JPH11277997A - Metal plate for transfer printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a thermal fusion between a dye receiving layer and a sublimation printing paper from occurring by a method wherein on a metal plate base material, at least an image receiving layer containing an ultraviolet ray hardening resin, is provided. SOLUTION: For example, an image receiving layer 4 containing an ultraviolet ray hardening resin such as acrylate of which the number of a functional group is 1-6, is formed on the surface of a metal plate base material 2 of a stainless steel plate or the like, directly or with an backing layer 3 or the like. For a binder of the backing layer 3, a resin having a high adhesion to both of them, such as a vinyl chloride based resin is used. Then, the backing layer 3 is formed in such a manner that on the surface of the metal plate base material 2, a coating liquid obtained by dissolving or dispersing the binder in an organic solvent or the like, is applied by a printing method such as a gravure printing, and is dried. Also, the image receiving layer 4 is formed in such a manner that a composition obtained by dissolving or dispersing a composition for the image receiving layer prepared by mixing an ultraviolet ray hardening resin and other required resin or the like, with a solvent, is applied on the metal plate base material 2 or the surface of the backing layer 3 by an application method such as an air knife coater, and is dried.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing metal plate used for producing a metal decorative plate. More specifically, the present invention relates to a transfer printing metal plate capable of transferring an image such as a picture or a pattern from a printing paper, and particularly to a transfer printing metal plate that can be suitably used for sublimation printing.

[0002]

2. Description of the Related Art Metallic decorative boards (decorative metal sheets) with images such as patterns and grain patterns on kitchen utensils such as system kitchens, furniture such as storage furniture, architectural interior materials, cabinets for light electrical equipment, and the like. In particular, decorative steel plates are used.
As a method of forming an image such as a pattern or a pattern on the surface of a metal plate to produce a metal decorative plate, an image is directly printed on the surface of a metal substrate by offset printing, gravure printing, or the like, or the image is printed. There is a method of laminating a printed resin film on the surface of a metal substrate via an adhesive layer. JP-A-6-247097 describes a method of forming an image on a surface of a metal substrate using an on-demand printer such as an electrostatic plotter or an inkjet printer without using a printing plate. . In addition, Japanese Unexamined Patent Publication
JP-A-246870 discloses a method of outputting an image on the surface of a resin film by using an on-demand printer such as an electrostatic plotter or an inkjet printer, and laminating the obtained patterned resin film on a metal substrate. Is described.

[0003] As another method, an image is formed on a recording paper for textile printing using a pigment ink by offset printing, gravure printing, or an on-demand type printing method, and the obtained pigment printed paper is adhered to a metal substrate. It is also known to transfer an image to the surface of a metal substrate by heating or pressurizing. However, pigments are not transparent. For this reason, when performing pigment printing on a metal substrate, the color and texture of the base are concealed due to the formed image. Cannot be expressed sufficiently.

In JP-A-49-17450, an image is gravure-printed on a recording paper for printing using a sublimation dye, and the obtained sublimation printing paper and a metal substrate are brought into close contact with each other and heated. A method for transferring a highly transparent image to the surface of a metal substrate has been proposed. The metal substrate is
No dyeing property for sublimation dyes. For this reason, in order to perform sublimation printing on a metal substrate, a dye receiving layer is provided on the metal substrate. Then, the dye receiving layer forming surface of the metal substrate and the image printing surface of the sublimation printing paper face each other and are brought into close contact with each other,
The image is transferred by heating. Since the sublimation dye has high transparency, the sublimation printing can produce a decorative metal plate that makes full use of the metallic luster of the base. In addition, when the transparency of the image is high, the intermediate color reproduced by overlapping the colors becomes beautiful.

[0005]

SUMMARY OF THE INVENTION The present inventors use a wet developer in which a sublimation dye is dispersed, and use an on-demand type printing system utilizing an electrostatic action such as an electrostatic plotter or an ion printer to print on a recording paper. The image was output to a sublimation printing paper. Then, using the obtained sublimation printing paper, sublimation printing was performed on the dye receiving layer of the metal substrate.

[0006] However, if the dye receiving layer forming surface of the metal substrate and the image output surface of the sublimation printing paper face each other and are closely contacted and heated, the result is that the sublimation printing paper and the dye receiving layer are easily thermally fused. became. When the printed paper is forcibly removed from the metal substrate, in a severe case, the so-called abnormal transfer occurs in which the image output surface of the printed paper is thinly peeled off and remains on the dye receiving layer. In addition, when the heating temperature at the time of transfer is reduced to avoid thermal fusion between the sublimation printing paper and the dye receiving layer, the transfer of the sublimation dye is reduced, and the density of the transferred image becomes insufficient. .

The present invention has been accomplished in view of the above situation, and a first object of the present invention is to provide a metal plate for transfer printing which is less likely to cause thermal fusion with a printing paper, especially a sublimation printing paper. It is in. A second object of the present invention is to
An object of the present invention is to provide a metal plate for transfer printing which can form an image having a sufficient density without causing thermal fusion with sublimation printing paper.

[0008]

In order to solve the above first and second objects, in the present invention, at least an image receiving layer containing an ultraviolet curable resin is provided on a metal plate substrate. A metal plate for transfer printing is provided.

When an ultraviolet curable resin is added to an image receiving layer such as a pigment receiving layer or a dye receiving layer which forms an image receiving surface of a transfer printing metal plate, thermal fusion of the printed paper hardly occurs. In particular, in the case of sublimation printing, if the heating temperature of the printing is lowered in order to avoid the thermal fusion of the printed paper, the transfer of the sublimation dye is reduced, and the density of the transferred image tends to be insufficient. On the other hand, when sublimation printing is performed with the addition of an ultraviolet curable resin to the dye receiving layer, the heating temperature of the transfer should be set sufficiently high to increase the transfer amount of the sublimation dye to the dye receiving layer. However, thermal fusion between the dye receiving layer and the sublimation printed paper can be prevented. Therefore, the image receiving layer 4 containing an ultraviolet curable resin is particularly effective when sublimation printing is desired.
The ultraviolet curable resin having a functional group number of 2 or more and less than 4 has excellent dyeing properties for a sublimation dye. Therefore, when preparing a metal plate for sublimation printing, it is preferable to use an ultraviolet curable resin having a functional group number of 2 or more and less than 4.

[0010] Among the ultraviolet curable resins, it is preferable to use polyester acrylate and / or urethane acrylate. The coating amount of the image receiving layer containing the ultraviolet curable resin is preferably in the range of 0.5 to 20 g / m ² .

In addition, by forming an underlayer to which a pigment is added between the metal plate substrate and the receiving layer, it is possible to adjust the feel and the ground color of the base of the decorative metal plate. In particular, when sublimation printing is performed, the transparency of the sublimation dye is high, so that the metal plate substrate below the image may be seen through. Therefore, in the case of sublimation printing, it is extremely effective to add a pigment to form an underlayer whose ground color and texture are adjusted.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. FIG. 1 is a diagram schematically showing a cross section of an example (1) of a printing metal plate according to the present invention. In FIG. 1, a metal plate 1 for transfer printing according to the present invention is provided with a base layer 3 on the surface of a metal plate base 2 and further provided on the base layer with an image receiving layer 4 containing an ultraviolet curable resin. It was done.

The metal plate substrate 2 is a known metal plate conventionally used as a decorative metal plate, for example, a steel plate such as a stainless steel plate, a plated steel plate, a cold rolled steel plate, or a non-ferrous metal such as an aluminum plate. A plate can be used. Further, a metal molded body having a three-dimensional shape can also be used as the metal plate base material. The metal plate for transfer printing of the present invention may be a three-dimensional molded body.

The image receiving layer 4 containing an ultraviolet curable resin is
It may be formed directly on the surface of the metal plate substrate 2,
Etc. may be formed via an intermediate layer. When the adhesion between the metal plate substrate 2 and the image receiving layer 4 is poor, it is preferable to interpose an underlayer for assisting the adhesion between the two. Further, even when the adhesion between the metal plate substrate 2 and the image receiving layer 4 is good, it is possible to form a base layer to which a pigment is added to adjust the texture and ground color of the base of the decorative metal plate. .

In particular, when sublimation printing is performed, the transparency of the sublimation dye is high, so that the metal plate base material below the transferred image can be seen through, and the design of the metal decorative plate may be impaired. . In such a case, if the image receiving layer is formed via a white base layer, for example, a beautiful image can be formed without being affected by the color and texture of the base material. Therefore, in the case of sublimation printing, it is extremely effective to add a pigment to form an underlayer whose ground color and texture are adjusted.

As a binder for the underlayer, a resin having high adhesiveness is used for both the metal plate substrate and the image receiving layer. For example,
Examples thereof include a vinyl chloride resin, a polyester resin, an acrylic resin, a fluorine resin, and a urethane resin. Known pigments can be added to the underlayer. For example, those used for pigment printing described below may be used. In addition, additives such as a surface roughening agent and an adhesion enhancer may be added to the underlayer as needed. When the pigment is added to the underlayer, usually 5 to 200 parts by weight of the pigment is added per 100 parts by weight of the binder resin.

In order to form an underlayer on a metal plate base material, components such as a binder resin and other necessary pigments are mixed with an organic solvent such as toluene, methyl ethyl ketone, ethanol, isopropyl alcohol, cyclohexane, and DMF. A base layer coating solution is prepared by dissolving or dispersing in a mixed solvent of a solvent and water. Then, the obtained coating liquid may be applied and dried on the surface of the metal plate substrate by a known method such as gravure printing, screen printing, or reverse coating printing using a gravure plate. The thickness of the underlayer is
Usually, it is about 1 to 100 μm.

On the image receiving surface of the metal plate for transfer printing of the present invention,
An image receiving layer 4 such as a pigment receiving layer or a dye receiving layer is provided with or without the underlayer 3 interposed therebetween. Since the metal plate substrate does not have dye-dyeing properties, when performing sublimation printing,
A dye receiving layer must be provided on a metal plate substrate. In addition, the pigment ink can exhibit adhesiveness to the metal plate base material by selecting a specific binder. Therefore, when performing pigment printing, it is not necessary to provide a pigment receiving layer. A pigment receiving layer is often provided in order to enhance the transfer or to enhance the transferability from the pigment printed paper to the metal plate substrate during transfer. When an ultraviolet-curable resin is used as such a dye-receiving layer or a pigment-receiving layer, thermal fusion of printed paper hardly occurs.

The image receiving layer 4 containing an ultraviolet curable resin is
In both cases of sublimation printing and pigment printing, heat fusion can be effectively prevented. In particular, in the case of sublimation printing, if the heating temperature of the printing is lowered in order to avoid the thermal fusion of the printed paper, the transfer of the sublimation dye is reduced, and the density of the transferred image tends to be insufficient. On the other hand, when sublimation printing is performed with the addition of an ultraviolet curable resin to the dye receiving layer, the heating temperature of the transfer should be set sufficiently high to increase the transfer amount of the sublimation dye to the dye receiving layer. However, thermal fusion between the dye receiving layer and the sublimation printed paper can be prevented. Therefore,
The image receiving layer 4 containing an ultraviolet curable resin is particularly effective when sublimation printing is desired.

Examples of the ultraviolet curable resin include acrylates having 1 to 6 functional groups, methacrylates, polyester acrylates, urethane acrylates, epoxy acrylates and the like. Specific examples of the acrylate include Aronix M-101 and M-10.
2, monofunctional acrylates such as M-120 (all manufactured by Toa Gosei Chemical); Aronix M-210, M-21
5, bifunctional acrylates such as M-240 (all manufactured by Toa Gosei Chemical Co., Ltd.); and Aronix M-305, M
Examples thereof include trifunctional acrylates such as -315 (all manufactured by Toa Gosei Chemical Co., Ltd.).

Specific examples of the polyester acrylate include beam sets 700 (number of functional groups: 6), 710 (number of functional groups: 4), 720 (number of functional groups: 3), and 750 (number of functional groups: 2). Arakawa Chemical Industry Co., Ltd.); Aronix M-6100 (functional group number 2),
M-6200 (functional group number 2), M-6250 (functional group number 2), M-6400 (functional group number 2), M-65
00 (functional group number 2), M-7100 (functional group number 3),
M-8030 (functional groups 3 to 4), M-8060
Aronix series (manufactured by Toa Gosei Chemical Co., Ltd.) such as (functional groups 3 to 4); and Kayarad PA-R300 (functional groups 4.1) and PA-R400 (functional groups 4.
1) and the Kayarad PA-R series (manufactured by Nippon Kayaku Co., Ltd.) such as PA-R500 (functional group number: 4.1).

Specific examples of urethane acrylate include:
Beam set 502H (functional group number 2), 504H (functional group number 2), 505A-6 (functional group number 2), 510
(Functional group number 2), 550B (functional group number 3), 551
Beam set 500 series (manufactured by Arakawa Chemical Industry Co., Ltd.) such as B (functional group number 2) and 575 (functional group number 6); Kayarad UX-2201 (functional group number 2), UX-2301
(Functional group number 2), UX-3204 (functional group number 2), UX-3301 (functional group number 2), UX-4101 (functional group number 2), UX-6101 (functional group number 2), UX
Kayarad UX series (manufactured by Nippon Kayaku Co., Ltd.) such as -7101 (functional group number 2) and UX-8101 (functional group number 2);
And Aronix M-1100 (functional group number 2), M-1200 (functional group number 2), M-1210 (functional group number 2), M-1310 (functional group number 2), M-160
Aronix M-1000 series (manufactured by Toa Gosei Chemical Co., Ltd.) such as 0 (functional group number 2) can be exemplified.

Specific examples of the epoxy acrylate include:
Kayarad R-011 (functional group number: 4.1), R-30
0 (number of functional groups: 4.1), R-130 (number of functional groups: 2),
R-190 (functional group number 2), EX-2320 (functional group number 2), R-205 (functional group number 4.1), R-1
Kayarad R & EX series (manufactured by Nippon Kayaku Co., Ltd.) such as No. 31 (functional group number 2), R-146 (functional group number 2) and R-280 (functional group number 2) can be exemplified.

Among these UV-curable resins, it is preferable to use one or more resins selected from polyester acrylate and urethane acrylate.

It is preferable that the number of functional groups of the ultraviolet curable resin is 2 or more. Here, the number of functional groups means the average number of functional groups contained in individual monomer units or oligomer units constituting the resin molecule. When the number of functional groups in the ultraviolet curable resin is 1, the coating film properties are often poor even after curing. When the number of functional groups of the ultraviolet-curable resin is 2 or more and less than 4, the resin has excellent dyeability to a sublimation dye. Therefore, when preparing a metal plate for sublimation printing, it is preferable to use an ultraviolet curable resin having a functional group number of 2 or more and less than 4.

The image receiving layer 4 may contain an additive such as an initiator, a diluting monomer, an ultraviolet ray blocking agent, and an appropriate amount of a coloring agent together with the ultraviolet curable resin. The image receiving layer 4 may contain, together with the ultraviolet curable resin, a resin component having excellent dyeing properties, adhesion properties, or fixing properties with respect to coloring materials such as pigments and sublimation dyes.

As the curing initiator, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one (Darocur 1173, manufactured by Merck), 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba-Geigy), 1- (4-isopropylphenyl) -2-
Hydroxy-2-methylpropan-1-one (Darocur 1116, Merck), benzyl methyl ketal (Irgacure 651, Ciba-Geigy), 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholinopropanone-1 (Irgacure 907, Ciba-Geigy), 2,4-diethylthioxanthone (Kayacure DETX, manufactured by Nippon Kayaku) and ethyl p-dimethylaminobenzoate (Kayacure EPA, manufactured by Nippon Kayaku) Of isopropylthioxanthone (Kuntacure.
ITX, manufactured by World Brekinsop Co., Ltd.) and ethyl p-dimethylaminobenzoate. Among these, liquid 2-hydroxy-2-methyl-1-
Phenylpropan-1-one is particularly preferred in terms of compatibility with resin-forming materials such as monomers or oligomers.

As the resin component having excellent adhesion or fixability to the pigment, for example, a known thermoplastic resin used for forming an image receiving surface of an image receiving sheet for hot melt transfer can be used. More specifically, synthetic rubber such as styrene butadiene rubber, acrylic resin, methacrylic resin, polyvinyl ether resin, vinyl acetate resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin,
Examples thereof include a styrene resin, a polyester resin, a polyamide resin, and a polyvinyl butyral resin.

As the resin component having excellent dyeing or fixing properties with respect to the sublimation dye, a known thermoplastic resin used for forming an image receiving surface of an image receiving sheet for sublimation heat transfer can be used. More specifically, polyvinyl chloride,
Halogenated polymers such as polyvinylidene chloride; polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride
Vinyl resins such as vinyl acetate copolymer, polyacrylester, polystyrene, and polystyrene acryl; acetal resins such as polyvinyl formal, polyvinyl butyral, and polyvinyl acetal; various saturated or unsaturated polyester resins; polycarbonate resins; cellulose acetate And the like. Cellulose resins such as polyolefin resins; amino resins such as urea resins, melamine resins and benzoguanamine resins.

Even when a resin component other than the UV-curable resin is added to the image-receiving layer, the UV-curable resin is usually contained in the image-receiving layer in an amount of 10% by weight or more based on all the cured resin components. Is added. In addition, as described above, the ultraviolet curable resin having a functional group number of 2 or more and less than 4 has excellent dyeability to a sublimation dye. When an ultraviolet curable resin having a functional group number of 2 or more and less than 4 is used, even if other resin components for improving dyeing properties and fixing properties of the dye are not added,
It is possible to form a dye-receiving layer that does not easily undergo thermal fusion with sublimation printed paper and has sufficient dyeing properties for sublimation dyes.

In order to form an image receiving layer on a metal plate substrate or an underlayer, first, a composition for an image receiving layer is prepared by mixing an ultraviolet curable resin with other necessary components such as a resin and additives. I do. The composition for an image receiving layer may be dissolved or dispersed in an appropriate amount of a solvent. In this case, toluene, aromatic hydrocarbons such as xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and methyl acetate, alcohols such as propanol and butanol, and these organic solvents A mixture of water, water and the like can be used. Then, the obtained composition is applied to the surface of the metal plate substrate or the underlayer by a known means such as an air knife coater, a roll coater, and a blade coater.
Thereafter, when a solvent is used, it is dried. Then, finally, the coating layer is irradiated with ultraviolet rays or ionizing radiation to be cured, whereby the image receiving layer is completed. The coating amount of the image receiving layer is not particularly limited, but is preferably about 0.5 to 20 g / m ² . When the coating amount of the image receiving layer is less than 0.5 g / m ² , there is a disadvantage that coating failure easily occurs. On the other hand, when this coating amount is more than 20 g / m ² , there are disadvantages such as ultraviolet curing failure and cost increase. is there.

By subjecting the metal plate for transfer printing of the present invention to sublimation printing or pigment printing by a known method, a decorative metal plate can be produced. For example, a wet developer in which a toner of a sublimation dye is dispersed and an electrostatic recording paper for sublimation printing are prepared, a sublimation printing paper is prepared using these, and the transfer of the present invention is performed using the obtained sublimation printing paper. When printing is performed on a printing metal plate, a decorative metal plate is completed. The sublimation printing paper and the pigment printing paper may be produced by printing such as gravure printing.

In order to prepare a wet developer in which a sublimation dye toner is dispersed, for example, a mixture of a sublimation dye, a copolymer resin for improving fixability or charging characteristics, and a charge control agent is electrically insulated. What is necessary is just to introduce | transduce into a dispersion medium and to fully disperse | distribute. As the sublimation dye, a disperse dye is preferably used. These dyes have a molecular weight of about 150 to 550, and are selected in consideration of sublimation or melting temperature, hue, light resistance, solubility in resins and developers, and the like.

For example, diarylmethane, triarylmethane, thiazole, methine, azomethine,
Xanthine, oxazine, azo and azo derivatives,
Anthraquinone derivatives, quinophthalone derivatives, spirodipyran-based, indolinospiropyran-based, fluoran-based,
Rhodamine lactam dyes are used.

For example, C.I.
I. Disperse Yellow 51, 3, 54, 79, 6
0, 23, 7, 141; I. Disperse Blue 2
4, 56, 14, 301, 334, 165, 19, 7
2, 87, 287, 154, 26, 359; I. Disperse threads 135, 146, 59, 1, 73, 6
0, 167; I. Disperse Violet 4, 1
3, 26, 36, 56, 31; I. Solvent Violet 13; C.I. I. Solvent Black 3;
I. Solvent Green 3; I. Solvent Yellow 56, 14, 16, 29, 105; C.I. I. Solvent Blue 70, 35, 63, 36, 50, 49, 11
1, 105, 97, 11; I. Solvent Red 1
35, 81, 18, 25, 19, 23, 24, 143,
146, 182 and the like.

For example, 3,3-diethyloxacyanine iodide, Astrazone Pink FG (CI.48)
015, manufactured by Bayer AG), 2,2-carbocyanine (C.I. 808), Astraphyloxine FF (C.I.
I. 148070), Astrazon Yellow 7GLL
(CI Basic Yellow 21), Aizen Carotene Yellow 3GLH (CI.48055, manufactured by Hodogaya Chemical Co., Ltd.), Aizen Carotene Red 6BH (CI.48
020) and the like; methine (cyanine) -based basic dyes such as dimethine-based and trimethine-based; diphenylmethane-based basic dyes such as auramine (CI.655); malachite green (CI.42000);
Brilliant green (C.I. 42040), magenta (C.I. 42510), methyl violet (C.I.
I. 42535), crystal violet (C.I.
42555), methyl green (C.I.684), Victorian blue B (C.I.44045) and other triphenylmethane-based basic dyes, and pyronin G (C.I.73).
9), xanthene-based basic dyes such as rhodamine B (CI. 45170) and rhodamine 6G (CI. 45160), acridine yellow G (CI. 785), and leonine AL (CI. 46075). Benzoflavin (CI.791), affine (CI.46045)
Acridine-based basic dyes, neutral red (CI.50040), Astrazone Blue BGE /
Xl 25% (CI. 50005), quinone imine-based basic dyes such as methylene blue (CI. 52015), and other basic dyes such as anthraquinone-based basic dyes having a quaternary amine. These dyes can be used as they are or in a form in which these dyes have been treated with alkali, and a counter ion exchanger or a leuco form of these dyes can also be used. When a colorless or light-colored leuco dye or the like is used in a normal state, a developer may be included in the image forming sheet side.

Further, these disperse dyes are used not only by one component but also by mixing two or more kinds. In particular, when mixed and melted, the thermal behavior greatly differs depending on what kind of mixture they form, and the vapor pressure also changes depending on the composition ratio accordingly. When it occurs, the activation energy is small and the sublimation sensitivity can be improved.

The resin for improving the fixing property includes a monomer effective for controlling the charging characteristics of the wet developer and a monomer effective for controlling the solubility and dispersibility of the wet developer in a solvent. In particular, the resin is a (meth) acrylic monomer (however, this expression expresses both acryl and methacryl, and the same applies to the following (meth) acryl). It is a resin obtained by copolymerizing a contained vinyl monomer mixture. Specific examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Having a short methylene chain such as butyl acrylate (meth)
Acrylates and the like, and nitrogen-containing acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
Acrylamide, isopropylacrylamide, methylenebisacrylamide, N-allylacrylamide, N
Acrylamide derivatives such as diacetone acrylamide, N, N-dimethylacrylamide, (meth) acrylic acid-2-hydroxyethyl ester, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, methylstyrene, Examples include monomers such as vinyl acetate. Particularly preferably, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Hexyl acrylate, methylstyrene and vinyl acetate are mentioned.

Particularly effective vinyl monomers for adjusting the solubility and dispersibility in a solvent include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate. (Meth) acrylate having a long methylene chain. Particularly preferred is 2-ethylhexyl (meth) acrylate.

The copolymer resin is obtained by copolymerizing at least one kind of a monomer suitable for controlling these charging characteristics and at least one monomer effective for controlling solubility and dispersibility in a solvent. However, the copolymerization ratio of both is 5 to 30.
% By weight, more preferably 10 to 20% by weight. If the amount is less than this, sufficient improvement in charging characteristics cannot be obtained, and if it is more than this, aggregation of the wet developer and a decrease in image density occur.

In particular, since the molecular weight of the copolymer resin affects the OD value and the image fog due to yellow, the preferred molecular weight of the copolymer resin is 50,000 to 200,000 in terms of polystyrene in terms of weight average molecular weight measured by GPC. is there. More preferably, it is 80,000 to 170,000. When the molecular weight is larger than this, fogging, that is, background stain is liable to occur, and when the molecular weight is smaller than this, the image density is reduced and image deletion is liable to occur.

As the resin for improving the charging characteristics, it is possible to use a resin such that when the resin is used as a fixing agent, the charge amount becomes too large to cause a decrease in image density. Specific examples include a monomer effective for adjusting the charging characteristics and a copolymer resin effective for adjusting the solubility and dispersibility of the wet developer in a solvent, and particularly, the resin has a basic group. It is a resin obtained by copolymerizing a vinyl monomer mixture containing a vinyl monomer.

Vinyl monomers having a basic group particularly good for controlling charging characteristics include nitrogen-containing acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; acrylamide; Isopropylacrylamide, methylenebisacrylamide, N-allylacrylamide, N-
Monomers such as acrylamide derivatives such as diacetone acrylamide and N, N-dimethylacrylamide.

Vinyl monomers effective for controlling the solubility and dispersibility in a solvent include (meth) acrylic acid-2
(Meth) acrylates having a long methylene chain, such as ethylhexyl, lauryl (meth) acrylate, and stearyl (meth) acrylate.

The copolymerization ratio of the resin is preferably such that the content of the vinyl monomer having a basic group is from 5 to 40% by weight, more preferably from 10 to 20% by weight. If the amount is less than this, the charging characteristics cannot be sufficiently improved, and if it is more than this, aggregation of the wet developer and a decrease in image density occur.

The preferable molecular weight of the resin used as the resin for improving the charging characteristics is several thousand to several hundred thousand in terms of styrene in terms of weight average molecular weight measured by GPC.
The content of the charge property improving resin is preferably 1 to 1000% by weight of the charge control agent contained in the wet developer. Particularly preferably, it is 10 to 100% by weight. If it is less than this, the effect of the charge control is small, and if it is more than this, the image density is reduced.

As the charge control agent, any charge control agent which is decomposed under sublimation thermal transfer conditions and does not harm the human body can be used as it is used in a wet developer. For example, dialkyl sulfosuccinate metal salts; manganese naphthenate, calcium naphthenate, zirconium naphthenate, cobalt naphthenate, iron naphthenate, lead naphthenate, nickel naphthenate, chromium naphthenate, zinc naphthenate, magnesium naphthenate, octylate Manganese, calcium octylate, zirconium octylate,
Iron octylate, lead octylate, cobalt octylate, chromium octylate, zinc octylate, magnesium octylate, manganese dodecylate, calcium dodecylate, zirconium dodecylate, iron dodecylate, lead dodecylate,
Metal soaps such as cobalt dodecylate, nickel dodecylate, chromium dodecylate, zinc dodecylate, magnesium dodecylate; metal salts of alkylbenzenesulfonic acid such as calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, barium dodecylbenzenesulfonate; lecithin And organic amines such as n-decylamine. Preferably,
Examples thereof include metal salts of naphthenic acid and octylic acid, and particularly preferred is zirconium naphthenate.

As the electrically insulating dispersion medium, for example, n-
Examples include paraffinic hydrocarbons, iso-paraffinic hydrocarbons, halogenated aliphatic hydrocarbons, and branched-chain aliphatic hydrocarbons. Particularly preferred are branched chain aliphatic hydrocarbons. Branched-chain aliphatic hydrocarbons are supplied by Exxon under the trade name Isopar. There are grades of Isopar E, Isopar G, Isopar H, Isopar L, Isopar M, etc.
An appropriate resin is selected according to the type of the copolymer resin.

To produce an electrostatic recording paper for sublimation printing, for example, a conductive material such as a polymer electrolyte such as a quaternary ammonium salt polymer or a surfactant is coated on the surface of paper or a heat-resistant plastic film. Prepare a conductive base paper by coating or impregnating, acrylate resin, butyral resin,
It is obtained by applying and drying a coating liquid in which an insulating resin such as a silicone resin is dissolved or dispersed to form a dielectric layer.

An electrostatic latent image is formed on the surface of the electrostatic recording paper on which the dielectric layer is formed by using an ion printer or an electrostatic plotter, and then the above-described toner of the sublimation dye is dispersed. When development is performed using the wet developer thus formed, an image of the sublimation dye is formed on the electrostatic recording paper, and a sublimation printing paper is completed. Then, the image forming surface of the obtained sublimation printed paper and the image receiving layer forming surface of the metal plate for transfer printing of the present invention face each other and are superimposed, and heating is performed at an appropriate temperature and time. The image is transferred, and a decorative metal plate is completed.

Sublimation dyes have poor light fastness compared to pigments. Therefore, it is preferable to further provide an ultraviolet cut layer on the image receiving surface of the decorative metal plate obtained by sublimation printing. To form an ultraviolet cut layer, an ultraviolet cut agent such as an organic ultraviolet absorber such as benzophenone, benzotriazole, or salicylic acid, or an inorganic ultraviolet cut agent such as zinc oxide or titanium oxide is used. With the binder resin for the layer, dissolved or dispersed in a solvent that does not adversely affect the underlayer and the already dyed image receiving surface, this is gravure printing, or reverse coater,
The coating may be performed by a coater such as a screen coater or a flow coater. As organic UV absorbers,
TINUVIN 328, KEMISORB 13, V
IOSORB90, UVINUL-35 and the like, and as an inorganic UV cut agent, ZR-10
0, 110, 120, ZnO-100, 200 (manufactured by Sumitomo Cement Co., Ltd.) and the like.

[0052]

EXAMPLES Hereinafter, the metal plate for transfer printing according to the present invention will be described in more detail through examples.

Example 1 (1) Production of Wet Developing Agent A cyan wet developing agent Cy having the following composition was produced.
First, the respective materials other than the dispersion medium for dilution were mixed, and the mixture was placed in a mixing container together with the glass beads for dispersion, and dispersed for 3 hours with a disperser (RC-5000 manufactured by Red Devil Co.), and then the glass beads for dispersion were removed. It was removed to obtain a master toner. Furthermore, 60 parts by weight of the obtained master toner was diluted with 660 parts by weight of a diluting isoper to adjust the total amount to 720 g to obtain a wet developer Cy. Further, the following cyan dye was mixed with the same amount of magenta dye (CI Di).
magenta wet developer Mg was obtained in the same manner as described above except that sparse red 60) was used. Further, the following cyan dye was replaced with the same amount of yellow dye (C.I.
I. Disperse Yellow 54) was carried out in the same manner as above, except that the yellow wet developer Y was used.
e was obtained.

<Composition of Wet Developer Cy> Varnish of 2-ethylhexyl methacrylate (EHMA) -ethyl acrylate (EA) copolymer resin (solid content: 40% by weight, dispersion medium: Isoper G (manufactured by Exxon)) , Weight ratio: EHMA / EA = 70/30, weight average molecular weight: 150,000): 10.0 parts by weight Cyan dye C.I. I. Disperse Blue
60: 4.0 parts by weight-Charge control agent Zirconium naphthenate (Nikka Naphtex Zr, manufactured by Nippon Chemical Industry Co., Ltd.): 6.0 parts by weight-Dispersion medium for master toner Trade name: Isopar G (manufactured by Exxon): 40. 0 parts by weight (subtotal: 60.0 parts by weight) Dispersion medium for dilution Isopar G (manufactured by Exxon): 660.0 parts by weight (total: 720.0 parts by weight)

(2) Measurement of Charge Amount The charge amount of toner particles was measured by the following method. A wet type developer is filled between a brass electrode plate having a spacing of 1.0 cm, a length of 5.0 cm, and a width of 4.5 cm, and a high voltage generator (type 237 manufactured by KEITHLEY) is used to fill the space between the two electrodes.
A voltage of 0 V was applied, and a current value was measured over time until 60 seconds had elapsed from the start of energization. Based on the measurements,
First, the initial total electric charge Q ₀ consumed until 60 seconds elapse from the start of energization was calculated by integrating the initial current amount (I ₀ ) at the start of energization to the current value (I ₆₀ ) after elapse of 60 seconds. .
Then, based on the current value after 60 seconds from the start of energization, and calculating a charge amount Q ₆₀ spent 60 seconds in the steady state. Then, to calculate the total charge Q _t of the toner particles by calculating the difference between the two charge amount. The equation for the above calculation is expressed as follows.

[0056]

[Equation 1] Q _t = Q ₀ −Q ₆₀ = Q ₀ −I ₆₀ × 60 seconds

Thereafter, the electrode plate on which the wet type developer was adhered was taken out of the current value measuring cell, dried, and the toner adhesion amount (M) on the electrode plate was measured. On the basis of the adhesion amount (M) and the total amount of charge Q _t, toner specific charge i.e. toner 1g
Per charge Q _t / M (μc / g) was calculated. Table 1 shows the measurement results.

[0058]

[Table 1]

(3) Development Wet developer C for sublimation printing produced as described above.
y, Mg, Ye and electrostatic plotter (VERSATEC
8900, manufactured by Xerox Co., Ltd.), solid images of Cy, Mg and Ye were respectively formed on the electrostatic recording paper to obtain a sublimation printed paper. Then, the reflection density (OD value) of each color image formed on the surface of the sublimation printed paper was measured using a Macbeth reflection densitometer (RD918). Measurement results (OD
[Paper]) is shown in Table 2.

(4) Preparation of a steel sheet for transfer printing The following coating liquid for an underlayer was prepared, and a coating liquid for an underlayer having the following composition was coated on a steel sheet having a thickness of 2 kg / m ² by a miller bar (# 24).
And dried to form a white underlayer. The coating amount after drying of the underlayer was 20 g / m ² . Next, a coating solution for an image receiving layer having the following composition was prepared, and was applied onto the underlayer using a Miyabar (# 12) and dried. The amount of coating after drying of the coating layer was 10 g / m ² . And 80m focusing type
Using a W ultraviolet lamp, the coating layer was irradiated with ultraviolet rays at an irradiation amount of 150 mJ / cm ² and cured while conveying the steel sheet at a belt speed of 6 m / min to prepare a steel sheet for transfer printing.

<Coating liquid for base layer> Acrylic resin (BR85, manufactured by Mitsubishi Rayon Co., Ltd.): 10
Parts by weight ・ Titanium white (R-820, manufactured by Ishihara Sangyo Co.): 2 parts by weight ・ Toluene: 100 parts by weight <Coating liquid for image receiving layer> ・ Ultraviolet curable resin Non-yellowing polyurethane acrylate (beam set 550B, number of functional groups) : 3, Arakawa Chemical Industries): 100 parts by weight Photoinitiator (Darocur 1173, Merck): 3
Parts by weight ・ Methyl ethyl ketone: 15 parts by weight

(5) Sublimation printing The sublimation printing paper obtained as described above and a steel plate for transfer printing are overlapped and heated at 200 ° C. for 30 seconds using a thermal transfer machine (HP-54A, manufactured by Hashima Co., Ltd.). , Cy, M on steel plate
Each pattern of g and Ye was printed and transferred. The reflection density of each color pattern formed on the steel plate was measured using a Gretag spectrophotometer. Table 2 shows the measurement results (OD [steel plate]) together with OD [paper].

(6) Calculation of apparent transfer rate Image density on steel plate formed by printing (OD [steel plate])
The apparent transfer efficiency (STY (%)) of each color was calculated from the following formula based on the image density (OD [paper]) on the sublimation printed paper before printing. Calculate the calculation results as OD (steel plate) and OD
The results are shown in Table 2 together with [Paper]. In the table, 10
The apparent transfer efficiency value exceeding 0% is due to the fact that the uncolored dye on paper is heat-transferred and colored on the steel plate.

[0064]

STY = [OD [steel sheet] / OD [paper]] × 100 (%) [Example 2] In Example 1, the same amount of acrylic resin was used instead of the acrylic resin used to form the receiving layer of the steel sheet. The same procedure was performed as in Example 1 except that bisphenol A-modified acrylate (beam set 750, functional group number: 2, manufactured by Arakawa Chemical Industries, Ltd.) was used. OD [steel plate], OD [paper] of Example 2
And STY are shown in Table 2.

Example 3 The same amount of glycerin propylene oxide adduct triacrylate (beam set 720, number of functional groups: 3, functional group: 3, Arakawa Chemical Co.) was used in place of the acrylic resin used to form the receiving layer of the steel sheet in Example 1. (Manufactured by Kogyo Co., Ltd.). Table 2 shows OD [steel plate], OD [paper] and STY of Example 3.

Example 4 The same operation as in Example 1 was performed except that the underlayer was not formed. As a result, a good image having excellent transparency was obtained on the steel plate.

Comparative Example 1 The same amount of pentaerythritol hexaacrylate (beam set 710, number of functional groups: 4; Arakawa Chemical Industries, Ltd.) was used instead of the acrylic resin used to form the receiving layer of the steel sheet in Example 1. ) Was carried out in the same manner as in Example 1 except that) was used. Table 2 shows OD [steel plate], OD [paper], and STY of Comparative Example 1.

Comparative Example 2 The same amount of dipentaerythritol hexaacrylate (beam set 700, functional groups: 6, functional group: Arakawa Chemical Industries, Ltd.) was used instead of the acrylic resin used to form the receiving layer of the steel sheet in Example 3. Ex.) Was used in the same manner as in Example 1. OD of Comparative Example 2
[Steel sheet], OD [paper] and STY are shown in Table 2.

Comparative Example 3 The same amount of thermoplastic acrylic resin (BR-10) as in Example 4 was used instead of the non-yellowing polyurethane acrylate used to form the receiving layer of the steel sheet.
1, manufactured by Mitsui Toatsu Co., Ltd.) except that the toluene solution was coated with a Miyabar. However,
The steel sheet and the printed paper were thermally fused.

Comparative Example 4 The same amount of thermoplastic acrylic resin (BR-8) as in Example 4 was used instead of the non-yellowing polyurethane acrylate used to form the receptor layer of the steel sheet.
5, manufactured by Mitsui Toatsu Co.) was carried out in the same manner as in Example 4, except that the solution was coated with a Miyabar. However,
The steel sheet and the printed paper were thermally fused.

Comparative Example 5 Instead of the non-yellowing polyurethane acrylate used for forming the receiving layer of the steel sheet in Example 4, the same amount of thermoplastic acrylic resin (BR-8) was used.
5, manufactured by Mitsui Toatsu Co., Ltd.) and the transfer temperature was set to 150 ° C. in order to avoid thermal fusion. As a result, thermal fusion could be avoided. However, the transfer density was low.

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

The metal plate for transfer printing of the present invention is less likely to cause thermal fusion with printed paper for sublimation printing or pigment printing. And
If sublimation printing is performed using the metal plate for transfer printing of the present invention, even if the heating temperature for transfer is sufficiently increased to increase the transfer amount of the sublimation dye to the dye receiving layer, the dye receiving layer and the sublimation printing paper are used. Can be prevented from being fused by heat, and a good image having a high density can be transferred.

[Brief description of the drawings]

FIG. 1 is a view schematically showing a cross section of a metal plate for transfer printing according to the present invention.

[Description of Signs] 1 ... Transfer printing metal plate 2 ... Metal plate base material 3 ... Underlayer 4 ... Image receiving layer

Claims (6)

[Claims] 1. A metal plate for transfer printing, wherein at least an image receiving layer containing an ultraviolet curable resin is provided on a metal plate substrate. 2. The transfer printing metal plate according to claim 1, wherein an image receiving layer containing an ultraviolet curable resin having a functional group number of 2 or more and less than 4 is provided. 3. The transfer printing metal plate according to claim 1, wherein the ultraviolet curable resin is polyester acrylate and / or urethane acrylate. 4. The coating amount of the image receiving layer is 0.5 to 20 g.
/ M ² , wherein the metal plate for transfer printing is according to claim 1. 5. The transfer printing metal plate according to claim 1, wherein the image receiving layer is formed on the metal plate base via a base layer containing a pigment. 6. The transfer printing metal plate according to claim 1, wherein the image receiving layer is a dye receiving layer capable of receiving a sublimation dye.