KR20160136992A - High heat resistant thermal paper - Google Patents

Abstract

Provided is high heat-resistant thermal paper which can be used at high temperatures of 150C or higher by preventing discoloration of being darkened when in use at high temperatures. According to an embodiment of the present invention, the high heat-resistant thermal paper comprises: a base layer; a thermal color forming layer formed on the base layer; and a protective layer formed on the thermal color forming layer. The thermal color forming layer includes: 100 parts by weight of a dereloper; and 20 to 50 parts by weight of a color former.

Description

{HIGH HEAT RESISTANT THERMAL PAPER}

The present invention relates to a high heat resistance thermal paper, and more particularly, to a high heat resistance thermal paper which can be used even at a high temperature because there is no discoloration due to color development at a high temperature of 150 캜 or more.

Thermal paper is paper coated with a thermosensitive material that reacts by heat, and information can be simply recorded by heating using a thermal head or the like. Thermal paper is used for various purposes such as fax paper, label paper, receipt, admission ticket.

A thermal paper is a structure in which a material such as a coloring agent or a color developing agent is coated on a base material such as paper together with a binder. When heat is applied to the thermal paper from the thermal head, the color developer and the color developer react and develop color.

There are a coloring method using a dye and a coloring method using a metallic salt, and a coloring method using a dye is mainly used. A coloring method using the dye is to use a coloring agent called a leuco dye and a color developing agent for coloring the leuco dye.

However, conventional thermal paper starts coloring at 60 ° C, and when used at a high temperature, the floor changes to black due to color development. As a result, black characters, bar codes, and the like recorded on the floor disappear, making identification difficult.

Japanese Laid-Open Patent Application No. 2015-30227 (published on February 16, 2015) Japanese Unexamined Patent Publication No. 2015-30237 (published on February 16, 2015)

The present invention provides a high heat-resistance thermal paper which can be used even at a high temperature of 150 占 폚 or more by preventing discoloration that turns black when used at a high temperature.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to an aspect of the present invention, there is provided a high heat resistant thermal paper comprising: a base layer; A thermo-sensitive coloring layer formed on the base layer; And a protective layer formed on the heat-sensitive coloring layer, wherein the heat-sensitive coloring layer comprises 100 parts by weight of a color developing agent and 20 to 50 parts by weight of a coloring agent.

In addition, the heat-sensitive color development layer may include a bisphenol-based color developing agent.

The heat-sensitive coloring layer may include a coloring agent having a melting point of 170 to 250 ° C.

The heat-sensitive color development layer may further include a sensitizer.

The heat-sensitive color development layer may include 100 parts by weight of the developer and 1 to 30 parts by weight of the sensitizer.

Other specific details of the invention are included in the detailed description and drawings.

According to the present invention, even at a high temperature of 150 ° C or higher, there is no discoloration due to color development, so that it can be used at a high temperature for a sticker or the like.

1 is a schematic cross-sectional view of a high heat-resistance thermal paper according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

Although the first, second, etc. are used to describe various elements, components and / or sections, it is needless to say that these elements, components and / or sections are not limited by these terms. These terms are only used to distinguish one element, element or section from another element, element or section. Therefore, it goes without saying that the first element, the first element or the first section mentioned below may be the second element, the second element or the second section within the technical spirit of the present invention.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. As used herein, the terms "comprises" and / or "made of" means that a component, step, operation, and / or element may be embodied in one or more other components, steps, operations, and / And does not exclude the presence or addition thereof.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

1 is a schematic cross-sectional view of a high heat-resistance thermal paper according to an embodiment of the present invention.

1, a high heat-resistance thermal paper 10 according to an exemplary embodiment of the present invention includes a base layer 11, a heat-sensitive color development layer 12 formed on the base layer 11, And a protective layer 13 formed on the substrate 12. At this time, the heat-sensitive coloring layer 12 may include 100 parts by weight of a color developing agent and 20 to 50 parts by weight of a coloring agent.

The base layer 11 may be made of paper, film or the like. Recycled paper, art paper, coated paper, cardboard, etc. can be used for paper. Further, the film is a plastic film, and films such as polyamide, polyethylene, polypropylene, polyvinylidene chloride, polyvinyl chloride, polyester, polyethylene terephthalate, and polyolefin resin can be used. It will be apparent to those skilled in the art that other species or films may be used.

The heat-sensitive color development layer 12 is formed on the base layer 11 and may include a coloring agent, a color developing agent, a binder, and the like. In particular, the heat-sensitive coloring layer 12 may use about 20 to 50% by weight of a coloring agent as a color developing agent. Preferably, the heat-sensitive coloring layer 12 may contain 30 to 40 parts by weight of a coloring agent relative to 100 parts by weight of the color developing agent. Further, the heat-sensitive color development layer 12 may further include a sensitizer. Here, the thermo-sensitive coloring layer 12 may include 1 to 30 parts by weight of the sensitizing dye based on 100 parts by weight of the developing agent.

Coloring agents use leuco dyes, which are colored when the conditions of the external environment are exposed or dissolved in acidic conditions. The leuco dye used as a coloring agent is a compound made by reducing a dye, and does not show color when it is in a reduced state, but has a property of returning to the original dye upon oxidation and developing color. These leuco dyes can be selected from the group consisting of dyes of triphenylmethane dyes, triphenylmethane dyes, triarylmethane dyes, lactone dyes, and fluorine dyes.

For example, 3-cyclohexylamino-6-chlorofluorane; 3-diethylamino-6-methyl-7-chlorofluorane; 3-diethylamino-6,7-dimethylfluororan; 3-diethylamino-7-chlorofluorane; 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran; 3-di (n-butyl) amino-6-methyl-7-anilinofluoran; 3-di (n-pentyl) amino-6-methyl-7-anilinofluoran; 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluoran; 3-di (n-butyl) amino-6-chloro-7-anilinofluoran; 3-pyrrolidino-6-methyl-7-anilinofluoran; 3-piperidino-6-methyl-7-anilinofluoran; 3- [2,2-bis (1-ethyl-2-methylindol-3-yl) -vinyl] -3- (4-diethylaminophenyl) phthalide; 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide; 3- (4-diethylamino-2-methylphenyl) -3- (4-dimethylaminophenyl) -6-dimethylaminophthalide; 3,3-bis [1- (4-methoxyphenyl) -1- (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide; 3-p- (p-dimethylaminoanilino) anilino-6-methyl-7-chlorofluorane; 3-p- (p-Chloroanilino) anilino-6-methyl-7-chlorofluorane; 3- [1,1-bis (1-ethyl-2-methylindol-3-yl)] - 3-p-diethylaminophenylphthalide; 3,3'-bis (1-n-butyl-2-methylindol-3-yl) phthalide; 3,6- bis (dimethylamino) fluorene-9-spiro-3 '- (6'-dimethylamino) phthalide can be used as a coloring agent. Of course, the present invention is not limited to these, and it is apparent to those skilled in the art that two or more kinds of them may be used in combination.

Preferably, a coloring agent having a melting point of 170 to 250 ° C can be used. Specifically, 2'-anilino-6 '- (dibutylamino) -3'-methyl spiro [phthalide-3,9'-xanthene] -methylspiro [phthalide-3,9'-xanthene]) and 2'-anilino-6 '- [N-ethyl- Amino] -3'-methyl-3H-spiro [isobenzofuran-1,9 ', 5'- -xanthene] -3-on) can be used as a coloring agent.

The Chemical Abstract Service (CAS) registration number of "2'-anilino-6 '- (dibutylamino) -3'-methyl spiro [phthalide-3,9'-xanthene]" is 89331-94- 2, the molecular formula is C35H36N2O3, and the structure is as shown in the following formula (1).

The above 2'-anilino-6 '- (dibutylamino) -3'-methyl spiro [phthalide-3,9'-xanthene] is black and has a melting point of about 182-183.5 ° C, Thermal resistance thermal paper using the above 2'-anilino-6 '- (dibutylamino) -3'-methyl spiro [phthalide-3,9'-xanthene] as a coloring agent (10) can be used for applications such as stickers at high temperatures.

3'-methyl-3H-spiro [isobenzofuran-1,9'-xanthene] -3-one " Has a Chemical Abstract Service (CAS) registration number of 59129-79-2, a molecular formula of C36H30N2O3, and a structure represented by the following chemical formula (2).

Amino] -3'-methyl-3H-spiro [isobenzofuran-1,9'-xanthene] -3-one was prepared from 2'-anilino- Anilino-6 '- [N-ethyl-N- (4-tolyl) amino] propionic acid was obtained in the same manner as in Example 1 except that there was no discoloration due to coloring even at a high temperature of 150 ° C., Heat-resistant thermal paper 10 using 3'-methyl-3H-spiro [isobenzofuran-1,9'-xanthene] -3-one as a coloring agent can be used for applications such as stickers at high temperatures.

(2'-anilino-6 '- (dibutylamino) -3'-methyl spiro [phthalide-3,9'-xanthene] methylspiro [phthalide-3,9'-xanthene]) and 2'-anilino-6 '- [N-ethyl- , 9'-xanthen] -3-one (2'-anilino-6'- [N-ethyl-N- (4-tolyl) amino] 3'- methyl-3H- spiro [isobenzofuran- xanthene] -3-on) is used as a coloring agent, it melts at a temperature of at least 170 < [chi] > C. Therefore, discoloration due to color development of the high heat- I will not.

The developer may be a bisphenol-based, alkylphenol-based, metal salt, or the like. Preferably, a bisphenol-based coloring agent such as bisphenol A or bisphenol S can be used. Particularly, the bisphenol-based color developing agent may be used in an amount of 20 to 50 parts by weight based on 100 parts by weight of the coloring agent.

The binder is used for dispersing and isolating the coloring agent and the coloring agent and for fixing the base layer 11. As the binder, polyvinyl alcohol, a cellulose derivative, a starch, a casein, a polyacrylamide and the like can be used.

The sensitizer may be added to the thermo-sensitive coloring layer 12 as needed in order to increase the recording sensitivity by lowering the heat-coloring temperature according to the use of the high-melting point coloring agent and the color developing agent. When a sensitizer is used, the thermo-sensitive coloring layer 12 may include 1 to 30 parts by weight of the sensitizer in 100 parts by weight of the developing agent. Preferably, 0 to 20% by weight of the sensitizer may be added to the color developing agent. These sensitizers may be selected from the group consisting of thiacaric acid amide, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, 2-naphthylbenzyl ether, p-benzylbiphenyl, p- tolylbiphenyl ether, di (p- methoxyphenoxyethyl) Di (4-methylphenoxy) ethane, 1- (4-methoxyphenoxy) -2- (3-methylphenoxy) Ethane, p-methylthiophenyl benzyl ether, 1,4-di (phenylthio) butane, p-acetaldehyde, p-acetaphenetide, N-acetacetyl- Phenyl ethoxy) benzene, di-p-chlorobenzyl oxalate, dibenzyl ester oxalate and the like. Particularly, when the color developer is a bisphenol-based compound represented by bisphenol A, it is preferable to use p-benzylbiphenyl, benzyl p-benzyloxybenzoate, benzylnaphthyl ether or the like as a sensitizer.

Further, the heat-sensitive coloring layer 12 may further include suitable additives as well as sensitizers. Pigments such as calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, aluminum hydroxide, barium sulfate, talc, kaolin, clay, calcined kaolin and urea / formalin resin filler; Surfactants such as sodium dioctylsulfosuccinate, sodium dodecibenzenesulfosuccinate and sodium lauryl alcohol sulfate ester; Lubricants such as zinc stearate, calcium stearate and calcium oleate; Waxes such as polyethylene wax, carnauba wax and paraffin. In addition, a defoaming agent, a curing agent, a stabilizer for improving preservability, a thickener, a pH adjuster, an ultraviolet absorber, and the like can be further added to the thermo-sensitive coloring layer 12.

The protective layer 13 is formed on the thermo-sensitive coloring layer 12. The protective layer 13 suppresses discoloration and discoloration and improves image stability. The heat-resistant thermal paper 10 can be improved in luster and heat resistance through the protective layer 13, and information damage, contamination, and the like can be prevented. The protective layer 13 can be composed of an acrylic resin, a polyester resin, a polycarbonate resin, a polystyrene resin, an epoxy resin, a polyurethane resin, or the like, alone or in combination. Particularly, the gloss, heat resistance, and anti-aging property of the thermal paper 10 can be increased by using an acrylic resin, an ultraviolet ray hardening resin, an ionizing radiation hardening resin or the like.

Further, the protective layer 13 may further include an appropriate additive. For example, a filler, a dispersant, a lubricant, a defoaming agent, and the like may be further added. The protective layer 13 may be formed by laminating a plurality of layers as well as a single layer.

Although not shown in the drawing, an arbitrary layer can be formed between the base layer 11 and the thermo-sensitive coloring layer 12 or between the thermo-sensitive coloring layer 12 and the protective layer 13, and the protective layer 13 Or on the lower surface of the base layer 11, as shown in Fig.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, You will understand. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

10: High heat resistant thermal paper
11: base layer 12: thermosensitive coloring layer
13: Protective layer

Claims (5)

A base layer;
A thermo-sensitive coloring layer formed on the base layer; And
And a protective layer formed on the heat-sensitive color development layer,
Wherein the heat-sensitive coloring layer comprises 100 parts by weight of a color developing agent and 20 to 50 parts by weight of a coloring agent. The method according to claim 1,
Wherein the heat-sensitive coloring layer comprises a bisphenol-based coloring agent. The method according to claim 1,
Wherein the heat-sensitive coloring layer comprises a coloring agent having a melting point of 170 to 250 ° C. The method according to claim 1,
Wherein the heat-sensitive coloring layer further comprises a sensitizer. 5. The method of claim 4,
Wherein the heat-sensitive color development layer comprises 100 parts by weight of the developer and 1 to 30 parts by weight of the sensitizer.

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