JP3836867B2 - New urea urethane compounds - Google Patents

Description

The present invention relates to a novel urea urethane compound. The present invention also relates to a novel color former using a urea urethane compound and a recording material using the same.
The color former of the present invention is useful, for example, as a color former of a recording material using recording energy such as heat and pressure, and in particular, a color former having improved storage stability of a non-colored portion (background) and a colored image, and The present invention relates to a recording material using the same, in particular, a heat-sensitive recording material.

  Conventionally, many chemical coloring systems using recording energy such as heat and pressure are known. Among them, a coloring system consisting of a two-component coloring system, usually a colorless or light-colored dye precursor and a color developer that comes into contact with the dye precursor, has been known for a long time and is widely applied to recording materials. Has been. For example, there are pressure-sensitive recording materials using pressure energy, heat-sensitive recording materials using thermal energy, and photosensitive recording materials using light energy.

  So far, pressure-sensitive recording materials using pressure energy have been most commonly used as a plain paper. In general, a pressure-sensitive recording material can be obtained by dissolving a dye precursor in a suitable solvent, emulsifying it to several microns, and then performing microencapsulation. An upper sheet formed by applying this microcapsule on a support, a lower sheet formed by applying a developer layer containing a developer on another support, a microcapsule application surface and a developer application surface. When they are overlapped so as to face each other and a writing pressure or a striking pressure is applied, the microcapsules are broken and the inclusions containing the dye precursor are released. The dye precursor is transferred to the developer layer and comes into contact with the developer, and a color development reaction occurs to record an image.

  In recent years, for example, in various information devices such as facsimiles, printers, recorders, and the like, many thermal recording systems that perform recording by thermal energy have been adopted. The thermal recording material used in the thermal recording system has many excellent properties such as high whiteness, appearance, touch close to plain paper, good recording suitability such as coloring sensitivity, etc. Has advantages such as small equipment, no maintenance, no noise generation, measuring recorder, facsimile, printer, computer terminal, label, automatic ticket vending machine for tickets, etc. The application has been expanded to the field.

  The thermal recording method mainly uses a recording material in which a color developing layer containing a two-component color former is provided on a support, and heat is applied thereto as a recording energy by a thermal head, a hot stamp, a laser beam or the like. In this method, the heat-sensitive agent components are brought into contact with each other on the recording material to perform color recording. As the color former, a colorless or light-colored electron-donating dye precursor (particularly a leuco dye) and an acidic developer such as a phenolic compound are often used. Examples of the recording material using the leuco dye include thermal paper (see Patent Document 1, etc.) using crystal violet lactone and 4,4′-isopropylidenediphenol (bisphenol A) as a thermal color former.

As the dye precursor and developer used in these recording methods, an electron donating compound and an electron accepting compound are mainly used, respectively. This is because a dye precursor that is an electron-donating compound and a developer that is an electron-accepting compound come into contact with each other, so that a color image with a high density can be obtained instantaneously and an appearance close to white can be obtained. This is because it has excellent characteristics such as various colored hues such as red, orange, yellow, green, blue, and black. However, on the other hand, the obtained color image is inferior in chemical resistance, and when it comes into contact with a plasticizer contained in a plastic sheet or eraser or a chemical contained in food or cosmetics, the record is easily lost, or relatively Due to the poor storage stability of records, such as fading or disappearing due to short-term exposure to sunlight, color formers composed of dye precursors and developers are subject to certain restrictions. The improvement is strongly desired.

In recent years, phenolic compounds typified by bisphenol A have been used due to the problem of environmental hormones, and a non-phenolic color developer has been demanded.
In response to such a request, for example, Patent Document 2 and Patent Document 3 disclose a recording material comprising a combination of a color former composed of an aromatic isocyanate compound and an imino compound as a recording material having good storage stability. ing. In the present invention, various recording materials are disclosed in which two kinds of color formers are brought into contact and reacted by applying recording energy such as heat, pressure, and light. In addition, it is described that various colors such as red, orange, yellow, brown, and brown can be developed by appropriately selecting a color former. However, the black color development that is strongly demanded in the recording materials that are currently widely used is still insufficient.

As thermal recording materials using a non-phenolic developer, Patent Documents 4 and 5 disclose thermal recording materials having a coloring layer containing a colorless or light-colored dye precursor and a urea compound. Yes. However, these recording materials have a low color density and insufficient storage stability.
Patent Document 6 discloses a heat-sensitive recording material having a heat-sensitive coloring layer containing a colorless or light-colored dye precursor and a sulfonylurea compound. However, these recording materials have low whiteness and insufficient storage stability.

US Pat. No. 3,539,375 JP 59-115887 A U.S. Pat. No. 4,521,793 JP-A-8-2111 JP-A-8-2112 Japanese Patent Laid-Open No. 5-164459

An object of the present invention is to provide a novel urea urethane compound exhibiting excellent performance when used as a color developer for a color former.
Another object of the present invention is to provide a novel color former excellent in image storability and color density and a recording material using the same, particularly a heat sensitive recording material, by using various urea urethane compounds.
Furthermore, the present invention relates to a novel color former whose performance has been improved by adding various additives to a urea urethane compound and a dye precursor, and a recording material using the same.

  As a result of intensive studies on the synthesis of various color former compounds, the present inventors have found that a specific compound exhibits surprisingly excellent performance, and have completed the present invention. Further, the inventors have found that a specific compound exhibits surprisingly excellent performance in combination with a dye precursor, and have completed the present invention.

That is, the present invention is as follows.
The first of the invention is a urea urethane compound represented by the following formula (III).

(In the formula, X represents a phenyl group, Y each independently represents a phenylene group or a methylene difel group, and each may independently have a methyl substituent, and α represents —Φ— or — Represents a divalent residue represented by Φ-ε- Φ-, where -Φ- represents a phenylene group, and each of the phenylene groups independently has a substituent selected from a methyl group and a methoxy group. at best,-.epsilon.-is _{-SO 2 -, - O -,} - CH 2 - and represents a group or a single bond selected from -CONH-).

A second aspect of the invention is a urea urethane compound represented by the following formula (V).

(In the formula, the hydrogen atom of the benzene ring may be substituted with a methyl group, and γ represents —SO ₂ —, —O—, — (S) _n —, — (CH ₂ ) _n —, —CO—, One selected from the group consisting of -CONH- and any of the groups represented by formula (a)

Or the case where it does not exist is shown, and n is 1 or 2. )

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

Hereinafter, the present invention will be described in detail.
Formula according to the first aspect of the present invention
10 ≧ (A + B) ≧ 3 (where A and B are integers of 1 or more)
The urea urethane compound satisfying the formula has at least one urea group (—NHCONH— group) and one urethane group (—NHCOO— group) in the molecular structure, and the total number of urea groups and urethane groups is 3 or more. Compounds present at 10 or less.

  Conventionally, such a compound has not been known and is a completely new compound. This novel compound is useful for recording materials that use recording energy such as heat and pressure. The molecular weight of the urea urethane compound is preferably 5000 or less, and more preferably 2000 or less. Further, the ratio of the urea group to the urethane group in the urea urethane compound molecular structure is preferably 1: 3 to 3: 1, and particularly preferably 1: 2 to 2: 1.

  In the synthesis method of the urea urethane compound according to the first aspect of the present invention, the total number of urea groups and urethane groups is 3 to 10 in the urea group (—NHCONH— group) and the urethane group (—NHCOO— group). There is no particular limitation as long as it is a method produced as described above, but a method of making it by a reaction of an isocyanate compound, an OH group-containing compound and an amine compound is easy and preferable.

  That is, the urea urethane compound according to the first aspect of the present invention uses, for example, an isocyanate having at least two or more isocyanate groups as a starting material, and leaves at least one isocyanate group of the isocyanate and other isocyanate groups and OH. A urethane group is formed by reacting with a group-containing compound, and then the remaining isocyanate groups of the two molecules of the urethane compound are reacted with water to bond them together, so that the total number of urea groups and urethane groups is at least three. A compound can be obtained.

  Further, for example, an isocyanate having at least two isocyanate groups is used as a starting material, and at least one isocyanate group of the isocyanate is left to react with another isocyanate group and an OH group-containing compound to form a urethane group. Next, the remaining isocyanate group and an amine compound having two or more amino groups are reacted to form a urea group, and the remaining amino group is reacted with the isocyanate compound to thereby form a urea group and a urethane group. A total of at least three urea urethane compounds can be obtained.

In addition, the isocyanato group is first reacted with an amine compound to form a urea group, and then the remaining isocyanato group is reacted with an OH group-containing compound having two or more OH groups to form a urethane group. A urea urethane compound having a total number of urea groups and urethane groups of at least 3 can also be obtained by reacting an isocyanate compound.
At this time, an isocyanate compound having two or more isocyanate groups is used as the isocyanate to be reacted last, and the remaining isocyanate group and an OH-containing compound having two or more OH groups or an amino group having two or more amino groups are used. By sequentially repeating the operation of reacting the compound, 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-eth Carbazole-3,6-diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenyl) Isocyanato) thiophos Fert, 4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ′, 4 ″ -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate Dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like. In addition, diisocyanate dimer, for example, dimer of toluene diisocyanate, N, N ′ (4,4′-dimethyl-3,3′-diphenyldiisocyanato) uretdione (trade name Desmodur TT) Or a trimer such as 4,4 ′, 4 ″ -trimethyl-3,3 ′, 3 ″ -triisocyanato-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 such as trimethylolpropane adduct of toluene diisocyanate (trade name) It may be a death module L) or an amine adduct body. Moreover, the 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) Of these, one having two or more isocyanato groups may be present.

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

The amine compound that reacts with the isocyanate that is the starting material of the urea urethane compound to form a urea group may be any compound having an amino group, such as aniline, o-toluidine, m-toluidine, and p-toluidine. O-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2 , 4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3- Xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xy Gin, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloro Aniline, 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, acetoacetanilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide 3,5-diaminochlorobenzene, diaminodiphenyl ester Ether, 3,3′-dichloro-4,4′diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2 -Chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, iso-propyl p-aminobenzoate, butyl p-aminobenzoate, p -Dodecyl aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methyl Benzamide, 3-amino-4-methylbenzene Zamide, 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-benzoyl) Amino) 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-diethylsulfone Famoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2′-chlorophenoxy) sulfonylaniline, 3- Anilinosulfonyl-4-methylaniline, [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'-dimethyldi Benzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzof Non, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-amino) Phenyl) 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, metol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol Sulfate, sulfanilic acid, methanyl 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'-dichloro Benzidine, 4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid, phenyl J acid, 1,4- Aromatic amines such as diamino-anthraquinone and 1,4-diamino-2,3-dichloroanthraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine , Α-amino-ε-caprolactam, acetoguanamine, 2, -Diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino- Heterocyclic compound amines such as 4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine, methylamine, ethylamine, dimethylamine, diethylamine, stearyl Amine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di- 2-Eth Ruhexylamine, 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- Aliphatic amines such as aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenedriamine, and hexamethylenediamine Kind and the like.
Further, among the above amine compounds, an aniline derivative having at least one amino group such as the following formula (VIII) is particularly preferable.

(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 an amino Represents a group or a group represented by formula (b),

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

Or the case where it does not exist is shown. n is 1 or 2. )

The OH group-containing compound that reacts with an isocyanate to form a urethane group may be any compound having an OH group. For example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcin, p -Tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2- Bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3 Methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis ( 4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro -4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) Sulfo 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 4-isopropylphenyl-4′-hydroxyphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, bis (2-methyl-3-tert-butyl- 4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-thiodiphenol, 4,4′-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4 '-Dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone, 2,4-dihydroxybenzophenone, 2,2' , 4,4'-Tetrahi Droxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4'-hydroxybenzoic acid) Ethyl, 1,5-bis (4′-hydroxybenzoic acid) pentyl, 1,6-bis (4′-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid 3-n-octanoyloxysalicylic acid, -n- octyloxycarbonyl-aminosalicylic acid, and phenols such as 4-n-octanoyl butyloxycarbonylamino salicylic acid. However, those having amino groups are not preferred as these phenols. Since the amino group is more reactive 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 the target compound. Also, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isoheptanol, 2-ethyl-1-hexanol, 1-decanol, 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, Alcohols such as cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin and glycerol; Pyrene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, phenol polyol, amine modified polyol and other polyether 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 polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylol Polyols such as tan, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, shoelace Is mentioned.

The urea urethane compounds of the formulas (I) to (VI) according to the second aspect of the present invention are also completely novel compounds. This novel compound is useful for a recording material using recording energy such as heat and pressure.
The urea urethane compound of the formula (I) according to the second aspect of the present invention is not limited to the production method. For example, the OH group-containing compound of the following general formula (IX), the isocyanate compound of the following general formula (X) and the following general formula ( It can obtain by making it react with the amine compound of XI), for example according to following Reaction formula (A).

(In the formula, 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. Y ₀ represents tolylene. Represents one selected from the group consisting of a group, a xylylene group, a naphthylene group, a hexamethylene group, and a -φ-CH ₂ -φ- group, and -φ- represents a phenylene group.
The term “aliphatic” as used in the present invention includes alicyclic.

  The urea urethane compound of the formula (II) according to the second aspect of the present invention is not limited to a production method. For example, an OH group-containing compound of the general formula (IX), an isocyanate compound of the following general formula (XII) and water are used. For example, it can obtain by making it react according to following Reaction formula (B).

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

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

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

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

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

The compounds of the general formulas (IX) to (XIV) that can be used when synthesizing the urea urethane compounds represented by the above formulas (I) 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 is a compound having one or more OH groups. For example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, Resorcin, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4 -Phenylphenol, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxypheny -4'-hydroxyphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, phenyl salicylate, salicylanilide Methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4′-chlorobenzyl), 1,2-bis (4′-hydroxybenzoic acid) ethyl, 1,5-bis (4 '-Hydroxybenzoic acid) pentyl, 1,6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4- n-octyloxysalicylic acid, 4- -Butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid And monophenols. 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-medoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, 4,4'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxy Phenyl) acetic acid benzyl, 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'-dihydroxy Diphenols such as diphenylamine and bis (4-hydroxy-3-methylphenyl) sulfide are also included. However, those having an amino group are not preferred as these OH group-containing compounds. When the amino group coexists, the reactivity with the isocyanato group is higher than that of the OH group, so that the amino group may react with the isocyanato group first to make it difficult to obtain the target compound. Also, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, 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, cyclohexyl Examples include monoalcohols such as methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, and glycerol. It is. Also, polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol, amine modified polyol, ethylene glycol, diethylene glycol, 1 , 3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1, 9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethyl Polyols such as roll ethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, shoelace It may be similar. Of these, monophenols are preferably used.

As the isocyanate compound of the general formula (X), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, And metaxylylene diisocyanate. Of these, toluene diisocyanates are preferred.
The isocyanate compound of the general formula (XII) is not particularly limited as long as it has two or more isocyanate groups. For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4 -Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris ( 4-Phenyl isocyanate) 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, methylcyclohexane diisocyanate and the like. In addition, diisocyanate dimer, for example, dimer of toluene diisocyanate, N, N ′-(4,4′-dimethyl-3,3′-diphenyldiisocyanate) uretdione (trade name Desmodur TT) ) And trimers such as 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 ( A product name Death Module L), an amine adduct body, etc. may be sufficient. Of 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 present. 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 one or more amino groups. 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-trichloro Aniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, p-aminobenzoic acid n- Propyl, 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-acetylamino 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-phenylsulfamoyl Aniline, 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, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2 , 3,4-trifluoroaniline, m-aminobenzotrifluoride, aromatic monoamines such as 2-amino-3-bromo-5-nitrobenzonitrile, 4,4'-diamino-3,3'-diethyldiphenylmethane 4,4′-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, Tolidine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfo , 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'-dithio Aniline, 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-bi (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 and other aromatic diamines. 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- ( Heterocyclic compound amines such as 2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine, methylamine, ethylamine, stearylamine, allylamine, isopropylamine, 2-ethylhexylamine, ethanol Amine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxy Propylamine, 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine , Methyl hydrazine, 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, diethylenedriamine Aliphatic amines such as hexamethylenediamine and the like. Of these, aromatic monoamines are preferably used.

The amine compound of general formula (XIII) is not particularly limited as long as it is a compound having two or more amino groups. For example, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diamino Benzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, tolidine base, dianisidine, bis [ 4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2 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 No-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'-diamino Benzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-amino) Phenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenyl) Enoxy) diphenyl, dianisidine, 3,3′-dichlorobenzidine, tolidine base, aromatic amines such as o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. Further, among the above amine compounds, aniline derivatives having at least two amino groups such as the following formula (VIII) are particularly preferable.

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

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

Or the case where it does not exist is shown. n is 1 or 2. )

The OH group-containing compound of the general formula (XIV) is not particularly limited as long as it is a compound having two or more OH groups. For example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( Hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, p, p ' -Biphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5 -Dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxy 4'-methylphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl -3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether,
4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis ( And diphenols such as 4-hydroxy-3-methylphenyl) sulfide. However, those having an amino group as these diphenols are not preferred. Since the amino group is more reactive 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 the target compound. Also, polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol, amine modified polyol, ethylene glycol, diethylene glycol, 1 , 3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1, 9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethyl Polyols such as roll ethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, shoelace Kind.

  The urea urethane compound of the formula (V) according to the second aspect of the present invention is not limited to the production method. It can obtain by making it react according to Reaction formula (G) or (H).

(In the formula, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. Each residue may have a substituent. Γ is —SO ₂ —, —O—, — (S) _n —, — (CH ₂ ) _n —, —CO—, —CONH—, any of the groups represented by formula (a),

Or the case where it does not exist is shown. n is 1 or 2. )

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

(In the formula, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. Further, each residue may have a substituent. Δ is —SO ₂ —, —O—, — (S) _n —, — (CH ₂ ) _n —, —CO—, —CONH—, —NH—, —CH (COOR ₁ ) —, —C ( CF ₃ ) ₂ —, —CR ₂ R ₃ —, or a case where it is absent, R ₁ , R ₂ and R ₃ each independently represents an alkyl group, and n is 1 or 2.

The compounds that can be used when synthesizing the urea urethane compounds of the formulas (V) and (VI) according to the second of the present invention will be described in detail below.
The monophenol compound that can be used when synthesizing the urea urethane compound of the formula (V) is not particularly limited as long as it is a compound having one OH group in the benzene ring. For example, phenol, cresol, xylenol, p -Ethylphenol, o-isopropylphenol, resorcin, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o- Chlorophenol, p-chlorophenol, 4-phenylphenol, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl-4'- Roxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-iso Propoxydiphenyl 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-octanoyloxy salicylic acid, 4-n-octyloxy carbonylamino salicylic acid, 4-n-phenols such as octanoyloxy carbonyl aminosalicylic acid. However, those having amino groups are not preferred as these phenols. Since the amino group is more reactive 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 the target compound.

The aromatic diisocyanate compound that can be used when synthesizing the urea urethane compounds of the formulas (V) and (VI) is any aromatic diisocyanate having two isocyanate groups bonded to a benzene ring. Is not particularly limited, and examples thereof include paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and the like. . Particularly preferred examples include toluene diisocyanates. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable, but in addition to this, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and inexpensive. It is possible to obtain it, but this is also acceptable. These toluene diisocyanate isomer mixtures are liquid at room temperature.
Examples of the diamine compound of the general formula (XV) that can be used when the urea urethane compound of the formula (V) is synthesized include, for example, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diamino. Benzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, tolidine base, dianisidine, bis [ 4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphe Nil, 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-a And aromatic diamines such as minophenoxy) diphenyl, dianisidine, and 3,3′-dichlorobenzidine.

The aniline derivative that can be used when synthesizing the urea urethane compound of the formula (VI) is not particularly limited as long as it is an aniline compound having one amino group in the benzene ring. Toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4 -Xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene O-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate Butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-amino Benzamide, p-amino-N-methylbenza Amide, 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- Methoxy-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-anilinos Sulfonyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4 -Chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, p-fluoroaniline O-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitro Examples include benzonitrile.

  Examples of the dihydroxy compound of the general formula (XVI) that can be used when synthesizing the urea urethane compound of the formula (VI) include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (hydroxyphenyl). ) Butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 4,4'-biphenol, butyl acetate of bis (4-hydroxyphenyl), bis (4-hydroxyphenyl) Benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (2-allyl-4-hydroxyphenyl) ) Sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphene) Sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxy And diphenols such as diphenylmethane, 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 is more reactive 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 the target compound.

In order to obtain the urea urethane compound according to the second aspect of the present invention, the reactant may be mixed with an isocyanate in an organic solvent or without solvent, and then the crystals may be taken out by filtration. You may use a reactive agent individually or in multiple types according to the objective. The solvent may be anything as long as it does not react with the isocyanate group and the functional group of the reactant, for example, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, chlorinated aliphatic hydrocarbon. Chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, ketones and the like. In particular, methyl ethyl ketone, toluene and the like which dissolve isocyanate and have low product solubility are preferable. The product obtained by the above reaction operation is not necessarily a single product, and may be obtained as a mixture of compounds having different substituent positions.

The following compounds can be illustrated as specific examples of the second urea urethane compound of the present invention. ((E-1) to (E-43))

The urea urethane compound according to the second aspect of the present invention is useful for recording materials, for example.
The urea urethane compound as the developer according to the third aspect of the present invention refers to a compound having at least one urea group (—NHCONH— group) and one urethane group (—NHCOO— group) in the molecule.
Until now, it has been known that compounds having a urea group show a developing action, but the color density is low and the storage stability is low, which is not practical. Surprisingly, however, a urea urethane compound in which a urea group and a urethane group are present simultaneously in one molecule is an excellent developer of a colorless or light-colored dye precursor. The recording material has a high color density and excellent storage stability.

Although the mechanism by which such a urea urethane compound exhibits an excellent color developing action is unknown, it is presumed to be due to the interaction between the urea group and the urethane group in the molecule.
The urea urethane compound as the developer according to the third aspect of the present invention may be any compound as long as both a urea group (—NHCONH— group) and a urethane group (—NHCOO— group) are present in the molecule. An aromatic compound or a heterocyclic compound is preferable. Further, those in which an aromatic compound residue or a heterocyclic compound residue is directly bonded to both ends of a urea group and a urethane group are preferable. More preferably, in addition to a urea group (—NHCONH— group) and a urethane group (—NHCOO— group) in the molecule, a sulfone group (—SO ₂ — group), an amide group (—NHCO— group) or an isopropylidene group (— It is desirable that C (CH3) ₂ -group) is present without being directly bonded to the urea group.

The molecular weight of the urea urethane compound is preferably 5000 or less, and more preferably 2000 or less. The total number of urea groups and urethane groups in the urea urethane compound is preferably 20 or less, and more preferably 10 or less. Moreover, the ratio of the urea group to the urethane group in the urea urethane compound molecular structure is preferably 1: 3 to 3: 1, and particularly preferably 1: 2 to 2: 1.
In the thermosensitive recording material, a urea urethane compound having a melting point is preferable, and the melting point is preferably in the range of 40 ° C. to 500 ° C., particularly preferably in the range of 60 ° C. to 300 ° C.

The method for synthesizing the urea urethane compound as the developer according to the third aspect of the present invention is not particularly limited as long as the urea group (-NHCONH-group) and the urethane group (-NHCOO-group) are generated. A method of making by reacting an isocyanate compound with an OH group-containing compound and an amine compound is easy and preferable.
That is, the urea urethane compound as a color developer according to the present invention uses an isocyanate having at least two or more isocyanate groups as a starting material, leaves at least one isocyanate group of the isocyanate and other isocyanate groups and OH. The group-containing compound can be reacted to form a urethane group, and then the remaining isocyanate group and the amine compound can be reacted to form a urea group. Alternatively, the isocyanate group and the amine compound may be reacted first to form a urea group, and then the remaining isocyanate group and OH group-containing compound may be reacted to form a urethane group.

The starting isocyanate is not particularly limited as long as it has two or more isocyanate groups. For example, paraphenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4 -Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl Carbazole-3,6-diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenyl) Isocyanato) thioho Sulfate, 4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ′, 4 ″ -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate Dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like. In addition, diisocyanate dimers such as 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-triphenyl cyanurate 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 The name death module L) or an amine adduct body may be used. Of the isocyanate compounds and isocyanate adduct compounds described in Japanese Patent Application No. 8-225445 and Japanese Patent Application No. 8-250623, two or more isocyanate groups may be present.
A particularly preferred example is toluene diisocyanate. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable, but in addition to this, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and can be obtained at low cost. It is possible, but this is also possible.

The amine compound that reacts with an isocyanate which is a starting material of a urea urethane compound as a developer to form a urea group may be any compound having an amino group, such as aniline, o-toluidine, m- Toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p -Phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol 2,3-Xylidine, 2,4-Xylidine, 3,4-Xylidine 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4 , 5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N- Butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetanilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4 ' -Diaminobenzanilide, 3,5-diaminochlorobenzene, diamy Nodiphenyl ether, 3,3′-dichloro-4,4′diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, p- Dodecyl aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-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-diethyl Sulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2′-chlorophenoxy) sulfonylaniline, 3 -Anilinosulfonyl-4-methyl Nilin, 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'-diaminobiff Nil, 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′-tetraaminodiphenyl sulfone, 3,3 ′, 4,4′-tetraaminobenzophenone, 3-aminobenzo Nitrile, 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-nitroben Nitrile, metol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoro Aniline, 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'-dichloro Benzidine, 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-2,3 -Aromatic amines such as 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, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-amino Propyl) morpholine and other heterocyclic compound 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) propyl Amine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclo Hexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2- Examples thereof include aliphatic amines such as propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine.

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

(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 an amino group. Or a group represented by formula (b),

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

Or the case where it does not exist is shown. n is 1 or 2. )

The OH group-containing compound that reacts with an isocyanate to form a urethane group may be any compound having an OH group. For example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcin, p- tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 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- Toxicatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, 4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro -4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) ) Sulfone 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, bis (2-methyl-3-tert-butyl-4 -Hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4 ' -Dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydride Roxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), ethyl 1,2-bis (4'-hydroxybenzoate) 1,5-bis (4′-hydroxybenzoic acid) pentyl, 1,6-bis (4′-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4 n- octyloxycarbonyl-aminosalicylic acid, and phenols such as 4-n- octanoyl butyloxycarbonylamino salicylic acid. However, those having an amino group as these phenols are not preferred. Since the amino group is more reactive 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 the target compound. Also, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, inpentanol, 2-ethyl-1-hexanol, 1-decanol, 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, cyclohexyl Alcohols such as methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin and glycerol; Polyethylene polyols such as lenglycol, 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, trimethylol ether Polyols such as ethylene, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, shoecloth Is mentioned.

As the urea urethane compound as the developer according to the fourth aspect of the present invention, the first urea urethane compound of the present invention can be used. The synthesis method has already been described in detail in the first description of the present invention.

  As the urea urethane compound as the developer according to the fifth aspect of the present invention, the urea urethane compound of the second general formulas (I) to (VI) of the present invention and the urea urethane compound of the general formula (VII) are used. be able to. The method for synthesizing the urea urethane compounds of the general formulas (I) to (VI) is as already described in detail in the second description of the present invention, but the method for synthesizing the urea urethane compound of the general formula (VII) is as follows. Although there is no particular limitation, for example, an OH group-containing compound of the general formula (IX), an isocyanate compound of the general formula (XII) and an amine compound of the general formula (XI) are reacted according to, for example, the following reaction formula (L) Can be obtained.

In addition, as a substituent of X couple | bonded with the urethane group of the urea urethane compound of general formula (VII), an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an amide group, an alkoxyl group, a nitro group, a nitroso group Nitrile group, toluenesulfonyl group, methanesulfonyl group, acetyl group, halogen atom, formyl group, dialkylamino group and isocyanato group are preferred.
Of these urea urethane compounds as the developers of the general formulas (I) to (VII), preferred are the compounds of the general formulas (II) to (VI), and particularly preferred are the general formulas (V) to (V). VI).

  Further, in the urea urethane compound as the developer according to the third aspect of the invention and the urea urethane compound as the developer of formulas (I) to (IV) and (VII), it is bonded to a urea group or a urethane group. When the residue is an aliphatic compound residue, the color density and print storage performance may decrease, and the residue bonded to the urea group or the urethane group is an aromatic compound residue or a heterocyclic compound residue. It is preferable that 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 alleviated by increasing the number of urea groups and urethane groups, and the formula (III), In the compound of the formula (IV), even if an aliphatic compound residue is present in the residue bonded to the urea group or the urethane group, there is almost no problem in performance.

The urea urethane compound as a developer of the present invention is usually a normal temperature solid colorless or light colored compound.
The molecular weight of the urea urethane compound as the developer of the present invention is preferably 5000 or less, and more preferably 2000 or less.
The total number of urea groups and urethane groups in the urea urethane compound as the developer of the present invention is preferably 20 or less, and more preferably 10 or less. Moreover, the ratio of the urea group to the urethane group in the urea urethane compound molecular structure is preferably 1: 3 to 3: 1, and particularly preferably 1: 2 to 2: 1.

In the thermosensitive recording material, a compound having a melting point is preferable, and the melting point of the urea urethane compound as the developer of the present invention is preferably in the range of 40 ° C. to 500 ° C., particularly preferably in the range of 60 ° C. to 300 ° C. .
In preparing a recording material using a urea urethane compound as a developer, one kind of the urea urethane compound or two or more kinds as necessary can be used in combination.
The colorless or light-colored dye precursor of the present invention is a compound already known as a color former used in a pressure-sensitive recording material or a heat-sensitive recording material, and is not particularly limited, but an electron-donating dye precursor is preferable. Further, leuco dyes are preferable, and triarylmethane leuco dyes, fluoran leuco dyes, fluorene leuco dyes, diphenylmethane leuco dyes, and the like are particularly preferable. Examples of typical dye precursors are shown below.

(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-Phenylindol-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-phenylindole-3-yl) -5-dimethylaminophthalide, 3-p-dimethylamino-phenylalanine 3- (1-methylpyrrole-2-yl) -6-dimethylaminophthalide and the like.

(2) Diphenylmethane compounds
4,4-bis-dimethylaminophenyl benzhydryl benzyl ether, N-halophenyl leucooramine, N-2,4,5-trichlorophenyl leucooramine and the like.

(3) Xanthene compounds
Rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-phenylfluorane, 3 -Diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-7- (3,4-dichloroanilino) fluorane, 3-diethylamino-7- (2-chloroanilino) ) Fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl- 7-anilinofluorane, 3- (N-ethyl-N-tolyl) amino-6-methyl 7-phenethylfluorane, 3-diethylamino-7- (4-nitroanilino) fluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-propyl) amino-6- Methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-cyclohexyl) amino-6-methyl- 7-anilinofluorane, 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluorane, and the like.

(4) Thiazine compounds
Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc.

(5) Spiro compounds
3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, 3-propylspiro Such as benzopyran.

  In addition, 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'-diethyl) Aminodiphthalide), 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-dimethylamino) Phenyl) -2- (4-methoxyphenyl) ethenyl] -4,5,6,7, -tetrachlorophthalide and the like having an absorption region in the near infrared And the like.

  The urea urethane compound as the developer is preferably used in an amount of 5 to 1000 parts by weight, more preferably 20 to 500 parts by weight, based on 100 parts by weight of the colorless or pale dye precursor. If the urea urethane compound as the developer is 5 parts by weight or more, it is sufficient to cause the dye precursor to develop color, and the color density is high. Moreover, if the urea urethane compound as a color developer is 1000 parts by weight or less, the urea urethane compound as an excessive color developer hardly remains, which is advantageous from the economical viewpoint.

Preservability is improved by adding an isocyanate compound to the color former of the present invention. The isocyanate compound used in addition to the color former of the present invention refers to a room-temperature solid colorless or light-colored aromatic isocyanate compound or heterocyclic isocyanate compound. For example, one or more of the following isocyanate compounds are used. It is done.
2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4 -Dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-methoxybenzene-2,5-diisocyanate, 1-ethoxybenzene-2,4-diisocyanate 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxybenzene-1,4-diisocyanate, 2,5-dibutoxybenzene-1,4-diisocyanate, azobenzene- 4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, naphthalene-1,4-di Isocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 3,3'-dimethyl-biphenyl-4,4'-diisocyanate 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, benzophenone-3,3′-di Isocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, pyrene-3,8-diisocyanate, naphthalene-1, 3,7-triisocyanate, biphenyl-2,4,4′-triisocyanate, 4,4 ′, 4 ″ -triisocyanate Examples include cyanato-2,5-dimethoxytriphenylamine, 4,4 ′, 4 ″ -triisocyanatotriphenylamine, p-dimethylaminophenyl isocyanate, tris (4-phenylisocyanate) thiophosphate. These isocyanates may be used in the form of so-called block isocyanate, which is an addition compound with phenols, lactams, oximes, etc., if necessary, and diisocyanates of diisocyanates such as 1- It may be used in the form of methylbenzene-2,4-diisocyanate dimer and trimer isocyanurate, or it can be used as a polyisocyanate adducted with various polyols. It is. Also, water adduct isocyanates such as 2,4-toluene diisocyanate and diphenylmethane diisocyanate, such as 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts such as toluene diisocyanate Methylolpropane adduct (trade name Desmodur L), phenol adduct isocyanate, amine adduct isocyanate, and the like, isocyanate compounds and isocyanate adducts described in JP-A-10-76757 and JP-A-10-95171 It may be a compound.

The isocyanate compound 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 light dye precursor. When the isocyanate compound is 5 parts by weight or more, the effect of improving the storage stability is sufficient, and the color density is high. Further, the isocyanate compound is 500 parts by weight or less, and an excess of the isocyanate compound hardly remains, which is economically advantageous and preferable.
Further, the storage stability is further improved by adding an imino compound thereto.

  The imino compound that can be added to the color former of the present invention is a compound having at least one imino group and is a colorless or light-colored compound that is solid at room temperature. Two or more imino compounds can be used in combination depending on the purpose. Examples of these imino compounds include those described in JP-A-9-141432, the contents of which are incorporated herein by reference. Among these, iminoisoindoline derivatives are particularly preferable, and 1,3-diimino-4,5,6,7-tetrachloroisoindoline, 3-imino-4,5,6,7-tetrachloroisoindoline- 1-one, 1,3-diimino-4,5,6,7-tetrabromoisoindoline is preferred.

The imino compound 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 light dye precursor. If the imino compound is 5 parts by weight or more, the effect of improving the storage stability is exhibited. Moreover, if the imino compound is 500 parts by weight or less, an excess of the imino compound is less likely to remain, which is economically advantageous and preferable.
Further, by adding an amino compound to the color former of the present invention, the background and printing storability are improved. The amino compound that can be added is a colorless or light-colored substance having at least one primary, secondary, or tertiary amino group. Examples of these amino compounds include those described in JP-A-9-143202. Among these, an aniline derivative having at least one amino group such as the following formula (VIII) is particularly preferable.

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

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

Or the case where it does not exist is shown. n is 1 or 2. )

The amino compound may be used alone or in combination of two or more, and 1 to 100 parts by weight of a colorless or light-colored dye precursor in order to improve print storage stability in plasticizer resistance. The amount is preferably 500 parts by weight. If the content of the amino compound is 1 part by weight or more with respect to the urea urethane compound, the print storage stability can be improved. On the other hand, if it is 500 parts by weight or less, the performance is sufficiently improved and advantageous in terms of cost.
In the color former of the present invention, the addition of an acidic developer further improves the sensitivity and provides a clear color former.

As the acidic developer when the color former of the present invention is used as a heat-sensitive recording material, generally used electron accepting substances are used, and in particular, phenol derivatives, aromatic carboxylic acid derivatives or their metal compounds, salicylic acid derivatives. Alternatively, metal salts thereof, N, N-diarylthiourea derivatives, sulfonylurea derivatives and the like are preferable. Particularly preferred are phenol derivatives, specifically 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, , 2-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), 1,2-bis (4'-hydroxybenzoic acid) ethyl, 1,5-bis (4'-hydroxybenzoic acid) pentyl, 1,6-bis (4'-hydroxybenzoic acid) hexyl, 3, -Dimethyl phthalate, stearyl gallate, gallate Lil, and the like. Further, as salicylic acid derivatives, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octoctanoyloxysalicylic acid, 4-n- Examples also include octyloxycarbonylaminosalicylic acid and 4-n-octanoyloxycarbonylaminosalicylic acid. Examples of sulfonylurea derivatives include 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4-bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4-bis (p-toluenesulfonylaminocarbonyl). Examples include compounds containing one or more arylsulfonylaminoureido groups such as amino) diphenyl sulfide, 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl ether, and N- (p-toluenesulfonyl) -N′-phenylurea. It is done.

  Furthermore, N-stearyl-N ′-(2-hydroxyphenyl) urea, N-stearyl-N ′-(3-hydroxyphenyl) urea, N-stearyl-N are used to improve the surface covering and thermal responsiveness. '-(4-hydroxyphenyl) urea, p-stearoylaminophenol, o-stearoylaminophenol, p-lauroylaminophenol, p-butyrylaminophenol, m-acetylaminophenol, o-acetylaminophenol, p-acetyl Aminophenol, o-butylaminocarbonylphenol, o-stearylaminocarbonylphenol, p-stearylaminocarbonylphenol, 1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, 1 , 1,3-Tris (3-ter -Butyl-4-hydroxy-6-ethylphenyl) butane, 1,1,3-tris (3,5-di-tert-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-tert -Butyl-4-hydroxy-6-methylphenyl) propane, 1,2,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-phenyl) -4-hydroxyphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-5-methylphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-6-methyl) Phenyl) butane, 1,1,3-tetra (3-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetra (3-cyclohexyl-4-hydride) Xyl-6-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, 1,1-bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) It is also possible to add phenolic compounds such as butane.

The acidic developer is preferably used in an amount of 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, based on 100 parts by weight of a colorless or pale dye precursor. When the acid developer is 5 parts by weight or more, the dye precursor is well colored and the color density is high. Moreover, if it is 500 parts weight or less, it is hard to remain acidic developer and it is economically advantageous and preferable.

Even when the color former of the present invention is used as a pressure-sensitive recording material, by adding an acidic developer, the image density is improved and a pressure-sensitive recording material having a clear color can be obtained.
As the acidic developer, an electron-accepting substance is still used, and examples thereof include acidic clay, activated clay, attapulgite, bennite, zeolite, colloidal silica, magnesium silicate, talc, and aluminum silicate. Inorganic compounds, or phenol, cresol, butylphenol, octylphenol, phenylphenol, chlorophenol, salicylic acid, or the like, or aldehyde condensed novolak resins and their metal salts derived therefrom, 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-dimethyl Njiru) salicylic acid, 3-phenyl-5-(alpha, alpha-dimethylbenzyl) salicylic acid derivatives and metal salts thereof, such as salicylic acid, and the like.

The color former of the present invention can be used as a recording material by forming a color development layer on some support by a method such as coating. The configuration differs depending on the type of recording material.
The color former 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 color development by heating is provided on the support. Specifically, a colorless or light-colored dye precursor such as the above urea urethane compound, a leuco dye, a thermofusible substance described later, and the like are coated on a support together with other necessary components in the form of a dispersion. It is necessary to use a heat-sensitive recording layer. The dispersion is prepared by pulverizing one or more of each of these compounds with a sand grinder or the like in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer and a surfactant. . The particle diameter of each dispersion liquid is preferably 0.1 to 10 μm, particularly around 1 μm. Specific examples of the compound having dispersibility that can be used in the present invention include water-soluble polymers such as polyvinyl alcohol, carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, and condensation. Naphthalene sulfonate, polyoxyethylene alkyl ether sulfate (eg, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate), sodium dialkyl sulfosuccinate, alkyl phosphorus Acid salts (for example, diethanolamine alkylphosphate, potassium alkylphosphate) and special carboxylic acid type polymers Surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyethylene glycol fatty acid ester, dicyanamide polyamine, tertiary amine And cationic surfactants such as salts and quaternary ammonium salts. Among these, polyvinyl alcohol, carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and methylcellulose are particularly preferable. These can be used alone or in combination. In particular, when the urea urethane compound is wet pulverized in an aqueous medium, it is desirable to maintain the liquid temperature of the aqueous medium at 60 ° C. or lower and pulverize in a neutral region where the pH is 5 to 10. Moreover, it is preferable that pH of the coating liquid containing a urea urethane compound and a colorless or light-colored dye precursor is 5-12.

In addition, as a pigment for the thermosensitive recording layer, diatomaceous earth, talc, kaolin, calcined kaolin,
Calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin and the like can also be contained. Also, for the purpose of preventing head wear and sticking, higher fatty acid metal salts such as zinc stearate and calcium stearate, waxes such as paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamide, and caster wax, dioctyl A dispersant such as sodium sulfosuccinate, an ultraviolet absorber such as benzophenone or benzotriazole, a surfactant, a fluorescent dye, or the like can be contained as required.

  Examples of binders that can be used to form the heat-sensitive recording layer include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylate ester copolymer A water-soluble binder such as a copolymer, an acrylamide / acrylic acid ester / methacrylic acid terpolymer, an alkali salt of a styrene / maleic anhydride copolymer, an alkali salt of an ethylene / maleic anhydride copolymer, and a styrene / butadiene copolymer. Examples thereof include latex water-insoluble binders such as polymers, acrylonitrile / butadiene copolymers, and methyl acrylate / butadiene copolymers.

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 papers, synthetic papers, metal foils, or composite sheets combining these are used depending on the purpose. Can be used arbitrarily. 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 by one to form a multilayer structure. Further, a protective layer composed of one layer or a plurality of layers may be provided on the thermosensitive recording layer, or an intermediate layer composed of one layer or a plurality of layers may be provided between the support and the thermosensitive recording layer. Good. 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, and applying and drying on a support. The coating amount is preferably 1 to 15 g / m ² with the coating solution dried.

When the color former of the present invention is used as a heat-sensitive recording material, a heat-fusible substance can be contained in the color former in order to improve the sensitivity. The heat-fusible substance preferably has a melting point of 60 ° C. to 180 ° C., and particularly preferably has a melting point of 80 ° C. to 140 ° C. For example, p-benzyloxybenzoic acid benzyl, stearic acid amide, palmitic acid amide, N-methylol stearic acid amide, β-naphthylbenzyl ether, N-stearyl urea, N, N′-distearyl urea, β-naphthoic acid phenyl Ester, 1-hydroxy-2-naphthoic acid phenyl ester, β-naphthol (p-methylbenzyl) ether, 1,4-dimethoxynaphthalene, 1-methoxy-4-benzyloxynaphthalene, N-stearoyl urea, p-benzylbiphenyl 1,2-di (m-methylphenoxy) ethane, 1-phenoxy-2- (4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate, metaterphenyl, dibenzyl oxalate, oxalic acid (P-chloroben Le) esters. Furthermore, 4,4′-dimethoxybenzophenone, 4,4′-dichlorobenzophenone, 4,4′-difluorobenzophenone, diphenylsulfone, 4,4′-dichlorodiphenylsulfone, 4,4′-difluorodiphenylsulfone, 4,4 '-Dichlorodiphenyl disulfide, diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N'-diphenyl-p-phenylenediamine, 1- (N-phenylamino) naphthalene, benzyl, 1,3-diphenyl-1,3 -Propansion or the like may be used.
Of these, diphenylsulfone is preferably used.

The heat-fusible substance may be used alone or in combination of two or more. In order to obtain sufficient heat response, 10 parts by weight with respect to 100 parts by weight of a colorless or pale dye precursor. It is preferable to use ˜300 parts by weight, and more preferably 20 to 250 parts by weight.
When the recording material is a pressure-sensitive recording material, for example, the forms disclosed in US Pat. Nos. 2,505,470, 2,712,507, 2,730,456, 2,730,457, 3,418,250, etc. Can take. That is, the dye precursors are used alone or in combination, and synthetic oils such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethane, and chlorinated paraffin, and vegetable oils, animal oils, mineral oils and the like alone Or an upper paper obtained by dissolving in a solvent consisting of a mixture and dispersing it in a binder or coating a dispersion containing microcapsules together with a binder on a support, and a urea urethane compound ( And a pressure sensitive recording paper in which the coated surfaces of the lower paper coated with a dispersion liquid of amino compound and / or color developer are coated on each other, and a urea urethane compound dispersion liquid is coated on one side and a dye is coated on the other side. The pressure sensitive recording paper in which the intermediate paper coated with the precursor is sandwiched between the upper paper and the lower paper, or the above-mentioned urine on the same surface of the support. A self-type in which a dispersion of a urethane compound (and an amino compound and / or a developer) and a dispersion containing the dye precursor are mixed or applied in multiple layers, or a dye precursor, a urea urethane compound (and an amino compound and Any of various forms such as a self-type obtained by microencapsulating and applying any one of the developer and the like) is possible.

As a microcapsule production method, the coacervation method disclosed in U.S. Pat. Nos. 2,800,547 and 2,800,498, Japanese Patent Publication No. 38-19574, No. 42-446, No. 42-771, etc. Disclosed in Japanese Patent Publication No. 36-9168, Japanese Patent Publication No. 51-9079, etc., British Patent No. 952807, No. 96-5074, etc. In addition, a melt dispersion cooling method, a spray drying method disclosed in US Pat. No. 3,111,140, British Patent No. 930422, and the like can be employed.
The color former of the present invention corresponds to the dye precursor and developer in each of the above publications.

In forming the pressure-sensitive recording layer, each component such as a urea urethane compound may be dissolved in a solvent or used after being dispersed. Further, in a color forming system including an amino compound and / or a developer, each is used alone, or a urea urethane compound and an amino compound are used in combination, and if necessary, a developer is used in combination with a developer or dissolved in a solvent. That's fine.
In the interfacial polymerization method used in forming the microcapsules, a film is formed at the interface using two types of monomers, oily and water-soluble. For example, polybasic acid chloride in the oil phase, polyamine in the water phase, a polyamide film at the interface, a polyhydric hydroxy compound in the water phase, a polyester film, and an oil phase in the polyphase. When an isocyanate is used, a method of forming a polyurethane film by using a polyhydric alcohol and a polyphenol in an aqueous phase and a polyurea film by using a polyamine in an aqueous phase is known. As described above, when the interfacial polymerization method is used for producing the 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 in the formation of the microcapsule film and does not directly participate in the color image, and the use of other water-soluble monomers is essential. It is distinguished from the use of the isocyanate compound used in the present invention.
Preparation of a dispersion of a compound without microencapsulation is obtained by pulverizing one or more of each compound in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer and a surfactant. It is done. The urea urethane compound may be dispersed simultaneously with the amino compound and the acidic developer.

Paper is mainly used as the support for the pressure-sensitive recording material, but in addition to paper, various woven fabrics, nonwoven fabrics, synthetic resin films, laminated paper, synthetic paper, metal foil, or composite sheets combining these It can be arbitrarily used depending on the case.
As the binder, various commonly used binders can be used. For example, starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid soda, acrylamide / acrylic acid Water-soluble binders such as ester copolymers, acrylamide / acrylic ester / methacrylic acid terpolymers, alkali salts of styrene / maleic anhydride copolymers, alkali salts of ethylene / maleic anhydride copolymers, and styrene And latex water-insoluble binders such as / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, and the like.

  Furthermore, 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-butylfel), 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'-diphenylacrylate, tetra (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarbonate.

Hereinafter, the present invention will be described in more detail with reference to examples.
In addition, analysis of each substance and evaluation of each physical property were performed by the following methods.
<IR spectrum>
It was measured by a diffuse reflection method using Shimadzu FTIR-8100M.
<Mass spectrum>
JMS-HX100 manufactured by JEOL Ltd., matrix is nitrobenzyl alcohol,
The primary gas was measured using xenon.

<Thermal paper color sensitivity>
Using a printing tester manufactured by Okura Electric Co., Ltd., KJT-256-8MGF1 manufactured by Kyocera was used as the thermal head, and the color density at an applied voltage of 24 V and a pulse width of 1.5 msec was measured with an optical densitometer.
<Plasticizer resistance>
A thermosensitive recording material is sandwiched between vinyl chloride wrap or vinyl chloride file, a load of 300 g / cm ² is applied from above, and it is allowed to stand at 40 ° C. for 24 hours. After standing, the density of printed and unprinted parts (background) is visually evaluated. In addition, print storability is good if the print density is low.

<Heat resistance>
The heat-sensitive recording material was allowed to stand in an environment of 60 ° C. and 25% RH for 24 hours to visually evaluate the color fading density of the print.
Further, the thermal recording material was allowed to stand for 24 hours in an environment of 80 ° C. and 25% RH, and the color fading density of the printing was visually evaluated. In addition, the color density of the background portion was visually evaluated, and those having little color development were considered to have good background preservation properties.

<Pressure sensitive paper color density>
The coated surfaces of the upper paper and the lower paper were superimposed and pressed so as to face each other, and a color image was obtained on the lower paper. The density of the color image was measured using a densitometer Macbeth RD917.
<Solvent resistance>
A hand cream (product name: ATRIX (manufactured by Kao Corporation)) is thinly applied to the color image portion obtained by the evaluation of the color density, and after standing for 7 days at room temperature, the density of the print portion is visually evaluated to determine the print density. Those with less color fading were considered to have good print storage stability.

Example 1
124 g of methyl ethyl ketone and 15 g of dimethylformamide were added to 88.2 g of 2,4-toluene diisocyanate as a solvent, and 6.3 g of 4,4′-diaminodiphenylsulfone was diluted with 25 g of methyl ethyl ketone and 3 g of dimethylformamide, and added dropwise. The reaction was carried out at 25 ° C. for 8 hours. After the reaction, methyl ethyl ketone was concentrated and removed, and toluene was added. The precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 10.0 g of a white crystalline compound. Next, 8.4 g of this compound was taken, 33 g of phenol and 180 g of methyl ethyl ketone were added, and 8.5 mg of triethylamine was further added, followed by reaction at 25 ° C. for 7 hours. After the reaction, toluene was added and the precipitated crystals were collected by filtration, washed with toluene, and vacuum dried overnight to obtain 10.0 g of white crystalline compound. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 990cm -1, 1110cm -1, 1320cm} -1, 1590cm -1, 1700cm -1, characteristic peaks appeared in 3350 cm ^-1. The IR spectrum is shown in FIG.
Mass spectrum measurement result: [M + H] ⁺ was detected at m / z 785.
The structural formula of the main component of this compound is presumed to be the compound (E-24).

Next, 2 g of this compound was taken and pulverized and dispersed in a paint shaker for 45 minutes together with 8 g of an aqueous solution of 2.5% by weight polyvinyl alcohol (Goselan L-3266 (trade name), manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). Obtained. The liquid temperature of the dispersion immediately after dispersion was 25 ° C. The dispersed particle size of this compound was 0.9 μm.
Further, 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane is pulverized and dispersed for 3 hours at a rotation speed of 2000 rpm with a sand grinder (Bessel capacity 400 ml, manufactured by Imex) together with 130 g of a 5.4 wt% aqueous polyvinyl alcohol solution. To obtain a dispersion.
Further, 70 g of diphenylsulfone was pulverized and dispersed for 3 hours at 130 rpm with a sand grinder (Bessel capacity 400 ml, manufactured by Imex Co., Ltd.) together with 130 g of a 5.4 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Further, 10 g of calcium carbonate was mixed with 30 g of water and stirred and dispersed with a stirrer to obtain a dispersion.

These dispersions were mixed with 20 parts by weight of the above-mentioned compound dispersion, 10 parts by weight of the dry solid of 3-dibutylamino-6-methyl-7-anilinofluorane dispersion, and the dry solids of the diphenylsulfone dispersion. 25 parts by weight, 40 parts by weight of dry solid content of calcium carbonate dispersion, 20 parts by weight of dry solid content of zinc stearate dispersion having a solid content concentration of 16% by weight, and 15 parts by weight of dry solid content of 15% by weight polyvinyl alcohol The mixture was stirred and mixed at a ratio (dry basis) to obtain a coating solution.
This coating solution was applied onto a base paper having a weight of 50 g / m ² with a bar coater rod number 10 and dried, and then processed with a super calender to obtain a heat-sensitive recording material.
The evaluation result of sensitivity was as good as 1.3 in optical density.
The evaluation result of the degree of discoloration due to the heat of the background (heat resistance) was good with little discoloration. Moreover, the fading of the printed part due to heat was small and good. The evaluation results of plasticizer resistance with vinyl chloride wrap were good with little discoloration. The results are summarized in Table 1.

Example 2
To 30 g of 2,4-toluene diisocyanate, 57 g of methyl ethyl ketone was added as a solvent, and 2.15 g of 4,4′-diaminodiphenyl sulfone was diluted with 12 g of methyl ethyl ketone and added dropwise, followed by reaction at 50 ° C. for 6 hours. After the reaction, the reaction mixture was cooled to room temperature, toluene was added, and the precipitated white solid was collected by filtration, washed with toluene, and vacuum dried overnight to obtain 4.1 g of a white crystalline compound. Next, 3.0 g of this compound was taken, 11.8 g of phenol and 78 g of methyl ethyl ketone were added, and 3 mg of triethylamine was further added, followed by reaction at 25 ° C. for 4 hours. After the reaction, toluene was added and the precipitated crystals were collected by filtration, washed with toluene, and vacuum dried overnight to obtain 3.9 g of white crystals of compound. The result of IR measurement of this white crystal was the same as in Example 1.
The structural formula of the main component of this compound is presumed to be the compound (E-24).

Next, 2 g of this compound was taken and pulverized and dispersed in a paint shaker for 45 minutes together with 8 g of an aqueous solution of 2.5% by weight polyvinyl alcohol (GOHSENOL KL-05 (trade name), manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). Obtained.
Subsequently, a thermosensitive recording material was prepared in the same manner as in Example 1 except that the above compound dispersion was used instead of the compound dispersion obtained in Example 1, and p-benzylbiphenyl was used instead of diphenylsulfone. Created and evaluated. The results are summarized in Table 1.

Example 3
31.5 g of 2,4-toluene diisocyanate was stirred at 60 ° C., and 21.5 g of 4,4′-diaminodiphenyl sulfone was diluted with 120 ml of methyl ethyl ketone and added dropwise over 4 hours. The reaction was performed for 2 hours. After the reaction, the reaction mixture was cooled to room temperature, toluene was added, and the precipitated white solid was collected by filtration, washed with toluene, and vacuum dried overnight to obtain 47 g of a white crystalline compound. 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 vacuum dried overnight to obtain 38.5 g of white crystals of compound. The result of IR measurement of this white crystal was the same as in Example 1.
The structural formula of the main component of this compound is presumed to be the compound (E-24).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Example 4
20 g of methyl ethyl ketone as a solvent was added to 10.4 g of 2,4-toluene diisocyanate, and 3.7 g of 4,4′-diaminodiphenyl sulfone was diluted with 30 g of methyl ethyl ketone and added dropwise, followed by reaction at room temperature for 20 hours. After the reaction, methyl ethyl ketone was concentrated and removed, and toluene was added. The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 8.8 g of a white crystalline compound. Next, 4 g of this compound was taken, 15 g of phenol was added, and a small amount of dibutyltin dilaurate was further added, followed by reaction at 50 ° C. for 4 hours. After the reaction, toluene was added and the precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 5.2 g of white crystalline compound.
The structural formula of the main component of this compound is presumed to be the compound (E-24).

Next, 2 g of this compound was taken, and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5% by weight aqueous methylcellulose solution to obtain a dispersion.
Subsequently, a thermosensitive recording material was prepared in the same manner as in Example 1 except that the above compound dispersion was used instead of the compound dispersion obtained in Example 1 and benzyloxynaphthalene was used instead of diphenylsulfone. And evaluated. The results are summarized in Table 1.

Example 5
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 2 g of this compound was taken, methyl ethyl ketone was added as a solvent, 0.9 g of 4,4′-diaminodiphenylsulfone was added thereto, reacted at 50 ° C. for 22 hours, and the precipitated crystals were collected by filtration, washed with hexane and vacuumed overnight. Drying gave 2.3 g of white crystalline compound. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 550cm -1, 1030cm -1, 1110cm} -1, 1150cm -1, 1590cm -1, 1700cm -1, characteristic peaks appeared in 3300 cm ^-1. The structural formula of the main component of this compound is presumed to be the compound (E-22).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Subsequently, a dispersion of the above compound was used in place of the dispersion of the compound obtained in Example 1, and oxalic acid di-p-methylbenzyl ester was used in place of diphenylsulfone. A thermal recording material was prepared and evaluated. The results are summarized in Table 1.

Example 6
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 2 g of this compound was taken, methyl ethyl ketone was added as a solvent, 0.9 g of 3,3′-diaminodiphenylsulfone was added thereto, the mixture was reacted at 50 ° C. for 22 hours, and the precipitated crystals were collected by filtration, washed with hexane and vacuumed overnight. Drying gave 2.5 g of white crystalline compound. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 620cm -1, 880cm -1, 1030cm} -1, 1300cm -1, 1590cm -1, 1700cm -1, characteristic peaks appeared in 3300 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-19).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Subsequently, a thermosensitive recording material was prepared in the same manner as in Example 1 except that the compound dispersion obtained in Example 1 was used instead of the compound dispersion and benzyl was used instead of diphenylsulfone. Evaluation was performed. The results are summarized in Table 1.

Example 7
20 g of methyl ethyl ketone as a solvent was added to 10.4 g of 2,4-toluene diisocyanate, and 3.7 g of 3,3′-diaminodiphenyl sulfone was diluted with 30 g of methyl ethyl ketone and added dropwise, followed by reaction at 15 ° C. for 3 hours. . The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.3 g of a white crystalline compound. Next, 3.0 g of this compound was taken, 15 g of phenol was added, 3 mg of dibutyltin dilaurate was further added, and the mixture was reacted at 50 ° C. for 3 hours. After the reaction, hexane was added to the reaction solution, and the precipitated crystals were collected by filtration, washed and dried in vacuo overnight to obtain 3.3 g of a white crystal compound. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 520cm -1, 880cm -1, 1030cm} -1, 1430cm -1, 1590cm -1, 1710cm -1, characteristic peaks appeared in 3300 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-21).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Subsequently, Example 1 was used except that the dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1, and 1,2-di (3-methylphenoxy) ethane was used instead of diphenylsulfone. A thermosensitive recording material was prepared and evaluated in the same manner as described above. The results are summarized in Table 1.

Reference example 1
111 g of toluene as a solvent was added to 27.8 g of 2,4-toluene diisocyanate, and 7.4 g of aniline dissolved in 37 g of toluene was added dropwise thereto, and the mixture was reacted at 10 ° C. for 8 hours. After the reaction, the precipitated white solid was collected by filtration and then vacuum-dried overnight to obtain 20.0 g of a white crystalline compound. Next, 6.6 g of this compound was taken and 20 g of dimethylformamide was added as a solvent, and 2.7 g of 2,2-bis (4-hydroxyphenyl) propane was added thereto and reacted at 15 ° C. for 5 hours. After the reaction, 8 g of acetone was added to the reaction solution, 160 g of water was further added, and the precipitated crystals were collected by filtration and then vacuum-dried overnight to obtain 9.3 g of a white crystal compound. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 750cm -1, 840cm -1, 1020cm} -1, 1500cm -1, 1600cm -1, 1720cm -1, characteristic peaks appeared in 3320 cm ^-1. The IR spectrum is shown in FIG.
Results of mass spectrum measurement: [M + H] ⁺ was detected at m / z 763.
The structural formula of the main component of this compound is presumed to be the compound (E-30).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference example 2
90 g of toluene as a solvent was added to 12.2 g of 2,4-toluene diisocyanate, and 5.2 g of aniline dissolved in 30 g of toluene was added dropwise thereto, 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 vacuum-dried overnight to obtain 14 g of a white crystalline compound. Next, 4.3 g of this compound was taken and 60 g of toluene was added as a solvent. To this, 1.73 g of 2,2-bis (4-hydroxyphenyl) propane and 0.043 mg of triethylamine were added and reacted at 70 ° C. for 8 hours. The temperature was raised to 80 ° C. and reacted for 1 hour. After the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with toluene, and vacuum-dried overnight to obtain 6.0 g of a white crystal compound. The results of IR measurement of the white crystals were the same as in Example 5.
The structural formula of the main component of this compound is presumed to be the compound (E-30).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference example 3
To 61 g of 2,4-toluene diisocyanate 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 vacuum dried overnight to obtain 70 g of a white crystalline compound. Next, 30 g of this compound was taken and 365 g of toluene was added as a solvent, and 12.2 g of 2,2-bis (4-hydroxyphenyl) propane and 0.3 mg of triethylamine were added thereto, followed by stirring at 60 ° C. for 4 hours. The mixture was further heated at 70 ° C. for 3 hours, and further reacted 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 vacuum dried overnight to obtain 42 g of a white crystal compound. The results of IR measurement of the white crystals were the same as in Example 5.
The structural formula of the main component of this compound is presumed to be the compound (E-30).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference example 4
111 g of toluene as a solvent was added to 27.8 g of 2,4-toluene diisocyanate, and 7.4 g of aniline dissolved in 37 g of toluene was added dropwise thereto, and the mixture was reacted at 10 ° C. for 8 hours. After the reaction, the precipitated white solid was collected by filtration and then vacuum-dried overnight to obtain 20.0 g of a white crystalline compound. Next, 2.8 g of this compound is taken, 65 g of toluene is added as a solvent, 1.14 g of 2,2-bis (4-hydroxyphenyl) propane and 2.7 mg of dibutyltin dilaurate are added thereto, and the mixture is reacted at 60 ° C. for 7 hours. It was. After the reaction, the reaction solution was concentrated, then acetone was added, 160 g of water was further added, and the precipitated crystals were collected by filtration and then vacuum-dried overnight to obtain 3.5 g of a white crystal compound.
The structural formula of the main component of this compound is presumed to be the compound (E-30).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 5
111 g of toluene as a solvent was added to 27.8 g of 2,4-toluene diisocyanate, and 7.4 g of aniline dissolved in 37 g of toluene was added dropwise thereto, and the mixture was reacted at 10 ° C. for 8 hours. After the reaction, the precipitated white solid was collected by filtration and then vacuum-dried overnight to obtain 20.0 g of a white crystalline compound. Next, 4.7 g of this compound is taken and 30 g of methyl ethyl ketone is added as a solvent. To this, 1.0 g of 2,2-bis (4-hydroxyphenyl) propane and 4.7 mg of dibutyltin dilaurate are added and reacted at 75 ° C. for 4 hours. It was. After the reaction, the reaction solution was concentrated, acetone was added, 160 g of water was further added, and the precipitated crystals were collected by filtration and then vacuum dried overnight to obtain 3.0 g of white crystalline compound.
The structural formula of the main component of this compound is presumed to be the compound (E-30).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 6
To 19.5 g of 2,4-toluene diisocyanate was added 155 g of toluene as a solvent, and 3.2 g of 2,2-bis (4-hydroxyphenyl) propane was added thereto.
Reacted for hours. After the reaction, the reaction solution was cooled to -20 ° C. and the precipitated white solid was collected by filtration, then dissolved in chlorobenzene, hexane was added and the precipitated crystals were collected by filtration and then vacuum dried overnight to give a white crystalline compound. 8.0 g was obtained. Next, 4 g of this compound was taken, 50 g of toluene was added as a solvent, 4 g of aniline was added thereto, and the mixture was reacted at 25 ° C. for 24 hours. After the reaction, the precipitated crystals were collected by filtration, washed with toluene, and vacuum dried overnight to obtain 5.0 g of white crystalline compound. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 750cm -1, 1840cm -1, 1020cm} -1, 1500cm -1, 1600cm -1, 1720cm -1, characteristic peaks appeared in 3300 cm ^-1. The structural formula of the main component of this compound is presumed to be the compound (E-32).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 7
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 1.5 g of this compound was taken, toluene was added as a solvent, and 1.44 g of 2-methoxy-5-N, N-diethylsulfamoylaniline was added thereto, reacted at 50 ° C. for 16 hours, and the precipitated crystals were collected by filtration. After washing with hexane and vacuum drying overnight, 2.3 g of white crystalline compound was obtained. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 750cm -1, 840cm -1, 1020cm} -1, 1500c m-1, 1600cm -1, 1700cm -1, characteristic peaks appeared in 3320 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-13).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 8
100 g of toluene as a solvent was added to 40 g of 2,4-toluene diisocyanate, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise thereto, and reacted at 5 ° C. for 1 hour. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 4 g of this compound was taken and 40 g of methyl ethyl ketone was added as a solvent. 4.23 g of phenol was diluted with 10 g of methyl ethyl ketone and reacted at 90 ° C. for 3 hours. After cooling at 5 ° C. for 6 days, the precipitated crystals were filtered. It was collected and dried in vacuo overnight to give 2.58 g of white crystalline compound. The analysis value of this white crystal is as follows. Result of IR ^{measurement: 880cm -1, 1000cm -1, 1040cm} -1, 1440cm -1, 1720cm -1, 1720cm -1, characteristic peaks appeared in 3300 cm ^-1. The structural formula of the main component of this compound is presumed to be the compound (E-1).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 9
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound.
Next, 5.4 g of this compound was taken, toluene was added as a solvent, 0.9 g of water was added thereto, a small amount of dibutyltin dilaurate was added, the mixture was reacted at room temperature for 10 hours, and the precipitated crystals were collected by filtration and washed with hexane. It was vacuum-dried overnight to obtain 2.1 g of white crystalline compound. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 990cm -1, 1030cm -1, 1300cm} -1, 1480cm -1, 1540cm -1, 1720cm -1, characteristic peaks appeared in 3300 cm ^-1. The structural formula of the main component of this compound is presumed to be the compound (E-17).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 10
100 g of toluene as a solvent was added to 40 g of 2,4-toluene diisocyanate, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise thereto, and reacted at 5 ° C. for 1 hour. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 5 g of this compound was taken, 40 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. To this, 2.58 g of p-methoxyphenol was diluted with 10 g of methyl ethyl ketone and reacted at 90 ° C. for 6 hours. The reaction solution was poured into hexane, and the precipitated crystals were collected by filtration and dried in vacuo overnight. 3.7 g of a purple crystal compound was obtained. The analysis value of this white purple crystal is as follows.
Result of IR ^{measurement: 840cm -1, 1040cm -1, 1440cm} -1, 1720cm -1, characteristic peaks appeared in 3300 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-3).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 11
100 g of toluene as a solvent was added to 40 g of 2,4-toluene diisocyanate, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise thereto, and reacted at 5 ° C. for 1 hour. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 5 g of this compound was taken, 40 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. To this, 2.22 g of p-cresol was diluted with 10 g of methyl ethyl ketone and reacted at 90 ° C. for 6 hours. Then, the reaction solution was poured into hexane, and the precipitated crystals were collected by filtration and dried in vacuo overnight to give white crystals. 3.7 g of the following compound was obtained. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 880cm -1, 1000cm -1, 1040cm} -1, 1500cm -1, 1720cm -1, characteristic peaks appeared in 3300 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-4).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 12
100 g of toluene as a solvent was added to 40 g of 2,4-toluene diisocyanate, and 5.66 g of p-methoxyaniline was diluted with 40 g of toluene and added dropwise thereto, and reacted at 10 ° C. for 1 hour. The white-purple solid precipitated after the reaction was collected by filtration, washed with hexane and dried in vacuo overnight to obtain 13.4 g of a white-purple crystalline compound. Next, 5 g of this compound was taken and 65 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. After 2.37 g of phenol was diluted with 15 g of methyl ethyl ketone and reacted at 90 ° C. for 4 hours, the reaction solution was concentrated, and after cooling at 5 ° C. for 1 day, the precipitated crystals were collected by filtration and vacuum-dried overnight. As a result, 2.50 g of a compound having white purple crystals was obtained. The analysis value of this white purple crystal is as follows.
Result of IR ^{measurement: 820cm -1, 1030cm -1, 1420cm} -1, 1730cm -1, characteristic peaks appeared in 3300 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-6).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 13
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 5.0 g of this compound was taken, 100 g of toluene was added as a solvent, 3.50 g of aniline was added thereto, and the mixture was reacted at 25 ° C. for 3 hours. The precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight. 5.5 g of crystalline compound was obtained. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 890cm -1, 1000cm -1, 1030cm} -1, 1440cm -1, 1720cm -1, characteristic peaks appeared in 3350 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-8).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 14
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 5.0 g of this compound was taken, 100 g of toluene was added as a solvent, 3.00 g of p-toluidine was added thereto, and the mixture was reacted at 25 ° C. for 3 hours. The precipitated crystals were collected by filtration, washed with hexane, and dried in vacuum overnight. As a result, 5.5 g of white crystalline compound was obtained. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 870cm -1, 1000cm -1, 1030cm} -1, 1460cm -1, 1720cm -1, characteristic peaks appeared in 3350 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-10).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
In addition, 70 g of 2,2-bis (4-hydroxyphenyl) propane was pulverized, dispersed and dispersed for 3 hours at a rotational speed of 2000 rpm with a sand glider (Bessel dose of 400 ml, manufactured by IMEX) together with 130 g of a 5.4 wt% polyvinyl alcohol aqueous solution. A liquid was obtained.
Subsequently, the dispersion of the above compound was used in place of the dispersion of the compound obtained in Example 1, and a 2,2-bis (4-hydroxyphenyl) propane dispersion was further added to the coating liquid as a dry solid content of 10 parts by weight. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that it was added at a ratio of. The results are summarized in Table 1.

Reference Example 15
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 5.0 g of this compound is taken, 100 g of toluene is added as a solvent, 3.58 g of p-chloroaniline is added thereto, and the mixture is reacted at 25 ° C. for 6 hours. As a result, 7.0 g of a compound having white purple crystals was obtained. The analysis value of this white purple crystal is as follows.
Result of IR ^{measurement: 870cm -1, 1030cm -1, 1390cm} -1, 1540cm -1, 1720cm -1, characteristic peaks appeared in 3350 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-11).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Subsequently, the above compound dispersion was used instead of the compound dispersion obtained in Example 1, and crystal violet lactone was used instead of 3-dibutylamino-6-methyl-anilinofluorane. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1. The results are summarized in Table 1.

Reference Example 16
120 g of methyl ethyl ketone as a solvent was added to 10 g of diphenylmethane-4,4′-diisocyanate, 3.72 g of aniline was diluted with 15 g of methyl ethyl ketone and added dropwise thereto, and reacted at 25 ° C. for 3 hours. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 11.8 g of a white crystalline compound. Next, 80 g of methyl ethyl ketone was added using 5 g of this compound as a solvent, and 2.06 g of phenol was diluted with 15 g of methyl ethyl ketone and reacted at 70 ° C. for 8 hours. The reaction solution was concentrated and cooled, and the precipitated crystals were filtered. And vacuum dried overnight to obtain 2.7 g of white crystalline compound. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 890cm -1, 1030cm -1, 1420cm} -1, 1720cm -1, characteristic peaks appeared in 3300 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-15).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Further, 70 g of 4-hydroxy-4′-isopropoxydiphenylsulfone is pulverized and dispersed at a rotational speed of 2000 rpm for 3 hours with a sand grinder (Bessel capacity 400 ml, manufactured by IMEX) together with 130 g of a 5.4 wt% polyvinyl alcohol aqueous solution. Got.
Subsequently, the dispersion of the above compound was used in place of the dispersion of the compound obtained in Example 1, and a 4-hydroxy-4'-isopropoxydiphenylsulfone dispersion was further added to the coating liquid with a dry solid content of 10 parts by weight. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that it was added in proportion. The results are summarized in Table 1.

Example 8
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 2.0 g of this compound is taken, 30 g of toluene is added as a solvent, 0.41 g of paraphenylenediamine is added thereto, the mixture is reacted at 50 ° C. for 10 hours, and the precipitated crystals are recovered by filtration, washed with hexane, and vacuum-dried overnight. As a result, 2.3 g of a white crystalline compound was obtained. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 840cm -1, 1000cm -1, 1200cm} -1, 1640cm -1, 1720cm -1, characteristic peaks appeared in 3300 cm ^-1.
The structural formula of the main component of this compound is presumed to be the compound (E-28).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Further, 70 g of bis (4-hydroxyphenyl) sulfone was pulverized and dispersed at 130 rpm with a sand grinder (Bessel capacity: 400 ml, manufactured by IMEX) together with 130 g of a 5.4 wt% aqueous polyvinyl alcohol solution to obtain a dispersion. .
Subsequently, the above-described compound dispersion was used instead of the compound dispersion obtained in Example 1, and a bis (4-hydroxyphenyl) sulfone dispersion was further added to the coating solution in a proportion of 10 parts by weight of dry solids. A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that a thermosensitive recording material was prepared in the same manner as in Example 1. The results are summarized in Table 1.

Example 9
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 2.0 g of this compound is taken, 30 g of toluene is added as a solvent, 0.90 g of o-dianisidine is added thereto, the mixture is reacted at 50 ° C. for 6 hours, and the precipitated crystals are collected by filtration, washed with hexane and dried overnight in vacuum. As a result, 2.6 g of white crystalline compound was obtained. The analysis value of this white crystal is as follows.
Result of IR ^{measurement: 820cm -1, 1000cm -1, 1030cm} -1, 1320cm -1, 1590cm -1, 1710cm -1, characteristic peaks appeared in 3300 cm ^-1. The structural formula of the main component of this compound is presumed to be the compound (E-29).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Example 10
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 2.7 g of this compound was taken and 30 g of dimethylformamide was added as a solvent, 1.2 g of 4,4′-diaminobenzanilide was added thereto, and 3 mg of dibutyltin dilaurate was further added, followed by reaction at 25 ° C. for 24 hours. Methanol was added to the reaction solution, and the precipitated crystals were collected by filtration, washed and dried in vacuo overnight to obtain 2.3 g of white crystalline compound.
The structural formula of the main component of this compound is presumed to be the compound (E-26).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 17
100 g of toluene as a solvent was added to 40 g of 2,4-toluene diisocyanate, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise thereto, and reacted at 5 ° C. for 1 hour. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 3 g of this compound was taken, 60 g of methyl ethyl ketone was added as a solvent, and a small amount of dibutyltin dilaurate was added, and then 1.4 g of 4,4′-dihydroxydiphenyl sulfone (bisphenol S) was diluted with 10 g of methyl ethyl ketone and 90 ° C. Was added dropwise and reacted for 16 hours. After the reaction, the crystals were collected by filtration, washed with methyl ethyl ketone and then vacuum dried overnight to obtain 2.1 g of white crystalline compound.
The structural formula of the main component of this compound is presumed to be the compound (E-33).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 18
100 g of toluene as a solvent was added to 40 g of 2,4-toluene diisocyanate, and 4.28 g of aniline was diluted with 40 g of toluene and added dropwise thereto, and reacted at 5 ° C. for 1 hour. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 12.2 g of a white crystalline compound. Next, 5 g of this compound was taken, 40 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. To this, 2.64 g of p-chlorophenol was diluted with 10 g of methyl ethyl ketone and reacted at 90 ° C. for 5 hours. Then, the reaction solution was poured into hexane, and the precipitated crystals were collected by filtration and dried in vacuo overnight. 1.1 g of crystalline compound was obtained.
The structural formula of the main component of this compound is presumed to be the compound (E-5).

Next, 1 g of this compound was taken and pulverized and dispersed with a paint shaker for 45 minutes together with 4 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Next, 2 g of 1,3-bis (3-isocyanato-4-methylphenyl) urea was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% aqueous polyvinyl alcohol solution to obtain a dispersion.
Subsequently, the dispersion of the above compound was used in place of the dispersion of the compound obtained in Example 1, and a 1,3-bis (3-isocyanato-4-methylphenyl) urea dispersion was dried and solidified as a coating liquid. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that it was added at a ratio of 10 parts by weight. The results are summarized in Table 1.

Reference Example 19
To 40 g of 2,4-toluene diisocyanate, 100 g of toluene was added as a solvent, 6.21 g of p-aminoacetophenone was diluted with 30 g of toluene and 30 g of methyl ethyl ketone, and the mixture was added dropwise and reacted at 25 ° C. for 20 hours. The white solid precipitated after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 13.0 g of a white crystalline compound. Next, 5 g of this compound was taken and 65 g of methyl ethyl ketone was added as a solvent, and 5 mg of dibutyltin laurate was further added. To this, 2.28 g of phenol was diluted with 15 g of methyl ethyl ketone and reacted at 90 ° C. for 4 hours. The reaction solution was concentrated, cooled at 5 ° C. for 1 day, and the precipitated crystals were collected by filtration and dried in vacuo overnight. As a result, 1.0 g of a white crystalline compound was obtained.
The structural formula of the main component of this compound is presumed to be the compound (E-7).

Next, 1 g of this compound was taken and pulverized and dispersed with a paint shaker for 45 minutes together with 4 g of a 2.5 wt% polyvinyl alcohol aqueous solution to obtain a dispersion.
Further, 70 g of 1,3-diimino-4,5,6,7-tetrachloroisoindoline, which is an imino compound, together with 130 g of a 5.4 wt% aqueous polyvinyl alcohol solution, a sand grinder (Bessel capacity 400 ml, manufactured by Imex), rotation speed A dispersion was obtained by grinding and dispersing at 2000 rpm for 3 hours.
Further, 70 g of 4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine, which is an isocyanate compound, is mixed with 130 g of a 5.4 wt% aqueous polyvinyl alcohol solution (400 ml of Bessel solution, Imex Corporation). Manufactured), and pulverized and dispersed at 1000 rpm for 1 hour to obtain a dispersion.

Furthermore, 70 g of 3,3′-diaminodiphenylsulfone was pulverized and dispersed for 3 hours at a rotational speed of 2000 rpm with a sand grinder (Bessel capacity: 400 ml, manufactured by IMEX) together with 130 g of a 5.4 wt% polyvinyl alcohol aqueous solution to obtain a dispersion. .
Subsequently, the dispersion of the above compound was used in place of the dispersion of the compound obtained in Example 1, and a 1,3-diimino-4,5,6,7-tetrachloroisoindoline dispersion was further added to the coating liquid. 8 parts by weight of dry solid content, 4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine dispersion liquid 5.3 parts by weight of dry solid content, 3,3′-diaminodiphenylsulfone dispersion liquid A thermal recording material was prepared and evaluated in the same manner as in Example 1 except that was added at a ratio of 5.3 parts by weight of the dry solid content. The results are summarized in Table 1.

Example 11
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 2.0 g of this compound was taken, 30 g of toluene was added as a solvent, 0.75 g of 4,4′-diaminodiphenyl ether was added thereto, the mixture was reacted at 50 ° C. for 16 hours, and the precipitated crystals were collected by filtration and washed with hexane. By vacuum drying overnight, 2.4 g of white crystalline compound was obtained.
The structural formula of the main component of this compound is presumed to be the compound (E-25).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Example 12
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 2.0 g of this compound was taken, 30 g of toluene was added as a solvent, 0.74 g of 4,4′-diaminodiphenylmethane was added together with 10 g of methyl ethyl ketone, the reaction was carried out at 50 ° C. for 10 hours, and the precipitated crystals were recovered by filtration and then hexane. And vacuum drying overnight gave 2.1 g of white crystalline compound.
The structural formula of the main component of this compound is presumed to be the compound (E-27).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Reference Example 20
30 g of toluene as a solvent was added to 30 g of 2,4-toluene diisocyanate, and 3.24 g of phenol was added thereto, followed by reaction at 100 ° C. for 1 hour and 30 minutes. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a white crystalline compound. Next, 1.5 g of this compound was taken, 30 g of toluene was added as a solvent, 0.3 g of ethylamine was added thereto, the mixture was reacted at 50 ° C. for 6 hours, and the precipitated crystals were collected by filtration, washed with hexane and dried in vacuo overnight. As a result, 1.8 g of white crystalline compound was obtained.
The structural formula of the main component of this compound is presumed to be the compound (E-44).

Next, 1 g of this compound was taken and pulverized and dispersed with a paint shaker for 45 minutes together with 4 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Example 13
150 g of 2,4-toluene diisocyanate is stirred at 50 ° C., and then a solution of 17.2 g of 4,4′-diaminodiphenylmethane and 120 ml of methyl ethyl ketone is added dropwise over 4 hours, followed by reaction at 50 ° C. for 2 hours. I let you. After the reaction, the reaction mixture was cooled to room temperature, toluene was added, and the precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 43 g of a white crystalline compound. Next, 30 g of this compound was taken, 51.5 g of phenol and 100 ml of methyl ethyl ketone were added, and 30 mg of triethylamine was further added, followed by reaction at 50 ° C. for 20 hours. After the reaction, toluene was added and the precipitated crystals were collected by filtration, washed with toluene, and vacuum dried overnight to obtain 38.5 g of white crystals of compound.
The structural formula of the main component of this compound is presumed to be the compound (E-27).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Example 14
3,1.5 g of 2,4-toluene diisocyanate was stirred at 60 ° C., and a solution of 21.5 g of 4,4′-diaminodiphenyl sulfone and 120 ml of methyl ethyl ketone was added dropwise thereto over 6 hours. Subsequently, the reaction solution was cooled to 25 ° C., 17.1 g of phenol was added, 30 mg of triethylamine was further added, and the mixture was reacted at 25 ° C. for 4 hours. After the reaction, methyl ethyl ketone was distilled off, and the resulting solid was pulverized and then vacuum dried overnight to obtain 70 g of a light yellow powdery compound.
The structural formula of the main component of this compound is presumed to be the compound (E-24).

Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

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

Comparative Example 2
50 g of toluene as a solvent was added to 10 g of 2,4-toluene diisocyanate, 30 g of aniline was added thereto, and the mixture was reacted at 25 ° C. for 3 hours. The white solid deposited after the reaction was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 17 g of white crystalline compound.
The estimated structural formula of the main component of this compound is the following compound (C-1).
Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Comparative Example 3
30 g of toluene was added as a solvent to 10 g of 2,4-toluene diisocyanate, and 30 g of phenol was added thereto and reacted at 100 ° C. for 3 hours. After the reaction, toluene was concentrated and removed, hexane was added, and the precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 15 g of a white crystalline compound.
The presumed structural formula of the main component of this compound is the following compound (C-2).
Next, 2 g of this compound was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5 wt% polyvinyl alcohol aqueous 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 above-described compound dispersion was used instead of the compound dispersion obtained in Example 1. The results are summarized in Table 1.

Comparative Example 4
A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that 1,3-diphenylurea was used instead of the urea urethane compound synthesized in Example 1. The results are summarized in Table 1.

1. The higher the optical density (OD value), the better the sensitivity.
2. Plasticizer resistance (print storage stability)
◎ ~ Almost no fading.
○ ~ There is a slight change in color tone, but there is no fading.
Δ: Obviously fading occurs.
× ~ The print color has disappeared.
3. Heat resistance (60 ° C, 80 ° C print storage stability)
◎ ~ Almost no fading.
○ ~ There is a slight change in color tone, but there is no fading.
Δ: Obviously fading occurs.
× ~ The print color has disappeared.
4). Heat resistance (80 ° C, background preservation)
◎ ~ There is almost no skin cover.
○ ~ There is a slight change in color tone, but the printed part can be read.
Δ: The printed part is difficult to read due to the background covering.
×-The cover is severe and the printed part is unreadable.

Example 15
(1) Create upper paper
Nisseki Hyzol in which 2.5 parts by weight of 3-diethylamino-7-chlorofluorane is dissolved in 100 parts by weight of a 5% aqueous solution of pH 4.0 in which a styrene-maleic anhydride copolymer is dissolved together with a small amount of sodium hydroxide. N-296 (trade name, Nippon Petrochemical oil) 80 parts by weight was emulsified. On the other hand, when 10 parts by weight of melamine, 25 parts by weight of 37% formalin aqueous solution and 65 parts by weight of water were adjusted to pH 9.0 with sodium hydroxide and heated to 60 ° C., it became transparent in 15 minutes, and the melamine-formalin initial condensate was gotten. This initial condensate was added to the emulsion and stirred for 4 hours while maintaining the temperature at 60 ° C., and then cooled to room temperature. The solid content of the obtained microcapsule dispersion was 45%.
The microcapsule dispersion thus obtained was applied to paper and dried to obtain an upper paper.

(2) Preparation of lower paper
15 g of a compound synthesized in the same manner as in Example 4 (the presumed structural formula of the main component is the above compound (E-22)) was taken and 45 minutes with a paint shaker at 45 ° C. together with 45 g of a 2 wt% aqueous polyvinyl alcohol solution. The dispersion was obtained by grinding and dispersing.
Further, 60 g of calcium carbonate was mixed with 90 g of water and dispersed by stirring with a stirrer to obtain a dispersion.
The coating solution was prepared by mixing and stirring 40 parts by weight of the above compound dispersion, 125 parts by weight of calcium carbonate dispersion, and 120 parts by weight of a 10% by weight polyvinyl alcohol aqueous solution.

This coating solution was applied onto a base paper having a weight of 40 g / m ² with a rod number of No. 10 of Bacoater to obtain a lower paper.
The evaluation result of the color density was a good optical density of 0.7.
The evaluation result of the solvent resistance with the hand cream was good because the printed part could be read. The results are summarized in Table 2.

Comparative Example 5
A pressure-sensitive recording material was prepared and evaluated in the same manner as in Reference Example 16 except that activated clay as a developer was used instead of the urea urethane compound used in Reference Example 16. The results are summarized in Table 2.

1. The higher the optical density (OD value), the better the color density.
2. Solvent resistance (hand cream)
◎ ~ Almost no fading.
○ ~ There is a slight change in color tone, but there is no fading.
Δ: Obviously fading occurs.
× ~ The print color has disappeared.

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

FIG. 1 is an IR spectrum of the white crystal obtained in Example 1. FIG. 2 is an IR spectrum of the white crystal obtained in Reference Example 1.

Claims (2)

Urea urethane compound represented by the following formula (III).
(In the formula, X represents a phenyl group, Y each independently represents a phenylene group or a methylene difel group, and each may independently have a methyl substituent, and α represents —Φ— or — Represents a divalent residue represented by Φ-ε- Φ-, where -Φ- represents a phenylene group, and each of the phenylene groups independently has a substituent selected from a methyl group and a methoxy group. at best,-.epsilon.-is _{-SO 2 -, - O -,} - CH 2 - and represents a group or a single bond selected from -CONH-). Urea urethane compound represented by the following formula (V).


(In the formula, the hydrogen atom of the benzene ring may be substituted with a methyl group, and γ represents —SO ₂ —, —O—, — (S) _n —, — (CH ₂ ) _n —, —CO—, One selected from the group consisting of -CONH- and any of the groups represented by formula (a)


Or the case where it does not exist is shown, and n is 1 or 2. )