JP2731851B2 - Colored image forming material and transfer image forming method using the material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a colored image forming material used for a color proof for color proofing in color printing, and more particularly, to improving the uniformity of a coating film of a colored photosensitive layer. The present invention relates to a colored image forming material, and a transfer image forming method capable of obtaining a transferred image extremely similar to the image quality of a printed matter using the material.

2. Description of the Related Art It is well known in the art that a color sheet for color proofing (also referred to as a color proof) is used to save labor and time of proof printing performed as a pre-process of main printing in multicolor printing. .

As a method of preparing a multicolor transfer image using a colored image forming material for color proofing, for example, a so-called direct transfer method in which a colored image is directly transferred to a final image receiving paper and laminated as described in JP-A-47-41830 For example, a so-called indirect transfer method in which a colored image is temporarily transferred and laminated on a temporary image receiving sheet and then transferred again to a final image receiving paper, as described in JP-A-59-97140, for example, Kaisho 56-501217
And a method of repeating the step of forming an image after transferring the colored photosensitive layer to the image receiving paper.

In each of the above methods, since the colored image surface on the material to be transferred is coated with a transparent thermoplastic organic polymer layer, the glossiness of the obtained image surface is too high, which is different from the image quality of the printed matter. It has the drawback of giving an impression.

Originally, a color proof for color proofing is used for predicting the image reproduction of a final printed matter. Therefore, a colored image forming material capable of obtaining a transfer image very similar to the image quality of the printed matter is strongly desired. To achieve the above object, the present inventors have already prepared a photosensitive composition, a binder, a colored image-forming material having a colored photosensitive layer containing a colorant, on a support, by imagewise exposure and After performing a development process and forming a colored image, by substantially transferring only the colored image portion onto the material to be transferred, a colored image formation that can form a transferred image extremely similar to the image quality of the printed matter can be formed. Material and transfer image forming method
No. 2783 and Japanese Patent Application No. 62-328616.

[Problems to be Solved by the Invention] In the colored image forming materials of the above-mentioned systems, usually, a photosensitive composition, a binder and a colorant are dissolved and dispersed in an appropriate solvent, and the dispersion is coated on a support and dried. However, in this case, coating defects such as so-called streak-like unevenness, pinholes, unevenness in the squeezed skin, wavy shading unevenness, and cissing may occur.
In particular, in the case of a colored image forming material of a system in which substantially only the colored image portion is transferred onto the material to be transferred, it is necessary to directly apply and dry a coating solution for forming a colored photosensitive layer on the release surface of the support. Therefore, the coating defect is easily generated.

In the colored image forming material, when the colored photosensitive layer has the above-mentioned coating defect, not only the appearance is impaired as a commercial product, but also it tends to cause instability in characteristics such as image reproducibility, sensitivity, and developability.

In view of the above-mentioned problems, the present invention provides a colored image-forming material having a colored photosensitive layer containing at least a photosensitive composition, a binder and a colorant on a support. Provided is a colored image forming material having a colored photosensitive layer having excellent coating uniformity without coating defects such as wavy shading unevenness and cissing, and transfer using the material, which is very close to the image quality of printed matter. An object of the present invention is to provide a transfer image forming method capable of obtaining an image.

[Means for Solving the Problems] The object of the present invention is to provide at least a photosensitive composition on a support,
In a colored image forming material having a colored photosensitive layer containing a binder and a colorant, the coloring photosensitive layer is achieved by containing a fluorine-based surfactant represented by the following general formula [I].

Further, the object is achieved by forming a colored image by subjecting the colored image forming material to at least imagewise exposure and development, and then substantially transferring only the colored image portion onto the material to be transferred. You.

General formula [I] (Wherein, R ¹ represents an alkyl group, R ² represents an alkylene group or a fluorinated alkylene group, R ³ represents an fluorinated alkylene group, an alkyleneoxy group or a fluorinated alkyleneoxy group, and a represents 1 to 10 And b represents a number from 1 to 30. However, when a and b each represent a number of 2 or more, each R ² and each R ³ may be the same or different. At least one R ³ represents a fluorinated alkylene group or a fluorinated alkyleneoxy group.) [Specific Configuration of the Invention] The fluorine-containing surfactant contained in the colored photosensitive layer constituting the colored image forming material of the present invention is It is represented by the following general formula [I].

General formula [I] Here, in the formula, R ¹ is an alkyl group, preferably having 1 carbon atom.
To 10, more preferably an alkyl group having 4 to 8 carbon atoms.

R ² represents an alkylene group or a fluorinated alkylene group, preferably an ethylene group or a fluorinated ethylene group. As the fluorinated ethylene group, the hydrogen atom of the ethylene group is 1 to 4 fluorine atoms, preferably 1 to 2 fluorine atoms.
Ones substituted by the number. A represents a number of 1 to 10, preferably 1 to 6. However, when a represents a number of 2 or more, each R ² may be the same or different, and in a number of R ² , an alkylene group and a fluorinated alkylene group may be present simultaneously. In this case, the alkylene group unit is selected from a number of 0 to 10, preferably 1 to 4, and the fluorinated alkylene group unit is selected from a number of 0 to 9, preferably 0 to 3.

R ³ represents a fluorinated alkylene group, an alkyleneoxy group or a fluorinated alkyleneoxy group. As the fluorinated alkylene group, the same as those described above for R ² can be mentioned. As the alkyleneoxy group, an ethyleneoxy group and an isopropyleneoxy group are preferable, and as the fluorinated alkyleneoxy group, a fluorinated ethyleneoxy group and a fluorinated isopropyleneoxy group are preferable. Examples of the fluorinated ethyleneoxy group include those in which a hydrogen atom of an ethyleneoxy group is substituted with 1 to 4 fluorine atoms, preferably 1 to 3 fluorine atoms. Examples of the fluorinated isopropyleneoxy group include those in which a hydrogen atom of an isopropyleneoxy group is substituted with 1 to 7 fluorine atoms, preferably 1 to 4 fluorine atoms. B is 1 to 3
0, preferably a number from 2 to 20. However, when b represents a number of 2 or more, each R ³ may be the same or different, and in b b R ³ , an alkylene fluoride group, an alkyleneoxy group and an alkyleneoxy group are simultaneously May be present. In this case, the number of the fluorinated alkylene group is 0 to 9, preferably 0 to 3, and the number of the alkyleneoxy group is 0 to 29, preferably 0 to 18. Is a number from 1 to 30, preferably 2
It is selected from the range of numbers up to 20. Furthermore, at least one
R ³ represents a fluorinated alkylene group or a fluorinated alkyleneoxy group.

Specific examples of the fluorine-based surfactant of the present invention include, for example, the following compounds.

Exemplary compound of the general formula [I] As a method for synthesizing the fluorine-based surfactant of the present invention, a method for synthesizing the exemplary compound (2) will be described below.

Other compounds can be easily synthesized in the same manner.

The amount of the fluorinated surfactant used in the present invention in the colored photosensitive layer is preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 2% by weight, based on the total solids.

The colored image forming material of the present invention is developed after imagewise exposure through a color separation network film to form a colored image, and then substantially only the image portion is directly transferred and laminated on the material to be transferred. At this time, in order to efficiently transfer the colored image onto the surface to be transferred and to facilitate peeling of the support after the image transfer, it is necessary to perform a release treatment with an appropriate oil-repellent substance on the support surface. Alternatively, it is preferable to provide a release layer on the support.

As the oil-repellent substance, for example, a silicone resin, a fluorine resin, a fluorine-based surfactant, a polyolefin or a polyamide can be used.

Polypropylene film and polyethylene film and the like show good releasability without being subjected to a special release treatment, so as a particularly preferred embodiment thinner than the thickness of the support,
Examples of providing a polypropylene layer or a polyethylene layer are given.

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 the adhesive is applied onto 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 of ethylene and acrylic acid ester, polyamide resin, petroleum resin, rosins, waxes or a mixture thereof are used as an adhesive, and these adhesives are heated as they are to keep them in a molten state. After applying on a support by a doctor blade method, roll coating method, gravure method, reverse roll method, etc., immediately attach a polypropylene film or polyethylene film, and if necessary, heat to a high temperature and then cool. So-called hot melt lamination method.

3) A so-called extrusion lamination method in which polypropylene or polyethylene is kept in a molten state, extruded into a film by an extruder, and while the molten state is in a molten state, the support is pressed and laminated.

4) When a film to be a support is formed by a melt extrusion method, 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. The so-called co-extrusion method of forming. And the like.

As the release layer, for example, alcohol-soluble polyamide, alcohol-soluble nylon, a blend of a partially esterified resin of a copolymer of styrene and maleic anhydride and a methoxymethylated nylon, polyvinyl acetate, polyacrylate, polymethyl Methacrylate and acrylate copolymer, polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate, 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, hydroxypropylmethyl Cellulose phthalate, hydroxypropylmethyl cellulose hexahydrophthalate, or mixtures thereof can be used.

The thickness of the release layer is suitably in the range of 0.01 μm to 30 μm, and particularly preferably in the range of 0.1 μm to 5 μm.

As the transparent support used in the colored image forming material used in the present invention, a polyester film, particularly a biaxially stretched polyethylene terephthalate film is preferable in terms of dimensional stability against water and heat, and an acetate film.
Polyvinyl chloride film, polystyrene film, polypropylene film, polyethylene film may also be used.

The colored photosensitive layer is one that is removed in an image form by development following imagewise exposure to form a colored image.

Various photosensitive compositions can be used as the photosensitive composition contained in the colored photosensitive layer in the present invention. On the other hand, when the solubility is changed and a certain solvent is applied, all compounds such as monomers, prepolymers, and polymers that can dissolve away the exposed or unexposed portions are included. Examples of the photosensitive composition that can be used include, as a so-called negative-positive type, in which the solubility of an exposed portion is reduced, and a photo-crosslinking type photosensitive represented by a product obtained by esterifying polyvinyl alcohol with cinnamic acid. Resin-based, diazonium salts and condensates thereof are mixed with polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and the like, and systems where an aromatic azide compound is used as a photo-crosslinking agent and mixed with a binder such as a cyclized rubber, and the like. A photosensitive resin using photoradical polymerization or photoion polymerization can also be used. Further, as a so-called boji-bodi type in which the solubility of an exposed portion is increased, for example, there is a photosensitive resin composition using o-quinonediazide as a photosensitive substance, and specifically, 1,2-benzoquinonediazide-4. -Sulfonyl chloride, 1,2-naphthoquinonediazide-4-manifonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2
A compound obtained by condensing -naphthoquinonediazide-6-sulfonyl chloride with a compound containing a hydroxyl group and / or an amino group is preferably 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, 4,4
-Diaminobenzophenone and the like.

With respect to the above-mentioned o-quinonediazide compound,
"Light Sensitive System" by J.KOSAR (Wiley & Sons,
New York, 1965) and Nagamatsu, Inui, “Photosensitive Polymers” (Kodansha, 1977).

Further, as a positive / positive type, i) a compound capable of generating an acid upon irradiation with actinic rays, ii) a compound having at least one bond decomposable by an acid, and ii.
i) A photosensitive resin composition containing a novolak resin containing two or three different phenols can also be used.

The content of the photosensitive composition in the colored photosensitive layer used in the present invention is suitably, for example, from 5 to 80% by weight.

As the binder constituting the colored photosensitive layer, a polymer compound which is film-forming and is soluble in a solvent, and is preferably soluble or swellable in an alkali developing solution is used.

Specific examples of such a polymer compound include, for example, a polymer compound containing a structural unit having an aromatic hydroxyl group represented by the following general formula [II] in its molecular structure.

General formula [II] Here, R ⁴ and R ⁵ are a hydrogen atom, an alkyl group or a carboxylic acid group, R ⁶ is a hydrogen atom, a halogen atom or an alkyl group,
R ⁷ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group, X is a divalent organic group connecting a nitrogen atom and an aromatic carbon atom, n is 0 or 1, and Y may have a substituent. It is a phenylene group or a naphthylene group which may have a substituent.

Specific examples of the monomer forming the structural unit represented by the above general formula [II] include N- (4-hydroxyphenyl)-(meth) acrylamide and N- (2-hydroxyphenyl)-(meth) acrylamide , N-
Monomers of (meth) acrylamides such as (4-hydroxynaphthyl)-(meth) acrylamide; more preferably N- (4-hydroxyphenyl)-(meth) acrylamide monomer.

In the present invention, it is preferable to use a copolymer of a monomer forming the structure represented by the general formula [II] and the following monomers and the like as the binder.

Here, R ⁸ represents a hydrogen atom, an alkyl group, or a halogen atom, and R ⁹ represents an alkyl group, a phenyl group, or a naphthyl group.

The proportion of the group having an aromatic hydroxyl group represented by the general formula [II] in the above copolymer is preferably 1 to 30 mol%.

The proportion of units formed from the acrylonitriles in the copolymer is preferably from 0 to 50 mol%, and more preferably from 5 to 40 mol% in view of developability. The proportion of the structural unit formed from the alkyl acrylates is preferably from 50 to 95 mol% from the viewpoint of developability with a low alkaline aqueous solution, and more preferably from 60 to 95 mol%.
95 mol% gives the most suitable developability.

The polymer compound may be copolymerized with the above-mentioned acrylic acids such as acrylic acid or methacrylic acid for the purpose of finely adjusting the developability, in addition to the structural units described above, and the polymer of the copolymer may be used. The ratio in the compound is preferably 0 to 20 mol%, and most preferably 0 to 10 mol%, in consideration of the development latitude.

The weight average molecular weight of such a high molecular compound is preferably from 100 to 100,000 in terms of developability when a low alkaline aqueous solution is used as a developer, or from the viewpoint of resolution, and more preferably in the range of 1,000 to 30,000. It is suitable. These polymer compounds can be synthesized by a well-known copolymerization method.

Specific examples of such a high molecular compound include a copolymer having the following structure.

In the present invention, a novolak resin obtained by polycondensation of at least one phenol and an active carbonyl compound may be used as a binder.

These phenols include all compounds in which at least one of the hydrogen atoms bonded to the aromatic ring is substituted with a hydroxyl group. Specifically, for example, phenol, o-cresol, m-cresol, p-cresol, 3 , 5-xylenol, 2,4-xylenol, 2,5-xylenol, carvacrol, thymol, catechol, resorcin, hydroquinone, pyrogallol, phloroglucin, phenol substituted with an alkyl group (1 to 8 carbon atoms), and the like.

Active carbonyl compounds include, for example, aldehydes, ketones and the like, specifically, for example, formaldehyde,
Acetaldehyde, benzaldehyde, acrolein,
Furfural, acetone and the like can be mentioned.

As the polycondensation resin, phenol formaldehyde novolak resin, m-cresol formaldehyde novolak resin, phenol / m-cresol / formaldehyde copolycondensate resin, phenol / p-cresol / formaldehyde copolycondensate resin, m-cresol / p-
Cresol / formaldehyde copolycondensate resin, o-cresol / p-cresol / formaldehyde copolycondensate resin, phenol / o-cresol / m-cresol / formaldehyde copolycondensate resin, phenol / o-
A cresol / p-cresol / formaldehyde copolycondensate resin, a phenol / m-cresol / p-cresol / formaldehyde copolycondensate resin, and the like can be given.

A preferred novolak resin is phenol formaldehyde novolak resin, the molecular weight of which is weight average molecular weight Mw.
The range of 3500 to 500 and the number average molecular weight Mn of 1000 to 200 are preferred.

The molecular weight of the resin is measured by GPC (gel permeation chromatography). Number average molecular weight
The calculation of Mn and the weight average molecular weight Mw is described in Morio Takuebu, Tatsuya Miyabayashi and Masayuki Tanaka, “The Chemical Society of Japan”, pp. 800-805 (1972
Year), a method of leveling the peak of the oligomer region (connecting the center of the peak with the center of the valley).

In the novolak resin, pyrolysis gas chromatography (PEG) is used as a method for confirming the quantitative ratio of different phenols used for the synthesis.
The principle of pyrolysis gas chromatography,
The apparatus and experimental conditions are described in, for example, The Chemical Society of Japan, edited by Takushoku, New Experimental Course, Vol. 19, Polymer Chemistry [I], pp. 474-485 (issued by Maruzen 1978), and the like. A qualitative analysis method for novolak resins by gas chromatography is described in Morio Takushoku, Takashi Tanaka, and Masayuki Tanaka, "Analytical Chemistry," Chapter 18
Volume, pages 47 to 52 (1969).

Further, other polymer compounds that can be used as a binder include sulfoalkyl esters of (meth) acrylic acid (co) polymer, vinyl acetal (co) polymer, vinyl ether (co) polymer, acrylamide (co) Polymers, styrene (co) polymers, cellulose derivatives, vinyl acetate (co) polymers and the like are also included.

In the present invention, a dye and a pigment are added as a colorant to the colored photosensitive layer. In particular, when used with color proofing, the usual colors required there, namely, yellow, magenta,
Pigments and dyes that match the colors of cyan and black are required, but other metal powders, white pigments, and fluorescent pigments are also used. The following examples are just a few of the many pigments and dyes known in the art.

(C.I means color index).

Victoria Pure Blue (CI 42595) Auramine (CI 41000) Katilon Priliant Flavin (CI Bake 13) Rhodamine 6GCP (CI 45160) Rhodamine B (CI 45170) Safranin OK 70: 100 (CI 50240) Erioglaucine X (CI 42080) First Black HB (CI 26150) No.1201 Lionol Yellow (CI 21090) Lionol Yellow GRO (CI 21090) Shimla First Yellow 8GF (CI 21105) Benzidine Yellow 4T-564D (CI 21095) Shimla First Red 4015 (CI 12355) Lionol Red 7B4401 (CI 15830) Fast Gen Blue TGR-L (CI 74160) Lionol Blue SM (CI 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black # 30, # 40, # 50 Cyanine Blue 4920 (Dainichi Seika Seika First Carmine 1483 (Dainichi Seika) Seika First Yellow H-7555 (Dainichi Seika) The content of the colorant in the colored photosensitive layer used in the light is suitably 5% to 50% by weight, for example.

The ratio of the colorant / binder in the colored photosensitive layer used in the present invention can be 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 a developer. For example, in the case of a dye, its content is 5% by weight.
% To 75%, in the case of pigments, the content is 5% to 90% by weight
Is appropriate.

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 its content. Within the allowable range, the smaller the thickness of the colored photosensitive layer, the higher the resolution and the better the image quality. Therefore, the film thickness is 0.1 μm
Usually, it is used in the range of ５5 μm.

In the colored photosensitive layer, in addition to the above-described materials, a plasticizer, a coating improver other than the fluorine-based surfactant, and the like can be further added as necessary.

Examples of the plasticizer include various low molecular weight compounds such as phthalate esters, triphenyl phosphates and maleate esters, and examples of the coatability improver include nonionic activators such as ethyl cellulose and polyalkylene ether. Surfactants can be mentioned.

Further, the colored photosensitive layer can be divided into two layers, a colorant layer composed of a colorant and a binder, and a photosensitive layer composed of a photosensitive composition and a binder. In this case, either layer may be present on the support side.

Examples of the coating method for applying the colored photosensitive layer on a support include roll coating, reverse roll coating, dip coating, air knife coating, gravure coating, gravure offset coating, hopper coating, blade coating, and rod coating. , Wire doctor coating, spray coating, curtain coating, extrusion coating and the like.

Drying is performed by blowing heated air onto the application surface. The heating temperature is preferably 30 ° C to 200 ° C,
Particularly, the range of 40 ° C to 140 ° C is suitable. During drying, a method of drying the colored photosensitive layer while keeping the temperature of the heated air constant is generally performed, but a method of drying by gradually increasing the temperature of the heated air may also be performed. it can. In addition, heated air is 0.1 m
/ Sec to 30 m / sec, preferably
It is preferable to supply at a rate of 0.5 m / sec to 20 m / sec.

When containing a photopolymerizable substance in the colored photosensitive layer, in order to prevent polymerization inhibition caused by the influence of oxygen,
An overcoat layer that can be dissolved or swelled in a developer can be provided on the colored photosensitive layer. Examples of the resin used for the overcoat layer include polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl methyl ether, polyvinyl pyrrolidone, polyamide, gum arabic, glue, gelatin, casein, and celluloses (for example, viscose,
Methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose,
Carboxymethylcellulose, etc.), starches (for example,
Soluble starch, modified starch, etc.).

The imagewise exposure of the colored image forming material is performed by bringing the color separation screen film and the colored image forming material corresponding to each color into close contact with each other and irradiating with ultraviolet rays. As a light source, a mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a tungsten lamp, a xenon lamp, a fluorescent lamp and the like are used.

Next, development is performed. As a developer for forming a colored image, an alkaline developer containing water as a main solvent is preferably used, and as an alkaline agent used in the developer, sodium carbonate, sodium hydrogen carbonate,
Sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate,
Inorganic alkaline agents such as dibasic potassium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, potassium carbonate, ammonium carbonate, ammonium silicate, and mono-, di- or triethanolamine and An organic alkali agent such as tetraalkylammonium hydroxide is used. The content of the alkali agent in the developer composition is preferably in the range of 0.05 to 30% by weight, and the alkaline developer is an organic solvent such as ethylene glycol monophenyl ether, benzyl alcohol, or n-propyl alcohol. ,
Surfactants, sulfites, chelating agents such as EDTA, antifoaming agents such as organic silane compounds, and the like can also be contained.

Further, as the material to be transferred for transferring the formed colored image by developing the colored image forming material after imagewise exposure, a general printing paper such as art paper, coated paper, high quality paper, synthetic paper, etc. may be used. it can.

The transfer is performed by bringing the colored image formed by the imagewise exposure and the development treatment into close contact with the material to be transferred, and performing pressure or pressure and heat treatment. Specifically, for example, the color image and the material to be transferred are brought into close contact with each other, and the color image is pressed or passed between a pair of nip rolls heated and pressed. Appropriate pressing conditions are 1.0 to 10 kg / _cm ² , heating conditions are 60 ° C. to 150 ° C., and a passage speed is suitably 20 to 160 cm / min.

 Hereinafter, the present invention will be described in more detail with reference to examples.

<Example 1> A colored photosensitive layer dispersion having the following composition was dried using a wire par on a polypropylene surface of a support obtained by laminating a 25 µm thick polypropylene film on a 50 µm thick polyethylene phthalate film by a dry lamination method. The coating was applied so that the film thickness became 1 μm, and dried to prepare four colored image forming materials.

(Colored photosensitive layer dispersion composition) (Face) Black: Carbon black MA-100 (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 (manufactured by Dainichi Seika) 0.68 g Uniform coating is obtained on the obtained colored image forming material without causing coating defects such as so-called streak-like unevenness, pinhole, yuzu skin unevenness, wavy shading unevenness, and cissing. A material having a colored photosensitive layer of the film was formed.

A color separation screen positive film of each color is superimposed on the polyethylene terephthalate film surface of the four colored image forming materials obtained as described above, and 50c is applied with a 4KW metal halide lamp.
The image was exposed for 20 seconds from a distance of m and developed by immersion in the following developer for 30 seconds to form four colored images.

(Developer) Sodium carbonate 15g Surfactant (Perox NBL manufactured by Kao Atlas) 50g Distilled water 1000g Next, the image surface of the black image and the art paper are adhered closely.
After passing between a pair of nip rolls heated to 90 ° C. at pressure conditions of 5Kg / c _m ² in 50 cm / min, it was subjected to a peeling of the support. Peeling was easy and a black image was transferred on 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 part is transferred to the art paper, that is, the non-image part is exposed,
The image quality obtained was very similar to the image quality of a normal offset print, formed with only ink on printing paper.

<Comparative Example 1> A colored image forming material was prepared in the same manner as in Example 1 except that the fluorine-containing surfactant (Exemplified Compound (2)) was omitted from the colored photosensitive layer dispersion of Example 1.

In the obtained colored image forming material, so-called wavy shading unevenness, yuzu silk unevenness, and cissing occurred, and a uniform coating film was not formed.

Thereafter, exposure, development, and image transfer processing were performed in the same manner as in Example 1 to form a color proofing image of four colors on art paper.

Even in color proofing images on art paper,
Defects such as image dropouts occurred in portions of the colored image forming material in which shading occurred in the images, and the repelled portions of the colored image forming material, and the obtained image quality was extremely unsatisfactory.

<Example 2> A 25 μm-thick polypropylene film was laminated on a 50 μm-thick polyethylene terephthalate film by a dry lamination method. A colored photosensitive layer dispersion having the following composition was dried on a polypropylene surface of a support using a wire bar. Coating and drying were performed so that the film thickness was 1 μm.

(Colored photosensitive layer dispersion liquid composition) 12 g of an alkali-soluble polymer composition having the following composition (weight-average molecular weight: 17,000, 50% methyl cellosolve solution) Pentaerythritol tetraacrylate 4.3 g Michler's ketone 0.04 g Benzophenone 0.25 g Paramethoxyphenol 0.01 g Methyl cellosolve 94 g Fluorosurfactant (Exemplified compound (4)) 0.1 g The following pigment (pigment) Black: Carbon black MA-100 (Mitsubishi) 1.98 g Cyan: Cyanine Blue 4920 (manufactured by Dainichi Seika) 1.10 g Magenta: Seika First Carmin 1483 (manufactured by Dainichi Seika) 1.36 g Yellow: Seika First Yellow H-7505 (manufactured by Dainichi Seika) 1.36 g The alkali-soluble polymer composition was synthesized by the following method.

In a four-neck flask, 8.85 g of N- (4-hydroxyphenyl) methacrylamide, 2.65 g of acrylonitrile,
33.11 g of methyl acrylate and 1.64 g of azobisisobutyronitrile (polymerization initiator) were weighed, and reacted at 77 ° C. for 6 hours using 200 g of ethyl alcohol as a solvent. Thereafter, 75 g of methyl cellosolve was added to stop the reaction.
Ethyl alcohol was distilled off for hours. As a result, about 95 g of the polymer composition was obtained as a 50% methyl cellosolve solution.

Next, on the colored photosensitive layer of each color, using a wire bar overcoat layer solution of the following composition, the dry film thickness is 0.3μm
And dried to prepare four colored image forming materials.

(Solution composition of overcoat layer) Polyvinyl alcohol (GL-05, manufactured by Nippon Synthetic Chemical Industry) 6 g Distilled water 97 g Methanol 3 g The obtained colored image forming material includes so-called streak-like unevenness, pinhole, yuzu skin unevenness, and wavy shading. No coating defects such as unevenness and cissing occurred, and a material having a colored photosensitive layer with a uniform coating film was formed.

The color separation network negative film of each color is superimposed on the overcoat layer surface of the four colored image forming materials obtained as described above, and image exposure is performed for 20 seconds from a distance of 50 cm with a 4KW metal halide lamp, and immersed in the following developer for 30 seconds. Then, development was performed to form four colored images.

(Developer) Sodium carbonate 15g Surfactant (Perox NBL manufactured by Kao Atlas) 50g Distilled water 1000g Next, the image surface of the black image and the art paper are adhered closely.
After passing between a pair of nip rolls heated to 90 ° C. at pressure conditions of 5Kg / c _m ² in 50 cm / min, it was subjected to a peeling of the support. Peeling was easy and a black image was transferred on 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 part is transferred to the art paper, that is, the non-image part is exposed,
The image quality obtained was very similar to the image quality of a normal offset print, formed with only ink on printing paper.

<Comparative Example 2> Example 2 was repeated except that the fluorinated surfactant (exemplified compound (4)) was omitted from the colored photosensitive layer dispersion of Example 2.
A colored image forming material was prepared in the same manner as described above.

In the obtained colored image forming material, so-called wavy shading unevenness, yuzu silk unevenness, and cissing occurred, and a uniform coating film was not formed.

Thereafter, exposure, development, and image transfer processing were performed in the same manner as in Example 2 to form a color proofing image of four colors on art paper.

Even in color proofing images on art paper,
Defects such as lack of images occur in the portions where the shading of the image has occurred and the repelling of the colored image forming material has occurred.
The image quality obtained was very unsatisfactory.

<Effects of the Invention> According to the present invention, there is provided a colored image forming material including a uniform colored photosensitive layer having no coating defects such as so-called streak-like unevenness, pinholes, unevenness of zigzag, wavy shading unevenness and cissing. We were able to. Further, a transfer image forming method for obtaining a transfer image extremely similar to the image quality of a printed material using the material can be provided.

 ──────────────────────────────────────────────────の Continued on the front page (72) Kunio Shimizu, Inventor Kunio 1 Sakuracho, Hino-shi, Tokyo Inside Konica Corporation (72) Inventor Toyoyoshi Urano 1000 Kamoshidacho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Within the research institute (72) Inventor Shinya Mayama 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Co., Ltd. (72) Inventor Tetsuya Masuda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Co., Ltd. In-house (56) References JP-A-2-28651 (JP, A) JP-A-2-29749 (JP, A) JP-A-2-1856 (JP, A)

Claims (2)

(57) [Claims] 1. A colored image-forming material comprising a colored photosensitive layer containing at least a photosensitive composition, a binder, and a colorant on a support rest, wherein the colored photosensitive layer is represented by the following general formula [I]. Forming a colored image by performing imagewise exposure and development processing characterized by containing a fluorine-containing surfactant, and then transferring substantially only the colored image onto a material to be transferred. Coloring image forming material. General formula [I] (Wherein, R ¹ represents an alkyl group, R ² represents an alkylene group or a fluorinated alkylene group, R ³ represents an fluorinated alkylene group, an alkyleneoxy group or a fluorinated alkyleneoxy group, and a represents 1 to 10 And b represents a number from 1 to 30. However, when a and b each represent a number of 2 or more, each R ² and each R ³ may be the same or different. At least one R ³ represents a fluorinated alkylene group or a fluorinated alkyleneoxy group.) 2. A colored image-forming material having a colored photosensitive layer containing at least a photosensitive composition, a binder, a colorant, and a fluorine-containing surfactant represented by the following general formula [I] on a support rest: Forming a colored image by performing at least imagewise exposure and development processing, and then substantially transferring only the colored image portion onto the material to be transferred. General formula [I] (Wherein, R ¹ represents an alkyl group, R ² represents an alkylene group or a fluorinated alkylene group, R ³ represents an fluorinated alkylene group, an alkyleneoxy group or a fluorinated alkyleneoxy group, and a represents 1 to 10 And b represents a number from 1 to 30. If a and b each represent a number of 2 or more,
Each R ² and each R ³ may be the same or different. At least one R ³ represents a fluorinated alkylene group or a fluorinated alkyleneoxy group. )