JPH0223349A - Colored image forming method - Google Patents

Abstract

PURPOSE:To increase the density contrast of a colored toner image by providing a photosensitive layer contg. a compd. which generates an acid by irradiation of active rays and a compd. having a bond which can be decomposed by an acid and an arom. hydroxyl group-contg. resin onto a base and sticking a colored toner to the exposed image part after image exposing. CONSTITUTION:The photosensitive layer contg. the compd. (acid generating agent) which can generate the acid by irradiation of the active rays and the compd. (acid decomposing compd.) which has at least a piece of the bond which can be decomposed by the acid and the arom. hydroxyl group-contg. resin is provided on the base. The colored toner is stuck to the exposed image part after image exposing. As a result, the latent image having a large difference in the adhesiveness of the colored toner between the image part and the non- image part is obtd. The density contrast of the image part and the non-image part of the colored toner image after the development with the colored toner is increased in this way and the image reproducibility is enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method of forming colored images, such as for obtaining color proofs.

[Conventional technology]

It is well known in the art that color sheets for color proofing (referred to as color proofs) are used to save the labor and time of proof printing, which is performed as a pre-printing process in multicolor printing.

Japanese Patent Publication No. 62-42258 discloses a method of obtaining a colored image by utilizing the difference in adhesiveness of toner between an exposed area and an unexposed area. It is known to provide negative-working photoimaging compositions containing certain pine goo resins, photoacid generators, and polymeric and/or monomeric acetals.

[Problem to be solved by the invention]

The above-mentioned technique is unique in that a negative color image can be obtained, unlike the positive type, but it is possible to obtain a colored toner image between the image area (light irradiated area) and the non-image area. The density contrast was insufficient and the image quality was not fully satisfactory.

SUMMARY OF THE INVENTION Accordingly, a main object of the present invention is to provide a colored image forming method in which the density contrast of a colored toner image between an image area and a non-image area is high and the image quality is good.

[Means to solve the problem]

The above-mentioned problem is to solve the following problems: (a) A compound that can generate an acid upon irradiation with actinic rays (hereinafter also referred to as a photoacid generator) (bl) A compound that has at least one bond that can be decomposed by an acid (hereinafter referred to as an acid generator) (c) A photosensitive layer containing an aromatic hydroxyl group-containing resin is provided, and after image exposure, a colored toner is attached to the exposed image area.

[Specific structure of the invention]

The present invention will be explained in more detail below.

The photosensitive layer of the present invention contains the above-mentioned (a), (bl and (c)).The photosensitive layer contains an aromatic hydroxyl group-containing resin, thereby creating a gap between the image area and the non-image area. A latent image with a large difference in the adhesion of the colored toner is obtained, and thus,
The colored toner image after color toner development exhibits good image reproducibility with high density contrast between the image area and the non-image area.

Photoacid generator> Photoacid generators that can be used in the present invention, that is, compounds that can generate acid upon irradiation with actinic rays, include many known compounds and mixtures, such as diazonium salts, phosphonium salts, sulfonium salts, and Iodonium BF4
-, PFa-, 5bFs-SiF (1z-1C10,
Salts such as -, organohalogen compounds, orthoquinonediazide sulfonyl chlorides, and organometallic/organohalogen compounds can also be used as actinic radiation-sensitive components that form or separate acids upon irradiation with actinic radiation.

In principle, all organic halogen compounds known as free-radical-forming photoinitiators can be used as photosensitive compounds capable of forming hydrohalic acids. Examples of such compounds are U.S. Pat. No. 3,515,552, 3,53
No. 6.489, No. 3,779,778 and West German Patent Application No. 2.243.621.

For example, West German Patent Publication No. 2,610,84
No. 2, JP-A-54-74728, JP-A No. 55-77742
No. 57-16323, No. 60-3626 G
Compounds that generate acids upon photolysis as described herein may also be used.

Furthermore, 0-naphthoquinonediazide-4-sulfonic acid halide described in JP-A-50-36209 can also be used.

<Acid-decomposable compound> Compounds having a bond that can be decomposed by an acid upon receiving the acid generated by the action of such a photoacid generator (acid-decomposable compound) include, for example, -〇-〇-C5 bond 5i
Compounds with -0-C,E bonds or ≧C-0-C
-bonds.

-C-O-C,: Specific compounds having a bond include, for example, a compound having an acetal or ketal group, an orthocarboxylic acid ester group and/or a carboxylic acid amide acetanol group described in JP-A-51-120714. Compounds having an acetal or ketal group in the main chain as described in JP-A-53433429, compounds containing enol ether groups as described in JP-A-55-12995, JP-A-55-126236 Compounds having an N-acylimino carbonate group described in the publication, or polymers having an orthocarboxylic acid ester group in the main chain described in JP-A-56-17345 can be mentioned.

Further, specific compounds having =Si-o-c= bonds include, for example, JP-A-60-37549, JP-A-60-528.
Examples thereof include compounds described in No. 45 or No. 60-121446.

Further, specific examples of compounds having an ester group include compounds described in JP-A-60-3625 or JP-A-60-10247.

Among these compounds having a bond that can be decomposed by an acid, compounds having a St OCE bond are preferred. Among them, described in Japanese Patent Application Laid-Open No. 60-121446]
has at least one sio, C-conjunction;
Furthermore, compounds having at least one hydrophilic group are particularly preferred.

These acid-decomposable compounds may be used alone or in combination of two or more.

Further, as the acid-decomposed compound, a compound containing at least one orthocarbonate group represented by the following general formula (X) can also be suitably used.

- Tsuzuriyo (X) The compound containing at least one orthocarbonate group (hereinafter referred to as an orthocarbonate compound) includes, for example, at least one phenolic OH group and/or at least one alcoholic group. (hereinafter referred to as OH group-containing compound) and tetraalkoxymethane in one or more steps of transesterification.

For the above transesterification reaction, for example, 5ven
sk Kem, Tidskr, 65.10 (19
53) etc. or the method described in I (U) can be used.

Examples of the OH group-containing compounds include monohydric alcohols, dihydric alcohols, trihydric alcohols, tetravalent or higher alcohols, monovalent phenolic compounds, divalent phenolic compounds, and trivalent phenolic compounds. Compounds, phenolic compounds having a valence of 4 or higher, or compounds having both a phenolic OH group and 0)1 g of an alcoholic group can be mentioned.

Examples of the monohydric alcohol include n-propyl alcohol, n-7'tyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl alcohol, n- Dodecyl alcohol, n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, isopropyl alcohol, isobutyl alcohol, 5ec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, activated amyl alcohol, tert-pentyl alcohol, Cyclopentasol, cyclohexanol, allyl alcohol,
Aliphatic alcohols and benzyl alcohols such as crotyl alcohol, methyl vinyl carbinol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether , α-phenylethyl alcohol, β-phenylethyl alcohol, diphenylcarbinol, triphenylcarbinol, cinnamyl alcohol, and other aromatic alcohols.

For dihydric alcohols, for example, JP-A-53-13342
Pentane-1,5-diol, n-hexane-1,6-diol, 2-ethyl-hexane-1 described in Publication No. 9
, 6-diol, 2,3-dimethyl-hexane-1,6
-diol, heptane-1,7-diol, cyclohexane-1,4-diol, nonane-1, fudiol,
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-jetanol, 2-methyl-cyclohexane-1,4-dibrobanol, thio-
Dipropylene glycol, 3-methyl-pentane-1,
5-diol, dibutylene-glycol, oxypivalic acid-neobentyl glycol ester, 4,8-bis-(hydroxymethyl)-tricyclodecane, n-butene-(2)-1,4 diol, n-budo 2-in-1
, 4-diol, n-hex-3-yn-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,
Aliphatic alcohols such as di-, tri-, tetra-, penta-, and hexaethylene glycol, di- and tripropylene glycol, and polyethylene glycol with an average molecular weight of 200, 300, 40 (l and 600), p-xylylene glycol, 2-methyl -2-phenyl-1,3-
Examples include aromatic alcohols such as propanediol.

For trihydric alcohols, for example, JP-A-56-17345
Glycerol, butane-12,4-triol, 2-hydroxymethyl-butane-1,4-diol, pentane-1,2,5-triol, 2-hydroxymethyl-pencune-1,5-diol, Hexane-1
, 2,5-triol, 2-hydroxymethyl-hexane-1,6-diol, hexane-1,2,6-)diol, 4-ethyl-hexane-1,4,5-triol, heptane-L4.5 - triol, 1-(1,2-
dihydroxyethyl)-4-hydroxymethyl-benzene, 2.4.6-driethyl-5-propyl-heptane-1,3,7-)diol, 1-(2,3-dihydroxy-propoxy)-4-hydroxymethyl- benzene,
1-(2,3-dihydroxypropyl)-4-hydroxymethyl-benzene, off-thi-3-nin-1.7.8-
) diol, octane-1,2,8 triol, octane-1,3,8-) diol, nonane-1,4,5
-) diol, 3-(1-hydroxy-1-methyl-ethyl)-5-oxa-octane-2,8-diol, 2
．． 6.8-Trimethyl-3-hydroxymethyl-nonane-6,7-diol, 2-hydroxymethyl-3-oxahebutane-1,7-diol and hexadecane-
Examples include aliphatic or aromatic alcohols such as 1,2,16-) diols.

Examples of tetrahydric or higher alcohols include aliphatic alcohols such as pentaerythritol, threitol, bentitol, sorbitol, and polyvinyl alcohol. It may also be an aromatic alcohol.

Examples of monovalent phenolic compounds include phenol, 0-talizol, m-cresol, p-crisol,
3,5-xylenol, carvacrol, thymol, α
-naphthol, β-naphthol, etc.

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

Examples of trivalent phenolic compounds include pyrogallol and phloroglucin.

Examples of phenolic compounds having a valence of 4 or more include 1.4, 9.
Examples include 10-tetrahydroxyanthracene.

Examples of the compound having both phenolic 011 and alcoholic OH include 2-(bis(4-hydroxyphenyl)methyl)benzyl alcohol.

Examples of the above-mentioned tetraalkoxymethane include tetramethoxymethane and tetraethoxymethane.

Tetraethoxymethane, for example, OrganicSy
nthenes, Co11. Vol, rV)
457 (1963) using chloropicrin and sodium ethoxide. Other tetraalkoxymethanes can also be synthesized by similar methods. Also, the Journal of Organic Chemistry (J, Org, Chem,
) 361176 (1971) or the Journal of Organic
Chemistry (J, Org, Chem, +) 3
7, 4198 (1972).

For example, the above ortho carbon ester compound can be prepared by combining 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.
It can be obtained by reacting at a temperature of °C. The liberated lower alcohol is optionally distilled off. At this time, it is preferable to carry out the reaction in the presence of an acidic catalyst such as p-toluenesulfonic acid or sulfuric acid. Further, depending on the case, the reaction may be carried out under reduced pressure. Also, solvents that are inert under the reaction conditions, such as benzene, toluene, xylene, dioxane,
Chlorinated hydrocarbons and the like can also be used as reaction solvents. The liberated lower alcohol is optionally distilled off together with a portion of the solvent.

The quantitative ratio in the reaction of the tetraalkoxymethane and the OH group-containing compound is such that the total amount of OH groups is 4 moles per 1 mole of tetraalkoxymethane, but depending on the case, a different quantitative ratio may be used. .

In addition, when two types of OH group-containing compounds are used, a total of three of the tetraalkoxymethane and two types of OH group-containing compounds may be reacted at the same time, or in some cases, first the tetraalkoxymethane and one of the OH group-containing compounds may be reacted simultaneously. The compounds may be reacted and then the product may be reacted with another 011 group-containing compound.

Even when three or more types of OH group-containing compounds are used, the reaction can be carried out in the same manner.

Also chemical berichte (chell, 8er, )
544 (1961) or a similar method. For example, there may be mentioned a method in which xydichloromethane obtained by the method described in this document is reacted with the above-mentioned OH group-containing compound.

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 the following orthocarbonate group units, or a mixture thereof.

Rs-0'C-0-Ra, R3-0-C-0--0
-C-0R.

R.

-o-c-o--o-c-o- The above R1, R3, and R4 each represent an alkyl group, an aral group, an aralkyl group, an alkenyl group, or the like. These include those having an alkyl group, an aryl group, an aralkyl group, an alkenyl group or a substituent. In addition, at least two of Rt ``'' Ra may be bonded to each other to form a ring, and the bond may be bonded through a substituted or unsubstituted alkylene group, arylene group, aralkylene group, alkenylene group, etc. In addition, it may be further bonded to the same or other orthocarbonate group unit mentioned above.

The compound having at least one orthocarbonate group unit is preferably one having 1 to 50 orthocarbonate group units in its molecule.

Specific examples of compounds having at least one orthocarbonate group are shown below.

Exemplary Compound Level 5 Reaction product of reaction product H between (cH30) 4C and (HOCH2) ac 8 (c) + 30) 4. C and ÷CH-CHz-+-
The reaction product R 11!19 (n-Cal(qOcl(zcHzO-
h-C Arashi 21 (cH:+0)tc 110 + C)l ZCII go→v-Reaction product with reaction product with H paraboloid HO+CHzC)lto+rH Reaction product with HO+CH2CIZ Reaction with H Polymer Binder by Formation> As the polymer binder for the photosensitive layer in the present invention, an aromatic hydroxyl group-containing resin is used.

As the aromatic hydroxyl group-containing resin, phenol-containing novolac resins or aromatic hydroxyl group-containing acrylic resins can be suitably used, and these may be used alone or in combination.

In the novolak resin, (i) novolak resin containing only one type of phenol; (ii) two types of novolak resin containing only one type of phenol as phenol (the phenol component of each novolak resin is different from each other) A mixture or preferably a copolycondensate of two different types of phenols and an active carbonyl compound 1(iii) A novolak resin containing only one type of phenol as the phenol. A mixture of at least one type of copolycondensed novolac resin containing two types of phenols as phenols and at least one type of novolac resin containing one type of phenol (a mixture of these resins) A mixture of two or more copolymerized novolac resins containing two types of phenols as phenols, or a copolymerized novolak resin containing at least three types of phenols as phenols. A condensed novolac resin etc. can be used, but preferably a copolycondensed novolac resin containing at least three types of phenols as the phenol, that is, a copolycondensate of at least three different types of phenols and an active carbonyl compound is used. be able to.

These phenols include all compounds in which at least one hydrogen atom bonded to an aromatic ring is substituted with a hydroxyl group, and specifically include phenol, O-cresol, m-cresol, p-cresol, 3, Examples include 5-xylenol, 2.4-xylenol, 25-xylenol, carvacrol, thymol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, and an alkyl group (1 to 8 carbon atoms) substituted phenol.

Active carbonyl compounds include, for example, aldehydes and ketones, and specific examples include formaldehyde, acetaldehyde, benzaldehyde, acrolein, furfural, and acetone.

Among the above novolac resins (ii) obtained from these phenols and active carbonyl compounds, preferred are those obtained by copolymerizing formaldehyde with two selected from phenol, O-cresol, m-cresol, and p-cresol. It is a resin obtained by condensation. For example, phenol/m-cresol/formaldehyde copolycondensate resin, phenol/p-cresol/formaldehyde copolycondensate resin, m-cresol/p-cresol/formaldehyde copolycondensate resin, 0-cresol, p-cresol Examples include formal aldehyde copolycondensate resins.

Among these, the most preferred novolak resin is m-cresol, p-cresol, and formaldehyde.
- Cresol/p-cresol/formaldehyde copolycondensation resin, and the preferred molar ratio of m-cresol and p-cresol is the molar ratio charged at the time of synthesis: m-cresol: p-cresol form, 5 = 3.5 to 9 .9:
The page area is 0.1.

Among the novolak resins listed above, preferred are resins obtained by copolycondensing formaldehyde with three selected from phenol, 0-cresol, m-cresol, and p-cresol. For example, phenol 0
-Cresol/m-cresol/formaldehyde copolycondensate resin, phenol/0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol/
Examples include m-cresol/p-cresol/formaldehyde copolycondensate resin.

Among these, the most preferred novolak resin is phenol,
It is a phenol/m-cresol/p-cresol/formaldehyde novolac resin consisting of m-cresol, p-cresol, and formaldehyde. Preferably, the molar ratio of phenol is in the range of 2% to 60%, more preferably 5% to 4%.
This is a 0% area.

These novolak resins mentioned above may be used alone or in combination of two or more.

The molecular weight (polystyrene standard) of the novolak resin is:
Preferably several thousand equal parts -7-fi M n is 3.00 x
lo"X7゜50X10', weight average molecular weight is 1.0
0X10' to 3.0OX10', more preferably Mn
is 5.00X10" ~ 4.0OX103, M- is 3.
00X103 to 2.0OxlO'.

The molecular weight of the resin is measured by GPC (gel permeation chromatography).

The number average molecular weight Mn and weight average molecular weight are calculated by smoothing the peaks in the oligomer region by the method described in Morio Takuue, Tatsuya Miyabayashi, and Masayuki Tanaka, "Journal of the Chemical Society of Japan," pages 800 to 805 (1972). This method shall be used to connect the center of the peak and the center of the valley.

In addition, as a method for confirming the quantitative ratio of two or three different phenols used in the synthesis of the novolak resin, pyrolysis gas chromatography (
Py, lysis-gaschromatorap
hy.

PGC) is used. Regarding pyrolysis gas chromatography, its principles, equipment, and experimental conditions are described, for example, by Nippon Kagaku Kinsen, Tsuge Shinsho New Experimental Chemistry Course Vol. )
The method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in Morio Tsuge, Takashi Tanaka, and Masayuki Tanaka, "Analytical Chemistry," Vol. 18, pp. 47-52 (1).
969).

On the other hand, aromatic hydroxyl group-containing acrylic resins are also very useful as polymer binders.

The aromatic hydroxyl group-containing acrylic resin is preferably one having structural units shown in the following (1) to (IV) in its molecular structure, and a homopolymer type having a repeating structure of only the structural units. Alternatively, there may be mentioned a copolymer-type product in which the structural unit is combined with one or more structural units having a structure in which the unsaturated double bonds of other vinyl monomers are cleaved.

(1) In the formula, R1 and R2 represent a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a carboxylic acid group, preferably a hydrogen atom, and R3 represents a hydrogen atom, a halogen atom such as bromine or chlorine, or a methyl group, represents an alkyl group such as an ethyl group, preferably a hydrogen atom or a methyl group, R4 represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an aralkyl group such as a phenyl group or a benzyl group, preferably a hydrogen atom; is an alkyl group such as a methyl group or an ethyl group,
A phenylene group which may have a substituent such as a halogen atom such as bromine or chlorine, an alkoxy group such as a carboxylic acid group, a methoxy group, or an ethoxy group, a hydroxyl group, a sulfonic acid group, a cyano group, a nitro group, an acyl group, or It represents a naphthylene group, preferably an unsubstituted or methyl-substituted phenylene group or naphthylene group, X represents a divalent organic group such as an alkylene group, and n represents O to 5, preferably O.

R8 1E C C-→-1... (I[[) R3 and R2 in formulas (n) to (IV) are the same as described above.

In the polymer compound of the present invention having a copolymer-type structure, examples of the structural units used in combination with the structural units represented by the above-mentioned -binding margins (1) to (IV) include ethylene, propylene, isobutylene, and butadiene. , ethylenically unsaturated olefins such as isoprene, styrene, α-
Styrenes such as methylstyrene, p-methylstyrene, p-chlorostyrene, aliphatic carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride or their anhydrides, methyl acrylate, ethyl acrylate , n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate,
Acrylic acid derivatives or methacrylic acid derivatives such as methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, vinyl acetate, propion Vinyl esters such as vinyl acid, vinyl benzoate, vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, halogenation or cyanide of vinyl chloride, vinylidene chloride, vinylidene cyanide, etc. vinyl, l-methyl-1
Ethylene derivatives such as '-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1'-ditroethylene, N-vinylpyrrole, N-vinyl Examples include those having a structure in which an unsaturated double bond of a vinyl monomer is cleaved, such as N-vinyl compounds such as carbazole, N-vinylindole, N-vinylpyrrolene, and N-vinylpyrrolidone.

Among the above monomers, acrylic acid, methacrylic acid or their esters and nitriles, particularly ethyl acrylate, acrylonitrile, methacrylic acid, and methyl methacrylate are preferred.

<Others> The weight ratio of the above (al: (b): (cl) is 3 to 2
5:20-60:2G-80 is preferred.

The above-mentioned photosensitive composition is dissolved in a solvent together with other additives if necessary, and then coated on a support to form a photosensitive layer. Transparent or opaque support materials include paper, cardboard, metal sheets, such as aluminium, copper, steel and others, wood, glass, natural or synthetic polymers, such as polyamides, rubber, polyethylene or polypropylene, wires, optionally treated with baryta. Polyesters such as polyethylene terephthalate, cellulose, cellulose esters, polyvinyl chloride or copolymers thereof, polyacrylonitrile and other films or fibrous webs may be mentioned.

Examples of additives include plasticizers and coating properties improvers, and specific examples of plasticizers include various low-molecular compounds,
For example, phthalate esters, triphenyl phosphates, maleate esters, and coating properties improvers include surfactants such as fluorine surfactants, nonionic surfactants such as ethyl cellulose polyalkylene ether, etc. can.

As a solvent, water, methanol, ethanol, acetone, ethyl acetate, methyl cellosolve, ethyl cellosolve,
dioxane, methyl ethyl ketone, cyclohexanone,
Diethylene glycol monomethyl ether, γ-butyrolactone, tetrahydrofuran, methylene chloride,
Examples include ethylene chloride, dimethyl sulfoxide, dimethyl formamide, etc., and these can be used alone or in combination of two or more.

The image forming material according to the present invention produced in this manner is first imagewise exposed to actinic light.

Various light sources are used for imagewise exposure, such as an ultra-high pressure mercury lamp, a tungsten lamp, a mercury lamp, a xenon lamp, a fluorescent lamp, a CRT light source, and a laser light source.

In the image-forming material imagewise exposed in this manner, the unexposed image areas do not exhibit toner adhesion, whereas the exposed image areas exhibit toner adhesion. Therefore, colored toner is applied to this exposed image area using a cotton pad method or a special application device.

As this colored toner, dyes and pigments can be used. Especially when used for color proofing, the required constant colors, i.e.
Pigments and dyes with tones matching yellow, magenta, cyan, and black are required, but metal powders, white pigments, and fluorescent pigments are also used. The following examples are some of the many pigments and dyes known in the art (c, I refer to Color Index).

Victoria Pure Blue (c, I 42595) Auramine 0 (c, I 41000) Rhodamine GGCP
(c, I 45160) Rhodamine B (c, + 4
5170) Safranin O 70:100 (c,I 5
0240) Eriogra'7 Schiff X (c, I 420
80) First Black) IB (c, I 2615
0) k1201 Lionor Yellow (c, I 210
90) Lionor Yellow GRO (c, I 21090
) Shimla Fast Yellow 8GF (c, I 21
105) Benzidine Yellow 4T-5640 (c, [2
1095) Shimla Firth Trend 4015 (c,
I 12355) Lionor Red 784401 (c
, 115830) First Gen Blue TGR-L (
c, I 74160) Lionor Blue SM (c, I
26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Blank 130. $40.150 During the deposition of the colored toner, the photosensitive layer can be heated to a temperature of, for example, 100° C. or less. The imagewise exposure may be carried out after the photosensitive layer has been transferred to the transfer material, such as paper, and then the colored toner is applied. This transcription includes
This can be carried out by overlapping the image forming material and the transfer material under heat and pressure or pressure, and then peeling off the support of the image forming material. In this case, in order to facilitate peeling off of the support, a release treatment can be applied between the support and the photosensitive layer.

An example of a mold release treatment is to provide a mold release layer, and this mold release layer may include methylcellulose, butylcellulose, hydroxyethylcellulose, carboxymethylcellulose, cyanoethylcellulose, cellulose acetate,
Cellulose triacetate, cellulose acetate butyrate, hydroxypropyl methyl cellulose phthalate, hydroxypropyl methyl cellulose hexahydrophthalate, or a mixture thereof can be used, but hydroxypropyl methyl cellulose phthalate and hydroxypropyl methyl cellulose hexahydrophthalate are particularly preferred. .

The thickness of the release layer is suitably in the range of 0.01 μm to 10 μm, particularly preferably in the range of 0.1 μm to 5 μm.

Another preferred example for improving mold releasability is an example in which a polypropylene layer and/or a polyethylene layer is preferably provided thinner than the thickness of the support.

A method for forming a polypropylene layer or a polyethylene layer on a support is 1> using a solution of polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. dissolved in an organic solvent as an adhesive; After applying these adhesives on a support and drying them with hot air or heating, a polypropylene film or a polyethylene film is layered and laminated by pressing under heat; 2) Ethylene and acetic acid A mixture of vinyl, a copolymer of ethylene and acrylic acid ester, a polyamide resin, a petroleum resin, a rosin, and a wax are used as adhesives, and while these adhesives are heated and kept in a molten state, a doctor blade is placed on the support. After applying the coating using a method such as a roll coating method, a gravure method, a reverse roll method, etc., a polypropylene film or a polyethylene film is immediately laminated and laminated by heating to a high temperature and then cooling as necessary. Melt lamination method; 3) So-called extrusion lamination method, in which polypropylene or polyethylene is kept in a molten state, extruded into a film using an extruder, and laminated by pressing a support while it is in the molten state; 4) Melt extrusion method When forming a film to serve as a support, multiple extruders are used to process polypropylene or polyethylene in a molten state.
Examples include so-called coextrusion method in which a polypropylene layer or a polyethylene layer is formed on a support film by multiple moldings.

A multicolor image can be obtained by superimposing exposed image areas to which colored toners are attached.

(Example〕 Next, the effects of the present invention will be clarified by examples.

(Examples 1 to 5 and Comparative Examples 1 to 3) A photosensitive composition having the following composition was stirred and mixed until homogeneous.

2-Trifuromomenal Sennozaline 2.0 g This photosensitive composition was coated onto the silicone side of a 25 μm thick Silicone Release polyethylene terephthalate film base with a 0.76 crane doctor knife and then air-dried. After the surface of the photosensitive layer on this base was overlapped with white synthetic paper, the paste was peeled off and the photosensitive layer was transferred onto the synthetic paper.

The photosensitive layer on the synthetic paper was then exposed to a bank of black light blue fluorescent bulbs through the target for 2 minutes. Thereafter, this was placed on a heated hot plate (~100° C.), and “Dupont 4C Cromarin” (registered trademark) red toner was sprinkled on it to color it.

The above-mentioned exemplified compounds are as follows.

O Exemplary Compound +1 Copolycondensation resin of tophenol, m-cresol, p-cresol, and formaldehyde (molar ratio of each of phenol, m-cresol, and p-cresol is 2.0:
4.8: 3.2, weight average molecular weight Mw=8.000
, dispersity Mw/Mn = 6.2, Mn: number average molecular weight) ○ Exemplary compound (2) - Copolycondensation resin of m-cresol, p-cresol and formaldehyde (each of m-cresol and p-cresol) Molar ratio is 9:1, weight average molecular weight Mw = 4.2
00, dispersity Mw/Mn=4.0, gate n; number average molecular weight) ○ Exemplary compound (3) CH3O Exemplary compound (5) Polyhydroxystyrene (Resin M: manufactured by Maruzen Sekiyu Co., Ltd.) On the other hand, the above-mentioned exemplified compound In addition to compounds (1) to (5), colored images were similarly obtained using the following comparative exemplified compounds (1) to (3).

r CH3 CH3 (MW=32,000, Mw/Mn=3.1, m
:n:l:ni=20:35:5:40) <Effect> Regarding the thus obtained transferred image, the image quality was evaluated using the following evaluation criteria A to D, and the results were as shown in Table 1. .

A: Image reflection density≧1.4 B: 1,4>Image reflection density≧1.0 C: l, Q>Image reflection density≧0.6 D: Image reflection density<0.6 On the surface land, A colored image with a good image reflection density of 1.55 was obtained.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a colored image in which the density contrast of the colored toner image between the image area and the non-image area is high and the image quality is good.

(Example 6) In the previous example, the acid decomposed compound was changed to the following compound:

Claims (1)

[Claims] (1) On the support, (a) a compound capable of generating an acid upon irradiation with actinic rays, (b) a compound having at least one bond that can be decomposed by an acid, and (c) an aromatic hydroxyl group-containing resin. A method for forming a colored image, which comprises providing a photosensitive layer and, after image exposure, attaching a colored toner to the exposed image area.