JPH04135796A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer image receiving material capable of high transfer density and superb transferred image preservability by providing an image receiving layer consisting of at least, polyester composed of dicarboxylic acid having an aliphatic ring and/or an aromatic ring in the main chain and a monomer component of diol, as an image receiving layer. CONSTITUTION:The typical components of monomer diol shown by formula(a) are HO(CH2)4OH, HO(CH2)5OH, HO(CH2)6OH, etc. In addition, the typical monomer diol shown by formula(b) is a diol component containing an aliphatic ring or an aromatic ring in the main chain. The monomer shown by formula(a) of the monomers is preferably of the applicable range of 5 to 30mol%. Further, the monomer shown by formula(b) is preferably of the applicable range of 20 to 45mol%. These polyesters are synthesized by a routine polymerization method or an ester exchange method. Subsequently, high transfer density can be obtained without thermal fusion to a thermal transfer color donotive material during transfer process. (in the formula, R is a linear or branched alkylene group and/or polyoxyalkylene group having a main chain of 4 or more carbon atoms.)

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a thermal transfer image-receiving material used in a thermal transfer method using a heat-transferable dye.
The present invention also relates to a thermal transfer image-receiving material with excellent storage stability of transferred images.

(Prior 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.The equipment used is lightweight, compact, noiseless, easy to operate,
It has excellent maintainability and can be easily colored, so it has been widely used recently. There are two main types of thermal transfer recording methods: thermal melting type and 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 to 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.

(Problems to be Solved by the Invention) However, the thermal transfer image receiving material used in this thermal transfer type thermal transfer recording method has the following problems.

(2) Various methods have been used to obtain high transfer density and high sensitivity in this thermal transfer type thermal transfer recording method, but each method has had the following problems.

(1) As a binder for the image-receiving layer, a polymer that softens or becomes rubbery during thermal transfer is used, or Ka111 is used.

However, when such means are used, the transfer surface at the highest density portion becomes uneven and also loses its gloss. Furthermore, there is a problem in that when the thermal transfer image-receiving material after transfer is stored for a long period of time, image blurring tends to occur.

(2) Lowering the glass transition point (Tg) of the dye-receiving polymer.

In this method, in order to obtain sufficient density, lowering the glass transition point below room temperature may cause the transferred image to blur, or if the transferred image-receiving materials are stacked, the transferred dye may be re-transferred to the adhesive surface. There is a problem called (so-called adhesive color transfer).

(3) A plasticizer such as oil that is soluble in dyes is contained in the image-receiving layer.

Similar to (2) above, this method has the problem of blurring of the transferred image over time and re-transfer. Furthermore, if raw image-receiving materials produced by this method are stored in piles, blocking failures are likely to occur.

(4) A porous layer containing porous particles is provided as a low thermal conductivity layer in order to prevent thermal diffusion during thermal transfer and increase the temperature of the transfer surface.

This method has the problem of reducing the gloss of the surface of the image-receiving material.

(5) Synthetic paper with voids is used as the support.

This method tends to curl after thermal transfer (and has high material costs).

(6) Raise the dye fourth degree of the dye-donating layer of the dye-donor material.

In this method, if the dye-providing material is stored for a long period of time, the dye may migrate to the bank side of the support or precipitate on the surface, resulting in a decrease in density and the occurrence of unevenness.

(7) Increase the voltage applied to the thermal head.

This method has problems in that it shortens the life of the thermal head and tends to cause thermal fusion of the image-receiving material and the dye-donating material.

As mentioned above, there are various problems when trying to obtain high transfer density and high sensitivity, but in particular, with conventional organic subsystem thermal transfer image receiving materials, when the transfer density is high, the transferred image tends to blur over time. Therefore, it has been extremely difficult to satisfy both high transfer density and image storage stability at the same time.

(2) Another problem is that the heat-transferable dye transferred to the image-receiving layer diffuses and precipitates on the surface of the image-receiving layer over a long period of time. This is particularly noticeable in pigments that have a high melting point and are easy to crystallize.

(2) Furthermore, there is a problem that the light fastness of transferred images is generally weak.

Therefore, there has been a strong desire to develop a thermal transfer image-receiving material with high transfer density and excellent storage stability of transferred images.

(Means for Solving the Problems) The above problems are as follows: (1) An image-receiving layer for forming an image by receiving the dye transferred from the thermal transfer dye-providing material when heated on the support. A thermal transfer image-receiving material comprising at least one layer of a dicarboxylic acid whose main chain contains an aliphatic ring and/or an aromatic ring and a diol monomer represented by the following general formulas (a) and (b). This was achieved using a thermal transfer image-receiving material characterized by having polyester as a constituent component.

General formula (a) HOROH In the formula, R represents a linear or branched alkylene group and/or polyoxyalkylene group having 4 or more carbon atoms in the main chain.

General formula (b) HOZOH In the formula, Z represents a group containing an aliphatic ring or an aromatic ring in the main chain.

The present invention will be explained in more detail below.

The image-receiving layer of the thermal transfer image-receiving material of the present invention receives the heat-transferable dye transferred from the thermal transfer dye-providing material during transfer, and
A dicarboxylic acid component whose main chain contains at least an aliphatic ring and/or an aromatic ring, a diol component represented by the above general formula (a), and the above-mentioned diol component as a dye-receiving substance that has the function of dyeing it. A polyester consisting of a diol component represented by the general formula (b) is used as a constituent component.

It is preferable that the dye-receiving substance is used alone or mixed or emulsified and dispersed in another binder substance, preferably a hydrophilic binder, and then applied to form a coating.

As the dicarboxylic acid containing an aliphatic ring and/or aromatic ring in the main chain, which is one of the monomer components of the polyester used in the present invention, the following can be used, for example.

From the viewpoint of solubility of the polyester in the container, it is preferable to use two or more of these monomers having different symmetries.

Preferred examples of the monomer diol component represented by general formula (a) include the following general formulas (a-1) and (a-2).
It is expressed as

General formula (a-1) HO-+CHJ-,OH General formula (a-2) HO(CHCH,O),H In the formula, m is 4-14, particularly preferably 4-8.

R8 represents a hydrogen atom or a CH,- group, and is particularly preferably a hydrogen atom. n is 2 to 10, particularly preferably 2 to 10
It is 6. Specific examples are given below.

HO(CHz)40HSHO(Cut)sol, [
0 (CHz)ioH.

80(C)lx)Jl(,HO(CHz)*OH,1(
O(CORIl@OH.

)IQ(CHz)+zO1(,HO(CHt)+nOH
, HO(C)lzcHto)J.

HO(CHC)120)J, )10(C[1,CH2
0)! H, lo(CHtCHzO)aH.

CH.

80(CHzCHJ)sH,flO(CHzC)IJ)
Preferred examples of the monomer diol component represented by the general formula (b) include diol components containing an aliphatic ring or an aromatic ring in the main chain, and specific examples thereof include the following.

has an excellent effect in improving light fastness.

Although diols having a bisphenol A skeleton have a remarkable effect of increasing concentration, they are not preferred from the viewpoint of improving light fastness.

In addition to these monomers, as a diol component, HO
(CHz)got(and HO(C)If)30)(etc.) can be used.

Among these monomers, the monomer represented by general formula (a) is preferably used in an amount of 5 to 30 mol%, more preferably 10 to 25 mol%.

If the amount exceeds 30 mol%, blurring of the transferred image over time and adhesive color transfer (referring to a failure in which the transferred dye is retransferred to the adhesive surface when transferred prints are placed one on top of the other) are likely to occur. 5
If the amount is less than mol%, no improvement in transfer density or image storage stability is observed.

Furthermore, the hexamer represented by the general formula (b) is preferably used in an amount of 20 to 45 mol%, more preferably 25 to 40 mol%. If it is less than 10 mol%, the transferred image will become blurred over time.
And adhesive color transfer is likely to occur.

The preferred average molecular weight of the polyester used in the present invention is about 5,000 to 50,000.

Next, specific examples of polyester compounds used in the present invention will be shown, but the present invention is not limited thereto.

Examples of polyester compounds Numbers in parentheses represent molar ratios.

P-37PA IPA C) IDM TEG
EGP-4TPA IPA CHDM P
EG-200EGP-5TPA TPA 5Sr
A CHDM TEG,EGP-6NDCIP
A BDM DEG NPGP-7TPA
IPA CHD TEG EGEC 01jlzCHz0 EC 0(C)IzCHzO+-z TEG 0(CHzCHzO+-3 G 0(CH,), 0- Abbreviation explanation CH.

NPG OCHz-C-CHzO CH3 PEG-200-0iCHzCHzO+, (MW=20
0) These polyesters used in the present invention can be synthesized by a normal direct polymerization method or a transesterification method, and a synthesis example of a particularly preferably used polyester (Compound Example P-2) is shown below.

Synthesis example (compound example P-2) 29.13 g (0.15 mol) of methyl terephthalate,
29.13 g (0.15 mol) of methyl isophthalate,
Diethylene glycol 9.54g (0°09mol),
Ethylene glycol 20. 5g (0°33 mole),
1.4-Cyclohexane dimetatool 25.92g (
0.18 mol) and calcium acetate 0 as condensation catalyst.
．． 05g, antimony oxide (I [I) 0. 0.5 g was placed in a Mitsuro flask equipped with a stirrer, a thermometer, and a naru tube, and was heated in an oil bath while supplying nitrogen.
506 for 30 minutes at 180°-200°C for 1 hour, the reaction takes place and a nearly stoichiometric amount of methanol 19.
2 g and about 5 g of ethylene glycol are distilled off. Next, the temperature was lowered to about 150°C, the nitrogen introduction pipe was closed, and while stirring, the pump was operated to gradually increase the degree of vacuum, and the degree of decompression was increased to 0.1~
The pressure is reduced to 0.3 mmHg. Ethylene glycol begins to distill out. Then, gradually increase the temperature to 260-27
0°C and react for 2.5 hours. Read the torque of the stirrer with a torque meter, and when it reaches a certain torque, stop heating, let it cool down a little, and transfer it to a Petri dish filled with water while still hot.

The composition ratio (molar ratio) of the produced polyester was determined by NMR to be terephthalic acid (24,5) and isophthalic acid (25,0).
), diethylene glycol (14,5), ethylene glycol (5,5), and 1,4-cyclohexane dimetatool (30,0). In addition, the molecular weight was approximately 15,000 by GPC (polystyrene standard)5.
Methylene chloride, toluene/methyl ethyl ketone
Dissolves well in 1/1 ratio.

By using the polyester of the present invention as a dye-receiving material in the image-receiving layer, troubles such as heat fusion, blurring of transferred images over time, and adhesive color transfer will not occur or worsen.
It has been found that the transfer density can be increased and image storage stability (particularly precipitation prevention and light fastness) can be greatly improved.

Furthermore, the above effects are obtained when the dye-receiving material is dispersed in a water-soluble binder than in an image-receiving material obtained by coating an organic solvent solution of a dye-receiving material containing the polyester as a constituent component. A greater effect was seen in image-receiving materials coated as image-receiving layers.

As a dye-receiving substance, together with the polyester of the present invention,
By containing a high boiling point organic solvent or a hot solvent,
The effects of the present invention are even more significant.

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. phthalate esters, phosphate esters, fatty acid esters), 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 thermal solvent, it must be: ■ Is it compatible with the dye? It must be incompatible with the water-soluble binder; ■ It must be solid at room temperature, or it must melt when heated by the thermal head during transfer (i.e., it must not be compatible with other components). Compounds are used that have the following properties: (1) they do not decompose when heated with a thermal head; Preferably 35~
Preference is given to compounds which exhibit a melting point of 250 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.
9 (1957).

Specific examples of high boiling point organic solvents and thermal solvents include JP-A-62-174754, JP-A-62-245253, and JP-A-62-245253.
No. 1-209444, No. 61-200538, No. 62
-8145, 62-9348, 62-3024
No. 7 and No. 62-136646.

Although the high boiling point organic solvent and/or thermal solvent can be used alone in the form of microdispersion in the image-receiving layer, it is preferable to use them in combination with the dye-receiving polymer.

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

In addition to the polyester of the present invention, polymers commonly used as materials that accept heat-transferable dyes can be used in combination. Examples of such dye-receiving polymers include the following resins.

(b) Those containing ester bonds Dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components may be substituted with sulfo groups, carboxyl groups, etc.), ethylene glycol, diethylene glycol, Polyester resin obtained by condensation of propylene glycol, neopentyl glycol, bisphenol A, etc., polyacrylic acid ester resin or polymethacrylic acid ester resin with polymethyl methacrylate, polybutyl methacrylate, polybutyl acrylate, polybutyl acrylate, etc.: Polycarbonate resin , polyvinyl acetate resin, nystyrene acrylate resin, and vinyl toluene acrylate resin. Specifically, JP-A-59-101395 and JP-A No. 6
No. 3-7971, No. 63-7972, No. 63-797
No. 3, No. 60-294862, may be mentioned. In addition, commercially available products include Byron 290, Byron 200, Byron 280, Pyro 300, Byron 103, Byron GK140, Byron GK-130 manufactured by Toyobo, ATR-2009 and ATR manufactured by Kao.
-2010 etc. can be used.
(Note) Products with urethane bonds, such as polyurethane resins.

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

(d) Those with urea bonds Urea resin.

(e) Those containing a sulfone bond.

Polysulfone resin.

(f) Other materials that foster highly polar bonds, such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, and polyacrylonitrile resin.

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

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which the dye-receiving material is coated on a support as it is, or it is preferable to have a structure in which the dye-receiving material is dispersed and supported in a water-soluble binder. The water-soluble binder used in this case is preferably one of various known water-soluble polymers or a water-soluble polymer having a group capable of crosslinking with a hardening agent.

The water-soluble polymers used in the present invention include polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridinium, cation-modified polyvinyl alcohol silkworm vinyl polymers and derivatives thereof (Japanese Patent Laid-Open No. 60-14587
No. 9, No. 80-220750, No. 61-143177
No. 61-235182, No. 61-245183, No. 61-237681, No. 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or its salt, acrylic acid- Polymers containing acrylic groups such as methacrylic acid copolymers or salts thereof, polymethacrylic acid or salts thereof, acrylic acid-vinyl alcohol copolymers or salts thereof (JP-A-60-168651, JP-A-62-9)
988), starch, starch oxide, starch acetate, starch amine, carboxyl starch, dialdehyde starch, cationic starch, dextrin, sodium alginate, gelatin, gum arabic, casein, pullulan, dextran, methyl cellulose, Natural polymers such as ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose or their derivatives (JP-A-59-174382, JP-A-60-2)
No. 62685, No. 61-143177, No. 61-18
No. 1679, No. 61-193879, No. 61-287
(See No. 782).

polyethylene glycol, polypropylene glycol,
Polyvinyl methyl ether, maleic acid-vinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer,
Maleic acid-alkyl vinyl ether copolymer, synthetic polymer with polyethyleneimine (Japanese Patent Application Laid-Open No. 61-327
No. 87, No. 61-237680, No. 61-27748
3) and the water-soluble polymers described in JP-A No. 56-58869.

Furthermore, various copolymers made water-soluble by monomer components containing SO,- groups, COO- groups, SO2- groups, etc. can also be used.

It is particularly preferable to use gelatin as the water-soluble binder because it can be dried in a set manner 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, and succinated gelatin, Bull, Sac, Pho
t, Japan, No. 16. P2O (196
Examples include enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products as described in 6).

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 dye-receiving substance have a weight ratio of dye-receiving substance/water-soluble binder=1 to 20, preferably 2.
-10, particularly preferably 2.5-7.

As a method for dispersing the dye-receiving substance in the 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 dye-receiving substance dissolved in a water-immiscible growth solvent and mixing it with an aqueous solution of a water-soluble binder; There are methods such as mixing with an aqueous binder solution.

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. synthetic paper), ■High-quality paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin interior Paper supports such as paperboard, 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 sheets made with a material that imparts 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 preferable because it has the following characteristics: it does not cause concave deformation due to heating during thermal transfer, has excellent whiteness, and has little curling.

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, use a synthetic resin with a higher glass transition point, minimize the amount of high-boiling point organic solvents and hot solvents, or avoid using them to prevent surface stickiness, adhesion with other substances, and post-transfer. It is desirable to have a structure that prevents failures such as re-transfer of the dye to other substances and blocking with the thermal transfer dye-providing material.

The total thickness of the image-receiving layer is 0.5 to 50 μm, especially 3 to 30 μm.
In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm.

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 soluble in a breeding solvent, 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.

The image receiving layer, cushion layer, porous layer, diffusion prevention layer, adhesive layer, etc. constituting the thermal transfer image receiving material of the present invention include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, Fine powders of synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina, etc. may also be included.

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

Examples include K, l/ee1) (atarama
Part nrThe Chemis-try of 5ynt
hetic DyesJ Volume 8 Chapter 8, JP-A-61-1
Compounds described in No. 43752 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, birapurin compounds, carbostyril compounds, 2,5-dibenzoxazolethiophene compounds, etc. It will be done.

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, and the dye is applied in a pattern to the image-receiving layer of the thermal transfer image-receiving material. The recording is performed by transitioning to .

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: fluoropolymer: 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.

For the dye-donating layer, a dye is selected so that a desired hue can be transferred when printed, and if necessary, two or more dye-donating layers with different dyes are arranged side by side in one thermal transfer dye-donating material. You can leave it there. For example, when printing each color repeatedly according to color separation signals to form an image such as a color photograph, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers containing the dye to be provided are arranged.

Alternatively, a dye-donating layer containing a dye that provides a black hue in addition to cyan, magenta, and yellow may be added. Alternatively, a layer may be added that supplies ultraviolet absorber to the image receiving material. 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.

Thermal transfer dye-providing materials using heat-transferable dyes essentially consist of growing a heat transfer layer on a support containing a dye that sublimes or becomes mobile with 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 a suitable solvent, and then applying this coating solution to the thermal transfer dye-providing material. On one side of the support for the material,
For example, it can be obtained by coating and drying the coating amount to give a dry film thickness of 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, examples include disperse dyes, basic dyes, oil-soluble dyes, and especially Sumikalon Yellow E.
4GL, Dianix Yellow H2G-FS, Miketon Boliertel Yellow 30SL, Kayasset Yellow 9
No. 37, Sumikaron Red EFBL, Dianic Red ACE, Migaton Polyeltel Red FB, Kayasset Red 126, Miguton Fast Brilliant Blue 81 Kayasset Blue 136, and the like are preferably used.

Also, JP-A No. 59-78895, No. 60-28451, No. 60-28453, No. 60-53564, No. 6
No. 1-148096, No. 60-239290, No. 60-
No. 31565, No. 6o-30393, No. 60-535
No. 65, No. 60-27594, No. 61-262191
No. 60152563, No. 61-244595,
No. 62-196186, No. 63-142062, No. 63-39380, No. 62-290583, No. 63
-111094, 63-111095, 63-
No. 122594, No. 63-71392, No. 63-74
No. 685, No. 63-74688, JP 1-2255
No. 92 (Describes the dye represented by the general formula below.

In the formula, RIa is a hydrogen atom, an alkyl group, an alkoxy group,
represents an aryl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group, R2 represents a hydrogen atom, an alkyl group or an aryl group, Rz represents an aryl group or a heteryl group, R4 and R5 may be the same or different,
Each represents a hydrogen atom or an alkyl group. The above substituent may be further substituted), etc., the yellow dye described in
JP 60-223862, JP 60-28452,
No. 60-31563, No. 59-78896, No. 60
-31564, 60-303391, 61-2
No. 27092, No. 61-227091, No. 60-30
No. 392, No. 60-30694, No. 60-13129
No. 3, No. 61-227093, No. 60-159091
No. 61-262190, No. 62-33688,
No. 63-5992, No. 61-12392, No. 62-
No. 55194, No. 62-297593, No. 63-74
No. 685, No. 63-74688, No. 62-97886
No. 62-132685, No. 61-163895, No. 62-211190, No. 62-99195, and JP-A No. 1-63194 (describing dyes of the following general formula).

In the formula, R, R, is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, a cyano group, an acylamino group, a sulfonylamino group, a ureido group, or an alkylthio group. , arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amide.

Rs and R4 represent an alkyl group, a cycloalkyl group, an aralkyl group, and an aryl group. R1 and R6 may be combined with each other to form a ring, or R2 and R, , R
2 and R4 may be combined to form a ring. n represents an integer of O to 3. X, Y and Z represent R3 -C= or a nitrogen atom (where R3 is a hydrogen atom,
represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryl oxo group, and an amino group).

R3 When X and Y, or Y and 1·-C=5, they may be bonded to each other to form a saturated or unsaturated carbon ring. The above-mentioned substituents may be further substituted), etc. Magenta dyes described in JP-A-59-78894, JP-A-60-31559, JP-A-60'-53563, Temi',! No. 9396, redundant o1
No. 22993, i7-3146~, Tsukasa 6i-35
No. 994, s+-49s93, 61-57651
No. 62-87393, No. 63-15790, No. 63-15853, No. 63-57293, No. 63-
No. 74685, No. 63-74688, No. 59-227
No. 490, No. 59-227493, No. 59-2279
No. 48, No. 60-131292, No. 60-13129
No. 4, No. 60-151097, No. 60-151098
No. 60-1721591, No. 60-217266
No. 60-239289, No. 60-239291, No. 60-239292, No. 6]-148269,
No. 61-244594, No. 61-255897, No. 61284489, No. 61-368493, No. 62
-132684, 62-138291, 62-
No. 191191, No. 62-255187, No. 62-2
No. 88656, No. 62-311190, No. 63-14
No. 4089, JP-A No. 1-20194 (describing the dye of the following general formula).

R1, Ql' (R4)n In the formula, Q represents an atomic group containing at least one nitrogen atom and necessary to form a 5-membered or more nitrogen-containing heterocycle with the bonded carbon atom, and R1 is represents an acyl group or a sulfonyl group, R2 represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, R3 represents a hydrogen atom or a halogen atom, an alkoxy group or an aliphatic group having 1 to 6 carbon atoms, and R4 represents It represents a halogen atom, an alkoxy group, or an aliphatic group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. R2 may be combined with R or R2 or R4 to form a ring. R5
and R3 represents a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, or an aromatic group. R5, R.

may be combined with each other to form a ring. In addition, cyan dyes described in (R3 and/or R6 may be combined with R4 to form a ring) are also preferably used.

Furthermore, as the binder resin used with the above dyes, any of the binder resins conventionally known for this purpose can be used, and they usually have high heat resistance and do not interfere with 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-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polyvinyl chloride resins (e.g. vinyl chloride-vinyl acetate copolymer) combination),
Polycarbonate 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 alcohol such as bovinyl alcohol and polyvinyl butyral), petroleum resins, rosin derivatives, coumaron
Indene resin, terpene resin, polyolefin resin (for example, borinitylene, polypropylene), etc. are used.

It is preferable to use binder resins such as No. 2 in an amount 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 used as the solvent for dissolving or dispersing the above pigment and binder resin.

(Left below) In order to prevent sticking caused by the heat of the thermal head and improve slippage when printing from the back of the dye-donating material, it is recommended to apply anti-sticking treatment to the side of the support where 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 a polyvinyl butyral resin and an isocyanate, (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 resin with a weight percentage of 15 to 40% in terms of the number of reaction sites with isocyanate. Good thing. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafac 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 hardens when heated and its curing agent,
For example, a combination of polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and a titanium chelating agent, or polyester and an organic titanium compound may be provided by coating.

The dye-donor element may also be provided with a hydrophilic barrier layer to prevent diffusion of the dye towards the support. Hydrophilic dye barrier layers contain hydrophilic materials useful for their intended purpose. Generally excellent results for gelatin, poly(acrylamide), poly(isopropylacrylamide),
Butyl methacrylate grafted gelatin, ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly(vinyl alcohol), poly(ethyleneimine), poly(acrylic acid), mixture of poly(vinyl alcohol) and poly(vinyl acetate) , by using 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, an undercoat layer may be used as long as it has the desired effect, but a preferred specific example is a (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (weight ratio 14:80:6).
), (butyl acrylate-2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear/saturated polyester such as Bostik 7650 (Emhart, Bostic) stick chemical group) or chlorinated high-density poly(ethylene-trichloroethylene) resins.

There is no particular limit to the amount of undercoat layer applied, but it is usually 0.1
It is used in an amount of ~2.0 g/m2.

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 incorporate a release agent into the layers constituting the image-receiving material, particularly preferably in the outermost layer, which is the surface in contact with both materials.

As mold release agents, conventionally known materials such as solid or wax-like substances such as polyethylene wax, amide wax, and Teflon powder, surfactants such as difluorine-based and phosphate ester-based oils, and paraffin-based, silicone-based, and fluorine-based oils are used. Although any mold release agent can be used, silicone oil is particularly preferred.

As the silicone oil, in addition to unmodified silicone oil, modified silicone oils such as carboxy-modified, amino-modified, and Epoquin-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 amino-modified silicone oil having a vine group that reacts with the crosslinking agent of the binder (for example, a vine group that reacts with isocyanate) is used, or when used after being emulsified and dispersed in a water-soluble binder. is a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd. IB trade name X-22-3710).

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 organic solvent-based polymers, JP-A-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. Patent No. 4,678.7
No. 39 No. 4 JP-A-59-116655, No. 132
Hardeners described in Japanese Patent Nos. 245261 and 61-18942 are suitable for use.

More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, etc.), vinylsulfone hardeners (N, N-ethylene-bis(vinylsulfonyl alcohol), cetamide) ethane, etc.),
N-methylol hardening agent (pacimethylol urea),
Alternatively, polymer hardeners (compounds described in JP-A No. 62-234157, etc.) may be used.

Antifading agents may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

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

Benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.),
Benzophenone compounds (JP-A-56-2784, etc.), other JP-A-54-48535, JP-A-62-136
There are compounds described in No. 6'41 and No. 61-88256. 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 of the same
4.195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27)-(29), Japanese Patent Application No. 1982-234103, JP-A No. 62-31096, JP-A-62 -230596 and the like.

An example of a light fading preventive agent is 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 impregnated in the image-receiving material in advance, or it may be supplied to the image-receiving material from the outside by a method that does not allow the dye to be transferred from the dye-providing material. You can do it like this.

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 purposes such as coating aids, improving releasability, improving slipperiness, preventing electrification, and promoting development.

Nonionic surfactants, anionic surfactants.

Amphoteric surfactants and cationic surfactants can be used. Specific examples of these are JP-A-62-173463,
It is described in No. 62-183457 and the like.

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-59-1. 1576
The surfactants described on pages 37-38 of No. 36 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 slipperiness, preventing static electricity, improving releasability, and the like. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053 No. 8-1711.
．． Fluorine surfactants described in JP-A-61-20944 and JP-A-62-135826, oily fluorine compounds such as fluorine oil, solid fluorine compound resins such as tetrafluoroethylene resin, etc. Examples include hydrophobic fluorine compounds.

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, polymethacrylate, etc.
In addition to the compounds described on page 29 of No. 1-88256, Japanese Patent Application No. 110064/1988, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There are compounds described in Nos. 62-110065.

In the present invention, a thermal transfer dye-providing material is superimposed on a thermal transfer image-receiving material, and thermal energy is applied according to image information from either side, preferably from the back side of the thermal transfer dye-providing material, using a heating means such as a thermal head. By this, the dye in the dye-donating layer can be transferred to the thermal transfer image-receiving material according to the amount of heating energy, and a color image with excellent clarity and resolution can be obtained. The head is not limited to the head, and any known head may be used, such as a laser beam (for example, a semiconductor laser), an infrared flash, or a thermal pen.

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. 60-348.
You can refer to the description in No. 95.

EXAMPLES The present invention will be explained in more detail by showing examples below.

(Leaving space below) Example = 1 (Preparation of thermal transfer dye-providing material (A)) A 6 μm thick polyester film (manufactured by others) with a heat-resistant slipping layer made of a thermosetting acrylic resin on one side was used as a support. A dye-providing material was obtained by applying a dye-providing layer forming ink having the following composition to the side opposite to the side on which the heat-resistant slippery layer was provided so that the coating amount after drying was 1.2 g/rd. Ta.

Cyan ink pigment-a 3 parts Polyvinyl butyral resin (Denka Butyral 5000A: electrochemical type) 2.5 parts Polyisocyanate C Takenate DI 1 ON: Shikinichi Yakuhin Co., Ltd.) 0, 1 part Amino-modified silicone oil (KF-857: Shin-Etsu) Chemical type) 0.004 parts methyl ethyl ketone 50 parts toluene
50 parts Dye-a Dye-b 2.5 parts Polyvinyl butyral resin (Slenx B'X-1: Sekisui Chemical) 2.5 parts Polyisocyanate (KP-90: Dainippon Ink Chemical) 0, 1 part Silicone oil (KF-857: Shin-Etsu Chemical type) 0.004 parts methyl ethyl ketone 70 parts toluene
30 parts Dye-S Dye-C Ethyl cellulose Methyl ethyl ketone Toluene 5 parts 3 parts 50 parts 50 parts Cf! (Preparation of dye-receptive polymer emulsion A) Superior colliculus-based gelatin (10 wt% water solution) 100
g Sodium dodecylbenzenesulfonate (5 wt% aqueous solution) 67-1 Polyester resin (see Table 1 for types of polymers) 0 g Toluene 60 g Methyl ethyl ketone 60 g Dicyclohexyl phthalate 6 g Silicone oil (X-
22-3701E.

(manufactured by Shin-Etsu Silicone) After preparing 3 g of liquid ■, add liquid ■ to it while stirring liquid ■, emulsify and disperse at 15,000 rpm for 9 minutes using a homogenizer to obtain emulsion A of dye-receptive polymer. was prepared.

(Preparation of coating solution for thermal transfer image-receiving material) 1st layer: Gelatin (10 wt% aqueous solution > 100 g
water
40af1.2-bis(vinylsulfonylacetamido)ethane (4-t% water volume a, > 60 dl
2nd layer: Dye-receptive polymer emulsion A 100g water
3
0#11! (contains), surfactant (])” (55wt%
Solution 5d fluorine-containing solid fine particles (1) 0 dispersion
2.5g (solid content 20-t%) In the above, C,H7 fluorine-containing surfactant (+)": C11F17SO□
NH2C0OK fluorine-containing solid fine particles (1) 0 dispersion (2
0 parts wt%): 2g of gelatin to 78d of water! Using 1 g of fluorine-containing surfactant (1) in a solution dissolved in
was prepared by dispersing for 5 minutes at 10.00 rpm using a homogenizer.

(Preparation of thermal transfer image-receiving material) The first layer and the second layer were coated on a support made of paper with a thickness of 180 g/rrf laminated on both sides with polyethylene in which titanium oxide was dispersed, and the wet film thickness was 20 and 70 + d, respectively.
/rrr and dried to produce thermal transfer image-receiving materials 101 to 108 as shown in Table 1.

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 a thermal head is used from the support side of the thermal transfer dye-providing material, and the output of the thermal head is 0.25W/dot, pulse width 0°15~15m5ec, dot density 6
Printing was carried out under dot/dot conditions, and magenta dye was dyed image-wise on the image-receiving layer of the thermal transfer image-receiving material.

(Performance evaluation) Heat fusion: The extent to which the dye-donating layer of the dye-donor material peeled off and adhered (heat fusion) to the surface of the obtained recorded thermal transfer image-receiving material was evaluated, and the results are shown in Table 1. . The evaluation criteria are as follows.

O: The dye-donor layer is not attached at all. The dye-donor layer is attached to some parts of ΔD. ×: The dye-donor layer is attached to the entire surface and the color is scratched. Stacked face to face, 500g per 30cmd
After storage for 1 day under a load of 60° (4'), both were peeled off and the degree of retransfer of the color image was evaluated, as shown in Table 1. The evaluation criteria are as follows.

O: Hardly retransferred Δ: Slightly retransferred ×: Significantly retransferred! ■±: The transferred image-receiving material was stored in an air thermostat at 60''C for one month, and the bleeding of the color image was evaluated, as shown in Table 1.The evaluation criteria are as follows.

○: Almost no stains △: Slightly blurred ×: Significant smudging The results are shown in Table-1.

Dmax: The reflection density of the saturated portion (Dmax) of the recorded thermal transfer image-receiving material was measured using a Status A filter.

The third unit of Kou was irradiated with light for two weeks using a fluorescent lamp fading tester, and the transfer density was approximately 1.
The density near 0 was measured using a status A filter before and after the test, and was expressed as a color image residual rate.

negative! Thermal transfer image-receiving material whose raw material ratio had been recorded was stored for one week under conditions of 50'C and 70% RH, and the decrease in Dmax (ΔDmax) was investigated (by microscopic observation), which was thought to be due to the precipitation of the dye on the surface. .

Table 1 shows the values for magenta dye.

In the table, Polyester (1) 0 Polyester (2) 0 Polyester (3)* represents.

As is clear from the results in Table 1, the thermal transfer dye-receiving material using the polyester of the present invention as a dye-receiving polymer in the image-receiving layer has a high transfer density without being thermally fused to the thermal transfer dye-providing material during transfer. In addition, there is almost no re-transfer color transfer that occurs when the transfer prints are stacked and stored, there is no image blurring that occurs during storage, there is no pigment precipitation on the surface of the transfer prints, and the light fastness is excellent. is extremely good.

Claims (1)

[Claims] (1) A thermal transfer image-receiving material in which at least one image-receiving layer is provided on a support to form an image by receiving the dye that migrates from the thermal transfer dye-providing material when heated, the image-receiving layer comprising: Thermal transfer characterized in that the constituent component is a polyester consisting of at least a monomer component of a dicarboxylic acid whose main chain contains an aliphatic ring and/or an aromatic ring and a diol represented by the following general formulas (a) and (b). Image receiving material: General formula (a) HOROH In the formula, R represents a linear or branched alkylene group and/or polyoxyalkylene group having 4 or more carbon atoms in the main chain. General formula (b) HOZOH In the formula, Z represents a group containing an aliphatic ring or an aromatic ring in the main chain.