JPH10297089A - Recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain superior sensitivity and self stability by adding to a recording material containing a coloring dye one kind of diphenyl sulfone-crosslinking compound expressed by a hydrocarbon group that can include a specific count of carbons through saturated, unsaturated or ether binding, and one kind of diphenyl sulfone derivative. SOLUTION: The heat-sensitive recording material contains at least one kind of diphenyl sulfone-crosslinking compound expressed by a formula I wherein X, Y is a 1-12C hydrocarbon group saturated, unsaturated or having ether linkage, a straight or branched chain, which may be different from each other, and at least one kind of diphenyl sulfone derivative expressed by formula II wherein G1 -G6 is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a halogen atom, a nitro group, a carboxyl group, an alkoxy group, a hydroxy group, an aralkyl group, an acyl group, an acyloxy group, an alkylene group, an alkenylene group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material having excellent color development sensitivity and excellent image storability, especially excellent oil and plasticizer resistance.

[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 as thermosensitive recording paper for output recording of a printer or the like, or pressure-sensitive copying paper for a form for copying several sheets simultaneously. As these recording materials, color development and non-color development parts (hereinafter referred to as “background”)
Are required to maintain the whiteness of the image, to provide a colored image and to have high fastness. Furthermore, in recent years, it has been used in a large amount in fields where the reliability of recorded images such as labels is emphasized, and is used for plasticizers and fats and oils contained in organic polymer materials used for packaging and the like. There is a need for recording materials that exhibit high storage stability. For this purpose, various auxiliaries such as a color-forming dye, a color developer, and a storage stabilizer have been developed. However, it has not been found that a color-sensitizing dye, a background, and a preservability of an image can be sufficiently satisfied in a well-balanced manner. It has not been.

[0003] Of these materials, WO 93 / 0WO is particularly effective as a material having a high effect on the background and preservation of images.
6074 and WO95 / 33714 disclose diphenylsulfone derivatives. However, recording materials using these compounds lack the sensitivity of color development, and by improving this sensitivity, a recording material excellent in both sensitivity and storage stability can be obtained. The technology to be provided is required.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned drawbacks of the conventional recording material, to provide a high color-forming sensitivity, and to provide a background and preservability of an image, particularly oil and plasticizer resistance. Is to provide an excellent recording material.

[0005]

According to the present invention, there is provided a recording material containing a chromogenic dye represented by the general formula [I]:

Embedded image (In the formula, X and Y may be different from each other, may be linear or branched, and may have 1 to 12 carbon atoms, a saturated or unsaturated hydrocarbon group which may have an ether bond, Or

Embedded image (R ₇ represents a methylene group or an ethylene group, T represents a hydrogen atom or a C ₁ -C ₄ alkyl group). R _{1 to} R ₆
Each independently represent a halogen atom, an alkyl group of C ₁ -C ₆ shows an alkenyl group. Also, m, n, p, q, r,
t represents an integer of 0 to 4, when two or more R ₁ to R
₆ may be different from each other. a represents an integer of 0 to 10. ) And at least one diphenylsulfone bridged compound represented by the general formula [II]

Embedded image (Wherein G _{1 to} G ₆ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a halogen atom, a nitro group, a carboxyl group, an alkoxy group, a hydroxy group, an aralkyl group, an acyl group, an acyloxy group Containing at least one diphenylsulfone derivative represented by formula (1), an alkylene group or an alkenylene group), whereby the coloration sensitivity is high and the background and image storability, especially oil and plasticizer resistance, are excellent. Provide materials.

The following are specific examples of the groups represented by X and Y in the general formula [I].
Methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group,
Methylmethylene group, dimethylmethylene group, methylethylene group, methyleneethylene group, ethylethylene group, 1,2
-Dimethylethylene group, 1-methyltrimethylene group, 1
-Methyltetramethylene group, 1,3-dimethyltrimethylene group, 1-ethyl-4-methyl-tetramethylene group,
Vinylene group, propenylene group, 2-butenylene group, ethynylene group, 2-butynylene group, 1-vinylethylene group,
Ethyleneoxyethylene group, tetramethyleneoxytetramethylene group, ethyleneoxyethyleneoxyethylene group, ethyleneoxymethyleneoxyethylene group, 1,3
-Dioxane-5,5-bismethylene group, 1,2-xylyl group, 1,3-xylyl group, 1,4-xylyl group, 2
-Hydroxytrimethylene group, 2-hydroxy-2-methyltrimethylene group, 2-hydroxy-2-ethyltrimethylene group, 2-hydroxy-2-propyltrimethylene group, 2-hydroxy-2-isopropyltrimethylene group, 2 -Hydroxy-2-butyltrimethylene group and the like.

The alkyl or alkenyl group of R _{1 to} R ₆ is a C _{1 to} C ₆ alkyl group or a C _{2 to} C ₄ alkenyl group, and specific examples include a methyl group, an ethyl group, -Propyl group, isopropyl group, n-butyl group,
sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, vinyl group, allyl Group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 2
-Methyl-2-propenyl group and the like. Also,
Halogen atoms represent chlorine, bromine, fluorine and iodine.
Particularly as the substituent of the diphenyl sulfone of the general formula [I], unsubstituted ones or those in which all of R _{1 to} R ₆ are the same and at the same position are advantageous for the production of the present compound.

Embedded image (Wherein, X, R ₁ , m and a are the same as above)

In the general formula [II], G _{1 to} G ₆ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a halogen atom, a nitro group, a carboxyl group, an alkoxy group, a hydroxy group, an aralkyl group. Represents an acyl group, an acyloxy group, an alkylene group, or an alkenylene group. Specific examples of the alkyl group, a linear or branched alkyl group of C ₁ -C _20, preferably a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, ter-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-
Examples include a pentyl group, an n-hexyl group, an isohexyl group, a 1-methylpentyl group, and a 2-methylpentyl group. Preferred examples of the aryl group include a phenyl group and a naphthyl group. Examples of the halogen atom include chlorine, bromine, fluorine, and iodine. Specific examples of the alkoxy group include linear or branched C ₁ -C ₂₀ alkoxy groups, preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy. Group, ter-
Butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, n-hexyloxy group, isohexyloxy group,
Examples thereof include a 1-methylpentyloxy group and a 2-methylpentyloxy group. As an aralkyl group,
Examples thereof include a benzyl group and a phenethyl group. Examples of the alkylene group include a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butanedienyl group, and a 2-methyl-2-propenyl group. Can be. Examples of the alkenylene group include a propargyl group and a 2-propynyl group. Examples of the substituent of the substituted alkyl group and the substituted aryl group include the above-mentioned alkyl group, aryl group, halogen atom, nitro group, carboxyl group, alkoxy group, hydroxy group, aralkyl group, acyl group, acyloxy group, alkylene group, alkenylene group Can be exemplified.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the recording material of the present invention, at least one diphenylsulfone cross-linked compound represented by the general formula [I] and at least one diphenylsulfone derivative represented by the general formula [II] are used. The diphenyl sulfone derivative represented by the general formula [II] may be used in an amount of 10 to 5 parts by weight based on 100 parts by weight of the diphenyl sulfone cross-linked compound represented by the general formula [I].
00 parts by weight, preferably 25 to 300 parts by weight, more preferably 50 to 200 parts by weight.

Further, in the recording material of the present invention, one or two or more diphenylsulfone cross-linkable compounds in which a of the general formula [I] is 0 and a of the general formula [I] is 1 to 10
By containing one or more of the diphenylsulfone cross-linking type compounds and one or more of the diphenylsulfone derivatives represented by the general formula [II],
Sensitivity and storage are synergistically improved. At this time, the general formula [I]
The diphenylsulfone derivative represented by the general formula [II] is 10 to 500 parts by weight, preferably 25 to 30 parts by weight based on 100 parts by weight of the diphenylsulfone crosslinked compound represented by the formula:
0 parts by weight, more preferably 50 to 200 parts by weight.

Further, in the recording material of the present invention, a of the general formula [I] is 1 to 10 parts by weight based on 100 parts by weight of the diphenylsulfone cross-linkable compound wherein a of the general formula [I] is 0.
Is 0.05 to 1
100 parts by weight, and 10 to 500 parts by weight, preferably 25 to 300 parts by weight, more preferably 50 parts by weight of the diphenylsulfone derivative represented by the general formula [II] based on 100 parts by weight of the diphenylsulfone crosslinked compound. ~ 20
Use 0 parts by weight.

The compound of the formula [I] wherein a is 0 is described in JP-A-7-149713, International Publication W
O93 / 06074 and WO95 / 33714, typically 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) phenyl Nonoxy] -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-hydroxyphenylsulfonyl) phenoxy] diethyl ether 1,2-bis [4- (4 -Hydroxyphenylsulfonyl) phenoxy] ethylene 1,4-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] -2-butene.

The compound of the present invention may have a different crystal form or form an adduct with a solvent depending on the conditions under which the crystal is precipitated, for example, the type of the solvent and the precipitation temperature. These can be clarified by the melting point of the crystal, infrared spectroscopic analysis, X-ray diffraction analysis, etc., and belong to the present invention. Next, a of the general formula [I] used in the present invention
The compound in which is 1 or more can be exemplified below.

(1-1) 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy-2-trans-butenyloxy} diphenyl sulfone Melting point (° C.) 176-180 (1-2) 4,4 ′ -Bis {4- (4-hydroxyphenylsulfonyl) phenoxybutyloxy} diphenylsulfone melting point (° C) 215 to 220 (1-3) 4,4'-bis {3- (4-hydroxyphenylsulfonyl) phenoxypropyloxy} Diphenylsulfone Melting point (° C) 237-242 (1-4) 4,4'-bis {2- (4-hydroxyphenylsulfonyl) phenoxyethyloxy} diphenylsulfone (1-5) 4- {4- (4-hydroxy Phenylsulfonyl) phenoxybutyloxy {-4 '-{3- (4-
(Hydroxyphenylsulfonyl) phenoxypropyloxydiphenylsulfone

(1-6) 4- {4- (4-hydroxyphenylsulfonyl) phenoxybutyloxy} -4'-
{2- (4-hydroxyphenylsulfonyl) phenoxyethyloxy} diphenylsulfone (1-7) 4- {3- (4-hydroxyphenylsulfonyl) phenoxypropyloxy} -4 ′-{2- (4
-Hydroxyphenylsulfonyl) phenoxyethyloxydiphenylsulfone (1-8) 4,4'-bis {5- (4-hydroxyphenylsulfonyl) phenoxypentyloxy} diphenylsulfone (1-9) 4,4'-bis} 5- (4-hydroxyphenylsulfonyl) phenoxyhexyloxy {diphenylsulfone (1-10) 4- {4- (4-hydroxyphenylsulfonyl) phenoxy-2-trans-butenyloxy}-
4 '-{4- (4-hydroxyphenylsulfonyl) phenoxyethyloxy} diphenylsulfone

(1-11) 4- {4- (4-hydroxyphenylsulfonyl) phenoxy-2-trans-butenyloxy} -4 '-{3- (4-hydroxyphenylsulfonyl) phenoxypropyloxy} diphenylsulfone (1 -12) 4- {4- (4-Hydroxyphenylsulfonyl) phenoxy-2-trans-butenyloxy}-
4 '-{2- (4-hydroxyphenylsulfonyl) phenoxyethyloxy} diphenylsulfone (1-13) 1,4-bis-4- [4- {4- (4-hydroxyphenylsulfonyl) phenoxy-2 (t ) Butenyloxy {phenylsulfonyl] phenoxy-cis-
2-butene Melting point (° C) 185-190 (1-14) 1,4-bis-4- [4- {4- (4-hydroxyphenylsulfonyl) phenoxy-2 (t) butenyloxy} phenylsulfonyl] phenoxy-trans -2-butene Melting point (° C) 240-243 (1-15) 4,4'-bis- [4- {4- (2-hydroxyphenylsulfonyl) phenoxy} butyloxy]
Diphenyl sulfone

(1-16) 4,4'-bis [4- {2-
(4-hydroxyphenylsulfonyl) phenoxy {butyloxy] diphenylsulfone (1-17) 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy} diphenylsulfone Melting point (° C) 130- 134 (1-18) 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenyl-1,4-phenylenebismethyleneoxy} diphenylsulfone (1-19) 4,4'-bis {4- ( 4-hydroxyphenylsulfonyl) phenyl-1,3-phenylenebismethyleneoxydiphenylsulfone (1-20) 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenyl-1,2-phenylenebismethyleneoxy ｝ Diphenyl sulfone

(1-21) 2,2'-bis-4- [4-
{4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy} phenylsulfonyl] phenoxy-diethyl ether (1-22) α, α′-bis-4- [4- {4- (4-hydroxyphenyl) Sulfonyl) phenyl-1,4-phenylenebismethyleneoxy {phenylsulfonyl] phenoxy-p-xylene (1-23) α, α'-bis-4- [4- {4- (4-hydroxyphenylsulfonyl) phenyl- 1,3-phenylenebismethyleneoxy {phenylsulfonyl] phenoxy-m-xylene (1-24) α, α'-bis-4- [4- {4- (4-hydroxyphenylsulfonyl) phenyl-1,2- [Phenylenebismethyleneoxy {phenylsulfonyl] phenoxy-o-xylene (1-25) 2,4'-bis} 2- 4-hydroxyphenyl sulfonyl) phenoxy-2 ethyleneoxy ethoxy} diphenylsulfone

(1-26) 2,4'-bis {4- (2-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy} diphenylsulfone (1-27) 4,4'-bis {3,5- Dimethyl-4-
(3,5-dimethyl-4-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxydiphenylsulfone (1-28) 4,4'-bis {3-allyl-4- (3-allyl-4-hydroxyphenyl) Sulfonyl) phenoxy-2-ethyleneoxyethoxydiphenylsulfone (1-29) 4,4'-bis {3,5-dimethyl-4-
(3,5-dimethyl-4-hydroxyphenylsulfonyl) phenyl-1,4-phenylenebismethyleneoxy {diphenylsulfone (1-30) 4,4'-bis} 3,5-dimethyl-4-
(3,5-dimethyl-4-hydroxyphenylsulfonyl) phenyl-1,3-phenylenebismethyleneoxydiphenylsulfone

(1-31) 4,4'-bis {3,5-dimethyl-4- (3,5-dimethyl-4-hydroxyphenylsulfonyl) phenyl-1,2-phenylenebismethyleneoxy} diphenylsulfone ( 1-32) 4,4'-bis {3-allyl-4- (3-allyl-4-hydroxyphenylsulfonyl) 1,4-phenylenebismethyleneoxy} diphenylsulfone (1-33) 4,4'-bis {3-allyl-4- (3-allyl-4-hydroxyphenylsulfonyl) 1,3-phenylenebismethyleneoxy} diphenylsulfone (1-34) 4,4'-bis} 3-allyl-4- (3- Allyl-4-hydroxyphenylsulfonyl) 1,2-phenylenebismethyleneoxy {diphenylsulfone (1-35) 4,4'-bis} 4 (4-hydroxyphenyl (Rusulfonyl) phenoxy-2-hydroxypropyloxy} diphenylsulfone (1-36) 1,3-bis-4- [4- {4- (4-hydroxyphenylsulfonyl) phenoxy-2-hydroxypropyloxy} phenylsulfonyl] Phenoxy
2-hydroxypropane

In the present invention, when a compound of the formula (I) wherein a is 0 and a compound of the formula (I) wherein a is 1 or more are used in combination, particularly preferred combinations are as follows: It is.

(2-1) 2,2'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy} diethyl ether and 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethylene Combination of oxyethoxy diphenyl sulfone (2-2) α, α'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy} -p-xylene and 4,
Combination of 4'-bis {4- (4-hydroxyphenylsulfonyl) phenyl-1,4-phenylenebismethyleneoxy} diphenylsulfone (2-3) α, α'-bis {4- (4-hydroxyphenylsulfonyl) Phenoxy-m-xylene and 4,
Combination of 4'-bis {4- (4-hydroxyphenylsulfonyl) phenyl-1,3-phenylenebismethyleneoxy} diphenylsulfone (2-4) α, α'-bis {4- (4-hydroxyphenylsulfonyl) Phenoxy di-o-xylene and 4,
Combination of 4'-bis {4- (4-hydroxyphenylsulfonyl) phenyl-1,2-phenylenebismethyleneoxy} diphenylsulfone (2-5) 2,2'-bis {4- (4-hydroxyphenylsulfonyl) Phenoxydiethyl ether and 4,
4'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy-2-ethyleneoxyethoxy} diphenylsulfone and 2,2'-bis-4- [4- {4-
(4-hydroxyphenylsulfonyl) phenoxy-2
-Ethyleneoxyethoxy {phenylsulfonyl] phenoxy-diethyl ether

(2-6) α, α'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy} -p-xylene and 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenyl-1 , 4-phenylenebismethyleneoxydiphenylsulfone and α, α'-bis-4
-[4- {4- (4-hydroxyphenylsulfonyl)
Combination of phenyl-1,4-phenylenebismethyleneoxy {phenylsulfonyl] phenoxy-p-xylene (2-7) α, α'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy} -m-xylene and 4 ,
4'-bis {4- (4-hydroxyphenylsulfonyl) phenyl-1,3-phenylenebismethyleneoxy} diphenylsulfone and α, α'-bis-4- [4
Combination of-{4- (4-hydroxyphenylsulfonyl) phenyl-1,3-phenylenebismethyleneoxy} phenylsulfonyl] phenoxy-m-xylene (2-8) α, α'-bis {4- (4-hydroxy Phenylsulfonyl) phenoxy {-o-xylene and 4,
4'-bis {4- (4-hydroxyphenylsulfonyl) phenyl-1,2-phenylenebismethyleneoxy} diphenylsulfone and α, α'-bis-4- [4
Combination of-{4- (4-hydroxyphenylsulfonyl) phenyl-1,2-phenylenebismethyleneoxy} phenylsulfonyl] phenoxy-o-xylene (2-9) 1,4-bis} 4- (4-hydroxyphenyl Combination of sulfonyl) phenoxy {-trans-2-butene and 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy-2-trans-butenyloxy} diphenylsulfone (2-10) 1,2-bis} Combination of 4- (4-hydroxyphenylsulfonyl) phenoxy} -ethane and 4,4'-bis {2- (4-hydroxyphenylsulfonyl) phenoxy-ethyloxy} diphenylsulfone

(2-11) 1,4-bis {4- (4-hydroxyphenylsulfonyl) phenoxy} -butane and 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy-butyloxy} diphenylsulfone Combination of (2-12) 1,6-bis {4- (4-hydroxyphenylsulfonyl) phenoxy} hexane and 4,4'-bis {6- (4-hydroxyphenylsulfonyl) phenoxy-hexyloxy} diphenylsulfone Combination (2-13) 1,3-bis {4- (4-hydroxyphenylsulfonyl) phenoxy} -2-hydroxypropane and 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy-2-hydroxy Propyloxy
Combination with diphenyl sulfone (2-14) 1,3-bis {4- (4-hydroxyphenylsulfonyl) phenoxy} -2-hydroxypropane and 4,4'-bis {4- (4-hydroxyphenylsulfonyl) phenoxy -2-hydroxypropyloxy}
Diphenyl sulfone and 1,3-bis-4- [4-
{4- (4-hydroxyphenylsulfonyl) phenoxy-2-hydroxypropyloxy} phenylsulfonyl] phenoxy-2-hydroxypropane.

In the present invention, the following compounds are particularly preferred among the diphenylsulfone derivatives represented by the general formula [II].

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The present invention can be used for any purpose as long as it is a recording material using a coloring dye, for example, a heat-sensitive recording material or a pressure-sensitive copying material. When the present invention is used for heat-sensitive recording paper, a known image storage stabilizer and a developer may be used in the same manner as described above.For example, fine particles of the compound of the present invention and fine particles of a color-forming dye may be used. It can be produced by mixing a suspension dispersed in an aqueous solution of a water-soluble binder such as polyvinyl alcohol or cellulose, coating the mixture on a support such as paper, and drying.

The general formulas [I] and [I] for the chromogenic dye
The compound represented by the formula (I) is used in an amount of 1 to 10 parts by weight, preferably 1.10 parts by weight, based on 1 part by weight of the chromogenic dye. 5 to 5 parts by weight. In the recording material of the present invention, in addition to the color-forming dye and the compounds represented by the general formulas [I] and [II], known developers, image stabilizers, sensitizers, fillers, dispersants, An antioxidant, a desensitizer, an antiadhesive, an antifoaming agent, a light stabilizer, a fluorescent brightener, and the like can be contained as necessary.

These agents may be contained in the color-forming layer. However, in the case of 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 fluoran 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-aralinofluoran, 3-piperidino-6-methyl-7-aralinofluoran, 3-dimethylamino-7- (m-trifluoromethylanilino) fluoran , 3-dipentylamino-6-methyl-7-anilinofluoran, 3- (N
-Ethoxypropyl-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-domethoxyfluoran 2,4-dimethyl-6- (4-dimethylaminophenyl) amino Fluoran and the like.

The near infrared absorbing dyes include 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.

Examples of the developer include 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; metal benzoates such as zinc benzoate and zinc 4-nitrobenzoate; 4- (2- (4-
Salicylic acids such as methoxyphenyloxy) ethyloxy) salicylic acid, zinc salicylate, metal salts of salicylic acid such as bis {4- (octyloxycarbonylamino) -2-hydroxybenzoic acid} zinc, 4,4′-dihydroxydiphenylsulfone, 2, 4'-dihydroxydiphenylsulfone, 4-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, 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-toluenesulfonylaminoca) Boniruamino) sulfonylureas such as diphenylmethane, tetracyanoquinodimethane compounds,
2,4-dihydroxy-2'-methoxybenzanilide and the like can be mentioned.

Examples of the image stabilizer include diphenyl sulfones containing an epoxy group, such as 4-benzyloxy-4 '-(2-methylglycidyloxy) -diphenylsulfone and 4,4'-diglycidyloxydiphenylsulfone; 1,4-diglycidyloxybenzene, 4- (α
-(Hydroxymethyl) benzyloxy) -4'-hydroxydiphenylsulfone, 2-propanol derivative,
Examples thereof include salicylic acid derivatives, metal salts of oxynaphthoic acid derivatives (particularly zinc salts), and other water-insoluble zinc compounds.

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, diethers of 4,4'-dihydroxydiphenylsulfone, 1,2-bis (phenoxy)
Ethane, 1,2-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 and the like. Preferably,
Examples thereof include ethers such as 1,2-bis (3-methylphenoxy) ethane and 2-naphthylbenzyl ether, and aromatic hydrocarbons such as m-terphenyl and 4-benzylbiphenyl.

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. Particularly in the recording material of the present invention, an alkaline earth metal salt is preferable. Further, carbonates are preferable, and calcium carbonate, magnesium carbonate and the like are preferable. The filler is used in an amount of 0.1 to 15 parts by weight per 1 part by weight of the coloring dye,
Preferably it is 1 to 10 parts by weight. 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),
2,2'-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-te
rt-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 and the like can be mentioned.

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 light stabilizers, 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 '
Benzophenone ultraviolet absorbers such as -dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone,
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-tert-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'-tert-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) henzotriazole, 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-tert-butyl-
Benzotriazole-based ultraviolet absorbers such as condensates with 5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl- A cyanoacrylate-based ultraviolet absorber such as 2-cyano-3,3-diphenylacrylate;
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-succinate)
4-piperidyl) ester, 2- (3,5-di-ter)
Hindered amine-based ultraviolet absorbers such as t-butyl) malonic acid-bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester and the like can be mentioned.

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'-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

The compound of the present invention can be used in pressure-sensitive copying paper in the same manner as in the case of using a known image storage stabilizer, developer or sensitizer. 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 is composed of an upper paper having a microcapsule containing an organic solvent solution of a chromogenic dye applied and carried on the lower surface, and a lower paper having a developer (acidic substance) applied and carried 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 to be used at that time, or as the developer to be used by mixing with the compound of the present invention, conventionally known ones can be used, for example, acid clay, activated clay, apattalite, bentonite, colloidal silica, silicic acid Inorganic acidic substances such as aluminum, 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 succinic acid; 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- (2,2-dimethylbenzyl) salicylic acid,
3,5-di- (2-methylbenzyl) salicylic acid, 2-
Aromatic carboxylic acids such as hydroxy-1-benzyl-3-naphthoic acid, metal salts of these aromatic carboxylic acids such as zinc, magnesium, aluminum, and titanium; p-phenylphenol-formalin resin; p-butylphenol-
Examples thereof include a phenol resin-based developer such as an acetylene resin, and a mixture of the phenol resin-based developer with the metal salt of the aromatic carboxylic acid.

[0045]

EXAMPLES Hereinafter, the recording material of the present invention will be described in detail with reference to examples, but the present invention is not necessarily limited thereto. The parts and percentages shown below are based on weight. Example 1 [Solution A] 3-di-n-butylamino-6-methyl-7-anilinofluoran 20 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water 60 parts [Solution B] 4,4 '-[oxybis ( Ethyleneoxy-p-phenylenesulfonyl)] 10 parts of polymer containing diphenol and the like = composition =

[Table 1] Polyvinyl alcohol 10% aqueous solution 25 parts Calcium carbonate 15 parts Water 60 parts [Solution C] 4-chloro-4'-methyldiphenylsulfone 20 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water 60 parts

A mixture comprising the above composition was prepared by mixing the mixture having an average particle size of 2
μm or less using a sand mill,
Solution] [solution B] and [solution C]. Next, [A solution] [B
Liquid] [liquid C] was mixed and stirred at a weight ratio of 1: 6: 2 to prepare a heat-sensitive liquid, coated and dried so that the dry adhesion amount was 4 to 5 g / m ^2, and then calendered. This was applied to obtain a heat-sensitive recording paper of the present invention.

Example 2 The procedure of Example 1 was repeated, except that 4,4'-dimethoxydiphenylsulfone was used instead of 4-chloro-4'-methyldiphenylsulfone in [Solution C]. A heat-sensitive recording material of the invention was prepared.

Example 3 The procedure of Example 1 was repeated, except that 4,4'-diallyloxydiphenylsulfone was used instead of 4-chloro-4'-methyldiphenylsulfone in [C solution] of Example 1. A heat-sensitive recording material of the present invention was prepared.

Comparative Example 1 A heat-sensitive recording material for comparison was obtained in the same manner as in Example 1 except that [solution C] was omitted.

Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Example 1 except that oxalic acid di-p-methylbenzyl ester was used instead of 4-chloro-4'-methyldiphenylsulfone in [C solution]. Thermosensitive recording material was obtained.

Each of the heat-sensitive recording materials obtained as described above was tested for dynamic color sensitivity and plasticizer resistance. Table 2 shows the results. The test was performed as follows. (1) Dynamic color sensitivity Using a thermal printing tester having a thin film head manufactured by Matsushita Electric Parts Co., Ltd., head power 0.45 W / dot, line recording time 4 msec / l, scanning line density 8 × 7.7. Printing was performed under a dot / mm condition with a pulse width of 0.2 to 1.2 ms, the print density was measured with a Macbeth densitometer RD-914, and the density at 0.8 ms was used as dynamic color development sensitivity. (2) Plasticizer resistance Printing was performed with a 200 ° C. heat block under a pressure of 2 kg / cm ² for 1 second, and three sheets of Shin-Etsu Polymer PVC (Polymer Wrap 300) were placed on the printed portion of each printed sample. After applying a load of 5 kg and storing for 15 hours in a 40 ° C. environment, the print density was measured with a Macbeth densitometer RD-914.

[0052]

[Table 2]

[0053]

The recording material of the present invention has a high color-forming sensitivity and excellent image storability, especially excellent oil resistance and plasticizer resistance.

Claims (3)

[Claims] 1. A recording material containing a chromogenic dye, which is represented by the general formula [I]: (Wherein, X and Y are different from each other, may be linear or branched, and may have 1 to 12 carbon atoms, a saturated or unsaturated hydrocarbon group which may have an ether bond) Or (R ₇ represents a methylene group or an ethylene group, T represents a hydrogen atom or a C ₁ -C ₄ alkyl group). R _{1 to} R ₆
Each independently represent a halogen atom, an alkyl group of C ₁ -C ₆ shows an alkenyl group. Also, m, n, p, q, r,
t represents an integer from 0 to 4, and when it is 2 or more, R _{1 to} R ₆
May be different from each other. a represents an integer of 0 to 10. ) And at least one diphenylsulfone bridged compound represented by the general formula [II]: (Wherein G _{1 to} G ₆ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a halogen atom, a nitro group, a carboxyl group, an alkoxy group, a hydroxy group, an aralkyl group, an acyl group, an acyloxy group , An alkylene group or an alkenylene group.). 2. The diphenylsulfone derivative as 4,
2. The heat-sensitive recording material according to claim 1, wherein 4'-dimethoxydiphenyl sulfone is used. 3. The diphenylsulfone derivative as 4,
2. The heat-sensitive recording material according to claim 1, wherein 4'-diallyloxydiphenyl sulfone is used.