JPH05281747A - Photosensitive transfer sheet - Google Patents

Abstract

PURPOSE:To obtain a photosensitive transfer sheet which produces no yellow color in nonpicture area of transferred images by specifying the photopolymn. initiator. CONSTITUTION:This photosensitive transfer sheet has a peeling layer comprising org. polymers and a photopolymerizable photosensitive resin layer containing a photopolymn. initiator formed in this order on a supporting body. The photopolymn. initiator contains at least one kind of photosensitive 8-triazine compd. expressed by formula. In formula, T is 4,6-bis(trihalomethyl)-8-triazine-2- yl group, R<1> and R<2> are same or different hydrogen atoms, alkyl groups, substd. alkyl groups, aryl groups, or substd. aryl groups, and further, R<1> and R<2> may form a heteroring with nitrogen atoms connecting with these, and R<3> and R<4> are same or different hydrogen atoms, halogen atoms, alkyl groups or alkoxy groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepress proof for color proofing, a photosensitive transfer sheet used for a display and the like.

[0002]

2. Description of the Related Art Conventionally, overlay methods and surprint methods have been used as color proofing methods (prepress proof) using photopolymers. The overlay method prepares a plurality of color proofing sheets with separated images of each color on a transparent support and stacks these sheets (the obtained one is called a color test sheet) for color proofing. Is the way to do it. According to this method, it is possible to obtain a multicolor image by superposing color proofing sheets of two to four colors each time, and therefore, it is convenient and can be used for continuous inspection. The surprint method is a method in which a separated image of each color is sequentially formed on a single support to obtain a multicolor image. According to this method, the color density is not affected by the support as in the overlay method, and the color distortion that occurs when the color proofing sheets are superposed can be avoided, and thus, it is more similar to the original printing method. It is a thing.

As an image forming material that can be used in both the overlay method and the surprint method, a release layer made of an organic polymer and a photosensitive resin layer are provided on a support (hereinafter also referred to as a temporary support). A photosensitive transfer sheet provided in order is known. For a color proofing sheet having a multicolor image for color proofing, the photosensitive transfer sheet is exposed and developed to form a decomposed image, and then the operation of transferring the decomposed image onto an arbitrary support is repeated. Is obtained by For example, as described in JP-B-49-441, a photosensitive transfer sheet is exposed through a color separation film and developed to form a decomposed image on the release layer, and then the transfer sheet is transferred to another support. A transfer image can be formed on the support together with the release layer by pressing the adhesive with an adhesive and then peeling off the temporary support.
In this case, an adhesive must be applied to the transfer sheet or the support for each transfer, which complicates the color proofing process and reduces the accuracy of alignment during transfer. Was.

Methods for simplifying the color proofing process are described in, for example, Japanese Patent Application Laid-Open Nos. 47-41380, 48-93337, 51-5101 and the like. In particular, JP-A-51-5101 describes a method of providing a heat-fusible polymer layer as an adhesive on a permanent support, and JP-A-47-41.
Japanese Patent Publication No. 380 also describes a method of directly transferring an image to a permanent support such as art paper or coated paper. However, these methods have the following drawbacks. One is that the final image is left-right reversed with respect to the original, and one of the many is that when a heat-meltable polymer is used, the melting point is high and the transfer temperature is high, so the support is heated by heat. The dimensional stability becomes poor, and the misregistration of the transfer position of each color occurs. Further, when a polymer having a low melting point is used, there are drawbacks such that the image forming portion is likely to be adhered and is easily scratched. JP-A-59-971
No. 40 discloses, as a method for improving the above-mentioned drawbacks, before transferring an image of each color onto a permanent support, once transferring the image of each color onto a sheet provided with a photopolymerizable image receiving layer,
Then, a method is disclosed in which the photopolymerizable image-receiving layer is re-transferred onto a permanent support and then the whole surface is exposed to harden the photopolymerizable image-receiving layer.

According to this method, a normal image can be formed on the mask original, and since the photopolymerizable image receiving layer itself is soft because it contains an ethylenic polyfunctional monomer, it is possible to transfer at a low temperature during transfer. However, since the photopolymerizable image-receiving layer is hardened by exposure afterwards, it has good adhesion resistance and is resistant to scratches, and the above-mentioned drawbacks are almost eliminated.

In a photosensitive transfer sheet having a support, a release layer made of an organic polymer, and a photopolymerization type photosensitive resin layer in this order, as a photopolymerization initiator used for the photopolymerization type photosensitive resin layer, It is well known in the field of photosensitive recording materials to use compounds (free-radical generators) that decompose to form free radicals when exposed to water. A halomethyl-s-triazine compound has been proposed as such a photopolymerization initiator. For example, U.S. Pat. No. 3,954,47
No. 5, and No. 3,987,037,
A compound in which an aromatic nucleus or a heterocyclic nucleus is bonded to a halomethyl-s-triazine ring via a carbon-carbon unsaturated bond group is disclosed, and in the specification of US Pat. A compound in which a ring or polycyclic aromatic nucleus or a heterocyclic aromatic ring is bonded to a halomethyl-s-triazine ring is disclosed, and JP-A-62-58241 discloses a carbon-
Disclosed are compounds in which an aromatic nucleus is bound to a halomethyl-s-triazine ring which is bound to the aromatic nucleus via a carbon triple bond.

However, when these compounds are used in the photopolymerization type photosensitive resin layer of the above-mentioned photosensitive transfer sheet, they are exposed and developed to form an image on the photosensitive transfer sheet, and then they are permanently formed. Before transferring the image onto the support, once transfer the image of each color onto the sheet provided with the photopolymerizable image receiving layer together with the release layer, and then retransfer onto the permanent support, and then the entire surface. When the operation of hardening the photopolymerizable image-receiving layer by exposure is carried out, there is a problem that a light yellow coloring is likely to occur in the non-image area where the image is transferred.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to form an image on a photosensitive transfer sheet by exposing and developing, and once form an image of each color on a sheet provided with a photopolymerizable image receiving layer. When transfer is carried out together with a release layer, then retransferred onto a permanent support, and then the whole surface is exposed to harden the photopolymerizable image-receiving layer, yellow coloring may occur in the non-image area where the image is transferred. To provide a photosensitive transfer sheet that does not have.

[0009]

SUMMARY OF THE INVENTION The present invention comprises:
In a photosensitive transfer sheet having a release layer made of an organic polymer and a photopolymerization type photosensitive resin layer containing a photopolymerization initiator in this order, the photopolymerization initiator is represented by the following general formula (1):

[0010]

[Chemical 2]

[In the formula, T represents a 4,6-bis (trihalomethyl) -s-triazin-2-yl group, R ¹ and R ² may be the same or different from each other, and a hydrogen atom,
It represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R ¹ and R ² together with the nitrogen atom to which they are attached may form a heterocycle, and R ³ and R ⁴ are the same as each other. May be different, hydrogen atom,
Represents a halogen atom, an alkyl group or an alkoxy group]
It is a photoinitiator containing at least 1 type of the photosensitive s-triazine compound represented by these, It is a photosensitive transfer sheet characterized by the above-mentioned.

The photosensitive transfer sheet of the present invention has a structure in which a release layer and a photopolymerizable photosensitive resin layer are provided in this order on a support.

As the material of the support, a substance which is chemically and thermally stable and has flexibility is used.
If necessary, it may be actinic radiation transparent. Specifically, for example, cellulose acetate, polyvinyl chloride,
Such as polystyrene, polypropylene, etc.
Various substances described in JP-A 7-41830, JP-A-48-9337 and JP-A-51-5101 can be used. Polyethylene terephthalate, polycarbonate and heat-treated products thereof are particularly preferable.

The surface of the support opposite to the side where the release layer is provided is made of a polymer material such as polyvinyl butyral, vinyl chloride / vinyl acetate copolymer or cellulose acetate for the purpose of improving processability. A back layer may be provided. Further, the back layer may contain various additives such as a matting agent.

A release layer made of an organic polymer is provided on the support. As the organic polymer material used for the release layer, known materials already used as the material for the release layer of the photosensitive transfer sheet can be appropriately selected and used. Examples of such a material include alcohol-soluble polyamide, hydroxystyrene-based polymer, polyvinyl acetate,
Poly (meth) acrylate, polyvinyl chloride, polyvinyl butyrate, methylmethacrylate / acrylate copolymer, polyethylene / (meth) acrylic acid copolymer, polyethylene / (meth) acrylic acid copolymer crosslinked metal, Cellulose acetate butyrate, vinyl chloride / vinyl acetate copolymer, cellulose diacetate, cellulose triacetate, polyvinyl alcohol, a blend of partially esterified resin of styrene / maleic anhydride copolymer and methoxymethylated nylon, etc. be able to. Particularly preferable as the above-mentioned organic polymer is a mixture of an alcohol-soluble polyamide and a hydroxystyrene-based polymer. In this case, the ratio of the alcohol-soluble polyamide to the hydroxystyrene polymer is 4: from the viewpoint of the releasability of the release layer from the support under high humidity and the adhesiveness to the support on the image receiving side during transfer and the like. It is preferably in the range of 6 to 9: 1 (mixing ratio by weight).

The release layer can be formed by dissolving the above organic polymer in a suitable solvent to prepare a coating solution, and then coating the coating solution on a support and drying. Various kinds of surfactants can be added to the coating solution as a surface condition improver, and fluorine-based surfactants are particularly effective. The layer thickness of the release layer is generally in the range of 0.1 to 20 μm, preferably in the range of 0.2 to 5 μm, and particularly preferably in the range of 0.3 to 3 μm.

As the material for the photopolymerizable photosensitive resin layer provided on the release layer, various materials used in known photosensitive transfer sheets can be used, but the photopolymerizable system of water or alkali developing type can be used. Photosensitive resins are preferred.

The photopolymerizable photosensitive resin layer usually has a boiling point of 150 ° C. or higher under normal pressure and has at least one monomer compound having a group capable of forming a photopolymer by addition polymerization, an organic polymer bond. Agent, and a photopolymerization initiator activated by actinic rays, and optionally a thermal polymerization inhibitor. The photopolymerizable photosensitive resin layer of the present invention is particularly characterized by the photopolymerization initiator contained therein.

Examples of the monomer compound that can be used for forming the photopolymerizable photosensitive resin layer include vinyl monomers and vinylidene monomers. For example, unsaturated esters of polyols, particularly esters of acrylic acid or methacrylic acid are preferable. Specific examples thereof include ethylene glycol diacrylate, glycerin triacrylate,
Polyacrylate, ethylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, polyethylene glycol dimethacrylate, 1,2,4-butanetriol trimethacrylate, trimethylolethane triacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate , Pentaerythritol tetramethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol-polyacrylate, 1,3-propanediol-diacrylate, 1,5-pentanediol- Dimethacrylate, bisacrylate of polyethylene glycol having a molecular weight in the range of 200-400, bismethacrylate It can be mentioned fine analogous compounds.

Unsaturated amides may be used as the above-mentioned monomer compound, and examples thereof include unsaturated amides of acrylic acid and methacrylic acid having α, ω-diamine and ethylenebismethacrylamide. The alkylene chain of the unsaturated amide may be opened by carbon atoms.

The above monomer compounds may be used alone or as a mixture of two or more kinds. However, the photopolymerizable monomer is not limited to these compounds.

Examples of the above organic polymer binder include addition polymers having a carboxylic acid in the side chain, for example, methacrylic acid copolymers (for example, copolymers of methyl methacrylate and methacrylic acid, ethyl methacrylate and methacrylic acid). A copolymer with an acid, a copolymer of butyl methacrylate and methacrylic acid, a copolymer of allyl methacrylate and methacrylic acid,
Copolymers of ethyl acrylate and methacrylic acid, copolymers of ethyl methacrylate and styrene and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, etc., acrylic acid copolymers (ethyl acrylate and acrylic) Acid copolymers, butyl acrylate and acrylic acid copolymers, ethyl acrylate and styrene and acrylic acid copolymers, etc.), and further itaconic acid copolymers, crotonic acid copolymers, partial Examples thereof include esterified maleic acid copolymers, and similarly acidic cellulose derivatives having a carboxylic acid in the side chain, but the invention is not limited thereto.

These organic polymer binders may be used alone, but the mutual compatibility of two or more kinds does not cause demixing during the manufacturing process from preparation of coating liquid to coating and drying. It is also possible to use a good organic polymer binder in a mixture in an appropriate ratio. The molecular weight of these organic polymer binders can take a wide range depending on the type of polymer, but in general, it is preferably in the range of 5,000 to 2,000,000, more preferably 10,000 to 1,000,000.

Here, the mixing ratio of the monomer compound and the organic polymer binder varies depending on the combination of the monomer compound and the organic polymer binder used, but generally the ratio is 1:10 to 2: The range of 1 (weight ratio) is preferable.

The photopolymerization initiator contained in the photopolymerization type photosensitive resin layer of the present invention is a photosensitizer represented by the general formula (1).
A photopolymerization initiator containing at least one triazine compound.

In the general formula (1), 4, which is represented by T,
The halogen atom of the 6-bis (trihalomethyl) -s-triazin-2-yl group may be a chlorine atom, a bromine atom, a fluorine atom or the like, but a chlorine atom is particularly preferable.

In the general formula (1), the alkyl group represented by R ¹ and R ² has 1 carbon atom such as methyl group, ethyl group, isopropyl group, butyl group, pentyl group and hexyl group. Alkyl groups from 6 to 6 are preferred. The aryl group represented by R ¹ and R ² is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group and a naphthyl group.

Examples of the substituent of the substituted alkyl group and the substituted aryl group represented by R ¹ and R ² are aryl groups such as phenyl group; halogen atoms such as chlorine atom; carbon number such as methoxy group and ethoxy group. 1 to 6 alkoxy group; carboxyl group; methoxycarbonyl group, ethoxycarbonyl group, octoxycarbonyl group, octadecyloxycarbonyl and other alkoxycarbonyl groups having 2 to 20 carbon atoms; aryloxycarbonyl group; cyano group; acetyl group An acyl group such as a benzoyl group; a nitro group; a dialkylamino group; and the following general formula (A) to
Examples thereof include a sulfonyl group represented by (C).

[0029]

[Chemical 3]

[In the general formulas (A) to (C), Z is
Represents a hydrogen atom or an alkyl group or an aryl group represented by R ^1. ]

Further, examples of the substituent of the substituted aryl group represented by R ¹ and R ² include the above-mentioned alkyl groups as well as the above-mentioned substituents.

Particularly preferred substituents of the substituted alkyl group or substituted aryl group represented by R ¹ and R ² are
An electron-withdrawing group such as a halogen atom, a carboxyl group, an alkoxycarbonyl group, a cyano group, an acyl group and a sulfonyl group.

When R ¹ and R ² form a heterocycle together with the nitrogen atom to which they are bonded, examples of the heterocycle include groups represented by the following formulas (D) to (H).

[0034]

[Chemical 4]

In the general formula (1), the alkyl group represented by R ³ and R ⁴ has a carbon number of 1 such as methyl group, ethyl group, isopropyl group, butyl group, pentyl group and hexyl group. Alkyl groups from 6 to 6 are preferred. R ³
And the halogen atom represented by R ⁴ is a chlorine atom,
Examples thereof include bromine atom and fluorine atom. Also,
Examples of the alkoxy group represented by R ³ and R ⁴ include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a pentoxy group and a hexoxy group. ..

Of the compounds represented by the general formula (1) as described above, particularly preferable compounds are those represented by the general formula (1):
R ¹ and R ² are a hydrogen atom, an alkoxycarbonylmethyl group, a chloromethyl group, a chloroethyl group, a cyanomethyl group, or a cyanoethyl group, and at least one of R ¹ and R ² is a group other than a hydrogen atom. Or R ¹ ,
R ² and a nitrogen atom form a group represented by the formula (E) or (F), and R ³ and R ⁴ are a hydrogen atom, a halogen atom or an alkyl group.

In the general formula (1), the group represented by T is preferably bonded to the para position with respect to —NR ¹ R ² .

Preferred specific examples of the photosensitive s-triazine compound contained in the photopolymerizable photosensitive resin layer of the photosensitive transfer sheet of the present invention include the compounds shown below. However, it goes without saying that in the present invention, the above-mentioned photosensitive s-triazine compound is not limited to the following compounds.

[0039]

[Chemical 5]

[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

[Chemical 8]

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

A synthesis example of the photosensitive s-triazine compound exemplified above is shown below. Synthesis of 4- [4-N, N-di (ethoxycarbonylmethyl) amino-3-bromophenyl] -2,6-bis (trichloromethyl) -S-triazine (P-11)

4- [4-N, N-di (ethoxycarbonylmethyl) amino] benzonitrile 29.0 g, trichloroacetonitrile 86.6 g and aluminum tribromide 2.8 g were mixed and stirred, and the mixture was heated at an internal temperature of 5 ° C. Hydrogen chloride gas was introduced therein for 1.5 hours. The internal temperature was returned to room temperature, and stirring was continued for another 20 hours. Next, 16 g of bromine was added dropwise to the mixture while stirring. After continuing stirring for further 3 hours, 400 ml of ethanol was added and the mixture was left overnight. The resulting crystals were collected by filtration, washed with ethanol and then dried to obtain the title compound. The obtained crystals had a melting point of 119 to 123 ° C. and a yield of 50.8 g. UV spectrum (in tetrahydrofuran) λ max: 372 nm (log ε = 4.39)

The photopolymerization initiator contained in the photopolymerizable photosensitive resin layer of the present invention can initiate photopolymerization of a compound having an ethylenically unsaturated bond in addition to the above-mentioned photosensitive s-triazine compound. Other compounds may be used in combination. Examples of other photopolymerization initiators that can be used in combination include those described in J. Co-
Examples of organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds and substituted benzophenone derivatives, aromatic ketones, lophine dimers and organic halogen compounds other than the present invention described in Chapter 5 of "Light Sensitive Systems" by Ser. Be done.

The content of the photopolymerization initiator in the photopolymerizable photosensitive resin layer is preferably in the range of 0.01 to 20% by weight with respect to the content of the monomer compound in the photopolymerizable photosensitive resin layer, and 0 The range of 0.1 to 15% by weight is more preferable. The most preferable content is in the range of 0.5 to 10% by weight. If the content of the photopolymerization initiator is less than 0.01% by weight, the sensitivity is insufficient, and if it exceeds 20% by weight, the whiteness of the non-image area is lowered. In addition, the content of the s-triazine compound represented by the general formula (1) is 40 in the total photopolymerization initiator used.
It is preferably at least wt%, more preferably at least 50 wt%.

In the photopolymerizable photosensitive resin layer, a reducing agent such as an oxygen scavenger and a chain transfer agent of an active hydrogen donor as an auxiliary agent for further promoting the polymerization, and further a chain transfer agent Other compounds that accelerate the polymerization can also be used in combination. As the oxygen scavenger, phosphine, phosphonate, phosphite,
Stannous salts and other compounds that are easily oxidized by oxygen. For example, N-phenylglycine, trimethylbarbituric acid, N, N-dimethyl-2,6-diisopropylaniline, N, N, N, -2,4,6-pentamethylaniline and the like. Further, thiols, thioketones, trihalomethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides and the like as shown below are also useful as the polymerization accelerator.

Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, naphthylamine, β-naphthol, phenathiazine, pyridine, nitrobenzene, o-toluquinone.
Aryl phosphite and the like can be mentioned, but the invention is not limited thereto.

The film thickness of the photopolymerizable photosensitive resin layer is generally in the range of 0.5 to 150 μm, preferably 2 to 10 μm.
It is in the range of 0 μm.

For the details of the materials for these photosensitive resin layers and the method for forming them, see, for example, Japanese Patent Publication No. 46-15326.
No. 46-35682, JP-A-47-41830.
No. 48, No. 48-93337, No. 49-441, No. 51.
No. 5101, No. 59-97140 and the like.

When a coloring substance is used, the coloring substance may be contained in the photopolymerization type photosensitive resin layer, or may be contained therein by separately providing a coloring material layer. The color material layer can be provided either above or below the photopolymerizable photosensitive resin layer, but from the viewpoint of the sensitivity of the photopolymerizable photosensitive resin layer in the image exposure step, it is provided on the color material layer. preferable. Known pigments and dyes can be used as the coloring substance, but it is preferable to use pigments (yellow, magenta, cyan, black) having a hue similar to that of the color ink for color calibration for printing. For details of the color pigment and the color material layer, see, for example, JP-A-59 / 59.
-97140 publication.

Further, it is preferable to provide a protective layer on the photopolymerizable photosensitive resin layer. The protective layer is, for example, polyvinyl alcohol, polyvinyl acetate, methyl vinyl ether
It can be formed by applying and drying a solution of a polymer substance such as a maleic anhydride copolymer, polyvinylpyrrolidone, gelatin and gum arabic.

The thus-produced photosensitive transfer sheet of the present invention can be used for color proofing, for example, by an operation according to the surprint method as described below.

1) Exposure is carried out by irradiating an actinic ray with the color separation mask superposed on the photosensitive transfer sheet (exposure step).

2) The transfer sheet is treated with a developing solution to form a decomposed image on the release layer (developing step).

3) Using another photosensitive transfer sheet, the exposure step and the development step are repeated to obtain a two- to four-color color proofing sheet.

4) A color proofing sheet having a first-color decomposed image is superposed so that the decomposed image side is in contact with the image receiving layer of the image receiving sheet comprising the support and the photopolymerizable image receiving layer, and then heated. Apply pressure to bond. The decomposed image is thermocompression bonded while embedded in the uncured image receiving layer. Next, the transfer sheet support (temporary support)
Is peeled off and the image is transferred together with the peeling layer (transfer step).

Further, the remaining color proofing sheets are used to perform the same operation to successively transfer the separated images of the second and subsequent colors onto the same image-receiving sheet while aligning the separated images of the second color and the separated images of the first color. On the image receiving sheet, two- to four-color separated images are transferred and formed in a state of being embedded in the image receiving layer.

5) The support of the image-receiving sheet on which the multicolor image is transferred is superposed on the white paper so that the multicolor image comes into contact with the white paper, and then heated and pressed to bond them.

6) The entire surface of the image-receiving sheet is irradiated with actinic rays to photo-cur the photopolymerizable image-receiving layer.

7) By peeling off the support (temporary support) of the image-receiving sheet, and if desired, a matte film or the like is overlaid on the image-receiving layer and heated and pressed to form fine irregularities on the surface of the image-receiving layer. It may be provided.

In the above description, white paper is used as an example of the support on which the decomposed image is finally transferred, but various papers, metals, films, glass, etc. can be used as the support. .. Also, without going through the image receiving sheet,
It is also possible to transfer directly to the final support.

Further, the two- to four-color color proofing sheets obtained in the third step can be directly used as they are for accurate color proofing and can be used for color proofing according to the overlay method.

[0069]

EXAMPLES Examples of the present invention and comparative examples will be described below. However, the following examples do not limit the present invention.

[Example 1] A polyethylene terephthalate film (thickness: 100 µm) was used as a support, and a release layer coating solution having the following composition was applied onto the support and dried to give a release layer having a dry film thickness of 0.5 µm. Was established.

Coating liquid for release layer Alcohol-soluble polyamide 5.4 g (CM-8000, viscosity: 23 cps, manufactured by Toray Industries, Inc.) Polyhydroxystyrene 3.6 g (resin M, average molecular weight: 5000, manufactured by Maruzen Petroleum Co., Ltd.) Methanol 400g Methyl Cellosolve 100g

Next, as a coating liquid for forming the photopolymerization type photosensitive resin layer, four colors of yellow (Y), magenta (M), cyan (C) and black (K) photosensitive coatings having the following compositions are applied. Each liquid was prepared.

Photopolymerization type photosensitive resin layer coating liquid Yellow photosensitive coating liquid Benzyl methacrylate / methacrylic acid copolymer 60 g (molar ratio: 73/27, viscosity η: 0.12) Pentaerythritol tetraacrylate 43.2 g Photopolymerization Initiator: Compound 1 (shown later) 1.81 g Seika First Yellow H-7055 9.4 g (manufactured by Dainichiseika Kogyo Co., Ltd.) Methyl cellosolve acetate 560 g Methyl ethyl ketone 280 g Fluorosurfactant 1 g (Florard FC-430, Sumitomo 3M) (Made by corporation)

Magenta photosensitive coating solution benzyl methacrylate / methacrylic acid copolymer 60 g (molar ratio: 73/27, viscosity η: 0.12) pentaerythritol tetraacrylate 43.2 g Photopolymerization initiator: compound 1 (shown later) 1 .81g Seika Fast Carmine 1483 5.2g (manufactured by Dainichiseika Kogyo Co., Ltd.) Methyl cellosolve acetate 560g Methyl ethyl ketone 280g Fluorosurfactant 1g (Florard FC-430, manufactured by Sumitomo 3M Limited)

Cyan photosensitive coating solution benzyl methacrylate / methacrylic acid copolymer 60 g (molar ratio: 73/27, viscosity η: 0.12) pentaerythritol tetraacrylate 43.2 g Photopolymerization initiator: Compound 1 (shown later) 1 .81 g Cyanine Blue 4920 5.6 g (manufactured by Dainichiseika Kogyo Co., Ltd.) Methyl cellosolve acetate 560 g Methyl ethyl ketone 280 g Fluorosurfactant 1 g (Florard FC-430, manufactured by Sumitomo 3M Limited)

Black photosensitive coating solution benzyl methacrylate / methacrylic acid copolymer 60 g (molar ratio: 73/27, viscosity η: 0.12) pentaerythritol tetraacrylate 43.2 g Photopolymerization initiator: compound 1 (shown later) 1 .81 g Mitsubishi Carbon Black MA-100 6.6 g (manufactured by Dainichiseika Kogyo Co., Ltd.) Methyl cellosolve acetate 560 g Methyl ethyl ketone 280 g Fluorosurfactant 1 g (Florard FC-430, manufactured by Sumitomo 3M Limited)

These four color photosensitive coating liquids were respectively coated on four supports provided with a release layer and dried to form a photopolymerizable photosensitive resin layer having a dry film thickness of 2.4 μm. ..

Separately, a coating liquid for forming a protective layer having the following composition was prepared, and the coating liquid was coated on each photopolymerizable photosensitive resin layer of each color and dried to give a dry film thickness of 1.5 μm. A protective layer was provided.

Coating liquid for protective layer Polyvinyl alcohol 60 g (GL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Water 970 g Methanol 30 g

In this way, a four-color photosensitive transfer sheet (negative-type colored photosensitive sheet) comprising a support, a peeling layer, a photopolymerizable photosensitive resin layer and a protective layer was manufactured in this order.

Example 2 The method of Example 1 except that the photopolymerization initiator contained in the coating liquid for forming the photopolymerization type photosensitive resin layer was changed to the compound 2 in Example 1. A four-color photosensitive transfer sheet was produced by performing the same treatment as described in (1).

[Example 3] Four-color photosensitivity was obtained by performing the same processing as in Example 1 except that the composition of the release layer coating liquid was changed to the following composition. A sex transfer sheet was produced.

Coating liquid for release layer Alcohol-soluble polyamide 7.2 g (CM-8000, viscosity: 23 cps, manufactured by Toray Industries, Inc.) Polyhydroxystyrene 1.8 g (resin M, average molecular weight: 5000, manufactured by Maruzen Sekiyu KK) Methanol 400g Methyl Cellosolve 100g

Comparative Example 1 The same treatment as in Example 1 except that the compound 3 was used as the photopolymerization initiator in the photopolymerization type photosensitive resin layer forming coating solution. Then, a four-color photosensitive transfer sheet was manufactured.

[Comparative Example 2] The same treatment as in Example 1 except that the compound 4 was used as the photopolymerization initiator in the coating solution for forming the photopolymerizable photosensitive resin layer. Then, a four-color photosensitive transfer sheet was manufactured.

The compounds 1 to 4 used in Examples 1 to 3 and Comparative Examples 1 and 2 are as follows.

[0087]

[Chemical 14]

[Evaluation of Photosensitive Transfer Sheet] In each of the examples and comparative examples, each of the obtained four-color photosensitive transfer sheets was subjected to the coloring test described below to give the degree of coloring of the non-image area. I asked.

Coloring Test Each of the four color photosensitive transfer sheets was overlaid with a corresponding color separation mask using a register pin, and image exposure was performed for 60 seconds with a 1 KW ultra-high pressure mercury lamp P-607FW (Dainippon Screen Mfg. Co., Ltd.). Then, it is automatically developed for 22 seconds at 31 ° C. by a 5-fold dilution of the color art developer CA-1 (trade name: manufactured by Fuji Photo Film Co., Ltd.) (Color Art Processor CA-600P: Fuji Photo Film Co., Ltd.). Manufactured) was used. In this way, a four-color photosensitive transfer sheet faithfully reproducing the color separation mask was obtained.

Separately, a coating solution having the following formulation was prepared on a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm, and a dry film thickness of 20 μm was formed by coating.
An image receiving sheet was created.

Coating liquid for image-receiving layer Methyl methacrylate polymer 90 g (average molecular weight: 100,000, manufactured by Wako Pure Chemical Industries, Ltd.) Pentaerythritol tetraacrylate 90 g 2,2-dimethoxy-2-phenylacetophenone 3.18 g p-methoxypheno -0.09 g methyl ethyl ketone 220 g

Next, the image side of the black photosensitive transfer sheet as the first color was overlaid so as to be in contact with the film surface of the image receiving sheet material, and a color art transfer machine CA-600T (manufactured by Fuji Photo Film Co., Ltd.) was used. After laminating, the support of the photosensitive transfer sheet was peeled off, and the black image was transferred onto the image receiving sheet. Next, the remaining three color photosensitive transfer sheets were sequentially transferred while aligning the positions to obtain an image receiving sheet on which four color halftone images were transferred and formed.

Next, the image receiving sheet on which the four-color image was transferred and the art paper (final support) were overlaid and laminated by the above transfer machine, and then P-607FW bright room printer (manufactured by Dainippon Screen Mfg. Co., Ltd.). The entire surface was exposed for 120 seconds from the image receiving sheet side using a 1 KW ultra-high pressure mercury lamp), then the support of the image receiving sheet was removed, and a final image (color proof) was obtained on art paper.

In the image-receiving sheet on which the four-color halftone image obtained above was transferred and formed, a reflection densitometer RD918 (B
Using a filter: manufactured by Macbeth Co., Ltd.), the coloring of the non-image area was measured to obtain a sample non-image area measurement value.

On the other hand, the image-receiving sheet and the art paper (final support) were overlaid and laminated using a color art transfer machine CA-600T (manufactured by Fuji Photo Film Co., Ltd.), and then P-607FW bright room printer (large size). The entire surface was exposed for 120 seconds from the image receiving sheet side with a 1 Kw ultra-high pressure mercury lamp (manufactured by Nippon Screen Mfg. Co., Ltd.), and then the support of the image receiving sheet was removed to obtain an image receiving layer transferred on art paper. The control sample (image receiving layer + art paper) thus obtained was measured for coloration using a reflection densitometer RD918 (using a B filter: manufactured by Macbeth Co., Ltd.) to obtain a control sample measurement value.

The coloring degree of the non-image area was calculated as a value obtained by subtracting the measurement value of the control sample from the measurement value of the sample non-image area. The results are shown in Table 1.

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[Table 1]

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INDUSTRIAL APPLICABILITY The photosensitive transfer sheet of the present invention has a remarkably excellent effect in that the non-image area is markedly less colored, the color proof is good, and the approximation of the printed matter is further improved.

[Fig. 2]

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03F 7/34 7124-2H

Claims (1)

[Claims] 1. A photosensitive transfer sheet having a release layer made of an organic polymer and a photopolymerization type photosensitive resin layer containing a photopolymerization initiator in this order on a support, wherein the photopolymerization initiator is: The following general formula (1): [In the formula, T is 4,6-bis (trihalomethyl) -s-
Represents a triazin-2-yl group, R ¹ and R ² may be the same or different from each other, a hydrogen atom, an alkyl group,
It represents a substituted alkyl group, an aryl group or a substituted aryl group, and R ¹ and R ² together with the nitrogen atom to which they are attached may form a heterocycle, and R ³ and R ⁴ are the same or different from each other. Which represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group], which is a photopolymerization initiator containing at least one photosensitive s-triazine compound.