JP2000218950A - Molten thermal transfer type ink receiving sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent blots of a blank part of an ink due to an abnormal transfer in a high temperature environment by providing an ink receptive layer containing a binder and pigment particles on a support made of a thermoplastic resin film, and blending fluorine water repellant and oil repellant within the receptive layer. SOLUTION: A molten thermal transfer type ink receiving sheet is manufactured by providing an ink receptive layer containing a binder and pigment particles on a support made of a thermoplastic resin film and blending fluorine water repellent and oil repellent within the receptive layer. A blending amount of the water repellent and oil repellent is preferably 0.1 to 30 wt.% of the total weight of the receptive layer. As the water repellent and oil repellent, a resin containing a perfluoroalkyl group or a phosphoric acid compound is preferably used. The number of carbons of the fluoroalkyl group is preferably 1 to 20. As the pigment particles used for the receiving sheet, silica particles are preferably used. As the resin film of the support, a porous resin oriented film is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a full-color fusion thermal transfer printer, which is free from white paper stains due to an abnormal transfer phenomenon of ink in a high-temperature environment, and provides a clear color image with good dot reproducibility and gradation. And a heat transfer type ink receiving sheet.

[0002]

2. Description of the Related Art Since color thermal transfer recording can be performed compactly and at low cost, it has been widely used for output of measurement data output such as CAD, business graphics, color copiers and chromatographs. Thermal transfer recording is to form an image on an ink receiving sheet by heating an ink ribbon with a thermal head,
There are two types of thermal transfer recording systems, a fusion thermal transfer type and a sublimation thermal transfer type. The fusion heat transfer type has a lower applied energy and lower running cost than the sublimation heat transfer type, and therefore has high industrial applicability.

[0003] In a conventional fusion thermal transfer type color printer, since the applied energy is not changed, the formed image is a simple one with poor gradation and perspective. For this reason, a special ink receiving sheet is not required for forming an image, and a high quality paper can be used to form a target image.

In recent years, however, higher gradation reproducibility has been required with the development of full-color thermal transfer recording, and the conventional method of obtaining gradation without changing the size of one dot has been changed to each dot. Is changing to a dot variable method that changes the size of the dot. Accordingly, in the ink receiving sheet, in a full-color recording from a low applied energy to a high applied energy, a performance (good dot reproducibility) that faithfully reproduces the dot shape of the ink that has been thermally transferred and a sufficient amount of ink are provided. A performance (high recording density) that can accept ink has been required.

[0005] When plain paper is used for such full-color recording, portions where ink is not transferred appear because the surface is too rough. On the contrary, when highly smooth paper for printing is used, the surface is too smooth and the ink is anchored. There is a case where the transferred ink is reversely transferred to the ink ribbon without effect. Also,
The low ink absorption of the ink receiving layer and the low heat insulation and cushioning properties of the support may cause poor dot reproducibility and reduced recording density. For this reason, there is a demand for providing an ink receiving sheet having characteristics that can be sufficiently adapted to full-color thermal transfer images.

[0006] In response to such demands, the use of a porous stretched resin film (synthetic paper) for the support of the ink receiving sheet, the use of ethylene resin as the resin component of the ink receiving layer, and the like.
It has been proposed to use a vinyl acetate copolymer.
For example, in Example 1 of JP-A-7-68956, there is described a melt heat transfer type ink in which an ink receiving layer comprising an ethylene / vinyl acetate copolymer, a synthetic acrylic wax and a styrene / sulfonate is formed on one side of a high quality paper. A receiving sheet is disclosed.

Japanese Patent Application Laid-Open No. 7-101167 discloses a support in which a core material and a porous resin sheet layer stretched and formed on at least one surface of the core material are laminated, and at least a porous resin sheet of the support material is provided. A melt transfer type ink receiving sheet having an ink receiving layer containing, on the layer side, an ethylene / vinyl acetate copolymer resin, at least one selected from a wax and a rosin compound, and a pigment as main components is disclosed. .

In the ink receiving layer of these inks, a wax or a rosin compound having good compatibility with the ink is mixed with the ethylene / vinyl acetate copolymer, so that polyester, SBR, A conventional ink receiving sheet in which an inorganic filler such as clay, zeolite, calcium carbonate or the like is blended with an acrylic resin (Japanese Patent Laid-Open No.
297873, JP-A-6-270557)
This has the advantage that the amount of transferred ink is large and the color density of the recorded image is high. However, in these melt heat transfer type receiving sheets, since the receiving layer is softened during the heat transfer of the ink, the adhesion between the ink ribbon and the receiving layer of the sheet becomes too high, and the ink ribbon and the ink receiving sheet are blocked. It also has the drawback.

Therefore, as a receiving sheet capable of transferring a color image with clear dots and good reproducibility without blocking with the ink ribbon, for example, as disclosed in
JP-A-86057 proposes a melt transfer type ink receiving sheet. This melt transfer type ink receiving sheet is characterized in that an ink receiving layer composed of a sedimentable silicon powder and an ethylene / vinyl acetate copolymer is formed on one surface of a microporous stretched resin film (synthetic paper). . However, even this fusion heat transfer type receiving sheet has a drawback in that an abnormal transfer phenomenon of ink occurs in which ink is transferred regardless of the thermal control of the thermal head in a high temperature environment of 35 ° C. or more. As described above, a sheet which sufficiently satisfies various conditions required for a melt thermal transfer type ink receiving sheet has not been developed so far.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve these problems of the prior art and to provide a melt heat transfer type ink receiving sheet having extremely excellent characteristics. That is, the present invention provides a full-color fusion heat transfer type printer that does not have a stain on a white paper portion due to abnormal transfer of ink in a high-temperature environment, has good dot reproducibility, and provides a clear color image with gradation. The task to be solved was to be solved.

[0011]

Means for Solving the Problems The present inventors have made intensive studies to solve these problems, and as a result, have found that an ink receiving layer having a fluorine-based water / oil repellent is formed on a support of a thermoplastic resin film. The present inventors have found that an excellent melt heat transfer type ink-receiving sheet having desired characteristics can be provided by forming the ink-receiving sheet.

That is, the present invention relates to a heat transfer type ink receiving sheet provided with an ink receiving layer containing a binder and pigment particles on a support made of a thermoplastic resin film. An object of the present invention is to provide a melt heat transfer type ink receiving sheet containing an oil agent. The content of the fluorine-based water / oil repellent is preferably 0.1 to 30% by weight based on the total weight of the ink receiving layer. Further, the fluorine-based water / oil repellent is preferably a resin having a fluoroalkyl group such as a perfluoroalkyl group or a phosphate compound. The fluoroalkyl group preferably has 1 to 20 carbon atoms. Further, the pigment particles used in the ink-receiving sheet of the present invention are preferably silica particles, and the thermoplastic resin film is preferably a porous resin stretched film.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the melt heat transfer type ink receiving sheet of the present invention will be described in more detail in the order of a support and an ink receiving layer.

Support The support used in the heat transfer type ink receiving sheet of the present invention comprises a thermoplastic resin film.

[Material of Thermoplastic Resin Film] The type of thermoplastic resin film used for the support is not particularly limited. For example, high-density polyethylene, ethylene resin such as medium-density polyethylene, or polyolefin resin such as propylene resin, polymethyl-1-pentene, ethylene / cyclic olefin copolymer, nylon-6, nylon-6,6, nylon -6, a polyamide resin such as T,
Polyethylene terephthalate or a copolymer thereof, polybutylene terephthalate, thermoplastic polyester resin such as aliphatic polyester, polycarbonate, atactic polystyrene, syndiotactic polystyrene and the like can be used. Among these thermoplastic resins, it is preferable to use a non-polar polyolefin resin.

Further, among the polyolefin resins, a propylene resin is preferable in terms of chemical resistance, cost and the like. As the propylene-based resin, propylene homopolymer is isotactic or syndiotactic and polypropylene showing various degrees of stereoregularity,
A copolymer obtained by copolymerizing propylene as a main component and an α-olefin such as ethylene, 1-butene, 1-hexane, 1-heptane, and 4-methyl-1-pentene can be used. This copolymer may be a binary system, a ternary system or more, and may be a random copolymer or a block copolymer. For the propylene-based resin, a resin having a melting point lower than that of the propylene homopolymer is 2 to 25% by weight.
It is preferable to use them in combination. High-density or low-density polyethylene can be exemplified as such a resin having a low melting point. As the thermoplastic resin for the support, one of the above thermoplastic resins may be selected and used alone, or two or more may be selected and used in combination.

The thermoplastic resin to be used as a support may include, if necessary, an inorganic fine powder, an organic fine powder, a stabilizer, a light stabilizer,
Dispersants, lubricants and the like can be added. When adding inorganic fine powder, the particle size is usually 0.01 to 15 μm,
Preferably, those having a size of 0.01 to 5 μm are used. Specifically, calcium carbonate, calcined clay, silica, diatomaceous earth, talc, titanium oxide, barium sulfate, alumina and the like can be used.

When adding an organic fine powder, it is preferable to select a resin different from the thermoplastic resin as the main component. For example, when the thermoplastic resin film is a polyolefin resin film, as the organic fine powder, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, nylon-6, T, cyclic olefin, A polymer such as polystyrene or polymethacrylate, which has a melting point higher than the melting point of the polyolefin resin (for example, 170
~ 300 ° C) or glass transition temperature (e.g. 170 ~
280 ° C.) can be used.

When a stabilizer is added, usually 0.001
It is added within the range of １1% by weight. Specifically, sterically hindered phenol-based, phosphorus-based, amine-based stabilizers and the like can be used. When a light stabilizer is used, it is usually used in the range of 0.001 to 1% by weight. Specifically, sterically hindered amines, benzotriazole-based, benzophenone-based light stabilizers and the like can be used. The dispersant and the lubricant are used, for example, for the purpose of dispersing the inorganic fine powder. The amount used is usually in the range of 0.01 to 4% by weight. Specifically, silane coupling agents, higher fatty acids such as oleic acid and stearic acid, metal soaps, polyacrylic acid, polymethacrylic acid or salts thereof can be used.

[Manufacturing Method] The method of forming the thermoplastic resin film is not particularly limited, and the film can be formed by appropriately selecting from known methods. For example, using a single-layer or multi-layer T-die or I-die connected to a screw-type extruder to extrude the molten resin into a sheet, cast molding, calender molding, roll molding, using a single-layer or multilayer inflation die. A method of removing a solvent or oil after inflation molding for extruding a molten resin into a tubular shape, casting or calender molding of a mixture of a thermoplastic resin and an organic solvent or oil, and removing the solvent after molding from a thermoplastic resin solution Methods and the like can be mentioned.

The thermoplastic resin film used for the support is
It may be stretched. Stretching can be performed by any of various methods commonly used. The stretching temperature is not lower than the glass transition temperature of the thermoplastic resin to be used in the case of the non-crystalline resin, and is not lower than the melting point of the crystal part in the case of the crystalline resin. Can be performed within a known temperature range suitable for Specifically, when the thermoplastic resin is a propylene homopolymer (melting point: 155 to 167 ° C), 152 to 164 ° C,
The temperature is preferably set to 110 to 120 ° C for high-density polyethylene (melting point 121 to 134 ° C), and to 104 to 115 ° C for polyethylene terephthalate (melting point 246 to 252 ° C). The stretching speed is preferably set to 20 to 350 m / min.

Examples of the stretching method include longitudinal stretching using a difference in peripheral speed between roll groups, transverse stretching using a tenter oven, rolling, and simultaneous biaxial stretching using a combination of a tenter oven and a linear motor. The stretching ratio is not particularly limited, and is appropriately determined in consideration of the characteristics of the thermoplastic resin used. For example, when using a propylene homopolymer or a copolymer thereof as a thermoplastic resin, when stretched in one direction, it is about 1.2 to 12 times, preferably 2 to 10 times, and in the case of biaxial stretching, Is 1.5 to 60 times, preferably 10 to 50 times in area magnification. When using other thermoplastic resins, when stretched in one direction, it is 1.2 to 10 times, preferably 2 to 5 times, and in the case of biaxial stretching, the area ratio is 1.5 to 20 times, preferably Is 4 to 12 times.

When a thermoplastic resin containing an inorganic fine powder or an organic fine powder is stretched, a stretched porous resin film having fine pores therein can be obtained. At this time,
It is preferable that the porosity calculated by the following equation is in the range of 5 to 60%.

(Equation 1) ρ0: true density of resin film before stretching ρ1: density of resin film after stretching

The physical properties of the stretched thermoplastic resin film are preferably a density of 0.650 to 1.20 g / cm ³ , an opacity of 75% or more, and a Beck smoothness of 50 to 25,000 seconds. . If a porous resin stretched film having pores formed by stretching in this manner is used as a support,
An ink receiving sheet that more effectively achieves the desired effects of the present invention can be formed. Although not wishing to be bound by any theory, if such a porous resin stretched film is used, the pores can serve as a cushion to maintain an appropriate level of adhesion between the thermal head and the ink receiving sheet. Therefore, it is considered that an extremely high-quality image can be formed.

[Layer Structure] The support of the ink-receiving sheet of the present invention may be composed of a single layer or a multilayer. For example, a single-layer support made of a polyolefin-based resin film,
A resin film comprising a resin composition containing 40 to 99.5% by weight of a polyolefin-based resin and 60 to 0.5% by weight of an inorganic fine powder is heated at a temperature lower than the melting point of the polyolefin-based resin (preferably 3 to 60C lower). At a temperature) and uniaxially or biaxially. Further, the support having a multilayer structure is stretched in the longitudinal direction at a temperature lower than the melting point of the polyolefin resin (preferably at a temperature lower by 3 to 60 ° C.), and at least one surface of the stretched film has a polyolefin resin weight of 25 to 100% by weight. % And a resin film containing a resin composition containing 75 to 0% by weight of inorganic fine powder. The surface layer to be laminated on the stretched film is
The resin layer may not be stretched.

As particularly preferred supports, calcined clay,
By uniaxially stretching a polyolefin resin film containing 8 to 65% by weight of an inorganic fine powder such as calcium carbonate, diatomaceous earth, barium sulfate, silica, titanium oxide and talc, the film is centered on the inorganic fine powder. A large number of cracks are formed to form a translucent or opaque film.
A film obtained by laminating a resin composition of about 65% by weight and then stretching this laminated film in a direction perpendicular to the uniaxial stretching direction can be mentioned. Specifically, Japanese Patent Publication No. 46-40794, Japanese Patent Publication No. 1-6041
No. 1, Japanese Patent Publication No. 2-44976, and the like, a synthetic paper as a laminate having a polyolefin resin film layer formed thereon can be used. The thickness of the support used in the present invention is usually in the range of 20 to 350 μm, preferably 35 to 300 μm.

Ink receiving layer The ink receiving layer contains a binder (a), pigment particles (b) and a fluorine-based water and oil repellent (c).

[Binder (a)] The binder used in the ink receiving layer of the present invention may be a water-soluble resin or a water-insoluble resin. The water-soluble resin can be applied as an aqueous solution, and the water-insoluble resin can be applied as a solution, emulsion or latex to the ink receiving layer of the present invention. As the water-soluble resin, for example, oxidized starch, etherified starch, methoxycellulose, carboxymethylcellulose, hydroxyethylcellulose, casein, gelatin, soybean protein, polyvinylhydrin, polyacrylamide, vinyl alcohol, polyacrylic acid and the like can be used. . As the water-insoluble resin, for example, urethane resin, terpene resin, petroleum resin, ethylene-
Vinyl acetate copolymer resin, vinyl chloride resin, vinyl chloride
Vinyl acetate copolymer, vinylidene chloride resin, vinyl chloride / vinylidene chloride copolymer, acrylate copolymer resin, methacrylate copolymer resin, butyral resin, silicone resin, polyester resin, nitrocellulose resin, styrene / acrylic copolymer Polymer resin, styrene
Butadiene copolymer resin and the like can be used.

One of these binders may be used alone, or two or more of them may be used in combination. Among these, preferred binders are acrylate copolymer resins, urethane resins, ethylene-
It is a vinyl acetate copolymer resin. The proportion of the binder in the ink receiving layer is 20 to 70% by weight, preferably 25 to 60%.
% By weight. If the binder component is less than 20% by weight,
Coating adhesion strength tends to decrease. 70% by weight
When the ratio is more than, the adhesion of the ink is reduced, the ink is missing, and the dot reproducibility is reduced, so that a clear image tends not to be obtained.

[Pigment Particles (b)] The pigment particles used in the ink receiving layer in the present invention may be inorganic fine powders or organic fine powders, and known ones can be used. When inorganic fine powder is used, for example, calcium carbonate, calcined clay, silica, diatomaceous earth, talc, titanium oxide, barium sulfate, alumina, zeolite and the like can be used. When using organic fine powder, for example, ethylene resin, propylene resin, styrene resin, acrylic resin, epoxy resin, melamine resin,
Phenol resins, styrene / acrylic copolymers, styrene / butadiene copolymers, powders of starch and cellulose, beads, hollow particles and the like can be used.
The particle size of the pigment particles is preferably 0.01 to 50 μm, more preferably 0.01 to 5 μm.

In order to obtain a clear image with good dot reproducibility, it is preferable to use silica alone or in combination with other pigment particles among these pigment particles.
As the silica, colloidal silica having an average particle diameter of 0.03 to 2 μm, an average particle diameter of 2 to 50 μm, and an average pore diameter of 8
Porous silica having a pore volume of about 0 to 500 ° and a pore volume of about 0.8 to 2.5 cc / g can be used. When silica is used as the pigment particles, the content is 30 to 30% of the ink receiving layer.
It is preferably 80% by weight, more preferably 40 to 75% by weight. If the content of silica is less than 30% by weight, the adhesion of the ink tends to be reduced, the ink may be missing, the dot reproducibility may be reduced, and a clear image may not be obtained. If the silica content exceeds 80% by weight, the adhesion strength of the coating film tends to decrease.

[Fluorine Water / Oil Repellent (c)] In the present invention, the fluorine water / oil repellent used in the ink receiving layer is
Any material can be used as long as it imparts water and oil repellency, and a known material can be used. A representative example is an organic compound containing a fluoroalkyl group. A fluoroalkyl group is one of the hydrogen atoms of an alkyl group.
At least one is a group substituted by fluorine, and an alkyl group having about 1 to 20 carbon atoms is generally used. In order to obtain a sufficient water / oil repellency, it is more preferable that the alkyl group is a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. Specific examples of such a fluorine-based water / oil repellent include those described in the following 1) to 5).

1) A polymer of a fluorine-containing ethylenically unsaturated monomer containing a fluoroalkyl group, or a copolymer of the fluorine-containing ethylenically unsaturated monomer with a monomer copolymerizable therewith. Examples of the fluorine-containing ethylenically unsaturated monomer include the following.

Embedded image

Examples of monomers copolymerizable with the fluorine-containing ethylenically unsaturated monomer include olefins, carboxylic acid vinyl esters, aralkyl vinyl ethers, alkyl vinyl ethers, cycloalkyl vinyl ethers, (meth) acrylic acid Esters and the like, and specific examples thereof include ethylene, propylene, butylene,
Butadiene, isoprene, chloroprene, vinyl chloride,
Vinylidene chloride, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl butyl benzoate, vinyl cyclohexane carboxylate, Acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylamide, N-methanol (meth) acryl Amide, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether,
Butyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether, benzyl vinyl ether and phenyl vinyl ether are particularly typical.
These monomers are used alone or as a mixture.

2) A fluoroalkyl group-containing phosphate obtained by reacting a fluoroalkyl group-containing alcohol with a phosphoric acid derivative, and an ammonium salt or an amine salt of the fluoroalkyl group-containing phosphate. Examples of the fluoroalkyl group-containing alcohol used in this case include those described below. These may be used alone or in combination with two or more. You may.

[0036]

Embedded image C ₉ F ₁₉ CH ₂ CH ₂ OH C ₇ F ₁₅ CH ₂ CH ₂ CH ₂ CH ₂ OH HOCH ₂ C [CH ₂ S (CF ₂ ) ₇ CF ₃ ] ₂ CH ₂ OH HOCH ₂ C [CH _{2 S (CF 2) 5 CF} 3] 2 CH 2 OH CF 3 (CF 2) 7 SO 2 N (C 2 H 5) CH 2 CH 2 OH CF 3 (CF 2) 6 SO 2 N (CH 2 CH 2 OH) ₂ CF ₃ (CF ₂ ) ₇ CON (CH ₃ ) CH ₂ CH ₂ OH CF ₃ (CF ₂ ) ₁₁ CONHCH ₂ CH ₂ OH

In the reaction between the fluoroalkyl group-containing alcohol and the phosphoric acid derivative, an alcohol having no fluoroalkyl group may coexist and react. Examples of such alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, 2- Ethylhexyl alcohol, n-decyl alcohol, n-dodecyl alcohol, n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, 2-hexyldecyl alcohol, heptylundecyl alcohol, oleyl alcohol, linoleyl alcohol and the like. Can be

Examples of the phosphoric acid derivative to be reacted include phosphoric acid, phosphorus pentoxide, phosphorus oxyhalide, alkyl phosphite, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid and the like. The phosphoric acid ester containing a fluoroalkyl group, which is a reaction product, can be converted into an ammonium salt or an amine salt according to a commonly used method.
Examples of the amine used for forming the amine salt include the following.

Embedded image NH ₂ CH ₂ OH NH (CH ₂ CH ₂ OH) ₂ N (CH ₂ CH ₂ OH) ₃ N (CH ₂ OH) (CH ₂ CH ₂ OH) ₂ NCH ₃ (CH ₂ OH) ₂

3) Polyester obtained by reacting an alcohol optionally having a fluoroalkyl group with a carboxylic acid optionally having a fluoroalkyl group (provided that at least one of an alcohol or a carboxylic acid as a reactant) is used. Has a fluoroalkyl group). The alcohol having a fluoroalkyl group is monovalent or polyvalent, and examples thereof include the compounds exemplified in the above [Chemical Formula 2]. Examples of the alcohol having no fluoroalkyl group include:
Examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butylene glycol, methylpentanediol, and trimethylolpropane.

The carboxylic acid having a fluoroalkyl group is monovalent or polyvalent, and examples thereof include the following compounds.

Embedded image Examples of carboxylic acids having no fluoroalkyl group include C ₇ F ₁₅ COOH C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOH C ₆ F ₁₃ CH ₂ CH ₂ CH (COOH) ₂ , Succinic acid, glutaric acid, adipic acid, sebacic acid,
Examples include terephthalic acid, maleic acid, and trimellitic acid tetrahydrophthalic acid. These alcohols which may have a fluoroalkyl group and carboxylic acids which may have a fluoroalkyl group may each be used alone in the reaction by selecting only one kind or in combination of two or more kinds. May be used for the reaction. Further, the alcohol and the carboxylic acid may be reacted by combining those having a fluoroalkyl group and those having no fluoroalkyl group. However, it is necessary that a fluoroalkyl group be present in either the alcohol or the carboxylic acid to be reacted.

4) A polymer of a fluoroalkyl group-containing epoxy compound and a polyether obtained by reacting a fluoroalkyl group-containing epoxy compound with an epoxy compound having no fluoroalkyl group. Examples of the fluoroalkyl group-containing epoxy compound include the following.

Embedded image

The fluoroalkyl group-containing epoxy compound may be a homopolymer by selecting and polymerizing only one kind, or a copolymer by combining and polymerizing two or more kinds. Examples of the epoxy compound having no fluoroalkyl group include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, epichlorohydrin and the like. Only one of these epoxy compounds having no fluoroalkyl group may be selected and used alone, or two or more may be used in combination.

5) Polyurethanes of the fluoroalkyl group-containing polyesters and / or fluoroalkyl group-containing polyethers described in 3) and 4) above and isocyanates.
Isocyanates are monovalent or polyvalent, such as tetramethylene diisocyanate, phenyl isocyanate,
Tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate and the like can be used. As such a fluorine-based water / oil repellent, Decgard F-90N (manufactured by Dainippon Ink Co., Ltd.), Asahiguard AG-530 (manufactured by Asahi Glass Co., Ltd.), Modispar F-220 (manufactured by Nippon Oil & Fats) and the like are commercially available. ing.

[Formation of Ink Receiving Layer] Pigment particles are dispersed using an appropriate dispersing machine such as a Cores dissolver, a detriter, a sand grinder or the like, and the dispersed pigment particles are mixed with a binder solution or a binder emulsion and a fluorine-based water / oil repellent. A mixed solution for forming the ink receiving layer can be prepared by mixing a solution or a fluorine-based water / oil repellent emulsion. At this time, if necessary, auxiliary chemicals such as an antifoaming agent, a conductive agent, a dispersant, a thickener, a lubricant, and a wetting agent may be added. The proportion of the fluorine-based water and oil repellent in the ink receiving layer is
0.1 to 30% by weight is preferred, and more preferably 1 to 2% by weight.
5% by weight.

When the content of the fluorine-based water / oil repellent in the ink receiving layer is less than 0.1% by weight, a sufficient effect cannot be obtained, and in a high-temperature environment, there is a tendency that stain on a blank portion due to abnormal transfer occurs. . On the other hand, if it exceeds 30% by weight, the adhesion of the ink tends to decrease, causing the ink to escape, the dot reproducibility to decrease, and a clear image tends not to be obtained. To form an ink receiving layer on a support, a Meyer bar method,
What is necessary is just to apply by a usual coating method such as a gravure roll method, a reverse roll method, a blade method, a knife method, an air knife method, a slit die method, a gate roll method and the like, and to dry and solidify.

Generally, in order to sufficiently exhibit the function of the ink receiving layer, the coating amount of the coating agent should be 0.1% after drying and solidification.
It is preferably あ る 20 g / m ² . Coating amount is 0.1
If it is less than g / m ² , the effect of the ink receiving layer is not exerted, and the dot reproducibility tends to decrease. Conversely, if it exceeds 20 g / m ² , it tends to be costly and not practical.

[0047]

EXAMPLES The present invention will be described more specifically with reference to Production Examples, Examples, Comparative Examples and Test Examples. The materials, usage amounts, ratios, operations, and the like shown below can be appropriately changed without departing from the spirit of the present invention. Therefore,
The scope of the present invention is not limited to the following specific examples. In addition,% described below is% by weight unless otherwise specified. The materials used are summarized in Table 1.

[0048]

[Table 1]

(Production Example 1) The production method of the support a used in Examples and Comparative Examples will be specifically described. Propylene homopolymer 80 with a melt flow rate of 0.8 g / 10 min.
% By weight, 4% by weight of high density polyethylene and particle size 1.
Composition (A) was prepared by mixing 16% by weight of 5 μm calcium carbonate. The composition (A) was kneaded with an extruder set at 270 ° C., extruded into a sheet, and cooled by a cooling device to obtain a non-stretched sheet.
The sheet was reheated to 155 ° C. and stretched 5 times in the machine direction.

A composition (B) was prepared by mixing 54% by weight of a propylene homopolymer having a melt flow rate of 4.0 g / 10 minutes and 46% by weight of calcium carbonate having a particle size of 1.5 μm. This composition (B) was kneaded with an extruder set at 270 ° C., and extruded into a sheet to prepare 5
The film was laminated on both sides of the double-stretched film to obtain a laminated film having a three-layer structure. Next, this three-layer laminated film was
After cooling to about 160 ° C., the film was heated again to about 160 ° C. and stretched 7.5 times in the transverse direction using a tenter. After cooling to 60 ° C and slitting the ears, a thickness of 120μ
m / three-layer synthetic paper (B / A / B = 20/80)
/ 20 μm). The porosity of this synthetic paper is 15%.
The Beck smoothness of the layer was 300 seconds.

(Production Example 2) A method for producing the support b used in the examples will be specifically described. Melt flow rate
80% by weight of polypropylene at 2 g / 10 min.
15% by weight of 5 μm calcium carbonate and particle size 0.2 μm
5% of titanium oxide was mixed. After kneading the composition with an extruder set at 270 ° C., extruding it into a sheet,
It was cooled by a cooling device to obtain an unstretched film having a thickness of 100 μm. The Beck smoothness of this unstretched film is 500
Seconds.

(Examples and Comparative Examples) Using a predetermined amount of the materials shown in Table 2, eight types of melt heat transfer type ink receiving sheets were produced according to the following procedures (Examples 1 to 5).
5 and Comparative Examples 1 to 3). A coating liquid for forming an ink receiving layer was prepared by mixing pigment particles, a binder emulsion, a fluorine-based water- and oil-repellent emulsion and water. This coating liquid was coated on a support so that the coating amount after drying was 5 g / m ² , and dried and solidified to form a receiving layer, thereby obtaining a melt heat transfer type ink receiving sheet.

(Test Example) Each of the produced heat transfer type ink receiving sheets was evaluated by the method described below. (1) Dot reproducibility A melt thermal transfer type ink receiving sheet was placed in a thermostatic chamber (temperature 20 ° C,
After storage at 65% relative humidity for 2 hours, a thermal transfer color printer (trade name "MD-10", manufactured by Alps Electric Co., Ltd.)
00 "), an image composed of cyan, magenta and yellow was recorded by fusion thermal transfer recording. The dots transferred from the ink ribbon to the ink receiving layer were observed with an optical microscope, and evaluated according to the following three grades. ：: good △: normal ×: bad

(2) Image Quality The melt heat transfer type ink receiving sheet is placed in a constant temperature room (temperature: 20 ° C.,
After storage at 65% relative humidity for 2 hours, a thermal transfer color printer (trade name "MD-10", manufactured by Alps Electric Co., Ltd.)
00 "), an image composed of cyan, magenta and yellow was recorded by fusion thermal transfer recording. This recorded image was visually observed and evaluated on the following four levels. ◎: Good ○: Somewhat good △: Normal ×: Poor

(3) Smearing of white paper part in high-temperature environment
After storing at 50% relative humidity for 2 hours, an image composed of cyan, magenta, and yellow was melt-transferred and recorded by a thermal transfer color printer (trade name “MD-1000”, manufactured by Alps Electric Co., Ltd.) under the same conditions. The ink transfer state of the blank portion of the recorded image was visually observed and observed with an optical microscope, and evaluated in the following three grades. ○: No transfer of ink △: Transfer can be confirmed only with an optical microscope ×: Ink transfer can be confirmed visually

(4) Adhesion strength of coating film The heat transfer type ink receiving sheet was placed in a thermostatic chamber (temperature 20).
After storage at 12 ° C. and a relative humidity of 65% for 12 hours, an adhesive tape (trade name “Cellotape” manufactured by Nichiban Co., Ltd.) was adhered to the surface of the receiving layer, and the adhesive tape was peeled off from the ink receiving sheet by hand. The ink receiving sheet after peeling was visually observed and evaluated according to the following three grades. ：: The ink receiving layer was not peeled at all. Δ: Slightly peeled. ×: Most of the ink was peeled.

Table 2 summarizes the results of these tests.

[Table 2]

The results in Table 2 show that the test results of the ink receiving sheets of the present invention (Examples 1 to 5) are excellent. In particular, the melt heat transfer type ink receiving sheets of Examples 1 to 4 are excellent in all of dot reproducibility, image quality, stain on a blank portion in a high temperature environment, and coating film adhesion strength. In contrast, a heat transfer ink receiving sheet not using a fluorine-based water / oil repellent (Comparative Example 1) and a heat transfer ink receiving sheet not using the essential components of the present invention (Comparative Examples 2 and 3) Are inferior in characteristics to the present invention.

[0059]

According to the present invention, a color image having good dot reproducibility and clear gradation can be transferred to the ink-receiving sheet of the present invention. Further, in the melt-heat transfer type ink receiving sheet of the present invention, the white paper portion is not stained due to the abnormal transfer phenomenon of the ink in a high temperature environment. Further, the melt heat transfer type ink receiving sheet of the present invention has high adhesion between the ink receiving layer and the support. The melt thermal transfer type ink receiving sheet of the present invention having these excellent properties can be effectively used for a thermal melt transfer type print.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiichiro Iida 23rd Towada, Kasu-gun, Kashima-gun, Ibaraki Pref. CA46 4D075 AE03 CA34 CA35 CA43 DA04 DB18 DC27 EA02 EB16 EB52 EB56 EC03 4F100 AA04B AA04H AA20B AA20H AH01B AH01H AK01A AK07 AK17B AK17H AK22 AK25 AK42 AK51 J06B13A00BBABJA13B00

Claims (7)

[Claims] 1. A melt heat transfer type ink receiving sheet having an ink receiving layer containing a binder and pigment particles provided on a support made of a thermoplastic resin film, wherein the ink receiving layer contains a fluorine-based water / oil repellent. A fusion heat transfer type ink receiving sheet. 2. The melt heat transfer type ink receiving sheet according to claim 1, wherein the content of the fluorine-based water / oil repellent is 0.1 to 30% by weight based on the total weight of the ink receiving layer. 3. The melt heat transfer type ink receiving sheet according to claim 1, wherein the fluorine-based water / oil repellent is a resin having a fluoroalkyl group or a phosphoric acid compound having a fluoroalkyl group. 4. The ink-receiving sheet according to claim 3, wherein the fluoroalkyl group is a perfluoroalkyl group. 5. The fluoroalkyl group has a carbon number of 1 to 5.
5. The ink-receiving sheet according to claim 3, wherein the number is 20. 6. 6. The ink-receiving sheet according to claim 1, wherein the pigment particles are silica particles. 7. The ink-receiving sheet according to claim 1, wherein the thermoplastic resin film comprises a stretched porous resin film.