JPH0412889A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer image receiving material imparting high image density and having excellent image preservability by providing an image receiving layer containing a dye receivable thermoplastic resin on a support and adding a resin containing a specific component to the thermoplastic resin. CONSTITUTION:In a thermal transfer image receiving material wherein an image receiving layer containing a dye receivable thermoplastic resin is provided on a support, the thermoplastic resin contains a resin containing a component represented by a structural formula I. As a known thermoplastic resin having a skeleton similar to the structural formula I, there are a polycarbonate resin and a copolymerized polyester resin containing bisphenol A as a diol component. It is pref. that 5mol.% or more of a monomer component containing the component represented by the structural formula is contained among all monomer components constituting the thermoplastic resin.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thermal transfer image-receiving material used in a thermal transfer recording method, and in particular a thermal transfer image-receiving material that can obtain images with high density and excellent image storage stability. It is related to.

(Background Art) In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and devices suitable for each information processing system have also been developed and adopted.

The thermal transfer recording method is one of these recording methods, and has recently become widely used because the equipment used is lightweight, compact, noiseless, has excellent operability and maintainability, and can be easily converted to color. . This thermal transfer recording method can be roughly divided into two types: a thermal melting type and a thermal transfer type. In the latter method, a thermal transfer dye-providing material having a dye-providing layer containing a binder and a heat-transferable dye on a support is superimposed on a thermal transfer image-receiving material, and heat is applied from the support side of the dye-providing material to create a pattern formed by the thermal application. This is a method of obtaining a transferred image by transferring a heat-transferable dye onto a recording medium (thermal transfer image-receiving material).

Note that the term "thermally transferable dye" as used herein refers to a dye that can be transferred from a thermal transfer dye-providing material to a thermal transfer image-receiving material by sublimation or diffusion in a medium.

(Issues to be Solved by the Invention) However, images obtained using conventional thermal transfer image-receiving materials do not have sufficient image a degree, or do not have sufficient storage stability, especially light fastness. When exposed to sunlight or fluorescent light, there were problems such as changes in the hue of the image and a decrease in image density.

(Means for Solving the Problem) The above problem is to provide a thermal transfer image-receiving material having an image-receiving layer containing a thermoplastic resin capable of receiving a dye on a support, in which the thermoplastic resin has the following structural formula a. The problem was solved by a thermal transfer image-receiving material characterized by containing a resin containing components.

Structural Formula a The support used in the thermal transfer image-receiving material of the present invention is not particularly limited, and any known support can be used.

General specific examples of supports are listed below.

■Synthetic paper (polyolefin-based, polystyrene-based, etc.), high-quality paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, paper impregnated with synthetic resin or Emulnoyon, paper impregnated with synthetic rubber latex, synthetic resin Paper supports such as internally lined paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), ■
Various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, etc., and films or notebooks treated to give white reflective properties to these plastics.

Moreover, a laminate formed by any combination of the above items (1) to (2) can also be used.

Among these, polyolefin coated paper is preferred because it has features such as not causing concave deformation due to heating during thermal transfer, excellent whiteness, and little curling.

Regarding polyolefin coated paper, for example, it is described in "Fundamentals of Photographic Engineering FM (Silver Salt Photography Edition)" edited by the Photographic Society of Japan (Corona Publishing, 1979), pages 223-240.
This polyolefin coated paper basically consists of a support sheet and a polyolefin layer coated on the surface of the support sheet. The support sheet is made of something other than synthetic resin, and -
High-quality paper is used for boat fishing. The polyolefin coat may be applied by any method as long as the polyolefin layer is in close contact with the surface of the support sheet, but it is usually applied by an extrusion method. The polyolefin coat layer may be provided only on the surface of the support sheet on which the receptor layer is provided, but it may also be provided on both the front and back surfaces. Polyolefins used include high density polyethylene, low density polyethylene,
Examples include polypropylene, but any material may be used. However, considering the heat insulation effect during transfer, it is preferable to use low-density polyethylene, which has lower thermal conductivity, on the side where the receiving layer is provided.

The thickness of the polyolefin coat is not particularly limited, but is usually preferably 5 to 100 mm thick on one side. However, in order to obtain a higher transfer density, it is preferable that the polyolefin coat on the receiving layer side be thinner. Pigments and fillers such as titanium oxide and ultramarine blue may be added to the polyolefin coat to increase whiteness.

In addition, polyolefin coated paper has 0.05 to 0.47
A gelatin layer as thin as r+ may be provided.

The thermal transfer image-receiving material is provided with a dye image-receiving layer.

This image-receiving layer functions to receive the dye transferred from the thermal transfer dye-providing material during printing and to dye the image. The image-receiving layer is preferably a film containing a dye-receiving substance alone or together with other binder substances and having a thickness of about 0.5 to 50 mm.

In the present invention, the thermoplastic resin used for this image-receiving layer includes:
It is characterized by using a thermoplastic resin containing a component represented by structural formula a.

Known thermoplastic resins having a skeleton similar to Structural Formula a include polycarbonate resins having repeating units of Structural Formula II below, copolymerized polyester resins containing bisphenol A component as a diol component, etc. Thermoplastic resins containing this bisphenol A component have higher dyeability than thermoplastic resins that do not contain this component. Therefore, a thermal transfer image-receiving material containing a thermoplastic resin containing a bisphenol A component in the image-receiving layer can obtain a high image density. However, on the other hand, the use of a resin containing a bisphenol A component has the disadvantage of deteriorating the storage stability of images, especially the light fastness.

On the other hand, the component of structural formula a in the thermoplastic resin of the present invention is similar to the bisphenol A component that improves image density (although it has this structure, it deteriorates the storage stability, especially the light fastness) of the obtained image. It has been found that it has the characteristic of not causing

Preferred specific examples of the thermoplastic resin having a monomer component containing the component of structural formula a are shown below, but the thermoplastic resin of the present invention is not limited thereto.

■ Thermoplastic resin structural formula 〇■ having a repeating unit of the following structural formula C Copolymerized thermoplastic polyester resin structural formula d ] l CH2CHz '''C)12' ■ The following structure Copolymerized thermoplastic polyester resin containing the component of formula e as a diol component Diol components other than structural formulas d and e contained in the copolymerized thermoplastic polyester resin of structural formulas Ethylene glycol, polyethylene glycol, opentyl glycol, propylene glycol, 1,4-butanediol, 1
, 5-bentanediol, 16-hexanediol, polytetramethylene glycol, 14-nochlorohexanedimethanol, trimethylolpropane, pentaerythritol and the like. In addition, dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,
6 naphthalene dicarboxylic acid, biphenyl dicarboxylic acid,
Adipic acid, sheric acid, azelaic acid, sehanic acid,
Examples include dodecanedioic acid, 1,4-chlorohexanedicarboxylic acid, and trimellitic acid. In addition, as a component containing both hydroxyl group and carboxyl group, ε-
Examples include oxicaproic acid and β-hydrokinoethquin benzoic acid.

The thermoplastic resin of the present invention preferably contains 5 mo1% or more of the monomer component containing the component of structural formula a out of all the monomer components constituting the thermoplastic resin.

Moreover, it is preferable to use the thermoplastic resin of the present invention in a coating amount of 1 g to 100 g per 1 rrf of support.

Furthermore, the thermoplastic resin of the present invention may be used by mixing two or more thermoplastic resins containing the component of structural formula a, or may be mixed with a dye-receiving resin that does not contain the component of structural formula a. You can use it as well. In this case, it is preferable that the thermoplastic resin of the present invention is contained in an amount of 5 to 100% by weight among the resin components contained in the image-receiving layer.

Examples of the dye-receiving resin that can be mixed with the thermoplastic resin of the present invention include the following resins.

(a) Those having an ester bond Dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic H components contain sulfone groups,
Polyester resins obtained by condensation of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc. with carboxyl groups (which may be substituted with carboxyl groups, etc.): polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl Polyacrylic acid ester resin or polymethacrylic acid ester resin such as acrylate: Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A No. 59-101395, No. 63-7971, No. 63-7972, and No. 63-79.
Examples include those described in No. 73 and No. 60-294862. In addition, commercially available products include Toyobo H's Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron G-140, Byron GK-130, Kao's ATR-2009, AT
R-2010 etc. can be used.

(b) Those with urethane bonds polyurethane resin, etc.

(c) Those with an amide bond polyamide resin, etc.

(d) Those with urea bonds urea resin etc.

(e) Those with a sulfone bond polysulfone resin, etc.

(v) Others containing highly polar bonds, such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

In addition to the synthetic resins mentioned above, mixtures or copolymers thereof can also be used.

In the thermal transfer image-receiving material, especially in the image-receiving layer, a high-boiling-point compound is used as a dye-receiving substance or as a dye diffusion aid! A solvent or a hot solvent can be included.

Examples of high boiling point organic solvents include JP-A-59-83154;
No. 59-178451, No. 59-178452, No. 59-178453, No. 59-178454, No. 5
Esters (e.g. phthalates, phosphoric esters, fatty acid esters R), amides (e.g. fatty acid amides, sulfamides), ethers as described in No. 9-178455, No. 59-178457, etc. Examples include compounds such as alcohols, paraffins, and silicone oils.

As a heat solvent, it must be: ■ compatible with the dye but incompatible with the water-soluble binder; ■ solid at room temperature;
Melts when heated by the thermal head during transfer (
Compounds that have various properties such as being able to be mixed and melted with other components and not being decomposed by thermal heating are used. Preferably 35-2
Preference is given to compounds which exhibit a melting point of 50 DEG C., especially 35 DEG to 200 DEG C., and have an (inorganic/organic) value <1.5. Here, inorganicity and organicity are concepts for predicting the properties of compounds.
1957).

Specific examples of high-boiling organic solvents and thermal solvents include JP-A-62-174754, JP-A-62-245253, and JP-A-6
No. 1-209444, No. 61-200538, No. 62
-8145, 629348, 62-30247
No. 62-136646.

High-boiling organic solvents and/or thermal carriers can be used alone in microdispersed form in the image-receiving layer;
It can also be used in combination with a dye-receiving polymer.

Further, the above-mentioned high boiling point organic solvent may be used for the purpose of improving shearability, peelability, curl balance, etc.

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which (1) a substance capable of receiving a heat-transferable dye is provided alone on a support, or (2) a substance capable of receiving a heat-transferable dye is provided in a water-soluble form. It may also be configured to be dispersed and supported in a binder. Various known water-soluble polymers can be used as the water-soluble binder used in the case (2), but water-soluble polymers containing groups capable of crosslinking with a hardening agent are preferred.

The water-soluble polymers used in the present invention include vinyl polymers such as polyvinyl alcohol, polyvinylpyridinium, cationic modified polyvinyl alcohol, and derivatives thereof.
No. 750, No. 61-143177, No. 61-2351
No. 82, No. 61-245183, No. 61-23768
1, No. 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or its salt, acrylic acid-methacrylic acid copolymer or its salt, polymethacrylic acid or its salt, acrylic Acrylic group-containing polymers such as acid-vinyl alcohol copolymers or salts thereof (JP-A-60-168651, JP-A-62-9)
988), starch, oxidized starch, starch acetate, amine starch, carboxyl starch, dialdehyde starch, cationic starch, dextrin, sodium alginate, gelatin, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxyl methylcellulose, Natural polymers or their derivatives such as hydroquine propyl cellulose (
JP 59-174382, JP 60-262685, JP 61-143177, JP 61-181679,
61-193879, 61-287782), polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, maleic acid vinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer, maleic acid-alkyl vinyl ether copolymer synthesis, synthetic polymers such as polyethyleneimine (JP-A-61-32
No. 787, No. 61-237680, No. 61-2774
83) and the water-soluble polymers described in JP-A No. 56-58869.

Furthermore, various copolymers made water-soluble by monomer components containing 503- groups, COO- groups, SO,- groups, etc. can also be used.

It is particularly preferable to use gelatin as the water-soluble binder because it can be dried centrifugally and the drying load is much lower. Specifically, gelatin and its derivatives such as lime-treated gelatin, decalcified lime-treated gelatin, acid-treated gelatin, phthalated gelatin, acetylated gelatin, succinated gelatin, Bull, Soc, Phot,
Examples include oxygen-treated gelatin, gelatin hydrolysates, and oxygen-decomposed products, as described in Japan, N. (116, P3 (1966)).

Only one type of these water-soluble polymers may be used,
Two or more types may be used in combination.

The water-soluble binder and the receptive substance have a weight ratio of receptive substance/water-soluble binder=1 to 20, preferably 2 to 10.
Particularly preferably, it is used in a range of 2.5 to 7.

When using a water-soluble binder, a receiving layer can be obtained by applying and drying an aqueous solution containing a dye-receiving substance.

As a method for dispersing a receptive substance in a water-soluble binder, any known dispersion method for dispersing a hydrophobic substance in a water-soluble polymer can be used.

Typical methods include emulsifying and dispersing a receptive substance dissolved in an organic solvent that is immiscible with water and mixing it with an aqueous solution of a water-soluble binder; There are ways to mix it with.

The water-based one? gH is an aqueous solution of a water-soluble dye-receiving resin or a blend i8 of it and a water-soluble polymer with low dye-receptivity.
It may be a liquid, or it may be a dye-receiving fine particle dispersion or a fluorinated solution of the dispersion and a water-soluble polymer having low dye-receptivity.

Also, the accepting substance (polymer) has a water-soluble group (for example, C00
M, So, gate, -0-503M, (-0CHzGH
z) 11; where M is an alkali metal ion, n-integer) may be introduced to form a water-soluble polymer, which may be used alone or in combination with the above-mentioned water-soluble binder.

A specific example of a receptive polymer latex or a receptive water-soluble polymer is Plus Coat Z- manufactured by Gooi Kagaku.
466, Z-448, Z-455, Z-461, Z-7
61, Z-771, Beth Resin A-124 manufactured by Takamatsu Yushi Co., Ltd.
3. A-2141, A-2151, Dainippon Ink Finetex ES611, ES-650, ES-6
70, ES-675, ES-850, etc.

On the other hand, in case (2) above, the polymer used in the receiving layer for the heat-transferable dye is soluble in organic solvents, so the coating solution for the receiving layer is organic solvent-based. Therefore, in order to apply an organic solvent-based coating liquid onto the porous layer according to the present invention as an image-receiving layer,
There is a disadvantage in that the porous layer mainly composed of cellulose acetate is partially dissolved in the V-organic solvent, reducing the heat insulating effect.

Furthermore, it is necessary to clean the equipment, containers, etc. used for manufacturing with an organic solvent. Therefore, explosion-proof equipment is required for coating liquid preparation equipment, coating equipment, etc., and since the 8g solvent is more expensive than water, it not only increases production costs, but also concerns health management of workers. There is also a problem. Furthermore, in order to obtain a high-density image, a polymer that softens or becomes rubbery during thermal transfer is used as a binder in the receiving layer, or a plasticizer is used. However, when such means are used, the transfer surface at the highest density portion becomes uneven and also loses its gloss. Furthermore, when the thermal transfer image-receiving material after transfer is stored for a long period of time, blurring of the image is likely to occur.

However, in the case of (2) above, the dye-receiving substance is not applied with an organic solvent as in the case of (2), but is applied by dispersing the dye-receiving substance in a water-soluble binder, so coating using water as a solvent is not possible. , there is no danger of explosion, the manufacturing cost is significantly reduced, and the negative impact on the health of workers is also very low.

In addition, the layer in which a dye-receiving material is dispersed in a water-soluble binder sufficiently receives heat-transferable dyes, resulting in images with high transfer density.Moreover, the resulting images do not become blurry even after long-term storage. It has the advantage of being extremely small.

Therefore, the image-receiving layer used in the present invention preferably has a structure in which a substance capable of receiving a heat-transferable dye is dispersed and supported in a water-soluble binder, as in the case (2) above.

The image receiving layer may be one layer or may be composed of two or more layers. When two or more layers are provided, a synthetic resin with a low glass transition point is used for the layer closer to the support, or a high boiling point organic solvent or a hot solvent is used to improve the dyeability of the dye.
For the outermost layer, a synthetic resin with a higher glass transition point is used, and the use of high boiling point solvents and thermal solvents is minimized or not used to prevent surface sagging, adhesion with other substances, etc. It is desirable to have a structure that prevents failures such as retransfer of the dye to other substances after transfer and blocking with the thermal transfer dye-providing material.

The total thickness of the image-receiving layer is 0.5 to 50 tM, especially 3 to 30 tM.
In the case of the p,2 Jil configuration, the outermost layer preferably has a density in the range of 0.1 to 20<-1>, particularly 0.2 to 10<-1>.

The thermal transfer image-receiving material of the present invention may have an intermediate layer between the support and the image-receiving layer.

The intermediate layer can be a cushion layer, a porous layer, or a
This layer has one of the functions of a dye diffusion prevention layer or a layer having two or more of these functions, and in some cases also serves as an adhesive.

The dye diffusion-preventing layer plays a role, in particular, in preventing the heat-transferable dye from diffusing into the support. The binder constituting this diffusion prevention layer may be water-soluble or organic solvent-soluble, but preferably a water-soluble binder.
Preferred examples include the water-soluble binders mentioned above as binders for the image-receiving layer, particularly gelatin.

The porous layer is a layer that prevents the heat applied during thermal transfer from diffusing from the image-receiving layer to the support and effectively utilizes the applied heat.

From this, a water-soluble polymer solution with bubbles generated is applied and dried. 3) A water-soluble polymer solution containing a foaming agent is foamed before application or foamed during the coating drying process. 4) Water-soluble Microvoids can be formed by emulsifying and dispersing an organic solvent (preferably a solvent with a boiling point higher than water) in a liquid polymer melt, and forming microvoids during the coating and drying process.

When using an organic solvent-soluble binder as the porous layer, ■) support a liquid in which air bubbles are generated by mechanically stirring a synthetic resin emulsion such as polyurethane or a synthetic rubber latex such as methyl methacrylate-butadiene. 2) Apply the above synthetic resin emulsion or synthetic rubber latte 2x mixed with a foaming agent onto the support and dry it. 3) Synthetic resin such as PVC plastisol, polyurethane, or styrene. A mixture of synthetic rubber such as butadiene and a foaming agent is applied onto a support and foamed by heating. A mixed liquid with a non-solvent (including those whose main component is water) that is compatible with the solvent and has no solubility in the thermoplastic resin or synthetic rubber is used as a support. A method such as coating on top and drying to form a microporous layer can be used.

When the image-receiving layer is on both sides of the support, the intermediate layer may be provided on both sides or only on one side.

The thickness of the intermediate layer is preferably 0.5 to 50μ, particularly preferably 1 to 20μ.

The image receiving layer, titanium layer, porous layer, diffusion prevention layer, adhesive layer, etc. that constitute the thermal transfer image receiving material of the present invention include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, silicic acid, etc. Fine powder of aluminum, synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina, etc. may be contained.

A fluorescent brightener may be used in the thermal transfer image-receiving material.

Examples include K, Veenkataraman g
'The Chemistry of 5ynthe
tic Dyes” Volume Chapter 8, JP-A-61-143
Examples include compounds described in No. 752 and the like. More specifically, stilhene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, birapurine compounds, carbostyryl compounds, and 2,5-dibenzuoxazolethiophene compounds. Examples include.

Optical brighteners can be used in combination with antifade agents.

The thermal transfer dye-providing material used in the present invention is a thermal transfer dye-providing material having a dye-providing layer containing a heat-transferable dye on a support, in which the dye is transferred in a pattern by applying heat to the image-receiving material of the thermal transfer image-receiving material. A thermal transfer dye-providing material having a heat-melting ink layer (dye-donating layer) on a support and a thermal transfer image-receiving material in which the ink is melted in a pattern by applying heat. This includes two types that are recorded by being transferred to a computer.

The dye-donor layer is formed by selecting a dye so that the desired hue can be transferred when printed, and if necessary, arranging two or more dye-donating layers with different dyes on one thermal transfer dye-donating material. It's okay. For example, when forming an image such as a color photograph by repeatedly printing each color in accordance with color separation signals, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers containing dyes that give .

Alternatively, a dye-donating layer containing a dye that provides a black hue in addition to cyan, magenta, and yellow may be added. It is preferable to provide a mark for position detection at the same time as the formation of any of the dye-donating layers, since this eliminates the need for an ink or printing process separate from the formation of the dye-donating layer.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. Examples include polyethylene terephthalate, polyamide; polycarbonate; glassine paper: condenser paper; cellulose ester; fluorine polymer; polyether; polyacetal; polyolefin; polyimide; polyphenylene sulfide; polypropylene; polysulfone; cellophane.

The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 mm.
μ. An undercoat layer may be provided if necessary. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye-donating layer. This further improves the transfer density.

As the hydrophilic polymer, the water-soluble polymers described above can be used.

A slipping layer may also be provided to prevent the thermal head from sticking to the dye-donating material. This slipping layer is composed of lubricating substances, such as surfactants, solid or liquid lubricants or mixtures thereof, with or without polymeric binders.

A thermal transfer dye-providing material using a heat-transferable dye basically has a dye-providing layer on a support containing a dye that sublimes or becomes mobile by heat and a binder. This thermal transfer dye-providing material is prepared by preparing a coating solution by dissolving or dispersing a dye that sublimes or becomes mobile by heat and a binder resin in an appropriate solvent, and applying this to one side of a support. The thermal transfer layer can be obtained by coating and drying the coating amount to give a dry film thickness of, for example, about 0.2 to 5 μm, preferably 0.4 to 2 μm to form a thermal transfer layer.

Dyes useful for forming such a thermal transfer layer include:
Although any dye conventionally used in thermal transfer dye-providing materials can be used, particularly preferred in the present invention are dyes of about 15
It has a small molecular weight of about 0 to 800, and is selected in consideration of transfer temperature, hue, light resistance, solubility in ink and binder resin, dispersibility, etc.

Specifically, for example, disperse dyes, basic dyes, oil-soluble dyes, etc. can be mentioned, but in particular, Sumikaron Yellow E
4GL, Dianix Yellow 82G-FS.

Miketon Polyeltel Yellow 3GSL, Kayanse Toyelo-937, Sumiriki Ronrendo EFBL, Dianix Red ACE, Miketon Polyeltel Lenod F
B, Kayanose Trend 126, Miketon Fast Fluid Ray B, Kaya Centric Ray 136, and the like are preferably used. Other known heat-transferable dyes can also be used.

Furthermore, as the binder resin used with the above dye, any binder resin conventionally known for this purpose can be used, and usually has high heat resistance and does not hinder the transfer of the dye when heated. things are selected. For example, polyamide resin, polyester resin,
Epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polyvinyl chloride resins (e.g. vinyl chloride-vinyl acetate) copolymers), polyolefin resins, polystyrene, polyphenylene oxide, cellulose resins (e.g. methylcellulose, ethylcellulose, carboxymethylcellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate) )
, polyvinyl alcohol resins (e.g. partially saponified polyvinyl alcohols such as polyvinyl alcohol and polyvinyl butyral), petroleum resins, rosin derivatives, coumaron-indene resins, terpene resins, polyolefin resins (e.g. polyethylene, polypropylene), etc. .

Such a binder resin is preferably used in a proportion of, for example, about 80 to 600 parts by weight per 100 parts by weight of the dye.

In the present invention, any conventionally known ink solvent can be freely used as the ink solvent for dissolving or dispersing the above pigment and binder resin.

A second embodiment of the thermal transfer dye-providing material is an embodiment in which the thermal transfer layer is a thermal melt transfer layer composed of an ink for forming a thermal transfer layer consisting of a wax containing a coloring agent such as a dye or a pigment. This ink is made of a wax with a suitable melting point, such as rose fin wax.

It is made by distributing and dispersing coloring agents such as carbon black and various dyes and pigments using wax, microcrystalline wax, Carnauch wax, and urethane wax as a binder. The ratio of colorant to wax used is approximately 10 to 65% in the heat-melting transfer layer to be formed.
The thickness of the formed layer is preferably in the range of about 1.5 to 6.0% by weight. The production of the ink and its application onto the support can be carried out according to known techniques.

In order to prevent sticking due to the heat of the thermal head and improve slippage when printing from the back side of the dye-donating material, it is preferable to apply an anti-sticking treatment to the side of the support on which the dye-donating layer is not provided.

For example, it is preferable to provide a heat-resistant slip layer mainly consisting of (1) a reaction product of polyvinyl butyral resin and isonoresuite, (2) an alkali metal salt or alkaline earth metal salt of a phosphoric acid ester, and (2) a filler. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000, a glass transition point of 80 to 110°C, and a vinyl butyral portion with a weight percentage of 15 to 40% from the viewpoint of having many reaction sites with isocyanate. The one is good. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafasoku RD720 manufactured by Toho Chemical Co., Ltd. is used, and it is preferably used in an amount of about 1 to 50% by weight, preferably about 10 to 40% by weight, based on the polyvinyl butyral resin.

It is desirable that the heat-resistant slip layer has heat resistance as the lower layer.
A combination of a synthetic resin that can be cured by heating and its curing agent,
For example, a combination of polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isonoanate, cellulose acetate and titanium chelate, or polyester and organic titanium compound may be applied by coating. A hydrophilic rear layer may be provided to prevent the diffusion of . The hydrophilic dye layer contains hydrophilic materials useful for the intended purpose. General Riko Yuna, the results were gelatin, poly(acrylamide), BoIJ (isopropylacrylamide), MEC 1-nole butyl grafted gelatin,
Ethyl methacrylate raft gelatin, cellulose monoacetate, methylcellulose, poly(vinyl alcohol), poly(ethyleneimine), poly(acrylic acid),
G obtained by using a mixture of poly(vinyl alcohol) and poly(vinyl acetate), a mixture of poly(vinyl alcohol) and poly(acrylic acid), or a mixture of cellulose monoacetate and poly(acrylic acid). . Particularly preferred are poly(acrylic acid), cellulose monoacetate or poly(vinyl alcohol).

The dye-providing material may be provided with a subbing layer. In the present invention, any undercoat layer may be used as long as it has the desired effect, but as a preferred example, (acrylonitrile-vinylidene chloride-acrylic acid) copolymer side 1 ratio: 14; 80:6)
, (butyl acrylate-2-aminoethyl methacrylate-2-hydroxoethyl methacrylate) copolymer (polymer ratio 30:20:50), linear/saturated polyester such as Bostik 7650 (Emhart, Bostik) chemical group) or chlorinated high-density poly(ethylene-trichloroethylene) resin.

There is no particular limit to the amount of undercoat layer applied, but it is usually 0.1
~2.0g/IT? used in amounts of

In the present invention, in order to improve the releasability of the thermal transfer dye-providing material and the thermal transfer image-receiving material, the dye-providing material and/or
Alternatively, it is preferable to include a release agent in the layers constituting the image-receiving material, particularly preferably in the outermost layer corresponding to the surface where both materials come into contact.

As mold release agents, solid or waxy substances such as polyethylene wax, amide wax, and Teflon powder; surfactants such as fluorine-based and phosphate esters; conventional oils such as paraffin-based, silicone-based, and fluorine-based oils; Although any known mold release agent can be used, silicone oil is particularly preferred.

As the silicone oil, in addition to unmodified silicone oils, modified silicone oils such as carboxy-modified, amine-modified, and epoxy-modified silicone oils can be used.

Examples include various modified silicone oils described on pages 6 to 18B of the "Modified Silicone Oil" technical data published by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, an amine-modified silicone oil having a group that can react with the crosslinking agent of the binder (for example, a group that can react with isonorsuite) is used after being emulsified and dispersed in a water-soluble noingoo. is a carboxy-modified silicone oil (e.g. manufactured by Shin-Etsu Silicone):
Product name X-22-3710) is valid.

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be hardened with a hardening agent.

When curing a solvent-based polymer, JP-A No. 61
Hardeners described in Japanese Patent No. 199997 and No. 58-215398 can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners.

For curing water-soluble polymers, U.S. Pat.
No. 9, column 41, JP-A-59-116655, JP-A No. 62-
Hardeners described in Japanese Patent No. 245261 and No. 61-18942 are suitable for use. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, etc.], vinyl sulfone hardeners (N,N'-ethylene bis(vinylsulfonylacetamide, etc.) ) ethane etc.), N
-Methylol-based hardeners (such as dimethylol urea), or polymer hardeners (compounds described in JP-A-62-234157, etc.).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Color protection agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

As ultraviolet absorbers, hensitriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, henzphenone compounds (JP-A No. 56-2784, etc.), and other JP-A Nos. 54-48535 and 62-13.
There are compounds described in No. 6641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, US Pat. No. 4,241,155,
No. 4,245,018, columns 3 to 36, No. 4,25
4,195 No. 3-8@, JP-A-62-174741, JP-A-61-88256, pages (27)-(29), Japanese Patent Application No. 1983-234103, JP-A No. 62-31096, JP-A-62 There are compounds described in No.-230596 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

An anti-fading agent for preventing fading of the dye transferred to the image-receiving material may be included in the image-receiving material in advance, or it may be supplied to the image-receiving material from the outside by a method such as transfer from a dye-donating material. It's okay.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

Various surfactants can be used in the constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material for the purposes of coating aids, improving peelability, improving shearability, preventing electrification, accelerating development, and the like.

Nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants can be used. Specific examples of these are disclosed in JP-A-62-173463 and JP-A-62-1.
It is described in No. 83457, etc.

In addition, when dispersing substances that can accept heat-transferable dyes, mold release agents, anti-fading agents, ultraviolet absorbers, optical brighteners, and other hydrophobic compounds in a water-soluble binder, the interface is used as a dispersion aid. Preferably, an activator is used. For this purpose, in addition to the above-mentioned surfactants, JP-A-59-15763
The surfactants described on pages 37-38 of No. 6 are particularly preferably used.

The constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving sheer properties, preventing static electricity, improving releasability, and the like. Typical examples of organic fluoro compounds include fluorine-based surfactants described in Japanese Patent Publication No. 579053, columns 8 to 17, Japanese Patent Application Laid-open Nos. 61-20944 and 62-135826, and oils such as fluorine oil. Examples include hydrophobic fluorine compounds such as solid fluorine compound resins such as solid fluorine compounds or tetrafluoroethylene resins. Specific examples include Daikin Industries@ Daifree MB-313, -E-413, ME-
414,? IE-810, MS-443, MS-743
, MS-043, MS-843, Asahi Glass Co., Ltd., Asahigato, AG-530, AG-533(S), AG-
550, 8G-650, AG-710, AG-730,
Examples include A[;-740, AG-780, AG-800, and Elast Gund 100 manufactured by Dai-Kogyo Pharmaceutical Co., Ltd.

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As a matting agent, silicon dioxide, polyolefin, polycarbonate, etc. are used.
In addition to the compounds described in No.-88256 (page 29), henzoguanamine resin beads, polycarbonate resin beads,
There are compounds described in Japanese Patent Application No. 62-110064 and No. 62-110065, such as AS resin beads.

In the present invention, a thermal transfer dye-providing material is superimposed on a thermal transfer image-receiving material, and thermal energy corresponding to image information is applied from either side, preferably from the back side of the thermal transfer dye-providing material, by a heating means such as a thermal head. As a result, the dye in the dye-donating layer can be transferred to the thermal transfer image-receiving material according to the magnitude of the heating process, and a color image with excellent clarity and resolution and gradation can be obtained.

The heating means is not limited to a thermal head, and known means such as a laser beam (for example, a semiconductor laser), an infrared furanone, a heat vent, etc. can be used.

In the present invention, by combining the thermal transfer dye-providing material with the thermal transfer image-receiving material, images can be printed by printing using various thermal printing printers, by facsimile, or by magnetic recording, magneto-optical recording, optical recording, etc. It can be used to create prints from , television, and CRT screens.

For details on the thermal transfer recording method, see Japanese Patent Application Laid-open No. 603489.
You can refer to the description in No. 5.

(Example) EXAMPLES The present invention will be explained in more detail by way of Examples below.

Example I (Preparation of thermal transfer dye-providing material) A polyethylene terephthalate film (Lumirror: manufactured by Toshi) with a thickness of 5.5 Ijm provided with a heat-resistant slipping layer made of a thermosetting acrylic resin on one side was used as a support. A coating composition for forming a thermal transfer dye-providing layer having the following composition is coated on the side opposite to the side on which the heat-resistant slipping layer is provided by wire bar coating so that the thickness after drying is 2t11n to form a thermal transfer dye-providing layer. I got the material.

Disperse dye-a 4g Polyvinyl butyral resin (Denka Butyral 5000-A: electrochemical type) 4g
Methyl ethyl ketone 40 1d Toluene 40ml 1 Polyisonoanate 0.2m (Bamboo name - D
IION: Sokoen Yakuhin Co., Ltd.) (Preparation of thermal transfer image-receiving material 1) As a support, 150 ㎡ thick synthetic paper (Tamago Yuka Co., Ltd.:
A thermal transfer image-receiving material 1 was prepared by applying a coating composition for an image-receiving layer having the following composition to the surface of YUPO-FPG-150) by wire bar coating so that the dry thickness was 104 mm. Drying was performed for 30 minutes in an oven at a temperature of 100°C after temporary drying with a hair dryer.

: Ryogas Chemical Kneepilon Z-20020g Amino modified silicone oil 1g (KF-857:
(Manufactured by Shin-Etsu Silicone) Polyisocyanate 3g (KP
-90, manufactured by Dainippon Ink) Methyl ethyl ketone 85d Toluene 85-Niepilon Z-200 manufactured by Mitsubishi Gas Chemical is a thermoplastic resin having a repeating unit of the following structural formula C.

Structural formula〇 Example 2 The same content as in Example 1 is used as the thermal transfer dye-providing material.

(Preparation of thermal transfer image-receiving material 2) A coating composition for an image-receiving layer having the following composition was coated on the surface of a support having the same content as in Example 1 by wire bar coating so that the dry thickness was 10-1, and a thermal transfer image-receiving material was prepared. Material 2 was produced. The drying method was the same as in Example 1.

Mitsubishi Gas Chemical Knee Pillow 7Z-20010g Toyobo thermoplastic polyester 10g Resin Vylon 29
0 Amino modified silicone oil 1g (KF
-857 + Shin-Etsu Silicone) Polyisocyanate 3g (KP
-90: Dainippon Ink) Methyl ethyl ketone 85-Toluene 85d Example 3 The same content as in Example 1 was used as the thermal transfer dye-providing material.

(Preparation of thermal transfer image-receiving material 30) A thermal transfer image-receiving material was prepared by applying a coating composition for an image-receiving layer having the following composition on the surface of the same support as in Example 1 by wire bar coating so that the dry thickness was 10-. 3 was prepared. The drying method was the same as in Example 1.

Mitsubishi Gas Chemical Kneepilon Z-200 10g Polyester resin a 10g Amino modified silicone oil 1g (KF-857: Shin-Etsu Silicone) Polyisocyanate 3g (KP
-90: manufactured by Dainippon Ink) Methyl ethyl ketone 85d Toluene 85sff The composition of polyester resin a is shown below. (Unit is mol%) TPA IPA 5IPA EG BI
S-A-EG polyester resin a 24.3 2
4.3 1.6 15TPA: Terephthalic acid IPA: Isophthalic acid EC: Ethylene glycol 15 A-EC: Example 4 The same thermal transfer dye-providing material as in Example 1 is used.

(Preparation of thermal transfer image-receiving material 4) A coating composition for an image-receiving layer having the following composition was coated on the surface of a support having the same content as in Example 1 by wire bar coating so that the dry thickness was 10-1, and thermal transfer was carried out. Image receiving material 4
was created. The drying method was the same as in Example 1.

Accepted, I month JJJ Suukeenri Mitsubishi Gas Chemical Kneepilon Z-20010g Denki Kagaku vinyl chloride vinyl acetate 10g Copolymer resin Eslenoku C Amino-modified silicone oil 1g (KF
-857: Shin-Etsu Silicone) Polyisocyanate 3g (KP
-90: Dainippon Ink) Methyl ethyl ketone 8511i!
Toluene 85 - Example 5 The same content as in Example 1 is used as the thermal transfer dye-providing material.

(Preparation of thermal transfer image-receiving material 5) Prepare resin-coated paper with polyethylene laminated to a thickness of 32-120-mm on both sides of 150-mm paper, and
A composition having the same content as the image-receiving layer coating composition of thermal transfer image-receiving material 1 was applied to the laminated surface with a thickness of Bn by wire bar coating so that the dry thickness was 10-1, thereby forming thermal transfer image-receiving material 5. Created. The drying method was the same as in Example 1.

Example 6 The same thermal transfer dye-providing material as in Example 1 was used.

(Preparation of thermal transfer image-receiving material 6) A thermal transfer image-receiving material was prepared by applying a coating composition for an image-receiving layer having the following composition to the surface of a support having the same contents as in Example 1 by wire bar coating so that the dry thickness was 10 IEn. 6 was produced. The drying method was the same as in Example 1.

Polyester resin b 20g Amino modified silicone oil Ig (KF-8
57-Manufactured by Shin-Etsu Silicone) Polyisocyanate 3g (KP
-90: manufactured by Dainippon Ink) Methyl ethyl ketone 85af toluene 85mN The composition of the polyester resin is shown below. (Unit is mol%) Polyester resin b 24.3 24.3
1.6 15TPA: Terephthalic acid IPA: Isophthalic acid EG: Ethylene glycol Comparative Example 1 The same thermal transfer dye-providing material as in Example 1 is used.

(Preparation of thermal transfer image-receiving material 7) A coating composition for an image-receiving layer having the following composition was coated on the surface of the support having the same content as in Example 1 by wire bar coating so that the dry thickness was 10 mm, and a thermal transfer image-receiving material was prepared. Material 7 was produced. The drying method was the same as in Example 1.

Support 11 paint ■ Futaiwa polyester resin a 20g amino modified silicone oil Ig (KF-8
57: Shin-Etsu Silicone) Polyisonoanate 3g (KP
-90: manufactured by Dainippon Ink) Methyl ethyl ketone 85m Toluene 85d Comparative Example 2 The same content as in Example 1 was used as the thermal transfer dye-providing material.

(Preparation of Thermal Transfer Image-Receiving Material 8) The coating composition for an image-receiving layer having the same contents as in Comparative Example 1 was coated with a wire bar on the surface of the support having the same contents as in Example 5, so that the dry thickness was 1OI! A thermal transfer image-receiving material 8 was prepared by coating the film in an amount of m. The drying method was the same as in Example 1.

Comparative Example 3 The same thermal transfer dye-providing material as in Example 1 was used.

(Preparation of thermal transfer image-receiving material $49) A coating composition for an image-receiving layer having the following composition was coated on the surface of the same support as in Example 1 by wire bar coating so that the dry thickness was 10%, and thermal transfer was carried out. Image receiving material 9 was produced. The drying method was the same as in Example 1.

Denki Kagaku Vinyl Chloride Vinyl Acetate 20g Copolymer Resin Eslenoku C Amino Modified Silicone Oil 1g (KF
-857: Shin-Etsu Silicone) Polyisonoanate 3g (KP
-90: Dainippon Ink) Methyl ethyl ketone 85! dToluene 85% The thermal transfer dye-providing material and the thermal transfer image-receiving material obtained as described above are superimposed so that the dye-providing layer and the image-receiving layer are in contact with each other, and using a thermal head from the support side of the thermal transfer dye-providing material, Thermal head output 0.25W/F-nod, pulse width 0.15~I5n+sec, dot density 6dot/
Printing was performed under the conditions of ff1ffl to dye the image-receiving layer of the thermal transfer image-receiving material with cyan dye imagewise.

The reflection density of the recorded thermal transfer image-receiving material was measured using a status A filter at a portion (Dmax) where the density was saturated. Also, the obtained image is 120001ux
Dn+a of images stored for one week under fluorescent lamp tester irradiation
The light fastness was evaluated by grading ``x'' when the reflection density value of the x portion was 85% or less of the reflection density value of the image before storage under irradiation, and ○ when it was above. The above results are shown in Table 1.

Table 1 (Effects of the Invention) According to the present invention, a thermal transfer image-receiving material having high image density and excellent image storage stability can be obtained.

(3 others)

Claims (1)

[Scope of Claims] A thermal transfer image-receiving material comprising an image-receiving layer containing a thermoplastic resin capable of receiving a dye on a support, wherein the thermoplastic resin contains a resin containing a component represented by the following structural formula a. A thermal transfer image-receiving material characterized by: Structural formula a ▲There are mathematical formulas, chemical formulas, tables, etc.▼