JPH04113893A - Image-receiving sheet for thermal transfer recording - Google Patents

Abstract

PURPOSE:To demonstrate satisfactory image shelf life against heat and light after thermal transfer, while an image of high density is obtained by forming an image-receiving layer containing binder resin and modified silicone resin. CONSTITUTION:The recommended available resins are copolymer resin of vinyl chloride and vinyl acetate, polyester resin and polyvinyl chloride resin. It is necessary to add modified silicone resin to an image-receiving layer. This modified silicone resin is a copolymer of a resin containing a polycyclohexane bond or monomer and other resin or monomer. If this modified silicone resin is added, the subject image-receiving sheet is more easily peeled off an ink sheet for thermal transfer recording. As a result, these sheets are no longer allowed to stick to each other due to their melting. The recommended modified silicone resin is such as of a solid phase at normal temperature (20 deg.C), especially a modified silicone resin which remains wax-like at normal temperature with a melting point of 35 to 100 deg.C. For example, these are modified polyester silicone resin, modified acrylic silicone resin and modified urethane silicone resin.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an image-receiving sheet for thermal transfer recording, and more particularly to an image-receiving sheet for thermal transfer recording, which prevents fusion with an ink sheet for thermal transfer recording, and which can obtain high-density images. The present invention relates to an image-receiving sheet for thermal transfer recording that has excellent image storage stability.

[Prior Art and Inventions to be Solved Section 1i1 Conventionally, color recording techniques such as ink sheets, electrophotography, and thermal transfer have been considered as methods for obtaining color hard copies.

Among these, the thermal transfer method in particular has advantages such as easy operation and maintenance, miniaturization of the device, and low cost.

There are two types of this thermal transfer method:

That is, a method in which a transfer sheet having a meltable ink layer on a support is imagewise heated by a laser or a thermal head, and the meltable ink layer is melt-transferred onto an image-receiving sheet for thermal transfer recording. and thermal diffusion transfer, in which the heat-diffusible dye is diffusely transferred to an image-receiving sheet for heat-sensitive transfer recording using an ink sheet for heat-sensitive transfer recording having an ink layer containing a heat-diffusible dye (sublimable dye) on a support. There are two types:

Among these, the thermal diffusion transfer method can control the gradation of the image by changing the amount of dye transferred according to changes in the thermal energy of the thermal head.
By overlapping magenta and yellow recording,
In recent years, this method has attracted attention as a method for obtaining color images with continuous changes in color shading.

However, this thermal diffusion transfer method has a problem with the image receiving sheet for thermal transfer recording used.

That is, the first problem is that it fuses with the ink sheet for thermal transfer recording during thermal transfer.

The second problem is that during thermal transfer, it is difficult to obtain a high density image unless high thermal energy is applied.

Furthermore, applying high thermal energy will slow down the printing speed and shorten the life of the thermal head.

The third problem is that the heat and light storage stability of the image is insufficient.

That is, if an image-receiving sheet for thermal transfer recording is placed in a high-temperature environment or exposed to light, the sharpness of the image may deteriorate over a long period of time, and the image may become colored or faded.

The present invention has been made to solve the various problems mentioned above.

That is, an object of the present invention is to prevent fusion with the ink sheet for thermal transfer recording during thermal transfer, obtain a high-density image, and provide a good heat-resistant storage property of the image after thermal transfer. An object of the present invention is to provide an image-receiving sheet for heat-sensitive transfer recording that can exhibit light storage stability.

[Means for Solving the Problems] The present invention for achieving the above objects is an image-receiving sheet for thermal transfer recording characterized by having an image-receiving layer containing a binder resin and a modified silicone resin.

The present invention will be explained in detail below.

(I) Image-receiving sheet for thermal transfer recording An image-receiving sheet for thermal transfer recording can usually be composed of a base material and an image-receiving layer formed thereon.

In some cases, an image-receiving sheet for thermal transfer recording may be formed using a self-supporting image-receiving layer.

In the image-receiving sheet for thermal transfer recording consisting of this self-supporting image-receiving layer, no particular base material is used, so
It is possible to reduce the number of parts.

Image-receiving layer - In the present invention, the image-receiving layer contains a binder resin and a modified silicone resin.

■Binder resin Examples of binder resins include polyvinyl chloride resin,
Vinyl chloride and other chemicals (e.g. vinyl acetate, etc.)
copolymer resin with, polyester resin, acrylic ester, polyvinylpyrrolidone, polycarbonate, cellulose triacetate, styrene acrylate resin, vinyltoluene acrylate resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone resin, styrene
Examples include maleic anhydride resin and polyacrylonitrile resin.

Among them, vinyl chloride-vinyl acetate copolymer resins, polyester resins, polyvinyl chloride resins, etc. are particularly preferred.

These binder resins can be used alone or in combination of two or more.

The above various resins may be newly synthesized and used, or commercially available products may be used.

For example, commercially available polyester resins include Vylon 2
En, Byron 290, Byron 6oo'tF [manufactured by Toyobo Co., Ltd.], KA-1038C [manufactured by Arayo Kagakusha Co., Ltd.]
, TP220. TP23S [Both Nippon Gosei-
You can also use the following.

The vinyl chloride-vinyl acetate copolymer resin has a vinyl chloride component content of 50 to 100% by weight and a degree of polymerization of 50%.
~2,500 or so is preferred.

The vinyl chloride-vinyl acetate copolymer resin preferably used in the present invention does not necessarily need to be composed only of a vinyl chloride component and a vinyl acetate component; The vinyl component may contain vinyl propionate, a hydroxyl group, a glycidyl group, an alkyl ether group, a sulfonic acid group, a carboxyl group-containing vinyl component, and the like.

As such vinyl chloride-vinyl acetate copolymer, 1
For example, S-LEC A, S-LEC C, S-LEC M [manufactured by Sekisui Chemical Co., Ltd.], Viny Light VACH, Viny Light VYHH, Viny Light VMCH, Viny Light vYH.
D, Vinylite ■YLF, Vinylite VYNS, Vinylite VMCC, Vinylite VMCA, Vinylite V
ACD, Vinylite VERR, Vinylite VROH [manufactured by Union Carbide], Denkabinyl 1000
G K T, Denkabinir 100OL, Denkabinir 1
000CK, Denkabinir 100OA, Denkabinir 1
000L 2, Denkabinil 100OA S, Denkabinil 1000M T2, Denkabinil 100OC
S, Denkabinir 100OCS, Denkabinir 100
OG K, Denkabinir 100OG SK, Denkabinir 100OG S, Denkabinir 100OLT, ,
Denkabinir 100OD, Denkabinir 100OW [
The above-mentioned products are manufactured by Denki Kagaku Kogyo Co., Ltd.].

In any case, from the viewpoint of physical properties, the binder resin has a glass transition point (Tg) of -20 to 150.
Resins having an Mw of 2,000 to 100,000 are preferable, particularly resins having a molecular weight of 30 to 12QC.

In addition, when forming the image-receiving layer, the various resins mentioned above utilize their reactive active sites (if there are no reactive active sites, give them to the resin), and crosslink with radiation, heat, moisture, catalysts, etc. Alternatively, it may be hardened.

In that case, a radiation active polymer such as epoxy or acrylic or a crosslinking agent such as isocyanate may be used.

(2) Modified silicone resin In the present invention, it is important that the image-receiving layer contains a modified silicone resin.

The term "modified silicone resin" as used herein means a resin having a polysiloxane bond or a copolymer of 100% and another resin or 70%.

When the image-receiving layer contains a modified silicone resin, the releasability of the image-receiving sheet for thermal transfer recording and the ink sheet for thermal transfer recording is improved, thereby preventing mutual fusion.

In addition, the heat-sensitive transfer recording image-receiving sheet containing modified silicone in the image-receiving layer has definitely improved heat resistance and light resistance, and the image clarity does not deteriorate even after long-term storage, and it does not fade or increase in color. The color is also difficult to produce.

Furthermore, it becomes easier to perform secondary processing such as adding black melted ink letters on the image receiving surface or applying heat lamination.

The modified silicone resin is preferably one that is solid at room temperature (20°C), particularly a wax-like modified silicone resin having a melting point of 35 to 100°C.

Specific examples of modified silicone resins used in the present invention include:
Examples include polyester-modified silicone resins, acrylic-modified silicone resins, urethane-modified silicone resins, cellulose-modified silicone resins, alkyd-modified silicone resins, and epoxy-modified silicone resins.

These may be used alone or in combination of two or more.

Among the above-mentioned modified silicone resins, polyester-modified silicone resins and urethane-modified silicone resins are preferred for the purpose of the present invention, and furthermore, those having a molecular weight of 50 (
1-20. (100 polyester-modified silicone resins and urethane-modified silicone resins are preferred.

The polyester portion of the polyester-modified silicone resin can be formed by copolymerization of a dicarboxylic acid and a diol or by opening a lactone ring.

The dimethylpolysiloxane bonding part and the polyester part in the polyester-modified silicone resin may have, for example, a polyester main chain and a dimethylpolysiloxane part grafted thereto, or a polyester part or a block-like polyester part may be grafted onto both sides or one side of the dimethylpolysiloxane. They may be combined. These commercially available products include Shin-Etsu Silicone (7)X24-8300. X2
4-8301゜X 24-111310,
23 etc. can be mentioned.

In addition, commercially available urethane-modified silicone resins include:
Thai Aroma-3P 2105S P 7 manufactured by Dainichiseika
12 etc. can be mentioned.

Furthermore, the modified silicone resin used in the present invention may have a reactive group such as a hydroxyl group or a carboxyl group at its terminal, and in that case, it can be crosslinked with a crosslinking agent such as diisocyanates.

In the present invention, the amount of the modified silicone resin blended in the image receiving layer is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight.

If the blending amount is less than 0.1% by weight, the effects of the present invention will not be fully exhibited, and if it exceeds 30% by weight, bleeding may occur during heat-resistant storage, which is not preferable.

■Additives Release agents, antioxidants, UV absorbers, light stabilizers, fillers (inorganic fine particles, organic resin particles), and pigments may be added to the image-receiving layer, and plasticizers and heat sensitizers may be added to the image-receiving layer. A solvent or the like may be added.

The release agent can improve the releasability between the ink sheet for thermal transfer recording and the image receiving sheet for thermal transfer recording.

Examples of such release agents include solid waxes such as silicone oil, polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants; among these, silicone oil is preferred. .

There are two types of silicone oil: a type in which it is simply added (simple addition type) and a type in which it is cured or reacted (curing reaction type).

In the case of a simple addition type, it is preferable to use modified silicone oil as the silicone oil in order to improve compatibility with the binder.

As modified silicone oil, polyester modified silicone resin (or silicone modified polyester resin)
, acrylic-modified silicone resin (or silicone-modified acrylic resin), urethane-modified silicone resin (or silicone-modified urethane resin), cellulose-modified silicone resin (or silicone-modified cellulose resin), alkyd-modified silicone resin (or silicone-modified alkyd) resin), epoxy-modified silicone resin (or silicone-modified epoxy resin), and the like.

In other words, a polyester-modified silicone resin containing a polysiloxane resin in its main chain and copolymerized with polyester in a flock form is bonded to the polyester main chain (1
Silicone-modified polyester resins having dimethylpolysiloxane moieties as m-chains, block copolymers, alternating copolymers, graft copolymers, random copolymers, etc. of dimethylpolysiloxane and polyester moieties are also used as modified silicone oils or resins. I have something to do.

In particular, in the present invention, it is preferable to add a polyester-modified silicone resin.

Typical polyester-modified silicone resins include, for example, a copolymer of diol and dibasic acid, a block copolymer of polyester and dimethylpolysiloxane, which is a ring-opening polymer of caprolactone, and a block copolymer of dimethylpolysiloxane at both ends or one end of dimethylpolysiloxane. (contains a copolymer in which the terminal end is flocked with the above polyester portion, or conversely, the above polyester or dimethylpolysiloxane is flocked), or the above polyester is used as the main chain and (dimethyl)polysiloxane is bonded to the side chain. At least one copolymer can be mentioned.

The amount of these simple addition type silicone oils cannot be determined uniformly because it varies depending on the type of silicone oil. The amount is 0.5 to 50% by weight, preferably 1 to 20% by weight.

As curing reaction type silicone oil, 1 reaction curing type,
Examples include photocuring type and catalyst curing type.

Reaction-curing silicone oils include those obtained by reaction-curing amino-modified silicone oil and synthetic/boxy-modified silicone oil.

In addition, as catalyst curing type or photo curing type silicone oil, KS-70SF-PS, KS-705F-PS-
1, KS-770-PL-3 [all catalytic curing silicone oils, manufactured by Shin-Etsu Chemical Co., Ltd.], S-720, S-774-PL-3 [all photo-curing silicone oils: Shin-Etsu Chemical Co., Ltd.] [made of a car] etc.

The amount of these curable silicone oils added is preferably 0.5 to 30% by weight of the binder for the image-receiving layer.

Note that a release agent layer can also be provided by dissolving or dispersing the above-mentioned release agent in a suitable solvent and applying the solution to a part of the surface of the image-receiving layer, followed by drying.

Next, as the antioxidant, JP-A-59-18278
No. 5, No. 60-1307:15, JP 1-1273
The antioxidants described in No. 87 and the like and compounds known to improve image durability in photographs and other image recording materials may be mentioned.

The UV absorber and Senan/Teishoku are disclosed in JP-A-59
-158287, 63-74686, 6:l-
No. 145089, No. 59-195292, No. 62-2
No. 29594, No. 63-122596, No. 61-28
3595, JP-A-1-204788, etc., and compounds known to improve image durability in photographs and other image recording materials.

Examples of the filler include inorganic fine particles and organic resin particles.

These inorganic fine particles include silica gel, calcium carbonate,
Titanium oxide, acid clay, activated clay, alumina, etc. can be cited as 41 fine particles, and fluorocarbon resin particles,
Examples include resin particles such as guanamine resin particles, acrylic resin particles, and silicone resin particles. These inorganic/organic resin particles are preferably added in an amount of 0.1 to 70% by weight, although this varies depending on the specific gravity.

Typical examples of the pigment include titanium white,
Examples include calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, and acid clay.

The facilitators and heat solvents include phthalate esters (e.g. dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, etc.), adipate esters (dioctyl adipate, methyl lauryl adipate, di-adipate, etc.). 2-ethylhexyl, ethyl lauryl adipate, etc.), other oleic acid esters, succinic acid esters, maleic acid esters, cehatic acid esters, citric acid esters, epoxy stearic acid, diacid epoxy, and phosphoric acid. Examples include phosphate esters such as triphenyl and tricresyl phosphate, and glycol esters such as ethyl phthalyl ethyl glycolate and butylphthalyl phthyl glycolate.

In the present invention, the total amount of additives added is usually in the range of 0.1 to 50% by weight based on the binder for the image-receiving layer.

■Formation of the image-receiving layer The image-receiving layer is prepared by, for example, dispersing or dissolving the components forming the image-receiving layer in a solvent to prepare a coating liquid for the image-receiving layer, and applying this coating liquid to the surface of the base material. However, it can be formed by a coating method in which the image-receiving layer is dried, or a lamination method in which a mixture containing the components forming the image-receiving layer is melt-extruded and laminated on the surface of a base material.

Solvents used in the above coating method include alcohols (e.g. methyl alcohol, ethyl alcohol, etc.), esters (e.g. ethyl acetate, isopropyl acetate, n-acetate
butyl), cellosols (e.g. methyl cellosol, ethyl cellosol, etc.), ketones (e.g. methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (e.g. tetrahydrofuran, dioxane, etc.), chlorinated solvents (e.g. chloroform, trichlorethylene, etc.), etc. I can list the following.

These may be used alone or in combination of two or more.

When employing the above lamination method, if the base material is a synthetic resin as described later, a coextrusion method may also be employed.

The image receiving layer may be formed over the entire surface of the base material, or may be formed on a part of the surface.

The thickness of the image receiving layer is generally 3 to SOBm, preferably 5 to SOBm.
It is about 15yLm.

On the other hand, since the image-receiving layer is self-supporting, when the image-receiving layer itself is used to form an image-receiving sheet for thermal transfer recording, the thickness of the image-receiving layer is usually 60 to 200 μm, preferably 90 to 100 μm.
It is about 50Bm.

-Substrate- Examples of this substrate include paper, coated paper, synthetic paper (polypropylene, polystyrene, or a composite material made of paper and paper), white polyethylene terephthalate base film, transparent polyethylene terephthalate base film, polyolefin coating. Paper or the like can be suitably used.

The thickness of the base material is usually 50 to 300 ILm, preferably 1
00-250 pot m.

-Other Layers- An overcoat layer may be laminated on the surface of the image-receiving sheet for thermal transfer recording for the purpose of improving image storage stability or preventing fusion with the ink sheet for thermal transfer recording.

This layer can be formed by a known coating method such as gravure coating, wire bar coating, or roll coating.

The thickness of this layer is usually 0.5-5 pm.

Further, a cushion layer may be provided between the base material and the image-receiving layer of the image-receiving sheet for thermal transfer recording in order to reduce noise and transfer and record an image corresponding to the image information with good reproducibility.

Examples of the material constituting this cushion layer include urethane resin, acrylic resin, ethylene resin, butadiene rubber, and epoxy resin.

The thickness of the cushion layer is usually preferably 5 to 25 pm.

(n) Ink sheet for thermal transfer recording An ink sheet for thermal transfer recording basically has a structure in which ink layers are laminated on a support.This ink layer is not limited to a single layer, but is composed of multiple layers. It's okay.

One Ink Layer - The ink layer basically contains a heat diffusible dye and a binder.

■ Heat-diffusible dye This heat-diffusible dye is not particularly limited as long as it is heat-diffusible or sublimable.

Examples of heat-diffusible dyes include cyan dyes, magenta dyes, and yellow dyes.

As the cyan dye, JP-A-59-78896;
No. 59-227948, No. 60-24966, No. 6
〇-5: No. 1553, No. 60-130735, No. 60
-131292, 60-2:19289, 61
-19396, 61-22993, 61-31
No. 292, No. 61-31467, No. 61-15994
No. 61-49893, No. 61-148269,
No. 62-191191, No. 63-91288, No. 6
Examples include naphthoquinone dyes, anthraquinone dyes, and azomethine dyes described in publications such as No. 3-91287 and No. 63-290793.

Examples of the magenta dye include JP-A-59-78896, JP-A-60-30392, and JP-A-60-:103.
No. 94, JP-A-60-253595, JP-A-61-2
No. 62190, JP-A No. 6:1-5992, JP-A No. 63
-205288, JP-A-64159, JP-A-64-
Examples include anthraquinone dyes, azo dyes, and azomethine dyes described in publications such as No. 63194.

As yellow pigments, JP-A-59-78896, JP-A-60-27594, JP-A-60-31560,
Methine dyes, azo dyes, quinophthalone dyes, and anthothiazole dyes described in JP-A-60-53565, JP-A-61-12394, JP-A-6:1-122594, etc. Examples include dyes.

In addition, as a heat-diffusible dye, an azomethine dye obtained by a coupling reaction of a compound having an open-chain or closed-chain active methylene group with an oxidized product of a p-phenylenecyamine derivative or an oxidized product of a p-aminophenol derivative is used. , and phenol or naphthol derivatives or p-
An indoaniline dye obtained by a coupling reaction of an oxidized product of a phenylenediamine derivative or an oxidized product of a p-aminophenol derivative can also be suitably used.

The heat-diffusible dye may be a yellow dye, a magenta dye, or a cyan dye, as long as the image to be formed is monochromatic.

Furthermore, depending on the tone of the image to be formed, it may contain two or more of the three types of heat-diffusible dyes or other colors.

The amount of the heat-diffusible dye used is usually 0.1 to 20 g, preferably 0.2 to 5 g per m 2 of the support.

(2) Binder In the present invention, it is possible to use resins known in the field of thermal transfer recording as the binder for the ink layer, but preferred are acetal resins and/or cellulose resins described below.

First, as the acetal resin, there are various compounds depending on the degree of acetalization and the content of acetyl groups, and typical examples include polyvinyl acetoacetal and polyvinyl butyral.

Among acetal resins, those having a polymerization degree of 300 or higher, preferably 1, SOD to 2 are preferable for the purpose of the present invention.
, 400, glass transition point (Tg) of 50 to 200°C,
It is an acetal resin having a degree of acetalization of 60 mol% or more and an acetyl group of 10 mol% or less.

The product names of acetal resins that meet these conditions include KS-1, KS-5, KS-8, BL-1, B
L-2, BL-3, BL-S, BM-1, BM-2, B
Examples include M-5, 8M-5, BH-3, and BX-1 [all manufactured by Okisui Kagaku Kogyo].

Examples of cellulose resins include nitrocellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, cellulose acetate,
Examples include cellulose acetate.

Among these cellulose resins, nitrocellulose is particularly preferred.

Furthermore, among the nitrocelluloses, those having a 1M element content of 10.7 to 12.2%, a degree of polymerization of 35 to 110, and a viscosity based on the test method of JIS K-6703 are preferable for the purposes of the present invention. are respectively 1.0 to 6.2 seconds (
Measured at 25.0% solids), 3-8 seconds (measured at 20.0% solids)
%), 1.5 to soo seconds (measured at 12.2% solids), 1.1 to 5.2 seconds (measured at 30% solids),
It is a nitrocellulose having a value of 100 to 140 cps (measured by dissolving 1.5 g of dry nitrocellulose in 100 cc of butyl acetate).

The product names of nitrocellulose that meet these conditions are HIGI/16, HIGI/8, and HIGI/4.
,)IIGI/2. HIGl, HIGl, )IIG7,
)IIG20. HIG60. HIG120, HIG50
0. LIGI/8. LIGI/4, LIGI 1/2
．． 5L--1, HI 1000. There are H12000, Clear H1/4, Chip H1/2, etc. (all manufactured by Asahi Kasei Corporation).

Next, in addition to the acetal resin and cellulose resin, binders conventionally known in the thermal transfer recording field include, for example, acrylic resin methacrylic resin, polyvinyl alcohol, polyvinyl formal, polydonyl chloride, polyvinyl ether, polyvinylpyrrolidone, and polystyrene. , polystyrene copolymers, ionomer resins, etc.

These may be used alone or in combination of two or more.

Further, the weight ratio of the binder and the heat-diffusible dye in the heat-sensitive layer is preferably in the range of 110 to 10 liters.

(2) Additives Various additives may be added to the ink layer as necessary.

The additives include fluororesins, surfactants, release compounds such as waxes, fillers such as fine metal powders, silica gel, carbon fluff, and fine resin powders, and hardening agents that can react with binder components (for example, incyanates). and radioactive compounds such as acrylics and epoxies).

Furthermore, in order to promote transcription, for example, JP-A-59-1
It is possible to use heat-melting substances such as waxes and higher fatty acid esters described in No. 06997 and the like.

The amount of additives to be added cannot be uniformly determined depending on the type of additive and the purpose of addition, or the amount of additives as a whole is usually in the range of 20% by weight or less based on the binder.

■Formation of the ink layer The ink layer is prepared by dispersing or dissolving the heat-diffusible dye, binder, and optional components added as necessary in a solvent to prepare a coating solution for forming the ink layer. It can be formed by coating on a support and drying.

Note that the above-mentioned binders do not have to be used by dissolving one or more kinds in a solvent, but may be dispersed in a latex form.

The above-mentioned solvents include water, alcohols (e.g., ethanol, propatool), selonrubes (e.g., methylselonruf, ethyl cellosolf, etc.), aromatics (e.g., toluene, xylene chlorobenzene, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.). ), esters (e.g. ethyl acetate, butyl acetate, etc.), ethers (
(e.g., tetrahydrofuran, dioxane, etc.), chlorinated solvents (e.g., chloroform, trichlorethylene, etc.)
I can list the following.

These solvents may be used alone.

Two or more types can be used in combination.

For the above-mentioned coating, commonly known surface sequential coating using a gravure roll, extrusion coating, wire bar coating, roll coating, etc. can be used.

The ink layer is desirably formed on the support to a thickness of 0.2 to 10 #Lm, more preferably 0.3 to 3 gm.

The ink layer may be a yellow ink layer containing a binder resin and a yellow dye, a magenta ink layer containing a binder resin and a magenta dye, and a cyan ink layer containing a binder resin and a cyan dye. Preferably, the structure is repeatedly formed on a support.

Furthermore, in addition to the three ink layers arranged along the planar direction, a black ink layer containing a black image forming substance may be interposed between any two layers adjacent in the planar direction.

In particular, with respect to the black ink layer, clear characters can be obtained by using a diffusion transfer type ink or a melt transfer type ink.

As a support, any support may be used as long as it has good dimensional stability and can withstand the heat of a heat source such as a heat-sensitive head during image recording. such as tissue paper, polyethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyamide,
Heat resistant plastic films such as polycarbonate, polysulfone, polyvinyl alcohol cellophane, polystyrene, polyimide are suitable.

The thickness of the support is usually preferably in the range of 2 to 10 Bm.

-Other Layers- An undercoat layer may be provided between the ink layer and the support in order to improve adhesion and the like.

Furthermore, an anti-fusing layer can also be provided on the ink layer.

Its thickness is usually 0.01 to 5 pm, preferably 0.05
~1 lm.

If the thickness is less than 0.01 gm, the effect of preventing fusion will not be sufficiently exhibited, and if it exceeds 5 Bm.

This is undesirable because diffusion of the heat-diffusible dye from the ink layer to the image-receiving layer is inhibited, making it difficult to obtain sufficient image density.

The anti-fusing layer can usually be formed from polyester, amide wax, solid waxes such as Teflon powder, phosphate ester surfactants, silicone oil, silicone resins, fluorine resins, and the like.

Further, the back side of the support (the side opposite to the ink layer) may have an anti-sticking layer for the purpose of preventing adhesion, sticking, and wrinkles from occurring on the head or support.

The thickness of this anti-stew kink layer is preferably in the range of 0-1 to 1 Bm.

Furthermore, by forming perforations on the ink sheet for thermal transfer recording, or by providing register marks for detecting the positions of areas with different hues, convenience in use can be improved.

(m) Image formation To perform image formation, the image-receiving layer surface of the image-receiving sheet for thermal transfer recording of the present invention and the ink layer surface of the ink sheet for thermal transfer recording are superimposed so as to be in contact with each other, and then this interface is formed. Add thermal energy to the image quiz.

Then, the heat-diffusible dye in the ink sheet for thermal transfer recording vaporizes or sublimates in an amount corresponding to the applied thermal energy, and migrates to the image-receiving sheet for thermal transfer recording.
It is fixed on the image-receiving layer to form an image there.

A thermal head is generally used as the heat source for providing the thermal energy, but other known heat sources such as a laser beam, an infrared flash, and a heat vent can also be used.

Thermal energy can be applied from the image receiving sheet for thermal transfer recording, from the ink sheet for thermal transfer recording, or from both sides.

However, from the viewpoint of effective use of thermal energy, it is preferable to carry out this process from the side of the ink sheet for thermal transfer recording.

Also, it is used for the purpose of controlling thermal energy to express the gradation of light and shade in images, or promoting the diffusion of dyes into image-receiving sheets for thermal transfer recording to ensure the expression of continuous gradations in images. It is preferable to apply thermal energy from the side of the image-receiving sheet for thermal transfer recording.

Furthermore, in the sense that the advantages of the three methods described above can be enjoyed at the same time, it is preferable to carry out the process from the side of the ink sheet for thermal transfer recording and the side of the image-receiving sheet for thermal transfer recording.

When a thermal head is used as a heat source for providing thermal energy, the applied thermal energy can be varied continuously or in multiple stages by modulating the voltage or pulse width applied to the thermal head.

When laser light is used as a heat source for providing thermal energy, the amount of heat energy provided can be varied by changing the amount of laser light and the irradiation area.

If a tod generator with a built-in 8' optical element is used, it is possible to provide heat energy corresponding to the size of the halftone dot.

When using laser light as a heat source, it is desirable that the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording be brought into close contact with each other, and that the surface to be irradiated with the laser beam should be in contact with the ink sheet for thermal transfer recording to improve absorption of the laser beam. For example, it is best to color it black.

When an infrared flash lamp is used as a heat source for providing thermal energy, irradiation from the lamp is preferably performed through a colored layer such as black, as in the case of using laser light.

In addition, irradiation with this lamp can be performed through a pattern or halftone dot pattern that continuously expresses five shades of an image such as black, and it can be applied to a colored layer such as black on the negative side and the negative of the pattern. With the corresponding negative pattern! You can also do it in combination with l[1.

When thermal energy is applied in this way, the amount of dye corresponding to the amount of energy is thermally transferred from the ink sheet for thermal transfer recording to the image receiving layer of the image receiving sheet for thermal transfer recording,
It is possible to record a one-color image there, or by replacing the ink sheet for thermal transfer recording, it is also possible to obtain a color photo-like color image.

For example, by sequentially replacing the yellow, magenta, cyan, and, if necessary, black thermal transfer recording ink sheets and performing thermal transfer for each color, it is possible to obtain a color photo-like color image consisting of a combination of each color. .

Incidentally, instead of using ink sheets for thermal transfer recording of each color as described above, the following method can also be used.

That is, an ink sheet for thermal transfer recording is prepared which has areas formed by painting each color in advance, and the yellow area is used to thermally transfer the yellow separation image, and then the magenta area is used to thermally transfer the magenta separation image. The color image is thermally transferred, and thereafter, by sequentially repeating this operation, yellow, magenta, cyan, and, if necessary, blank and color separation images are thermally transferred.

This method has the advantage that there is no need to replace the ink sheet for thermal transfer recording.

[Example] Next, the present invention will be explained in more detail based on Examples.

3. In the following, "r part" represents "part by weight."

(Example 1) A coating liquid for forming an ink layer having the following composition was applied to the corona-treated surface of a 9 gm thick Bot ethylene terephthalate film [trade name 5PET: manufactured by Toyobo Co., Ltd.] as a support by a wire bar coating method. Thickness after drying is 1μ
Apply silicone oil (X-41,400
3A (manufactured by Shin-Etsu Silicone Co., Ltd.) was applied with a dropper and spread over the entire surface, and a backside treatment coating was performed to obtain an ink sheet for thermal transfer recording.

Ink - Disperse dye: 4 parts [Kayasect Flu 1361 Copolyvinyl butyral manufactured by Nippon Kayaku Co., Ltd.: 5 parts [degree of polymerization: 1700, trade name] BX-
1゜Building Chemical Industry -] Methyl ethyl ketone...90 parts Cyclohexanone...5 parts Next, as a base material, synthetic paper with a thickness of 150 JLm [trade name Yubo FPG - 150
：Egg oil synthetic paper■ Coating liquid for forming an image receiving layer having the following composition was applied on the paper using the wire bar coach ink method, and then temporarily dried in a dryer, and then dried in an oven at a temperature of 100''C for 1 hour. An image-receiving sheet for thermal transfer recording was obtained by forming an image-receiving layer with a thickness of 5 μm on synthetic paper.

Polyester modified silicone...4 parts [Product name
-24-8310: Shin-Etsu Chemical Co., Ltd.] Donyl chloride -
Vinyl pyropionate copolymer・・・・・・・・・・・・
・10 parts [trade name Ryuron QC-640: manufactured by Tosoh ■] Methyl ethyl ketone 90 parts Next, after storing the ink sheet for thermal transfer recording at 50°C for 8 days, the sheet and the above-mentioned image-receiving sheet for thermal transfer recording are stacked so that the ink layer surface of the former is in contact with the image-receiving layer surface of the latter, and a thermal head is used to output 01SW/dot, dot damage level from the support side of the ink seed for thermal transfer recording. By heating under the conditions of 8 dots/mm,
Image recording was performed.

After image recording, the fusing properties between the ink sheet for thermal transfer recording and the image receiving sheet for thermal transfer recording, lamination properties of the image receiving layer, melt printing properties, transfer density, heat resistance, and light resistance were evaluated based on the following criteria.

The results are shown in Table 1.

Fusion property ○: Only the dye was transferred to the receiving R layer, and the ink layer was peeled off from the support.

x: The entire ink layer was not transferred to the image receiving layer.

Lamination property ○...The image-receiving layer was completely fused to the laminating agent.

×: The image-receiving layer is not completely fused to the laminating agent.

Fusing printing property: ○... It has been possible to print clearly using a commercially available word processor.

×...I couldn't print clearly with a commercially available word processor.

Transfer density: The reflection density OD value was measured using an optical densitometer.

◎・・・OD value is 2.3 or more.

○・・・OD value is 2.0 or more.

△・・・OD value 1.7~2.0° X...OD value is 1.7 or less.

Heat resistance: ○: No bleed-out of one dye occurred even after holding at 77°C for 3 days.

Δ: When kept at 77°C for 3 days, some bleed-out of the dye occurred.

X: When kept at 77°C for 3 days, obvious dye bleed-out occurred.

Lightfastness 2O: No change in color even when placed in a weather meter for 3 days.

△...When placed in a weather meter for 3 days, the color changed slightly.

×: When placed in a weather meter for 3 days, the color changed significantly.

(Example 2) The same procedure as in Example 1 was carried out except that the composition of the coating liquid for forming an image-receiving layer in Example 1 was changed to the following composition and the thickness of the image-receiving layer was changed to 10 gm.

The results are shown in Table 1.

^ Engineered hinyl chloride resin 10 parts (degree of polymerization 600) Methyl ethyl ketone 100 parts Cyclohexanone 50 parts Polyester modified silicone ...4 parts [manufactured by Shin-Etsu Chemical Co., Ltd.]
X-24-8310] (Example 3) TPP was added to the composition of the coating liquid for forming the image receiving layer in Example 2.
The same procedure as in Example 2 was carried out except that 2 parts of ()-riphenylphosphate) were added.

The results are shown in Table 1.

(Example 4) Example 1 was repeated except that the polyester-modified silicone, which was a component of the coating solution for forming the image-receiving layer in Example 1, was replaced with urethane-modified silicone E manufactured by Dainichiseika Co., Ltd., 5P712]. It was carried out in the same manner.

The results are shown in Table 1.

(Example 5) The same procedure was carried out as in Example 3 except that the polyester-modified silicone, which was a component of the image-receiving and forming coating liquid, was replaced with acrylic-modified silicone [manufactured by Toagosei Co., Ltd., Saimauku US-270]. It was carried out in the same manner as in Example 1.

The results are shown in Table 1.

(Example 6) The same procedure as in Example 1 was carried out except that the composition of the coating liquid for forming an image-receiving layer in Example 1 was changed to the following composition.

The results are shown in Table 1.

A, /.

Polyester resin: 10 parts [manufactured by Toyobo M, Vylon 200] Polyester modified silicone: 4 parts [manufactured by Shin-Etsu Chemical Co., Ltd., X-24-8:lOO] incyanate Curing agent: 2 parts [manufactured by Nippon Polyurethane Co., Ltd., Coronat] Methyl ethyl ketone...
100 parts (Comparative Example 1) A sample was prepared in the same manner as in Example 1 except that a certain polyester-modified silicone was not used in the composition of the coating solution for forming an image-receiving layer.

The results are shown in Table 1.

(Comparative Example 2) Comparative Example 2 was carried out in the same manner as in Example 3, except that the use of polyester-modified silicone, which is one of the components of the coating liquid for forming an image-receiving layer, was omitted.

The results are shown in Table 1.

(Comparative Example 3) Comparative Example 3 was carried out in the same manner as in Example 1, except that dimethylpolysiloxane was used in place of polyester-modified silicone, which is one of the components of the coating solution for forming an image-receiving layer.

The results are shown in Table 1.

(Hereinafter, blank spaces) Table 1 [Effects of the Invention] The image-receiving sheet for thermal transfer recording of the present invention is prevented from fusing with the ink sheet for thermal transfer recording during thermal transfer, thereby obtaining a high-density image. In addition to this, it is easy to perform secondary processing, and after thermal transfer, the image exhibits good heat resistance and light resistance, so it maintains a clear, high-quality image for a long time. I'll come.

1. Indication of the case 2. Procedural amendment to the name of the invention 1990 Patent Application No. 234167 Image receiving sheet for thermal transfer recording 3. Person making the amendment Relationship to the case Patent applicant address 1-26 Nishi-Shinjuku, Shinjuku-ku, Tokyo Number 2 Name (127) Konica Co., Ltd. Representative Takanori Rayu 4, Agent address 5-18-20 Nishi-Shinjuku 7-chome, Shinjuku-ku, Tokyo, No date of amendment order: Voluntary action 7, Contents of amendment (1) Details "Thai Aroma-5P2105.5P7 manufactured by Dainichiseika" is written from the first line to the second line on page 12 of the book.
12 etc. can be mentioned. " is corrected to "Thai Aroma-5P2105 manufactured by Dainichiseika."

(2) “Urethane-modified silicone [Dainichiseika Co., Ltd., 5P71] described from line 3 to line 4 on page 43 of the specification
2] J is urethane-modified silicone [manufactured by Dainichiseika, S
P2105] Correct to J.

that's all

Claims (4)

[Claims] (1) An image-receiving sheet for thermal transfer recording, characterized by having an image-receiving layer containing a binder resin and a modified silicone resin. (2) The image-receiving sheet for thermal transfer recording according to claim 1, wherein the binder resin is a vinyl chloride resin. (3) The image-receiving sheet for thermal transfer recording according to claim 1, wherein the modified silicone resin is solid at room temperature. (4) The image-receiving sheet for thermal transfer recording according to claim 1, wherein the modified silicone resin is a polyester-modified silicone resin or a urethane-modified silicone resin.