JPH1035104A - Coloring recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material which excels in storage stability of colored images. SOLUTION: The recording material contains at least one type of carbonylthiourea compounds which are expressed by the formula. In the formula, R1 , R2 represent an alkyl, an alkoxy, an aralkyl, an aralkyloxy, a phenyl, a phenoxy, a naphthyl, a naphthyloxy, a cycloalkyl, and a cycloalkyloxy and m represents 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material excellent in image storage stability, and more particularly to a recording material excellent in light stability of an image using a chromogenic dye which is colored by an acidic substance or the like.

[0002]

2. Description of the Related Art A recording material utilizing color development by a reaction between a color-forming dye and a developer can be recorded in a relatively simple apparatus in a short time without performing complicated processing such as development and fixing. It is widely used for thermal recording paper for output recording of a printer or the like, or pressure-sensitive copying paper for a form for simultaneously copying several sheets. As these recording materials, those which rapidly develop color, maintain the whiteness of uncolored portions (hereinafter referred to as "background"), and have high color fastness of developed images and background are demanded. In particular, these recording materials are strongly demanded to have improved light fastness since printed images are significantly faded by exposure to light such as sunlight or fluorescent light. For this purpose, various auxiliaries such as a color-forming dye, a developer and a storage stabilizer have been developed, but none of them have been found to be sufficiently satisfactory.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a recording material having excellent storage stability, especially light fastness, of a color image in the recording material.

[0004]

The present invention provides a compound represented by the general formula (I):

[0005]

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[Wherein R ₁ and R ₂ each independently may be a straight-chain or branched saturated or unsaturated alkyl group having 1 to 12 carbon atoms, or may have a straight-chain or branched Good carbon number 1
To 12 saturated or unsaturated alkoxy groups, aralkyl groups, aralkyloxy groups, phenyl groups, phenoxy groups,
A naphthyl group, a naphthyloxy group, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyloxy group having 5 to 12 carbon atoms, and m represents 0 or 1]. It is a color-forming recording material characterized by containing.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The compounds of the present invention can be used for any purpose as long as they are recording materials using chromogenic dyes, for example, heat-sensitive recording materials or pressure-sensitive copying materials.

Specific examples of the groups represented by R ₁ and R ₂ in the carbonylthiourea compound represented by the general formula (I) are as follows.

Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclohexyl, phenyl, benzyl, naphthyl Group, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, se
Examples include a c-butyloxy group, a tert-butyloxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group, an octyloxy group, a cyclohexyloxy group, a phenoxy group, a benzyloxy group, and a naphthyloxy group.

In the general formula (I), when m is 1, the two carbonylthiourea groups may be substituted at any of the ortho, meta and para positions, but a compound substituted at the ortho position is preferably used. Used.

Next, particularly preferred compounds in the present invention will be exemplified, but the invention is not limited thereto.

[0012]

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A recording material containing a color-forming dye may be produced by a commonly used method, and is produced by using together with various assistants such as a color developer and a sensitizer.

When the recording material of the present invention is used for heat-sensitive recording paper, it may be carried out in the same manner as in the production of a known heat-sensitive paper. For example, a color-forming dye, a developer and a compound of the formula (I) may be used. It can be produced by mixing a suspension in which each of the fine particles is dispersed in an aqueous solution of a water-soluble binder such as polyvinyl alcohol or cellulose, applying the suspension to a support such as paper, and drying.

The ratio of the compound of the formula (I) to the chromogenic dye is from 0.1 to 5 per 1 part by weight of the chromogenic dye.
Parts by weight, preferably 0.2 to 2 parts by weight.

The recording material of the present invention contains a color developer, and further includes an image stabilizer, a sensitizer, a filler, a dispersant, an antioxidant, a desensitizer, an antiblocking agent, an antifoaming agent, a light stabilizer, A fluorescent whitening agent or the like can be contained as needed.

These chemicals may be contained in the color-forming layer. However, when they have a multilayer structure, they may be contained in any layer such as a protective layer. In particular, when an overcoat layer or an undercoat layer is provided above and / or below the color-forming layer, these layers can contain an antioxidant, a light stabilizer, and the like. In addition, antioxidants,
The light stabilizer can be contained in these layers in the form of being encapsulated in microcapsules as required.

Examples of the chromogenic dye used in the recording material of the present invention include leuco dyes such as fluoran dyes, phthalide dyes, lactam dyes, triphenylmethane dyes, phenothiazine dyes and spiropyran dyes. It is not limited, and any color-forming dye that can be colored by contact with a color developer, which is an acidic substance, can be used.
These color-forming dyes are used alone, and a recording material of the color to be formed is of course manufactured, but two or more of them can be mixed and used. For example, red,
A recording material that develops a true black color can be produced by using a mixture of three primary color developing dyes of blue and green or a black coloring dye.

Among these dyes, fluoran-based dyes are exemplified by 3-diethylamino-6-methyl-7-.
Anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluoran, 3- (N- Methyl-N-propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N
-Isopentylamino) -6-methyl-7-anilinofluoran, 3-diethylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3- (N-ethyl -P-toluidino) -6-methyl-7-anilinofluoran, 3
-(N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3-pyrrolidino-6
Methyl-7-anilinofluoran, 3-piperidino-6
-Methyl-7-anilinofluoran, 3-dimethylamino-7- (m-trifluoromethylanilino) fluoran, 3-dipentylamino-6-methyl-7-anilinofluoran, 3- (N-ethoxy Propyl-N-ethylamino) -6-methyl-7-anilinofluoran, 3-
Dibutylamino-7- (o-fluoroanilino) fluoran, 3-diethylaminobenzo [a] fluoran, 3-
Dimethylamino-6-methyl-7-chlorofluoran,
3-diethylamino-5-methyl-7-dibenzylaminofluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-5-chlorofluoran, 3-diethylamino-6- (N, N'- Dibenzylamino) fluoran, 3,6-dimethoxyfluoran 2,4-dimethyl-6- (4-dimethylaminophenyl) aminofluoran, and the like. Further, as the near infrared absorbing dye, 3- (4- (4- (4-anilino)-
Anilino) anilino-6-methyl-7-chlorofluoran, 3,3-bis (2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) vinyl) -4,
5,6,7-tetrachlorophthalide, 3,6,6′-tris (dimethylamino) spiro [fluorene-9,3 ′
-Phthalide] and the like. Other examples include 3,3-bis (4'-diethylaminophenyl) -6-diethylaminophthalide.

Typical examples of the color developer of the thermosensitive recording paper include bisphenol A, 4,4'-sec-
Butylidenebisphenol, 4,4'-cyclohexylidenebisphenol, 2,2-dimethyl-3,3-bis (4-hydroxyphenyl) butane, 2,2'-dihydroxydiphenyl, pentamethylene-bis (4-hydroxybenzoate ), 2,2-dimethyl-3,3-di (4-hydroxyphenyl) pentane, 2,2-di (4
Bisphenol compounds such as -hydroxyphenyl) hexane, 4,4'-dihydroxydiphenylthioether, 1,7-di (4-hydroxyphenylthio) -3,
Sulfur-containing bisphenol compounds such as 5-dioxaheptane, 2,2'-bis (4-hydroxyphenylthio) diethyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenylthioether, benzyl 4-hydroxybenzoate Ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, chlorobenzyl 4-hydroxybenzoate, methyl 4-hydroxybenzoate Benzyl,
4-hydroxybenzoic esters such as diphenylmethyl 4-hydroxybenzoate; metal benzoates such as zinc benzoate and zinc 4-nitrobenzoate; 4- (2- (4-methoxyphenyloxy) ethyloxy) salicylic acid; Salicylic acids, zinc salicylate, metal salts of salicylic acid such as bis {4- (octyloxycarbonylamino) -2-hydroxybenzoic acid} zinc, 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, -Hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-butoxydiphenylsulfone, 4,4'-dihydroxy-3,3 '
Hydroxysulfones such as -diallyldiphenylsulfone, 3,4-dihydroxy-4'-methyldiphenylsulfone, 4,4'-dihydroxy-3,3 ', 5,5'-tetrabromodiphenylsulfone, and 4-hydroxyphthalic acid Dimethyl, 4-hydroxyphthalic acid diesters such as 4-hydroxyphthalic acid dicyclohexyl, 4-hydroxyphthalic acid diesters and the like, hydroxynaphthoic acid esters such as 2-hydroxy-6-carboxynaphthalene and the like, hydroxyacetophenone, p-phenylphenol, Benzyl 4-hydroxyphenylacetate, p-benzylphenol, hydroquinone-monobenzyl ether, trihalomethylsulfones such as tribromomethylphenylsulfone, and 4,4′-bis (p-toluenesulfonylaminocarbonyl) Amino) sulfonylureas of diphenylmethane, tetracyanoquinodimethane compounds,
2,4-dihydroxy-2'-methoxybenzanilide and the like can be mentioned.

Also, compounds described in JP-A-7-149713, WO 93/06074, and WO 95/33714 can be used. For example, 1,3-bis [4- (4-hydroxyphenylsulfonyl) Phenoxy] -2-hydroxypropane 1,1-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] methane 1,2-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] ethane 1,3-bis [4 -(4-hydroxyphenylsulfonyl) phenoxy] propane 1,4-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] butane 1,5-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] pentane 1,6 -Bis [4- (4-hydroxyphenylsulfonyl) phenoxy] Hexane α, α'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] -p-xylene α, α'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] -m-xylene α, α'- Bis [4- (4-hydroxyphenylsulfonyl) phenoxy] -o-xylene 2,2'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] diethyl ether 4,4'-bis [4- (4-hydroxy Phenylsulfonyl) phenoxy] dibutyl ether 1,2-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] ethylene 1,4-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] -2-butene.

Further, the following bisphenol compounds can also be used.

4,4'-bis [4- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2-trans-butenyloxy] diphenylsulfone Melting point (° C.) 176 to 180 4,4'-bis [4- ( 4-hydroxyphenylsulfonyl) phenoxy-4-butyloxy] diphenylsulfone Melting point (C) 215-220 4,4'-Bis [4- (4-hydroxyphenylsulfonyl) phenoxy-3-propyloxy] diphenylsulfone Melting point (C) 237-242 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyloxy] diphenylsulfone 4- [4- (4-hydroxyphenylsulfonyl) phenoxy-4-butyloxy] -4 '-[ 4- (4-hydroxyphenylsulfonyl) phenoxy- 3-propyloxy] diphenylsulfone 4- [4- (4-hydroxyphenylsulfonyl) phenoxy-4-butyloxy] -4 '-[4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyloxy] diphenylsulfone 4- [ 4- (4-hydroxyphenylsulfonyl) phenoxy-3-propyloxy] -4 '-[4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyloxy] diphenylsulfone 4,4'-bis [4- (4- Hydroxyphenylsulfonyl) phenoxy-5-pentyloxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-6-hexyloxy] diphenylsulfone Melting point (° C) 133-136 4- [4- [4- (4-hydroxyf Nirusuruhoniru) phenoxy] -2-trans - butenyloxy] -
4 '-[4- (4-hydroxyphenylsulfonyl) phenoxy-4-butyloxy] diphenylsulfone 4- [4- (4-hydroxyphenylsulfonyl) phenoxy-2-trans-butenyloxy] -4'-[4
-(4-hydroxyphenylsulfonyl) phenoxy-
3-propyloxy] diphenylsulfone 4- [4- [4- (4-hydroxyphenylsulfonyl) phenoxy] -2-trans-butenyloxy]-
4 '-[4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyloxy] diphenylsulfone 1,4-bis [4- [4- [4- [4- (4-hydroxyphenylsulfonyl) phenoxy-2-trans-butenyloxy]] Phenylsulfonyl] phenoxy] -cis-
2-butene Melting point (° C) 185-190 1,4-bis [4- [4- [4- (4-hydroxyphenylsulfonyl) phenoxy-2-trans-butenyloxy] phenylsulfonyl] phenoxy] -trans-2-butene Melting point (° C) 240-243 4,4'-bis [4- [4- (2-hydroxyphenylsulfonyl) phenoxy] butyloxy] diphenylsulfone 4,4'-bis [4- [2- (4-hydroxyphenylsulfonyl) ) Phenoxy] butyloxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy] diphenylsulfone Melting point (° C) 130-134 4,4'-bis [4- ( 4-hydroxyphenylsulfonyl) phenyl-1,4-phenylenebisme Lenoxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenyl-1,3-phenylenebismethyleneoxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenyl -1,2-phenylenebismethyleneoxy] diphenylsulfone 2,2'-bis [4- [4- [4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy] phenylsulfonyl] phenoxy] diethyl ether α , Α'-bis [4- [4- [4- (4-hydroxyphenylsulfonyl) phenyl-1,4-phenylenebismethyleneoxy] phenylsulfonyl] phenoxy]-
p-xylene α, α'-bis [4- [4- [4- (4-hydroxyphenylsulfonyl) phenyl-1,3-phenylenebismethyleneoxy] phenylsulfonyl] phenoxy]-
m-xylene α, α'-bis [4- [4- [4- (4-hydroxyphenylsulfonyl) phenyl-1,2-phenylenebismethyleneoxy] phenylsulfonyl] phenoxy]-
o-xylene 2,4'-bis [2- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy] diphenylsulfone 2,4'-bis [4- (2-hydroxyphenylsulfonyl) phenoxy-2-ethylene Oxyethoxy] diphenylsulfone 4,4'-bis [3,5-dimethyl-4- (3,5-
Dimethyl-4-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy] diphenylsulfone 4,4'-bis [3-allyl-4- (3-allyl-4-
(Hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy] diphenylsulfone 4,4'-bis [3,5-dimethyl-4- (3,5-dimethyl-4-hydroxyphenylsulfonyl) phenyl-1,4-phenylenebis Methyleneoxy] diphenylsulfone 4,4'-bis [3,5-dimethyl-4- (3,5-dimethyl-4-hydroxyphenylsulfonyl) phenyl-1,3-phenylenebismethyleneoxy] diphenylsulfone 4,4 ' -Bis [3,5-dimethyl-4- (3,5-dimethyl-4-hydroxyphenylsulfonyl) phenyl-1,2-phenylenebismethyleneoxy] diphenylsulfone 4,4'-bis [3-allyl-4- (3-allyl-4-
(Hydroxyphenylsulfonyl) 1,4-phenylenebismethyleneoxy] diphenylsulfone 4,4′-bis [3-allyl-4- (3-allyl-4-
(Hydroxyphenylsulfonyl) 1,3-phenylenebismethyleneoxy] diphenylsulfone 4,4'-bis [3-allyl-4- (3-allyl-4-
(Hydroxyphenylsulfonyl) 1,2-phenylenebismethyleneoxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-hydroxypropyloxy] diphenylsulfone 1,3-bis [4- [ 4- [4- (4-hydroxyphenylsulfonyl) phenoxy-2-hydroxypropyloxy] phenylsulfonyl] phenoxy] -2-hydroxypropane

2-hydroxy-4,6-di [4- (4-
Hydroxyphenylsulfonyl) phenoxy] -1,
3,5-triazine 2-methoxy-4,6-di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5-triazine 2-ethoxy-4,6-di [4- (4-hydroxy Phenylsulfonyl) phenoxy] -1,3,5-triazine 2-isopropoxy-4,6-di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5-triazine 2-butoxy-4,6 -Di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5-triazine 2-hexyloxy-4,6-di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5 -Triazine 2-phenoxy-4,6-di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5-triazine 2-anilino-4, 6-di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5-triazine 2- (4-hydroxyphenyl) thio-4,6-di [4
-(4-hydroxyphenylsulfonyl) phenoxy]
-1,3,5-triazine 2-dimethylamino-4,6-di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5-triazine 2-diethylamino-4,6-di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5-triazine 2-dibutylamino-4,6-di [4- (4-hydroxyphenylsulfonyl) phenoxy] -1,3,5-triazine

4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-methoxy-1,
3,5-triazin-6-yl-4-oxy] diphenyl sulfone Melting point (° C) 180-182 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-diethylamino-1,3,5 −
Triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-hydroxy-1,3,5-triazin-6-yl-4-oxy] Diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethoxy-1,3,5-triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4 -(4-hydroxyphenylsulfonyl) phenoxy-2-isopropoxy-1,3,5-
Triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-propoxy-1,3,5-triazin-6-yl-4-oxy] Diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-butoxy-1,3,5-triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4 -(4-hydroxyphenylsulfonyl) phenoxy-2-hexyloxy-1,3,5-
Triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-phenoxy-1,3,5-triazin-6-yl-4-oxy] Diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-anilino-1,3,5-triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4 -(4-Hydroxyphenylsulfonyl) phenoxy-2- (4-hydroxyphenyl) thio-1,3,5-triazin-6-yl-4-oxy]
Diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-methylamino-1,3,5-triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [ 4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethylamino-1,3,5-triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) Phenoxy-2-propylamino-1,3,5-
Triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-butylamino-1,3,5-triazin-6-yl-4-oxy ] Diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-dimethylamino-1,3,5-
Triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-dibutylamino-1,3,5-
Triazin-6-yl-4-oxy] diphenylsulfone 2,4'-bis [4- (2-hydroxyphenylsulfonyl) phenoxy-2-methoxy-1,3,5-triazin-6-yl-4-oxy] Diphenylsulfone 2,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-2-methoxy-1,3,5-triazin-6-yl-2-oxy] diphenylsulfone 4,4'-bis [3 , 5-Dimethyl-4- (3,5-dimethyl-4-hydroxyphenylsulfonyl) phenoxy-2-methoxy-1,3,5-triazin-6-yl-4-oxy] diphenylsulfone 4,4'-bis [3-allyl-4- (3-allyl-4-
(Hydroxyphenylsulfonyl) phenoxy-2-methoxy-1,3,5-triazin-6-yl-4-oxy] diphenylsulfone

These compounds can be used alone or in combination of two or more.

Typical examples of the image storage stabilizer include 4-benzyloxy-4 '-(2-methylglycidyloxy) -diphenylsulfone and 4,4'-.
Epoxy group-containing diphenylsulfones such as diglycidyloxydiphenylsulfone, 1,4-diglycidyloxybenzene, 4- (α- (hydroxymethyl) benzyloxy) -4′-hydroxydiphenylsulfone,
Metal salts (especially zinc salts) of 2-propanol derivatives, salicylic acid derivatives, oxynaphthoic acid derivatives, metal salts of 2,2-methylenebis (4,6-tert-butylphenyl) phosphate, and other water-insoluble zinc compounds. Can be mentioned.

Examples of the sensitizer include higher fatty acid amides such as stearic acid amide, benzamide, stearic acid anilide, acetoacetic anilide, thioacetanilide, dibenzyl oxalate, di (4-methylbenzyl) oxalate, and di (oxalate) 4-chlorobenzyl), dimethyl phthalate, dimethyl terephthalate, dibenzyl terephthalate, dibenzyl isophthalate, bis (tert-butylphenol) s, diphenylsulfone and derivatives thereof,
4,4'-dimethoxydiphenyl sulfone, 4,4'-
Diethoxydiphenylsulfone, 4,4'-dipropoxydiphenylsulfone, 4,4'-diisopropoxydiphenylsulfone, 4,4'-dibutoxydiphenylsulfone, 4,4'-diisobutoxydiphenylsulfone, 4,4 ' -Dipentyloxydiphenyl sulfone,
4,4'-dihydroxydiphenylsulfone diethers such as 4,4'-dihexyloxydiphenylsulfone;2,4'-dimethoxydiphenylsulfone;
4'-diethoxydiphenylsulfone, 2,4'-dipropoxydiphenylsulfone, 2,4'-diisopropoxydiphenylsulfone, 2,4'-dibutoxydiphenylsulfone, 2,4'-diisobutoxydiphenylsulfone, 2 2,4'-dihydroxydiphenylsulfone diethers such as 4,4'-dipentyloxydiphenylsulfone and 2,4'-dihexyloxydiphenylsulfone; 1,2-bis (phenoxy) ethane;
-Bis (4-methylphenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 2-naphthol benzyl ether, diphenylamine, carbazole, 2,
3-di-m-tolylbutane, 4-benzylbiphenyl,
4,4′-dimethylbiphenyl, m-terphenyl, di-
β-naphthylphenylenediamine, phenyl 1-hydroxy-naphthoate, 2-naphthylbenzyl ether, 4
-Methylphenyl-biphenyl ether, 2,2-bis (3,4-dimethylphenyl) ethane, 2,3,5,6
-Tetramethyl-4'-methyldiphenylmethane, diphenyl carbonate and the like. Preferably, 1,
Examples include ethers such as 2-bis (3-methylphenoxy) ethane and 2-naphthylbenzyl ether, and aromatic hydrocarbons such as m-terphenyl, 4-benzylbiphenyl, and di (4-methylbenzyl) oxalate. be able to.

As the filler, silica, clay, kaolin, calcined kaolin, talc, satin white, aluminum hydroxide, calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, barium sulfate, magnesium silicate,
Aluminum silicate, plastic pigment and the like can be used. The filler is used in an amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the coloring dye. It is also possible to use a mixture of the above-mentioned other fillers.

Examples of the dispersant include sulfosuccinates such as dioctyl sodium sulfosuccinate, sodium dodecylbenzenesulfonate, sodium salts of lauryl alcohol sulfate and fatty acid salts.

As antioxidants, 2,2'-methylenebis (4-methyl-6-tert-butylphenol),
2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-propylmethylenebis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert -Butylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 1,1,3-tris (2-methyl-
4-hydroxy-5-tert-butylphenyl) butane,
1,1,3-tris (2-methyl-4-hydroxy-5
-Cyclohexylphenyl) butane, 4- [4- {1,
1-bis (4-hydroxyphenyl) ethyl} -α, α
-Dimethylbenzyl] phenol and the like.

Examples of the desensitizer include higher aliphatic alcohols, polyethylene glycol and guanidine derivatives.

Examples of the antiadhesive include stearic acid, zinc stearate, calcium stearate, carnauba wax, paraffin wax, ester wax and the like.

As the light stabilizer, phenyl salicylate, p-tert-butylphenyl salicylate, p-
Salicylic acid-based ultraviolet absorbers such as octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-
Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-
Dihydroxy-4-methoxybenzophenone, 2,2 ′
-Dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-
Benzophenone-based ultraviolet absorbers such as benzoylphenyl) methane, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-
5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-butylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-5'-ter
t-octylphenyl) benzotriazole, 2-
[2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-
Methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-undecyl-5′-methylphenyl)
Benzotriazole, 2- (2'-hydroxy-3'-
Undecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tridecyl-5 '
-Methylphenyl) benzotriazole, 2- (2'-
Hydroxy-3′-tetradecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-
3'-pentadecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-hexadecyl-5'-methylphenyl) benzotriazole,
-[2'-hydroxy-4 '-(2 "-ethylhexyl) oxyphenyl] benzotriazole, 2- [2'
-Hydroxy-4 '-(2 "-ethylheptyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4'-(2" -ethyloctyl) oxyphenyl]
Benzotriazole, 2- [2'-hydroxy-4'-
(2 "-propyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '-(2"-
Propylheptyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(2 ″ -propylhexyl) oxyphenyl] benzotriazole, 2-
[2'-hydroxy-4 '-(1 "-ethylhexyl)
Oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(1 ″ -ethylheptyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-
4 '-(1'-ethyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4'-
(1 "-propyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '-(1"-
Propylheptyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(1 ″ -propylhexyl) oxyphenyl] benzotriazole,
2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-
Yl)] benzotriazole-based ultraviolet absorbers such as condensates of phenol, polyethylene glycol and methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate 2,2′-ethylhexyl-2-cyano-3,
3-diphenyl acrylate, ethyl-2-cyano-
Cyanoacrylate-based ultraviolet absorbers such as 3,3-diphenylacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-succinate) Hindered amine ultraviolet absorbers such as 4-piperidyl) ester and 2- (3,5-di-tert-butyl) malonic acid-bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester; , 8-dihydroxy-2-acetyl-3-methyl-6-methoxynaphthalene and related compounds.

Examples of the fluorescent dye include the following. 4,4'-bis [2-anilino-4- (2-hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4,4 ' -Bis [2-anilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4,4'-bis [2- Methoxy-4- (2-hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4,4'-bis [2-methoxy-4- (2-Hydroxypropyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4,4'-bis [2-m-sulfoanilino-4-bi 2- (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = disodium salt 4- [2-p-sulfoanilino-4-bis (hydroxyethyl) amino- 1,3,5-triazinyl-6-amino] -4 '-[2-m-sulfoanilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-
6-amino] stilbene-2,2'-disulfonic acid = tetrasodium salt 4,4'-bis [2-p-sulfoanilino-4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino ] Stilbene-2,2'-disulphonic acid = tetrasodium salt 4,4'-bis [2- (2,5-disulphoanilino)-
4-phenoxyamino-1,3,5-triazinyl-6
-Amino] stilbene-2,2'-disulfonic acid = hexasodium salt 4,4'-bis [2- (2,5-disulfoanilino)-
4- (p-methoxycarbonylphenoxy) amino-
1,3,5-triazinyl-6-amino] stilbene-
2,2'-disulfonic acid = hexasodium salt 4,4'-bis [2- (p-sulfophenoxy) -4-
Bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = tetrasodium salt 4,4'-bis [2- (2,5-disulfoanilino)-
4-formalinylamino-1,3,5-triazinyl-
6-amino] stilbene-2,2'-disulfonic acid = hexasodium salt 4,4'-bis [2- (2,5-disulfoanilino)-
4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid hexasodium salt

When the compound of the formula (I) is used for pressure-sensitive copying paper, it can be produced in the same manner as when a known image storage stabilizer, developer or sensitizer is used. For example, a color-forming dye microencapsulated by a known method is dispersed with a suitable dispersant, and is applied to paper to prepare a color-forming sheet. Also, a developer dispersion sheet is applied to paper to produce a developer sheet. In that case, when the compound of the present invention is used as an image storage stabilizer, it may be used by dispersing it in any dispersion of a color former sheet or a developer sheet. The pressure-sensitive copying paper is manufactured by combining the two sheets thus manufactured. The pressure-sensitive copying paper consists of an upper paper carrying a microcapsule containing an organic solvent solution of a chromogenic dye on the lower surface, and a lower paper carrying a developer (acidic substance) on the upper surface. It may be a unit or a so-called self-content paper in which microcapsules and a developer are applied on the same paper surface. As the developer used at that time, conventionally known ones are used, for example, acid clay, activated clay, apattalite, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, talc, etc. Inorganic acidic substances such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid and other aliphatic carboxylic acids, benzoic acid, p-tert-butylbenzoic acid, phthalic acid, gallic acid, salicylic acid, 3-isopropylsalicylic acid , 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5-
Aromatic carboxylic acids such as (2,2-dimethylbenzyl) salicylic acid, 3,5-di- (2-methylbenzyl) salicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, and zinc of these aromatic carboxylic acids , A metal salt of magnesium, aluminum, titanium, etc., a phenolic resin developer such as p-phenylphenol-formalin resin, p-butylphenol-acetylene resin, a metal salt of these phenolic resin developer and the above aromatic carboxylic acid And the like.

[0037]

EXAMPLES Hereinafter, the recording material of the present invention will be described in detail with reference to examples, but is not necessarily limited thereto.

Example 1 (Preparation of Thermal Recording Paper) Dye Dispersion (Solution A) 2-anilino-3-methyl-6-dibutylaminofluorane 20.0 g 10% aqueous solution of polyvinyl alcohol 105.0 g Developer dispersion (Solution B) 4-hydroxy-4'-isopropoxydiphenylsulfone 20.0 g 10% aqueous solution of polyvinyl alcohol 105.0 g Dispersion of general formula (I) (Solution C) Compound of compound No. 1 20.0 g Polyvinyl alcohol 10% Aqueous solution 105.0 g Filler dispersion (D solution) 10% aqueous solution of polyvinyl alcohol 26.2 g Filler (calcium carbonate) 27.8 g Pure water 71.0 g Sensitizer dispersion (Solution E) Bis (4-methylbenzyl oxalate) 20.0 g 10% aqueous solution of polyvinyl alcohol 105.0 g

Each mixture of the above compositions was sufficiently ground by a sand grinder to prepare dispersions of Solution A, Solution B, Solution C and Solution D, and 1 part by weight of Solution A, 2 parts by weight of Solution B, C
2 parts by weight of the liquid, 4 parts by weight of the liquid D, and a dispersion of zinc stearate (Hydrin Z-7-30 manufactured by Chukyo Yushi Co., Ltd.)
A coating solution was prepared by mixing 0.5 parts by weight. Apply this coating solution to white paper using a wire rod (No.12).
After drying, the sheet was subjected to a calendering process to prepare a heat-sensitive recording paper (applied amount: about 5.5 g / m ^{2 by} dry weight).

Comparative Example 1 A thermal paper was prepared in the same manner as in Example 1 except that Liquid E was used instead of Liquid C in Example 1.

Test Example 1 (Light fastness test of heat-sensitive recording paper) The heat-sensitive recording paper prepared in Example 1 and Comparative Example 1 was subjected to a heat-sensitive paper coloring tester (TH-PMD manufactured by Okura Electric Co., Ltd.).
And a checkerboard pattern under the conditions of a printing voltage of 22 V and a pulse width of 1.8 ms. A fade meter using this color image as a light source with a carbon arc (manufactured by Suga Test Machine)
For 6 to 36 hours with a Macbeth reflection densitometer RD-514 (filter used:
# 106). The results are shown in Table 1.

[0042]

[Table 1]

The measured values in Table 1 indicate that the larger the numerical value, the higher the color density.

[0044]

According to the present invention, the recording material containing the carbonylthiourea compound of the general formula (I) is excellent in storage stability of a color image, especially in light resistance.

Claims (1)

[Claims] 1. A compound of the general formula (I) [Wherein, R ₁ and R ₂ each independently represent a linear or branched saturated or unsaturated alkyl group having 1 to 12 carbon atoms, or a linear or branched carbon number. 1 to 12 saturated or unsaturated alkoxy groups, aralkyl groups, aralkyloxy groups, phenyl groups, phenoxy groups, naphthyl groups,
Represents a naphthyloxy group, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyloxy group having 5 to 12 carbon atoms,
m represents 0 or 1], wherein at least one of the carbonylthiourea compounds represented by the formula (1) is contained.