JP2002144746A - New coupler and recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material which shows outstanding color development sensitivity, resistance to plasticizer and whiteness. SOLUTION: This coupler contains a colorless or pale-colored leuco dye and an urea-urethane compound developer. In addition, a specific dispersant is used as a leuco dye dispersant and thus the performance of the coupler is upgraded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material using a novel urea urethane compound. The present invention relates to a urea urethane compound-based recording material having high whiteness.

[0002]

2. Description of the Related Art Conventionally, many chemical color forming systems using recording energy such as heat and pressure are known. Among them, a color forming system composed of a two-component color forming system of a colorless or pale-colored leuco dye and a color developer which forms a color in contact with the leuco dye has been known for a long time and widely applied to recording materials. . For example, there are a pressure-sensitive recording material using pressure energy, a heat-sensitive recording material using heat energy, and a photosensitive recording material using light energy. Until now, a pressure-sensitive recording material using pressure energy has been extremely commonly used as a plain paper.

In general, a pressure-sensitive recording material is prepared by dissolving a leuco dye in a suitable solvent, emulsifying it to several microns, and then performing microencapsulation. The microcapsules are composed of an upper paper coated on a support and a lower paper coated with a developer layer containing a color developer on another support. The microcapsules are destroyed by applying writing pressure or pressing pressure, and the inclusions containing the leuco dye are released, which transfer to the color developer layer and come into contact with the color developer, causing a color-forming reaction. To obtain an image record.

[0004] In recent years, for example, in various information devices such as facsimile machines, printers, recorders, etc., a heat-sensitive recording system in which recording is performed by thermal energy has been widely adopted. These heat-sensitive recording materials have many excellent properties such as high whiteness, good appearance and feel close to plain paper, good recording suitability such as color sensitivity, and the like. It has advantages such as maintenance-free and no noise generation, and has been used in a wide range of fields, such as measurement recorders, facsimile machines, printers, computer terminals, labels, and automatic ticket vending machines such as tickets.

The mainstream of these recording systems uses a recording material in which a coloring layer containing a two-component coloring agent is provided on a support, and heat as recording energy is applied to the recording material by a heat-sensitive head, a hot stamp, a laser beam, or the like. In this method, the heat-sensitive agent components are brought into contact with each other on a recording material to perform color recording. Among them, many use colorless or light-colored electron-donating dye precursors (particularly leuco dyes) and acidic developers such as phenolic compounds as color formers. Recording materials using these dye precursors include, for example, heat-sensitive paper using crystal violet lactone and 4,4′-isopropylidenediphenol (bisphenol A) as heat-sensitive agents (see US Pat. No. 3,539,375) and the like. Be represented.

As the dye precursor and the color developer used for these, an electron donating compound and an electron accepting compound are generally used, respectively. This is because the reactivity of the dye precursor, which is the electron-donating compound, is high, and by contact with the developer, which is the electron-accepting compound, a color-developed image with a high density can be obtained instantaneously, This is because they have excellent characteristics such as obtaining a close appearance and obtaining various color hues such as red, orange, yellow, green, blue, and black. However, on the other hand, the obtained color-developed image has poor chemical resistance, so that it comes in 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 recorded portion is inferior, the recording has a disadvantage that the storage stability of the recording is inferior, such as fading or even disappearing of the recording by exposure to sunlight for a relatively short period of time. At present, certain restrictions are imposed on applications, and improvements are strongly desired.

In recent years, phenolic compounds represented by bisphenol A have been concerned about their use as environmental hormones, and non-phenolic color developers have been demanded. As a recording material capable of obtaining a recorded image with good storability in response to such demands, for example, JP-A-59-1158
No. 87 and U.S. Pat. No. 4,521,793 disclose a recording material comprising a combination of a color former comprising an aromatic isocyanate compound and an imino compound.
In this publication, various recording materials are illustrated by contacting and reacting two types of coloring agents by applying recording energy such as heat, pressure, and light. In addition, it is described that various colors such as red, orange, yellow, brown, and brown can be developed by appropriately selecting a coloring agent. However,
While black color is particularly demanded in recording materials widely used at present, the publication cannot provide such knowledge.

Further, as a heat-sensitive recording material using a non-phenol type developer, JP-A-8-2111 and JP-A-8-111
Japanese Patent No. 2112 discloses a thermosensitive recording medium having a color-forming layer containing a colorless or light-colored leuco dye and a urea compound, but has a low color density and insufficient storage stability.
Further, Japanese Patent Application Laid-Open No. Hei 5-116459 discloses a thermosensitive recording medium having a thermosensitive coloring layer containing a colorless or pale-colored leuco dye and a sulfonylurea compound. However, these recording materials had low whiteness and insufficient storage stability.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material which is excellent in color sensitivity and plasticizer resistance and has high whiteness.

[0010]

Means for Solving the Problems The present inventors have found that surprisingly excellent performance is exhibited by using a urea urethane compound color developer and a color former containing a specific dye precursor. Was completed. That is, the present invention is as follows. A first aspect of the invention is a color former containing a colorless or pale leuco dye and a urea urethane compound developer. A second aspect of the present invention is a urea urethane compound developer comprising a urea urethane compound and a diluent. A third aspect of the present invention is the urea urethane compound developer according to the second aspect, wherein the diluent is a urea compound and / or a urethane compound.

According to a fourth aspect of the present invention, the diluent is a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound. Agent.
A fifth aspect of the invention is the color former according to the first aspect, wherein the urea urethane compound developer is the urea urethane compound developer according to the second to fourth aspects of the invention. In a sixth aspect of the invention, the leuco dye is at least one selected from a triarylmethane leuco dye, a fluoran leuco dye, a fluorene leuco dye, and a diphenylmethane leuco dye. Or the color former according to 5.

A seventh aspect of the present invention is that the leuco dye has the following formula (a):
The coloring agent according to the first or fifth aspect of the invention, which is a compound represented by the following formula:

Embedded image(Where Y₁And Y_TwoAre alkyl groups or
Represents a alkoxyalkyl group, Y_ThreeIs a hydrogen atom,
And an alkoxy group. Also, Y_FourAnd Y _FiveIs water
Elemental atom, halogen atom, alkyl group or alkoxy group
Represents )

An eighth aspect of the present invention is that the leuco dye has the following formula (b):
The coloring agent according to the first or fifth aspect of the invention, which is a compound represented by the following formula:

Embedded image [Where R ₁ and R ₂ are represented by the formula (c) or the formula (d)
Represents any of the groups represented by

[0014]

Embedded image (Wherein, R ₇ to R ₁₁ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, .R _12, R ₁₃ showing a -NR ₁₂ R ₁₃ groups , Carbon number 1
8 alkyl groups. )

[0015]

Embedded image (Here, R ₁₄ and R ₁₅ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.) R _{3 to} R ₆ represent a hydrogen atom, a halogen atom, and an alkyl having 1 to 8 carbon atoms. indicating group, an alkoxy group having 1 to 8 carbon atoms, an -NR ₁₆ R ₁₇ groups. R
₁₆ and R ₁₇ are an alkyl group having 1 to 8 carbon atoms. Ninth aspect of the invention is that the urea urethane compound developer has a melting point of 60
The color forming agent according to any one of the first to fifth to eighth aspects of the invention, wherein the temperature is from 300C to 300C.

In a tenth aspect of the present invention, the urea urethane compound developer is one selected from the following formulas (VI) and (VII). 8. The color former according to any one of 8.

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, and is preferably a nitro group, a hydroxyl group, a carboxyl group, Nitroso group, nitrile group, carbamoyl group, ureido group, isocyanato group, mercapto group, may be substituted by a sulfo group, a sulfamoyl group or a halogen atom, each residue may have a substituent, γ is -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 (f),

[0017]

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

[0018]

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, but is preferably a hydroxyl group, a nitro group, a nitrile group, Carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group,
It may be substituted with an isocyanato group, a mercapto group, a sulfo group or a halogen atom, and each residue may have a substituent, and δ is -SO _2- , -O-,-
(S) _n -,-(CH ₂ ) _n- , -CO-, -CONH
-, - NH -, - CH (COOR 1) -, - C (C
F ₃ ) ₂ — and —CR ₂ R ₃ — represent one selected from the group consisting of, or absent, R ₁ , R ₂ and R ₃
Each independently represents an alkyl group, and n is 1 or 2. )

An eleventh invention is characterized in that the urea urethane compound developer is any one selected from the following structural formulas (g) and (h). 8. The coloring agent according to any one of 8.

Embedded image

[0020]

Embedded image

A twelfth aspect of the present invention is the color former according to any one of the first or fifth to eleventh aspects of the present invention, further comprising an acidic developer. According to a thirteenth aspect of the present invention, the acid developer is 2,2-
Bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4′-hydroxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone and 4,4 ′-[ Oxybis (ethyleneoxy-p-phenylenesulfonyl)] The color former according to the twelfth aspect of the invention, which is at least one selected from a mixture containing diphenol as a main component.

A fourteenth aspect of the present invention is the color former according to any one of the first to fifth to thirteenth aspects, further comprising a heat-fusible substance. In a fifteenth aspect of the present invention, the heat-fusible substance is β-
Naphthylbenzyl ether, p-benzylbiphenyl,
It is at least one selected from 1,2-di (m-methylphenoxy) ethane, di-p-methylbenzyl oxalate, 1,2-diphenoxymethylbenzene, and metaterphenyl. The fourteenth aspect of the invention
The coloring agent according to (1). A sixteenth aspect of the present invention is the color former according to any one of the first to fifth to fifteenth aspects, further comprising a fluorescent dye. According to a seventeenth aspect of the present invention, there is provided a recording material comprising a support and a coloring layer containing the coloring agent according to any one of the first to fifth aspects of the invention.

An eighteenth aspect of the present invention is the invention wherein at least one selected from a water-soluble polymer, a nonionic surfactant and an anionic surfactant is used as a dispersant for the leuco dye. 18. The recording material according to item 17, wherein The nineteenth aspect of the invention uses, as a dispersant for the leuco dye, at least one selected from methyl cellulose, hydroxypropylmethyl cellulose, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether sulfate, and sodium 2-ethylhexylsulfosuccinate. A recording material according to a seventeenth aspect of the invention, wherein the recording material is characterized in that: A twentieth aspect of the invention is the recording material according to any one of the seventeenth to nineteenth aspects of the invention, wherein the recording material is a thermosensitive recording material.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. The color former of the present invention contains a colorless or pale leuco dye and a urea urethane compound developer (a developer containing a urea urethane compound). The colorless or light-colored leuco dye of the present invention is a compound already known as a color former used in a pressure-sensitive recording material or a heat-sensitive recording material, and is not particularly limited. I do.

(1) Triarylmethane compounds 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5 -Dimethylaminophthalide, 3-p
-Dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like.

(2) Diphenylmethane compounds 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-halophenylleucouramine, N-2,4,5-trichlorophenylleucouramine and the like. (3) Xanthene compounds rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-dimethylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran, 3-diethylamino-6- Methyl-fluoran, 3
-Diethylamino-7-methyl-fluoran, 3-diethylamino-7-chloro-fluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-7 -Octylaminofluoran, 3-diethylamino-7-phenylfluoran,

3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-
7-p-methylanilinofluoran, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3-diethylamino-7- (2- Chloroanilino)
Fluoran, 3-diethylamino-6-methyl-7-
(O, p-dimethylanilino) fluoran, 3- (N-
Ethyl-N-tolyl) amino-6-methyl-7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) Fluoran, 3-diethylamino-6-methyl-7- (o-chloroanilino) fluoran, 3-diethylamino-6
Methyl-7- (p-chloroanilino) fluoran, 3-
Diethylamino-6-methyl-7- (o-fluoroanilino) fluoran, 3-diethylamino-6-methyl-7- (pn-butylanilino) fluoran, 3-diethylamino-6-methyl-7-n-octyl Aminofluoran, 3-diethylamino-6-chloro-7-anilinofluoran,

3-Diethylamino-6-ethoxyethyl-7-anilinofluoran, 3-diethylamino-benzo [a] fluoran, 3-diethylamino-benzo [c] fluoran, 3-diethylamino-6-methyl-
7-benzylaminofluoran, 3-diethylamino-
6-methyl-7-dibenzylaminofluoran, 3-diethylamino-7-di (p-methylbenzyl) aminofluoran, 3-diethylamino-6-methyl-7-diphenylmethylaminofluoran, 3-diethylamino-
7-dinaphthylmethylaminofluoran, 10-diethylamino-4-dimethylaminobenzo [a] fluoran, 3-diethylamino-7,8-benzfluoran,
3-diethylamino-6-methyl-7- (m-trichloroanilino) fluoran, 3-diethylamino-7-
(O-chloroanilino) fluoran,

3-dibutylamino-7- (o-chloroanilino) fluoran, 3-diethylamino-6-methyl-7- (2 ′, 4′-dimethylanilino) fluoran,
3- (N, N-diethylamino) -5-methyl-7-
(N, N-dibenzylamino) fluoran, 3-morpholino-7- (N-propyltrifluoromethylanilino) fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3-diethylamino-5-chloro -7- (N-benzyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluoran, 3-diethylamino-5-chloro-7- (α-phenylethylamino )
Fluoran, 3- (N-ethyl-Np-toluidino)
-7- (α-phenylethylamino) fluoran, 3-
Diethylamino-7- (o-methoxycarbonylphenylethyl) fluoran, 3-diethylamino-5-methyl-7- (α-phenylethylamino) fluoran,

3-diethylamino-7-piperidinoaminofluoran, 2-chloro-3- (N-methyltoluidino) -7- (p-N-butylanilino) fluoran, 3
-(N-ethyl-N-cyclohexylamino) -5,6
-Benzo-7-α-naphthylamino-4′-bromofluorane, 3-diethylamino-6-methyl-7-mesitidino-4 ′, 5′-benzofluoran, 3-dibutylamino-6-methyl-fluoran, 3-dibutylamino-
6-methyl-7-chlorofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-p-methylanilinofluoran, 3-dibutylamino- 6-methyl-7- (o, p
-Dimethylanilino) fluoran, 3-dibutylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran,

3-Dibutylamino-6-methyl-7- (
o-chloroanilino) fluoran, 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluoran, 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluoran, 3-dibuethyl Amino-6-methyl-7- (pn-butylanilino) fluoran, 3-dibutylamino-6-methyl-7-n-octylaminofluoran, 3-dibutylamino-6-chloro-7-anilinofluoran , 3-dibutylamino-6
-Ethoxyethyl-7-anilinofluoran, 3-di-n
-Pentylamino-6-methyl-7-anilinofluoran, 3-di-n-pentylamino-6-methyl-7- (
o, p-Dimethylanilino) fluoran, 3-di-n-pentylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran, 3-di-n-pentylamino-6-methyl-7- ( o-chloroanilino) fluoran,

3-di-n-pentylamino-6-methyl-
7- (p-chloroanilino) fluoran, 3-di-n-pentylamino-6-methyl-7- (o-fluoroanilino) fluoran, 3-pyrrolidino-6-methyl-7-
Anilinofluoran, 3-piperidino-6-methyl-7
-Anilinofluoran, 3-cyclohexylamino-6
-Chlorofluorane, 3-dimethylamino-5,7-dimethylfluoran, 3- (N-methyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3-
(N-methyl-NN-propylamino) -6-methyl-7-anilinofluoran, 3- (N-methyl-N-amylamino) -6-methyl-7-anilinofluoran,
3- (N, N-di-n-amylamino) -6-methyl-
7-anilinofluoran, 3- (N-methyl-N-is
o-propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-Nn-propylamino)
-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-iso-propylamino) -6-methyl-7
-Anilino fluoran,

3- (N-ethyl-NNn-butylamino) -6-methyl-7-anilinofluoran, 3- (N
-Ethyl-N-iso-butylamino) -6-methyl-
7-anilinofluoran, 3- (N-ethyl-Nn-
Hexylamino) -6-methyl-7-p-methylanilinofluoran, 3- (N-ethyl-Nn-hexylamino) -6-methyl-7- (o, p-dimethylanilino) fluoran, 3- (N-ethyl-Nn-hexylamino) -6-methyl-7- (m-trifluoromethylanilino) fluoran, 3- (N-ethyl-Nn-hexylamino) -6-methyl -7- (o-chloroanilino) fluoran, 3- (N-ethyl-N-iso-amylamino) -6-methyl-7-anilinofluoran, 3
-(N-ethyl-N-iso-amylamino) -6-chloro-7-anilinofluoran,

3- (N-ethyl-N-3-methylbutylamino) -6-methyl-7-anilinofluoran,
(N-ethyl-Np-toluidino) -6-methyl-7
-Anilinofluoran, 3- (N-ethyl-N-p-toluidino) -6-methyl-7- (p-methylanilino)
Fluoran, 3- (N-ethyl-Np-toluidino)
-6-methyl-7- (o, p-dimethylanilino) fluoran, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran, 3
-(N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-methylamino) -7-anilinofluoran,
3- (N-ethyl-N-3-methoxypropylamino)
-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-3-ethoxypropylamino) -6-methyl-7-anilinofluoran,

2- (4-oxahexyl) -3-dimethylamino-6-methyl-7-anilinofluoran, 2-
(4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluoran, 2- (4-oxahexyl) -3-dipropylamino-6-methyl-7-anilinofluoran, 3, 6-bis (diethylamino) fluoran-γ- (2′-nitro) anilinolactam,
6-bis (diethylamino) fluoran-γ- (3′-
Nitro) anilinolactam, 3,6-bis (diethylamino) fluoran-γ- (4′-nitro) anilinolactam, 3,6-bis (diethylamino) fluoran-γ
-Anilinolactam and the like.

(4) Thiazine compounds Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue and the like. (5) Spiro compound 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) Spiropyran, 3-propylspirobenzopyran and the like.

Also, 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6'-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'- (6′-dimethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9- Spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3,6-bis (dimethylamino) ) Fluorene-9-spiro-3 '-(6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-di Chill amino phthalide),

3-Dibutylamino-6-dimethylaminofluorene-9-spiro-3 '-(6'-diethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3'-(6 ' -Diethylaminophthalide), 3,6-bis (dimethylamino) fluorene-
9-spiro-3 '-(6'-dibutylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3'-(6'-diethylaminophthalide), 3-diethylamino-6-dimethyl Aminofluorene-9-spiro-3 '-(6'-dibutylaminophthalide), 3,3-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl]-
Compounds having an absorption region in the near infrared, such as 4,5,6,7, -tetrachlorophthalide. Among these, triarylmethane leuco dyes, fluoran leuco dyes, fluorene leuco dyes, and diphenylmethane leuco dyes are particularly preferred from the viewpoint of sensitivity and plasticizer resistance. Are preferred.

[0039]

Embedded image(Where Y₁And Y_TwoAre alkyl groups or
Represents a alkoxyalkyl group, Y_ThreeIs a hydrogen atom,
And an alkoxy group. Also, Y_FourAnd Y _FiveIs
Hydrogen atom, halogen atom, alkyl group or alkoxy
Represents a group. )

[0040]

Embedded image [Where R ₁ and R ₂ are represented by the formula (c) or the formula (d)
Represents any of the groups represented by

[0041]

Embedded image (Wherein, R ₇ to R ₁₁ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, .R _12, R ₁₃ showing a -NR ₁₂ R ₁₃ groups , Carbon number 1
8 alkyl groups. )

[0042]

Embedded image (Here, R ₁₄ and R ₁₅ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.) Further, R _{3 to} R ₆ represent a hydrogen atom, a halogen atom, and a C 1-8 carbon atom. Alkyl group, alkoxy group having 1 to 8 carbon atoms,-
It represents an NR ₁₆ R ₁₇ group. R ₁₆ and R ₁₇ are an alkyl group having 1 to 8 carbon atoms. Note that two or more of these colorless or light-colored leuco dyes can be used as needed.

The urea urethane compound developer according to the present invention includes a urea group (-NHCONH- group) and a urethane group
(-NHCOO- group) refers to a compound in which at least one or more are present. 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 colorless or light-colored leuco dye developer. Has a high color density and excellent storage stability. The mechanism by which such a urea urethane compound exhibits an excellent color developing effect is not clear, 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 has a urea group (-NHCONH- group) and a urethane group (-
Any compound may be used as long as it contains both (NHCOO-group), but is preferably an aromatic compound or 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, a urea group (-NHCONH-
Group) and urethane group (-NHCOO- group), as well as sulfone group (-SO ₂
It is desirable that an amide group (—NHCO— group) or an isopropylidene group (—C (CH ₃ ) ₂ — group) be present without being directly bonded to the urea group.

The urea urethane compound developer according to the present invention has one or more urethane groups (-NHCOO- groups) and one or more urea groups (-NHCONH- groups) in one molecule, and the total number thereof is 2-10. And preferably contains 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more of a urea urethane compound having a molecular weight of 5000 or less. By using such a urea urethane compound developer together with a colorless or light-colored leuco dye, it can be used as a color former for a heat-sensitive recording material or a pressure-sensitive recording material. This coloring agent has an effect that the coloring ability is excellent and the storage stability of printing is excellent.

The urea urethane compound which is a main component of the urea urethane compound developer has at least one urea group and one urethane group in one molecule. It is desirable that the urea group and the urethane group are adjacent to each other via at least one compound residue (hereinafter, such a portion is referred to as a urea urethane structure portion). The total number of urethane groups and urea groups is 2
10 or more, preferably 3 or more and 10 or less, more preferably 4 or more and 10 or less. The ratio of urethane groups to urea groups in one molecule of the urea urethane compound is 1:
It is preferably from 3 to 3: 1, more preferably from 1: 2 to 2: 1, and still more preferably 1: 1. The molecular weight of the urea urethane compound is 5,000 or less, more preferably 2,000 or less.

The reason why such a ureaurethane compound has excellent performance is not clear, but it is speculated that it may be due to the interaction between the urethane group and the urea group in the ureaurethane structure. Further, the content of the urea urethane compound in the urea urethane compound developer according to the present invention is preferably 50% by weight or more. Such a urea urethane compound developer can be produced by a relatively simple production method, while the color developing agent has an excellent color developing ability and a high ratio of the urea urethane compound capable of exhibiting storage performance is high. Therefore, excellent performance can be exhibited. The urea urethane compound may be used alone or as a mixture of two or more kinds including isomers.

Further, a mixture of two or more urea urethane compounds including isomers may be used for the purpose of improving color sensitivity and storage performance. On the other hand, in the urea urethane compound developer of the present invention, the urea urethane compound can be optionally diluted with a substance that does not inhibit the effects of the present invention. Examples of such a diluent include a heat-fusible substance, an acidic developer, an amine compound,
Examples include isocyanate compounds, urea compounds, and urethane compounds. Among these, urea compounds and urethane compounds having a structure similar to that of the urea urethane compound are preferable because the sensitivity can be improved. Further, a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound is preferable.

These diluents are preferably contained in an amount of 0.0001 to 50% by weight based on the total weight of the urea urethane compound and the diluent. The content of the diluent is more preferably 40% by weight or less, and further preferably 30% by weight or less, from the viewpoint of exhibiting storage performance. Further, the content of the diluent is more preferably 0.01% by weight or more, and further preferably 1% by weight or more, from the viewpoint of improving sensitivity. Further, these diluents may be generated during the synthesis reaction of the urea urethane compound, but when they are added, they are preferably added during the synthesis reaction in order to improve the sensitivity. For example, in a urea urethane compound developer comprising a urea urethane compound having at least one or more urea groups and at least one urethane group in the molecular structure in total and having a molecular weight of 5,000 or less and a diluent, a diluent Is a urea urethane compound developer containing 0.0001 to 50% by weight.

The method for synthesizing the 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 it is a method of producing (—NHCOO—group), 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 comprises, as a starting material, an isocyanate having at least two or more isocyanate groups, and leaving at least one isocyanate group of the isocyanate and containing another isocyanate group and an OH group. The compound can be reacted to form a urethane group, and then the remaining isocyanate group can be reacted with the amine compound to form a urea group. Further, a urea group may be formed by first reacting an isocyanate group with an amine compound, and then a urethane group may be formed by reacting the remaining isocyanate group with an OH group-containing compound.

The starting materials will be described below in detail. These starting materials may be used alone or in combination of two or more. The starting material 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, 2,2 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 "-tri Isocyanato-2,5-
Dimethoxytriphenylamine, 4,4 ', 4 "-triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, diisocyanate diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethanediene Isocyanate, methylcyclohexane diisocyanate and the like can be mentioned.

Also, diisocyanate dimer, for example, N, N 'which is toluene diisocyanate dimer
(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. Also, water adduct isocyanates such as toluene diisocyanate and 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.
Among the isocyanate compounds and isocyanate adduct compounds described in JP-A-757 and JP-A-10-95171 (the contents of which are incorporated herein by reference), the isocyanate group having 2 isocyanate groups
The above may exist. A particularly preferred example is toluene diisocyanate. Toluene diisocyanate is preferably 2,4-toluene diisocyanate, and in addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and is available at a low cost. It is possible, but this is fine.

The urea urethane compound The amine compound which forms a urea group by reacting with isocyanate, which is a starting material of a developer, may be any compound having an amino group. Examples thereof include aniline and 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-xylysine,

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′-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, p-amino Methyl benzoate, 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-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenyl Sulfamoylaniline, 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 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-
Heterocyclic compounds such as (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine, amines, methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropyl Amine, 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-
Examples thereof include aliphatic amines such as 1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-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 (e);

[0065]

Embedded image Y _{1 is, -SO 2 -, - O -} , - (S) n -, - (CH
₂ ) _n- , -CO-, -CONH-, any of the groups represented by the formula (f),

[0066]

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 as long as it has an OH group.
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, 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, 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, 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'-benzyloxyphenyl sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone,

4-hydroxy-4'-isopropoxydiphenylsulfone, 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 ' -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, 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,
Those having an amino group are not preferred among these phenols. 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.

Further, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol, -Pentanol, 3-hexanol,
tert-butanol, tert-amyl alcohol,
Methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propene
1-ol, benzyl alcohol, 4-pyridine methanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3
-Alcohols such as hydroxypropane, glycerin, glycerol,

Polypropylene glycol, polytetramethylene ether glycol, adipate polyol,
Epoxy-modified polyol, polyetherester polyol, polycarbonate polyol, polycaprolactonediol, phenol-based polyol, polyether-based polyols such as 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, Machine oil based polyol, polymer polyol, methyl pentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, alpha-methyl glucoside, sorbitol, polyols such as shoe close the like.

The urea urethane compound developer according to the present invention is preferably 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. 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 satisfying ≧ (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 method for synthesizing a urea urethane compound in which the number of urea groups (A) and the number of urethane groups (B) satisfy Expression 10 ≧ (A + B) ≧ 3 (where A and B are integers of 1 or more) is based on the urea 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 producing the isocyanate compound by reacting the OH group-containing compound and the amine compound with each other is easy and preferable.

That is, the ureaurethane compound according to the present invention is obtained, for example, by starting from an isocyanate having at least two or more isocyanate groups, leaving at least one isocyanate group of the isocyanate and other isocyanate groups and an OH group. The resulting compound is reacted to form a urethane group, and the remaining isocyanato groups of the two molecules of the urethane compound are then reacted with each other with water to form a urea urethane compound having a total number of urea groups and urethane groups of at least three. 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 while leaving at least one isocyanate 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 further 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 isocyanato group and an amine compound are reacted to form a urea group, and then the remaining isocyanato group is reacted with an OH group-containing compound having two or more OH groups to form a urethane group. Further, by reacting an isocyanate compound, 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 isocyanate as a starting material 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-
Trizine 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-phenylisocyanate) thiophosphate,
4,4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, dimer acid dimer Examples include isocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexane diisocyanate.

Further, diisocyanate dimer, for example, N, N ′ which is toluene diisocyanate dimer
(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. Also, water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, for example, 1,3-bis (3 -Isocyanato-4-methylphenyl) urea or a polyol adduct, for example, trimethylolpropane adduct (trade name: Desmodur L) of toluene diisocyanate, an amine adduct, or the like.
No. 57 and Japanese Patent Application Laid-Open No. 10-95171 may be compounds having two or more isocyanate groups among the isocyanate compounds and isocyanate adduct compounds.

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 an isocyanate as a starting material of a urea urethane compound may be any compound as long as it is a compound having an amino group. Examples thereof include 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-xylysine, 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'-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, p -Dodecyl aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methyl Benzamide, 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-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'-diaminodiphenylsulfone, 3,3 '
-Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyl Dibenzyl, 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'-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-
Aminopropyl) heterocyclic compounds such as 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,
-Methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,
Examples thereof include aliphatic amines such as 3-diamino-2-hydroxypropane, 2-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 preferred.

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 (e);

[0093]

Embedded image Y _{1 is, -SO 2 -, - O -} , - (S) n -, - (CH
₂ ) _n- , -CO-, -CONH-, any of the groups represented by the formula (f),

[0094]

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 as long as it has an OH group.
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, 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, 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, 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'-benzyloxyphenyl sulfone,

4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 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′-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,
-Hydroxybenzoic acid (4'-chlorobenzyl),

Ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), 3- Dimethyl hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate,
4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, Examples include phenols such as 3-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.

Also, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol, -Pentanol, 3-hexanol,
tert-butanol, tert-amyl alcohol,
Methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propene
1-ol, benzyl alcohol, 4-pyridine methanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3
-Hydroxypropane, glycerin, alcohols such as glycerol, polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyetherester polyol,

Polyether polyols such as polycarbonate polyol, polycaprolactone diol, phenolic 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, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine,
and polyols such as α-methylglucoside, sorbitol, and souce.

As the urea urethane compound developer according to the present invention, urea urethane compounds of the general formulas (II) to (VIII) are further preferable.

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,
Represents one selected from the group consisting of a xylylene group, a naphthylene group, a hexamethylene group, and a -φ-CH ₂ -φ- group, wherein -φ- represents a phenylene group. ),

[0102]

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. ),

[0103]

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. ),

[0104]

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. ),

[0105]

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, and is preferably a nitro group, a hydroxyl group, a carboxyl group, Nitroso group, nitrile group, carbamoyl group, ureido group, isocyanato group, mercapto group, may be substituted by a sulfo group, a sulfamoyl group or a halogen atom, each residue may have a substituent, γ is -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 (f),

[0106]

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

[0107]

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, but is preferably a hydroxyl group, a nitro group, a nitrile group, Carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group,
It may be substituted with an isocyanato group, a mercapto group, a sulfo group or a halogen atom, and each residue may have a substituent, and δ is -SO _2- , -O-,-
(S) _n -,-(CH ₂ ) _n- , -CO-, -CONH
-, - NH -, - CH (COOR 1) -, - C (C
F ₃ ) ₂ — and —CR ₂ R ₃ — represent one selected from the group consisting of, or absent, R ₁ , R ₂ and R ₃
Represents an alkyl group, and n is 1 or 2. ),
as well as

[0108]

Embedded image (Wherein, 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 and Y
And Z are preferably aromatic compound residues or heterocyclic compound residues. ). General formulas (II) to (VIII)
Is an entirely new compound. This novel compound is useful for a recording material using recording energy such as heat and pressure.

The production method of the urea urethane compound of the formula (II) according to the present invention is not particularly limited. For example, an OH group-containing compound of the following general formula (IX) and a compound of the following general formula (X)
And an amine compound of the following general formula (XI), for example, according to the following reaction formula (A).

Embedded image

[0110]

Embedded image

[0111]

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. Y ₀ is a tolylene group, a xylylene group, a naphthylene group, a hexamethylene group,
Alternatively, it represents one selected from the group consisting of a -φ-CH ₂ -φ- group, and -φ- represents a phenylene group. )

[0112]

Embedded image The term “aliphatic” in the present invention includes alicyclic.

The production method of the ureaurethane compound of the formula (III) according to the present invention is not particularly limited. For example, an OH group-containing compound of the formula (IX)
It can be obtained by reacting the isocyanate compound of I) and water, for example, according to the following reaction formula (B).

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.)

[0114]

Embedded image

The production method of the urea urethane compound of the formula (IV) according to the present invention is not particularly limited. For example, an OH group-containing compound of the general formula (IX), an isocyanate compound of the general formula (XII) and the following general formula It can be obtained by reacting the amine compound of the formula (XIII), for example, according to the following reaction formula (C) or (D).

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.)

[0116]

Embedded image

[0117]

Embedded image

The ureaurethane compound of the formula (V) according to the present invention is not particularly limited in its production method. For example, an amine compound of the general formula (XI), an isocyanate compound of the general formula (XII) and It can be obtained by reacting the OH group-containing compound of XIV) 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.)

[0119]

Embedded image

[0120]

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 (V) 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, and examples thereof include 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'-
Benzyloxyphenyl sulfone,

4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate,
Benzyl hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4'-hydroxybenzoic acid) ethyl, 1,5-bis (4'-hydroxybenzoic acid) pentyl, 6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde,
-N-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3
And monophenols such as -n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid.

Further, 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, benzyl bis (4-hydroxyphenyl) 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-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-
And diphenols such as (hydroxy-3-methylphenyl) sulfide. However, those having an amino group are not preferred as these OH-containing compounds. 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.

Further, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol, -Pentanol, 3-hexanol,
tert-butanol, tert-amyl alcohol,
Methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propene
1-ol, benzyl alcohol, 4-pyridine methanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3
Monohydric alcohols such as hydroxypropane, glycerin and glycerol.

Further, 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, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucosidorubitol, Polyols such as shoe rose may be used. Of these, monophenols are preferably used.

Examples of the isocyanate compound of the general formula (X) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and 1,5-naphthylene diisocyanate. Isocyanate, meta-xylylene diisocyanate and the like can be mentioned. 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, metaxylylenediisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4 -Cyclohexyl isocyanate,
Dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, and the like.

Further, diisocyanate dimer, for example, N, N'- which is a dimer of toluene diisocyanate
(4,4'-dimethyl-3,3'-diphenyldiisocyanate) uretdione (trade name; Desmodur T
T) and trimers such as 4,4 ', 4 "-trimethyl-
3,3 ', 3 "-triisocyanate-2,4,6-triphenylcyanurate and the like. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, for example, 1,3-bis (3
Isocyanato 4-methylphenyl) urea and polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name; Desmodur L)
Or an amine adduct. Also, Japanese Patent Application Laid-Open No. H10-7
Of the isocyanate compounds and isocyanate adduct compounds described in JP-A-65757 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, and o-amine. 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, 2
B acid, p-fluoroaniline, o-fluoroaniline,
3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-
Aromatic monoamines such as aminobenzotrifluoride and 2-amino-3-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, tolidine 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'-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'-diaminodiphenylsulfone, 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 Aromatics such as (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4′-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3′-dichlorobenzidine Diamines and the like can be mentioned.

Further, 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, stearylamine,
Allylamine, isopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, 3- (diethylamino) propylamine, 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. Of these, aromatic monoamines are preferably used.

The amine compound of 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, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 3,3'-dichloro-4,4'-
Diaminodiphenylmethane, 3,3′-dimethyl-4,
4'-diaminodiphenylmethane, tolidine 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'-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,
Examples thereof include aromatic amines such as 4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, tolidine base, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.

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.

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 (e);

[0143]

Embedded image Y _{1 is, -SO 2 -, - O -} , - (S) n -, - (CH
₂ ) _n- , -CO-, -CONH-, any of the groups represented by the formula (f),

[0144]

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 has two or more OH groups. For example, 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, p, p'-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, 3,4-dihydroxyphenyl-
4'-methylphenyl 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,
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.

Also, 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, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, Polyols such as shoe closes are exemplified.

The production method of the ureaurethane compound of the formula (VI) according to the present invention is not particularly limited. For example, a monophenol compound, an aromatic diisocyanate compound and a diamine compound of the following general formula (XV) may be used. It can be obtained by reacting according to the following reaction formula (G) or (H).

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, and is preferably a nitro group, a hydroxyl group, a carboxyl group, It may be substituted with a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanato group, a mercapto group, a sulfo group, a sulfamoyl group, or a halogen atom, and 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 (f),

[0149]

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

[0150]

Embedded image

[0151]

Embedded image

The production method of the ureaurethane compound of the formula (VII) according to the second aspect of the present invention is not particularly limited. For example, an aniline derivative, an aromatic diisocyanate compound and a dihydroxy compound of the following general formula (XVI) may be used. For example, by reacting according to the following reaction formula (J) or (K).

Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, but is preferably a hydroxyl group, a nitro group, a nitrile group, It may be substituted with a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanato group, a mercapto group, a sulfo group, or a halogen atom. May have a substituent, and δ is -SO _2- , -O-,-(S)
_{n -, - (CH 2)} n -, - CO -, - CONH -, -
_{NH -, - CH (COOR 1} ) -, - C (CF 3)
_2- , -CR ₂ R _3- or absent. R ₁ , R ₂ and R ₃ each independently represent an alkyl group, and n is 1 or 2. )

[0153]

Embedded image

[0154]

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 phenol 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 or more OH groups on the benzene ring. Other than aromatic compound residue or aliphatic compound residue or heterocyclic compound residue, nitro group, carboxyl group, nitroso group, nitrile group, carbamoyl group, ureido group, isocyanato group, mercapto group, sulfo group, sulfamoyl group or It may be substituted by a halogen atom.

Preferred phenol compounds include, for example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-phenol
Octylphenol, 2-cyclohexylphenol,
2-allylphenol, 4-indanol, thymol,
2-naphthol, nitro-substituted phenol p-nitrophenol, halogen-substituted phenol 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, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4
-N-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3
And phenols such as -n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid. Also, carboxyl group, nitroso group, nitrile group,
A phenol compound having a substituent such as a carbamoyl group, a ureido group, an isocyanato group, a mercapto group, a sulfo group, or a sulfamoyl group may be used. 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.

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. There is no particular limitation as long as it is present. For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,
4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and the like. 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) includes, for example, 4,4′-diamino-diamine.
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-tolidinesulfone, 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 ′
-Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 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'-
And aromatic diamines such as dichlorobenzidine.

The aniline derivative which can be used when synthesizing the urea urethane compound of the formula (VI) is not particularly limited as long as it is an aniline compound having one or more amino groups on a benzene ring. , The hydrogen atom of the benzene ring is an aromatic compound residue or an aliphatic compound residue or a heterocyclic compound residue or a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, oxyamino Group, nitroamino group, hydrazino group, ureido group, isocyanato group,
It may be substituted by a mercapto group, a sulfo group or a halogen atom.

Preferred aniline compounds include, for example, aniline, 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, carboxy-substituted aniline p-aminobenzoic acid, hydroxyl-substituted aniline o-aminophenol,
2,3-xylysine such as m-aminophenol, 2-amino-4-chlorophenol, p-aminophenol,
2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile which is a nitrile-substituted aniline,

Anthranilic acid, p-cresidine, 2,5-dichloroaniline which is a halogen-substituted aniline,
6-dichloroaniline, 3,4-dichloroaniline,
3,5-dichloroaniline, 2,4,5-trichloroaniline, o-chloroaniline, m-chloroaniline, p
-Chloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, p-
Butyl 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
Carbamoylanilines such as-[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-chloro-5-N-phenylsulfamoylaniline, 2-methoxy- 5-N, N-
Sulfamoylanilines such as diethylsulfamoylaniline and 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline , 4-diethylaminosulfonylaniline, sulfathiazole,

4-aminodiphenylsulfone, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4
-Methylaniline, nitro-substituted aniline, o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, o-nitro Aniline, m-
Nitroaniline, p-nitroaniline, 2-methyl-4
-Nitroaniline, m-nitro-p-toluidine, 2-
Amino-5-nitrobenzonitrile, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3
4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile and the like. In addition, an aniline derivative having a substituent such as a carboxyl group, a nitroso group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanato group, a mercapto group, or a sulfo group may be used.

The compound represented by the general formula (XV) which can be used when synthesizing the ureaurethane compound of the formula (VII)
As the dihydroxy compound of I), 2,2-bis (4
-Hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 4,4′-biphenol, 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, 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, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane And diphenols such as 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.

The method for synthesizing the urea urethane 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 the general formulas (II) to (VIII), preferred are the general formulas (III) to
Compounds of formula (VII), particularly preferred are compounds of formulas (VI) to (VII).

Further, the following structural formula (g) or (h)
The urea urethane compound developer is particularly preferred.

Embedded image

[0173]

Embedded image

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 decrease, and the urea group or the urethane group may The bonded residue is preferably an aromatic compound residue or a heterocyclic compound residue. However, the reduction 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.

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 that does not cause a reaction with the isocyanate group and the functional group of the reactant, for example, an aliphatic hydrocarbon, an alicyclic hydrocarbon,
Examples thereof include aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and ketones. Particularly, methyl ethyl ketone, acetone, 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 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 as needed.

In the heat-sensitive recording material, a compound having a melting point is preferred, and the melting point of the ureaurethane compound developer of the present invention is preferably from 40 ° C. to 500 ° C., particularly preferably from 60 ° C. to 300 ° C. Is desirable. 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 leuco dye. When the urea urethane compound developer is at least 5 parts by weight, it is sufficient to cause the leuco dye to develop color,
High color density. When the amount of the urea urethane compound developer is 1,000 parts by weight or less, an excessive amount of the urea urethane compound developer hardly remains, which is economically advantageous and preferable.

The whiteness is improved by further adding a fluorescent dye to the color former of the present invention. As the fluorescent dye used in addition to the color former of the present invention, various known dyes can be used, and examples thereof include stilbene derivatives, coumarin derivatives, pyrazoline derivatives, bisstyryl biphenyl derivatives, naphthalimide derivatives, and bisbenzooxazolyl derivatives. Although not limited to these, diaminostilbene disulfonic acid derivatives are particularly preferred. The amount of the fluorescent dye used was 0.0% based on the total solid content of the color former.
It is preferably present in an amount of 1 to 3% by weight, more preferably in the range of 0.1 to 2% by weight. The amount of fluorescent dye used is 3
If the amount exceeds the weight%, the coloring agent may be colored,
If it is less than 0.01% by weight, the effect on whiteness is reduced. By adding an acidic developer to the color former of the present invention, the sensitivity is improved and a color former having a clear color is obtained.

As the acidic developer when the present invention is used as a heat-sensitive recording material, generally used electron-accepting substances are used. Or a metal salt thereof, an N, N-diarylthiourea derivative,
Sulfonylurea derivatives and the like are preferred. Particularly preferred are phenol derivatives, and specifically, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, , 2-bis (hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) Sulfone,
2,4'-dihydroxydiphenyl sulfone, bis (3
-Methyl-4-hydroxyphenyl) sulfone,

4-hydroxyphenyl-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, bis (3-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), 1,2-bis (4'-hydroxybenzoic acid) ethyl,

Pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, etc. be able to. Examples of the salicylic acid derivative include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octoctanoyloxysalicylic acid, and 4-n-octyloxysalicylic acid. -Octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid and the like.

Examples of the sulfonylurea derivative include 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane and 4,4-bis (o-
Toluenesulfonylaminocarbonylamino) diphenylmethane 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylsulfide, 4,4-bis (p-toluenesulfonylaminocarbonylamino)
Diphenyl ether, N- (p-toluenesulfonyl)
Compounds containing one or more arylsulfonylaminoureido groups such as -N'-phenylurea are exemplified. Furthermore, 4,4 ′-[oxybis (ethyleneoxy-p-
[Phenylenesulfonyl]] diphenol and a mixture containing the same as a main component (for example, D-90: trade name, manufactured by Nippon Soda Co., Ltd.).

Further, in order to improve the background fog 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-te
rt-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-
It is also possible to add a phenol compound such as methylphenyl) butane and 1,1-bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane.

The acid developer is preferably used in an amount of 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the colorless or pale leuco dye. When the amount of the acidic developer is 5 parts by weight or more, the coloration of the leuco dye is good, and the coloring 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. Also when the present invention is used as a pressure-sensitive recording material, the addition of an acidic developer improves the image density and enables a clear color developer to be obtained.

As the acidic developer, an electron-accepting substance is used, and examples thereof include acid clay,
Activated clay, attapulgite, benite, zeolite, colloidal silica, magnesium silicate, talc,
Inorganic compounds such as aluminum silicate, or phenol, cresol, butylphenol, octylphenol, phenylphenol, chlorophenol, salicylic acid, or aldehyde condensed novolak resins derived therefrom and metal salts thereof, 3-isopropylsalicylic acid, 3-phenylsalicylic acid , 3-cyclohexylsalicylic acid, 3,5-di-t-butylsalicylic acid, 3,
5-di (α-methylbenzyl) salicylic acid, 3,5-di-t-octylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3,5-di (α, α-dimethylbenzyl)
Salicylic acid derivatives such as salicylic acid and 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, and metal salts thereof.

In the present invention, a color-forming agent containing a colorless or pale-colored leuco dye and a urea urethane compound developer is formed on a support by a method such as coating to form a color-forming layer, thereby obtaining a recording material. be able to. The configuration differs depending on the type of recording material. The recording material of the present invention can be used as various recording materials such as a heat-sensitive recording material and a pressure-sensitive recording material, and is particularly suitable as a heat-sensitive recording material.

When the recording material is a heat-sensitive recording material, a heat-sensitive recording layer which develops color by heating is provided on the support. Specifically, the above-mentioned urea urethane compound, colorless or light-colored leuco dye, a heat-fusible substance to be described later, and the like are coated on a support together with other necessary components in the form of a dispersion and a heat-sensitive recording layer. There is a need to. The dispersion can be prepared by finely pulverizing one or more of these compounds in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer or a surfactant using a sand grinder or the like. . The particle diameter of each dispersion is preferably 0.1 to 10 μm, particularly preferably about 1 μm. In particular, when the urea urethane compound developer is wet-pulverized in an aqueous solvent, it is desirable to maintain the liquid temperature of the aqueous solvent at 50 ° C. or lower.

As a dispersant for wet-grinding a leuco dye in an aqueous solvent, at least one selected from a water-soluble polymer, a nonionic surfactant and an anionic surfactant may be used. It is effective in preventing background fogging due to the plasticizer, and among these, methyl cellulose, hydroxypropyl methyl cellulose, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether sulfate, and 2-ethylhexyl sulfosuccinate are preferred. In addition, the p of a coating solution containing a urea urethane compound, a colorless or pale color leuco dye,
H is preferably 5 to 12.

In addition, the thermal recording layer contains diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin and the like as pigments. You can also. In addition, for the purpose of preventing head abrasion and sticking, zinc stearate, higher fatty acid metal salts such as calcium stearate, paraffin,
Waxes such as paraffin oxide, polyethylene, polyethylene oxide, stearamide, caster wax, etc., dispersants such as sodium dioctyl sulfosuccinate, ultraviolet absorbers such as benzophenone type and benzotriazole type, and a surfactant are also required. It can be contained as needed.

Examples of the binder that can be used for forming the heat-sensitive recording layer include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylic acid. Water-soluble binders such as ester copolymers, acrylamide / acrylate / methacrylic acid terpolymers, styrene / maleic anhydride copolymer alkali salts, ethylene / maleic anhydride copolymer alkali salts, and styrene Latex-based water-insoluble binders such as styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, and methyl acrylate / butadiene copolymer.

As the support of the heat-sensitive recording layer, paper is mainly used. In addition to paper, various woven fabrics, nonwoven fabrics, synthetic resin films, laminated paper, synthetic paper, metal foil, or composite sheets obtained by combining these are used. It can be used arbitrarily according to the purpose. The basis weight of this support is 40 g
/ M ^{2 to} 200 g / m ² is desirable, and as the heat-sensitive recording material is desired to have as high a flatness as possible, a material having excellent surface smoothness and flatness is desirable. It is preferable to perform surface treatment by applying pressure and pressure.
The thermal recording layer may be composed of a single layer or a plurality of layers. For example, each color forming component may be contained one layer at a time to form a multilayer structure. This heat-sensitive recording layer can be obtained by mixing each aqueous dispersion obtained by finely pulverizing each color-forming component or other components, a binder and the like, applying the mixture on a support, and drying.

When the present invention is used as a thermosensitive recording material, a thermofusible substance can be contained in the thermosensitive coloring layer in order to improve the sensitivity. Heat fusible material is 60
C. to 180.degree. C. are preferred, especially 80.degree.
Those having a melting point of from 140C to 140C are preferred. For example,
benzyl p-benzyloxybenzoate, stearic acid amide, palmitic acid amide, N-methylol stearic acid amide, β-naphthylbenzyl 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,
-Methoxy-4-benzyloxynaphthalene, N-stearoylurea, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, 1-phenoxy-2
-(4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate, metaterphenyl, dibenzyl oxalate, di-p oxalate
-Methylbenzyl ester, oxalic acid (p-chlorobenzyl) ester, 1,2-diphenoxymethylbenzene and the like.

Further, 4,4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4,4'-
Difluorobenzophenone, diphenylsulfone, 4,
4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'dichlorodiphenyldisulfide, diphenylamine, 2-methyl-4-
Methoxydiphenylamine, N, N'-diphenyl-p
-Phenylenediamine, 1- (N-phenylamino) naphthalene, benzyl, 1,3-diphenyl-1,3-propanedione and the like may be used. Of these, diphenyl sulfone, di-p-methylbenzyl oxalate, and benzyl are preferably used. The heat-fusible substance may be used alone or as a mixture of two or more kinds, and in order to obtain a sufficient thermal response, 10 to 10 parts by weight of a colorless or pale leuco dye is used. It is preferable to use 300 parts by weight, and it is more preferable to use 20 to 250 parts by weight.

When the recording material is a pressure-sensitive recording material, for example, US Pat.
No. 507, No. 2730456, No. 273
It can take a form as disclosed in Japanese Patent No. 0457, No. 3418250 and the like. That is,
Leuco dyes are used alone or as a mixture, consisting of synthetic oils such as alkylated naphthalenes, alkylated diphenyls, alkylated diphenylmethanes, alkylated diarylethanes, chlorinated paraffins, and vegetable oils, animal oils, and mineral oils alone or in mixtures. An upper paper obtained by dissolving in a solvent and dispersing the same in a binder, or by coating a dispersion containing microcapsules together with a binder or the like on a support, and a urea urethane compound developer (and acidic Pressure-sensitive recording paper with the coated surfaces of the lower paper coated with a dispersion of a color developer, etc., or medium paper with a urea urethane compound dispersion coated on one side and a leuco dye coated on the other side The pressure-sensitive recording paper sandwiched between the upper paper and the lower paper, or the urea urethane compound Of a self-type in which a dispersion of an agent (and an acid developer) and a dispersion containing the above leuco dye are mixed or coated in multiple layers, or a leuco dye, a urea urethane compound developer (and an acid developer, etc.) Various forms such as a self-type in which all are microencapsulated and mixed and applied are possible.

The method for producing microcapsules includes the coacervation method disclosed in US Pat. No. 2,800,457 and US Pat.
-19574, 42-446, 42-
Interfacial polymerization method disclosed in Japanese Patent Publication No. 771
No. 9168, Japanese Patent Publication No. 51-9079, etc., the in-situ method disclosed in British Patent Nos. 952807 and 965074, and the melting dispersion cooling method disclosed in U.S. Pat. And the spray drying method disclosed in UK Patent No. 930422 and the like can be employed. The color former of the present invention corresponds to the leuco dye and the developer in the above publications.

In forming the pressure-sensitive recording layer, each component such as a urea urethane compound developer may be used by dissolving it in a solvent or by dispersing it. In the case of a color developing system including an acidic developer, the color developing system may be used alone or
The urea urethane compound developer and, if necessary, an acidic developer may be used in combination or dissolved or dispersed in a solvent. In the above-described interfacial polymerization method used in forming microcapsules, a film is formed at the interface using two types of oil-based and water-soluble monomers. For example, use a polybasic acid chloride in the oil phase, a polyamine in the aqueous phase with a polyamide film, a polyester film in the aqueous phase with a polyhydroxy compound, and a polyisocyanate in the oil phase. It is known that a method of forming a polyurethane film using a polyhydric alcohol or polyhydric phenol in an aqueous phase when a natto is used, and a method of forming a polyurea film using a polyhydric amine in an aqueous phase is used. When the interfacial polymerization method is used for producing microcapsules, an isocyanate compound may be used as one of the reactive monomers for forming a film.

In this case, the isocyanate compound is consumed for forming the film of the microcapsules and is not directly involved in the color image, and the use of another water-soluble monomer is indispensable. This is distinguished from the use of the isocyanate compound used in the present invention.
The preparation of the dispersion of the compound without microencapsulation,
It can be obtained by pulverizing one or more of each compound in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer and a surfactant. Further, the urea urethane compound may be dispersed simultaneously with the acidic developer.

As the support used for the pressure-sensitive recording material, paper is mainly used.
A synthetic resin film, a laminated paper, a synthetic paper, a metal foil, or a composite sheet combining these can be used arbitrarily according to the purpose. As the binder, various commonly used binders can be used. For example, starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide /
Acrylic ester copolymer, acrylamide / acrylic ester / methacrylic acid terpolymer, styrene /
Water-soluble binders such as alkali salts of maleic anhydride copolymer, alkali salts of ethylene / maleic anhydride copolymer, and styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer And latex-based water-insoluble binders.

Further, the recording material according to the present invention may contain a hindered phenol compound or an ultraviolet absorber in the recording layer. 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′-diphenyl acrylate, tetra (2,2,6,
6-tetramethyl-4-piperidyl) 1,2,3,4-
Butane tetracarboate.

The method for forming the color-forming layer is not particularly limited, and a coating solution for the color-forming layer may be appropriately coated by, for example, a free-fall curtain, an air knife coating, a variver blade coating, a pure blade coating, or a short dwell coating. It is formed by a method of coating and drying on a support by a method. In the case of the coating solution for the coloring layer,
The coating amount is not particularly limited, and is usually 1 to 15 by dry weight.
g / m ^2, it is preferably adjusted in the range of about 3 to 10 g / m ^2. Further, an intermediate layer can be provided between the heat-sensitive recording layer and the support to improve the thermal responsiveness. The undercoat layer is mainly composed of an organic, inorganic pigment, a hollow particle, a water-soluble polymer, an aqueous binder such as latex, and the same organic, inorganic pigment and aqueous binder as the heat-sensitive recording layer can be used. . The method for forming the intermediate layer is not particularly limited, and a method similar to the method for forming the heat-sensitive recording layer can be used. The dry coating amount is 2.0 to 15.
A range of 0 g / m ² is preferred.

Further, in the present invention, if necessary, a protective layer containing a water-soluble polymer as a main component can be provided on the heat-sensitive recording layer. Specific examples of the water-soluble polymer in this case include the water-soluble polymer binder exemplified in relation to the heat-sensitive recording layer. The water-soluble polymer can be used together with a conventional water-proofing agent for making it water-resistant. Specific examples of the water-proofing agent include, for example, formaldehyde, glyoxal, chrome alum, melamine, melamine-formaldehyde resin, Polyamide resins, polyamide-epichlorohydrin resins, and the like are included.

The protective layer may further contain, if necessary, conventional auxiliary additives such as fillers, heat-fusible substances (lubricants), surfactants and fluorescent dyes. Specific examples of the substance and the fluorescent dye include those exemplified in relation to the heat-sensitive recording layer. Further, the recording material produced by the method of the present invention includes:
If a back layer (back coat layer) is provided on the opposite side of the recording layer as needed, it is possible to prevent the recording paper from curling. The coating liquid components and the coating method of the back layer may be the same as those of the protective layer. The dry coating amount is 0.2 to 10.
A range of 0 g / m ² is preferred.

Hereinafter, the present invention will be described in more detail by way of examples. In addition, each physical property was evaluated by the following methods. <Color Sensitivity of Thermal Paper> Using a printing tester manufactured by Okura Electric Co., Ltd., the color density at an applied voltage of 24 V and a pulse width of 1.5 msec was measured with an optical densitometer using KJT-256-8MGF1 manufactured by Kyocera. <Plasticizer resistance> The thermosensitive 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. <Whiteness of Thermal Paper> The whiteness of the background of the thermal recording material was measured with a Hunter whiteness meter (JIS-P8123).

[0205]

EXAMPLE 1 31.5 g of 4-toluene diisocyanate
Was stirred at 60 ° C., and 21.5 g of 4,4′-diaminodiphenyl sulfone was added to methyl ethyl ketone 12.
The solution was diluted with 0 ml and added dropwise over 4 hours.
Allowed to react for hours. After the reaction, the reaction mixture was cooled to room temperature, and toluene was added. The precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to give a white crystalline compound 47.
g was obtained. Next, 30 g of this compound was taken and phenol 9.
After 5 g and 95 ml of methyl ethyl ketone were added, and 30 mg of triethylamine was further added, 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 in vacuo overnight to obtain 38.5 g of a white crystalline compound. Result of IR measurement of the white crystals, 990cm ^-1, 1110cm ^-1, 1320
cm ^-1 , 1590 cm ^-1 , 1700 cm ^-1 , 3350c
A characteristic peak appeared at m ^-1 . As a result of mass spectrum measurement, [M + H] ⁺ was detected at m / z 785.
The structural formula of the main component of this compound is assumed to be the aforementioned compound (g).

Next, 2 g of this compound was taken, and 2.5% by weight
The mixture was crushed and dispersed with a paint shaker for 6 hours together with 8 g of an aqueous polyvinyl alcohol solution 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. Also, 70 g of 3-dibutylamino-6-methyl-7-anilinofluoran was 5.4% by weight of hydroxypropyl methylcellulose (Shin-Etsu Chemical Co., Ltd., Metrose 60SH-03: trade name).
Sand grinder (Vessel capacity 400 ml, manufactured by IMEX Co., Ltd.) with 130 g of aqueous solution, rotation speed 2000 r
The mixture was ground and dispersed at pm for 3 hours to obtain a dispersion. Further, 70 g of diphenyl sulfone and 130 g of an 8% by weight aqueous solution of polyvinyl alcohol are sand-grindered (vessel capacity 400 ml, manufactured by Imex Co., Ltd.), and the number of rotations is 2,000 r.
The mixture was ground and dispersed at pm for 3 hours to obtain a dispersion. Further, 10 g of calcium carbonate was mixed with 30 g of water, and the mixture was stirred and dispersed with a stirrer to obtain a dispersion.

These dispersions were prepared by adding 20 parts by weight of the solid dispersion of the above compound dispersion to 3-dibutylamino-6-methyl-
10 parts by weight of dry solid content of 7-anilinofluorane dispersion, 25 parts by weight of dry solids of diphenylsulfone dispersion, 40 parts by weight of dry solids of calcium carbonate dispersion, and stearic acid having a solids concentration of 16% by weight The coating liquid was obtained by stirring and mixing at a ratio of 20 parts by weight of the dry solid content of the zinc dispersion and 15 parts by weight of the dry solid content of 15% by weight polyvinyl alcohol (on a dry basis). This coating solution was applied to a base paper having a weighing of 50 g / m ^{2 using} a rod coater rod No. 10. The coating amount of the coating liquid was 5 g / m ² in terms of dry weight. After drying, it was treated with a super calender to obtain a heat-sensitive recording material. The evaluation result of the sensitivity of the obtained heat-sensitive recording material was as good as the optical density of 1.3. In addition, the print preservability with the vinyl chloride wrap was good. The whiteness of the background was 82, which was good. Table 1 summarizes the results of these evaluations.

[0208]

Examples 2-3 In place of 3-dibutylamino-6-methyl-7-anilinofluoran used in Example 1, 3
Example except that -diethylamino-6-methyl-7-anilinofluoran (Example 2) and 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (Example 3) were used. In the same manner as in Example 1, a thermosensitive recording material was prepared and evaluated. The results are summarized in Table 1.

[0209]

Examples 4-6 In Example 1, 3-dibutylamino-6-
Instead of the hydroxypropylmethylcellulose used in the dispersion of methyl-7-anilinofluoran, methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrolose M-15: trade name) (Example 4), polyoxyethylene alkyl ether sulfate ( Example 1 except that Kao Corporation, Revenol WX: trade name) (Example 5) and 2-ethylhexyl sulfosuccinate sodium (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neocol SWC: trade name) (Example 6) were used. In the same manner, a thermosensitive recording material was prepared and evaluated. The results are summarized in Table 1.

[0210]

Example 7 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.

The result of IR measurement of this white crystal was 750.
^{cm -1, 840cm -1, 1020cm -1} , 1500cm
^{-1, 1600cm -1, 1720cm -1,} 3350cm -1
, A characteristic peak appeared. As a result of the mass spectrum measurement, [M + H] ⁺ was detected at m / z 763. The structural formula of the main component of this compound is assumed to be the above-mentioned compound (h). Next, 2 g of this compound was taken and pulverized and dispersed for 6 hours with a paint shaker together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0212]

Example 8 30 g of 2,4-toluene diisocyanate
To the mixture was added 30 g of toluene as a solvent, and 3.24 g of phenol was added thereto. 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 6.9 g of a compound as white crystals. Next, 5.0 g of this compound was taken, 100 g of toluene was added as a solvent, and 3.50 g of aniline was added thereto.
The reaction mixture was reacted for 3 hours, and the precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight to obtain a white crystalline compound 5.5.
g was obtained. Next, 2 g of this compound was taken and pulverized and dispersed with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol on a paint shaker for 45 minutes to obtain a dispersion. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0213]

Example 9 17 g of 2,4-toluene diisocyanate
To the mixture was added 40 g of methyl ethyl ketone as a solvent, 3.8 g of methanol was added dropwise, and the mixture was reacted at 60 ° C. for 5 hours with stirring. Next, 9.9 g of 4,4′-diaminodiphenylsulfone was added, and the mixture was reacted at 60 ° C. for 4 hours with stirring. After the reaction, the reaction solution was cooled to room temperature, poured into 800 g of acetonitrile, and the precipitated crystals were collected by filtration, washed with hexane, and vacuum-dried overnight to obtain 15 g of a white crystalline compound. Then take 2 g of this compound,
The mixture was ground and dispersed in a paint shaker together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol for 6 hours to obtain a dispersion. Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0214]

Example 10 Urea urethane compound developer dispersion liquid, 3
-Dibutylamino-6-methyl-7-anilinofluorane dispersion, diphenylsulfone dispersion and calcium carbonate dispersion were prepared in the same manner as in Example 1. Also, 2,2
70 g of bis (4-hydroxyphenyl) propane was ground with 130 g of a 5.4% by weight aqueous solution of polyvinyl alcohol in a sand grinder (vessel capacity: 400 ml, manufactured by IMEX Co., Ltd.) for 3 hours at a rotation speed of 2,000 rpm.
Dispersion gave a dispersion.

These dispersions were treated with a urea urethane compound dispersion at a dry solid content of 10 parts by weight, and 3-dibutylamino-6
-Methyl-7-anilinofluoran dispersion 10% by weight of dry solids, diphenylsulfone dispersion 2
0 parts by weight, 10 parts by weight of dry solids of 2,2-bis (4-hydroxyphenyl) propane dispersion, 20 parts by weight of dry solids of calcium carbonate dispersion, and solids concentration of 16 parts
The coating liquid was obtained by stirring and mixing 10 parts by weight of the dry solid content of the zinc stearate dispersion of 10% by weight and 10 parts by weight of the dry solid content of 15% by weight of polyvinyl alcohol (dry basis). Using this coating solution, a thermosensitive recording material was prepared and evaluated in the same manner as in Example 1. The results are summarized in Table 1.

[0216]

Examples 11 to 14 Instead of 2,2-bis (4-hydroxyphenyl) propane used in Example 10, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone (Nippon Soda Co., Ltd., D-8: (Product name) (Example 1)
1), bis (3-allyl-4-hydroxyphenyl) sulfone (manufactured by Nippon Kayaku Co., Ltd., TG-SA: trade name) (Example 12), 2,4′-dihydroxydiphenylsulfone (manufactured by Nika Chemical Co., Ltd.) 24BPS: trade name) (Example 1)
3), 4,4 '-[oxybis (ethyleneoxy-p-
Phenylenesulfonyl)] a mixture containing diphenol as a main component (manufactured by Nippon Soda Co., Ltd., D-90, content of perforated component 88%)
Above: A thermosensitive recording material was prepared and evaluated in the same manner as in Example 10 except that (trade name) (Example 14) was used. The results are summarized in Table 1.

[0219]

Examples 15 to 44 Instead of diphenyl sulfone used in Examples 10 to 14, β-naphthyl benzyl ether (BON: trade name, manufactured by Ueno Pharmaceutical Co., Ltd.) (Examples 15 to 19), p-benzylbiphenyl (PBBP: trade name, manufactured by Nippon Steel Chemical Co., Ltd.) (Examples 20 to 24), 1, 2
-Di (m-methylphenoxy) ethane (KS, manufactured by Sanko Co., Ltd.)
-235: trade name) (Examples 25 to 29), oxalic acid di-p-methylbenzyl ester (manufactured by Dainippon Ink and Chemicals, HS3520: trade name) (Examples 30 to 34),
1,2-diphenoxymethylbenzene (manufactured by Nichika Chemical Co., Ltd.
Examples 10-1 except that PMB-2: trade name) (Examples 35-39) and metaterphenyl (manufactured by Nippon Steel Chemical Co., Ltd., mtp: trade name) (Examples 40-44) were used, respectively.
In the same manner as in Example 4, a thermosensitive recording material was prepared and evaluated.
The results are summarized in Table 1.

[0218]

Example 45 The procedure of Example 10 was repeated, except that 1 part by weight of a stilbene-based fluorescent dye (Kayahole 3BS, trade name, manufactured by Nippon Kayaku Co., Ltd.) was added to 100 parts by weight of the dry solid content of the coating solution. A heat-sensitive recording material was prepared in the same manner as in Example 10 and evaluated. The results are summarized in Table 1.

[0219]

Example 46 2,4-Toluene diisocyanate 1
To 0.4 g, 20 g of methyl ethyl ketone was added as a solvent, and 4,4'-diaminodiphenylsulfone was added to this.
7 g was diluted with 30 g of methyl ethyl ketone and added dropwise, and reacted at room temperature for 20 hours. After the reaction, methyl ethyl ketone was concentrated and removed, and then toluene was added. The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 8.8 g of a white crystalline compound. Next, this compound 4
g, 15 g of phenol was added, and a small amount of dibutyltin dilaurate was further added, followed by reaction at 50 ° C. for 4 hours. After the reaction, toluene was added, and the precipitated crystals were collected by filtration, washed with hexane, and vacuum-dried overnight to obtain 5.2 g of a ureaurethane compound as white crystals.

Next, 30 g of toluene as a solvent was added to 10 g of 2,4-toluene diisocyanate, 30 g of phenol was added thereto, and the mixture was reacted at 100 ° C. for 3 hours. After the reaction, 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 a urethane compound as white crystals (15 g). Next, 3 g of the above urea urethane compound and 2 g of the urethane compound were taken and mixed to obtain a urea urethane compound developer. Subsequently, 2 g of the urea urethane compound developer
Was taken out and dispersed in a paint shaker for 45 minutes together with 8 g of a 2.5% by weight aqueous solution of methylcellulose 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 compound developer obtained in Example 1 was used instead of the dispersion of the compound developer obtained in Example 1. Was. The results are summarized in Table 1.

[0221]

Example 47 A urea urethane compound obtained by mixing and mixing 4.5 g of the urea urethane compound synthesized in Example 46 and 0.5 g of the urethane compound instead of the urea urethane compound developer used in Example 46. A thermosensitive recording material was prepared in the same manner as in Example 46 except that a developer was used,
An evaluation was performed. The results are summarized in Table 1.

[0222]

Example 48 Instead of the urea urethane compound developer used in Example 46, after the synthesis reaction of the urea urethane compound synthesized in Example 46, 2.2 g of diphenyl sulfone was reacted before adding toluene to precipitate. After adding to the system and stirring, toluene was added and the precipitated crystals were collected by filtration, washed with hexane, and vacuum-dried overnight to obtain 7.4 g of a white crystalline ureaurethane compound developer. In the same manner as in Example 46, a heat-sensitive recording material was prepared and evaluated. The results are summarized in Table 1.

[0223]

Comparative Example 1 A heat-sensitive recording material was prepared and evaluated 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 done. The results are summarized in Table 1.

[0224]

[Table 1] In the table, 1. The higher the optical density (OD value), the better the sensitivity of the photosensitive paper. 2. Plasticity (print storage stability) ほ と ん ど Almost no fading ○ Although there is a slight change in color tone, there is no fading. Δ: Discoloration has clearly occurred. × The print color has disappeared. 3. The higher the number, the better the whiteness. If the whiteness is 80 or more, there is no practical problem.

[0225]

As described above, according to the present invention, a recording material having excellent sensitivity (coloring characteristics), plasticizer resistance and whiteness was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 275/40 B41M 5/12 101 317/42 104 C09B 11/24 105 11/28 108 5/18 101C 104 105 (72) Inventor Kazuo Kabashima 1-3-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term in Asahi Kasei Corporation 2H026 AA07 BB04 BB06 BB12 BB24 BB28 BB30 BB39 DD02 DD40 DD43 DD45 DD48 DD53 2H085 AA07 BB02 BB02 BB12 BB24 BB28 BB30 BB39 DD02 DD40 DD43 DD45 DD48 4H006 AB76 TB13 4H056 BA02 BB01 BB05 BB15 BC01 BD01 BF02F BF26 BF26F BF28E FA03 FA04

Claims (20)

[Claims] 1. A color former comprising a colorless or pale leuco dye and a urea urethane compound developer. 2. A urea urethane compound developer comprising a urea urethane compound and a diluent. 3. The urea urethane compound developer according to claim 2, wherein the diluent is a urea compound and / or a urethane compound. 4. The urea urethane compound developer according to claim 2, wherein the diluent is a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound. 5. A urea urethane compound color developer.
The color former according to claim 1, which is a urea urethane compound developer according to any one of (1) to (4). 6. The leuco dye according to claim 1, wherein the leuco dye is at least one selected from a triarylmethane leuco dye, a fluoran leuco dye, a fluorene leuco dye, and a diphenylmethane leuco dye. The color former according to 1. 7. A leuco dye represented by the following formula (a):
6. The compound according to claim 1, wherein the compound is a compound.
Color former. Embedded image(Where Y₁And Y_TwoAre alkyl groups or
Represents a alkoxyalkyl group, Y_ThreeIs a hydrogen atom,
And an alkoxy group. Also, Y_FourAnd Y _FiveIs water
Elemental atom, halogen atom, alkyl group or alkoxy group
Represents ) 8. The color former according to claim 1, wherein the leuco dye is a compound represented by the following formula (b). Embedded image [Where R ₁ and R ₂ are represented by the formula (c) or the formula (d)
Represents any of the groups represented by Embedded image (Wherein, R ₇ to R ₁₁ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, .R _12, R ₁₃ showing a -NR ₁₂ R ₁₃ groups , Carbon number 1
8 alkyl groups. ) (Here, R ₁₄ and R ₁₅ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.) Further, R _{3 to} R ₆ represent
A hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms,
It represents an alkoxy group having 1 to 8 carbon atoms and a -NR ₁₆ R ₁₇ group.
R ₁₆ and R ₁₇ are an alkyl group having 1 to 8 carbon atoms. ] 9. The urea urethane compound developer has a melting point of:
The color former according to claim 1, wherein the temperature is 60 ° C. or more and 300 ° C. or less. 10. The urea urethane compound developer is one selected from the following formulas (VI) and (VII).
The color former according to any one of the above. Embedded image (Wherein, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, and is preferably a nitro group, a hydroxyl group, a carboxyl group, Nitroso group, nitrile group, carbamoyl group, ureido group, isocyanato group, mercapto group, may be substituted by a sulfo group, a sulfamoyl group or a halogen atom, each residue may have a substituent, γ is -SO _2- , -O-,-(S) _n
One selected from the group consisting of —, — (CH ₂ ) _n —, —CO—, —CONH—, and a group represented by formula (f): Or it shows the case where it does not exist. n is 1 or 2. ) (Wherein, the hydrogen atom of the benzene ring may be substituted, and the substituent is preferably an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue, but is preferably a hydroxyl group, a nitro group, a nitrile group, Carbamoyl group, sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group,
It may be substituted with an isocyanato group, a mercapto group, a sulfo group or a halogen atom, and each residue may have a substituent, and δ is -SO _2- , -O-,-
(S) _n -,-(CH ₂ ) _n- , -CO-, -CONH
-, - NH -, - CH (COOR 1) -, - C (C
F ₃ ) ₂ — and —CR ₂ R ₃ — represent one selected from the group consisting of, or absent, R ₁ , R ₂ and R ₃
Each independently represents an alkyl group, and n is 1 or 2. ) 11. The urea urethane compound developer may be any one of the following structural formulas (g) and (h):
The color former according to any one of claims 1 to 5, wherein Embedded image Embedded image 12. The color former according to claim 1, further comprising an acidic developer. 13. An acidic developer comprising 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4′-hydroxyphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone,
2,4'-dihydroxydiphenyl sulfone, 4,4
Any one selected from '-[oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol
The color former according to claim 12, wherein the number is at least one. 14. The color former according to claim 1, further comprising a heat-fusible substance. 15. The heat-fusible substance is β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di (m
15. It is any one or more selected from the group consisting of -methylphenoxy) ethane, di-p-methylbenzyl oxalate, 1,2-diphenoxymethylbenzene, and metaterphenyl. Color former. 16. The method according to claim 1, further comprising a fluorescent dye.
Or the color former according to any one of 5 to 15. 17. A recording material comprising a support on which a color-forming layer containing the color-forming agent according to claim 1 is provided. 18. The method according to claim 17, wherein at least one selected from a water-soluble polymer, a nonionic surfactant and an anionic surfactant is used as a dispersant for the leuco dye. Recording material. 19. A dispersing agent for the leuco dye, wherein at least one selected from the group consisting of methylcellulose, hydroxypropylmethylcellulose, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether sulfate, and sodium 2-ethylhexylsulfosuccinate is used. 18. The recording material according to claim 17, wherein: 20. The recording material according to claim 17, wherein the recording material is a thermosensitive recording material.