JP2003237241A - Heat-sensitive recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-sensitive recording medium showing outstanding water resistance and color fastness. <P>SOLUTION: This heat-sensitive recording medium has a polyvinyl alcohol (A) containing an acetoacetic acid ester group and a chemical compound (B) containing an amino group represented by formula (I): R-[(CH<SB>2</SB>)<SB>n</SB>-NHR<SB>1</SB>]<SB>m</SB>(wherein R is a residue, excepting a hydrogen of a cyclic compound, selected from among an aromatic ring, an aliphatic ring and a complex ring; R<SB>1</SB>is either of hydrogen or an alkyl group; n is either of 0 or a positive integer; and m is a positive integer) added to a heat-sensitive color developing layer and/or a protecting layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosensitive recording medium excellent in water resistance and discoloration resistance.

[0002]

2. Description of the Related Art Conventionally, polyvinyl alcohol resins have been used as a binder for a thermosensitive coloring layer of a thermosensitive recording paper or a coating agent for a protective layer, and have an acetoacetic acid ester group for the purpose of further improving water resistance. The introduced polyvinyl alcohol-based resin is also adopted.

For example, the applicant of the present invention also discloses Japanese Patent Laid-Open No. 59-1236.
In Japanese Patent Laid-Open No. 97, it was proposed to use a polyvinyl alcohol (hereinafter sometimes abbreviated as AA-PVA) containing an acetoacetic acid ester group and a cross-linking agent together with a color-forming substance and a developer. Further, JP-A-59-106995, JP-A-60-245591, and JP-A-1-12038.
No. 5, for example, a heat-sensitive recording material having AA-PVA as a protective layer is described.

[0004]

However, although polyaldehydes such as glyoxal, which is a cross-linking agent for AA-PVA described in each of the above publications, have excellent water resistance, they may change with time depending on the use conditions. There is a problem of yellowing, and linear polyamine compounds such as ethylenediamine and hexamethylenediamine do not have the problem of yellowing, but the water resistance is insufficient, and the thermosensitive recording is excellent in water resistance and discoloration resistance. This is where media for use are desired.

[0005]

[Means for Solving the Problems] Therefore, the present inventor has conducted diligent research in view of the above circumstances, and as a result, AA-PVA
A thermosensitive recording medium comprising a composition containing (A) and an amino group-containing compound (B) represented by the following general formula (1) in a thermosensitive coloring layer and / or a protective layer, or acetoacetic acid. Ester group-containing polyvinyl alcohol (A)
According to the present invention, it has been found that a heat-sensitive recording medium containing in a protective layer and containing an amino group-containing compound (B) represented by the following general formula (1) in a heat-sensitive color forming layer can solve the above problems. Has been completed. R - [(CH _{2) n} -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, R ₁ Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer. In the present invention, the amino group-containing compound represented by the general formula (1) ( B) is metaxylenediamine,
Particularly preferred is either 1,3-bisaminomethylcyclohexane or norbornanediamine.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The AA-modified PVA (A) used in the present invention is obtained by reacting polyvinyl alcohol with diketene, or by reacting polyvinyl alcohol with acetoacetic ester to transesterify the polyvinyl alcohol to form an acetoacetic acid ester group. Introduced, as such polyvinyl alcohol, generally, a saponified product or a derivative thereof obtained by saponifying a lower alcohol solution of polyvinyl acetate with a saponification catalyst such as an alkali or an acid is used. It is also possible to use a saponified product of a copolymer of a copolymerizable monomer and vinyl acetate.

Examples of such a monomer include ethylene,
Olefin such as propylene, isobutylene, α-octene, α-dodecene, α-octadecene, vinylene carbonates, acrylic acid, methacrylic acid, crotonic acid,
Maleic acid, maleic anhydride, unsaturated acids such as itaconic acid or salts or mono- or dialkyl esters thereof, acrylonitrile, nitriles such as methacrylonitrile, amides such as acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, Olefin sulfonic acids such as methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, N-acrylamidomethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, dimethyl allyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride , Polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, etc. Ether, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate and other polyoxyalkylene (meth) acrylates, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide and other polyoxyalkylene (meth) Acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxy Examples include propylene vinylamine.

The polyvinyl alcohol used as the raw material for the AA-modified PVA (A) is not particularly limited, but the saponification degree is 70 mol% or more (further 75 mol% or more, particularly 8 mol%).
0 mol% or more) is preferable, and if the saponification degree is less than 70 mol%, the water solubility is poor and it becomes difficult to prepare a coating solution, which is not preferable. The average degree of polymerization of the polyvinyl alcohol (according to JIS K6726) is not particularly limited, either, but is 100 to 5000 (further 200 to 4).
500, particularly 300 to 4000) is preferable, and when the average degree of polymerization is less than 100, sufficient water resistance cannot be obtained. On the contrary, when the average degree of polymerization is more than 5000, the viscosity of the aqueous solution becomes too high and the material is mixed with other materials. Is unfavorable because the workability of (3) and the uniform coating on the substrate become difficult.

To obtain AA-PVA (A), a method of reacting polyvinyl alcohol with diketene as described above,
Examples include a method of transesterifying polyvinyl alcohol and acetoacetate ester, a method of copolymerizing vinyl acetate and vinyl acetoacetate, and the like. However, since the production process is simple and high-quality AA-PVA can be obtained. Preferably, it is produced by a method of reacting polyvinyl alcohol (powder) with diketene. As a method of reacting polyvinyl alcohol and diketene, polyvinyl alcohol and gaseous or liquid diketene may be directly reacted, or after organic acid is adsorbed and absorbed in polyvinyl alcohol in advance, it is liquid or under an inert gas atmosphere. A method of spraying and reacting gaseous diketene, or spraying and reacting polyvinyl alcohol with a mixture of an organic acid and liquid diketene is used.

As a reaction apparatus for carrying out the above reaction, an apparatus capable of heating and equipped with a stirrer is sufficient. For example, a kneader, a Henschel mixer, a ribbon blender, other various blenders, and a stirring / drying device can be used.

The content of acetoacetic acid ester group in the thus obtained AA-PVA (A) is 0.1 to 40 mol%.
(Further, 0.3 to 30 mol%, particularly 0.5 to 20 mol%) is preferable, and if the content is less than 0.1 mol%, sufficient water resistance cannot be obtained, and conversely 40 mol% If it exceeds the range, the water solubility in the coating solution is lowered and the storage stability of the obtained coating solution is lowered, which is not preferable.

The amino group-containing compound (B) used in the present invention is represented by the following general formula, wherein R is a cyclic compound selected from an aromatic ring, an aliphatic ring and a heterocycle. residue obtained by removing a hydrogen, R ₁ is hydrogen, with either an alkyl radical, n is 0 or a positive integer, m is intended to represent a positive integer, respectively. R - [(CH _{2) n} -NHR _{1] m} ··· (1) according alkylamino group-containing compound as (B) is meta-xylene diamine, norbornane diamine, 1,3
Bisaminomethylcyclohexane, bisaminopropylpiperazine, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodiphenylmethane, 3,3 ′, 5 5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,
3'-dimethyl-4,4'-diamino-5,5'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, diaminodiphenyl sulfone, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,
4-phenylenediamine, 3-methyl-1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2 -Methyl-4,
6-diethyl-1,3-phenylenediamine, 2,4-
Diethyl-6-methyl-1,3-phenylenediamine,
Examples thereof include 2,4,6-trimethyl-1,3-phenylenediamine and 2-chloro-1,4-phenylenediamine, but water-soluble or water-dispersible ones are preferable, and among them, metaxylenediamine, 1 It is particularly preferable to use any of 3,3-bisaminomethylcyclohexane and norbornanediamine.

The heat-sensitive recording medium of the present invention comprises a composition containing the above-mentioned AA-PVA (A) and the amino group-containing compound (B) in the heat-sensitive color forming layer and / or the protective layer. Alternatively, the above-mentioned AA-modified PVA (A) is contained in the protective layer, and the amino group-containing compound (B) is contained in the heat-sensitive color developing layer, wherein the AA-modified PVA (A) and the amino group-containing compound (B Is not particularly limited, but the content ratio (A / B) of the AA-modified PVA (A) and the amino group-containing compound (B) is 100 / 0.1 to 100/30.
(Further 100 / 0.3 to 100/25, especially 10
(0 / 0.5 to 100/20) (weight ratio) is preferable, and when the content ratio exceeds 100 / 0.1, the water resistance tends to decrease, and conversely, when it is less than 100/30, the water resistance tends to decrease. The discoloring property tends to decrease, which is not preferable.

The heat-sensitive recording medium of the present invention comprises the above composition or the AA-modified PVA (A) and the amino group-containing compound (B) in the heat-sensitive color forming layer or the protective layer.
A method of manufacturing such a recording medium will be described. It should be noted that such a composition can be applied to the above two layers at the same time.

Each of these layers will be described in detail below. The thermosensitive color-developing layer is obtained by coating the above-mentioned AA-PVA (A) and amino group-containing compound (B) with a color-developing substance and a color developer, and then applying the aqueous solution to a substrate. Can be formed. AA PV at this time
A suitable amount of A (A) is 10 to 200% by weight based on the total amount of the color-forming substance and the color developer. The solid content concentration of the aqueous solution is selected from the range of 10 to 40% by weight in consideration of workability.

Examples of the above-mentioned color forming substance include 3,3-
Bis (P-dimethylaminophenyl) -phthalide, 3,
3-bis (P-dimethylaminophenyl) -6-dimethylaminophthalide [crystal violet lactone], 3,3-bis (P-dimethylaminophenyl)-
6-diethylaminophthalide, 3,3-bis (P-dimethylaminophenyl) -6-chlorophthalide, 3-dimethylamino-6-methoxyfluorane, 7-acetamino-3-diethylaminofluorane, 3-diethylamino-5. 7-dimethylfluorane, 3-diethylamino-5,7-dimethylfluorane, 3,6-bis-β
Examples thereof include leuco forms of triphenylmethane dyes such as -methoxyethoxyfluorane and 3,6-bis-β-cyanoethoxyfluorane.

Further, as the color developer, those which react with the above-mentioned color-forming substance to develop color when heated and liquefy or vaporize at room temperature or higher, preferably at 70 ° C. or higher, for example, phenol, P-methylphenol, P-tersia Libutylphenol, P-phenylphenol, α-naphthol, β-naphthol, 4,4′-isopropylidenediphenol [bisphenol A], 4,4′-secondary butylidene diphenol, 4,4′-cyclohexylidene diphenol, 4,4'-isopropylidene bis (2-tert-butylphenol), 4,4'-
(1-methyl-n-hexylidene) diphenol, 4,
4'-isopropylidene dicatechol, 4,4'-pentylidene diphenol, 4,4-isopropylidene bis (2-chlorophenol), phenyl-4-hydroxybenzoate, salicylic acid, 3-phenylsalicylic acid,
5-Methylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 1-oxy-2-naphthoic acid, m-oxybenzoic acid, 4-oxyphthalic acid, gallic acid, etc. are mentioned, but they are color-forming substances and color-developing substances. The agents are not limited to these.

In coating the base material with the aqueous solution, any known method such as a roll coater method, an air-coater method, a blade coater method, a bar coater method, a size press method, and a gate roll method can be used. The coating amount of the aqueous solution is 0.1 to 20 g / m ² (further 0.5
To 15 g / m ^2, particularly preferably used so that 1 to 10 g / m ²⁾ degree.

Next, the protective layer will be described. The protective layer is a layer formed (coated) on a thermosensitive coloring layer composed of a color-forming substance, a color-developing agent, and a binder (for example, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, starches, latexes, etc.). That is.

In the coating, an aqueous solution containing the above-mentioned AA-PVA (A) and the amino group-containing compound (B) and, if necessary, the following pigments and various auxiliaries are mixed and stirred to obtain a coating. A working solution may be used, and the coating amount at this time is preferably about 0.5 to 10 g / m ^{2 in} dry weight. After coating, the target coating layer is formed by performing air-drying or mild heat treatment. It is also possible to separately prepare an aqueous solution containing each of the AA-PVA (A) and the amino group-containing compound (B), and laminate-coat these to form a protective layer. The agent is preferably blended in an aqueous solution of AA-PVA (A), resulting in the AA-PVA in the protective layer.
Since (A) and the amino group-containing compound (B) are contained, the content ratio (A / B), the coating amount, etc. may be adjusted according to the above. Examples of the pigment include inorganic pigments such as calcium carbonate, zinc oxide, aluminum oxide, talc, kaolin, and clay, nylon resin fillers, urea / formalin resin fillers, and organic pigments such as starch particles. Lubricants such as zinc stearate, calcium stearate, and paraffin wax, surfactants, ultraviolet absorbers, fluorescent dyes, release agents,
Examples include antioxidants.

Further, in order to suppress thickening due to the cross-linking agent, an acid (organic acid, inorganic acid), a metal compound (alum,
It is also useful to add aluminum sulfate, etc.) and β-diketone compounds (acetylacetone, methyl acetoacetate, etc.). The coating can be carried out by any means such as a roll coater method, an eardactor method, a blade coater method, a bar coater method, a size press method, and a gate roll method. AA-PVA is contained in the protective layer, and When the group-containing compound (B) is contained in the thermosensitive color-developing layer, the coating liquid containing the AA-modified PVA (A) and the amino group-containing compound (B) is separately prepared according to the above to prepare a protective layer. Each coating may be applied to the thermosensitive coloring layer.

There are no particular restrictions on the base material used in the above-mentioned thermal recording medium, and paper (manila balls, white balls, paperboard such as liners, printing paper such as general high-quality paper, medium-quality paper, gravure paper, etc.). , Upper / middle / lower grade paper, newsprint paper, release paper, carbon paper, non-carbon paper, glassine paper, etc.) and plastic films (polyester film, nylon film, polyolefin film, polyvinyl chloride film and laminates of these), etc. Can be used.

The heat-sensitive recording medium obtained is as follows.
Substrate / Undercoat layer / Thermal coloring layer / Protective layer, Substrate /
It is possible to have a layer structure such as undercoat layer / thermosensitive coloring layer, substrate / thermosensitive coloring layer / protective layer or substrate / thermosensitive coloring layer.

The heat-sensitive recording medium of the present invention thus obtained contains the above-mentioned AA-modified PVA (A) and the specific amino group-containing compound (B) in its heat-sensitive color forming layer and / or protective layer. Therefore, it has excellent water resistance and discoloration resistance.

[0025]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "parts" and "%" are based on weight unless otherwise specified.

Example 1 A thermal recording medium was prepared and evaluated in the following manner. First, the following aqueous solutions (liquids A to C) were prepared. [Liquid A] Crystal violet lactone 10 parts 5% aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, average degree of polymerization 1100) 10 parts water 15 parts

[0027] [B liquid]   Bisphenol A 50 parts   5% water of polyvinyl alcohol (saponification degree 98 mol%, average degree of polymerization 1100)   50 parts of solution   75 parts of water

[0028] [C liquid]   AA-PVA (saponification degree 99.2 mol%, average degree of polymerization 1200, acetoacetic acid   Containing 5 mol% of stell group) (A) 10% aqueous solution 100 parts   Metaxylenediamine (B) 0.5 part   Kaolin clay 15 copies

The above liquids A and B were separately pulverized with a sand grinder until the average particle size became about 2 μ, and then A
Solution, solution B, 50 parts of calcium carbonate and the same 5% aqueous solution of polyvinyl alcohol resin as used in solution A 25
0 parts were mixed to obtain a color developing solution. Next, the color-developing liquid is applied onto a high-quality paper (base material) having a basis weight of 50 g / m ² so that the coating amount after drying is 8 g / m ² , and dried to form a thermosensitive coloring layer. After that, using a Dickson coater, the liquid C is applied on the layer so that the coating amount after drying is 5 g / m ² to form a protective layer, and the layer is dried at 60 ° C. The surface was smoothed with a calendar to obtain a heat-sensitive recording paper. The water resistance and discoloration resistance of the resulting thermal recording paper were evaluated according to the following procedures.

(Water resistance) Thermal inclination tester (manufactured by Toyo Seiki Co., Ltd.)
120 ° C., is printed color under the conditions of 2 kg / cm ^2, 5 seconds, the printing color development density Macbeth densitometer by (Macbeth "RD-100R type", amber filter used)
At 20 ° C.
After being soaked in water for 24 hours, it was naturally dried and the color density of the printed portion was measured in the same manner, and the ratio of the print density after immersion to the print density before immersion was calculated to be used as an index of water resistance.

(Discoloration resistance) The obtained thermal recording paper was
After leaving it in an atmosphere of 60 ° C and 60% RH for 30 days, the YI (yellow index) value was measured by a reflection method using a color difference meter (“SZ-Σ90” manufactured by Nippon Denshoku Industries Co., Ltd.).

Example 2 The same procedure as in Example 1 was carried out except that as the AA-modified PVA (A), an AA-modified PVA having a saponification degree of 95 mol%, an average degree of polymerization of 1700, and an acetoacetic ester group of 3 mol% was used. A recording paper was obtained and evaluated in the same manner.

Example 3 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that norbornanediamine (B) was used instead of metaxylenediamine (B), and the same evaluation was performed.

Example 4 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the mixing amount of meta-xylenediamine (B) was changed to 0.3 part.
It evaluated similarly.

Example 5 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the amount of norbornanediamine (B) mixed was changed to 1 part, and the same evaluation was performed.

Example 6 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that 0.8 part of 1,3-bisaminomethylcyclohexane (B) was used instead of metaxylenediamine (B). It evaluated similarly.

Example 7 A thermal recording paper was prepared in the following manner and evaluated in the same manner as in Example 1. First, the following aqueous solutions (liquids A and B) were prepared. [Liquid A] Crystal violet lactone 10 parts 5% aqueous solution of AA-PVA (saponification degree 99.2 mol%, average degree of polymerization 1200, acetoacetate ester group 5 mol% contained) (A) 10 parts water 15 parts

[0038] [B liquid]   Bisphenol A 50 parts   AA-PVA (saponification degree 99.2 mol%, average degree of polymerization 1200, acetoacetic acid   50 parts by weight of 5% aqueous solution of (A) (containing 5 mol% stele group)   75 parts of water

The above-mentioned solutions A and B were separately pulverized with a sand grinder until the average particle size became about 2 μ, and then A
Solution, solution B, 50 parts of calcium carbonate and the same 5% aqueous solution of polyvinyl alcohol resin as used in solution A 25
0 part and 1 part of metaxylenediamine (B) were mixed to obtain a color developing solution. Next, the color-developing liquid is applied onto a high-quality paper (base material) having a basis weight of 50 g / m ² so that the coating amount after drying is 8 g / m ² , and dried to form a thermosensitive coloring layer. After that, the surface was smoothed with a super calendar to obtain a thermal recording paper.

Example 8 The same procedure as in Example 7 was carried out except that as the AA-PVA (A), an AA-PVA having a saponification degree of 95 mol%, an average polymerization degree of 1700, and an acetoacetic acid ester group containing 3 mol% was used. A recording paper was obtained and evaluated in the same manner.

Example 9 A thermosensitive recording paper was obtained in the same manner as in Example 7, except that norbornanediamine (B) was used instead of metaxylenediamine (B), and the same evaluation was performed.

Example 10 A thermosensitive recording paper was obtained in the same manner as in Example 7 except that 1.5 parts of 1,3-bisaminomethylcyclohexane (B) was used instead of metaxylenediamine (B). It evaluated similarly.

Example 11 A thermosensitive recording paper was obtained in the same manner as in Example 7 except that the mixing amount of the meta-xylenediamine (B) was changed to 2 parts, and the same evaluation was performed.

Example 12 In Example 7, after the thermosensitive coloring layer was formed, the C liquid of Example 1 was dried on the layer so that the coating amount after drying was 5 g / m ² . After forming a protective layer by coating on the above, the surface was smoothed with a super calender to obtain a thermal recording paper, and the same evaluation as in Example 1 was carried out.

Example 13 A thermosensitive recording paper was prepared in the same manner as in Example 1 except that 2 parts of meta-xylenediamine (B) was contained in solution A and metaxylenediamine (B) was not contained in solution C. Obtained and evaluated in the same manner.

Comparative Example 1 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that glyoxal was used instead of metaxylenediamine (B), and the same evaluation was performed.

Comparative Example 2 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that hexamethylenediamine was used instead of metaxylenediamine (B), and the same evaluation was performed.

Comparative Example 3 A thermosensitive recording paper was obtained in the same manner as in Example 7 except that glyoxal was used instead of metaxylenediamine (B), and the same evaluation was performed.

Comparative Example 4 A thermosensitive recording paper was obtained in the same manner as in Example 7 except that hexamethylenediamine was used instead of metaxylenediamine (B), and the same evaluation was performed.

Table 1 shows the evaluation results of the examples and comparative examples.

[0051]

[0052]

The heat-sensitive recording medium of the present invention is made of AA-PV.
Since A (A) and the specific amino group-containing compound (B) are contained in the thermosensitive coloring layer and / or the protective layer,
Excellent water resistance and discoloration resistance.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 2, 2002 (2002.12.
2)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

[0005]

[Means for Solving the Problems] Therefore, the present inventor has conducted diligent research in view of the above circumstances, and as a result, AA-PVA
A thermosensitive recording medium comprising a composition containing (A) and an amino group-containing compound (B) represented by the following general formula (1) in a thermosensitive coloring layer and / or a protective layer, or acetoacetic acid. Ester group-containing polyvinyl alcohol (A)
According to the present invention, it has been found that a heat-sensitive recording medium containing in a protective layer and containing an amino group-containing compound (B) represented by the following general formula (1) in a heat-sensitive color forming layer can solve the above problems. Has been completed. R - _{[(CH 2)} n -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, _{R 1} Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer. In the present invention, the amino group-containing compound represented by the general formula (1) ( B) is Metakishi Li diamine, and particularly preferably one of 1,3-bis-aminomethyl cyclohexane or norbornane diamine.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

The amino group-containing compound (B) used in the present invention is represented by the following general formula, wherein R is a cyclic compound selected from an aromatic ring, an aliphatic ring and a heterocycle. residue obtained by removing a hydrogen, R ₁ is hydrogen, with either an alkyl radical, n is 0 or a positive integer, m is intended to represent a positive integer, respectively. R - _{[(CH 2)} n -NHR _{1] m} ··· (1) according alkylamino group-containing compound as (B) is Metakishi re diamine, norbornane diamine, 1,3
-Bisaminomethylcyclohexane, bisaminopropylpiperazine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 3,3 ', 5 , 5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,
3'-dimethyl-4,4'-diamino-5,5'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, diaminodiphenyl sulfone, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,
4-phenylenediamine, 3-methyl-1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2 -Methyl-4,
6-diethyl-1,3-phenylenediamine, 2,4-
Diethyl-6-methyl-1,3-phenylenediamine,
2,4,6-trimethyl-1,3-phenylenediamine, 2-chloro-1,4 can be cited phenylenediamines, etc., but is preferably a water-soluble or water-dispersible, among others Metakishi Li diamine, It is particularly preferable to use either 1,3-bisaminomethylcyclohexane or norbornanediamine.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

[0028] [C liquid] AA reduction PVA (saponification degree 99.2 mol%, average polymerization degree of 1200, acetoacetic an ester group 5 mol% content) of 10% aqueous solution of 100 parts of Metakishi Li diamine (A) (B ) 0.5 copies Kaolin clay 15 copies

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

[0033] In Example 3 Example 1, instead of the Metakishi Li diamine (B), except for using the norbornane diamine (B) to obtain a heat-sensitive recording paper was similarly evaluated in the same manner.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[0034] In Example 4 Example 1, except for changing the mixing amount of Metakishi Li diamine (B) 0.3 parts to obtain a heat-sensitive recording paper was similarly evaluated in the same manner.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

[0036] In Example 6 Example 1, instead of the Metakishi Li diamine (B), 1,3-bis-aminomethyl cyclohexane (B)
Thermal recording paper was obtained in the same manner except that 0.8 parts of was used and evaluated in the same manner.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041] In Example 9 Example 7, instead of the Metakishi Li diamine (B), except for using the norbornane diamine (B) to obtain a heat-sensitive recording paper was similarly evaluated in the same manner.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042] In Example 10 Example 7, instead of the Metakishi Li diamine (B), 1,3-bis-aminomethyl cyclohexane (B)
A thermosensitive recording paper was obtained in the same manner except that 1.5 parts of was used and evaluated in the same manner.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043] In Example 11 Example 7, except for changing the mixing amount of Metakishi Li diamine (B) to 2 parts to obtain a heat-sensitive recording paper was similarly evaluated in the same manner.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

[0045] In Example 13 Example 1, Metakishi re diamine in A solution (B) is contained 2 parts, likewise heat sensitive recording except that did not contain Metakishi Li diamine (B) in the C solution Paper was obtained and evaluated in the same manner.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046] In Comparative Example 1 Example 1, instead of the Metakishi Li diamine (B), except for using glyoxal to obtain a heat-sensitive recording paper was similarly evaluated in the same manner.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

[0047] In Comparative Example 2 Example 1, instead of the Metakishi Li diamine (B), except for using hexamethylenediamine obtain a heat-sensitive recording paper was similarly evaluated in the same manner.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048] In Comparative Example 3 Example 7, instead of the Metakishi Li diamine (B), except for using glyoxal to obtain a heat-sensitive recording paper was similarly evaluated in the same manner.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[0049] In Comparative Example 4 Example 7, instead of the Metakishi Li diamine (B), except for using hexamethylenediamine obtain a heat-sensitive recording paper was similarly evaluated in the same manner.

Claims (4)

[Claims] 1. A thermosensitive color-forming layer and / or a protective layer comprising a composition containing a polyvinyl alcohol (A) containing an acetoacetic acid ester group and an amino group-containing compound (B) represented by the following general formula (1). A heat-sensitive recording medium characterized by having. R - [(CH _{2) n} -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, R ₁ Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer.) 2. A polyvinyl alcohol (A) containing an acetoacetic acid ester group is contained in the protective layer, and an amino group-containing compound (B) represented by the following general formula (1) is contained in the thermosensitive coloring layer. A heat-sensitive recording medium characterized by: R - [(CH _{2) n} -NHR _{1] m} ··· (1) (wherein, R represents residues except for hydrogen of an aromatic ring, aliphatic ring, cyclic compound selected from heterocyclic, R ₁ Is hydrogen or an alkyl group, n is 0 or a positive integer, and m is a positive integer.) 3. The amino group-containing compound (B) represented by the general formula (1) is any of metaxylenediamine, 1,3-bisaminomethylcyclohexane or norbornanediamine. 1 or 2
The heat-sensitive recording medium described. 4. The ratio (A / B) of the acetoacetic acid ester group-containing polyvinyl alcohol (A) and the amino group-containing compound (B) represented by the general formula (1) is 100 / 0.1.
The thermal recording medium according to claim 1, wherein the thermal recording medium is 100/30 (weight ratio).