JP4999358B2 - Thermal recording material - Google Patents

Description

  The present invention relates to a heat-sensitive recording material having sufficient color development sensitivity and stick resistance, and excellent water resistance and color development prevention during storage.

Generally, a heat-sensitive recording material that obtains a recorded image by utilizing a color development reaction caused by heat between a colorless or light-colored basic leuco dye (hereinafter referred to as a dye) and an electron-accepting developer (hereinafter referred to as a developer). In the facsimile and computer fields, various measuring instruments, etc. due to advantages such as very clear coloring, relatively inexpensive and compact equipment, no noise during recording, and easy maintenance. Widely used. In addition to labels and tickets, the application has been rapidly expanding as an output medium for various printers and plotters such as outdoor measurement handy terminals and delivery slips.
In particular, labels, tickets, handy terminal paper, delivery slips, etc. are used outdoors, so they can withstand use in harsh environments such as moisture and humidity such as rain, sunlight, and high temperatures in the car in midsummer. Quality such as water resistance that can be produced and color prevention during storage is required.
Therefore, in order to improve the water resistance of the heat-sensitive recording material, polyvinyl alcohol and an isocyanate compound are added to the heat-sensitive recording layer (Patent Document 1), and acrylic polymer, acrylic emulsion resin and colloidal silica are added to the heat-sensitive recording layer. Are used in combination (Patent Documents 2 and 3), and a styrene-acrylic resin or an acrylic emulsion resin is used for the back layer (Patent Document 4).

JP-A-55-159993 JP-A-9-207435 JP 7-266711 A JP 2005-81626 A

Conventionally, various methods have been adopted to improve the film performance such as water resistance of the thermal recording material, but it has not been sufficient.
For example, when a water-soluble polymer such as polyvinyl alcohol or starch is used for the heat-sensitive recording layer or its protective layer (Patent Document 1), the minimum film-forming temperature is low and the glass transition temperature is high, but the water-soluble polymer itself is Since it has a hydroxyl group, sufficient water resistance cannot be obtained.
Furthermore, when an acrylic resin and colloidal silica are contained in the thermosensitive recording layer and the apparent minimum film-forming temperature and glass transition temperature are controlled (Patent Documents 2 and 3), the effect of the activity of the colloidal silica itself is exerted. The white paper portion is colored because it reacts with the dye and developer contained in the heat-sensitive recording layer during storage.
Therefore, the present invention provides a thermal recording material having sufficient color sensitivity and stick resistance and excellent in water resistance and prevention of color development during storage, particularly a thermal recording material that does not require a protective layer on the thermal recording layer. The purpose is to provide.

In the present invention, it was first considered to use an acrylic resin in order to improve film performance such as water resistance of the heat-sensitive recording material. In general, when an acrylic resin is used for the heat-sensitive recording layer, the water resistance is improved, but the film performance such as stick resistance becomes insufficient. In order to solve this problem, if the thermosensitive recording layer contains a resin having a high minimum film-forming temperature, the film is not sufficiently formed and sufficient water resistance cannot be obtained.
In order to solve these conflicting problems, in the present invention, the thermal recording layer contains a styrene-acrylic resin having a specific performance, and the film performance such as water resistance and stick resistance of the thermal recording layer is improved in a balanced manner. Tried to do.
In order to prevent color development during production, the thermal recording medium is usually produced by controlling drying so that the maximum temperature of the thermal recording medium is 60 ° C. For this reason, it is preferable to use a resin having a low minimum film-forming temperature (MFT) that can be sufficiently formed at about 60 ° C.
In general, since the minimum film-forming temperature and the glass transition temperature (Tg) are correlated, if a thermal recording layer contains a resin having a low minimum film-forming temperature, that is, a resin having a low glass transition temperature, the thermal head of the thermal recording printer The resin softens due to the heat of the sticking, causing sticking and head debris.
However, the present inventors selected a styrene-acrylic resin that has a characteristic that the glass transition point is not less than a certain value and not more than a certain value for the minimum film-forming temperature, and this styrene-acrylic resin is contained in the thermosensitive recording layer. The present inventors have found that the thermosensitive recording layer can have a balanced film performance and have completed the present invention.

That is, the present invention
A thermosensitive recording medium comprising a thermosensitive recording layer containing a colorless or light-colored basic leuco dye and an electron-accepting developer on a support, wherein the thermosensitive recording layer further has a glass transition point of 50 ° C. or higher and a minimum film formation. A heat-sensitive recording material comprising a styrene-acrylic resin having a temperature of 20 ° C. or less and not containing a styrene-acrylic resin other than the styrene-acrylic resin .
The thermosensitive recording layer further comprises a styrene-acrylic resin having a glass transition point of 90 ° C. or higher and a minimum film-forming temperature of 70 ° C. or lower, and a styrene-acrylic resin having a glass transition point of 50 ° C. or higher and a minimum film-forming temperature of 20 ° C. or lower. You may contain so that a weight ratio may be 20%-70%.

  In the heat-sensitive recording material of the present invention, a styrene-acrylic resin having a glass transition temperature of 50 ° C. or higher and a minimum film-forming temperature of 20 ° C. or lower is contained in the heat-sensitive recording layer, so that it can be sufficiently produced under low temperature drying conditions. Since the film is formed and the resin is not softened by heat from the thermal head of the thermal recording printer, the water resistance, head debris resistance and anti-sticking resistance are good. Further, since the heat-sensitive recording layer does not need to contain colloidal silica, it has color-preventing properties during storage. Since the heat-sensitive recording material of the present invention is excellent in water resistance and the like as described above, a protective layer can be omitted on the heat-sensitive recording layer.

  The heat-sensitive recording layer of the present invention contains a colorless or light-colored basic leuco dye and an electron-accepting developer, and further contains a styrene-acrylic resin having a glass transition point of 50 ° C. or higher and a minimum film-forming temperature of 20 ° C. or lower. . The heat-sensitive recording layer may further contain a sensitizer, a stabilizer, a binder, a pigment, a lubricant and the like as necessary.

The composition of the styrene-acrylic resin having a glass transition temperature of 50 ° C. or higher and a minimum film-forming temperature of 20 ° C. or lower used in the present invention is not particularly limited, but acrylic, styrene acrylic or styrene methacrylic resin is used for the core portion. can shell type emulsion is exemplified with styrene-acrylic or styrene methacrylic resin in the shell portion, as specific examples, Joncryl 352, di Yonkuriru 7641 (manufactured by Johnson polymer Co., Ltd.).
The blending amount of the resin having a glass transition temperature of 50 ° C. or higher and a minimum film forming temperature of 20 ° C. or lower used in the present invention is 1 to 30% by weight (hereinafter, parts by weight are solids) with respect to the total solid content of the thermosensitive recording layer. Conversion), and 2 to 10% by weight is more preferable. When the amount of the resin having a glass transition temperature of 50 ° C. or higher and a minimum film forming temperature of 20 ° C. or lower is 1% by weight or less, water resistance cannot be obtained, and when it is 30% by weight or more, high color development sensitivity is difficult to obtain.

In the present invention, by using a styrene-acrylic resin having a glass transition temperature of 90 ° C. or higher and a minimum film forming temperature of 70 ° C. or lower in a certain ratio in the heat-sensitive recording layer, the color-preventing property during storage can be further enhanced. The composition of the styrene-acrylic resin having a glass transition point of 90 ° C. or higher and a minimum film forming temperature of 70 ° C. or lower is not particularly limited, but acryl, styrene acrylic or styrene methacrylic resin is used for the core portion and styrene is used for the shell portion. Examples of the core-shell type emulsion using an acrylic or styrene methacrylic resin include John Crill 7610 and PDX7177 manufactured by Johnson Polymer Co., Ltd.
The amount of the styrene-acrylic resin having a glass transition point of 90 ° C. or higher and a minimum film forming temperature of 70 ° C. or lower to be used in combination is preferably relative to a styrene-acrylic resin having a glass transition point of 50 ° C. or higher and a minimum film forming temperature of 20 ° C. or lower. Is 20% to 70% by weight, more preferably 30% to 50% by weight.

The glass transition point is measured with a scanning differential calorimeter (a 10 mg sample is heated at 20 ° C./min in a nitrogen atmosphere) in accordance with JIS K-7122 for each single component (monomer) constituting the resin. The glass transition temperature of the resin (Tg) = Tg1 × α1 + Tg2 × α2 +... + Tgn × αn (Tg1, Tg2,... Glass transition temperature, α1, α2,... Αn: obtained from a calculation formula of weight fraction (%) of each composition simple substance with respect to the total weight of the resin.
Also, the minimum film increasing temperature is based on JIS K-6828. The resin adjusted to 20% by weight is spread over the entire surface of the slide glass, dried at a predetermined temperature, and the dried resin is a uniform continuous film. It was set to the lowest temperature at which the film was not clouded.

As the developer used in the present invention, any known ones in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used and are not particularly limited. For example, 4,4′-isopropyl Dendiphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4′-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, 4-hydroxy Benzyl benzoate, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-n-propoxydiphenylsulfone, bis (3 -Allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'- Allyloxydiphenylsulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, JP-A-8-59603 Aminobenzenesulfonamide derivatives, bis (4-hydroxyphenylthioethoxy) methane, 1,5-di (4-hydroxyphenylthio) -3-oxapentane, butyl bis (p-hydroxyphenyl) acetate, bis (p -Hydroxyphenyl) methyl acetate, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,3 -Bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene , Di (4-hydroxy-3-methylphenyl) sulfide, 2,2′-thiobis (3-tert-octylphenol), 2,2′-thiobis (4-tert-octylphenol), described in International Publication No. WO 97/16420 Phenolic compounds such as diphenylsulfone crosslinkable compounds, developer compositions described in International Publication WO02 / 098674, compounds described in International Publication WO02 / 081229 or JP-A No. 2002-301873, 4,4′- Thiourea compounds such as bis (3- (phenoxycarbonylamino) methylphenylureido) diphenylsulfone (trade name: UU, manufactured by Asahi Kasei Co., Ltd.), N, N′-di-m-chlorophenylthiourea, p-chlorobenzoic acid, gallic acid Stearyl, bis [4- (n-octyloxycarbonylamino) salicylate zinc] Hydrate, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl ] Aromatic carboxylic acids of salicylic acid, and salts of these aromatic carboxylic acids with polyvalent metal salts such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, and further antipyrine complexes of zinc thiocyanate, Examples include composite zinc salts of terephthalaldehyde acid and other aromatic carboxylic acids. A phenolic compound such as the diphenylsulfone cross-linking compound described in International Publication No. WO 97/16420 is available as a trade name D-90 manufactured by Nippon Soda Co., Ltd.
The compounds described in International Publication No. WO02 / 081229 or JP-A-2002-301873 are available as trade names D-102 and D-100 manufactured by Nippon Soda Co., Ltd. These developers can be used alone or in combination of two or more. Among these, 4-hydroxy-4′-isopropoxydiphenyl sulfone is particularly preferable because of excellent color development sensitivity. In addition, a metal chelate color-developing component such as a higher fatty acid metal double salt and a polyvalent hydroxyaromatic compound described in JP-A-10-258577 can also be contained.

As the dye used in the present invention, any known dyes in the field of conventional pressure-sensitive or thermal recording paper can be used, and are not particularly limited, but include triphenylmethane compounds, fluorane compounds, fluorene compounds. , Divinyl compounds and the like are preferable. Specific examples of typical colorless or light-colored dyes (dye precursors) are shown below. These dye precursors may be used alone or in combination of two or more.
<Triphenylmethane leuco dye>
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide (also known as malachite green lactone)

<Fluoran leuco dye>
3-diethylamino-6-methylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane, 3-diethylamino- 6-methyl-7-chlorofluorane, 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane, 3- Diethylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane 3-diethylamino-6-methyl-7-n-octylanilinofluorane, 3-di Tilamino-6-methyl-7-n-octylaminofluorane, 3-diethylamino-6-methyl-7-benzylaminofluorane, 3-diethylamino-6-methyl-7-dibenzylaminofluorane, 3-diethylamino- 6-chloro-7-methylfluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-6-chloro-7-p-methylanilinofluorane, 3-diethylamino-6-ethoxy Ethyl-7-anilinofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7- (m-trifluoromethylanilino) fluorane, 3-diethylamino- 7- (o-chloroanilino) fluorane, 3-diethylamino-7- (p Chloroanilino) fluorane, 3-diethylamino-7- (o-fluoroanilino) fluorane, 3-diethylamino-benzo [a] fluorane, 3-diethylamino-benzo [c] fluorane, 3-dibutylamino-6-methyl-fluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluorane, 3-dibutylamino-6-methyl-7- ( o-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-dibutylamino-6 -Methyl-7- (m-trifluoromethylanilino) fluorane, 3-dibutylamino- 6-methyl-7-chlorofluorane, 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane, 3-dibutylamino-6-chloro-7-anilinofluorane, 3-dibutylamino-6- Methyl-7-p-methylanilinofluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-fluoroanilino) fluorane, 3-di-n-pentylamino -6-methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-di-n-pentylamino-7- (m-trifluoro Methylanilino) fluorane, 3-di-n-pentylamino-6-chloro-7-anilinofluorane, 3-di-n-pentylamino-7- (p-chloro) Nilino) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane 3- (N-methyl-N-propylamino) -6-methyl- 7-anilinofluorane, 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-cyclohexylamino) -6-methyl-7- Anilinofluorane, 3- (N-ethyl-N-xylamino) -6-methyl-7- (p-chloroanilino) fluorane, 3- (N-ethyl-p-toludino) -6-methyl-7-anilino Fluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-chloro-7-ani Nofluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofur Oran, 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 2- (4-oxahexyl) -3-dimethyl Amino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-dipropyl Amino-6-methyl-7-anilinofluorane, 2-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane, 2-methoxy-6-p (P-dimethylaminophenyl) aminoanilinofluorane, 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane, 2-chloro-6-p- (p-dimethyl) Aminophenyl) aminoanilinofluorane, 2-nitro-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 2-amino-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 2 -Diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 2-phenyl-6-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane, 2-benzyl-6- p- (p-phenylaminophenyl) aminoanilinofluorane, 2-hydroxy-6-p- (p-phenylamino) Nophenyl) aminoanilinofluorane, 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluorane, 3-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane, 3 -Diethylamino-6-p- (p-dibutylaminophenyl) aminoanilinofluorane, 2,4-dimethyl-6-[(4-dimethylamino) anilino] -fluorane

<Fluorene leuco dye>
3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′-phthalide], 3,6,6′-tris (diethylamino) spiro [fluorene-9,3′-phthalide]
<Divinyl leuco dye>
3,3-bis- [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide, 3,3-bis- [2- (P-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide, 3,3-bis- [1,1-bis (4-pyrrolidinophenyl) ) Ethylene-2-yl] -4,5,6,7-tetrabromophthalide, 3,3-bis- [1- (4-methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene-2- Yl] -4,5,6,7-tetrachlorophthalide

<Others>
3- (4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- ( 1-octyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-cyclohexylethylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl)- 4-azaphthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,6-bis (diethylamino) fluorane-γ- (3′-nitro) anilinolactam, 3,6 -Bis (diethylamino) fluorane-γ- (4′-nitro) anilinolactam, 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylamino) Enyl) -ethenyl] -2,2-dinitrileethane, 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2- β-naphthoylethane, 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,2-diacetylethane, bis- [2, 2,2 ′, 2′-Tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester

As the binder used in the present invention, generally known binders are used, and specifically, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol having a polymerization degree of 200 to 1900. , Sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl alcohol, other modified polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, acetyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene Copolymer, polyvinyl chloride,
Examples thereof include polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyllar, polystyrene and copolymers thereof, polyamide resin, silicon resin, petroleum resin, terpene resin, ketone resin, and coumaro resin. Polyvinyl alcohol having a polymerization degree of 1200 to 2000 and a saponification degree of 95 mol% or more is particularly preferred from the viewpoint of surface strength.
These polymer substances are used by dissolving in water, alcohol, ketone, ester, hydrocarbon, or other solvents, and are used in the form of emulsification or paste dispersion in water or other media to achieve the required quality. It is also possible to use it together.
As a compounding quantity of a binder, 1 to 30 weight% is preferable with respect to the heat-sensitive layer total solid. When the blending amount of the binder is 1% by weight or less, the water resistance and surface strength are low, and when it is 30% by weight or more, high color development sensitivity is difficult to obtain.

Moreover, in this invention, a conventionally well-known sensitizer can be used in the range which does not inhibit the desired effect with respect to the said subject. Such sensitizers include ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di- (3-methylphenoxy) ethane, p-benzylbiphenyl, β-benzyloxynaphthalene, 4-biphenyl-p-tolyl ether. , M-terphenyl, 1,2-diphenoxyethane, 4,4'-ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, 1,2-di (3-methylphenoxy) ethylene, 1 , 2-diphenoxyethylene, bis [2- (4-methoxy-phenoxy) ethyl] ether, methyl p-nitrobenzoate, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, di (p-methyl oxalate) Benzyl), dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-to Carbonate, phenyl-α-naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, 4- (m-methylphenoxymethyl) biphenyl, orthotoluenesulfonamide, paratoluenesulfonamide. Although it can illustrate, it is not restrict | limited in particular to these. These sensitizers may be used alone or in combination of two or more.

Next, various materials used in the present invention are exemplified, but binders, pigments and the like can be used for the heat-sensitive recording layer as long as they do not impair the desired effects on the above-mentioned problems, and protection provided as necessary. It can also be used for each coating layer such as a layer and an undercoat layer.
Examples of the filler used in the present invention include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide and aluminum hydroxide, and these are used alone or in combination of two or more. Can be used. The pigment contained in the heat-sensitive recording layer is preferably silica or calcium carbonate, and it is desirable to use calcium carbonate and silica in combination from the viewpoint of coating layer strength and stick resistance. In particular, calcium carbonate having an average particle diameter of 3 μm or more, silica having an average particle diameter of 5 to 10 μm, an oil absorption of 150 ml / 100 g or more, and a specific surface area of 150 m ² / g or less are preferably used in combination. When calcium carbonate and silica are used, the weight ratio of calcium carbonate / silica is preferably 20/80 to 80/20, more preferably 40/60 to 60/40, based on 1 part by weight of the dye. About 0.5 to 10 parts by weight is preferable.
In the present invention, lubricants such as waxes, benzophenone and triazole UV absorbers, water resistance agents such as glyoxal, dispersants, antifoaming agents, antioxidants, fluorescent dyes and the like can be used.

  In the present invention, 4,4′-butylidene (6-tert-butyl-3-methylphenol), 2, and the like are used as stabilizers for imparting oil resistance and the like of recorded images within a range that does not impair the desired effect on the above problems. 2'-di-t-butyl-5,5'-dimethyl-4,4'-sulfonyldiphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1, Add 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenylbutane, 4-benzyloxy-4 '-(2,3-epoxy-2-methylpropoxy) diphenylsulfone, epoxy resin, etc. You can also

The types and amounts of the basic leuco dye, developer, and other various components used in the heat-sensitive recording material of the present invention are determined according to the required performance and recording suitability, and are not particularly limited. About 1 to 10 parts, about 0.5 to 10 parts of developer and 0.5 to 10 parts of filler are used.
By applying the coating liquid having the above composition to any support such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, non-woven fabric, etc., the desired thermal recording material can be obtained. Moreover, you may use the composite sheet which combined these as a support body.

Basic leuco dye, color developer, and materials to be added as necessary are finely pulverized to a particle size of several microns or less by a pulverizer such as a ball mill, attritor, sand glider, or an appropriate emulsifying device. Depending on the conditions, various additive materials are added to obtain a coating solution. The application means is not particularly limited, and can be applied according to well-known conventional techniques. For example, an off-machine coating machine equipped with various coaters such as an air knife coater, a rod blade coater, a bill blade coater, and a roll coater, A machine coater is appropriately selected and used. The coating amount of the heat-sensitive recording layer is not particularly limited, and usually 2 to 12 by dry weight.
in the range of g / ^{m 2.}

The heat-sensitive recording material of the present invention may further be provided with a protective layer on the heat-sensitive recording layer for the purpose of improving the storage stability. However, since the thermal recording layer of the present invention has excellent film performance, sufficient film performance can be provided without using this protective layer.
When the protective layer is used, a film-forming resin may be a main component, and the film-forming resin is usually composed of a water-soluble resin and a crosslinking agent.

  Preferred water-soluble resins include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy modified polyvinyl alcohol, amide modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl alcohol, and olefin modified polyvinyl alcohol. , Nitrile modified polyvinyl alcohol, pyrrolidone modified polyvinyl alcohol, silicone modified polyvinyl alcohol, other modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer and ethyl cellulose, Cellulose derivatives such as acetylcellulose , Casein, arabic gum, oxidized starch, etherified starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic ester, polyvinyl butyral, polystyrose and copolymers thereof, polyamide resin Examples thereof include silicone resin, petroleum resin, terpene resin, ketone resin, and coumaro resin. These polymer substances are used by dissolving them in solvents such as water, alcohol, ketones, esters, hydrocarbons, etc., and are used in the state of being emulsified or pasted in water or other media to achieve the required quality. It can also be used in combination.

  In addition to the epichlorohydrin resins and polyamine / amide resins described above as preferred crosslinking agents, melamine resins such as glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyethyleneimine resin, potassium persulfate, persulfate, Examples include ammonium sulfate, sodium persulfate, ferric chloride, magnesium chloride, borax, boron compounds such as boric acid, alum, ammonium chloride, and the like.

  Further, an undercoat layer such as a polymer material containing a filler may be provided under the heat-sensitive recording layer for the purpose of increasing the color development sensitivity. It is also possible to correct the curl by providing a backcoat layer on the opposite side of the support from the thermosensitive recording layer. Also, various known techniques in the heat-sensitive recording material field can be added as appropriate, such as applying a smoothing process such as supercalendering after coating each layer.

Hereinafter, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto. In each example, “parts” means “parts by weight” unless otherwise specified.
The glass transition point is the glass transition temperature of the resin contained in the heat-sensitive recording layer. Each composition alone is a scanning differential calorimeter (in accordance with JIS K-7122, 10 mg sample is increased at 20 ° C./min in a nitrogen atmosphere. (Tg) = Tg1 × α1 + Tg2 × α2 +... + Tgn × αn (Tg1, Tg2,... Tgn: each measured value) The glass transition temperature of the composition simple substance, α1, α2,... Αn: obtained from the calculation formula of the weight fraction (%) of each composition simple substance with respect to the total weight of the resin.
Moreover, the minimum film increasing temperature was measured based on JIS K-6828.

[Example 1]
A composition comprising the following composition was stirred and dispersed to prepare an undercoat layer coating solution, and the coating amount of the undercoat layer coating solution was 8.0 g / m ^{2 on} one side of a support (high-quality paper having a basis weight of 50 g / m ² ). Then, drying was performed to obtain an undercoat layer-coated paper.
<Undercoat layer coating solution>
Firing kaolin (trade name: Ansilex 90, manufactured by Engelhard) 100 parts Styrene-butadiene latex (48% solids) 40 parts 10% polyvinyl alcohol aqueous solution 30 parts Water 160 parts

Next, each material of the dye, the developer and the sensitizer was prepared in advance as a dispersion having the following composition, and wet grinding was performed with a sand grinder until the average particle size became 0.5 μm.
<Developer dispersion>
4-hydroxy-4'-isopropoxydiphenylsulfone 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts
<Dye dispersion>
3-Di-n-butylamino-6-methyl-7-anilinofluorane (ODB-2)
3.0 parts 10% aqueous polyvinyl alcohol solution 6.9 parts water 3.9 parts
<Sensitizer dispersion>
1,2-di- (3-methylphenoxy) ethane 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts

The above dispersions were mixed at the ratio shown below to obtain a thermal recording layer coating solution. The coating solution is applied and dried on the undercoat layer coated paper so that the coating amount after drying is 6.0 g / m ^2, and processed with a super calender so that the Beck smoothness is 200 to 600 seconds. A record was obtained.
Developer dispersion 36.0 parts Dye dispersion 13.8 parts Sensitizer dispersion 36.0 parts Silica (trade name: Carplex 101, average particle size: 7 μm, oil absorption: 178 ml / 100 g, BET specific surface area , 65 m ² / g, manufactured by Degussa Japan) 50% dispersion
13.0 parts calcium carbonate (trade name: Tunex E, average particle size: 4.4 μm, manufactured by Shiraishi Calcium Co.) 50% dispersion 13.0 parts 30% zinc stearate dispersion 6.7 parts 10% partially saponified Polyvinyl alcohol aqueous solution (trade name, manufactured by Kuraray Co., Ltd .: PVA217, polymerization degree: 1750, saponification degree: 88 mol%) 20.0 parts styrene-acrylic resin (trade name, manufactured by Johnson Polymer Co., Ltd .: Johncrill 7641, solid content 49%, glass transition Point 86 ° C, minimum film-forming temperature 14 ° C) 10.0 parts

[Example 2 ]
The blending number of styrene-acrylic resin (Johncrill 7641) was 7.0 parts, and Johncrill 7610 (Styrene-acrylic resin manufactured by Johnson Polymer Co., Ltd., glass transition point 96 ° C., minimum film-forming temperature 63 ° C., solid content 52 %) Was obtained in the same manner as in Example 1 except that 3.0 parts was added.
[Example 3 ]
A heat-sensitive recording material was prepared in the same manner as in Example 2 except that the blending number of styrene-acrylic resin (Johncrill 7641) was 5.0 parts and styrene-acrylic resin (Johncrill 7610) was 5.0 parts. Obtained.
[Example 4 ]
Except for changing the styrene-acrylic resin (John Crill 7641) to John Crill 352 (manufactured by Johnson Polymer Co., Ltd., glass transition point 56 ° C., minimum film-forming temperature 10 ° C., solid content concentration 45%), the same as in Example 1. A heat-sensitive recording material was obtained.

[Comparative Example 1]
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that styrene-acrylic resin (John Krill 7641) was not used.
[Comparative Example 2]
Except for changing the styrene-acrylic resin (John Crill 7641) to John Crill 775 (manufactured by Johnson Polymer Co., Ltd., glass transition point 37 ° C., minimum film forming temperature 15 ° C., solid content concentration 45%), the same procedure as in Example 1 was performed. A heat-sensitive recording material was obtained.
[Comparative Example 3]
A styrene-acrylic resin (John Crill 7641) was changed to Jon Crill 7640 (Johnson Polymer Co., Ltd., glass transition point 85 ° C., minimum film forming temperature 45 ° C., solid content concentration 42%). A heat-sensitive recording material was obtained.
[Comparative Example 4]
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that styrene-acrylic resin (Joncrill 7641) was not used, and Movinyl 8050 (acrylic colloidal silica composite resin manufactured by Clariant Polymer Co.) was used instead.

The following evaluation was performed on the heat-sensitive recording materials obtained in the above Examples and Comparative Examples. The results are shown in Table 1.
[Color development sensitivity]
Using TH-PMD manufactured by Okura Electric Co., Ltd., printing was performed on the created thermal recording medium with an applied energy of 0.34 mJ / dot. The image density after printing and after the quality test was measured with a Macbeth densitometer (RD-914, using an amber filter).
[water resistant]
-Image remaining rate Using a TH-PMD manufactured by Okura Electric Co., Ltd., a thermal recording medium printed with an applied energy of 0.34 mJ / dot was immersed in water and allowed to stand at 23 ° C. for 24 hours. Measurement was performed with a Macbeth densitometer, and the image residual ratio was calculated by the following formula.
Image residual ratio (%) = density after test / density before test × 100
Water blocking resistance 50 μl of water drops are hung on the surface of the heat-sensitive recording medium, folded in half so that the recording surface is inside, a load of 100 g / cm ² is applied on the recording medium on which the water drops have been dropped, and 23 ° C. and 50% Rh. The recording surface was peeled off for 24 hours, and then the recording surface was peeled off, and the color was developed at 105 ° C. for 2 minutes. The degree of peeling of the recording surface was visually determined and evaluated according to the following criteria.
○: There is almost no peeling of the recording surface. Δ: Some peeling of the recording surface is observed. X: There is much peeling of the recording surface.

[Blank paper storage stability during storage]
The heat-sensitive recording material was allowed to stand for 72 hours in a blower dryer maintained at 60 ° C., and the difference in whiteness before and after the test was measured using a Hunter whiteness meter (filter: Am).
○: Whiteness decrease is less than 2 points Δ: Whiteness is decreased by 2 points or more and less than 10% ×: Whiteness is decreased by 10 points or more [stick resistance]
In a −5 ° C. atmosphere, a black solid print having a length of 5 cm was performed with a handy terminal printer (printer name: HT-180) manufactured by Lower Canon Inc., and the print samples were visually evaluated.
○: No sticking occurred ×: Sticking occurred [Head residue]
30 cm long grid printing was performed with a label printer (printer name: Respre R-8) manufactured by SATO, and the head residue and print samples adhering to the thermal head after printing were visually observed.
○: Head debris hardly adheres to the thermal head ×: Head debris adheres to the thermal head and the printed part is faded

In the heat-sensitive recording materials of Examples 1 to 4, the heat-sensitive recording layer contains the styrene-acrylic resin of the present invention, so that the water resistance, white paper storage stability, stick resistance, and head residue are all good. In particular, when comparing the heat-sensitive recording material of Example 1 and Comparative Example 1, the heat-sensitive recording layer of Example 1 contains the styrene-acrylic resin of the present invention. ing. The heat-sensitive recording material of Comparative Example 2 has a low minimum film-forming temperature (MFT) of the styrene-acrylic resin contained in the heat-sensitive recording layer, so that the stick resistance and the head residue are inferior. Since the glass transition temperature (Tg) of the styrene-acrylic resin contained in the recording layer is low, it is considered that the water resistance is inferior. Further, in the heat-sensitive recording material of Comparative Example 4, since the heat-sensitive recording layer does not contain the styrene-acrylic resin of the present invention and contains colloidal silica, the white paper portion storage stability is inferior and the water resistance is not sufficient.

Claims (4)

A thermosensitive recording medium comprising a thermosensitive recording layer containing a colorless or light-colored basic leuco dye and an electron-accepting developer on a support, wherein the thermosensitive recording layer further has a glass transition point of 50 ° C. or higher and a minimum film formation. A heat-sensitive recording material comprising a styrene-acrylic resin having a temperature of 20 ° C. or less and not containing a styrene-acrylic resin other than the styrene-acrylic resin. 2. The heat-sensitive recording layer contains 1 to 30% by weight of a styrene-acrylic resin having a glass transition point of 50 ° C. or more and a minimum film-forming temperature of 20 ° C. or less based on the total solid content of the heat-sensitive recording layer. Thermal recording material. In a heat-sensitive recording material provided with a heat-sensitive recording layer containing a colorless or light-colored basic leuco dye and an electron-accepting developer on the support, the heat-sensitive recording layer further contains a styrene-acrylic resin, styrene - acrylic resin, glass transition point 50 ° C. or higher and a minimum film forming temperature 20 ° C. or less styrene - acrylic resins and glass transition point 90 ° C. or higher and a minimum film-forming temperature 70 ° C. the following styrene - were mixed acrylic resin is intended, the glass transition point 50 ° C. or higher and a minimum film forming temperature 20 ° C. or less styrene - the glass transition point for the acrylic resin 90 ° C. or higher and a minimum film-forming temperature 70 ° C. the following styrene - weight ratio of the acrylic resin is 20 A heat-sensitive recording material, characterized in that the content is in the range of% to 70%. The heat-sensitive recording layer contains 1 to 30% by weight of a styrene-acrylic resin having a glass transition point of 50 ° C or higher and a minimum film-forming temperature of 20 ° C or lower based on the total solid content of the heat-sensitive recording layer. Thermal recording material.