaking, such as argon ion lasers and helium-cadmium lasers, emit most of their emitted energy in the visible region of 440 nm or more, and conventional photosensitive materials using sensitizers cannot In reality, because the photosensitivity in the visible region is insufficient, it is necessary to use a large, high-power laser and emit energy in the ultraviolet region. For this reason, it is desired to increase the sensitivity of photosensitive materials in the visible light region.

[Problem that the invention seeks to solve]

An object of the present invention is to provide an aqueous developer having a photosensitive layer containing a sensitizer that has a sensitizing effect on a photocrosslinkable photosensitive resin having an ethylenically unsaturated double bond and has an affinity for an aqueous developer. An object of the present invention is to provide a photosensitive image forming material that can be developed with a liquid.

Another object of the present invention is to provide a photosensitive image forming material having a photosensitive layer containing a sensitizer that exhibits a high photosensitizing effect in a wide wavelength range from the ultraviolet region to the visible region.

[Means to solve the problem]

The present invention provides a photosensitive image forming material that can be developed with an aqueous developer and has a photosensitive layer containing a photocrosslinkable photosensitive resin having an ethylenically unsaturated double bond and a photosensitizer. has a structural unit represented by the general formula O (wherein R1 and R2 each independently represent a hydrogen atom, an alkoxy group, a dialkylamino group, or a halodane atom-nitro group), and ( c) At least one hydrophilic compound selected from the group consisting of general formula-8o, M (wherein M represents an alkali metal), (b) Cal is a xyl group, and (c) a phenolic hydroxyl group. The present invention relates to a photosensitive image forming material characterized by using a compound having a group (hereinafter referred to as compound (A)).

Furthermore, in the structural unit represented by the general formula (1) used in the present invention, the alkoxyl group preferably has 1 to 6 carbon atoms, and the dialkylamino group preferably has a carbon number of 1 to 6 in each alkyl group. 1 to 4 are preferred.

The compound (A) used in the present invention is, for example, the following 0)
~(Can be manufactured by the method of 110.

(1) Contains dicarzanoic acid or a derivative thereof represented by the general formula (wherein R1 and R2d each independently represent a hydrogen atom, an alkoxy group, a dialkylamino group, a halogen atom, or a nitro group), and , a polyhydric carunic acid component containing a dicarnic acid or a derivative thereof having a group represented by the general formula -8o, M (wherein M represents an alkali metal, the same applies hereinafter), and a polyhydric alcohol component. How to react.

([r) reacting a polycarboxylic acid component containing a dicarboxylic acid represented by general formula (2) or a derivative thereof with a polyhydric alcohol component to synthesize an ester compound having a hydroxyl group at the end of the molecule, A method in which the terminal hydroxyl group is reacted with a cyclic acid anhydride.

0 Reacting a polyhydric alcohol component with a polycarboxylic acid component containing a dicarboxylic acid represented by general formula (2) or a derivative thereof, and containing a dicarboxylic acid or a derivative thereof having a phenolic hydroxyl group. How to do it.

It is also possible to produce compound (A) by combining the methods (1) and (2) above.

A preferred example of the dicarboxylic acid or derivative thereof represented by the general formula (2) used in the present invention is 2,4-bis(p
-dimethylaminobenzylidene)-3-oxoglutaric acid, 2,4-bis(m-dimethylaminobenzylidene)
-3-oxoglutaric acid.

2.4-bis(p-dimethylaminobenzylidene)-3
-oxoglutaric acid, 2,4-bis(m-diethyl 7i
nopenzylidene)-3-oxoglutaric acid #2e4-
His(p-methoxybenzylidene)-3-oxoglutaric acid, 2,4-bis(In-methoxybenzylidene)
-3-oxoglutaric acid, 2,4-bis(o-methoxybenzylidene)-3-oxoglutaric acid, 2,4-bis(p-ethoxybenzylidene)-3-oxoglutaric acid, 2,4-bis(m-ethoxybenzylidene) )-3-oxoglutaric acid, 2,4-bis(o-ethoxybenzylidene)-3-oxoglutaric acid, 2,4-bisbenzyritine-3-oxoglutaric acid, etc., or their dimethyl esters, diethyl esters, etc. Pheasant alkyl ester; like di(ethylene glycol) ester, di(furopylene gelicol) ester! p (alkylene glycol) ester; dicarboxylic acid halides such as dicarboxylic acid chloride; and the like.

Examples of the dicarnic acid or derivative thereof having a 18o, M group include 5-sodium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid, and
Potassium sulfoisophthalic acid, 3-sodium sulfophthalic acid, 3-potassium sulfophthalic acid, 4-sodium sulfophthalic acid, 4-potassium sulfophthalic acid, α-sodium sulfosuccinic acid, α-potassium sulfosuccinic acid, β-sodium sulfoadipine Acid, 2,5-disodium sulfoadipic acid 55-(γ-sodium sulfopropoxy)isophthalic acid, 5-(r-potassium sulfophenoxy)isophthalic acid *5-(p-sodium sulfophenoxy)isophthalic acid, 5-( Zocarganic acids such as p-potassium sulfophenoxy) isophthalic acid, etc.:
The dimethyl ester of the dicarboxylic acid, ? ) Dialkyl ester of ethyl ester;
Radicals like esternidicarbic acid chloride? Examples include acid halides.

Examples of the cyclic acid anhydride include pyromellitic dianhydride, 3. π,4.4'-benzophenonetetracarganic dianhydride, 3.3',4.4'-diphenyltetracarganic dianhydride, 2,3,6.7-naphthalenetetracarganic dianhydride Acid dianhydride, 1,4,5.8-naphthalenetetracarnic dianhydride, 4'-sulfonyl siphthalic dianhydride, 2,2-bis(3,4-dical is xyphenyl) Anhydride, bis(3,4-xyphenyl)ether anhydride elJ, 4,4
'-(3ta'-(alkylphosphoryldiphenylene)
-bis(iminocarbyl)]cyphthalic dianhydride.

Aromatic tetracarboxylic acid dianhydride such as an adduct of hydroquinone diacetate and trimellitic anhydride, an adduct of diacetyl diamine and trimellitic anhydride: 5-
(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (
Manufactured by Dainippon Ink Chemical Industry KK, Epicon B-4400
) tl#2,394-1 Alicyclic groups such as cupentane tetracarnoic dianhydride, 1,2,4.5-cyclohexanetetracarnoic dianhydride, tetrahydrofuran tetracarnodic dianhydride, etc. Tetracarboxylic dianhydride:
1,2.3,4-butanatodic acid dianhydride,
Aliphatic tetracarboxylic acid dianhydride such as 1,2,4.5-pentanetetracarboxylic acid dianhydride, succinic anhydride,
Octadecylsuccinic anhydride, camphoric anhydride, maleic anhydride, 7-thalic anhydride, 4-methylphthalic anhydride.

3-nitrophthalic anhydride, tetrabromophthalic anhydride, naphthalene dicarboxylic anhydride, O-sulfobenzoic anhydride, etc. can be used.

A radical that seals a phenolic hydroxyl group or its vj
Examples of 4-isomers include dicarboxylic acids represented by the following general formulas (2) to (6): dicarboxylic acid esters and diethyl esters of these dicarboxylic acids; di(ethylene glycol) esters of these dicarboxylic acids; ,
Di(alkylene glycol) esters such as di(propylene gellicol) esters; examples of dicarganes such as dicarboxylic acid chlorides include hasides.

0OH 1(C-COOH (In the above general formulas (f) to (7), R5 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halodane atom, or a nitro group. , R4 and R
5 represents a hydrogen atom, a halodane atom, a nitro group, or a cyano group, i represents an integer of 1 to 5, and j is (5-1)
represents an integer of , k represents 0 or 1, f represents 0 or l
, h and h' represent integers from 1 to 4, and g represents (
gl represents an integer of (4-h'), X represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom,
Suitable compounds of dicarboxylic acids and derivatives thereof having sulfuric phenolic hydroxyl groups include, for example, 4-hydroxybenzylidenemalonic acid, 3-hydroxybenzylidenemalonic acid, 3,4-dihydroxybensyritenemalonic acid #4-hydroxy -3-methoxybenzylidenemalonic acid, 3-hydroxy-4-methoxybenzylidenemalonic acid, 4-hydroxy-3-nitropenzylidenemalonic acid, 4-hydroxycinnamylidenemalonic acid, 3-hydroxycinnamylidenemalonic acid, 4-hydroxy-3
-methoxycinnamylidenemalonic acid, 4-hydroxy-
Dicarnic acids such as 3-nitrocinnasarydenmalonic acid; 3-hydroxyphthalic acid, 4-hydroxyphthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, hydroxyterentalic acid, 3,6-hydroxyphthalic acid acid, 2,5-cyhydroxyisophthalic acid, 4,
5-dihydroxyisophthalic acid, 2,3-dihydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid s
L4#6-trihydroxyisophthalm a 4#5#
6-) Lyhydroxyisophthalic acid, 4-hydroxy-5-nido-p-isophthalic acid, 4-hydroxy-5-chloroisophthalic acid, 3-hydroxy-6-medoxyphthalic acid, 2,4-dihydroxy-6-methylisophthalic acid, etc. Phosphoric acids such as: L3'-methylenebis(4-hydroxybenzoic acid), 4,6'-dihydroxy-3
, 3'-biphenyldicarboxylic acid e L6'-dihydroxy-5,5'-dimethoxy-3,3I-biphenyldicarboxylic acid, 4,5-dihydroxy-2,4'-oxydibenzoic acid, etc. Acid: 2-hydroxy-p
-Benzenedioacetic acid, 2,5-dihydroxy-p-benzenenediacetic acid, α,α′-dicia/ -2,5-dihydroxy-p-benzenenediacetic acid, αed′-N2) o”
2t5-dihydroxy-p-benzenydiacetic acid.

Dicarboxylic acids such as α, α'-cyclo2,5-dihydroxy-p-benzene diacetic acid, s-hydroxy-m-phenylene di(oxyacetic acid), etc.; dicarboxylic acids such as dimethyl esters and diethyl esters of the above dicarboxylic acids; Dialkyl esters include di(ethylene glycol) esters, di(propylene glycol) esters, and di(alkylene glycol) esters of the dicarboxylic acids.

In the production of compound (A), a dicarboxylic acid represented by the general formula (2), a dicarboxylic acid having a group represented by the general formula -805M, and a dicarboxylic acid having a phenolic hydroxyl group or a derivative thereof In addition, other polycarboxylic acids or derivatives thereof can be used in combination; examples of such compounds include succinic acid, adipic acid, azelaic acid, and cepacic acid.

7-thalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydronthalic acid, tetrabromophthalic acid, tetrachloro7-thalic acid e 1#4-cyclohexanedicarganic acid, maleic acid, 7-malic acid, itaconic acid, cal Male xynol can be lunanacetic acid, trimellitic acid, hysuccinic acid, # polyhydric carboxylic acid, anhydride thereof, or ester derivative thereof.

However, the use of large amounts of these polyhydric carboxylic acids or their derivatives should be avoided since it will cause a decrease in the sensitizing effect of compound [A]. It is preferable to keep the amount of carboxylic acid components to about 30% or less of the total acid component.On the other hand, as the polyhydric alcohol component, various types can be used without particular restrictions, such as ethylene glycol, diethylene glycol, triethylene glycol, Ropylene glycol, diethylene glycol, 4-lyethylene glycol, 'polypropylene glycol, neopentyl glycol.

1.3-tstylene glycol, 1.6-hexanediol, 2-fthene-1,4-diol, 2.2.4-trimethyl-1#3-hentanediol, 1.4-bis-β- Hydroxyethoxycyclohexane, cyclohexane dimetatool-tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, bisphenol F is zolopyrene oxide adduct, hydrogenated bisphenol A is ethylene oxide adduct, hydrogenated bisphenol A is pyrene oxide adduct, tricyclodecane dimetatool ethylene oxide adduct, tricyclodecane dimetatool pre Pyrene oxide adduct, 5-nor is lunene-2,3-dimethatol, 5-norgornene-2,2-
Dimethatol, trimethylolsilone, pentaerythritol, etc. can also be used.

The above-mentioned compound [A] can be prepared by means known in the field of ordinary polyester synthesis, for example, Seiyo, "Lecture on Polymerization Reactions 9, Polycondensation", written by Ogata, published by Kagaku Dojinsha, or
It can be easily manufactured by the method described in US Pat. No. 3,622,320.

That is, for example, after the dicarboxylic acid component and the glycol component are reacted (esterification reaction or transesterification) in the presence of a catalyst added as necessary, the pressure inside the reactor is gradually reduced to remove excess It can be produced by distilling glycol.

The reaction temperature is preferably 150 to 250°C, and the reduced pressure is preferably 3 ■Hg or less.

Examples of the catalyst used in the reaction include organometallic compounds such as diptyltin oxide, diptyltin laurate, diptyltin diacetate, lithium ethoxide, tetraisoglobyl titanate, tetrabutoxytitanate, and zinc acetate; titanium dioxide; , antimony trioxide, calcium oxide, and other inorganic metal compounds can be used. The amount used is 50 to 10,000 ppm as metal components.
is preferred.

In the method ([[)] of the above-mentioned method for producing compound (A), the reaction between the ester compound having a hydroxyl group at the end of the molecule and the cyclic acid anhydride is as follows. Reaction system with fixed amount added, or (
b) The reaction can be carried out in a reaction system in which a polyester precursor is dissolved in an organic solvent and a predetermined amount of a cyclic acid anhydride is added. Preferred reaction conditions naturally vary depending on the reactivity of the cyclic acid anhydride used, the presence or absence of a catalyst, etc., but generally speaking, the reaction temperature is preferably from room temperature to 250°C. This reaction can be carried out by mixing and stirring the two in an ordinary reactor under melting or solution conditions, or in the case of
It is also possible to react.

Examples of organic solvents used in the reaction include chlorinated solvents such as methylene chloride, chloroform, trichloroethane, trichloroethylene, chlorobenzene, dichlorobenzene, and carbon tetrachloride; tetrahydrone, ? ) Ether solvents such as oxane; glycol methyl ether acetate)
Ester solvents such as ethyl ether acetate and ethyl acetate; Keine solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-methyl-4-methoxy-i-pentanone; dimethyl formand, Containing elemental solvents such as methylacetamide, N-methylbinyridone, and nitrobenzene; and dimethylsulfoxide, etc. The above solvents can be used alone or in a mixture of 211 or more.

Compound [A] may optionally be a chain extender having two or more functional groups that can react with the hydroxyl group contained in compound (A), such as a diaryl phthalate compound, a diisocyanate compound, or a bisoxacylone compound. , screw (N
-Acyllactam) compounds, bisbenzoxazinone compounds, etc. may be reacted to increase the molecular weight.

Compound (A) was produced as described above, and the compound (A) used in the present invention (as Al, compound (A) 10
0Of, the content of the structural unit represented by general formula (1) is 0.3 mol or more), and (a), (b)
It is preferable that the m content of the group selected from the group consisting of , and (C) is 0.15 to 2.5 moles.
- In the present invention, in order to obtain a photosensitive image forming material having sufficient photosensitivity, the content of the structural unit represented by the general formula (1) is as follows with respect to 100 parts by weight of the photocrosslinkable photosensitive resin. Preferably, compound (A) is added in an amount of 1 part by weight or more, more preferably 5 parts by weight or more. A composition in which a photocrosslinkable photosensitive resin is dissolved in a suitable solvent,
Or, if necessary, sensitizers, pigments, dyes, fillers,
This can be done by preparing a composition containing additives such as a stabilizer, a crosslinking agent, a plasticizer, etc., applying this composition to the surface of a support, and drying it.

The photocrosslinkable photosensitive resin used in the present invention is a polymer having a cinnamic acid photosensitive group and a carboxyl group in the side chain (JP-A-50-6404, JP-A-52-86488%): A polymer having a phenylene diacrylic acid residue and a xyl group in the chain (Japanese Patent Publication No. 52-112681): A polymer having a cinnamic acid photosensitive group and a phenolic hydroxyl group in the side chain (Japanese Patent Publication No. 49-44601): A cinnamic acid-based photosensitive group and an 8o group on the side chain.
, a polymer having an M group (Japanese Unexamined Patent Publication No. 48-55282): p
-Phenylene diacrylic acid, 2,5-dimethoxy-p-phenylene diacrylic acid, 2-nitro-p-7-enylene diacrylic acid, p-carxycinnamic acid, cinnamyl Dicarboxylic acids such as denmalonic acid, bis(p-cinnamic acid) diethylene glycol ether, bis(p-carboxybenzal)cyclohexanone, bis(p-carboxybenzal)cyclopentanone e, P#P'-chalcone dicarboxylic acid, General formula-803M
A photosensitive polyester resin obtained by the polycondensation reaction of a dicarnic acid having a group represented by the following and/or a dicarnic acid having a phenolic hydroxyl group or a derivative thereof with a polyhydric alcohol (Patent Application No. 58-185198, Patent Application No. 58-244627.49), and a photosensitive resin further reacted with a chain extender (Patent Application No. 58-244627.49 No. 5)
9-77557): A photosensitive polyester resin having the photosensitive dicarboxylic acid unit and a xyl group (Japanese Patent Application No. 59-20739), and a photosensitive resin further reacted with a chain extender (Japanese Patent Application No. 59-1989) -46429): Photosensitive polyester resin having the photosensitive dicarboxylic acid unit and a water-soluble disulfonamide group (Japanese Patent Publication No. 57-42858):
Polymer having a photosensitive quaternary base in the side chain (% disclosure 55-1
3020), etc.

Suitable solvents vary depending on the composition and molecular weight of the resin and compound (A), but include, for example, the solvent used in the reaction of the cyclic acid anhydride; alcohol-based solvents such as dihydrofurfuryl alcohol and benzyl alcohol; Glycol monomethyl ether.

Examples include glycol monoalkyl ether solvents such as glycol monoethyl ether, and these solvents can be used alone or in a mixture of two or more.

The compound used in the present invention (A?1I-1) may be used in combination with other sensitizers, and as other sensitizers, those that can be used in this field are used, benzophenone ms Benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, ketocoumarin compounds, pyrylium salts, thiapyrylium salts, and the like can be used.

The photosensitive resin composition may be coated with a whirler coating, dip coating, curtain coating, roll coating, spray coating, air knife coating, or doctor knife coating.

It is applied to the support by well known coating methods such as spinner coating.

Specific examples of the support include aluminum plates, zinc plates, copper plates, stainless steel plates, and other metal plates; Liethylene terephthalate, polycarbonate.

Sheets and plates of synthetic resin such as cellulose conductors;
Examples include paper coated with a synthetic resin melt-coated or a synthetic resin solution; composite materials in which a metal layer is provided on a synthetic resin by techniques such as vacuum deposition or lamination; silicon wafers; and the like.

Supports for printing plates include mechanical, chemical, electrochemical,
Metals such as aluminum, silk, zinc, plates, etc. with roughened surfaces are used, and a photosensitive layer having a thickness of usually 0.1 to 2.5 .mu.m is formed thereon.

After image-wise exposing the photosensitive layer of this image-forming material using a negative image to harden and insolubilize the exposed portion of the photosensitive layer,
By developing with an aqueous developer and dissolving and removing the unexposed areas, a corresponding image can be formed on the support.

At that time, the aqueous developer is one that has water as its main component and to which water-soluble inorganic compounds such as alkaline metal silicates, bicarbonates, carbonates, or hydroxides, amines, etc. are added. Depending on the case, those containing additives such as organic solvents and surfactants can be used.

Suitable light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metallurgical lamps, lasers, and the like.

Hereinafter, the present invention will be specifically explained using examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

〔Example〕

Each mixture having the composition listed in Table 2 was charged together with a catalyst (0.37% dibutyltin oxide) into a reactor equipped with a stirring device, a nitrogen gas introduction tube, a thermometer, and a distillation tube.
The reaction was started by heating to 190° C. while stirring under a nitrogen gas atmosphere.

Thereafter, the mixture was heated and stirred for 3 hours, and after the distillation of the alcohol produced by the reaction stopped, the pressure inside the reactor was gradually reduced to 11 uHg at the same temperature. Subsequently, heating and stirring were continued for 2 hours under the same reduced pressure, and after the distillate stopped distilling, the pressure inside the reactor was returned to normal pressure by introducing nitrogen gas, and the produced resin was taken out. .

(II) Method... Compound in which Cal has a xyl group [A
] Each mixture having the composition listed in Table 2 was charged together with a catalyst (0.3 f of diptyltin oxide) into a reactor equipped with a stirring device, a nitrogen gas introduction tube, a thermometer, and a distillation tube. The reaction was started by heating to 190° C. while stirring under a nitrogen gas stream. Thereafter, heating and stirring were continued for 3 and a half hours to completely distill off the alcohol produced by the reaction to obtain a polyester.

Next, this polyester 50f was heated to 140°C and stirred, and the tetracarboxylic dianhydride listed in Table 2 was charged, and under the conditions (reaction time) shown in Table 2 under nitrogen atmosphere and normal pressure. After continued stirring, the resulting resin was taken out.

(G) Method... Compounds having phenolic hydroxyl groups (
Production of A) Each mixture having the composition listed in Table 2 was charged together with a catalyst (dibutyltin oxide o, aP) into a reactor equipped with a stirring device, a nitrogen gas introduction tube, a thermometer, and a distillation tube. The reaction was started by heating to 190°C while stirring under a gas atmosphere.

He heated and stirred the mixture for 3 hours, and after the alcohol produced by the reaction stopped distilling out, the pressure inside the reactor was gradually reduced to 1 wHg at the same temperature. Thereafter, heating and stirring were continued for 2 hours under the same reduced pressure, and after the distillate had stopped distilling out, the pressure inside the reactor was returned to normal pressure with nitrogen gas.

Next, as a chain extender, diphenyl terephthalate listed in Table 2 was charged, and the pressure inside the reactor was again increased to l flll (g
After stirring at 180°C for 30 minutes, return to normal pressure.
The produced resin was taken out.

Compound (A) IFI- obtained in (1) above was treated with the following aqueous developer 10? was added to evaluate its solubility.

Table 1 Note 1) Niracol NP-100: manufactured by Nikko Chemicals @), a nonionic surfactant.

Note 2) Perex NBL: Manufactured by Kao Atlas@), t
srt-butylnaphthalenesulfonate sodium a=
On-type surfactant.

(3) Preparation of photosensitive resin composition Photocrosslinkable photosensitive resin 3 from (a) to P3 below? 971
7) It was dissolved in a solvent (methyl cellosolve was used for resin (a), and cyclohexanone was used for resin (b) and tt) to prepare a photosensitive solution. This photosensitive liquid 30f
P and 0.08p of blue dye (in the case of resin (a)) or blue pigment (in the case of resin (b), e) and o as a sensitizer;
Various compounds (A) produced in the above (2) of 11FI-
was added to prepare a photosensitive resin composition.

Resin (a): 0.5 mol of diethyl p-phenylene diacrylate, 0.5 mol of 5-sodium sulfoine heptatalate, 0.4 mol of tricyclodecane dimetatool, polyethylene glycol (molecular weight 300 )0.6
A photosensitive resin obtained by chain-extending a polyester precursor obtained by transesterifying and polycondensing 1 mole of ethylene glycol with diphenyl terephthalate (3% by weight based on the polyester precursor).

Resin (b)... A polyester precursor obtained by reacting 0.75 mol of diethyl p-phenylene diacrylate with 1 mol of ethylene oxide (6.2 mol) adduct of bisphenol A (1 mol), Mellitic dianhydride 0.
A photosensitive resin with an acid value of 43.5 in which 25 moles were completely reacted.

m Fat P3... 0.5 mol of diethyl p-phenylene diacrylate, 0.5 mol of diethyl 4-hydroxybenzylidene malonate, 1 mol of ethylene oxide (6.2 mol) adduct of bisphenol A (1 mol), and A polyester precursor obtained by subjecting 1 mole of ethylene glycol to transesterification and polycondensation reaction is converted into a polyester precursor obtained by transesterification and polycondensation reaction of 1 mole of ethylene glycol.
! j photosensitive resin chain-extended with 3% by weight based on the ester precursor. (Weight average molecular weight: 51,200) The composition prepared in (3) above was coated on an anodic oxidized Alonium plate after sanding, and dried to form a photosensitive layer having a thickness of 1 μm. A photosensitive image forming material (hereinafter referred to as photosensitive plate) was prepared.

(4) -2 Measurement of photosensitivity A step wedge (a degree step θ ~ 15) with a step difference of 0.15 was brought into close contact with the photosensitive plate obtained in (4) -1 above.
A metal halide lamp with an output of 1 kW installed at a position 1 m away from the photosensitive plate [Idol fin 1] manufactured by Iwasaki Electric @
00OJ], or ■500W equipped with an interference filter [1”V-Y44J manufactured by Toshiba Glass Corporation] that cuts light of 440 nm or less and placed 0.5m* away from the photosensitive plate. Exposure was carried out using a xenon lamp [[L-500DJ] manufactured by Ushio Electric Co., Ltd.].

The light beam obtained by method (2) has a radiation wavelength in the ultraviolet wavelength region, and shows particularly strong radiation in the wavelength range of 400 to 420 nm.The light beam obtained by method (2) has a radiation wavelength in the long wavelength region of 440 nm. It has the following. Like this 2
．． The reason why the photosensitivity was measured using different types of light sources is to clarify that the photosensitive resin composition of the present invention exhibits particularly high photosensitivity in the long wavelength region.

Thereafter, this photosensitive plate is developed with the developer shown in Table 1 above, and the exposure time required to insolubilize the fifth stage of the step wedge (however, in the case of a metal halide lamp, the exposure time is 7.5
In the case of second exposure and xenon lamp, the number of insolubilization stages of 4 second exposure was converted. ) was taken as photosensitivity.

For comparison, o and osy blue dyes (in the case of resin (a)) or blue pigments (resin (b), G
-1) and the known sensitizers shown in Table 2 (0,11
? ) was prepared, and a photosensitive plate was prepared under the same conditions as in the example, exposed and developed, and the photosensitivity was measured.

The contents and results of each side above are summarized in Table 2.

〔Effect of the invention〕

The photosensitive image-forming material of the present invention has relatively high sensitivity in the wavelength range from the ultraviolet light range to the visible range of 440 million by using the compound [A] as a photosensitizer. . The compound [A] used as a sensitizer in the present invention has an affinity for an aqueous developer because it has a group selected from (c), (b), and (C). .

Therefore, when the photosensitive image forming material of the present invention using this compound [A] is developed with an aqueous developer, no sensitizer remains on the substrate in the unexposed areas.

The image forming material of the present invention is particularly excellent as a photosensitive material for photosensitive lithographic printing plates, but is not necessarily limited to photosensitive lithographic printing plates. It can also be used as an otoresist for microfabrication required when manufacturing parts.

Claims (1)

[Scope of Claims] 1. A photosensitive image forming material developable with an aqueous developer having a photosensitive layer containing a photocrosslinkable photosensitive resin having an ethylenically unsaturated double bond and a photosensitizer, As a photosensitizer, there are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼...(1) (In the formula, R_1 and R_2 each independently represent a hydrogen atom,
Alkoxyl group, dialkylamino group, halogen atom,
(representing a nitro group), and (a) general formula -SO_3M (in the formula, M represents an alkali metal), (b) carboxyl group, and (c) phenolic A photosensitive image-forming material characterized by using a compound [A] having at least one hydrophilic group selected from the group consisting of hydroxyl groups. 2. The image forming material according to claim 1, wherein the content of the structural unit represented by the general formula (1) is 0.3 mol or more per 1000 g of compound [A]. 3. The total content of groups selected from the group consisting of (a), (b), and (c) is 0 per 1000 g of compound [A]
．． The image forming material according to claim 1 or 2, wherein the amount is 15 to 2.5 mol.