JPH06255272A - Thermal transfer material - Google Patents

Abstract

PURPOSE:To provide a thermal recording material having a high melt releasability and a good adhesion to a transfer surface and providing a sharp, glossy, and high-quality color printed result even on plain paper by forming a release layer, an ink layer containing a colorant and a binder resin, and an adhesive layer on a substrate. CONSTITUTION:In a thermal transfer material provided with an ink layer 3 for thermal transfer recording, a release layer 2 and the ink layer 3 containing a colorant and a binder resin are formed on one surface of a substrate sheet 1, and an adhesive layer 4 is formed on the ink layer 3. By making printing by a thermal head using this thermal transfer material, the ink layer 3 containing the colorant and a thermoplastic resin as the binder resin is transferred to a paper surface, and the ink layer 3 is easily liberated from the substrate sheet 1 by the thermally softening release layer 2. Sufficiently colored, glossy, and high-quality color printing is made on an exclusive image-receiving paper, plain paper, or other recording paper through the adhesive layer 4.

Description

Detailed Description of the Invention

[0001]

[Industrial application] In recent years, thermal transfer recording devices have been widely used as various output methods for computers, facsimiles, etc. because of their low noise, maintenance-free property, device simplicity, and size reduction. It is used.

[0002]

2. Description of the Related Art A heat-sensitive transfer recording paper used in a heat-sensitive transfer recording method is prepared by mixing a coloring material with a binder having a low melting point substance such as wax which softens or melts upon heating, on the surface of a substrate having good heat conductivity. It is a painted one,
Printing is performed on the recording medium by bringing the recording medium into contact with the transfer layer of the transfer recording paper and printing with a thermal head in an arbitrary pattern. When forming a multicolor image of two or more colors such as yellow, red, indigo, and black by the thermal transfer recording method, prepare thermal transfer recording paper of two or more of these colors, and transfer each color sequentially to the transfer material. The image is transferred and superposed on the surface of to form a multicolor image. The hot-melt coating method has hitherto been used for producing the heat-sensitive transfer paper of each of these colors. As the heat-sensitive transfer material, a paper such as condenser paper or paraffin paper having a thickness of 10 to 20 μm or a plastic film such as cellophane or polyester having a thickness of 3 to 20 μm is used as a base film, and a heat-melting property is provided on the upper surface thereof. Ink layer is applied. In a heat-sensitive transfer material having such a structure, if a large amount of a coloring material is mixed for the purpose of clearer printing, the adhesion of the heat-meltable ink to the paper to be printed becomes insufficient, and the print quality is rather poor. There is. This tendency is particularly remarkable when a paper having low surface smoothness is used as the material to be transferred. In addition, the gloss of the print is low, and it is not fully satisfactory in terms of beauty and beauty.

[0003]

The object of the present invention is to improve the drawbacks of the conventional heat-sensitive transfer material, to obtain a high melt peeling property, to have a good adhesiveness to the transfer surface, and to make it clear even on plain paper. Another object of the present invention is to provide a heat-sensitive recording material which gives high-quality colored printed matter having high gloss.

[0004]

The heat-sensitive transfer material of the present invention has a release layer, an ink layer containing a colorant and a binder resin, and an adhesive layer provided on one surface of a substrate.
Further, in the heat-sensitive transfer material of the present invention, the thickness of the peeling layer, the ink layer and the adhesive layer are respectively 1 to 50 μm and 0.05 to 20.
It is a heat-sensitive transfer material having a thickness of 0.1 μm and 0.1 to 10 μm. Further, it is a heat-sensitive transfer material in which the substrate is a plastic film and a heat-resistant protective layer for preventing stacking on the thermal head is provided on the surface opposite to the side provided with the ink layer.
The ink layer contains 20 to 80 parts by weight, 10 to 80 parts by weight and 3 to 20 parts by weight of the colorant, the binder resin and the softening agent, respectively.
The heat-sensitive transfer material according to claim 1, wherein the heat-sensitive transfer material is an ink layer having a thickness of 1 to 10 µm, which is compounded in a proportion of 35 parts by weight. The ink layer has a melting point of 40 to 170 ° C. and a viscosity of 10 to 10,000 c.
It is a thermal transfer material of P.

The ink used in the ink layer of the present invention comprises an olefin resin having a carboxyl group or an ester group containing a coloring agent such as a pigment or a dye, and a color resin solution prepared by dissolving a heat-meltable wax in an organic solvent. ,
Resin particles are precipitated and granulated by a difference in solubility due to a temperature difference, and melted by heat during thermal transfer. Coloring resin solution 20 to 80 parts by weight, 10 to 80 parts by weight and 3 to 3 parts by weight of the coloring agent, the binder resin and the softening agent are added to 100 parts by weight of the solid content in the coating liquid.
Any resin may be used as long as it is resin granulated in a proportion of 35 parts by weight. Preferably, solid content 1
The resin granulation is carried out by including the resin and the softening agent capable of resin granulation in a total amount of 30 parts by weight with respect to 00 parts by weight. Further, the ink layer of the heat-sensitive transfer material of the present invention is characterized in that it can contain a coloring agent up to 80% by weight.

In the heat-sensitive transfer material of the present invention, as shown in FIG. 1, a release layer 2 and an ink layer 3 are formed on a base sheet 1, and an adhesive layer 4 is formed on the ink layer. As the base sheet used in the present invention, many base sheets can be used as long as they have the strength not to be stretched or damaged during thermal transfer and are not deformed or partially melted by the heat of the recording thermal head. Include polyester, polypropylene, polystyrene, polycarbonate, polyimide and other plastic films,
Examples thereof include glassine paper, condenser paper, form paper, Indian paper and other papers, metal foil, and aluminum-paper composite sheet, metal vapor-deposited paper or metal vapor-deposited film which is a composite of the above materials.

When a plastic film is used as the substrate sheet, it is preferable to provide a heat-resistant protective layer on the side opposite to the ink surface, which is in contact with the thermal head, to prevent stacking on the thermal head. The heat resistant protective layer contains a heat resistant resin and a substance acting as a thermal release agent or a lubricant as basic constituent components.

The heat-resistant protective layer usable in the present invention is a thin film made of silicone resin, epoxy resin, melamine resin, phenol resin, fluororesin, polyimide resin, nitrocellulose or the like. The heat-resistant protective layer is formed by applying a varnish containing a resin as a main component to the base film and heating it, or by laminating these films on the base film. For example, as a silicone resin varnish, a softening agent such as a metal salt of an organic acid is mixed with a 50% by weight xylene solution of the silicone resin in a proportion of 1 to 30% by weight with respect to the silicone resin, and 120 to 2
It is heated at 20 ° C. to be softened.

In particular, in the present invention, the substance acting as a thermal release agent or lubricant used as the heat-resistant protective layer is
A heat-resistant protective composition having the following composition was prepared and applied to a polyethylene terephthalate film (S-PET Toyobo Co., Ltd.) having a thickness of 9 μm with Miyabar # 8, dried with warm air, and further heated in an oven at 60 ° C. for 20 hours. It was then cured. The dry coating amount was 0.9 g / m ² . (Heat-resistant protective layer composition) Polyvinyl butyral 4.5 parts by weight (S-REC BX-1 Sekisui Chemical Co., Ltd.) Toluene 45.0 parts by weight Methyl ethyl ketone 45.5 parts by weight Phosphate ester 0.45 parts by weight (Plysurf A- 208S Daiichi Kogyo Seiyaku Co., Ltd. 2.0 parts by weight of diisocyanate (Takenate D-110N Takeda Pharmaceutical Co., Ltd.) 75% ethyl acetate solution.

Further, as the binder resin used in the ink, an olefin resin is preferable, and an ethylene-vinyl acetate copolymer is particularly preferable. As the ethylene-vinyl acetate copolymer, Tosoh Corporation
Ultrasen series, for example 510X, 515F, 530,537,
537L, 537S, 525,520F, 540,540F, 541,541L, 625,630,630
F, 682,627,631,633,680,681,635,634,710,720,722,725,
Sumitomo Chemical Co., Ltd.'s Summit series, such as 751,750,760, DD-10, HA-20, HC-10, HE-10, KA-10, KA-20,
KA-31, KC-10, KE-10, MB-11, RB-11 etc. Evaflex series manufactured by Mitsui DuPont Polychemical Co., Ltd., eg 45
X, YW, 150,210,220,250,260,310,360,410,420,450,460,
550,560, etc., Soagoren series manufactured by Nippon Gohsei Co., Ltd., for example, BH, CH, CI, DH etc., Soarex series,
For example, RBH, RCH, RDH etc., Takeda Pharmaceutical Co., Ltd. Dumiran series, for example Dumiran D-219, D-229, D-251
S, C-2280, C-2270, C-1590, C-1570, C-1550 and the like can be mentioned. Further, Yucaron-Eva manufactured by Mitsubishi Petrochemical Co., Ltd., Elpax manufactured by DuPont, USA and the like can be used.

In addition, a product obtained by modifying a polyolefin resin to introduce a carboxyl group, an example of which is a product name,
Nippon Petrochemical Co., Ltd. N polymer, Tonen Petrochemical Co., Ltd.
Tonen CMP-HA series manufactured by Mitsubishi Petrochemical Co., Ltd. MOD
IC, Sumitomo Precision Chemical Co., Ltd. Saixen, Mitsui Toatsu Chemical Co., Ltd. Ronply, Mitsui Petrochemical Co., Ltd.
Examples of Admer manufactured by Dow Chemical Co., Ltd. and a copolymer of ethylene and acrylic acid include Dow E manufactured by Dow Chemical Company.
AA copolymer, Mitsubishi Yuka Co., Ltd. Yucaron EAA, Mitsui DuPont Polychemical Co., Ltd. Nucrel, Sumitomo Chemical Co., Ltd. Acryft, etc., and further copolymers of ethylene and acrylic acid or methacrylic acid, or those Cross-linked so-called ionomers, trade names such as Surlyn manufactured by DuPont in the United States, Himilan manufactured by Mitsui DuPont Polychemical Co., Ltd., Corbolen latex manufactured by Asahi Kasei Co., Ltd., EVA1 wax manufactured by BASF, and ethylene and vinyl acetate are used. Partially saponified product of the above copolymer, trade name: Dumilan manufactured by Takeda Pharmaceutical Co., Ltd., copolymer of ethylene and acrylic ester, trade name: Nippon Unicar Co., Ltd. DPD-6169. Etc., and a polyolefin resin containing a carboxylic carbonyl group. These resins may be used as a mixture of at least one or two.

Next, the solvent for the olefin resin is
A solvent that dissolves a resin when heated and does not dissolve at room temperature, or a solvent that dissolves at room temperature and insolubilizes by cooling, and that has temperature dependence in solubility, in particular, a solvent that disperses a colorant By using a hydrocarbon-based solvent used as, in the manufacturing process of the colorant, the solvent used to dissolve the precipitated particles and the resin is separated, or the solvent of the colorant and the solvent used to dissolve the resin It is not necessary to provide a process such as replacement.

Examples of liquid aliphatic hydrocarbons include n
-Paraffinic hydrocarbons, iso-paraffinic hydrocarbons, or mixtures thereof, halogenated aliphatic hydrocarbons and the like. Branched-chain aliphatic hydrocarbons are particularly preferable, and for example, Isopar G, Isopar H, Isopar K, Isopar L, Isopar M, Isopar V manufactured by Exxon Co. are preferably used. These have little solubility at room temperature in olefinic resins having a carboxyl group or an ester group,
For example, regarding the solubility of the resin in Isopar H, the solubility difference between 25 ° C. and 65 ° C. is 0.001 g / ml of solvent or less. When the olefinic resin having a carboxyl group or an ester group is dissolved using these liquid aliphatic hydrocarbons as a solvent, the temperature of the solvent needs to be 70 ° C. or higher, but in order to dissolve the resin. The heating conditions for
The minimum temperature required to dissolve the resin is sufficient, and heating more than necessary causes problems such as increasing the amount of volatilization from the solvent. Therefore, the temperature of the solvent is preferably 110 ° C. or lower. The amount of the resin dissolved in the total amount of the solvent and the resin may be arbitrary, but if the resin ratio is too high, the resin particles may come into contact with each other in the precipitation step of the resin particles, resulting in a gel-like mass. It is preferable to set it in the range of 80% by weight. Further, liquid aliphatic hydrocarbons are required to have a relatively low dissolving power for ink components, which prevents deterioration as a colorant.

Next, as the colorant, a known organic or inorganic colorant can be used. Examples of the black colorant include inorganic carbon black, ferric tetroxide, and organic cyanine black. Examples of the yellow colorant include inorganic yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, ocher and the like.
Further, as an acetoacetic acid anilide monoazo pigment of a poorly soluble metal salt (azo lake), Hansa Yellow G (CIN
o. pigment Yellow 1, hereafter, the same), Hansa Yellow 10G (pigment Yellow 3), Hansa Yellow RN
(Pigment Yellow 65), Hansa Brilliant Yellow 5GX (pigment Yellow 74), Hansa Brilliant Yellow 10GX (pigment Yellow 98), Permanent Yellow FGL (pigment Yellow 97), Shimura Lake Fast Yellow 6G (pigment Yellow 13)
3), Lionol Yellow K-2R (pigment Yellow
169), and as acetoacetic acid anilide disazo pigments, disazo yellow G (pigment Yellow 12), disazo yellow GR (pigment Yellow 13), disazo yellow 5G (pigment Yellow 14), disazo yellow 8G (pigment Yellow 17), disazo yellow R (pigment Yellow 55) and permanent yellow HR (pigment Yellow 83).

Examples of condensed azo pigments include chromophthal yellow 3G (pigment Yellow 93), chromophthal yellow 6G (pigment Yellow 94), and chromophthal yellow GR (pigment Yellow 95). Further, as the benzimidazolone monoazo pigment, Hosta Palm Yellow H3G (pigment Yellow 154),
Hosta Palm Yellow H4G (pigment Yellow 15
1), Hosta Palm Yellow H2G (pigment Yellow
120), Hosta Palm Yellow H6G (pigmentYell
ow 175), Hosta Palm Yellow HLR (pigment
Yellow 156). Further, as an isoindolinone-based pigment, Irgadine Yellow 3RLTN (p
igment Yellow 110), Irgadine Yellow 2RL
T, Irgadine Yellow 2GLT (pigment Yellow 1
09), Fastgen Super Yellow GROH (pig
ment Yellow 137), Fastgen Super Yellow GRO (pigment Yellow 110), Sandrin Yellow 6GL (pigment Yellow 173), and flantron (pigment Yel) which is a slene-based pigment.
low 24), anthramyrimidine (pigment Yellow 1
08), phthaloylamide type anthraquinone (pigment
Yellow 123), Heliofast Yellow E3R (p
igment Yellow 99), an azo nickel complex pigment (pigment Green 10) which is a metal complex pigment, a nitroso nickel complex pigment (pigment Yellow 153), an azomethine copper complex pigment (pigment Yellow 117), and a phthalimido quinophthalone pigment which is a quinophthalone pigment. (Pig
ment Yellow 138) and the like.

Examples of magenta colorants include inorganic cadmium red, red iron oxide, silver vermilion, red lead and antimony vermilion. As an azo lake type azo pigment, Brilliant Carmine 6B (pigment Red 57:
1), lake red (pigment Red53: 1), permanent red F5R (pigment Red48), resole red (pigment Red49), persia orange (pigme
nt Orange17), Kurosei Orange (pigment Orange
18), Helio Orange TD (pigment Orange1
9), pigment scarlet (pigment Red60:
1), Brilliant Scarlet G (pigment 64:
1), Helio Red RMT (pigment Red51), Bordeaux 10B (pigment Red63), Helio Bordeaux BL
(Pigment Red 54), and as the insoluble azo type (monoazo, disazo type, condensed azo type), Para Red (pigment Red 1), Lake Red 4R (pigme
nt Red3), Permanent Orange (pigment Orange)
5), Permanent Red FR2 (pigment Red2),
Permanent Red FRLL (pigment Red9), Permanent Red FGR (pigment Red112), Brilliant Carmine BS (pigment Red114), Permanent Carmine FB (pigment Red5), P.I. V. Carmine HR (pigment Red150), Permanent Carmine FBB (pigmentRed146), Nova Palm Red F3
RK-F5RK (pigment Red170), Nova Palm Red HFG (pigment Orange38), Nova Palm Red HF4B (pigment Red187), Nova Palm Orange HL. HL-70 (pigment Orange36), P.I.
V. Carmine HF4C (pigment Red185), Hostabum Brown HFR (pigment Brown25), Vulcan Orange (pigment Orange16), Pyrazolone Orange (pigment Orange13), Pyrazolone Red (pi
gment Red38), and as a condensed azo pigment, Chromophtal orange 4R (pigment Orange3)
1), Chromophtal Scarlet R (pigment Red1
66), chromophthal red BR (pigment Red14
4) is mentioned.

Further, pyranthrone orange (pigment Orange) is used as an anthraquinone pigment which is a condensed polycyclic pigment.
40), Antoanthrone Orange (pigment Orange
168), dianthraquinonyl red (pigment Red1
77), thioindigo magenta (pigment Violet38), thioindigo violet (pigment Violet36), thioindigo red (pigment Red88), and perinone orange (pigment Orange43). In addition, as perylene pigments, perylene red (pigment Red190), perylene vermillion (pig
ment Red123), Perylene Maroon (pigment Red1)
79), perilence scarlet (pigment Red14
9) and perylene red (pigment Red 178), and as a quinacridone-based pigment, quinacridone red (p
igment Violet19), quinacridone magenta (pigme
nt Red122), quinacridone maroon (pigment Red
206), quinacridone scarlet (pigment Red2
07), and other condensed polycyclic pigments include pyrocholine pigments, red fluorbin pigments, and dyed lake pigments (water-soluble dye + precipitating agent → lake fixing).

As the cyan colorant, an inorganic ultramarine blue,
Navy blue, cobalt blue, cerulean blue, etc. are mentioned, and as the phthalocyanine type, Fast Gemble-BB (pigment Blue 15), Sumiton cyanine.
Blue HB (pigment Blue 15), cyanine blue 5
020 (pigment Blue 15: 1), Sumika print
Cyanine Blue GN-O (pigment Blue 15), Fast Sky Blue A-612 (pigment Blue 1
7), cyanine green GB (pigment Green7),
Cyanine Green S537-2Y (pigment green3
6), Sumiton Fast Violet RL (pigment
Violet 23), and indanthrone blue (PB-60P, PB-22, P) which is a slene-based pigment.
B-21, PB-64), a basic dye lake pigment, methyl violet / phosphorus / molybdic acid lake (PV
-3) and the like. In addition, a colorant called a so-called processed pigment in which the surface of the colorant is coated with a resin can be similarly used. Further, in consideration of the storage stability of the heat-sensitive transfer material, the transparency of the obtained image, and the color mixing property, among the above-mentioned colorants, the black type is a color.
It is preferable to use a mixture of benzidine yellow and Hansa yellow as the bonblack and yellow type, brilliant carmine 6B for the magenta type, and phthalocyanine blue for the cyan type.

The colorant has a particle size of 30 to 15 in the secondary aggregation state.
It is advisable to use a powder of 0 μm, and the amount used is 0.0001 to 2000% by weight based on the weight of the resin.
However, in order to reproduce the multi-tone continuous gradation equivalent to that of offset printing, it is necessary that the optical reflection density after transfer of each color ink to the transfer target be 0.7 or more. And 1.0 especially for cyan and black
It is desirable to have more than one. In order to make the optical reflection density of 0.7 or more for each color, in the case of black and cyan, it is 10 to 150% by weight based on the same weight as above, in the case of magenta 40 to 150% by weight, and in the case of yellow 10 to 10.
It is advisable to set it to 100% by weight. If any of the colors exceeds the above range, the background stain is likely to occur after development.

A charge control agent can be added when the ink is granulated. As a charge control agent, a metal salt of dialkyl sulfosuccinate, manganese naphthenate, calcium naphthenate, zirconium naphthenate, cobalt naphthenate, iron naphthenate, lead naphthenate, nickel naphthenate, chromium naphthenate, zinc naphthenate, magnesium naphthenate, Manganese octylate, calcium octylate, zirconium octylate, iron octylate, lead octylate, cobalt octylate, chromium octylate, zinc octylate, magnesium octylate, manganese dodecylate, calcium dodecylate, zirconium dodecylate,
Metal soaps such as iron dodecylate, lead dodecylate, cobalt dodecylate, nickel dodecylate, chromium dodecylate, zinc dodecylate, magnesium dodecylate, calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, barium dodecylbenzenesulfonate, etc. Alkylbenzene sulfonates, phospholipids such as lecithin and cehaline, organic amines such as n-decylamine and the like can be preferably added. In particular, it is desirable to use a transition metal salt of dialkylsulfosuccinic acid (cobalt, manganese, zirconium, yttrium, nickel, etc.).
The addition amount may be the minimum amount showing the charge adjusting effect, but it is generally preferable to be 0.01 to 50% by weight in the electrically insulating liquid.

The charge control agent is a resin solution, a colorant dispersion,
It may be added at any stage of the mixed solution thereof, the granulation step, and the final ink dispersion, but it is preferably added to the resin solution. This has the advantage that the charge control agent that can be used is not limited by the electrically insulating liquid. That is, since the charge control agent remarkably lowers the electric resistance of the electrically insulating liquid, it is desirable that the amount of the charge control agent present in the electrically insulating liquid is as small as possible. It is desirable that the charge control agent concentration in the insulating liquid is high, and the two conditions are in conflict. However, it is possible to keep the amount of the charge control agent in the electrically insulating liquid at a sufficiently low value by adding the charge control agent to the resin solution and sufficiently adsorbing it to the ink particles.

The ink particles contain a wax together with an olefin resin, and many conventionally known waxes can be used. Examples of the waxes include carnauba wax, montan wax, beeswax, rice wax, candeli wax, lanolin wax, paraffin wax, microlisterin, polyethylene wax, sazol wax, oxidation wax, amide wax, silicone wax and the like. . Among them, specific examples of waxes particularly suitable for the present invention include WAX E, WAX F, and WAX as ester waxes.
KPS and WAS BJ are mentioned, and as a partially saponified ester wax, WAX OP, WAX OM, WA
Examples include XV and WAX FL3 (both manufactured by Hoechst).

As the additives, various surface active agents, higher fatty acids (stearic acid, pamitic acid, lauric acid, etc.), long chain alcohols (stearyl alcohol, etc.), metal salts of long chain fatty acids (calcium stearate,
Zinc palmitate, etc.), antioxidants, various plasticizers, surface modifiers such as silane coupling agents and lubricants, silicone oil, anti-slip powder, metal fine particles and powders for adjusting thermal conductivity. The body etc. are mentioned. A release layer is preferably formed between the substrate and the thermal transfer layer. The release layer is used in combination with waxes, thermoplastic resins, additives and the like used in the thermal transfer layer. It may be a layer which itself can undergo cohesive failure by melting or softening at the time of heating, or a resin which is relatively unlikely to show an adhesive force in combination with another resin, for example, a silicone resin, a perfluoro resin, Fluorine-containing acrylic resins and other fluorine-based resins, polysiloxane resins, acetal resins (polyvinyl butyral, polyvinyl acetal, polyvinyl formal, etc.), ethylene-based resins (ethylene vinyl resins, ethylene acrylate-based resins, ethylene acrylic acid-based ionomer resins) It can be composed of layers. However, in the case of the latter layer structure made of a resin that does not easily exhibit adhesive strength, the material of the release layer greatly changes depending on the composition of the layer adjacent thereto, and the above-mentioned one is one example. The release layer is preferably heat-softening.

Alternatively, a heat softening layer may be separately provided between the support and the release layer. The release layer or the heat-softening layer having the heat-softening property is made of a thermoplastic resin and has the property of softening at the temperature at the time of heat transfer. The thermoplastic resin preferably has a softening point of -30 to 150 ° C.
The softening point temperature shown here is a value shown by the VICAT softening point or the ring and ball method. Specifically, polyolefins such as polyethylene and polypropylene, ethylene and vinyl acetate, ethylene and acrylic acid ester, ethylene and acrylic acid copolymers such as acrylic acid, polyvinyl chloride, vinyl chloride and vinyl chloride copolymers such as vinyl acetate. , Polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymers such as acrylic ester vinyl and maleic anhydride, acrylic ester copolymers such as acrylic ester and vinyl, polymethacrylic acid ester, methyl methacrylate and acetic acid Methacrylic acid ester copolymers such as vinyl, methyl methacrylate and acrylic acid, polyvinyl acetate, vinyl acetate copolymer, vinyl butyral resin, nylon, copolymerized nylon, polyamides such as N-alkoxymethylated nylon. Butter, synthetic rubber, chlorinated rubber, polyethylene glycol, polyvinyl alcohol hydrogel Gin phthalate, cellulose derivatives,
Examples thereof include cellulose acetate phthalate, cellulose acetate succinate, shellac and wax. The thickness of the heat-softening layer is appropriately in the range of 1 to 50 μm, preferably 5 to 30 μm.

Furthermore, it is preferable that an adhesive layer is formed on the side opposite to the substrate as viewed from the thermal transfer layer, that is, on the thermal transfer layer. The adhesive layer is used in combination with the waxes, thermoplastic resins and additives used in the release layer. The resin may be a resin that easily cohesively destroys itself by being melted or softened during heating to easily exhibit an adhesive force between the ink layer and a dedicated image-receiving paper or recording paper such as plain paper. As the wax used for the purpose of cohesive failure and increasing compatibility with recording paper, any wax conventionally used for this purpose can be used, for example, montan wax, beeswax, rice wax, and candeli. Waxes such as wax, lanolin wax, paraffin wax, microcrystalline wax, polyethylene wax, sazol wax, oxidative wax, amide wax and silicone wax can be mentioned.

Among them, as a concrete example of the wax particularly suitable for the present invention, an ester wax WAX is particularly preferable.
E, WAX KPS and WAX BJ,
WAX OP, W as partially saponified ester wax
Examples include AX OM and WAX VWAX GL3 (both manufactured by Hoechst). Furthermore, carnauba wax,
Hoechst wax-V, Hoechst wax 2106 (both manufactured by Hoechst), EVA 1 WAX BASF
(Polyethylene wax containing ethylene-vinyl acetate copolymer as the main component), Diacarna 30L, 30K
(Made by Mitsubishi Kasei), high wax 220P, 660P, 1
105A (manufactured by Mitsui Petrochemical) and the like.

Examples of the latter resin for increasing the adhesive force include vinyl resins such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymer, polyolefin resins such as polyethylene and polypropylene, polyvinyl alcohol, polycarbonate and polyamide resins. , Polyamideimide, polyester resin, polysulfone resin, polyimide resin,
Examples thereof include cellulosic resins such as nitrocellulose, cellulose diacetate, and cellulose triacetate, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyphenylene oxide, and copolymers thereof. The thickness of the adhesive layer is appropriately in the range of 1 to 40 μm, preferably 3 to 2
It is in the range of 5 μm. As the transferred material used for recording using the multicolor heat-sensitive transfer recording paper of the present invention, a plastic film, paper, metal, wood, glass, fiber or the like can be used.

[0028]

With the heat-sensitive transfer material of the present invention, the layer of the thermoplastic resin containing the colorant is transferred to the paper surface by printing using a thermal head, and sufficiently colored and glossy printing can be performed. The wax layer containing no colorant has high adhesion to the paper surface and can give high quality printing even to paper having low surface smoothness. Further, since the thermoplastic resin layer containing the colorant is made of ink particles composed of a pigment-coated heat-sensitive melting material, the content of the pigment with respect to the solid content is much higher than that of the conventional melt-type ink. Therefore, high density printing is possible.

[0029]

EXAMPLES Examples will be shown below. Example 1 (Ink manufacturing method) EVA in a 200 ml round bottom flask
(Ethylene-vinyl acetate copolymer, Mitsui DuPont Polychemical Co., Ltd., Evaflex 250) 1.0
g, EVA1 Wax BASF (polyethylene wax containing ethylene-vinyl acetate copolymer as a main component, manufactured by BASF) 1.0 g, Hoechst WAX
V (Hoechst) 1.0 g, charge control agent BBP (barium petronate, manufactured by Witco Chemical) 250 mg
And tetrahydrofuran (80 mg) were mixed and heated and stirred at 80 ° C. for 1 hour to prepare a resin solution.

On the other hand, in another container, 3.0 g of SUMIKA GNO-PP (metal phthalocyanine pigment, manufactured by Sumitomo Chemical Co., Ltd.),
108 mg of poly-12-hydroxystearic acid ester trimer (manufactured by Ito Oil Co., Ltd.) was dispersed in 100 mg of tetrahydrofuran using an ultrasonic homogenizer (Nippon Seiki Seisakusho, Ltd., US-300T). This was put into a flask in which the resin had been previously dissolved at once, and further stirred and mixed at 90 ° C. for 1 hour to obtain a colorant-containing resin solution.
Isopar G (manufactured by Exxon) cooled to -5 ° C after lowering the colorant-containing resin solution to about 60 ° C at room temperature.
The mixture was dispersed and mixed in 100 ml using an ultrasonic homogenizer. This colorant-containing resin solution is a rotary evaporator (Tokyo Science Machinery Co., Ltd., EYELA NE-
(1T type) was used to replace the solvent with Isopar G. Furthermore, the same Isopar G was used to adjust the concentration of the ink liquid to a printing concentration of 1%. The particle size distribution was measured with Microtrac Mark IISRA type (Nikkiso Co., Ltd.). As a result of measuring the particle size distribution of the resin particle size, the resin particle is 0.17 to
It was uniformly distributed at 1.01 μm and d ₅₀ = 0.44 μm. The particle size distribution is shown in FIG.

Example 2 (Preparation of heat-sensitive transfer material) The peeling layer was a 6 μm thick easily-adhesive PET (Diafoil Mitsubishi resin, 6FK302E).
A 10% by weight solution of carnauba wax (manufactured by Hoechst) using a mixed solvent of acetone: toluene = 1: 1 as a solvent was coated on the above with a miya bar to form a single layer. The release layer had a thickness of 2.2 g / m ² . For the ink layer, a solid image was created by coating the release layer with a single layer of ink liquid. The coating amount of the ink layer was 4.1 g / m ² . The adhesive layer was produced by coating the ink layer with a single layer of a 10% by weight solution of carnauba wax in the same mixed solvent as the solvent. Application amount of adhesive layer is 3.4g
/ M ² .

130 ° C. by a heat transfer ironing device (Harillon Presser HP-1000WE, manufactured by Hashima Co., Ltd.)
It was heated for 2 minutes to melt-transfer to plain paper. Almost all ink layers were transferred. The gloss of the image surface was excellent. A thermal transfer printer (manufactured by NEC Corporation, PC-
A print test was conducted using a PR201TH color thermal transfer printer. Very high print density (OD value 1.03), no background stain, high melt peeling property, good adhesion to transfer surface, clear and glossy plain paper, high quality colored print I gave you something.

Example 3 The coating amount was 2.0 g / m ² as in Example 2 except that E-Flakes (manufactured by Hoechst) was used in place of the carnauba wax of the release layer in Example 1. A release layer was prepared, and an ink layer having a coating amount of 3.9 g / m ² was prepared on the release layer. The amount of adhesive layer applied is 3.5 g /
It was m ² . When a printing test was conducted in the same manner as in Example 2, almost all solid images were transferred. The gloss of the image surface was excellent. In a printing test with a thermal transfer printer, the printing density was also very high, the OD value was 1.00, there was no background stain, the melt peelability was high, and the adhesion to the transfer surface was good, and it was clear even on plain paper. To give a glossy, high quality colored print.

Example 4 The coating amount was 2.3 g / m ² as in Example 2 except that OP-Flakes (manufactured by Hoechst) was used in place of the carnauba wax of the release layer in Example 1. A release layer was produced, and an ink layer having a coating amount of 4.5 g / m ² was produced on the release layer. The amount of adhesive layer applied is 3.1 g.
/ M ² . When a printing test was conducted in the same manner as in Example 2, almost all solid images were transferred. The gloss of the image surface was excellent. In the print test with a thermal transfer printer, the print density was very high, and the OD value was 0.98.
A high-quality colored print having no background stain, high melt-peelability, good adhesion to a transfer surface, and clear and glossy even on plain paper was provided.

Example 5 A silicone-containing polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) was used in place of the carnauba wax of the release layer in Example 2, except that
A release layer having a coating amount of 1.8 g / m ² was prepared in the same manner as in Example 2, and an ink layer having a coating amount of 4.3 g / m ² was formed on the release layer. The amount of the adhesive layer applied was 3.4 g / m ² . When a printing test was conducted in the same manner as in Example 2, almost all solid images were transferred. The gloss of the image surface was excellent. In a printing test using a thermal transfer printer, the print density was also very high, the OD value was 0.96, there was no background stain, the melt peelability was high, and the adhesion to the transfer surface was good, making it clear even on plain paper. A high-quality colored printed matter having a gloss was obtained.

Example 6 Hoechs, the wax used in Example 1
Except for 1.0 g of t WAX V (manufactured by Hoechst), Hoechst WAX E FLAKES instead of this
An ink solution was prepared using 1.0 g (manufactured by Hoechst). The printing and other evaluations were the same as in Example 1. As a result of measuring the particle size distribution of the resin particles, the resin particles are 0.17-
It had a distribution of 1.01 μm and d ₅₀ = 0.40 μm. The particle size distribution is shown in FIG.

The peeling layer was made of carnauba wax (manufactured by Hoechst Co.) having a mixture solvent of ketone: toluene = 1: 1 on 6 μm thick easy-adhesion PET (6FK302E, manufactured by Mitsubishi Diafoil) as a solvent. It was prepared by coating the solution with a single layer using a Miya bar. The coating amount of the release layer was 2.4 g / m ² . For the ink layer, a solid image was prepared by coating the release layer with the coating liquid as a single layer. The coating amount of the ink layer was 4.3 g / m ² . The adhesive layer was prepared by coating the ink layer with a 10% by weight solution of carnauba wax (solvent is the above mixed solvent).
The coating amount of the adhesive layer was 3.3 g / m ² . A printing test was conducted in the same manner as in Example 2. In melt transfer to plain paper, almost all solid images were transferred, and the gloss of the image surface was excellent. In a printing test using a thermal transfer printer, the printing density is very high, the OD value is 0.98, there is no background stain, the melt peeling property is high, and the adhesion to the transfer surface is good. Also gave clear, glossy and high quality colored prints.

Comparative Example 1 A thermal transfer material was prepared in the same manner as in Example 2 except that it had no adhesive layer. The coating amount of the release layer was 2.0 g / m ² , and the ink layer was a single layer coated with the ink liquid, and the coating amount was 4.5 g / m ² . A printing test was conducted in the same manner as in Example 2. In melt transfer to plain paper, almost all solid images were transferred, and the gloss of the image surface was excellent. In a print test using a thermal transfer printer, the print density is high, the OD value is 0.80, and scumming occurs.
The adhesion to the transfer surface was good, but the gloss was slightly poor.

Comparative Example 2 A thermal transfer material was prepared in the same manner as in Example 3 except that it had no adhesive layer. The coating amount of the release layer was 2.5 g / m ² , and the ink layer was a single layer coating of the ink liquid on the release layer, and the coating amount was 4.0 g / m ² . A printing test was conducted in the same manner as in Example 2. In melt transfer to plain paper, almost all solid images were transferred, and the gloss of the image surface was excellent. In a print test using a thermal transfer printer, the print density is high, the OD value is 0.78, and scumming occurs.
The adhesion to the transfer surface was good, but the gloss was slightly poor.

Comparative Example 3 A thermal transfer material was prepared in the same manner as in Example 4 except that it had no adhesive layer. The coating amount of the release layer was 2.2 g / m ² , and the ink layer was a single layer coated with the ink liquid, and the coating amount was 4.2 g / m ² . A printing test was conducted in the same manner as in Example 2. In melt transfer to plain paper, almost all solid images were transferred, and the gloss of the image surface was excellent. In a print test using a thermal transfer printer, the print density is high, the OD value is 0.78, and scumming occurs.
The adhesion to the transfer surface was good, but the gloss was slightly poor.

Comparative Example 4 A thermal transfer material was prepared in the same manner as in Example 5 except that it had no adhesive layer. The silicone-containing polyester resin used for the release layer is a polyester resin (Vylon 20) using a mixed solvent of acetone: toluene = 1: 1 as a solvent.
Silicone (X-62-1212, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a 30% by weight solution of 0, manufactured by Toyobo Co., Ltd., in an amount of 10% by weight based on the polyester resin, and an appropriate amount of platinum catalyst was added. I adjusted it by doing. The coating amount of the release layer is
The ink layer was 2.4 g / m ² , and the release layer had a single layer of the ink liquid coated thereon, and the coating amount was 4.0 g / m ² . A printing test was conducted in the same manner as in Example 2. In melt transfer to plain paper, almost all solid images were transferred, and the gloss of the image surface was excellent. In a printing test using a thermal transfer printer, the printing density was not so high, the OD value was 0.64, and the gloss was poor.

Comparative Example 5 A thermal transfer material was prepared in the same manner as in Example 2 except that it had no peeling layer. The base sheet was coated with a single layer of the ink layer, and the coating amount was 4.5 g / m ² . The adhesive layer is
It was formed on the ink layer in the same manner as in Example 2. The coating amount of the adhesive layer was 3.6 g / m ² . A printing test was conducted in the same manner as in Example 2. In melt transfer to plain paper, almost all solid images were transferred, and the gloss of the image surface was excellent. Further, in a printing test using a thermal transfer printer, the printing density was high, the OD value was 0.76, scumming occurred, and the adhesion to the transfer surface was good, but the gloss was slightly poor.

Comparative Example 6 A thermal transfer material was prepared in the same manner as in Example 2 except that the adhesive layer and the peeling layer were not provided. The ink layer was formed by coating the release layer with a single layer of the coating liquid.
The coating amount of the ink layer was 4.5 g / m ² . Example 2
A printing test was conducted in the same manner as in. In melt transfer to plain paper,
The transfer efficiency was not favorable and the gloss of the image surface was lacking. In a printing test using a thermal transfer printer, the printing density was low and the OD value was 0.40.

Comparative Example 7 A transfer ink composition of each of the following colors was added to PET having a heat-resistant protective layer having a thickness of 9 μm in an amount of 2.5 g / m ^{2 on} a dry basis.
A comparative heat-sensitive transfer paper of the present invention was obtained by dividing each color by a two-color gravure printing machine, applying and drying.

Hoechst WAX-V 30 parts by weight Coloring material 3 parts by weight Toluene 67 parts by weight Coloring material Yellow ink CI21090 Red ink CI15850 Blue ink CI17460 Black ink Carbon black pigment Heat transfer ironing device (trade name: Hariron Presser H
P-1000WE, manufactured by Hashima Co., Ltd., was heated at 130 ° C. for 2 minutes to perform melt transfer on plain paper. Almost all solid images were transferred. A printing test was conducted using a thermal transfer printer (PC-PR201TH Japanese color thermal transfer printer manufactured by NEC Corporation) with the easy-adhesion PET film provided with the solid image as a ribbon. The print density is high (OD value is 1.01), but scumming occurs. The gloss of the print was also low, and it was not completely satisfactory in terms of beauty and beauty.

[0046]

The image obtained by the heat-sensitive transfer recording material of the present invention is clear and has a high resolution. It has a high melt peeling property and a good adhesion to the transfer surface and is clear even on plain paper. It can give high-quality colored prints with a gloss, and can be used in any shape such as a typewriter ribbon or a wide tape such as a line printer. Therefore, it can be used in a color printer using a thermal printer, a color facsimile, a color video printer, a color copying machine, and the like.
Furthermore, the heat-sensitive transfer material of the present invention has a much higher pigment content relative to the solid content than the conventional melt-type ink, and also has a peeling layer that weakens the adhesive strength with the substrate and the adhesive strength with the transfer paper. By providing an adhesive layer for strengthening, high density printing is possible.

[Brief description of drawings]

FIG. 1 is a diagram illustrating a layer structure of a heat-sensitive transfer material of the present invention.

FIG. 2 is a diagram illustrating a particle size distribution of ink particles of the present invention.

FIG. 3 is a diagram illustrating a particle size distribution of another example of the ink particles of the present invention.

[Explanation of symbols]

1 ... Substrate sheet, 2 ... Release layer, 3 ... Ink layer, 4 ... Adhesive layer

Claims (6)

[Claims] 1. A thermal transfer material having an ink layer for thermal transfer recording, wherein a release layer, an ink layer containing a colorant and a binder resin, and an adhesive layer are formed on one surface of a substrate. Thermal transfer material. 2. The peeling layer, the ink layer, and the adhesive layer have a thickness of 1 to 50 μm, 0.05 to 20 μm, and 0.1 to 1, respectively.
The thermal transfer material according to claim 1, wherein the thermal transfer material has a thickness of 0 μm. 3. The substrate is a plastic film,
The heat-sensitive transfer material according to claim 1, wherein a heat-resistant protective layer for preventing stacking on the thermal head is provided on the surface opposite to the side provided with the ink layer. 4. A coloring agent, a binder resin and a softening agent for forming an ink layer are respectively 20 to 80 parts by weight and 10 to 10 parts by weight, respectively.
2. The heat-sensitive transfer material according to claim 1, which is an ink layer having a thickness of 1 to 10 [mu] m, which is formed by mixing 90 parts by weight and 3 to 35 parts by weight. 5. The heat-sensitive transfer material according to claim 1, wherein the ink layer has a melting point of 40 to 170 ° C. and a viscosity of 10 to 10,000 cP. 6. The ink used in the ink layer comprises a color resin solution prepared by dissolving an olefin resin having a carboxyl group or an ester group containing a colorant such as a pigment or a dye and a heat-meltable wax in an organic solvent, The heat-sensitive transfer material according to claim 1, wherein resin particles are precipitated and granulated by a difference in solubility due to a temperature difference.