JPS63153189A - Thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To provide a thermal transfer recording medium capable of forming images with high transferring sensitivity even on a low-smoothness surface and with low energy, by incorporating a polymer of a specified compound and a polyoxyethylene compound in combination into a coloring material layer, in a thermal transfer recording medium having a coloring material layer comprising a heat-fusible substance and a coloring material on a base. CONSTITUTION:A coloring material layer comprises a copolymer obtained from ethylene, an acrylic acid derivative of formula 1 (wherein R<1> is hydrogen or methyl, and R<2> is a 1-8C straight chain or branched alkyl) and maleic anhydride, and a polyoxyethylene compound. A thermal transfer recording medium having the coloring material layer is capable of further suppressing fogging and of transferring high-resolution images with high transferring sensitivity, low energy and favorable fixability, not only on a smooth-surfaced ordinary paper but also on the surface of low-smoothness paper. In addition, the medium is capable of alleviating a load on a printer through reducing a take-up torque.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thermal transfer recording medium, and more specifically, the present invention relates to a thermal transfer recording medium, which has high transfer sensitivity, can be printed with low energy, and can be printed on a recording sheet such as low-smooth paper. The present invention relates to a thermal transfer recording medium that can suppress the occurrence of background smear (fog), has excellent fixing properties to a recording sheet, and provides a dye transfer image with high resolution.

[Prior art and its problems] Thermal transfer recording media have traditionally been used as recording media for transferring and forming images on recording sheets such as plain paper using thermal printers, thermal facsimiles, etc. There is.

This thermal transfer recording medium has at least one coloring material layer on a support. As this coloring material layer, a layer containing a coloring agent made of a dye such as a pigment and a heat-melting substance which is a low melting point substance such as a wax or the like is known.

In addition, films with excellent surface smoothness and dimensional stability are used as the support in order to obtain good reproducibility of the dye transfer image obtained from the color material layer coated on the support. There is.

Regarding conventional heat-sensitive transfer recording media of this type, various improvements and proposals have been made so that images can be clearly transferred with good fixability onto recording sheets with smooth surfaces.

However, at present, there has been a strong demand for a thermal transfer recording medium that can transfer images with good quality even on so-called low-smooth surfaces whose surfaces are not necessarily smooth.

This is because, for example, when making a test print of a document using a thermal printer with a thermal head, there is no need to use expensive smooth paper, but rather it is desirable to use an inexpensive recording sheet with a low smooth surface. In many cases, the back side of plain paper (this front side is usually rough) is used, either after an image has been transferred to the front side or when it is no longer needed.

In addition, in order to prevent document forgery or to highlight the characteristics of the destination of the document, it is therefore necessary to transfer the printed image onto a recording sheet having a low smooth surface at α. Moreover, it is not enough to simply print or transfer an image on a low-smooth surface, and it is possible to print or transfer images with high transfer sensitivity, low energy, no fogging, good fixing properties, and high resolution. There has been an increasing need to form an image using a thermal transfer recording medium on a recording sheet with a specially roughened surface.

Despite these demands, various inventions and ideas regarding the ink layer in thermal transfer recording media are mostly for plain paper with a smooth surface, and for low-smooth paper, as mentioned above, the number of inventions and ideas has increased. It is no exaggeration to say that there are almost no thermal transfer recording media equipped with an ink layer that satisfies all of these demands.

[Objective of the Invention] An object of the present invention is to provide a thermal transfer recording medium that is capable of forming an image with high transfer sensitivity and low energy consumption not only on a smooth surface but also on a low smooth surface. It is.

Another object of the present invention is to form print images with good fixability, high resolution, and high print quality, while further suppressing the occurrence of fog not only on smooth surfaces but also on low smooth surfaces. It is an object of the present invention to provide a thermal transfer recording medium that can be used.

Still another object of the present invention is to provide a thermal transfer recording medium that can further reduce the load on the printer, such as winding torque.

[Means for achieving the above object] In order to achieve the above object, as a result of intensive research by this inventor, a thermal transfer recording medium having a coloring material layer containing a heat-fusible substance and a coloring material on a support is provided. The inventors have discovered that the above object can be achieved by incorporating a particular combination of a copolymer of a specific compound and a polyoxyethylene compound in the color material layer, and have thus arrived at the present invention.

That is, the gist of the present invention to achieve the above object is to provide a heat-sensitive transfer recording medium in which a coloring material layer containing a heat-fusible substance and a coloring material is formed on a support.
;'1Right IJ- or Exin and 斤古R dish (Tatashi, in the formula, R1 represents a hydrogen atom or a methyl group, and R2 has a carbon number of 1 to 8, a linear or This is a heat-sensitive transfer recording medium characterized by containing a copolymer obtained from an acrylic acid derivative (representing a branched alkyl group) and maleic anhydride, and a polyoxyethylene compound.

11 copolymer 11 The copolymer can be represented by the following second formula.

...(2) In the second formula, R1 represents a hydrogen atom or a methyl group.

R2 is a linear or branched alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, n-protyl group, isopropyl group, butyl group, isobutyl group, t-butyl group. Base.

Examples include pentyl group, hexyl group, heptyl group, and octyl group.

The above a, b and C represent the copolymerization ratio, among which a,
If the sum of b and C is 100%, then a is 50~
90%, preferably 79-62%, where the percentage is 10
-50%, preferably 20-35%, and C is desirably 0.5-15%, preferably 0.5-10%.

Specifically, examples of the copolymer represented by the second formula include ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-propyl acrylate-maleic anhydride copolymer, and ethylene-n-maleic anhydride copolymer. Butyl acrylate-maleic anhydride copolymer, ethylene-isobutyl acrylate-maleic anhydride copolymer, ethylene-pentyl acrylate-maleic anhydride copolymer.

Ethylene-hexyl acrylate-maleic anhydride copolymer, ethylene-octyl-acrylate-maleic anhydride copolymer, etc., ethylene-ethyl methacrylate-maleic anhydride copolymer, ethylene-propyl methacrylate-maleic anhydride copolymer, etc. Polymer, ethylene-n-butyl methacrylate-maleic anhydride copolymer, ethylene-isobutyl methacrylate-maleic anhydride copolymer, ethylene-pentyl methacrylate-maleic anhydride copolymer, ethylene-hexyl methacrylate Examples include maleic anhydride copolymer, ethylene-octyl-methacrylate-maleic anhydride copolymer, and the like.

Furthermore, a copolymer in which a part of the maleic anhydride in the copolymer is hydrolyzed to form one maleic acid monomer unit, an alkyl acrylate having ethylene and an alkyl group having 1 to 8 carbon atoms, and/or Alternatively, a copolymer obtained by copolymerizing alkyl methacrylate and maleic acid can also be included in the copolymer in the present invention.

In short, this copolymer may be obtained by any production method as long as it can be produced from ethylene, an acrylic acid derivative, and maleic anhydride. and a binary copolymer obtained by first copolymerizing any two monomers of ethylene, an acrylic acid derivative, and maleic anhydride, and any of the remaining seven. A copolymer obtained by copolymerizing with Zimmer can also be included in the copolymer in this invention. Furthermore, the copolymer in this invention may be a block copolymer or a random copolymer.

However, the preferred copolymer in the present invention has a Vicat softening point (according to Hescho 11 D 1525) of 30
°C or higher and 200 °C or lower, and elongation at break (JI
SK6301) is 200% or more, and the breaking strength (
JIS 6:1O1) is: 10kg/crn' or more. If it has such properties, - among the various copolymers mentioned above, A1 O': t & 61 1 heart 1 I A pattern 919 1 ÷ tsu^ (Lh book, and The above-mentioned various copolymers may be used alone or in combination of two or more. Furthermore, this copolymer may be blended with other known resins. May be used.

Among these various copolymers, the softening point (ring and ball method)
is preferably in the range of 200°C or less, particularly in the range of 30 to 200°C. Furthermore, the melt flow index (M
l) is Ig/10 minutes or more, preferably 1 to 40
It is desirable to use a copolymer in a range of 0 g/10 min, particularly preferably 1 to 50 g/10 min, and even more preferably 1.5 to 40 g/10 min.

Such copolymers include, for example, rBONDINE HX-8140J [manufactured by Jumatsu CDF C-7n, MI=20 g/10 min], rBONDINE AX-8040J [manufactured by Jumatsu CDF $1, MI depth 4.5 g 710 min].

rBOIIDfNE 1 (X-8020J [manufactured by Resident CDF ■, MI = 10 g / 10 minutes], rBONDINE llX-8060J [manufactured by Resident CD L 7 n, MI = 10 g / 10 minutes], rRONDINE riX-829D J [manufactured by Resident CDF 11 , MI = 65 g / 10 minutes], r BONDINE HX-8210 [Manufactured by Resident C.D.F. Co., Ltd., MI = 200 g 710 minutes,
r NUC-ACE GA-003” [Nippon Unicar-
manufactured by Nippon Unicar, MI=1.7 g/10 min], rNUc-ACE GA-004J [Nippon Unicar
[manufactured by Nippon Unicar, MI=1.8 g/10 min], rNUc-AC:E GA-201J [manufactured by Nippon Unicar, MI=5.0 g/10 min], r NUC-ACE GA-:l Old' [Japan Unicar
(MI=4.0 g/10 min]).

11 Polyoxyethylene Compound -- Next, the polyoxyethylene compound has the following formula % formula % (3) in the molecule [where, in the third formula, n is an integer of 2 or more, Preferably it is an integer of 4 to 50. ] There is no particular restriction as long as the compound has the moiety shown. However, polyethylene compounds.

Derivatives are preferable to those in which both ends are -OH.For example, one or two alcoholic hydroxyl groups of polyethylene glycol can be reacted with various organic compounds to form ether bonds, esters, etc. Starting with the combination.

Examples include derivatives with bonds with sulfur atoms or nitrogen atoms, urethane bonds, and various other bond forms. Note that this bonding form is not particularly essential to this invention;
There are no particular limitations.

Rather, proper derivation is performed based on molecular design, such as molecular weight, miscibility with heat-melting substances, and number of polar groups, in order to achieve blocking performance, prevention of bleed-out, cohesive force, and viscosity. Should be. Preferred derivations include ether derivations. This is because a coloring material layer containing this ether-derived polyoxyethylene compound generally has excellent blocking performance.

In any case, the polyoxyethylene compound that can be used in the present invention should be in a solid or semi-solid state at a melting point or softening point of 30 to +20°C, especially 40 to 100°C. Or preferable.

Furthermore, when the molecule has a plurality of polyoxyethylene chains represented by the third formula, the total molecular weight of the polyoxyethylene chain portions represented by the third formula may have a great influence on the effects of the present invention.

The preferred molecular weight of the polyoxyethylene chain moiety represented by the third formula differs depending on the molecular weight of the entire compound or the structure or molecular weight of the compound other than the polyoxyethylene moiety, but in many cases, the molecular weight of the polyoxyethylene chain moiety is Total molecular weight: 40 to zooo
o, particularly preferably 40 to 2000.

Examples of polyoxyethylene compounds having such molecular weights include the following various compounds.

(1) Mono- or diester derivatives of polyethylene glycol Those belonging to this range include, for example, those having a carbon number of 8 to 50
For example, (a) linear monoenoic acids, (b) polyenoic acids such as dienoic, trienoic and tetraenoic acids, (C) synthetic and natural fatty acids, (d ) secondary fatty acids and tertiary fatty acids, (e) straight chain fatty acids and branched fatty acids, (f) timer acids, (g) polybasic acids such as dibasic acids and acid-base acids, (h) oxycarboxylic acids, (i ) fatty acid chloride,
Examples include (j) fatty acid anhydride, and (k) other compounds containing one or more carboxyl groups in the molecule, and polyethylene glycol mono or shiflicol.

Among these, preferred are those having 8 to 30 carbon atoms, such as caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, valmitic acid, margaric acid, stearic acid, octacosanoic acid, and melisic acid.
Examples include mono- or diesters of polyethylene glycol esters with monocarboxylic acids such as nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, fradisic acid, tricosanoic acid, lignoceric acid, pentacosonic acid, etc. .

Compared to polyethylene monoester, polyethylene glycol exhibits better dispersion characteristics in the colorant layer and material, and also has the excellent effect of not deteriorating the dispersibility of the colorant. It is excellent in that it can stably transfer a high-density printed image onto the surface of a recording sheet with low smoothness. Therefore, the polyethylene glycol diesters of the various fatty acids mentioned above can be pointed out as preferred polyoxyethylene compounds in the present invention.

In addition, in the case of a diester, the two polyoxyethylene chains bonded to the two carboxylic acids may have the same molecular weight or structure, or may have different molecular weights or structures.

Specific examples of the diester include polyethylene glycol distearate [PEG4000]
, polyethylene glycol dibehenate [PEG 14
000 ], polyethylene glycol civalmitate [PEG 600 ], polyethylene glycol dilaurate [PEG 10], and the like. In addition,[
The numbers in brackets indicate the average molecular weight of the polyoxyethylene chain.

(2) Alkyl of polyoxyethylene glycol,
Aryl alkyl, aryl or aryl monoether (one hydroxyl or etherified derivative of polyoxyethylene glycol) Those belonging to this category include, for example, the number of carbon atoms in the ether residue is 6 or more, preferably 18 Examples include alkyl and aralyl monoether derivatives having a molecular weight of 50 to 50. In addition, the alkyl group and the aralyl group may be linear or branched.

Specifically, for example, polyethylene glycol mono-
Examples include p-nonylphenyl ether, polyethylene glycol monobehenyl ether, and polyethylene glycol monooleyl ether.

Furthermore, in this invention, as a special case, the ether residue may be derived from an unsaturated hydrocarbon, a synthetic alcohol, an oxycarboxylic acid, a nitrogen-containing compound, and a sulfur-containing compound.

(v) An ether or ester derivative of the monoether derivative shown in (2) above, that is, one in which the remaining hydroxyl group in the monoether derivative of polyethylene glycol is ether-derived or ester-derived.

In this case, the ester derivative is as in the case (1) above,
In addition, the ether derivatives correspond to the case (2) above.

Specifically, polyethylene glycol mono-p-nonylphenyl ether monobehenate [PEG300]
, polyethylene glycol monostearyl ether monostearate [PEG 9000F], polyethylene glycol dibehenyl ether [PEG 600RO],
Examples include polyethylene glycol monooleyl ether monobehenyl ether [PEG 40001, etc.].

(4) Polyoxyethylene glycol ether derivatives of polyhydric alcohols The polyhydric alcohols include compounds having two or more alcoholic hydroxyl groups in the molecule, such as glycerin, propylene glycol, pentaerythritol, polypropylene glycol, sorbitan (l, 5-Sorbitan,
1,4-sorbitan, co-sorbitan, 6-sorbitan, isosorbite, etc.), mannitol, and poval having a molecular weight of 800 or less.

Furthermore, two or more sets of polyhydric alcohols may be bonded to each other by a polyoxyethylene chain or other molecular chain.

The polyoxyethylene glycol ether derivative described above is one in which polyoxyethylene glycol is ether bonded to one hydroxyl group of the polyhydric alcohol.
It may be an ether derivative (this is a polyoxyethylene glycol diether derivative) according to 2), or an ester derivative of the remaining hydroxyl group.

From another perspective, the polyoxyethylene glycol ether derivative described may have one or more polyoxyethylene chains in its molecule, and
The hydroxyl group at the end of the polyoxyethylene chain of this polyoxyethylene glycol ether derivative is
Or, according to (2), ester-derived or ether-derived is preferable.

Specific examples of the polyoxyethylene glycol ether derivatives shown below are shown below.

Polyoxyethylene monostearate of glycerin, di(polyoxyethylene monostearate) of glycerin, polyoxyethylene monobehenate of sorbitan monobehenate, polyoxyethylene ether of batyl alcohol, polyoxyethylene of propylene glycol monooleate Monooleate, block copolymer of polypropylene glycol and polyoxyethylene glycol, polyoxyethylene ether behenate of pentaerythritol distearyl ether, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of pentaerythritol, polyglycerin Polyoxyethylene ether of ester, ester of polyoxyethylene ether of batyl alcohol ester, polyoxyethylene ether of mannitol ester, (5) polyoxyethylene derivatives of molecules having two atoms or nitrogen atoms, Specific examples of these include alkylthiopolyoxyethylene, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, and the like.

(6) Polyoxyethylene derivatives of polymers or copolymers Specific examples of those belonging to this category include alkylaryl formaldehyde condensation polyoxyethylene ether, copolymer polyoxyethylene ether ester,
Examples include polyoxyethylene ether derivatives of α-olefin maleic anhydride copolymers.

(7) Solock polymer of synthetic polymer such as polyester or polyurethane and boxyethylene glycol (8) Compounds having anionic properties Examples of such compounds include carbon salt-resistant polyoxyethylene alkyl ether, polyoxyethylene aryl Ether carboxylate, polyoxyethylene fatty acid ester sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene aryl ether carboxylate, polyoxyethylene alkyl ether phosphate, polyoxyethylene aryl ether Examples include polyoxyethylene-containing anion activators such as phosphates, polyoxyethylene alkylamide phosphates, polyoxyethylene arylamide phosphates, and carboxylates of polyoxyethylene fatty acid esters.

(9) Compounds having cationic properties Examples of such compounds include alkyl polyoxyethylene ether ammonium salts, aryl polyoxyethylene ether ammonium salts, and polyoxyethylene hydroxy ammonium salts.

Although various polyoxyethylene compounds have been exemplified above,
Colorant layer set J& can be prepared by mixing such a polyoxyethylene compound with the copolymer, heat-fusible compound, and colorant according to the present invention.

1, depending on the type of polyoxyethylene compound, it may not be sufficiently dispersed in the colorant layer composition and may not be mixed. For example, if the polyoxyethylene chain is 1000 or more, If the molecular weight is too large, the miscibility of the polyoxyethylene compound with the copolymer, the heat-melting substance described below, etc. may be reduced.

However, although the reason is not necessarily clear, whether the polyoxyethylene compound is in a clearly dispersed state, a pseudo-mixed state, or a mixed state in the colorant layer composition, the present invention It can be effective.

- Coloring material layer 11 The coloring material layer in this invention contains a coloring material and a heat-fusible substance as in conventional heat-sensitive transfer recording media. Its major feature is that it contains Furthermore, when a specific adhesive resin is contained as a third component, the effects of the present invention can be enhanced.

As the adhesive resin as the third component, for example,
Rosins such as gum rosin, tall rosin, and wood rosin; Modified rosins obtained by modifying the above rosins by hydrogenation, disproportionation, dimerization, esterification, liming, and combinations thereof; terpene resins, hydrogenated modified terpenes, and terpenes Phenolic resins: natural resins such as dammar, copal and shellac; petroleum resins such as aliphatic, aromatic, copolymerized and cycloaliphatic and coumaron indene resins; oil-soluble phenols such as alkyl phenolic resins and modified phenolic resins Examples include resins, and xylene resins such as xylene resins and modified xylene resins.

Among these, rosin, modified rosin, terpene resin,
Natural resin systems such as hydrogenated modified terpenes and petroleum resins such as C5 and C9 systems are preferred.

Furthermore, among the various types mentioned above, the softening point is 60°C to 13°C.
Adhesive resins in the range of 8°C are preferred.

- Heat-melting substance - Examples of the heat-melting substance include: (1) Ester wax (natural ester wax such as carnauba wax and montan wax; Hoechst manufactured by Hoechst);
I#ax E, F, ni P, KPS, BJ, OP, OM
,
-6114, PETR0NABA manufactured by East W Vetrolite
-C:.

CARDI3314 and Hoechst's l1oechsL
Wax S, L and LP, etc.), ■Low molecular polyethylene wax (particularly with a molecular weight of 300 to 1000, manufactured by Toyo Vetrolite■ (7) POLYWAX 500
and 655), ■Paraffin wax (145.150,155°HN P-3, HN manufactured by Nippon Seiro ■
P-10, etc.), ■Micro wax (such as 0 stone micro wax 155, 180 manufactured by Nippon Oil ■, former IC-1080, III-MIG-20 manufactured by Nippon Seiro ■)
65゜Old-MIC-2095, +11-Steel Knee 1
070. Old-old G-1045, III-MIG, -20
45, etc., Toyo Vetrolite ■ STA W to X10
0, BE 5QUARE 175,185. VICTO
RY, ULTRAFLEX, etc. ■Others include higher fatty acids such as stearic acid, myristic acid, behenic acid, and margaric acid, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol,
Higher alcohols such as eicosa and nol, cetyl palmitate, myricyl valmitate, cetyl stearate,
Higher fatty acid esters such as myrcyl stearate and dodecyl stearate, vegetable waxes such as wood wax, auriculie wax, and nispar wax, animal waxes such as beeswax, insect wax, shellac wax, spermaceti wax, stearone, sorbitan monostearate, polyoxy Examples include ethylene monostearate. In addition to this, maleic anhydride and α
- Olefin polymer waxes consisting of copolymers with olefins such as ethylene, propylene or butene-1 can also be suitably used.

The various thermofusible substances exemplified above may be used alone or in combination of two or more.

Among these various heat-melting substances, ester wax, paraffin wax, olefin polymer wax, etc. are preferred, and carnauba wax, paraffin wax, polyethylene wax, etc. are particularly preferred.

11 Coloring agent 11 The coloring agent contained in the color material layer in this invention can be appropriately selected from conventionally known pigments, such as direct dyes, acid dyes, J! ! The dye may be appropriately selected from among base dyes, disperse dyes, oil-soluble dyes, and the like. The dye used in the coloring material layer in this invention may be any dye that can be transferred (migrated) and circulated together with the heat-fusible substance, and thus pigments can also be used in addition to the above.

Specifically, as the yellow pigment, for example, Kayalon Polyester Light Yellow 5G-3 (Nippon Gunpowder Product),
Oil Yellow 5-7 (white clay), Eisenspiron GR
Examples include H Special (Hodogaya Chemical v4 product).
Examples of red pigments include Diaceritone Fastlet I'l (Mitsubishi Kasei product), Tire Examples of blue pigments include Tolletto IIGF (a product of Sumima Kagaku Kogyo), Kayalon Polyester Pink RCL-E (a Japanese dog seasoning product), and Eisenspironlet GE 11 Special (a product of Hodogaya Chemical). , Diaceriton Fast Brilliant Flu R (
Mitsubishi Kasei product), Dianic Sprue EB-E (Mitsubishi Kasei product), Kayalon Polyester Blue B-3
F Conch (Japanese Gunpowder - product), Sumiplast Blue 3R
(Suminant Chemical Industry ■product), Sumiplast Blue G (Suminant Chemical Industry ■product), etc. Examples of yellow pigments include Hansa Yellow 3G (manufactured by Sumitomo Chemical Co., Ltd.) and Taldrazine Lake, and examples of red pigments include Brilliant Carmine FB-
Pure (Nanyo pigment ■ product), Flilliant Carmine 6
Examples of blue pigments include Cerulean Blue, Alizarin Lake, etc.
Examples of the black pigment include Sumikablin Tocyanine Blue GN-0 (manufactured by Sumika Kagaku Kogyo M) and phthalocyanine blue. Examples of the black pigment include carbon black and oil black.

- Additives 11 In the coloring material layer of this invention, various additives may be added in addition to the above-mentioned components as long as they do not impede the object of the invention.

Such additives include, for example, vegetable oils such as castor oil, linseed oil, olive oil, whale oil, etc. as fabric softeners.
Animal and mineral oils, such as, can be suitably used.

m - Combination of each component - 1. A combination of the above-mentioned copolymer, polyoxyethylene compound, heat-melting substance, coloring agent, and adhesive resin, which is the 3rd Q component, forming the coloring material layer in this invention. And, the percentage is not limited. Normally, for the total amount of color material layer,
The composition of the copolymer is 5 to 40%,
The blending amount of the polyoxyethylene compound is 0.5 to 20
% by weight, preferably from 1 to 10% by weight. Further, when the adhesive resin as the third component is blended, the proportion thereof is 0.5 to 20% by weight, preferably 3 to 15% by weight, based on the total amount of the coloring material layer. Regarding the heat-fusible substance, 5 to 90 parts, preferably 10 to 8 parts, per 100 parts by weight of the total amount of the coloring material layer (hereinafter, "parts by weight" is abbreviated as "parts").
The amount of the colorant is 5 to 40 parts, preferably 10 to 20 parts.

The above-mentioned copolymer, polyoxyethylene compound, heat-melting substance, coloring agent, adhesive resin as a third component, and various additives may be blended by conventionally known methods, for example. There is also a method of mixing each of the above components at the same time.

In order to obtain a colorant layer composition in which the components such as the copolymer and the polyoxyethylene compound are thoroughly mixed, the components are mixed using a disilver, mixer, sand grinder, ball mill, etc. It is better to use a suitable disperser. The particle size dispersed by these dispersers is IOpm
It is best to set it to the following.

The dispersion state can be easily examined by observing the coloring material composition excluding the coloring material in a hot melt state or in a coated state. Based on this observation, it can be determined that when a sea/island structure, cloudiness, liquid droplet (oil droplet) state, or phase separation state is formed, this is an immiscible state.

m-Support (substrate) - 1. The support used as a substrate for the thermal transfer recording medium according to the present invention preferably has heat-resistant strength and high dimensional stability and surface smoothness. Then, this support has heat resistance strength to the extent that it does not soften or plasticize when heated by a heat source such as a thermal head, and has mechanical strength and dimensional stability as a support,
It is desirable that the coloring material layer on the support has sufficient smoothness to exhibit a good transfer rate.

The smoothness was measured by a smoothness test using a Beck tester (
JKS P 8119) is preferably 100 seconds or more, and if it is 300 seconds or more, a printed image with better transfer rate and reproducibility can be obtained.

Materials for the support with the above-mentioned preferred properties include, for example, paper sheets such as plain paper, condenser paper, laminated paper, and coated paper, polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyimide, and polyamide. Suitable examples include sheets or films made of thermoplastic resin such as (nylon), composites of the above-mentioned paper sheets and the above-mentioned thermoplastic resin films or sheets, and metal sheets such as metal foil such as aluminum. It will be done.

The thickness of this support is usually about 604 m or less, particularly preferably 2 to 20 ILm, in order to obtain good thermal conductivity. In the thermal transfer recording medium according to the present invention, the structure of the back surface of the support may be arbitrary. That is,
on the back of the support.

A sticking layer may be applied if necessary.

m-Formation of a coloring material layer on the support - Since a technique suitable for forming a coloring material layer on the surface of the support is known in this type of technical field, the thermal transfer recording according to the present invention Regarding the medium, a coloring material layer can also be formed on the surface of the support using such a known technique.

For example, the colorant layer can be formed by hot-melt coating with the composition, or by solvent coating with a coating solution in which the composition is dissolved or dispersed in an appropriate solvent.
Can be formed.

As the coating method, for example, a reverse roll coater method, an extrusion coater method, a gravure coater method, a wire bar coater method, or any other arbitrary technique can be employed. In addition.

The thickness of the coloring material layer is usually 15 pm, preferably 1 to 9 pm.
-m.

The thermal transfer recording medium thus obtained has a breaking strength of 30 kg/cm' or more, particularly 45 kg/crrf.
Therefore, if the elongation at break is 2% or more, particularly 5% or more, clear printing can be achieved.

[Effects of the Invention] According to the present invention, in a heat-sensitive transfer recording medium in which a coloring material layer containing a heat-melting substance and a coloring agent is formed on the surface of a support, a special copolymer and a polyester are contained in this coloring material layer. Since it contains an oxyethylene compound, (1) it is not only suitable for plain paper with a smooth surface;
Even on low-smooth surfaces, ■Fog can be further suppressed, ■High transfer sensitivity, ■Moreover, low energy, good fixing properties, and ■High resolution images can be transferred. (2) It is possible to provide a thermal transfer recording medium that can reduce the winding torque and reduce the load on the printer side.

[Example] Examples are shown below, but the present invention is not limited to the following examples. In addition, "department" in the following is
It indicates "parts by weight."

(Example 1) 15% of carbon black, 4% by weight of polyoxyethylene compound such as polyethylene chestnut, coal monobehenyl ether (PEG n=10), 40% by weight of paraffin wax (melting point 68°C), polyethylene wax (melting point 64°C) 11% by weight, ethylene-acrylic acid derivative-maleic anhydride copolymer Bondine HX-8140 [manufactured by Tensei CDF ■] 15
A colorant layer composition having a composition of 15% by weight and Diakaruna 30 [manufactured by Mitsubishi Kasei ■] was applied to the surface of a 1.54m thick polyethylene terephthalate film support to a dry thickness of 5.071m. A thermal transfer recording medium sample was obtained.

This thermal transfer recording medium sample was printed at 400g/head and 600g/head on low smooth paper with a Beck smoothness of 10 seconds using a thermal printer (prototype a equipped with a thin film type line thermal head with a heating element density of 8 dots/mm). Printing was performed with a printing pressure of When I observed the stains other than the printed areas using a louver, I found that there was only background stains at all.

(Example 2) In Example 1, M I = 65 was used in place of the ethylene-Aphrylmi v derivative-maleic anhydride copolymer [Bontine HX-8140, manufactured by Jujutsu CDF ■].
Samples of thermal transfer recording media were obtained in the same manner, except that the same amount of ethylene-acrylic acid derivative-maleic anhydride copolymer [Bondine HX-8290; manufactured by Jumin CDF ■] of g/10 minutes was used.

Printing was performed on this thermal transfer recording medium sample at a printing pressure of 40og/head in the same manner as in the above example. When the stains other than the printed area were observed using a louver, there was no background stain at all.

(Example 3) In Example 1, M I = 200 was used instead of the ethylene-acrylic acid derivative-maleic anhydride copolymer [Bondine HX-8140, manufactured by Jujutsu CDF ■].
Samples of thermal transfer recording media were obtained in the same manner, except that the same amount of ethylene-acrylic acid derivative-maleic anhydride copolymer [Bondine HX-8210, manufactured by Jumin CDF ■] of g/10 minutes was used.

Printing was performed on this thermal transfer recording medium sample at a printing pressure of 400 g/head in the same manner as in the above example. When the stains other than the printed area were observed using a louver, there was no background stain at all.

(Example 4) Carbon black 15i%, polyethylene glycol distearate (M
w=400) 10% by weight, ester wax 8% by weight,
A coloring material layer composition having a composition of 45% by weight of paraffin, 10% by weight of terpene resin, and 12% by weight of Bondine HX-8140 [manufactured by Jujutsu CDF ■] as an ethylene-acrylic acid derivative-maleic anhydride copolymer,
A thermal transfer recording medium sample was obtained by coating the surface of a 3.54 m thick polyethylene terephthalate film support to a dry thickness of 5.0 gm.

Printing was carried out on this thermal transfer recording medium sample at a printing pressure of 40og/head in the same manner as in the above example. When I observed the stains other than the printed areas using a louver, I found that there was only background stains at all.

(Examples 5 to 13) 15% by weight of carbon black, 10% by weight of polyoxyethylene compounds of the types shown in Table 1, 8% by weight of ester wax, 45% by weight of paraffin, 10% by weight of terpene resin
, and ethylene-acrylic acid derivative-maleic anhydride copolymer Bondine HX-8040 [manufactured by Jujutsu CDF ■] A coloring material layer composition having a composition of 12% by weight: Supported by a 1.54 m thick polyethylene terephthalate film A thermal transfer recording medium sample was obtained by coating the surface of the body to a dry thickness of 5.0 JLm.

The nine types of thermal transfer recording media thus obtained were printed on low-smooth paper with a Bekk smoothness of 10 seconds using the same rotary thermal printer as used in Example 1.
A checkered pattern was printed using a printing pressure of OOg/head, and the print quality was observed and evaluated using a louver. The results are shown in Table 1. The symbols in Table 1 indicate the following evaluation details.

◎...The edges of the print are sharp.

○...The number 11 is slightly lower than the letter III, Soji.

X: Defects and blurring occur in printing.

Furthermore, for the thermal transfer recording medium samples according to Examples 5 and 6, the ink breaking elongation and ink breaking strength were
Measured according to ASTM D 638.

The results are shown in Table 2.

(Example 14) In Example 5, the amount of ester wax was changed to O
and the blending ratio of Bondine HX8040 is 20% by weight.
A thermal transfer recording medium sample was obtained in the same manner as in Example 6 except for the following.

The print quality of this thermal transfer recording medium was evaluated in the same manner as in the above example. The results are shown in Table 1.

Regarding this thermal transfer recording medium sample, the ink elongation at break and the ink break strength were measured in the same manner as in Examples 5 and 6 above.

The results are shown in Table 2.

(Example 15) In Example 5, the blending amount of ester wax was 1
A thermal transfer recording medium sample was obtained in the same manner as in Example 5 except that the blending ratio of Bondine HX 8040 was 3% by weight.

The print quality of this thermal transfer recording medium was evaluated in the same manner as in the above example. The results are shown in Table 1.

Regarding this thermal transfer recording medium sample, the ink elongation at break and the ink break strength were measured in the same manner as in Examples 5 and 6 above.

The results are shown in Table 2.

(Comparative Examples 1 to 3) Thermal transfer recording medium samples were obtained in the same manner as in Example 3, except that the compounds shown in Table 1 were blended instead of the polyoxyethylene compound. The print quality was evaluated. The results are shown in Table 1.

Table 2 As is clear from Tables 1 and 2, the thermal transfer recording medium samples according to the present invention are capable of high-quality printing without background smearing on low-smooth paper. I know what's coming.

Claims (1)

[Claims] (1) In a thermal transfer recording medium in which a coloring material layer containing a heat-fusible substance and a coloring material is formed on a support, the coloring material layer is made of ethylene and has the following formula ▲ Numerical formula, chemical formula, table, etc. (1) (In the formula, R^1 represents a hydrogen atom or a methyl group, and R^2 represents a linear or branched alkyl group having 1 to 8 carbon atoms.) A thermal transfer recording medium comprising a copolymer obtained from the acrylic acid derivative shown above and maleic anhydride, and a polyoxyethylene compound.