JP2003104965A - Bisphenol compound and recording material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound that can be a manufacturing raw material of a recording material having excellent color-developing sensitivity, light resistance of an image, plasticizer resistance or the like, and further to provide the recording medium including the compound. SOLUTION: This compound is represented by formula [I] [R<1> is a hydroxy group, a 1-6C alkyl group or a 1-6C alkoxy group; (a) and b are each 0-2; R<4> is a hydrogen atom or a 1-6C alkyl group; A and B are each an alkylene group obtained by bonding 2-10 repeating units represented by formula [II] (R<2> and R<3> are each a hydrogen atom or a 1-6C alkyl group), with the proviso that the repeating units are same or different; and Z is a 1-6C alkylene group or a divalent organic group such as a phenylene group and a diphenylene group]. The recording medium includes the compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel bisphenol compound and a recording material containing the compound.

[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 a recording material which is excellent in various factors of image storability such as image light resistance and plasticizer resistance.

The following are known examples of conventional recording materials with improved image storability. (1) JP-A-10-29969 describes that the use of crosslinked diphenyl sulfone improves the plasticizer resistance and oil resistance of the recording material. (2) JP-A-8-290661 and JP-A-10-2
Japanese Patent No. 64531 discloses that a recording material comprising a combination of 2,4′-dihydroxydiphenyl sulfone, a specific dye and an auxiliary agent has excellent light resistance of an image. (3) Japanese Patent Application Laid-Open Nos. 7-172068 and 6-04
No. 8048 describes that a combination of 4-hydroxy-4′-isopropoxydiphenyl sulfone with a specific dye, a sensitizer and an auxiliary agent is effective for improving the light resistance of an image. (4) Further, JP-A-7-25141 and JP-A-7-251
JP-A-149046, JP-A-7-314894 and the like describe adding an antioxidant or an ultraviolet absorber to improve light resistance. However, these recording materials did not improve all the factors of image storability such as light resistance and plasticizer resistance.

On the other hand, as a method of obtaining a recording material having excellent image storability such as light resistance and plasticizer resistance, a method of adding an antioxidant or an ultraviolet absorber to a color developer or a method of forming a recording material layer on the recording material layer Although a method of forming an overcoat layer on the substrate is also conceivable, it causes an increase in the manufacturing cost, and the manufacturing process becomes multi-step.
There were problems such as complicated operations.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and a novel bisphenol compound useful as a color developer, color developing sensitivity, light resistance of an image,
An object of the present invention is to provide a recording material which is excellent in various factors of image storability such as plasticizer resistance.

[0006]

The present invention firstly provides a general formula:
[I]

[0007]

[Chemical 4]

[In the formula, R ¹ represents a hydroxyl group, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group, a and b each independently represent 0, 1 or 2, and R ⁴ Represents a hydrogen atom or a C ₁ -C ₆ alkyl group, and A and B are each independently the following formula:

[0009]

[Chemical 5]

(In the formula, R ² and R ³ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group.) Represent However, the repeating units may be the same or different. Z is a C ₁ -C ₆ alkylene group or the following formula

[0011]

[Chemical 6]

(Wherein * represents a bonding position) represents any one of divalent organic groups. ] The bisphenol compound represented by these is provided.

Secondly, the present invention provides a recording material containing at least one color forming dye and at least one bisphenol compound represented by the general formula [I].

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The first aspect of the present invention is a bisphenol compound represented by the general formula [I]. The bisphenol compound represented by the general formula [I] can be used as a developer of a recording material containing a color forming dye.

In the general formula [I], R ¹ is a hydroxyl group; methyl group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, sec- butyl group, t- butyl group, n- pentyl group, n- hexyl C ₁ -C ₆ alkyl group such as a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy Represents a C ₁ -C ₆ alkoxy group such as a group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group.

A and b each independently represent 0, 1 or 2. R ⁴ is a hydrogen atom; or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, n
- represents a C ₁ -C ₆ alkyl groups such as hexyl.

Z represents any one of a C ₁ -C ₆ alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group; or a divalent organic group represented by the following formula.

[0018]

[Chemical 7]

(In the formula, * represents a bonding position.) A and B are each independently the following formula

[0020]

[Chemical 8]

Represents an alkylene group in which 2 to 10 repeating units represented by Here, R ² and R ³ are each independently a hydrogen atom; or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1-
It represents a C ₁ -C ₆ alkyl group such as a methylpentyl group, a 2-methylpentyl group, and an n-hexyl group.

The repeating units constituting the alkylene group may be the same or different.
Specific examples of the alkylene group represented by A and B are shown in Table 1. In addition, in the table, * represents a bonding position, and each abbreviation represents the following meaning. Me: methyl group, Et: ethyl group, Pr: propyl group,
n: normal, i: iso

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

Table 2 shows specific examples of the compound represented by the general formula [I] of the present invention. In addition, A and B in Table 2
Represents any of the groups exemplified in Table 1 above.

[0027]

[Table 4]

[0028]

[Table 5]

[0029]

[Table 6]

[0030]

[Table 7]

[0031]

[Table 8]

[0032]

[Table 9]

[0033]

[Table 10]

[0034]

[Table 11]

[0035]

[Table 12]

[0036]

[Table 13]

The compound represented by the general formula [I] can be produced as follows. 1) Among the compounds represented by the general formula [I], the compound in which b is 0 is represented by the general formula [II]

[0038]

[Chemical 9]

[Wherein R ¹ and a have the same meanings as described above], and a compound of the general formula [III]

[0040]

[Chemical 10]

(Wherein R ⁴ , A, B and Z have the same meanings as described above, and X represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom). It can be obtained by reacting in the presence of a base in an organic solvent.

The organic solvent used in this reaction is
For example, aromatic hydrocarbons such as benzene, toluene, xylene; diethyl ether, tetrahydrofuran, 1,
Ethers such as 2-dimethoxyethane and dioxane;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and hexamethylphosphoric triamide;
Halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; dimethyl sulfoxide, acetonitrile and the like. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is usually 1 to 50 parts by weight, preferably 5 to 30 parts by weight, relative to 1 part by weight of the compound represented by the general formula [II].

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal salts such as sodium carbonate and potassium carbonate. Carbonates; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; metal hydrides such as sodium hydride and calcium hydride; sodium ethoxide, sodium methoxide, potassium t-butoxide, magnesium methoxide, magnesium ethoxide Metal alkoxides such as; triethylamine, diisopropylethylamine, pyridine, 1,4-diazabicyclo [2,2]
2,2] octane (DABCO), 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [5,5]
An organic base such as 4,0] unde-7-ene (DBU) can be used. These bases may be used alone or in combination of two or more. The amount of the base used is usually in the range of 1 to 3 mol with respect to 1 mol of the compound represented by the general formula [II]. The reaction is usually -5
The reaction proceeds smoothly in the temperature range of 0 ° C. to the boiling point of the solvent used, and is completed in a few minutes to a few hours.

2) In the general formula [I], b is 1 or 2 is a compound obtained by the above method in a suitable solvent such as hydrogen peroxide, peracetic acid or m-chloroperbenzoic acid. It can be obtained by oxidizing with an oxidizing agent. The compound represented by the general formula [III] as a raw material is, for example, the compound represented by the general formula [I]
V]

[0045]

[Chemical 11]

A compound represented by (R ⁴ and Z have the same meanings as described above) is added with an acid halide ((the following formula (i)) or an acid anhydride (the following formula (ii)) in the presence of a base. Can be obtained by a method such as a method of reacting with carboxylic acid (the following formula (iii)) and dehydration condensation in the presence of a dehydrating agent, or a method of reacting with an ester (the following formula (iv)).

[0047]

[Chemical 12]

(Wherein X represents the same meaning as described above, Y represents a halogen atom such as chlorine and bromine, and Q represents A or B described above.
And r represents an alkyl group such as a methyl or ethyl group. )

The recording material of the present invention is characterized by containing at least one kind of a color forming dye and at least one kind of the bisphenol compound represented by the general formula [I]. The color-forming dye used in the present invention is not particularly limited as long as it is a color-forming dye that develops color when brought into contact with a color developer. Examples thereof include fluoran-based, phthalide-based, lactam-based, triphenylmethane-based, phenothiazine-based, spiropyran-based leuco dyes and the like. Among these, fluoran-based and phthalide-based color-forming dyes are preferably used.

Examples of the fluorane 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)
Fluoran, 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 phthalide type color forming 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), 3,
3-bis (4'-diethylaminophenyl) -6-diethylaminophthalide and the like can be mentioned.

These color forming dyes can be used alone or in combination of two or more. For example,
It is possible to produce 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 forming dye. The compounding amount of the compound represented by the general formula [I] is usually 1 to 10 parts by weight with respect to 1 part by weight of the color forming dye,
It is preferably in the range of 1.5 to 5 parts by weight.

The recording material of the present invention further includes known color developers, image stabilizers, sensitizers, fillers, dispersants, antioxidants,
A desensitizing agent, an anti-adhesive agent, an antifoaming agent, a light stabilizer, an optical brightening agent and the like can be contained as necessary.

Examples of the color developer include those for heat-sensitive recording materials and those for pressure-sensitive recording materials. As the former, for example, bisphenol A, 4,4'-sec-butylidene bisphenol, 4 , 4'-Cyclohexylidene bisphenol, 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, 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′-butoxydiphenyl sulfone,
4,4'-dihydroxy-3,3'-diallyldiphenyl sulfone, 3,4-dihydroxy-4'-methyldiphenyl sulfone, 4,4'-dihydroxy-3,3 ',
Hydroxysulfones such as 5,5′-tetrabromodiphenylsulfone; dimethyl 4-hydroxyphthalate, 4
4-hydroxyphthalic acid diesters such as dicyclohexyl hydroxyphthalate and diphenyl 4-hydroxyphthalate; esters of hydroxynaphthoic acid such as 2-hydroxy-6-carboxynaphthalene; trihalomethyl sulfones such as tribromomethylphenyl sulfone ,
Sulfonylurea such as 4,4′-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane; hydroxyacetophenone, p-phenylphenol, benzyl 4-hydroxyphenylacetate, p-benzylphenol, hydroquinone-monobenzyl ether, 2,4 -Dihydroxy-2'-methoxybenzanilide, tetracyanoquinodimethanes, and the following formula

[0057]

[Chemical 13]

(In the formula, n represents 0 or an integer of 1 to 6) A diphenyl sulfone cross-linking compound or the like can be used.

Further, as the color developing agent for the pressure sensitive recording material,
For example, acid clay, activated clay, apatite, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, inorganic acid substances such as talc; oxalic acid, maleic acid, tartaric acid,
Aliphatic carboxylic acids such as citric acid, succinic acid, 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- (2,2
-Dimethylbenzyl) salicylic acid, 3,5-di- (2-
Aromatic carboxylic acids such as methylbenzyl) salicylic acid and 2-hydroxy-1-benzyl-3-naphthoic acid; metal salts of these aromatic carboxylic acids such as zinc, magnesium, aluminum and titanium; p-phenylphenol-formalin resin, A phenol resin-based developer such as p-butylphenol-acetylene resin; a mixture of these phenol resin-based developer and the above metal salt of aromatic carboxylic acid can be used.

Examples of image storage stabilizers include 4-benzyloxy-4 '-(2-methylglycidyloxy).
-Diphenyl sulfone, 4,4'-diglycidyloxydiphenyl sulfone and other epoxy group-containing diphenyl sulfones; 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
Examples include metal salts of -butylphenyl) phosphate and other water-insoluble zinc compounds.

Examples of the sensitizer include higher fatty acid amides such as stearic acid amide; anilides such as benzamide, stearic acid anilide, acetoacetic acid anilide and thioacetanilide; dibenzyl oxalate and oxalic acid di (4).
-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'-dihexyloxydiphenyl sulfone and other 4,4'-dihydroxydiphenyl sulfone diethers; 2,4'-dimethoxydiphenyl sulfone, 2,4'-diethoxydiphenyl sulfone,
2,4'-dipropoxydiphenyl sulfone, 2,4 '
-Diisopropoxydiphenyl sulfone, 2,4'-dibutoxydiphenyl sulfone, 2,4'-diisobutoxydiphenyl sulfone, 2,4'-dipentyloxydiphenyl sulfone, 2,4'-dihexyloxydiphenyl sulfone, etc. 4'-dihydroxydiphenyl sulfone diethers;

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,
Examples thereof include 3,5,6-tetramethyl-4′-methyldiphenylmethane and diphenyl carbonate. Among these, preferably, ethers such as 1,2-bis (3-methylphenoxy) ethane and 2-naphthylbenzyl ether; m-terphenyl, 4-benzylbiphenyl, di (4-methylbenzyl) oxalate and the like. Aromatic hydrocarbons; diphenyl sulfone, derivatives of diphenyl sulfone; 4,4'-dihydroxydiphenyl sulfone diethers and 2,4'-dihydroxydiphenyl sulfone diethers.

Examples of the filler include silica, clay,
Examples thereof include kaolin, calcined kaolin, talc, satin white, aluminum hydroxide, calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, barium sulfate, magnesium silicate, aluminum silicate, and plastic pigment. Examples of the dispersant include sulfosuccinates such as dioctyl sodium sulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of 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-
Examples include dimethylbenzyl} phenol.

As the desensitizer, aliphatic higher alcohols,
Examples of the anti-tacking agent include polyethylene glycol and guanidine derivatives, and stearic acid, zinc stearate, calcium stearate, carnauba wax, paraffin wax, ester wax and the like.

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 ′ -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- [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, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6
-(2H-benzotriazol-2-yl)] phenol, polyethylene glycol and methyl-3- [3-t-
Butyl-5- (2H-benzotriazol-2-yl)
Benzotriazole-based UV absorbers such as condensation products with 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 used.

Further, as the fluorescent whitening agent, for example, 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-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 used.

The above-mentioned color developer, image stabilizer, sensitizer, filler, dispersant, antioxidant, desensitizer, anti-tacking agent, defoaming agent, light stabilizer, fluorescent whitening agent, etc. are each They may be used alone or in combination of two or more. The amount of each compounded is usually 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, relative to 1 part by weight of the color forming dye.

The recording material of the present invention comprises a color forming dye and a general formula
A predetermined amount of the compound represented by [I] can be produced by adding and mixing other components, if desired.
Examples of the method of mixing the respective components include a method of mixing without using a dispersion medium or a method of mixing with a dispersion medium.

As a method of mixing without using a dispersion medium, for example, a method of mixing powders with each other, a melt mixing method of melting and mixing each component, and the like can be mentioned. Further, as a method of mixing using a dispersion medium, for example, a method of adding each component to a dispersion medium such as polyvinyl alcohol or cellulose to prepare a dispersion liquid, and then mixing each dispersion liquid Etc. Among these, from the viewpoint of more uniform mixing, it is preferable to prepare a dispersion liquid containing each component and then mix the dispersion liquid.

The use of the recording material of the present invention is not particularly limited as long as it is used as a recording material. For example, it can be used as a heat-sensitive recording material, a pressure-sensitive copying material and the like. When the recording material of the present invention is used for a heat-sensitive recording paper, it may be carried out in the same manner as a known method of using an image storage stabilizer and a color developer. For example, a suspension prepared by dispersing fine particles of the bisphenol compound of the present invention and fine particles of a color forming dye in an aqueous solution of a water-soluble binder such as polyvinyl alcohol or cellulose, and mixing the suspensions is prepared. Can be produced by applying to a support such as paper and drying.

The pressure-sensitive copying paper is prepared, for example, by dispersing a color-forming dye microencapsulated by a known method with an appropriate dispersant to prepare a color-forming dye dispersion, which is then dispersed in the first paper base. Coated on a material sheet to create a color forming dye sheet, while a developer dispersion is applied to a second paper base sheet to create a developer sheet, and the obtained two sheets are combined. To produce pressure-sensitive copying paper. that time,
The recording material of the present invention is dispersed in either or both of a color forming dye dispersion liquid and a color developer dispersion liquid.

The pressure-sensitive copying paper is an upper paper having microcapsules containing an organic solvent solution of a color-forming dye applied and carried on the lower surface, and a lower paper having a developer (acidic substance) applied and carried on the upper surface. Or a so-called self-content paper in which microcapsules containing an organic solvent solution of a color forming dye and a color developer are coated on the same paper surface.
Examples of the color developer include the same as those listed as the color developer that can be used as the color developer for the pressure-sensitive recording material.

[0078]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Example 1 Synthesis of 4,4'-bis [3- (4-hydroxyphenylthio) propionamido] diphenylsulfone In a 400 ml four-necked flask equipped with a stirrer and a thermometer, 4.40 g (34 g) of 4-mercaptophenol was used. .9m
mol), potassium hydroxide 2.30 g (34.9 mmo)
1) and 100 ml of methanol were added at room temperature. After confirming the dissolution of potassium hydroxide, cool to 10 ℃ and
7.50 g (17.5 mmol) of 4 ′-[bis (3-chloropropionamide)] diphenyl sulfone was added,
The mixture was stirred at room temperature for 24 hours. After completion of the reaction, methanol was distilled off under reduced pressure, the mixture was neutralized with hydrochloric acid, and the precipitated crystals were collected by filtration. The obtained crude crystal was recrystallized to obtain 8.7 g of the desired product. yield:
81%, melting point: 166-171 ° C

Example 2 (Preparation of thermal recording paper) First, a dispersion liquid (liquids A to C) containing the following components was prepared.
Each component was used after being sufficiently ground with a sand grinder. In addition, "part" means "part by weight". -Dye dispersion liquid (A liquid) 3-di-n-butylamino-6-methyl-7-anilinofluorane 16 parts Polyvinyl alcohol 10% aqueous solution 84 parts-Developer dispersion liquid (B liquid) 4,4 ' -Bis [3- (4-hydroxyphenylthio) propionamide] diphenylsulfone 16 parts Polyvinyl alcohol 10% aqueous solution 84 parts Filler dispersion (C liquid) calcium carbonate 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 71 copies

These dispersions were mixed with 1 part of solution A, 2 parts of solution B,
The C liquid was mixed at a ratio of 4 parts to prepare a coating liquid for a recording material for thermal recording paper. Then, the coating liquid of the recording material was coated on a white paper using a wire rod (trade name: wire bar, No. 12, manufactured by Webster Co., Ltd.) (coating amount = about 5.5 g / m ^{2 in} dry weight). After drying, it was calendered to prepare a heat-sensitive recording paper.

Comparative Example 1 4-isopropoxy-4'as a color developer dispersion (liquid B)
A thermal recording paper was prepared in the same manner as in Example 2 except that -hydroxydiphenyl sulfone was used.

Comparative Example 2 A thermosensitive recording paper was prepared in the same manner as in Example 2 except that 2,4'-dihydroxydiphenyl sulfone was used as the color developer dispersion (liquid B).

Test Example 1 (Lightfastness Test) With respect to the thermal recording paper prepared in Example 2 and Comparative Examples 1 and 2, a thermal paper color tester (trade name: TH-PMD type, manufactured by Okura Electric Co., Ltd.) was used. It was used and color was developed under the conditions of a printing voltage of 22 V and a pulse width of 1.8 ms. Then, on each test paper,
Using a light resistance tester (trade name: UV long life fade meter FAL-5 type, manufactured by Suga Test Instruments Co., Ltd.), the image density (Macbeth value) of each test paper after 48 hours
Was measured with a Macbeth reflection densitometer (trade name: RD-514, filter used: # 106, manufactured by Macbeth). The measurement results and the residual rate (= image density (after test) / image density (before test) × 100) are summarized in Table 3. As is clear from Table 3,
It was found that the thermal recording paper of Example 2 had excellent light resistance as compared with the thermal recording papers of Comparative Examples 1 and 2.

Test Example 2 (Plasticizer Resistance Test) The thermal recording papers prepared in Example 2 and Comparative Examples 1 and 2 were colored in the same manner as in Test Example 1. On the coloring surface,
A vinyl chloride wrap (trade name: Polymer Wrap 300, manufactured by Shin-Etsu Chemical Co., Ltd.) was brought into close contact with it, and the image density (Macbeth value) was measured after maintaining the temperature at 40 ° C. for 16 hours. The measurement results and the residual rate are shown in Table 3. As is clear from Table 3, the thermosensitive recording paper of Example 2 was found to have excellent plasticizer resistance as compared with the thermosensitive recording papers of Comparative Examples 1 and 2.

[0085]

[Table 14]

[0086]

As described above, according to the present invention,
Provided are a novel bisphenol compound useful as a color developer, and a recording material excellent in various image storability factors such as color development sensitivity, light resistance of an image, and plasticizer resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H026 AA07 BB30 BB32 BB35                 4H006 AA01 AA03 AB93 TA02 TA04                       TB13 TB42 TB56 TC32

Claims (2)

[Claims] 1. A compound represented by the general formula [I]: [In the formula, R ¹ is a hydroxyl group, a C _{1 to} C ₆ alkyl group, or a C ₁ to
Represents a C ₆ alkoxy group, a and b each independently represent 0, 1 or 2, and R ⁴ represents a hydrogen atom or C _{1 to} C ₆
Represents an alkyl group, and A and B are independently of the following formula: (In the formula, R ² and R ³ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group.) Represents an alkylene group formed by 2 to 10 bonds of repeating units. However, the repeating units may be the same or different. Z is a C ₁ -C ₆ alkylene group or the following formula: (In the formula, * represents a bonding position) and represents any one of divalent organic groups. ] The bisphenol compound represented by these. 2. At least one color forming dye and at least one bisphenol compound represented by the general formula [I].
A recording material containing seeds.