JPH04175191A - Thermal transfer sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat-sensitive transfer sheet having a transfer layer on one side of a base material and a heat-resistant anti-sticking layer on the other side.

[Prior art] In recent years, heat-melting ink layers containing pigments and dyes, sublimation ink layers containing sublimable dyes in binders, or heat-reactive coloring components have been developed on base materials such as plastic films. Using a heat-sensitive transfer sheet with a heat-sensitive transfer layer that
A widely used method is to perform thermal printing according to image information using a heating means such as a thermal head to form an image on a receiving sheet.

Conventionally, plastic films such as polyester films, polyimide films, polypropylene films, aromatic polyamide films, cellulose acetate films, and cellophane films with a thickness of 2 to 15 μm have been used as substrates for such heat-sensitive transfer sheets. Among these, polyester film is preferably used because it is easy to form a uniform thickness, has excellent surface smoothness, and is easy to operate in a printer.

However, thermal transfer sheets using this polyester film as a base material require high energy to obtain sufficient print density, so a so-called sticking phenomenon occurs in which the polyester itself fuses with the thermal head. In addition, to maintain the thermal head pressure and the heat-sensitive transfer sheet, bat pressure in the cassette or contact resistance with the roll in the printer may cause poor running performance, resulting in irregularities in print density, background smearing, etc. However, in severe cases, the base material may break.

In order to prevent these phenomena, for example, a method of providing a metal oxide layer or an anti-friction layer made of silicon oxide on the base material (Japanese Patent Application Laid-Open Nos. 54-143152 and 57-74195), silicone resin, etc. A method of providing a heat-resistant resin layer such as or epoxy resin (Japanese Patent Application Laid-Open No. 55-7467), a method of providing a resin layer to which a surfactant, etc. that is solid or semi-solid at room temperature is added (Japanese Patent Application Laid-Open No. 57-129789) Alternatively, a method of providing a heat-sensitive resin layer containing a lubricating inorganic pigment (Japanese Patent Application Laid-open No. 5
6-155794) etc. have been proposed.

However, these methods require expensive processes such as vapor deposition, use a large amount of thermal energy for thermosetting, and require long periods of time to provide sufficient heat resistance. It requires aging, has insufficient lubricity, and has the disadvantage that dirt may adhere to the thermal head. 'Furthermore, since the heat-sensitive transfer sheet used in the conventional method described above is generally stored rolled up, the heat-resistant layer and the transfer layer come into contact with each other during storage, resulting in a blocking phenomenon, which causes background smudges and image fading when printed. There was a problem.

In addition, the method of using a wax that melts and exhibits lubricity as a lubricant by the heat from the thermal head, such as the method of JP-A No. 58-187396, may cause sticking phenomenon or failure of the heat-sensitive transfer sheet when heat is absorbed. There was a drawback that feeding etc. occurred.

Furthermore, when a heat-resistant slip layer is processed into a base material, since the base material is thin, drying wrinkles occur when the base material is dried at high temperatures, and image breakage occurs when printing is performed.

On the other hand, drying at a low temperature results in insufficient curing and has the disadvantage that sufficient heat resistance cannot be obtained.

[Problems to be Solved by the Invention] An object of the present invention is to provide a thermal transfer sheet that is stable against the thermal energy of a thermal head during printing, exhibits excellent running properties, and is free from blocking. .

[Means for Solving the Problems] According to the present invention, (1) A transfer ink layer is provided on one side of a plastic film, and an anti-sticking layer made of polyvinyl butyral, melamine resin, and a filler is provided on the other side. (2) A transfer ink layer is provided on one side of the plastic film, and an anti-sticking layer made of phenoxy resin, melamine resin, and filler is provided on the other side. (3) A transfer ink layer is provided on one side of a plastic film, and an anti-sticking layer made of an acrylic resin or alkyd resin, a melamine resin, and a filler is provided on the other side. Thermal transfer sheet; (4) A thermal transfer sheet characterized in that a transfer ink layer is provided on one side of a plastic film, and an anti-sticking layer made of a cellulose resin, a melamine resin, and a filler is provided on the other side. be done.

The present invention will be explained in more detail below.

The resin to be contained in the anti-sticking layer of the present invention has the following four types.

<1) Polyvinyl butyral, melamine resin, filler, (2) Phenoxy resin, melamine resin, filler, (3)
Acrylic resin or alkyd resin, melamine resin, filler, (4) Cellulose resin, melamine resin, filler.

The polyvinyl butyral used in the present invention preferably has a high degree of polymerization from the viewpoint of heat resistance. For example, Denka Butyral #5000A manufactured by Denki Kagaku Kogyo (product name
000), the same #BOOOC (degree of polymerization 2400) and the product Meiko Sletsku BX-1 (degree of polymerization 175) manufactured by Building Block Chemical Industry ■.
0) etc. are particularly preferred.

In addition, examples of melamine resins include Super Beckamine J-820-60 and Super Beckamin G manufactured by Dainippon Ink Chemical Co., Ltd.
-121-60, TD-139-60, L-117
-60, 47-580-60, L-105-60
, Mitsui Toatsu Chemical Co., Ltd.'s product name Kneepan 20SE, same 2
Examples include 020, 2060, and 22R.

Phenoxy resin is a resin synthesized from divalent phenols and epichlorohydrin, and the divalent phenols include bisphenol A1 dichlorobisphenol A1 bisphenol F1 bisphenol ACP, bisphenol L1 bisphenol v1 bisphenol S,
For example, the product names PKHC and PKHJ manufactured by Tomoe Kogyo ■.

Product name Phenoart YP manufactured by PKHH and Tobu Kasei ■
-50 and Union Carbide product name BAKEL
There are ITE etc.

Examples of the acrylic resin to be contained in the anti-sticking layer of the present invention include Acridic A-157, Acridic A-165, Acridic A-190 manufactured by Dainippon Ink Chemical Co., Ltd.;
Same A L-169-45, Same B L-705-B, and Mitsubishi Rayon ■ product name Dianal BR-80, same BR-85, same BR-95, same BR-1,05, same B
R-108 and the like may be used alone or in combination of two or more.

Examples of alkyd resins include Dainippon Ink Chemical Co., Ltd.
Product names: Betsukosol ES-4020-55, EL-4501-50, EL-5007, P
-470-70, J-51.0, J-55, etc., and these may be used alone or in combination of two or more.

Further, these alkyd resins may be modified with phenol, vinyl, epoxy ester, silicone, etc.

Examples of the cellulose resin include ethyl cellulose, cellulose acetate, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose acetate butyrate, and cellulose acetate prebionate. Cellulose acetate butyrate is particularly preferred, and among them, those with high molecular weight are preferred from the viewpoint of heat resistance.

The proportion of polyvinyl butyral and melamine resin used is 5 to 80 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of polyvinyl butyral.

The proportion of phenoxy resin and melamine resin used is 5 to 80 parts by weight, preferably 10 to 50 parts by weight, of melamine resin per 100 parts by weight of phenoxy resin.

The proportion of cellulose resin and melamine resin used is 5 to 80 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of cellulose resin.

The ratio of acrylic resin, alkyd resin and melamine resin used is 5 to 80 parts by weight, preferably 1 part by weight of melamine resin per 100 parts by weight of acrylic resin or alkyd resin.
It is contained in an amount of 0 to 50 parts by weight.

Examples of fillers include inorganic particles such as talc, silica, calcium carbonate, magnesium oxide, alumina, titanium white, clay, and boron nitride; waxes such as polyethylene wax and paraffin wax; and amides, esters, and salts of higher fatty acids. , fluororesin, and guanamine resin powder, and these may be used alone or in combination of two or more. 'The thickness of the heat-resistant anti-sticking layer of the present invention depends on the feedability of the printer,
Although it varies depending on the applied energy etc., it is usually 0.05~
A suitable value is 3.0 μm, preferably 0.1 to 2 μm.

As the plastic film used as the base material in the present invention, those formed from various conventionally known thermoplastic resins can be used, such as polyester film, polyamide film, polyolefin film,
Examples include polycarbonate film and cellulose film. Its thickness is usually about 0.5 to 50 μm, preferably about 3 to 10 μm.

In the present invention, the type of the transfer ink layer formed on the base material is not limited, and a non-reactive type or a reactive type can be arbitrarily used. Examples of the non-reactive type include, for example, thermal For example, a transfer ink layer made of a meltable ink or a transfer layer made of a sublimable dye can be mentioned, and as a reactive type, for example, one of the reactive components of a color-forming reaction system in the following combinations can be mentioned. Examples include a transfer layer containing.

(1) Combination of leuco dye and color developer (electron-accepting substance).

(2) Combinations of long-chain aliphatic iron salts such as ferric stearate and ferric myristate with phenols such as tannic acid, gallic acid, and ammonium salicylate.

(3) Combinations of heavy metal sulfates such as silver, lead, mercury, and thorium sulfates with sulfur compounds such as Na-tetrathionate, sodium thiosulfate, and thiourea.

(4) A combination of a noble metal salt of an organic acid such as silver hehenate or silver stearate and an aromatic organic reducing agent such as protocatechuic acid, spiroindane or hydroquinone.

(5) Combinations of organic acid lead salts such as lead caproate, lead pelargonate, and lead behenate with thiourea derivatives such as ethylenethiourea and N-dedosylthiourea.

When using a heat-sensitive transfer sheet having a reactive heat transfer layer as described above, the receiving sheet receiving the transfer is as follows:
A sheet having a receptor layer containing a reactive component that causes color development by reacting with a reactive component contained in a thermal transfer layer of a color-forming reaction system consisting of the combination described above is used. For example, when the thermal transfer layer contains a leuco dye, a receiving sheet containing a color developer such as a phenolic substance may be used as the receiving sheet.

Further, the color-forming reaction system consisting of a combination of the two types of reaction components described above can be contained in the thermal transfer layer in a state in which the color-forming reaction is prevented in advance.

A thermal transfer sheet having a thermal transfer layer containing such a color-forming reaction component can transfer an image made of a molten deposit of a color-forming reaction product onto a paper serving as a receiving sheet by thermal transfer. Taking a non-reactive heat-sensitive transfer layer as an example, the method for forming it will be explained by hot-melt coating a composition comprising a colorant, a binder, etc. on a film base material, or by dispersing the composition in an appropriate melt state. Approximately 1 to 20μ of coated paper is solvent coated.
It can be formed of m layers. As the colorant, any of various dyes conventionally used in the field of copying paper or pigments such as carbon black can be used, and as the binder, waxes such as carnauba wax, wood wax, and beeswax can be used. It can be used.

Embodiments The present invention will now be described in more detail based on the following embodiments.

Example 1 Butyral resin; Eslec BX-1 (manufactured by Blockchain Chemical Co., Ltd.) 3.0 parts by weight Melamine resin varnish - Parvelacamine L-145-8 [1 (manufactured by Dainippon Ink Chemical Company) 2
．． 0 parts by weight boron nitride 1.0 parts by weight toluene
45.0 parts by weight methyl ethyl ketone
50.0 parts by weight The above composition was applied to a 4.5 μm thick polyester film to a thickness of approximately 1 μm using a wire spar, and dried at 100° C. for 1 minute and 60° C. for 20 hours to form an anti-sticking layer. A base material for a heat-sensitive transfer sheet was obtained.

An ink composition having the following formulation was dissolved on this base material with stirring, and then coated on the opposite side from the anti-sticking layer to a film thickness of 1 μm using a wire bar to obtain an ink sheet for sublimation thermal transfer.

Butyral resin: Eslec BX-1 (manufactured by Tsukimizu Kagaku Kogyo ■) 5.0 parts by weight Dye: Kayaset Bluff 14 (manufactured by Nippon Kayaku ■) 4.0 parts by weight Toluene 45.0 parts by weight Methyl ethyl ketone 50.0 parts by weight Part Example 2 Butyral resin; 3.5 parts by weight of Esle Tsuku BX-7 (manufactured by Tsukimizu Kagaku Kogyo ■) Melamine resin; Superbe Socamin G-821-60 (manufactured by Dainippon Ink Chemical Co., Ltd.) 1.
5 parts by weight Magnesium stearate 1.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone
50.0 parts by weight The above composition was used in the same manner as in Example 1 to obtain a base material for a thermal transfer sheet having a 4.5 μM polyester film prevention layer.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Example 3 Butyral resin; Denka Butyral #5000A (manufactured by Denki Kagaku Kogyo ■) 3.0 parts by weight Melamine resin; Yuhan 208E (manufactured by Mitsui Toatsu Chemical ■) 2.0 parts by weight Talc 1.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone
50.0 parts by weight The above composition was coated on a 4.5 μF polyester film in the same manner as in Example 1, and a stay-on film was applied.
A base material for a thermal transfer sheet having an anti-soaking layer was obtained.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 1 Butyral resin; Eslec BX-1 4.0 parts by weight Isocyanate; Coronate L (manufactured by Nippon Polyurethane) 1.0 parts by weight boron nitride
1.0 parts by weight toluene
45.0 parts by weight Methyl ethyl ketone 50.0
Part by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 1 to obtain a base material for a thermal transfer sheet having a stain/inking prevention layer.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 2 Butyral resin; Eslec BX-7 4.0 parts by weight Isocyanate; Burnock D-750 (manufactured by Dainippon Ink Chemical Co., Ltd.) 1.0 parts by weight Magnesium stearate 1.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone
50.0 parts by weight of the above composition in the same manner as in Example 1.
．． A base material for a thermal transfer sheet having an anti-sticking layer was obtained by coating a 5 μm polyester film.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 3 Butyral resin; Denka Butyral #5000A 4.0 parts by weight Isocyanate; Burnock DN-950 (manufactured by Dainippon Ink & Chemicals) 1.0 parts by weight Talc 1.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone
50.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 1 to obtain a base material for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

The storage stability and printability of each of the heat-sensitive transfer sheets obtained above were tested. The test method and results are shown below.

[Tests and Results] 1 Preservation Acceleration Test Two of the same heat-sensitive transfer sheets obtained were placed one on top of the other so that the ink layer and the anti-sticking layer were in contact with each other, and sandwiched between two sheets of paper. °C, 50%R
A preservation acceleration test was conducted by placing the sample in a constant temperature bath. As a result, in Examples 1 to 3 and Comparative Examples 1 to 3, no abnormalities such as blocking or back bleed were observed.

2. Printing test image receptor - Printed under the following conditions using a partial glaze type thermal head using VY-8100 image receptor paper, a supply for the Hitachi video printer VY-50, which is an image receptor for dye-sublimation thermal recording. did.

Applied power: 442 mw/dot Application time: 0 to 8II1 msec Applied energy: 0 to 3.54 mJ/dot Example 1~
The thermal transfer sheet No. 3 had quiet printing noise and smooth feeding in the printer, and no sticking phenomenon occurred at all, probably due to the thermal energy of the thermal head.

Furthermore, no wrinkles were observed in the ink removal area, and there was no image disturbance caused by the stick.

Furthermore, with the ink sheet of Comparative Example 1, the printing sound was loud, the feeding performance within the printer was poor, and a sticking phenomenon occurred due to the thermal energy of the thermal head, resulting in noticeable disturbances in the printed image. Furthermore, the ink sheets of Comparative Examples 2 and 3 broke at the initial stage of printing and could not be printed.

Example 4 Phenoxy resin: Phenoate YP-50 (manufactured by Tobu Kasei ■) 3.0 parts by weight Melamine resin; Super Beckamine L-145-60 (manufactured by Dainippon Ink Chemical ■) 2.0 parts by weight boron nitride 1. 0 parts by weight toluene
45.0 parts by weight tetrahydrofuran
50.0 parts by weight The above composition was applied to a 4.5 μm thick polyester film using a wire bar to a thickness of about 1 μm, and dried at 100° C. for 1 minute and at ZO° C. for 20 hours to form an anti-sticking layer. A base material for a heat-sensitive transfer sheet was obtained.

An ink composition having the following formulation was dissolved on this base material with stirring, and then applied to the surface opposite to the anti-sticking layer using a wire bar to a film thickness of 1 μm to obtain an ink sheet for sublimation thermal transfer.

Butyral resin: S-LEC BX-1 (manufactured by Block Chemical Industry ■) 5.0 parts by weight Dye: Kayaset Bluff 14 (manufactured by Nippon Kakami) 4.0 parts by weight Toluene 45.0 parts by weight Methyl ethyl ketone 50.0 parts by weight Examples 5 Phenoxy resin; 3.5 parts by weight of PKHH (manufactured by Tomoe Kogyo ■) Melamine resin Nis-Perhetsum G-821-60 (manufactured by Dainippon Ink Chemical ■) 1.5 parts by weight Magnesium stearate 1.0 parts by weight Toluene
45.0 parts by weight tetrahydrofuran
50.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 4 to obtain a base material for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Example 6 Phenoxy resin, BAKELITE (manufactured by Union Carbide) 3.0 parts by weight Melamine resin; Kneepan 20SE (manufactured by Mitsui Toatsu Chemicals) 2.0 parts by weight Talc 1.0 parts by weight Toluene
45.0 parts by weight tetrahydrofuran
50.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 4 to obtain a substrate for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 4 Phenoxy resin: Phenoate YP-50 (manufactured by Tobu Kasei ■) 4.0 parts by weight isocyanate; Coronate L (manufactured by Nippon Polyurethane ■) 1.0 parts by weight boron nitride
1.0 parts by weight toluene
45.0 parts by weight Tetrahydrofuran 50.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 1 to obtain a base material for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 4 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 5 Phenoxy resin, PKHH (manufactured by Tomoe Kogyo ■) 4.0 parts by weight isocyanate, Parnock DN-750 (manufactured by Dainippon Ink Chemical ■) 1.0 parts by weight magnesium stearate
1.0 parts by weight Toluene 45.0 parts Tetrahydrofuran 50.0 parts by weight The above composition was applied to a 4.5 μn polyester film in the same manner as in Example 4 to obtain a substrate for a thermal transfer sheet having an anti-sticking layer. Obtained.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 6 Phenoxy resin, BAKEL ITE (manufactured by Union Carbide) 4.0 parts by weight isocyanate; Burnock DN-950 (manufactured by Dainippon Ink Chemical ■)
1.0 parts by weight Talc 1.0 parts by weight Toluene 45.0 parts by weight Tetrahydrofuran 50.0 parts by weight The above composition was applied to a 4.5 μl polyester film in the same manner as in Example 4 to form a thermal transfer film having an anti-sticking layer. A base material for a sheet was obtained.

The ink composition of Example 1 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

The storage stability and printability of each of the heat-sensitive transfer sheets obtained above were tested. The test method and results are shown below.

[Tests and Results] 1. Preservation Acceleration Test The same two heat-sensitive transfer sheets obtained were stacked so that the ink layer and the anti-sticking layer were in contact with each other, sandwiched between two sheets of paper, and a load of lOg was applied. 60℃, 50%R
A preservation acceleration test was conducted by placing the sample in a thermostatic bath. As a result, in Examples 4 to 6 and Comparative Examples 4 to 6, no abnormalities such as blocking or back bleed were observed.

2. Printing Test Printing was carried out under the following conditions using a partial glaze type thermal head using image receiving paper supplied for Hitachi video printer VY-50, VY-8100, which is an image receptor for sublimation type thermal recording, as an image receptor.

Applied power: 442 mw/dot Application time: 0 to 811 m5ec Applied energy: 0 to 3.54 mJ/dot Example 4~
The thermal transfer sheet No. 6 had quiet printing noise and smooth feeding in the printer, and no sticking phenomenon occurred due to the thermal energy of the thermal head.

Further, no wrinkles were observed in the ink removed portions, and no image disturbance caused by the stick occurred.

Furthermore, the ink sheet of Comparative Example 4 had a loud printing sound, poor feeding performance within the printer, and a sticking phenomenon occurred due to the thermal energy of the thermal head, resulting in noticeable disturbances in the printed image. Furthermore, the ink sheets of Comparative Examples 5 and 6 broke at the initial stage of printing and could not be printed.

Example 7 Acrylic resin; Dianal B R-85 (manufactured by Mitsubishi Rayon ■) 3.0 parts by weight Alkit resin; Hetsukosol E L-4501-50 (solid content 50%) (manufactured by Inu Nippon Ink Chemical ■) 7.0 parts by weight Parts by weight Melamine resin, Super Beckamine L-145-60 (solid content 6096) (manufactured by Dainippon Ink Chemical Co., Ltd.) 6.0 parts by weight Boron nitride
2.0 parts by weight toluene
45.0 parts by weight Methyl ethyl ketone 45
．． 0 parts by weight The above composition was applied to a 4.5 μm thick polyester film using a wire bar to a thickness of about 1 μm, and dried at 100° C. for 1 minute and 60° C. for 20 hours.
A base material for a thermal transfer sheet having an anti-sticking layer was obtained.

An ink composition having the following formulation was dissolved on this base material with stirring, and then applied to the surface opposite to the anti-sticking layer using a wire bar to a film thickness of 1 μm to obtain an ink sheet for sublimation thermal transfer.

Butyral resin; S-LEC BX-1 (manufactured by Block Chemical Industry Co., Ltd.) 5.0 parts by weight Dye; Kayaset Bluff 14 (manufactured by Nippon Kakami Co., Ltd.) 4.0 parts by weight Toluene 45.0 parts by weight Methyl ethyl ketone 50.0 parts by weight Examples 8 Acrylic resin; Acrydic A-157 (solid content 50%) (manufactured by Dainippon Ink Chemical ■) 7.0 parts by weight Alkyd resin; Betsukosol J-557 (solid content 50%) (manufactured by Dainippon Ink Chemical ■) 7 .0 parts by weight melamine resin;
Super Beckamine G-821-60 (solid content 60%) (manufactured by Dainippon Ink Chemical) 5.0 parts by weight Magnesium stearate 2.0 parts by weight Toluene
45.0 parts by weight Methyl ethyl ketone 45.0
Part by Weight The above composition was applied to a 4.5 μl polyester film in the same manner as in Example 1 to obtain a base material for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 7 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Example 9 Acrylic resin; Acrydic CL-1185 (solid content 50%) (Dainippon Ink Chemical Co., Ltd.) 9.5 parts by weight Alkyd resin; Beccosol 1334-EL (solid content 50%) (Dainippon Ink Chemical Co., Ltd.) (manufactured by Mitsui Toatsu Chemical Co., Ltd.) 5.5 parts by weight Melamine resin; Kneepan 20SE (solid content 60%) (manufactured by Mitsui Toatsu Chemicals) 3.3 parts by weight Talc 2.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone
45.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 7 to obtain a base material for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 7 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 7 Acrylic resin: Dianal B R-85 (manufactured by Mitsubishi Rayon ■) 3.0 parts by weight Alkyd resin; Hetsukosol E L -4501-50 (solid content 50%) (manufactured by Dainippon Ink Chemical ■) 7.0 Part by weight Isocyanate; Coronate L (manufactured by Nippon Polyurethane) 2.5 parts by weight Boron nitride
2.0 parts by weight toluene
45.0 parts by weight Methyl ethyl ketone 45.0
Part by Weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 1 to obtain a base material for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 7 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 8 Acrylic resin; Acrydic A-157 (solid content: 5096 N (manufactured by Dainippon Ink Chemical Co., Ltd.) 7.0 parts by weight Alkyd resin; Betsukosol J-557 (solid content: 50%) (manufactured by Dainippon Ink Chemical Co., Ltd.) 7.0 parts by weight Isocyanate; Coronate L (Japan Polyurethane Corporation) 3.0 parts by weight Magnesium stearate 2.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone 45.
0 parts by weight The above composition was prepared in the same manner as in Example 7 to give a thickness of 4.5 μm.
A base material for a thermal transfer sheet having an anti-sticking layer was obtained by coating a polyester film.

The ink composition of Example 7 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 9 Acrylic resin; Acrydic CL-1185 (solid content 50%) (manufactured by Dainippon Ink Chemical Co., Ltd.) 9.5 parts by weight Alkyd resin; Betsukosol 1334-EL (solid content 5090) (manufactured by Dainippon Ink Chemical Co., Ltd.) 5.5 parts by weight Isocyanate, Harnosoku D\-950 (manufactured by Dainippon Ink Chemical ■) 2.5 parts by weight Talc 2.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone
45.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 7 to obtain a base material for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 7 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

The storage stability and printability of each of the heat-sensitive transfer sheets obtained above were tested. The test method and results are shown below.

[Tests and Results] Preservation Acceleration Test The two obtained heat-sensitive transfer sheets were placed one on top of the other so that the ink layer and anti-sticking layer were in contact with each other, sandwiched between two sheets of paper, and a load of 10 g was applied. 60℃, 50%R
A preservation acceleration test was conducted by placing the sample in a constant temperature bath. As a result, in Examples 7 to 9 and Comparative Examples 7 to 9, no abnormalities such as blocking or back bleed were observed.

2. Printing Test Printing was carried out under the following conditions using a partial glaze type thermal head using image receiving paper supplied for Hitachi video printer VY-50, VY-8100, which is an image receptor for sublimation type thermal recording, as an image receptor.

Applied power: 442 mv/dot Application time: 0 to 81 nmSee Applied energy: 0 to 3.54 mJ/dot Example 7~
Thermal transfer sheet No. 9 had quiet printing noise, smooth feeding in the printer, and no sticking phenomenon caused by the thermal energy of the thermal head occurred.

Furthermore, no wrinkles were observed in the solid areas after the ink was removed, and there was no image disturbance caused by the stick.

In addition, the ink sheets of Comparative Examples 7 and 8 had loud printing noise, poor feeding performance within the printer, and a sticking phenomenon occurred due to the thermal energy of the thermal head, resulting in significant disturbance of the printed image. Furthermore, the ink sheet of Comparative Example 9 broke at the initial stage of printing, and printing could not be performed.

Example 10 Cellulose resin, CA B 381-20 (manufactured by Eastman Kodak ■) 3.0 parts by weight Melamine resin; Super Hetsukamine L-145-60 (manufactured by Dainippon Ink Chemical ■) 2.0 parts by weight Boron nitride 1 .0 parts by weight toluene
45.0 parts by weight Methyl ethyl ketone 50.0 parts by weight The above composition was applied to a 4.5 μm thick polyester film using a wire bar to a thickness of about 1 μm, and dried at 100°C for 1 minute and at 60°C for 20 hours. Thus, a base material for a thermal transfer sheet having an anti-sticking layer was obtained.

An ink composition having the following formulation was dissolved on this base material with stirring, and then applied to the surface opposite to the anti-sticking layer using a wire bar to a film thickness of 1 μm to obtain an ink sheet for sublimation thermal transfer.

Butyral resin, S-LEC BX-1 (manufactured by Block Chemical Industry ■) 5.0 parts by weight Dye, Kayaset Bluff 14 (manufactured by Nippon Kayaku ■) 4.0 parts by weight Toluene 45.0 parts Methyl ethyl ketone 50.0 parts by weight Example 11 Cellulose resin, CAP 482-20 (manufactured by Eastman Kodak ■) 3.5 parts by weight Melamine resin; Super Veracamine G-82]-60 (manufactured by Dainippon Ink Chemical Co., Ltd.) 1.
5 parts by weight Magnesium stearate 1.0 parts by weight Toluene
450 parts by weight methyl ethyl ketone
50.0 parts by weight of the above composition was applied to a 4.5 μm polyester film in the same manner as in Example 0 to obtain a base material for a thermal transfer sheet having an anti-sticking layer. The ink composition of Example 0 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Example 12 Cellulose resin; CA B 500-5 (manufactured by Eastman Kodak ■) 3.0 parts by weight Melamine resin; Kneepan 2
03E (manufactured by Mitsui Toatsu Chemical Co., Ltd.) 2.0 parts by weight Talc 1.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone
50.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 10 to obtain a base material for a thermal transfer sheet having an anti-sticking layer.

The ink composition of Example 10 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 10 Cellulose resin, CA B 381-20 (manufactured by Eastman Kodak ■) 5.0 parts by weight boron nitride
1.0 parts by weight toluene 45,
0 parts by weight Methyl ethyl ketone 50.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 10 to obtain a base material for a thermal transfer sheet having an anti-sticking layer. The ink composition of Example 10 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 11 Cellulose resin, CAP 482-20 (manufactured by Eastman Kodak ■) 5.0 parts by weight Magnesium stearate 1.0 parts by weight Toluene 45
, 0 parts by weight Methyl ethyl ketone 50.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 10 to obtain a substrate for a thermal transfer sheet having an anti-sticking layer. Example 10 on this base material
The ink composition was applied in the same manner to obtain an ink sheet for sublimation type thermal transfer.

Comparative Example 12 Butyral resin; Denka Butyral #5000A 4.0 parts by weight Isocyanate; Burnock DN-950 (manufactured by Dainippon Ink Chemical) 1.0 parts by weight Talc 1.0 parts by weight Toluene
45.0 parts by weight methyl ethyl ketone
50.0 parts by weight The above composition was applied to a 4.5 μm polyester film in the same manner as in Example 10 to obtain a base material for a thermal transfer sheet having an anti-sticking layer. The ink composition of Example 10 was similarly applied to this base material to obtain an ink sheet for sublimation type thermal transfer.

The storage stability and printability of each of the heat-sensitive transfer sheets obtained above were tested. The test method and results are shown below.

[Tests and Results] Preservation Acceleration Test The same two heat-sensitive transfer sheets obtained were placed one on top of the other so that the ink layer and the anti-sticking layer were in contact with each other, and sandwiched between two sheets of paper. °C150%
A preservation acceleration test was conducted by placing the sample in a thermostat at RH. As a result, in Examples 10 to 12 and Comparative Examples 10 to 12, no abnormalities such as blocking or back bleed were observed.

2. Printing Test Printing was carried out under the following conditions using a partial glaze type thermal head using image receiving paper supplied for Hitachi video printer VY-50, VY-8100, which is an image receptor for sublimation type thermal recording, as an image receptor.

Applied power: 442 mv/dot Application time: 0 to 8II1 msec Applied energy: 0 to 3.54 mJ/dot Example 10
Thermal transfer sheets No. 1 to 12 had quiet printing noise, smooth feeding in the printer, and no sticking phenomenon caused by the thermal energy of the thermal head occurred. Furthermore, no wrinkles were observed in the solid areas after the ink was removed, and there was no image disturbance caused by the stick.

In addition, the ink sheet of Comparative Example 10 had a loud printing sound, poor feeding performance within the printer, and a sticking phenomenon occurred due to the thermal energy of the thermal head, resulting in noticeable disturbance of the printed image. Furthermore, the ink sheets of Comparative Examples ] and ]2 broke at the initial stage of printing and could not be printed.

[Effects] As explained above, the thermal transfer sheet of the present invention has a specific anti-sticking layer on one side of the base material, so it has quiet printing noise, good feeding performance, and reduces the thermal energy of the thermal head. It has the advantage that it is stable and does not cause sticking, and does not cause blocking during storage.

Claims (4)

[Claims] (1) A thermal transfer sheet characterized in that a transfer ink layer is provided on one side of a plastic film, and an anti-sticking layer made of polyvinyl butyral, melamine resin, and a filler is provided on the other side. (2) A thermal transfer sheet, characterized in that a transfer ink layer is provided on one side of a plastic film, and an anti-sticking layer made of phenoxy resin, melamine resin, and filler is provided on the other side. (3) A heat-sensitive transfer sheet, characterized in that a transfer ink layer is provided on one side of a plastic film, and an anti-sticking layer made of an acrylic resin or alkyd resin, a melamine resin, and a filler is provided on the other side. (4) A heat-sensitive transfer sheet, characterized in that a transfer ink layer is provided on one side of a plastic film, and a staking prevention layer made of a cellulose resin, a melamine resin, and a filler is provided on the other side.