JP3215900B2 - Negative 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 negative photosensitive lithographic printing.
Relates plate, more particularly, negative photosensitive having formed from a photosensitive composition suitable as a sensitive light component photosensitive layer Rights
For printing plates .

[0002]

2. Description of the Related Art Heretofore, a photosensitive composition containing a photosensitive diazo compound as a photosensitive component has been used in a photosensitive layer of a negative photosensitive lithographic printing plate. As this kind of photosensitive composition or a photosensitive component thereof, Japanese Patent Publication No. 2-47738 discloses a photosensitive composition obtained by mixing a cationic latex polymer (microgel) having a quaternary nitrogen atom and a photosensitive diazo resin compound. Composition, JP-A-4-172353 and JP-B-57-43890, a photosensitive composition containing a diazonium salt whose counter anion is a low molecular organic compound or inorganic compound, U.S. Pat. West German Patent 1,114,7
No. 04 discloses a solvent-soluble diazo polymer, Am.
Rev. Mater. Sci., 1983, 13, 178, discloses an onium salt of an inorganic compound whose counter anion is an inorganic compound, and EP-A-94915 (1984) discloses an iron-arene complex whose inorganic anion is a counter anion.

[0003]

However, the photosensitive layer formed from these known photosensitive compositions has a problem that the sensitivity, mechanical strength of the cured film and chemical resistance are not sufficient.

Accordingly, an object of the present invention is, first, to provide a high-sensitivity negative photosensitive lithographic printing plate . Second
The excellent mechanical strength of the cured film is to provide a negative photosensitive lithographic printing plate high have printing endurance can be obtained. Third
The excellent chemical resistance, high have printing durability can be obtained is to provide a negative photosensitive lithographic printing plate etching resistance is excellent when applied to a photoresist.

[0005]

The object of the present invention is as follows.
Serial thus be achieved.

A photosensitive composition containing a photosensitive microgel chemically modified with diazo, or an anionic microgel
Counter cations are onium salts and iron / arene
A photosensitive microparticle that is at least one selected from complexes
A photosensitive layer formed from a photosensitive composition containing a gel;
A negative photosensitive lithographic printing plate characterized by having:

[0007]

Hereinafter, the present invention will be described in detail.

The photosensitive microgel chemically modified with diazo according to the present invention is a compound in which a compound having a diazo group (hereinafter referred to as "diazo compound") and the microgel are bonded by ionic bond or covalent bond.

(1) A compound in which a diazo compound and a microgel are bonded by an ionic bond. A compound in which the counter anion of a cationic microgel is a diazo compound having an anionic group and a counterion of a diazonium salt in which an anionic microgel is used. Can be

(1-1) Microgel wherein the counter anion of the cationic microgel is a diazo compound having an anionic group The cationic microgel is a latex polymer having a quaternary nitrogen atom, that is, water or a polar solvent. Used is a granular polymer dispersed in the polymer. The cationic latex polymer preferably contains a quaternary nitrogen atom in the side chain of the latex polymer. Representative examples of the monomer units forming such a latex polymer include those represented by the following general formulas [1] to [5].

[0012]

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[0013]

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[0014] In general formula [1] to [5], X ^- represents an anion. That is, halogen ions, sulfate ions,
Phosphate ion, sulfonate ion, acetate ion and the like. The Rs bonded to N ⁺ may be the same or different, and each R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl) , Decyl), an alkenyl group (eg, propenyl, butynyl), or an aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl), an aralkyl group (eg, benzyl, phenethyl, Each group of naphthylmethyl),
Alternatively, it represents an alkaryl group (for example, each group of tolyl and xylyl). Z represents a group of nonmetal atoms necessary for forming an unsaturated heterocyclic ring, and is preferably an imidazole, pyridine, piperidine, pyrrole or morpholine ring. n
Represents an integer.

The cationic monomer forming the cationic latex polymer preferably forms a copolymer with a non-cationic monomer in order to control water solubility.
Such non-cationic monomers include acrylic acid, esters of methacrylic acid, styrene, alkylene,
Ether, vinyl acetate, acrylonitrile and the like can be mentioned. In the present invention, the cationic latex polymer is preferably cross-linked by a monomer having two or more functional groups such as divinylbenzene and dimethacrylate,
It is desirably produced by emulsion polymerization.

When the copolymer is formed, the cationic monomer is preferably contained in the cationic latex polymer in an amount of from 5 to 95% by weight, more preferably from 25 to 65% by weight. Further, the non-cationic monomer preferably contains 5 to 95% by weight of the cationic latex polymer.
% By weight.

As an example of the synthesis of a cationic latex polymer, vinyl benzyl chloride is emulsion-polymerized with other monomers as described in Examples of JP-A-51-73440, followed by tertiary amine. A quaternization technique is known.

Particularly preferred cationic latex polymers are latex polymers prepared by quaternizing a tertiary amine-containing latex polymer obtained by emulsion polymerization with a quaternizing agent. As an example of this synthesis, there is a technique described in JP-A-55-22766.

Another particularly preferred cationic latex polymer having a quaternary nitrogen atom is a latex polymer produced by emulsion-polymerizing a quaternary nitrogen-containing monomer with a lipophilic monomer. The synthesis method is selected from various known methods and used. One example is described in JP-A-56-17352.

The photosensitive layer formed by applying the photosensitive resin composition according to the present invention is cured by the reaction between the diazo resin and the cation in the exposed portion, loses hydrophilicity, and becomes water repellent.

However, if a large amount of cations are present inside the latex particles, the cations remain in the particles even after exposure, the hydrophilicity is maintained, the penetration of the aqueous developer cannot be prevented, and swelling occurs during development. It becomes easy to cause a decrease in film strength.

In view of the above, it is particularly desirable that the cationic latex polymer in the photosensitive resin composition according to the present invention is produced by a synthesis method in which cations are more oriented on the surface of latex particles. As the production method, a method of first synthesizing a latex polymer having a tertiary amine by emulsion polymerization and then quaternizing with a quaternizing agent is most suitable.

Another useful method for synthesizing a cationic latex polymer is a method for producing a quaternary nitrogen atom-containing monomer by emulsion polymerization with a suitable lipophilic monomer. This synthesis method is based on cationic latex polymer,
Ratio of small amount of cationic monomer units (preferably 5 to 5)
30% by weight).

In the photo-curing reaction of the photosensitive layer obtained from the photosensitive resin composition according to the present invention, the cationic group in the cationic latex polymer plays an important role. Although the reaction mechanism is not clear, a cationic latex polymer having a useful cationic group is, as described above, 4
Selected from those having a secondary nitrogen atom.

Specific examples of the cationic latex polymer include the following compounds. (Specific examples of the molar ratio are shown in parentheses.)

[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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As diazo compounds having an anionic group, diazo compounds described in JP-B-2-47738, JP-A-4-72353 and JP-B-57-43890 are further introduced with an anionic group. Compounds can be used. Specific examples include, for example, sodium 4-diazostilbene-2-sulfonate, sodium 4-diazo-1-phenylamino-2-sulfonate, sodium 4,4′-diadiastilbene-2-sulfonate, 4-diazo Sodium benzophenone-4'-carboxylate, sodium 1-diazopyrene-6-sulfonate, 4,4'-diadiazophenylazonaphthalene-5-
Examples include sodium sulfonate, sodium diazonaphthalene-4-sulfonate, sodium diazobenzene-m-carboxylate, and the like.

In order to synthesize a microgel in which the counter anion of the cationic microgel is a diazo compound having an anionic group, an aqueous solution of the diazo compound having an anionic group is mixed with an aqueous dispersion of the cationic microgel. The precipitate obtained by mixing is collected by suction filtration,
The desired product can be obtained by washing with water.

(1-2) The microgel diazonium salt in which the counter anion of the diazonium salt is an anionic microgel is a negative photosensitive lithographic printing plate (P
A photosensitive diazo compound commonly used as a photosensitive component in the photosensitive layer of the (S plate) is used. In general, such diazo compounds are diazo-aromatics, more particularly diazo-arylamines, preferably p-diazo-diphenylamine and derivatives thereof, which can be substituted on the aromatic nucleus or on the amino-nitrogen. For example, aldehydes and their condensation products with organic condensing agents containing reactive carbonyl groups such as acetal, in particular condensates with compounds such as formaldehyde zinc chloride and paraformaldehyde. The preparation of such highly suitable condensation products is described in U.S. Pat. Nos. 2,922,715 and 2,946,683.

As the anionic microgel, those having an acrylic group or a methacryl group as a monomer unit of a latex polymer and having a carboxylic acid group, a sulfonic acid group and a phosphonic acid group are used. Specific examples of the unit include the compounds shown below.

[0035]

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[0036]

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It is preferred that the above-mentioned monomer component is contained in the photopolymerizable composition of the present invention in an amount of 0.5 to 50% by weight, particularly 2 to 30% by weight.

The latex polymer of the present invention can be synthesized by copolymerizing the above-mentioned monomer and a non-anionic monomer. Examples of the non-anionic monomer used include acrylic acid, methacrylic acid ester, styrene, Examples include alkylene, ether, vinyl acetate, acrylonitrile and the like, which are preferably cross-linked by a monomer having two or more functional groups such as divinylbenzene and dimethacrylate. Such non-anionic monomer is present in the photopolymerizable composition of the present invention in an amount of 5 to 95% by weight.
Monomers such as divinylbenzene dimethacrylate are preferably contained in the composition in an amount of 0.1 to 10% by weight.

The latex polymer of the present invention can be synthesized according to the emulsion polymerization method described in, for example, JP-A-51-73440 and JP-A-55-22766.

As a method for synthesizing a microgel in which the counter anion of the diazonium salt is an anionic microgel, a precipitate obtained by mixing the aqueous solution of the diazonium salt and the aqueous dispersion of the anionic microgel is used. The target substance can be obtained by collecting by suction filtration and washing with water.

(2) Compound in which diazo compound and microgel are covalently bonded The amino group of the microgel having an amino group on the particle surface is diazotized with sodium nitrite under acidic conditions.

A microgel having an amino group is usually produced by emulsion polymerization using a monomer having an amino group. Generally, microgels have a polymer component of 99-99.5.
% By weight and 10 to 0.5% by weight of a crosslinking agent. The polymer components can be varied during the polymerization process to produce core and shell microgels with different compositions on the inside and the outside. If a polymeric binder is used, the weight ratio of microgel to binder is from 1:20 to 1: 1.
It can be changed widely within the range.

Microgels can be made from a variety of starting materials. Usually, monomers having one ethylenically unsaturated bond are used to make up most microgels, but the crosslinking agent has at least two double bonds.

Examples of the monomer having an amino group include acrylamide, methacrylamide, 2-aminoethyl vinyl ether, p-aminostyrene and the like.

Preferred monomers copolymerized with these are methyl methacrylate, ethyl acrylate,
Methacrylic acid, butyl methacrylate, ethyl methacrylate, glycidyl methacrylate, styrene and allyl methacrylate; other useful monomers include acrylonitrile, methacrylonitrile,
Acrylic acid, methacrylic acid and 2-methyl-hexyl acrylate are included.

The preferred crosslinking agent is butanediol diacrylate, but others include ethylene glycol dimethacrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, tetraethylene glycol dimethacrylate, methylene bisacrylamide. , Methylenebismethacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl benzene, glycerin trimethacrylate, pentaerythritol tetramethacrylate, triallyl cyanurate, divinyl acetylene, divinyl ethane, divinyl Sulfide, divinyl sulfone, hexatriene, triethylene glycol dimethacrylate, Arirushianamido, glycol diacrylate, ethylene glycol divinyl ether,
Diallyl phthalate, divinyl dimethyl silane, glycerol trivinyl ether and the like.

Usually, in preparing microgels, one or several monomers and a crosslinking agent are dispersed in water together with a suitable emulsifier and an initiator. Usually anionic, cationic or nonionic emulsifiers and water-soluble initiators are used. Examples of emulsifiers include sodium lauryl sulfate, lauryl pyridine chloride, polyoxyethylene, polyoxypropylene, colloidal silica, anionic organic phosphates, magnesium montmorillonite, the reaction product of one mole of octylphenol and 12-13 moles of ethylene oxide. , Sodium alkyl sulfate and mixtures thereof. Examples of initiators are potassium persulfate, sodium persulfate, ammonium persulfate, t-butyl hydroperoxide, hydrogen peroxide, azobis (isobutyronitrile), azobis (isobutylimidine hydrochloride), hydrogen peroxide-sulfuric acid Various redox (oxidation-reduction) systems such as ferrous iron and the well-known persulfate-bisulfite combination.
0.05 to 5 based on the weight of the normally copolymerized monomer
% By weight of initiator is used.

Another method for introducing a hydroxyl group or an amino group into the particle surface is described in, for example, "Chemical reaction of polymer (above)".
(Below) "(Nobuo Ogawara, Kagaku Doujin, l972)," Polymer Fine Chemicals "(Ryohei Oda, Kodansha, 1976)," Reactive Polymers "(Keita Kurita, Yoshio Iwakura, Kodansha, l977), etc. For example, after a microgel having a reactive group is synthesized, the reactive group may be chemically modified with a compound having an amino group, or the reactive group may be modified with a polymerizable monomer having an amino group. A method of graft polymerization at the starting point is used.

In order to synthesize a compound in which the diazo compound and the microgel are bonded by a covalent bond, the aqueous dispersion of the microgel having an amino group is acidified with sulfuric acid, hydrochloric acid or the like, and
The solution was cooled to around 0 ° C., and a concentrated aqueous solution of sodium nitrite was added dropwise with stirring. After the addition, it was confirmed that the solution was acidic. Then, the solution was stirred for 30 minutes to complete diazotization. If a salt of a desired counter anion (eg, zinc chloride, ammonium hexafluorophosphate) is added to this solution and shaken well and allowed to stand, a microgel having a diazo group precipitates.

Next, a photosensitive composition containing a photosensitive microgel in which the counter cation of the anionic microgel is at least one selected from an onium salt and an iron-arene complex will be described.

As the onium salt, a compound represented by the following general formula [6] or [7] is used.

[0052]

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In the general formulas [6] and [7], Ar ¹ and Ar ² may be the same or different and represent a substituted or unsubstituted aryl group. Preferred substituents are alkyl, haloalkyl, cycloalkyl, aryl, alkoxy,
Nitro, carboxy, alkoxycarbonyl, hydroxy and mercapto groups and halogen atoms, more preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group and a chlorine atom.

R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms and an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof.

Preferred substituents are alkoxy having 1 to 8 carbon atoms, alkyl having 1 to 8 carbon atoms, nitro, carboxy, hydroxy group and halogen atom for the aryl group. Is an alkoxy, carboxy, or alkoxycarbonyl group having 1 to 8 carbon atoms.

Further, two of R ⁴ , R ⁵ and R ⁶ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

X ^- represents an anion (counter ion). Specific examples include halogen atom anions, BF ₄ ⁻ , BC
l ₄ ⁻ , ZrCl ₅ ⁻ , SbCl ₆ ⁻ , FeCl ₄ ⁻ , GaCl ₄ ⁻ , GaB
r ₄ ⁻ , AlI ₄ ⁻ , AlCl ₄ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , PF
₆ ^-, BPh ₄ ^-, naphthalene-1-sulfonic acid, anthracene
Examples thereof include, but are not limited to, condensed polynuclear aromatic sulfonic acid anions such as -1-sulfonic acid, anthraquinone sulfonic acid anions, anthracene sulfonic acid anions, and sulfonic acid group-containing dyes.

Specific examples of the compound represented by the general formula [6] are shown below.

[0059]

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[0060]

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[0061]

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[0062]

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Specific examples of the compound represented by the general formula [7] used in the present invention are shown below.

[0064]

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[0065]

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In the present invention, the amount of the onium compound used is in the range of 0.01 to 50 parts by weight, particularly preferably 0.1 to 20 parts by weight, based on 100 parts of the photopolymerizable ethylenically unsaturated compound.

The compounds represented by the general formulas [6] and [7] are described, for example, in J. Am. W. Knapczyk et al. Am. Che
m. Soc., Vol. 91, pp. 145 (1969); L. Myac
ock et al. Org. Chem., 35, 2532 (1970
Year), E. Goethals et al., Bull. Soc. Chem. Bel
g., 73, 546 (1964); M. Leicester
Author, J. et al. Am. Chem. Soc., Vol. 51, p. 3587 (1929
Year), J.M. V. Crivello et al. Polym. Soc. Po
lym. Chem. Ed., 18: 2677 (1980); U.S. Pat. Nos. 2,807,648 and 4,247,473; M. Ber
inger et al. Am. Chem. Soc., Vol. 75, p. 2705 (1953), JP-A-53-101331, and the like.

As the anionic microgel, the anionic microgel described in the above (1-2) can be used.

In order to synthesize a photosensitive microgel in which the counter cation of the anionic microgel is an onium salt from the onium salt and the anionic microgel, the aqueous solution of the onium salt and / or the polar solvent solution and the anionic microgel are combined with the anionic microgel. The precipitate obtained by mixing with the aqueous dispersion of the gel is collected by suction filtration, and washed with water to obtain the desired product.

The photosensitive microgel in which the counter cation of the anionic microgel is an iron-arene complex is as follows:
The precipitate obtained by mixing the aqueous solution of the iron / arene complex and / or the polar solvent solution with the aqueous dispersion of the anionic microgel is collected by suction filtration, and washed with water to obtain the desired product. As the anionic microgel, those described above can be used.

The iron-arene complex used in the present invention is
It is represented by the following general formula [8].

[0072]

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In the general formula [8], R ¹ and R ² represent C ₁ to
Alkyl C _12, alkenyl group of C ₂ ~C _12, C ₂ ~C
₁₂ alkynyl groups, C ₁ -C ₈ alkoxy groups, cyano groups, alkylthio groups, phenoxy groups, C ₂ -C ₆ monocarboxylic acids and esters and amide groups, phenyl groups, C ₂
Alkanoyl group, an ammonium group -C _5, a pyridinium group, a nitro group, an alkylsulfinyl group, selected from alkylsulfonyloxy groups and sulfamoyl groups.

The iron-arene complex represented by the general formula [8] is described in Chemiker-Zeitung, 108 (II) 345-354 (198
Many compounds are described in 4).

Specifically, (η ⁶ -benzene) (η ⁵ -cyclopentadienyl) iron (II) -hexafluorophosphate, (η ⁶ -toluene) (η ⁵ -cyclopentadienyl) iron (II) Hexafluorophosphate, (η ⁶ -cumene)
(Η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate, (η ⁶ -benzene) (η ⁵ -cyclopentadienyl) iron (II) hexafluoroarsenate, (η ^6-
Benzene) (η ⁵ -cyclopentadienyl) iron (II) tetrafluoroborate, (η ⁶ -naphthalene) (η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate, (η ⁶ -anthracene) (η ⁵ - cyclopentadienyl) iron (II) hexafluorophosphate, (eta ⁶ - pyrene) (eta ⁵ - cyclopentadienyl) iron (II) hexafluorophosphate, (eta ⁶ - benzene) (eta ⁵ - Shianoshikuro pentadienyl) iron (II) hexafluorophosphate, (eta ⁶ - toluene) (eta ⁵ - acetyl cyclopentadienyl) iron (II) hexafluorophosphate, (eta ⁶ - cumene) (eta ⁵ - chloro cyclopentadienyl (Enyl) iron (II) tetrafluoroborate, (η ⁶ -benzene) (η ⁵ -carboethoxycyclohexadienyl) iron (II) hexafluorophosphate, (η ⁶ -benzen Zen) (η ⁵ -1,3-dichlorocyclohexadienyl) iron (II) hexafluorophosphate, (η ⁶ -cyanobenzene) (η ⁵ -cyclohexadienyl) iron (II) hexafluorophosphate, (η ⁶ -
Acetophenone) (η ⁵ -cyclohexadienyl) iron (I
I) Hexafluorophosphate, (η ⁶ -methylbenzoate) (η ⁵ -cyclopentadienyl) iron (II) Hexafluorophosphate, (η ⁶ -benzenesulfonamide) (η ⁵ -cyclopentadienyl) iron (II) ) Tetrafluoroborate, (η ⁶ -benzenesulfonamide) (η ^5-
Cyclopentadienyl) iron (II) hexafluorophosphate, (η ⁶ -cyanobenzene) (η ⁵ -cyanocyclopentadienyl) iron (II) hexafluorophosphate,
(Η ⁶ -chloronaphthalene) (η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate, (η ⁶ -anthracene) (η ⁵ -cyanocyclopentadienyl) iron (I
I) Hexafluorophosphate and the like. These compounds are available from Dokl. Akd. Nauk SSSR 149 61
5 (1963).

The microgel and photosensitive microgel of the present invention have a particle diameter of 0.005 to 1 μm, have a crosslinked structure inside the particles, are insoluble in a solvent, can be dispersed in water or an organic solvent, and Is a gel having a microscopically inhomogeneous structure, even if it is visually transparent when formed.

Next, a synthesis example of the photosensitive microgel of the present invention will be described. Synthesis Examples 1 to 4 are synthesis examples of photosensitive microgels chemically modified with diazo, Synthesis Examples 5 and 6 are photosensitive microgels in which the counter cation of an anionic microgel is an onium salt, and Synthesis Example 7 is also a counter. It is a synthesis example of a photosensitive microgel whose cation is an iron-arene complex.

Synthesis Example 1 In accordance with the method for synthesizing a cationic microgel described in JP-A-55-22766, Exemplified Compound (1) of JP-B-2-47738 was synthesized. A precipitate obtained by mixing a solution in which 66 g of this microgel was dispersed in water and a solution obtained by dissolving 26.8 g of sodium diazonaphthalene-4-sulfonate in water was collected by suction filtration, washed with water, and then washed under reduced pressure. Dry and photosensitive microgel (1)
I got

Synthesis Example 2 A photosensitive microgel (2) was prepared in the same manner as in Synthesis Example 1 except that sodium diazobenzene-m-carboxylate was used instead of sodium diazonaphthalene-4-sulfonate in Synthesis Example 1. I got

Synthesis Example 3 The emulsion polymerization apparatus was equipped with a stirring stirrer in a 5-liter four-necked flask.
It is equipped with a 1 liter addition funnel, thermometer, nitrogen gas inlet tube, water-cooled condenser, and placed in a heating mantle. 3360 g of deionized water and 20 g of a 30% aqueous solution of sodium lauryl sulfonate were added to the flask, and the activator system was heated to 80 ° C. under a nitrogen atmosphere. At this temperature, 420 g of methyl methacrylate, 240 g of ethyl acrylate, 165 g of styrene sulfonic acid, 16 g of allyl methacrylate
And 25% of the monomer mixture containing 16 g of 1,4-butanediol diacrylate were added at once. To this, 10 ml of a 5% aqueous solution of potassium persulfate and 10 ml of a 7% aqueous solution of potassium phosphate were immediately added. The reaction mixture became milky and exothermic to 85 ° C. The remainder of the monomer mixture was added over a period of 90 minutes while maintaining the temperature between 80-88 ° C. When the addition was completed, the reaction mixture was heated at 80-85 ° C for another 2 hours. The bluish emulsion was cooled to room temperature and coagulated by addition of methanol. Filtering the resulting slurry,
Washed twice with water, dried by suction and the fine powder obtained was dried in a 100 ° C. oven for 4 hours. The spherical shape of the powder particles was confirmed by microscopy.

A liquid obtained by dispersing 57 g of this microgel in water
A precipitate obtained by mixing a solution obtained by dissolving 26.8 g of p-diazodiphenylamine sulfate in water is collected by suction filtration, washed with water and dried under reduced pressure to obtain a photosensitive microgel (3).
I got

Synthesis Example 4 A photosensitive microgel (4) was obtained in the same manner as in Synthesis Example 3 except that methacrylic acid was used instead of styrene sulfonic acid in Synthesis Example 3.

Synthesis Example 5 A microgel was synthesized in the same manner as in Synthesis Example 1 except that p-aminostyrene was used instead of styrenesulfonic acid in Synthesis Example 3, and 25 g of this microgel was added to a 5% hydrochloric acid solution. After cooling to about 0 ° C., a concentrated aqueous solution in which 6.9 g of sodium nitrite is dissolved in water is added dropwise little by little while stirring the solution. When 17.1 g of an aqueous solution of ammonium hexafluorophosphate is added to this solution, a photosensitive diazo microgel of hexafluorophosphate is obtained (photosensitive microgel (5)).

Synthesis Example 6 A liquid obtained by dispersing 57 g of the microgel synthesized in Synthesis Example 3 in water and a solution in which 28.9 g of diphenyliodonium salt was dissolved in water / methanol was mixed, and the precipitate obtained was subjected to suction filtration. The resultant was washed with water, dried under reduced pressure to obtain a photosensitive microgel (6).

Synthesis Example 7 A solution prepared by dispersing 57 g of the microgel synthesized in Synthesis Example 3 in water and 25.1 g of (η ⁶ -benzene) (η ⁵ -cyanocyclopentadienyl) iron (II) in water / methanol. The precipitate obtained by mixing the dissolved solutions was collected by suction filtration, washed with water and dried under reduced pressure to obtain a photosensitive microgel (7).

[0086]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 A photosensitive lithographic printing plate was obtained by coating the following photosensitive composition on a grained and anodized aluminum plate so that the film thickness after drying was 2 μm.

Photosensitive Composition Photosensitive Microgel (1) 1.1 g N- (4-hydroxyphenyl) methacrylamide / acrylonitrile / methyl methacrylate / methacrylic acid (molar ratio: 10/40/45/5) Copolymer ( 11.0 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.13 g Methyl cellosolve 100 g A 4 kW metal halide lamp (manufactured by Iwasaki Electric Co., Ltd., idol fin) 20
Using (00) as a light source, a negative original of a photograph and a step tablet (TPS-A manufactured by Konica Corporation) were closely adhered and baked for 40 seconds. Next, this sample was subjected to SDN-2 (manufactured by Konica Corporation).
When the developing solution was developed at 27 ° C. for 20 seconds with a developing solution diluted 6 times with water, unexposed portions were removed and a negative relief image having excellent oil sensitivity was obtained. When this was given water retention with dampening water and applied to an offset printing machine, a printed matter having good image reproducibility was obtained. Table 1 shows the sensitivity and printing durability at this time.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the photosensitive microgel (2) was used in place of the photosensitive microgel (1) in the photosensitive composition of Example 1. 1 was obtained.

Example 3 An experiment was conducted in the same manner as in Example 1 except that the photosensitive microgel (3) was used instead of the photosensitive microgel (1) in the photosensitive composition of Example 1. 1 was obtained.

Example 4 An experiment was conducted in the same manner as in Example 1 except that the photosensitive microgel (4) was used instead of the photosensitive microgel (1) in the photosensitive composition of Example 1. 1 was obtained.

Example 5 Same as Example 1 except that the copolymer was removed from the photosensitive composition of Example 1 and that photosensitive microgel (5) was used instead of photosensitive microgel (1). The experiment shown in Table 1 was obtained.

Example 6 The same experiment as in Example 1 was performed except that the following photosensitive composition was used as the photosensitive composition. Table 1 shows the results.

Photosensitive composition Photosensitive microgel (6) 1.1 g p-hydroxystyrene / 2,3-epithiopropyl methacrylate (molar ratio: 30/70) copolymer (Mw = 4000) 11.0 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.13 g Methyl cellosolve 100 g Example 7 Instead of the photosensitive microgel (6) in Example 6,
The procedure was performed in the same manner as in Example 6 except that the photosensitive microgel (7) was used, and the results shown in Table 1 were obtained.

Example 8 The procedure of Example 3 was repeated, except that the N- (4-hydroxyphenyl) methacrylamide / acrylonitrile / methyl methacrylate / methacrylic acid copolymer was omitted from the photosensitive composition of Example 3. A lithographic printing plate sample was prepared and tested. As a result, a positive relief image in which the exposed portion was removed by a developer was obtained. Table 1 shows the results.

Comparative Example 1 The same experiment as in Example 1 was performed except that the following photosensitive composition was used. Table 1 shows the results.

Photosensitive composition Photosensitive microgel (1) 4 g diazo resin (reaction product of condensate of p-diazodiphenylamine and formaldehyde with ammonium hexafluorophosphate) 2 g liquid polybutadiene (NISSO manufactured by Nippon Soda Co., Ltd.) -PB1000) 10% methyl ethyl ketone solution 40 g methyl cellosolve 100 g Comparative Example 2 The same experiment as in Example 1 was performed except that the following photosensitive composition was used. Table 1 shows the results.

Photosensitive composition Diazo resin (reaction product of condensate of p-diazodiphenylamine and formaldehyde with ammonium hexafluorophosphate) 1.0 g N- (4-hydroxyphenyl) methacrylamide / acrylonitrile / methyl methacrylate / methacryl 10. Acid (molar ratio: 10/40/45/5) copolymer (Mw = 70,000)
0 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.13 g Methyl cellosolve 100 g Comparative Example 3 Example 5 was repeated except that the following photosensitive digel polymer was used in place of the photosensitive microgel (5) of Example 5. When the same experiment was performed, the results shown in Table 1 were obtained.

[0099]

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Comparative Example 4 Instead of the photosensitive microgel (6) in Example 6,
The same experiment as in Example 6 was performed except that diphenyliodonium hexafluorophosphate was used, and the results in Table 1 were obtained.

Comparative Example 5 Instead of the photosensitive microgel (7) in Example 7,
(Η ⁶ -benzene) (η ⁵ -cyanocyclopentadienyl)
The same experiment as in Example 7 was performed except that iron (II) hexafluorophosphate was used, and the results in Table 1 were obtained.

[0102]

[Table 1]

<Sensitivity> The exposure energy required for setting the number of curing steps (solid number) of the photosensitive lithographic printing plate corresponding to the step tablet to 3 (however, in the case of a positive relief image, the number of elution steps (clear number)) Exposure energy required for three steps). The smaller the numerical value, the higher the sensitivity (excellent sensitivity) because a predetermined sensitivity can be obtained with less exposure energy.

<Printing endurance> The number of printed sheets on which printing is performed with an offset printing machine and the image reproducibility of the printed matter is clearly deteriorated as compared with the start of printing due to wear of the photosensitive layer. The larger the numerical value, the larger the amount of printed matter that can be printed, and thus the higher the printing durability (excellent in mechanical strength and chemical resistance).

[0105]

According to the present invention, the following effects can be obtained.

A high-sensitivity negative photosensitive lithographic printing plate is obtained.

[0107] superior mechanical strength of the cured film, negative photosensitive lithographic printing plate high have printing endurance can be obtained is obtained.

[0108] excellent chemical resistance, high not printing force can not be obtained,
When applied to a photoresist, a negative photosensitive lithographic printing plate having excellent etching resistance can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03F 7/016 G03F 7/00 503 G03F 7/029

Claims (1)

(57) [Claims] 1. A photosensitive composition containing a photosensitive microgel chemically modified with diazo, or an anionic microgel.
The counter cation of the gel is an onium salt or iron / array
Photosensitive microphone which is at least one member selected from the group consisting of
Photosensitive layer formed from photosensitive composition containing rogel
A negative photosensitive lithographic printing plate comprising: