JPH05297585A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive compsn. giving a satisfactory visible image by exposure and having high sensitivity. CONSTITUTION:This photosensitive compsn. contains an o-quinonediazido compd., an alkali-soluble resin, a compd. which generates an acid or a free radical when irradiated with active light, a coloring material which alters its color tone by interaction with the photodegraded product of the generating compd. and a compd. represented by the formula (where R is aryl or a heterocyclic group and X is halogen).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition which can be used for a photosensitive lithographic printing plate, and more particularly to a photosensitive composition which has a good exposure visible image property and a high sensitivity.

[0002]

2. Description of the Related Art A photosensitive lithographic printing plate is one in which an ink-receptive photosensitive layer is provided on a hydrophilic support. For example, in a positive type photosensitive lithographic printing plate, an ultraviolet ray or the like on the hydrophilic support is used. An ink-receptive photosensitive layer that is solubilized by exposure to actinic rays is formed. Imagewise exposure is performed on the photosensitive layer of such a positive-working photosensitive lithographic printing plate, and then development is performed to remove the photosensitive layer in the exposed area and expose the surface of the hydrophilic support, while removing the photosensitive layer in the unexposed area. It remains on the support to form an ink receiving layer.

In lithographic printing, the difference in properties that the exposed area is hydrophilic and the unexposed area is lipophilic is utilized.

Usually, the photosensitive layer of a positive-type photosensitive lithographic printing plate contains an o-quinonediazide compound as a photosensitive component and an alkali-soluble resin as a component for enhancing film strength and alkali solubility.

These photosensitive lithographic printing plates are required to have high sensitivity in order to improve workability.

Therefore, among the above-mentioned o-quinonediazide compounds, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester compounds and 1,2-naphthoquinone-2-diazide-4- compounds are preferred in terms of sensitivity and cost. Sulfonate compounds are commonly used as useful.

In plate making, for example, exposure operations such as so-called "multi-sided printing" are performed in which the positions of a plurality of film originals are changed and printing is performed one after another. In these exposure operations, if the exposed portion and the unexposed portion cannot be discriminated, the position of the exposed portion cannot be confirmed, so that the exposure operation becomes difficult and incorrect exposure is performed. In order to avoid these, the photosensitive composition is required to form a visible image that can be recognized even under the yellow safety light used for the exposure operation by exposure (exposure visibility). There is.

In order to obtain an exposure visible image property, a photosensitive composition has been incorporated with a printout material which forms a visible image upon exposure. The printout material is composed of an organic dye which changes its color tone by interacting with a compound which produces an acid or a free radical upon exposure to light, and as a compound which produces an acid or a free radical upon exposure to light, there is, for example, JP-A-53 And the halomethyl-s-triazine compounds described in JP-A-55-77742.

However, it has been found that the sensitivity of these compounds, which generate an acid or a free radical upon exposure to light, which has hitherto been publicly known, decreases when the amount of addition is increased.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems to be solved, and an object thereof is to provide a photosensitive composition having a good exposure visible image property and a high sensitivity. It is in.

[0011]

In order to achieve the above object, the photosensitive composition of the present invention comprises (a) an orthoquinonediazide compound, (b) an alkali-soluble resin, (c) an acid or A compound that produces a free radical, (d)
It is characterized by containing a dye which changes its color tone by interacting with the photolysis product of (c), and (e) a compound represented by the following general formula [I].

[0012]

[Chemical 2] (In the formula, R represents an aryl group or a heterocyclic group, and X represents a halogen atom.)

The present invention will be described in more detail below.

In the compound of the general formula [I] used in the present invention, examples of the aryl group represented by R include a phenyl group and the like, and examples of the heterocyclic group include a thienyl group, a furanyl group and a pyrimidinyl group. Be done. R
The aryl group or heterocyclic group represented by may have a substituent, and examples of the substituent in this case include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, a carbamoyl group, an amino group and a nitro group. , Cyano group,
_{-COOR 2, -COR 2, -SO 2} R 2, -SO 3 R 3 (R
₃ represents a hydrogen atom, an alkyl group or an aralkyl group. ) And the like. Moreover, examples of the halogen atom represented by X include a chlorine atom and a bromine atom.

Specific examples of the compound represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0016]

[Chemical 3] These compounds of the general formula [I] are used alone or in combination of two or more, and are used in an amount of 0.01 to 5 with respect to the total photosensitive composition.
wt%, more preferably 0.05 to 2 wt% is used. If the addition amount of the compound of the general formula [I] in the present invention is too small, the effect of the present invention cannot be obtained, and conversely, if the addition amount is too large, the visible image after exposure may be difficult to see.

The photosensitive composition of the present invention includes, for example, a halomethyloxadiazole compound and a halomethyl-containing compound as a compound which forms an acid or a free radical upon irradiation with actinic rays.
An s-triazine compound or the like is used.

The halomethyloxadiazole compound is
It is a compound having a halomethyl group, preferably a trichloromethyl group, on the oxadiazole ring.

These compounds are known, for example, Japanese Patent Publication Nos. 57-6096, 61-51788, Japanese Patent Publication No. 1-28369, JP-A-60-138539 and 60-177340. ,same
60-241049, etc.

The halomethyloxadiazole compound preferably used in the present invention is specifically shown below, but the halomethyloxadiazole compound used in the present invention is not limited thereto.

[0021]

[Chemical 4]

[0022]

[Chemical 5]

[0023]

[Chemical 6]

The halomethyl-s-triazine compound is a compound having one or more halomethyl groups on the s-triazine ring, preferably a trichloromethyl group.

Halomethyl-which is preferably used in the present invention
As the s-triazine compound, the following general formula (I)
Examples thereof include compounds having the structure (III).

[0026]

[Chemical 7] In the formula, R ₁ , R ₂ and R ₆ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group or a substituted alkoxy group. R ₃ represents a haloalkyl group or a haloalkenyl group having 1 to 3 carbon atoms. R ₄ and R ₅ represent a hydrogen atom, a halogen atom, an alkyl group or a substituted alkyl group. R ₇ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. X represents O or S.
m represents 1 or 2, and n represents 0 or 1.

These halomethyl-s-triazine compounds can be prepared from 2,4-bis (halomethyl) -6- (substituted) alkyl-s-triazines by the known method described in JP-A No. 50-36209. , 2,4-bis (halomethyl) -6- (substituted) aryl-s-triazine and the corresponding aromatic (heterocyclic) aldehyde.

Suitable aldehydes include p-methoxybenzaldehyde, p-ethoxybenzaldehyde and p-methoxybenzaldehyde.
-Propoxybenzaldehyde, p-butoxybenzaldehyde, p-pentoxybenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde,
p-propylbenzaldehyde, p-butylbenzaldehyde, p-pentylbenzaldehyde, m-methoxybenzaldehyde, m-ethoxybenzaldehyde, m
-Propoxybenzaldehyde, m-butoxybenzaldehyde, m-pentoxybenzaldehyde, m-methylbenzaldehyde, m-ethylbenzaldehyde,
m-Propylbenzaldehyde, m-butylbenzaldehyde, m-pentylbenzaldehyde, m-, p-dimethoxybenzaldehyde, m-, p-diethoxybenzaldehyde, m-, p-dipropoxybenzaldehyde, m-, p-dibutoxybenzaldehyde , M-,
p-dipentoxybenzaldehyde, m-, p-dimethylbenzaldehyde, m-, p-diethylbenzaldehyde, m-, p-dipropylbenzaldehyde, m-,
p-dibutylbenzaldehyde, m-, p-dipentoxybenzaldehyde, 2-thiophenaldehyde, 3-
Methyl-2-thiophene aldehyde, 5-Bromo-2-
Thiophene aldehyde, 2-furyl aldehyde, 3-
(2-furyl) acrolein etc. are mentioned.

Examples of preferable halomethyl-s-triazines include those having the following structures.

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

The amount of the compound that forms an acid or a free radical upon irradiation with actinic rays in the photosensitive composition of the present invention is preferably 0.01 to 10% by weight, more preferably 0.
It is 1 to 5% by weight, and particularly preferably 0.2 to 3% by weight.

The dye used in the present invention to change its color tone by interacting with the photodecomposition product of the compound which forms an acid or a free radical upon irradiation with the above-mentioned actinic rays, can be a coloring substance and a fading or discoloring substance. There are two types, one that does and one that does. As the dye that fades or discolors, various dyes such as diphenylmethane, triphenylmethane-based thiazine, oxazine-based, xanthene-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes are effectively used.

Specific examples of these are as follows. Brilliant Green, Eosin,
Ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsine, phenolphthalein, 1,3-diphenyltriazine,
Alizarin Red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, para Methyl Red, Congo Red, Benzopurpurin 4
B, α-naphthyl red, Nile blue 2B, Nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin, Victoria pure blue BOH (Hodogaya Chemical Co., Ltd.), oil blue # 603
[Orient Chemical Co., Ltd.], Oil Pink # 312
[Orient Chemical Co., Ltd.], Oil Red 5B
[Orient Chemical Co., Ltd.], Oil Scarlet # 308 [Orient Chemical Co., Ltd.], Oil Red OG [Orient Chemical Co., Ltd.], Oil Red R
R [manufactured by Orient Chemical Industry Co., Ltd.], oil green #
502 [manufactured by Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [manufactured by Hodogaya Chemical Industry Co., Ltd.], m-
Cresol purple, cresol red, rhodamine B, rhodamine 6G, first acid violet R, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carb Stearylamino-4-p-dihydrooxyethylamino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-
o'-methylphenyliminoacetanilide, cyano-
p-diethylaminophenyliminoacetanilide, 1
-Phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-
p-Diethylaminophenylimino-5-pyrazolone.

Examples of dyes that develop color include arylamines. Aryl amines suitable for this purpose include so-called leuco dyes in addition to simple aryl amines such as primary and secondary aromatic amines, and examples thereof include the following.

Diphenylamine, dibenzylaniline,
Triphenylamine, diethylaniline, diphenyl-
p-phenylenediamine, p-toluidine, 4,4'-
Biphenyldiamine, o-chloroaniline, o-bromoaniline, 4-chloro-o-phenylenediamine, o-
Bromo-N, N-dimethylaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, aniline, 2,5-dichloroaniline, N
-Methyldiphenylamine, o-toluidine, p, p '
-Tetramethyldiaminodiphenylmethane, N, N-dimethyl-p-phenylenediamine, 1,2-dianilinoethylene, p, p ', p "-hexamethyltriaminotriphenylmethane, p, p'-tetramethyldiaminotriamine Phenylmethane, p, p'-tetramethyldiaminodiphenylmethylimine, p, p ', p "-triamino-
o-methyltriphenylmethane, p, p ′, p ″ -triaminotriphenylcarbinol, p, p′-tetramethylaminodiphenyl-4-anilinonaphthylmethane,
p, p ', p "-triaminotriphenylmethane, p,
p ', p "-hexapropyltriaminotriphenylmethane.

The proportion of the above dye in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.

In the photosensitive composition of the present invention, a positive type photosensitive substance or an orthoquinonediazide compound is used as a photosensitive substance.

Examples of the orthoquinonediazide compound preferably used in the present invention include reaction products of a compound containing an orthoquinonediazide group and an alkali-soluble resin.

As a typical reaction product of a compound containing an orthoquinonediazide group and an alkali-soluble resin, an ester compound of o-naphthoquinonediazidesulfonic acid and a polycondensation resin of phenols and aldehydes or ketones can be mentioned. Be done.

Examples of phenols used for producing a polycondensation resin of phenols and aldehydes or ketones which form such ester compounds include phenol and o.
-Cresol, m-cresol, p-cresol, 3,
Examples include monohydric phenols such as 5-xylenol, carvacrol and thymol, divalent phenols such as catechol, resorcinol and hydroquinone, and trivalent phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these aldehydes are formaldehyde and benzaldehyde. Further, as the ketone, for example, acetone,
Mention may be made of methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m-, p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin. ..

The polycondensation resin of these phenols and aldehyde or ketone can be produced by a known method.

The reaction product of the compound containing the orthoquinonediazide group and the alkali-soluble resin is o-
An ester compound of naphthoquinone diazide sulfonic acid and a vinyl polymer having a phenolic hydroxyl group can also be used.

A vinyl polymer having a phenolic hydroxyl group which forms such an ester is disclosed in Japanese Patent Application No. 2-29.
The vinyl polymer having a phenolic hydroxyl group described in No. 709 can be used.

Further, a compound containing an orthonaphthoquinonediazide group and 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxy. Condensation compounds with benzophenone and 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone can also be used.

An alkali-soluble resin is further used in the photosensitive composition of the present invention.

Examples of alkali-soluble resins include novolac resins, vinyl polymers having phenolic hydroxyl groups, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. It is also possible to use these resins together.

Examples of the novolac resin include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde copolycondensation resin as described in JP-A-55-57841, JP-A-55-127553. P-substituted phenol or cresol.
Formaldehyde copolycondensation resin etc. are mentioned.

Examples of the non-novolak resin include vinyl polymers having a phenolic hydroxyl group, particularly vinyl polymers having a unit having a phenolic hydroxyl group in the molecular structure.

The vinyl polymer having a structural unit having a phenolic hydroxyl group in the molecular structure, which is preferably used in the present invention, is a polymer produced by the cleavage of a carbon-carbon double bond and is shown below. Polymers containing at least one structural unit represented by the general formulas [1] to [6] are preferably used.

[0058]

[Chemical 16] In the formula, R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
Alternatively, it represents a carboxyl group, preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably a hydrogen atom. A represents an alkylene group which may have a substituent which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents phenylene which may have a substituent. Represents a naphthylene group which may have a group or a substituent. In the present invention, among these, a copolymer containing at least one structural unit represented by the above general formula [2] is preferable.

The vinyl polymer preferably has a copolymer type structure, and in such a copolymer, the structural unit represented by each of the general formulas [1] to [6] is used. Examples of the monomer unit that can be used in combination with at least one kind include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene, α-methylstyrene, p-methylstyrene, p -Styrenes such as chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, such as methyl acrylate, ethyl acrylate, acrylic acid n -Butyl, isobutyl acrylate, dodecyl acrylate, 2-chloroethane acrylate , Phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl ethacrylic acid and other α-methylene aliphatic monocarboxylic acid esters such as acrylonitrile, methacrylonitrile and other nitriles such as acrylamide. Amides such as acrylic anilide, p
-Chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, and other anilides, such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, and other vinyl esters, such as methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether. , Vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxy. Carbonyl ethylene, ethylene derivatives such as 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene,
There are vinyl monomers such as N-vinyl compounds such as N-vinylpyrrolidone. These vinyl monomers have a structure in which unsaturated double bonds are cleaved and are present in the polymer compound.

Among the above monomers, the general formulas [1] to
As the one used in combination with at least one structural unit represented by [6], (meth) acrylic acid, esters of aliphatic monocarboxylic acid, and nitriles are preferable because they show comprehensively excellent performance. More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate and the like.

These monomers may be bound to the vinyl polymer in either a block or random state.

The content of the structural unit represented by each of the general formulas [1] to [6] in the vinyl polymer is preferably 5 to 70 mol%, particularly preferably 10 to 40 mol%.

The above polymers may be used alone or in combination of two or more in the photosensitive composition.

Typical specific examples of the vinyl polymer used in the present invention will be given below. In the compounds exemplified below, Mw is a weight average molecular weight, Mn is a number average molecular weight,
s, k, l, o, m and n each represent mol% of the structural unit.

[0065]

[Chemical 17]

[0066]

[Chemical 18]

[0067]

[Chemical 19]

[0068]

[Chemical 20]

[0069]

[Chemical 21]

The proportion of the alkali-soluble resin in the photosensitive composition of the present invention is preferably 50 to 95% by weight, more preferably 60 to 90% by weight.

Considering coating properties, these alkali-soluble resins preferably have a weight average molecular weight of 1,000 or more, more preferably 1,500 or more.

If necessary, the photosensitive composition of the present invention may contain other additives usually used in these photosensitive compositions. Examples of the additives preferably used in the present invention include organic acids, surfactants, oil sensitizers, fluorine-based surfactants and the like.

As the organic acid used in the present invention, all known various organic acids can be used, but an organic acid having a pKa value of 2 or more is preferable, and a pKa value of 3.0 is more preferable.
˜9.0, particularly preferably 3.5 to 8.0 organic acid is used. However, the pKa value used in the present invention is the value at 25 ° C.

Examples of such an organic acid include the organic acids described in Kagaku Binran Basic Edition II (Maruzen Co., Ltd., 1966, pp. 1054-1058), which are compounds capable of exhibiting the pKa value of the present invention. I can list all. Examples of such compounds include benzoic acid, adipic acid, azelaic acid,
Isophthalic acid, p-toluic acid, q-toluic acid, β-
Ethyl glutaric acid, m-oxybenzoic acid, p-oxybenzoic acid, 3,5-dimethylbenzoic acid, 3,4-dimethoxybenzoic acid, glyceric acid, glutaconic acid, glutaric acid, p-anisic acid, succinic acid, sebacine Acid, β, β-diethylglutaric acid, 1,1-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentane Dicarboxylic acid, β,
β-dimethylglutaric acid, dimethylmalonic acid, α-tartaric acid, speric acid, terephthalic acid, pimelic acid, phthalic acid, fumaric acid, β-propylglutaric acid, propylmalonic acid, mandelic acid, mesotartaric acid, β-methylglutaric acid , Β, β-methylpropylglutaric acid, methylmalonic acid, malic acid, 1,1-cyclohexanedicarboxylic acid,
1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, erucic acid, undecenoic acid, lauric acid, n-capric acid , Pelargonic acid, n-undecanoic acid and the like. In addition, organic acids having an enol structure such as Meldrum's acid and ascorbic acid can also be preferably used. The ratio of the organic acid in the photosensitive layer is 0.05 to 10
Weight% is suitable, preferably 0.1 to 5 weight%.

Further, an acid anhydride can be used in the present invention, and various known acid anhydrides can be used for this,
Preferably cyclic acid anhydrides, such as for example as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ -
Tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, glutaric anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride,
Pyromellitic acid and the like can be mentioned. These acid anhydrides are preferably contained in the photosensitive layer in an amount of 0.05 to 10% by weight, particularly 0.1 to 5% by weight.

As the surfactant used in the present invention,
For example,

[0077]

[Chemical formula 22] (However, including block polymer and random polymer) Polyoxyethylene-polyoxypropylene alkyl ether (terminal forms alkyl ether) (However, includes random polymer)

[0078]

[Chemical formula 23]

[0079]

[Chemical formula 24] Etc.

Specifically, for example, the following are preferable. That is, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene tetraoleate Sorbit, polyethylene glycol monolaurate, polyethylene glycol monostearate , Polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensate, polyoxyethylene polyoxypropylene block copolymers, polyethylene glycol, tetraethylene glycol and the like.

The proportion of the above-mentioned surfactant in the photosensitive composition is preferably 0.1 to 20% by weight, more preferably 0.2 to 10% by weight, based on the entire composition.

The above-mentioned compounds may be used alone or in combination of two or more as long as they are within the above-mentioned contents.

Examples of the oil sensitizer used in the present invention include a condensation resin of a substituted phenol represented by the following general formula [A] and an aldehyde, and / or 1,2-
A naphthoquinone-2-diazide-5-sulfonic acid ester compound may be mentioned.

[0084]

[Chemical 25] In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a halogen atom, and R ₃ represents an alkyl group or a cycloalkyl group having 2 or more carbon atoms.

In the substituted phenols represented by the general formula [A], R ₁ and R ₂ each include a hydrogen atom and an alkyl group (including those having 1 to 3 carbon atoms. 1 to 2 carbon atoms). Alkyl groups are particularly useful.) Or halogen atoms (of the fluorine, chlorine, bromine and iodine atoms, chlorine and bromine atoms are particularly preferable).
R ₃ represents an alkyl group having 2 or more carbon atoms (preferably having 15 or less carbon atoms, an alkyl group having 3 to 8 carbon atoms is particularly useful) or a cycloalkyl group (having 3 to 15 carbon atoms). Including those containing a carbon atom number, a cycloalkyl group having 3 to 8 carbon atoms is particularly useful).

Examples of the above-mentioned substituted phenols include isopropylphenol, tert-butylphenol, tert-
Amylphenol, hexylphenol, tert-octylphenol, cyclohexylphenol, 3-methyl-4-chloro-5-tert-butylphenol, isopropylcresol, tert-butylcresol, tert-amylcresol, hexylresole, tert-octylcresol, cyclohexylcresol Etc., among which tert-octylphenol and
tert-Butylphenol may be mentioned.

Examples of the above-mentioned aldehydes include formaldehyde, benzaldehyde, acetaldehyde,
Examples thereof include aliphatic and aromatic aldehydes such as acrolein, crotonaldehyde and furfural, and include those having 1 to 6 carbon atoms. Of these, formaldehyde and benzaldehyde are preferred.

The resin obtained by condensing the substituted phenol and the aldehyde in the present invention is synthesized by polycondensing the substituted phenol represented by the general formula [A] and the aldehyde in the presence of an acidic catalyst. It The acidic catalyst used is an inorganic or organic acid such as hydrochloric acid, oxalic acid, sulfuric acid or phosphoric acid. The compounding ratio of substituted phenols and aldehydes is 1 part by mole of substituted phenols and aldehydes. Is used in an amount of 0.7 to 1.0 part by mole. As the reaction solvent, alcohols, acetone, water, tetrahydrofuran, etc. are used.

Predetermined temperature (-5 to 120 ° C), predetermined time (3
(-48 hours) After the reaction, the reaction product is obtained by heating under reduced pressure, washing with water and dehydration, or by water precipitation.

1,2-naphthoquinone-2-diazide-of a polymerized resin of the substituted phenols and aldehydes of the present invention
The 5-sulfonic acid ester compound is prepared by dissolving the condensation resin in a suitable solvent, for example, dioxane, and adding 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride to the solution, and stirring with heating. It can be obtained by esterification by dropping an alkali such as alkali carbonate to the equivalent point.

In the above esterified product, the condensation rate (reaction rate% with respect to one hydroxyl group) of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride with respect to hydroxyl groups of phenols is preferably 5 to 80%, It is preferably 20 to 70%, more preferably 30 to 60%. The condensation rate is calculated by obtaining the content of the sulfur atom of the sulfonyl group by elemental analysis.

The amount of the oil-sensitizing agent in the photosensitive composition of the present invention is preferably 0.05 to 15% by weight, particularly preferably 1 to
10% by weight.

The oil sensitizer of the present invention has a weight average molecular weight Mw.
Is preferably in the range of 5.0 × 10 ^{2 to} 5.0 × 10 ³ , and more preferably in the range of 7.0 × 10 ^{2 to} 3.0 × 10 ³ . The number average molecular weight Mn is preferably in the range of 3.0 × 10 ^{2 to} 2.5 × 10 ³ , and more preferably in the range of 4.0 × 10 ^{2 to} 2.0 × 10 ³ .

The molecular weight of the sensitizer is measured by GPC (gel permeation chromatography method). The number average molecular weight Mn and the weight average molecular weight Mw are calculated by Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka "Journal of the Chemical Society of Japan".
Level the peaks in the oligomer region by the method described on pages 800 to 805 (1972) (connect the peak and valley centers)
Method.

Examples of the fluorine-containing surfactant used in the present invention include (meth) acrylate polymers having a fluorinated alkyl group in the side chain. In this case, the standard polystyrene equivalent number average molecular weight is preferably 30,000. Below, those in the range of 2,000 to 10,000 are more preferably used. When the number average molecular weight of the (meth) acrylate polymer exceeds 30,000, the effect of improving coatability becomes insufficient.

Examples of the acrylate structural unit or the methacrylate structural unit of the portion having a fluorinated alkyl group in the side chain in the (meth) acrylate polymer include those represented by the following general formula:

[0097]

[Chemical formula 26] (In the formula, R is a hydrogen atom or a methyl group, and n is 0 to
20, a is 0 to 2, and b is an integer of 0 to 1. ) Or the following general formula

[0098]

[Chemical 27] (In the formula, R is a hydrogen atom or a methyl group, and n is 1 to
10, m is 0 to 20, and a is an integer of 0 to 2. ), Specifically

[0099]

[Chemical 28]

[0100]

[Chemical 29]

[0101]

[Chemical 30]

[0102]

[Chemical 31]

[0103]

[Chemical 32]

[0104]

[Chemical 33]

[0105]

[Chemical 34]

[0106]

[Chemical 35]

[0107]

[Chemical 36]

[0108]

[Chemical 37]

[0109]

[Chemical 38]

[0110]

[Chemical Formula 39]

[0111]

[Chemical 40] And so on. It is preferable that the (meth) acrylate polymer having a fluorinated alkyl group in its side chain further has an alkylene oxide group or an alkyl group in its side chain. Examples of the acrylate structural unit or the methacrylate structural unit of the portion having the alkylene oxide group in the side chain in the (meth) acrylate polymer having a fluorinated alkyl group in the side chain include, for example, the following general formula:

[0112]

[Chemical 41] (In the formula, R represents a hydrogen atom or a methyl group, and n is 1 to
6 and m are integers from 1 to 10. ), Specifically,

[0113]

[Chemical 42]

[0114]

[Chemical 43]

[0115]

[Chemical 44] And so on.

The acrylate structural unit or the methacrylate structural unit of the portion having the alkyl group in the side chain in the (meth) acrylate polymer having the fluorinated alkyl group in the side chain is, for example, the following general formula:

[0117]

[Chemical 45] (In the formula, R is a hydrogen atom or a methyl group, and n is 1 to
Indicates an integer of 22. ), Specifically,

[0118]

[Chemical 46]

[0119]

[Chemical 47]

[0120]

[Chemical 48] And so on.

Further, the (meth) acrylate polymer having a fluorinated alkyl group in the side chain may have an aryl group, an arylene group or the like in the side chain, and the acrylate structure of the portion having the aryl group, the arylene group or the like. As the unit or the methacrylate structural unit, for example,

[0122]

[Chemical 49] And so on.

Further, the (meth) acrylate polymer having an alkyl fluoride in the side chain used in the present invention has a structural unit other than those described above, for example,

[0124]

[Chemical 50] And so on.

Also,

[0126]

[Chemical 51] Fluorine-based surfactants such as can be used. Further, a commercially available product may be used as the fluorine-based surfactant in the present invention. For example, Surflon "S-38", "S"
-382 "," SC-101 "," S-381 "," SC-10 "
2 "," SC-103 "," SC-104 "(all manufactured by Asahi Glass Co., Ltd.), Florard" FC-430 "," FC-43 "
1 "," FC-173 "(both made by Fluorochemical-Sumitomo 3M), F-top" EF352 "," EF301 ",
"EF303" (all manufactured by Shin-Akita Kasei Co., Ltd.), Schvego Fluor "8035", "8036" (all manufactured by Schvegman), "BM1000", "BM1100" (all manufactured by BM Himmy) And so on.

The above various fluorosurfactants can be used alone or in combination.

It is desirable to use the fluorine-containing surfactant in a proportion of 0.01 to 1%, preferably 0.1 to 0.5%.

In the photosensitive composition of the present invention, each of these components is dissolved in the following solvent, and the solution is applied onto the surface of a suitable support and dried to form a photosensitive layer,
A photosensitive lithographic printing plate can be formed.

Solvents that can be used for dissolving each component of the photosensitive composition of the present invention include methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolves such as ethyl cellosolve acetate, methyl carbitol, ethyl carbitol. , Dimethyl carbitol, diethyl carbitol, diethylene glycol ethers and / or esters such as methyl carbitol acetate, dimethyl-3-methoxy-1-butanol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, methyl ethyl ketone, formamide, dimethyl sulfoxide, Dioxane, acetone,
Cyclohexanone, trichloroethylene, methyl ethyl ketone, etc. are mentioned. These solvents can be used alone or in admixture of two or more.

The coating method used when the photosensitive composition of the present invention is provided on the surface of a support is a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating. It is also possible to use curtain coating and the like. The coating amount varies depending on the use, but is preferably 0.1 to 5.0 g / m ² (as solid content). The drying temperature is, for example, 20 to 150 ° C, preferably 30 to 100 ° C.

In the present invention, the coating amount of the photosensitive coating liquid on the support varies depending on the use, but generally a solid content of 0.5 to 3.5 g / m ² is suitable.

The support on which the photosensitive layer using the photosensitive composition of the present invention is provided is a metal plate of aluminum, zinc, steel, copper or the like, and chromium, zinc, copper, nickel, aluminum, iron or the like is plated or Examples thereof include vapor-deposited metal plates, papers, plastic films and glass plates, papers coated with a resin, papers coated with a metal foil such as aluminum, and plastic films subjected to hydrophilic treatment. Among these, an aluminum plate is preferable. It is more preferable to use an aluminum plate which has been subjected to surface treatment such as graining treatment, anodizing treatment and optionally sealing treatment as a support of a photosensitive lithographic printing plate using the photosensitive composition of the present invention. preferable.

A known method can be applied to these treatments.

The photosensitive lithographic printing plate using the photosensitive composition of the present invention can be developed by a usual method. For example, it is exposed through a transparent positive film with a light source such as an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, and the like, and then developed with various alkaline developers. As a result, only the unexposed portion remains on the surface of the support, and a positive-positive relief image is formed.

Examples of the alkali developer include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate. An aqueous solution of The concentration of the alkali metal salt is preferably 0.1 to 20% by weight. Further, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developing solution, if necessary.

[0137]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Example 1 [Production of Aluminum Plate] An aluminum plate having a thickness of 0.24 mm (material 1050, tempered H16) was subjected to a degreasing treatment at 60 ° C. for 1 minute in a 5% by weight aqueous sodium hydroxide solution. Electrolytic etching treatment was carried out in 1 liter of 0.5 mol hydrochloric acid aqueous solution under conditions of a temperature of 25 ° C., a current density of 60 A / dm ² , and a treatment time of 30 seconds. Then, after desmutting treatment in a 5 wt% sodium hydroxide aqueous solution at 60 ° C. for 10 seconds, the anode is treated in a 20 wt% sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² , and a treatment time of 1 minute. Oxidation treatment was performed. Further, hot water sealing treatment was performed with hot water at 80 ° C. for 20 seconds to prepare an aluminum plate as a lithographic printing plate support.

[Application of Photosensitive Composition Coating Liquid] The aluminum plate prepared as described above was coated with the photosensitive composition coating liquid 1 having the following composition using a spin coater and dried at 90 ° C. for 4 minutes. A positive photosensitive lithographic printing plate (Sample 1) was prepared.

The film thickness of the dry coating film of this sample was 2.2 g / m ² .

(1 Composition of Photosensitive Composition Coating Liquid) (1) o-naphthoquinonediazide compound (QD-1) 1.8 g (2) novolac resin (1) 4.3 g (3) non-novolak resin (2) 2.5 g ( 4) Halomethyl oxadiazole compound (rad-1) 0.07 g (5) Fluorine nonionic surfactant S-381 (70 wt% ethyl acetate solution, Asahi Glass Co., Ltd.) 0.02 g (6) Dye (Victoria Pure Blue BOH) (Hodogaya Chemical Co., Ltd.) 0.07g (7) Methyl cellosolve 100ml (8) Compound of general formula [I] No. (1) 0.4g

Examples 2 and 3 The procedure of Example 1 was repeated except that the compound No. (1) of the general formula [I] was replaced with the compound shown in Table 1 in the composition of the photosensitive composition coating liquid 1. Photosensitive composition coating liquids 2 and 3 were prepared in the same manner as in Example 1, and positive photosensitive lithographic printing plate samples 2 and 3 were prepared using the same.

Comparative Example 1 In the composition of 1 of the photosensitive composition coating liquid of Example 1, all of Example 1 except that the compound of the general formula [I] was not added.
A photosensitive composition coating liquid 4 was prepared in the same manner as in 1. and a positive photosensitive lithographic printing plate sample 4 was prepared.

Comparative Example 2 In the composition of the photosensitive composition coating liquid 1 of Example 1, the compound of the general formula [I] was not added, and the halomethyloxadiazole compound (rad-1) was used instead of 0.07 g. To 0.14 g
A photosensitive composition coating liquid 5 was prepared in the same manner as in Example 1 except that the positive type photosensitive lithographic printing plate sample 5 was prepared.

[0145]

[Chemical 52] Novolac resin (1) Copolymerization compound of phenol, m-cresol, p-cresol and formaldehyde (the molar ratio of each of phenol, m-cresol and p-cresol is 20:48:32,
Mw = 6000, Mw / Mn = 5.0)

[0146]

[Chemical 53]

<Evaluation of Sensitivity> Each of the obtained photosensitive lithographic printing plate samples 1 to 5 was subjected to a sensitivity measurement step tablet (No. 2, Eastman Kodak Co., Ltd., a density difference of 0.15, and 21 steps of gray scale). ), And the 2kw metal halide lamp (Iwasaki Denki Idol Fin 2000)
Was used as a light source and exposed from a distance of 90 cm. Next, this sample was developed for 20 seconds at 27 ° C. with a developer obtained by diluting SDR-1 (manufactured by Konica Corp.) developer 6 times with water.

The sensitivity was defined as the exposure time at which 3.0 steps of the step tablet was completely cleared.

<Evaluation of Exposure Visibility> The density difference between the exposed and unexposed areas of the sample exposed under the above conditions was visually evaluated under a yellow lamp to evaluate the exposure visibility. In addition, measurement was performed using a densitometer (Konica Densitometer PDA-65), and the absolute value ΔD of the density difference between the exposed portion and the unexposed portion was obtained. The larger the ΔD, the better the exposure visibility.

Table 1 shows the evaluation results of sensitivity and exposure visibility.

[0151]

[Table 1] * 1 Visibility of exposed image (visual inspection) The state of good visible image of exposure was evaluated as ◯, and the poor state of exposed image was evaluated as x. ○ Above is the practical level. Exposure visibility (excellent) ← ○, △, × → (poor) From the results in Table 1, the photosensitive lithographic printing plate samples 1 to 3 using the photosensitive composition of the present invention have good exposure visibility. It can be seen that the sensitivity is high.

On the other hand, Comparative Sample 4 which does not contain the compound of the general formula [I] is inferior in the visible image quality upon exposure, and Comparative Sample 5 in which the amount of the halomethyloxadiazole compound (rad-1) is increased. Although the exposure visibility is improved to a practical level, the sensitivity is reduced.

[0153]

As described above in detail, according to the photosensitive composition of the present invention, it is possible to provide a photosensitive lithographic printing plate which has a good exposure visibility and a high sensitivity.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Takeo Akiyama 1 Sakura Town, Hino City, Tokyo Konica Stock Company (72) Inventor Tomoyuki Matsumura 1 Sakura Town, Hino City, Tokyo Konica Stock Company (72) Inventor Mitsuru Sasaki 1000, Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Co., Ltd. (72) Inventor Jiro Uemura 1000, Kamoshita-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Co., Ltd.

Claims (4)

[Claims] 1. An (a) orthoquinonediazide compound,
(B) an alkali-soluble resin, (c) a compound that produces an acid or a free radical upon irradiation with actinic rays, (d) a dye that changes its color tone by interacting with the photolysis product of (c), and ( e) A photosensitive composition containing a compound represented by the following general formula [I]. [Chemical 1] (In the formula, R represents an aryl group or a heterocyclic group, and X represents a halogen atom.) 2. The photosensitive composition according to claim 1, wherein the photosensitive composition contains an organic acid. 3. The photosensitive composition according to claim 1, wherein the photosensitive composition contains an oil sensitizer. 4. The photosensitive composition according to claim 1, wherein the photosensitive composition contains a fluorine-based surfactant.