JP2003335749A - Phenolic compound and recording material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a recording material having excellent preservability of an image, especially excellent light resistance of the image. <P>SOLUTION: The phenolic compound is represented by formula (I) [R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom or a 1-6C alkyl group; n is an integer of 0-6; R<SP>3</SP>and R<SP>4</SP>are each independently a hydrogen atom, a 1-6C alkyl group or a phenyl group which may contain a substituent group; X is a single bond or a group represented by formula (2) (R<SP>5</SP>s are each a halogen atom, a 1-6C alkyl group or a 1-6C alkoxy group; m is an integer of 0-4 and when m is ≥2, R<SP>5</SP>s may be the same or different). The recording material contains at least one kind of the compound. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phenolic compound and a recording material containing the same which is excellent in storage stability.

[0002]

2. Description of the Related Art A recording material utilizing color development due to a reaction between a color forming dye and a color developer can be recorded in a short time by a relatively simple device without performing complicated processing such as development and fixing. It is widely used as a thermal recording paper for output recording of a printer or the like or a pressure-sensitive copying paper for a form for copying several sheets at the same time. These recording materials develop color rapidly, retain the whiteness of the uncolored portion (hereinafter referred to as “background”), and have a high fastness of the colored image, especially from the viewpoint of long-term storage stability, There is a demand for recording materials having excellent light resistance of images.

Conventionally, 2,4'-dihydroxydiphenyl sulfone has been known as a color developing agent excellent in light fastness of images, but it is still insufficient. On the other hand, as a method for improving this drawback, JP-A-8-290661, JP-A-10-264531 and the like disclose a combination of 2,4′-dihydroxydiphenyl sulfone with a specific dye and an auxiliary agent. It is described that the light resistance of the image is excellent. Further, JP-A-7-25141 and JP-A-7-25141
JP-A-149046, JP-A-7-314894 and the like describe that an antioxidant or an ultraviolet absorber is added to improve light resistance. However, these methods have problems that the manufacturing cost is increased, the number of manufacturing processes is increased, and the operation becomes complicated.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a recording material having excellent image storability, and particularly excellent image light fastness.

[0005]

The present invention provides formula (I)

[0006]

[Chemical 5]

[In the formula, R ¹ and R ² each independently represent a hydrogen atom or a C1 to C6 alkyl group, n represents an integer of 0 to 6, and R ³ and R ⁴ each independently represent Hydrogen atom, C
1-C6 alkyl group, a phenyl group which may have a substituent, X is a single bond or the following formula

[0008]

[Chemical 6]

(In the formula, R ⁵ is a halogen atom, C 1 to C ⁶
Represents an alkyl group or a C1 to C6 alkoxy group, m is 0 to
Represents an integer of 4, and when m is 2 or more, R ^{5 s} may be the same or different. ) Represents. ] A recording material containing a phenolic compound represented by the following formula and at least one of these compounds.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The present invention is a phenolic compound represented by the formula (I), wherein the phenolic compound represented by the formula (I) is
It can be used as a developer of a recording material containing a color forming dye.

In formula (I), R ¹ and R ² are hydrogen atoms; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n Examples thereof include C1-C6 alkyl groups such as -pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, 1-methylpentyl group and 2-methylpentyl group.

R ³ and R ⁴ are a hydrogen atom; a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, C1-C6 alkyl group such as 1-methylpentyl group and 2-methylpentyl group, phenyl group which may have a substituent (as a substituent, hydrogen atom; hydroxyl group; fluorine atom, chlorine atom, bromine atom, iodine Halogen atom such as atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-
Hexyl group, isohexyl group, 1-methylpentyl group,
C1-C6 alkyl group such as 2-methylpentyl group; C1-C6 alkoxy group such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group. Can be mentioned. ) Can be mentioned.

R ⁵ is a halogen atom such as fluorine atom, chlorine atom, bromine atom or iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t- C1-C6 alkyl groups such as butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group; methoxy group, ethoxy Group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group,
Examples thereof include C1-C6 alkoxy groups such as t-butoxy group.

The compound represented by the formula (I) used in the present invention has the formula (II)

[0015]

[Chemical 7]

A compound represented by the formula (III)

[0017]

[Chemical 8]

[In the formula, R ¹ , R ² , R ³ , R ⁴ , X and n have the same meanings as described above, and Y ¹ represents a halogen atom such as a chlorine atom or a bromine atom. ] It can be obtained by reacting the compound represented by the following in an organic solvent such as methanol in the presence of a base.

The compound represented by the formula (III) has the formula (II)
And a compound of formula (IV)

[0020]

[Chemical 9]

[Wherein R ¹ , R ² , R ³ , R ⁴ , X, Y ¹ ,
n represents the same meaning as described above, and Y ² represents a halogen atom such as a chlorine atom and a bromine atom. ] It can be obtained by reacting with a compound represented by.

The compounds that can be synthesized in this manner are shown in Table 1.

[0023]

[Table 101]

[0024]

[Table 102]

The present invention can be used in any application as long as it is a recording material using a color forming dye, for example, it can be used as a heat-sensitive recording material or a pressure-sensitive copying material.

When the present invention is used for a thermal recording paper,
The known image storage stabilizer may be used in the same manner as the method of using the color developer. For example, each of the fine particles of the compound of the present invention and the fine particles of the color forming dye may be used in an aqueous solution of a water-soluble binder such as polyvinyl alcohol or cellulose. It can be manufactured by mixing the suspensions dispersed in the above, coating on a support such as paper, and drying.

The ratio of the compound represented by the formula (I) to the color forming dye is 1 to 10 parts by weight, preferably 1 part by weight of the compound represented by the formula (I) per 1 part by weight of the color forming dye. 0.5 to 5 parts by weight.

The recording material of the present invention includes a color-forming dye and a known developer other than the compound represented by the formula (I),
An image stabilizer, a sensitizer, a filler, a dispersant, an antioxidant, a desensitizer, an anti-adhesive agent, a defoaming agent, a light stabilizer, and a fluorescent whitening agent may be contained in one kind or two or more kinds as necessary. be able to.

These agents may be contained in the color-developing layer, but when they have a multi-layer 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 may contain an antioxidant, a light stabilizer and the like. Further, the antioxidant and the light stabilizer can be contained in these layers in the form of being encapsulated in microcapsules, if necessary.

Examples of the color-forming dye used in the recording material of the present invention include fluoran-based, phthalide-based, lactam-based, triphenylmethane-based, phenothiazine-based and spiropyran-based leuco dyes. The dye is not limited, and any color-forming dye can be used as long as it is a color-forming dye that develops color when brought into contact with a developer that is an acidic substance.
Further, it goes without saying that these color forming dyes are used alone to produce a recording material having a color that develops the color, but two or more kinds of them can be mixed and used. For example, it is possible to manufacture a recording material that develops a true black color by mixing and using a color-forming dye of three primary colors of red, blue and green or a black-coloring dye.

Examples of fluorane-based color-forming dyes include 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, and 3- (N- Ethyl-N-isobutylamino) -6-methyl-7-anilinofluorane, 3-
(N-methyl-N-propylamino) -6-methyl-7
-Anilinofluorane, 3- (N-ethyl-N-isopentylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7- (o-chloroanilino)
Fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluorane, 3- (N
-Cyclohexyl-N-methylamino) -6-methyl-
7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-dimethylamino-7
-(M-trifluoromethylanilino) fluorane, 3-
Dipentylamino-6-methyl-7-anilinofluorane, 3- (N-ethoxypropyl-N-ethylamino)
-6-Methyl-7-anilinofluorane, 3-dibutylamino-7- (o-fluoroanilino) fluorane, 3-
Diethylaminobenzo [a] fluorane, 3-dimethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-5-methyl-7-dibenzylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-5-chlorofluorane,
3-diethylamino-6- (N, N'-dibenzylamino) fluorane, 3,6-dimethoxyfluorane, 2,
4-dimethyl-6- (4-dimethylaminophenyl) aminofluorane and the like can be mentioned.

Further, as the near infrared absorbing dye, 3- [4
-[4- (4-anilino) -anilino] anilino] -6
-Methyl-7-chlorofluorane, 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.

As the developer, bisphenol A, 4,4'-sec-butylidene bisphenol,
4,4'-Cyclohexylidenebisphenol, 2,2
-Dimethyl-3,3-bis (4-hydroxyphenyl)
Butane, 2,2'-dihydroxydiphenyl, pentamethylene-bis (4-hydroxybenzoate), 2,2
-Bisphenol compounds such as dimethyl-3,3-di (4-hydroxyphenyl) pentane and 2,2-di (4-hydroxyphenyl) hexane; 4,4'-dihydroxydiphenylthioether, 1,7-di (4- Hydroxyphenylthio) -3,5-dioxaheptane, 2,2 '
-Sulfur-containing bisphenol compounds such as bis (4-hydroxyphenylthio) diethyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenylthioether;

Benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, 4-hydroxybenzoic acid. 4-hydroxybenzoic acid esters such as chlorobenzyl, methylbenzyl 4-hydroxybenzoate and diphenylmethyl 4-hydroxybenzoate; metal benzoates such as zinc benzoate and zinc 4-nitrobenzoate; 4- [2- Salicylic acids such as (4-methoxyphenyloxy) ethyloxy] salicylic acid; metal salicylates such as zinc salicylate and bis [4- (octyloxycarbonylamino) -2-hydroxybenzoic acid] zinc;

4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-
Hydroxy-4′-methyldiphenyl sulfone, 4-hydroxy-4′-isopropoxydiphenyl sulfone,
4-hydroxy-4'-benzyloxydiphenyl sulfone, 4-hydroxy-4'-butoxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-diallyldiphenyl sulfone, 3,4-dihydroxy-4'-methyldiphenyl Sulfone, 4,4'-dihydroxy-3,
Hydroxysulfones such as 3 ', 5,5'-tetrabromodiphenylsulfone; N- (2-hydroxyphenyl) benzenesulfonamide, N- (2-hydroxyphenyl) -p-toluenesulfonamide, N- (2- Hydroxyphenyl) -p-ethylbenzenesulfonamide, N- (2-hydroxyphenyl) -p-methoxybenzenesulfonamide, N- (2-hydroxyphenyl) -p-chlorobenzenesulfonamide, N- (2-
Benzenesulfonamides such as hydroxyphenyl) -p-phenylbenzenesulfonamide, N- (2-hydroxyphenyl) -p-allylbenzenesulfonamide and N- (2-hydroxyphenyl) -p-benzylbenzenesulfonamide;

4-hydroxyphthalic acid diesters such as dimethyl 4-hydroxyphthalate, dicyclohexyl 4-hydroxyphthalate and diphenyl 4-hydroxyphthalate; esters of hydroxynaphthoic acid such as 2-hydroxy-6-carboxynaphthalene; Trihalomethylsulfones such as tribromomethylphenyl sulfone; 4,
Sulfonylureas such as 4'-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane; hydroxyacetophenone, p-phenylphenol, 4
-Benzyl hydroxyphenylacetate, p-benzylphenol, hydroquinone-monobenzyl ether, tetracyanoquinodimethanes, 2'-hydroxy- (4-hydroxyphenylthio) acetanilide, 3'-hydroxy- (4-hydroxyphenylthio) Acetanilide, 4'-hydroxy- (4-hydroxyphenylthio) acetanilide, 2,4-dihydroxy-2'-methoxybenzanilide, or formula (V),

[0038]

[Chemical 10] Examples thereof include a diphenyl sulfone cross-linking compound represented by and a mixture thereof.

Examples of image stabilizers include epoxy group-containing diphenyl sulfones such as 4-benzyloxy-4 '-(2-methylglycidyloxy) -diphenyl sulfone and 4,4'-diglycidyloxydiphenyl sulfone; 1 , 4-diglycidyloxybenzene, 4- [α-
(Hydroxymethyl) benzyloxy] -4′-hydroxydiphenyl sulfone, 2-propanol derivative, salicylic acid derivative, metal salt of oxynaphthoic acid derivative (particularly zinc salt), 2,2-methylenebis (4,6-t-butylphenyl) ) Phosphate metal salts and other water-insoluble zinc compounds can be mentioned.

Examples of the sensitizer include higher fatty acids such as stearic acid amide, oleic acid amide, N-methylstearic acid amide, erucic acid amide, methylol behenic acid amide, methylenebisstearic acid amide and ethylenebisstearic acid amide. Amides; higher fatty acid anilides such as stearic acid anilide and linoleic acid anilide; amides such as benzamide and benzylamide; acetoacetic acid anilide, 4-acetotoluidide, salicylanilide,
Anilides such as 4-hydroxybenzanilide and thioacetanilide; dibenzyl oxalate and di (4-oxalate)
Methylbenzyl), di (4-chlorobenzyl) oxalate, dimethyl phthalate, dimethyl terephthalate, dibenzyl terephthalate, dibenzyl isophthalate, bis (t-butylphenol) s;

Diphenyl sulfone and its derivatives; 4,
4'-dimethoxydiphenyl sulfone, 4,4'-diethoxydiphenyl sulfone, 4,4'-dipropoxydiphenyl sulfone, 4,4'-diisopropoxydiphenyl sulfone, 4,4'-dibutoxydiphenyl sulfone, 4, 4'-diisobutoxydiphenyl sulfone,
4,4'-dipentyloxydiphenyl sulfone, 4,
4, such as 4'-dihexyloxydiphenyl sulfone
Diethers of 4'-dihydroxydiphenyl sulfone; 2,4'-dimethoxydiphenyl sulfone, 2,
4'-diethoxydiphenyl sulfone, 2,4'-dipropoxydiphenyl sulfone, 2,4'-diisopropoxydiphenyl sulfone, 2,4'-dibutoxydiphenyl sulfone, 2,4'-diisobutoxydiphenyl sulfone, 2 Diethers of 2,4'-dihydroxydiphenyl sulfone such as 4,4'-dipentyloxydiphenyl sulfone and 2,4'-dihexyloxydiphenyl sulfone;

1,2-bis (phenoxy) ethane, 1,
2-bis (4-methylphenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 2-naphtholbenzyl ether, diphenylamine, carbazole,
2,3-di-m-tolylbutane, 4-benzylbiphenyl, 4,4'-dimethylbiphenyl, m-terphenyl, di-β-naphthylphenylenediamine, 1-hydroxy-naphthoic acid phenyl, 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 can be mentioned.

As the filler, for example, 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. Particularly in the recording material of the present invention, an alkaline earth metal salt is preferable. Further, carbonate is preferable, and calcium carbonate, magnesium carbonate and the like are preferable. The proportion of the filler used is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the color forming dye. It is also possible to mix and use the above-mentioned other fillers.

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

Examples of the antioxidant include 2,2'-
Methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-)
Butylphenol), 4,4'-propylmethylenebis (3-methyl-6-t-butylphenol), 4,4 '
-Butylidene bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-t-butyl-5-methylphenol), 1,1,3-tris (2-methyl-)
4-hydroxy-5-t-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 can be mentioned.

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

Examples of the anti-sticking agent include stearic acid, zinc stearate, calcium stearate, carnauba wax, paraffin wax and ester wax.

Examples of the light stabilizer include phenyl salicylate, pt-butylphenyl salicylate, p-
Salicylic acid-based UV 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,
Benzophenone-based UV absorbers such as 2-hydroxy-4-methoxy-5-sulfobenzophenone and bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane; 2- (2'-hydroxy-5'-methylphenyl) ) Benzotriazole, 2- (2'-hydroxy-)
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3',
5'-di-t-amylphenyl) benzotriazole,
2- [2'-hydroxy-3 '-(3 ", 4", 5 ",
6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′- Screw (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- [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, polyethylene glycol and methyl-3- [3-t-butyl-5-
A benzotriazole-based ultraviolet absorber such as a condensate with (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate;

2'-ethylhexyl-2-cyano-3,
3-diphenyl acrylate, ethyl-2-cyano-
Cyanoacrylate UV absorbers such as 3,3-diphenyl acrylate; bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid-bis (2,2,6,6-tetramethyl) Hindered amine UV absorbers such as 4-piperidyl) ester and 2- (3,5-di-t-butyl) malonic acid-bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester;
1,8-dihydroxy-2-acetyl-3-methyl-6
-Methoxynaphthalene and the like can be mentioned.

Examples of the fluorescent dye include 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-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-bis (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'-disulfonic acid = tetrasodium salt,

4,4'-bis [2- (2,5-disulfoanilino) -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 and the like can be mentioned.

When the compound of the present invention is used in pressure-sensitive copying paper, it can be prepared in the same manner as in the case of using a known image storage stabilizer, color developer or sensitizer. For example, a color-forming dye that has been microencapsulated by a known method is dispersed with a suitable dispersant and applied to paper to form a color-forming sheet. Further, the developer dispersion is applied to paper to prepare a developer sheet. At that time, when the compound of the present invention is used as an image storage stabilizer, it may be dispersed in any dispersion liquid of a color former sheet or a developer sheet. The pressure-sensitive copy paper is created by combining the two sheets created in this way. The pressure-sensitive copying paper is composed of an upper paper on which microcapsules containing an organic solvent solution of a color forming dye are applied and carried on the lower surface, and a lower paper on which a developer (acidic substance) is applied and carried. It may be a unit or so-called self-content paper in which the microcapsules and the color developer are applied on the same paper surface.

As the developer used at that time or as a developer used by mixing with the compound of the present invention, conventionally known ones are used, for example, acid clay, activated clay, apatargite, bentonite, colloidal silica, Inorganic acidic substances such as aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin and talc; aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid and stearic acid; benzoic acid, p-t -Butylbenzoic acid, phthalic acid, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-t-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 , Metal salts of magnesium, aluminum, titanium and the like; phenol resin type developers such as p-phenylphenol-formalin resin and p-butylphenol-acetylene resin, and metal salts of these phenol resin type developers and the above aromatic carboxylic acids. And the like.

The support used in the present invention is a conventionally known paper,
Synthetic paper, film, plastic film, foamed plastic film, non-woven fabric, recycled paper such as waste paper pulp can be used. Also, a combination of these may be used as a support.

[0056]

EXAMPLES The compounds of the present invention will be described in more detail below with reference to examples. The parts shown below are based on weight.

Example 1 (4-hydroxyphenylthio) thioacetic acid S- (4-
(Hydroxyphenyl) (Compound No. 5) was added to a 200 ml 4-neck flask equipped with a stirrer and a thermometer.
-2.52 g (20 mmol) of mercaptophenol,
1.32 g (20 mmol) of 85% potassium hydroxide and 50 ml of methanol were added at room temperature. After confirming that potassium hydroxide was dissolved, the internal temperature was cooled to 10 ° C. and 4.05 g of chlorothioacetic acid S- (4-hydroxyphenyl)
(20 mmol) was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the mixture was acidified with hydrochloric acid, 50 ml of water was added, and the precipitated crystals were separated by filtration to obtain 5.0 g of (4-hydroxyphenylthio) thioacetic acid S- (4-hydroxyphenyl). The yield was 86% and the melting point was 145-148 ° C.

Example 2 4- (4-hydroxyphenylthiomethyl) thiobenzoic acid S- (4-hydroxyphenyl) (Compound No. 1
6) Synthesis Example 1 4-chloromethylthiobenzoic acid S-in place of chlorothioacetic acid S- (4-hydroxyphenyl) in Example 1.
The reaction was performed in the same manner as in Example 1 except that (4-hydroxyphenyl) was used to obtain 4- (4-hydroxyphenylthiomethyl) thiobenzoic acid S- (4-hydroxyphenyl). The melting point was 202-209 ° C.

Example 3 Dye dispersion (Liquid A) 3-di-n-butylamino-6-methyl-7-anilinofluorane 16 parts Polyvinyl alcohol 10% aqueous solution 84 parts Developer dispersion (liquid B) (4-Hydroxyphenylthio) thioacetic acid S- (4-hydroxyphenyl) 16 parts Polyvinyl alcohol 10% aqueous solution 84 parts Filler dispersion (liquid C) Calcium carbonate 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 71 As for the coating liquid, a mixture of each composition of liquids A to C is sufficiently ground by a sand grinder to prepare a dispersion liquid of each component of liquids A to C, and 1 part by weight of liquid A and 2 parts by weight of liquid B are prepared. And 4 parts by weight of C liquid were mixed to prepare. After applying and drying this coating solution on white paper using a wire rod (No. 12),
It was calendered to prepare a thermosensitive recording paper (coating amount was about 5.5 g / m ^{2 in} dry weight).

Example 4 (4-hydroxyphenylthio) thioacetic acid as a developer 4- (4 instead of S- (4-hydroxyphenyl)
-Hydroxyphenylthiomethyl) thiobenzoic acid S-
A thermosensitive recording paper was prepared in the same manner as in Example 3 except that (4-hydroxyphenyl) was used.

Comparative Example 1 (4-Hydroxyphenylthio) thioacetic acid as a color developer 2,4 'instead of S- (4-hydroxyphenyl)
A thermal recording paper was prepared in the same manner as in Example 3 except that dihydroxydiphenyl sulfone was used.

Test Example 1 (Image Lightfastness Test) A part of the thermal recording paper prepared in Examples 3 and 4 and Comparative Example 1 was cut out and used as a test paper. Each test paper was saturated with a thermosensitive paper coloring device (trade name: TH-PMD type, manufactured by Okura Electric Co., Ltd.). Then
Light resistance tester (trade name: UV long life fade meter FAL-5 type, Suga Tester Co., Ltd.)
The image density of each test paper was measured 48 hours after irradiation with ultraviolet rays having a wavelength of 380 nm. The measurement results are shown in Table 2. Image residual rate (%) = (CI _t / CI ₀ ) × 100 CI ₀ : print density before test CI _t : print density after t days

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[Table 201]

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As described above, according to the present invention,
It is possible to provide a novel phenolic compound and a recording material using the same, which is excellent in storability of images and particularly excellent in light fastness of images.

Claims (2)

[Claims] 1. A compound represented by the formula (I): [In the formula, R ¹ and R ² are each independently a hydrogen atom, C 1
Represents an ~C6 alkyl group, n represents an integer of 0~6, R ^3, R ⁴ are each independently a hydrogen atom, C1 -C6 alkyl group, a phenyl group which may have a substituent , X is a single bond or the following formula: (In the formula, R ⁵ is a halogen atom, a C1 to C6 alkyl group,
Represents a C1 to C6 alkoxy group, m represents an integer of 0 to 4, and when m is 2 or more, R ⁵ may be the same or different. ) Represents. ] The phenolic compound represented by. 2. A recording material containing a color forming dye,
Formula (I): [In the formula, R ¹ and R ² are each independently a hydrogen atom, C 1
Represents an ~C6 alkyl group, n represents an integer of 0~6, R ^3, R ⁴ are each independently a hydrogen atom, C1 -C6 alkyl group, a phenyl group which may have a substituent , X is a single bond or the following formula: (In the formula, R ⁵ is a halogen atom, a C1 to C6 alkyl group,
Represents a C1 to C6 alkoxy group, m represents an integer of 0 to 4, and when m is 2 or more, R ⁵ may be the same or different. ) Represents. ] The recording material containing at least 1 sort (s) of the phenolic compound represented by these.