JP3322769B2 - Photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive lithographic printing plate, and more particularly to a positive photosensitive lithographic printing plate containing a naphthoquinonediazide compound.

[0002]

2. Description of the Related Art A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolak-type phenol resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate or as a photoresist. However, due to the properties of the novolak type phenol resin used as the main component, the adhesion to the base plate is poor, the film is brittle, the abrasion resistance is poor, and the printing durability when used in lithographic printing plates is not sufficient. There is a point to be improved, and furthermore, development must be carried out with an alkaline aqueous solution having a high pH of usually 13 or more. However, such a high pH developer is never used in view of safety of handling or processing suitability of a development waste liquid. It was not preferred.

In order to solve such a problem, various polymers have been studied as binders. For example, the polyhydroxystyrene or hydroxystyrene copolymer described in Japanese Patent Publication No. 52-41050 has improved film properties, but has the disadvantage of poor abrasion resistance. Furthermore, when a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound is used as a photosensitive substance, it is characterized by suitability for exposure light source, but has the following problems. In general, as a method of preparing a positive photosensitive lithographic printing plate, a lithographic film is exposed by overlapping with a photosensitive layer of a lithographic printing plate material, and the exposed material is developed with a developer to form a printing plate. Is being done. In this plate making process, the time from exposure to development is not uniform. If the time is long, development is performed several days after exposure. However, when a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a conventional polyhydroxy compound is used as a photosensitive substance, there is a large variation in sensitivity during development due to long-term aging after exposure. Normal printed matter could not be obtained.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a lithographic printing plate having a high developability even in an alkaline aqueous solution having a relatively low pH, having good adhesion to a substrate, providing a flexible film, and having a large printing durability. To provide a version. Still another object of the present invention is to provide a method for preparing a photosensitive material, which uses a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound, with a slight decrease in performance such as sensitivity fluctuation with time after exposure. To provide a photosensitive lithographic printing plate.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention. That is, an object of the present invention is to provide at least one kind of 1,2- (or 2,1) -naphthoquinonediazide-4-polyhydroxy compound represented by the following general formula (1) on a support.
Photosensitive substance comprising (or -5) sulfonic acid ester, and acrylic polymer having sulfonamide group
-, Urethane-based polymer having carboxylic acid and activity
Selected from among acrylic polymers with imino groups
The positive photosensitive composition comprising at least one alkali-soluble resin can be achieved by a photosensitive lithographic printing plate formed by coated.

[0006]

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In the formula (1), A represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an arylene group, or a substituted arylene group. B represents a hydrogen atom, an alkyl group or a substituted alkyl group. R ^{1 to} R ⁸
Are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group,
An alkenyl group having 1 to 4 carbon atoms or a hydroxyl group.

That is, the present invention provides a polyhydroxy compound having a specific structure, that is, a polyhydroxy compound having a specific structure containing four benzene rings having at least one hydroxyl group. Even when treated with a developer having a relatively low pH, the developability is high, the adhesion to the substrate is good, a flexible film is provided, and the printing durability is large. Even if a naphthoquinonediazide-4-sulfonic acid ester is used, it is possible to prevent a decrease in performance such as a change in sensitivity over time after exposure.

As described above, when a conventional polyhydroxy compound and a 1,2-naphthoquinonediazide-4-sulfonic acid ester are used, a large change in sensitivity occurs when the resist is developed for a long time after exposure. . This can be estimated that the 1,2-naphthoquinonediazide-4-sulfonic acid ester is due to the instability of indenecarboxylic acid generated after exposure. This instability is
Since this does not occur when 1,2-naphthoquinonediazide-5-sulfonic acid ester is used, it is considered to be a problem due to the structure of 1,2-naphthoquinonediazide-4-sulfonic acid ester. That is, it is considered that the performance deterioration such as the sensitivity fluctuation with the elapse of time after the exposure is caused by the indene carboxylic acid generated by the exposure causing decarboxylation and hydrolysis of the sulfonic acid ester.

According to the present invention, 1,2-naphthoquinonediazide-4 is produced by using a specific polyhydroxy compound.
-Even when a sulfonic acid ester is used, stability over time after exposure can be improved, and a better printed matter can be obtained.

In the formula (1), A is an alkylene group, a substituted alkylene group, an alkenyl group, a substituted alkenyl group, an arylene group or a substituted arylene group, preferably an alkylene group having 1 to 3 carbon atoms or a phenylene group. . B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group, and is preferably a hydrogen atom or a methyl group. R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group,
An alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms or a hydroxyl group, preferably a hydrogen atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 2 carbon atoms.

As the alkali-soluble resin used in the present invention, various acrylic, vinyl or urethane resins having this property can be used. Preferred resins are styrene-acrylic acid copolymer, methyl methacrylate - methacrylic acid copolymer, alkali-soluble polyurethane resin, and JP Application Sho 63-27008
No. 7 (JP-A-2-866) , an acrylic polymer having a sulfonamide group, an acrylic polymer having a sulfonamide group disclosed in JP-A-63-226641, JP-A-63-
There is a urethane-based polymer having a carboxylic acid disclosed in No. 124047, an acrylic polymer having an active methylene group disclosed in JP-A-63-127237, an acrylic polymer having an active imino group, and the like. Preferred alkali-soluble resins include acrylic polymers having a sulfonamide group, urethane polymers having a carboxylic acid, and acrylic polymers having an active imino group. More preferably, an acrylic polymer containing the structural unit represented by the following general formula (2) at a ratio of 3 mol% or more and less than 60 mol% is exemplified. For image formation, the structural unit represented by the general formula (2) needs to be contained in the range of 3 mol% or more and less than 60 mol%, and more preferably in the range of 10 mol% or more and less than 60 mol%. included.

[0013]

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In the formula (2), A is a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine) or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl). , T-butyl), and more preferably a hydrogen atom or methyl. R ¹
Represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or an alkoxy group having 1 to 6 carbon atoms, and more preferably includes a methyl group, an ethyl group, a fluorine atom, a chlorine atom, a methoxy group, and an ethoxy group. m represents an integer of 1 to 5.

As these alkali-soluble resins, those having a wide range of molecular weights can be used. When measured by gel permeation chromatography using polystyrene as a standard, or when measured by light scattering in THF, Weight average molecular weight (Mw) of 1,000 to
It is preferably 1,000,000, and more preferably 4,000 to 500,000.

Representative examples of the vinyl monomer used in combination with the structural unit represented by the general formula [2] include the following. However, it is not limited to these vinyl monomers. For example, ethylene, propylene, isobutylene, butadiene emissions of any ethylenically unsaturated olefins; for example, styrene, alpha-methyl styrene, o- methyl styrene, m- methyl styrene, p- methyl styrene, o- chlorostyrene, p- chloro Styrenes such as styrene; for example, acrylic acid,
Methyl acrylate, ethyl acrylate, acrylic acid iso
Acrylic acid such as -butyl, n-butyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-cyanoethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, and esters thereof And the like; for example, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-methacrylate
Butyl, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid 2
Methacrylic acid and its esters such as -hydroxyethyl, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, and vinyl benzoate;
For example, nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, and cyclohexyl vinyl ether;
Acrylamides such as -methylacrylamide, N, N-dimethylacrylamide, N-tert-butylacrylamide, N-octylacrylamide and diacetoneacrylamide; for example, p-hydroxyphenylacrylamide, o-hydroxyphenylacrylamide, p
-Hydroxyphenyl methacrylamide, p-hydroxyphenyl acrylate, monomers having a phenolic hydroxyl group described in JP-A-64-35436 and JP-B-52-34932;
-Sulfamoylphenyl) methacrylamide, N-
A monomer having a sulfamoyl group such as (p-sulfamoylphenyl) acrylamide; and the like.

In addition, coupler-based monomers described in Japanese Patent Application No. 6-37206 are also useful.

Particularly preferred as the structural unit used together with the structural unit represented by the general formula [2] is a structural unit obtained by polymerizing a vinyl monomer represented by the following general formulas [3] and [4]. It is.

[0019]

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[0020]

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In the formulas [3] and [4], A is a hydrogen atom,
Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms. Z
Represents an oxygen atom or —NR ² —, and R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. B represents an alkyl group, a substituted alkyl group, an aromatic group, a substituted aromatic group, or a heterocyclic group which may have a substituent. The carbon number of the alkyl group portion in the alkyl group and the substituted alkyl group of B is preferably 1 to 9. Preferred examples of the substituent in the substituted alkyl group of B include a halogen atom, an alkoxy group, a substituted alkoxy group, a hydroxy group, an acetoxy group, a phenyl group and a substituted phenyl group. Preferred examples of the aromatic group and the substituted aromatic group of B include a phenyl group, a substituted phenyl group, a naphthyl group, and a substituted naphthyl group. The heterocyclic group of B is preferably a group containing at least one nitrogen, oxygen or sulfur atom.
A 7-membered monocyclic or polycyclic heterocyclic group is exemplified.

In the formulas [3] and [4], A is particularly preferably hydrogen and methyl. Z is particularly preferably an oxygen atom or -NH-. B is particularly preferably an alkyl group having 1 to 6 carbon atoms; a halogen atom, an alkoxy group, a substituted alkoxy group, a hydroxy group, a phenyl group or a substituted alkyl group having 1 to 6 carbon atoms substituted with a substituted phenyl group; And a 5- to 7-membered monocyclic or polycyclic heterocyclic group containing a nitrogen atom.

Preferred examples of the compound represented by the formula [3] include acrylonitrile and methacrylonitrile. Preferred examples of the compound represented by the formula [4] include methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methacrylic acid,
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, acrylate of diethylene glycol monomethyl ether, acrylate of diethylene glycol monophenyl ether, N- (p-sulfamoylphenyl) methacrylamide, N- (p-
Sulfamoylphenyl) acrylamide and a coupler monomer represented by the following structure [5] can be mentioned.

[0024]

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The proportion of the monomers represented by the general formulas [3] and [4] in the polymer is independently 3 mol% or more and 80 mol% or less, preferably 5 mol% or more and 70 mol% or less. % Or less. Next, typical examples of the polymer having an active imino group in the present invention are shown below. However, the polymer of the present invention is not limited to these.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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These alkali-soluble resins can be used alone or in combination of two or more. As these alkali-soluble resins, those having a wide range of acid values (moles of acidic groups per unit weight) can be used, but 0.5 to 4.0.
(Meq / g), and more preferably 1.0 to 3.0 (meq / g).

The photosensitive substance (photosensitive agent) used in the present invention is not particularly limited as long as it is a quinonediazide sulfonic acid ester of the compound represented by the general formula (1). As a specific example, the ester moiety is 1,
2-naphthoquinonediazide-4-sulfonic acid ester,
Compounds such as 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, and other sulfonic acid esters of quinonediazide derivatives However, the present invention is not limited to this.

The following are specific examples of the compound represented by the general formula (1).

[0037]

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[0038]

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[0039]

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[0040]

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The compound represented by the above general formula (1) is preferably prepared by reacting the corresponding phenol or substituted phenol with a bifunctional aldehyde or ketone in the presence of an acidic catalyst such as hydrochloric acid. Obtained in yield. The compound represented by the general formula (1) thus obtained is crystallized in an organic solvent such as alcohol, acetone, acetic acid, benzene, and toluene or a mixed solvent thereof, or by silica gel column chromatography. It can be purified.

The photosensitive material of the present invention may be prepared, for example, by adding a part or all of the hydroxyl groups of the polyhydroxy compound to 1,2-
It is obtained by performing a normal esterification reaction with naphthoquinonediazide-5-sulfonyl chloride in the presence of a basic catalyst. That is, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride, and a solvent such as dioxane, acetone, methyl ethyl ketone, N-methylpyrrolidone and the like are charged in a flask, and a basic catalyst such as sodium hydroxide, Sodium bicarbonate, triethylamine and the like are added dropwise for condensation. The obtained product is washed with water, purified and dried.

In the above esterification reaction, a mixture having various esterification numbers and esterification positions is obtained. Therefore, the esterification rate referred to in the present invention is defined as an average value of this mixture. The esterification rate thus defined is determined by comparing the raw material polyhydroxy compound and 1,2
-Naphthoquinonediazide-5-sulfonyl chloride. That is, virtually all of the added 1,2-naphthoquinonediazide-5-sulfonyl chloride causes an esterification reaction, so that the molar ratio of the raw materials may be adjusted to obtain a mixture having a desired esterification rate. The esterification rate is not particularly limited, but is preferably 5 to 100%, and more preferably 10 to 100%.

Similarly, the photosensitive substance of the present invention can be obtained by reacting with 2,1-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride or the like. The reaction temperature by the above method is usually -20 to 60 ° C, preferably 0 to 40 ° C.
° C.

The photosensitive substance synthesized by the above method is used when used as the positive photosensitive composition of the present invention.
It is used alone or as a mixture of two or more kinds and blended in an alkali-soluble resin or the like. The blending amount is 5 to 100 parts by weight, preferably 10 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. is there. If the use ratio is less than 5 parts by weight, the residual film ratio is remarkably reduced, and if it exceeds 100 parts by weight, sensitivity and solubility in a solvent are reduced.

In the present invention, it is not always necessary, but if necessary, a known photosensitive material may be used in combination with the photosensitive material. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, and JP-A-48-63803.
No. 96575, No. 49-38701, No. 48-133
No. 54, Japanese Patent Publication No. 37-18015, 41-1122
No. 2, No. 45-9610, No. 49-17481, U.S. Pat. Nos. 2,797,213 and 3,45.
No. 4,400, No. 3,544,323, No. 3,5
No. 73,917, No. 3,674,495, No. 3,
785,825, British Patent No. 1,227,602,
Nos. 1,251,345 and 1,267,005
No. 1,329,888, No. 1,330,93
No. 2, German Patent No. 854,890 and the like can be used in combination.

In this case, it can be used in a proportion of 1 to 100 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the photosensitive substance of the present invention.

Various additives can be further added to the positive photosensitive composition of the present invention, if necessary. For example, cyclic acid anhydrides, phenols, and organic acids can be used in combination for the purpose of improving sensitivity. Cyclic acid anhydride include US Patent has been and phthalic anhydride described in 4,115,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride acid,
Maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane, etc. Further, examples of the organic acids include sulfonic acids, sulfinic acids, and alkyl sulfates described in JP-A-60-88942 and JP-A-2-96755. , Phosphonic acids, phosphoric acid esters, carboxylic acids, and the like. Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phosphorus Phenyl acid, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxy Benzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid,
Erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned.

The proportion of the above cyclic acid anhydride, phenols and organic acids in the photosensitive composition is 0.05 to 2%.
It is preferably 0% by weight, more preferably 0.1 to 15% by weight, particularly preferably 0.1 to 10% by weight.

In the photosensitive composition of the present invention, in order to widen the stability of processing under development conditions, the photosensitive composition described in JP-A-62-251740 or JP-A-3-208514 is used. Nonionic surfactant, JP-A-59-121044
And an amphoteric surfactant described in JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearic acid, and polyoxyethylene nonyl phenyl ether.

Specific examples of the surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N
-Tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo KK) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by weight, and more preferably 0.1 to 5% by weight.

In the photosensitive composition of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure,
Dyes and pigments as image colorants can be added.
Representative examples of the printing-out agent include a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. In particular,
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53-3622
No. 3, 54-74728, 60-3626, 61-143748
And combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A Nos. 61-151644 and 63-58440. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the salt-forming organic dyes described above. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink #
312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), ethyl violet, rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, JP-A-62-2932
The dyes described in JP-B-47 are particularly preferred. These dyes are used in an amount of 0.01 to 10 based on the total solid content of the photosensitive composition.
% By weight, preferably 0.1 to 3% by weight, can be added to the photosensitive composition.

Further, a plasticizer may be added to the photosensitive composition of the present invention, if necessary, for imparting flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid, and the like are used.

The lithographic printing plate of the present invention can be usually produced by dissolving each of the above-mentioned components in a solvent and coating the solution on a suitable support. As the solvent used here,
Ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-
2-propanol, 2-methoxyethyl acetate, 1
-Methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, Examples include, but are not limited to, toluene.

These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. Also apply,
The coating amount (solid content) on the support obtained after drying is generally preferably from 0.5 to 5.0 g / m ² . As a method of applying, various methods can be used, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating,
Roll coating and the like can be mentioned. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate.

In the photosensitive layer in the present invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant as described in JP-A-62-170950 may be added. Can be. A preferable addition amount is 0.01 to 1% by weight of the total photosensitive composition, more preferably 0.05 to 0.5% by weight.

The support used in the present invention is a dimensionally stable plate-like material, such as paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate ( For example, aluminum, zinc, copper, etc.), plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic film on which a metal is laminated or vapor-deposited as described above.

As the support of the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in aluminum alloys include silicon, iron, manganese,
Copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Aluminum which is particularly preferred in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.3 mm.
It is.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution for removing the rolling oil on the surface is performed. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

The aluminum plate thus roughened is
After an alkali etching treatment and a neutralization treatment as necessary, an anodic oxidation treatment is performed as required to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes for forming a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The conditions of the anodizing treatment vary depending on the electrolyte to be used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , voltage 1-100V, electrolysis time 1
A range of 0 seconds to 5 minutes is appropriate. If the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area of the lithographic printing plate is easily damaged, and the ink adheres to the damaged area during printing. So-called "scratch dirt" tends to occur.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. U.S. Pat.No. 2,714,066 as the hydrophilization treatment used in the present invention,
Nos. 3,181,461, 3,280,734 and 3,902,734
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in US Pat. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Patent Nos. 3,276,868, 4,153,461 and 4,68.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in US Pat. No. 9,272 is used.

The lithographic printing plate of the present invention has a positive photosensitive composition provided on a support. If necessary, an undercoat layer may be provided between the positive photosensitive composition and a matt layer on the photosensitive composition layer. Layers can be provided. As the undercoat layer component, various organic compounds are used, for example, carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and phenylphosphonic acid optionally having a substituent Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphinic acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloric acid of triethanolamine Hydroxy such as salt -Alanine, and hydrochlorides of amines having a group may be used in combination of two or more.

This organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, or the like is used. A method in which an aluminum plate is immersed in a solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof to adsorb the above compound by immersing the aluminum plate, and then washed and dried with water or the like to provide an organic undercoat layer. . In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, and the immersion temperature is 20 to 90 ° C, preferably 25 to 50%.
° C and the immersion time is from 0.1 second to 20 minutes, preferably from 2 seconds to 1 minute. The solution used for this can be adjusted to pH 1 to 12 with a basic substance such as ammonia, triethylamine, potassium hydroxide or the like, or an acidic substance such as hydrochloric acid or phosphoric acid. Further, a yellow dye can be added for improving the tone reproducibility of the image recording material.

The coating amount of the organic undercoat layer is 2 to 200 mg / m
² is suitable, preferably 5 to 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² .

Further, a mat layer can be provided on the surface of the positive photosensitive composition layer of the present invention in order to prevent abrasion, adhesion failure and the like. Specifically, a method of providing a mat layer as described in JP-A-50-125805, JP-B-57-6658 and JP-B-61-28986 is described in JP-B-62-62337. And a method of thermally fusing such solid powder.

The average diameter of the mat layer used in the present invention is 1
00 μm or less, more preferably 2 μm or less.
８8 μm. When the average diameter is large, it is difficult to form a thin line and the number of highlight dots is reduced, which is not preferable in tone reproduction. If the average diameter is 2 μm or less, it is not preferable in terms of scratches and the like. The coating amount of the mat layer is preferably from 5 to 200 mg / m ^2, more preferably from 20~150mg / m ^2. A coating amount larger than this range causes abrasion, while a coating amount smaller than this range is not preferable in terms of adhesion failure. The positive image recording material prepared as described above is usually subjected to image exposure and development processing.

The light source of the actinic ray used for the image exposure includes, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp and the like.
In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. In the present invention, a light source having an emission wavelength in the near ultraviolet to ultraviolet region is preferable, and a mercury lamp and a metal halide lamp are particularly preferable.

As the developer and replenisher for the lithographic printing plate of the present invention, conventionally known aqueous alkali solutions can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium, ammonium, sodium hydroxide,
And inorganic alkali salts such as ammonium, potassium and lithium. Also, monomethylamine,
Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, Organic alkali agents such as pyridine are also used.

These alkali agents are used alone or in combination of two or more. Among these alkaline agents, preferred developers are aqueous solutions of silicic acid such as sodium silicate and potassium silicate, aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, carbonates and carbonates. It is an aqueous solution of a hydrogen salt. Particularly preferred is a combination of a carbonate and a bicarbonate having a relatively low pH.

Further, when developing using an automatic developing machine, an aqueous solution having a higher alkali strength than the developing solution (replenisher)
It has been known that a large amount of PS plates can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. This replenishment system is also preferably applied in the present invention. Various surfactants and organic solvents can be added to the developing solution and the replenishing solution as required for the purpose of accelerating or suppressing the developing property, dispersing the developing residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

The developing solution and the replenisher may further include, if necessary, reducing agents such as sodium salts and potassium salts of inorganic acids such as hydroquinone, resorcin, sulfurous acid and bisulfite, organic carboxylic acids, antifoaming agents, and hard water. Softeners can also be added. The printing plate developed using the above developer and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As the post-processing, these processings can be used in various combinations.

In recent years, in the plate making and printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a printing plate, each processing solution tank and a spray device, and while pumping the exposed printing plate horizontally, each pumped by a pump. The developing process is performed by spraying a processing liquid from a spray nozzle. Recently, a method has been known in which a printing plate is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like.

Further, a so-called disposable processing method in which processing is performed with a substantially unused processing solution can also be applied. Further, if the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming has an unnecessary image portion (for example, a film edge mark of the original film),
The unnecessary image portion is erased. Such erasing is preferably carried out by applying an erasing liquid as described in, for example, Japanese Patent Publication No. 2-13293, to an unnecessary image portion, leaving it for a predetermined time, and then rinsing with water. A method described in JP-A-59-174842, in which active light guided by an optical fiber is applied to an unnecessary image portion and then developed, can also be used.

[0076]

Next, the present invention will be described in more detail with reference to examples. All percentages in the following examples are percentages by weight unless otherwise specified. Examples 1 to 8 and Comparative Examples a to c An aluminum plate having a thickness of 0.30 mm was
The surface was grained with an aqueous suspension of pumicestone of 00 mesh, and then thoroughly washed with water. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% nitric acid, and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution at an anode electricity of 160 coulomb / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was 0.6 μm ( _Ra display). Then immersed in a 30% aqueous sulfuric acid solution at 55 ° C
After desmutting for 2 minutes, the substrate (I) was obtained by anodizing in a 20% aqueous sulfuric acid solution at a current density of 2 A / dm ^{2 so} that the thickness became 2.7 g / m ² . This substrate (I)
It was immersed in a 2.5% aqueous solution of sodium silicate at 0 ° C. for 1 minute, washed with water, and dried. The undercoat liquid (A) having the following composition was applied to the surface of the substrate thus treated, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 30 mg / m ² .

Undercoat solution (A) Phenylphosphonic acid 0.064 g 1% aqueous sulfuric acid solution 6.0 g 1% aqueous phosphoric acid solution 6.0 g Methanol 70 g Pure water 18 g In this way, a substrate (II) was prepared.

Next, the following photosensitive solution (A) was coated on the substrate (II) at 25 ml / m ^{2 and} dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The coated amount after drying was about 1.7 g / m ² . Photosensitive solution (A) Photosensitive substance described in Table 1 0.75 g Alkali-soluble resin shown in Table 2 (1) 2.0 g 2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine 0.02 g naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.03 g crystal violet 0.01 g oil blue 3 # 603 0.015 g (manufactured by Orient Chemical Industry Co., Ltd.) 1-methoxy-2-propanol 18 g 12 g of 2-methoxyethyl acetate Each of these photosensitive lithographic printing plates was passed through a positive transparent original from a distance of 1 m with a 2 kW metal halide lamp at a distance of 1 m.
Exposure for seconds.

The exposed photosensitive lithographic printing plate was developed under the following conditions. That is, first, a developer obtained by diluting the following developer 1 by 4 times with water and a finisher FP-2 manufactured by Fuji Photo Film Co., Ltd. were respectively charged into an automatic developing machine Stublon 900NP manufactured by Fuji Photo Film Co., Ltd. The development processing was performed under the conditions of 30 ° C. and a development time of 30 seconds.

Developer-1 Sodium carbonate / monohydrate 7 g Sodium bicarbonate 4.5 g Ethylenediaminetetraacetic acid 2 g Water 100 g After the development, the obtained lithographic printing plate was printed with an offset printing machine to test the printing durability. Was done. If the printing durability is poor, the image portion wears out with a small number of sheets, and the ink does not adhere to the printed portion, so that a normal printed matter cannot be obtained.

Further, in order to examine the change in sensitivity (sensitivity change with time) from time to time from exposure to development, after exposure under the above conditions, development was performed after aging at 35 ° C. and 85% humidity for 16 hours. Immediately after, the sensitivity was compared with the lithographic printing plate developed. If the sensitivity hardly fluctuated,
X, those that did not produce normal printed matter due to large changes
The middle is indicated by △. Table 1 shows the results.
From these results, it can be seen that the positive planographic printing plate of the present invention has extremely excellent performance as compared with Comparative Examples. Further, when developing with a developer having a relatively low pH such as Developer-1, the effect of the present invention is remarkable.

[0082]

[Table 1] No. Photosensitive substance Printing durability (sheets) Change in sensitivity over time Example 1 (1) 230,000 ○ Example 2 (2) 220,000 ○ Example 3 (3) 240,000 ○ Example 4 (4) 220,000 ○ Example 5 (5) 250,000 ○ Example 6 (6) 220,000 △ Example 7 (7) 210,000 ○ Example 8 (8) 200,000 △ Comparative example a (a) 180,000 ○ Comparative example b (b) 19 10,000 △ Comparative Example c (c) 180,000 ×

(1) 1,2naphthoquinonediazide-5-sulfonic acid ester of compound (1) (esterification rate 8
(2) 1,2 naphthoquinonediazide of compound (1)
4-sulfonic acid ester (esterification rate 85%) (3) 1,2 naphthoquinonediazide of compound (2)
5-sulfonic acid ester (esterification rate 85%) (4) 1,2 naphthoquinonediazide of compound (2)
4-sulfonic acid ester (esterification rate 85%) (5) 1,2-naphthoquinonediazide of compound (5)
5-Sulfonate (esterification rate 85%) (6) 1,2-naphthoquinonediazide of compound (5)
4-sulfonic acid ester (esterification rate 85%) (7) 1,2-naphthoquinonediazide of compound (14)
5-Sulfonate (esterification rate 90%) (8) 1,2-naphthoquinonediazide of compound (14)
4-sulfonic acid ester (esterification rate 90%) (a) Esterified product of pyrogallol-acetone resin and 1,2 naphthoquinonediazide-5-sulfon chloride (described in Example 1 of U.S. Pat. No. 3,635,709) (B) Esterified product of 2,3,4-trihydroxybenzophenone and 1,2 naphthoquinonediazide-5-sulfonyl chloride (esterification rate 77%) (c) 2,3,4-trihydroxybenzophenone Esterified product with 1,2 naphthoquinonediazide-4-sulfonyl chloride (esterification rate 77%)

[0084]

[Table 2]

Examples 9 to 12 and Comparative Examples de to e Substrates (II) were prepared by treating aluminum plates under the same conditions as in Examples 1 to 8. Next, the following photosensitive liquid (B) was applied onto the substrate (II) and dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying is about 1.
It was 7 g / m ² . Photosensitive solution (B) Photosensitive substance described in Table 1 0.45 g Alkali-soluble resin (binder) described in Table 2 1.2 g Naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.01 g Tetrahydrophthalic anhydride 0.02 g Benzoic acid 0.02 g Pyrogallol 0.05 g 4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine 0.02 g N- ( 1,2-naphthoquinone-2-diazido-4-sulfonyloxy) -cyclohexane-1,2-dicarboxylic acid imide 0.01 g The counter anion of Victoria Pure Blue BOH (produced by Hodogaya Chemical Co., Ltd.) is 1-naphthalenesulfonic acid. 0.045g Megafac F-177 (Dai Nippon Ink Chemical Industry Co., Ltd. Fluorine) Surfactant) 0.015 g Methyl ethyl ketone 25 g Propylene glycol monomethyl ether 10 g

Next, these photosensitive lithographic printing plates were each passed through a transparent positive film for 1 m in a vacuum furnace.
1 min. From a 3 kW metal halide lamp from a distance of 1 mm, then developed by Fuji Photo Film Co., Ltd., DP-4
Processing was carried out through an automatic developing machine charged with a (1: 8) rinse solution FR-3 (1: 7). Next, the plate surface was treated with a solution obtained by diluting Gum GU-7, a product of Fuji Photo Film Co., Ltd., with water two-fold, left for one day, and then printed on an offset printing machine to perform a printing durability test. Further, a test for a change in sensitivity over time was performed in the same manner as in Examples 1 to 8. Table 3 shows the results.

The planographic printing plate obtained by processing according to a conventional method was printed by an offset printing machine, and a printing durability test was performed. Further, a test for a change in sensitivity over time was performed in the same manner as in Examples 1 to 8. Table 3 shows the results. As is clear from Table 3, the photosensitive composition of the present invention has extremely excellent performance.

[0088]

[Table 3] No. Photosensitive material Binder Printing durability (sheets) Change in sensitivity over time Example 9 (1) (2) 230,000 Example 10 (1) (3) 220,000 Example 11 (2) (2) 240,000 Example Example 12 (2) (3) 220,000 ○ Comparative example d (a) (2) 200,000 ○ Comparative example e (b) (2) 190,000 ×

Examples 13 to 16 and Comparative Examples f to g A substrate (I) was prepared by treating an aluminum plate under the same conditions as in Examples 1 to 8. Next, the undercoat liquid (B) was applied to the substrate (I) and dried at 80 ° C. for 30 seconds. The coating amount after drying was 30 mg / m ² . Undercoat liquid (B) Aminoethylphosphonic acid 0.1 g Phenylphosphonic acid 0.15 g β-alanine 0.1 g Methanol 40 g Pure water 60 g In this way, a substrate (III) was prepared.

Next, on this substrate (III), a photosensitive solution (B)
And dried at 100 ° C. for 1 minute to obtain a positive photosensitive printing plate. The coated amount after drying was about 1.7 g / m ² .

Next, these photosensitive lithographic printing plates were each passed through a transparent positive film in a vacuum furnace for 1 m.
1 min. From a 3 kW metal halide lamp from a distance of 1 mm, then developed by Fuji Photo Film Co., Ltd., DP-4
Processing was carried out through an automatic developing machine charged with a (1: 8) rinse solution FR-3 (1: 7). Next, the plate surface was treated with a solution obtained by diluting Gum GU-7, a product of Fuji Photo Film Co., Ltd., with water two-fold, left for one day, and then printed on an offset printing machine to perform a printing durability test. Further, a test for a change in sensitivity over time was performed in the same manner as in Examples 1 to 8. Table 4 shows the results.

As is clear from Table 4, the photosensitive composition of the present invention has extremely excellent performance.

[0093]

[Table 4] No. Photosensitive material Binder Printing durability (sheets) Change in sensitivity over time Example 13 (1) (2) 250,000 ○ Example 14 (1) (3) 230,000 ○ Example 15 (2) (2) 240,000 ○ Example 16 (2) (3) 220,000 ○ Comparative example f (a) (2) 190,000 ○ Comparative example g (b) (2) 180,000 ×

[0094]

According to the present invention, there is provided a photosensitive lithographic printing plate having high developability even in an aqueous alkaline solution having a relatively low pH, having good adhesion to a substrate, providing a flexible film, and having high printing durability. Can be. Furthermore, the present invention relates to a photosensitive lithographic printing plate having a slight decrease in performance such as a change in sensitivity over time after exposure even when a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound is used as a photosensitive substance. Can be provided.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Noriaki Watanabe 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd. (56) References JP-A-6-35185 (JP, A) JP-A-6 JP-A-43636 (JP, A) JP-A-4-1652 (JP, A) JP-A-4-301185 (JP, A) JP-A-4-343359 (JP, A) JP-A-5-249665 (JP, A) JP-A-5-27430 (JP, A) JP-A-5-289333 (JP, A) JP-A-6-59447 (JP, A) JP-A-63-226441 (JP, A) JP-A-63-264 124047 (JP, A) (58) Fields studied (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claims] 1. A polyhydroxy compound represented by the following general formula (1): 1,2 (or 2,1) -naphthoquinonediazide-4- (or-
5-) a photosensitive substance comprising a sulfonic acid ester ;
Acrylic polymer having sulfonamide group, carbo
Urethane-based polymer having acid and active imino group
At least selected from among acrylic polymers having
Photosensitive lithographic printing plate comprising coated with a positive photosensitive composition containing a one alkali-soluble resin. Embedded image In the formula (1), A represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an arylene group, or a substituted arylene group. B represents a hydrogen atom, an alkyl group or a substituted alkyl group. R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms or a hydroxyl group. is there.