JP2001246854A - Recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material, which is excellent in plasticizer resistance and scratch resistance and onto which abrasion marks are hard to accumulate even after its long term storage and use under the state that a new coloring layer excellent in coloring sensitivity is employed therein. SOLUTION: In this recording material, a coloring layer including a colorless or light-colored basic dyestuff precursor and a urea urethane compound developer is provided on a support and, in addition, its protective layer is provided on the coloring layer. As the protective layer, a water-soluble polymer, various pigments, a lubricant or the like can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material using a novel urea urethane compound, and more particularly, to a sensitivity (color-forming property), a plasticizer resistance and a scratch resistance which can be used as a heat-sensitive recording material or a pressure-sensitive recording material. The present invention relates to a urea urethane compound-based recording material having excellent properties.

[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.

Until now, pressure-sensitive recording materials using pressure energy have been used very much like plain paper.

In general, a pressure-sensitive recording material is prepared 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 developer layer containing a developer on another support. The microcapsule-coated surface and the developer-coated surface face each other. Then, by applying a pen pressure or a pressing pressure, the microcapsules are broken, and the inclusions containing the dye precursor are released. This is transferred to the color developer layer and comes into contact with the color developer, thereby producing a color-forming reaction, thereby obtaining image recording. The self-coloring pressure-sensitive recording material developed from this pressure-sensitive recording material has a two-layer structure in which a microcapsule containing a dye precursor is applied on a support, and a developer layer is further provided on the coating layer. A recording material is known in which a material or at least one of the above two components is microencapsulated, uniformly mixed, and coated on a support. However, in these self-coloring pressure-sensitive recording materials, both the dye precursor and the color developer are present in close proximity, and there is a problem that the color is formed by a slight friction or pressure.

[0005] In recent years, for example, in various information devices such as facsimile machines, printers, recorders, etc., a heat-sensitive recording system in which recording is performed using thermal energy has been widely adopted. These heat-sensitive recording materials have many excellent properties such as high whiteness, good appearance and feel close to plain paper, good recording suitability such as color sensitivity, and the like. It has advantages such as maintenance-free and no noise generation, and 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 material in which a color-forming layer containing a two-component color-forming agent is provided on a support, and to apply heat as recording energy thereto using a heat-sensitive head, a hot stamp, a laser beam, or the like. In this method, heat-sensitive agent components are brought into contact with each other on a recording material to perform color recording. Among them, many use colorless or light-colored electron-donating dye precursors (particularly leuco dyes) and acidic developers such as phenolic compounds as color formers. Recording materials using these leuco dyes include, for example, heat-sensitive paper using crystal violet lactone and 4,4′-isopropylidene diphenol (bisphenol A) as heat-sensitive agents (see, for example, US Pat. No. 3,539,375).
And so on.

As the dye precursor and the developer used for these, an electron-donating compound and an electron-accepting compound are generally used, respectively. This is because the reactivity of the dye precursor, which is the electron-donating compound, is high, and by 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 ,
Due to the poor light fastness of the recording part, the recording has a disadvantage that the storage stability of the recording is inferior, such as fading or even disappearing of the recording due to exposure to sunlight for a relatively short period of time. At present, there are certain restrictions, and improvements are strongly desired.

In recent years, phenolic compounds typified 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 having good storability in response to such a demand, for example, Japanese Patent Application Laid-Open No.
Japanese Patent No. 1158887 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 kinds of coloring agents by applying recording energy such as heat, pressure, light and the like. 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.

Japanese Patent Application Laid-Open No. Hei 5-116459 discloses a thermosensitive recording medium having a thermosensitive coloring layer containing a colorless or pale color dye precursor and a sulfonylurea compound. However, these recording materials had low whiteness and insufficient storage stability.

[0012] Even with these conventional recording materials, if rubbing traces or the like occur during the handling of the recording material, the rubbing traces tend to develop color and cause image unevenness. Have not been used for a long time because they are not enough.

Further, since the conventional recording material does not have print preservability, even if a rubbing trace is generated, it disappears in the same manner as printing, so that the rubbing trace resistance particularly when stored and used for a long time is a problem. I never did.

However, when a urea urethane compound developer excellent in color sensitivity and printing long-term storage resistance is used, the sensitivity is high and rubbing marks are easily generated, but the rubbing marks once formed are stored forever. , Save
There is a problem in that rubbing marks accumulate each time it is used, and the paper becomes dirty when stored and used for a long time.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material using a novel coloring layer having excellent coloring sensitivity,
Another object of the present invention is to provide a recording material which is excellent in plasticizer resistance and abrasion resistance and hardly accumulates rubbing traces even when stored and used for a long time.

[0016]

Means for Solving the Problems The present inventors have developed a recording material using a colorless or light-colored basic dye precursor and a color developer in a color-forming layer. By providing a protective layer on the color-forming layer, it was found that surprisingly excellent performance was exhibited, and the present invention was completed.

That is, the present invention is as follows. A first aspect of the invention is characterized in that a color-forming layer containing a colorless or pale-colored basic dye precursor and a urea urethane compound developer is provided on a support, and a protective layer of the color-forming layer is provided on the color-forming layer. Recording material.

A second aspect of the present invention is the recording material according to the first aspect, wherein the protective layer contains a water-soluble polymer.

A third aspect of the invention is that the protective layer contains an inorganic pigment and / or an organic pigment.
2. The recording material according to any one of 2.

According to a fourth aspect of the present invention, there is provided the recording material according to any one of the first to third aspects of the invention, wherein the protective layer contains a lubricant.

A fifth aspect of the present invention is the recording material according to any one of the first to fourth aspects of the present invention, wherein a back coat layer is provided on the back surface of the support on which the color forming layer is provided.

A sixth aspect of the present invention is the recording material according to any one of the first to fifth aspects, wherein an intermediate layer is provided between the support and the color-forming layer.

A seventh aspect of the invention is the recording material according to any one of the first to sixth aspects of the invention, wherein the recording material is a thermosensitive recording material.

By adopting such a constitution, the present invention has a unique effect that it has excellent color sensitivity, plasticizer resistance and abrasion resistance, and hardly accumulates rubbing traces even when stored and used for a long period of time. Have.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. In the present invention, a protective layer for a color-forming layer is formed on a color-forming layer formed on a support. The protective layer of the coloring layer contains a water-soluble polymer.

As the water-soluble polymer contained in the protective layer of the color-forming layer, those known in the protective layer can be used. Examples thereof include polyvinyl alcohol, modified polyvinyl alcohol, and cellulose derivatives (methyl cellulose, methoxy cellulose). Cellulose, hydroxycellulose, etc.),
Starch, casein, gelatin, polyvinylpyrrolidone, styrene / maleic anhydride copolymer, styrene / acrylic acid copolymer, diisobutylene / maleic anhydride copolymer, polyacrylamide, modified polyacrylamide, methyl vinyl ether / maleic anhydride Polymers, carboxyl-modified polyethylene, polyvinyl alcohol / acrylamide block copolymer, melamine / formaldehyde resin, urea / formaldehyde resin, and the like. Among these, polyvinyl alcohol or a derivative thereof, acrylic resin, starch, styrene / maleic anhydride copolymer, styrene / acrylic acid copolymer and the like are particularly preferable.

The protective layer of the color forming layer of the present invention may contain an inorganic pigment and / or an organic pigment as a pigment. As the inorganic pigment, for example, calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide,
Inorganic pigments such as aluminum hydroxide, zinc hydroxide, barium sulfate, zinc sulfate, talc, kaolin, clay, calcined clay, and colloidal silica can be exemplified. Also,
It is also possible to mix other pigments such as inorganic fine powders such as surface-treated calcium and silica. As organic pigments, urea-formalin resin, styrene / methacrylic acid copolymer, polystyrene resin, vinylidene chloride resin,
Organic fine powders such as a crosslinkable polymethyl methacrylate resin are exemplified. In the recording material of the present invention, a urea urethane compound developer excellent in long-term storage resistance of printing is used, and the oil absorption of a pigment that can be used in the protective layer is 10%.
It is sufficient if the amount is at least ml / 100 g, and even relatively inexpensive general-purpose pigments can be used.

The weight ratio of the inorganic pigment and / or the organic pigment to the water-soluble polymer in the protective layer varies depending on the kind of the pigment, the particle size thereof, the kind of the water-soluble polymer and the like.
Parts by weight: 95 to 50 parts by weight is desirable.

A lubricant may be further added to the protective layer of the color-forming layer of the present invention to prevent sticking.
Specific examples include, for example, candelilla wax, carnauba wax, rice wax, wood wax, vegetable wax such as jojoba oil, beeswax, lanolin, animal wax such as whale wax, mineral wax such as ceresin and derivatives thereof, Petroleum waxes such as paraffin, vaseline, microcrystan, petrolactam, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, hydrogenated waxes of hydrogenated castor oil and hydrogenated castor oil derivatives, stearic acid, oleic acid, erucic acid, lauric acid Acid, sebacic acid,
Examples include fatty acids such as behenic acid and palmitic acid, amides such as adipic acid and isophthalic acid, bisamides, esters, ketones, metal salts and derivatives thereof, and alkyl-modified or amide-modified silicone resins. Of course, these lubricants may be used in combination. Among these, zinc stearate and synthetic polymer wax are particularly preferable.

The weight ratio of the lubricant to the water-soluble polymer in the protective layer is 90 to 10 parts by weight: 10 to 90 parts by weight, more preferably 70 to 30 parts by weight: 30 to 70 parts by weight.

Further, in the protective layer, in addition to an inorganic pigment and / or an organic pigment and a water-soluble polymer, if necessary, sodium hexametaphosphate, sodium dioctylsulfosuccinate,
Surfactants such as sodium dodecylbenzenesulfonate and perfluoroalkyl carboxylate, defoaming agents, optical brighteners, water-proofing agents and the like can be added as long as the effects of the present invention are not impaired. As the water-proofing agent, a conventionally known crosslinking agent can be used. Specific examples include, for example, formalin, glyoxal, melamine resin, polyamide resin, polyamide-epichlorohydrin resin, ketone-
Aldehyde resins, polyethyleneimine resins, and the like are included.

When a particularly high level of light resistance is required, a known ultraviolet absorber is preferably used in the protective layer and / or the color forming layer, if necessary. As the ultraviolet absorber, for example, 2- (2′-hydroxy-
5′-methylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3'-5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,
1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2 ′
-Hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-
4 '-(2 "-ethylhexyl) oxyphenyl] benzotriazole, 5-tert-butyl-3- (5-chloro-
2H-benzotriazol-2-yl) -4-hydroxybenzene-octyl propionate, methyl-3- [3
-Tert-butyl-5- (2H-benzotriazole-2-
Yl) -4-hydroxyphenyl] propionate Condensate of polyethylene glycol, benzotriazole ultraviolet absorber such as 2- (2′-hydroxy-3 ′, 5′-secondary amylphenyl) benzotriazole, 2,4 A benzophenone-based ultraviolet absorber such as dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-ethylhexyl-2-cyano- 3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-
And cyanoacrylate-based ultraviolet absorbers such as diphenylacrylate.

The coating amount of the protective layer is 0.5 to 10 g /
m ² , more preferably 1 to 5 g / m ² . When the coating amount of the protective layer is less than 0.5 g / m ^2, the scratch resistance is deteriorated, while when it exceeds 10 g / m ^2, not preferable because sensitivity is lowered. The protective layer may be a single layer or a plurality of layers.

Next, the coloring layer in the recording material of the present invention comprises:
It contains a colorless or pale basic dye precursor and a developer containing a urea urethane compound.

The colorless or pale color dye precursor of the present invention comprises
It 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, but is preferably an electron-donating dye precursor, more preferably a leuco dye, and particularly preferably a triarylmethane. Leuco dye,
Preferred are fluoran leuco dyes, fluorene leuco dyes, diphenylmethane leuco dyes, and the like. Hereinafter, typical dye precursors will be exemplified.

(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-dimethylaminophenylbenzhydryl benzyl 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-chlorofluorane, 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 compounds 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3- Methoxybenzo) spiropyran, 3-propylspirobenzopyran and the like.

Also, 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6'-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'- (6′-dimethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9- Spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3,6-bis (dimethylamino) ) Fluorene-9-spiro-3 '-(6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-di 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. These colorless or light-colored basic dye precursors can be used in combination of two or more as necessary.

The urea urethane compound as a color developer according to the present invention refers to a compound having at least one urea group (—NHCONH— group) and at least one urethane group (—NHCOO— group) in the molecule.

Although it has been known that a compound having a urea group exhibits a color developing effect, it is not practical because of low color density and low storage stability. However, surprisingly, a urea urethane compound in which a urea group and a urethane group are simultaneously present in one molecule is an excellent colorless or light-colored dye precursor, a color former containing both, and a recording using the same. The material has a high coloring density and excellent storage stability.

The mechanism by which such a urea urethane compound exhibits an excellent color developing effect is unknown, but is presumed to be due to the interaction between a urea group and a urethane group in the molecule.

The urea urethane compound as a developer according to the present invention may be any compound as long as it has both a urea group (-NHCONH- group) and a urethane group (-NHCOO- group) in the molecule. , An aromatic compound or a heterocyclic compound. Further, it is preferable that an aromatic compound residue or a heterocyclic compound residue is directly bonded to both ends of a urea group and a urethane group. More preferably urea group in the molecule (-NHCONH- group) and in addition to a sulfone group of the urethane group (-NHCOO- group) (-SO ₂ - group) or an amide group (-NHCO- groups) or isopropylidene groups (- It is desirable that C (CH ₃ ) ₂ — group) be present without being directly bonded to the urea group.

The method of synthesizing the urea urethane compound as a color developer according to the present invention is not particularly limited as long as a urea group (-NHCONH- group) and a urethane group (-NHCOO- group) are formed. A method of making an isocyanate compound by reacting an OH group-containing compound and an amine compound is preferable because it is easy.

That is, the urea urethane compound as a color developer according to the present invention starts with an isocyanate having at least two or more isocyanate groups, and leaves at least one isocyanate group of the isocyanate other than the other isocyanate group. The group can be reacted with an OH group-containing compound to form a urethane group, and then the remaining isocyanate group can be reacted with an amine compound to form a urea group. Alternatively, a urea group may be formed by first reacting an isocyanate group with an amine compound, and then a urethane group may be formed by reacting the remaining isocyanate group with an OH group-containing compound.

The isocyanate as a starting material is not particularly limited as long as it has two or more isocyanate groups.
For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole −
3,6-diisocyanate, 3,3′-dimethyl-4,
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Triphenylmethane triisocyanate, tris (4-
Phenyl isocyanate) thiophosphate, 4,
4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ′, 4 ″ -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, dimer acid dimer Examples include isocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexane diisocyanate. Further, diisocyanate dimers, for example, N, N ′ (4,4′-dimethyl-3,3′-diphenyldiisocyanato) uretdione (trade name: Desmodur TT) which is a dimer of toluene diisocyanate, It may be a trimer, for example, 4,4 ′, 4 ″ -trimethyl-3,3 ′, 3 ″ -triisocyanato-2,4,6-triphenylcyanurate. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name: Dess) Module L) or an amine adduct may be used. Also, isocyanate compounds and isocyanate adduct compounds described in JP-A-10-76757 and JP-A-10-95171 (the contents of these publications are incorporated herein by reference). Among them, those having two or more isocyanato groups may be used.

A particularly preferred example is toluene diisocyanate. The toluene diisocyanate is preferably 2,4-toluene diisocyanate,
In addition, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate
Mixtures of toluene diisocyanates are generally commercially available and can be obtained at low cost, but this is also acceptable.

The amine compound which forms a urea group by reacting with an isocyanate which is a starting material of a urea urethane compound as a color developer may be any compound having an amino group, for example, aniline, o-toluidine, m-amine. -Toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-
p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol,
p-aminophenol, 2,3-xylysine, 2,4-
Xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-
Cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α
-Naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p
-Chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline,
N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide, 4,4′-diamino-3,
3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 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 , P-aminobenzoic acid n
-Propyl, isopropyl p-aminobenzoate, p-
Butyl aminobenzoate, dodecyl p-aminobenzoate,
Benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino- 4-methylbenzamide,
3-amino-4-methoxybenzamide, 3-amino-
4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5 (N
-Phenylcarbamoyl) aniline, 2-methoxy-5
-[N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2 '
-Chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino)
Aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-
Benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2-
(N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole,
4-aminodiphenyl sulfone, 2-chloro-5-N-
Phenylsulfamoylaniline, 2-methoxy-5
N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline,
2-methoxy-5-benzylsulfonylaniline, 2-
Phenoxysulfonylaniline, 2- (2′-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) ) Phenyl] sulfone, bis [3-methyl-
4- (p-aminophenoxy) phenyl] sulfone,
3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5
5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-
Trizine sulfone, 2,4'-diaminobiphenyl,
2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl,4,4'-thiodianiline,2,2'-dithiodianiline,4,4'-dithiodianiline, 4,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4 '
-Diaminodiphenylmethane, bis (3-amino-4-
Chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 3,
4'-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′-tetraaminodiphenyl sulfone,
3,3 ′, 4,4′-tetraaminobenzophenone, 3
-Aminobenzonitrile, 4-phenoxyaniline, 3
-Phenoxyaniline, 4,4'-methylenebis-o-
Toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6-xylysine), o-chloro-
p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m- Nitroaniline, p
-Nitroaniline, 2-methyl-4-nitroaniline,
m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, methol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B Acid, C
Acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m- Toluylenediamine, 2-aminothiophenol, 2-amino-
3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine , 4,4 '
-Diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthonic acid, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, Aromatic amines such as 4-diamino-2,3-dichloroanthraquinone, and further 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε -Caprolactam, acetoguanamine, 2,4-diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine,
3-diaminopyridine, 2,5-diaminopyridine,
Heterocyclic compounds such as 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, and N- (3-aminopropyl) morpholine Amines,
Methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine,
2-ethylhexylamine, ethanolamine, 3-
(2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t
-Butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4
-Diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine,
2-bromoethylamine, 2-methoxyethylamine,
2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine And aliphatic amines such as hexamethylenediamine.

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

[0052]

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(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 each independently represent Represents an amino group or a group represented by the formula (b),

[0054]

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Y ₁ represents —SO ₂ —, —O—, — (S) _n —,
— (CH ₂ ) _n —, —CO—, —CONH—, any of the groups represented by the formula (a),

[0056]

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

The OH group-containing compound which reacts with the isocyanate to form a urethane group may be any compound having an OH group. Examples thereof include phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, and resorcinol. , P-tert-butylphenol, p-tert-octylphenol,
2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p
-Nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, bis ( 4-hydroxyphenyl) butyl acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-) (Hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyl Oxyphenyl-4 ' Hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 4-isopropylphenyl-4′-hydroxyphenylsulfone, 4-hydroxy-4′-iso Propoxydiphenyl sulfone, bis (2
-Methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-thiodiphenol, 4,4′-dihydroxybenzophenone, 2,2-bis (4-hydroxy Phenyl) 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, 4-
Methyl hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4′-chlorobenzyl), ethyl 1,2-bis (4′-hydroxybenzoate), 1,5-bis (4′-hydroxy Pentyl benzoate, hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy) Phenol, 4
-Hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-
Phenols such as n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid. . However, those phenols having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. Further, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol,
Pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve,
Butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol,
Cyclohexylmethanol, cyclopentanol, 2-
Alcohols such as chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol, polypropylene glycol, polytetramethylene ether glycol, adipate-based polyol, epoxy-modified polyol, polyetherester polyol, polycarbonate polyol, polycaprolactonediol, phenol Polyols, polyether polyols such as amine-modified polyols, 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 Triol, polybutadiene polyols, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol,
Examples include castor oil-based polyols, polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, α-methylglucoside, sorbitol, and polyols such as sucrose.

As the urea urethane compound as a color developer according to the present invention, a urea urethane compound in which the number of urea groups (A) and the number of urethane groups (B) in the molecular structure satisfy the following formula is preferable. 10 ≧ (A + B) ≧ 3
(However, A and B are integers of 1 or more)

A urea urethane compound in which the number of urea groups (A) and the number of urethane groups (B) satisfy the formula: 10 ≧ (A + B) ≧ 3 (where A and B are integers of 1 or more) Urea group (-NHCONH- group) and urethane group (-NHCO
O-group) is present, and the total number of urea groups and urethane groups is 3 or more and 10 or less.

Conventionally, such a compound has not been known and is a completely novel compound. This novel compound is useful for a recording material using recording energy such as heat and pressure.

The number of urea groups (A) and the number of urethane groups (B) satisfy the formula 10 ≧ (A + B) ≧ 3 (where A and B are integers of 1 or more). Group (-NHCONH- group) and urethane group (-NHCOO-
Group) is not particularly limited as long as the method is such that the total number of urea groups and urethane groups is 3 to 10
A method of preparing an isocyanate compound by reacting with an OH group-containing compound and an amine compound is easy and preferable.

That is, the urea urethane compound according to the present invention can be prepared by, for example, starting from an isocyanate having at least two or more isocyanate groups, leaving at least one isocyanate group of the isocyanate and other isocyanate groups and an OH group. The resulting compound is reacted to form a urethane group, and the remaining isocyanato groups of the two molecules of the urethane compound are then reacted with each other with water to form a urea urethane compound having a total number of urea groups and urethane groups of at least three. Can be obtained.

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

The starting isocyanate is not particularly limited as long as it has two or more isocyanate groups.
For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole −
3,6-diisocyanate, 3,3′-dimethyl-4,
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Triphenylmethane triisocyanate, tris (4-
Phenyl isocyanate) thiophosphate, 4,
4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ′, 4 ″ -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, dimer acid dimer Examples include isocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexane diisocyanate. Further, diisocyanate dimers, for example, N, N ′ (4,4′-dimethyl-3,3′-diphenyldiisocyanato) uretdione (trade name: Desmodur TT) which is a dimer of toluene diisocyanate, A trimer such as 4,4 ′, 4 ″ -trimethyl-3,3 ′, 3 ″ -triisocyanato-2,4,6-triphenylcyanurate may be used. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name: Dess) Module L) or an amine adduct may be used. Further, the isocyanate compound and the isocyanate adduct compound described in JP-A-10-76757 and JP-A-10-95171 may have two or more isocyanate groups.

A particularly preferred example is toluene diisocyanate. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable, and in addition, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and inexpensive. Although it is possible to obtain, this may be sufficient. These toluene diisocyanate isomer mixtures are liquid at room temperature.

The amine compound which forms 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. 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'-diaminobenzanilide,
3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, o-phenylenediamine, m-phenylene Diamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, p -Butyl aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N -Methylbenzamide, 3-
Amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p
-[N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl]
Aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- ( 2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2
-Methoxyaniline, 4-acetylaminoaniline, 4
-(N-methyl-N-acetylamino) aniline, 2,
5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4- Sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4
-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [ 4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy)
Phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diamino Biphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,
4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,
2'-dichloro-4,4'-diaminobiphenyl, 3,
3'-dichloro-4,4'-diaminobiphenyl, 2,
2′-dimethyl-4,4′-diaminobiphenyl, 4,
4′-thiodianiline, 2,2′-dithiodianiline,
4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '
-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,
3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4 '
-Ethylenedianiline, 4,4'diamino-2,2'-
Dimethyldibenzyl, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4 ′ -Bis (4-aminophenoxy) diphenyl, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenylsulfone, 3,3 ', 4,4'-
Tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4′-methylenebis-o-toluidine, 4,
4 '-(p-phenyleneisopropylidene) -bis-
(2,6-xylidine), o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino- 4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p
-Toluidine, 2-amino-5-nitrobenzonitrile, methol, 2,4-diaminophenol, N- (β
-Hydroxyethyl) -o-aminophenol sulfate,
Sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid,
p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2
-Aminothiophenol, 2-amino-3-bromo-5
-Nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2
-Methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine,
3,3'-dichlorobenzidine, 4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid, phenyl J Acid, 1,4
-Diamino-anthraquinone, 1,4-diamino-2,
Aromatic amines such as 3-dichloroanthraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
α-amino-ε-caprolactam, acetoguanamine,
2,4-diamino-6- [2′-methylimidazolyl-
(1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine,
Heterocyclic compounds such as 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine, amines, methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine Isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine,
3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine,
-Methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,
Examples thereof include aliphatic amines such as 3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine.

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

[0068]

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 each independently represent Represents an amino group or a group represented by the formula (b),

[0070]

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Y ₁ is —SO ₂ —, —O—, — (S) _n —,
— (CH ₂ ) _n —, —CO—, —CONH—, any of the groups represented by the formula (a),

[0072]

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

The OH group-containing compound which reacts with the isocyanate to form a urethane group may be any compound having an OH group. Examples thereof include phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, and resorcinol. , P-tert-butylphenol, p-tert-octylphenol,
2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p
-Nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, bis ( 4-hydroxyphenyl) butyl acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-) (Hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyl Oxyphenyl-4 ' Hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 4-isopropylphenyl-4′-hydroxyphenylsulfone, 4-hydroxy-4′-iso Propoxydiphenyl sulfone, bis (2
-Methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-thiodiphenol, 4,4′-dihydroxybenzophenone, 2,2-bis (4-hydroxy Phenyl) 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, 4-
Methyl hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4′-chlorobenzyl), ethyl 1,2-bis (4′-hydroxybenzoate), 1,5-bis (4′-hydroxy Pentyl benzoate, hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy) Phenol, 4
-Hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-
Phenols such as n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid. . However, as these phenols, those having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.
Further, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol,
2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, Phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol,
Alcohols such as 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin and glycerol;
Polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol,
Polyether polyols such as phenolic polyols and amine-modified polyols, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2
-Propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-
Hexane glycol, 1,9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol,
Phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside,
Polyols such as sorbitol and shoe rose.

The urea urethane compound as a developer according to the present invention further includes compounds represented by the following general formulas (II) to (VII):
The urea urethane compounds of I) are also preferred.

[0075]

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(Wherein X and Z each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and each residue may have a substituent;
₀ represents one selected from the group consisting of a tolylene group, a xylylene group, a naphthylene group, a hexamethylene group, and a -φ-CH ₂ -φ- group, and -φ- represents a phenylene group. ),

[0077]

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(In the formula, X and Y each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and each residue may have a substituent. Good.),

[0079]

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(Wherein, X and Y each independently represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue, and α represents a divalent or higher valent residue.) ,
n represents an integer of 2 or more, and each residue may have a substituent. ),

[0081]

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

[0083]

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

[0085]

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

[0086]

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(Wherein the hydrogen atom of the benzene ring may be substituted by an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, and each residue has a substituent. Δ may be -SO _2- , -O-,-(S)
_{n -, - (CH 2)} n -, - CO -, - CONH -, - N
H-, -CH (COOR ₁ )-, -C (CF ₃ ) _2- , and -CR ₂ R _3- represent one or none of the groups selected from the group consisting of R ₁ , R ₂ and R _3. Represents an alkyl group, and n is 1 or 2. ),as well as

[0088]

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(Wherein, X, Y and Z each independently represent an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, and each residue may have a substituent. Here, X, Y and Z are preferably an aromatic compound residue or a heterocyclic compound residue.)

The urea urethane compounds of the general formulas (II) to (VIII) are also novel compounds. This novel compound is useful for a recording material using recording energy such as heat and pressure.

The ureaurethane compound of the formula (II) according to the present invention is not particularly limited in the production method, but may be, for example, a compound represented by the following general formula (I)
It can be obtained by reacting the OH group-containing compound of X) with the isocyanate compound of the following general formula (X) and the amine compound of the following general formula (XI), for example, according to the following reaction formula (A).

[0092]

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[0093]

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[0094]

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

[0096]

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

[0097]

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

[0099]

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The ureaurethane compound of the formula (IV) according to the present invention is not particularly limited in the production method, but may be, for example, a compound of the formula (IX)
By reacting the OH group-containing compound of formula (XII) with the isocyanate compound of formula (XII) and the amine compound of formula (XIII) below, for example, according to the following reaction formula (C) or (D).

[0101]

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

[0102]

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[0103]

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

[0105]

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

[0106]

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[0107]

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The compounds of the general formulas (IX) to (XIV) which can be used when synthesizing the ureaurethane compounds represented by the above formulas (II) to (IV) will be described in more detail.

The OH group-containing compound represented by the general formula (IX) is not particularly limited as long as it has one or more OH groups. Phenol, resorcinol, p-tert-butylphenol,
p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4
-Phenylphenol, 4-hydroxyphenyl-4 '
-Methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl -4'-
Benzyloxyphenylsulfone, 4-isopropylphenyl-4′-hydroxyphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate,
-Hydroxybenzoic acid (4'-chlorobenzyl), 1,
Ethyl 2-bis (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, 4-n-octyloxysalicylic acid,
4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid,
Monophenols such as 3-n-octanoyloxysalicylic acid, 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, -Methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, 4,4'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) ) Benzyl acetate, bis (4-hydroxyphenyl)
Sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4′methylphenylsulfone, bis (2-allyl-4)
-Hydroxyphenyl) sulfone, bis (2-methyl-
3-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)
And diphenols such as sulfides. However,
As these OH-containing compounds, those having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. Further, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol, 2-pentanol, 3-hexanol, t
tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propene-1
-Ol, benzyl alcohol, 4-pyridine methanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-
Monoalcohols such as hydroxypropane, glycerin, and glycerol can be mentioned. Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol, amine modified polyol, ethylene glycol, diethylene glycol,
1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,6-hexaneglycol, 1,9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl Polyols such as glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucosidorubitol, and souce rose may be used. Of these, monophenols are preferably used.

Examples of the isocyanate compound of the formula (X) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and 1,5-naphthylene diisocyanate. Isocyanate, meta-xylylene diisocyanate and the like can be mentioned. Of these, toluene diisocyanate is preferred.

The isocyanate compound of the general formula (XII) is not particularly limited as long as it has two or more isocyanate groups. 1,4
-Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6
-Diisocyanate, 3,3'-dimethyl-4,4'-
Diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, 4,4 ′,
4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ', 4" -triisocyanatotriphenylamine, metaxylylene diisocyanate,
Lysine diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate,
And methylcyclohexane diisocyanate. Further, diisocyanate dimer, for example, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanate) uretdione (trade name: Desmodur TT) which is a dimer of toluene diisocyanate And a trimer such as 4,4 ′, 4 ″ -trimethyl-3,3 ′, 3 ″ -triisocyanate-2,4,6-triphenylcyanurate. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, for example, 1,3-bis (3-isocyanato-4-methylphenyl) urea, and polyol adducts, for example, trimethylolpropane adduct of toluene diisocyanate (trade name: Dess Module L) or an amine adduct body may be used. Further, among the isocyanate compounds and isocyanate adduct compounds described in JP-A-10-76757 and JP-A-10-95171, those having two or more isocyanate groups may be used. A particularly preferred example is toluene diisocyanate.

The amine compound of the general formula (XI) is not particularly limited as long as it is a compound having at least one amino group. p-anisidine, p-phenetidine, 2,4-dimethoxyaniline,
2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p
-Aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine,
4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p
-Isopropyl aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o- Aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide,
3-amino-4-methylbenzamide, 3-amino-4
-Methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl]
Aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N-
(2′-methyl-3′-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2′-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 2-methoxy-4- (N-benzoylamino)-
5-methylaniline, 4-sulfamoylaniline, 3
-Sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5- N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-p
-Chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-
4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, sulfanilic acid, methanyl 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, diaminodiphenylether, 3,3'-dichloro-4,
4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) Phenyl] sulfone, bis [3-methyl-4-
(P-aminophenoxy) phenyl] sulfone, 3,
3′-dimethoxy-4,4′-diaminobiphenyl,
3,3′-dimethyl-4,4′-diaminobiphenyl,
2,2'-dichloro-4,4'-diamino-5,5'-
Dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'
-Diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether,
4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4′-diaminodiphenylsulfone, 3, 3'-diaminodiphenyl sulfone, 3,4 '
-Diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'- 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
Aromatic diamines such as -aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3'-dichlorobenzidine. Furthermore, 3-amino-1,2,4
-Triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6
[2′-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine,
Heterocyclic compounds such as N- (3-aminopropyl) morpholine amines, methylamine, ethylamine, stearylamine, allylamine, isopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3 -Ethoxypropylamine, 3- (diethylamino) propylamine,
3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-
Methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine , 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-
Examples thereof include aliphatic amines such as aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine. Of these, aromatic monoamines are preferably used.

The amine compound represented by the general formula (XIII) is not particularly limited as long as it has two or more amino groups. For example, 4,4′-diamino-3,3′-diethyldiphenylmethane, 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'-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'-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 -Aromatic amines such as phenylenediamine, m-phenylenediamine and p-phenylenediamine. Further, among the above amine compounds, in particular, at least two of the following formula (I):
An aniline derivative having two amino groups is preferred.

[0114]

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(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 each independently represent Represents an amino group or a group represented by the formula (b),

[0116]

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Y ₁ represents —SO ₂ —, —O—, — (S) _n —,
— (CH ₂ ) _n —, —CO—, —CONH—, any of the groups represented by the formula (a),

[0118]

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

The OH group-containing compound of the general formula (XIV) is not particularly limited as long as it has two or more OH groups, and examples thereof include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) propane. Bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, p, p'-biphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4 -Hydroxyphenyl)
Benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4′-
Methylphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-t
tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,
4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl)
Examples include phenols such as hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, and bis (4-hydroxy-3-methylphenyl) sulfide. However, those having an amino group are not preferred as these diphenols. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.
Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol, 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 Examples include polyols such as a system polyol, a polymer polyol, methylpentanediol, a halogen-containing polyol, a phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, and sucrose.

The ureaurethane compound of the formula (VI) according to the present invention is not limited to a specific production method. (G)
Alternatively, it can be obtained by reacting according to (H).

[0121]

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(Wherein, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue has a substituent. Γ is -SO _2- , -O-,-(S)
_{n -, - (CH 2)} n -, - CO -, - CONH-, or a group of formula (a),

[0123]

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

[0124]

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[0125]

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

[0127]

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(Wherein, the hydrogen atom of the benzene ring may be substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue has a substituent. Δ is -SO _2- , -O-,-(S)
_{n -, - (CH 2)} n -, - CO -, - CONH -, - N
_{H -, - CH (COOR 1} ) -, - C (CF 3) 2 -, -
CR ₂ R ₃ — indicates either the absence or absence of CR ₂ R ₃ —.
R ₁ , R ₂ and R ₃ represent an alkyl group, and n is 1 or 2. )

[0129]

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[0130]

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Formulas (VI) and (VII) according to the present invention
Compounds that can be used when synthesizing the urea urethane compound of the above are described in detail below.

The monophenol compound that can be used when synthesizing the urea urethane compound of the formula (VI) is not particularly limited as long as it is a compound having one OH group on the benzene ring.
Xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol , O-chlorophenol, p-chlorophenol, 4-phenylphenol, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone,
-Isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-
4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4
-Hydroxy-4'-isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), dimethyl 3-hydroxyphthalate , 4-methoxyphenol, 4- (benzyloxy) phenol, 4-
Hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n
-Pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid,
4-n-octyloxycarbonylaminosalicylic acid,
Examples include phenols such as 4-n-octanoyloxycarbonylaminosalicylic acid. However, as these phenols, those having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

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

The diamine compound of the general formula (XV) which can be used when synthesizing the ureaurethane compound of the formula (VI) is, for example, 4,4′-diamino-3,
3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 3,3'-dichloro-4,
4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, trizine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) Phenyl] sulfone, bis [3-methyl-4-
(P-aminophenoxy) phenyl] sulfone, 3,
3′-dimethoxy-4,4′-diaminobiphenyl,
3,3′-dimethyl-4,4′-diaminobiphenyl,
2,2'-dichloro-4,4'-diamino-5,5'dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4 '-Diaminobiphenyl, 2,2'-
Diaminobiphenyl, 4,4′-diaminobiphenyl,
2,2′-dichloro-4,4′-diaminobiphenyl,
3,3′-dichloro-4,4′-diaminobiphenyl,
2,2′-dimethyl-4,4′-diaminobiphenyl,
4,4'thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,
3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,
4'-ethylenedianiline, 4,4'diamino-2,
2′-dimethyldibenzyl, 3,3′-diaminobenzophenone, 4,4′-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,
Aromatic diamines such as 3,3′-dichlorobenzidine are exemplified.

The aniline derivative which can be used when synthesizing the ureaurethane compound of the formula (VII) is not particularly limited as long as it is an aniline compound having one amino group on a benzene ring. , O
-Toluidine, m-toluidine, p-toluidine, o-
Anisidine, p-anisidine, p-phenetidine, N,
N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic Acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,
4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p
-Cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-
Dichloroaniline, 2,4,5-trichloroaniline,
α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline,
p-chloroaniline, methyl p-aminobenzoate, p-
Ethyl aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-
Aminoacetophenone, p-aminoacetophenone, m
-Aminobenzamide, o-aminobenzamide, p-
Aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p -[N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N −
(2′-methyl-3′-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2′-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy- 4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N
-Ethyl-N-phenylaminosulfonyl) aniline,
4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole,
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-chloro Phenol, 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 general formula (XVI) which can be used when synthesizing the ureaurethane compound of the formula (VII)
Examples of the dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, and 2,2-bis (hydroxyphenyl) Heptane, 4,4'-biphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl)
Sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert)
-Butyl-4-hydroxyphenyl) sulfide, 4,
4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3 ' Diphenols such as -dihydroxydiphenylamine and bis (4-hydroxy-3-methylphenyl) sulfide. However, those having an amino group are not preferred as these diphenols. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

The method for synthesizing the ureaurethane compound of the general formula (VIII) is not particularly limited. For example, an OH group-containing compound of the general formula (IX), an isocyanate compound of the general formula (XII) and a compound of the general formula (XI) Can be obtained, for example, by reacting the amine compound according to the following reaction formula (L).

[0138]

Embedded image

The substituent of X bonded to the urethane group of the urea urethane compound of the general formula (VIII) includes an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an amide group, an alkoxyl group and a nitro group. , Nitroso group, nitrile group, toluenesulfonyl group, methanesulfonyl group, acetyl group, halogen atom, formyl group,
Dialkylamino groups and isocyanato groups are preferred.

Of these ureaurethane compounds as color developers of formulas (II) to (VIII), preferred are compounds of formulas (III) to (VII), and particularly preferred are compounds of formula (VI) ) To (VII).

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

In order to obtain the urea urethane compound according to the present invention, the desired product can be obtained by mixing and reacting the isocyanate with the reactant in an organic solvent or in the absence of a solvent and then removing the crystals by filtration. A single or a plurality of reactants may be used depending on the purpose. The solvent may be any solvent as long as it does not react with the isocyanato group and the functional group of the reactant. Examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and chlorinated aliphatic hydrocarbons. Examples include hydrogen, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and ketones. In particular, methyl ethyl ketone, toluene, and the like, which dissolve the isocyanate and have low solubility of the product, are preferable. The product obtained by the above-mentioned reaction operation is not necessarily a single product, and may be obtained as a mixture of compounds having different substituent positions.

The ureaurethane compound as the color developer of the present invention is a colorless or pale color compound which is usually a solid at room temperature.

The molecular weight of the urea urethane compound as the color developer of the present invention is preferably 5,000 or less, more preferably 2,000 or less.

The total number of urea groups and urethane groups in the urea urethane compound as the color developer of the present invention is preferably 20 or less, more preferably 10 or less. Further, the ratio of the urea group to the urethane group in the molecular structure of the urea urethane compound is preferably 1: 3 to 3: 1, and particularly preferably 1: 2 to 2: 1.

In preparing a recording material using a urea urethane compound as a color developer, one type of the urea urethane compound may be used, or two or more types may be used in combination, if necessary.

In the heat-sensitive recording material, a compound having a melting point is more preferable, and the melting point of the urea urethane compound as a color developer of the present invention is preferably 40 ° C. to 500 ° C.
Particularly preferably, the temperature is in the range of 60 ° C to 300 ° C.

The urea urethane compound as a color developer is 5 to 10 parts by weight per 100 parts by weight of the colorless or pale color dye precursor.
It is preferably used in an amount of 00 parts by weight, more preferably 20 to 500 parts by weight. When the amount of the urea urethane compound as a color developer is 5 parts by weight or more, it is sufficient to form a color of the dye precursor, and the coloring density is high. When the amount of the urea urethane compound as the color developer is 1000 parts by weight or less, an excess amount of the urea urethane compound as the color developer hardly remains, which is economically advantageous and preferable.

By adding an acidic developer to the color-forming layer of the recording material of the present invention, the sensitivity is improved and a recording material having a clear color can be obtained.

As the acidic developer when the present invention is used as a heat-sensitive recording material, generally used electron-accepting substances are used. Particularly, phenol derivatives, aromatic carboxylic acid derivatives or metal compounds thereof, and salicylic acid derivatives are used. Or a metal salt thereof, an N, N-diarylthiourea derivative,
Sulfonylurea derivatives and the like are preferred. Particularly preferred are phenol derivatives, specifically, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, , 2-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-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-
Methylphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, 4-isopropylphenyl-4′-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4′-hydroxyphenylsulfone, bis (2-allyl-4 -Hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl)
Sulfide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), ethyl 1,2-bis (4'-hydroxybenzoate), 1,5-bis ( Pentyl 4'-hydroxybenzoate), 1,6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate and the like can be mentioned. Further, as salicylic acid derivatives, 4-
n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-
Examples thereof include n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid. Examples of the sulfonylurea derivative include 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane and 4,4-bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane 4,4-bis (p-toluenesulfonylaminocarbonyl) Amino) diphenyl sulfide, 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl ether, N- (p
Compounds containing one or more arylsulfonylaminoureido groups, such as-(toluenesulfonyl) -N'-phenylurea.

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

The acid developer is preferably used in an amount of 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, based on 100 parts by weight of the colorless or pale color dye precursor. When the amount of the acidic developer is 5 parts by weight or more, the coloration of the dye precursor is good and the color density is high. Also, an acidic developer 50
When the amount is 0 part by weight or less, the acidic developer hardly remains, which is economically advantageous and preferable.

When the present invention is used as a pressure-sensitive recording material, the image density is improved by adding an acidic developer, so that a pressure-sensitive recording material with clear color development 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,
Inorganic compounds such as aluminum silicate, or phenol, cresol, butylphenol, octylphenol, phenylphenol, chlorophenol, salicylic acid, or aldehyde condensed novolak resins derived therefrom and metal salts thereof, 3-isopropylsalicylic acid, 3-phenylsalicylic acid , 3-cyclohexylsalicylic acid, 3,5-di-t-butylsalicylic acid, 3,
5-di (α-methylbenzyl) salicylic acid, 3,5-di-t-octylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3,5-di (α, α-dimethylbenzyl)
Salicylic acid derivatives such as salicylic acid and 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, and metal salts thereof.

In the present invention, a color former containing a colorless or pale color dye precursor and a color developer containing a urea urethane compound is formed on a support by a method such as coating to form a color developing layer. A recording material can be obtained by forming a protective layer on the layer. The configuration differs depending on the type of recording material.

The recording material of the present invention can be used as various recording materials such as a heat-sensitive recording material and a pressure-sensitive recording material, and is particularly suitable as a heat-sensitive recording material.

When the recording material is a heat-sensitive recording material, a heat-sensitive recording layer for coloring by heating is provided on the support. Specifically, the above urea urethane compound, a colorless or pale color dye precursor such as a leuco dye, a heat-fusible substance described below, etc., in the form of a dispersion, are coated on a support together with other necessary components. 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 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 thermosensitive 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 wear 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 basis weight of this support is 40 g
/ M ^{2 to} 200 g / m ² is desirable, and as high a flatness as possible is desired as a heat-sensitive recording material, a material having excellent surface smoothness and flatness is desirable. The surface treatment is preferably performed by applying heat and pressure.

The thermosensitive 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, an intermediate layer composed of one or more layers may be provided between the support and the thermosensitive recording layer. This heat-sensitive recording layer can be obtained by mixing each aqueous dispersion obtained by finely pulverizing each color-forming component or other components, a binder and the like, applying the mixture on a support, and drying.

When the present invention is used as a thermosensitive recording material, a thermofusible substance can be contained in the thermosensitive coloring layer in order to improve the sensitivity. Heat fusible material is 60
C. to 180.degree. C. are preferred, especially 80.degree.
Those having a melting point of from 140C to 140C are preferred. For example,
benzyl p-benzyloxybenzoate, 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-stearoylurea, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, 1-phenoxy-2
-(4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate, metaterphenyl, dibenzyl oxalate, oxalic acid (P-chlorobenzyl) ester and the like. In addition, 4,
4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4,4'-difluorobenzophenone, diphenylsulfone, 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'dichlorodiphenyldiphenyl Sulfide, diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N'-diphenyl-p-phenylenediamine, 1- (N-phenylamino) naphthalene, benzyl, 1,3-diphenyl-1,3-propanedione, etc. May be used. Of these, diphenyl sulfone is preferably used.

The above-mentioned heat-fusible substances may be used alone or as a mixture of two or more kinds. In order to obtain a sufficient thermal response, 100 parts by weight of a colorless or pale-color dye precursor is used. It is preferable to use 10 to 300 parts by weight,
Further, it is more preferable to use 20 to 250 parts by weight.

When the recording material is a pressure-sensitive recording material, for example, US Pat.
Nos. 07, 2730456 and 273045
No. 7, No. 3,418,250, and the like. That is, the dye precursor is used alone or as a mixture, and synthetic oils such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethane, chlorinated paraffin, and vegetable oils, animal oils, mineral oils, etc. Or 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 in which the coated surfaces of a lower paper coated with a dispersion of an acidic developer, etc.) were superimposed, or a dispersion of a urea urethane compound was further coated on one side and a dye precursor was coated on the other side The pressure-sensitive recording paper with the middle paper sandwiched between the upper paper and the lower paper, or the urea urethane on the same surface of the support A self-type in which a dispersion of a product (and an acid developer) and a dispersion containing the above-mentioned dye precursor are mixed, or a multi-layer coating, or a dye precursor, a urea urethane compound (and an acid developer, etc.) Various forms such as a self-type in which microcapsules are microencapsulated and mixed and applied are also possible.

The method for producing microcapsules includes 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, In-s Itu method disclosed in Japanese Patent Publication No. 51-9079 and the like, 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 coloring agent of the present invention corresponds to the dye precursor and the developer in the above publications and the like.

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 color developing system including an acidic developer, it may be used alone or in combination with a urea urethane compound and an acidic developer dissolved or dispersed in a solvent.

In the 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 microcapsules and is not directly involved in the color image, and other water-soluble monomers must be used. This is distinguished from the use of the isocyanate compound used in the present invention.

The preparation of the dispersions of the compounds without microencapsulation is carried out by adding one or more of each compound
It can be obtained by pulverization in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer and a surfactant. Further, the urea urethane compound may be dispersed simultaneously with the acidic developer.

As the support used for the pressure-sensitive recording material, paper is mainly used.
A synthetic resin film, a laminated paper, a synthetic paper, a metal foil, or a composite sheet combining these can be used arbitrarily according to the purpose.

As the binder, various binders which are usually used can be used. For example, starches, hydroxyethyl cellulose, methyl cellulose,
Carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylate copolymer, acrylamide / acrylate / methacrylic acid terpolymer, styrene / maleic anhydride copolymer Water-soluble binders such as alkali salts of ethylene and maleic anhydride copolymers, and water-insoluble latexes such as styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, and methyl acrylate / butadiene copolymers Binders and the like.

Further, the recording material according to the present invention may contain a hindered phenol compound or an ultraviolet absorber in the recording layer. For example, 1,1,3-tris (3 ′
-Cyclohexyl-4'hydroxyphenyl) butane,
1,1,3-tris (2-methyl-4-hydroxy-5-
tert-butylphenyl) butane, 4,4′-thiobis (3-methyl-6-tert-butylphenol),
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, p-octylphenyl salicylate, 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, ethyl-2-cyano-3,3'-
Diphenyl acrylate, tetra (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboate.

The method for forming the color-forming layer and the protective layer is not particularly limited, and the coating solution for the color-forming layer or the coating solution for the protective layer may be coated, for example, with a free-fall curtain, an air knife coating, a variver blade coating, a pure blade coating, It is formed on the support or on the color-forming layer by a suitable coating method such as short dwell coating or the like, followed by drying. In the case of the coating solution for the color-forming layer, the coating amount is not particularly limited, and is usually 1 to 15 g by dry weight.
/ M ² , preferably in the range of about 3 to 10 g / m ² .

The recording material produced by the method of the present invention may be provided with a back layer (back coat layer) on the surface opposite to the recording layer, if necessary, so that the recording paper is less likely to curl. Can be. The coating liquid components and the coating method of the back layer may be the same as those of the protective layer. Dry coating amount is 0.2 ~
A range of 10.0 g / m ² is preferred.

Further, an intermediate layer can be provided between the heat-sensitive recording layer and the support to improve the thermal responsiveness. The undercoat layer is mainly composed of an organic, inorganic pigment, a hollow particle, a water-soluble polymer, an aqueous binder such as latex, and the same organic, inorganic pigment and aqueous binder as the heat-sensitive recording layer can be used. . The method for forming the intermediate layer is not particularly limited, and the same method as the method for forming the heat-sensitive recording layer can be used. The dry coating amount is 2.0 to 15.
A range of 0 g / m ² is preferred.

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

<Plasticizer resistance> The heat-sensitive recording material was sandwiched between vinyl chloride wraps or vinyl chloride files.
After applying a load of 00 g / cm ² and leaving at 40 ° C. for 24 hours, the densities of the printed portion and the unprinted portion (background) were visually evaluated after the standing. did.

<Scratch Resistance> It was visually evaluated whether or not a trace of rubbing was formed when the surface of the heat-sensitive recording material was strongly rubbed with a nail. Those with no noticeable rubbing marks were regarded as having good scratch resistance.

<Test for Accumulating Rubbing Traces> A cylinder having a surface of 5 cm in diameter (weight 2 kg) was moved 50 times on the same surface having a length of 20 cm at a speed of 20 cm / sec on the recording surface of the produced thermal recording material. After that, it was left at room temperature for one week. 1
After a week, the readability of the recorded image was visually evaluated, and the one in which the recorded image was sufficiently legible was evaluated as good.

[0180]

Example 1 2,4-Toluene diisocyanate
5 g was stirred at 60 ° C., and 21.5 g of 4,4′-diaminodiphenylsulfone was diluted with 120 ml of methyl ethyl ketone and added dropwise over 4 hours.
For 2 hours. After the reaction, after cooling to room temperature, toluene was added, and the precipitated white solid was collected by filtration,
After washing with toluene and vacuum drying overnight, 47 g of a white crystalline compound was obtained. Next, 30 g of this compound was taken, 9.5 g of phenol and 95 ml of methyl ethyl ketone were added, 30 mg of triethylamine was further added, and the mixture was reacted at 25 ° C. for 4 hours. After the reaction, toluene was added, and the precipitated crystals were collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 38.5 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
The mixture was crushed and dispersed with a paint shaker for 6 hours together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. The liquid temperature of the dispersion immediately after the dispersion was 25 ° C. The dispersed particle size of this compound was 0.6 μm.

Further, 3-dibutylamino-6-methyl-
70 g of 7-anilinofluoran together with 130 g of an 8% by weight aqueous solution of polyvinyl alcohol, a sand grinder (vessel capacity 400 ml, manufactured by Imex Co., Ltd.), rotation speed 2
The mixture was ground and dispersed at 000 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 (400 ml vessel volume, manufactured by Imex Co.) for 3 hours at a rotation speed of 2000 rpm to obtain a dispersion.

In addition, 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 using} a rod coater rod No. 10. After drying, it was treated with a super calender to form a thermosensitive coloring layer on the support. The coating amount of the coating liquid was 5 g / m ² in terms of dry weight.

Next, 40 g of kaolin was pulverized and dispersed together with 60 g of a 0.7% aqueous sodium hexametaphosphate solution in a sand grinder (vessel capacity: 400 ml, manufactured by Imex Co.) for 3 hours at a rotation speed of 2000 rpm to obtain a dispersion.

20 parts by weight of a dry solid content of this kaolin dispersion, 10 parts by weight of a dry solid content of a zinc stearate dispersion having a solid content concentration of 16% by weight, 40 parts by weight of a dry solid content of an aqueous carboxy-modified polyvinyl alcohol solution, polyacrylamide The epichlorohydrin crosslinking agent aqueous solution was stirred and mixed at a dry solid content of 5 parts by weight (dry basis) to obtain a coating liquid for forming a protective layer.

The coating liquid for forming a protective layer was applied on the thermosensitive coloring layer with a rod number 5 of a bar coater. After drying, it was processed with a super calender to obtain a heat-sensitive recording material. The coating amount of the protective layer forming coating liquid was 2 g / m ² in terms of dry weight. The evaluation result of the sensitivity of the obtained thermosensitive recording material was as good as the optical density of 1.3.

The print preservability of the vinyl chloride wrap was good. In addition, it was visually evaluated whether or not a rubbing mark was formed when the surface was strongly rubbed with a nail, and the rubbing mark was not conspicuous and the scratch resistance was good. In addition, the results of the long-term scratch resistance test were satisfactory, since the recorded images could be read sufficiently.
Table 1 summarizes the results of these evaluations.

[0191]

Examples 2-3 In the same manner as in Example 1, except that polyvinyl alcohol (Example 2) and an acrylic copolymer (Example 3) were used instead of the carboxy-modified polyvinyl alcohol used in Example 1. To produce a thermosensitive recording material,
An evaluation was performed. The results are summarized in Table 1.

[0192]

Examples 4 to 6 In place of kaolin used in Example 1, aluminum hydroxide (Example 4), crosslinkable polymethyl methacrylate resin (Example 5), and silicon dioxide (Example 6) were used. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except for the above. The results are summarized in Table 1.

[0193]

Example 7 61 g of 2,4-toluene diisocyanate
To this was added 450 g of toluene as a solvent, and 26 g of aniline dissolved in 150 g of toluene was added dropwise over 6 hours, and the mixture was reacted at 5 ° C. for 7 hours. After the reaction, the precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 70 g of a white crystalline compound. Next, 30 g of this compound was taken, 365 g of toluene was added as a solvent, 12.2 g of 2,2-bis (4-hydroxyphenyl) propane and 0.3 mg of triethylamine were added, and the mixture was stirred at 60 ° C. for 4 hours, followed by 4 hours. The reaction was performed at 70 ° C. for 3 hours, and further heated at 80 ° C. for 3 hours. After the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with toluene, and dried under vacuum overnight to obtain 42 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
The mixture was crushed and dispersed with a paint shaker for 6 hours together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion.

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

[0196]

Example 8 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, 5.0 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.

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.
The results are summarized in Table 1.

[0199]

Example 9 17 g of 2,4-toluene diisocyanate
To the mixture was added 40 g of methyl ethyl ketone as a solvent, 3.8 g of methanol was added dropwise, and the mixture was reacted at 60 ° C. for 5 hours with stirring. Next, 9.9 g of 4,4′-diaminodiphenylsulfone was added, and reacted at 60 ° C. for 4 hours with stirring. After the reaction, the reaction solution was cooled to room temperature, poured into 800 g of acetonitrile, and the precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 15 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight
The mixture was crushed and dispersed with a paint shaker for 6 hours together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion.

Subsequently, a heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1.
The results are summarized in Table 1.

[0202]

Example 10 An intermediate layer coating liquid was obtained by stirring and mixing a mixture of 100 parts by weight of a 33% by weight calcined kaolin dispersion and 12 parts by weight of a 50% by weight aqueous styrene / butadiene latex dispersion (on a dry basis).

Next, 100 parts by weight of an acrylic emulsion of 20% by weight and 7 parts by weight of a 10% by weight dispersion of silica fine powder (Fine Seal SP-10) were mixed by stirring (dry basis) to form a back coat coating solution. I got

Subsequently, one side of the base paper (50 g / m ² ) was coated with the above-mentioned coating solution for the intermediate layer so as to have a solid content of 10 g / m ² , dried, and dried on the same side in Example 1. The prepared heat-sensitive coating liquid was applied so as to have a solid content of 5 g / m ² , dried, and the protective layer coating liquid prepared in Example 1 was coated on the same surface with a solid content of 2 g / m ² . Coated and dried to form Further, the above-mentioned back coat coating solution was applied to the uncoated surface so as to have a solid content of 1 g / m ² , dried and calendered to prepare a heat-sensitive recording material and evaluated. Was. The results are summarized in Table 1.

[0205]

Comparative Example 1 A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the coating liquid for forming a protective layer was not applied on the heat-sensitive coloring layer. The results are summarized in Table 1.

[0206]

Comparative Example 2 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea urethane compound synthesized in Example 1. Was done. The results are summarized in Table 1.

[0207]

[Table 1]

[0208]

As described above, according to the recording material of the present invention, the sensitivity (coloring properties), plasticizer resistance, and scratch resistance are excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B41M 5/18 101E 101C 101D (72) Inventor Kazuo Kabashima 1-3-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Asahi Kasei Corporation F term (reference) 2H026 AA07 BB02 BB24 DD02 DD32 DD42 DD48 DD55 FF11 FF13 FF17 2H085 BB02 BB24 DD02 DD32 DD42 DD48 FE05 FE07

Claims (7)

[Claims] 1. A color-forming layer containing a colorless or pale-colored basic dye precursor and a urea urethane compound developer on a support, and a protective layer for the color-forming layer is provided on the color-forming layer. The recording material to do. 2. The recording material according to claim 1, wherein the protective layer contains a water-soluble polymer. 3. The recording material according to claim 1, wherein the protective layer contains an inorganic pigment and / or an organic pigment. 4. The recording material according to claim 1, wherein the protective layer contains a lubricant. 5. The recording material according to claim 1, wherein a back coat layer is provided on the back surface of the support on which the color forming layer is provided. 6. The recording material according to claim 1, wherein an intermediate layer is provided between the support and the color forming layer. 7. The recording material according to claim 1, wherein the recording material is a heat-sensitive recording material.
7. The recording material according to any one of items 1 to 6.