JPH03270978A - Thermal recording material - Google Patents

Abstract

PURPOSE:To enhance sticking aptitude, sensitivity and preservability and to obtain good printing surface gloss by providing a surface gloss layer containing at least one of a hydrophobic high-molecular compound and an alkyl fluoride modified silicone compound as a main component on a thermal color forming layer through an intermediate layer based on a water-soluble high-molecular compound. CONSTITUTION:A thermal color forming layer containing colorless or light- colored electron donating dye and an electron acceptive developer is provided on a support. Further, a surface gloss layer containing a hydrophobic high- molecular compound composed of a saturated polyester resin obtained by the polycondensation reaction of dimethyl terephthalate, isophthalic acid, ethylene glycol, neopentyl glycol and bisphenol A dihydroxyethyl ether and an alkyl fluoride modified silicone compound as main components is provided on the thermal color forming layer through an intermediate layer based on a water-soluble high-molecular compound.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a heat-sensitive recording material.

More specifically, the present invention relates to a heat-sensitive recording material that maintains excellent qualities in sticking suitability, sensitivity, and storage stability, and also has improved print surface gloss.

[Prior Art] Thermosensitive recording materials generally consist of a support such as paper, synthetic paper, or plastic film, in which a color-forming substance such as an electron-donating leuco dye and an organic acidic substance such as an electron-accepting phenolic compound are deposited on a support such as paper, synthetic paper, or plastic film. The color developing layer is provided with a heat-sensitive coloring layer containing a color developing substance as a main component, and a recorded image is obtained by reacting the layers with thermal energy. Heat-sensitive recording materials are used for computer output, facsimiles, automatic ticket vending machines,
It is widely used in printers for scientific measuring instruments, printers for CRT medical measurement, and the like.

However, in the case of conventional heat-sensitive recording materials in which only a heat-sensitive color-forming layer is coated on support L using a color-forming substance and a color-developing substance as active ingredients and a binder, light, water, temperature, Because it is unstable to plasticizers, oils, etc., changes over time during storage are always a problem. Furthermore, since such heat-sensitive recording materials contain the above-mentioned materials as main components, they have a drawback in that the gloss of image areas and non-image areas is quite low.

Therefore, in order to improve storage stability, it was proposed to provide a surface layer on the heat-sensitive coloring layer. For example, JP-A-58-14
Those using a hydrophobic polymer compound emulsion etc. as seen in Publication No. 6794, etc., or those using JP-A-58-19
As seen in Publication No. 9189, a water-soluble polymer compound or a hydrophobic polymer compound emulsion is provided as an intermediate layer on the heat-sensitive coloring layer, and a surface layer made of an oil-based paint containing a hydrophobic polymer compound as a resin component is applied thereon. What has been set up has been reported.

[Problems to be Solved by the Invention] However, when such a surface layer is provided, the surface layer may stick to the thermal head during image recording, especially at low temperatures (0°C). However, the current situation is that it cannot be said to be satisfactory in terms of recording suitability. Particularly when recording images with rich gradation, such as in the case of video printers, quality design to prevent sticking is essential.

The present invention solves these problems and has excellent recording properties that do not cause the sticking phenomenon to the thermal head especially at low temperatures, as well as a gloss level equivalent to that of silver halide photographic paper. In particular, it provides a heat-sensitive recording material that has long-term storage properties such as water resistance, plasticizer resistance, and oil resistance, and has high recording density and excellent gradation. In addition to being suitable for use as printer paper for video printers (thermal recording devices for CRT images) that provide high-quality rS-tone images, it can also be used for coupons and commuter passes that require preservation, and barcode values for PO8. The attachment is suitable for use as label paper, etc. to be attached to the packaging surface when fresh foods and meat with high oil content are packaged with polyvinyl chloride film, and is also suitable for use as facsimile paper and printer paper for long-term storage. The purpose of this invention is to provide a heat-sensitive recording material that can be used as a heat-sensitive recording material.

[Means for Solving the Problems] As a result of extensive research in order to solve the above problems, the present inventors have developed a method that utilizes a color reaction between an electron pentavalent dye and a color developer on a support. In a heat-sensitive recording material provided with a heat-sensitive color-forming layer, at least one weight of a hydrophobic polymer compound and a fluorinated alkyl ester-modified silicone compound is placed on the heat-sensitive color-forming layer via an intermediate layer containing a water-soluble polymer compound as a main component. It has been found that by providing a surface gloss layer containing as a main component, it is possible to provide a heat-sensitive recording material that has desired properties and can be used for the above-mentioned purposes.

As the hydrophobic polymer compound used in the surface gloss layer, a saturated polyester resin obtained using a dibasic acid and a specific polyhydric alcohol including bisphenol A dihydroxyethyl ether is particularly suitable.

In this case, the dibasic acids used include compounds such as dimethyl terephthalate and isophthalic acid, and the polyhydric alcohols used include compounds such as ethylene glycol and neopentyl glycol in addition to bisphenol A dihydroxyethyl ether. A saturated polyester obtained by mixing these, performing a transesterification reaction, making a polybond, and deglycolizing the polyester by a reduced pressure reaction is used.

The fluorinated alkyl ester-modified silicone compounds that can be used here include those having various isomers, and any of them can be used, but for example, the general formula (1) (wherein R is an alkylene group having 1 to 30 carbon atoms, m and n are each an integer of 5 to 300) can be preferably used. However, it is not limited to this. This compound is added in an amount of 0.5 to 25 parts by weight, preferably 5 to 1 parts by weight, per 100 parts by weight of the hydrophobic polymer compound.
It is contained in a range of 5 parts by weight.

If the amount is less than 0.5 parts by weight, sticking occurs because sufficient releasability cannot be imparted when the hydrophobic polymer compound is thermally fused to the thermal head. On the other hand, if 25 parts by weight or more is present, a large amount of the fluorinated alkyl ester-modified silicone compound bleeds onto the surface, causing problems such as dust adhesion, which is not preferable.

In forming the surface gloss layer, 0.5 to 5 g/
The coating amount is preferably in the range of 1 to 3 g/rd.

It can be used in combination with other resins, such as fluororesins, silicone-acrylic copolymer resins, acrylic resins, urethane resins, epoxy resins, and ethyl cellulose, as long as they do not particularly affect the achievement of the objects of the present invention.

In order to heat cure the above saturated polyester resin, melamine curing type, acid anhydride curing type, isocyanate curing type,
An epoxy curing type crosslinking agent may be added. When adding these crosslinking agents, the amount added is set according to the resin OH value, etc., but it is 1 to 20 parts by weight per 100 parts by weight of the resin.
Preferably, it is a proportion of parts by weight.

The surface gloss layer can be formed by any known coating method such as air knife, blade, gravure, roll coater, spray, dip, bar, or extrusion.

In addition to this, the surface gloss layer of the present invention may contain other lubricants and/or pigments for compatibility with the thermal head, particularly for preventing sticking. As a lubricant,
Higher fatty acid metal salts such as zinc stearate and calcium stearate; solid waxes such as polyethylene wax and amide wax; fluorine-based and phosphate ester-based surfactants; silicone oil, alcohol-modified silicone oil, epoxy-modified silicone oil, amino Modified silicone oil etc. are used. Pigments include kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, silica, synthetic silicic acid, aluminum, polystyrene fine particles, urea-formalin resin fine particles, melamine-formaldehyde resin fine particles, silicone powder, fluorine. At least one of powder, mica, etc.
1 to 20 parts by weight of seeds can be contained per 100 parts by weight of the hydrophobic polymer compound.

As the support, papers such as wood-free paper, medium-quality paper, art paper, cast-coated paper, paperboard, and tissue paper are generally used, and plastic film, synthetic paper, laminated paper, aluminum foil, etc. can also be used.

The color-forming dye used for forming the heat-sensitive color-forming layer in the present invention is not particularly limited, and any dye used for general pressure-sensitive recording paper, heat-sensitive recording paper, etc. can be used. Specific examples include (1) triarylmethane compounds, such as 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (crystal violet lactone), 3-(p-dimethyl aminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-
3-(2-phenylindol-3-yl)phthalide,
3,3-bis-(9-ethylcarbazol-3-yl)
-5-dimethylaminophthalide, 3.3-bis-(2-
(phenylindol-3-yl)-5-dimethylaminophthalide, etc.: (2) Diphenylmethane compounds, such as 4,4'-bis-dimethylaminobenzhydrinbenzhydrin-7-/l/, N-halophenylleuco aurami>, N-2,4,5-to') chlorophenylleucoauramine, etc.: (3> xanthine compounds, for example, rhodamine B
-Anilinectam, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-butylaminofluorane, 3-diethylamino-7-(2-
chloroanilino)fluoran, 3-diethylamino-6
-Methyl-7-anilinofluorane, 3-piperidino-
6-Methyl-7-anilinofluorane, 3-ethyl-tolylamino-6-methyl-7-anilinofluorane, 3
-cyclohexyl-methylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-
7-(β-ethoxyethyl)aminofluorane, 3-diethylamino-6-chloro-7-(γ-chloropropyl)aminofluorane, 3-(N-ethyl-N-isoamyl)6-methyl-7-phenyl Aminofluorane, 3
-dibutylamino-6-methyl-7-anilinofluorane, etc.: (4) Thiazine compounds, such as benzoylleucomethylene blue, p-nitrobenzoylleucomethylene blue, etc.: (5) Spiro compounds, such as 3-methyl-spiro −
Examples include dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methylnaphtho-(3-methoxy-benzo)-spiropyran, and the like. These may be used alone or as a mixture of 2Pf1 or more. These dyes are selected and used depending on the purpose and desired properties.

A known method may be used to form the heat-sensitive coloring layer on the support.

All known binders can be used as the binder for the thermosensitive coloring layer. However, it is preferable that the liquid does not develop color, aggregate, or become highly viscous when mixed with each dispersion liquid of the color-forming dye and the color-developing substance, and the formation of a heat-sensitive recording sheet should be avoided. It is required that the film be strong and have no desensitizing effect.

Typical water-based binders include polyvinyl alcohol, modified starch, gum arabic, gelatin, methylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, polyvinylpyrrolidone, diisobutylene-maleic anhydride copolymer, carboxymethylcellulose, acrylic amide-acrylic ester copolymer, Polymer, isobutylene-maleic anhydride copolymer salt, alginate, polyvinyl acetate, polyurethane, ethylene-acrylic acid copolymer, polyacrylate, polyacrylamide, styrene-maleic anhydride copolymer, methyl vinyl ether −
Emulsions of maleic anhydride copolymer, isopropylene-maleic anhydride copolymer, styrene-butadiene latex, acrylic ester copolymer, etc. can be used. In order to impart water resistance to the coating film, a combination of a water-soluble polymeric substance containing a reactive group, such as an acetoacetyl group, a carboxyl group, an amide group, etc., and a crosslinking agent is preferred.

Examples of crosslinking agents include dialdehydes such as glyoxal and polyaldehyde, polyamines such as polyethyleneamine, epoxy systems, polyamide resins, diglycidyls such as glycerin diglycidyl ether, dimethylolurea, ammonium persulfate, ferric chloride, etc. Known compounds such as ammonium chloride and magnesium chloride are used.

Examples of pigments include calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcined clay, silica,
In addition to inorganic fine powders such as diatomaceous earth, synthetic aluminum silicate, zinc oxide, titanium oxide, aluminum hydroxide, barium sulfate, and surface-treated calcium carbonate and silica,
Examples include organic fine powders such as urea-formalin resin, styrene/methacrylic acid copolymer, polystyrene resin, styrene powder, nylon powder, polyethylene powder, and raw starch particles.

In addition to this, the heat-sensitive coloring layer may further contain auxiliary additive components commonly used in heat-sensitive recording materials of this scale, such as fillers, surfactants, heat-fusible substances (or lubricants), etc. There is no problem in doing so. Thermofusible substances include, for example, stearic acid amide, stearic acid ethylene bisamide, oleic acid amide, palmitylic acid amide, coconut aliphatic amide,
Aliphatic amides such as behenic acid amide, zinc stearate, montanic acid amide, montanic acid wax, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, waxes such as ester wax, dimethyl terephthalate, dibutyl terephthalate, Terephthalic acid dibenzyl ester, isophthalic acid dibutyl ester, 1-hydroxynaphthoic acid phenyl ester, 1,2-di(3-methylphenoxy)ethane, 1,2-diphenoxyethane, 1-phenoxy-2-(4-methyl) phenoxy)ethane, diphenyl carbonate, p-benzylbiphenyl, 2.2'-methylenebis(4-methyl-6-t-butylphenol), 4.
4'-Butylidenebis(6-t-butyl-3-methylphenol), 1.1.3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 2.2'
-Hinders such as methylenebis(4-ethyl-6-t-butylphenol), 2,4-di-t-butyl-3-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), etc. Phenols, 2-(2'-
Hydroxy-5'-methylphenyl)benzotriazole, dibenzyl terephthalate, 1-hydroxy-2-
Sensitizers such as phenyl naphthoate, dibenzyl oxalate, -chlorobenzyl adipate, dip-chlorobenzyl oxalate, 2-hydroxy-4-benzyloxybenzophenone, lubricants, antioxidants, ultraviolet inhibitors, etc. Examples include various thermofusible substances. The amount of the thermofusible substance added is generally preferably 4 parts by weight or less per 1 part by weight of the color developer. A pulverizer such as a ball mill, attritor, or sand grinder (vertical or horizontal) is used to disperse the dye, developer, sensitizer, and other additives.

As a method for forming the thermosensitive coloring layer, any known coating method such as air knife, blade, gravure, roll coater, spray, dip, bar, extrusion, etc. can be used.

The coating weight of this heat-sensitive coloring layer is generally 3 to 10g/rrr.

In the heat-sensitive recording material of the present invention, an intermediate layer is formed on the heat-sensitive coloring layer. Since this intermediate layer usually consists of a water-soluble polymeric substance as a main component, a pigment and a crosslinking agent are usually added thereto. The purpose of the intermediate layer is to improve the water resistance, plasticizer resistance, and oil resistance of the heat-sensitive recording material, especially the heat-sensitive coloring layer. With the improvement of these properties, water,
Adverse effects caused by plasticizers, oils, etc., such as fading of the coloring area, can be reliably avoided.

As the water-soluble polymer substance used for this purpose, those having a barrier effect such as polyvinyl alcohol resin and casein can be used.

As polyvinyl alcohol resin, any degree of polymerization,
Polyvinyl alcohol having a degree of saponification can be used.

Further, as polymeric substances, unsaturated carboxylic acids or partial or complete esters thereof, salts, anhydrides, nitriles, amides, unsaturated sulfonic acids or salts thereof, α-olefins having 2 to 3 carbon atoms, vinyl ethers, saturated branched fatty acid vinyls, etc. It is also possible to use polyvinyl alcohol that has been specifically polymerized and modified, such as polyvinyl alcohol that has been subjected to urethanization, acetalization, etherification, grafting, phosphoric acid esterification, sulfuric acid esterification, or acetoacetic esterification. can. The degree of polymerization of the polymer substance is preferably in the range of 3oo to 1,700, particularly preferably 500 to 1,000 from the viewpoint of paint viscosity and coatability.

In the composition of the intermediate layer, the amount of the water-soluble polymeric substance or the total amount of the water-soluble polymeric substance and the crosslinking agent is preferably 50% by weight or more of the total weight of the intermediate layer. If it is less than this, the resulting heat-sensitive recording material may have insufficient plasticizer resistance, oil resistance, and solvent resistance.

Water-soluble crosslinking agents used in the intermediate layer include dialdehyde compounds such as glyoxal and polyaldehyde, polyamine compounds such as polyethyleneimine, epoxy polyamide resins, diglycidyl compounds such as glycerin diglycidyl ether, dimethylol urea, Other examples include metal salts such as ammonium persulfate, ferric chloride, and magnesium chloride, and inorganic compounds such as ammonium chloride and boric acid.

There is no particular limitation on the amount of the crosslinking agent added, but it is generally preferably 3 to 30% based on the weight of the water-soluble polymer substance.

The pigment added to the intermediate layer is preferably one that adsorbs the melt of the surface gloss layer and improves its smoothness.

Such pigments include kaolin, clay talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth,
Silica, synthetic aluminum silicate, synthetic magnesium silicate, aluminum oxide, polystyrene fine particles, urea
It is possible to use at least one type of formalin resin fine particles.

The pigment content in the intermediate layer is preferably 50% or less based on the total weight of the intermediate layer.

The coating amount of the intermediate layer is adjusted as appropriate to the extent that heat conduction from the thermal head to the coloring layer is not inhibited.
It is usually 1 to LOg/rrr, preferably 2 to 7g/-. As a result, desired effects can be obtained without reducing thermal sensitivity.

After coating the intermediate layer, it is preferable to subject the intermediate layer to a surface smoothing treatment using a supercalender or the like.

If the Bekk smoothness of the intermediate layer is 1000 seconds or less, even if a glossy layer is provided on the intermediate layer, a highly glossy surface may not be obtained.
Preferably, the Bekk smoothness is adjusted to 3000 to 7000 seconds.

[Examples] The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is of course not limited to these. In each example, "1 part" indicates "part by weight."

Example 1 The following solutions were prepared with the following compositions.

(1) Preparation of liquid A (thermosensitive coloring layer - for dye) 7 parts of 3-(N-ethyl-N-cyclohexylamino)-6-methyl 7-anilite fluorane 10 parts of 8% hydroxyethyl cellulose aqueous solution 5 parts of water (2 > Preparation of liquid B (for heat-sensitive coloring layer - developer) 15 parts of 2.4-dihydroxydiphenylsulfone 20 parts of 8% carboxymethylcellulose aqueous solution 15 parts of water (3) Preparation of liquid C (for intermediate layer) 10% polyvinyl alcohol aqueous solution ( NM-11Q: manufactured by Nippon Gosei Kagaku Kogyo) 100 parts 50% kaolin aqueous dispersion 75 parts 10% glyoxal aqueous solution 8 parts 20% polyester aqueous solution 15 parts water
25 parts (4> Preparation of liquid D (for surface gloss layer) Saturated polyester resin 85 parts 5% zinc stearate toluene dispersion 40 parts 15% fluorinated alkyl-ester modified silicone toluene solution 50 parts (X-24
-8714: Shin-Etsu Chemical) 20% calcium carbonate toluene dispersion 25 parts toluene
180 parts ethyl acetate
50 parts However, as the saturated polyester resin, a polybonded material (molecule ffi M n = 18000, glass transition temperature 76° C.) having the following component composition was used.

Acid component: 25 parts of dimethyl terephthalate 25 parts of isophthalic acid Polyhydric alcohol: 16 parts of ethylene glycol Dispersion and pulverization were performed until the following contents were obtained. Solution C was stirred with a stirrer until it became homogeneous. Solution D was stirred until it became a complete solution.

(5) Formation of thermosensitive coloring layer A coating liquid for a heat-sensitive coloring layer was prepared with the following composition.

A liquid 1
Part 2 B liquid
46 parts 60% calcium carbonate 40
Part 20% zinc stearate aqueous dispersion 20 parts 10
% polyvinyl alcohol aqueous solution 150 parts water
18 parts of this coating solution was coated on the surface of a support made of 50 g/- of high-quality paper so that the dry weight was 7 g/rriI and dried to provide a heat-sensitive coloring layer.

(6) Formation of intermediate layer After coating and drying liquid C on the coloring layer so that the dry weight is 3 g/rd, calendering is performed thereon,
An intermediate layer having a Beck smoothness of 3000 seconds was provided.

(7> Formation of surface gloss layer) Liquid D was coated and dried to form a surface gloss layer on the intermediate layer at a dry weight of 2 g/rrr.

A heat-sensitive recording material having a three-layer structure of the thus obtained heat-sensitive coloring layer, intermediate layer and surface gloss layer on a support was prepared.

Example 2 A solution prepared by adding 10 parts of 20% silicone powder (Tospar 120: Toshiba Silicone) toluene dispersion to the D solution (for surface gloss layer) used in Example 1 (
A heat-sensitive recording material was obtained by using the same components as in Example 1 and carrying out the same treatment except that Liquid D1) was used.

Example 3 In the D liquid (for surface gloss layer) used in Example 1, (5
% fluorinated alkyl ester modified silicone In place of X-24-8714 (manufactured by Shin-Etsu Chemical) as a toluene solution, use X-24-8715 (manufactured by Shin-Etsu Chemical), which has a higher molecular weight.
A heat-sensitive recording material was obtained by using the same components as in Example 1 and processing in the same manner, except that a solution (D2 solution) prepared using the same amount of was used.

Example 4 A liquid (D3) was prepared by adding 10 parts of 10% alkyl phosphate ester sodium salt (Gafac RE 410) to the D liquid (for surface gloss layer) used in Example 1.
The same ingredients as in Example 1 were used, except for the use of
A heat-sensitive recording material was obtained by the same treatment.

Comparative Example 1 The same ingredients as in Example 1, except that in Solution D (for surface gloss layer) of Example 1, a solution (D4 solution) prepared without adding 15% fluorinated alkyl ester modified silicone toluene solution was used. A heat-sensitive recording material was obtained by the same treatment.

Comparative Example 2 In the D liquid (for surface gloss layer) used in Example 1, 1
Instead of 5% fluorinated alkyl ester modified silicone, the same amount of 15% amino modified silicone (X-22-16
A heat-sensitive recording material was obtained by using the same components as in Example 1 and processing in the same manner, except that a solution (D5 solution) prepared by adding 1C) was used.

Comparative Example 3 Saturated polyester resin (molecular weight Mn = 18000) used in Liquid D (for surface gloss layer) used in Example 1
; glass transition temperature 76°C), the same amount of saturated polyester resin having the following component composition (molecular weight Mn = 20
A heat-sensitive recording material was obtained by using the same components as in Example 1 and carrying out the same treatment, except that a solution (D ertk ) prepared by adding 000; glass transition temperature = 51°C) was used.

The saturated polyester resin was a polycondensate having the following component composition.

Acid component: 25 parts of dimethyl terephthalate 25 parts of isophthalic acid Polyhydric alcohol: 4 parts of ethylene glycol 1 part of neopentyl glycol After each heat-sensitive recording material produced in the above examples and comparative examples was left at room temperature for 3 days,
Solid black recording was performed on this using a thermal printer UP-811 (trademark, a video thermal printer manufactured by Sony Corporation), the sticking suitability in this recording operation was evaluated, and the color density of the obtained recorded image was measured using a Macbeth reflection densitometer. R
D-914 type). Furthermore, the writability of the surface of the heat-sensitive recording material before recording and the glossiness of the surface of the solid black recording area (the incident angle and the light receiving angle were 75 degrees) were tested and evaluated.

Next, a predetermined test piece was prepared from the recording material by a conventional method, and the water resistance, oil resistance, and polyvinyl chloride film resistance of the colored area were measured by a test method.

(1) Water resistance test: After immersing the test piece in water for 24 hours (at room temperature), take it out and observe the elution state of the coating film and the residual concentration after drying.
Measured and evaluated.

(2) Polyvinyl chloride film resistance test: A soft polyvinyl chloride film was superimposed on the specimen, and after contacting the two for 24 hours under a load of 300 g/c+J at a temperature of 20°C, the residual image density was determined. Measured and evaluated.

<3) Oil resistance test: Cottonseed oil was applied to a test piece using a conventional method, and after being left at a temperature of 20° C. for 24 hours, the residual image density was measured and evaluated.

The results of these tests are summarized in Table 1.

As is clear from Table 1, the heat-sensitive recording materials of each example according to the present invention have excellent long-term storage properties such as anti-sticking properties, water resistance, oil resistance, and polyvinyl chloride film resistance, and have suitable properties. However, each comparative example had poor anti-sticking properties, poor oil resistance, and was unsatisfactory in some other properties.

[Effects of the Invention] The present invention makes it possible to provide excellent water resistance, plasticizer resistance, gloss, and oil resistance, and significantly improves the storage stability and gloss of heat-sensitive recording materials. , it was possible to provide even better anti-sticking properties. As a result, the heat-sensitive recording material of the present invention can be used especially for CRT medical printer paper, which requires full-scale long-term storage stability.
This has the effect of expanding the possibilities of use in a wider range of applications, such as image printer paper, commuter passes, coupon tickets, label paper, and printer paper for various measuring devices.

Claims (1)

[Claims] 1. In a heat-sensitive recording material in which a heat-sensitive coloring layer containing a colorless or light-colored electron-donating dye and an electron-accepting color developer is provided on a support, a water-soluble highly water-soluble coloring layer is formed on the support. A hydrophobic polymer compound consisting of a saturated polyester resin obtained by polycondensation reaction of dimethyl terephthalate, isophthalic acid, ethylene glycol, neopentyl glycol, and bisphenol A dihydroxyethyl ether through an intermediate layer mainly composed of a molecular compound. and a fluorinated alkyl ester-modified silicone compound as main components.