JPH04179584A - Image receiving sheet for heat-sensitive transfer recording - Google Patents

Abstract

PURPOSE:To contrive the improvement of coating ability, heat resistance and preservability and of glossiness after image formation by providing an image receiving layer containing vinyl chloride resin and vinyl chloride copolymer. CONSTITUTION:As a binder for an image receiving layer, vinyl chloride resin and vinyl chloride copolymer are used. The degree of polymerization of the vinyl chloride resin is usually from 200 to 3000, preferably from 20 to 1000. It is preferable to use the copolymer of vinyl chloride and monomer as the vinyl chloride copolymer. By way of example, the monomer may be the alkyl ester of unsaturated fatty acid (vinyl acetate, vinyl propionate, etc.) and aromatic unsaturated compounds including benzoylvinyl ether. However, the aromatic unsaturated compound is desirable in terms of solubility to organic solvent and light resistance and preservability of images. Preferably, the copolymer contains 50-100wt.% vinyl chloride component and has a degree of polymerization of about 50-2500.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to an image-receiving sheet for thermal transfer recording, and more specifically, the present invention relates to an image-receiving sheet for thermal transfer recording. The present invention relates to an image-receiving sheet for thermal transfer recording, which is used to record images by thermal transfer.

rPrior art and problems to be solved by the invention] In recent years, inkjet,
Color recording technologies using electrophotography, thermal transfer, etc. are being considered.

Among these, the thermal transfer method in particular has many advantages, such as ease of operation and maintenance, the ability to make the device smaller, and the ability to reduce costs.

This thermal transfer method includes 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 to melt and transfer the meltable ink layer onto a transfer sheet. A thermal diffusion transfer method (sublimation transfer method) in which only the heat diffusible dye is diffusely transferred to a transfer sheet using a transfer sheet having an ink layer containing a heat diffusible dye (for example, a sublimable dye) on a support. There are two types.

The latter thermal diffusion transfer method can control image gradation by changing the amount of thermally diffusible dye transferred in accordance with changes in thermal energy of a thermal head.

Therefore, the thermal diffusion transfer method has been attracting attention in recent years as a method that can transfer and record a color image having continuous changes in color density by overlapping recording of cyan, magenta, and yellow.

By the way, this thermal diffusion transfer method is image-wise, high-speed, and high-quality based on electrical signals.

The biggest challenge is to achieve high image preservation, and material technology for this purpose is still under development.

The present inventors have already reported that vinyl chloride resin is preferable as the resin for the image-receiving layer (Japanese Unexamined Patent Publication No. 60-24996). Since then, there have been reports on the use of vinyl chloride resins in image-receiving layers.

Although vinyl chloride resins are generally known to have good light resistance after image formation, unmodified vinyl chloride resins have low solubility in organic heating media and are not suitable for producing image-receiving layer sheets.

Therefore, the use of various modified vinyl chloride resins has been devised for the purpose of improving the dissolution properties of vinyl chloride resins or increasing the dye-receiving ability.

For example, Japanese Patent No. 61-283595 reports that a combination of vinyl chloride-vinyl acetate copolymer and polyester is effective as a resin for the image-receiving layer.

However, if vinyl chloride is modified by copolymerizing with other polymers, or if vinyl chloride resin is internally plasticized, the light resistance, which is an advantage of vinyl chloride resin, may deteriorate, and the heat resistance of the image-receiving layer may deteriorate. Deterioration occurs, and the image receiving layer is deformed by heating during image formation, resulting in defects such as loss of gloss.

The present invention has been made to improve the above situation.

An object of the present invention is to provide an image-receiving sheet for thermal transfer recording that is excellent in coating properties and light storage stability and has good gloss after one image is formed.

[Means for Solving the Problems] The present invention for achieving the above object is an image receiving sheet for thermal transfer recording, characterized by having an image receiving layer containing a vinyl chloride resin and a vinyl chloride copolymer. .

The present invention will be explained in detail below.

[1] Image-receiving sheet for thermal transfer recording An image-receiving sheet for thermal transfer recording can generally be composed of a support and an image-receiving layer formed thereon.

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

In the image-receiving sheet for thermal transfer recording comprising this self-supporting image-receiving layer, no support is used, so the number of parts and manufacturing steps can be reduced.

Image-Receiving Layer This image-receiving layer can be formed from a binder and various additives.

In addition, depending on the case, it can also be formed from only a binder.

1. Binder In the present invention, a vinyl chloride resin and a vinyl chloride copolymer are used as essential components as a binder for the image-receiving layer.

The vinyl chloride resin used in the present invention usually has a degree of polymerization of 200 to 3,000, preferably 20 to 1.
,000.

As the above-mentioned vinyl chloride copolymer, a copolymer of vinyl chloride and the following copolymer is preferred.

In other words, these seven polymers include alkyl esters of unsaturated fatty acids (vinyl acetate, vinyl propionate, etc.)
, acrylic acid and its alkyl esters (methyl, ethyl, butyl, 2-ethylhexyl), maleic acid and its alkyl esters (diethyl, dibutyl, dioctyl), vinylidene chloride, ethylene, propylene, acrylonitrile, imbutylene, alkyl vinyl ethers (methyl, 2-ethylhexyl, lauryl, palmityl, stearyl, etc.), icotanic acid, crotonic acid and their alkyl esters, thenohalogenated olefins, styrene, chlorostyrene, methacrylic acid esters and their derivatives (alkyl esters, hydroxyethyl, hydroxypropyl, etc.) ), methacrylonitrile, di- and polyhalogenated olefins (dichloroethylene, di- and trifluoroethylene, etc.), acrylic acid with polar groups, icotanic acid derivatives (compounds with methylol groups, aldehyde groups, etc.), aconitic acid esters, Examples include aromatic unsaturated compounds such as butene-1, butene-2, various isopentenes, cycloolefin derivatives (cyclopentene derivatives), halogenated or cyanated cycloolefins, vinyl benzoate, and benzoyl vinyl ether.

Among the above monomers, alkyl esters of unsaturated fatty acids (vinyl acetate, vinyl propionate, etc.), acrylic acid and its alkyl esters (methyl, ethyl, butyl, 2-ethylhexyl, etc.), ethylene, propylene, alkyl vinyl ethers, icotanic acid and Aromatic unsaturated compounds such as crotonic acid and its alkyl esters, styrene, vinyl benzoate, and benzoyl vinyl ether are preferred in terms of solubility in organic solvents and light storage stability of images.

The vinyl chloride copolymer has a vinyl chloride component content of 5
Preferably, the amount is 0 to 100% by weight and the degree of polymerization is about 50 to 2,500.

The vinyl chloride copolymer used in the present invention may contain three or more types of copolymerizable monomers as long as the effects of the present invention are not impaired.

As the ternary or higher vinyl chloride copolymer, for example, a vinyl chloride copolymer represented by the following general formula [1] can be suitably used.

In addition, the order of the blocks of repeating units enclosed in small brackets in the large brackets indicating the vinyl chloride copolymer of -6 formula [1] may be in a specific order or in any order. Good too.

In the general formula [1], R', R'' and R2 represent a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.).

Further, R1, R1' and R2 may be the same or different within each repeating unit block.

X is a substituent containing -SO3M -A-5O3M,
' is a substituent containing -C00M -A'-COO&l
and Yυ.

Here, M is a hydrogen atom or an alkali metal atom such as Li, Na, etc.

Moreover, A, A', and B are linking groups that link -5O, M, -COON, and epoxy groups to the main chain of the vinyl chloride copolymer, respectively. Examples of the linking group include the following.

-C0NHC-R', -0- (-CH2-1-1-COOI-CH, -1-
, -r rCONH-
, -1-CHz-) ,-(:0NH-(-CHz-
1-0 However, R5 and R6 each represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or a phenyl group,
Further, R7 represents an alkylene group having 1 to 15 carbon atoms.

γ represents an integer of 0 to 20.

Next, Z is a repeating unit inserted as necessary to improve the properties of the epoxy group-containing vinyl chloride copolymer.

That is, Z is added for the purpose of adjusting the solvent solubility, flexibility, compatibility with other resins, and curing and crosslinking properties of the epoxy group-containing vinyl chloride copolymer, preventing fusion, and improving image storage stability. It is something that will be done.

Specific examples of this repeating unit include units with the following structure.

I R'R' Here, R3 represents H or a lower alkyl group (eg, methyl group, ethyl group).

■ is H or -(-CHz-)q-0H1-'-CH2
CH20-IQ-H1W is OM (M is H or alkali metal atom) -(-0CH2GHz-IQ-0)1do1
-OCH2-IQ-OHfq=1 to 4).

Moreover, p is 1-50.

R4 is an unsubstituted hydrocarbon having 1 to 20 carbon atoms, such as methyl, ethyl, octyl, hexadecyl, and the like.

Other copolymerizable structural units such as vinylidene chloride, ethylene, styrene, maleic anhydride, maleic acid, and maleic esters can also be used as -f-2-1n.

-fi formula [I] j, ms ite, k ha 200-8
00,! and no° are 0 to 100 (however, !, 1' are never both 0), m is l-10 (! and n are 0 to
Represents an integer of 200.

The degree of polymerization (Pn) of the epoxy group-containing vinyl chloride copolymer used in the present invention, including the epoxy group-containing vinyl chloride copolymer represented by formula [1], is usually 250 or more and 500 or less, - It is preferable that at least one SO3M or -COOM exists in the vinyl chloride copolymer, the repeating unit containing -5O,M or -COOM is 0 to 3 wt%, and the repeating unit containing an epoxy group is 0.5 to 3 wt%. 9wt%, vinyl chloride unit is 95-80wt%
It is preferable that

When the epoxy group-containing vinyl chloride copolymer is used as the image-receiving layer binder, if the vinyl chloride component is too small, the image-receiving layer will fuse with the ink layer of the ink sheet for thermal transfer recording, and if it is too large, Poor solubility in solvents.

In addition, the repeating unit having an epoxy group increases the amount of heat-diffusible dye transferred and provides a high-density transferred image.

Examples of commercially available epoxy group-containing vinyl chloride copolymers include MR-110 and MR-120 (both manufactured by Nippon Zeon Co., Ltd.).

Note that the epoxy group-containing vinyl chloride copolymer can be synthesized by a known method.

For example, in the formula [1] above, -3O,M and -C
When the parent wood group or functional group is reacted and added to a copolymer without OOM, for example, a vinyl chloride copolymer having 10H groups such as vinyl chloride-vinyl alcohol copolymer, the epoxy group-containing vinyl chloride Copolymers can be synthesized.

In addition, in order to avoid separation of by-products and ring opening of the epoxy group, a predetermined amount of the reactive monomer having an unsaturated bond from which the repeating unit in formula [1] is derived is added to a reaction vessel such as an autoclave. Synthesis can also be carried out using a radical polymerization initiator such as a radical polymerization initiator such as BPOlAIBN, a redox polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, etc.

2. 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. Furthermore, a plasticizer, a hot drop agent, etc. may be added as a sensitizer.

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

Such release agents include silicone oil (including what is called silicone resin); solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants, etc. Among them, 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 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.

Specifically, polyester-modified silicone resin containing polysiloxane resin in the main chain and copolymerized with polyester in block form, silicone-modified polyester resin having dimethylpolysiloxane moiety as a side chain bonded to the polyester main chain, and dimethylpolyester resin. Block copolymers, alternating copolymers, kraft copolymers, random copolymers, etc. of siloxane and polyester can also be used as modified silicone oils or resins.

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, or a block copolymer of polyester, which is a ring-opening polymer of caprolactone, and dimethylpolysiloxane (both ends or one end of dimethylpolysiloxane). Contains a copolymer in which the terminal end is blocked with the above polyester moiety, or conversely, the above polyester is blocked with dimethylpolysiloxane), 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 uniformly determined as it may vary depending on the type of silicone oil. The amount is 0.5 to 50% by weight, preferably 1 to 20% by weight.

Curing reaction type silicone oils include reaction curing type,
Examples include photo-curing type and catalyst-curing type.

Examples of reaction-curing silicone oils include those obtained by reaction-curing amino-modified silicone oil and epoxy-modified silicone oil.

In addition, KS-, 705F-PS%KS-705F-PS is used as catalyst curing type or photo-curing type silicone oil.
-1, KS-770-PL-3 [all catalyst curing silicone oils: manufactured by Shin-Etsu Chemical Co., Ltd.], KS-7
20, KS-774-PL-3 [all photocurable silicone oils: manufactured by Shin-Etsu Chemical Co., Ltd.], and the like.

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
5, 60-130735, JP 1-127387
Examples include the antioxidants described in et al., and compounds known to improve image durability in photographs and other image recording materials.

As the UV absorber and light stabilizer, JP-A-59-
158287, 63-74686, 63-145
089, 59-196292, 62-2295
94.63-122596, 61-283595,
Examples include compounds described in JP-A-1-204788 and other 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,
Examples of the organic particles include titanium oxide, acid clay, activated clay, and alumina. Examples of organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicone resin particles. These inorganic/organic resin particles vary depending on their specific gravity, but they range from 0°1 to 70% by weight.
The addition of is preferred.

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

Examples of the plasticizer include phthalate esters (for example, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate,
didecyl phthalate, etc.), trimellitic acid esters (
For example, trimellitic acid octyl ester, trimellitic acid isononyl ester, trimellitic acid isodesol ester, etc.), pyromellitic acid esters such as pyromellitic acid octyl ester, adipate esters (dioctyl adipate, methyl lauryl adipate, etc.) , di-2-ethylhexyl adipate, ethyl lauryl adipate, etc.), other oleic acid esters, succinic acid esters, maleic acid esters, sepatic acid esters, citric acid esters, distearic acid epoxy, and phosphoric acid. Orthophosphoric esters such as triphenyl and tricresyl phosphate, phosphorous esters such as triphenyl phosphite and trisene phosphite, and glycol esters such as ethyl phthalyl ethyl glycolate and butylphthalyl butyl glycolate. can give.

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.

1.Support 1. Supports for the image-receiving sheet for thermal transfer recording include paper, coated paper, synthetic paper (polypropylene, polystyrene, or a composite material made by gluing these together with paper), white polyethylene terephthalate base film, transparent polyethylene terephthalate Examples include base film, transparent polyethylene naphthalate base film, polyolefin-coated paper, and the like. The thickness of the support is usually 20 to 300 mm
μm, preferably 20 to 300 μm.

[2] Production of image-receiving sheet for thermal transfer recording The image-receiving sheet for thermal transfer recording H is prepared by preparing a coating liquid for the image-receiving layer by dispersing or dissolving the components forming the image-receiving layer in a solvent, and then applying the coating solution for the image-receiving layer. It can be manufactured by a coating method in which a coating solution is applied to the surface of a support and dried.

It can also be produced by a lamination method, etc., in which a mixture containing the components forming the image-receiving layer is melt-extruded and laminated onto the surface of a support.

Examples of the solvent used in the coating method include conventionally known solvents such as water, alcohol, methyl ethyl ketone, toluene, dioxane, and cyclohexanone.

When employing the lamination method, a coextrusion method may also be employed.

The image receiving layer may be formed over the entire surface of the support, or may be formed on a part of the surface of the support. The thickness of the image receiving layer formed on the surface of the support is generally about 2 to 50 um, preferably about 3 to 20 Jfm.

On the other hand, when the image-receiving layer itself forms an image-receiving sheet for thermal transfer recording because the image-receiving layer is self-supporting, the thickness of the image-receiving layer is 60 to 200 μm, preferably 9 OLLm to
It is about 150 μm.

In addition, in this image-receiving sheet for thermal transfer recording, in order to more effectively prevent fusion with the ink layer of the ink sheet for thermal transfer recording, a release material (the above-mentioned silicone resin, modified silicone resin, A release layer containing a silicone oil film or a cured product thereof may be further laminated.

The thickness of this release layer is usually 0.03 to 2.0 am.

Further, in the image-receiving sheet for thermal transfer recording of the present invention, a cushion layer may be provided between the support and the image-receiving layer.

By providing a cushion layer, it is possible to transfer and record an image corresponding to image information with good reproducibility with less noise.

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

The thickness of the cushion layer is usually 1 to 50 μm, preferably 3 to 30 μm.

[3] Ink sheet for thermal transfer recording The ink sheet for thermal transfer recording can be composed of a support described below and an ink layer formed thereon.

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

1. Heat-diffusible dyes 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
No. 0-53563, No. 60 130735, No. 60-
No. 131292, No. 6゜-239289, No. 61-1
No. 9396, No. 61-22993, No. 61-3129
No. 2, No. 61-31467, No. 61-35994,
No. 61-49893, No. 61-148269, No. 6
No. 2-191191, No. 63-91288, No. 63-
Examples include naphthoquinone dyes, anthraquinone dyes, and azomethine dyes described in publications such as No. 91287 and No. 63-290793.

Examples of the magenta dye include JP-A-59-78896, JP-A-60-30392, and JP-A-60-30394.
No., JP-A-60-253595, JP-A-61-262
No. 190, JP-A-63-5992, JP-A-63-20
No. 5288, JP-A-64-159, JP-A-64-63
Examples include anthraquinone dyes, azo dyes, and azomethine dyes described in various publications such as No. 194.

As yellow pigments, JP-A-59-78896, JP-A-60-27594, JP-A-60-31560,
Methine dyes, azo dyes, quinophthalone dyes, which are described in JP-A-60-53565, JP-A-61-12394, JP-A-63-122594, etc.
Examples include andrainthiazole dyes.

Particularly preferable heat-diffusible dyes are those obtained by coupling a compound having an open-chain or closed-chain active methylene group with an oxidized product of a p-phenylenediamine derivative or an oxidized product of a p-aminophenol derivative. It is an indoaniline dye obtained by a coupling reaction between an azomethine dye and an oxidized product of a phenol or naphthol derivative, a p-phenylenediamine derivative, or an oxidized product of a p-aminophenol derivative.

The heat-diffusible dye contained in the ink layer may be any of a yellow dye, a magenta dye, and a cyan dye, as long as the image to be formed is monochromatic.

Further, depending on the tone of the image to be formed, two or more of the above three types of dyes or other heat-diffusible dyes may be included.

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. Binders used in the binder ink layer include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, and cellulose butyrate; polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, and polyester. , polyvinyl acetate, polyacrylamide, polyvinyl acetoacetal, styrene resin, styrene copolymer resin, polyacrylic acid ester, polyacrylic acid, vinyl resin such as acrylic acid copolymer, rubber resin, ionomer resin, olefin resin Examples include resin.

Among these resins, polyvinyl butyral, polyvinyl acetoacetal, or cellulose resins, which have excellent acid resistance, are preferred.

The above-mentioned various binders can be used alone or in combination of two or more.

The weight ratio of the binder and the heat diffusible dye is 1:1O
-10:1 is preferred, and a range of 2:8-8:2 is particularly preferred.

3. Other optional components Furthermore, various additives can be added to the ink layer within a range that does not impede the object of the present invention.

As additives, silicone resin, silicone oil (
Reaction curing type is also available), silicone modified resins, fluororesins, surfactants, and release compounds such as waxes, fillers and binder components such as fine metal powders, silica gel, metal oxides, carbon black, and fine resin powders. curing agents (for example, radiation-active compounds such as incyanates, acrylics, and epoxies) that can react with the curing agent.

Furthermore, examples of additives include heat-melting substances for promoting transfer, such as waxes and higher fatty acid esters, which are described in JP-A-59-106997.

1.Support 1.As a support for the ink sheet for thermal transfer recording, any material can be used as long as it has good dimensional stability and can withstand the heat during recording with a thermal head, but thin paper such as condenser paper or glassine paper can be used. Heat resistant plastic films such as , polyethylene terephthalate, polyethylene naphthalate, polyamide, polycarbonate, polysulfone, polyvinyl alcohol cellophane, polystyrene can be used.

The thickness of the support is preferably 2 to IO μm, and the support may have a subbing layer for the purpose of improving adhesion with the binder and preventing transfer and dyeing of the dye to the support side. .

Furthermore, an anti-sticking layer may be provided on the back surface of the support (the side opposite to the ink layer) for the purpose of preventing the head from fusing, sticking, or wrinkling the support.

The thickness of this anti-sticking layer is usually 0.1 to lu
It is m.

The shape of the support is not particularly limited, and may be of any shape, such as a wide sheet or film, or a narrow tape or card.

[4] Manufacture of ink sheet for thermal transfer recording The ink sheet for thermal transfer recording is produced by preparing a coating liquid for forming an ink layer by dispersing or dissolving the various components forming the ink layer in a solvent, and then applying the coating liquid. It can be manufactured by coating the surface of a support and drying it.

Note that one or more of the binders are used by dissolving them in a solvent or dispersing them in a latex form.

The solvents include water, alcohols (e.g. ethanol, propatool), cellosolve I (e.g. methyl cellosolve, ethyl cellosolve), aromatics (e.g. toluene, xylene, chlorobenzene), ketones (e.g. acetone, methyl ethyl ketone), Examples include ester solvents (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, dioxane), and chlorine solvents (eg, chloroform, trichloroethylene, etc.).

For the coating, conventional methods such as surface sequential coating using a gravure roll, extrusion coating, wire bar coating, roll coating, etc. can be employed.

The ink layer may be formed as a layer containing a monochromatic heat-diffusible dye on the entire surface or a part of the surface of the support, or a yellow ink layer containing a binder and a yellow dye, or a layer containing a binder and a yellow dye. Even if a magenta ink layer containing a binder and a magenta dye and a cyan ink layer containing a binder and a cyan dye are formed on the entire surface or a part of the surface of the support in a constant repetition along the planar direction, good.

Further, in addition to the three ink layers arranged along the plane direction, a black ink layer containing a black image forming substance may be interposed.

Note that with regard to the black ink layer, clear images can be obtained with either the diffusion transfer type or the melt transfer type.

The thickness of the ink layer thus formed is usually 0.2~
IOam, preferably 0.3 to 3 μm.

In the present invention, it is also possible to facilitate use by forming a perforation shim on the ink sheet for thermal transfer recording, or by providing a detection mark for detecting the position of areas with different hues. .

Note that the ink sheet for thermal transfer recording is not limited to the structure consisting of a support and a heat-sensitive layer formed thereon, and other layers may be formed on the surface of the ink layer.

For example, an overcoat layer may be provided for the purpose of preventing fusion with the image-receiving sheet for thermal transfer recording and setting-off (blocking) of the heat-diffusible dye.

[5] Image formation (thermal transfer recording) To form an image, the ink layer of the ink sheet for thermal transfer recording and the image-receiving layer of the image-receiving sheet for thermal transfer recording are overlapped, and an image is formed on the interface between the ink layer and the image-receiving layer. Gives heat energy to Wise.

Then, the heat-diffusible dye in the ink layer is vaporized or sublimated in an amount corresponding to the applied thermal energy, transferred to the image-receiving layer side, and received.

As a result, an image is formed on the image-receiving layer.6 In the present invention, since the image-receiving layer of the image-receiving sheet for thermal transfer recording contains a vinyl chloride resin and a vinyl chloride copolymer, it has good coating properties and is It has excellent storage stability and has good gloss after image formation.

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

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

In this case, to make it easier to absorb laser light.

Laser light absorbing materials (for example, in the case of semiconductor lasers,
Carbon black, infrared absorbing substances, etc.) may be present in the ink layer or near the ink layer.

If a dot generator with a built-in acousto-optic element is used, thermal energy can be applied depending on the size of the halftone dot.

When using a laser beam, it is preferable to bring the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording into close contact with each other.

When using an infrared flash lamp as a heat source that provides thermal energy, as with laser light,
Heating is preferably performed through a colored layer such as black.

Alternatively, heating may be performed through a pattern or halftone dot pattern that continuously expresses the shading of an image, such as black, or a colored layer such as black on the side and a negative pattern corresponding to the negative of the above pattern. Heating may be performed in combination.

Thermal energy may be applied from the ink sheet side for thermal transfer recording, from the image receiving sheet side for thermal transfer recording, or from both sides, but if priority is given to effective use of thermal energy, It is desirable to perform this from the ink sheet side for thermal transfer recording.

By the above thermal transfer recording, it is possible to record a one-color image on the image receiving layer of the image receiving sheet for thermal transfer recording, but according to the method described below, it is also possible to obtain a color photo-like color image consisting of a combination of layers of each color. can.

For example, sequentially replace the yellow, magenta, cyan, and, if necessary, black heat-sensitive sheets for thermal transfer recording.
By performing thermal transfer according to each color, it is also possible to obtain a color photographic color image consisting of a combination of each color.

The following method is also effective.

That is, instead of using ink sheets for heat-sensitive transfer recording of each color as described above, an ink sheet for heat-sensitive transfer recording is used that has areas pre-painted in each color.

Then, first, the yellow area is used to thermally transfer the yellow color separation image, then the magenta area is used to thermally transfer the magenta color separation image, and then the process is repeated sequentially to create yellow, magenta, cyan, and the necessary A method is adopted in which the image is thermally transferred in order with the black separated color image.

Although it is possible to obtain a color photographic-like color image with this method as well, this method has the further advantage that there is no need to replace the heat-sensitive sheet for heat-sensitive transfer recording as described above.

[Example] Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In addition, in the following, "part F" means "part by weight".

(Example 1) On the corona-treated surface of a 6 μm thick polyethylene terephthalate film [manufactured by Toshiku Co., Ltd.] as a support,
A coating solution for forming an ink layer with the following composition is applied by wire bar coating method so that the thickness after drying becomes 1 lum, and while drying, silicone oil [manufactured by Shin-Etsu Silicone Co., Ltd., x-41
.

Coating liquid for forming ink layer Disperse dye・・・・・・・・・・・・・・・4 parts [manufactured by Nippon Kayaku C Co., Ltd., Kayaset Blue 136] Polyvinyl butyral・・・・・・・・・・・・・5 parts [degree of polymerization 1700, manufactured by Blockchain Chemical Industry Co., Ltd., trade name BX-1] Methyl ethyl ketone 90 parts cyclohexanone 5 parts Next, A coating solution for forming an image-receiving layer having the following composition was coated on a 150-μm-thick synthetic paper [YUBO FPG-150, manufactured by Tamago Yuka Synthetic Paper Co., Ltd.] as a support by wire bar coating, and then temporarily coated with a dryer. After drying, it was dried in an oven at a temperature of 100° C. for 1 hour to obtain an image-receiving sheet for thermal transfer recording in which an image-receiving layer with a thickness of 5 μm was formed on synthetic paper.

Coating liquid for image-receiving layer formation: Vinyl chloride resin... 5 parts vinyl chloride-isobutyl ether copolymer......
...4 parts [manufactured by BASF, Laroflex-MP25] Polyester modified silicone resin ...1 part [manufactured by Shin-Etsu Silicon Co., Ltd., X-24-83001 Methyl ethyl ketone ...3 ( ll cyclohexanone...
...... 10 copies Next, the ink sheet for heat-sensitive transfer recording and the image-receiving sheet for heat-sensitive transfer recording are overlapped so that the surface of the ink layer of the former is in contact with the surface of the image-receiving layer of the latter, Output of 0.4 W/dot using a thermal head from the support side of an ink sheet for thermal transfer recording.

Image recording was performed by heating under the conditions of a pulse width of 0.3 to 1 m sec and a dot density of 6 dots/mm.

After recording the image, the light storage stability of the image and the glossiness of each image were evaluated. The coatability in forming the image-receiving layer was also evaluated. The results are shown in Table 1.

Light storage stability: The image-receiving sheet for thermal transfer recording on which an image was recorded was exposed to light for 72 hours using a xenon weather meter, and then the image was visually evaluated.

○: There is little discoloration or fading of the pigment.

×: Significant discoloration and fading of pigment.

Gloss: 60 degrees incident on the surface of the image-receiving layer after image formation.

The gloss level at 60 degree reflection was measured.

(Example 2) The same procedure as in Example 1 was carried out except that the coating liquid for forming an image-receiving layer in Example 1 had the following composition.

The results are shown in Table 1.

Coating liquid for forming image-receiving layer Vinyl chloride-vinyl propionate copolymer [manufactured by Tosoh Corporation, Ryuron Q640] 4 parts Vinyl chloride resin 5 parts C Shin-Etsu Chemical Co., Ltd. Manufactured by Co., Ltd.
TK-300, degree of polymerization 300] Urethane-modified silicone resin...1 part [Dialomer-5P-7121 manufactured by Dainichiseika C Co., Ltd.] Methyl ethyl ketone...30 parts Cyclohexanone...
10 parts (Example 3) 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.

Coating liquid for image-receiving layer formation Glycidyl group-containing vinyl chloride copolymer [manufactured by Nippon Zeon Co., Ltd., MR-1201...4 parts Vinyl chloride resin......5 parts [Shin-Etsu Chemical Co., Ltd.] Polyester modified silicone resin: 0.5 part [X-24-8300, manufactured by Shin-Etsu Silicone Co., Ltd.] Triphenyl phosphate (plasticizer)・0.5 parts methyl ethyl ketone 30 parts cyclohexanone
...10 parts (Comparative Example 1) In Example 1, the vinyl chloride-isobutyl ether copolymer, which is one of the components of the coating solution for forming the image-receiving layer, was replaced with vinyl chloride resin, and the solid content concentration was reduced to 10 parts. The same procedure as in Example 1 was carried out except that the weight percent was used.

The results are shown in Table 1.

(Comparative Example 2) The same procedure as in Example 1 was carried out except that the vinyl chloride resin, which was one of the components of the coating solution for forming the image-receiving layer in Example 1, was entirely replaced with vinyl chloride-vinyl isobutyl ether copolymer. .

The results are shown in Table 1.

[Effects of the Invention] According to the present invention, by containing a vinyl chloride resin and a vinyl chloride copolymer in the image-receiving layer, 1. Good coating properties, excellent lamp storage stability, and relatively low gloss after image formation are achieved. A good image-receiving layer sheet can be obtained.

, April 19, 1991

Claims (1)

[Claims] (1) An image-receiving sheet for thermal transfer recording, characterized by having an image-receiving layer containing a vinyl chloride resin and a vinyl chloride copolymer.