JPH01177027A - Image forming material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming material, and more particularly to a highly sensitive colored image forming material useful as a negative color sheet for color proofing.

[Conventional technology]

With advances in computers and lasers, image editing has become more computerized, and computer signals are sent to a laser exposure device and scanned directly onto the photosensitive printing plate by a laser beam, without creating any silver halide film. Laser plate making that performs exposure has been introduced, and plate making work is becoming more efficient.

On the other hand, in the past, when creating a printing plate that met customer requests, there were many proof printing methods in which a color image was reproduced by printing halftone film corresponding to each color, and corrections to be made to the halftone film were considered. It is being done. This method has the disadvantage that the quality is unstable due to many variable factors such as printing press settings, ink-water balance, ink amount, etc., and it takes a long time. A highly sensitive image reproduction method that can reproduce images is desired.

Up to now, the methods described in the simple colored image reproduction method (color calibration method)-97/DAO publication and JP-A-60-KOZA-GDE publication are known, but these methods are , generally had low sensitivity and was impossible to expose with a laser beam.

In addition, if a photopolymerizable material that is highly sensitive to visible light is used,
There was a problem in that the yellow sensitizing dye that absorbs visible light remained in the formed image, giving the image a yellowish tone.

The object of the present invention is to have sufficiently high sensitivity to laser exposure and change in color tone (yellowness) due to visible light sensitizing dye.
The purpose of the present invention is to provide image reproduction materials that are free from damage.

[Means for solving problems]

As a result of many years of research into high-sensitivity image-forming materials suitable for visible laser exposure, the present inventors have discovered that by using an image-forming material that has a colored recording layer that is cured by ultraviolet light and a photopolymerizable resist layer on a support, yellow The inventors have learned that it is possible to form tasteless images, and have arrived at the present invention.

That is, the gist of the present invention is to provide an image forming material having a colored recording layer and a photopolymerizable resist layer on a support,
An image-forming material in which the colored recording layer does not have strong absorption in the visible light region and contains a photosensitizer that is photocurable with ultraviolet light.The support used in the present invention can be used as an image-forming material. Either can be used. For example, films of polymers such as Eva, polyethylene terephthalate, polyacetate, polyvinyl chloride, polystyrene, polyethylene, polypropylene, metal sheets such as nickel, iron, etc. can be used.

Particularly good transparency and thermal stability, thickness O0S~S
It is preferable to use a biaxially oriented polyethylene terephthalate film of about OO μm.

These supports may be used as they are, but in order to improve the transferability of the image after image formation, they should be subjected to mold release treatment using an appropriate oil-repellent substance such as silicone resin, fluororesin, or fluorosurfactant. Alternatively, a subbing layer of alcohol-soluble polyamide, alcohol-soluble nylon, partial esterified product of styrene/maleic anhydride copolymer, polyvinyl alcohol, etc. may be provided with a thickness of about 7 μm.

The colored recording layer in the present invention usually contains colored particles and a photosensitizer that does not have strong absorption in the visible light region and is photocurable with ultraviolet light.

As the colored particles, pigments and dyes having a tone corresponding to each of the ordinary colors, yellow, magenta, cyan, and black required for color proofing are used. In particular, it is suitable to use pigments of each color used in printing ink to obtain a color image that resembles a printed matter. The following examples are some of the many pigments and dyes known in the art. (C
, 1, means color index) Victoria Pure Blue (C, 1, 4uj?&) Auramine (C, t
, Da1ooo) Cararon Brilliant Flavin (C, 1, Paging/
3) Rhodamine AGCP (C,1,lIs/bo) Rhodamine B (C,1, Dani/70) Safranin 0K70: / 00 (C,1,!02
1IO) Erioglaucine X (C, 1, +20g0)
First Black HB (C,1,,26/!;0
) rot/20/Lionor yellow (C, 1,: 110
90) Lionor Yellow GRO (C8■, 21090
) Shimla Fast Yellow gGF (C, 1, 2i
10s) Benzidine Yeo-taT-sbtaD (
C, 1,510qs) Shimla Fast Red 110
/j (C, 1, / 23!;!;) Lionor Red Ku B Guda 0 / (C, 1, / jza 30) First Genblue-TGR-L (C, 1, ?lI/Ao) Rio Nord Blue SM (C, 1, 2b/so) Mitsubishi Carbon Black MA -/ 00 Mitsubishi Carbon Black +30. Φ
qb, 5° Such pigments and dyes may be used as colored particles as they are, but they are preferably used after surface treatment with polysiloxane or the like, and they are dispersed in a photocurable photosensitive composition. Colored particles may be obtained by grinding the particles to a suitable effective particle size. The effective particle size of colored particles is 0.
2 to SOμm is strongly solidified by exposure to external light, and when the photocured resist is removed with a solvent, it must be insolubilized to the extent that it will not be dissolved or peeled off by the solvent.

As the photocurable photosensitizer that satisfies the above performance, known ones can be used. Specifically, for example, a photosensitive composition containing a diazo compound, a photo-addition polymerizable photosensitive composition, a composition containing photo-two-view photosensitive composition, and a photo-addition polymerizable photosensitive composition are preferable.

The photosensitive composition containing the diazo compound is a polymeric diazonium salt having a plurality of diazonium groups in the molecule (for example, a condensate of a substituted or unsubstituted diphenylamine-derdiazonium salt and formalin or acetaldehyde).
Diazo compounds such as halogenated Lewis salts or organic acid salts of (meth)acrylic acid, methyl (meth)acrylate,
Contains an alkaline aqueous solution or a water-soluble polymer (conjugate) obtained by appropriately (co)polymerizing monomers such as ethyl (meth)acrylate, acrylonitrile, and hydroxyphenyl (meth)acrylamide. The amount of the diazo compound in the photosensitive composition is preferably 5 to 70% by weight, particularly preferably 70 to 60% by weight, and the amount of the high molecular weight polymer is preferably 10 to 90% by weight, particularly 0% by weight of 4O-ff. A range can be preferably used.

In addition, the photoaddition polymerizable photosensitive composition includes (1) a compound having a boiling point of 70θ°C or higher under normal pressure and containing one or more polymerizable terminal ethylene groups; (2) a compound that is activated by ultraviolet light and has a visible light range; It is preferable to use a photopolymerization initiator that does not have strong absorption and a high molecular weight polymer (binder).It has a boiling point of 100℃ or more under normal pressure and contains two or more polymerizable terminal ethylene groups. Examples of the compound include those described in JP-A-59-10'1g, specifically, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane. Examples include tri(meth)acrylate, pentaerythritol triacrylate, hydroquinone di(meth)acrylate, Viloga C1-#)reacrylate, 2,2'-bis(4'-7 chlorodiethoxyphenyl)propane, and the like. Other examples include (meth)acrylamides such as ethylenebis(meth)acrylamide and hexamethylenebis(meth)acrylamide, vinyl urethane compounds, and epoxy(meth)acrylate.

As the photopolymerization initiator that is activated by ultraviolet light and does not have strong absorption in the visible light region, conventionally known ones can be used, such as benzoin, benzoin alkyl ether, benzophenone, anthraquinone, benzyl, Michler's ketone, biimidazole and Michler's ketone. Any of the composite systems with and the like can be suitably used.

As the polymer, known alkali-soluble and
A water-soluble high molecular weight polymer can be used. Such polymers include, for example, α, β-unsaturated carboxylic acids or esters thereof such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate; acrylonitrile, acetic acid; Examples include (co)polymers of monomers selected from unsaturated (anhydrous) carboxylic acids such as vinyl, maleic anhydride, maleic acid, maleic acid half esters, and itaconic acid; and styrenes such as styrene. Specifically, for example, methyl methacrylate/methacrylic acid/acrylonitrile/ethyl acrylate copolymer (7
Eight pieces/6. Z// 2// o mol%, weight average molecular weight MW, ? X104), methyl methacrylate/acrylic acid/ethyl acrylate copolymer (7゜770720 mol%
, Mw Q X / 0'), and the like.

The photopolymerizable photosensitive composition contains a compound having a boiling point of 100° C. or higher under normal pressure and containing one or more polymerizable terminal ethylene groups, /Q to 90% by weight, particularly 73 to go% by weight, and UV light. The photoinitiator activated by 0. /~7
It is preferable that o weight %, particularly o, st, o weight %, and the high molecular weight polymer are selected from the range of 10% to 90 weight %, especially 15-80 weight %, respectively.

The thickness of the colored recording layer is 0. /~-θθμm is preferable,
In particular, it is formed to a thickness of 0.3 to 100 μm and photocured with actinic rays, and during development, the unexposed resist layer and colored recording layer are removed by dissolving and/or swelling, and the photocured resist layer and colored recording layer are removed. In order to form a colored image consisting of a recording layer, and then perform a resist peeling process, only the resist layer photocured with a solvent is required to be removed in order to form a colored image consisting of a colored recording layer. .

A photopolymerizable resist layer that satisfies the above performance is: ■ A compound containing one or more terminal ethylene groups that can be polymerized at a boiling point of /00°C or higher under normal pressure; ■ A photopolymerization initiator that is activated by actinic light. and ■ Contains a high molecular weight polymer (binder).

The compound having a boiling point of 100° C. or higher under normal pressure and containing one or more polymerizable terminal ethylene groups is one of the compounds containing a polymerizable terminal ethylene group used in the photopolymerizable photosensitive composition of the colored recording layer mentioned above. They can be appropriately selected and used.

Photopolymerization initiators activated by actinic rays include:
Conventionally known ones can be used, and for example, benzine, benzoin alkyl ether, benzophenone, anthraquinone, benzyl, Michler's ketone, a complex system of biimidazole and Michler's ketone, etc. can all be suitably used. In particular, a composite system of argon ion laser (rolomethyl) -/, J, &-triazine and a cyanine dye derivative is suitable.

The polymer can be appropriately selected from among the polymers used in the photopolymerizable photosensitive composition of the colored recording layer mentioned above, and specifically, methyl methacrylate/methacrylic acid/acrylic Acid methyl copolymer (Q 7 / /
3/'I 0 mol%, Mw -3X/04
), methyl methacrylate/acrylonitrile/acrylic acid/methyl acrylate copolymer=, (4(!;// 0
//! ;/J 0 mol%, Mwjt X /iρ4)
etc. can be mentioned.

The proportion of each of the above-mentioned components constituting the photopolymerizable resist layer of the present invention is usually 10% for a compound having a boiling point of 100°C or higher under normal pressure and containing one or more polymerizable terminal ethylene groups.
~90% by weight, in particular is-go% by weight, photopolymerization initiators activated by actinic radiation 0.1-70% by weight,
In particular, O, S ~ 60% by weight, and the high molecular weight polymer is 10-
Preferably, each is selected from the range of 90% by weight, particularly from 73% to go.

The thickness of the photopolymerizable resist layer is preferably θ,/~SOO μm, and particularly preferably 003 to 1008 m.

An organic acid or acid anhydride may be added to the colored recording layer and photopolymerizable resist layer for the purpose of improving developability,
Lipophilic plasticizers may also be added. Furthermore, a thermal polymerization inhibitor may be added to the photopolymerizable resist layer.

The organic acid usually contains about 100 mol% of a monomer unit having a carboxylic acid, and 100 m/l of water is used.
9 or more dissolved, molecular weight /, 000 ~ / 00.00
0, preferably! , 000~. ．． 70.000, for example, polymeric organic acids such as acrylic acid polymers and copolymers thereof, methacrylic acid polymers and copolymers thereof, and carboxylic acid-modified novolac resins. Among these, acrylic acid polymers are particularly preferred. Organic acids such as Schereric acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, phthalic acid, benzoic acid, gallic acid, and tartaric acid can also be used.

Examples of the acid anhydride include glutaric anhydride, phthalic anhydride, and tetrahydrophthalic anhydride.

The organic acid or acid anhydride is preferably added in an amount of O, S to -0% by weight, particularly preferably about 70% by weight in each layer.

The lipophilic plasticizers include phthalic acids such as dibutyl phthalate, di-n-octyl phthalate, di(coethylhexyl) phthalate, dinonyl phthalate, dilauryl phthalate, butyl lauryl phthalate, and butyl benzyl phthalate. Diester; di(-monoethylhexyl)adipate,
Aliphatic dibasic acid esters such as di(2-ethylhexyl) sebacate; tricresyl phosphate, tri-1.2-phosphate
and glycol esters such as polyethyl glycol ester. Particularly preferred are phthalic acid diesters.

A suitable content of SO in each layer is 5 to 5% by weight, particularly 7 to 1.10% by weight.

As thermal polymerization inhibitors, alkylated phenols such as di-6-ditertiary-butyl-gu-methylphenol, alkylated bisphenols such as co-, co-methylene-bis-(
p-mef-6-tert-butylphenol), /, j,
&-) Limethylruko, q, t, -) Lis-(3,5-ditert-butyl-ghydroxybenzyl)benzene, Co(tI-hydroxy-3,S-ditertiary-butylanilino), 6- Pisu (n-octylthio) −/, J
.

can be lost. Its content is 0. It is preferable to select from the range of /-10% by weight.

When a polymerizable resist layer is provided on the color development layer in the image forming material of the present invention, a transparent cover sheet is usually provided thereon. As such a transparent cover sheet, for example, a plastic sheet having low oxygen permeability such as polyvinyl alcohol, polypropylene, polyacetate, polyvinyl chloride, polystyrene, polyethylene terephthalate, etc. can be used, but is not limited thereto.

The thickness of the transparent cover sheet is 0. /~/, 000μm
is preferable, and particularly preferably o, s-gooμm.

Further, the image forming material of the present invention may have a distance between the support and the colored recording layer of 0.7 to 508 m, preferably O
, S to about 30 μm may be provided.

As such a release layer, a heat-fusible release layer or a photopolymerizable release layer whose adhesion to the support is reduced by photocuring upon exposure to light is used.

The heat-fusible release layer is transparent and non-adhesive at room temperature, but is preferably one that can be heat-fusible in a temperature range of goC to /40C.

This includes: 70°C to iq as listed below.

A film-forming thermoplastic resin having a softening point of °C is used. For example, olefin (co)polymers, vinyl chloride (
co)polymer, vinylidene chloride (co)polymer, vinyl acetate (co)polymer, (meth)acrylic ester (co)polymer, styrene/(meth)acrylic ester copolymer,
Polyester, vinyl butyral resin, chlorinated rubber, cellulose derivative, preferably styrene/(meth)acrylate copolymer, polyester, novolak resin, etc., these may be used alone or in combination, and furthermore, other resins may be used. After being laminated onto a type or transferable surface, the release layer is cured by exposure to light and has the property of reducing the adhesion between the support of the image forming material and the photopolymerizable release layer, making it easier to peel off the support. Needed.

The photopolymerizable mold release layer satisfying the above properties includes, for example, 70 to 90% by weight of a compound containing a terminal ethylene group such as trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, diethylene glycol di(meth)acrylate, 0.1 to 70% by weight of a known photopolymerization initiator such as benzoin, benzoin alkyl ether, benzophenone, Michler's ketone, and (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, styrene, maleic anhydride. (Co)polymer of selected monomers such as acids and maleic acid half esters 1
Photopolymerizable compositions containing from 0 to 90% by weight are used.

The image-forming material of the present invention may be applied to a colored recording layer or a transfer object as required. An adhesive layer having a thickness of /~50 μm, preferably about 0.3~30 μm may be provided.

As such an adhesive layer, a heat-fusible adhesive layer or a photopolymerizable adhesive layer that is photocured by exposure to increase the adhesiveness between the photosensitive image forming material and the transfer target is used.

For the heat-fusible adhesive layer, an appropriate thermoplastic resin can be selected from among the thermoplastic resins used for the heat-fusible release layer.

Further, for the photopolymerizable adhesive layer, an appropriate photopolymerizable composition can be selected from among the photopolymerizable compositions used for the photopolymerizable release layer.

A method of forming an image using the above image forming material will be explained.

The image forming material of the present invention has, depending on its layer structure, for example:
■ An image forming material in which a colored recording layer, a photopolymerizable resist layer, and a transparent cover sheet are provided in this order on a support;
There is one type of image forming material in which a photopolymerizable resist layer and a colored recording layer are provided in this order on a support, and the image forming methods are different for each.

First, the image forming method using the image forming material (2) will be explained.

First, the photosensitive image forming material is imagewise exposed from the side of the transparent cover sheet. Applicable exposure light sources include carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, krypton laser, etc., including ultraviolet rays of / g Onm or more, and visible light. Examples include general-purpose light sources.

Next, after peeling off the transparent cover sheet as necessary,
The unexposed areas of the photopolymerizable resist layer and the colored recording layer are developed and dissolved and removed.

As such a developer, a known organic solvent, an alkaline aqueous solution, or an alkaline aqueous solution containing a small amount of organic solvent can be used. Aqueous solutions are preferred.

The alkaline agents used in the developer include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tertiary sodium phosphate, and tertiary sodium phosphate.
Inorganic alkaline agents such as sodium phosphate, sodium bicarbonate, and trimethylamine, diethylamine, monoisopropylamine, n-butylamine, monoethano can be used alone or in combination. As the organic solvent, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, diacetone alcohol, etc. can be included as necessary, and it is particularly preferable to select one from those that are miscible with water.

Furthermore, the developer may contain a surfactant.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acids; Anionic surfactants such as Class W, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids can be used; %! It is appropriate to contain it within a range of % by weight.

Next, the entire surface of the developed sample is exposed to ultraviolet light from the transparent support or the colored recording layer side to harden the colored recording layer. The photocured photopolymerizable resist layer is removed by dissolving and/or peeling. As for the solvent used in this case, the photocured resist layer is removed by dissolving and/or peeling off, but the photocured colored recording layer is not dissolved and/or peeled off.

As the solvent, it is preferable to use an organic solvent, an alkaline aqueous alkaline solution, or an alkaline aqueous solution containing a small amount of an organic solvent.

The alkaline agent, organic solvent, and surfactant used in the solvent may be selected from those used in the above-mentioned developer, and may be appropriately selected.1 Usually, under stronger alkaline conditions and/or conditions than the developer. Alternatively, a solvent containing an increased amount of organic solvent is used.

A colored image consisting of the colored recording layer is formed in this way, and then the colored image is transferred to the transfer target at a temperature of usually 25 to 200°C.
~200 kg/cnT2, o, os ~h.

After pressing with a rubber roller or the like at rrL/min, the support is peeled off and a desired image can be formed by transferring the colored image to the transfer target.

As the material to be transferred, paper such as high quality paper, art paper, coated paper, etc.; plastic film such as polyester, acetate, polypropylene, etc.; metal glue such as aluminum, copper, etc., or composite materials thereof are used.

The object to be transferred may be provided with a heat-fusible receptor layer or a photopolymerizable receptor layer. Examples of materials used for these receptor layers include those described above in connection with the heat-fusible release layer and the photopolymerizable release layer.

The film thickness of these receptor layers is 0. /~SOμm is preferable, and more preferably selected from the range of 083 to 30μm.

Next, the image forming method using the image forming material (2) will be explained.

First, a photosensitive image forming material is applied to the above-mentioned transfer target, usually from -5 to
-00℃, / ~200 kg/cm2, o, o
Press with a rubber roller or the like at s-'s o m/min.

Next, image exposure is performed from the side of the transparent support or the transparent transfer object.

After peeling off the support, the unexposed areas of the photopolymerizable resist layer and the colored recording layer are developed and removed using the above developing solvent.

First, the resulting sample was exposed to ultraviolet light from the photopolymerizable resist layer side to cure the colored recording layer, and then only the photocured resist layer was dissolved. And/or the photohard resist layer is removed using the above-mentioned peeling solvent, and a colored image consisting of a colored recording layer is formed on the transfer target.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. In addition,
Hereinafter, Mw indicates the weight average molecular weight, and parts indicate parts by weight.

Synthesis example/(Synthesis of photopolymerizable copolymer) Styrene/maleic anhydride copolymer (Sankyo Kaseisha Riva, Styrite CM-, 2L, Mw about sooo) g, ogg,
4.32 g of pentaerythritol triacrylate and hydroquinone θ■ were dissolved in dioxane soy, and 1
After heating and stirring at 00° C. for several hours, the mixture was dropped into a large amount of water to precipitate, and then dried under vacuum to synthesize a carboxylic acid half ester polymer.

Synthesis Example 2 (Synthesis of diazo resin) p-diazodiphenylamine sulfate/11. 9 (s)
1) mol) was dissolved in 110.99 mol of concentrated sulfuric acid under water cooling. In this reaction solution/! rg (!; 0 mmol) of rose formaldehyde was slowly added dropwise. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, water cooling was continued for 2 hours.

This reaction mixture was added dropwise to soo rat ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100 ml of pure water, and a cold concentrated aqueous solution containing 6.3 g of zinc chloride was added to this solution. The resulting precipitate was filtered, washed with ethanol, and dissolved in 30 rnl of pure water. A cold concentrated aqueous solution of gI ammonium hexafluorophosphate was added to this liquid. The resulting precipitate was collected by filtration, washed with water, and then heated at 30°C.
A diazo resin was obtained by drying day and night.

Example 1 An n-butyl acrylate/ethyl acrylate copolymer (/, o/y.

Using a coating rod, a methyl selonlupe solution with a molar ratio of MWlolooo) was applied to a dry film thickness of 6 μm, a heat-fusible release layer was provided, and colored recording layer dispersions of each of q colors having the following composition were applied. (S) was adjusted and applied so that the dry film thickness was 1 μm.

Next, a polyvinyl alcohol solution was applied onto a polypropylene film having a thickness of SO μm so that the dry film thickness was approximately 1 μm, and then the following photopolymerizable resist layer coating solution was applied so that the dry film thickness was approximately 1 μm. , a photopolymerizable resist layer is provided, and then the polypropylene film and the polyethylene terephthalate film are heated at 20 kg/crr at room temperature so that the photopolymerizable resist layer and the colored recording layer are in close contact with each other.
The material was laminated with L2 to obtain nine colors of photosensitive colored image forming materials.

On the cover sheet layer (polypropylene film) of the green colored image forming material obtained above, each color of the color separation mesh negative film was overlaid at an accurate position using register pins, and further sensitivity measurement and resolution evaluation were performed. Control wedge (UGRA PCW, continuous tone wedge...density difference of 0. /, !r, 73 levels of gray scale, micro line...q to 70μ line circular batch) is placed in close contact with the control wedge. , 2kW high pressure mercury lamp Jet
.

Light, 2000 (oak production tear), from a distance of 502, image exposure (solid three-step exposure) where three steps of the continuous tone wedge remain as a photosensitive image after development, and after peeling off the polypropylene film, development for negative PS plate Liquid 5DN-1
/ (manufactured by Konishiroku Photo Industry ■) using a 20-fold diluted solution,
By performing rubbing development at 3° C. for 1 minute, image-forming colored materials of 9 colors that faithfully reproduced the color separation mask were obtained. However, these image forming materials still had a yellowish tinge due to the visible sensitizing agent due to the presence of a photocured photopolymerizable layer on the colored recording layer.

In order to dissolve and remove this photocured photopolymerizable resist layer, the dark color image-forming coloring material was exposed to g 00 mJ from the polyethylene terephthalate side with a high pressure mercury lamp, and then exposed to a diluted solution of 5DN-J/2. Rub development was carried out at 25 DEG C. for a period of time to obtain an image-forming colored material of -q color with no yellowish tinge.

Next, the obtained yellow color image is accurately brought into close contact with the coated paper of the image receiving sheet using a register bin, and passed between 7 pairs of nip rolls heated at 100°C to transfer the color image to the coated paper. The polyethylene terephthalate film on the side was peeled off. Subsequently, color images were simultaneously transferred in the order of magenta, cyan, and black to obtain a multicolor color proofing sheet on coated paper.

Table 7 shows the evaluation results of the sensitivity (exposure amount at which the three steps of the continuous tone image are completely removed by development) for each color.

Table 1 Examples The following photopolymerizable release layer coating solution (0
) was applied to a dry film thickness of 7 μm to provide a photopolymerizable release layer.

Furthermore, the following colored recording layer dispersion (T) was coated to give a dry film thickness of micrometers to form a colored recording layer.

Next, a polyvinyl alcohol solution was applied onto a polypropylene film with a thickness of 503 m to a dry film thickness of 2 μm, and then the photopolymerizable resist coating solution (A) was applied to a dry film thickness of 1 μm. Then, a photopolymerizable resist layer was provided, and the polypropylene film and the above-mentioned polyethylene terephthalate film were heated at -20 kl at room temperature so that the photopolymerizable resist layer and the colored recording layer were in close contact with each other.
/cIrL'' to obtain a photosensitive colored image-forming material of .

A color separation negative film was placed on the cover sheet (adjusted to polypropylene film) of the photosensitive colored image forming material of 9 colors obtained above, and after exposure and development in the same manner as in Example, the polypropylene film side was Exposure was carried out with a high-pressure mercury lamp at /o OmJ, and then rubbing development was carried out at 2S°C for 2 minutes using a 5DN-J/2 times diluted solution to obtain image-forming colored materials in seven colors without yellowing.

Next, the obtained yellow color image is accurately brought into contact with the coated paper of the image receiving sheet using register pins, and the color image is transferred to the coated paper by passing between a pair of nip rolls heated to 100°C, and the color image is transferred to the coated paper. After exposure to g 00 mJ using a mercury lamp, the polyethylene terephthalate film on the image side was peeled off. Subsequently, color images were simultaneously transferred in the order of magenta, cyan, and black to obtain a multicolor proofing sheet on coated paper.

Example 3 On a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm, the following colored recording layer coating liquid (U) was applied to a dry film thickness of 2 μm to provide a colored recording layer.

Next, a polyvinyl alcohol solution was applied to a polypropylene film with a thickness of 503 m to a dry film thickness of 1 μm, and then a photopolymerizable resist coating solution (A) was applied to a dry film thickness of 1 μm. , a photopolymerizable resist layer was provided, and the polypropylene film and the above polyethylene terephthalate film were heated at 20 kg/crrL at room temperature so that the photopolymerizable resist layer and the colored recording layer were in close contact with each other.
2 to obtain nine colors of photosensitive colored image forming materials.

The photosensitive colored image forming material was subjected to exposure, development, post-exposure, and resist peeling treatment in the same manner as in Example/9.
A multicolored color proofing sheet was obtained by sequentially transferring the colored images onto coated paper.

Example The above photopolymerizable resist layer coating solution (
A) was applied using coach-in-blonde so that the dry film thickness was 1 μm.

Next, the colored recording layer dispersions (S) of the nine colors were applied onto a polypropylene film with a thickness of 30 μm to a dry film thickness of 1 μm.
It was applied so that

Next, the polypropylene film and the above-mentioned polyethylene terephthalate sheet were coated with 9/c7IE2 at 20°C at room temperature so that the photopolymerizable resist layer and the colored recording layer were in close contact with each other.
The resulting material was laminated with 9 colors of photosensitive colored image forming materials.

Among the nine color photosensitive color forming materials obtained above,
After peeling off the polypropylene film, the magenta color image was obtained using n-butyl acrylate/ethyl acrylate copolymer (t, o/ta).

io so that the methyl seronlupe layer with a molar ratio of Mw//0.000 and the heat-fusible adhesive layer are in close contact with each other.

℃, laminated at 20' to 9/crrt'', then
A color separation mesh negative film was superimposed on the polyethylene terephthalate film at an accurate position using a resistor bin, and a Chondrol wedge (UGRA PCW g 2 ) for sensitivity measurement and resolution evaluation was closely attached to the film, and a KW high-pressure mercury lamp Jet, Lightaoooo (new oak production)! From a distance of OCm, perform image exposure (3-stage solid exposure) in which 3 stages of continuous tone after development remain as a photosensitive image, and peel off the polyethylene terephthalate film. Using a diluted solution of Roku Konishi Photo Industry ■) at 1.2S℃, -
A colored image faithfully reproducing the color separation mask was formed by rubbing development for 1 minute. However, these formed images were still tinged with yellow due to the presence of the photocured photopolymerizable layer on the colored recording layer due to the visible sensitizing agent.

In order to dissolve and remove this photocured photopolymerizable resist layer, the formed image was exposed to 7000 mJ of light using a high pressure mercury lamp, and then 2
A non-yellow image was formed on the coated paper by rubbing development at 5°C for -minutes.

Next, yellow, cyan, and black photosensitive coloring materials were similarly coated on coated paper with the magenta image (
The repeated images were laminated to obtain a multicolor proofing sheet on coated paper. Sensitivity evaluation results are shown in s%.

No. 2 coating [Example S] Example q was completed except that the heat-fusible adhesive layer was changed to a photopolymerizable adhesive layer with the following composition (in the same way, a multicolor proofing sheet was placed on coated paper). Obtained.

Example 6 The above-mentioned photopolymerizable resist layer coating solution (I) was applied onto a coaxially stretched polyethylene terephthalate film having a thickness of 700 μm so that the dry film thickness was 1 μm.

Next, n-butyl acrylate/ethyl acrylate copolymer (6θ
/lIθ molar ratio, Mw/2000) was applied to a dry film thickness of 6 μm to form a heat-fusible adhesive layer, and a colored recording layer dispersion of seven colors having the following composition (v
) was applied so that the dry film thickness was 1 μm.

Next, the polypropylene film and the above-mentioned polyethylene terephthalate sheet were heated at room temperature at 20 kl so that the photopolymerizable resist layer and the colored recording layer were in close contact with each other. /crn
2 to obtain a dark photosensitive colored image forming material.

After peeling off the polypropylene film, the magenta color image was laminated onto coated paper at 100°C and 20 kg/cIIL2 so that the heat-fusible adhesive layer and the coated paper were in close contact with each other, and then the image was formed in the same manner as in Example D. Exposure and development were performed to form a colored image that faithfully reproduced the color separation mask.

Furthermore, in order to dissolve and remove this photocured photopolymerizable resist layer, the formed image was exposed to 7000 mJ of light using a high-pressure mercury lamp, and then 1.2&'C1- A non-yellowing image was formed on the coated paper by rubbing development for 1 minute.

Next, images of the yellow, cyan, and black photosensitive coloring materials were similarly laminated repeatedly on the coated paper on which the magenta image had been provided, to obtain a multicolor proof-in sheet on the coated paper.

〔Effect of the invention〕

As described above, according to the present invention, a colored image forming material is provided which has high sensitivity and does not have a yellowish tint caused by a visible sensitizer.

Therefore, the present invention is industrially useful.

Claims (5)

[Claims] (1) In an image forming material having a colored recording layer and a photopolymerizable resist layer on a support, the colored recording layer contains a photosensitizer that does not have strong absorption in the visible light region and is photocurable with ultraviolet light. An image forming material characterized by: (2) The image forming material according to claim 1, wherein a colored recording layer, a photopolymerizable resist layer, and a transparent cover sheet are provided in this order on a support. (3) The image forming material according to claim 2, further comprising a release layer between the support and the colored recording layer. (4) The image forming material according to claim 1, wherein a photopolymerizable resist layer and a colored recording layer are provided in this order on a support. (5) The image forming material according to claim 4, which has an adhesive layer on the colored recording layer.