JP2001246857A - Multicolor heat-sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multicolor heat-sensitive recording material of good picture quality and high image storage properties. SOLUTION: The multicolor heat-sensitive recording material contains a urea urethane compound developer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a multicolor heat-sensitive recording material. More specifically, the present invention relates to a heat-sensitive recording material capable of reproducing full color having high image storability in addition to good image quality.

[0002]

2. Description of the Related Art A thermosensitive recording material generally comprises a support made of paper, synthetic paper, plastic film or the like, on which a thermosensitive coloring layer containing a coloring substance, a developer and an adhesive as main components is provided. Thus, a color-recorded image can be obtained by reacting these color-forming substances with a color developer by thermal energy. Such a thermal recording method has advantages such as a compact and inexpensive recording device and easy maintenance, such as a facsimile, an automatic ticket vending machine,
Not only as a recording medium for scientific measuring instruments, but also various printers for POS labels, CAD, CRT medical images, etc.
Also widely used as output media for plotters. On the other hand, in recent years, visualization of information has been advanced, and there has been a demand for a simple, economical and high-quality color hard copy technology.
Therefore, recently, a method of outputting a multi-color image or a full-color image by a thermal recording method which does not require complicated maintenance and has high recording reliability has been proposed.

In the case of performing multi-color recording by thermal recording, generally, heating by different applied energies causes
This is realized by laminating a plurality of heat-sensitive recording layers that develop different colors. Examples of the combination of a color-forming substance and a color developer used in these multicolor heat-sensitive recording layers include JP-A-48-8251 and JP-A-49-825.
No. 96738, JP-A-1-186373 and the like, a combination of an electron-donating dye precursor and an electron-accepting substance, or, for example, JP-A-57-2120.
No. 95, Japanese Unexamined Patent Publication No. Sho 62-170387, etc. have proposed a combination of a diazo compound and a coupling component. Further, Japanese Patent Application Laid-Open No. 57-144
Japanese Patent Application Laid-Open No. 789-79, Japanese Patent Application Laid-Open No. 2-107476, and the like also propose multicoloring by combining both.

[0004] The combination of these electron-donating dye precursors with an electron-accepting substance and the combination of a diazo compound and a coupling component have high reactivity and can provide a color image with high density instantaneously. In addition, it has an excellent property such that an appearance close to white can be obtained and various color hues such as red, orange, yellow, green, blue and black can be obtained. However, on the other hand, the obtained color-developed image has poor chemical resistance, so that it comes into contact with a plasticizer contained in a plastic sheet or an eraser or a chemical contained in food or cosmetics, and the record is easily lost, or However, since the light resistance of the recording portion is inferior, the recording has a disadvantage that the storage stability of the recording is poor, such as fading or even disappearing by exposure to sunlight for a relatively short period of time, and improvement thereof is strongly desired. ing.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional multicolor heat-sensitive recording material, and provides a multicolor heat-sensitive recording material having not only good image quality but also high image storability. To provide.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the use of a urea urethane compound developer in a multicolor heat-sensitive recording material has provided good image quality. In addition, it has been found that a multicolor heat-sensitive recording material having high image storability can be obtained, and the present invention has been completed. That is, the present invention is as follows.
A first aspect of the present invention is a multicolor heat-sensitive recording material containing a urea urethane compound color developer. Second of the invention
Is a multicolor heat-sensitive recording material provided with at least two heat-sensitive recording layers on one surface of a support, wherein at least one of the heat-sensitive recording layers contains a urea urethane compound developer. It is a color heat-sensitive recording material.

A third aspect of the present invention is the multicolor heat-sensitive recording material according to the second aspect, wherein an intermediate layer is provided between the heat-sensitive recording layers. A fourth aspect of the present invention is to form two heat-sensitive recording layers, each having a different coloring temperature and a different color tone, on one surface of the support by laminating the heat-sensitive recording layers. A multicolor heat-sensitive recording material containing a reversible color developer and a urea urethane compound color developer in a lower heat-sensitive recording layer. Fifth invention
The invention according to the fourth aspect, wherein the two heat-sensitive recording layers are a low-temperature coloring layer in which the upper layer develops color at low temperature and decolorizes at high temperature, and the lower layer is a high-temperature coloring layer which develops color at high temperature. This is a multicolor heat-sensitive recording material.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The multicolor heat-sensitive recording material of the present invention contains a ureaurethane compound developer. The urea urethane compound developer according to the present invention refers to a compound having at least one urea group (—NHCONH— group) and at least one urethane group (—NHCOO— group) in the molecule. It has been known that a compound having a urea group exhibits a color developing effect, but it is not practical because of low color density and low storage stability. However, surprisingly, a urea urethane compound in which a urea group and a urethane group are simultaneously present in one molecule is an excellent color developer of a colorless or light-colored dye precursor. The recording material has a high coloring density and excellent storage stability.

The mechanism by which such a urea urethane compound exhibits an excellent color developing effect is unknown, but is presumed to be due to the interaction between a urea group and a urethane group in the molecule. The urea urethane compound developer according to the present invention may be any compound as long as both a urea group (—NHCONH— group) and a urethane group (—NHCOO— group) are present in the molecule, and may be an aromatic compound or It is preferably a heterocyclic compound. Further, it is preferable that an aromatic compound residue or a heterocyclic compound residue is directly bonded to both ends of a urea group and a urethane group. More preferably, the urea group (-NHCONH- group) and the urethane group in the molecule
(-NHCOO- group) in addition to a sulfone group of the (- SO ₂ - group) or an amide group (-NHCO- groups) or isopropylidene groups (-C (C
It is desirable that H ₃ ) ₂ -group) be present without being directly bonded to the urea group.

The method for synthesizing a urea urethane compound developer according to the present invention comprises a urea group (-NHCONH- group) and a urethane group.
There is no particular limitation as long as the (-NHCOO- group) is produced, but a method of producing the isocyanate compound by reacting an OH group-containing compound and an amine compound is preferred because it is easy. That is, the urea urethane compound developer according to the present invention starts with an isocyanate having at least two or more isocyanate groups as a starting material, and retains at least one isocyanate group of the isocyanate and another isocyanate group.
The H-containing compound can be reacted to form a urethane group, and then the remaining isocyanato group can be reacted with the amine compound to form a urea group. Also, first, an isocyanate group and an amine compound are reacted to form a urea group,
Next, the remaining isocyanate group and the OH group-containing compound may be reacted to form a urethane group.

The starting isocyanate is not particularly limited as long as it has two or more isocyanate groups.
For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole −
3,6-diisocyanate, 3,3′-dimethyl-4,
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Triphenylmethane triisocyanate, tris (4-
Phenyl isocyanate) thiophosphate, 4,
4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine, meta-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate Isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, and the like.

Further, diisocyanate dimer such as toluene diisocyanate dimer N, N '(4,
4′-dimethyl-3,3′-diphenyldiisocyanato) uretdione (trade name Desmodur TT) and trimers such as 4,4 ′, 4 ″ -trimethyl-3,3 ′,
3 "-triisocyanato-2,4,6-triphenyl cyanurate and the like. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4- (Methylphenyl) urea and polyol adducts, for example, trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L), amine adducts, etc. Also, Japanese Patent Application Laid-Open Nos. 10-76757 and 10-95171 (these are incorporated herein by reference). In the isocyanate compound and the isocyanate adduct compound described in Japanese Patent Application Laid-Open No. H11-163, the content of which is incorporated herein by reference, a compound having two or more isocyanate groups may be used. List diisocyanates DOO can. Toluene diisocyanate is preferably 2,4-toluene diisocyanate, the addition of 2,4-toluene diisocyanate and 2,
A mixture of 6-toluene diisocyanate is generally commercially available and can be obtained at low cost, but this is also acceptable.

The urea urethane compound The amine compound which forms a urea group by reacting with an isocyanate which is a starting material of a color developer may be any compound having an amino group, for example, aniline, o-toluidine, m-toluidine. , P-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p
-Phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-
Dimethoxyaniline, 3,4-dimethoxyaniline, p
-Aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine,
3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine,
2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o
-Chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N
-Propylaniline, N-butylaniline,

N, N-diglycidylaniline, N, N-
Diglycidyl-o-toluidine, acetoacetic anilide,
Trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4 '
-Diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3 '
-Dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p
-Phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, Benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N
-Methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-
Amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline,

P- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl)
Carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5
[N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-
Chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) Aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2-
(N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole,
4-aminodiphenyl sulfone, 2-chloro-5-N-
Phenylsulfamoylaniline, 2-methoxy-5
N, N-diethylsulfamoylaniline,

2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-aniline Linosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) Phenyl] sulfone, 3,3′-dimethoxy-4,
4'-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 2,2'-dichloro-4,
4'-diamino-5,5'-dimethoxybiphenyl,
2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-
Diaminobiphenyl, 2,2′-diaminobiphenyl,
4,4'-diaminobiphenyl, 2,2'-dichloro-
4,4'-diaminobiphenyl, 3,3'-dichloro-
4,4'-diaminobiphenyl, 2,2'-dimethyl-
4,4′-diaminobiphenyl,

4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,
4'-diaminodiphenylmethane, bis (3-amino-
4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone,
3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4′-ethylenedianiline, 4,4′diamino-2,2′-dimethyldibenzyl, 3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene,
1,3-bis (4-aminophenoxy) benzene, 1,
3-bis (3-aminophenoxy) benzene, 9,9-
Bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane,

4,4'-bis (4-aminophenoxy)
Diphenyl, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenylsulfone, 3,3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile , 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-O-toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6-xylidine), o-chloro-p -Nitroaniline, o-nitro-
p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2 -Methyl-4-
Nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, methol, 2,4-
Diaminophenol, N- (β-hydroxyethyl)-
o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid,

P-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediene Amine, 2-aminothiophenol, 2-amino-
3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine , 4,4 '
-Diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthonic acid, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, Aromatic amines such as 4-diamino-2,3-dichloroanthraquinone, and further 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε -Caprolactam, acetoguanamine, 2,4-diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine,
3-diaminopyridine,

2,5-diaminopyridine, 2,3,5-
Triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl)
Heterocyclic compound amines such as morpholine, methylamine,
Ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (Diethylamino) propylamine, di-2-ethylhexylamine, 3-
(Dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, , 4-Diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-aminobutanol Amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-
Examples thereof include aliphatic amines such as aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine.

Further, among the above-mentioned amine compounds, an aniline derivative having at least one amino group represented by the following formula (I) is particularly preferable.

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently
Represents a hydrogen, a halogen, an alkyl group, an alkoxy group or an amino group; X ₁ and X ₂ each independently represent an amino group or a group represented by the formula (b);

[0022]

Embedded image Y ₁ is _{-SO 2 -, - O -,} - (S) n -, - (C
H ₂ ) _n- , -CO-, -CONH-, any one of the groups represented by the formula (a):

[0023]

Embedded image Or indicates that it does not exist. n is 1 or 2. )

The OH group-containing compound which reacts with the isocyanate to form a urethane group may be any compound having an OH group. Examples thereof include phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol and resorcinol. , P-tert-butylphenol, p-tert-octylphenol,
2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p
-Nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, bis ( 4-hydroxyphenyl) butyl acetate, bis (4-hydroxyphenyl) benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone,

Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-
Methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4′-methylphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone,
4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone , 4-hydroxy-4'-isopropoxydiphenylsulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenylether, 4,4'-thiodiphenol, , 4 '
-Dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4 '
-Dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone,

2,4-dihydroxybenzophenone,
2,2 ′, 4,4′-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4′-chlorobenzyl), 1,2 -Ethyl bis (4'-hydroxybenzoate), 1,5-bis (4'-hydroxybenzoic acid) pentyl, 1,6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, gallic Stearyl acid, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy) phenol,
-Hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-
Phenols such as n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid. .

However, those phenols having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. In addition, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol,
Isobutanol, isopentanol, 2-ethyl-1-
Hexanol, 1-decanol, lauryl alcohol,
Stearyl alcohol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4- Pyridine methanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol, 1-
Alcohols such as chloro-3-hydroxypropane, glycerin and glycerol, polypropylene glycol,
Polytetramethylene ether glycol, adipate polyol,

Polyether polyols such as epoxy-modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, phenol-based polyol and amine-modified polyol;
Ethylene glycol, diethylene glycol, 1,3-
Propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1,9
-Nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol,
Polyols such as polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, and souce rose.

As the urea urethane compound developer according to the present invention, a urea urethane compound in which the number of urea groups (A) and the number of urethane groups (B) in the molecular structure satisfy the following formula is preferable. 10 ≧ (A + B) ≧ 3 (where A and B are integers of 1 or more) The number of urea groups (A) and the number of urethane groups (B) are expressed by the following formula (10).
A urea urethane compound that satisfies ≧ (A + B) ≧ 3 (where A and B are integers of 1 or more) is defined as having at least a urea group (—NHCONH— group) and a urethane group (—NHCOO— group) in the molecular structure. A compound in which at least one is present and the total number of urea groups and urethane groups is 3 or more and 10 or less.
Heretofore, such a compound has not been known and is a completely novel compound. This novel compound is useful for a recording material using recording energy such as heat and pressure.

The number of urea groups (A) and the number of urethane groups (B) satisfy the formula 10 ≧ (A + B) ≧ 3 (where A and B are integers of 1 or more). Group (-NHCONH- group) and urethane group (-NHCOO-
Group) is not particularly limited as long as the method is such that the total number of urea groups and urethane groups is 3 to 10
A method of preparing an isocyanate compound by reacting with an OH group-containing compound and an amine compound is easy and preferable. That is,
The urea urethane compound according to the present invention is obtained, for example, by reacting an isocyanate having at least two or more isocyanate groups as a starting material with another isocyanate group and an OH group-containing compound while leaving at least one isocyanate group of the isocyanate. Then, the remaining isocyanato groups of the two molecules of the urethane compound are reacted with water to be bonded to each other, whereby a urea urethane compound having a total number of urea groups and urethane groups of at least 3 can be obtained.

Further, for example, an isocyanate having at least two or more isocyanate groups is used as a starting material,
An OH group-containing compound is reacted with another isocyanate group leaving at least one isocyanato group of the isocyanate to form a urethane group, and then the remaining isocyanate group is reacted with an amine compound having two or more amino groups. By forming a urea group and reacting the remaining amino group with an isocyanate compound, a urea urethane compound having a total number of urea groups and urethane groups of at least 3 can be obtained. Further, first, an isocyanate group is reacted with an amine compound to form a urea group, and then the remaining isocyanate group is reacted with an OH group-containing compound having two or more OH groups to form a urethane group. By reacting the compounds, a urea urethane compound having a total number of urea groups and urethane groups of at least 3 can be obtained. At this time, an isocyanate compound having two or more isocyanate groups is used as an isocyanate to be reacted last, and an OH-containing compound having the remaining isocyanate group and two or more OH groups or an amino acid having two or more amino groups is used. By sequentially repeating the operation of reacting the compounds, a urea urethane compound having a total number of urea groups and urethane groups of 3 to 10 can be obtained.

The starting isocyanate is not particularly limited as long as it has two or more isocyanate groups.
For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole −
3,6-diisocyanate, 3,3′-dimethyl-4,
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Triphenylmethane triisocyanate, tris (4-
Phenyl isocyanate) thiophosphate, 4,
4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine, meta-xylylene diisocyanate, lysine diisocyanate,

Dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like can be mentioned. Dimer of diisocyanate, for example, dimer of toluene diisocyanate
N, N '(4,4'-dimethyl-3,3'-
Diphenyldiisocyanato) uretdione (trade name Desmodur TT) and trimers such as 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,
6-triphenyl cyanurate and the like may be used. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name: Dess) Module L) or an amine adduct may be used. In addition, Japanese Patent Application Laid-Open
Among the isocyanate compounds and isocyanate adduct compounds described in JP-A-76757 and JP-A-10-95171, those having two or more isocyanate groups may be used. A particularly preferred example is toluene diisocyanate. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable, and in addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and inexpensive. Although it is possible to obtain, this may be sufficient. These toluene diisocyanate isomer mixtures are liquid at room temperature.

The amine compound for forming a urea group by reacting with the isocyanate which is a starting material of the urea urethane compound may be any compound having an amino group. Toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline,
N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,
4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5
-Dichloroaniline, 2,6-dichloroaniline, 3,
4-dichloroaniline, 3,5-dichloroaniline,
2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline,

N-ethylaniline, N-propylaniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide,
4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether,
3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2- Chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, p-butyl
Dodecyl aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone,

M-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-
Methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) Carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5
-(N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N
-(2'-chlorophenyl) carbamoyl] aniline,
5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5- Dimethoxy-4-
(N-benzoylamino) aniline, 2-methoxy-4
-(N-benzoylamino) -5-methylaniline, 4
-Sulfamoylaniline,

3-sulfamoylaniline, 2- (N-
Ethyl-N-phenylaminosulfonyl) aniline, 4
-Dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N
-Diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline , 3-anilinosulfonyl-4
-Methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4-
(P-aminophenoxy) phenyl] sulfone, 3,
3′-dimethoxy-4,4′-diaminobiphenyl,
3,3′-dimethyl-4,4′-diaminobiphenyl,
2,2'-dichloro-4,4'-diamino-5,5'-
Dimethoxybiphenyl, 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl,

Ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl,
4,4'-diaminobiphenyl, 2,2'-dichloro-
4,4'-diaminobiphenyl, 3,3'-dichloro-
4,4'-diaminobiphenyl, 2,2'-dimethyl-
4,4′-diaminobiphenyl, 4,4′-thiodianiline, 2,2′-dithiodianiline, 4,4′-dithiodianiline, 4,4′-diaminodiphenyl ether,
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4- Diaminophenyl) sulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenylmethane,

4,4-diaminodiphenylamine, 4,
4'-ethylenedianiline, 4,4'diamino-2,
2′-dimethyldibenzyl, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 1,4
-Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4
-Aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ', 4
4'-tetraaminodiphenyl ether, 3,3 ',
4,4′-tetraaminodiphenyl sulfone, 3,
3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-O-toluidine, 4,4'-(p-phenyleneisopropylidene ) -Bis- (2,6-xylysine), o-chloro-p
-Nitroaniline, o-nitro-p-chloroaniline,
2,6-dichloro-4-nitroaniline, 5-chloro-
2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline,

M-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p
-Toluidine, 2-amino-5-nitrobenzonitrile, methol, 2,4-diaminophenol, N- (β
-Hydroxyethyl) -o-aminophenol sulfate,
Sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid,
p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2
-Aminothiophenol, 2-amino-3-bromo-5
-Nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2
-Methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine,
3,3'-dichlorobenzidine, 4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid, phenyl J acid,

1,4-diamino-anthraquinone,
Aromatic amines such as 4-diamino-2,3-dichloroanthraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine,
-Aminopyridine, α-amino-ε-caprolactam,
Acetoguanamine, 2,4-diamino-6- [2′-methylimidazolyl- (1)] ethyl-S-triazine,
2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4
-Methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-
Heterocyclic compounds such as aminopropyl) morpholine amines, methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3
-(2-ethylhexyloxy) propylamine, 3-
Ethoxypropylamine, diisobutylamine, 3-
(Diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine,

Propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine,
1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-
Bromoethylamine, 2-methoxyethylamine, 2-
Ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine,
Examples thereof include aliphatic amines such as diethylenetriamine and hexamethylenediamine.

Further, among the above-mentioned amine compounds, an aniline derivative having at least one amino group represented by the following formula (I) is particularly preferable.

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently
Represents a hydrogen, a halogen, an alkyl group, an alkoxy group or an amino group; X ₁ and X ₂ each independently represent an amino group or a group represented by the formula (b);

[0044]

Embedded image Y ₁ is _{-SO 2 -, - O -,} - (S) n -, - (C
H ₂ ) _n- , -CO-, -CONH-, any one of the groups represented by the formula (a):

[0045]

Embedded image Or indicates that it does not exist. n is 1 or 2. )

The OH group-containing compound which reacts with the isocyanate to form a urethane group may be any compound having an OH group. Examples thereof include phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, and resorcinol. , P-tert-butylphenol, p-tert-octylphenol,
2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p
-Nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, bis ( 4-hydroxyphenyl) butyl acetate,

Benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4 '
-Methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl- 4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-
Hydroxyphenylsulfone, 4-hydroxy-4'-
Isopropoxydiphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, , 2-bis (4-hydroxyphenyl) hexafluoropropane,

4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide,
Bis (4- (2-hydroxy) phenyl) sulfone,
2,4-dihydroxybenzophenone, 2,2 ′, 4
4'-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4'-hydroxy Ethyl benzoate, 1,5-bis (4'-hydroxybenzoic acid) pentyl, 1,6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, Methyl gallate, 4-methoxyphenol, 4
-(Benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid,
-N-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3
And phenols such as -n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid.

However, as these phenols, those having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. Methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-
1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2
-Propen-1-ol, benzyl alcohol, 4-pyridine methanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol,
Alcohols such as -chloro-3-hydroxypropane, glycerin and glycerol, polypropylene glycol, polytetramethylene ether glycol, adipate polyol,

Polyether polyols such as epoxy-modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, phenol-based polyol and amine-modified polyol;
Ethylene glycol, diethylene glycol, 1,3-
Propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1,9
-Nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol,
Polyols such as polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, and souce rose. The urea urethane compound developer according to the present invention further includes a compound represented by the general formula (I)
The urea urethane compounds of I) to (VIII) are also preferred.

[0051]

Embedded image (Wherein, X and Z each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, each residue may have a substituent, and Y ₀ is Tolylene group, xylylene group, naphthylene group, hexamethylene group,
And one selected from the group consisting of -φ-CH ₂ -φ- groups, wherein -φ- represents a phenylene group. ),

[0052]

Embedded image (Wherein X and Y each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue;
Further, each residue may have a substituent. ),

[0053]

Embedded image (Wherein X and Y each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue;
α represents a residue having a valence of 2 or more, n represents an integer of 2 or more, and each residue may have a substituent. ),

[0054]

Embedded image (Wherein, Z and Y each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue;
β represents a residue having a valence of 2 or more, n represents an integer of 2 or more, and each residue may have a substituent. ),

[0055]

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, and each residue may have a substituent. , Γ are -SO _2- , -O-,-(S) _n -,-(CH
_{2) n -, - CO -} , - CONH-, one selected from the group consisting of any of the groups represented by the formula (a),

[0056]

Embedded image Or it shows the case where it does not exist. n is 1 or 2. ),

[0057]

Embedded image(Wherein the hydrogen atom of the benzene ring is an aromatic compound residue or
Substituted by an aliphatic compound residue or a heterocyclic compound residue
And each residue may have a substituent.
Δ is -SO_Two-, -O-,-(S)_n-,-(CH
_Two)_n-, -CO-, -CONH-, -NH-, -CH
(COOR₁)-, -C (CF_Three)_Two-, And -CR_Two
R_ThreeOne selected from the group consisting of-or not present
And R ₁, R_TwoAnd R_ThreeRepresents an alkyl group, and n represents
1 or 2. ),as well as

[0058]

Embedded image (In the formula, X, Y, and Z each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and each residue may have a substituent. X, Y
And Z are preferably aromatic compound residues or heterocyclic compound residues. )

The ureaurethane compounds of the general formulas (II) to (VIII) are also novel compounds. This novel compound is useful for a heat-sensitive recording material using recording energy such as heat and pressure. Formula (II) according to the present invention
The urea urethane compound of formula (II) is not limited to a production method. For example, an OH group-containing compound of the following general formula (IX), an isocyanate compound of the following general formula (X) and the following general formula (XI)
Can be obtained, for example, by reacting the amine compound according to the following reaction formula (A).

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image (Wherein, X and Z represents an aromatic compound residue or heterocyclic compound residue or an aliphatic compound residue, each independently, may .Y ₀ be the residue have a substituent, Tolylene group, xylylene group, naphthylene group, hexamethylene group,
Alternatively, it represents one selected from the group consisting of a -φ-CH ₂ -φ- group, and -φ- represents a phenylene group. In addition, the term "aliphatic" in the present invention includes an alicyclic compound.

[0063]

Embedded image The production method of the ureaurethane compound of the formula (III) according to the present invention is not limited. It can be obtained by reacting according to (B).

[0064]

Embedded image (In the formula, Y represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. The residue may have a substituent.)

[0065]

Embedded image The ureaurethane compound of the formula (IV) according to the present invention comprises
Although there is no limitation on the production method, for example, an OH group-containing compound of the general formula (IX), an isocyanate compound of the general formula (XII) and an amine compound of the following general formula (XIII) can be prepared, for example, by the following reaction formula (C) or (D) By reacting according to the following formula.

[0066]

Embedded image (In the formula, α represents a residue having a valence of 2 or more, and n represents an integer of 2 or more.)

[0067]

Embedded image

[0068]

Embedded image

The ureaurethane compound of the formula (V) according to the present invention is not particularly limited in its production method. It can be obtained by reacting an OH group-containing compound according to, for example, the following reaction formula (E) or (F).

Embedded image (In the formula, β represents a residue having a valence of 2 or more, and n represents an integer of 2 or more.)

[0070]

Embedded image

[0071]

Embedded image

The compounds of the general formulas (IX) to (XIV) which can be used when synthesizing the ureaurethane compounds represented by the above formulas (II) to (IV) will be described in more detail. The OH group-containing compound represented by the general formula (IX) is not particularly limited as long as it has one or more OH groups. For example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol , P-tert-butylphenol,
p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4
-Phenylphenol, 4-hydroxyphenyl-4 '
-Methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4′-methylphenylsulfone, 4-isopropylphenyl-4′-hydroxyphenylsulfone,

4-isopropyloxyphenyl-4'-
Hydroxyphenylsulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 4-isopropylphenyl-4′-hydroxyphenylsulfone,
4-hydroxy-4'-isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4'-hydroxybenzoic acid) ethyl, 1,5-bis (4'-hydroxybenzoic acid) pentyl, 1,6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, 4-methoxy Phenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-
Pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4
-N-octyloxycarbonylaminosalicylic acid, 4
And monophenols such as -n-octanoyloxycarbonylaminosalicylic acid. Also, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane,

2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane,
Catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, 4,4'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4 -Hydroxyphenyl) benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl -4'methylphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-te
rt-butyl-4-hydroxyphenyl) sulfide,
4,4′-dihydroxydiphenyl ether, 4,4 ′
-Thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane,

Diphenols such as 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide and the like can be mentioned. However, these OH
A compound having an amino group is not preferable as the containing compound. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. ) Also, methanol, ethanol, propanol, butanol,
Pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol, 2-
Pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve,
Butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol,
Cyclohexylmethanol, cyclopentanol, 2-
Monoalcohols such as chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol and the like can be mentioned. Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol, amine modified polyol, ethylene glycol, diethylene glycol,

1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexane Glycol, 1,9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol,
Polyols such as castor oil-based polyols, polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucosidolbitol, and shoe rose may be used. Of these, monophenols are preferably used.
As the isocyanate compound of the general formula (X), 2,4
-Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, meta-xylylene diisocyanate and the like. Of these, toluene diisocyanate is preferred.

The isocyanate compound of the general formula (XII) is not particularly limited as long as it has two or more isocyanate groups. For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene- 1,4
-Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6
-Diisocyanate, 3,3'-dimethyl-4,4'-
Diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, 4,4 ', 4 "
-Triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ', 4 "-triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate,

[0078] Isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like can be mentioned. Further, diisocyanate dimer, for example, N, N '-(4,
4'-dimethyl-3,3'-diphenyldiisocyanato) uretdione (trade name Desmodur TT) and trimers such as 4,4 ', 4 "-trimethyl-3,3', 3"
-Triisocyanate-2,4,6-triphenyl cyanurate and the like. Also, toluene diisocyanate,
Water adduct isocyanates such as diphenylmethane diisocyanate, for example, 1,3-bis (3 isocyanato 4
-Methylphenyl) urea or a polyol adduct, for example, trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L), an amine adduct, or the like. Further, among the isocyanate compounds and isocyanate adduct compounds described in JP-A-10-76757 and JP-A-10-95171, those having two or more isocyanate groups may be used. A particularly preferred example is toluene diisocyanate.

The amine compound of the general formula (XI) is not particularly limited as long as it has one or more amino groups. Examples thereof include aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, 2,4-dimethoxyaniline,
2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p
-Aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine,
4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate,

N-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone , P-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-
Amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p
-[N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl]
Aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- ( 2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2
-Methoxyaniline, 4-acetylaminoaniline, 2
-Methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline,

3-Sulfamoylaniline, 2- (N-
Ethyl-N-phenylaminosulfonyl) aniline, 4
-Dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N
-Diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline , 3-anilinosulfonyl-4
-Methylaniline, o-chloro-p-nitroaniline,
o-nitro-p-chloroaniline, 2,6-dichloro-
4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2
-Methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid,

P-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino- 3
Aromatic monoamines such as -bromo-5-nitrobenzonitrile, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide,
3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, trizine base, dianisidine, bis [4- ( m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy-4, 4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl,

2,2 ', 5,5'-tetrachloro-4,
4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,
2'-dichloro-4,4'-diaminobiphenyl, 3,
3'-dichloro-4,4'-diaminobiphenyl, 2,
2′-dimethyl-4,4′-diaminobiphenyl, 4,
4′-thiodianiline, 2,2′-dithiodianiline,
4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '
-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,
3′-diaminodiphenyl sulfone,

3,4′-diaminodiphenyl sulfone,
3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy)
Benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl)
Aromatic diamines such as propane, 4,4′-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3′-dichlorobenzidine are exemplified. 3 more
-Amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-
Amino-ε-caprolactam, acetoguanamine, 2,
4-diamino-6- [2'-methylimidazolyl-
(1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine,
1- (2-aminoethyl) piperazine,

Bis (aminopropyl) piperazine, N-
Heterocyclic compounds such as (3-aminopropyl) morpholine amines, methylamine, ethylamine, stearylamine, allylamine, isopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxy Propylamine, 3- (diethylamino) propylamine, 3-
(Dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, , 4-Diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-aminobutanol Amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-
Examples thereof include aliphatic amines such as aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine. Of these, aromatic monoamines are preferably used.

The amine compound represented by the general formula (XIII) is not particularly limited as long as it has two or more amino groups. For example, 4,4′-diamino-3,3′-diethyldiphenylmethane, -Diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-
Diaminodiphenylmethane, trizine base, dianisidine, bis [4- (m-aminophenoxy) phenyl]
Sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy-4,4′-diaminobiphenyl, , 3'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4 , 4'-diaminobiphenyl, ortho-tolidine sulfone, 2,
4′-diaminobiphenyl, 2,2′-diaminobiphenyl, 4,4′-diaminobiphenyl,

2,2′-dichloro-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,
4'-diaminodiphenylmethane, bis (3-amino-
4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone,
3,4′-diaminodiphenyl sulfone,

3,3′-diaminodiphenylmethane,
4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone,
4,4′-diaminobenzophenone, 1,4-bis (4
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, trizine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine And the like. Further, among the above-mentioned amine compounds, an aniline derivative having at least two amino groups such as the following formula (I) is particularly preferable.

[0089]

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently
Represents a hydrogen, a halogen, an alkyl group, an alkoxy group or an amino group; X ₁ and X ₂ each independently represent an amino group or a group represented by the formula (b);

[0090]

Embedded image Y ₁ is _{-SO 2 -, - O -,} - (S) n -, - (C
H ₂ ) _n- , -CO-, -CONH-, any one of the groups represented by the formula (a):

[0091]

Embedded image Or indicates that it does not exist. n is 1 or 2. )

The OH group-containing compound of the general formula (XIV) is not particularly limited as long as it is a compound having two or more OH groups. Bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, p, p'-biphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4 -Hydroxyphenyl)
Benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4′-
Methylphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-t
tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,
4'-thiodiphenol,

4,4′-dihydroxybenzophenone,
Phenols such as 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, and bis (4-hydroxy-3-methylphenyl) sulfide . However, those having an amino group are not preferred as these diphenols.
Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol and amine modified polyol, ethylene glycol, diethylene glycol, , 3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol,

1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1,9-
Nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol,
Polyols such as polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, and souce rose. The production method of the ureaurethane compound of the formula (VI) according to the present invention is not limited, and for example, a monophenol compound, an aromatic diisocyanate compound and a diamine compound of the following general formula (XV) may be used.
For example, it can be obtained by reacting according to the following reaction formula (G) or (H).

[0095]

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Further, each residue may have a substituent. Γ is -SO _2- , -O-,-(S) _n -,-(CH
₂ ) _n- , -CO-, -CONH-, any of the groups represented by the formula (a),

[0096]

Embedded image Or it shows the case where it does not exist. n is 1 or 2. )

[0097]

Embedded image

[0098]

Embedded image

The ureaurethane compound of the formula (VII) according to the second aspect of the present invention is not particularly limited in its production method. It can be obtained by reacting according to reaction formula (J) or (K).

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Further, each residue may have a substituent. .δ is _{-SO 2 -, - O -,} - (S) n -, - (CH
₂ ) _n- , -CO-, -CONH-, -NH-, -CH
(COOR ₁ )-, -C (CF ₃ ) _2- , -CR ₂ R ₃
Indicates either-or does not exist. R ₁ , R ₂ ,
R ₃ represents an alkyl group, and n is 1 or 2. )

[0100]

Embedded image

[0101]

Embedded image

Formulas (VI) and (VII) according to the present invention
Compounds that can be used when synthesizing the urea urethane compound of the above are described in detail below. Equation (V
The monophenol compound that can be used when synthesizing the urea urethane compound of I) is not particularly limited as long as it is a compound having one OH group on the benzene ring. For example, phenol, cresol, xylenol, p
-Ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-te
rt-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4-phenylphenol, 4-hydroxyphenyl-4 '-Methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone,

4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-
4'-hydroxyphenylsulfone, 4-hydroxy-
4′-isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4′-chlorobenzyl), dimethyl 3-hydroxyphthalate, Methoxyphenol, 4-
(Benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-
n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-
Examples include phenols such as n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid. However, as these phenols, those having an amino group are not preferred. The amino group is O
Since the reactivity with the isocyanato group is higher than that of the H group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

The aromatic diisocyanate compound which can be used when synthesizing the urea urethane compounds of the formulas (VI) and (VII) is an aromatic diisocyanate having two isocyanate groups bonded to a benzene ring. Although there is no particular limitation, for example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-
Examples thereof include diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. Particularly preferred examples include toluene diisocyanates. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable. In addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available, and is inexpensive. It is possible to obtain it, but this may be sufficient. These toluene diisocyanate isomer mixtures are liquid at room temperature.

The diamine compound of the general formula (XV) which can be used when synthesizing the ureaurethane compound of the formula (VI) is, for example, 4,4′-diamino-3,
3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 3,3'-dichloro-4,
4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) Phenyl] sulfone, bis [3-methyl-4-
(P-aminophenoxy) phenyl] sulfone, 3,
3′-dimethoxy-4,4′-diaminobiphenyl,
3,3′-dimethyl-4,4′-diaminobiphenyl,
2,2'-dichloro-4,4'-diamino-5,5'dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4 '-Diaminobiphenyl, 2,2'-
Diaminobiphenyl, 4,4′-diaminobiphenyl,
2,2′-dichloro-4,4′-diaminobiphenyl,
3,3′-dichloro-4,4′-diaminobiphenyl,
2,2′-dimethyl-4,4′-diaminobiphenyl,
4,4'thiodianiline,

2,2'-dithiodianiline, 4,4'-
Dithiodianiline, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,
4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,
4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,
4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone,
4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis Aromatic diamines such as (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4′-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3′-dichlorobenzidine And the like.

The aniline derivative which can be used when synthesizing the urea urethane compound of the formula (VII) is not particularly limited as long as it is an aniline compound having one amino group on a benzene ring. , O
-Toluidine, m-toluidine, p-toluidine, o-
Anisidine, p-anisidine, p-phenetidine, N,
N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic Acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,
4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p
-Cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-
Dichloroaniline, 2,4,5-trichloroaniline,
α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline,
p-chloroaniline,

Methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-aminobenzoate
Isopropyl aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-amino Benzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3
-Amino-4-methylbenzamide, 3-amino-4-
Methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline,
p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [ N- (2 '
-Methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2
-Methoxyaniline, 4-acetylaminoaniline, 4
-(N-methyl-N-acetylamino) aniline,

2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-
Benzoylamino) aniline, 2-methoxy-4- (N
-Benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2
-(N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-
N-phenylsulfamoylaniline, 2-methoxy-
5-N, N-diethylsulfamoylaniline, 2,5
-Dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline,
2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6 −
Dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-
Nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, p-fluoroaniline, o-fluoroaniline,
-Chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino-3-bromo-
5-nitrobenzonitrile and the like.

Further, the compound represented by the general formula (XVI) which can be used when synthesizing the urea urethane compound of the formula (VII)
Examples of the dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, and 2,2-bis (hydroxyphenyl) Heptane, 4,4'-biphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl)
Sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert)
-Butyl-4-hydroxyphenyl) sulfide, 4,
4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3 ' Diphenols such as -dihydroxydiphenylamine and bis (4-hydroxy-3-methylphenyl) sulfide. However, those having an amino group are not preferred as these diphenols. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

The method for synthesizing the ureaurethane compound of the general formula (VIII) is not particularly limited. Can be obtained, for example, by reacting the amine compound according to the following reaction formula (L).

Embedded image

The substituent of X bonded to the urethane group of the urea urethane compound of the general formula (VIII) includes an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an amide group, an alkoxyl group and a nitro group. , Nitroso group, nitrile group, toluenesulfonyl group, methanesulfonyl group, acetyl group, halogen atom, formyl group,
Dialkylamino groups and isocyanato groups are preferred. Among these urea urethane compound developers of general formulas (II) to (VIII), preferred are those of general formulas (III) to
The compound of the formula (VII), and particularly preferred are the compounds of the general formulas (VI) to (VII).

Further, formulas (II) to (V) and (VIII)
In the urea urethane compound developer, when the residue bonded to the urea group or the urethane group is an aliphatic compound residue, the coloring density and print storage performance may be reduced, and the urea group or the urethane group The bonded residue is preferably an aromatic compound residue or a heterocyclic compound residue. However, the decrease in color density and print storage performance that may be caused by the introduction of an aliphatic compound residue into the compound is reduced by increasing the number of urea groups and urethane groups, and the formula (IV): In the compound of the formula (V), even if an aliphatic compound residue is present in a residue bonded to a urea group or a urethane group, there is almost no problem in performance.

In order to obtain the urea urethane compound according to the present invention, the desired product can be obtained by mixing and reacting the isocyanate with the reactant in an organic solvent or without a solvent, and then removing the crystals by filtration. A single or a plurality of reactants may be used depending on the purpose. The solvent may be any solvent as long as it does not react with the isocyanato group and the functional group of the reactant. Examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and chlorinated aliphatic hydrocarbons. Examples include hydrogen, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and ketones. In particular, methyl ethyl ketone, toluene, and the like, which dissolve the isocyanate and have low solubility of the product, are preferable. The product obtained by the above-mentioned reaction operation is not necessarily a single product, and may be obtained as a mixture of compounds having different substituent positions.

The urea urethane compound developer of the present invention comprises:
It is a colorless or pale-colored compound which is usually a solid at room temperature. The molecular weight of the urea urethane compound developer of the present invention is preferably 5,000 or less, more preferably 2,000 or less. The total number of urea groups and urethane groups in the urea urethane compound developer of the present invention is preferably 20 or less, more preferably 10 or less. Further, the ratio of the urea group to the urethane group in the molecular structure of the urea urethane compound is preferably 1: 3 to 3: 1, and particularly preferably 1: 2 to 2: 1.

In preparing a multicolor heat-sensitive recording material using a urea urethane compound developer, one kind of the urea urethane compound may be used, or two or more kinds thereof may be used in combination, if necessary. In the heat-sensitive recording, a compound having a melting point is more preferable, and the melting point of the urea urethane compound developer of the present invention is preferably in the range of 40 ° C. to 500 ° C., particularly preferably in the range of 60 ° C. to 300 ° C. . By using the urea urethane compound developer according to the present invention, it is possible to obtain a multicolor heat-sensitive recording material having a sufficient coloring density and free from the disadvantage that the recorded image formed is discolored and discolored by oils, fats, chemicals, fingerprints and the like. In the multicolor heat-sensitive recording material of the present invention, at least two heat-sensitive recording layers are provided on one surface of the support, and at least one of the heat-sensitive recording layers contains a urea urethane compound developer.

The support used in the present invention was prepared by heating and kneading a polyolefin resin and a white inorganic pigment, extruding from a die, and stretching in the machine direction. ~ 2
Synthetic paper manufactured by laminating layers and stretching in the transverse direction to make it translucent or opaque, and thermoplastic resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, polyvinyl chloride, polystyrene, polyester, etc. Is heated and kneaded, extruded from a die, biaxially stretched, and a film obtained by mixing these resins with a white inorganic pigment, biaxially stretched opaque film, woodfree paper,
Those manufactured from pulp fibers such as medium paper, roll paper, recycled paper, and coated paper can be used. In order to improve the uniformity of the image, the support made of pulp fibers is preferably provided with a coating layer in advance and then coated with a heat-sensitive layer.

The thermosensitive coloring layer of the present invention contains, as main components, a coloring agent and an adhesive which cause a coloring reaction upon contact of a substance by heating. As the color former, specifically, a colorless or pale-colored dye precursor and the urea urethane developer described above, which develops the color of the dye precursor by heating, or a coupler that reacts with a diazo compound and the diazo compound to form a color And the like. Further, a crosslinking agent, a pigment, and a heat-fusible substance can be added as needed. The coating amount of the heat-sensitive coloring layer is generally 3 to 15 in terms of coloring sensitivity and coloring density.
g / m ² is preferred. As a coating method, a method conventionally used by those skilled in the art such as an air knife method, a Meyer bar method, a blade method, a reverse roll method, a slit die method, a multi-slide method, and a curtain coating method can be used. Further, the surface of the heat-sensitive coloring layer is subjected to a smoothing treatment using a super calender, a gloss calender, a machine calender, or the like, so that coatability can be improved, and recording density and sensitivity can be improved.

As the color-forming dye, a colorless or light-colored dye precursor capable of forming a color by reacting with a urea urethane compound developer under heating is used. Specific examples of the colorless or light-colored dye precursor used in the present invention include 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-chlorofluorane, and 3-diethylamino-
7,8-benzofluoran, 3,6-dimethoxyfluoran, 3,3-bis (p-dimethylaminophenyl)-
6-dimethylaminophthalide, 3 (1-ethyl-2-methylindol-3-yl) -3 (2-methyl-4-diethylaminophenol) -4-azaphthalide, 3-
(N-ethyl-Nn-hexylamino) -7-anilinofluoran, 3-diethylamino-7-dibenzylaminofluoran, 2,2-bis (4- (6 ′-(N-cyclohexyl-N -Methylamino) -3'-methylspiro (phthalide-3,9'-xanthen) -2'-ylamido) phenyl) propane, 3-diethylamino-6methyl-7-anilinofluoran, 3-dibutylamino-
6-methyl-7-anilinofluoran, 3-piperidino-
6-methyl-7-anilinofluoran,

3- (N-methyl-N-cyclohexyl)
Amino-6-methyl-7-anilinofluoran, 3-dimethylamino-7-chloroanilinofluoran, 3-
(N-ethyl-N- (p-methylphenyl) amino)-
6-methyl-7-anilinofluoran, 3-diethylamino-7- (metatrifluoromethyl) anilinofluoran, 3- (N-ethyl-N-tetrahydrofurfuryl) amino-6-methyl-7-ani Linofluoran, 3
-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilinofluoran, 3- (N, N-dibutyl)
Amino-6-methyl-7-anilinofluoran and the like.

These colorless or light-colored dye precursors can be used in combination of two or more as necessary.
The urea urethane compound developer is preferably used in an amount of 5 to 1000 parts by weight, more preferably 20 to 500 parts by weight, based on 100 parts by weight of the colorless or pale color dye precursor. When the amount of the urea urethane compound developer is 5 parts by weight or more, it is sufficient to form a color of the dye precursor, and the coloring density is high. Further, the urea urethane compound developer is 100
When the amount is 0 parts by weight or less, an excessive amount of the urea urethane compound developer hardly remains, which is economically advantageous and preferable.
In the heat-sensitive recording layer containing a colorless or light-colored dye precursor of the heat-sensitive multicolor heat-sensitive recording material of the present invention, a multicolor heat-sensitive recording material having improved sensitivities by adding an acidic color developer as needed to provide a clear color development. can get.

As the acidic developer, generally used electron-accepting substances are used. In particular, phenol derivatives, aromatic carboxylic acid derivatives or metal compounds thereof, salicylic acid derivatives or metal salts thereof, N, N-diarylthiophenes are used. Urea derivatives and sulfonylurea derivatives are preferred. Particularly preferred are phenol derivatives, specifically,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (hydroxyphenyl) butane, 2,2-
Bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, 4-hydroxy Phenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-
Isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-
4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, methyl 4-hydroxybenzoate, 4-hydroxybenzoate Benzyl acid, 4-hydroxybenzoic acid (4'-chlorobenzyl),

Ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), 3- Examples thereof include dimethyl hydroxyphthalate, stearyl gallate, and lauryl gallate. Examples of the salicylic acid derivatives include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octoctanoyloxysalicylic acid, -Octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid and the like. Examples of the sulfonylurea derivative include 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane,
4,4-bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl sulfide, 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl ether, N- Compounds containing one or more arylsulfonylaminoureido groups, such as (p-toluenesulfonyl) -N'-phenylurea, may be mentioned.

Further, in order to improve the background fogging and the thermal responsiveness, N-stearyl-N '-(2-hydroxyphenyl) urea, N-stearyl-N'-(3-hydroxyphenyl) urea, N-stearyl-N '-(3-hydroxyphenyl) urea Stearyl-N ′-(4-hydroxyphenyl) urea, p-stearoylaminophenol, o-stearoylaminophenol, p-lauroylaminophenol, p-butyrylaminophenol, m-acetylaminophenol, o-acetylaminophenol, p-acetylaminophenol, o-butylaminocarbonylphenol, o-stearylaminocarbonylphenol, p-stearylaminocarbonylphenol, 1,1,3-tris (3-tert-
Butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-tert-butyl-4-
(Hydroxy-6-ethylphenyl) butane, 1,1,3
-Tris (3,5-di-tert-butyl-4-hydroxyphenyl) butane,

1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) propane,
1,2,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-phenyl-4-hydroxyphenyl) butane, 1,1,3- Tris (3-cyclohexyl-4-hydroxy-5-methylphenyl) butane, 1,1,3-
Tris (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tetra (3-phenyl-4-hydroxyphenyl) propane, 1,1,
3,3-tetra (3-cyclohexyl-4-hydroxy-6-methylphenyl) propane, 1,1-bis (3-
tert-butyl-4-hydroxy-6-methylphenyl) butane, 1,1-bis (3-cyclohexyl-4-)
It is also possible to add a phenol compound such as (hydroxy-6-methylphenyl) butane.

The above-mentioned acidic developer is preferably used in an amount of 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, based on 100 parts by weight of the colorless or pale color dye precursor. When the amount of the acidic developer is 5 parts by weight or more, the coloration of the dye precursor is good and the color density is high. Also, an acidic developer 50
When the amount is 0 part by weight or less, the acidic developer hardly remains, which is economically advantageous and preferable. On the other hand, the compound used in the heat-sensitive recording layer containing a diazo compound and a coupler that reacts with the diazo compound to form a color, as a main component, is a known photodegradable diazo compound, and reacts with the diazo compound to form a dye. It is a coupler which can be used, and if necessary, a basic substance or the like can be added to promote the reaction between the diazo compound and the coupler. It is preferable to use 10 to 1000 parts by weight of the coupler and 10 to 2000 parts by weight of the basic substance in a mixture with respect to 100 parts by weight of the diazo compound.

The photodegradable diazo compound in the present invention includes a diazonium salt, a diazosulfonate compound,
A diazo photosensitive material that reacts with a coupling component to form a dye when heated, such as a diazoamino compound or a quinonediazide compound. The diazonium salt formula _{^{Ar - N 2 + · X -}} ( wherein Ar represents an aromatic moiety, N ₂ ⁺ diazonium group, X ^- represents a counter anion) is a compound represented by. These have various maximum absorption wavelengths depending on the position and type of the substituent in the Ar portion.

Specific examples of the diazonium compound used in the present invention include 4-dimethylaminobenzenediazonium, 4-diethylaminobenzenediazonium,
Dipropylaminobenzenediazonium, 4-methylbenzylaminobenzenediazonium, 4-dibenzylaminobenzenediazonium, 4-ethylhydroxyethylaminobenzenediazonium, 4-diethylamino-
2-methoxybenzenediazonium, 4-dimethyl-3
-Methylbenzenediazonium, 4-benzoylamino-2,5-diethoxybenzenediazonium, 4-morpholinobenzenediazonium, 4-morpholino-2,5
-Diethoxybenzenediazonium, 4-morpholino-
2,5-dibutoxybenzenediazonium, 4-anilinobenzenediazonium, 4-toluylmercapto-
2,5-diethoxybenzenediazonium, 4- (N,
N-dioctylcarbamoyl) benzenediazonium,
2-octadecyloxybenzenediazonium,

4- (4-tert-octylphenoxy) benzenediazonium, 4- (2,4-di-ter
(t-amylphenoxy) benzenediazonium, 2-
(4-tert-octylphenoxy) benzenediazonium, 5-chloro-2- (4-tert-octylphenoxy) benzenediazonium, 2,5-bis-octadecyloxybenzenediazonium, 2,4-bis-
Octadecyloxybenzenediazonium, 4- (N-
Octylteuroylamino) benzenediazonium and the like. Specific examples of the counter anion of the diazonium salt used in the present invention include Cl.1 / 2 ZnCl
₂ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , B (Ph) ₄ ⁻ , C _n F
_{2n + 1} COO ⁻ (n represents 3 to 9), C _m F _{2m + 1} SO ₃
^- (m represents an _{2~8), (C k F 2k} + 1 SO 2) 2 CH
^- (K represents 1 to 18).

The diazosulfonate compound used in the present invention is a compound represented by the general formula Ar—N ₂ —SO ₃ Na (wherein Ar represents an aromatic moiety). Specific examples of the diazosulfonate compound used in the present invention include 2-methoxy, 2-phenoxy, 2-methoxy-4-phenoxy, 2,4-dimethoxy, 2-methyl-4-methoxy, 2,4-dimethyl, 2,4,6-
Trimethyl, 2,4,6-trimethoxy, 2,4-dimethoxy-5-chloro, 2-methoxy-5-nitro, 2-
Methoxy-5-acetamide, 2-methoxy-5-N,
N-diethylsulfonamide, 2-methoxy-5-N-
Sodium benzenediazosulfonate having a substituent such as phenylcarbamyl, 3-methyl, 4-methyl, 4-methoxy, 4-ethoxy, 4-phenyl, 4-phenoxy, 4-acetamide,

Alternatively, 4- (N-ethyl-N-benzylamino), 4- (N, N-dimethylamino),
(N, N-diethylamino), 4- (N, N-diethylamino) -3-chloro, 4- (N-ethylamino) -3
-Methyl, 4- (N, N-diethylamino) -2-methyl, 4- (N-ethyl-N-β-hydroxyethylamino), 4-pyrrolidino-3-chloro, 4-pyrrolidino-
3,5-dichloro, 4-morpholino, 4-morpholino-
3-chloro, 4-morpholino-2-methoxy, 4-morpholino-2,5-diethoxy, 4-morpholino-2,5
-Dibutoxy, 4- (4'-tolylmercapto) -2,
5-dibutoxy, 4- (4'-tolylmercapto)-
Sodium benzenediazosulfonate having a substituent such as 2,5-diethoxy, 4- (4′-methoxybenzoylamino) -2,5-dibutoxy, and 4-diphenylamino. When using these diazosulfonate compounds, it is desirable to activate the diazosulfonate by irradiating the diazosulfonate with light before printing. Examples of the diazoamino compound that can be used in the present invention include a diazo group having a dicyandiamide, sarcosine, methyltaurine, N-ethylanthranic acid-5-sulfonic acid,
It is a compound coupled with monoethanolamine, diethanolamine, guanidine, or the like.

The quinonediazide used in the present invention is
Structurally, it is also considered to be an inner salt type diazonium salt, for example, o-quinonediazide, o-naphthoquinonediazide, etc., and 1,2-quinonediazide-4-sulfonic acid,
1,2-naphthoquinonediazide-5-sulfonic acid,
It contains salts, esters or amide compounds such as 2-naphthoquinonediazide-4-sulfonic acid. Specific examples of the quinonediazide used in the present invention include:
Sodium 2-quinonediazide-4-sulfonate, 1,
Sodium 2-naphthoquinonediazide-5-sulfonate, sodium 1,2-naphthoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-5-sulfonate-p-cumylphenyl, 1,2-naphthoquinonediazide-4-sulfone Acid-p-cumylphenyl, 1,2-
Methyl naphthoquinonediazide-5-sulfonate, 1,2
-Ethyl naphthoquinonediazide-5-sulfonate, 1,
Examples thereof include 2-naphthoquinonediazide-5-sulfonic acid-dimethylamide and esters of 1,2-naphthoquinonediazide-5-sulfonic acid and a novolak resin. Furthermore, two or more of these photodegradable diazo compounds can be used in combination.

The coupler used in the present invention reacts with a diazo compound to form a dye. For example, a typical coupler that produces a yellow dye is one in which a methylene group is activated by an adjacent carbonyl group, and has the general formula RCOCH ₂ CO-R ′ (where R is an alkyl group or an allyl group. , R ′ represents an aromatic amine). Further, as a magenta coupler, 1)
Cyanoacetyl derivatives of cyclic compounds, or 2) heterocyclic compounds having active methylene or other coupling moieties in the heterocycle, such as pyrazolone compounds and indazolone compounds. Examples of the cyan coupler include phenols and naphthols.

Specific examples of the coupler used in the present invention include 4- (p-toluenesulfonylamino) -ω-
Benzoylacetanilide, α-benzoyl-o-methoxyacetanilide, 2-cyanoacetyl-coumarone,
1- (2,4,6-trichlorophenyl) -3-p-nitroamino-2-pyrazolone-5-one, resorcinol,
Phloroglucin, 2,3-dihydroxynaphthalene,
Examples thereof include 2,6-dibromo-1,5-dihydroxy-naphthalene and N- (o-acetamidophenethyl) -1-hydroxy-2-naphthamide. Further, two or more of these couplers can be used in combination.

The coupling reaction between the diazo compound and the coupler proceeds more smoothly in a basic atmosphere. Therefore, it is desirable to add a basic substance to the thermosensitive coloring layer. As the basic substance, a poorly water-soluble or water-insoluble basic substance or a substance that generates an alkali by heating is used. For example, inorganic and organic ammonium salts,
Organic amines, amides, ureas and thioureas and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formamidines, And nitrogen-containing compounds such as pyridines.

Specific examples thereof include tricyclohexylamine, tribenzylamine, octadodecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, and 4-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-undecylimidazoline, 2,4,5-trifuryl-2-
Imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-dicyclohexylguanidine, 1,2,3-tri Cyclohexylguanidine, guanidine trichloroacetate, N,
N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-aminobenzothiazole, 2-benzoylhydrazinobenzothiazole and the like. Two or more of these basic substances may be used in combination.

In the present invention, the thermosensitive coloring layer formed of a combination of a diazo compound and a coupler is added with a weakly acidic substance such as citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. to improve the storage stability. Can be improved.
The color-forming component used in the present invention is used in the form of a solid dispersion obtained by dispersing in an aqueous solution of a water-soluble polymer and coating and drying, as is generally used in thermosensitive recording materials. Of course you can. Also, JP-A-59-19088
No. 6, JP-A-60-49991, JP-A-60-4991
As described in JP-A-169281, the color former is microencapsulated to prevent contact between the color former and the developer at room temperature by the isolation effect of the capsule wall, thereby improving the raw preservability. it can. The microcapsules have a property that the color former and the developer can come into contact only while being heated to a certain temperature or higher. The temperature at which the contact between the color former and the developer starts can be controlled by appropriately selecting the capsule wall material, the capsule core substance, the additives, and the like. As the wall material of the microcapsules in the present invention, conventionally known microcapsule walls such as polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, gelatin, polyvinylpyrrolidone, and polyvinyl alcohol Materials. Further, two or more of these polymers can be used in combination.

In the present invention, as the adhesive contained in the thermosensitive coloring layer, either a water-soluble resin or a water-dispersible resin can be used. For example, polyvinyl alcohol, starch, modified starch, gum arabic, gelatin, casein, chitosan, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyacrylate, polyacrylamide, polyester resin, styrene-acrylate Water-soluble resins such as polymerized resin, styrene-maleic anhydride copolymer resin, methyl vinyl ether-maleic anhydride copolymer resin, isopropylene-maleic anhydride copolymer resin, and vinyl acetate emulsion, acrylate ester emulsion, Methacrylate copolymer emulsion, polyurethane emulsion, polyvinyl chloride emulsion, S
A water-dispersible resin having an excellent film-forming property having a minimum film-forming temperature of 20 ° C. or less, which is an emulsion such as BR latex or MBR latex, can be used alone or in combination.

However, it is necessary that the mixture does not develop color, aggregate, or become highly viscous when mixed with the dispersion of the color-forming dye and the developer. That the heat-sensitive recording layer film is tough,
It is necessary that there is no desensitizing effect. The amount of the adhesive in the heat-sensitive coloring layer is preferably 5 to 20% with respect to the solid content of the heat-sensitive coloring layer.
If it exceeds 0%, there is a problem that the sensitivity is reduced. In order to improve the water resistance of the thermosensitive coloring layer, a crosslinking agent for curing the resin can be used. For example, aldehyde compounds such as formaldehyde and glyoxal, polyamine compounds, epoxy compounds, polyamide resins, melamine resins, diglycidyl compounds such as glyceryl glycidyl ether, dimethylol urea compounds, aziridine compounds, block isocyanate compounds, and An inorganic compound such as ammonium sulfate, ferric chloride, and magnesium chloride, sodium tetraborate, potassium tetraborate, or boric acid, boric acid triester, or a boron-based polymer is used in an amount of 1 to 10% based on the solid content of the thermosensitive coloring layer. Can be used in a range.

As the pigment, a fine particle pigment having a high whiteness and an average particle diameter of 5 μm or less can be used to improve the whiteness of the thermosensitive coloring layer and the uniformity of the image. For example, calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcined clay, silica, diatomaceous earth, synthetic aluminum silicate, zinc oxide, titanium oxide, aluminum hydroxide, barium sulfate, surface-treated calcium carbonate and silica Such as inorganic pigments, and urea-formalin resin,
Organic pigments such as styrene-methacrylic acid copolymer resin and polystyrene resin can be used. The amount of the pigment is 40% based on the solid content of the thermosensitive coloring layer so as not to lower the coloring density.
% Is desirable.

As the heat-fusible substance, 60 ° C. to 180 ° C.
The melting point is preferably 80 ° C. to 140 ° C.
Are preferred. For example, benzyl p-benzyloxybenzoate, stearamide, palmitamide, N-methylol stearamide, β
-Naphthyl benzyl ether, N-stearyl urea,
N, N′-distearyl urea, β-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid phenyl ester, β-naphthol (p-methylbenzyl) ether, 1,4-dimethoxynaphthalene, 1-methoxy-
4-benzyloxynaphthalene, N-stearoylurea, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, 1-phenoxy-2- (4-chlorophenoxy) ethane, 1,4-butanediolphenyl Ether, dimethyl terephthalate, metaterphenyl, dibenzyl oxalate, oxalic acid (P-chlorobenzyl) ester and the like. Further, 4,4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4,4'-difluorobenzophenone, diphenylsulfone, 4,4'-dichlorodiphenylsulfone,
4,4′-difluorodiphenyl sulfone, 4,4 ′ dichlorodiphenyl disulfide, diphenylamine,
2-methyl-4-methoxydiphenylamine, N, N '
-Diphenyl-p-phenylenediamine, 1- (N-phenylamino) naphthalene, benzyl, 1,3-diphenyl-1,3-propanedione, or the like may be used.

Of these, diphenyl sulfone is preferably used. The heat-fusible substance may be used alone or as a mixture of two or more kinds. In order to obtain a sufficient thermal response, the colorless or light-colored dye precursor 10 is used.
It is preferably used in an amount of 10 to 300 parts by weight, more preferably 20 to 250 parts by weight, based on 0 parts by weight. In addition, for the purpose of preventing head abrasion and sticking, zinc stearate, higher fatty acid metal salts such as calcium stearate, paraffin, paraffin oxide,
Waxes such as polyethylene, polyethylene oxide, stearamide, caster wax, etc., dispersants such as dioctyl sodium sulfosuccinate, UV absorbers such as benzophenone and benzotriazole, surfactants, fluorescent dyes, etc. are also required. Can be contained according to

Further, for example, 1,1,3-tris (3′-
Cyclohexyl-4′hydroxyphenyl) butane,
1,1,3-tris (2-methyl-4-hydroxy-5-
tert-butylphenyl) butane, 4,4′-thiobis (3-methyl-6-tert-butylphenol),
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, p-octylphenyl salicylate, 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, ethyl-2-cyano-3,3'-
A heat sensitive recording layer may contain a hindered phenol compound such as diphenyl acrylate, tetra (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboate or an ultraviolet absorber. . Among these substances, phenolic compounds, alcoholic compounds, amide compounds, sulfonamide compounds, etc., act on the wall material of the microcapsule containing the color former, to thereby lower the contact start temperature of the color former-color developer. Includes those that have a lowering effect and can improve color sensitivity.

In the multicolor heat-sensitive recording material of the present invention, it is effective to provide an intermediate layer between the heat-sensitive recording layers in order to improve thermal separability. This intermediate layer contains, as a main component, the same water-soluble resin and water-dispersible resin used as the adhesive in the above-mentioned heat-sensitive recording layer, and may further contain a pigment, a crosslinking agent, and the like. The coating amount of the intermediate layer is 1.0 to
5.0 g / m ² is preferred. If the coating amount is less than 1.0 g / m ^2, there is no sufficient effect of preventing diffusion between the recording layers, which causes deterioration in image quality. If the coating amount exceeds 5.0 g / m ² , there is a disadvantage that the sensitivity is reduced. As one preferred form of the multicolor heat-sensitive recording material of the present invention, two heat-sensitive recording layers each having a different coloration temperature and a different color tone are formed by laminating on one surface of a support. Examples of the multicolor heat-sensitive recording material include an upper heat-sensitive recording layer containing a developer and a reversible developer, and a lower heat-sensitive recording layer containing a urea urethane compound developer.

Among these, the color-reducing agent used in the upper heat-sensitive recording layer expresses a color-developing function at the time of low-temperature heating and a color-erasing function at the time of high-temperature heating. It is an amphoteric compound having a group and a basic group having a role of a decoloring function. The acidic group is typically a phenolic hydroxyl group or a carboxyl group, and the basic group is typically an amino group. The basic group may be present as a functional group, but is preferably present as a part of a salt compound such as a complex of a phenol carboxylic acid compound and an amine compound. Specific examples of such a color-reducing agent include the following, for example. Examples of the phenol carboxylic acid compound constituting the color-reducing agent include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and 2,3. -Dihydroxybenzoic acid,
2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, gallic acid,
Bis (4-hydroxyphenyl) acetic acid, 3,3-bis (4-hydroxyphenyl) propionic acid and the like can be mentioned.

Examples of the amine compound which forms a salt or a complex salt with the phenol carboxylic acid compound include octylamine, nonylamine, decylamine, laurylamine, tetradecylamine, heptadecylamine, stearylamine, behenylamine, 3-methoxypropylamine,
Hexamethylene diamine and the like. The reversible developer is, for example, a phenolic compound or a phosphonic acid compound having an aliphatic hydrocarbon group having 8 or more carbon atoms. Specific examples of such a reversible color developer include, for example, those shown below, but may be any as long as they exhibit a color developing function at the time of low-temperature heating and have a color erasing function at the time of high-temperature heating. However, the present invention is not limited to this.

4- (octadecylthio) phenol, 4
-(Docosylthio) phenol, 4- (octadecyloxy) phenol, 4- (docosyloxy) phenol, N-octadecyl-4-hydroxybenzamide,
4'-hydroxydocosaneanilide, N- (4-hydroxyphenyl) -N'-n-octadecylurea, docosylphosphonic acid and the like. When recording is performed by a thermal printer or the like using the multicolor heat-sensitive recording material of the present invention, only the low-temperature coloring layer develops color in low-temperature heating printing, and the low-temperature coloring layer in the printed portion is decolorized in high-temperature heating printing to remove the high-temperature coloring layer. Only color develops. Hereinafter, the present invention will be described in more detail with reference to Examples.
It is not limited to these.

[0148]

[Embodiment 1] Yellow, magenta and cyan three
A production example of a full-color thermosensitive recording material capable of thermally recording each color independently will be described. -Preparation of paint for cyan-colored thermosensitive recording layer Liquid A (thermochromic dye dispersion) 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 20 parts by weight and 10% polyvinyl alcohol aqueous solution 20 parts by weight Parts, 10 parts by weight of water,
It was dispersed and pulverized with a sand grinder (manufactured by Imex Co., Ltd.) to prepare an average particle size of 0.7 μm. Liquid B (Developer dispersion)

2,4-toluene diisocyanate 31.
5 g was stirred at 60 ° C., and 21.5 g of 4,4′-diaminodiphenylsulfone was diluted with 120 ml of methyl ethyl ketone and added dropwise over 4 hours.
For 2 hours. After the reaction, after cooling to room temperature, toluene was added, and the precipitated white solid was collected by filtration,
After washing with toluene and vacuum drying overnight, 47 g of a white crystalline compound was obtained. Next, 30 g of this compound was taken, 9.5 g of phenol and 95 ml of methyl ethyl ketone were added, 30 mg of triethylamine was further added, and the mixture was reacted at 25 ° C. for 4 hours. After the reaction, toluene was added, and the precipitated crystals were collected by filtration, washed with toluene, and dried under vacuum overnight to obtain 38.5 g of a ureaurethane compound as white crystals.

Next, 30 g of this compound was taken and pulverized and dispersed with a sand grinder for 3 hours together with 120 g of a 2.5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. The liquid temperature of the dispersion immediately after the dispersion was 25 ° C. The dispersed particle size of this compound was 0.6 μm. Solution A 30 parts by weight, Solution B 120 parts by weight, 60% calcium carbonate slurry 52 parts by weight, 10% polyvinyl alcohol aqueous solution 40 parts by weight, SBR latex (solid content 50%, Asahi Kasei, trademark: L-1537) 28 parts by weight, Stearic acid amide (solid content: 26.5%, manufactured by Chukyo Yushi, trademark: cellosol A
-877) 11 parts by weight of water and 82 parts by weight of water were mixed to obtain a cyan coloring thermosensitive coloring layer coating.

Preparation of paint for magenta coloring heat-sensitive recording layer Liquid A (thermosensitive coloring dye dispersion) 4-N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazinobenzenediazonium hexafluoro 20 parts by weight of phosphate, 20 parts by weight of a 10% aqueous polyvinyl alcohol solution, and 10 parts by weight of water were mixed, dispersed and pulverized with a sand glider to prepare an average particle size of 0.7 μm. Liquid B (coupler dispersion liquid) 1- (2'-octylphenyl) -3-methyl-5-pyrazolone 50 parts by weight, 1,2,3-triphenylguanidine 50 parts by weight, 10% polyvinyl alcohol aqueous solution 50 parts by weight , Water and 25 parts by weight of water, and dispersed and pulverized with a sand glider to prepare an average particle size of 1.0 μm. Solution A 30 parts by weight, Solution B 90 parts by weight, 60% calcium carbonate slurry 52 parts by weight, 10% polyvinyl alcohol aqueous solution 40 parts by weight, SBR latex (solid content 5
0%, 28 parts by weight of Asahi Kasei, trademark: L-1537), 11 parts by weight of stearic acid amide (solid content: 26.5%, manufactured by Chukyo Yushi Co., Ltd., trademark: Cellol A-877), and 82 parts by weight of water were mixed, and magenta was mixed. This was a coloring heat-sensitive coloring layer paint.

Preparation of coating material for yellow-colored thermosensitive recording layer Liquid A (thermosensitive dye-dispersing solution) 2,5-dibutoxy-4-tolylthiobenzenebenzenediazonium hexafluorophosphate 20 parts by weight, 10% polyvinyl alcohol aqueous solution 20 Parts by weight,
10 parts by weight of water were mixed, dispersed and pulverized with a sand glider to prepare an average particle size of 0.7 μm. Liquid B (coupler dispersion) 50 parts by weight of 2-chloro-5- (3- (2,4-di-tert-pentyl) phenoxypropylamino) acetoacetanilide, 1,2,3-triphenylguanidine 5
0 parts by weight, 50 parts by weight of a 10% aqueous polyvinyl alcohol solution and 25 parts by weight of water were mixed, dispersed and pulverized with a sand glider to prepare an average particle size of 1.0 μm. Solution A 30 parts by weight, Solution B 90 parts by weight, 60% calcium carbonate slurry 52 parts by weight, 10% polyvinyl alcohol aqueous solution 40 parts by weight, SBR latex (solid content 50
%, Asahi Kasei, trademark: L-1537) 28 parts by weight, stearamide (solid content: 26.5%, manufactured by Chukyo Yushi, trademark:
11 parts by weight of cellosol A-877) and 82 parts by weight of water were mixed to prepare a yellow coloring thermosensitive coloring layer coating.

Preparation of paint for intermediate layer paint (solid content 15%) 42 parts by weight of 60% kaolinite clay (average particle size 0.6 μm) dispersion, carboxylic acid-modified polyvinyl alcohol aqueous solution (solid content 10%, Nihon Gosei) 200 parts by weight, manufactured by Kagaku Co., Ltd., trademark: Gohsenal T-330, acrylic emulsion (solid content: 40%, manufactured by Nippon Shokubai Co., Ltd., trademark: SC
-2250) 100 parts by weight, dimethylol urea solution (solid content 30%, manufactured by Showa Denko KK, trademark: J-001) 3
3 parts by weight, 40% zinc stearate dispersion (average particle size 0.9 μm, manufactured by Chukyo Yushi Co., Ltd., trademark: Himicron F
-930) 13 parts by weight, heavy calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd., trade name: NS-1000) 70 parts by weight, urethane acrylate emulsion (solid content 40%, Arakawa Chemical Co., trade name: EM90) 25 weight parts Parts, polysiloxane (solid content 33%, manufactured by Toray Dow Corning Silicone, trademark:
SM7025), and 5 parts by weight of water and 40 parts by weight of water were mixed to prepare an intermediate layer coating.

Preparation of Multicolor Thermosensitive Recording Material A thermosensitive coloring layer and an intermediate layer coating shown below were coated on one side of a commercially available 75 μm thick polyethylene terephthalate film (trade name: Lumirror E) in the order of cyan from the support side. Multi-layer coating was performed so as to form a coloring heat-sensitive recording layer, an intermediate layer, a magenta coloring heat-sensitive recording layer, an intermediate layer, a yellow coloring heat-sensitive recording layer, and an intermediate layer. The coating amount of the heat-sensitive recording layer and the intermediate layer after drying, respectively 6.5 g / m ^2, and bar coating so as to 2.0 g / m ^2, to obtain a multi-color heat-sensitive recording material, and evaluated Was. The results are summarized in Table 1.

[0155]

Example 2 61 g of 2,4-toluene diisocyanate
To this was added 450 g of toluene as a solvent, and 26 g of aniline dissolved in 150 g of toluene was added dropwise over 6 hours, and the mixture was reacted at 5 ° C. for 7 hours. After the reaction, the precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 70 g of a white crystalline compound. Next, 30 g of this compound was taken and 365 g of toluene was added as a solvent,
To this were added 12.2 g of 2,2-bis (4-hydroxyphenyl) propane and 0.3 mg of triethylamine, and the mixture was stirred at 60 ° C. for 4 hours, then at 70 ° C. for 3 hours, and further heated to 80 ° C. The reaction was performed for 3 hours. After the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with toluene, and dried under vacuum overnight to obtain 42 g of a white crystalline compound. Next, 30 g of this compound was taken.
The mixture was ground and dispersed with a sand grinder for 3 hours together with 120 g of a 5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. Subsequently, a thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the above compound was used instead of the dispersion of the urea urethane compound obtained in Example 1. The results are summarized in Table 1.

[0156]

Example 3 2,4-Toluene diisocyanate 300
300 g of toluene as a solvent was added to the g, 32.4 g of phenol was added thereto, and the mixture was reacted at 100 ° C. for 1 hour 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added. The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 69 g of a white crystalline compound. Next, 50 g of this compound was taken and toluene 1 was used as a solvent.
Then, 35 g of aniline was added thereto, and the mixture was added at 25 ° C for 3 hours.
After reacting for hours, the precipitated crystals were collected by filtration, washed with hexane, and dried under vacuum overnight to obtain 55 g of a white crystalline compound. Next, 30 g of this compound was taken and pulverized and dispersed in a sand grinder for 3 hours together with 120 g of a 2.5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. Subsequently, a thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the above compound was used instead of the dispersion of the urea urethane compound obtained in Example 1. The results are summarized in Table 1.

[0157]

Example 4 51 g of 2,4-toluene diisocyanate
120 g of methyl ethyl ketone as a solvent was added to the mixture, and 11.4 g of methanol was added dropwise thereto.
The reaction was performed at 5 ° C. for 5 hours. Next, 29.7 g of 4,4′-diaminodiphenyl sulfone was added, and the mixture was stirred at 60 ° C.
For 4 hours. After the reaction, the reaction solution was cooled to room temperature, poured into 2400 g of acetonitrile, and the precipitated crystals were collected by filtration, washed with hexane, and vacuum-dried overnight to obtain 45 g of a white crystalline compound. Next, this compound 3
0 g was taken and pulverized and dispersed in a sand grinder for 3 hours together with 120 g of a 2.5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. Subsequently, a thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the above compound was used instead of the dispersion of the urea urethane compound obtained in Example 1. The results are summarized in Table 1.

[0158]

Example 5 An example of the production of a two-color heat-sensitive recording material is described below. (A) Dye precursor for high-temperature coloring layer: 3- (4'-dibutylamino-2'-hydroxyphenyl) -3- (5'-anilino-4'-methyl-2'-methoxyphenyl) phthalide (B) Dye precursor for low-temperature coloring layer: 3-diethylamino-
7-Chlorofluorane (C) Developer: urea urethane compound synthesized in Example 1 (D) Sensitizer: diphenyl sulfone 40 g of each of the above organic compounds (A) to (D) is a 10% solution of polyvinyl alcohol. (Polymerization degree 500, saponification degree 9
0%) and 20 g of water, and each of these compositions was separately prepared using a vertical sand mill (manufactured by Imex Corporation,
(Sand grinder) so as to have a particle size of 1 μm, and liquids (A) to (D) corresponding to compounds A to D were prepared from the respective dispersions. In addition, light calcium carbonate (Brilliant 15, average particle size 0.15 μm manufactured by Shiraishi Kogyo) 4
0 g and 60 g of a 0.7% sodium hexametaphosphate solution were mixed, and this composition (E) was dispersed with a Cowles disperser.
Separately, a 21% zinc stearate dispersion was prepared as a lubricant dispersion (F) solution, and a 10% polyvinyl alcohol (NM11, manufactured by Nippon Synthetic Chemical Industry) was prepared as an adhesive (G) solution.

Preparation of High-Temperature Coloring and Sensitive Coating Liquid (I) The weight ratio after drying using the liquids (A), (C), (E) and (G) is (A) :( C): (E): (G) = 2
0: 40: 25: 15 was added to prepare a coating solution for a high-temperature coloring heat-sensitive layer. -Formation of high-temperature coloring heat-sensitive layer The heat-sensitive layer coating solution (I) was weighed 6 using a Mayer bar.
8 g / m ² (dry) on 0 g / m 2 high quality paper (neutral paper)
To form a high-temperature coloring heat-sensitive layer. Preparation of low-temperature coloring heat-sensitive layer coating liquid (II) Further, the above (B), (C), (D), (E), (F) and (G) liquids are dried at a weight ratio of: (B): (C):
(D): (E): (F): (G) = 10: 20: 20:
A low-temperature coloring heat-sensitive layer coating liquid was prepared by blending at a ratio of 20:10:10. Preparation of two-color heat-sensitive recording material A low-temperature color-forming layer coating liquid (II) was applied on the high-temperature color-forming heat-sensitive layer so that the coating amount was 5 g / m ² (dry). Thereafter, a smoothing process using a super calender is performed to increase the Beck smoothness (JIS-P8119) of the heat-sensitive recording surface to 150.
Adjusted to seconds, a two-color heat-sensitive recording material was obtained.

[0160]

Comparative Example 1 A multicolor heat-sensitive recording material was prepared in the same manner as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound synthesized in Example 1. , Was evaluated. Table 1 summarizes the results
Shown in

Comparative Example 2 A two-color heat-sensitive recording material was prepared in the same manner as in Example 5 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound used in Example 5. , Was evaluated. Table 1 summarizes the results
Shown in

Evaluation of multicolor heat-sensitive recording material The multicolor heat-sensitive recording materials obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were commercially available using a heat-sensitive printer (trade name: NC-1 manufactured by Fuji Photo Film Co., Ltd.). The image quality and the image storability when recording was performed were evaluated by the following methods. <Image Quality> Regarding the recording materials, five images were visually evaluated for sharpness, contrast, image density unevenness, and the like, and evaluated on a five-point scale. (Good: Good, Good-Good: Somewhat good, Good: Normal, Good-Good: Somewhat bad, Good: Bad) <Image preservation> The recording material is sandwiched between vinyl chloride wraps or vinyl chloride files, and 300 g / cm from the top. ^After applying a load of ² and leaving at 40 ° C. for 24 hours, the densities of the printed portion and the unprinted portion (background) were visually evaluated after the standing, and those having little decoloration of the printed density were regarded as having good image storability. The results are as shown in Table 1. In Examples 1 to 5, the image quality was good and excellent image storability was exhibited.
2 was inferior to Examples 1-5.

[0162]

[Table 1]

[0163]

According to the multicolor heat-sensitive recording material of the present invention, a recorded image having good image quality and high image storability can be obtained, and is extremely useful in practical use.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuo Kabashima 1-3-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term in Asahi Kasei Kogyo Co., Ltd. 2H026 AA07 AA14 BB24 BB41 DD03 DD46 DD53 FF07 FF13

Claims (5)

[Claims] 1. A multicolor heat-sensitive recording material comprising a urea urethane compound color developer. 2. A multicolor heat-sensitive recording material having at least two heat-sensitive recording layers on one surface of a support, wherein at least one of the heat-sensitive recording layers contains a ureaurethane compound developer. Multicolor heat-sensitive recording material. 3. The multicolor heat-sensitive recording material according to claim 2, wherein an intermediate layer is provided between the heat-sensitive recording layers. 4. A layer of two heat-sensitive recording layers, each having a different coloring temperature and a different color tone, are formed on one surface of the support, and the uppermost heat-sensitive recording layer is provided with a developer or a reversible colorant. A multicolor heat-sensitive recording material comprising a color developer and a urea urethane compound color developer in a lower heat-sensitive recording layer. 5. The thermosensitive recording layer according to claim 4, wherein the two heat-sensitive recording layers are a low-temperature coloring layer in which the upper layer develops color at low temperature and decolorizes at high temperature, and the lower layer is a high-temperature coloring layer which develops color at high temperature. The multicolor heat-sensitive recording material as described above.