JP2777665B2 - Image forming method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an image forming method using an image forming material having a photosensitive composition. INDUSTRIAL APPLICABILITY The present invention can be used, for example, as a color proof transfer image forming method for color proofing in color printing.

[Conventional technology and its problems]

A photosensitive composition containing an o-quinonediazide compound or a photosensitive composition containing a photoacid generator and a compound having at least one bond decomposable by an acid is used, for example, in the field of photosensitive materials for printing. . Before main printing in multicolor printing, a color sheet called a color proof may be used for proof printing,
For example, a photosensitive composition of this type may be used as a photosensitive composition for forming the color proof.

The compounds as described above are generally used together with a polymer compound that can function as a binder.

As a prior art of this kind, JP-A-56-501217, JP-A-59-97140, and JP-A-47-41830 describe a photosensitive composition having an o-quinonediazide compound and a novolak-type phenol resin. And JP-A-62-247348,
Nos. 62-247349 and 62-291634 include a photoacid generator, a compound having at least one bond decomposable by an acid,
And examples of photosensitive compositions containing novolak-type phenolic resins.

However, when the conventional photosensitive composition is used as a photosensitive material, an image is obtained by exposing and developing the material, and the image is transferred to a material to be transferred such as paper, the transfer requires high-temperature heating. . Therefore, the material to be transferred, such as paper, or the photosensitive material itself may expand or deform due to heat, which causes a dimensional deviation of the transferred image.

Such dimensional deviation is extremely problematic when used as a color proof for calibration as described above, for example. This is because a dimensional deviation between multicolor images may be caused.

Further, the photosensitive composition using the above-mentioned conventional novolak-type phenol resin also has a problem that the discoloration resistance is poor.

Further, image forming materials using a vinyl acetate / crotonic acid copolymer resin as a binder are disclosed in JP-A-63-2040 and JP-A-63-298337, each of which is a colored image. And an image forming method for transferring an image to a transfer paper together with a release layer. Therefore, there is a problem that the non-image portion has gloss and the texture differs from that of an actual printed matter.

The present invention solves the above-mentioned problems of the prior art, and does not require high-temperature heating for transfer even when applied to a transfer-type photosensitive material, and thus uses a photosensitive material using a photosensitive composition that does not cause dimensional deviation and the like. Accordingly, an object of the present invention is to provide an image forming method capable of obtaining a transfer image obtained by transferring only an image.

Another object of the present invention is to provide an image forming method as described above using a photosensitive composition having good discoloration resistance.

[Means for solving the problem]

The object of the present invention is to form an image area by exposing and developing an image forming material having a photosensitive composition, and to transfer only the image area by exposing the image area of the material to be transferred to transfer a transferred image. In the obtained image forming method, the photosensitive composition contains both (1) (a) an o-quinonediazide compound and (b) a photoacid generator and a compound having at least one bond decomposable by an acid. And (2) a polymer compound having a vinyl carboxylate polymerized unit represented by the following general formula in its molecular structure: RCOOCH = CH _{2 In the} formula, R represents an alkyl group having _{2 to} 17 carbon atoms. This is achieved by an image forming method characterized by containing.

In the present invention, the content of the o-quinonediazide compound in the photosensitive composition is 5 to 5% of the total solid content of the photosensitive composition.
It is preferably 50% by weight, more preferably 10 to 30% by weight.

In the present invention, the content of the photoacid generator in the photosensitive composition is preferably from 0.1 to 10% by weight, more preferably from 0.2 to 5% by weight, based on the total solid content of the photosensitive composition. . Similarly, the content of the acid-decomposable compound is preferably from 5 to 70% by weight, more preferably from 10 to 50% by weight. The polymer compound is also 30 to 95% by weight.
And more preferably 50 to 90% by weight.

 Hereinafter, the present invention will be described in more detail.

The photosensitive composition used in the present invention (hereinafter, also referred to as “photosensitive composition of the present invention” as appropriate) is a composition containing (a) an o-quinonediazide compound and (b) both a photoacid generator and an acid-decomposable compound. It contains at least one of (a) and (b).

As the o-quinonediazide compound used in the present invention, any compound can be used as long as it can function as a photosensitive agent.

Specifically, for example, 1,2-benzoquinonediazide-4
-Sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride, a hydroxyl group and / or
Alternatively, a compound obtained by condensation with an amino group-containing compound is suitably used.

Examples of the hydroxyl-containing compound include trihydroxybenzophenone, dihydroxyanthraquinone, bisphenol A, phenol novolak resin, resorcinol benzaldehyde condensed resin, and pyrogallol acetone condensed resin. Examples of the amino group-containing compound include, for example, aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4′-diaminodiphenylamine,
4'-diaminobenzophenone and the like.

With respect to the quinonediazide compounds, including those described here, furthermore, J. Kosar, "Light Sensitive System" (New York City, John Wiley & Sons, 1965) , And Nagamatsu, Inui, "Photosensitive Polymers" (Kodansha, 19
(Issued in 1977).

The photoacid generator used in the present invention means a compound capable of generating an acid upon irradiation with actinic rays. Such photoacid generators include many known compounds and mixtures, such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆
^2-, ClO ₄ ^-, an organic halogen containing compound, can be used o-quinonediazide sulfonyl chloride and the like,
In addition, an organometallic / organohalogen compound can also be used as an actinic ray-sensitive component that forms or separates an acid upon irradiation with actinic light.

In principle, all organic halogen compounds known as free-radical-forming photoinitiators can be used as photoacid generators capable of forming hydrohalic acids. Examples of such compounds are U.S. Patents 3,515,552, 3,536,489,
No. 3,779,778 and West German Patent Publication No. 2,243,621
No.

Also, for example, West German Patent Publication No. 2,610,842
No., JP-A-54-74728, JP-A-55-77742, JP-A-57-16323
And the compounds capable of generating an acid by photolysis described in JP-A Nos. 60-3626 and 60-32626 can also be used.

Further, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209 can also be used.

Preferred specific examples of the photoacid generator that can be preferably used in the present invention are shown below. However, as a matter of course,
It is not limited to the following examples.

Next, when the photosensitive composition of the present invention contains the above-mentioned photoacid generator, it also contains an acid-decomposable compound.
Compounds having a bond that can be decomposed by an acid upon receiving an acid generated by the action of the photoacid generator (acid-decomposable compound) include, for example, a C—O—C bond and a Si—O
A compound having a -C bond or And the like.

Specific compounds having a C—O—C bond include, for example, compounds having an acetal or ketal group,
Compounds having an orthocarboxylic acid ester group and / or a carboxylic acid amide acetanol group described in JP-A-51-120714, polymers having an acetal or ketal group in the main chain described in JP-A-53-133429, Showa 55-12
No. 995, a compound containing an enol ether group, a compound having an N-acylimino carbonate described in JP-A-55-126236, or a compound having an ortho-group in the main chain described in JP-A-56-17345. Examples thereof include polymers having a carboxylic acid ester group.

Specific compounds having a Si-OC bond include:
For example, JP-A-60-37549, JP-A-60-52845 or JP-A-60-37545
And the compounds described in JP-A-121446.

Specific compounds having an ester group include, for example, compounds described in JP-A-60-3625 and JP-A-60-10247.

Among these compounds having a bond that can be decomposed by an acid, a compound having a Si—O—C bond is preferable.
Among them, Si-OC as described in JP-A-60-121446
Compounds having at least one bond and at least one hydrophilic group are particularly preferred.

One of the compounds decomposable by these acids may be used alone, or two or more of them may be used in combination.

In the present invention, as the acid-decomposable compound as described above,
For example, the following can be preferably used.
However, it is needless to say that the present invention is not limited to the following example.

Further, as the acid-decomposable compound, a compound containing at least one orthocarbonate group represented by the following general formula [X] can be suitably used.

As a compound containing at least one orthocarbonate group (hereinafter referred to as an orthocarbonate compound), for example, a compound having at least one phenolic OH group and / or at least one alcoholic OH group ( Compounds which can be synthesized by subjecting at least one of OH group-containing compounds) and a tetraalkoxymethane to a transesterification reaction in one step or two or more steps can be mentioned.

For this transesterification reaction, for example, Svensk K
A method similar to or similar to the method described in em. Tidskr. 65, 10 (1953) can be used.

Examples of the OH group-containing compound include a monohydric alcohol, a dihydric alcohol, a trihydric alcohol, a tetrahydric alcohol, a monohydric phenol compound, a dihydric phenol compound, and a trihydric phenol compound. Examples thereof include compounds, phenolic compounds having four or more valences, and compounds having both a phenolic OH group and an alcoholic OH group.

Examples of the monohydric alcohol include n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl alcohol, and n-dodecyl alcohol. , N-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, active amyl alcohol, tert-pentyl alcohol, cyclopentanol ,
Cyclohexanol, allyl alcohol, crotyl alcohol, methyl vinyl carbinol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether,
Aliphatic alcohols such as diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, benzyl alcohol, α-phenylethyl alcohol, β-
Phenylethyl alcohol, diphenylcarbinol,
Examples thereof include aromatic alcohols such as triphenylcarbinol and cinnamyl alcohol.

Examples of the dihydric alcohol include, for example, JP-A-53-1334.
No. 29 pentane-1,5-diol, n-hexane-1,6-diol, 2-ethyl-hexane-1,6-diol, 2,3-dimethyl-hexane-1,6-diol, Heptane-1,7-diol, cyclohexane-1,4-diol, nonane-1,7-diol, nonane-1,9-diol,
3,6-dimethyl-nonane-1,9-diol, decane-1,10
-Diol, dodecane-1,12-diol, 1,4-bis-
(Hydroxymethyl) -cyclohexane, 2-ethyl-
1,4-bis- (hydroxymethyl) -cyclohexane,
2-methyl-cyclohexane-1,4-diethanol, 2
-Methyl-cyclohexane-1,4-dipropanol, thio-dipropylene glycol, 3-methyl-pentane-
1,5-diol, dibutylene-glycol, oxypivalic acid-neopentyl glycol ester, 4,8-bis- (hydroxymethyl) -tricyclodecane, n-butene- (2) -1,4-diol, n- But-2-yne-1,4
-Diol, n-hex-3-yne-2,5-diol,
1,4-bis- (2-hydroxyethoxy) -butyne-
(2), p-xylylene glycol, 2,5-dimethyl-
Hex-3-yne-2,5-diol, bis- (2-hydroxyethyl) -sulfide, 2,2,4,4-tetramethylcyclobutane-1,3-diol, di-, tri-, tetra-, Penta- and hexaethylene glycol, di- and tripropylene glycol, and having an average molecular weight of 200,30
Aliphatic alcohols such as 0,400 and 600 polyethylene glycol, p-xylylene glycol, 2-methyl-
Aromatic alcohols such as 2-phenyl-1,3-propanediol and the like can be mentioned.

Examples of the trihydric alcohol include, for example, JP-A-56-1734.
No. 5 glycerol, butane-1,2,4-triol, 2-hydroxymethyl-butane-1,4-diol,
Pentane-1,2,5-triol, 2-hydroxymethyl-pentane-1,5-diol, hexane-1,2,5-triol, 2-hydroxymethyl-hexane-1,6-diol, hexane-1, 2,6-triol, 4-ethyl-hexane-1,4,5-triol, heptane-1,4,5-triol, 1- (1,2-dihydroxyethyl) -4-hydroxymethyl-benzene, 2, 4,6-triethyl-5-propyl-heptane-1,3,7-triol, 1- (2,3-dihydroxy-propoxy) -4-hydroxymethyl-benzene, 1- (2,3-dihydroxypropyl)- 4-hydroxymethyl-benzene, oct-3-yn-1,7,8-triol, octane-1,2,8-triol, octane-
1,3,8-triol, nonane-1,4,5-triol, 3-
(1-hydroxy-1-methyl-ethyl) -5-oxa-octane-2,8-diol, 2,6,8-trimethyl-3-
Examples thereof include aliphatic or aromatic alcohols such as hydroxymethyl-nonane-6,7-diol, 2-hydroxymethyl-3-oxa-heptane-1,7-diol and hexadecane-1,2,16-triol. it can.

Examples of the tetravalent or higher alcohol include aliphatic alcohols such as pentaerythritol, threitol, pentitol, sorbitol, and polyvinyl alcohol. Further, an aromatic alcohol may be used.

Examples of the monovalent phenol compound include phenol, o-crisol, m-cresol, p-crisol, 3,5-xylenol, carvacrol, thymol,
α-naphthol, β-naphthol and the like.

Divalent phenolic compounds include catechol, resorcin, hydroquinone, 2,2-bis (4-hydroxyphenyl) butane, bis (p-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propyne,
Examples thereof include 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

As the trivalent phenolic compound, pyrogallol,
Phloroglucin and the like.

1,4,9,10-
Examples thereof include tetrahydroxyanthracene.

Compounds having both phenolic OH and alcoholic OH include 2- (bis (4-hydroxyphenyl)
Methyl) benzyl alcohol and the like.

As the tetraalkoxymethane, for example, tetramethoxymethane or tetraethoxymethane is generally used.

Tetraethoxymethane is available, for example, from Organic Synthesis Collect, Volume IV (Organic Synthenes Co.).
ll. Vol. IV) 457 (1963), and can be synthesized with chloropicrin and sodium ethoxide. Other tetraalkoxymethanes can be synthesized by the same method. Also, Journal of Organic Chemistry (J.Org.Chem.,) 36, 1176 (197
1) The same method as described in
Of Organic Chemistry (J.Org.Chem.,) 3
7,4198 (1972), a method similar to that described in
Can be synthesized.

The ortho carbon ester compound can be obtained, for example, by reacting the tetraalkoxymethane and the OH group-containing compound at a temperature of 60 to 170 ° C, preferably 80 to 150 ° C, without using a solvent. The liberated lower alcohol is optionally distilled off. The reaction is preferably carried out in the presence of an acidic catalyst such as p-toluenesulfonic acid or sulfuric acid. In some cases, the reaction may be performed under reduced pressure. In addition, solvents inert under the above reaction conditions, for example, benzene, toluene, xylene, dioxane, chlorinated hydrocarbons and the like can also be used as reaction solvents. The liberated lower alcohol is optionally distilled off with some of the solvent.

The molar ratio in the reaction between the tetraalkoxymethane and the OH group-containing compound is generally such that the total number of OH groups is 4 mol per 1 mol of tetraalkoxymethane. The ratio may be different from the above.

When two types of OH group-containing compounds are used, a total of three compounds, tetraalkoxymethane and two types of OH group-containing compounds, may be reacted simultaneously. The containing compound may be reacted, and then the product may be reacted with the other OH group-containing compound. When three or more OH group-containing compounds are used, the reaction can be similarly performed.

It can also be synthesized by a method similar to or similar to the method described in Chemical Berichte (Chem. Ber.) 544 (1961). For example, obtained by the method of the literature A method of reacting diphenyloxydichloromethane with the above-mentioned OH group-containing compound is exemplified.

The product obtained by the above method is an orthocarbonate compound, and examples thereof include a compound containing one of the following orthocarbonate group units, a compound containing two or more of them, or a mixture thereof.

R ₁ , R ₂ , R ₃ , and R ₄ each represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or the like. These alkyl group, aryl group, aralkyl group,
Includes those having an alkenyl substituent. Also, R ₁ ~
At least two of R ₄ may be mutually bonded to form a ring.

In addition, the bonding moiety may be further bonded to the above-described or the same having another orthocarbonate group unit via a substituted or unsubstituted alkylene group, arylene group, aralkylene group, alkenyl group, or the like. .

The compound having at least one orthocarbonate group unit preferably has an orthocarbonate group unit in the range of 1 to 50 in the molecule.

Hereinafter, specific examples of the compound having at least one orthocarbonate group will be described.

Next, the photosensitive composition used in the method of the present invention contains a polymer compound having a carboxylic acid vinyl ester polymerized unit represented by the following general formula in the molecular structure.

RCOOCH = CH ₂ where R represents an alkyl group having _{2 to} 17 carbon atoms.

Any polymer compound having the structure as described above can be used arbitrarily, but as the carboxylic acid vinyl ester monomer for constituting the polymerized unit represented by the above general formula, the following examples are preferable. The name and chemical formula are shown together.

Vinyl propionate CH ₃ CH ₂ COOCH = CH ₂ butyrate _{CH 3 (CH 2) 2 COOCH} = CH 2 vinyl pivalate _{(CH 3) 3 CCOOCH = CH} 2 vinyl caproate _{CH 3 (CH 2) 4 COOCH} = CH 2 Vinyl caprylate CH ₃ (CH ₂ ) ₆ COOCH = CH ₂ Vinyl caprate CH ₃ (CH ₂ ) ₈ COOCH = CH ₂ Vinyl laurate CH ₃ (CH ₂ ) ₁₀ COOCH = CH ₂ Vinyl myristate CH ₃ (CH _{2 12} COOCH = CH ₂ vinyl palmitate CH ₃ (CH ₂ ) ₁₄ COOCH = CH ₂ vinyl stearate CH ₃ (CH ₂ ) ₁₆ COOCH = CH ₂ vinyl versatate (R ¹ and R ² are alkyl groups, and the total number of carbon atoms is 7.
That is, R ¹ + R ² = C ₇ H ₁₆ ) In addition, the above R also includes an alkyl group having a substituent,
That is, a vinyl ester of a substituted carboxylic acid is also included in the polymerized unit.

The polymer compound may be a polymer obtained by polymerizing one kind of vinyl carboxylate, a polymer obtained by copolymerizing two or more kinds of vinyl carboxylate, or a polymer that can be copolymerized with vinyl carboxylate. The copolymer may be a copolymer having an arbitrary component ratio with the monomer.

Examples of the monomer unit that can be used in combination with the polymerization unit represented by the above general formula include, for example, ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene, α-methylstyrene, p Styrenes such as -methylstyrene and p-chlorostyrene; for example, acrylic acids such as acrylic acid and methacrylic acid; for example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride; for example, diethyl maleate and maleic acid Dibutyl, di-2-ethylhexyl maleate, dibutyl fumarate,
Diesters of unsaturated dicarboxylic acids such as di-2-ethylhexyl fumarate, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methylene aliphatic monocarboxylic acid esters such as α-methyl methyl chloroacrylate, methyl methacrylate and ethyl methacrylate; for example, nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide such as acrylanilide; Anilides such as chloroacrylanilide, m-nitroacrylanilide and m-methoxyacrylanilide, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and β-chloroethyl vinyl ether; Nyl ethers, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1 Ethylene derivatives such as -nitroethylene, for example, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene,
-Vinyl monomers such as N-vinyl compounds such as vinylpyrrolidone. These vinyl monomers and the like exist in a polymer compound in a structure in which an unsaturated double bond is cleaved.

Particularly preferred as the polymer compound used in the present invention are those having a vinyl acetate polymerized unit in the molecular structure. Among them, 40-95wt of vinyl acetate polymerized units
%, Number average molecular weight (MN) is 1,000 to 100,000
And those having a weight average molecular weight (MW) of 5,000 to 500,000 are preferred.

More preferably, vinyl acetate polymerized units (especially when this is 40
9595 wt%) and vinyl carboxylate polymer units having a longer chain than that of vinyl acetate, preferably having 4 to 17 carbon atoms, particularly vinyl versatate polymer units (in particular,
Polymer compounds having a weight average molecular weight (MN) of 2,000 to 60,000 and a weight average molecular weight (M
Preferably, W) is 10,000 to 150,000.

In this case, as a monomer constituting a polymer compound having a vinyl acetate polymerized unit by copolymerizing with vinyl acetate,
Any monomer can be used as long as it can form a copolymer, and for example, it can be arbitrarily selected from the monomers exemplified above.

Hereinafter, copolymers that can be used as the polymer compound in the present invention will be listed by showing the monomer components. However, as a matter of course, the present invention is not limited to the following example.

Vinyl acetate-ethylene vinyl acetate-styrene vinyl acetate-crotonic acid vinyl acetate-maleic acid vinyl acetate-2-ethylhexyl acrylate vinyl acetate-di-2-ethylhexyl maleate vinyl acetate-methyl vinyl ether vinyl acetate-vinyl chloride vinyl acetate-N- Vinyl pyrrolidone vinyl acetate-vinyl propionate vinyl acetate-vinyl pivalate vinyl acetate-vinyl versatate vinyl acetate-vinyl laurate vinyl acetate-vinyl stearate vinyl acetate-vinyl versatate-ethylene vinyl acetate-vinyl versatate-2-ethylhexyl Acrylate Vinyl acetate-vinyl versatate-vinyl laurate Vinyl acetate-vinyl versatate-crotonic acid vinyl propionate-vinyl versatate propion Vinyl acid acid-vinyl versatate-crotonic acid pivalic acid-vinyl stearate-maleic acid The photosensitive composition used in the method of the present invention can be used to constitute an image forming material. For example, it can be used as a colored image forming material for use as a color proof.

In this case, the colored photosensitive layer of the colored image forming material is removed imagewise by development following imagewise exposure to form a colored image.

Dyes and pigments are added to the colored photosensitive layer as colorants. In particular, when used for color proofing, pigments and dyes having the same color as the required ordinary colors, that is, yellow, magenta, cyan, and black are required, but other metal powders, white pigments, and fluorescent pigments are required. Also used. When applying the present invention to a color proof, many pigments and dyes known in the art can be used, as described below.

 (C.I means color index).

Victoria Pure Blue (CI 42595) Auramine (CI 41000) Katilon Brilliant Flavin (CI Basic 1
3) Rhodamine 6GCP (CI 45160) Rhodamine B (CI 45170) Safranin OK70: 100 (CI 50240) Erioglaucine X (CI 42080) Fast Black HB (CI 26150) No.1201 Lionol Yellow (CI 21090) Lionol Yellow GRO (CI 21090) Shimla First Yellow 8GF (CI 21105) Benzin Yellow 4T-564D (CI 21095) Shimla Fur Red 4015 (CI 12355) Lionol Red 7B4401 (CI 15830) Fast Gemble-TGR-L (CI 74160) Rio Nord Blue SM (CI 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black # 30, # 40, # 50 Lionol Blue FG7391G Lionol Blue FG7393G Lionol Blue 700-10FG Lionol Yellow SGR-H Lionol Yellow FGN-H Cyanine Blue KRG Cyanine Blue 4012 Cyanine Blue RS-30 Phthalocyanine Blue 4933GNEP Lionol Blue FG7330 Squid First Carmine 1478 Lionol Red 6BFG-4219X No.1206 Lionol Yellow In the present invention, the pigment component of the colored photosensitive layer does not remain in the non-image area after the development of the colored photosensitive layer, and the finished quality is high. Although essential for the above, among the above-mentioned pigments, anionic or cationic pigments are preferable, and for example, a pigment having an inert salt such as sulfonic acid, carboxylic acid, or amine is preferably used. Such a pigment may be obtained by converting the soluble group of a water-soluble dye into an inert salt, or may be lecithin, a metal salt of naphthenic acid, an alkylbenzene sulfonate, a dialkylnaphthalene sulfonate, a mono- or dialkylnaphthalene. Processed anionic or cationic pigments treated with a treating agent such as a sulfonate, mono- or dialkylsulfosuccinate, dialkylphosphate salt, rosinate, or organic amine may be used.

When a colorant is used in the present invention, the ratio of the colorant / binder in the colored photosensitive layer is determined by a method known to those skilled in the art in consideration of the target optical density and the removability of the colored photosensitive layer from the developer. Can be. For example, in the case of a dye, the content is preferably 5% to 75% by weight, and in the case of a pigment,
Preferably, the content is 5% to 90% by weight.

The thickness of the colored photosensitive layer can be determined by a method known to those skilled in the art according to the target optical density, the type of the coloring agent (dye, pigment, carbon black) used in the colored photosensitive layer and the content thereof. If the thickness is within the allowable range, the smaller the thickness of the colored photosensitive layer is, the higher the resolution becomes,
The image quality is good. Therefore, the film thickness is preferably
It is normally being used in the range of ^{0.1g / m 2 ~5g / m 2} .

In the practice of the present invention, a plasticity, a coating property improver, and the like may be further added to the photosensitive composition as necessary.

Examples of the plasticizer include various low molecular compounds such as phthalates, triphenyl phosphates and maleates, and examples of the coating improver include surfactants such as a fluorine-based surfactant and ethyl cellulose polyalkylene ether. Nonionic activators and the like.

When an image forming material, in particular, a colored image forming material is formed by using the photosensitive composition used in the method of the present invention, the colored photosensitive layer is a colored layer comprising a colorant and a binder, and a photosensitive layer comprising a photosensitive composition. It can also be divided into two layers. In this case, either layer may be arranged on the support side.

When an image forming material is formed using the photosensitive composition used in the method of the present invention, a support to be used is optional, but a transparent support is preferably used. As the transparent support, a polyester film, particularly a biaxially stretched polyethylene terephthalate film, is preferable in terms of dimensional stability against water and heat. In addition, acetate film,
A polyvinyl chloride film, a polyethylene film, a polypropylene film, a polyethylene film and the like can be used.

The image forming material thus obtained can be used in a form of transferring an image to a material to be transferred. In order to efficiently transfer the material onto the material to be transferred at this time, and to facilitate the peeling of the support after the image transfer, that is, to enhance the releasability between the support and the image forming layer, A release treatment can be performed on the body surface, or a release layer can be provided on the support surface. These will be described later.

In the image forming method of the present invention, the image forming material comprises:
Usually, after imagewise exposure through a color separation mask or the like, development is performed to form an image. At this time, only the image portion is directly transferred and laminated on the material to be transferred from the image obtained on the support. That is, only the colored image layer that substantially forms an image is transferred and laminated. In this case, the surface of the support may be subjected to a release treatment with an appropriate oil-repellent substance, or the support may be subjected to efficient transfer onto the transfer-receiving surface and easy release of the support after image transfer. It is preferable to provide a release layer thereon.

As such an oil-repellent substance, for example, a silicone resin, a fluorine resin, a fluorine-based surfactant, polyolefin, polyamide, or the like can be used.As the release layer, for example, alcohol-soluble polyamide, alcohol-soluble nylon, styrene and the like can be used. Blend of partially esterified resin of copolymer with maleic anhydride and methoxymethylated nylon, polyvinyl acetate, polyacrylate, copolymer of polymethyl methacrylate and acrylate, polyvinyl chloride, vinyl chloride and vinyl acetate A copolymer with
Polyvinyl butyrate, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, cellulose diacetate, cellulose triacetate, polyvinyl alcohol, butyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, hydroxypropyl methyl cellulose phthalate , Hydroxypropyl methylcellulose hexahydrophthalate, or a mixture thereof, and the like.

The thickness of the release layer is preferably in the range of 0.01 μm to 100 μm, particularly preferably in the range of 0.1 μm to 50 μm.

As a particularly preferred embodiment for improving the releasability, an example in which a polypropylene layer or a polyethylene layer thinner than the thickness of the support is provided.

Preferred examples of the polyethylene layer used in the present invention include ethylene-vinyl acetate copolymer resin,
5% by weight of vinyl acetate in the copolymer resin
~ 33% is preferable, and the VICAT
The softening point is preferably 80 ° C. or lower. In addition, various polymers, supercooled substances, surfactants, and dispersing agents can be added to the ethylene-vinyl acetate copolymer resin within a range where the softening point does not substantially exceed 80 ° C.

The method of providing a polypropylene layer or a polyethylene layer on a support is as follows: (1) A solution obtained by dissolving polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, or the like in an organic solvent is used as an adhesive. A so-called dry lamination method in which these adhesives are applied to a support, dried by hot air or heating, and then a polypropylene film or a polyethylene film is laminated and pressed and laminated under heating; (2) ethylene And vinyl acetate copolymer, ethylene and acrylic acid ester copolymer, polyamide resin, petroleum resin, rosins, waxes or a mixture of these as an adhesive. While applying a doctor blade method, roll coating method, gravure method, A so-called hot-melt lamination method in which a polypropylene film or a polyethylene film is immediately laminated after being applied by a sroll method or the like, and then, if necessary, is heated to a high temperature and then cooled, (3) polypropylene or polyethylene. Is kept in a molten state and extruded into a film by an extruder, and while this is in a molten state, a support is pressed and laminated, so-called extrusion lamination method; (4) A film to be a support is formed by a melt extrusion method In this case, a so-called co-extrusion method may be used in which a plurality of extruders are used to form a polypropylene layer or a polyethylene layer on a support film by a single molding together with polypropylene or polyethylene in a molten state. it can.

In the image forming method of the present invention, a developer used for developing the image forming material can be arbitrarily used as long as it has a developing action of developing the material to be processed. Preferably, a developer containing an alkali agent and an anionic surfactant is used.

Examples of usable alkali agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium phosphate dibasic or tribasic, sodium metasilicate, sodium carbonate, ammonia (2) mono, di, or trimethylamine, mono, di, etc.
And organic amine compounds such as triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triethanolamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, and the like.

Examples of anionic surfactants that can be used include: (1) higher alcohol sulfates (eg, sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, secondary sodium alkyl sulfate, etc.) (2) aliphatic alcohol phosphate ester salts (for example,
(3) Alkyl aryl sulfonates (for example, sodium dodecylbenzenesulfonate, sodium isopropylnaphthalenesulfonate, sodium dinaphthalenesulfonate, sodium sodium metanitrobenzenesulfonate, etc.) (4) Alkyl amide sulfonates (5) Sulfonates of dibasic aliphatic esters (eg, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.) (6) Formaldehyde condensate of alkyl naphthalene sulfonate (eg, formaldehyde condensation of sodium dibutyl naphthalene sulfonate) Products).

The alkali agent and the anionic surfactant can be used in any combination.

〔Example〕

 Hereinafter, examples of the present invention and comparative examples will be described.

Needless to say, the present invention is not limited to the embodiments described below, but can take various forms.

Example 1 A dispersion of a colored photosensitive composition having the following composition was dried using a wire bar on a polypropylene surface of a support obtained by laminating a 25 μm-thick polypropylene film on a 50 μm-thick polyethylene terephthalate film by a dry lamination method. After coating so that the film thickness becomes 1 μm,
After drying, four colored image forming materials were prepared.

Binder polymer (polymer compound according to the present invention) Vinyl acetate-vinyl versatate (80:20 parts by weight) copolymer MN = 22,000 MW = 60,000 Face black: carbon black MA-100 (manufactured by Mitsubishi Chemical) 0.99 g cyan : Cyanine Blue 4920 (Dainichi Seika) 0.55 g Magenta: Seika First Carmin 1483 (Dainichi Seika) 0.68 g Yellow: Seika First Yellow H-7705 (Dainichi Seika) 0.68 g A color separation net positive film of each color is superimposed on the polyethylene terephthalate film surface of the colored image forming material, and 50c with 4KW metal halide lamp
Image exposure was performed for 20 seconds from a distance of m, and development was performed by immersion in the following developer for 30 seconds to form four colored images.

<Developer> Na ₂ CO ₃ 15 g Surfactant (Perox NBL manufactured by Kao Atlas) 50 g Distilled water 1000 g Next, the image surface of the black color image and the art paper are adhered closely.
After passing through a heated pair of nip rolls at a speed of 50 cm / min under a pressure of 5 kg / cm ² , the support was peeled off. Peeling was easily performed, and only the black image portion was transferred onto the art paper.

Subsequently, a colored image was transferred in the order of cyan, magenta, and yellow, whereby a color proofing image composed of four colors was obtained on art paper. Table 1 shows the transfer temperature, the dimensional deviation between the four colors, and the degree of discoloration of the image over time.
In this example, since only the image portion was transferred, the finish was very close to the actual printed matter.

Example 2 A colored photosensitive composition dispersion was prepared using the following composition: A color image of four colors was formed and transferred exactly in the same manner as in Example 1 except that the color image was changed to Example 1. As a result, a color proofing image composed of four colors was obtained on the art paper. Transfer temperature,
The dimensional deviation between the four colors and the degree of discoloration of the image over time are shown in Table 1 below. In this example, since only the image portion was transferred,
The finish was very close to the actual printed matter.

Example 3 On a polyethylene terephthalate film having a thickness of 75 μm, a polyurethane-based adhesive layer was applied to a thickness of 0.2 μm.
On top of this, a 25 μm-thick ethylene-vinyl acetate copolymer resin layer (EVAFLEX P-140 manufactured by Mitsui-Dupont Polychemical Co., Ltd.)
5, vinyl acetate content 14% by weight, VICAT softening point 68 ° C)
On the surface of the vinyl acetate copolymer resin layer, a colored photosensitive layer dispersion having the following composition was dried using a wire bar to a dry film thickness of 1.5 μm.
m, and dried to prepare four colored image forming materials.

p-cresol novolak resin and naphthoquinone-1,2
-Esterified product with diazide-4-sulfonic acid chloride 0.616 g Vinyl acetate-vinyl versatate copolymer (80:20 w
t%, weight average molecular weight 50,000, 50% methanol solution) 8.768 g The following pigment The following amount Cyclohexanone 35.2 g Fluorosurfactant (3M, FC-430) 0.01 g Pigment Black: Carbon black MA-100 (Mitsubishi) Chemical: 0.99 g Cyan: Lionol Blue FG7330 (Toyo Ink) 0.55 g Magenta: Seika First Carmin 1483 (Dainichi Seika) 0.68 g Yellow: No. 1206 Lionol Yellow (Toyo Ink) 0.68 g The color separation screen positive film of each color is superimposed on the polyethylene terephthalate film surface of the four colored image forming materials obtained, and 50c is applied with a 4KW metal halide lamp.
m for 20 seconds from a distance of m.
Development was performed by immersion at 0 ° C. for 30 seconds to form four colored images.

<Developer> Konica PS plate developer SDR-1 (manufactured by Konica) 20 ml Belex NBL (manufactured by Kao Atlas) 50 ml distilled water 400 ml Next, the image surface of the black color image and the art paper are adhered closely.
After passing between a pair of nip rolls heated to 90 ° C. under a pressure of 5 kg / cm ² at a speed of 50 cm / min, the support was peeled off. Peeling was easily performed at the interface between the ethylene-vinyl acetate copolymer resin layer and the colored image, and a black image was transferred onto the art paper. Subsequently, a colored image was transferred in the order of cyan, magenta, and yellow, and a color proofing image composed of four colors was obtained on art paper.
Only the colored image portion was transferred to the art paper, that is, the non-image portion of the paper was exposed, and the obtained color proofing image was very similar to the image quality of the printed matter created by ordinary offset printing. Was.

Example 4 A polyurethane-based adhesive layer having a thickness of 0.2 μm was applied on a 75 μm-thick polyethylene terephthalate film, and a 25 μm-thick ethylene-vinyl acetate copolymer resin layer (Mitsui-Dupont Polychemical Co., Ltd.) was formed thereon. EVAFLEX P
1007, vinyl acetate content 10% by weight, VICAT softening point 72
C) on a surface of an ethylene-vinyl acetate copolymer resin layer of a support formed by extrusion lamination, and using a wire bar, a colored photosensitive layer dispersion of the following composition was dried to a thickness of 1.
It was applied to a thickness of 5 μm and dried to prepare four colored image forming materials.

p-cresol novolak resin and naphthoquinone-1,
Esterified with 2-diazide-4-sulfonic acid chloride 0.616 g Vinyl acetate-vinyl stearate-2-ethylhexyl acrylate copolymer (70:20:10 wt%, weight average molecular weight 70,000, 50% methanol solution) 8.768 g Pigment Following amount Cyclohexanone 35.2 g Fluorosurfactant (3M, FC-430) 0.01 g Pigment Black: Carbon black MA-100 (Mitsubishi Kasei) 0.99 g Cyan: Cyanine blue 4933GNEP (Dainichi Seika) 0.55 g Magenta: Seika First Carmine 1483 (manufactured by Dainichi Seika) 0.68 g Yellow: Lionol Yellow SGR-H (manufactured by Toyo Ink) 0.68 g In the same manner as in Example 3, the exposure, development and image transfer treatments were carried out. A color proofing image consisting of 4 was obtained on paper. Only the colored image portion was transferred to the art paper, that is, the non-image portion of the paper was exposed, and the obtained color proofing image was very similar to the image quality of the printed matter created by ordinary offset printing. Was.

Comparative Example 1 In Example 1, as the binder polymer,
Using the following novolak resin, SDR-1
(Konica PS plate developer; manufactured by Konica Corporation) was used in the same manner as in Example 1.

Table 1 shows the same data as in the above embodiment.

Binder polymer (Novolak resin) PR-50716 (Novolak type phenol-formaldehyde resin) manufactured by Sumitomo Durres Co., Ltd. Transfer temperature, dimensional deviation in X direction and Y direction, and color sensitivity in each of the above Examples and Comparative Examples. The measurement results of the temporal coloring degree of the layer binder are shown in Table 1 below.

In Table 1, the dimensional deviation refers to the deviation between the register marks at the four corners of the image in the transfer direction (referred to as X direction) and the width direction during transfer (referred to as Y direction). (Μm). The registration marks are arranged at a distance of 400 mm in the X direction and 600 mm in the Y direction.

The coloring degree with time is a value obtained by measuring the binder coloring degree (brown coloring degree) of an image transferred to paper as a yellow reflection density. For the measurement, Macbeth reflection densitometer RD-918
Was used. If the degree of coloring increases with the passage of time, discoloration is large and discoloration resistance is poor. When the degree of coloring increases, the colors of the transferred images, particularly cyan, magenta, and yellow, become turbid, and the image reproducibility deteriorates.

As can be understood from Table 1, Examples 1-4 of the present invention
Regarding the above, good transfer is achieved even when the transfer temperature is relatively low, and the dimensional deviation is small. In contrast, Comparative Example 1
Requires a very high transfer temperature, and the dimensional deviation is much larger than in each of the examples.

In addition, when the degree of coloring of the binder of the colored photosensitive layer with time was observed, in Examples 1 to 4 of the present invention, little change in the degree of coloring was observed, whereas in Comparative Example 1, the degree of coloring changed considerably. It can be seen that discoloration has occurred.

From Table 1, the embodiment of the present invention has a small dimensional deviation,
Further, it can be seen that the change in the degree of coloring with time of the colored photosensitive layer binder is small.

〔The invention's effect〕

As described above, according to the present invention, when a transfer type is used, an image forming method using a photosensitive composition which does not require a high temperature for transfer, can prevent dimensional deviation, and has good discoloration resistance Can be provided.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Manabu Watanabe 1 Sakura-cho, Hino-shi, Tokyo Inside Konica Corporation (72) Inventor Toyoyoshi Urano 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Inside the research institute (72) Inventor Shinya Mayama 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Co., Ltd. (72) Inventor Tetsuya Masuda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Co., Ltd. (56) References JP-A-63-2039 (JP, A) JP-A-63-298337 (JP, A) JP-A-63-127243 (JP, A) JP-A-63-143535 (JP, A) JP-A-63-2040 (JP, A) JP-A-62-247348 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F ^7/ 00-7/18

Claims (11)

(57) [Claims] An image is formed by exposing and developing an image forming material having a photosensitive composition to form an image portion, and transferring only the image portion by exposing a non-image portion of a material to be transferred to obtain a transfer image. In the forming method, the photosensitive composition is selected from (1) a composition containing both (a) an o-quinonediazide compound and (b) a photoacid generator and a compound having at least one bond decomposable by an acid. And (2) a polymer compound having a carboxylic acid vinyl ester polymerization unit represented by the following general formula in its molecular structure: RCOOCH = CH _{2 wherein} R represents an alkyl group having _{2 to} 17 carbon atoms. An image forming method comprising: 2. The content of the photoacid generator in the total solid content of the photosensitive composition is from 0.1 to 10% by weight, and the content of the compound having at least one bond decomposable by the acid is preferably not less than 0.1% by weight. 5-
2. The image forming method according to claim 1, wherein the amount is 70% by weight. 3. The image forming method according to claim 1, wherein the content of the o-quinonediazide compound in the total solid content of the photosensitive composition is 5 to 50% by weight. 4. The image forming method according to claim 1, wherein the content of the polymer compound in the total solid content of the photosensitive composition is 30 to 95% by weight. 5. The photoacid generator is a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium BF ₄ ⁻ , PF
^{_{6 -, SbF 6 -, SiF}} 6 2-, ClO 4 - salt, organic halogen compounds,
2. The image forming method according to claim 1, wherein the image forming method is selected from the group consisting of orthoquinonediazidosulfonyl chloride and an organic metal / organic halogen compound. 6. A compound having at least one bond decomposable by an acid, wherein the compound has a C—O—C bond, a Si—O—C bond, The image forming method according to claim 1, wherein the compound is a compound having a compound selected from the group of compounds having: (7) at least one bond decomposable by the acid;
The image forming method according to claim 1, wherein the compound having at least one compound has at least one orthocarbonate group represented by the following general formula [X]. 8. The method according to claim 8, wherein the bond decomposable by the acid is at least one.
Is a reaction product of (CH ₃ O) ₄ C and HOCH ₂ CH ₂ O ₃ H (n-C ₄ H ₉ OCH ₂ CH ₂ O ₄ C (CH ₃ O) ₄ C and HOCH ₂ CH Reaction products of ₂ OH, HOCH ₂ CH ₂ O ₃ H, and (CH ₃ O) ₄ C with HOCH ₂ CH ₂ O ₂ H, The image forming method according to claim 7, wherein the method is selected from the group consisting of: 9. The method of claim 1, wherein the o-quinonediazide compound is 1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2
-Naphthoquinonediazide-4-sulfonyl chloride,
The compound is selected from the group of compounds obtained by condensing 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride and a compound containing a hydroxyl group and / or an amino group. 1
2. The image forming method according to 1., 10. The image forming method according to claim 1, wherein the polymer compound has a vinyl carboxylate monomer constituting a polymerized unit selected from the group consisting of vinyl acetate and vinyl versatate. . 11. The polymer compound having polymerized vinyl acetate units in the molecular structure, having 40 to 95% by weight of polymerized vinyl acetate units, and having a number average molecular weight (MN) of 1,000 to 10%.
2. The image forming method according to claim 1, wherein the weight average molecular weight (MW) is 5,000 to 500,000.