JP2000143611A - New color former and recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a color former excellent in image preservability and color density, and useful for a recording material (especially a thermosensitive recording material) by including an ureaurethane compound and a colorless or light- colored dye precursor. SOLUTION: This color former includes (A) an ureaurethane compound and (B) a colorless or light-colored dye precursor. The ingredient A is e.g. a compound of formula I (wherein, X, Y and Z are each an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue), a compound of formula II [wherein, α is a residue having >=2 valence; (n) is >=2], a compound of formula III [wherein, γ is SO2, O, (S)n or the like or not present; (n) is 1 or 2] or the like. The ingredient B is e.g. a triarylmethane-based compound, a diphenylmethane-based compound, a xanthene-based compound, a thiazine-based compound, a spiro-based compound or the like. The weight content ratio of (the component A/the component B) is preferably (5-1,000)%, especially preferably (20-500)%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring agent and a recording material using the same, and more particularly, to a coloring agent having improved storage stability of an uncolored portion (background) and a colored image, and a recording material using the same. In particular, it relates to a heat-sensitive recording material.

[0002]

2. Description of the Related Art Heretofore, many chemical color developing systems using recording energy such as heat and pressure have been known. Among them, a color forming system composed of a two-component color forming system of a colorless or pale-colored dye precursor and a color developing agent that forms a color in contact with the dye precursor has been known for a long time, and has been widely applied to recording materials. ing. 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.

[0003] A pressure-sensitive recording material using pressure energy has been very commonly used as if it were plain paper. In general, a pressure-sensitive recording material is obtained by dissolving a dye precursor in an appropriate solvent, emulsifying the solution 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 color developer layer containing a color developer on another support. Then, by applying a pen pressure or a pressing pressure or the like, the microcapsules are broken and the inclusions containing the dye precursor are released. This transfers to the color developer layer and comes into contact with the color developer, thereby producing a color development reaction, thereby obtaining image recording.

[0004] In recent years, for example, in various information devices such as facsimile machines, printers, recorders, and the like, a heat-sensitive recording system in which recording is performed by using thermal energy has been widely used. 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 its use has been expanded to 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 methods is to use a recording sheet in which a coloring layer containing a two-component coloring agent is provided on a support, and to which heat is applied as recording energy by a thermal 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 sheet to perform color recording. Above all, many colorants use a colorless or pale-colored electron-donating dye precursor (particularly a leuco dye) and an acidic developer such as a phenolic compound. Recording sheets using these leuco dyes, for example,
Typical examples thereof include thermal paper (see U.S. Pat. No. 3,539,375) which uses crystal violet lactone and 4,4'-isopropylidene diphenol (bisphenol A) as thermal agents.

The dye precursor and the developer used for these are mainly electron donating compounds and electron accepting compounds, respectively. This is because the reactivity of the dye precursor, which is the electron-donating compound, is high, and by contacting with the developer, which is the electron-accepting compound, a color-developed image having 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 into contact with a plasticizer contained in a plastic sheet or an eraser or a chemical contained in food or cosmetics, and the record is easily lost, or , The light resistance of the recording part is inferior, so that the recording fades or disappears after a relatively short exposure to sunlight,
There is a disadvantage that the storage stability of the recording is inferior. Due to this disadvantage, the use of the recording is under certain restrictions at present, and improvement thereof is 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 US 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 exemplified 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 a recording material that is widely used at present is particularly required to have a black color, the publication cannot obtain the 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 pale-colored dye precursor and a urea compound, but has a low color density and insufficient storage stability.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color former excellent in image storability and color density, and a recording material using the same, particularly a heat-sensitive recording material.

[0010]

Means for Solving the Problems As a result of intensive synthesis studies of various color former compounds, the present inventors have found that a specific compound exhibits surprisingly excellent performance in combination with a dye precursor. Was completed. That is, the present invention is as follows.

A first aspect of the present invention is a color former containing a urea urethane compound and a colorless or pale color dye precursor. A second aspect of the invention is the color former according to the first aspect, wherein the urea urethane compound is a compound represented by any one of the following formulas (I) to (VI).

[0012]

Embedded image (Here, X, Y, and Z represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent.)

[0013]

Embedded image (X and Y represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent.)

[0014]

Embedded image (Where X and Y 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, and n represents an integer of 2 or more. And each residue may have a substituent.)

[0015]

Embedded image (Where Z and Y 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, and n represents an integer of 2 or more. And each residue may have a substituent.)

[0016]

Embedded image (Here, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent. γ is -SO _2- , -O-,-(S) _n -,-(CH
₂ ) _n- , -CO-, -CONH-, any one of the formula (a),

[0017]

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

[0018]

Embedded image (Here, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent. δ is -SO _2- , -O-,-(S) _n -,-(CH
₂ ) _n- , -CO-, -CONH-, -NH-, -CH
(COOR ₁ ) —, —C (CF ₃ ) ₂ ——CR ₂ R ₃ —
Shows either of the above or the case where it does not exist. R ₁ , R ₂ , R
₃ represents an alkyl group, and n is 1 or 2. A third aspect of the invention is the color former according to any one of the first to second aspects of the invention, which contains an isocyanate compound.

A fourth aspect of the present invention is the color former according to any one of the first to second aspects of the present invention, which comprises an isocyanate compound and an imino compound. A fifth aspect of the invention is the color former according to any one of the first to fourth aspects of the invention, which contains an amino compound. A sixth aspect of the invention is the color former according to any one of the first to fifth aspects of the invention, which contains an acidic developer.

According to a seventh aspect of the invention, there is provided a recording material having a color-forming layer containing the color-forming agent according to any one of the first to sixth aspects of the invention provided on a support. An eighth aspect of the present invention is the recording material according to the seventh aspect, wherein the recording material is a thermosensitive recording material. Hereinafter, the present invention will be described in detail.

The urea urethane compound according to the present invention includes a urea group (-NHCONH- group) and a urethane group (-NH
COO- group). 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 becomes an excellent color developer of a colorless or pale color precursor, a color former containing both, and a recording using the same. The material has a high coloring density and excellent storage stability.

The urea urethane compound according to the present invention comprises:
A urea group (-NHCONH- group) and a urethane group (-NHCOO-
Any compound may be used as long as the group (1) is present, but is preferably an aromatic compound or a heterocyclic compound. More preferably, the urea group (-NHCONH- group) and the urethane group (-
It is desirable that a sulfone group (-SO2- group) or an anilide group (-NHCO- group) besides the direct bonding to the urea group besides the (NHCOO- group).

The method for synthesizing the urea urethane compound according to the present invention comprises a urea group (—NHCONH— group) and a urethane group (—NHCOH—).
There is no particular limitation as long as it is a method capable of forming an O-group), but a method of making 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 according to the present invention is obtained by using an isocyanate having at least two or more isocyanate groups as a starting material, and excluding at least one isocyanate group of the isocyanate and an isocyanate group and an OH group-containing compound. The urethane group can be formed by reacting, and then the remaining isocyanate group can be reacted with the amine compound to form a urea group. Alternatively, a urea group may be formed by 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 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,
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-phenylisocyanate) thiophosphate,
4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ′, 4 ″ -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, hexa Methylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate,
Dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, and the like.

Further, diisocyanate dimer such as toluene diisocyanate dimer N, N '(4,
4′-dimethyl 3,3′-diphenyl diisocyanate) uretdione (trade name Desmodur TT) and trimers such as 4,4′4 ″ -trimethyl 3,3 ′, 3 ″
-Triisocyanate 2,4.6-triphenyl cyanurate and the like. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-
Methylphenyl) urea or a polyol adduct, for example, a trimethylolpropane adduct (trade name Desmodur L) of toluene diisocyanate, an amine adduct, or the like may be used. The isocyanate compound and the isocyanate adduct compound described in Japanese Patent Application Nos. 8-225445 and 8-250623 may have two or more isocyanate groups.

A particularly preferred example is toluene diisocyanate. The toluene diisocyanate is preferably 2,4-toluene diisocyanate.
A mixture of 6-toluene diisocyanate is generally commercially available and can be obtained at low cost, but this is also acceptable. These toluene diisocyanate isomer mixtures are liquid at room temperature.

The amine compound for forming a urea group by reacting with an isocyanate which is a starting material of a urea urethane compound may be any compound having an amino group. Examples thereof include aniline, o-toluidine, m-toluidine and p-amine. Toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline,
N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,
4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,
5-dichloroaniline, 2,6-dichloroaniline,
3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-
Chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-
Propylaniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide, 4,4′-diamino-3,3′-diethyldiphenylmethane , 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-
Diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine,
Dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate,
-Iso-propyl 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-
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'-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'-diamino Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl,

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

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

P-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediene Amine, 2-aminothiophenol, 2-amino-
3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine , 4,4 '
-Diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthonic acid, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, Aromatic amines such as 4-diamino-2,3-dichloroanthraquinone;

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

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
Aliphatic amines such as diamino-2-hydroxypropane and 2-aminoethanethiol, tetrakis (1,2,2
2,6,6-pentamethyl-4-piperidyl) -1,
2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)
-1,2,3,4-butanetetracarboxylate,
1,2,3,4-butanetetracarboxylic acid
2,6,6-pentamethyl-4-piperidinol / β,
β, β ′, β′-tetramethyl-3,9- (2,4,
8,10-tetraoxaspiro [5,5] undecanediethanol condensate, 1,2,3,4-butanetetracarboxylic acid · 2,2,6,6-tetramethyl-4-piperidinol · β, β, β ', Β'-tetramethyl-3,9-
(2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate, poly [{6- (1,1,
3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2 , 6,6-tetramethyl-4-piperidyl)
Imino}], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N-
(1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, 2- (3,5-di-t-butyl-4-hydroxy Benzyl) -2-n-butylmalonic acid-bis (1,2,2
Hindered amine compounds such as 2,6,6-pentamethyl-4-piperidyl) and succinic acid-bis (2,2,6,6-tetramethyl-4-piperidienyl) ester.

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

[0036]

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

[0037]

Embedded image Y ₁ is _{-SO 2 -, - O -,} - (S) n -, - (C
H ₂ ) _n- , -CO-, -CONH-, any one of formulas (a),

[0038]

Embedded image Or indicates that it does not exist. n is 1 or 2. As the OH group-containing compound for forming a urethane group by reacting with an isocyanate, any compound having an OH group may be used. For example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, -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, -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,
-Hydroxyphenyl-4'-benzyloxyphenylsulfone, 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, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4'-hydroxy Ethyl benzoate, pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, Methyl gallate, 4-methoxyphenol, 4
-(Benzyloxy) phenol, 4-hydroxybenzaldehyde and the like.

Examples of the salicylic acid derivatives include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octoctanoyloxysalicylic acid, Examples include phenols such as 4-n-octyloxycarbonylaminosalicylic acid and 4-n-octanoyloxycarbonylaminosalicylic acid.
(However, these phenols are not preferably those having an amino group. When an amino group is present, the reactivity with an isocyanate group is higher than that of an OH group. It may be difficult to obtain.) Also, methanol, ethanol, propanol,
Butanol, pentanol, hexanol, heptanol, octanol, isopropanol, 2-pentanol, 3-hexanol, tert-butanol, ter
t-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-
Methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenylcellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin , Alcohols such as glycerol,

Polypropylene glycol, polytetramethylene ether glycol, adipate polyol,
Polyether polyols such as epoxy modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, phenolic 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-hexaneglycol, 1,9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, Polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, Shea 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 ureaurethane compound of the formula (I) according to the present invention is not particularly limited in the production method, but may be, for example, a compound represented by the general formula (VIII):
Can be obtained by reacting the OH group-containing compound of formula (I) with the isocyanate compound of formula (IX) and the amine compound of formula (X), for example, according to the following reaction formula (A).

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image (Here, X, Y, and Z represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent.)

[0046]

Embedded image The ureaurethane compound of the formula (II) according to the present invention comprises
Although the production method is not limited, it can be obtained, for example, by reacting an OH group-containing compound of the general formula (VIII) with an isocyanate compound of the general formula (IX) and water according to the following reaction formula (B).

[0047]

Embedded image The ureaurethane compound of the formula (III) according to the present invention can be produced by, for example, but not limited to, the method of formula (VIII).
It can be obtained by reacting an H group-containing compound with an isocyanate compound of the general formula (IX) and an amine compound of the general formula (XI), for example, according to the following reaction formula (C) or (D).

[0048]

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

[0049]

Embedded image

[0050]

Embedded image The ureaurethane compound of the formula (IV) according to the present invention comprises
Although the production method is not limited, for example, an amine compound of the general formula (X), an isocyanate compound of the general formula (IX), and an OH group-containing compound of the general formula (XII) can be used, for example, in the following reaction formula (E) or (F). Therefore, it can be obtained by reacting.

[0051]

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

[0052]

Embedded image

[0053]

Embedded image The general formula (VII) which can be used when synthesizing the urea urethane compounds represented by the above formulas (I) to (IV)
The compounds I) to (XII) will be described in more detail. The OH group-containing compound represented by the general formula (VIII) is not particularly limited as long as it has one or more OH groups. For example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcin , P-tert-butylphenol, p
-Tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4
-Phenylphenol, 4-hydroxyphenyl-
4′-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4′-methylphenylsulfone, 4
-Isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-
4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4
-Hydroxy-4'-isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis ( Ethyl 4'-hydroxybenzoate, 1,5-bis (4'-hydroxybenzoic acid) pentyl, 1,6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, 4-methoxyphenol , 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde and the like.

Examples of the salicylic acid derivatives include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octoctanoyloxysalicylic acid, Monophenols such as 4-n-octyloxycarbonylaminosalicylic acid and 4-n-octanoyloxycarbonylaminosalicylic acid are exemplified. Also, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane,
2,2-bis (hydroxyphenyl) pentane, 2,2
-Bis (hydroxyphenyl) heptane, catechol,
3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone,
-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, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3 ' Diphenols such as -dihydroxydiphenylamine and bis (4-hydroxy-3-methylphenyl) sulfide.

(However, those phenols which do not have an amino group are not preferred. When an amino group is present, the reactivity with the isocyanate group is higher than that of the OH group. May be difficult to obtain.) Also, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol,
2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, Phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol,
Monoalcohols such as 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol and the like can be mentioned. Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenolic 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 System polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol,
Polyols such as ethylenediamine, α-methylglucoside, sorbitol, and souce may be used. Of these, monophenols are preferably used.

The isocyanate compound of the formula (IX) 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 4, 4 ',
4 "-triisocyanatotriphenylamine, triphenylmethanetriisocyanate, tris (4-phenylisocyanate) thiophosphate, 4,4 ', 4"
-Triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ', 4 "-triisocyanatotriphenylamine,

Meta-xylylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate,
Dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like can be mentioned. Also, diisocyanate dimers, for example, N, N '(4,4'-dimethyl3,3'diphenyldiisocyanate) uretdione (trade name Desmodur TT) which is a dimer of toluene diisocyanate and 3 Monomer such as 4,4′4 ″ -trimethyl 3,
3 ', 3 "-triisocyanate 2,4.6-triphenyl cyanurate and the like. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3 isocyanato 4 -Methylphenyl) urea and polyol adducts, for example, trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L), amine adducts, etc. Also, the specifications of Japanese Patent Application Nos. 8-225445 and 8-250623. Of the isocyanate compounds and isocyanate adduct compounds described in (1), those having two or more isocyanate groups may be used, and a particularly preferred example is toluene diisocyanate.

The amine compound of the general formula (X) is not particularly limited as long as it has at least one 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-xylidine, 2,4-xylidine, 3,
4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,
5-dichloroaniline, 2,6-dichloroaniline,
3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-
Chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-
Propyl aniline, N-butyl aniline,

Methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-aminobenzoate
-Iso-propyl 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-
Phenylsulfamoylaniline, 2-methoxy-5
Benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-
p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2 -Methyl-4-
Nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, sulfanilic acid,
Metanylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4
Aromatic monoamines such as trifluoroaniline, m-aminobenzotrifluoride, 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'-diamino Diphenylmethane, 3,3'-dimethyl-4,4'-
Diaminodiphenylmethane, trizine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) ) Phenyl) sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5 , 5'-Dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'
-Diaminobiphenyl, ortho-tolidine sulfone,
2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-
Dichloro-4,4'-diaminobiphenyl, 3,3'-
Dichloro-4,4'-diaminobiphenyl, 2,2'-
Dimethyl-4,4'-diaminobiphenyl, 4,4'-
Thiodianiline, 2,2'dithiodianiline, 4,4'-
Dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,

Bis (3-amino-4-chlorophenyl)
Sulfone, bis (3,4-diaminophenyl) sulfone, 4,4′-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, 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.

Further, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
Aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6- [2′-methylimidazolyl- (1)] ethyl-S-triazine,
2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4
-Methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-
Heterocyclic compounds such as aminopropyl) morpholine amines, methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3
-(2-ethylhexyloxy) propylamine, 3-
Ethoxypropylamine, diisobutylamine, 3-
(Diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxy Propylamine, 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, and 2-aminoethanethiol. Of these, aromatic monoamines are preferably used.

The amine compound of the general formula (XI) is not particularly limited as long as it has two or more amino groups, and examples thereof include 4,4′-diamino-3,3′-diethyldiphenylmethane and 4,4 ′. -Diaminobenzanilide,
3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, dianisidine, bis [4- (M-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4 , 4'-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5 , 5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,
4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diamino Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl,

4,4'-thiodianiline, 2,2'dithiodianiline, 4,4'-dithiodianiline, 4,4'-
Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-
Diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4 ′
-Diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'- Diaminobenzophenone, 4,4'-diaminobenzophenone,
1,4-bis (4-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 1,3-
Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4
-Aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, trizine base,
o-phenylenediamine, m-phenylenediamine, p
-Aromatic amines such as phenylenediamine. Further, among the above amine compounds, the following formula (V
An aniline derivative having at least two amino groups as in II) is preferred.

[0067]

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

[0068]

Embedded image Y ₁ is _{-SO 2 -, - O -,} - (S) n -, - (C
H ₂ ) _n- , -CO-, -CONH-, any one of formulas (a),

[0069]

Embedded image Or indicates that it does not exist. n is 1 or 2. ) Further, as the OH group-containing compound of the general formula (XII), OH
The compound is not particularly limited as long as it is a compound having two or more 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′-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, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3 ' And phenols such as dihydroxydiphenylamine and bis (4-hydroxy-3-methylphenyl) sulfide. (However, these phenols are not preferably those having an amino group. When an amino group is present, the reactivity with an isocyanate group is higher than that of an OH group. It may be difficult to obtain.)

Also, polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol and amine modified polyol, ethylene glycol, Diethylene glycol, 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, trimethylolpro , Trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyols, polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, sorbitol And the like.

The ureaurethane compound of the formula (V) according to the present invention is not particularly limited in its production method.
The diamine compound of III) is prepared, for example, by the following reaction formula (G)
Alternatively, it can be obtained by reacting according to (H).

[0072]

Embedded image (Here, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent. γ is -SO _2- , -O-,-(S) _n -,-(CH
₂ ) _n- , -CO-, -CONH-, any one of the formula (a),

[0073]

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

[0074]

Embedded image

[0075]

Embedded image The ureaurethane compound of the formula (VI) according to the present invention comprises
Although the production method is not limited, it can be obtained, for example, by reacting an aniline derivative with a diisocyanatophenyl compound and a dihydroxy compound of the general formula (XIV) according to the following reaction formula (J) or (K).

[0076]

Embedded image (Here, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent. δ is -SO _2- , -O-,-(S) _n -,-(CH
₂ ) _n- , -CO-, -CONH-, -NH-, -CH
(COOR ₁ ) —, —C (CF ₃ ) ₂ ——CR ₂ R ₃ —
Shows either of the above or the case where it does not exist. R ₁ , R ₂ , R
₃ represents an alkyl group, and n is 1 or 2. )

[0077]

Embedded image

[0078]

Embedded image The compounds that can be used when synthesizing the ureaurethane compounds of the formulas (V) and (VI) according to the present invention will be described in detail below. The monophenol compound that can be used when synthesizing the compound of the formula (V) is not particularly limited as long as it is a compound having one OH group on the benzene ring, and examples thereof include phenol, cresol, xylenol, and p-ethyl. Phenol, 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,
-Isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-
4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4
-Hydroxy-4'-isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis ( Ethyl 4'-hydroxybenzoate, 1,5-bis (4'-hydroxybenzoic acid) pentyl, 1,6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, 4-methoxyphenol , 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde and the like.

Examples of the salicylic acid derivatives include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octoctanoyloxysalicylic acid, Examples thereof include phenols such as 4-n-octyloxycarbonylaminosalicylic acid and 4-n-octanoyloxycarbonylaminosalicylic acid.
(However, these phenols are not preferably those having an amino group. When an amino group is present, the reactivity with an isocyanate group is higher than that of an OH group. The diisocyanate phenyl compound that can be used when synthesizing the compounds of the formulas (V) and (VI) is not particularly limited as long as it is a phenyl isocyanate having two isocyanate groups. Although there is no particular limitation, for example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4
-Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and the like. 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.
These toluene diisocyanate isomer mixtures are liquid at room temperature.

Examples of the diamine compound of the general formula (XIII) which can be used when synthesizing the compound of the formula (V) include, for example, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diamino Benzanilide, 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'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4 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 4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,
3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,
4'-ethylenedianiline, 4,4'diamino-2,
2'-dimethyldibenzyl,

3,3'-diaminobenzophenone, 4,
4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis Aromatic diamines such as (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine and 3,3'-dichlorobenzidine And the like.

The aniline derivative which can be used when synthesizing the compound of the formula (VI) is not particularly limited as long as it is an aniline compound having one amino group on a benzene ring. -Toluidine, m
-Toluidine, p-toluidine, o-anisidine, p-
Anisidine, p-phenetidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-
p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5
-Dimethoxyaniline, 3,4-dimethoxyaniline,
p-aminoacetanilide, p-aminobenzoic acid, o-
Aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline,
o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline,
N-propylaniline, N-butylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-aminobenzoic acid-i
so-propyl, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o
-Aminobe

Nzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3- Amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide,
p- (N-phenylcarbamoyl) aniline, p- [N
-(4-chlorophenyl) carbamoyl] aniline, p
-[N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl)
Aniline, 2-methoxy-5- [N- (2'-methyl-
3'-chlorophenyl) carbamoyl] aniline, 2-
Methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5 -Diethoxy-4- (N-benzoylamino) aniline, 2,5
-Dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5
-Methylaniline, 4-sulfamoylaniline, 3-
Sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline,

Sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4 -N-
Phenylsulfamoylaniline, 2-methoxy-5
Benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-
p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2 -Methyl-4-
Nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3 4-
Trifluoroaniline, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile and the like.

The dihydroxy compounds of the general formula (XIV) which can be used when synthesizing the formula (VI) include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (hydroxyphenyl) Butane, 2,
2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 4,4′-biphenol, butyl bis (4-hydroxyphenyl) acetate,
Benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5
-Dimethyl-4-hydroxyphenyl) sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert.-butyl-4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether , 4,4'-thiodiphenol, 4,
4'-dihydroxybenzophenone, 2,2-bis (4
-Hydroxyphenyl) hexafluoropropane, 4,
4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3
And diphenols such as (-methylphenyl) sulfide. (However, those having an amino group are not preferred among these diphenols. When an amino group is present, the reactivity with an isocyanate group is higher than that of an OH group. In order to obtain the urea urethane compound according to the present invention, the reactant is mixed with an isocyanate in an organic solvent or without a solvent and reacted, and then the crystals are taken out by filtration. The desired product is obtained. A single or a plurality of reactants may be used depending on the purpose. The solvent may be any solvent as long as it does not react with the isocyanate group and the functional group of the reactant, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatics. Examples include hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and the like. In particular, methyl ethyl ketone, toluene, and the like, which dissolve the isocyanate and have low solubility of the product, are preferable. The product obtained by the above reaction operation is not necessarily a single product, and may be obtained as a mixture of compounds having different substituent positions, but may be used.

Among these ureaurethane compounds of the formulas (I) to (VI), preferred are the compounds of the formulas (II) to (IV)
The compounds of the formulas (V) to (V
It is a compound of I). The ureaurethane compound according to the present invention is a colorless or pale-colored compound which is usually a solid at room temperature. The molecular weight of the urea urethane compound of the present invention is 5000
Or less, more preferably 2,000 or less.

In the heat-sensitive recording material, a compound having a melting point is preferable, and the melting point is preferably from 40 ° C. to 5 ° C.
It is desirably in the range of 00 ° C., particularly preferably 60 ° C. to 300 ° C. The total number of urea groups and urethane groups in the urea urethane compound is preferably 20 or less, and more preferably 10 or less.

The ratio of the urea group to the urethane group is from 1: 3 to
3: 1 is preferable, and especially 1: 2 to 2: 1 is preferable. In preparing the recording material, one kind of the urea urethane compound may be used, or two or more kinds thereof may be used in combination as needed. Leuco dye, which is an example of the colorless or light-colored dye precursor 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. One.

(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-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3-diethylamino-7 -Phenylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3-diethylamino- 7
-(2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N
-Ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6 Methyl-7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-
6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6 Methyl-7-anilinofluoran, 3
-(N-ethyl-N-tetrahydrofuryl) amino-6
-Methyl-7-anilinofluoran 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.

Further, 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 Butylaminophthalide), 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-dimethylaminofluorene-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.

The urea urethane compound is preferably used in an amount of 5 to 1000% by weight, more preferably 20 to 500% by weight, based on the colorless or pale color dye precursor. An amount of the urea urethane compound of 5% by weight or more is sufficient for coloring the dye precursor, and the coloring density is high. Also,
When the amount of the urea urethane compound is 1000% by weight or less, an excessive amount of the urea urethane compound hardly remains, which is economically advantageous and preferable.

The storage stability is improved by further adding an isocyanate compound to the color former of the present invention. The isocyanate compound used in addition to the color former of the present invention,
Refers to a colorless or pale-colored aromatic isocyanate compound or heterocyclic isocyanate compound of a room temperature solid, for example,
One or more of the following isocyanate compounds are used.

2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-methoxybenzene-2,5-diisocyanate, 1-ethoxybenzene-2,4- Diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxybenzene-1,4-diisocyanate, 2,5-dibutoxybenzene-1,4
Diisocyanate, azobenzene-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-
2,6-diisocyanate, naphthalene-2,7-diisocyanate, 3,3'-dimethyl-biphenyl-4,
4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, benzophenone-
3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, bilen-3,8-di Isocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-
2,4,4'-triisocyanate, 4,4 ', 4''
-Triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ', 4''-triisocyanatotriphenylamine, p-dimethylaminophenylisocyanate, tris (4-phenylisocyanate) thiophosphate and the like. is there. If necessary, these isocyanates may be used in the form of so-called block isocyanates, which are addition compounds with phenols, lactams, oximes, etc., and diisocyanate dimers, for example, 1- It may be used in the form of isocyanurate, which is a dimer and trimer of methylbenzene-2,4-diisocyanate, or may be used as a polyisocyanate adducted with various polyols. is there. Also, water adduct isocyanates such as 2,4-toluene diisocyanate, diphenylmethane diisocyanate, phenol adduct isocyanate, amine adduct isocyanate, etc. are described in Japanese Patent Application Nos. 8-225445 and 8-250623. The isocyanate compound and the isocyanate adduct compound described in this document may be used.

The isocyanate compound is preferably used in an amount of 5 to 500% by weight, more preferably 20 to 200% by weight, based on the colorless or pale color dye precursor.
When the amount of the isocyanate compound is 5% by weight or more, the effect of improving the storage stability is sufficient, and the coloring density is high. When the content of the isocyanate compound is 500% by weight or less, excess isocyanate compound hardly remains, which is economically advantageous and preferable.

Further, by adding an imino compound to this, the storage stability is further improved. The imino compound that can be added to the color forming agent of the present invention is a compound having at least one imino group, and is a colorless or light-colored solid that is solid at room temperature. Two or more imino compounds can be used in combination depending on the purpose. Specific examples are shown below.

3-iminoisoindoline-1-one, 3
-Imino-4,5,6,7-tetrachloroisoindoline-1-one, 3-imino-4,5,6,7-tetrabromoisoindoline-1-one, 3-imino-4,5,
6,7-tetrafluoroisoindoline-1-one, 3
-Imino-5,6-dichloroisoindoline-1-one, 3-imino-4,5,7-trichloro-6-methoxy-isoindoline-1-one, 3-imino-4,5,
7-trichloro-6-methylmercapto-isoindoline-1-one, 3-imino-6-nitroisoindoline-1-one, 3-imino-isoindoline-1-spiro-dioxolan, 1,1-dimethoxy-3 -Imino-isoindoline, 1,1-diethoxy-3-imino-4,
5,6,7-tetrachloroisoindoline, 1-ethoxy-3-imino-isoindoline, 1,3-diiminoisoindoline, 1,3-diimino-4,5,6,7-tetrachloroisoindoline, 1,3-diimino-6-methoxyisoindoline, 1,3-diimino-6-cyanoisoindoline, 1,3-diimino-4,7-dithia-
5,5,6,6-tetrahydroisoindoline,

7-amino-2,3-dimethyl-5-oxopyrrolo [3,4b] pyrazine, 7-amino-2,3-
Diphenyl-5-oxopyrrolo [3,4b] pyrazine,
1-iminonaphthalimide, 1-iminodiphenimide, 1-phenylimino-3-iminoisoindoline, 1- (3'-chlorophenylimino) -3-iminoisoindoline, 1- (2 ', 5'-dichlorophenylimino) ) -3-Iminoisoindoline, 1- (2 ',
4 ', 5'-trichlorophenylimino) -3-iminoisoindoline, 1- (2'-cyano-4'-nitrophenylimino) -3-iminoisoindoline, 1-
(2'-chloro-5'-cyanophenylimino) -3-
Iminoisoindoline, 1- (2 ', 6'-dichloro-
4'-nitrophenylimino) -3-iminoisoindoline, 1- (2 ', 5'-dimethoxyphenylimino)
-3-iminoisoindoline, 1- (2 ', 5'-diethoxyphenylimino) -3-iminoisoindoline,
1- (2'-methyl-4'-nitrophenylimino)-
3-iminoisoindoline, 1- (5'-chloro-2 '
-Phenoxyphenylimino) -3-iminoisoindoline, 1- (4'-N, N-dimethylaminophenylimino) -3-iminoisoindoline, 1- (3'-
N, N-dimethylamino-4'-methoxyphenylimino) -3-iminoisoindoline, 1- (2'-methoxy-5'-N-phenylcarbamoylphenylimino)
-3-iminoisoindoline, 1- (2'-chloro-5 '
-Trifluoromethylphenylimino) -3-iminoisoindoline, 1- (5 ', 6'-dichlorobenzothiazolyl-2'-imino) -3-iminoisoindoline,
1- (6'-methylbenzothiazolyl-2'-imino)
-3-iminoisoindoline, 1- (4'-phenylaminophenylimino) -3-iminoisoindoline, 1
-(P-phenylazophenylimino) -3-iminoisoindoline,

1- (naphthyl-1'-imino) -3-iminoisoindoline, 1- (anthraquinone-1'-imino) -3-iminoisoindoline, 1- (5'-chloroanthraquinone-1 ' -Imino) -3-iminoisoindoline, 1- (N-ethylcarbazolyl-3'-imino) -3-iminoisoindoline, 1- (naphthoquinone-1'-imino) -3-iminoisoindoline, 1 −
(Pyridyl-4'-imino) -3-iminoisoindoline, 1- (benzimidazolone-6'-imino) -3-iminoisoindoline, 1- (1'-methylbenzimidazolone-6'-imino) -3-iminoisoindoline,
1- (7'-chlorobenzimidazolone-5'-imino) -3-iminoisoindoline, 1- (benzimidazolyl-2'-imino) -3-iminoisoindoline,
1- (benzimidazolyl-2'-imino) -3-imino-4,5,6,7-tetrachloroisoindoline;

1- (2 ', 4'-dinitrophenylhydrazone) -3-iminoisoindoline, 1- (indazolyl-3'-imino) -3-iminoisoindoline, 1
-(Indazolyl-3'-imino) -3-imino-4,
5,6,7-tetrabromoisoindoline, 1- (indazolyl-3'-imino) -3-imino-4,5,6,
7-tetrafluoroisoindoline, 1- (benzimidazolyl-2'-imino) -3-imino-4,7-dithiatetrahydroisoindoline, 1- (4 ', 5'-dicyanoimidazolyl-2'-imino) -3-imino-
5,6-dimethyl-4,7-pyradiisoindoline, 1
-(Cyanobenzoylmethylene) -3-iminoisoindoline, 1- (cyanocarbonamidomethylene) -3-
Iminoisoindoline, 1- (cyanocarbomethoxymethylene) -3-iminoisoindoline, 1- (cyanocarboethoxymethylene) -3-iminoisoindoline,

1- (cyano-N-phenylcarbamoylmethylene) -3-iminoisoindoline, 1- [cyano-N- (3′-methylphenyl) -carbamoylmethylene] -3-iminoisoindoline, 1- [cyano -N-
(4'-chlorophenyl) -carbamoylmethylene]-
3-iminoisoindoline, 1- [cyano-N- (4 ′
-Methoxyphenyl) -carbamoylmethylene] -3-
Iminoisoindoline, 1- [cyano-N- (3'-chloro-4'-methylphenyl) -carbamoylmethylene] -3-iminoisoindoline, 1- (cyano-p-
Nitrophenylmethylene) -3-iminoisoindoline, 1- (dicyanomethylene) -3-iminoisoindoline, 1- [cyano-1 ', 2', 4'-triazolyl- (3 ')-carbamoylmethylene] -3 -Iminoisoindoline, 1- [cyanothiazoyl- (2 ')-carbamoylmethylene] -3-iminoisoindoline, 1-
[Cyanobenzimidazolyl- (2 ')-carbamoylmethylene] -3-iminoisoindoline,

1- [Cyanobenzothiazolyl- (2 ')
-Carbamoylmethylene] -3-iminoisoindoline, 1- [cyanobenzimidazolyl- (2 ')-methylene] -3-iminoisoindoline, 1- [cyanobenzimidazolyl- (2')-methylene] -3-imino −
4,5,6,7-tetrachloroisoindoline, 1-
[(Cyanobenzimidazolyl-2 ')-methylene]-
3-imino-5-methoxyisoindoline, 1-[(cyanobenzimidazolyl-2 ')-methylene] -3-imino-6-chloroisoindoline, 1-[(1'-phenyl-3'-methyl-5 -Oxo) -pyrazolidene-
4 ']-3-iminoisoindoline, 1-[(cyanobenzimidazolyl-2')-methylene] -3-imino-
4,7-dithiatetrahydroisoindoline, 1-
[(Cyanobenzimidazolyl-2 ')-methylene]-
3-imino-5,6-dimethyl-4,7-pyradiisoindoline, 1-[(1'-methyl-3'-n-butyl)
-Barbituric acid-5 ']-3-iminoisoindoline,

3-imino-1-sulfobenzoic acid imide,
3-imino-1-sulfo-6-chlorobenzoic acid imide,
3-imino-1-sulfo-5,6-dichlorobenzoimide, 3-imino-1-sulfo-4,5,6,7-tetrachlorobenzoimide, 3-imino-1-sulfo-
4,5,6,7-tetrabromobenzoimide, 3-imino-1-sulfo-4,5,6,7-tetrafluorobenzoimide, 3-imino-1-sulfo-6-nitrobenzoimide, 3-imino-1-sulfo-6-methoxybenzoic acid imide, 3-imino-1-sulfo-4,5,7
-Trichloro-6-methylmercaptobenzoic imide,
3-imino-1-sulfonaphthoic imide, 3-imino-1-sulfo-5-bromonaphthoic imide, 3-imino-2-methyl-4,5,6,7-tetrachloroisoindoline-1-one and the like. is there.

Of these, iminoisoindoline derivatives are particularly preferred, and 1,3-diimino-4,
5,6,7-tetrachloroisoindoline, 3-imino-4,5,6,7-tetrachloroisoindoline-1-
On, 1,3-diimino-4,5,6,7-tetrabromoisoindoline is preferred. The imino compound is preferably used in an amount of from 5 to 500% by weight, more preferably from 20 to 200% by weight, based on the colorless or pale color dye precursor.
It is. When the amount of the imino compound is 5% by weight or more, the effect of improving storage stability is exhibited. Further, when the imino compound content is 500% by weight or less, excess imino compound hardly remains, which is economically advantageous and preferable.

Further, by adding an amino compound to the color former of the present invention, the background and the storage stability of the print are improved. Amino compounds that can be added include at least one 1
It is a colorless or pale-colored substance having a secondary or secondary or tertiary amino group. Specific examples of these amino compounds include tallow or coconut oil-derived aliphatic amines, cetylamine, stearylamine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, -iso-propyl 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-
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'-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'-diamino Biphenyl, 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, bis (4-amino Phenyl) sulfone, bis (3-aminophenyl) sulfone, 3,4′-diaminodiphenyl sulfone,

3,3'-diaminodiphenylmethane,
4,4'-ethylenedianiline, 4,4'diamino-
2,2'-dimethyldibenzyl, 4,4'-diamino-
3,3'-dichlorodiphenylmethane, 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,
4-aminobenzonitrile, 3-aminobenzonitrile, p-phenylenediamine, m-phenylenediamine, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-diaminodiphenylmethane, 4,4'-
Aniline derivatives such as methylenebis-O-toluidine, 4,4 ′-(p-phenyleneisopropylidene) -bis- (2,6-xylidine);

Further, acetoguanamine, 2,4-diamino-6- [2′-methylimidazolyl- (1)] ethyl-S-triazine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, Heterocyclic compounds such as 3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine and tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-
Piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid
1,2,2,6,6-pentamethyl-4-piperidinol β, β, β ′, β′-tetramethyl-3,9-
(2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate, 1,2,3,4-butanetetracarboxylic acid · 2,2,6,6-tetramethyl-4
-Piperidinol-β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate;

Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4
-Diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6
-Tetramethyl-4-piperidyl) imino}], N,
N'-bis (3-aminopropyl) ethylenediamine
2,4-bis [N-butyl-N- (1,2,2,6,6
-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid -Bis (1,2,2,6,6-pentamethyl-4-piperidyl), bis-succinate (2,2,6,
Hindered amine compounds such as 6-tetramethyl-4-piperidienyl) ester are included.

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

[0113]

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

[0114]

Embedded image Y ₁ is _{-SO 2 -, - O -,} - (S) n -, - (C
H ₂ ) _n- , -CO-, -CONH-, any one of formulas (a),

[0115]

Embedded image Or indicates that it does not exist. n is 1 or 2. The amino compound may be used alone or as a mixture of two or more kinds. In order to improve the print preservability in the plasticizer resistance, the amino compound is used in an amount of 1 to 500% by weight based on the colorless or pale color dye precursor. %. When the content of the amino compound is 1% by weight or more with respect to the urea urethane compound, improvement in print preservability can be obtained. If it is used in an amount of 500% by weight or less, the performance is sufficiently improved and the cost is advantageous.

The sensitivity of the color former of the present invention is improved by further adding an acidic developer, whereby a clear color developer can be obtained. As the acidic developer when the color former of the present invention is used as a heat-sensitive recording material, generally used electron-accepting substances are used. Alternatively, a metal salt thereof, an N, N-diarylthiourea derivative, a sulfonylurea derivative and the like are preferable. Particularly preferred are phenol derivatives, specifically,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (hydroxyphenyl) butane, 2,2-
Bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, 4-hydroxy Phenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-
Isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-
4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, bis (2-methyl-3-tert.-butyl-4-hydroxyphenyl) sulfide, methyl 4-hydroxybenzoate, 4-hydroxy Benzyl benzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4'-hydroxybenzoic acid) ethyl, 1,5-bis (4'-hydroxybenzoic acid) pentyl, 1,6 -Bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate and the like. Examples of salicylic acid derivatives include 4-n-octyloxysalicylic acid and 4-n-octyloxysalicylic acid.
-Butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n
-Octoctanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid and the like. Examples of sulfonylurea derivatives include 4,4-
Bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4-bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylsulfide, 4,4-bis ( p-
Toluenesulfonylaminocarbonylamino) diphenyl ether, N- (p-toluenesulfonyl) -N'-
Examples include compounds containing one or more arylsulfonylaminoureido groups such as phenylurea.

Further, in order to improve the background fogging and the thermal responsiveness, N-stearyl-N '-(2-hydroxyphenyl) urea, N-stearyl-N'-(3-hydroxyphenyl) urea, N-stearyl-N '-(3-hydroxyphenyl) urea Stearyl-N ′-(4-hydroxyphenyl) urea, p-stearoylaminophenol, o-stearoylaminophenol, p-lauroylaminophenol, p-butyrylaminophenol, m-acetylaminophenol, o-acetylaminophenol, p-acetylaminophenol, o-butylaminocarbonylphenol, o-stearylaminocarbonylphenol, p-stearylaminocarbonylphenol, 1,1,3-tris (3-tert.
-Butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-tert.-butyl-4)
-Hydroxy-6-ethylphenyl) butane, 1,1,
3-tris (3,5-di-tert.-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-
tert. -Butyl-4-hydroxy-6-methylphenyl) propane, 1,2,3-tris (3-tert.
-Butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-phenyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-5) -Methylphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-
Tetra (3-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetra (3-cyclohexyl-
4-hydroxy-6-methylphenyl) propane, 1,
1-bis (3-tert.-butyl-4-hydroxy-
It is also possible to add phenol compounds such as 6-methylphenyl) butane and 1,1-bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane.

The color developer is preferably used in an amount of 5 to 500% by weight, more preferably 20 to 200% by weight, based on the colorless or pale color dye precursor. When the amount of the acidic developer is 5% by weight or more, the coloring of the dye precursor is good, and the coloring density is high. Also, at an acid developer of 500% by weight or less,
An acidic developer hardly remains, which is economically advantageous and preferable.

When the color former of the present invention is used as a pressure-sensitive recording material, the image density is improved by adding an acidic developer, and a clear color-developed pressure-sensitive recording material can be obtained. As the acidic developer, an electron-accepting substance is also used. Examples thereof include acid clay, activated clay, attapulgite, benite, zeolite, colloidal silica, magnesium silicate, talc, aluminum silicate, and the like. Inorganic compounds, or phenol, cresol, butylphenol, octylphenol, phenylphenol, chlorophenol, salicylic acid or the like, or an aldehyde condensed novolak resin derived therefrom and a metal salt 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-
Salicylic acid derivatives such as octylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3,5-di (α, α-dimethylbenzyl) salicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, and their metals And the like.

A recording material can be obtained by forming a color-forming layer on any support with the color-forming agent of the present invention by a method such as coating. The configuration differs depending on the type of recording material. The coloring agent 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 that develops color by heating is provided on the support. Specifically, the above urea urethane compound, a colorless or light-colored dye precursor such as a leuco dye, a heat-fusible substance to be described later, etc. are coated on a support together with other necessary components in the form of a dispersion. It is necessary to use a heat-sensitive recording layer. 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 liquid is preferably 0.1 to 10 μm, particularly preferably about 1 μm. In particular, when the urea urethane compound is wet-pulverized in an aqueous solvent, it is desirable to maintain the liquid temperature of the aqueous solvent at 50 ° C. or lower. The pH of the coating solution containing the urea urethane compound and the colorless or pale color dye precursor 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, stearic acid amide, caster wax, etc .; dispersants such as dioctyl sodium sulfosuccinate; ultraviolet absorbers such as benzophenone and benzotriazole; surfactants and fluorescent dyes Etc. 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 for the heat-sensitive recording layer, paper is mainly used. In addition to paper, various woven fabrics, non-woven 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 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. Further, a protective layer composed of one layer or a plurality of layers may be provided on the heat-sensitive recording layer, or between the support and the heat-sensitive recording layer.
A layer or an intermediate layer composed of a plurality of layers may be provided. 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. The coating amount is 1 to 15 g /
m ² is preferred.

When the coloring agent of the present invention is used as a heat-sensitive recording material, a heat-fusible substance can be contained in the coloring agent in order to improve the sensitivity. The heat-fusible substance preferably has a melting point of 60C to 180C, and particularly preferably has a melting point of 80C to 140C. For example, benzyl p-benzyloxybenzoate, stearamide, palmitamide, N-methylol stearamide, 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, 1-methoxy-4-benzyloxynaphthalene, N
-Stearoyl urea, p-benzylbiphenyl, 1,
2-di (m-methylphenoxy) ethane, 1-phenoxy-2- (4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate, metaterphenyl, dibenzyl oxalate, oxalic acid (Pchloro Benzyl) ester and the like. Furthermore, 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, or the like may be used.

Of these, diphenyl sulfone is preferably used. The heat-fusible substance may be used alone or as a mixture of two or more kinds, and in order to obtain a sufficient thermal response, 10 to 300 weight parts with respect to a colorless or pale color dye precursor. %, More preferably 20 to 250% by weight.

When the recording material is a pressure-sensitive recording material, for example, US Pat.
Nos. 07, 2730456 and 273045
7 and 3,418,250 can be employed. That is, the dye precursors are used alone or in combination, and synthetic oils such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethane, and chlorinated paraffin, and vegetable oils, animal oils, and mineral oils alone are used. Alternatively, an upper paper obtained by dissolving in a solvent composed of a mixture and dispersing the same in a binder, or applying a dispersion liquid contained in microcapsules together with a binder or the like on a support, and a urea urethane compound (and Pressure-sensitive recording paper with the coated surfaces of the lower paper coated with a dispersion of an amino compound and / or a developer) or a dispersion of a urea urethane compound coated on one side and a dye precursor on the other side Pressure-sensitive recording paper with the middle paper coated with the body sandwiched between the upper paper and the lower paper, or the same A dispersion of the above urea urethane compound (and amino compound and / or color developer) and a dispersion containing the above dye precursor, or a multi-layer coated self-type, or a dye precursor, urea urethane compound (and Various forms such as a self-type in which any one of an amino compound and / or a developer is microencapsulated and mixed and applied are possible.

As the method for producing the microcapsules, the coacervation method disclosed in US Pat. Nos. 2,800,457 and 2,800,458, and JP-B-38-1
9574, 42-446, 42-77
No. 1, JP-B-36-91.
No. 68, Japanese Patent Publication No. 51-9079, the in-situ method disclosed in British Patent No. 952807,
96-5074, etc., the melting dispersion cooling method disclosed in U.S. Pat. No. 3,111,140, and British Patent No. 930.
For example, a spray drying method disclosed in Japanese Patent No. 422 or the like can be employed.

The color former of the present invention corresponds to the dye precursor and the developer in the above publications. In forming the pressure-sensitive recording layer, each component such as a urea urethane compound may be used by dissolving it in a solvent or by dispersing it. In the case of a coloring system containing an amino compound and / or a color developing agent, they are used alone or in combination with a urea urethane compound and an amino compound, and, if necessary, in combination with a color developing agent, dissolved or dispersed in a solvent. I just need.

In the above-described interfacial polymerization method used for 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, use a polyamine in the aqueous phase, use a polyamide film in the interface, use a polyhydroxy compound in the water phase, use a polyester film, and use the polyisocyanate in the oil phase. It is known to form a polyurethane film using a polyhydric alcohol or polyhydric phenol in an aqueous phase when a naat is used, and a polyurea film using a polyhydric amine in an aqueous phase. 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 microcapsule and does not directly participate 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.
Preparation of the dispersion of the compound without microencapsulation
It can be obtained by finely pulverizing one or more of each compound in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer or a surfactant. Further, the urea urethane compound may be dispersed simultaneously with the amino compound and 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. Examples of the binder include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, 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 copolymers, alkali salts of ethylene / maleic anhydride copolymers, and styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, and methyl acrylate / butadiene copolymers And latex 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),
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′-diphenylacrylate, tetra (2,2,6,6-tetramethyl-4-piperidyl) 1,2,2 3,4-butanetetracarboate and the like.

[0134]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following 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., and using a KJT-256-8MGF1 manufactured by Kyocera, the color density at an applied voltage of 24 V and a pulse width of 1.5 msec was measured with an optical densitometer. <Plasticizer resistance> A thermosensitive recording sheet is sandwiched between vinyl chloride wraps or vinyl chloride files, and 300 g / c from the top.
m ² , and allowed to stand at 40 ° C. for 24 hours. After the standing, the density of the printed portion and the unprinted portion (background) was visually evaluated.
Those with little decoloration of print density were regarded as having good print storability. <Heat resistance> The heat-sensitive recording sheet was allowed to stand for 24 hours in an environment of 60 ° C. and 25% RH, and the fading density of the print was visually evaluated. <Pressure-sensitive paper color density> The upper paper and the lower paper were superposed so that the coated surfaces faced each other and pressed to obtain a color image on the lower paper. The density of the color image was measured using a densitometer Macbeth RD917. <Solvent resistance> Hand cream (product name: ATRIX (manufactured by Kao Corporation)) on the color image area obtained by the evaluation of color density
Was coated thinly and allowed to stand at room temperature for 7 days, and then the density of the printed portion was visually evaluated.

[0135]

Example 1 2,4-Toluene diisocyanate
To 4 g, 20 g of methyl ethyl ketone was added as a solvent, and 3.7 g of 4,4'-diaminodiphenylsulfone was diluted with 30 g of methyl ethyl ketone and added dropwise.
The reaction was performed for 0 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, 4 g of this compound was taken, 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 dried in vacuo overnight to obtain 5.2 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. Also, 3
70 g of dibutylamino-6-methyl-7-anilinofluoran in 8% by weight aqueous solution of polyvinyl alcohol 130
g with sand grinder (vessel capacity 400m
l, manufactured by Imex Co., Ltd.) and pulverized and dispersed at 2000 rpm for 3 hours to obtain a dispersion.

Further, 70 g of diphenyl sulfone was pulverized and dispersed together with 130 g of an 8% by weight aqueous solution of polyvinyl alcohol in a sand grinder (vessel capacity: 400 ml, manufactured by Imex) for 3 hours at a rotation speed of 2000 rpm 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-anilinofluoran 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 solid 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 of polyvinyl alcohol (dry basis).

This coating solution was applied to a base paper having a weighing of 50 g / m ² with a rod No. 10 of a bacoater, dried and treated with a super calender to obtain a thermosensitive recording material. The evaluation result of the sensitivity was as good as the optical density of 1.3. The evaluation result of the degree of discoloration (heat resistance) of the background due to heat was good with little discoloration. The evaluation result of the covering property with the vinyl chloride wrap was good with little discoloration. The results are shown in Table 1.

[0140]

Example 2 30 g of 2,4-toluene diisocyanate
To the mixture was added 30 g of toluene as a solvent, 3.24 g of phenol was added thereto, and the mixture was reacted at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 1.5 g of this compound was taken, toluene was added as a solvent, and 1.44 g of 2-methoxy-5-N, N-diethylsulfamoylaniline was added. The mixture was reacted at 50 ° C. for 16 hours, and the precipitated crystals were collected by filtration. Thereafter, it was washed with hexane and dried under vacuum overnight to obtain 2.3 g of a compound as white crystals.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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.

[0142]

Example 3 30 g of 2,4-toluene diisocyanate
To the mixture was added 30 g of toluene as a solvent, 3.24 g of phenol was added thereto, and the mixture was reacted at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 2 g of the compound was taken, methyl ethyl ketone was added as a solvent, and 0.9 g of 3,3′-diaminodiphenylsulfone was added. The mixture was reacted at 50 ° C. for 22 hours, and the precipitated crystals were collected by filtration, washed with hexane, and vacuumed overnight. Drying gave 2.5 g of a compound as white crystals.

Next, 2 g of this compound was taken, and 2.5% by weight was obtained.
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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.

[0144]

Example 4 40 g of 2,4-toluene diisocyanate
Then, 100 g of toluene was added as a solvent, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise thereto, and reacted at 5 ° C. for 1 hour. After the reaction, a white solid precipitated was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 4 g of the compound was taken, 40 g of methyl ethyl ketone was added as a solvent, and 4.23 g of phenol was diluted with 10 g of methyl ethyl ketone. The mixture was reacted at 90 ° C. for 3 hours, and cooled at 5 ° C. for 6 days. The crystals were collected and dried overnight under vacuum to obtain 2.58 g of a compound as white crystals.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 2 summarizes the results
Shown in

[0146]

Example 5 30 g of 2,4-toluene diisocyanate
To the mixture was added 30 g of toluene as a solvent, 3.24 g of phenol was added thereto, and the mixture was reacted at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals.

Next, 5.4 g of this compound was taken, toluene was added as a solvent, 0.9 g of water was added thereto, a little amount of dibutyltin dilaurate was further added, and the mixture was reacted at room temperature for 10 hours. Washing and drying under vacuum overnight gave 2.1 g of a compound as white crystals. 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 sheet 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. Table 2 summarizes the results.

[0149]

Example 6 40 g of 2,4-toluene diisocyanate
Then, 100 g of toluene was added as a solvent, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise thereto, and reacted at 5 ° C. for 1 hour. After the reaction, a white solid precipitated was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 3 g of this compound was taken, 60 g of methyl ethyl ketone was added as a solvent, and a small amount of dibutyltin dilaurate was added. And reacted for 16 hours. After the reaction, the crystals were collected by filtration, washed with methyl ethyl ketone, and vacuum dried overnight to obtain 2.1 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight was obtained.
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 2 summarizes the results
Shown in

[0151]

Example 7 2,4-Toluene diisocyanate
To 2 g, 124 g of methyl ethyl ketone and 15 g of dimethylformamide as a solvent were added, and 6.3 g of 4,4'-diaminodiphenylsulfone was added thereto.
Dilute with 5 g and 3 g of dimethylformamide and add dropwise.
The reaction was performed at 5 ° C. for 8 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 toluene, and dried in vacuo overnight to obtain 10.0 g of a white crystalline compound. Next, 8.4 g of this compound was taken, 33 g of phenol and 180 g of methyl ethyl ketone were added, and 8.5 mg of triethylamine was further added.
Was added, and the mixture was reacted at 25 ° C. for 7 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 a white crystalline compound 10.0.
g was obtained.

Next, 2 g of this compound was taken, and 2.5% by weight was obtained.
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 1 summarizes the results
Shown in

[0153]

Example 8 2,4-Toluene diisocyanate
155 g of toluene was added as a solvent to 5 g, and 2,
3.2 g of 2-bis (4-hydroxyphenyl) propane
And reacted at 80 ° C. for 12 hours. After the reaction, the reaction solution was cooled to −20 ° C., and the precipitated white solid was collected by filtration, dissolved in chlorobenzene, hexane was added, and the precipitated crystals were collected by filtration and dried in vacuo overnight to give a white crystalline compound. 8.0 g were obtained. Next, 4 g of this compound was taken, 50 g of toluene was added as a solvent, 4 g of aniline was added, and the mixture was reacted at 25 ° C. for 24 hours. After the reaction, the precipitated crystals were collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 5.0 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 1 summarizes the results
Shown in

[0155]

Example 9 2,4-Toluene diisocyanate 27.
To 8 g, 111 g of toluene as a solvent was added, and 7.4 g of aniline dissolved in 37 g of toluene was added dropwise thereto, and the mixture was reacted at 10 ° C. for 8 hours. After the reaction, the precipitated white solid was collected by filtration, and then dried under vacuum overnight to obtain 20.0 g of a compound as white crystals. Next, 6.6 g of this compound was taken, 20 g of dimethylformamide was added as a solvent, and 2.7 g of 2,2-bis (4-hydroxyphenyl) propane was added thereto, followed by reaction at 15 ° C. for 5 hours. After the reaction,
8 g of acetone was added to the reaction solution, 160 g of water was further added, and the precipitated crystals were collected by filtration and dried in vacuo overnight to obtain 9.3 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 1 summarizes the results
Shown in

[0157]

Example 10 2,4-Toluene diisocyanate 2
To 7.8 g, 111 g of toluene as a solvent was added, and 7.4 g of aniline dissolved in 37 g of toluene was added dropwise thereto, and the mixture was reacted at 10 ° C. for 8 hours. After the reaction, the precipitated white solid was collected by filtration, and then dried under vacuum overnight to obtain 20.0 g of a compound as white crystals. Then 2.8 g of this compound
And as a solvent, 65 g of toluene was added.
-Bis (4-hydroxyphenyl) propane 1.14 g
And 2.7 mg of dibutyltin dilaurate,
For 7 hours. After the reaction, the reaction solution was concentrated, acetone was added, 160 g of water was further added, and the precipitated crystals were collected by filtration and vacuum-dried overnight to obtain 3.5 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 1 summarizes the results
Shown in

[0159]

Example 11 2,4-Toluene diisocyanate 2
To 7.8 g, 111 g of toluene as a solvent was added, and 7.4 g of aniline dissolved in 37 g of toluene was added dropwise thereto, and the mixture was reacted at 10 ° C. for 8 hours. After the reaction, the precipitated white solid was collected by filtration, and then dried under vacuum overnight to obtain 20.0 g of a compound as white crystals. Then 4.7 g of this compound
Was taken as a solvent, and 30 g of methyl ethyl ketone was added. To this, 1.0 g of 2,2-bis (4-hydroxyphenyl) propane and 4.7 mg of dibutyltin dilaurate were added and reacted at 75 ° C. for 4 hours. After the reaction, the reaction solution was concentrated, acetone was added, 160 g of water was further added, and the precipitated crystals were collected by filtration and vacuum-dried overnight to obtain 3.0 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight was obtained.
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 1 summarizes the results
Shown in

[0161]

Example 12 2,4-Toluene diisocyanate 30
30 g of toluene as a solvent was added to the g, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 2.7 g of this compound was taken, 30 g of dimethylformamide was added as a solvent, 1.2 g of 4,4'-diaminobenzanilide was added, and 3 mg of dibutyltin dilaurate was further added, followed by reaction at 25 ° C. for 24 hours.
The reaction solution was charged with methanol, and the precipitated crystals were collected by filtration, washed, and dried in vacuo overnight to give a white crystalline compound 2.3.
g was obtained.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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.

[0163]

Example 13 2,4-Toluene diisocyanate 1
To 0.4 g, 20 g of methyl ethyl ketone was added as a solvent, and 3,3′-diaminodiphenylsulfone was added to this.
7 g was diluted with 30 g of methyl ethyl ketone and added dropwise.
The reaction was performed at 5 ° C. for 3 hours. The precipitated white solid was collected by filtration, washed with hexane, and dried under vacuum overnight to obtain 6.3 g of a white crystalline compound. Then 3.0 g of this compound
Was added, 15 g of phenol was added, and 3 mg of dibutyltin dilaurate was further added, followed by a reaction at 50 ° C. for 3 hours. After the reaction, hexane was added to the reaction solution, and the precipitated crystals were collected by filtration, washed, and dried in vacuo overnight to obtain 3.3 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 1 summarizes the results
Shown in

[0165]

Example 14 2,4-Toluene diisocyanate 40
To the resulting solution, 100 g of toluene was added as a solvent, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise.
For 1 hour. After the reaction, a white solid precipitated was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 5 g of this compound was taken, 40 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. This is p-
2.58 g of methoxyphenol was added to methyl ethyl ketone 1
After diluting with 0 g and adding and reacting at 90 ° C. for 6 hours, the reaction solution was poured into hexane, and the precipitated crystals were collected by filtration and dried under vacuum overnight to obtain 3.7 g of a compound of white purple crystals.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 2 summarizes the results
Shown in

[0167]

Example 15 2,4-Toluene diisocyanate 40
To the resulting solution, 100 g of toluene was added as a solvent, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise.
For 1 hour. After the reaction, a white solid precipitated was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 5 g of this compound was taken, 40 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. This is p-
After diluting 2.22 g of cresol with 10 g of methyl ethyl ketone and reacting at 90 ° C. for 6 hours, the reaction solution was poured into hexane, and the precipitated crystals were collected by filtration and dried in vacuo overnight to give a white crystalline compound. 7 g were obtained.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 2 summarizes the results
Shown in

[0169]

Example 16 2,4-Toluene diisocyanate 40
To the resulting solution, 100 g of toluene was added as a solvent, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise.
For 1 hour. After the reaction, a white solid precipitated was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 5 g of this compound was taken, 40 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. This is p-
2.64 g of chlorophenol was added to methyl ethyl ketone 10
The reaction mixture was poured into hexane, and the precipitated crystals were collected by filtration.
The residue was dried under vacuum overnight to obtain 1.1 g of a compound as white crystals.

Next, 1 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 4 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 2 summarizes the results
Shown in

[0171]

Example 17 2,4-Toluene diisocyanate 40
100 g of toluene as a solvent was added to the g, and 5.66 g of p-methoxyaniline was diluted with 40 g of toluene and added dropwise, and reacted at 10 ° C. for 1 hour. The white purple solid precipitated after the reaction was recovered by filtration, washed with hexane, and dried in vacuo overnight to obtain 13.4 g of a compound of white purple crystals. Next, 5 g of this compound was taken, 65 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added.
added. After diluting 2.37 g of phenol with 15 g of methyl ethyl ketone and reacting at 90 ° C. for 4 hours,
The reaction solution was concentrated, cooled at 5 ° C. for 1 day, and the precipitated crystals were collected by filtration and vacuum-dried overnight to obtain 2.50 g of a compound as white purple crystals.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 2 summarizes the results
Shown in

[0173]

Example 18 2,4-Toluene diisocyanate 40
100 g of toluene as a solvent was added to the resulting mixture, and 6.21 g of p-aminoacetophenone was diluted with 30 g of toluene and 30 g of methyl ethyl ketone, and added dropwise.
Allowed to react for hours. The white solid precipitated after the reaction was recovered by filtration, washed with hexane, and dried in vacuo overnight to obtain 13.0 g of a white crystalline compound. Next, 5 g of this compound was taken, 65 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. After diluting 2.28 g of phenol with 15 g of methyl ethyl ketone and reacting at 90 ° C. for 4 hours, the reaction solution was concentrated, cooled at 5 ° C. for 1 day, and the precipitated crystals were collected by filtration and dried in vacuo overnight. Thus, 1.0 g of a compound as white crystals was obtained.

Next, 1 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 4 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 2 summarizes the results
Shown in

[0175]

Example 19 2,4-Toluene diisocyanate 30
30 g of toluene as a solvent was added to the g, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 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 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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. Table 2 summarizes the results.

[0177]

Example 20 2,4-Toluene diisocyanate 30
30 g of toluene as a solvent was added to the g, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 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 3.00 g of p-toluidine was added thereto. The mixture was reacted at 25 ° C. for 3 hours, and the precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight. Thus, 5.5 g of a white crystalline compound was obtained.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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. Table 2 summarizes the results.

[0179]

Example 21 2,4-Toluene diisocyanate 30
30 g of toluene as a solvent was added to the g, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 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, 3.58 g of p-chloroaniline was added, and the mixture was reacted at 25 ° C. for 6 hours. The precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight. As a result, 7.0 g of a compound as white purple crystals was obtained. Then take 2 g of this compound,
The mixture was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5% by weight aqueous polyvinyl alcohol solution to obtain a dispersion.

Subsequently, a thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1.
Table 2 summarizes the results.

[0181]

Example 22 Diphenylmethane-4,4'-diisocyanate was added to 10 g of methyl ethyl ketone 120 as a solvent.
g was added thereto, and 3.72 g of aniline was diluted with 15 g of methyl ethyl ketone and added dropwise, and reacted at 25 ° C. for 3 hours. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to give compound 1 as white crystals.
1.8 g were obtained. Next, 5 g of this compound was taken, 80 g of methyl ethyl ketone was added as a solvent, 2.06 g of phenol was diluted with 15 g of methyl ethyl ketone, and the mixture was reacted at 70 ° C. for 8 hours. The reaction solution was concentrated and cooled, and the precipitated crystals were filtered. And vacuum dried overnight to obtain 2.7 g of a compound as white crystals.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
A heat-sensitive recording sheet 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. Table 2 summarizes the results
Shown in

[0183]

Example 23 2,4-Toluene diisocyanate 30
30 g of toluene as a solvent was added to the g, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 2.0 g of this compound was taken, 30 g of toluene was added as a solvent, and paraphenylenediamine 0.41 was added thereto.
g was added and reacted at 50 ° C. for 10 hours. The precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 2.3 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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. Table 2 summarizes the results.

[0185]

Example 24 2,4-Toluene diisocyanate 30
30 g of toluene as a solvent was added to the g, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 2.0 g of this compound was taken, 30 g of toluene was added as a solvent, 0.90 g of o-dianisidine was added, and the mixture was reacted at 50 ° C. for 6 hours, and the precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight. As a result, 2.6 g of a white crystalline compound was obtained.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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. Table 2 summarizes the results.

[0187]

Example 25 2,4-Toluene diisocyanate 30
30 g of toluene as a solvent was added to the g, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 2.0 g of the compound was taken, 30 g of toluene was added as a solvent, 0.75 g of 4,4'-diaminodiphenyl ether was added, and the mixture was reacted at 50 ° C. for 16 hours. The precipitated crystals were collected by filtration and washed with hexane. After vacuum drying overnight, 2.4 g of a white crystalline compound was obtained.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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. Table 2 summarizes the results.

[0189]

Example 26 2,4-Toluene diisocyanate 30
30 g of toluene as a solvent was added to the g, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 2.0 g of this compound was taken, 30 g of toluene was added as a solvent, 0.74 g of 4,4'-diaminodiphenylmethane was added together with 10 g of methyl ethyl ketone, and the reaction was carried out at 50 ° C. for 10 hours. And dried under vacuum overnight to obtain 2.1 g of a compound as white crystals.

Next, 2 g of this compound was taken, and 2.5% by weight
It was pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. continue,
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. Table 2 summarizes the results.

[0191]

Comparative Example 1 A heat-sensitive recording sheet 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.

[0192]

Comparative Example 2 A thermosensitive recording sheet was prepared and evaluated in the same manner as in Example 1 except that 4,4'-diphenylurea was used instead of the urea urethane compound synthesized in Example 1. Table 2 summarizes the results.

[0193]

[Table 1]

[0194]

[Table 2]

[0195]

EXAMPLE 27 Preparation of Top Paper 3-Diethylamino-7-chlorofluorane 2.5 in 100 parts by weight of a 5% aqueous solution of pH 4.0 in which a styrene-maleic anhydride copolymer was dissolved together with a small amount of sodium hydroxide. 80 parts by weight of Nisseki Hisol N-296 (trade name, Nippon Petrochemical Oil) in which parts by weight were dissolved were emulsified.
On the other hand, melamine 10 parts by weight, 37% formalin aqueous solution 2
5 parts by weight and 65 parts by weight of water are adjusted to pH 9 with sodium hydroxide.
When the temperature was set to 0 and heated to 60 ° C., the mixture became transparent in 15 minutes, and a melamine-formalin precondensate was obtained. This initial condensate is added to the emulsion,
After stirring for an hour, the mixture was cooled to room temperature. The solid content of the obtained microcapsule dispersion was 45%.

The thus obtained microcapsule dispersion was applied to paper and dried to obtain an upper paper. Preparation of Lower Paper To 30 g of 2,4-toluene diisocyanate was added 30 g of toluene as a solvent, and 3.24 g of phenol was added thereto, followed by a reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added. The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 2 g of this compound was taken, methyl ethyl ketone was added as a solvent, and 0.9 g of 4,4'-diaminodiphenylsulfone was added thereto. The mixture was reacted at 50 ° C. for 22 hours, and the precipitated crystals were collected by filtration, washed with hexane and vacuumed overnight. Drying yielded 2.3 g of a compound as white crystals.

Next, 15 g of this compound was taken and pulverized and dispersed together with 45 g of a 2% by weight aqueous solution of polyvinyl alcohol at room temperature for 45 minutes using a paint shaker to obtain a dispersion.
Further, 60 g of calcium carbonate was mixed with 90 g of water, and the mixture was stirred and dispersed with a stirrer to obtain a dispersion. The coating liquid was 40 parts by weight of the above compound dispersion, 125 parts by weight of a calcium carbonate dispersion, and a 10% by weight aqueous solution of polyvinyl alcohol 1
20 parts by weight were obtained by mixing and stirring.

This coating solution was applied to base paper having a basis weight of 40 g / m ^{2 using} a bar coater rod No. 10 to obtain a lower paper. The evaluation result of the coloring density was as good as the optical density of 0.7. The evaluation result of the solvent resistance with the hand cream was good because the printed portion could be read. Table 3 summarizes the results.

[0199]

Comparative Example 3 A pressure-sensitive recording material was prepared and evaluated in the same manner as in Example 8, except that activated terra clay as a color developer was used instead of the urea urethane compound used in Example 5. Table 3 summarizes the results.

[0200]

[Table 3]

[0201]

By using a specific urea urethane compound, a color former and a recording material having excellent image storability and color sensitivity can be provided at low cost.

Claims (8)

[Claims] 1. A color former containing a urea urethane compound and a colorless or pale color dye precursor. 2. The urea urethane compound represented by the following formula (I):
The color former according to claim 1, which is a compound represented by any of (VI). Embedded image (Here, X, Y, and Z represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Further, each residue may have a substituent.) ] (Here, X and Y represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Further, each residue may have a substituent.) (Where X and Y 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, and n represents an integer of 2 or more. And each residue may have a substituent.) (Where Z and Y 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, and n represents an integer of 2 or more. And each residue may have a substituent.) (Here, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent. γ is -SO _2- , -O-,-(S) _n -,-(CH
₂ ) _n- , -CO-, -CONH-, any one of the formulas (a): Or it shows the case where it does not exist. n is 1 or 2. ) (Here, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent. δ is -SO _2- , -O-,-(S) _n -,-(CH
₂ ) _n- , -CO-, -CONH-, -NH-, -CH
(COOR ₁ ) —, —C (CF ₃ ) ₂ ——CR ₂ R ₃ —
Shows either of the above or the case where it does not exist. R ₁ , R ₂ , R
₃ represents an alkyl group, and n is 1 or 2. ) 3. The color former according to claim 1, further comprising an isocyanate compound. 4. The color former according to claim 1, comprising an isocyanate compound and an imino compound. 5. The color forming agent according to claim 1, further comprising an amino compound. 6. The color former according to claim 1, further comprising an acidic developer. 7. A recording material provided with a color-forming layer containing the color-forming agent according to claim 1 on a support. 8. The recording material is a thermosensitive recording material.
Recording material described in 1.