JP2985577B2 - Image forming material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material. More specifically, it is an image forming material formed by superimposing a single color or a multicolor using the difference in adhesiveness between an exposed portion and an unexposed portion of a photosensitive layer, and as a prepress proof for color proofing, obtains a transferred material similar to a printed material. The image forming material.

[0002]

2. Description of the Related Art In the printing industry, it has been known to use a prepress proof as a means for confirming the finish, color tone, and the like of a finally printed product before printing. The prepress proof includes an overlay method and a surprint method, and the prepress proof is used depending on the image quality to be finally obtained and the purpose of use in plate making and printing processes. In the overlay method, a film in which a photosensitive layer containing a color material corresponding to a color separation mask is provided on a transparent base film is brought into close contact with the mask, exposed and developed, and the respective films are overlaid. Perform calibration.

[0003] The surprint method has a high utility value since a hard copy is obtained unlike the overlay method, and for example, as described in US Patent Nos. 3060023, 3060024 and 3060025. In this method, several layers of photopolymer-photosensitive layers are laminated on a single support to sequentially form color-separated images. Also, JP-A-59-97410,
There is also a prepress proof that can be used for both the overlay method and the surprint method as described in Japanese Patent Application Laid-Open No. Sho 61-1885377. Use this method if you just want to check characters etc. according to the purpose of use.
The versatility is large in that the hard copy can be obtained by checking only the burley and obtaining a hard copy for checking a delicate color portion such as a picture, by transferring the hard copy to the transfer target. However, there is a disadvantage that the working environment is deteriorated due to the necessity of a developing step using an organic solvent.

On the other hand, the present inventors have formed a photosensitive layer containing a dye and / or a pigment on a transparent support, exposed the image, and carried out the tackiness in the transfer of the exposed and unexposed portions of the photosensitive layer. And a prepress pull obtained by transferring an image to an image receptor by cohesion failure of a photosensitive layer between roll nips using an image forming material such as paper which transfers an image to an image receptor. Unlike conventional pre-press proofs, the image and texture look very similar to the actual printed matter because there is no layer such as an adhesive layer between the printing material and the image forming material, unlike the conventional prepress proof. Has already been headed.

[0005] These image-forming materials usually comprise three layers: a transparent support, a photosensitive layer containing a dye and / or a pigment, and a protective film. When using the image forming material, the transparent support is brought into close contact with the image surface of the mask master and the like, and image exposure is performed from the mask side.
Next, the protective film is removed, and the photosensitive layer and the image receptor are transferred between the nipples while applying heat and pressure. However, after the image exposure and the difference in the adhesiveness in the transfer of the exposed part and the unexposed part in the photosensitive layer,
When the protective film is peeled from the photosensitive layer, the image-forming material receives heat due to radiation from the pre-warmed image receptor, and a part of the unexposed portion of the photosensitive layer is transferred to the protective film. Due to the so-called blocking, a part of the unexposed portion that should be transferred is not transferred, and the image may not be able to be faithfully reproduced as the original.

In order to prevent blocking due to heat, it is important that the surface tension of the photosensitive layer does not change due to heat. It is well known that a silicone compound or a low molecular weight wax may be generally added to lower the surface tension. When a silicone compound or wax is incorporated into the photosensitive layer, blocking can be prevented because a part of the silicone compound or wax floats on the surface. However, when the silicone compound or wax is blended in the photosensitive layer, the silicone compound or wax partially emerges on the surface of the photosensitive layer after the photosensitive layer is cured after the transfer. In addition, not only the unexposed portion of the photosensitive layer, that is, the transfer portion, but also the surface of the photosensitive layer cured by light emerges. Therefore, when transferring to the image receptor, post-exposure, and then transferring the image-exposed photosensitive layer of another original to another original, a silicone compound is applied to part or all of the transfer surface during the first transfer. The surface tension of the image receptor is partially too low, so that the photosensitive layer of the next color cannot be transferred due to the partial transfer or transfer of the wax or wax. Thus, blocking and transfer properties are contrary properties, and it is difficult to design a photosensitive layer.

[0007]

Accordingly, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by including a photoreactive silicone compound in the photosensitive layer, blocking by heat was prevented, and It has been found that the silicone compound in the portion cured by light does not migrate to the surface of the photosensitive layer even by heat, and the present invention has been completed.

[0008]

Means for Solving the Problems A photosensitive layer containing a colorant is formed on a support, and a protective film is further formed on the photosensitive layer. Due to the difference in adhesiveness in the transfer of the unexposed portion and, in the image forming material to transfer the image to an image receptor such as paper,
With respect to 1 part by weight of the silicone in which the photosensitive layer has two or more methacryloyl groups, the silicone and the acrylic oligomer each having one or more methacryloyl groups are added in an amount of 0.1 part by weight.
The present invention provides an image-forming material characterized by containing a mixture containing 1 to 10 parts by weight as a solid content of 0.01 to 5% by weight of a colorant.

The support is preferably made of a material that is stable to heat, chemicals, light, etc., and that sufficiently transmits actinic rays. For example, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate,
Examples include films or sheets of polycarbonate, polypropylene and the like, and polyethylene terephthalate is particularly preferred in terms of transparency, heat stability, dimensional stability and the like.

The photosensitive layer comprises a mixture of a methacryloyl group-containing silicone and an acrylic oligomer, and (a) a photopolymerizable compound and a colorant; (b) a photopolymerizable compound, a thermoplastic resin and a colorant. Although the layer has a thickness of 5 μm, a photopolymerization initiator, a photosensitizer, a thermal polymerization inhibitor, a resin plasticizer, a pigment dispersant, and the like may be used in combination as additives. The mixture of the methacryloyl group-containing silicone and the acrylic oligomer contains 0.01 to 5% by weight of the colorant as a solid content.
If the content of the mixture is less than 0.01% by weight of the colorant, blocking cannot be sufficiently prevented. Also, 5
If the amount is more than 100% by weight, a proper adhesion to the protective film cannot be obtained, and the gloss may be increased after the image is transferred.

A mixture of a methacryloyl group-containing silicone and an acrylic oligomer has two methacryloyl groups.
It is preferable that the silicone and the acrylic oligomer each having one methacryloyl group are contained in the range of 0.1 to 10 parts by weight with respect to 1 part by weight of the silicone having one or more silicones. As the acrylic oligomer, one or two or more of a pentaerythritol triacrylate oligomer having a molecular weight of 500 to 2,000, an ethylene glycol diacrylate oligomer, a diethylene glycol diacrylate oligomer, and a trimethylolpropane triacrylate oligomer are used. The mixture has good compatibility with the photopolymerizable compound and uniformly forms the coated surface of the photosensitive layer. Further, the mixture has a function of lowering the surface tension of the photosensitive layer, but has a characteristic that when cured by light, does not transfer to the surface of the photosensitive layer even by heat.

As the photopolymerizable compound, a monomer having an ethylenically unsaturated double bond, a prepolymer, or the like can be used, but a compound capable of plasticizing a thermoplastic resin at room temperature is preferable. Representative compounds include 2-hydroxyethyl (meth) acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate,
6-hexanediol di (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the like. These photopolymerizable compounds may be used alone, or two or more as needed. Is also good.

[0013] As the thermoplastic resin, a thermoplastic resin having no compatibility with a photopolymerizable compound and having no photopolymerizability can be used. For example, polyvinyl chloride, poly (meth)
Acrylic esters, epoxy resins, polyurethane resins, cellulose derivatives (eg, ethyl cellulose, cellulose acetate, nitrocellulose), polyvinyl chloride-vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, butadiene-acrylonitrile copolymers And one or more of these thermoplastic resins are used depending on the required physical properties.

As the photopolymerization initiator, those which mainly absorb little in the visible light region and those which have good compatibility with the photopolymerizable compound are preferable. For example, benzophenone, benzoin ethyl ether, benzyldimethyl ketal, azobisisobutane Butyronitrile, 2-chlorothiozanzone, 2-methylthiozanzone, 2-ethylthiozanzone, 2-isopropylthiozanzone, 4'-isopropyl-2-hydroxy-2-
Methyl propiophenone and the like. Further, in order to increase the photopolymerization initiation efficiency, a photosensitizer may be used in combination. As the photosensitizer, an aromatic-fatty acid tertiary amine or the like can be used, and for example, 4,4′-bisdiethylaminobenzophenone can be used. Since the photosensitizer may be yellowed depending on the photosensitizer, it is selected in consideration of the acceleration efficiency and yellowing, the compatibility with the initiator, the energy of the active light to be used, and the wavelength range.

Further, a thermal polymerization inhibitor may be used to suppress radicals for photopolymerization. What is important when using a thermal polymerization inhibitor is the amount added and the compatibility, and the amount of the radical must not inhibit the radical generation for photopolymerization, and the radical must be thermally suppressed. Generally, aromatic derivatives such as hydroquinone, p-methoxyphenol, t-butylcatechol, and pyrogallol are used, but compounds other than aromatic compounds may be used in combination. . Colorants applied to the photosensitive layer include:
Conventionally used dyes and pigments such as organic pigments, dyes and carbon black can be used. Several dyes and pigments can be mixed to obtain the required hue. The pigment or dye added to the photosensitive layer should be 5 to 50% of the total solids.
% Is suitable, and preferably 9 to 20% by weight.

The protective film may be composed of a single layer or a plurality of layers. However, the surface in contact with the photosensitive layer has few fish eyes, has good releasability from the photosensitive layer, and is unnecessary. Those in which the plasticizer does not precipitate are preferred. Further, a layer having gas barrier properties may be provided on the protective film. The layer having gas barrier properties may or may not be in direct contact with the photosensitive layer. Examples of the compound used for the layer having gas barrier properties include high molecular compounds such as polyvinyl alcohol (PVA) and ethylene vinyl alcohol (EvOH). Further, for the purpose of securing the rigidity of the image forming material, the protective film may be lined with another material having high rigidity on a surface that is not in direct contact with the photosensitive layer. The material to be backed at this time is not particularly limited.

As such a protective film, a rigid sheet or film of polyethylene terephthalate, biaxially oriented polypropylene, high-density polyethylene or the like, one or two or more of these bonded with an adhesive, or as much as possible Gas barrier and rigid sheet made of thin high-density polyethylene, medium-density polyethylene, polystyrene, polypropylene, cellulose acetate, etc.
For example, a material obtained by laminating polyethylene terephthalate or the like with an adhesive may be used.

[0018]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the examples, “parts” indicates “parts by weight” and “%” indicates “% by weight”. [Example 1] A dispersion having the following composition was dispersed in a sand mill for 2 hours, and then filtered through a 1-micron filter to prepare a coating solution for a photosensitive layer. Diallyl isophthalate prepolymer (Daiso) 11.40 parts Kayarad DPHA (Nippon Kayaku) 7.10 parts Kayarad TPGDA (Nippon Kayaku) 0.90 parts Irgacure 907 (Nippon Ciba Geigy) 1.20 parts Kayacure DETX-S (Nippon Kayaku Co., Ltd.) 0.60 part Irgacure 369 (Nippon Ciba Geigy Co., Ltd.) 0.20 part Solspers 24000 (ICI Japan Co., Ltd.) 0.10 part Mixed solution of methacryloyl group-containing silicone and acrylic oligomer 0.20 part ( Silicone having two methacryloyl groups / silicone / pentaerythritol triacrylate oligomer having one methacryloyl group (molecular weight: 800) = 1/1 part / 2 parts of a mixture of toluene and xylene, NV10%) MA-7 ( 2.50 parts R-51 (Hoechst) Yapan Co., Ltd.) 0.80 parts P- methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.18 parts Methyl ethyl ketone 75.00 parts

On a 12 μm transparent support (Q-21, manufactured by Toray Industries Co., Ltd.), the above coating solution for a photosensitive layer is applied and dried to form a 2 μm photosensitive layer, and a protective film (100 μ OPP film) is further applied. An image forming material (black sheet) was obtained by laminating with a laminator so as to be in contact with the photosensitive layer. The transparent support side of the image forming material and the silver halide surface of the original positive mask
50mj with UV printer (HMW-201KB manufactured by Oak Manufacturing Co., Ltd.)
/ cm ² of actinic radiation. Next, the image forming material and the original plate positive mask are peeled off, the protective film is further peeled off, and the coated paper (pearl coat manufactured by Mitsubishi Paper Mills) is brought into close contact with the image forming material, and the first laminator (Taisei Laminator Co., Ltd.)
8B-700 special type), pressure 4kg / cm ² , passage speed 35cm
/ min, roller surface temperature 90 ° C, transfer by nip between rollers, unexposed photosensitive layer (thickness 2.0
μ) was transferred, and a transfer product having the same texture as that of a normal print product was obtained. Also, the image forming material was stored in a thermostat at 25 ° C for 1 month, and the image was exposed and transferred under the same exposure conditions. I was able to get things.

Example 2 A coating solution for a cyan photosensitive layer having the following composition was prepared in the same manner as in Example 1. Diallyl isophthalate prepolymer (manufactured by Daiso) 11.81 parts Kayarad DPHA (manufactured by Nippon Kayaku) 7.49 parts Kayarad TPGDA (manufactured by Nippon Kayaku) 0.78 parts Irukagua 907 (manufactured by Ciba-Geigy) 1.19 parts Kayacure DETX-S (Japan) 0.57 parts Irkagua 369 (manufactured by Ciba Geigy Corporation) 0.04 parts Lionol Blue FG7330 (manufactured by Toyo Ink Manufacturing Co., Ltd.) 3.12 parts Mixed solution of methacryloyl group-containing silicone and acrylic oligomer 0.22 parts (has two methacryloyl groups) Silicone / silicone / pentaerythritol triacrylate oligomer having one methacryloyl group (molecular weight: 1000) = 1/2 parts / 1 part of a mixture of toluene and xylene, NV 10%) 75.00 parts of methyl ethyl ketone

A yellow photosensitive layer coating solution having the following composition was prepared in the same manner as in Example 1. Diallyl isophthalate prepolymer (manufactured by Daiso) 11.81 parts Kayarad DPHA (manufactured by Nippon Kayaku) 7.49 parts Kayarad TPGDA (manufactured by Nippon Kayaku) 0.78 parts Irukagua 907 (manufactured by Ciba-Geigy) 1.19 parts Kayacure DETX-S (Japan) 0.54 parts Irkaguar 369 (manufactured by Ciba-Geigy Corporation) 0.04 parts Lionol Yellow FG1310 (manufactured by Toyo Ink Mfg. Co., Ltd.) 3.12 parts Mixed solution of methacryloyl group-containing silicone and acrylic oligomer 0.39 parts (having two methacryloyl groups) Silicone / Silicon / pentaerythritol triacrylate oligomer having one methacryloyl group (molecular weight 800) = 2 parts / 1 part / 2 parts mixture in toluene / xylene solution, NV 10%) methyl ethyl ketone 75.00 parts

A coating liquid for a magenta photosensitive layer having the following composition was prepared in the same manner as in Example 1. Diallyl isophthalate prepolymer (manufactured by Daiso) 11.81 parts Kayarad DPHA (manufactured by Nippon Kayaku) 7.49 parts Kayarad TPGDA (manufactured by Nippon Kayaku) 0.78 parts Irukagua 907 (manufactured by Ciba-Geigy) 1.19 parts Kayacure DETX-S (Japan) 0.57 parts Irkagua 369 (manufactured by Ciba-Geigy Corporation) 0.04 parts Lionol Red Carmine 6BFG4200 (manufactured by Toyo Ink Manufacturing Co., Ltd.) 3.10 parts Mixed solution of methacryloyl group-containing silicone and acrylic oligomer 0.24 parts (2 methacryloyl groups) Silicone / silicone / pentaerythritol triacrylate oligomer having one methacryloyl group (molecular weight 1200) = 2 parts / 1 part / 2 parts mixture in toluene / xylene solution, NV 10%) methyl ethyl ketone 75.00 parts

On a 12 μm support (polyethylene terephthalate sheet), a photosensitive layer coating solution
The solution was applied to a thickness of μm, and the solvent component was evaporated by drying. Next, a protective film made by laminating 8 μm polypropylene and 100 μm polyethylene terephthalate (Toray T-60) with a 5 μm thick adhesive (Toyo Moton Co., Ltd. Adcot 329A / 329B = 1/1) was laminated. Then, image forming materials (cyan sheet, yellow sheet and magenta sheet) were obtained.

The transcribed material of the black sheet obtained in Example 1 is subjected to post-exposure, and then an ero sheet, a magenta sheet and a cyan sheet are sequentially transferred thereon, and then post-exposed, as in Example 1. Was formed. In the sheet of each color, even if the protective film was peeled off, no blocking of the photosensitive layer to the protective film was observed. In addition, no repelling was observed even when the overlapping transfer of each color was performed, and a good image could be obtained. Furthermore, the peelability immediately after laminating the protective film was sufficiently maintained after three months.

Comparative Example 1 An image forming material was produced in the same manner as in Example 1 except that a coating solution was prepared except for the mixed solution of the methacryloyl group-containing silicone and the acrylic oligomer in Example 1. In this sheet, the coated surface was partly yuzu-skinned and did not have a uniform coated surface. In addition, when the protective film was peeled off, the photosensitive layer was blocked, and the transferred image could not sufficiently reproduce the pattern of the positive mask. [Comparative Example 2] A coating solution was prepared using dimethyl silicone oil modified with a mercapto group instead of the mixed solution of methacryloyl group-containing silicone and acrylic oligomer of Example 2, and three colors were prepared in the same manner as in Example 2. Was produced. In each color sheet, when the protective film was peeled off, the photosensitive layer was not blocked and good peeling could be performed. However, when the transferred images were overlapped, the image was partially repelled.

[Comparative Example 3] A coating liquid was prepared using dimethylsiloxane modified with an acrylic photosensitive group instead of the mixed solution of methacryloyl group-containing silicone and acrylic oligomer of Example 2, and the same as in Example 2 Thus, an image forming material was manufactured. In each of the color sheets, when the protective film was peeled off, the photosensitive layer was not blocked and good peeling could be performed. However, when the transferred images were overlapped, the image was partially repelled. Also, the peeling of the protective film was good immediately after lamination, but blocking was partially observed after 2 weeks.

Example 3 Instead of the protective film of Example 2, 25 μRPP (manufactured by Nishiishi Kazuki) and 100 μL mirror were used.
A three-color image forming material was manufactured using a protective film obtained by laminating # 100 T type (manufactured by Toray Industries Inc.) via an adhesive, and a transferred image was formed in the same manner as in Example 2. In addition, RPP was obtained by forming an EvOH layer between the polypropylene layers on both sides by a co-extrusion method in order to secure gas barrier properties, and the oxygen permeability was 1.44 cc / m ³ · 24 hours. In each color sheet, even when the protective film was peeled off, the blocking of the photosensitive layer to the protective film did not occur. Also, no image repelling was observed in the superimposed portion of each color, and good image transfer was observed. Also, the peelability immediately after lamination was sufficiently maintained after three months.

Evaluation of the presence or absence of blocking of the photosensitive layer at the time of peeling of the protective film is performed by mounting the image forming material on the image forming material mounting roll (40 ° C.) of the exclusive transfer machine, and removing the protective film when the protective film is peeled off. The presence or absence of blocking of the active layer was visually determined.

[0029]

Since the image forming material of the present invention contains a photoreactive silicone compound, the surface tension of the surface of the photosensitive layer is low, and no blocking occurs due to heat. Also,
When the silicone compound is cured by light, it does not migrate to the surface of the photosensitive layer. Therefore, when superimposing multiple colors, the silicone compound is not transferred to the entire transfer surface during the transfer of the first color. It does not hinder subsequent transfer of the image forming material. Therefore, by using the image forming material of the present invention, it is possible to obtain a high-quality transfer product having the same texture as a normal print product.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/004 522 G03F 7/004 522 7/027 511 7/027 511 (56) References JP-A-3-96953 (JP, A) ( 58) Field surveyed (Int.Cl. ⁶ , DB name) G03F 7/075 G03F 7/004 G03F 7/027

Claims (1)

(57) [Claims] 1. A photosensitive layer containing a colorant is formed on a support, and a protective film is further formed on the photosensitive layer.
Image exposure, by the difference in tackiness in the transfer of the exposed portion and the unexposed portion of the photosensitive layer, the image-forming material for transferring an image to an image receptor such as paper, light-sensitive layer Metaku
For 1 part by weight of silicone having two or more liroyl groups
A silicone having at least one methacryloyl group,
And 10 to 10 parts by weight of acrylic oligomer
An image-forming material comprising the mixture as a solid content of 0.01 to 5% by weight of the colorant.