JPH06255267A - Thermal melt transfer material and its production - Google Patents

Abstract

PURPOSE:To provide a thermal melt transfer 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 incorporating a specific poly-12-hydroxycarboxylate, a specific charge regulator, and a thermally meltable wax. CONSTITUTION:A thermal melt transfer material is composed of an olefin thermoplastic resin having carboxyl group or ester group used for producing a thermal transfer recording medium, an olefin resin having carboxyl group or ester group with a colorant loaded, and liquid aliphatic hydrocarbon for the most part in the presense of poly-12-hydroxycarboxylate prepared by trimerizing to decamerizing hydroxycarboxylate as a monomer, a charge regulator having a compatibility with the liquid aliphatic hydrocarbon, and a thermally meltable wax.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive melt transfer material used for heat-sensitive transfer and a method for producing the same.

[0002]

2. Description of the Related Art A heat-sensitive transfer recording method is used in a variety of computers, facsimiles, etc. because of its low noise, easy maintenance, and simple apparatus and small size and light weight as compared with other recording methods. Is widely used as an output device of the. The heat-sensitive transfer recording medium has at least one heat-transferable coloring material layer on the surface of a substrate having good heat conductivity. The coloring material layer is a wax or other low-melting substance that softens or melts when heated. Etc. and a coloring material such as carbon black are coated, and a desired pattern is heated by the thermal head in a state where the recording medium and the thermal transfer recording medium are in close contact with each other. Is a method of printing from a thermal transfer recording medium onto a recording medium.

In addition to the method of forming an image while forming a desired pattern with a thermal head, the heat-sensitive transfer method involves developing an electrostatic latent image formed on a substrate with a heat-melt transfer material containing a coloring material. There is also a method of printing by forming an image of a coloring material on a substrate and then thermally transferring it to a recording medium such as recording paper by heating.

Further, in the recording method by thermal transfer, printing is not limited to one black color, but multicolor recording is also performed.
When forming a multicolor screen consisting of two or more colors such as yellow, red, indigo, and black, prepare a heat-sensitive transfer material of two or more colors and sequentially apply each color to the same surface of the same transfer material. And transferred to form a multicolor image.

Using such a thermal transfer recording medium,
When a large amount of a coloring material is mixed for the purpose of clear printing, there is a problem that the adhesion of the coloring material layer to the paper to be printed becomes insufficient and the printing quality is rather deteriorated. This tendency is remarkable especially when a paper having a low surface smoothness is used. Also,
The gloss of the print is low, and it is not satisfactory in terms of beauty and beauty.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high melt-peeling property when heating with a thermal head or when an image formed by developing an electrostatic latent image is thermally transferred, and to a transfer surface. It is an object of the present invention to provide a heat-sensitive recording material which gives a high-quality colored printed matter having good adhesion and being clear and glossy even on plain paper.

[0007]

The present invention relates to a heat-sensitive transfer material containing a colorant which is transferred onto a recording medium by heating, wherein an olefinic thermoplastic resin having a carboxyl group or an ester group, or a colorant is used. A heat-sensitive melt transfer material comprising an added olefinic resin having a carboxyl group or an ester group and most of liquid aliphatic hydrocarbons, wherein a poly (12-hydroxycarboxylic acid) of 3 to 10 mer containing a hydroxycarboxylic acid ester as a monomer is used. A heat-sensitive melt transfer material in which a charge control agent having compatibility with an acid ester and a liquid aliphatic hydrocarbon and a heat-meltable wax are present.

Further, it has a thermoplastic resin which is developable with respect to the formed electrostatic latent image and does not impair the charging property, and has a glass transition temperature of -30 ° C. to 150 ° C. A heat-sensitive melt transfer material comprising a wax having a molecular weight of 000. Further, it is a heat-sensitive melt transfer material in which the ratio of the pigment to the total solid content is 20 to 75% by weight.

Further, an olefinic thermoplastic resin having a carboxyl group or an ester group, or an olefinic resin having a carboxyl group or an ester group added with a colorant is heated and dissolved in a solvent having a large temperature dependence of solubility. After forming the resin solution, the resin solution is used as a monomer of hydroxycarboxylic acid ester as a monomer
The resin particles are precipitated by pouring them into a liquid aliphatic hydrocarbon cooled in the presence of a 12-hydroxycarboxylic acid ester, a charge control agent and a heat-meltable wax, and a solvent in which the resin is dissolved is added to the aliphatic hydrocarbon. Is a method for manufacturing a heat-sensitive melt transfer material.

The heat-sensitive melt transfer material of the present invention will be described in detail below. As the olefin resin, an ethylene-vinyl acetate copolymer is preferable. As the ethylene-vinyl acetate copolymer, Tosoh Corporation Ultrasen series, for example 510X, 515F, 53
0,537,537L, 537S, 525,520F, 540,540F, 541,541L, 625,63
0,630F, 682,627,631,633,680,681,635,634,710,720,72
Sumitomo Chemical Co., Ltd.'s Sumitate series such as 2,725,751,750,760 etc., eg 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 Chemicals Co., Ltd., for example
45X, YW, 150,210,220,250,260,310,360,410,420,450,46
0,550,560 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.

As waxes, carnauba wax,
Montan wax, beeswax, rice wax, candy wax, lanolin wax, paraffin wax,
Microlistalin, polyethylene wax, sazol wax, oxide wax, amide wax, silicone wax and the like 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 F, WAX KPS and WAS BJ, and WAXO as a partially saponified ester wax.
P, WAX OM, WAX VWAX FL3 (all manufactured by Hoechst) can be mentioned.

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 type monoazo pigment of a poorly soluble metal salt (azo lake), Hansa Yellow G (CINo. Pigment)
Yellow 1, hereafter, the same), Hansa Yellow 10G (p
igment Yellow 3), Hansa Yellow RN (pigment Y
ellow 65), Hansa Brilliant Yellow 5GX (p
igment Yellow 74), Hansa Brilliant Yellow 1
0GX (pigment Yellow 98), Permanent Yellow FGL (pigment Yellow 97), Shimura Lake Fast Yellow 6G (pigment Yellow 133), Rionol Yellow K-2R (pigment Yellow 169), and as acetoacetic anilide disazo pigment, disazo yellow. G (pigment Yellow 12), disazo yellow GR (pigment Yellow 13), disazo yellow 5
G (pigment Yellow 14), Disazo Yellow 8G
(Pigment Yellow 17), Disazo Yellow R (pig
ment Yellow 55), Permanent Yellow HR (pig
ment 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 Red 63), 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 (pigment Red).
3), permanent orange (pigment Orange5),
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 F3RK-
F5RK (pigment Red170), Nova Palm Red H
FG (pigment Orange38), Nova Palm Red HF
4B (pigment Red187), Nova Palm Orange H
L. 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 (pigment R
ed38), and further examples of condensed azo pigments include Chromophtal Orange 4R (pigment Orange31), Chromophtal Scarlet R (pigment Red 166), and Chromophtal Red BR (pigment Red 144).

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.

Considering the storage stability of the heat-sensitive melt transfer material or the transparency and color mixture of the obtained image, among the above colorants, black is carbon black and yellow is benzidine yellow. Hansa Yellow mixture, brilliant carmine 6 for magenta
For B and cyan, it is preferable to use phthalocyanine blue.

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 a continuous multi-tone gradation similar to that of offset printing, the optical reflection density after the melt transfer of the heat-sensitive melt transfer material of each color to the transfer target is 0.
It is necessary to be 7 or more, and particularly preferably 1.0 or more for cyan and black. In order to obtain an optical reflection density of 0.7 or more for each color, in the case of black and cyan, the weight is the same as the above, and is 10 to 150.
% By weight, preferably 40 to 150% by weight for magenta and 10 to 100% by weight for yellow. If any of the colors exceeds the above range, the background stain is likely to occur after development.

Further, 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, dodecyl Zirconium acid,
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 in the mixed solution thereof, the granulating step, and the final heat-sensitive transfer material, 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, but to ensure that the charge control agent is adsorbed to the heat-sensitive melt transfer material particles. In addition, it is desirable that the charge control agent concentration in the electrically insulating liquid is high, and the two conditions are in conflict. However, it is possible to maintain 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 the charge control agent particles to the particles. Become.

Next, the polyhydroxycarboxylic acid ester will be described. The polyhydroxycarboxylic acid ester has a granulation adjusting function because the resin particles obtained when added to the granulation step have a uniform particle size distribution, and further has resin particles in the heat-sensitive melt transfer material. It has been found that it also has a function as a dispersant because it has an affinity with.

The hydroxycarboxylic acid ester which is a raw material for polymerization is a derivative such as an ester of the formula HO-X-COOH, wherein X is a divalent saturated or unsaturated aliphatic hydrocarbon containing at least 12 carbon atoms. , Or a divalent aromatic hydrocarbon containing at least 6 carbon atoms and there are at least 4 carbon atoms between the hydroxy and carboxyl groups. Preferable examples of such hydroxycarboxylic acid derivatives include hydroxycarboxylic acid alkyl esters such as 12-hydroxystearic acid methyl ester and 12-hydroxystearic acid ethyl ester, 12-hydroxycarboxylic acid lithium, 12
Examples include metal salts of hydroxycarboxylic acids such as aluminum hydroxycarboxylate, amides of hydroxycarboxylic acid, and hydrogenated castor oil.

The polyhydroxycarboxylic acid ester is obtained by polymerizing the hydroxycarboxylic acid ester by partially saponifying it in the presence of a small amount of amines or a catalyst, and its polymerization form is intermolecular esterification. It also contains various forms such as those obtained by esterification in the molecule. The polyhydroxycarboxylic acid ester in the present invention is preferably a hydroxycarboxylic acid ester 3- to 10-mer, and is a light gray brown wax-like substance. If the degree of polymerization of the polyhydroxycarboxylic acid ester is less than 3 or greater than 10, the polyhydroxycarboxylic acid ester is not compatible with the liquid aliphatic hydrocarbon and the particle size distribution of the resin particles is expected even when used in the granulation process. I can't get one. The addition amount of the polyhydroxycarboxylic acid ester is not particularly limited, but is 0.01 to 2 per resin weight.
Used in a proportion of 00% by weight.

The polyhydroxycarboxylic acid ester may be added to the resin solution or the pigment dispersion liquid, or may be mixed in a solution for forming micelles of the polyhydroxycarboxylic acid ester and further dispersed by ultrasonic waves. ,
You may add in a granulation process.

In the granulating step of the present invention, the resin solution, polyhydroxycarboxylic acid ester, colorant, charge control agent and the like are stirred and mixed, and then charged into an electrically insulating liquid composed of a liquid aliphatic hydrocarbon. It is done by It is not necessary to stir in the granulation step, but it is preferable to stir and / or
Alternatively, it is desirable to improve the dispersion of the precipitated resin particles by a dispersion means such as ultrasonic irradiation. Regarding the cooling rate, dry ice, liquid nitrogen or the like may be used for rapid cooling, cooling may be performed on the electrically insulating liquid, or natural cooling may be performed. When the resin solution is poured into the electrically insulating liquid, the resin particles are precipitated due to the temperature difference of the resin solution, and at the same time, the resin particles are precipitated due to the difference in solubility with the electrically insulating liquid which is a poor solvent for the resin. .

In this granulation step, the polyhydroxycarboxylic acid ester is compatible with the electrically insulating liquid and has a strong affinity with the resin particles, so that the resin particles to be precipitated have a particle size of submicron unit. It is considered that the above-mentioned product can be obtained and the one having a narrow particle size distribution can be obtained. That is, the particle size of the obtained particles is in the range of 0.1 to 10 μm, and a single peak with an average particle size D ₅₀ of 0.6 to 0.8 μm is shown, which is required in the conventional method. Needless to say, the ball milling of the resin particles, classification, etc. are not necessary, but the particles may be further finely pulverized by a pulverizer such as a ball mill, pin pill or jet mill, if necessary.

Next, after granulating the resin particles, it is desirable to remove other solvent contained in the electrically insulating liquid. As the method, the concentration of the electrically insulating liquid may be increased after separating and washing the precipitated resin particles by means such as standing or centrifugation to remove the solvent, or using a solvent of a resin with large volatility. In such a case, it can be easily removed by a natural evaporation method, a method of sending hot air to the liquid surface in a container having a large area, a method such as vacuum distillation.

The resin particles in the heat-sensitive melt transfer material thus obtained are positively or negatively charged. For example, those which are positively charged are those which give a positive image on an electrophotographic photosensitive member used for negative charging, for example, a zinc oxide / resin photosensitive member.

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 heat-sensitive melt transfer material, 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, but to ensure that the charge control agent is adsorbed to the heat-sensitive melt transfer material particles In addition, it is desirable that the charge control agent concentration in the electrically insulating liquid is high, and the two conditions are in conflict. However, it becomes possible to maintain 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 particles of the thermal transfer material. .

Further, other additives can be used in the heat-sensitive melt transfer material obtained in the present invention. For example, various resins soluble in an electrically insulating liquid, such as modified or unmodified alkyd resin, ordinary acrylic resin, synthetic rubber, polyalkylene oxide, polyvinyl acetal containing polyvinyl butyral, vinyl acetate resin, etc. can be added as a fixing agent. .

In addition, a large amount of anionic, cationic, amphoteric or nonionic surfactants can be added as a dispersant to the heat-sensitive melt transfer material obtained in the present invention. The above-mentioned aliphatic acid salt, the synthetic resin used as the above-mentioned fixing agent, or the like can be used as the dispersant.

When the heat-sensitive melt transfer material according to the present invention is developed with an electrostatic latent image and then heat-transferred to an object to be transferred such as ordinary paper, the melt-releasability is high and the adhesion to the transfer surface is good. , You can get clear and high quality images.

The case where the heat-sensitive melt transfer material of the present invention is one in which a thermoplastic resin layer containing a colorant and a wax layer are provided on one surface of a base film will be described. A thermosensitive melt transfer material obtained by granulating a synthetic resin, a wax, and a colorant as a main component is mixed with a binder resin, a softening agent and the like to prepare a coating liquid. Solid content in coating liquid 100
It is preferable that the colorant, the binder resin, and the wax are blended in the proportions of 20 to 80 parts by weight, 10 to 90 parts by weight, and 3 to 35 parts by weight with respect to parts by weight, respectively.

The substrate film used in the present invention is
Any material may be used as long as it has strength that does not extend or break during thermal transfer and that is not deformed or partially melted by the heat of the recording thermal head, and specifically, polyester, polypropylene, polystyrene, polycarbonate, polyimide. And other plastic films, glassine paper, capacitor paper, form paper, Indian paper and other paper, metal foil and aluminum-paper composite sheet, metal vapor-deposited paper or metal vapor-deposited film which is a composite of the above materials. Can be given.

When a plastic film is used as the substrate film, the thermal head is in contact with the surface opposite to the surface on which the heat-sensitive transfer layer is formed. Therefore, the heat-resistant protective layer for preventing stacking on the thermal head is made of a heat-resistant material. A resin layer, a thermal release agent, a substance acting as a lubricant, or the like can be the main component.

The release layer formed on the surface of the substrate film or the adhesive layer formed on the surface of the heat-sensitive transfer ink layer contains wax as a main component, and any conventionally known wax can be used. Examples of the waxes include carnauba wax, montan wax, beeswax, rice wax, candy wax, lanolin wax, paraffin wax, microlisterin, polyethylene wax, sazol wax, oxide wax, amide wax, and silicone wax.

Among them, as a concrete example of the wax particularly suitable for the present invention, an ester wax WAX is particularly preferable.
E, WAX F, WAX KPS and WAS BJ, and WAXO as a partially saponified ester wax.
P, WAX OM, WAX VWAX FL3 (all manufactured by Hoechst) can be mentioned.

As the additives, various surfactants, 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 stepalmitic acid) Zinc, etc.), antioxidants, various plasticizers, surface modifiers such as silane coupling agents and lubricants, silicone oil, anti-slip powder, and metal fine particles and powders for controlling the thermal conductivity. And so on.

The release layer preferably formed between the support (base) and the thermal transfer layer is a combination of waxes, thermoplastic resins, additives and the like used in the thermal transfer layer.
It may be a layer capable of cohesively breaking itself by melting or softening during heating, or a resin that is relatively unlikely to exhibit adhesive force in combination with another resin, for example, a silicone resin, a fluorine resin ( Polytetrafluoro resin, fluorine-containing acrylic resin, etc.), polysiloxane resin, acetal resin (polyvinyl butyral, polyvinyl acetal, polyvinyl formal, etc.), ethylene resin (ethylene vinyl resin, ethylene acrylate resin, ethylene acrylic acid ionomer resin) 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 is an example thereof. The release layer is preferably heat-softening.

Alternatively, a heat softening layer may be separately provided between the support and the peeling layer. The release layer or the heat-softening layer having a heat-softening property is made of a thermoplastic resin and has a property of softening 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, polyethylene,
Polyolefin such as polypropylene: ethylene and vinyl acetate, ethylene and acrylic acid ester, ethylene and acrylic acid such as acrylic acid copolymer: polyvinyl chloride:
Vinyl chloride copolymers such as enca vinyl and vinyl acetate: Polyvinylidene chloride: Vinylidene chloride copolymers: Polystyrene: Acrylic ester Styrene copolymers such as vinyl and maleic anhydride: Acrylic ester copolymers such as acrylic ester and vinyl : Polymethacrylic acid ester: Methyl methacrylate and vinyl acetate, Methacrylic acid ester copolymer such as methyl methacrylate and acrylic acid: Polyvinyl acetate: Vinyl acetate copolymer: Vinyl butyral resin: Nylon, Copolymerized nylon, N-
Polyamide resin such as alkoxymethylated nylon:
Synthetic rubber: Petroleum resin: Chlorinated rubber: Polyethylene glycol: Polyvinyl alcohol hydrogen phthalate: Cellulose derivative, Cellulose acetate phthalate, Cellulose acetate succinate: Shellac: Wax.

The thickness of the heat-softening layer is appropriately in the range of 1 to 50 μm, preferably 5 to 30 μm. When recording using the multicolor heat-sensitive transfer recording paper of the present invention,
The material to be transferred used is not particularly limited. For example, plastic film, paper, metal, wood, glass, fiber and the like can be used.

[0044]

According to the present invention, in the granulation step of pouring the resin solution melted by heating into the electrically insulating liquid and cooling it to precipitate the resin particles, the polycarboxylic acid ester of 3 to 10-mer containing hydroxycarboxylic acid ester as a monomer is used. In addition to the presence of hydroxycarboxylic acid ester, wax and colorant are used. As a result, the polyhydroxycarboxylic acid ester has compatibility with the electrically insulating liquid, affinity with the resin particles, and has a granulation adjusting function. By using carbon black having physical properties, it is possible to obtain a resin particle having a particle size of submicron and an extremely narrow particle size distribution, which does not require a ball milling operation, etc. It is possible to produce a heat-sensitive melt transfer material having an excellent distribution. Further, the obtained heat-sensitive melt transfer material has a high melt peeling property and a good adhesiveness to the transfer surface, so that a high quality image can be formed even on plain paper.

The present invention will be described in more detail with reference to the following examples.

[0046]

【Example】

Preparation of Electrostatic Recording Sheet A heat-resistant protective layer composition having the following composition was prepared and a polyethylene terephthalate film “S-PET” having a thickness of 9 μm was prepared.
(Toyobo Co., Ltd.) was coated with Miyabar # 8 on the surface opposite to the surface on which the heat-sensitive melt transfer layer is formed, dried with warm air, and further 6
It was cured in an oven at 0 ° C. for 20 hours. The coating amount after drying was 0.9 g / m ² . (Heat-resistant protective layer composition) Polyvinyl butyral "S-REC BX-1" (Sekisui Chemical Co., Ltd.) 4.5 parts by weight Toluene 45.0 parts by weight Methyl ethyl ketone 45.5 parts by weight Phosphate ester ("Prysurf A-208S" Daiichi Kogyo) Pharmaceuticals) 0.45 parts by weight diisocyanate "Takenate D-110N" / 75% ethyl acetate solution (Takeda Yakuhin) 2.0 parts by weight The electrostatic recording sheet obtained above is used as a substrate for the heat-sensitive melt transfer material in each example. used.

Example 1 In a 200 ml round bottom flask, 1.0 g of EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Polychemical Co., Ltd., Evaflex 250), EVA1W.
ax BASF (polyethylene wax containing ethylene-vinyl acetate copolymer as a main component, manufactured by BASF)
1.0 g, Hoechst Wax V (manufactured by Hoechst) 1.0 g, charge control agent BBP (manufactured by Barium Petronate Witco Chemical) 250 mg and tetrahydrofuran 80 ml were mixed, and heated and stirred at 80 ° C. for 1 hour,
A resin solution was prepared.

On the other hand, Sumika GNO-in another container.
PP (metal phthalocyanine pigment, manufactured by Sumitomo Chemical Co., Ltd.)
3.0 g, 108 mg of poly-12-hydroxystearate trimer (manufactured by Ito Oil Co., Ltd.) were dispersed in 100 ml of tetrahydrofuran using an ultrasonic homogenizer (Nippon Seiki Seisakusho, Ltd., US-300T). . This was put at once into the flask in which the resin had been dissolved, and further stirred and mixed at 90 ° C. for 1 hour to obtain a pigment dispersion. After lowering the temperature of the pigment dispersion to about 60 ° C. at room temperature,
100m Isopar G (manufactured by Exxon Co.) cooled to 5 ° C
1 was dispersed and mixed in an ultrasonic homogenizer. This pigment dispersion liquid was subjected to solvent substitution with Isopar G using a rotary evaporator (EYELA NE-1T type manufactured by Tokyo Rika Kikai Co., Ltd.). Further, the same Isopar G was used to adjust the concentration of the developer to a print concentration of 1%. The particle size distribution was measured with Microtrac Mark II SRA type (manufactured by Nikkiso Co., Ltd.). As a result of measuring the particle size distribution of the resin particle size, the resin particles are 0.17 to 1.01 μm, and d ₅₀ =
It had a single distribution at 0.44 μm. The particle size distribution is shown in FIG.

After forming various electrostatic patterns having a surface charge of 50 to 150 V on the electrostatic recording paper, the developing and printing characteristics were evaluated by a roller developing machine. Developing speed is 2.6m
/ Min and 10.0 m / min. In addition, a micro ammeter 237 HIGH VOLT manufactured by Keythley
Using AGE SOURCE MEASURE UNIT, the above-mentioned pigment dispersion liquid was filled between metal electrode plates having an area of 4.5 × 5.0 cm at an interval of 1 cm, and the space between the electrodes was 1000.
A direct current voltage of V was applied to measure the current value and evaluate the electrophoretic characteristics. The photometric and colorimetric evaluation of the printed matter is performed with a spectrophotometer system (CM-1000 Minolta Co., Ltd.).
The D value was measured by Macbeth RD914. The electrophoretic characteristics are measured by a zeta electrometer measuring device (MATEC APP
LIED SCIENCE product, device name ESA-800
0, ultrasonic zeta potential analysis system). The developing property shows a positive polarity (a negative electrostatic latent image can be printed).
OD value of 1.4 or more, initial current value of 606 nA when applying a DC voltage of 1000 V, current value of 157 nA after 60 seconds, Q /
The characteristic was m = 178 μC / g. Mobility is 4.57
× 10 ⁻¹¹ m ² / sec · V, and zeta potential is 16.6.
It was mV.

A negative electrostatic latent image is formed on the entire surface of the electrostatic recording sheet on which the heat-resistant protective layer has been formed by corona charging, and then the resulting heat-sensitive melt transfer material is developed with a roller developing machine to perform heat-sensitive melt transfer. Created a sheet. When the thermal-melting transfer sheet was combined with coated paper (S-Top Coated Paper manufactured by Kanzaki Paper Co., Ltd.), a printer equipped with a Toshiba thermal head was energized under the conditions of an applied voltage of 12 V and an applied time of 2 ms. A blue image with good print quality was obtained. The OD value was 1.0.

Separately from this, a heat transfer ironing device (trade name: Hariron Presser HP-1000WE, manufactured by Hashima Co., Ltd.) was used to heat for 2 minutes at 130 ° C., and the heat-sensitive melt transfer sheet was coated with coated paper (manufactured by Kanzaki Paper Co., Ltd.). , S-top coated paper). 90% transfer efficiency
It was about. However, peel shear force is 0.6g / 1cm
It was small and the break was good. Acetone: Toluene = 1: on the heat-sensitive melt transfer sheet prepared by the same method.
A 10% solution of carnauba wax using the mixed solvent of No. 1 as a solvent was coated in a single layer with a miya bar. After that, a thermal transfer ironing device (trade name: HARILON PRESSER HP-100
0WE, manufactured by Hashima Co., Ltd., is heated at 130 ° C. for 2 minutes, and the heat-sensitive melt transfer sheet is coated onto coated paper (Kanzaki Paper Co.
Melt-transferring to S-top coated paper). The transfer efficiency was about 70%.

Example 2 Hoechst WAX V (manufactured by Hoechst) in Example 1
A pigment dispersion liquid was prepared in the same manner as in Example 1 except that 1.0 g of Hoechst WAX E flakes (manufactured by Hoechst) was used instead. 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, it was found that the resin particles had a single distribution at 0.17 to 1.01 μm and d ₅₀ = 0.40 μm. The particle size distribution is shown in FIG.

Development characteristics are negative (possible to print positive electrostatic latent image)
Indicates. OD value of 1.4 or more. Initial current value of 140 nA when applying 1000 V DC voltage, current value of 66 after 60 seconds
The toner showed physical properties of nA and Q / m = 100 μC / g.
The mobility was 2.90 × 10 ⁻¹¹ m ² / sec · V and the zeta potential was 10.6 mV.

After a negative electrostatic latent image was formed on the electrostatic recording sheet, the heat-sensitive melt transfer material thus prepared was used for development with a roller developing machine to prepare a heat-sensitive transfer sheet.

Next, the thermal transfer sheet was combined with coated paper (S-Top Coated Paper manufactured by Kanzaki Paper Co., Ltd.), and a printer equipped with a Toshiba thermal head was energized under conditions of an applied voltage of 12 V and an applied time of 2 msec. As a result, a blue image with good print quality was obtained. The OD value was 0.98.

A heat transfer ironing device (trade name: HARILON PRESSER HP-1000WE, manufactured by Hashima Co., Ltd.) was heated at 130 ° C. for 2 minutes, and the melted transfer paper was coated with a coated paper (Kanzaki Paper Co., S-Top Coat). Melt transfer to paper) was performed. The transfer efficiency was about 90%. On a thermal transfer sheet prepared by the same method, 1 part of carnauba wax using a mixed solvent of acetone: toluene = 1: 1 as a solvent.
The 0% solution was coated in a single layer with a Miya bar. After that, a thermal transfer ironing device (trade name: HARILON PRESSER HP-
1000 WE, manufactured by Hashima Co., Ltd., was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 70%.

Example 3 Hoechst WAX V (manufactured by Hoechst) in Example 1
Instead of Hoechst WAX 2106 (made by Hoechst)
A pigment dispersion liquid was prepared in the same manner as in Example 1 except that 1.0 g was used. 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 contained 1.69 to 3.73 μm and contained 0.17 to 3.73.
It had a distribution in the region of μm, d ₅₀ = 0.65 μm, and had two peaks in this region. The particle size distribution is shown in FIG. The developing property shows a positive polarity (a negative electrostatic latent image can be printed). The OD value was 1.4 or more. Initial current value 56121 nA when applying 1000 V DC, current value 298 after 60 seconds
The toner physical properties were 80 nA and Q / m = 5972 μC / g. The mobility was 1.21 × 10 ⁻¹⁰ m ² / sec · V and the zeta potential was 44.6 mV.

After forming a negative electrostatic latent image on the electrostatic recording sheet, the resulting developing solution was used to develop with a roller developing machine to prepare a heat-sensitive transfer sheet. The obtained thermal transfer recording sheet was coated with a coated paper (Kanzaki Paper Co., Ltd., S-
Applied voltage 12V and application time 2mse to the printer equipped with Toshiba thermal head together with top coat paper)
When electricity was turned on under the condition of c, a blue image with good print quality was obtained. The OD value was 0.88.

A thermal transfer ironing device (trade name: HARILON PRESSER HP-1000WE, manufactured by Hashima Co., Ltd.) was heated at 130 ° C. for 2 minutes, and the thermal transfer sheet was coated with coated paper (Kanzaki Paper Co., S-Top Coat). Melt transfer to paper) was performed. The transfer efficiency was about 90%.

On the heat-sensitive transfer sheet prepared by the same method, a 10% solution of carnauba wax using a mixed solvent of acetone: toluene = 1: 1 as a solvent was coated in a single layer with a miya bar. After that, a heat transfer ironing device (trade name: Hariron Presser HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 70%.

Example 4 Hoechst WAX V (manufactured by Hoechst) in Example 1
1.0 g, EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Polychemical Co., Ltd., Evaflex 250) 1.0 g, and Sumika GNO-PP
(Metal phthalocyanine pigment, manufactured by Sumitomo Chemical Co., Ltd.) 3.0
High wax 1105A (Mitsui Petrochemical Co., Ltd.)
Manufactured by Takeda Yakuhin Kogyo Co., Ltd.) and Monastral Blu.
e FBR (made by ICI, metal phthalocyanine pigment)
A pigment dispersion was prepared in the same manner as in Example 1 except that 3.0 g was used. 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, it was found that the resin particles had a uniform distribution at 0.17 to 1.01 μm and d ₅₀ = 0.38 μm. The particle size distribution is shown in FIG. The developing property shows a negative polarity (possible to print a positive electrostatic latent image).
The OD value was 1.4 or more. 1000V DC application / initial current value 2834nA, current value 1106nA after 60 seconds,
The toner showed physical properties of Q / m = 88.2 μC / g. The mobility was 3.58 × 10 ⁻¹¹ m ² / sec · V and the zeta potential was 13.1 mV.

After a positive electrostatic latent image was formed on the electrostatic recording sheet, the resulting developing solution was used for development with a roller developing machine to prepare a heat-sensitive transfer sheet. Then, the thermal transfer sheet was combined with coated paper (S-Top Coated Paper manufactured by Kanzaki Paper Co., Ltd.), and a printer equipped with a Toshiba thermal head was energized under the conditions of an applied voltage of 12 V and an applied time of 2 ms. , A blue image with good print quality was obtained. The OD value was 0.96.

Further, a heat transfer ironing device (trade name: HARILON PRESSER HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to coated paper (S-top coated paper manufactured by Kanzaki Paper Co., Ltd.). The transfer efficiency was about 90%.

On a heat-sensitive transfer sheet prepared by the same method, a 10% solution of carnauba wax using a mixed solvent of acetone: toluene = 1: 1 as a solvent was coated with a single layer by a miya bar. After that, a heat transfer ironing device (trade name: Hariron Presser HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 50%.

Example 5 Hoechst WAX V (manufactured by Hoechst) in Example 1
1.0 g, EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Chemical Co., Ltd., Evaflex 25)
0) 1.0 g and Sumika GNO-PP (metal phthalocyanine pigment, manufactured by Sumitomo Chemical Co., Ltd.) 3.0 g were excluded, and instead of these, high wax 1105A (manufactured by Mitsui Petrochemical Co., Ltd.) 1.0 g, Priorite- 1.0 g of VTAC (Vinyltoluene-acrylic copolymer resin manufactured by Goodyear) and Monastral Blue F
BR (manufactured by ICI, metal phthalocyanine pigment) 3.0 g
A pigment dispersion liquid was prepared in the same manner as in Example 1 except that each of the above was used.

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 were 0.17 to 3.73 μm, d ₅₀ = 0.80 μm and 2
It had a distribution in the region of 9.85 to 60.00 μm and had two peaks in this region. The particle size distribution is shown in FIG. The developing property shows a positive polarity (a negative electrostatic latent image can be printed). The OD value was 1.4 or more. 1,000 V DC application / initial current value 19826 nA, current value after 60 seconds 88
The toner physical properties were 19 nA and Q / m = 3390 μC / g. The mobility was 8.01 × 10 ^-11 m ² / sec · V. The zeta potential was 29.3 mV.

After a negative electrostatic latent image was formed on the heat-sensitive transfer sheet, the heat-sensitive transfer sheet was prepared by developing the prepared developer with a roller developing machine. When this thermal transfer sheet was combined with coated paper (S-Top Coated Paper manufactured by Kanzaki Paper Co., Ltd.), a printer equipped with a Toshiba thermal head was energized under the conditions of an applied voltage of 12 V and an applied time of 2 ms. A blue image with good print quality was obtained. The OD value was 0.85.

Further, a thermal transfer ironing device (trade name: HARILON PRESSER HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the melt transfer paper to the coated paper (S-top coated paper manufactured by Kanzaki Paper Co., Ltd.). The transfer efficiency was about 70%.

On the heat-sensitive transfer sheet prepared by the same method, a single layer of a 10% solution of carnauba wax using a mixed solvent of acetone: toluene = 1: 1 as a solvent was coated with a miya bar. After that, a heat transfer ironing device (trade name: Hariron Presser HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 50%.

Example 6 Hoechst WAX V (manufactured by Hoechst) in Example 1
1.0 g, EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Chemical Co., Ltd., Evaflex 25)
0) 1.0 g and Sumika GNO-PP (metal phthalocyanine pigment, manufactured by Sumitomo Chemical Co., Ltd.) 3.0 g were excluded, and instead of these, high wax 1105A (manufactured by Mitsui Petrochemical Co., Ltd.) 1.2 g, Dumiran 2270 ( Ethylene-vinyl acetate copolymer partially saponified modified product, Takeda Yakuhin Kogyo Co., Ltd. 0.6 g and Monastral B
3.0 g of lue FBR (manufactured by ICI, metal phthalocyanine pigment) is used, and EVA 1 Wa
Example 1 except that the amount of xBASF used was 1.2 g.
A pigment dispersion liquid was prepared in the same manner as in.

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 had two peaks at 0.17 to 3.73 μm and d ₅₀ = 0.57 μm. The particle size distribution is shown in FIG.
The developing property shows a positive polarity (a negative electrostatic latent image can be printed). OD
The value was 1.4 or more. Application of 1000 V DC / initial current value was 158 nA, and current value after 60 seconds was 97 nA. The mobility was 2.28 × 10 ⁻¹¹ m ² / sec · V and the zeta potential was 8.33 mV.

After forming a negative electrostatic latent image on the electrostatic recording sheet, the resulting developing solution was used to develop with a roller developing machine to prepare a heat-sensitive transfer sheet. After that, a heat transfer ironing device (trade name: Hariron Presser HP
-1000WE, 2 at 130 ° C by Hashima Co., Ltd.
After heating for a minute, the heat-sensitive transfer sheet was melt-transferred to a coated paper (S-top coated paper manufactured by Kanzaki Paper Co., Ltd.). The transfer efficiency was about 80%.

On the heat-sensitive transfer sheet prepared by the same method, a 10% solution of carnauba wax using a mixed solvent of acetone: toluene = 1: 1 as a solvent was coated with a single layer by a miya bar. After that, a heat transfer ironing device (trade name: Hariron Presser HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 70%.

Example 7 Hoechst WAX V (manufactured by Hoechst) in Example 1
1.0 g, EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Chemical Co., Ltd., Evaflex 25)
0) 1.0 g and Sumika GNO-PP (metal phthalocyanine pigment, manufactured by Sumitomo Chemical Co., Ltd.) 3.0 g were replaced with high wax 1105A (manufactured by Mitsui Petrochemical Co., Ltd.) 1.5 g, EVA 1 Wax. (BASF
1.5g and Monastral Blue
FBR (made by ICI, metal phthalocyanine pigment) 3.0
A pigment dispersion liquid was prepared in the same manner as in Example 1 except that the amount was changed to g.

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 had a distribution in the region of 0.17 to 7.46 μm and d ₅₀ = 0.67 μm. The particle size distribution is shown in FIG. The developing property shows a positive polarity (a negative electrostatic latent image can be printed). The OD value was 1.4 or more. Application of 1000 V DC / initial current value was 74 nA, and current value was 20 nA after 60 seconds. The mobility was 3.75 × 10 ⁻¹¹ m ² / sec · V and the zeta potential was 13.7 mV.

After a negative electrostatic latent image was formed on the electrostatic recording sheet, the resulting developing solution was used to develop with a roller developing machine to prepare a heat-sensitive transfer sheet. After that, a heat transfer ironing device (trade name: Hariron Presser HP
-1000WE, 2 at 130 ° C by Hashima Co., Ltd.
After heating for a minute, the heat-sensitive transfer sheet was melt-transferred to a coated paper (S-top coated paper manufactured by Kanzaki Paper Co., Ltd.). The transfer efficiency was about 80%.

On the heat-sensitive transfer sheet prepared by the same method, a 10% solution of carnauba wax using a mixed solvent of acetone: toluene = 1: 1 as a solvent was coated with a single layer by a miya bar. After that, a heat transfer ironing device (trade name: Hariron Presser HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 70%.

Example 8 Hoechst WAX V (manufactured by Hoechst) in Example 1
1.0 g, EVA 1Wax (manufactured by BASF) 1.5
EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Chemical Co., Ltd., Evaflex 25)
A pigment dispersion liquid was prepared in the same manner as in Example 1 except that the amount of 0) used was 3.0 g.

As a result of measuring the particle size distribution of the resin particles, the resin particles had a single distribution in the region of 0.17 to 5.27 μm and d ₅₀ = 1.55 μm. Figure 8 shows the particle size distribution
Shown in. The developing property shows a positive polarity (a negative electrostatic latent image can be printed). The OD value was 1.4 or more. 1000V DC application /
Initial current value 1592nA, current value 602n after 60 seconds
A, Q / m = 461 μC / g. The mobility was 8.76 × 10 ⁻¹¹ m ² / sec · V and the zeta potential was 32.0 mV.

After forming a negative electrostatic latent image on the electrostatic recording sheet, it was developed with a roller developing machine using the developing solution thus prepared to prepare a heat-sensitive transfer sheet. After that, a heat transfer ironing device (trade name: Hariron Presser HP
-1000WE, 2 at 130 ° C by Hashima Co., Ltd.
After heating for a minute, the image was not melt-transferred from the heat-sensitive transfer sheet to coated paper (S-top coated paper manufactured by Kanzaki Paper Co., Ltd.).

A thermal transfer sheet prepared by the same method was coated with a 10% solution of carnauba wax in a single layer using a mixed solvent of acetone: toluene = 1: 1 as a solvent. After that, a heat transfer ironing device (trade name: Hariron Presser HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 30%.

Example 9 Hoechst WAX V (manufactured by Hoechst) in Example 1
1.0 g, EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Chemical Co., Ltd., Evaflex 25)
0) 1.0 g, EVA 1 Wax (manufactured by BASF)
Except for 1.0 g and 3.0 g of Sumika GNO-PP (metal phthalocyanine pigment, manufactured by Sumitomo Chemical Co., Ltd.)
Dumilan 2270 (ethylene-vinyl acetate copolymer partially saponified modified product, Takeda Pharmaceutical Co., Ltd.) 3.0 g
And Monastral Blue FBR (ICI
A pigment dispersion liquid was prepared in the same manner as in Example 1 except that 3.0 g of a metal phthalocyanine pigment manufactured by Co., Ltd.) was used.

As a result of measuring the particle size distribution of the resin particles, the resin particles had a single distribution in the region of 0.17 to 3.73 μm and d ₅₀ = 0.95 μm. The particle size distribution is shown in FIG. The developing property shows a positive polarity (a negative electrostatic latent image can be printed). The OD value was 1.4 or more. 1000V DC application / initial current value 9202nA, current value 1391 after 60 seconds
The physical properties were nA and Q / m = 102 μC / g. The mobility was 1.90 × 10 ⁻¹¹ m ² / sec · V and the zeta potential was 6.9 mV.

After a negative electrostatic latent image was formed on the electrostatic recording sheet, the resulting developing solution was used for development with a roller developing machine to prepare a heat-sensitive transfer sheet. After that, a heat transfer ironing device (trade name: Hariron Presser HP
-1000WE, 2 at 130 ° C by Hashima Co., Ltd.
After heating for a minute, the image was not melt-transferred from the heat-sensitive transfer sheet to coated paper (S-top coated paper manufactured by Kanzaki Paper Co., Ltd.).

On the heat-sensitive transfer sheet prepared by the same method, a 10% solution of carnauba wax using a mixed solvent of acetone: toluene = 1: 1 as a solvent was coated with a single layer by a miya bar. After that, a heat transfer ironing device (trade name: Hariron Presser HP-1000WE, manufactured by Hashima Co., Ltd.)
Was heated at 130 ° C. for 2 minutes to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 30%.

Comparative Example 1 A transfer ink composition of each of the following colors was applied to PET with a heat-resistant protective layer having a thickness of 9 μm at a rate of 2.5 g / m ^{2 on} a dry basis.
A comparative heat-sensitive transfer sheet of the present invention was obtained by dividing each color by a color gravure printing machine, applying and drying. -HAXIST WAX-V 30 parts-Color material 3 parts-Toluene 67 parts The following color materials were used. -Yellow ink: C.I. I. 21090 ・ Red ink: C.I. I. 21090 ・ Ai ink: C.I. I. 21090 Ink ink: Carbon black pigment The evaluation method for melt transfer characteristics is shown below.

When this thermal transfer sheet was combined with coated paper (S-Top Coated Paper manufactured by Kanzaki Paper Co., Ltd.), a printer equipped with a Toshiba thermal head was energized under conditions of an applied voltage of 12 V and an applied time of 2 msec. A blue image with good print quality was obtained. The OD value was 1.01.

Separately from this, a thermal transfer ironing device (trade name: Hariron Presser HP-1000 type, manufactured by Hashima Co., Ltd.) was used to heat at 130 ° C. for 2 minutes, and the heat-sensitive transfer sheet was coated with coated paper (manufactured by Kanzaki Paper Co., Ltd.). , S-top coated paper). The transfer efficiency was about 90%. However, the peel shear force is large (1g / 1c
m), it took some force to break.

A 10% solution of carnauba wax using a mixed solvent of acetone: toluene = 1: 1 as a solvent was coated on the heat-sensitive transfer sheet prepared by the same method as a single layer with a miya bar. Then, it was heated at 130 ° C. for 2 minutes by a heat transfer ironing device (trade name: Hariron Presser HP-1000 type, manufactured by Hashima Co., Ltd.) to perform melt transfer from the heat-sensitive transfer sheet to plain paper. The transfer efficiency was about 70%.

[0091]

When the melt transfer type developer of the present invention is used,
An electrostatic latent image formed by corona charging or the like can be developed, and thermal fusing transfer can be realized at the same time. Therefore, the modal transfer type developer is not only intended as a developing solution for the usual visualization of an electrostatic latent image, but also can be recorded and stored as a melt transfer paper on which an image is formed by development. Since electrostatic writing is performed and this is developed with a melt transfer type developer of opposite charge, the expressible gradation in this image can be easily controlled by the configured system. Furthermore, because the pigment is used for the resin layer that can be melt-transferred, it is possible to obtain a higher gradation image than the gradation expression by the conventional combination of the melt ribbon and the thermal transfer printer, and peeling. Is easy. Further, since the melt transfer paper can be heat-sensitive melt transferred as required, transfer printing can be performed on various products regardless of the base material.

[Brief description of drawings]

FIG. 1 is a diagram illustrating a particle size distribution of resin particles of Example 1.

FIG. 2 is a diagram illustrating a particle size distribution of resin particles of Example 2.

FIG. 3 is a diagram illustrating a particle size distribution of resin particles of Example 3.

FIG. 4 is a diagram illustrating a particle size distribution of resin particles of Example 4.

FIG. 5 is a diagram illustrating a particle size distribution of resin particles of Example 5.

FIG. 6 is a diagram illustrating a particle size distribution of resin particles of Example 6.

FIG. 7 is a diagram illustrating a particle size distribution of resin particles of Example 7.

FIG. 8 is a diagram illustrating a particle size distribution of resin particles of Example 8.

FIG. 9 is a diagram illustrating a particle size distribution of resin particles of Example 9.

Claims (2)

[Claims] 1. An olefinic thermoplastic resin having a carboxyl group or an ester group used for the production of a thermal transfer recording medium, an olefin resin having a carboxyl group or an ester group added with a colorant, and most of the liquid aliphatic carbonization. In a heat-sensitive melt transfer material composed of hydrogen, a charge control agent compatible with poly-12-hydroxycarboxylic acid ester of 3 to 10 mer containing hydroxycarboxylic acid ester as a monomer and liquid aliphatic hydrocarbon, and heat-meltable Heat sensitive transfer material characterized by the presence of transparent wax. 2. A resin solution prepared by heating and dissolving an olefinic thermoplastic resin having a carboxyl group or an ester group or an olefinic resin having a carboxyl group or an ester group to which a colorant is added in a solvent having a large temperature dependence of solubility. After that, the resin solution was cooled in the presence of a 3- to 10-mer poly-12-hydroxycarboxylic acid ester having a hydroxycarboxylic acid ester as a monomer and a heat-meltable wax in a liquid aliphatic hydrocarbon. A method for producing a heat-sensitive melt transfer material, which comprises charging the resin particles to deposit the resin particles and replacing the solvent in which the resin is dissolved with the aliphatic hydrocarbon.