JPH02150387A - Novel thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To enable low energy printing to be performed by a method wherein a thermal fusing color material layer is established on a base material via an adhesive layer, and the thermal fusing color material layer contains one or not less than two types thereof selected from novel styrene-ethylene-butylene- styrene block copolymer and a specific compound group. CONSTITUTION:One or not less than two thermal fusible color material layers are established on a base material via an adhesive. The thermal fusible color material is composed by containing one or not less than two types of thermal fusible substance selected from novel styrene-ethylene-butylene-styrene block copolymer having a polyethylene terminal block and a crystalline ethylene- butylene rubber block for an intermediate block and from animal wax, plant wax, mineral wax, petroleum wax, synthetic hydrocarbon wax, and modified wax. It is preferable to use at most within 30wt.% novel styrene-ethylene- butylene-styrene block copolymer resin, of which weight average molecular weight is within a range of 5,000 to 2,000,000, of which polyethylene content is a range of 5 to 45wt.%, and of which intermediate block material has crystalline ethylene-butylene block, in a thermal transfer recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION [Graduation Field of Use] The present invention relates to a novel thermal transfer recording medium that can be used multiple times. Specifically, it is a thermal transfer recording medium that can be printed with low energy, has good printability and print retention durability even on uneven paper such as plain paper, and can provide clear and high quality print quality. Regarding.

[Prior Art] As a heat-sensitive transfer recording medium intended to be used multiple times, which has been disclosed as a prior art, for example, Japanese Patent Laid-Open No. 55-105579 discloses a technique in which a fine porous layer is formed. JP-A No. 57-160691 describes a technique of forming a network structure using organic or inorganic fine powder and impregnating the layer with ink. Also, JP-A-57-1851
No. 92 describes a technique for impregnating porous paper with ink.

Furthermore, JP-A-54-68253 discloses that a resin and a solid component immiscible therewith are dissolved and dispersed in a volatile solvent, and after the solvent evaporates, a fine porous layer of the resin component is formed on a support. Techniques for forming this are described.

Further, JP-A-61-162395 describes a technology for a thermal transfer recording medium made of polyethylene glycol diester or wax that is solid at room temperature.

[Problems to be Solved by the Invention] One of the above-mentioned conventional technologies is that they are all designed to allow ink to seep out little by little from a porous solid base material. Because the solid base material to be formed does not melt or mix with heat-fusible substances when energy is applied, and the solid base material is not substantially transferred, the density of the dye transfer image is low ( , there is a problem that it does not provide clear print quality many times, and high energy is required to obtain clear prints with high density, resulting in a significant drop in resolution. .

This type of idea can be seen as simply utilizing the technology disclosed in Japanese Patent Application Laid-Open No. 35-13426 for a thermal transfer ribbon, and due to the problem of the transfer principle, the printing sensitivity is extremely poor, which is inconvenient.

On the other hand, as an attempt to solve the first problem, there have been disclosed, for example, JP-A-57-36698 and JP-A-51-9699.
No. 2 discloses a method of interposing an adhesive layer as a technique for adjusting the transfer amount of a heat-fusible coloring material layer.

However, according to this method, there are problems such as low dye transfer image density for transfer paper with low surface smoothness and a severe decrease in density after multiple printings.

Further, as an attempt to solve the first and second problems, for example, Japanese Patent Application Laid-Open No. 162395/1983 discloses a technique for adjusting the transfer amount of a heat-fusible coloring material layer through an adhesive layer.
A technique is disclosed in which solid polyethylene glycol diester or wax is used as a thermal transfer recording medium.

According to this method, it is stated that it is possible to print with high dye transfer image density by printing multiple times with low energy on transfer paper with low surface smoothness. From the viewpoint of reliability, thermal transfer recording media other than those made mainly of carnauba wax cannot withstand use.

According to the thermal transfer recording medium of the above method, the dye transfer image lacks adhesion to the transfer paper with low surface smoothness, is hard, and is difficult to handle after printing due to its stiffness. In other cases, carnauba wax is acceptable, but in other cases, including other known technologies, the problem is that the print durability and pigment resolution are significantly reduced. As a result, a thermal transfer recording medium with high printing durability after printing is desired.

In other words, in recent years, thermal transfer recording media mainly made of known carnauba wax have been widely used. There is a problem with the price etc.
There is a strong desire for a new thermal transfer recording medium that can replace carnauba wax, has high printing performance (high quality), and can solve the above-mentioned problem of page reliability of dye transfer images.

The present invention is capable of low-energy printing, has little density loss with the number of uses, and can produce high-density dye transfer images many times, and can also be applied to paper with low surface smoothness. The object of the present invention is to provide a new thermal transfer recording medium that can be printed clearly and with high density and has extremely good adhesion durability of dye transfer images.

[Means for Solving the Problems] As a result of intensive research, the present inventor has discovered that a thermal transfer recording medium having a heat-melting coloring material layer on a support via an adhesive layer has a nuclear heat capacity. A new styrene-ethylene-butylene-styrene block copolymer resin in which the partial colorant layer has a polystyrene terminal block and the intermediate block has a crystalline ethylene-butylene rubber block, and the following compound group (
[Wax compound group] Contains one or more heat-melting substances selected from animal waxes, vegetable waxes, mineral waxes, petroleum waxes, synthetic hydrocarbon waxes, and modified waxes. The inventors have discovered that the above technical problem can be solved by doing this, and have completed the present invention.

The present invention will be further explained in detail below.

In the heat-sensitive transfer recording medium of the present invention, one layer or two or more heat-melting coloring material layers are provided on a support via an adhesive.

Note that when two or more heat-melting coloring material layers are formed, an intermediate layer may be provided between each layer.

In the thermal transfer recording medium of the present invention, preferably, the intermediate block is a novel styrene-ethylene-butylene-styrene block copolymer resin having a polystyrene content in the range of 5 to 45% by weight and consisting of a crystalline ethylene-butylene block. can be used.

More preferably, the intermediate block is crystalline ethylene-
It consists of a butylene block, and its intermediate block is
A new styrene ethylene-butylene-styrene block copolymer resin having a high proportion of crystalline polyethylene (60% by weight or more) can be used.

More preferably, a novel styrene-ethylene having a weight average molecular weight in the range of 5,000 to 200,000, a polystyrene content in the range of 5 to 45% by weight, and an intermediate block having a crystalline ethylene-butylene block. -Butylene-styrene block copolymer resin can be used.

Most preferably, a new styrene-based material having a weight average molecular weight of 5,000 to 200,000, a polystyrene content of 5 to 45% by weight, and an intermediate block having a crystalline ethylene-butylene block is most preferable. ethylene-butylene-
A novel thermal transfer recording medium in which a styrene block copolymer resin is used in the thermal transfer recording medium in an amount of at most 30% by weight is preferred.

Further, in the thermal transfer recording medium of the present invention, the wax compound group includes a heat-melting substance selected from animal waxes, vegetable waxes, mineral waxes, petroleum waxes, synthetic hydrocarbon waxes, and modified waxes. Type 1 or 2
It is preferable to use ethylene-vinyl acetate copolymer resin containing at least 70% by weight or more as an essential component in a thermal transfer recording medium. , weight average molecular weight is 40
Polyethylene glycol diester in the range of 0 to 30,000, ethylene-ethyl acrylate copolymer resin containing 35% by weight or less of ethyl acrylate, aromatic tackifier resin,
Alicyclic tackifier resin, rosin ester tackifier resin, crystalline polyester resin, styrene-ethylene-butylene-styrene block copolymer resin consisting of an amorphous intermediate block, ethylene-butadiene-styrene block copolymer resin , styrene-isoprene-styrene block copolymer resins (hereinafter referred to as resin materials), one or two or more of them are used together in a thermal transfer recording medium in an amount of at most 10% by weight or less. This is highly preferable as a new thermal transfer recording medium.

Further, in the thermal transfer recording medium of the present invention, the elongation rate of the molded product of the thermal transfer recording medium alone is at least 10% or more, and the melt viscosity of the thermal transfer recording medium alone is 11%.
In addition, the softening point temperature of the thermosensitive recording medium alone by the ring and ball method must be within the range of 5 to 2000 cps at 0°C.
It has been found that it is particularly preferable to maintain the temperature within the range of 130°C to 130°C.

The novel styrene-ethylene-butylene-styrene block copolymer resin having polystyrene terminal prongs and having a crystalline ethylene-butylene rubber block in the intermediate block used in the present invention is a conventionally known amorphous intermediate block copolymer resin having a crystalline ethylene-butylene rubber block in the intermediate block. The styrene-ethylene-butylene-styrene block copolymer resin having a block body is essentially completely different from that in which the intermediate ethylene-butylene rubber block chain portion of the resin exhibits crystallinity in a normal state. A new styrene-ethylene-butylene-styrene block copolymer resin resin, or specific crystalline resin, whose compatibility with wax compounds is extremely improved by controlling and adjusting the ethylene content to a sufficiently high ratio. Either crystalline low-molecular or medium-molecular polyethylene in a styrene-ethylene-butylene-styrene block copolymer resin having a polyethylene intermediate block, or crystalline ethylene-butene copolymer resin having a high proportion of polyethylene. As a result, the resin is modified so that it has a high enough ethylene content to exhibit crystallinity under normal conditions, and its compatibility with the wax compound group is extremely improved. It refers to a new styrene-ethylene-butylene-styrene block copolymer resin containing a crystalline polyethylene-based or crystalline polyethylene-butene-based chain polymer.

The novel styrene-ethylene-butylene-styrene block copolymer resin having the above-mentioned polystyrene end blocks and having a crystalline ethylene-butylene rubber block in the middle block described in the present invention was presented, for example, at a conference held in Atlanta, USA in 1988. At the TAPPI International Conference, Shell
It is published by Chemical Company and is easily available on the market.

i.e. with polystyrene end blocks, a high proportion of 1,4-butadiene in the middle block, and a low proportion of 1.2-butadiene.
- A method in which a styrene-butadiene-styrene bronocopolymer with a controlled distribution of butadiene is obtained and then hydrogenated to make the intermediate block exhibit crystallinity, and a method in which a high proportion of ethylene is added to the polystyrene terminal radicals is obtained. and a low proportion of 1-butene, respectively, are polymerized and coupled with a known coupling compound to obtain a resin having a moderately crystalline intermediate rubber block. Crystalline low-molecular or medium-molecular polyethylene, or crystalline ethylene with a high proportion of polyethylene added to a styrene-ethylene-butylene-styrene block copolymer resin having a rubber block.
Crystalline polyethylene-based or crystalline polyethylene-butene-based A novel resin having the polystyrene terminal block described in the present invention and having a crystalline ethylene-butylene rubber block in the intermediate block, etc. This is a typical synthesis example of a styrene-ethylene-butylene-styrene block copolymer resin.

The crystallinity described in the present invention means that the intermediate rubber block body is
It exhibits behavior similar to the crystalline properties of low-density polyethylene, especially in the range from room temperature to about 120°C, preferably in the range of 20°C to 70°C, as a melting heat absorption peak in a differential scanning calorimeter. means an observed property.

Another aspect of the present invention can be achieved by using a new styrene-ethylene-butylene-styrene block copolymer resin having the polystyrene end blocks described in the present invention and having a crystalline ethylene-butylene rubber block in the intermediate block. The miscibility with the above-mentioned wax compound group compounds, which are components, is significantly improved, and as a result, the hard and brittle thermal transfer recording media in the prior art, which is the technical problem typified by solid wax compounds, is solved. The properties are significantly improved (the effect of improving toughness without impairing the M properties), and the pigment dispersion stability is also improved when an ink pigment such as carbon black is contained in the heat-melting color material layer. It has excellent thermal stability, hue stability, and weathering stability, making it possible to perform stable, high-density transfer multiple times.

In addition, even in the case of transfer paper such as plain paper with low surface smoothness, it exhibits the effects of high density and high print quality, that is, excellent print adhesion and durability, sharpening print resolution and dye transfer images. The mechanical adhesion durability retention rate is greatly improved.

The wax compound group substance used in the present invention is a wax that is solid at room temperature, preferably with a melting point of 40°C to 80°C.
Waxes in the range of C are preferable, and specifically the waxes listed below are typical.

That is, examples of animal waxes used in the present invention include spermaceti wax, wool wax, insect wax, shellac wax, and beeswax, and examples of vegetable waxes include carnauba wax, tree wax, auricular wax, and espartol wax. , candelilla wax, etc.; examples of mineral waxes include montan wax, osikelite, ceresin, etc.; examples of petroleum waxes include paraffin waxes, microcrystalline waxes, ester waxes, petrolatum, and polyethylene gelcol. Examples of the synthetic hydrocarbon waxes include Fischer Trobutsch wax, polyethylene wax, low molecular weight polypropylene wax, low molecular weight polyethylene wax and derivatives thereof, and modified waxes. Examples of the wax include oxidized wax, monk's wax derivatives, paraffin, and microcrystalline wax derivatives, and one type or two or more types may be used in combination. In the present invention, hydrogenated waxes such as castor wax and opal wax which do not belong to the above wax compound group may be used in combination.

The present invention also uses the following resin materials, such as ethylene-vinyl acetate copolymer resin with a vinyl acetate content of 28% by weight or less, polyethylene glycol diester with a weight average molecular weight in the range of 400 to 30,000, and ethyl acrylate with a weight average molecular weight of 35% or less. Weight% or less of ethylene-ethyl acrylate copolymer resin, (hydrogenated) terpene resin, (hydrogenated) terpene phenol resin, (hydrogenated) C9 petroleum resin, (hydrogenated) C5-C9
Copolymerized petroleum resin, low molecular weight polystyrene resin2. Aromatic tackifying resins such as styrene-modified petroleum resins, low-molecular α-methylstyrene resins, alicyclic tackifying resins such as (hydrogenated) dicyclopentadiene petroleum resins, and rosin esters. or alicyclic tackifier resin represented by derivatives thereof, crystalline polyester resin, styrene-ethylene-butylene-styrene prong copolymer resin consisting of an amorphous intermediate rubber block, styrene-butadiene styrene block copolymer Using one or more selected from resins, styrene-isoprene-styrene block copolymer resins, polyethylene, polypropylene, etc. in a thermal transfer recording medium in an amount of at most 10% by weight is effective in maintaining appropriate viscosity. The effects of modification, adjustment of softening temperature, high resolution in low energy printing, and improvement in the strength of printed transfer images are exhibited, and they may be used in combination for such purposes.

In the present invention, a novel styrene-ethylene-butylene-styrene block copolymer resin having the polystyrene terminal block described above in the heat-melting coloring material layer and having crystalline ethylene-butylene rubber prongs in the intermediate rubber block is used. There is no particular limitation on the means for containing the above wax compounds, and generally they can be obtained by melting and mixing.

In cases where some of the wax compounds show immiscibility,
For example, it may be used by stirring vigorously and uniformly dispersing it. Alternatively, it is also possible to use fusing to form a compatible state and then remove the solvent to form a finely dispersed state.

In the present invention, there is no particular limitation on the method of forming the heat-melting coloring material layer in the form of an ink, and the method of forming the heat-melting coloring material layer in the form of an ink is not particularly limited. A method of co-dispersing a styrene-ethylene-butylene-styrene block copolymer resin and the above wax compound group with a colorant (dye or pigment), optionally containing a resin substance;
Alternatively, one of the components of the present invention and the colorant may be separately dispersed in advance.

That is, in the present invention, the colorant is dispersed before the dispersion of the novel styrene-ethylene-butylene-styrene block copolymer resin having the polystyrene terminal block and having a crystalline ethylene-butylene rubber block in the intermediate block. or later.

The coloring agent used in the heat-melting coloring material layer of the present invention may be appropriately selected from various pigments, and particularly preferably direct dyes, acid dyes, basic dyes, disperse dyes, oil-soluble dyes ( Indoaniline dyes, azomethine dyes, and the like can also be preferably used.

Further, the pigment used in the color material layer of the present invention may be any pigment that can basically be transferred (transferred) together with a heat-fusible substance, and thus organic or inorganic pigments may be used in addition to the above.

Specific examples of the coloring agent used in the heat-melting coloring material layer of the present invention include the following.

That is, examples of yellow dyes include PS Yellow GG (Mitsui Toatsu Chemical Co., Ltd.), PS Yellow SK (Mitsui Toatsu Chemical Co., Ltd.), and Kayalon Polyester Light Yellow 5G-3 (Mitsui Toatsu Chemical Co., Ltd.).
Nippon Kayaku), Oil Ye o-5-7 (white clay), Eisen Suviron Yellow GRH Special (Hodogaya), Sumiplast Ye o-FC; (resident), Eisen Spiron Yellow GRH (Hodogaya), etc. are red. As a pigment,
For example, PS Red G (Mitsui Toatsu Chemical Co., Ltd. product), MS Red VP (Mitsui Toatsu Chemical Co., Ltd. product), Diaceritone Fast Red R (Mitsubishi Kasei), Sumipura Tread FB (Resident)
, Sumipurasu Tread RFC; (Resident), Kayalon Polyester Pink RCL-E (Japan Hojo), Eizen Subiron Red GHR Special (Hodogaya), etc. As a blue pigment, for example, Miketon Polyester Blue FBL Conch (Mitsui Higashi) Pressure Chemical Company product), PET Blue #2000 (
Mitsui Toatsu Chemical Co., Ltd.), PS Blue BN (Mitsui Toatsu Chemical Co., Ltd. product), Diaceriton Fast Brilliant Blue (Mitsubishi Kasei), Dianic Sprue EB-E (Mitsubishi Kasei), Kayalon Polyester Blue B-3F Conc. (Japan Hojo), Sumiplast Blue 3R (Jinja), Sumiplast Blue G (Jinja), etc. Yellow coloring pigments include Hansa Yellow 3G, Taldrazine Lake, etc. Red coloring pigments include, for example. Brilliant Carmine FB-Pure (Nanyo Pigment), Brilliant Carmine 6B (Nanyo Pigment), Alizarin Lake, etc., and examples of blue coloring pigments include Carlian Blue, Sumikabrintocyanine Blue GN-0 (Dweller), Phthalocyanine Blue, etc. Typical examples of black colored pigments include carbon black and oil black, and the most preferred coloring agent in the present invention is carbon blank.

Although the composition ratio of the heat-melting coloring material layer of the present invention is not limited,
Based on 100 parts by weight of the solid content of the heat-melting coloring material layer, the heat-melting substance is 5 to 80 parts by weight, preferably 10 to 60 parts by weight, and the coloring material is 5 to 50 parts, preferably 10 to 40 parts. It is preferable to use within this range.

In addition to the above components, various additives may be added to the heat-melting coloring material layer of the present invention, such as castor oil, linseed oil,
Vegetable oils such as olive oil, animal oils and mineral oils such as whale oil, synthetic oils such as liquid polybutene, liquid hydrogenated polyisoprene, paraffin oil, and naphthenic oil, conductors such as metal particles, graphite, and graphite powder, polyalkylene glycol, and sulfuric acid. Lubricating oils such as oil and silicone oil, inorganic compounds such as bicarbonates, carbonates, and nitrites, or thermally decomposable blowing agents such as sulfonyl hydrazide organic compounds, thermally expandable microparticles, polymerization inhibitors, and antiaging agents. , UV stabilizer (Kinai stabilizer), UV absorber (Kinai absorbent), dispersion stabilizer, viscosity modifier (thixotropic or gelling improver), surfactant for paint or ink, high boiling point solvent It is preferable to use various additives such as these depending on the purpose.

In the heat-sensitive transfer recording medium of the present invention, a suitable technique for applying the heat-melting coloring material layer onto the support may be any known technique, such as hot-melt coating or applying the composition. There are coating techniques that use a coating liquid dissolved in a solvent to form a solvent coating, and a coating method in which emulsion silane is dispersed in water. are reverse roll coater method, extrusion coater method, gravure coater method, wire bar coating method, etc.
Known techniques can be employed.

Further, the thickness of the coating film for forming the heat-melting coloring material layer of the present invention is not limited, but - for boat fishing, it is preferably 15 microns or less, preferably 5 microns or less, more preferably 3 microns or less.

In the present invention, examples of the adhesive layer include polyvinyl butyral resin, epoxy resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer resin, and vinyl chloride. One type or a combination of two or more types of thermoplastic resins or thermosetting resins such as resins, polyacrylate resins, polyamide resins, polyimide resins, styrene block copolymer resins, phenol resins, melamine resins, and polyurethane resins. It is good to use it.

The thickness of the adhesive layer is not particularly limited, but is usually 0. 1 to 5
Micron, preferably 0.3 to 2 micron.

As the support used in the thermal transfer recording medium of the present invention, a material having high thermal rigidity (heat-resistant strength), dimensional stability, and surface smoothness may be selected and used.

Specifically, as heat resistance strength, it has both toughness and dimensional stability that do not soften or plasticize due to the heating temperature of a heat source such as a thermal head, and the surface smoothness is a color containing a heat-fusible substance on the support. It is desirable that the material layer has sufficient smoothness to exhibit a good thermal transfer rate (high print density and high resolution).

Examples of such materials include papers such as plain paper, condenser paper, laminated paper, and coated paper, and resins such as polyethylene, polyethylene terephthalate, polyester, polystyrene, polypropylene, polyamide, polyimide, polyether sulfone terephthalate, polyphenylsulfone, and polycarbonate. Films and paper - Resin film composites, metal films such as aluminum foil, and metal foils such as aluminum -
Resin film composites, aluminum-metal composites such as aluminum, paper-metal foil-resin film composites, etc. can be suitably used.

The thickness of the support is generally 60μ or less, preferably 30μ or less, and particularly preferably 2μ to 20μ in order to obtain good thermal conductivity.

Further, the support used in the thermal transfer recording medium of the present invention is
There are no particular restrictions on the structure of the back side of the support, and it is arbitrary; for example, any support may be provided with a backing layer such as an anti-blocking layer or an anti-sticking layer.

[Examples] Examples of the present invention are shown below, but the invention is not particularly limited, and the terms % and parts shown in the examples below mean % by weight and parts by weight, respectively.

Example 1.

3. Using a wire bar, dry film thickness is 1.0 on a polyethylene terephthalate film support with a thickness of 5 μm.
An adhesive layer is obtained by applying a solution of ethylene-ethyl acrylate copolymer (product of Nippon Unicar Co., Ltd. + 1JC6070) so that the coating thickness is 1 μm, and after drying, the following coloring material layer coating composition is applied using the true melt coating method. Then, the film thickness is 1
A thermal transfer recording medium sample (a ribbon-shaped test piece with a width of 8 mm) A of the present invention was obtained by coating the film to a thickness of 0 μm.

Further, the colorant layer alone of thermal transfer recording medium A was found to have appropriate hardness and toughness, and had an elongation property of about 50% or more.

A new styrene-ethylene-butylene-styrene block copolymer resin that has a crystalline ethylene-butylene rubber block in the intermediate rubber block and contains 15% polystyrene (Shell Chemical Co. product GR-1)
: 8 parts Paraffin wax (softening point 64°C) Hiki Seirosha product HNP-3 : 20 parts °? Icrocrystalline wax (softening point 80°C) Nippon Seirosha product Hi-Mic-1070: 56.8 parts Carbon black (paint grade) Mitsubishi Chemical Industries product MA100: 15 parts Benataerythrityl Tetrakis [3-(3 .

5-di-L-butyl-4-hydroxyphenyl)propionate] Anti-aging agent 20.2 parts This thermal transfer recording medium sample A was printed using a thermal printer (equipment with a built-in thermal head with a heating element of 16 DoL/mm). , giving an applied energy of 0.5 mj/Dot,
The recording (printing) test was repeated twice on commercially available plain paper (Beck smoothness: 100 sec) and copy paper (Beck smoothness: 30 sec).

In addition, using the gi for which printing was completed in Example 1 (the gi printed out in Example 1 and provided with the printed recording transfer image),
Table 1 shows the results of two 360° bending tests and a nail peeling test.

Example 2.

In Example 1, a new styrene-ethylene-butylene-styrene block copolymer resin (GR-, a product of Sikuru Chemical Company) having a crystalline ethylene-butylene rubber block as an intermediate rubber block and containing 15% polystyrene was used. 1)
Instead, a styrene-ethylene-butylene-styrene block having an amorphous ethylene-butylene rubber block in the intermediate rubber block and containing 13% polystyrene,
Copolymer resin (Shell Chemical Company product Kraton G-1
657
00 Mitsui Hiwax 220P) was subjected to graft polymerization modification in a nitrogen stream using a peroxide catalyst (benzoyl peroxide), most of which was in the side chains,
A thermal transfer recording medium sample of the present invention (a ribbon-shaped test piece with a width of 8 mm) was prepared in the same manner as in Example 1 except that a new styrene-ethylene-butylene-styrene block copolymer resin containing crystalline polystyrene was used. I got a B.

The coloring material layer alone of thermal transfer recording medium B was found to have appropriate hardness and toughness, and had an elongation property of about 10% or more.

Using this thermal transfer recording medium sample B, a printing test was conducted using a thermal printer in the same manner as in Example 1, and a 360° bending LK test was conducted twice using the paper on which printing was completed in Example 2. , and the results of the nail peeling ji1f test are listed in Table 1.

Comparative Example 1 In Example 1, a new styrene-ethylene-butylene-styrene block copolymer resin containing a crystalline ethylene-butylene rubber block in the intermediate rubber block and containing 15% polystyrene (GR-, a product of Shell Chemical Company) was used. 1)
Instead, an ethylene-vinyl acetate copolymer (Evaflex #410, a product of Mitsui Polychemical Co., Ltd.) was used, except that the color material layer alone had hard and brittle properties with no elongation. Comparative thermal transfer recording medium sample (8mm
A ribbon-shaped specimen) C was obtained.

Using this thermal transfer recording medium sample C, a printing test was conducted with a thermal printer in the same manner as in Example 1, and in Comparative Example 1.
Table 1 shows the results of two 360° bending tests and a nail peeling test using the printed paper.

Table 1 360° bending ◎: Almost no print transfer image force Vl or 116 was observed (reflection density retention rate 95% or more).

O: Very slight blurring or blurring of the printed transfer image was observed.
(Reflection density retention rate of 80% or more).

×: Terrible print transfer image strength @1 Reya Izumi 1 was criticized.

(Reflection density retention rate 70% or less).

11 nails ◎: Almost no cracks, Sake 1 Fuchi, or fading were observed in the printed transfer image (reflection density retention rate of 95% or higher O: Very few cracks, Ei 1 Fuchi, or fading were observed in the printed transfer image).

(Fi!4 Keiden ``80% side temple rate Lhi)''.

×: The printed transfer image is badly scratched! In one stream, cassoulet was observed.

(Reflection density retention rate 70% or less).

As is clear from the results in Table 1 above, sample A of the present invention
, B, not only high-quality paper with a Beck smoothness of 100 seconds, but also copy paper with a Beck smoothness of 30 seconds.
There was no decrease in the resolution density of the printed transfer image from the first to the second time, and high density transfer was possible with low energy printing, but in comparison sample C, the density decreased from the first time to the second time. It was clear that this was a big problem.

Furthermore, from the results of the mechanical durability of the printed transfer image, samples A and B of the present invention showed that the transferred print body had excellent towability and adhesion, resulting in high printing durability and reliability. However, in comparison sample C, because the transfer print body was originally hard and brittle,
The results showed extremely low print durability and reliability.

Example 3 In Example 1, samples of thermal transfer recording media were obtained by varying the roughness of the coloring material layer (applied as a dispersion using Daysilver) as described below.

A new styrene-ethylene-butylene-styrene block copolymer resin that has a crystalline ethylene-butylene rubber block in the intermediate rubber block and contains 15% polystyrene (Shell Chemical Co. product GR-3)
: 10 parts Ethylene-ethyl acrylate copolymer (contains 17% ethyl acrylate) (Mikata Polychemical Co., Ltd. product Evaflex-1 EA, A-107): 5 parts Oxidized wax (Nippon Seiro Co., Ltd. product NFS91.25) ):2
0 parts Microcrystalline wax (softening point 84°C) Nippon Seirosha product Natsu (i-Mtc-1080: 50 parts Carbon black (paint grade) Mitsubishi Chemical Industries product MA200: 15 parts Regarding this thermal transfer recording medium sample, In the same manner as in Example 1, a recording (printing) test was carried out on copy paper (Benk smoothness 30 seconds).
I did it several times.

Table 2 shows the results of two 360° bending tests and a nail peeling M test using the printed paper.

Further, in Example 3 above, ethylene-ethyl acrylate copolymer was used, and in E of Table 2, ethylene-vinyl acetate (Evaflex EVA manufactured by Mikata Polychemical Co., Ltd., #410) was used.
) D. In F of Table 2, amorphous styrene-ethylene-butylene-styrene block copolymer resin (Asahi Kasei H
Thermal transfer recording medium sample E was prepared in the same manner except that G in Table 2 was changed to oxidized wax (Nippon Sei tJINPs9], 25), and H in Table 2 was changed to carnauba wax. H was obtained from

Using these thermal transfer recording medium samples E to H, Example 1
In the same manner as above, a recording (printing) test was repeated twice on copy paper (Henk smoothness: 30 seconds).

Table 2 shows the results of two 360° bending tests and a nail peeling test using the printed paper.

In addition, each sample was tested for blocking property (W
-Results of a blocking resistance test method in which film-like samples with a thickness of 5 μm were stacked with polyethylene terephthalate film, left under a load of 15 gr/cm2 at 40°C/95% RH for one day, then taken out and peeled off. Also listed in Table-2.

Table 2 360° bending ◎: Almost no print transfer image strength or sababuchi was observed (reflection density retention rate 95% or more).

○: A very slight amount of print transfer image strength was observed.

(Reflection density retention rate of 80% or more).

11 nails ◎: Printed transfer image 1 (JFII scratches, folds, and fading were hardly observed (reflection density retention rate of 95% or more).

O: Extremely low power of mapping 'III Reyao! Hesitation and cassoulet were observed.

(Reflection density retention rate of 80% or more).

[Eye gamma type 1 type of old and hardened iron fruit] Very good 2 Printing power is clear and the optical reflection density is 1
, 0 or more, and the second concentration decrease is within ±10%.

Good: Bright printing force, optical resistance! l-1 concentration is 0
．． 9 or more, and the second concentration decrease is within ±20%.

As is clear from the results in Table 2, the samples of the present invention have excellent bronking resistance, can print clearly many times, and have at least the mechanical durability of the printed transferred image after printing. It can be seen that the concentration retention rate is particularly excellent with a concentration retention rate of 80% or more.

[Effects of the Invention] According to the present invention, low-energy printing is possible, and the print density decreases little with respect to the number of uses. Even when printing on film, etc., the above performance is better than the base,
To obtain a transfer printed body which has extremely excellent mechanical durability, which was not achieved with conventional products, and has toughness and adhesiveness that fully corresponds to the toughness of the transfer paper or uneven film. It is possible to achieve the effect that color fading, fading over time, and low density of the transfer print do not occur at all.

Furthermore, the thermal transfer recording medium of the present invention has excellent blocking resistance.

Claims (1)

[Claims] 1. In a heat-sensitive transfer recording medium having a heat-melting coloring material layer on a support via an adhesive layer, the heat-melting coloring material layer has a polystyrene end block, and an intermediate block. New styrene with crystalline ethylene-butylene rubber block
Ethylene-butylene-styrene block copolymer resin,
A novel thermal transfer recording medium characterized by containing one or more heat-melting substances selected from the following compound group. Compound Group: Animal-based waxes, vegetable-based waxes, mineral-based waxes, petroleum-based waxes, synthetic hydrocarbon-based waxes, modified waxes 2, a novel product consisting of a crystalline ethylene-butylene block with a polystyrene content ranging from 5 to 45% by weight; A novel thermal transfer recording medium according to claim 1, characterized in that a styrene-ethylene-butylene-styrene block copolymer resin is used. 3. The intermediate block body consists of a crystalline ethylene-butylene block, and the intermediate block has at least 60
Claim 2, characterized in that a new styrene-ethylene-butylene-styrene block copolymer resin having a high proportion of crystalline polyethylene of at least % by weight is used.
A novel thermal transfer recording medium described in Section 1. 4. A novel styrene-ethylene-butylene having a weight average molecular weight in the range of 5,000 to 200,000, a polystyrene content in the range of 5 to 45% by weight, and an intermediate block having a crystalline ethylene-butylene block. A novel thermal transfer recording medium according to claim 3, characterized in that a styrene block copolymer resin is used. 5. A novel styrene-ethylene-butylene having a weight average molecular weight in the range of 5,000 to 200,000, a polystyrene content in the range of 5 to 45% by weight, and an intermediate block having a crystalline ethylene-butylene block. 5. A novel thermal transfer recording medium according to claim 4, characterized in that the styrene block copolymer resin is used in the thermal transfer recording medium in an amount of at most 30% by weight. 6. At least one or more heat-melting substances selected from animal waxes, vegetable waxes, mineral waxes, petroleum waxes, synthetic hydrocarbon waxes, and modified waxes are added to the thermal transfer recording medium. 6. A novel thermal transfer recording medium according to any one of claims 1 to 5, characterized in that it contains 70% by weight or more as an essential component. 7. A novel thermal transfer recording medium according to any one of the claims, characterized in that the elongation rate of a molded product of the thermal transfer recording medium alone is at least 10% or more. 8. A novel thermal transfer recording medium according to any one of the claims, characterized in that the thermal transfer recording medium alone has a melt viscosity in the range of 5 to 2,000 cps at 110°C. 9. A novel thermal transfer recording medium according to any one of the claims, characterized in that the softening point temperature of the thermal transfer recording medium alone, measured by the ring and ball method, is in the range of 60°C to 130°C. 10. Ethylene-vinyl acetate copolymer resin with a vinyl acetate content of 28% by weight or less, polyethylene glycol diester with a weight average molecular weight in the range of 400 to 30,000, and ethylene-ethyl acrylate copolymer with a ethyl acrylate content of 35% by weight or less resin, aromatic tackifier resin, alicyclic tackifier resin, rosin ester tackifier resin, crystalline polyester resin, styrene-ethylene-butylene-styrene block copolymer resin consisting of an amorphous intermediate block body, The softening point of the resin selected from styrene-butadiene-styrene block copolymer resin and styrene-isoprene-styrene block copolymer resin was determined by ring and ball method.
Claim 1, characterized in that the heat-sensitive transfer recording medium contains at most 10% by weight of one or more heat-melting resin substances exhibiting a temperature of 30°C or less. New thermal transfer recording medium.