JP2001246859A - Heat-sensitive recording label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-sensitive recording label of superior sensitivity of the heat-sensitive recording and superior resistance to chemicals for a heat- sensitive colored image. SOLUTION: A heat-sensitive recording label is characterized by the formation of a heat-sensitive recording layer containing a urea urethane compound developer on one face of a substrate while forming an adhesive layer on the other face.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a label for thermal recording, and more particularly to a label for thermal recording having improved sensitivity and chemical resistance of recorded images.

[0002]

2. Description of the Related Art Recording materials using an electron-donating dye precursor and an electron-accepting compound are well known as pressure-sensitive recording paper, heat-sensitive paper, photosensitive pressure-sensitive recording paper, and current-sensitive recording paper.
For example, British Patent No. 2140449, U.S. Pat.
No. 2, No. 4336920, Japanese Patent Publication No. 60-23222, Japanese Patent Application Laid-Open No. Sho 57-179836, No. 60-123556,
See, for example, JP-A-60-123557. The recording material should have the following properties: (1) sufficient color density and color sensitivity, (2) no fogging, (3) sufficient robustness of the colored body after color development, ( 4) The color hue is appropriate and suitable for copying machines, and (5) The chemical resistance of the color forming body is sufficient, but none of them has been completely satisfied at present.

[0003] In particular, the development of thermosensitive recording materials has been remarkable in recent years.
These heat-sensitive recording materials have many excellent properties such as high whiteness, good appearance and feel close to plain paper, good recording suitability such as color sensitivity, and the like. It has advantages such as maintenance-free and no noise generation, and its use has been expanded to a wide range of fields such as measurement recorders, facsimile machines, printers, computer terminals, labels, and automatic ticket vending machines such as tickets. Particularly in recent years, with the reform of distribution systems, POS (pointofsa
les) Label applications are increasing, and further expansion in this field is expected in the future. The mainstream of these recording methods is to use a recording material in which a color-forming layer containing a two-component color-forming agent is provided on a support, and to apply heat as recording energy thereto using a heat-sensitive head, a hot stamp, a laser beam, or the like. In this method, heat-sensitive agent components are brought into contact with each other on a recording material to perform color recording. Among them, many use colorless or light-colored electron-donating dye precursors (particularly leuco dyes) and acidic developers such as phenolic compounds as color formers. Recording materials using these leuco dyes include, for example, crystal violet lactone and 4,
Thermal paper using 4'-isopropylidene diphenol (bisphenol A) as a thermal agent (US Pat. No. 3,539,375)
No., etc.).

As the dye precursor and the color developer used for these, an electron-donating compound and an electron-accepting compound are mainly used, respectively. This is because the reactivity of the dye precursor, which is the electron-donating compound, is high, and by contacting with the developer, which is the electron-accepting compound, a color-developed image having a high density can be obtained instantaneously. This is because they have excellent characteristics such as obtaining a close appearance and obtaining various color hues such as red, orange, yellow, green, blue and black. However, on the other hand, the obtained color-developed image has poor chemical resistance, so that it comes into contact with a plasticizer contained in a plastic sheet or an eraser or a chemical contained in food or cosmetics, and the record is easily lost, or , The light resistance of the recording part is inferior, so that the recording fades or disappears after a relatively short exposure to sunlight,
There is a disadvantage that the storage stability of the recording is inferior. Due to this disadvantage, the use of the recording is under certain restrictions at present, and improvement thereof is strongly desired.

In recent years, phenolic compounds represented by bisphenol A have been concerned about their use as environmental hormones, and non-phenolic color developers have been demanded. As a recording sheet capable of obtaining a recorded image having good storability in response to such demands, for example, Japanese Patent Application Laid-Open No. 59-115
No. 887 and U.S. Pat. No. 4,521,793 disclose recording sheets comprising a combination of a color former comprising an aromatic isocyanate compound and an imino compound. In this invention, various recording sheets are disclosed in which two types 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 coloring agent. However, black coloring, which is strongly demanded in thermal recording sheets widely used at present, is still insufficient.

Further, as a heat-sensitive recording sheet using a non-phenol type developer, JP-A-8-2111 and JP-A-8-2112 contain a colorless or pale color dye precursor and a urea compound. A thermosensitive recording medium having a coloring layer is disclosed. However, these recording materials had low color density and insufficient storage stability. Also, Japanese Patent Application Laid-Open No. Hei 5-1164
No. 59 discloses a thermosensitive recording medium having a thermosensitive coloring layer containing a colorless or pale color dye precursor and a sulfonylurea compound. However, these recording materials had low whiteness and insufficient storage stability. Further, when these conventional recording sheets are used for labels, it has been practiced to further suppress the penetration of a plasticizer or the like from the back surface of the recording sheet provided with the coloring layer. The label recording sheet is characterized in that a coloring layer is provided on one side of the support, and an adhesive layer is provided on the other side and can be attached to an adherend,
Generally, it is supplied in a state where a release paper is adhered to an adhesive layer.

In some cases, a label recording sheet is used by attaching it to a plastic film containing a plasticizer at a retail store or the like. At that time, the plasticizer may permeate from the back surface, and fading of the recorded image may occur. . Further, an emulsifier or the like contained in the pressure-sensitive adhesive may penetrate from the back surface, causing fading of the recorded image, and these improvements have been strongly desired. In order to solve such a problem, Japanese Utility Model Application Laid-Open No. 56-140461 proposes a method of providing a back coat layer mainly composed of a water-soluble polymer between a support and an adhesive layer. JP-A-6-227119 discloses a method of providing a back coat layer containing a soap-free type acrylic emulsion, and JP-A-6-239019 discloses a method mainly comprising a two-layer acrylic ester copolymer. Although a method of providing a back coat layer is disclosed, the storability of the developer used for the recording layer is low, and the storability of a recorded image is insufficient.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosensitive recording label having improved sensitivity and chemical resistance of a recorded image.

[0009]

Means for Solving the Problems The present inventors have found that surprisingly excellent performance is exhibited by using a urea urethane compound developer in a label for thermal recording, and have completed the present invention. That is, the present invention is as follows. A first aspect of the present invention is a label for thermal recording containing a urea urethane compound color developer. Second of the invention
Is a label for heat-sensitive recording, wherein a heat-sensitive recording layer containing a urea urethane compound developer is provided on one surface of a support and an adhesive layer is provided on the other surface.

A third aspect of the present invention is the label for thermosensitive recording according to the second aspect of the present invention, wherein the thermosensitive recording layer contains a colorless or pale color dye precursor. According to a fourth aspect of the present invention, there is provided a label for thermal recording, wherein a back coat layer is provided between the adhesive layer and the support of the label for thermal recording according to any one of the second and third aspects of the invention. A fifth aspect of the invention is a label for thermal recording, wherein an intermediate layer is provided between the thermal recording layer and the support of the thermal recording label according to any one of the second to fourth aspects of the invention. According to a sixth aspect of the present invention, there is provided a label for thermal recording, wherein a protective layer is provided on the thermal recording layer of the label for thermal recording according to any one of the second to fifth aspects of the present invention.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. The label for thermal recording of the present invention contains a urea urethane compound developer. The urea urethane compound developer according to the present invention refers to a compound having at least one urea group (—NHCONH— group) and at least one urethane group (—NHCOO— group) in the molecule. It has been known that a compound having a urea group exhibits a color developing effect, but it is not practical because of low color density and low storage stability. However, surprisingly, a urea urethane compound in which a urea group and a urethane group are simultaneously present in one molecule is an excellent color developer of a colorless or light-colored dye precursor. The recording material has a high coloring density and excellent storage stability.

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

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

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

[0015] Methylcyclohexane diisocyanate and the like can be mentioned. Further, diisocyanate dimer such as toluene diisocyanate dimer N, N ′ (4,
4′-dimethyl-3,3′-diphenyldiisocyanato) uretdione (trade name Desmodur TT) and trimers such as 4,4 ′, 4 ″ -trimethyl-3,3 ′,
3 "-triisocyanato-2,4,6-triphenyl cyanurate and the like. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-) (Methylphenyl) urea and polyol adducts, for example, trimethylolpropane adduct of toluene diisocyanate (trade name Desmodur L), amine adducts, etc. Also, JP-A-10-76757 and JP-A-10-95171 (these publications are referred to). The content of the publication is incorporated herein by reference.) Among the isocyanate compounds and isocyanate adduct compounds described above, those having two or more isocyanate groups may be used.

Particularly preferred examples include toluene diisocyanate. The toluene diisocyanate is preferably 2,4-toluene diisocyanate,
In addition, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate
Mixtures of toluene diisocyanates are generally commercially available and can be obtained at low cost, but this is also acceptable. The amine compound which forms a urea group by reacting with an isocyanate which is a starting material of a urea urethane compound color developer may be any compound having an amino group, such as aniline, o-toluidine, m-toluidine, Toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline,
N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine,

3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-
Cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α
-Naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p
-Chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline,
N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide, 4,4′-diamino-3,
3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 3,3'-dichloro-4,
4'-diaminodiphenylmethane,

3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, p-amino Methyl benzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, p
-Dodecyl aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methyl Benzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide,
p- (N-phenylcarbamoyl) aniline, p- [N
-(4-chlorophenyl) carbamoyl] aniline, p
-[N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl)
Aniline,

2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2
-Methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-
Methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,
5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5
-Methylaniline, 4-sulfamoylaniline, 3-
Sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-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-aniline Linosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) Phenyl] sulfone, 3,3′-dimethoxy-4,
4'-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 2,2'-dichloro-4,
4'-diamino-5,5'-dimethoxybiphenyl,
2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, ortho-tolidine sulfone, 2,4'-
Diaminobiphenyl, 2,2′-diaminobiphenyl,

4,4'-diaminobiphenyl, 2,2 '
-Dichloro-4,4'-diaminobiphenyl, 3,3 '
-Dichloro-4,4'-diaminobiphenyl, 2,2 '
-Dimethyl-4,4'-diaminobiphenyl, 4,4 '
-Thiodianiline, 2,2'-dithiodianiline, 4,
4′-dithiodianiline, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether,
3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone,
4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenylmethane,
4,4-diaminodiphenylamine, 4,4′-ethylenedianiline, 4,4′diamino-2,2′-dimethyldibenzyl, 3,3′-diaminobenzophenone, 4,
4′-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene,

1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis ( 4-aminophenoxy) diphenyl, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminodiphenylsulfone, 3,3 ′, 4,4′-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4′-methylenebis-O-toluidine, 4,4 ′-(p-phenyleneisopropylidene) -bis- (2,6-xylidine),
o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4
-Chlorophenol, o-nitroaniline, m-nitroaniline,

P-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, methol, 2,4-diaminophenol, N- (β-hydroxy Ethyl) -o
-Aminophenol sulfate, sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o
-Fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride,
m-toluylenediamine, 2-aminothiophenol,
2-amino-3-bromo-5-nitrobenzonitrile,
Diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3′-dichlorobenzidine, 4,4′-diaminostilbene-2 , 2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J
Aromatic amines such as acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone;

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

3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino)
Propylamine, t-butylamine, propylamine,
3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, -Methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-
Examples thereof include aliphatic amines such as amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine.

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

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

[0027]

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

[0028]

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

The OH group-containing compound which reacts with the isocyanate to form a urethane group may be any compound having an OH group, such as phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol. , P-tert-butylphenol, p-tert-octylphenol,
2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p
-Nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol,

3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, bis ( 4-hydroxyphenyl) benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl- 4′-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4′-methylphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, 4-isopropyloxyphenyl-4′-hydroxyphenylsulfone,

Bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4'-isopropoxy Diphenyl sulfone, bis (2
-Methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-thiodiphenol, 4,4′-dihydroxybenzophenone, 2,2-bis (4-hydroxy Phenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy)
Phenyl) sulfone, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone,

Phenyl salicylate, salicylanilide,
Methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-bis (4'-hydroxybenzoic acid)
Ethyl, pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, 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 And phenols such as 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid.

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

Alcohols such as cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol, polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol , Polycarbonate polyols, polycaprolactone diols, phenolic polyols, polyether polyols such as amine-modified polyols, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1,9-nonane All, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing Polyols, phosphorus-containing polyols,
And polyols such as ethylenediamine, α-methylglucoside, sorbitol, and souce.

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

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

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

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

Examples include meta-xylylene diisocyanate, lysine diisocyanate, diisocyanate diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like. Further, diisocyanate dimer, for example, 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 may be used. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name: Dess) Module L) or an amine adduct may be used.

The isocyanate compound and the isocyanate adduct compound described in JP-A-10-76757 and JP-A-10-95171 may have two or more isocyanate groups. A particularly preferred example is toluene diisocyanate. As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable.
A mixture of -toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available and can be obtained at low cost, but this is also acceptable. These toluene diisocyanate isomer mixtures are liquid at room temperature.

The amine compound for forming a urea group by reacting with an isocyanate which is a starting material of a urea urethane compound may be any compound having an amino group. Examples thereof include aniline, o-toluidine, m-toluidine and p-amine. Toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline,
N, N-diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,
4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine,

2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α
-Naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p
-Chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline,
N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic anilide, trimethylphenylammonium bromide, 4,4′-diamino-3,
3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 3,3'-dichloro-4,
4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine,

2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-
Isopropyl aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide , P-aminobenzamide, p-amino-N-methylbenzamide, 3-
Amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p
-[N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl]
Aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline,

2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2
-Methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-
Methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,
5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5
-Methylaniline, 4-sulfamoylaniline, 3-
Sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N -Phenylsulfamoylaniline,

2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline , 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] Sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrac Loro-4,4'-diaminobiphenyl,

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

3,3′-diaminodiphenyl sulfone,
3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4′-ethylenedianiline, 4,4′diamino-2,2′-dimethyldibenzyl, 3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene,
1,3-bis (4-aminophenoxy) benzene, 1,
3-bis (3-aminophenoxy) benzene, 9,9-
Bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4 ′
-Bis (4-aminophenoxy) diphenyl, 3,
3 ′, 4,4′-tetraaminodiphenyl ether,
3,3 ′, 4,4′-tetraaminodiphenyl sulfone, 3,3 ′, 4,4′-tetraaminobenzophenone,

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

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

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

3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino)
Propylamine, t-butylamine, propylamine,
3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, -Methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-
Examples thereof include aliphatic amines such as amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine.

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

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

[0053]

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

[0054]

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

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

3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, bis ( 4-hydroxyphenyl) benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 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'-isopropoxy Diphenyl sulfone, bis (2
-Methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxy Phenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy)
Phenyl) sulfone, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, 4-
Methyl hydroxybenzoate,

Benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), 1,2-
Ethyl bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, gallic acid Stearyl, lauryl gallate, methyl gallate, 4-methoxyphenol,
4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid,
4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid,
Examples include phenols such as 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid.

However, as these phenols, those having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. Methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-
1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2
-Propen-1-ol,

Benzyl alcohol, 4-pyridinemethanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3
-Alcohols such as hydroxypropane, glycerin, glycerol, polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyetherester polyol, polycarbonate polyol, polycaprolactone diol, phenolic polyol, amine modified polyol, etc. 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-hexane glycol, 1,9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil System polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol,
And polyols such as ethylenediamine, α-methylglucoside, sorbitol, and souce.

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

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

[0063]

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

[0064]

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

[0065]

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

[0066]

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

[0067]

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

[0068]

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

[0069]

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

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

[0071]

Embedded image

[0072]

Embedded image

[0073]

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

[0074]

Embedded image

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

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

[0076]

Embedded image

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

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

[0078]

Embedded image

[0079]

Embedded image

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

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

[0081]

Embedded image

[0082]

Embedded image

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

3-chloro-4-hydroxyphenyl-
4'-methylphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl- 4'-
Hydroxyphenylsulfone, 4-hydroxy-4'-
Isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4′-chlorobenzyl),

Ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), 3- Dimethyl 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- Monophenols such as n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid are exemplified.

Further, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, 4,4'-biphenol, 4-cumylphenol, bis ( 4-hydroxyphenyl) butyl acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-) Hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4 ′ methylphenyl sulfone,

Bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4′-
Dihydroxydiphenyl ether, 4,4′-thiodiphenol, 4,4′-dihydroxybenzophenone,
Diphenols such as 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, and bis (4-hydroxy-3-methylphenyl) sulfide; Can be However, these OH
A compound having an amino group is not preferable as the containing compound. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound. )

Also, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, lauryl alcohol, stearyl alcohol, Pentanol, 3-hexanol, t
tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propene-1
-Ol, benzyl alcohol, 4-pyridine methanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol,

2-chloroethanol, 1-chloro-3-
Monoalcohols such as hydroxypropane, glycerin, and glycerol can be mentioned. Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol, amine modified polyol, ethylene glycol, diethylene glycol,
1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,6-hexaneglycol, 1,9-nonanediol,

Acrylic polyol, fluorine polyol,
Polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane,
Hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine,
Polyols such as α-methylglucosidorubitol and puffed rose may be used. Of these, monophenols are preferably used. Examples of the isocyanate compound of the general formula (X) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, Meta-xylylene diisocyanate and the like. Of these,
Toluene diisocyanate is preferred.

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

4,4 ', 4''-triisocyanato-
2,5-dimethoxytriphenylamine, 4,4 ',
4 ′ ″-triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate,
Dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and the like can be mentioned. Further, diisocyanate dimer, for example, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanate) uretdione (trade name: Desmodur TT) which is a dimer of toluene diisocyanate And trimers such as 4,4 ′, 4 ′ ″-trimethyl-3,3 ′, 3 ′ ″-triisocyanate-2,4,
6-triphenyl cyanurate and the like may be used.

Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea and polyol adducts such as trimethylolpropane adduct of toluene diisocyanate The trade name may be Death Module L) or an amine adduct. Also, JP-A-10-76757 and JP-A-1
Of the isocyanate compounds and isocyanate adduct compounds described in JP-A-95171, those having two or more isocyanate groups may be used. A particularly preferred example is toluene diisocyanate.

The amine compound of the general formula (XI) is not particularly limited as long as it is a compound having at least one amino group. Examples thereof include aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, 2,4-dimethoxyaniline,
2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p
-Aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine,
4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene,

O-Ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, p-ethylaniline
N-propyl aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-
Aminoacetophenone, m-aminobenzamide, o-
Aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-
Phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N-
(4-aminophenyl) carbamoyl] aniline,

2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-
Methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2
-Methoxyaniline, 4-acetylaminoaniline, 2
-Methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylamino Sulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenylsulfone,

2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-
Phenylsulfamoylaniline, 2-methoxy-5
Benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-
p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2 -Methyl-4-
Nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, sulfanilic acid, metanylic acid, 4B acid, C acid, 2B acid,

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

Bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-
4,4'-diaminobiphenyl, 3,3'-dimethyl-
4,4'-diaminobiphenyl, 2,2'-dichloro-
4,4′-diamino-5,5′-dimethoxybiphenyl, 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, ortho-tolidine sulfone, 2,
4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diamino Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-
Dithiodianiline,

4,4′-diaminodiphenyl ether,
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4- Diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone,

4,4'-diaminobenzophenone,
4-bis (4-aminophenoxy) benzene, 1,3-
Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4
-Aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine,
And aromatic diamines such as 3,3'-dichlorobenzidine. Furthermore, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6
[2′-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine,

1-amino-4-methylpiperazine, 1-
Heterocyclic compounds such as (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine, amines, methylamine, ethylamine, stearylamine, allylamine, isopropylamine, 2-ethylhexylamine, Ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) Propylamine, 3- (dimethylamino)
Propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane,

Cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol,
Examples thereof include aliphatic amines such as 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, and hexamethylenediamine. . Of these, aromatic monoamines are preferably used.

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

2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5
5'-tetrachloro-4,4'-diaminobiphenyl,
Ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro -4,4'-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'-Diaminodiphenyl sulfone, 3,3 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,
4 'diamino-2,2'-dimethyldibenzyl, 3,
3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy)
benzene,

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

[0108]

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

[0109]

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

[0110]

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

The OH group-containing compound of the general formula (XIV) is not particularly limited as long as it has two or more OH groups, and examples thereof include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) propane. Bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, p, p'-biphenol, butyl bis (4-hydroxyphenyl) acetate, bis (4 -Hydroxyphenyl)
Benzyl acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone,

3,4-dihydroxyphenyl-4'-methylphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-te
rt-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,
And phenols such as bis (4-hydroxy-3-methylphenyl) sulfide. However, those having an amino group are not preferred as these diphenols. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

Polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenolic polyol and amine modified polyol, ethylene glycol, Diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol , 1,9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxy polyol, trimethylol pro Down, trimethylol ethane,

Polyols such as hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, and souce rose And the like. The ureaurethane compound of the formula (VI) according to the present invention is not particularly limited in the production method. For example, a monophenol compound, an aromatic diisocyanate compound and a diamine compound of the following general formula (XV) can be prepared by, for example, the following reaction formula (G) Alternatively, it can be obtained by reacting according to (H).

[0115]

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

[0116]

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

[0117]

Embedded image

[0118]

Embedded image

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

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

[0120]

Embedded image

[0121]

Embedded image

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

4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-isopropyloxyphenyl-4 '-Hydroxyphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'
-Hydroxyphenylsulfone, 4-hydroxy-4 '
-Isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4'-chlorobenzyl), dimethyl 3-hydroxyphthalate,

4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyl Examples include phenols such as oxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid. However, as these phenols, those having an amino group are not preferred. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

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

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

3,3'-Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5 'Dimethoxybiphenyl, 2,2', 5
5'-tetrachloro-4,4'-diaminobiphenyl,
Ortho-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro -4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'thiodianiline, 2,2'-
Dithiodianiline, 4,4′-dithiodianiline, 4,
4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane,

3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenyl Sulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4 -Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy)
Benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl)
Aromatic diamines such as propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, and 3,3'-dichlorobenzidine are exemplified.

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

O-Ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, p-ethylaniline
N-propyl aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-
Aminoacetophenone, m-aminobenzamide, o-
Aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-
Phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N-
(4-aminophenyl) carbamoyl] aniline,

2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-
Methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2
-Methoxyaniline, 4-acetylaminoaniline, 4
-(N-methyl-N-acetylamino) aniline, 2,
5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4- Sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline,

4-diethylaminosulfonylaniline,
Sulfathiazole, 4-aminodiphenyl sulfone,
2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy- 5-benzylsulfonylaniline,

2-phenoxysulfonylaniline, 2-phenoxysulfonylaniline
(2′-chlorophenoxy) sulfonylaniline, 3-
Anilinosulfonyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino -4-chlorophenol, o-nitroaniline, m-nitroaniline, p
-Nitroaniline, 2-methyl-4-nitroaniline,
m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4
-Difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino-
3-bromo-5-nitrobenzonitrile and the like.

The compound represented by the general formula (XVI) which can be used when synthesizing the ureaurethane compound of the formula (VII)
Examples of the dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, and 2,2-bis (hydroxyphenyl) Heptane, 4,4'-biphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl)
Sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert)
-Butyl-4-hydroxyphenyl) sulfide;

4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane And diphenols such as 3,3'-dihydroxydiphenylamine and bis (4-hydroxy-3-methylphenyl) sulfide. However, those having an amino group are not preferred as these diphenols. Since the amino group has higher reactivity with the isocyanato group than the OH group, the amino group may react with the isocyanato group first, and it may be difficult to obtain a target compound.

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

Embedded image

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

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

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

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

In preparing a label for thermal recording using a urea urethane compound developer, one kind of the urea urethane compound may be used, or two or more kinds thereof may be used in combination, if necessary. In the label for thermal recording, a compound having a melting point is more preferable, and the melting point of the urea urethane compound developer of the present invention is preferably 40 ° C. to 50 ° C.
The temperature is preferably 0 ° C., particularly preferably in the range of 60 ° C. to 300 ° C. By using the urea urethane compound developer according to the present invention, it is possible to obtain a heat-sensitive recording material which has a sufficient color density and a remarkably stable recorded image, and hardly discolors or fades even when heated or humidified for a long time. This is particularly advantageous from the viewpoint of long-term storage of records. Further, since there is no defect that the recorded image is discolored or discolored by fats and oils, chemicals, fingerprints, etc., it shows almost ideal performance as a color developer.

Next, the heat-sensitive recording layer in the heat-sensitive recording label of the present invention contains a colorless or light-colored dye precursor.
The colorless or light-colored dye precursor is a compound known as a color former already used in a heat-sensitive recording material, and is not particularly limited, but is preferably an electron-donating dye precursor, and more preferably a leuco dye, Particularly, a triarylmethane leuco dye, a fluoran leuco dye, a fluorene leuco dye, a diphenylmethane leuco dye, or the like is preferable. Hereinafter, typical dye precursors will be exemplified.

(1) Triarylmethane compounds 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide,

3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3
-Bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide,
3-p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like. (2) Diphenylmethane compounds 4,4-bis-dimethylaminophenylbenzhydryl benzyl ether, N-halophenyl leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like.

(3) Xanthene compounds Rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3- Diethylamino-7-phenylfluoran, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3 -Diethylamino-7
-(2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N
-Ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran,

3- (N-ethyl-N-tolyl) amino-
6-methyl-7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-
Dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N
-Isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-
Ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluoran and the like.

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

Further, 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6'-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'- (6′-dimethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9- Spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3,6-bis (dimethylamino) ) Fluorene-9-spiro-3 ′-(6′-diethylaminophthalide),

3-Diethylamino-6-dimethylaminofluorene-9-spiro-3 ′-(6′-diethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3 ′-(6 ′ -Diethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3 '-(6'-diethylaminophthalide), 3,6-bis (dimethylamino) fluorene-9-spiro-3'- (6'-dibutylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3 '-(6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro- 3 ′-(6′-dibutylaminophthalide), 3,3-bis [2- (4-dimethylaminophenyl) -2- (4-methoxy Phenyl) ethenyl] -
Compounds having an absorption region in the near infrared, such as 4,5,6,7, -tetrachlorophthalide. These colorless or light-colored dye precursors can be used in combination of two or more as necessary.

The urea urethane compound developer is preferably used in an amount of 5 to 1000 parts by weight, more preferably 20 to 5 parts by weight, based on 100 parts by weight of the colorless or pale color dye precursor.
00 parts by weight. When the amount of the urea urethane compound developer is 5 parts by weight or more, it is sufficient to form a color of the dye precursor, and the coloring density is high. When the amount of the urea urethane compound developer is 1,000 parts by weight or less, an excessive amount of the urea urethane compound developer hardly remains, which is economically advantageous and preferable. By adding an acidic developer to the heat-sensitive recording layer of the heat-sensitive recording label of the present invention, the sensitivity is improved, and a heat-sensitive recording label with clear coloring can be obtained.

As the acidic developer, generally used electron accepting substances are used. In particular, a phenol derivative, an aromatic carboxylic acid derivative or a metal compound thereof, a salicylic acid derivative or a metal salt thereof, N, N-diarylthiol is used. Urea derivatives and sulfonylurea derivatives are preferred. Particularly preferred are phenol derivatives, specifically,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (hydroxyphenyl) butane, 2,2-
Bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone,

4-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,

Examples thereof include dimethyl 3-hydroxyphthalate, stearyl gallate and lauryl gallate. Examples of the salicylic acid derivative include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid,
4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octoctanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid and the like. . Examples of the sulfonylurea derivative include 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane,
-Bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylsulfide, 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylether, N- (p- Compounds containing one or more arylsulfonylaminoureido groups such as toluenesulfonyl) -N'-phenylurea are exemplified.

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

1,1,3-Tris (3,5-di-ter
t-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, 1,3-tris (3-phenyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-5-methylphenyl) butane, 1,1,3-tris (3- Cyclohexyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tetra (3-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetra (3-
Cyclohexyl-4-hydroxy-6-methylphenyl) propane, 1,1-bis (3-tert-butyl-
4-hydroxy-6-methylphenyl) butane, 1,1
It is also possible to add a phenol compound such as -bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) 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 the colorless or pale color dye precursor. When the amount of the acidic developer is 5 parts by weight or more, the coloration of the dye precursor is good and the color density is high. Also, an acidic developer 50
When the amount is 0 part by weight or less, the acidic developer hardly remains, which is economically advantageous and preferable. In the present invention, a color former containing a colorless or light-colored dye precursor and a urea urethane compound color developer, forming a heat-sensitive recording layer on any support by a method such as coating, and further forming an adhesive layer Thus, a thermosensitive recording label can be obtained.

The heat-sensitive recording layer is formed by dispersing the above urea urethane compound, a colorless or light-colored dye precursor such as leuco dye, a heat-fusible substance to be described later in the form of a dispersion, together with other necessary components. It is applied on the body. The preparation of the dispersion comprises one or more of each of these compounds,
It can be obtained by finely pulverizing 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 size of each dispersion is 0.1 to 10
It is preferable that the thickness be about 1 μm, especially about 1 μm. In particular, when the urea urethane compound is wet-pulverized in an aqueous solvent, it is desirable to maintain the liquid temperature of the aqueous solvent at 50 ° C. or lower. The pH of the coating solution containing the urea urethane compound and the colorless or pale color dye precursor is preferably 5 to 12.

In addition, the thermosensitive recording layer contains diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, and the like as pigments. You can also. In addition, for the purpose of preventing head wear and sticking, zinc stearate, higher fatty acid metal salts such as calcium stearate, paraffin,
Waxes such as paraffin oxide, polyethylene, polyethylene oxide, stearic acid amide, caster wax, etc .; dispersants such as dioctyl sodium sulfosuccinate; ultraviolet absorbers such as benzophenone and benzotriazole; surfactants and fluorescent dyes Etc. can be contained as needed.

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

As the support on which the heat-sensitive recording layer and the like are provided, paper is mainly used. In addition to paper, various woven fabrics, nonwoven fabrics, synthetic resin films, laminated paper, synthetic paper, metal foil, or a combination thereof are used. A composite sheet can be used arbitrarily according to the purpose. The basis weight of the support, desirably ^{40g / m 2 ~200g / m 2} , since only a high flatness can be as heat-sensitive recording material is one having excellent smoothness and flatness of the surface since it is desirable that desired, since the The surface treatment is preferably performed by applying heat and pressure using a machine calender, a soft calender, a super calender, or the like. The thermal recording layer may be composed of a single layer or a plurality of layers. For example, each color forming component may be contained one layer at a time to form a multilayer structure. This heat-sensitive recording layer can be obtained by mixing each aqueous dispersion obtained by finely pulverizing each color-forming component or other components, a binder and the like, applying the mixture on a support, and drying.

In order to improve the sensitivity of the thermosensitive recording label of the present invention, a thermofusible substance can be contained in the thermosensitive coloring layer. The heat-fusible substance preferably has a melting point of 60C to 180C, and particularly preferably has a melting point of 80C to 140C. For example, benzyl p-benzyloxybenzoate, stearamide, palmitamide, N-methylol stearamide, β-naphthylbenzyl ether, N-stearyl urea, N, N ′
-Distearyl urea, β-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid phenyl ester, β-naphthol (p-methylbenzyl) ether,
1,4-dimethoxynaphthalene, 1-methoxy-4-benzyloxynaphthalene,

N-stearoylurea, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, 1-phenoxy-2- (4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl Examples include terephthalate, metaterphenyl, dibenzyl oxalate, and oxalic acid (P-chlorobenzyl) ester. Furthermore, 4,4′-dimethoxybenzophenone, 4,4′-dichlorobenzophenone, 4,4′-difluorobenzophenone, diphenylsulfone,
4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'dichlorodiphenyldisulfide,

Diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N'-diphenyl-p-phenylenediamine, 1- (N-phenylamino) naphthalene, benzyl, 1,3-diphenyl-1,3-propanedione Etc. may be used. Of these, diphenyl sulfone is preferably used. The heat-fusible substance may be used alone or as a mixture of two or more kinds. In order to obtain a sufficient thermal response, 10 to 10 parts by weight of a colorless or pale color dye precursor is used. It is preferably used in an amount of from 300 to 300 parts by weight, and more preferably from 20 to 250 parts by weight.

Further, the label for thermal recording according to the present invention may contain a hindered phenol compound or an ultraviolet absorber in the thermal recording layer. For example, 1,1,3-tris (3′-cyclohexyl-4′hydroxyphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,
4'-thiobis (3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, , 2'-dihydroxy-4,
4'-dimethoxybenzophenone, p-octylphenyl salicylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, ethyl-2-cyano-3,3'-diphenylacrylate, tetra (2
2,6,6-tetramethyl-4-piperidyl) 1,2,2
3,4-butanetetracarboate and the like.

In the heat-sensitive recording label of the present invention, a heat-sensitive recording layer containing a urea urethane compound developer is provided on one surface of the support, and an adhesive layer is provided on the other surface.
The pressure-sensitive adhesive layer of the heat-sensitive recording material of the present invention has a pressure-sensitive adhesive as a main component. Examples of the pressure-sensitive adhesive include a synthetic rubber-based emulsion-type adhesive, an acrylic emulsion-type adhesive, and a natural rubber-based solvent-type adhesive. Agents, acrylic solvent-based pressure-sensitive adhesives, and silicon-based solvent-based pressure-sensitive adhesives, with acrylic emulsion-based pressure-sensitive adhesives being particularly preferred. Further, the thermosensitive recording label produced by the method of the present invention may be provided with a back layer (backcoat layer) between the pressure-sensitive adhesive layer and the support, if necessary, to correct the curl of the thermosensitive recording label, prevent static electricity, and improve friction. Coefficient adjustment can be performed. The coating liquid component of the back layer, coating method, etc.
The same method as the method for forming the heat-sensitive recording layer can be used. The dry coating amount is preferably in the range of 0.2 to 10.0 g / m ² .

The order of coating in the production of the heat-sensitive recording material of the present invention is not particularly limited. For example, after a heat-sensitive recording layer is provided on a support, a back coat layer is provided on another surface, and an adhesive layer is further provided. It is possible to produce with
Alternatively, it can be prepared by providing a back coat layer on a support, providing a heat-sensitive recording layer on another surface, and further providing an adhesive layer on the back coat layer. Further, as a method of providing an adhesive layer on the back coat layer, the adhesive layer liquid may be applied directly on the back coat layer and dried, or a method in which the adhesive layer liquid is previously applied to release paper and dried, Before the agent layer is provided, the heat-sensitive recording material may be bonded to the backcoat layer side.

Furthermore, an intermediate layer comprising one or more layers may be provided between the heat-sensitive recording layer and the support to improve the thermal response. The intermediate layer is mainly composed of an organic, inorganic pigment, hollow particles, a water-soluble polymer, and an aqueous binder such as latex.
Inorganic pigments and aqueous binders can be used. The method for forming the intermediate layer is not particularly limited, and the same method as the method for forming the heat-sensitive recording layer can be used. The dry coating amount is preferably in the range of 2.0 to 15.0 g / m ² .

If a protective layer is provided on the heat-sensitive recording layer of the heat-sensitive recording label of the present invention, if necessary, the abrasion resistance of the heat-sensitive recording label can be improved. The main component of the protective layer is a film-forming polymer. Examples of the polymer used for the protective layer include methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, starches, gelatin, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate, and styrene-maleic anhydride copolymer half ester. Hydrolysates, isobutylene-maleic anhydride copolymer hydrolysates, water-soluble polymers such as polyvinyl alcohol, silica-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide derivatives, polyvinylpyrrolidone, sodium polystyrenesulfonate and sodium alkinate And styrene-butadiene rubber latex, acrylonitrile-
There are water-insoluble polymers such as butadiene rubber latex, methyl acrylate-butadiene rubber latex, and polyvinyl acetate emulsion, and these polymers can be used alone or in combination of two or more.

Pigments, metal soaps, waxes, cross-linking agents, and the like are added to the protective layer for the purpose of improving matching with a thermal head during printing and improving the water resistance of the protective layer. Pigments include zinc oxide, calcium carbonate, barium sulfate, titanium oxide, lithopone, talc, lime, kaolin, aluminum hydroxide, silica, amorphous silica, etc., and the amount of these added is 0.5 to the total weight of the polymer. 4
Times, particularly preferably 0.8 to 3.5 times. If the amount is less than the lower limit of the above range, it is ineffective for improving the head matching property. If the amount is more than the upper limit, the sensitivity of the heat-sensitive recording material is remarkably reduced, and its commercial value is impaired.

Examples of the metal soap include emulsions of higher fatty acid metal salts such as zinc stearate, calcium stearate, and aluminum stearate. 0.5 to 20% by weight, preferably 1 to 10% by weight of the total weight of the protective layer. It is added in an amount. Waxes include emulsions of paraffin wax, microcrystalline wax, carnauba wax, methylol stearamide, polyethylene wax, etc., added in an amount of 1 to 20% by weight, preferably 1 to 10% by weight of the total weight of the protective layer. Is done.

In forming the protective layer on the heat-sensitive layer, a surfactant is added to the coating liquid for forming the protective layer in order to form a uniform coating layer. Surfactants include sulfosuccinic acid-based alkali metal salts, fluorine-containing surfactants, etc.
Specific examples include sodium or ammonium salts such as di- (2-ethylhexyl) sulfosuccinic acid and di- (n-hexyl) sulfosuccinic acid. Generally, any anionic surfactant is effective. It is. Dry coating amount of the protective layer is preferably about 0.5 to 10 g / m ^2, in particular the amount of about 1 to 5 g / m ² is preferred.

Hereinafter, the present invention will be described in more detail by way of examples. In addition, each physical property was evaluated by the following methods. <Coloring sensitivity> Using a printing tester manufactured by Okura Electric Co., Ltd., and using a Kyocera KJT-256-8MGF1 thermal head, the coloring 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 label for thermosensitive recording is sandwiched between vinyl chloride wraps, and a load of 300 g / cm ² is applied from above to 40 ° C.
For 24 hours, and after the standing, the density of the printed portion was visually evaluated.

[0173]

Example 1 A) Preparation of coating solution for heat-sensitive recording layer 31.5 g of 2,4-toluene diisocyanate was added to 60 ° C.
Then, 21.5 g of 4,4'-diaminodiphenylsulfone was diluted with 120 ml of methyl ethyl ketone and added dropwise over 4 hours, followed by reaction at 60 ° C. for 2 hours. After the reaction, after cooling to room temperature, toluene was added,
The precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo 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 dried in vacuo overnight to obtain 38.5 g of a white crystalline compound.

Next, 2 g of this compound was taken, and 2.5% by weight was obtained.
The mixture was crushed and dispersed with a paint shaker for 6 hours together with 8 g of an aqueous polyvinyl alcohol solution to obtain a dispersion. The liquid temperature of the dispersion immediately after the dispersion was 25 ° C. The dispersed particle size of this compound was 0.6 μm. Also, 70 g of 3-dibutylamino-6-methyl-7-anilinofluoran was pulverized together with 130 g of a 5.4% by weight aqueous solution of polyvinyl alcohol in a sand grinder (400 ml vessel volume, manufactured by IMEX Co., Ltd.) for 3 hours at a rotation speed of 2000 rpm.
Dispersion gave a dispersion.

Further, 70 g of diphenyl sulfone was added to 5.4 g
A dispersion was obtained by pulverizing and dispersing with a sand grinder (vessel capacity 400 ml, manufactured by IMEX Co., Ltd.) at a rotation speed of 2000 rpm for 3 hours together with 130 g of a weight% aqueous polyvinyl alcohol solution. In addition, 10 g of calcium carbonate is added to 30 pieces of water.
g and mixed by stirring with a stirrer to obtain a dispersion. These dispersions were dried at a solid content of 2
0 parts by weight, 10 parts by weight of dry solids of 3-dibutylamino-6-methyl-7-anilinofluoran dispersion, 25 parts by weight of dry solids of diphenylsulfone dispersion, 40 parts of dry solids of calcium carbonate dispersion Parts by weight, and a dry solid content of a zinc stearate dispersion having a solid content concentration of 16% by weight.
The coating liquid was obtained by stirring and mixing at 0 parts by weight and further 15 parts by weight of 15% by weight of polyvinyl alcohol (dry basis).

Next, the coating solution of the heat-sensitive recording layer prepared in A) was applied on a high-quality paper surface having a basis weight of 150 g / m ² by dry weight of 7 g / m ^2.
And dried with a super calender to prepare a heat-sensitive recording layer coated sheet. B) Preparation of Release Sheet To a base paper having a basis weight of 40 g / m ² , a release agent composed of oily dimethyl silicone was added in an amount of 1 g / g using a gravure coater.
m ^{2 was} applied to provide a release layer. Then, on the release layer,
An adhesive layer component consisting of 100 parts by weight of chlorinated rubber, 20 parts by weight of ester gum, and 120 parts by weight of dibutyl phthalate
g / m ² .

C) Preparation of Label for Thermosensitive Recording The non-coated side of the thermosensitive recording layer coated sheet prepared in A) above and the adhesive layer coated side of the release sheet prepared in B) above were bonded so as to face each other. In addition, a thermosensitive recording label was produced. The evaluation result of the coloring sensitivity of the obtained label for thermal recording was as good as the optical density of 1.3. Further, the print preservability of the vinyl chloride wrap was good without fading. The results are summarized in Table 1.

[0178]

Example 2 61 g of 2,4-toluene diisocyanate
To this was added 450 g of toluene as a solvent, and 26 g of aniline dissolved in 150 g of toluene was added dropwise over 6 hours, and the mixture was reacted at 5 ° C. for 7 hours. After the reaction, the precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 70 g of a white crystalline compound. Next, 30 g of this compound was taken and 365 g of toluene was added as a solvent,
To this were added 12.2 g of 2,2-bis (4-hydroxyphenyl) propane and 0.3 mg of triethylamine, and the mixture was stirred at 60 ° C. for 4 hours, then at 70 ° C. for 3 hours, and further heated to 80 ° C. The reaction was performed for 3 hours. After the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with toluene, and dried under vacuum overnight to obtain 42 g of a white crystalline compound. Next, 2 g of this compound was taken and 2.5 g
The mixture was pulverized and dispersed with a paint shaker for 6 hours together with 8 g of a polyvinyl alcohol aqueous solution by weight to obtain a dispersion. Subsequently, a thermosensitive recording label was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the above compound was used instead of the dispersion of the compound obtained in Example 1. The results are summarized in Table 1.

[0179]

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

[0180]

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

[0181]

Example 5 D) Preparation of Backcoat Layer Coating Solution A styrene-maleic acid copolymer (100 parts by weight) and kaolin (50 parts by weight) were mixed to prepare a backcoat layer coating solution.
This coating liquid was applied and dried so that the dry weight was 1 g / m ² on the surface of the heat-sensitive recording label of Example 1 opposite to the surface on which the heat-sensitive recording layer was applied, except that a back coat layer was provided. In the same manner as in Example 1, a thermosensitive recording label was prepared and evaluated. The results are summarized in Table 1.

[0182]

Example 6 E) Preparation of Coating Solution for Intermediate Layer An intermediate comprising a ratio of 80 parts by weight of dry solids of a 48% polystyrene fine particle dispersion and 20 parts by weight of dry solids of a 40% styrene / acrylate copolymer emulsion. A layer coating solution was prepared. The weight of the coating solution when dried between the heat-sensitive recording layer of the heat-sensitive recording label of Example 5 and the support was 8 g / m2.
^A thermosensitive recording label was prepared and evaluated in the same manner as in Example 5 except that the intermediate layer was formed by coating and drying to obtain No. ² . The results are summarized in Table 1.

[0183]

Example 7 F) Preparation of Coating Solution for Protective Layer 20 parts by weight of zinc stearate, 20 parts by weight of a 5% by weight aqueous solution of methylcellulose and 60 parts by weight of water were mixed and dispersed by a sand grinder for 2 hours. Next, 20 parts by weight of a 10% by weight aqueous solution of carboxy-modified polyvinyl alcohol, 1.5 parts by weight of silica, 12.5 parts by weight of polyamide epichlorohydrin
6.5 parts by weight of a 1% by weight aqueous solution and 15.0 parts by weight of water were mixed and dispersed by a sand grinder for 2 hours. Next, 0.7 parts by weight of the above zinc stearate dispersion and 45 parts of the silica dispersion.
0 parts by weight and 11.3 parts by weight of water were mixed to prepare a coating liquid for the protective layer, and this coating liquid was dried on the heat-sensitive recording layer of the heat-sensitive recording label of Example 6 to a weight of 3 g / m ² when dried. A thermosensitive recording label was prepared and evaluated in the same manner as in Example 6 except that a protective layer was formed by coating and drying as described above. The results are summarized in Table 1.

[0184]

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

[0185]

[Table 1]

[0186]

As described above in detail and specifically, the label for thermosensitive recording of the present invention is excellent in the sensitivity of thermosensitive recording and the chemical resistance of thermosensitive coloring images.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41M 5/18 EF (72) Inventor Kazuo Kabashima 1-3-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kawasaki, Asahi Kasei Industrial Co., Ltd. F term (reference) 2H026 AA07 BB02 BB24 DD53 FF01 FF11 FF13 FF17 4J004 AA04 AA05 AA10 AA11 AB01 CC03 CD01 DB02 FA01

Claims (6)

[Claims] 1. A heat-sensitive recording label containing a urea urethane compound color developer. 2. A label for heat-sensitive recording, wherein a heat-sensitive recording layer containing a urea urethane compound developer is provided on one side of a support and an adhesive layer is provided on the other side. 3. The heat-sensitive recording label according to claim 2, wherein the heat-sensitive recording layer contains a colorless or light-colored dye precursor. 4. A heat-sensitive recording label according to claim 2, wherein a back coat layer is provided between the pressure-sensitive adhesive layer and the support of the heat-sensitive recording label according to claim 2. 5. A heat-sensitive recording label according to claim 2, wherein an intermediate layer is provided between the heat-sensitive recording layer and the support. 6. A heat-sensitive recording label according to claim 2, wherein a protective layer is provided on the heat-sensitive recording layer of the heat-sensitive recording label according to claim 2.