JP3147582B2 - 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 found.

[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, when the protective film is peeled off from the photosensitive layer after the image exposure and the difference in the adhesiveness in the transfer between the exposed and unexposed areas in the photosensitive layer, the pre-warmed image receptor The image-forming material receives heat due to the radiation of the photosensitive layer, so that a part of the unexposed portion of the photosensitive layer is transferred to the protective film, so-called blocking occurs. In some cases, the image cannot 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 a normal unmodified silicone compound such as polydimethylsiloxane is used, the blocking effect is significantly reduced because the silicone compound is transferred from the photosensitive layer to the protective film due to storage over time. Further, if the amount of the silicone compound is increased to such an extent that the blocking does not cause any problem, the surface tension of the transfer surface is too low, so that the next color photosensitive layer cannot be transferred.

[0007]

The inventors of the present invention have made intensive studies to solve the above-mentioned problems. As a result, the photosensitive layer contains a silicone compound modified with alcohol at both ends to prevent blocking by heat. In addition, they have found that the effect of preventing blocking over time can be prevented from being reduced, and have completed the present invention.

[0008]

According to the present invention, 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 between the exposed and unexposed areas of the layer, in the image forming material that transfers an image to an image receptor such as paper, the photosensitive layer has a silicone compound modified with alcohol at both ends as a solid. Image forming material containing from 1 to 30% by weight of

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,
A film or sheet such as polyethylene naphthalate may be mentioned, and polyethylene terephthalate is particularly preferred in terms of transparency, thermal stability, dimensional stability and the like.

The photosensitive layer is composed of a silicone compound modified with alcohol at both ends and (a) a photopolymerizable compound and a colorant, and (b) a photopolymerizable compound, a thermoplastic resin and a colorant, and has a thickness of 1 to 5 μm. Although it is a layer, 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 silicone compound modified with alcohol at both ends has a solid content of 1 to 1
30% by weight is contained. If the content of the silicone compound is less than 1% by weight of the coloring agent, blocking cannot be prevented. On the other hand, if it exceeds 30% by weight, problems occur such that repelling occurs on the coated surface and a photosensitive layer of the next color cannot be formed.

The molecular weight of the silicone compound modified with alcohol at both ends is preferably in the range of 500 to 10,000. Molecular weight
If it is less than 500, blocking may occur depending on the drying conditions of the coating liquid due to high volatility. On the other hand, when the molecular weight exceeds 10,000, the effect of preventing blocking is reduced, and the painted surface becomes turtle-like. The silicone compound has good compatibility with the photopolymerizable compound and uniformly forms the coated surface of the photosensitive layer at the time of coating. In addition, the silicone compound has the function of lowering the surface tension of the photosensitive layer, but has strong affinity with the resin because both ends are alcohol-modified, and migrates to the protective film over time even at 40 ° C storage. There is no phenomenon to do. Therefore, it has the feature of preventing blocking over time and blocking during heating.

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), vinyl 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-aliphatic tertiary amine or the like can be used, and for example, 4,4′-bisdiethylaminobenzophenone can be used. Since the photosensitizer may be yellowed, the photosensitizer is selected in consideration of the acceleration efficiency and yellowing, compatibility with the initiator, the energy of the active light beam to be used, and the wavelength range.

Further, a thermal polymerization inhibitor may be used to suppress radicals for photopolymerization. When using a thermal polymerization inhibitor, what is important is the amount of addition and compatibility, and the amount of radicals for photopolymerization should not be disturbed, and the radicals 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. As the coloring agent applied to the photosensitive layer, 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 is suitably from 5 to 50% by weight of the total solids, and more preferably from 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. The protective film may be provided with a layer having gas barrier properties. The layer having gas barrier properties may or may not be in direct contact with the photosensitive layer. Compounds used in the layer having gas barrier properties include, for example, polyvinyl alcohol (PVA) and ethylene vinyl alcohol (E
vOH) and the like. 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. At this time,
There is no particular limitation.

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 Examples thereof include thin high-density polyethylene, medium-density polyethylene, polystyrene, polypropylene, cellulose acetate, biaxially oriented polypropylene, and the like, and a sheet having gas barrier properties and rigidity, such as polyethylene terephthalate, which is bonded with an adhesive.

[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” means “parts 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 (ICC Japan Co., Ltd.) 0.10 part KF-6001 (Shin-Etsu Chemical Co., Ltd. double-ended alcohol-modified silicone) 0.20 parts MA-7 (manufactured by Mitsubishi Kasei) 2.50 parts R-54 (manufactured by Hoechst Japan) 0.80 parts P-methoxyphenol (manufactured by Tokyo Kasei Kogyo) 0.20 parts methyl ethyl ketone 75.00 parts 12μ transparent support (manufactured by Toray Industries Q) -21) On top of this, apply the above photosensitive layer coating solution and dry to form a 2μ photosensitive layer.
Further, a protective film (100 μ OPP film) was laminated with a laminator so as to be in contact with the photosensitive layer, to obtain an image forming material (black sheet).

The transparent support side of the image forming material was brought into close contact with the silver halide surface of the original positive mask, and actinic rays of 50 mj / cm ² were applied with a UV printer (HMW-201KB, manufactured by Oak Manufacturing Co., Ltd.). 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 (Taishi Laminator 8B- 700 special type), pressure 4kg / cm ² , passage speed 35cm / min, roller surface temperature 90 ℃
When the image was transferred by the nip between the rollers under the conditions described above, the unexposed portion of the photosensitive layer (thickness: 2.0 μm) was transferred, and a transferred material having the same texture as a normal printed material could be obtained. When the image forming material was stored in a thermostat at 40 ° C. for one month and subjected to image exposure under the same exposure conditions and transferred, no blocking occurred when the protective film was peeled off.
A transcript that was the same as one month ago could be obtained.

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 (Manufactured by Nippon Kayaku) 0.57 parts Irkagua 369 (manufactured by Ciba-Geigy Corporation) 0.04 parts Rio Noble FG7330 (manufactured by Toyo Ink Mfg. Co., Ltd.) 3.12 parts X-22-160AS 0.22 part (manufactured by Shin-Etsu Chemical Co., Ltd. 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 (Manufactured by Nippon Kayaku Co., Ltd.) 0.54 parts Irkaguar 369 (manufactured by Ciba-Geigy Corporation) 0.04 parts Lionol Perelow FG1310 (manufactured by Toyo Ink Mfg. Co., Ltd.) 3.12 parts KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) Department

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 (Manufactured by Nippon Kayaku Co., Ltd.) 0.57 parts Irkagua 369 (manufactured by Ciba-Geigy Corporation) 0.04 parts Lionol Red Carmine 6BFG4200 (manufactured by Toyo Ink Mfg. Co.) 3.10 parts F-99-199 0.24 part (manufactured by Nippon Unicar Co., Ltd. Silicone) 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. In addition, no blocking was observed when these sheets were stored at 40 ° C. for one month.

Comparative Example 1 An image forming material was produced in the same manner as in Example 1 except that a coating liquid was prepared except for the silicone modified at both ends with alcohol. 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 unmodified polydimethylsiloxane (L-45, manufactured by Nippon Unicar) in place of the silicone modified at both ends with alcohol at the same time as in Example 2; Color imaging materials were produced. Although blocking did not occur immediately after the production of each color sheet, blocking was remarkable when left at 25 ° C. for 7 days.

[Comparative Example 3] A coating liquid was prepared by changing the amount of the silicone modified with alcohol at both ends in Example 1 to 1.25 parts.
An image forming material was produced in the same manner as in Example 1. In this sheet, when the protective film was peeled off, blocking of the photosensitive layer did not occur and good peeling could be performed.
The transfer of the photosensitive layer of the next color could not be partially performed. [Comparative Example 4] A coating liquid was prepared using X-22-176B (single-terminal alcohol-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd.) in place of the double-terminal alcohol-modified silicone of Example 1, and carried out in the same manner as in Example 1. An imaging material was produced. In this sheet, a lot of repelling was observed, and blocking of the photosensitive layer also occurred. In addition, the blocking became severe over time. [Comparative Example 5] An image forming material was prepared in the same manner as in Example 1 except that a coating liquid was prepared using A-151 (a silane coupling agent manufactured by Nippon Unicar Co.) instead of the silicone modified with alcohol at both ends in Example 1. Was manufactured. Even after drying at 40 ° C. for 30 seconds, blocking of the photosensitive layer occurred.

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 repelling of the image was observed in the overlapping portion of each color, and good image transfer was observed. No blocking occurred even after storage at 25 ° C. for 3 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 silicone compound modified with alcohol at both ends, the surface tension of the surface of the photosensitive layer is low, and blocking by heat does not occur. Further, since this silicone compound has a high affinity for the resin, even if it is stored over time, it does not migrate to the protective film at all, and blocking does not occur. Further, the transfer of the second and subsequent color image forming materials is not prevented. 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.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-191238 (JP, A) JP-A-4-220649 (JP, A) JP-A-3-96953 (JP, A) JP-A-4- 112085 (JP, A) JP-A-2-58058 (JP, A) JP-A-2-196692 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/004 G03F 3 /Ten

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. The photosensitive layer is exposed to light, and exposed and unexposed areas in the photosensitive layer are provided. The photosensitive layer contains 1 to 30% by weight of a colorant as a solid content of a silicone compound modified at both ends with alcohol in an image forming material for transferring an image to an image receptor such as paper due to a difference in adhesiveness in the transfer of the toner. An image forming material comprising: