JP6865656B2 - Thermal recording material - Google Patents

Description

The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material using an N-substituted amino acid derivative as a color developer and an N, N'-diarylurea derivative together with the color developer.

Generally, the heat-sensitive recording material is a heat-sensitive recording in which a color development record can be obtained by applying heat energy (Joule heat) of a heat-sensitive head, a heat pen, etc. to a colorless or light-colored basic dye and an organic color developer at room temperature. The material has already been widely put into practical use.

The performance required for the thermal recording material includes the whiteness of the unprinted portion, the whiteness of the unprinted portion under various environmental conditions, the color density of the printed portion, and the storage stability of the printed portion. The storage stability of the printed part means that the printed image does not disappear even when it is placed in a high humidity environment, when water adheres, when oils adhere, or when a plasticizer adheres. To do.

On the other hand, the required performance of printing formed by the heat-sensitive recording material largely depends on the dye, the color developer, and the sensitizer, which are the main components of the heat-sensitive recording material, and the influence of the color developer is particularly large. Therefore, synthetic compounds derived from petrochemistry such as phenolic compounds and sulfonylurea compounds have been proposed as color developers that satisfy the above-mentioned required performance. Among them, many phenolic compounds have been developed and put into practical use.

However, some phenolic compounds are suspected of being endocrine disruptors, and their use tends to be suppressed. For example, bisphenol A (2,2-bis (4-hydroxyphenyl) propane) was used in large quantities as a raw material for polyesters and as a developer for thermal paper, but before the revision, examination and production of chemical substances, etc. In the regulation law, it is recognized as a second and third monitoring chemical substance, and in the revised law, it is recognized as a priority evaluation chemical substance, and its use is suspected to be an endocrine disruptor in the EU, the United States, Canada, and Japan. It has already been refrained from doing so in countries.

Bisphenol S (4,4'-dihydroxydiphenylsulfone) is registered as a designated chemical substance under the Law Concerning the Examination and Production of Chemical Substances before the Amendment due to suspicion of chromosomal abnormalities, etc., and is regulated as a second monitoring chemical substance. It had been.

As a non-phenolic color developer such as a sulfonylurea compound, there is a proposal to use a synthetic compound such as 4,4'-diaminodiphenylalkane as a raw material (Patent Document 1). The use of a non-phenolic color developer using an acylated amino acid made from a natural amino acid as a main raw material has also been proposed (Patent Document 2). Further, a heat-sensitive recording material for obtaining an image by applying a browning reaction (Maillard reaction) by heating amino acids and sugars has also been proposed (Patent Document 3).

Japanese Unexamined Patent Publication No. 05-147357 Japanese Unexamined Patent Publication No. 07-109423 Japanese Unexamined Patent Publication No. 2005-254764 International Publication No. 2017/047572

However, the sulfonylurea compound proposed in Patent Document 1 has problems such as using a synthetic compound having a molecular structure similar to that of bisphenol A as a raw material as a constituent component thereof, and is also required as a color developer for a heat-sensitive recording material. It was not sufficient for performance.

The use of a color developer using an acylated amino acid made from a natural amino acid as a main raw material in Patent Document 2 is not in the category of the causative agent of endocrine disrupting described above, but the acylated product has a color development density, whiteness and not yet. In terms of various storage stability of the printed part, the printed part, etc., the quality performance does not reach the required performance as a color developer of the heat-sensitive recording material.

The proposal to obtain an image by applying the browning reaction (Maillard reaction) by heating amino acids and sugars in Patent Document 3 does not satisfy the required performance as a color developer.

The present invention has been made in view of the above circumstances, and N, N'in order to improve the water resistance of the printed portion, to an N-substituted amino acid derivative having no concern about color density, whiteness, and endocrine disrupting action. -A heat-sensitive recording material using a diarylurea derivative is provided.

The present inventors have studied from the viewpoint of whether amino acids, which are also foods, can be used as a color developer for heat-sensitive recording materials. As a result, it was found that the amino acid does not develop color even when it comes into contact with the basic dye because the basic amino group and the acidic carboxyl group coexist in the same molecule and are intramolecularly neutralized. The present inventors have eliminated the intramolecular neutralization by introducing a functional group that contributes to the required performance and color-developing ability of the heat-sensitive recording material as a color developer as a protective group for the amino group of the amino acid, and further, the amino acid. Has been proposed, in particular, an invention relating to a heat-sensitive recording material using an N-substituted amino acid derivative made from a natural amino acid as a developing agent.

The present inventors further improved the storage stability of the printed portion, particularly the water resistance, without lowering the color development density, whiteness, and heat resistance of the thermal recording material using the N-substituted amino acid derivative as a color developer. We considered providing a heat-sensitive recording material. As a result, when the N-substituted amino acid derivative was used as the color developer, by using the N, N'-diarylurea derivative in combination as the storage stabilizer, the N-substituted amino acid derivative was used as the color developer. It has been found that the storage stability of the printed portion, particularly the water resistance, is further improved without deteriorating the color development density, whiteness, and heat resistance of the recording material, and the present invention has been completed.

That is, the present invention is a heat-sensitive recording material provided with a heat-sensitive recording layer on a support containing a colorless or light-colored basic dye at room temperature and a color developer that can come into contact with the dye and develop a color by heating. The color developer contains an N-substituted amino acid derivative represented by the following general formula (1), and as a storage stabilizer, N, N'-diaryl represented by the following general formula (2). A thermal recording material containing a urea derivative is provided.

(R ^0- X) _m- Y- (Z) _m ... (1)
(In the formula (1), R ⁰ is an alkyl group having an aryl group of C6 to C10, an alkyl group of C1 to C8, an aralkyl group of C7 to C11, an aryl group of C6 to C10, or an alkoxy of C1 to C8. Represents an aryl group that may have a substituent of a group.
X is a group attached to the N-terminus of _{Y, -OCO -, - SO 2} NHCO -, - NHCO -, - NHCS-, or -SO ₂ - represent.

Y represents an amino acid residue or a peptide residue, and the OH group of the serine residue, threonine residue, aspartic acid residue, glutamate residue, or tyrosine residue in the Y group is OR ⁰ group or OR ". The SH group of the cysteine residue may be substituted with an SR ⁰ group or an SR "group, and the NH group of the histidine residue ^{may be substituted with an NR 0} group or an NR'group. _{The two} NH groups of the lysine residue or the ornithine residue may ^{be substituted with an NHR 0} group or an NHR'group, where R'represents an amino-protecting group and R'represents a carboxy-protecting group. ..

Z is a group attached to the C-terminus of Y and represents an OH group or an OR "group.

The plurality of R ^0s , R', R'may be the same or different, and may be combined with each other to form a ring.

However, Y is an amino acid residue other than the cystine residue or a peptide residue having no cystine residue, and m = 1. )

（式中、Ｒはアルキル基を表し、ｎは０〜３の整数を表す。）

(In the formula, R represents an alkyl group and n represents an integer from 0 to 3.)

The N, N'-diarylurea derivative may be represented by the following formula (3) or (4).

The color formers are N- (m-tolylaminocarbonyl) -phenylalanine, N- (m-tolylaminocarbonyl) -methionine, N- (p-tolylaminocarbonyl) -methionine, N- (phenylaminocarbonyl) -methionine. , N- (m-trillaminocarbonyl) -valine, N- (m-trillaminocarbonyl) -phenylglycine and N- (m-trillaminocarbonyl) -tyrosine, even at least one selected from the group. Good.

The content of the N, N'-diarylurea derivative represented by the general formula (2) may be 10 to 400 parts by mass with respect to 100 parts by mass of the color developer.

The color developer of the derivative derived from the N-substituted amino acid constituting the present invention satisfies the required performance of the heat sensitive recording material equivalent to that of the conventional color developer, and is safe heat sensitive without endocrine disrupting action. It is possible to provide a heat-sensitive recording material which is a recording material and further has high storage stability of a printed portion, particularly water resistance, without deteriorating the color development density, whiteness, and heat resistance of the heat-sensitive recording material.

The IR chart of N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea is shown. The IR chart of N, N'-di- [3- (benzenesulfonyloxy) phenyl] urea is shown.

The heat-sensitive recording material of the present invention is a heat-sensitive recording layer provided on a support with a heat-sensitive recording layer containing a colorless or light-colored basic dye at room temperature and a color developer that can come into contact with the dye and develop color by heating. As a material, the color developer contains an N-substituted amino acid derivative represented by the general formula (1), and as a storage stabilizer, N, N'-diaryl represented by the general formula (2). It is characterized by containing a urea derivative.

In the heat-sensitive recording material of the present invention, the color developer is at least one of the N-substituted amino acid derivatives represented by the following general formula (1).
( _{RX) m-} Y- (Z) _m ... (1)

In formula (1), R is an alkyl group having an aryl group of C6 to C10, an alkyl group of C1 to C8, an aralkyl group of C7 to C11, an aryl group of C6 to C10, or an alkoxy group of C1 to C8. Represents an aryl group that may have a substituent. Examples of the alkyl group having an aryl group of C6 to C10 include a benzyl group, a phenethyl group, an o-tolylmethyl group, an m-tolylmethyl group, a p-tolylmethyl group, an o-tolylethyl group, an m-tolylethyl group and a p-tolylethyl group. Can be mentioned. Examples of the aryl group which may have a substituent of the alkyl group of C1 to C8 include o-tryl group, m-trill group, p-tryl group, 1-ethylphenyl group, 2-ethylphenyl group and 3-ethyl. Phenyl group, 1-propylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 1-butylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 1-pentylphenyl group, 2-pentylphenyl group , 3-Pentylphenyl group and the like. Examples of the aryl group which may have a substituent of the aralkyl group of C7 to C11 include a p-benzylbiphenyl group and the like. Examples of the aryl group which may have a substituent of the aryl group of C6 to C10 include a biphenyl group and a 3,3'-dimethylbiphenyl group. Examples of the aryl group which may have a substituent of the alkoxy group of C1 to C8 include a 6-methoxyphenyl group.

X is a group attached to the N-terminus of _{Y, -OCO -, - SO 2} NHCO -, - NHCO -, - NHCS-, or -SO ₂ - represents a (sulfonyl group).

Y represents an amino acid residue or a peptide residue, and the OH group of the serine residue, threonine residue, aspartic acid residue, glutamate residue, or tyrosine residue in the Y group is an OR group or an OR "group. The SH group of the cysteine residue may be substituted with an SR group or an SR "group, and the NH group of a histidine residue may be substituted with an NR group or an NR'group. _{Often, the two} NH groups of a lysine or ornithine residue may be substituted with an NHR or NHR'group, where R'represents an amino-protecting group and R'represents a carboxy-protecting group. As an amino-protecting group (R'group) that protects the NH group of the histidine residue or the NH ₂ group of the lysine residue or the ornithine residue, an RX group is mentioned, and in addition, an acyl group and an alkyl group are used. Examples of the carboxy-protecting group (R "group) that protects the aspartic acid residue or the glutamate residue in the Y group include an alkoxy group, an aryloxy group, an amino group, an alkylamino group, and an arylamino group. Further, as a protective group of a serine residue, a threonine residue, or a tyrosine residue of an OH group in a Y group, or an SH group of a cysteine residue, the above-mentioned carboxy protecting group (R "group) can be mentioned.

Y represents an amino acid residue or a peptide residue, and the OH group of the serine residue, threonine residue, aspartic acid residue, glutamate residue, or tyrosine residue in the Y group is an OR group or an OR "group. The SH group of the cysteine residue may be substituted with an SR group or an SR "group, and the NH group of a histidine residue may be substituted with an NR group or an NR'group. _{Often, the two} NH groups of a lysine or ornithine residue may be substituted with an NHR or NHR'group, where R'represents an amino-protecting group and R'represents a carboxy-protecting group. As an amino-protecting group (R'group) that protects the NH group of the histidine residue or the NH ₂ group of the lysine residue or the ornithine residue, an RX group is mentioned, and in addition, an acyl group and an alkyl group are used. Examples of the carboxy-protecting group (R "group) that protects the aspartic acid residue or the glutamate residue in the Y group include an alkoxy group, an aryloxy group, an amino group, an alkylamino group, and an arylamino group. Further, as a protective group of a serine residue, a threonine residue, or a tyrosine residue of an OH group in a Y group, or an SH group of a cysteine residue, the above-mentioned carboxy protecting group (R "group) can be mentioned.

Z is a group attached to the C-terminus of Y and represents an OH group or an OR "group.
The plurality of R, R', R "may be the same or different, and may be combined with each other to form a ring.
However, Y is an amino acid residue other than the cystine residue or a peptide residue having no cystine residue, and m = 1.

The N-substituted amino acid derivative represented by the general formula can be easily produced from an amino acid or an amino acid derivative and a sulfonated product, an isocyanate compound or the like by applying a known method such as the Schotten-Baumann reaction.

The amino acids, peptides and their esters and amides used as constituents of the compounds represented by the general formula may be L-form, D-form or DL-form. It may be a natural amino acid, an unnatural amino acid, an α-amino acid, or a β-amino acid. Esters are C1-C4 alkyl esters, aryl esters, aralkyl esters, and amides are amides, alkyl-substituted amides, aryl-substituted amides and the like.

Specifically, ester derivatives such as glycine, glycine methyl ester, glycine ethyl ester, glycine-t-butyl ester, glycine phenyl ester, glycine p-cresyl ester, glycine m-cresyl ester, glycine benzyl ester, glycine amide, N. '-Amid derivatives such as methylglycine amide and glycylanilide, ester derivatives such as phenylglycine, phenylglycine methyl ester, phenylglycine ethyl ester and phenylglycine benzyl ester, phenylglycin amide, alanine, alanine methyl ester, alanine ethyl ester, Ester derivatives such as alanine benzyl ester, ester derivatives such as alanine amide, phenylalanine, naphthylalanine, phenylalanine methyl ester, phenylalanine ethyl ester, phenylalanine benzyl ester, amide derivatives such as phenylalanine amide, N'-methylphenylalanine amide, phenylalanine anilide , Valin, valine methyl ester, valine methyl ester, valine isopropyl ester, valine-t-butyl ester, valine benzyl ester and other ester derivatives, valine amide, leucine, leucine methyl ester, isoleucine, serine, o-methylserine, o-benzylserine Ester derivatives such as o-substituted serine, serine methyl ester, serine benzyl ester, etc., o-substituted threonine such as threonine, o-methyl threonine, o-benzyl threonine, ester such as threonine methyl ester, threonine-t-butyl ester, etc. Derivatives, tyrosine, o-methoxytyrosine, o-benzyloxytyrosine, o-substituted tyrosine such as tyrosine, ester such as 3- (3', 4'-dihydroxyphenyl) alanine (DOPA), tyrosine methyl ester, tyrosine benzyl ester Derivatives, tyrosine amides, proline, hydroxyproline, proline methyl ester, proline-t-butyl ester, proline benzyl ester and other ester derivatives, proline amide, lysine, ornithine, lysine methyl ester, lysine ethyl ester, lysine benzyl ester, ornithine methyl Esters, ester derivatives such as ornithine ethyl ester, ornithine benzyl ester, arginine, arginine methyl ester, arginine ethyl ester, histi S-substituted cysteines such as gin, histidine methyl ester, tryptophan, tryptophan methyl ester, tryptophan benzyl ester, tryptophanamide, cysteine, cystine, S-methylcysteine, S-ethylcysteine, S-benzylcysteine, S-phenylcysteine, cysteine Ester derivatives such as methyl ester and cysteine benzyl ester and S-oxidized derivatives such as cysteine sulfoxide and sulfone, S-oxidized derivatives such as methionine, methionine sulfoxide and methionine sulfone, ester derivatives such as methionine methyl ester and methionine benzyl ester, methionine amide , Asparaginic acid, asparagic acid methyl ester, aspartic acid ethyl ester, aspartic acid benzyl ester and other ester derivatives, asparagine, glutamic acid, glutamic acid methyl ester, glutamic acid ethyl ester, glutamic acid benzyl ester and other ester derivatives, and glutamine. Further, it may be an amino acid such as homoserine, homocysteine, norleucine and a derivative thereof. In addition, C1-C8 aminocarboxylic acids such as β-alanine, 5-aminovaleric acid, and 7-aminoenanthic acid are also selected.

Peptides are glycylglycine, glycylglycine methyl ester, glycyl glycine amide, glycyl alanine, glycyl alanine methyl ester, glycyl valine, glycyl leucine, glycyl phenylalanine, glycyl phenylalanine methyl ester, glycyl phenylalanine amide, glycyl. Examples thereof include proline, alanylalanine, alanylproline, alanylmethionine, alanylmethionine methyl ester, alanylphenylalanine, and glycylglycylglycine.

The compounds represented by the above general formulas are amino acids and peptides having an amino group protected and derivatives thereof, and the protecting groups are widely used in the fields of amino acid chemistry or peptide synthesis chemistry.

As the functional group (-XNH- group) formed by the N-substituted group of the N-substituted amino acid derivative represented by the general formula (1) in the heat-sensitive recording material of the present invention, a sulfonylamino group, a urethane group, ( Tio) urea group (ureid), sulfonylurea group, and these functional groups, for example, the sulfonylamino group is derived from arylsulfonyl chloride. The urethane group is derived from a chloroformate ester such as benzyl chloroformate or a carbonic acid ester such as diphenyl carbonate. The (thio) urea group is derived from an iso (thio) cyanate ester such as phenyl iso (thio) cyanate. Sulfonyl urea is derived from sulfonyl urea such as toluene sulfonyl isocyanate.

Specifically, examples of the compound (X1) forming a sulfonylamino group include benzenesulfonyl chloride, p-toluenesulfonyl chloride, m-toluenesulfonyl chloride, o-toluenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, and p-chloride. Examples thereof include chlorides such as xylene sulfonyl, m-xylene sulfonyl chloride, mecitylene sulfonyl chloride, 1-naphthalene sulfonyl chloride and 2-naphthalene sulfonyl chloride, bromide and iodide.

Examples of the compound (X2) forming a urethane group include halogenated formic acid esters such as chloroformic acid benzyl ester and chloroformic acid phenyl ester, and carbonic acid esters such as diphenyl carbonate and dibenzyl carbonate.

Examples of the compound (X3) forming the (thio) urea group include benzyl isocyanate, phenyl isocyanate, p-tolyl isocyanate, m-tolyl isocyanate, o-tolyl isocyanate, 1-naphthyl isocyanate, 2-naphthyl isocyanate, and phenylene 1,4. -Diisocyanate, phenylene 1,3-diisocyanate, tolylen 2,4-diisocyanate, tolylen-2,6-diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, naphthalene 1,5-diisocyanate, 4,4' -Diisocyanate-3,3'-dimethylbiphenyl, methylenediphenyl-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenylmethane, phenylisocyanate, m-tolyliso Examples thereof include thiocyanate and p-tolylisocyanate.

Examples of the compound (X4) forming a sulfonylurea group include benzenesulfonylisocyanate and p-toluenesulfonylisocyanate.

Examples of the N-substituted amino acid derivative obtained by using the compound (X1) forming a sulfonylamino group according to the general formula (1) include N-benzenesulfonyl-glycine and N-benzenesulfonyl-glycine methyl ester. N-Benzenesulfonyl-glycineamide, N-benzenesulfonyl-methionine methyl ester, N-benzenesulfonyl-cysteine-S-benzyl, N- (p-toluenesulfonyl) -glycine, N- (p-toluenesulfonyl) -alanine, N- (p-toluenesulfonyl) -β-alanine, N- (p-toluenesulfonyl) -phenylalanine, N- (p-toluenesulfonyl) -phenylalanine methyl ester, N- (p-toluenesulfonyl) -phenylalanine benzyl ester, N- (p-toluenesulfonyl) -methionine, N- (p-toluenesulfonyl) -methionine benzyl ester, N- (m-toluenesulfonyl) -isoleucine, 3-N- (o-toluenesulfonyl) aminocaproic acid, N- (2,4-Xylenesulfonyl) -alanine, N- (2,4,6-mesitylensulfonyl) -serine, N- (p-ethylbenzenesulfonyl) -threonine, N, N'-di (pt-butylbenzene) N-arylsulfonyl-amino acids such as sulfonyl) -lysine, N, N'-di (pt-butylbenzenesulfonyl) -ornithine, N- (1-naphthalenesulfonyl) -tryptophan, N-2-naphthalenesulfonyl-asparagin , Esters and amides, N-aralkylsulfonyl-amino acids such as N-benzylsulfonyl-valine, N-benzylsulfonyl-tyrosine, N-benzylsulfonyl-phenylglycine, esters and amides and the like.

Examples of the N-substituted amino acid derivative obtained by using the compound (X3) forming a urea group in the general formula (1) include N-phenylaminocarbonyl-glycine and N-phenylaminocarbonyl-glycine-methyl. Estel, N-Phenylaminocarbonyl-glycinebenzyl ester, N-Phenylaminocarbonyl-glycinamide, N-Phenylaminocarbonyl-alanine, N-Phenylaminocarbonyl-alanine-methyl ester, N-Phenylaminocarbonyl-β-alanine, N-Phenylaminocarbonyl-methionine, N-phenylaminocarbonyl-methionine-methylester, N-phenylaminocarbonyl-glutamine, N, N'-di (phenylaminocarbonyl) -lysine, N, N'-di (phenylamino) Carbonyl) -ornithine, N-phenylaminocarbonyl-phenylalanine, N-phenylaminocarbonyl-norvaline, N- (p-tolylaminocarbonyl) -glycine, N- (p-tolylaminocarbonyl) -alanine, N- (p-) Trillaminocarbonyl) -valine, N- (p-tolylaminocarbonyl) -phenylalanine, N- (p-tolylaminocarbonyl) -cysteine-S-benzyl, N- (p-tolylaminocarbonyl) -methionine, N-( p-tolylaminocarbonyl) -glutamic acid, N- (p-tolylaminocarbonyl) -glutamine, N- (m-tolylaminocarbonyl) -glycine, N- (p-tolylaminocarbonyl) -glycylglycine, N- ( p-Tolylaminocarbonyl) -glycylglycylglycine, N- (m-tolylaminocarbonyl) -glycylalanine, N- (m-tolylaminocarbonyl) -leucylalanine, N- (m-tolylaminocarbonyl)- Methionine, N- (m-tolylaminocarbonyl) -methionine-sulfone, N- (m-tolylaminocarbonyl) -valine, N- (m-tolylaminocarbonyl) -tyrosine, N- (m-tolylaminocarbonyl)- Tyrosine-methyl ester, N- (m-tolylaminocarbonyl) -phenylalanine, N- (m-tolylaminocarbonyl) -methionine, N- (m-tolylaminocarbonyl) -valine, N- (m-tolylaminocarbonyl) -Phenylglycine, N-phenylglycine, N- (3-isopropenyl-α, α-dimethylbenzyl) aminocarbonyl- It is good to use at least one selected from the group consisting of methionine and N- (m-tolylaminocarbonyl) -tyrosine.

N- (m-Trillaminocarbonyl) -Phenylalanine-Methylester, N- (m-Trillaminocarbonyl) -Phenylalanine-Ethylester, N- (m-Trillaminocarbonyl) -Phenylalanine-benzylester, N- (m-) Trillaminocarbonyl) -β-Phenylalanineamide, N, N'-di (m-tolylaminocarbonyl) -lysine, N, N'-di (m-tolylaminocarbonyl) -lysine-methylester, N, N'- Di (m-tolylaminocarbonyl) -ornithine, N, N'-di (m-tolylaminocarbonyl) -ornithine-methyl ester, N- (m-tolylaminocarbonyl) -glutamic acid, N- (o-tolylaminocarbonyl) ) -Alanine, N- (o-tolylaminocarbonyl) -homoseline, N- (o-tolylaminocarbonyl) -valine, 1,6-hexamethylenebis (N-aminocarbonyl-phenylalanine), 2,4-phenyllenbis (N-Aminocarbonyl-Phenylalanine), 1,3-trilenbis (N-aminocarbonyl-Phenylalanine) and the like can be mentioned.

Examples of the N-substituted amino acid derivative obtained by using the compound (X3) forming a thiourea group according to the general formula (1) include N-phenylaminothiocarbonyl-phenylalanine and N-phenylaminothiocarbonyl-. Phenylalanine-methyl ester, N-phenylaminothiocarbonyl-valine-isopropyl ester, N-phenylaminothiocarbonyl-tyrosine-methyl ester, N-phenylaminothiocarbonyl-methionine-methyl ester, N-phenylaminothiocarbonyl-glycyl Glycin, N-phenylaminothiocarbonyl-glycylalanine, Nm-tolylaminothiocarbonyl-phenylalanine, Nm-tolylaminothiocarbonyl-phenylalanine-benzyl ester, Nm-tolylaminothiocarbonyl-phenylalaninamide, Nm-trillaminothiocarbonyl-valine, Nm-tolylaminothiocarbonyl-valine-isopropyl ester, Nm-tolylaminothiocarbonyl-methionine-methyl ester, Nm-tolylaminothiocarbonyl-glycyl Glycin, Np-tolylaminothiocarbonyl-phenylalanine, Np-tolylaminothiocarbonyl-phenylalanine-benzyl ester, Np-tolylaminothiocarbonyl-phenylalanine amide, Np-tolylaminothiocarbonyl-valine, Examples thereof include Np-tolylaminothiocarbonyl-valine-isopropyl ester, N-p-tolylaminothiocarbonyl-methionine-methyl ester, and N-p-tolylaminothiocarbonyl-glycylglycine.

Examples of the N-substituted amino acid derivative obtained by using the compound (X2) forming a urethane group in the general formula (1) include N-benzyloxycarbonyl-glycine and N-benzyloxycarbonyl-phenylglycine. N-benzyloxycarbonyl-valine, N-benzyloxycarbonyl-methionine, N-benzyloxycarbonyl-tyrosine, N-benzyloxycarbonyl-hydroxyproline, N-benzyloxycarbonyl-arginine, N-benzyloxycarbonyl-glycine, etc. Can be mentioned.

Examples of the N-substituted amino acid derivative obtained by using the compound (X4) forming a sulfonylurea group according to the general formula (1) include N- (p-toluenesulfonylaminocarbonyl) -glycine and N- ( p-Toluenesulfonylaminocarbonyl) -phenylalanine, N- (p-toluenesulfonylaminocarbonyl) -phenylalanine-methyl ester, N- (p-toluenesulfonylaminocarbonyl) -phenylalanine-ethyl ester, N- (p-toluenesulfonylamino) Carbonyl) -phenylalanamide, N- (p-toluenesulfonylaminocarbonyl) -β-alanine, N- (p-toluenesulfonylaminocarbonyl) -β-alanine-methylester, N- (p-toluenesulfonylaminocarbonyl)- Methionine-methyl ester, N- (p-toluenesulfonylaminocarbonyl) -leucine, N, N'-di (p-toluenesulfonylaminocarbonyl) -lysine-methylester, N, N'-di (p-toluenesulfonylamino) Carbonyl) -ornithine-methyl ester and the like can be mentioned.

Protects _{the NH group of histidine residue in the Y group or the NH 2} group of lysine residue or ornithine residue of the N-substituted amino acid derivative represented by the general formula (1) in the heat-sensitive recording material of the present invention. Examples of the amino-protecting group (R'group) to be used include an RX group, and other examples include an acyl group and an alkyl group. These amino protecting groups (R'groups) can be introduced by known methods. For example, the acyl group can be introduced using an acid anhydride. The alkyl group can be introduced, for example, by an alkyl halide such as trityl chloride in the presence of an amine or the like.
As a carboxy-protecting group (R "group) that protects an aspartic acid residue or a glutamate residue in the Y group of the N-substituted amino acid derivative represented by the general formula (1) in the heat-sensitive recording material of the present invention, alkoxy Examples thereof include a group, an aryloxy group, an amino group, an alkylamino group, an arylamino group, etc. Further, an OH group of a serine residue, a threonine residue, or a tyrosine residue in a Y group, or an SH group of a cysteine residue. Examples of the protective group of the above include the carboxy protective group (R "group). These carboxy protecting groups (R "groups) can be introduced by known methods.

Preferred N-substituted amino acid derivatives as a color developer in the heat-sensitive recording material of the present invention include N- (p-toluenesulfonyl) -glycine, N- (p-toluenesulfonyl) -alanine, and N- (p-toluenesulfonyl). N-allylsulfonyl-amino acids such as -β-alanine, N-phenylaminocarbonyl-glycine, N-phenylaminocarbonyl-valine, N- (m-tolylaminocarbonyl) -phenylalanine, N- (m-tolylaminocarbonyl) -Cysteine-S-benzyl, N- (m-trillaminocarbonyl) -methionine, N- (m-trillaminocarbonyl) -tyrosine, N- (p-trillaminocarbonyl) -phenylalanine, N- (p-trillamino) Carbonyl) -cysteine-S-benzyl, N- (p-tolylaminocarbonyl) -methionine, N- (p-tolylaminocarbonyl) -methionine, N- (phenylaminocarbonyl) -methionine, N- (p-tolylamino) N-aminocarbonyl-amino acids such as carbonyl) -tyrosine, particularly preferably N- (m-tolylaminocarbonyl) -phenylalanine, N- (m-tolylaminocarbonyl) -methionine, N- (p-tolylamino). Carbonyl) -methionine, N- (phenylaminocarbonyl) -methionine, N- (m-tolylaminocarbonyl) -valine, N- (m-tolylaminocarbonyl) -phenylglycine and N- (m-tolylaminocarbonyl)- Tyrosine can be mentioned.
One or more of these N-substituted amino acid derivatives may be used in combination.

Further, Z is preferably an OH group, X is preferably a -NHCO- group, and specifically, the N-substituted amino acid derivative is N- (m-tolylaminocarbonyl) -phenylalanine, N- ( m-trillaminocarbonyl) -methionine, N- (p-trillaminocarbonyl) -methionine, N- (phenylaminocarbonyl) -methionine, N- (m-trillaminocarbonyl) -valine, N- (m-trillamino) It is good to use at least one selected from the group consisting of carbonyl) -phenylglycine and N- (m-tolylaminocarbonyl) -tyrosine.

In the present invention, it may be used in combination with an existing color developer as long as the effect of the present invention is not impaired.

The heat-sensitive recording layer of the heat-sensitive recording material of the present invention is stable in storage of the basic dye, the color developer represented by the general formula, and the N, N'-diarylurea derivative represented by the following general formula (2). Contains the agent.

（式中、Ｒはアルキル基を表し、ｎは０〜３の整数を表す。）

(In the formula, R represents an alkyl group and n represents an integer from 0 to 3.)

The N, N'-diarylurea derivative may be represented by the following formula (3), (4) or (5).

In the present invention, the N, N'-diarylurea derivative represented by the general formula (2) used in combination as a storage stabilizer reduces the color development concentration and whiteness of the heat-sensitive recording material when used together with the N-substituted amino acid derivative. It is possible to maintain the heat resistance of the skin without causing it to occur, and further improve the storage stability of the printed portion, particularly the water resistance.

The content of the N, N'-diarylurea derivative represented by the general formula (2) is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the color developer represented by the general formula (1), and is 20 to 200 parts by mass. Parts by mass are more preferred.

(Method for synthesizing N, N'-diarylurea derivative)
The N, N'-diarylurea derivative represented by the general formula (2) is synthesized by reacting the compound represented by the following formula (6) with the aromatic amine compound represented by the following formula (7). be able to.

（式中、Ｒ１はアルキル基、又はアリール基を表わし、Ｒはアルキル基を表し、ｎは０〜３の整数を表す。）

(In the formula, R1 represents an alkyl group or an aryl group, R represents an alkyl group, and n represents an integer of 0 to 3.)

For example, it can be synthesized by the following method.

Step 1.3-[(R) n-PhSO ₃ ] -Ph-NH ₂ / antacid + XCOOR
→ 3-[(R) n-PhSO ₃ ] -Ph-NHCOOR1 + HCl / antacid Step 2.3-[(R) n-PhSO ₃ ] -Ph-NHCOOR1 + 3-[(R) n-PhSO ₃ ] -Ph-NH ₂ / salt
→ {3-[(R) n−PhSO ₃ ] −Ph −NH} ₂ = CO + R1OH
(In the formula, R1 represents an alkyl group or an aryl group, R represents an alkyl group, and n represents an integer of 0 to 3.)

The alkyl groups of R1 and R are the same as those of the alkyl group of R.

XCOOR used in step 1 of the above synthesis method is a halogenated carbonic acid ester or a carbonic acid diester, X is chlor, brom, OMe, OEt, OPro or OPh, and R1 is a Me, Et, Pro, Ph group or the like. .. In particular, methyl monochlorocarbonate, ethyl monochlorocarbonate, phenyl monochlorocarbonate, diethyl carbonate, and diphenyl carbonate are preferable.

Organic bases and inorganic bases are used as deoxidizers and bases in the reaction.
Examples of the inorganic base include LiOH, NaOH, KOH _{, LVDS 3} , KHCO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , MeONa, EtONa and the like.
Examples of the organic base are organic bases such as trimethylamine, triethylamine, tributylamine, pyridine, N, N-dimethylpyridine and 1,8-diazabicyclo [5,4,0] undecane-7-ene (DBU). Preferred are K ₂ CO ₃ , triethylamine, pyridine, N, N-dimethylpyridine, 1,8-diazabicyclo [5,4,0] undecane-7-ene (DBU).

3-[(R) n-PhSO ₃ ] -Ph-NH ₂ can also be synthesized by directly O-sulfonylating 3-hydroxyaniline, and after O-sulfonylifying a nitrophenol compound, nitro It can also be easily obtained by reducing the group.

As 3-[(R) n-PhSO ₃ ] -Ph-NH ₂ , 3-benzenesulfonyloxyaniline, 3- (p-toluene) sulfonyloxyaniline, 3- (m-toluene) sulfonyloxyaniline, 3- Examples thereof include (o-toluene) sulfonyloxyaniline, 3- (p-xylene) sulfonyloxyaniline, and 3-mesitylene sulfonyloxyaniline. Preferred are 3-benzenesulfonyloxyaniline and 3- (p-toluene) sulfonyloxyaniline.

Generally, the reaction solvent is carried out in an aprotic solvent at a reaction temperature of 0 ° C. to 180 ° C. In the present invention, the reaction temperature is in the range of 0 ° C. to 180 ° C., preferably 10 ° C. to 100 ° C., and the solvent and reaction temperature are preferably according to the boiling point of the solvent and the stability of the reaction product. Be selected.

Aprotic solvents include aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane and chlorobenzene, ethyl acetate, propyl acetate, butyl acetate, phenyl acetate and benzyl acetate. Examples thereof include ether compounds such as acetate, diethyl ether, dimethoxyethane, diethoxyethane, diethylene glycol dimethyl ether, dioxane, tetrahydrofuran and anisole, ketone compounds such as acetone, methyl ethyl ketone and MIBK, acetonitrile, DMF, DMSO and DMI.

Step 2 is carried out by reacting 3-[(R) n-PhSO ₃ ] -Ph-NHCOOR obtained in Step 1 with 3-[(R) n-PhSO ₃ ] -Ph-NH ₂ in the presence of a base. Will be done.
As the base, reaction solvent, and reaction temperature used in step 2, the above reaction conditions used in step 1 can be used.

Further, in order to simplify the reaction operation, it is possible to proceed the steps 1 and 2 at the same time by using 2 equivalents or more of 3-[(R) n-PhSO ₃ ] -Ph-NH _2.

As the N, N'-diarylurea derivative represented by the general formula (2), N, N'-di- [3- (p-xylenesulfonyloxy) phenyl] urea, N, N'-di- [3- (Mesitylene sulfonyloxy) phenyl] urea, N, N'-di- [3- (o-toluenesulfonyloxy) phenyl] urea, N, N'-di- [3- (m-toluenesulfonyloxy) phenyl] urea , N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea, N, N'-di- [3- (benzenesulfonyloxy) phenyl] urea and the like.

In the heat-sensitive recording material of the present invention, triphenylmethane-based, fluorane-based, diphenylmethane-based, spiro-based, fluorene-based, and thiazine-based compounds are examples of basic dyes that are colorless or pale at room temperature, and are selected from conventionally known leuco dyes. Can be done.
For example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide,
3- (4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3,3-bis (P-methylaminophenyl) -6-dimethylaminophthalide,
3-Diethylamino-7-dibenzylaminobenzo [α] fluorane,
3- (1-Ethyl-2-methylindol-3-yl) -3- (4-diethylamino) -2-n-hexyloxyphenyl-4-azaphthalide, 3- (1-ethyl-2-methylindol-3) -Il) -3- (4-Diethylamino) -2-methylphenyl-4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) phthalide, 3- (2-Methyl-1-n-octylindole-3-yl) -3- (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 3- (N-ethyl-N-isopentylamino) -6- Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane,

3- (N-ethyl-N-p-toluidino) -6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7 -Anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-diethylamino-7- ( m-trifluoromethylanilino) fluorane, 3-di (n-pentyl) amino-6-methyl-7-anilinofluorane, 3- [N- (3-ethoxypropyl) -N-ethylamino] 6- Methyl-7-anilinofluorane, 3- (Nn-hexyl-N-ethylamino) -7- (o-chloroanilino) fluorane, 3- (N-ethyl-N-2-tetrahydrofurfurylamino)- 6-Methyl-7-anilinofluorane, 2,2-bis {4- [6'-(N-cyclohexyl-N-methylamino) -3'-methylspiro [phthalide-3,9'-xanthene] -2 '-Ilamino] phenyl} propane and 3-dibutylamino-7- (o-chloroanilino) fluorane,

3,6-dimethoxyfluorane, 3-pyrrolidino-6-chlorofluorine, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7-chlorofluorine, 3-diethylamino-7,8- Dibenzofluorane, 3-diethylamino-6,7-dimethylfluorane, 3- (N-methyl-p-toluizino) -7-methylfluorane, 3- (N-methyl-N-isoamylamino) -7,8 -Benzylfluorane, 3,3'-bis (1-n-amyl-2-methylindol-3-yl) phthalide, 3- (N-methyl-N-isoamylamino) -7-phenoxyfluorane, 3, 3'-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3'-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,3'-bis (P-Dimethylaminophenyl) phthalide, 3- (N-ethyl-N-p-tolylamino) -7- (N-phenyl-N-methylamino) fluorane, 3-diethylamino-7-anilinofluorane, 3- Diethylamino-7-benzylaminofluorane, 3-pyrrolidino-7-dibenzylaminofluorane and the like can also be selected, and the present invention is not limited thereto, and two or more kinds may be used in combination. ..

A conventionally known sensitizer can be used in combination as the sensitizer of the present invention.
For example, fatty acid amides such as stearic acid amides, bisstearic acid amides and palmitic acid amides, p-toluenesulfonamides, stearic acids, calcium such as bechenic acid and palmitic acid, fatty acid metal salts such as zinc or aluminum, p-benzylbiphenyl. , Diphenylsulfone, benzyl benzyloxybenzoate, 2-benzyloxynaphthalene, 1,2-bis (p-tolyloxy) ethane, 1,2-bis (phenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane , 1,3-Bis (phenoxy) propane, dibenzyl oxalate, p-methylbenzyl oxalate, m-terphenyl, 1-hydroxy-2-naphthoic acid and the like.

Further, the present invention can be used in combination with a conventionally known storage stabilizer.
For example, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-ethylidenebis (4,6- Di-tert-butylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl m-cresol), 1,1,3-tris ( 2-Methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4'-bis [(4-4-bisulfone) Methyl-3-phenoxycarbonylaminophenyl) ureido] diphenyl sulfone, tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 4,4'-thiobis (3-methylphenol), 4 , 4'-dihydroxy-3,3', 5,5'-tetrabromodiphenyl sulfone, 4,4'-dihydroxy 3,3', 5,5'-tetramethyldiphenyl sulfone, 2,2-bis (4- Hinders such as hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, etc. Dophenol compound, 1,4-diglycidyloxybenzene, 4,4'-diglycidyloxydiphenylsulfone, 4-benzyloxy-4'-(2-methylglycyloxy) diphenylsulfone, glycidyl terephthalate, bisphenol A type Epoxy compounds such as epoxy resin type, cresol novolac type epoxy resin, phenol novolac type epoxy resin, N, N'-di-2-naphthyl-p-phenylenediamine, 2,2'-methylenebis (4,6-di-tert) -Butylphenyl) Phosphate sodium or polyvalent metal salts, bis (4-ethyleneiminecarbonylaminophenyl) methane, 4,4'-bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] diphenyl sulfone and , Diphenyl sulfone cross-linked compound represented by the following general formula (8), and the like, and these storage stabilizers contribute to the storage stability of the printed portion of the heat-sensitive recording material.

（式中、ｎは１〜７の整数を表す。）

(In the formula, n represents an integer of 1 to 7.)

Among these storage stabilizers, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5) At least selected from −cyclohexylphenyl) butane, 4,4′-bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] diphenylsulfone, and the diphenylsulfone crosslinked compound represented by the above general formula (8). It is preferable to contain one or more of them, and by containing these storage stabilizers, the water resistance of the printed portion in the heat-sensitive recording material is particularly improved.

The content of the storage stabilizer (excluding the N, N'-diarylurea derivative represented by the general formula (2)) is preferably 2.5 to 100 parts by mass with respect to 100 parts by mass of the color developer. , 5 to 50 parts by mass is more preferable.

Examples of the auxiliary agent include dispersants such as sodium dioctiol succinate, sodium dodecylbenzene sulfonate, sodium lauryl alcohol sulfate, and fatty acid metal salts, zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, and the like. Waxes such as ester wax, hydrazide compounds such as adipic acid dihydrazide, water resistant agents such as glioxal, boric acid, dialdehyde starch, methylol urea, glyoxyphosphate, epoxy compounds, defoaming agents, coloring dyes, fluorescent dyes, etc. And pigments and the like.

The binder used for the heat-sensitive recording layer in the present invention includes fully saponified polyvinyl alcohol having a degree of polymerization of 200 to 1900, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acetacetyl-modified polyvinyl alcohol, and amide-modified. Polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl acetate , Polyacrylamide, polyacrylic acid ester, polyvinyl butyral polystyrene and copolymers thereof, polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin, chroman resin and the like. These binders can be used alone or in combination of two or more, and can be used by being dissolved in a solvent, or can be used in a state of being emulsified or dispersed in a paste in water or another medium.

Pigments to be blended in the heat-sensitive recording layer include silica, calcium carbonate, kaolin, calcined kaolin, keiso soil, talc, titanium oxide, zinc oxide, aluminum hydroxide, polystyrene resin, urea-formalin resin, and styrene-methacrylic acid copolymer. Examples thereof include inorganic or organic pigments such as coalescing, styrene-butadiene copolymers and hollow plastic pigments.

The types and amounts of basic dyes, color formers, sensitizers, binders, pigments and other additives used in the heat-sensitive recording layer in the present invention are appropriately determined according to the quality performance required for the heat-sensitive recording layer. It is determined.

In the heat-sensitive recording layer of the present invention, the content of the N-substituted amino acid derivative represented by the general formula (1) as a color developer is based on 1 part by mass of the basic dye of the heat-sensitive recording layer from the viewpoint of color development concentration. Therefore, 0.3 to 5 parts by mass is preferable, and 0.4 to 3 parts by mass is more preferable.

Further, 0.2 to 4 parts by mass of the sensitizer is suitable for 1 part of the leuco dye, and 5 to 50% by mass of the binder is suitable for the total solid content. As the support, paper, recycled paper, synthetic paper, plastic film, non-woven fabric, metal foil and the like can be used. In addition, a composite sheet in which these are combined can also be used.

Further, an overcoat layer made of a polymer substance containing an organic pigment may be provided for the purpose of improving storage stability. Further, an undercoat layer containing an organic pigment, an inorganic pigment, hollow fine particles, or the like may be provided for the purpose of preventing the adhesion of debris to the thermal head, improving the print image quality, and improving the sensitivity.

The basic dyes, color formers, sensitizers and, if necessary, storage stabilizers used in the heat-sensitive recording layer in the present invention are averaged by a stirring pulverizer such as a ball mill, an attritor, or a sand mill using water as a dispersion medium. It is finely dispersed and used so that the particle size is 2 μm or less.
The heat-sensitive recording layer coating material is prepared by mixing and stirring a pigment, a binder, an auxiliary agent, and the like, if necessary, with the finely dispersed dispersion liquid.
The heat-sensitive recording layer coating material thus obtained is applied onto the support so that ^{the coating amount after drying is about 1.5 to 12 g / m 2} , more preferably about 3 to 7 g / m ^2. , Formed by drying.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass".

An example of synthesis of the N-substituted amino acid derivative used in the examples is shown below.
Synthesis Example 1: N- (m-Phenylalaninecarbonyl) -Phenylalanine After charging 16.5 g of L-phenylalanine and 50 g of water in a four-necked flask equipped with a thermometer, a dropping funnel, and a stirrer, the internal temperature is 15 ° C. L-Phenylalanine was dissolved by adding 50 g of an 8% aqueous sodium hydroxide solution. The internal temperature was maintained at 15 ° C., 13.3 g of m-tolyl isocyanate dissolved in ethyl acetate was added dropwise, and the mixture was stirred for 5 hours. Ethyl acetate was added to the reaction mixture, neutralized with dilute hydrochloric acid, and the product was extracted with ethyl acetate. Ethyl acetate of the extract was concentrated, and then toluene was added to the concentrated residue for crystallization. The crystals were separated by filtration and dried to obtain N- (m-tolylaminocarbonyl) -phenylalanine as white crystals. The melting point was 151 ° C.

Synthesis Example 2: N- (m-trylaminocarbonyl) -methionine White crystals by the same operation as in Synthesis Example 1 except that 14.9 g of L-methionine is used instead of 16.5 g of L-phenylalanine in Synthesis Example 1. N- (m-trillaminocarbonyl) -methionine was obtained. The melting point was 142 ° C.

Synthesis Example 3: N- (m-tolylaminocarbonyl) -valine By the same operation as in Synthesis Example 1, white crystals are obtained by the same operation as in Synthesis Example 1 except that 11.7 g of L-valine is used instead of 16.5 g of L-phenylalanine in Synthesis Example 1. N- (m-tolylaminocarbonyl) -valine was obtained. The melting point was 169 ° C.

Synthesis Example 4: N- (m-tolylaminocarbonyl) -cysteine-S-benzyl With Synthesis Example 1 except that 21.1 g of L-cysteine-S-benzyl is used instead of 16.5 g of L-phenylalanine in Synthesis Example 1. By the same operation, white crystals of N- (m-tolylaminocarbonyl) -cysteine-S-benzyl were obtained. The melting point was 164 ° C.

Synthesis Example 5: N- (m-tolylaminocarbonyl) -tyrosine By the same operation as in Synthesis Example 1, white crystals are obtained by the same operation as in Synthesis Example 1 except that 18.1 g of L-tyrosine is used instead of 16.5 g of L-phenylalanine in Synthesis Example 1. N- (m-tolylaminosulfonyl) -tyrosine was obtained. The melting point was 161 ° C.

Synthesis Example 6: N-Phenylaminothiocarbonyl-glycylglycine 13.2 g of glycylglycine, 50 g of water, and 50 g of THF were charged in the same apparatus as in Synthesis Example 1, and 50 g of an 8% sodium hydroxide aqueous solution was added to dissolve glycylglycine. .. While maintaining the internal temperature at 20 to 25 ° C., 13.5 g of phenylisothiocyanate was added dropwise and the mixture was stirred for 5 hours. The same reaction treatment as in Synthesis Example 1 was carried out to obtain white crystals of N-phenylaminothiocarbonyl-glycylglycine. The melting point was 157 ° C.

Synthesis Example 7: N- (p-Phenylalanine-methylester carbonyl) -phenylalanine-methyl ester In a four-necked flask equipped with a thermometer, a dropping funnel, and a stirrer, 21.5 g of L-phenylalanine-methyl ester hydrochloride and 120 g of ethyl acetate. Was charged, and 10.1 g of triethylamine was added dropwise while maintaining the internal temperature at 10 ° C. While maintaining the internal temperature at 8 to 10 ° C., 19.7 g of p-toluenesulfonyl isocyanate was added dropwise, and stirring was continued for 5 hours. After completion of the reaction, a small amount of acetic acid was added to the reaction solution, water was added, and the organic layer was washed and separated. Toluene was added to the residue obtained by concentrating the organic layer under reduced pressure to precipitate crystals, and white crystals of N- (p-toluenesulfonylaminocarbonyl) -phenylalanine-methyl ester were obtained by filtration. The melting point was 162 ° C.

Synthesis Example 8: 8.9 g of β-alanine, 30 g of water, and an 8% aqueous sodium hydroxide solution are charged in a four-necked flask equipped with an N- (p-toluenesulfonyl) -β-alanine thermometer, a dropping funnel, and a stirrer. The internal temperature was cooled to 10 ° C. 30 g of a THF solution in which 19.1 g of p-toluenesulfonyl chloride was dissolved and 50 g of 8% sodium hydroxide were each divided into four, and each fraction was alternately added dropwise to a flask to carry out a reaction. After stirring for 4 hours, it was acidified with dilute hydrochloric acid. The reaction solution was subjected to a reaction treatment in the same manner as in Synthesis Example 1 to obtain white crystals of N- (p-toluenesulfonyl) -β-alanine. The melting point was 125 ° C.

An example of synthesis of the N, N'-diphenylurea derivative used in the examples is shown below.

Synthesis Example 9: Synthesis of N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea 3- (p-toluenesulfonyloxy) in a four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel. 5.26 g of aniline and 2.20 g of triethylamine were dissolved in ethyl acetate to bring the internal temperature to 20 ° C. 3.29 g of phenyl chlorocarbonate was added dropwise under a nitrogen atmosphere while controlling the internal temperature to 20 ° C., and the mixture was stirred for 4 hours and allowed to stand for 1 day and night. Water was added to the reaction solution, the organic layer was washed with water, anhydrous ceramic ₄ was added to the organic layer, and the organic layer was dried. The solvent was distilled off under reduced pressure with an evaporator to obtain a concentrated residue of N-phenoxycarbonyl-3- (p-toluenesulfonyloxy) aniline, which was dissolved in dioxane.

Next, 5.26 g of 3- (p-toluenesulfonyloxy) aniline, DBU, and dioxane were added to the four-necked flask and heated to 100 ° C. The solution of N-phenoxycarbonyl-3- (p-toluenesulfonyloxy) aniline concentrated residue dissolved in this dioxane solution was added dropwise while maintaining the internal temperature, and the reaction was carried out for 7 hours. The internal temperature was cooled to 40 ° C., ethyl acetate was added to the reaction solution, and the organic layer was washed with dilute hydrochloric acid, sodium bicarbonate solution, and water. After drying the organic layer with anhydrous sulfonyl ₄ , the solvent was distilled off and MeOH was added to the concentrated residue to precipitate crystals.

The crystals were filtered off to give 8.6 g of light brown crystals of N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea. Melting point 164-168 ° C. FIG. 1 shows an IR chart.

Synthesis Example 10: Synthesis of N, N'-di- [3- (benzenesulfonyloxy) phenyl] urea 5.26 g of 3- (p-toluenesulfonyloxy) aniline of Synthesis Example 1 is added to 3- (benzenesulfonyloxy) aniline. N, N'-di- [3- (benzenesulfonyloxy) phenyl] urea was synthesized by the same operation as in Synthesis Example 1 except that it was replaced with 4.98 g.
It was a white crystal and had a melting point of 130.9 ° C. FIG. 2 shows an IR chart.

A thermal recording material was prepared by the following operation.

[Creation of paint for undercoat]
100 parts of plastic hollow particles (trade name: Low Pake SN-1055: hollow ratio: 55% solid content 26.5%), 100 parts of 50% dispersion of calcined kaolin, styrene-butadiene latex (trade name: L-1571 solid) 25 parts (48%), 50 parts of a 10% aqueous solution of oxidized starch and 20 parts of water were mixed to prepare an undercoat paint.

(Example 1)
[Creation of paint for thermal recording]
Liquid A (preparation of dye dispersion)
3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran 10 parts 10% polyvinyl alcohol aqueous solution 10 parts Water 16.7 parts

Liquid B (preparation of color developer dispersion)
N- (m-trillaminocarbonyl) -methionine 20 parts 10% polyvinyl alcohol aqueous solution 20 parts Water 33.3 parts

Solution C (preparation of storage stabilizer)
N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea
20 parts 10% polyvinyl alcohol aqueous solution 20 parts water 33.3 parts

Liquid D (preparation of sensitizer dispersion)
1,2-bis (m-tolyloxy) ethane 15 parts 10% polyvinyl alcohol aqueous solution 15 parts water 25 parts

The dispersions of solutions A, B, C and D were pulverized with a sand grinder until the average particle size became 1 μm or less, and the dispersions were mixed at the following ratios to prepare a coating solution.
Liquid A (dye dispersion) 36.7 parts Liquid B1 (color developer dispersion) 55.0 parts Liquid C (dispersion) 18.3 parts Liquid D (sensitizer dispersion) 55.0 parts

Aluminum hydroxide (trade name: Heidilite H-42) 27 parts, amorphous silica (trade name: Mizukasil P-605) 10 parts, 10% solution of oxidized starch 100 parts, zinc stearate dispersion: (trade name) : Hydrin Z-8-36) 19.4 parts and 20 parts of water were mixed to prepare a heat-sensitive recording paint.

[Creation of thermal recording material]
As a support, an undercoat paint is applied to high-quality paper (acid paper) having a basis weight of 53 g ^{so that the mass per area after drying is 6 g / m 2,} and then the heat-sensitive paint is applied to the dried area. It was applied and dried so that the contact mass was 3.8 g / m ^2.
This sheet was processed with a super calendar so that the smoothness (JIS P8155: 2010) was 900 to 1200 s to prepare a heat-sensitive recording material.

[Various tests]
1. 1. Thermal recordability test (color development test)
The prepared thermal recording material was applied with an applied energy of 0.38 mJ / dot using a thermal recording paper printing tester (TH-PMD manufactured by Okura Electric Co., Ltd.). The print density of the recording unit was measured with a Macbeth reflection densitometer RD-914.

2. Heat resistance test After leaving the heat-sensitive recording material recorded in the heat-sensitive recording test for 24 hours in a constant temperature environment at a test temperature of 60 ° C., the density of the printed part and the density of the unprinted part of the test piece were measured with a Macbeth reflection densitometer. ..

3. 3. Moisture resistance test After leaving the heat-sensitive recording material recorded in the heat-sensitive recordability test in an environment with a test temperature of 40 ° C and 90% RH for 24 hours, the density of the printed part and the density of the unprinted part of the test piece are measured with a Macbeth reflection densitometer. Measured in.

4. Oil resistance test The heat-sensitive recording material recorded in the heat-sensitive recording test was immersed in salad oil for 1 minute, and then the oil of the test piece was wiped off, and the image density was measured with a Macbeth reflection densitometer.

5. Water resistance test The thermal recording paper recorded in the thermal recording property test was immersed in water for 24 hours, then the test piece was air-dried, and the image density and the unprinted portion were measured with a Macbeth reflection densitometer.

6. Plasticizer resistance test Wrap a wrap film (trade name: High Wrap KMA Mitsui Kagaku Co., Ltd.) on a polycarbonate pipe (48 mmφ) in three layers, place the thermal recording paper recorded in the thermal recordability test on it, and then place the wrap film on it. It was wrapped in three layers and left to stand in an environment of 20 ° C. and 65% RH for 24 hours, after which the image density and the unprinted portion were measured with a Macbeth reflection densitometer.

The results of various tests of the thermal recording material according to this example are as shown in Table 1.

(Example 2)
The same operation as in Example 1 was carried out except that N- (m-tolylaminocarbonyl) -methionine in the solution B of Example 1 was replaced with N- (m-tolylaminocarbonyl) -phenylalanine.
The results of various tests of the thermal recording material according to this example are as shown in Table 1.

(Example 3)
The same operation as in Example 1 was carried out except that N- (m-tolylaminocarbonyl) -methionine in the solution B of Example 1 was replaced with N- (phenylaminocarbonyl) -methionine.
The results of various tests of the thermal recording material according to this example are as shown in Table 1.

(Example 4)
The same operation as in Example 1 was carried out except that N- (m-tolylaminocarbonyl) -methionine in the solution B of Example 1 was replaced with N- (p-tolylaminocarbonyl) -methionine.
The results of various tests of the thermal recording material according to this example are as shown in Table 1.

(Example 5)
The same operation as in Example 1 was carried out except that N- (m-tolylaminocarbonyl) -methionine in B of Example 1 was replaced with N- (m-tolylaminocarbonyl) -valine.
The results of various tests of the thermal recording material according to this example are as shown in Table 1.

(Example 6)
The same operation as in Example 1 was carried out except that N- (m-tolylaminocarbonyl) -methionine in Solution B of Example 1 was replaced with N- (m-tolylaminocarbonyl) -phenylglycine. The results of various tests of the thermal recording material according to this example are as shown in Table 1.

(Example 7)
The same operation as in Example 1 was carried out except that N- (m-tolylaminocarbonyl) -methionine in Solution B of Example 1 was replaced with N- (m-tolylaminocarbonyl) -tyrosine. The results of various tests of the thermal recording material according to this example are as shown in Table 1.

(Example 8)
Except for replacing the N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea of the C solution of Example 1 with N, N'-di- [3- (benzenesulfonyloxy) phenyl] urea. The same operation as in Example 1 was performed.

[Reference Examples 1 to 7]
In Examples 1 to 7, 77.3 parts of each solution B was used, and the same operation as in Examples 1 to 7 was performed except that solution C was not used. The results of various tests of the thermal recorder according to this reference example are as shown in Table 1.

As is clear from Examples and Table 1, the heat-sensitive recording material made from the amino acid derivative shows a good color density with a high degree of whiteness, particularly for Z being an OH group, X being −NHCO−, and further. N-substituted amino acid derivatives are N- (m-tolylaminocarbonyl) -phenylalanine, N- (m-tolylaminocarbonyl) -methionine, N- (m-tolylaminocarbonyl) -valine, N- (m-tolylaminocarbonyl) ) -Phenylglycine and N- (m-tolylaminocarbonyl) -tyrosine had good heat resistance, moisture resistance, and oil resistance in the printed and unprinted areas.

Further, it contains at least one of N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea or N, N'-di- [3- (benzenesulfonyloxy) phenyl] urea as a storage stabilizer. The heat-sensitive recording material contains at least one of N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea or N, N'-di- [3- (benzenesulfonyloxy) phenyl] urea. It was excellent in water resistance as compared with no heat-sensitive recording material.

In the heat-sensitive recording material of the present invention, since the developing agent used can be made from natural amino acids as the main raw material, there is no concern about endocrine disturbance, the color development density is excellent, and the whiteness of the non-printed portion is high. Moreover, the storage stability of the printed portion is also good, and as a storage stabilizer, N, N'-di- [3- (p-toluenesulfonyloxy) phenyl] urea or N, N'-di- [3-( Benzenesulfonyloxy) Phenyl] By containing an N, N'-diarylurea derivative such as at least one type of urea, the water resistance of the N-substituted amino acid derivative of the color developer can be further improved. Industrial availability as an alternative to heat-sensitive recording materials is extremely promising.

Claims (4)

A heat-sensitive recording material provided on a support with a heat-sensitive recording layer containing a colorless or light-colored basic dye at room temperature and a color-developing agent capable of developing a color in contact with the dye by heating. Thermal recording that the agent contains an N-substituted amino acid derivative represented by the following general formula (1) and contains an N, N'-diarylurea derivative represented by the following general formula (2) as a storage stabilizer. material.
(R ^0- X) _m- Y- (Z) _m ... (1)
(In the formula (1), R ⁰ is an alkyl group having an aryl group of C6 to C10, an alkyl group of C1 to C8, an aralkyl group of C7 to C11, an aryl group of C6 to C10, or an alkoxy of C1 to C8. Represents an aryl group that may have a substituent of a group.
X is a group attached to the N-terminus of _{Y, -OCO -, - SO 2} NHCO -, - NHCO -, - NHCS-, or -SO ₂ - represent.
Y represents an amino acid residue or a peptide residue, and the OH group of the serine residue, threonine residue, aspartic acid residue, glutamate residue, or tyrosine residue in the Y group is OR ⁰ group or OR ". The SH group of the cysteine residue may be substituted with an SR ⁰ group or an SR "group, and the NH group of the histidine residue ^{may be substituted with an NR 0} group or an NR'group. _{The two} NH groups of the lysine residue or the ornithine residue may ^{be substituted with an NHR 0} group or an NHR'group, where R'represents an amino-protecting group and R'represents a carboxy-protecting group. ..
Z is a group attached to the C-terminus of Y and represents an OH group or an OR "group.
The plurality of R ^0s , R', R'may be the same or different, and may be combined with each other to form a ring.
However, Y is an amino acid residue other than the cystine residue or a peptide residue having no cystine residue, and m = 1. )

(In the formula, R represents an alkyl group and n represents an integer from 0 to 3.) The heat-sensitive recording material according to claim 1, wherein the N, N'-diarylurea derivative is represented by the following formula (3) or (4).

The color formers are N- (m-tolylaminocarbonyl) -phenylalanine, N- (m-tolylaminocarbonyl) -methionine, N- (p-tolylaminocarbonyl) -methionine, N- (phenylaminocarbonyl) -methionine. , N- (m-trillaminocarbonyl) -valine, N- (m-trillaminocarbonyl) -phenylglycine and N- (m-trillaminocarbonyl) -tyrosine, which is at least one selected from the group. The heat-sensitive recording material according to 1 or 2. The item according to any one of claims 1 to 3, wherein the content of the N, N'-diarylurea derivative represented by the general formula (2) is 10 to 400 parts by mass with respect to 100 parts by mass of the color developer. The heat-sensitive recording material described.

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