JP2000335119A - Manufacture of receptive sheet for heat transfer recording and receptive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a receptive sheet for heat transfer recording which is excellent in a transfer density, a resistance to fingerprint, a resistance to light and preservability without changing performance of the receptive layer resin, excellent in a fusion resistance, a separating property from ribbon and a running property, having a high luster. SOLUTION: The manufacturing method of a receptive sheet for heat transfer recording includes the process of coating of a resin for a receptive layer on a substrate, the forming process of the receptive layer by curing the resin for receptive layer under a condition that a formed body containing a parting agent is contacted with the surface of the coating, and the separating process of the receptive sheet from the formed body containing the parting agent. In this case, less than 0.03 g/m2 of organopolysiloxane exists on the surface of the receptive layer, and the existence of silicon element on the surface of the receptive layer measured by the ESCA method is specified to be 1-30%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording receiving sheet for a printer which transfers a dye by heat to form a dyed image. More specifically, the present invention relates to a method for producing a receptor sheet suitable for sublimation dye thermal transfer recording which can be used for high-quality full-color images and the like.

[0002]

2. Description of the Related Art In recent years, a thermal printer capable of printing a compact and clear full-color image, particularly a dye thermal transfer printer, has attracted attention. This dye thermal transfer printer is often used for OHP, card transfer, video image, computer graphics, print proofing, etc. as a mainstream of small non-impact full color printers. For these uses,
A sufficient image cannot be obtained by the conventional fusion type thermal transfer system, and a sublimation type dye thermal transfer system has recently been adopted. The present invention
Mainly related to sublimation type dye thermal transfer receiving sheet,
Hereinafter, the sublimation dye thermal transfer receiving sheet will be described.

In a dye thermal transfer printer, a dye-coated surface of an ink sheet in which yellow, magenta, and cyan dye inks are coated on a film, and a surface of a receiving sheet coated with a dye-dyeing receiving resin, are overlapped. The dye of the ink sheet is transferred by the heat supplied from the thermal head according to the electric signal corresponding to the desired image, and the receiving sheet is dyed to form an image.

[0004] A conventional thermal transfer receiving sheet is provided with a dye receiving layer mainly composed of a thermoplastic resin such as polyester, polyamide, cellulose acetate or acrylic resin on a support such as paper, synthetic paper or a film filled with white pigment. It was manufactured by coating. Technical issues associated with high-speed printing, higher definition of images, and downsizing of printers in dye thermal transfer printers include the prevention of thermal fusion between the ink sheet and the receiving sheet during printing, and mild peeling failure ( This is referred to as sticking phenomenon), and the friction between sheets is reduced.

[0005] To solve these problems, a method of applying a release agent on the receiving layer or a method of bleeding out the release agent previously mixed in the resin of the receiving layer (Japanese Patent Publication No. 5-254265). JP-A-6-94232). Also, although not a thermal transfer recording receiving sheet, as a method of localizing the release agent on the surface of the receiving layer,
A method has been proposed in which a release agent supply sheet and a receiving layer are treated under heat / pressure (JP-A-8-238859).

However, in the method of applying a release agent, since the release agent layer is too thick, the dye transferability of the resin of the receiving layer is originally inhibited, the transfer density is reduced by the release agent, and the image bleeds. . In addition, in the method of bleeding out the release agent, the amount of the bleedout of the release agent cannot be controlled due to the influence of seasonal factors, work environment, and the like, and at present, the effect of the release agent cannot be sufficiently obtained. On the other hand, in the method of treating the release agent supply sheet and the receiving layer under heat / pressure,
High temperature and pressure are required, and the amount of release agent to be transferred is large,
In addition, it was difficult to apply this technique to a thermal transfer recording receiving sheet because of poor adhesion to the receiving layer resin.

In recent years, with the spread of digital signals,
There is a growing desire to easily and personally obtain photo-like images, and there is a further need to develop a high-speed dye thermal transfer printer and a high gloss transfer receiving sheet. When the printing speed is increased by the thermal transfer method, the dye must be transferred in a short time, and the thermal energy applied to the thermal head increases. The problem of the occurrence of the ribbon peeling line resulting from the problem becomes more serious.

There is also a high demand for a photo-like receiving sheet for a high-quality thermal transfer, and there is a demand for a mirror-like surface and a high gloss on the surface on which an image is printed, but as the gloss increases, the smoothness of the surface of the receiving layer increases. Therefore, there is a tendency that the occurrence of fusion and peeling lines during printing as described above is further promoted.
In addition, with the smoothing of the surface of the receiving layer, there is also a concern about the problem of runnability that two sheets of paper are fed while being overlapped during printing.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides excellent transfer density, fingerprint resistance, light resistance, storage stability, fusion resistance, and peelability from a ribbon without changing the performance of the receiving layer resin. It is another object of the present invention to provide a method for producing a thermal transfer recording receiving sheet having good running properties and high gloss.

[0010]

In order to solve the above problems, the present invention employs the following manufacturing method. That is, the first invention of the present invention relates to a method for producing a thermal transfer recording receiving sheet having a dye receiving layer provided on at least one surface of a support, wherein (1) a resin for a receiving layer is coated on the support. Process,
(2) a step of curing the resin for the receiving layer to form a receiving layer in a state where the molded body containing the release agent is brought into contact with the coated surface, and (3) a molded article containing the releasing agent. A method for producing a receiving sheet for thermal transfer recording, comprising the step of separating a receiving sheet from a receiving sheet.

According to a second aspect, in the first aspect,
The molded article containing the release agent is a method for producing a thermal transfer recording receiving sheet, which is a molded article having a release agent-containing layer on a substrate or a resin molded article containing the release agent.

A third invention is a method for producing a thermal transfer recording receiving sheet according to the above inventions, wherein the release agent is an organopolysiloxane.

According to a fourth aspect, in the second aspect,
Thermal transfer, in which a layer containing a release agent is a cured organopolysiloxane-based resin layer, and a resin mold containing the release agent is a cured resin-containing organopolysiloxane. This is a method for producing a receiving sheet for recording.

According to a fifth aspect, in the fourth aspect,
In the resin layer or the resin molded product, the organopolysiloxane has a methyl group bonded to silicon of a polysiloxane skeleton, and is measured at room temperature for protons derived from the methyl group measured by a solid NMR pulse method. Wherein the relaxation time (T _{1 ρ} ) obtained is 0.02 sec or more.

In a sixth aspect based on any one of the first to fifth aspects, the step of curing the resin for the receptor layer is performed by irradiating an active energy ray. The method for producing a thermal transfer recording receiving sheet according to any one of the above.

The seventh invention of the present invention is directed to a thermal transfer recording receiving sheet having a dye receiving layer obtained by curing a curable resin on at least one surface of a support. A receptor sheet for thermal transfer recording, characterized in that an organopolysiloxane of less than 0.03 g / m ² is present and silicon is 1 to 30% in terms of the proportion of elements on the surface of the receptor layer as measured by the ESCA method. It is.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION As the release agent used in the present invention, any type of release agent known and used without particular limitation can be used, and solid wax, fluorine-based or phosphate-based surfactants can be used. And a fluorine-based resin, but an organopolysiloxane having a polysiloxane skeleton is preferable.

The organopolysiloxane includes silicone oil, silicone rubber, silicone resin, silicone fine powder, and the like. Silicone oil includes fiber treatment agents, release agents, water repellents, resin modifiers, defoamers Agent, foam stabilizer,
Includes grease compounds, electrical insulating oils, organically modified silicone oils, and curable silicone oils.

In the present invention, solid materials such as silicone rubber and silicone resin are preferably used. Among them, a part of the polysiloxane chain is cross-linked two-dimensionally or three-dimensionally by a cross-linking reaction. Are preferred. Before crosslinking, it may be liquid. Thus, the partially crosslinked organopolysiloxane is generally
This is called silicone for release paper, and is hereinafter abbreviated as silicone for release paper. In the present invention,
The reason why silicone for release paper is suitable is as follows.

That is, when the glass transition point and the softening point of the receiving layer resin are low, high transfer density and high image quality are easily obtained, but generally, the receiving layer resin is softened by the energy applied from the thermal head and shows tackiness. It is easy to cause fusion during printing, generation of ribbon peeling line, and poor running property. In order to prevent the above-mentioned failure without changing the performance of the receiving layer, a very small amount of silicone must be present on the surface of the receiving layer. In addition, in order to transfer only a preferable trace amount, the silicone needs to be appropriately crosslinked.

The degree of cross-linking can be determined by measuring the surface of the molded article containing the release agent before being transferred to the surface of the receptor layer (the resin layer containing solid organopolysiloxane as a main component or the resin molding containing solid organopolysiloxane). The resin on the body surface) can be selected by measuring the resin by a solid NMR pulse method. That is, the relaxation time (T1ρ) of a proton derived from a methyl group bonded to silicon of a polysiloxane skeleton measured at room temperature, which is measured by a solid NMR pulse method, is as follows:
It is good to select a thing of 0.02 sec or more. Since the amount of the release agent migrating to a trace amount can be increased as the relaxation time is increased, the relaxation time may be selected according to the intrinsic quality of the receiving layer resin. Relaxation time 0.02s
If it is smaller than ec, the amount of the release agent migrating to an extremely small amount will be at an insufficient level, and the effects on the fusion during printing, the ribbon peeling line, and the running property will not be sufficient.

Preferably, the organopolysiloxane present on the surface of the receiving layer is less than 0.03 g / m ² ,
Less than 0.01 g / m ² is more preferred. If the amount is too large, the transfer density is lowered, bleeding, fingerprint resistance, light resistance and the like are deteriorated. Since it is difficult to measure such a small amount of weight, a method of controlling the abundance of silicon by measuring the abundance ratio of silicon by the ESCA method is actually good. That is, when the surface of the receiving layer is analyzed by the ESCA method, the content ratio of the element is measured.
% Means that the proper amount of silicone has been transferred. The ratio of the silicon is more preferably 10 to 10.
26%.

As the silicone for release paper used in the present invention, any known and used silicone for release paper can be used without any particular limitation, and specific examples thereof include a solvent type, an emulsion type and a non-solvent type. . The solvent type and the emulsion type include an addition type reaction type and a condensation type reaction type, and the non-solvent type includes an addition reaction type, an ultraviolet curing type and an electron beam curing type. Addition-type silicone is generally a solvent-type addition-reaction silicone obtained by the addition reaction of a dimethylsiloxane / methylvinylsiloxane copolymer and polymethylhydrogensiloxane in the presence of a platinum catalyst. In some cases, a dimethylsiloxane / methylhexenylsiloxane copolymer is used instead of the dimethylsiloxane / methylvinylsiloxane copolymer, and a cured film can be obtained at a lower temperature than a general one.

The condensation reaction type silicone is obtained by reacting silanol polydimethylsiloxane at both ends with polymethylhydrogensiloxane or polymethylmethoxysiloxane in the presence of a catalyst such as a tin compound to form a cured film. Since a very small amount of tin remains in the formed film,
It is environmentally preferable not to use it unless it is applied to a support containing an addition reaction type nitrogen, sulfur, phosphorus compound or the like which is a catalyst poison of a platinum catalyst. UV-curable and electron beam-curable silicones include hydrosilylation addition reaction types, those that contain epoxy groups in silicone and undergo cationic polymerization, those that undergo radical addition reactions with mercapto groups and vinyl groups, and those that undergo radical polymerization with acrylic groups. And the like.

More specifically, examples of the silicone for additional release paper include SD7333 and SD723.
7, SRX357, BY24-179, SP7259,
LTC300B, LTC1000M (all manufactured by Dow Corning Toray), KM3950, KS3703, KS
776 (manufactured by Shin-Etsu Chemical Co., Ltd.), and condensation-type release silicones such as SRX290, SD7206 (manufactured by Dow Corning Toray), X52-170 (manufactured by Shin-Etsu Chemical), and active energy ray-curable silicone include BY24
-536, BY24-551A / B (manufactured by Dow Corning Toray) and X62-7296A · B (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited thereto.

Next, a molded product containing a release agent will be described. In the present invention, in a state where the resin for a receiving layer is coated on a support and has fluidity, the resin for a receiving layer is cured while being in contact with a molded product containing a release agent. is there. Thereafter, the receiving sheet and the molded body are separated.In this case, a very small amount of the release agent is transferred to the surface of the receiving layer, and the release agent is transferred while the resin for the receiving layer is being cured. Is firmly fixed to the surface of the receptor layer.

The molded article containing the release agent may be in the form of a roll or a sheet. The first embodiment of the molded article containing a release agent is a molded article that is a release agent resin or a resin molded article in which a release agent is mixed in a synthetic resin. As the synthetic resin, a commonly used synthetic resin such as polyolefin, polyester and polyamide can be used. In the case of the first embodiment, the molded body is preferably in the form of a sheet, and the sheet needs to be flexible and excellent in smoothness.

A second embodiment of the molded article containing a release agent is a molded article in which a layer containing a release agent is formed on a substrate. The layer containing the release agent is a release agent resin layer or a resin layer in which a release agent is mixed in a synthetic resin. In this case, any of metal, ceramic, and synthetic resin can be used as the substrate. Also, when using a synthetic resin for the layer containing a release agent, as the synthetic resin, such as polyolefin, polyester, polyamide,
Conventionally used synthetic resins can be used.

In the second embodiment, the substrate may be in the form of a roll. However, in practice, the substrate is preferably in the form of a sheet. The material is not limited, but specifically, a plastic film such as polyethylene terephthalate, synthetic paper, metal sheet, resin-coated paper, metal-deposited film,
Metal-deposited paper is preferred. If the support is not sufficiently smooth, the surface roughness is transferred to the surface of the receiving sheet for thermal transfer recording, and a receiving layer having a high gloss surface cannot be obtained. As an example, a polyethylene terephthalate film having a thickness of 20 to 150 μm is preferable. When the layer containing the release agent is a silicone resin layer for release paper, the resin is used as a solvent liquid, a crosslinking agent is mixed, and the thickness after drying is 0.2 to 5 μm.
It is a simple method to form a release agent resin layer by applying and drying to a degree.

As the resin forming the receiving layer of the receiving sheet of the present invention, a thermoplastic resin, a thermosetting resin, or an active energy ray-curable resin can be used. As the thermoplastic resin, those used in the above-described conventional receiving layer for thermal transfer recording can be used, but it is necessary to mix a substance that is cross-linked by heating or active energy rays to cure the receiving layer. . In the case of a thermoplastic resin, a liquid obtained by dissolving the resin in a solvent is applied, but it is necessary to contact the molded product containing the release agent and cure while the solvent is in a fluid state where the solvent is not completely dried. The production conditions must be carefully examined. The same applies to thermosetting resins, by mixing a curing agent with the resin,
It may be diluted with a solvent, if necessary, applied on a support, and cured while contacting a molded product containing a release agent in a fluid state. The most suitable for the receiving layer of the present invention is an active energy ray-curable resin, and in the active energy ray-curable resin, a thermoplastic resin,
A thermosetting resin may be mixed. Hereinafter, the active energy ray-curable resin will be described in detail.

The active energy ray-curable resin used in the receptor layer of the present invention is obtained by irradiating an active energy ray-curable composition with an active energy ray and curing the composition to form a receptor layer. Known active energy ray polymerizable monomers and active energy ray polymerizable oligomers can be used as the active energy ray curable composition. In the following description, acrylic and methacryl are collectively referred to as (meth)
Notation like acrylic.

Examples of the active energy ray polymerizable monomer include (1) aliphatic, alicyclic and araliphatic mono- to hexavalent alcohols and (meth) acrylates of polyalkylene glycols. (2) aliphatic and alicyclic (Meth) acrylates obtained by adding an alkylene oxide to an aromatic or araliphatic mono- to hexavalent alcohol (3) poly (meth) acryloylalkyl phosphates (4) polybasic acids and polyols (5) Reaction product of isocyanate, polyol, (meth) acrylic acid (6) Reaction product of epoxy compound and (meth) acrylic acid (7) Epoxy compound, polyol, (meth) ) Reaction products of acrylic acid (8) Reaction products of melamine and (meth) acrylic acid, etc. If, it preferably contains a compound having a hexahydrophthalic imide skeleton.

More specifically, the above-mentioned general active energy ray polymerizable monomers are methyl acrylate, ethyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl. Methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2
-Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclohexyl acrylate, isobornyl acrylate, isobornyl methacrylate, benzyl acrylate, Benzyl methacrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypropylene glycol acrylate, phenoxy polyethylene glycol acrylate, phenoxy polypropylene glycol acrylate, ethylene oxide-modified phenoxy acrylate,
N, N-dimethylaminoethyl acrylate, N, N
-Dimethylaminoethyl methacrylate, 2-ethylhexyl carbitol acrylate, ω-carboxypolycaprolactone monoacrylate, monohydroxyethyl phthalate, acrylic acid dimer, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid-9,10-epoxy Oleyl fluoride, ethylene glycol monoacrylate maleate, dicyclopentenyloxyethylene acrylate, 4,4-dimethyl-
1,3-dioxolane caprolactone adduct acrylate, 3-methyl-5,5-dimethyl-1,3-dioxolane caprolactone adduct acrylate, polybutadiene acrylate, ethylene oxide-modified phenoxylated phosphoric acid acrylate, ethanediol diacrylate, Ethanediol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate,
1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, Polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, neopentyl glycol diacrylate, 2-butyl-2-ethylpropanediol diacrylate, ethylene oxide-modified bisphenol A diacrylate,
Polyethylene oxide-modified bisphenol A diacrylate, polyethylene oxide-modified hydrogenated bisphenol A
Diacrylate, propylene oxide-modified bisphenol A diacrylate, polypropylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified isocyanuric acid diacrylate, pentaerythritol diacrylate monostearate, 1,6-hexanediol diglycidyl ether acrylic acid adduct, polyoxy Ethylene epichlorohydrin-modified bisphenol A diacrylate, trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, polyethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, polypropylene oxide-modified trimethylolpropane triacrylate Acrylate, pentaerythris Litol triacrylate, ethylene oxide-modified isocyanuric acid triacrylate, ethylene oxide-modified glycerol triacrylate, polyethylene oxide-modified glycerol triacrylate,
Propylene oxide-modified glycerol triacrylate, polypropylene oxide-modified glycerol triacrylate, pentaerythritol tetraacrylate,
Ditrimethylolpropane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, polycaprolactone-modified dipentaerythritol hexaacrylate, and the like. It is not limited.

The active energy ray-polymerizable oligomer usable in the present invention has a molecular weight of 400 to 5,000 having a (meth) acryloyl group at a molecular chain terminal.
A degree of active energy ray curable resin can be used. The active energy ray-polymerizable oligomer has a (meth) acryloyl group at a molecular chain terminal,
There is no particular limitation as long as the resin has a molecular weight of about 0 to 5000, and for example, polyurethane poly (meth) acrylate resins such as polyurethane-modified polyether poly (meth) acrylate and polyurethane-modified polyester poly (meth) acrylate are preferable. .

Further, the above-mentioned active energy ray polymerizable oligomer is specifically described as PEG1000, PEG200
0, PPG400, PPG700, PPG1000, PPG2000, PPG3000, PTMG
650, PTMG1000, PTMG2000, PPG700-MD, PPG1000-MD, PP
G2000-MD, EGAA1000, EGAA2000, PGAA1000, PGAA2000,
BGAA1000, BGAA2000, HGAA1000, HGAA2000, MPAA1000,
MPAA2000, NPAA2000, OA130B (all, manufactured by Arakawa Chemical) and the like, CJ8-1, CJ11-3, CJ11-4, K-7553 (all, manufactured by Nippon Kasei) and the like can be used in the present invention. The active energy ray-curable resin having a (meth) acryloyl group at a molecular chain terminal is not limited to these.

Next, the production method of the present invention will be described. Here, an active energy ray-curable resin will be described as an example of the receptor layer resin. Further, as a molded article containing a release agent, an example will be described in which a continuous winding (hereinafter, referred to as a release agent-containing film) obtained by applying and curing a silicone resin layer on a base film is used. In the manufacturing method of the present invention, the term “resin for receiving layer” is a term that includes the state of a monomer or oligomer before being cured by an active energy ray.

As a method of coating the resin for the receiving layer on the support and then bonding it to the release agent-containing film, any known and publicly-known means for bonding sheets such as paper and synthetic paper together can be used. Can be done. In the case of a single sheet sample, the workability is good if a rubber roller or a calendar used for smoothing coated paper is used.

As an example of an industrial process, a rolled-up support sheet is unwound, a curable resin solution for a receiving layer is applied with an optional coater head, and then a release agent-containing film is coated on the silicone resin layer surface. Is extended to a position where it overlaps with the receiving layer resin coating surface, is pressed with a roller, and in a state where the support coated with the receiving layer resin liquid and the release agent-containing film are bonded together, the active energy ray Is applied to cure the resin for the receiving layer, and thereafter, the release agent-containing film is peeled off with a peeling guide roller, and the support sheet having the cured receiving layer resin layer and the release agent-containing film are separately wound up. Can be mentioned. In this case, the thickness of the release agent resin layer is 0.2 to 5 μm, and a thickness of about 1/50 to 1/1000 of the thickness is transferred to the receiving layer.

As another manufacturing method, for example, when a liquid active energy ray-curable resin is applied and cured by irradiating an active energy ray while contacting the metal roll, liquid silicone is applied to the metal roll. Then, a method in which drying and curing are performed while forming an extremely thin silicone resin film is also conceivable.

The active energy rays used in the present invention include ionizing radiation such as electron beams, ultraviolet rays, and γ rays. Among these, electron beams and ultraviolet rays are preferable, and when the resin for the receiving layer is cured with active energy rays, it is preferable to perform the curing at room temperature. When heat is applied, the amount of the release agent to be transferred may not be controlled and may be excessive, or the specularity of the surface as expected may not be obtained.

When electron beam irradiation is used, the accelerating voltage is from 100 to 1,000 KV, preferably from 100 to 300 KV, and more preferably from 100 to 300 KV in terms of penetrating power and curing power. It is preferable to make it 20 Mrad. If the accelerating voltage or the amount of electron beam irradiation is lower than this range, the penetrating power of the electron beam is too low to sufficiently cure the inside of the support, and if it is higher than this range, not only does energy efficiency deteriorate. In addition, undesirable effects on quality such as a decrease in the strength of the support and decomposition of the resin and additives appear.

As the electron beam accelerator, for example, any of an electro curtain system, a scanning type and a double scanning type may be used, but a curtain beam type electron beam accelerator which is relatively inexpensive and can obtain a large output is used. preferable. In this curtain beam system, the acceleration voltage is preferably 100 to 300 KV, and the absorbed dose is preferably 0.5 to 10 Mrad.

In the electron beam irradiation, if the oxygen concentration is high, the curing of the electron beam curable resin is hindered.
Irradiation is preferably performed in an atmosphere in which replacement with an inert gas such as helium or carbon dioxide is performed and the oxygen concentration is controlled to 600 ppm or less, preferably 500 ppm or less.

In the case of ultraviolet irradiation, it is preferable to use a lamp of 80 W / cm or more. For example, low-pressure mercury lamps,
There are medium-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and the like, and there is also an ozone-less type that generates less ozone. In addition, a photoreaction initiator can be mixed with the resin. Photoinitiators include acetophenones such as di and trichloroacetophenone, benzophenone,
Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyl dimethyl ketal, tetramethylthiuram monosulfide, thioxanthones,
There are azo compounds and the like.

The thickness of the receiving layer obtained by curing the active energy ray-curable composition varies depending on the type and smoothness of the support, but is preferably 1 to 100 μm, more preferably 2 to 5 μm.
0 μm. If the thickness is less than 2 μm, sufficient dye receptivity, whiteness, and opacity cannot be obtained,
In addition, since uniform application is difficult, density unevenness occurs due to unevenness of the surface of the support, and further, the tone reproducibility of the superimposed color portion of the printed image deteriorates. On the other hand, if the thickness exceeds 50 μm, it is difficult to provide a smooth and uniform coating layer, which is not preferable in terms of quality.

In the active energy ray-curable resin composition of the present invention, various additives such as an antioxidant, an ultraviolet absorber, a dispersant, a stabilizer, a pigment and a lubricant can be added in an appropriate combination. Further, a white pigment may be added for the purpose of improving whiteness and opacity, and a fluorescent dye or a colored dye may be added for the purpose of adjusting the color tone of the receiving layer, if necessary.

Further, a layer containing an antistatic agent may be provided on at least one surface of the receiving sheet in order to prevent static electricity from being generated during traveling of the receiving sheet in the printer and causing running trouble. As the antistatic agent, a cationic hydrophilic high molecular compound can be used.

On the back surface of the thermal transfer recording receiving sheet of the present invention, a resin is formed by applying a polyolefin resin by a melt extrusion method, or by applying an active energy ray-curable composition and then irradiating with an active energy ray to form a film. A back coat layer can be provided for forming a coating layer or for preventing curling, preventing static charge, and imparting writability. The back coat layer may contain an antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like in appropriate combination.

As the support of the receiving sheet used in the present invention, ordinary natural pulp paper, coated paper,
Laminated paper, glass paper, plastic film, synthetic fiber, synthetic resin film, or synthetic paper or so-called synthetic paper or non-woven fabric made of synthetic resin film can be used. For plastic films and synthetic paper, pigments such as clay, talc, kaolin, calcium carbonate, titanium dioxide, magnesium hydroxide, metal soaps such as zinc stearate, dispersants such as various surfactants, and colored pigments One or more types may be included.
The thickness of the support is not particularly limited, but is preferably smooth and the basis weight is preferably from 30 to 300 g / m ² .

In the present invention, a precoat layer may be provided between the receiving layer and the support for the purpose of averaging unevenness of the support and improving whiteness and opacity. Examples of the material constituting such a precoat layer include inorganic coat layers such as clay, talc, kaolin, and ansilex, polyethylene (high-density polyethylene, low-density polyethylene, and medium-density polyethylene), polypropylene, polybutene, polypentene, and polyethylene terephthalate. Organic materials such as a homopolymer of a thermoplastic resin or a copolymer of two or more olefins such as an ethylene / propylene copolymer can be used, and these resins can be used alone or in combination. . Further, hollow particles may be contained for the purpose of improving the adhesion to the ink sheet and the heat insulating property of the receiving layer.

As a method for preparing the active energy ray-curable composition, a general kneader can be used. For example, two rolls, three rolls, cowless resolver,
Examples include a homomixer, a sand grinder, a planetary mixer, a ball mill, a kneader, a high-speed mixer, and a homogenizer. Further, an ultrasonic disperser or the like can be used.

Examples of the method of applying the active energy ray-curable composition on the surface of the sheet-like support include a blade coating method, an air doctor coating method, a blade coating method, a squeeze coating method, an air knife coating method, and a roll coating method. Method, gravure coating method, transfer coating method, spray coating method, comma coating method, smoothing coating method, microgravure coating method, reverse roll coating method, multi-roll coating method, dip coating method, kiss coating method, gate roll coating method, Methods such as extrusion coating, curtain coating, falling curtain coating, slide coating, fountain coating, and slit die coating are used.

[0053]

EXAMPLES The present invention will be described below in detail with reference to examples, but the contents of the present invention are not limited to the examples. Parts in Examples are parts by weight unless otherwise specified. <Example 1> A silicone (BY24-17) for release paper was formed on a polyethylene terephthalate film having a thickness of 75 µm.
9: To 100 parts of Dow Corning Toray), 0.6 part of catalyst for addition-type crosslinking reaction (SRX-212: Dow Corning Toray) was added, and the paint concentration was 5% using toluene. Thickness 0.5μ using a Meyer bar
m was applied and crosslinked and dried at 120 ° C. for 60 seconds in an explosion-proof dryer to prepare a sheet having a release agent layer. On the other hand, an acrylic monomer having a hexahydrophthalimide structure as a receiving resin for thermal transfer (TO1429: Toagosei Co., Ltd.) on a corona-treated synthetic paper having a thickness of 150 μm (trademark: FPG-150: manufactured by Oji Yuka Synthetic Paper Co., Ltd.) Made)
Using a Mayer bar, 80 parts and 20 parts of a urethane-modified acrylate oligomer of polyneopentyl glycol adipate (molecular weight: 1,000) (OA130B, manufactured by Arakawa Chemical Co., Ltd.) using a Meyer bar so that the coating amount after curing becomes 8.0 g / m ^2. After applying, and after bonding the coated surface and the release agent layer surface of a 75 μm-thick polyethylene terephthalate film having the release agent layer prepared in advance, to the multilayer body, from the polyethylene terephthalate film side Electron beam is accelerated at 175 KV, absorbed dose is 3 Mrad, oxygen concentration is 50
Irradiation under the condition of 0 ppm or less to cure the coating liquid layer,
Thereafter, the polyester film was peeled off from the electron beam-curable resin layer to obtain a thermal transfer recording receiving sheet having the electron beam-curable resin layer.

<Example 2> In forming a release agent layer in Example 1, a release silicone (SR) having a different relaxation time was used.
X357: manufactured by Dow Corning Toray Co., Ltd.), and a receiving sheet for thermal transfer recording was produced in the same manner as in Example 1.

<Example 3> In forming a release agent layer in Example 1, a release silicone (SD) having a different relaxation time was used.
7237: manufactured by Dow Corning Toray Co., Ltd.), and a receiving sheet for thermal transfer recording was produced in the same manner as in Example 1.

Example 4 In forming a release agent layer in Example 1, the release silicone (KS) having a different relaxation time was used.
839L: manufactured by Shin-Etsu Chemical Co., Ltd.), and a receiving sheet for thermal transfer recording was produced in the same manner as in Example 1.

<Comparative Example 1> After the same receiving resin for thermal transfer as in Example 1 was applied, nothing was bonded and an electron beam was applied from the coated surface side at an acceleration voltage of 175 KV, an absorbed dose of 3 Mrad, and an oxygen concentration of 500 ppm or less. Irradiation was performed under the conditions to cure the coating liquid layer to obtain a thermal transfer recording receiving sheet.

<Comparative Example 2> Instead of laminating a sheet having a release agent layer, a thickness of 75 μm without coating was applied.
A thermal transfer recording receiving sheet was obtained in the same manner as in Example 1 except that the polyethylene terephthalate film was used for bonding.

Comparative Example 3 A release silicone layer (SRX357: manufactured by Dow Corning Toray Co., Ltd.) was used as a release agent layer on the receiving sheet for thermal transfer recording obtained in Comparative Example 2 using a Meyer bar. A coating of 0.5 μm was formed, and a release agent layer was formed on the resin of the receiving layer to obtain a receiving sheet for thermal transfer recording.

Comparative Example 4 80 parts of an acrylic monomer (TO1429: manufactured by Toagosei Co., Ltd.) and polyneopentyl glycol adipate (molecular weight: 100) were used as the receiving resin for thermal transfer.
0) urethane-modified acrylate oligomer (OA13
0B: Arakawa Chemical Co., Ltd.), and a thermal transfer recording receiving sheet was obtained in the same manner as in Comparative Example 2, except that amino-modified silicone (KF393: Shin-Etsu Chemical Co., Ltd.) was added to 20 parts and 100 parts of resin to 1 part. Was.

The eight types of thermal transfer recording receiving sheets thus obtained were placed on a commercially available sublimation color video printer (trade name: UP)
5500, manufactured by Sony Corporation) to print a pattern with 16 gradations of black. <Fusion evaluation> Regarding fusing at the time of printing, a state where no fusing was observed was evaluated as ○, a state where fusing but printing was possible was evaluated as △, and a state where fusing occurred and printing was evaluated as ×, and the result was Are shown in Table 1.

<Evaluation of Ribbon Peeling> Regarding the ribbon peeling line generated in the print, there is no ribbon peeling sound at the time of printing and no trace of the ribbon peeling line is recognized on the printing screen. The state where no trace of the peeling line was observed was evaluated as Δ, and the state where ribbon peeling sound was generated and the ribbon peeling trace was clearly recognized on the printing screen was evaluated as x. The results are shown in Table 1.

<Transfer Density> The transfer density was evaluated by measuring the maximum density with a Macbeth densitometer RD-914, and the results are shown in Table 1. <Fingerprint resistance> The fingerprint resistance test of the transferred image was performed by rubbing the transferred image immediately after printing with a finger. Those with a mark were evaluated as x, and the results are shown in Table
It was shown to.

<Light fastness> The light fastness test of the transferred image was performed at 63 ° C. and 50% R using an atlas fade meter.
H, for 72 hours. In the evaluation of light fastness, the residual ratio of the image density at the initial density D = 1.0 was determined and evaluated according to the following criteria. The results are shown in Table 1. [Light Resistance Evaluation Criteria] The image density remaining rate is 85% or more,
60% or more to less than 85% is rated as Δ, and less than 60% is rated as ×.

<Runability> The runnability of the thermal transfer recording receiving sheet was measured at room temperature, high temperature and high humidity (45 ° C., 50% RH) using the above-mentioned commercially available sublimation color video printer (trade name: UP5500, manufactured by Sony). Under and low temperature (0-5
C., Dry), 100 sheets of black solid were continuously printed,
状態 indicates the state where normal printing can be performed without causing troubles on one sheet. が な い indicates that there is no problem at room temperature but one or two sheets of double-running occurs at high or low temperature. The state in which heavy running or jamming occurred even on a single sheet was evaluated as x, and the results are shown in Table 1.

<Relaxation Time> The relaxation time is determined by the solid-state NMR pulse method using a nuclear magnetic resonance apparatus (JNM-LA400, manufactured by JEOL Ltd.) using the proton relaxation time derived from a methyl group bonded to silicon of polysiloxane. T _{1 ρ} (sec)
Was measured at room temperature, and the results are shown in Table 1.

<Gloss> The gloss of the receiving sheet for thermal transfer recording was measured by a gloss meter (VG) according to JIS-Z8741.
S-1D: manufactured by Nippon Denshoku Industries Co., Ltd.), and the gloss at 60/60 degrees and 20/20 degrees was evaluated. The results are shown in Table 1.

<Amount of Release Agent> The amount of the release agent on the surface of the receptor layer is E
Performed by the SCA method. That is, the photoelectron spectroscopy analyzer (E
SCALAB-250 (manufactured by VG Scientific) was used to measure the abundance of the elements, and the proportion of silicon among them was measured. In addition, about Examples 1-4, when measured by a gravimetric method, although it cannot measure with sufficient precision, it is about 0.005 g / m < ² >,
It was less than 1 g / m ² .

[0069]

[Table 1]

Examples 1 to 3 in which the sheet on which the release agent layer having a relaxation time of 0.02 sec or more was formed and the resin of the receiving layer before curing were bonded and cured, show the inherent properties of the resin of the receiving layer. The fusion sheet, ribbon peeling line and running property were improved without impairing the transfer density, fingerprint resistance and light resistance of Comparative Example 1, and a high gloss thermal transfer recording receiving sheet was obtained.

Example 4 in which the sheet on which the release agent layer having a relaxation time of 0.02 sec or less was formed and the receiving layer resin before curing were bonded and cured, the properties inherent in the thermal transfer recording receiving layer resin were obtained. A highly glossy thermal transfer recording receiving sheet was obtained without impairing the transfer density, fingerprint resistance and light resistance of Comparative Example 1 shown in the figure. Improvements in fusion resistance, ribbon peelability, and running properties were not necessarily sufficient, but were at a practical level.

In Comparative Example 2, which was laminated and cured with a sheet having no release agent layer, the transfer density, fingerprint resistance, and light resistance of Comparative Example 1 showing the inherent properties of the thermal transfer recording receiving layer resin were impaired. Thus, a high gloss receiving sheet for thermal transfer recording was obtained, but the fusion resistance, ribbon peeling property and running property could not be improved.

In Comparative Example 3 in which the release agent layer was applied directly on the receiving resin, the fusion resistance, the ribbon peeling property, and the running property were improved, but the properties inherent in the thermal transfer recording receiving layer resin were originally obtained. In addition to significantly lowering the transfer density of Comparative Example 1 shown, bleeding was severe, fingerprint resistance and light resistance were reduced, and the glossiness was lowered by coating.

In Comparative Example 4 in which silicone oil was internally added to the receiving layer resin, the release agent deteriorated the adhesiveness between the support and the receiving layer resin, the receiving layer resin adhered to the polyethylene terephthalate side, and thermal transfer recording was performed. No receiving sheet was obtained.

[0075]

As is evident from the results in Table 1, in the receiving sheet for thermal transfer recording, after the receiving layer resin is applied, a sheet having a release agent layer in advance or a sheet having a resin layer containing a release agent in advance. After the resin of the receiving layer is cured, the sheet having the releasing agent layer or the sheet having the resin layer containing the releasing agent layer is removed, whereby the releasing layer is separated from the receiving layer resin surface. A highly glossy thermal transfer recording receiving sheet with a very small amount of mold agent transferred was obtained. Further, by setting the relaxation time of the release agent layer and the resin layer containing the release agent layer to 0.02 sec or more, the fusion resistance, the ribbon peeling property, and the traveling property can be maintained without lowering the transfer density. Thus, a receiving sheet for thermal transfer recording having high gloss and excellent in fingerprint resistance and light resistance was obtained. According to the method of the present invention, for the first time, it is less than 0.03 g / m ² or less than 0.01 g / m ² , and the amount of silicon element on the surface by the ESCA method is 1 to 30% (preferably 10 to 26%).
Such a trace amount of cured silicone could be present in a form firmly fixed on the surface of the receptor layer.

[Brief description of the drawings]

FIG. 1 is a process chart showing a typical manufacturing method of the present invention.
(Equivalent to Example 1)

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H111 AA01 AA08 AA09 AA27 CA03 CA12 CA30 CA33 CA41 DA00 DA01 DA04 4D075 BB42Z CA35 DA06 DB18 DC27 EA21 EB43

Claims (7)

[Claims] 1. A method for producing a thermal transfer recording receiving sheet having a dye receiving layer provided on at least one surface of a support, wherein (1) a step of applying a resin for the receiving layer to the support;
(2) a step of curing the resin for the receiving layer to form a receiving layer in a state where the molded body containing the release agent is brought into contact with the coated surface, and (3) a molded article containing the releasing agent. Separating the receiving sheet from the heat-transfer recording sheet. 2. The molded article according to claim 1, wherein the molded article containing the release agent is a molded article in which a layer containing the release agent is provided on a substrate or a resin molded article containing the release agent. A method for producing a thermal transfer recording receiving sheet. 3. The method for producing a thermal transfer recording receiving sheet according to claim 1, wherein the release agent is an organopolysiloxane. 4. A layer containing a release agent is a resin layer containing a cured organopolysiloxane as a main component, and a resin containing a release agent containing a cured organopolysiloxane is contained in a resin. The method for producing a thermal transfer recording receiving sheet according to claim 2, which is a molded article. 5. In the resin layer or the resin molded product,
The organopolysiloxane has a methyl group bonded to silicon of a polysiloxane skeleton, and the relaxation time (T _{1 ρ} ) of a proton derived from the methyl group measured by a solid NMR pulse method measured at room temperature is as follows: 5. The method for producing a thermal transfer recording receiving sheet according to claim 4, wherein the time is 0.02 sec or more. 6. The step of curing the resin for a receiving layer,
The method for producing a thermal transfer recording receiving sheet according to claim 1, wherein the method is performed by irradiating an active energy ray. 7. A thermal transfer recording receiving sheet having a dye receiving layer obtained by curing a curable resin on at least one surface of a support, wherein the surface of the receiving layer has 0.03 g / m 2.
^A receptor sheet for thermal transfer recording, comprising less than ² organopolysiloxanes and 1 to 30% silicon, based on the proportion of elements present on the surface of the receptor layer as measured by the ESCA method.