JP5441248B2 - Developable composition and recording material containing the same - Google Patents

Description

  The present invention relates to a composition containing a diphenylsulfone cross-linking compound and a recording material containing the composition and excellent in heat resistance.

  As a developer or image storage stabilizer, a diphenylsulfone cross-linked compound represented by the following formula (II) is known. (For example, refer to Patent Document 1.)

[Wherein, X and Y each represent a hydrocarbon group optionally having a C1-C12 saturated, unsaturated or ether bond, which may be different from each other and may have a straight chain or a branch, or

(R ′ represents a methylene group or an ethylene group, and T represents a hydrogen atom or a C1-C4 alkyl group). R _{1 to} R ₆ each independently represents a halogen atom, a C1 to C6 alkyl group, or a C2 to C4 alkenyl group. M, n, p, q, r, and t represent integers of 0 to 4, and R _{2 to} R ₆ may be different from each other when the number is 2 or more. a represents an integer of 0 to 10. ]

  However, when the composition is used as a recording material, the heat resistance is still inadequate, although the storage stability is much better than that of the conventional composition.

Japanese Patent Laid-Open No. 10-29969

  An object of the present invention is to provide a recording material having excellent heat resistance, and to provide a composition containing a diphenylsulfone cross-linking compound used therefor. Another object of the present invention is to provide a composition having a low content of 4,4'-dihydroxydiphenylsulfone, which is a raw material designated as a second type monitoring chemical substance in the Chemical Substances Control Law.

  The present inventors obtained a composition produced by the reaction of 4,4′-dihydroxydiphenylsulfone and bis (2-chloroethyl) ether, because it is a mixture of diphenylsulfone bridged compounds having different degrees of polymerization. The product obtained was found to have various thermal properties. In particular, when a composition containing n = 1 body and exhibiting a specific endothermic pattern by DSC measurement and / or a composition having a disintegration point of 119 ° C. or higher is used as a developer or the like as a developer, the heat resistance is improved. The present invention has been completed by finding that it can be remarkably improved.

That is, the present invention
(1) Formula (I)

(Wherein n represents an integer of 1 to 6), and the content of n = 1 body is 5% by mass or more of the solid content of the whole composition. In the composition, the calorific value of the endothermic portion in the range of 100 ° C. to 120 ° C. measured by DSC (Differential Scanning Calorimetry) is 20% or less of the total calorific value of the endothermic portion of 100 ° C. or more. ,
(2) The composition as described in (1) above, further having an endothermic peak from 70 ° C. to 90 ° C. measured by DSC (Differential Scanning Calorimetry).

The present invention also provides:
(3) Formula (I)

(Wherein n represents an integer of 1 to 6), and the content of n = 1 body is 5% by mass or more of the solid content of the whole composition. In the composition, the disintegration point is 119 ° C. or higher.

Furthermore, the present invention provides
(4) The composition according to any one of (1) to (3) above, wherein the content of 4,4′-dihydroxydiphenylsulfone is 2% by mass or less.

The present invention also provides:
(5) Formula (I) obtained by reaction of 4,4′-dihydroxydiphenylsulfone with bis (2-chloroethyl) ether

In the method for producing a reaction composition containing a mixture of compounds represented by the formula (wherein n represents an integer of 1 to 6), the content of 4,4′-dihydroxydiphenylsulfone is once 10 The composition according to any one of (1) to (4) above, wherein after producing a reaction composition of less than or equal to mass%, a heat treatment with an alkaline aqueous solution and a mixing treatment with an organic solvent are performed again. It is a manufacturing method.

The present invention also provides:
(6) A recording material containing the composition according to any one of (1) to (4) above.

  According to the present invention, a recording material having excellent heat resistance can be provided, and at the same time, the content of 4,4′-dihydroxydiphenylsulfone in the color developing composition is 2% by mass or less, further 1% by mass or less. Can be reduced.

It is a figure which shows the DSC measurement result of the composition of this invention Example 1. FIG. 2 is a diagram showing a DSC measurement result of the composition of Comparative Example 1. FIG.

(Developing composition)
The composition of the present invention is preferably composed of a mixture of reaction products having different degrees of polymerization and containing all compounds of n = 1 to 6 represented by the formula (I), depending on the reaction conditions and the like. The generation ratios are different, and it is sufficient that one or more kinds of compounds with n = 2 or more are included. 2,2′-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] diethyl ether in which n = 1 is essential and is 5 to 80% by mass, preferably 10 to 60% by mass in the solid content of the reaction composition. %, Particularly preferably 20 to 50% by mass.

The composition of the present invention is characterized in that the calorific value of the endothermic portion in the range of 100 ° C. to 120 ° C. is 20% or less of the total calorific value of the endothermic portion of 100 ° C. or higher as measured by DSC (differential scanning calorimeter). .
The melting start temperature and end temperature of the composition vary depending on the content ratio of the compound of formula (I) in the composition, but are generally between 100 ° C. and 180 ° C. In addition, although there is a difference in the endothermic pattern in DSC due to the difference in content ratio, crystal condition, etc. and the temperature rise condition, the heat quantity of the endothermic portion in a specific range of 100 ° C. to 120 ° C. is not affected by these in the present invention. The composition which becomes 20% or less of the whole calorie | heat amount of the endothermic part of 100 degreeC or more is meant. Preferably it is 15% or less, More preferably, it is 10% or less. In some cases, there is no endotherm in the range of 100 ° C. to 120 ° C., which is also included in the present invention. Thus, a composition in which the heat quantity of the initial endothermic part such as melting is 20% or less of the total endothermic part such as melting, when used as a recording material, is much higher than the conventional one. In addition, the heat resistance of the background portion is improved.

  Further, when the composition has an endothermic peak derived from crystal water in the vicinity of 80 ° C., that is, between 70 ° C. and 90 ° C., as measured by DSC (differential scanning calorimeter), this effect is more remarkably exhibited. The amount of heat and the shape of the endothermic peak derived from crystal water vary depending on the measurement conditions and the like, but it is only necessary to be able to confirm the endothermic portion regardless of them. However, in the measurement, it is necessary to perform a pretreatment for distinguishing between crystal water and adhering water. For example, once the temperature is raised to 100 ° C. (10 ° C./min), the temperature is maintained for 10 minutes, the temperature is lowered to 60 ° C. at 2 ° C./min, and the measurement is started.

  Further, the present invention is a composition having a disintegration point of 119 ° C. or higher, preferably 120 ° C. or higher, more preferably 125 ° C. or higher, particularly preferably 130 ° C. or higher. The collapse point indicates the state of the sample specified in the JIS melting point measurement method (K-0064). That is, when a sample is heated for measuring the melting point, the sample melts through a wet point, a contraction point, a collapse point, a liquefaction point, and a melting end point. The collapse point is defined as when the contracted sample collapses downward and liquefaction begins. When the disintegration point of the composition is 119 ° C. or higher, when the composition is used as a recording material, it exhibits excellent background heat resistance as compared with that of 119 ° C. or lower.

  Further, when a reaction composition is produced by a method as shown in the production method below, a composition defined by the above DSC and a reaction composition having a decay point of 119 ° C. or higher can be obtained, and the raw material 4, 4′-dihydroxydiphenyl sulfone can be 2% by mass or less, and further 1% by mass or less in the solid content of the reaction composition.

(Method for producing composition)
The composition of the present invention is obtained by subjecting a composition produced by the reaction of 4,4′-dihydroxydiphenylsulfone and bis (2-chloroethyl) ether as described in JP-A-10-29969, to a heat treatment again with an alkaline aqueous solution, It can be obtained by mixing an organic solvent with the aqueous solution, adjusting the pH, and filtering the product. Here, the “composition produced as in JP-A-10-29969” is filtered from the reaction solution, and it may or may not be dried, and is once taken out of the reaction system. It is a thing. In the production method of the composition of the present invention, the content of 4,4′-dihydroxydiphenyl sulfone in the composition produced by this first reaction is 10% by mass or less, preferably 5% by mass or less. It is necessary.

The organic solvent to be mixed is not particularly limited as long as it is a solvent that can dissolve n = 1 body, but is preferably an alcohol solvent, a ketone solvent, or the like. The addition amount is 5% by mass or more in the entire solution.
As the alcohol solvent, a single or two or more mixed solvents such as chain or cyclic alcohols such as methanol, ethanol, propanol, and isopropanol can be used.
As the ketone solvent, a single or two or more mixed solvents such as chain or cyclic ketones such as acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone can be used.

(Recording material)
When the composition of the present invention is used as a color developing composition on a thermal recording paper, it may be carried out in the same manner as the known image storage stabilizer and the method of using the color developer. For example, the composition of the present invention A recording material is prepared by mixing a suspension in which fine particles and fine particles of a color-forming dye are dispersed in an aqueous solution of a water-soluble binder such as polyvinyl alcohol and cellulose, applying the mixture to a support such as paper, and drying. Can be manufactured. Further, in addition to the method of containing in the color developing layer as described above, when it has a multilayer structure, it can also be contained in an arbitrary layer such as a protective layer or an undercoat layer.

  The use ratio of the composition of the present invention with respect to the color-forming dye is 0.01 to 100 parts by weight with respect to 1 part by weight of the color-forming dye, and when used as an auxiliary developer, 1 part by weight of the color-forming dye. Is preferably 0.01 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, and when used as a developer, preferably 1 to 1 part by weight of the color developing dye. The proportion is 10 parts by mass, particularly preferably 1.5 to 5 parts by mass.

  In the recording material of the present invention, two or more kinds of the composition of the present invention may be used in combination as a color developing composition. For example, one of the developer compositions of the present invention can be used as an image storage stabilizer and the other as a developer. As a method for preparing such a mixture of two or more kinds, they may be mixed in advance or may be mixed at the time of use. Further, as a mixing method with the color forming dye or the like, it may be mixed as a powder, added at the time of preparing and dispersing the coating liquid, or added in the state of a dispersion. In particular, when the composition of the present invention is used as a developer, it is very effective.

  In addition, the n = 1 body of the present invention includes those in which the crystal form varies depending on the conditions for precipitating the crystal, for example, the type of solvent, the precipitation temperature, or the like, or an adduct is formed with the solvent. All belong to the compounds of the invention. These can be clarified by the melting point of the crystal, infrared spectroscopic analysis, X-ray diffraction analysis or the like.

  The recording material of the present invention further includes other color developers, other image storage stabilizers, sensitizers, fillers, dispersants, antioxidants, desensitizers, anti-tacking agents, antifoaming agents, and light stabilizers. In addition, one or two or more kinds of fluorescent brighteners can be contained as required. The amount of each used is usually in the range of 0.01 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 1 part by mass of the chromogenic dye. These chemicals may be contained in the coloring layer, but 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 coloring layer, these layers can contain an antioxidant, a light stabilizer, and the like. Furthermore, an antioxidant and a light stabilizer can be contained in these layers in the form of being encapsulated in a microcapsule if necessary.

  Examples of the chromogenic dye used in the recording material of the present invention include leuco dyes such as fluorane, phthalide, lactam, triphenylmethane, phenothiazine, and spiropyran, but are not limited thereto. Instead, any color-forming dye that develops color by contact with an acidic substance can be used. In addition, these color-forming dyes are used alone to produce a recording material having the color to be developed, but two or more of them can be used in combination. For example, it is possible to produce a recording material that develops true black color by using a mixture of red, blue, and green primary color developing dyes or black coloring dyes.

Of these coloring dyes, for example,
3-diethylamino-6-methyl-7-anilinofluorane, 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-cyclohexylamino) -6 -Methyl-7-anilinofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-methyl -7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7- Anilinofluorane, 3-diethylamino-7- (m-trifluoromethylanilino) fluorane, 3-di (n-pentyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl- N-e Xylpropylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-n-octylaminofluorane, 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane, 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3 -Dibutylamino-7- (o-chloroanilino) fluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3-dibutylamino-7- (o-fluoro) Anilino) fluorane, 3-diethylamino-7- (o-fluoroanilino) fluorane, 2,4-dimethyl Ru-6-[(4-dimethylamino) anilino] fluorane, 2-chloro-3-methyl-6-p (p-phenylaminophenyl) aminoanilinofluorane, 3,3-bis [1- (4-methoxy) Phenyl) -1- (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, 3,6,6′-tris (dimethylamino) spiro [fluorene-9, 3'-phthalide], 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 10-benzoyl-3,7-bis (dimethylamino) phenothiazine, 3- (4-diethylamino-2- (Hexyloxyphenyl) -3- (1-ethyl-2-methyl-3-indolyl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- 1-ethyl-2-methyl-3-indolyl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methyl-3-indolyl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-octyl-2-methyl-3-indolyl) -4-azaphthalide, 3-diethylamino-5-methyl-7-dibenzylaminofluorane, 3 -Diethylamino-7-dibenzylaminofluorane, 3- (N-ethyl-p-tolyl) amino-7-N-methylanilinofluorane, 3,3-bis (4-diethylamino-2-ethoxyphenyl)- 4-Azaphthalide, 3- [2,2-bis (1-ethyl-2-methylindol-3-yl) vinyl] -3- [4- (diethylamino) phen L] isobenzofuran-1-one, 3,6,6'-tris (dimethylamino) spiro [fluorene-9,3'-phthalide], 2- [3,6-bis (diethylamino) -9- (o- Chloroanilino) xanthyl] lactam benzoate, 3-diethylamino-7-chlorofluorane, 3,6-bis- (diethylamino) fluorane-γ- (4′-nitro) -anilinolactam, 3-diethylamino-benzo [a] Fluorane, 3- (N-ethyl-N-isopentylamino) -benzo [a] fluorane, 2-methyl-6- (N-ethyl-Np-tolylamino) fluorane, 3,3-bis (1-butyl) 2-methyl-3-indolyl) phthalide, 3-diethylamino-6-methyl-7-chlorofluorane, 3-dibutylamino-6-methyl-7-bromo Oran, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6,8-dimethylfluorane, 4,4'-isopropylidenedi (4-phenoxy) bis [4- (quinazolin-2-yl)- N, N-diethylaniline],
Etc.

The black dye is preferably 3-diethylamino-6-methyl-7-anilinofluorane, 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N -Cyclohexylamino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamyl) Amino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluorane, 3-diethylamino-7- (m-trifluoromethylani Lino) fluorane, 3-di (n-pentyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluor 3-diethylamino-6-methyl-7-n-octylaminofluorane, 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-ani Linofluorane, 3-dibutylamino-7- (o-fluoroanilino) fluorane,
Can give.

Particularly preferably,
3-diethylamino-6-methyl-7-anilinofluorane, 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6 -Methyl-7-anilinofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluorane, 3-di (n-pentyl) amino-6-methyl-7-ani Renofluorane,
It is.

  Further, as a near infrared absorbing dye, 3,3-bis [1- (4-methoxyphenyl) -1- (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetra Examples thereof include chlorophthalide, 3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′-phthalide].

In addition, as blue, green, red, yellow
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methyl-3-indolyl) -4 -Azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-octyl-2-methyl-3-indolyl) -4-azaphthalide, 3-diethylamino-7-dibenzylaminofluorane, 3- (N-ethyl-p-tolyl) amino-7-N-methylanilinofluorane, 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 3,6,6′-tris ( Dimethylamino) spiro [fluorene-9,3′-phthalide], 3-diethylamino-7-chlorofluorane, 3-diethylamino-benzo [a] fluora 3-diethylamino-6-methyl-7-chlorofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6,8-dimethylfluorane, 4,4′-isopropylidenedi (4-phenoxy ) Bis [4- (quinazolin-2-yl) -N, N-diethylaniline],
And so on.

Examples of the developer used when the developer composition of the present invention is used in combination with another developer can include the following. These may be used alone or in combination of two or more as required.
Bisphenol A, 4,4′-sec-butylidene bisphenol, 4,4′-cyclohexylidene bisphenol, 2,2′-bis (4-hydroxyphenyl) -3,3′-dimethylbutane, 2,2′- Dihydroxydiphenyl, pentamethylene-bis (4-hydroxybenzoate), 2,2′-dimethyl-3,3′-di (4-hydroxyphenyl) pentane, 2,2′-di (4-dihydroxyphenyl) hexane, 2 , 2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4 ′-(1- Phenylethylidene) bisphenol, 4,4′-ethylidenebisphenol, (hydroxyphenyl) methylphenol, 2,2-bis (4-h Loxyphenyl) -4-methylpentane, 4,4-isopropylidenebis-o-cresol, 4,4′-dihydroxy-diphenylmethane, 2,2′-bis (4-hydroxy-3-phenyl-phenyl) propane, 4 , 4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4,4 ′-(1,4-phenylenediisopropylidene) bisphenol, bisphenol compounds such as 2,2-bis (4-hydroxyphenyl) butyl acetate 4,4′-dihydroxydiphenylthioether, 1,7-di (4-hydroxyphenylthio) -3,5-dioxaheptane, 2,2′-di (4-hydroxyphenylthio) diethyl ether, 4,4 '-Dihydroxy-3,3'-dimethylphenylthioether, 1,5-di (4-hydroxyphenylthio) -3 Sulfur-containing bisphenols such as oxapentane, bis (4-hydroxyphenylthioethoxy) methane, and condensation mixtures mainly composed of 2,2′-methylenebis (4-tert-butylphenol) dinuclear condensate described in JP-A-2003-154760 Benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, chlorobenzyl 4-hydroxybenzoate 4-hydroxybenzoates such as methyl benzyl 4-hydroxybenzoate and diphenylmethyl 4-hydroxybenzoate, metal benzoates such as zinc benzoate and zinc 4-nitrobenzoate, 4-hydroxybenzoic acid and poly Condensate with hydric alcohol Salicylic acids such as bis (4- (2- (4-methoxyphenoxy) ethoxy)) salicylic acid, 3,5-bis (α-methylbenzyl) salicylic acid, 3,5-bis-tert-butylsalicylic acid, zinc salicylate, bis (4- (octyloxycarbonylamino) -2-hydroxybenzoic acid) salicylic acid metal salts such as zinc, 4,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4 ′ -Butoxydiphenylsulfone, 4-hydroxy-4'-phenylsulfonyloxy-3,3'-phenylsulfonyldiphenylsulfone, 4,4'-dihydroxy-3,3'-diallyldiphenylsulfone, 3,4-dihydroxy-4 ' -Methyldiphenylsulfone, 4,4'-dihydroxy-3,3 ', 5 , 5′-tetrabromodiphenylsulfone, 2- (4-hydroxyphenylsulfonyl) phenol, a mixture of 2- (4-hydroxyphenylsulfonyl) phenol and 4,4′-sulfonyldiphenol, 4- (4-methylphenylsulfonyl) ) Equivalent mixture of phenol and 2- (4-methylphenylsulfonyl) phenol, 4,4′-sulfonylbis (2- (2-propenyl)) phenol, 4-((4- (propoxy) phenyl) sulfonyl) Hydroxy such as phenol, 4-((4- (allyloxy) phenyl) sulfonyl) phenol, 4-((4- (benzyloxy) phenyl) sulfonyl) phenol, 2,4-bis (phenylsulfonyl) -5-methyl-phenol Sulfones, 4-phenylsulfonylphenoxyzinc magnesium , Polyvalent metal salts of hydroxysulfones such as aluminum and titanium, 4-hydroxyphthalic acid diesters such as dimethyl 4-hydroxyphthalate, dicyclohexyl 4-hydroxyphthalate and diphenyl 4-hydroxyphthalate, 2-hydroxy-6 -Hydroxynaphthalene esters such as carboxynaphthalene, hydroxyacetophenone, p-phenylphenol, benzyl 4-hydroxyphenylacetate, p-benzylphenol, hydroquinone monobenzyl ether, trihalomethyl sulfones, 4,4'-bis (( Sulfonylureas such as 4-methylphenylsulfonyl) aminocarbonylamino) diphenylmethane, N- (4-methylphenylsulfonyl) -N ′-(3- (4-methylphenylsulfonyloxy) phenyl) urea Rares, tetracyanoquinodimethanes, 2,4-dihydroxy-2'-methoxybenzanilide, N- (2-hydroxyphenyl) -2-((4-hydroxyphenyl) thio) acetamide, N- (4- Hydroxyphenyl) -2-((4-hydroxyphenyl) thio) acetamide, 4-hydroxybenzenesulfonanilide, 4′-hydroxy-4-methylbenzenesulfonanilide, 4,4′-bis ((4-methyl-3- Examples include phenoxycarbonyl) aminophenylureido) diphenylsulfone, 3- (3-phenylureido) benzenesulfonamide, octadecylphosphoric acid, dodecylphosphoric acid and the like.

Preferably,
4,4′-isopropylidenediphenol, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4′-isopropylidenebis-o-cresol, 4,4 ′-(1-phenylethylidene) ) Bisphenol, 4,4′-cyclohexylidene bisphenol, 2,2-bis (4-hydroxy-3-phenyl-phenyl) propane, 4,4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4, 4 ′-(1,4-phenylenediisopropylidene) bisphenol, butyl bis (p-hydroxyphenyl) acetate, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, bis (3-allyl-4) -Hydroxyphenyl) sulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4- Droxy-4′-n-propoxydiphenylsulfone, 4-hydroxy-4′-allyloxydiphenylsulfone, 4-hydroxy-4′-benzyloxydiphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, N -(2-hydroxyphenyl) -2-[(4-hydroxyphenyl) thio] acetamide, N- (4-hydroxyphenyl) -2-[(4-hydroxyphenyl) thio] acetamide, N- (2-hydroxyphenyl) ) -2-[(4-hydroxyphenyl) thio] acetamide and an equivalent mixture of N- (4-hydroxyphenyl) -2-[(4-hydroxyphenyl) thio] acetamide, benzyl p-hydroxybenzoate, di ( 4-hydroxy-3-methylphenyl) sulfide, 4-hydroxyben Sulfone anilide, hydroquinone monobenzyl ether, a condensation mixture mainly composed of 2,2′-methylenebis (4-tert-butylphenol) 2 nuclear condensate described in JP-A-2003-154760, 4,4′-bis (N— p-tolylsulfonylaminocarbonylamino) diphenylmethane, Np-tolylsulfonyl-N′-3- (p-tolylsulfonyloxy) phenylurea, 4,4′-bis [(4-methyl-3-phenoxycarbonylaminophenyl) Ureido)] diphenylsulfone, 3- (3-phenylureido) benzenesulfonamide, bis [4- (n-octyloxycarbonylamino) salicylate] dihydrate, 4- [2- (4-methoxyphenoxy) ethoxy ] Zinc salicylate, 3,5-bis (α-methylbenzyl) salicylic acid It is possible to increase the lead.

  More specifically, these developers can be appropriately used at a ratio of 0.1 to 10 parts by mass with respect to 1 part by mass of the color developing composition of the present invention, for example, 3-di (n-butyl) as a dye. ) 1 part by mass of the developer composition of the present invention with respect to 1 part by mass of amino-6-methyl-7-anilinofluorane, and 4-hydroxy-4'-isopropoxydiphenylsulfone 1 as the other developer. A thermal recording paper can be produced by combining the mass parts. Similarly, the above developers such as 4-hydroxy-4'-n-propoxydiphenylsulfone, 4-hydroxy-4'-allyloxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone may be combined.

Examples of the image storage stabilizer used when the color developing composition of the present invention is used in combination with another image storage stabilizer include the following. These may be used alone or in combination of two or more as required.
1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-cyclohexylphenyl) butane, 4,4′-butylidenebis (6-t-butyl-3-methylphenol), 2,2′-methylenebis (6-t-butyl-4-methylphenol), 2,2′-methylenebis (6-t-butyl) -4-ethylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) ) Isocyanurate, 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-triazine-2,4,6 (1H) , 3H, 5H)-G Rion, 2-methyl-2-[[4-[[4- (phenylmethoxy) phenyl] sulfonyl] phenoxy] methyl] -oxirane, 2,4,8,10- (tetra (t-butyl) -6-hydroxy -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide sodium salt, 2,2-bis (4'-hydroxy-3 ', 5'-dibromophenyl) propane, 4 , 4′-sulfonylbis (2,6-dibromophenol), 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 4-benzyloxy-4- (2-methylglycidyloxy) -diphenylsulfone 4,4′-diglydyloxydiphenylsulfone, 1,4-diglydyloxybenzene, 4- (α- (hydroxymethyl) benzyloxy) -4′-hydroxydiph Examples thereof include phenyl sulfone and 2,2-methylenebis (4,6-tert-butylphenyl) phosphate.

Preferably,
1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-cyclohexylphenyl) butane, 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 1,3,5-tris (2,6-dimethyl) -4-t-butyl-3-hydroxybenzyl) isocyanurate, 2-methyl-2-[[4-[[4- (phenylmethoxy) phenyl] sulfonyl] phenoxy] methyl] -oxirane, 4,4′-sulfonyl Bis (2,6-dibromophenol), 2- (2′-hydroxy-5′-methylphenyl) benzotriazole can be mentioned.

Moreover, the following can be illustrated as a sensitizer. These may be used alone or in combination of two or more as required.
Higher fatty acid amides such as stearic acid amide, benzamide, stearic acid anilide, acetoacetanilide, thioacetanilide, dibenzyl oxalate, di (4-methylbenzyl) oxalate, di (4-chlorobenzyl) oxalate, dimethyl phthalate, Dimethyl terephthalate, dibenzyl terephthalate, dibenzyl isophthalate, bis (tert-butylphenol), 4,4′-dimethoxydiphenylsulfone, 4,4′-diethoxydiphenylsulfone, 4,4′-dipropoxydiphenylsulfone, 4, 4′-diisopropoxydiphenylsulfone, 4,4′-dibutoxydiphenylsulfone, 4,4′-diisobutoxydiphenylsulfone, 4,4′-dipentyloxydiphenylsulfone, 4,4′-dihexylphenylsulfone, 2, 4'-di Toxidiphenylsulfone, 2,4′-diethoxydiphenylsulfone, 2,4′-dipropoxydiphenylsulfone, 2,4′-diisopropoxydiphenylsulfone, 2,4′-dibutoxydiphenylsulfone, 2,4′- Diphenylsulfone and derivatives thereof such as dipentyloxydiphenylsulfone, 2,4′-dihexyloxydiphenylsulfone, diethers of 4,4′-dihydroxydiphenylsulfone, diethers of 2,4′-dihydroxydiphenylsulfone, 1,2- Bis (phenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, diphenylamine, carbazole, 2,3-di-m-tolylbutane, 4-benzylbiphenyl 4,4′-dimethylbiphenyl, m Terphenyl, di-β-naphthylphenylenediamine, 1-hydroxy-2-naphthoic acid phenyl ester, 2-naphthylbenzyl ether, 4-methylphenyl-biphenyl ether, 1,2-bis (3,4-dimethylphenyl) ethane 2,3,5,6-tetramethyl-4′-methyldiphenylmethane, 1,2-bis (phenoxymethyl) benzene, acrylic acid amide, diphenylsulfone, 4-acetylbiphenyl, diphenyl carbonate and the like.

Preferably,
2-naphthylbenzyl ether, m-terphenyl, p-benzylbiphenyl, benzyl oxalate, di (p-chlorobenzyl) oxalate, a mixture of benzyl oxalate and di (p-chlorobenzyl) oxalate, oxalic acid Di (p-methylbenzyl), equivalent mixture of di (p-chlorobenzyl) oxalate and di (p-methylbenzyl) oxalate, 1-hydroxy-2-naphthoic acid phenyl ester, 1,2-diphenoxyethane 1,2-di- (3-methylphenoxy) ethane, 1,2-bis (phenoxymethyl) benzene, dimethyl terephthalate, stearic acid amide, amide AP-1 (7: 3 of stearic acid amide and palmitic acid amide Mixture), diphenylsulfone, and 4-acetylbiphenyl.

  More specifically, these sensitizers can be appropriately used at a ratio of 0.1 to 10 parts by mass with respect to 1 part by mass of the dye, for example, 3-di (n-butyl) amino-6-methyl as a dye. A thermosensitive recording paper is prepared with 2 parts by mass of the color developing composition of the present invention and 1 part by mass of di (p-methylbenzyl) oxalate as a sensitizer for 1 part by mass of -7-anilinofluorane. Can do. Similarly, the above sensitizers such as 1,2-di- (3-methylphenoxy) ethane, 1,2-bis (phenoxymethyl) benzene, and diphenylsulfone may be combined.

  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. In particular, alkaline earth metal salts are preferred in the recording material of the present invention. Further, carbonates are preferable, and calcium carbonate, magnesium carbonate and the like are preferable. The use ratio of the filler is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight with respect to 1 part by weight of the coloring dye. It is also possible to use a mixture of the above fillers.

  Examples of the dispersant include sulfosuccinic acid esters such as dioctyl sodium sulfosuccinate, sodium dodecylbenzene sulfonate, sodium salt of lauryl alcohol sulfate, fatty acid salt, and the like.

  Antioxidants include 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-tert-butyl-5-methylphenol), 1, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane, 4- [4- {1,1-bis (4-hydroxyphenyl) ethyl} -α, α′-dimethylbenzyl] Phenol, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 2,2'-methylenebi (6-tert-butyl-4-methylphenol), 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), 4,4′-thiobis (6-tert-butyl-3-methyl-) Phenol), 1,3,5-tris ((4- (1,1-dimethylethyl) -3-hydroxy-2,6-dimethylphenyl) methyl-1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, 1,3,5-tris ((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) -1,3,5-triazine-2, 4, 6 (1H, 3H, 5H) -trione 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, ester wax and the like.

  Examples of the light stabilizer include salicylic acid-based UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- 4-benzyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-methoxy Benzophenone ultraviolet absorbers such as -5-sulfobenzophenone and bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- ( '-Hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3-tert- Butyl-5′-methylphenyl) -5-chloro-benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′) , 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1 '', 1 '', 3 '', 3 ''-tetramethylbutyl) phenyl) 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) benzo Triazole, 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 ′-(2 ″ -propylheptyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′-(2 ″ -propylhexyl) oxyphenyl] Benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzo Benzazolazoles such as condensates of riazol-2-yl) phenol, polyethylene glycol and methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate UV absorbers, cyanoacrylate UV absorbers such as 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebecate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidyl) ester, 2- (3,5-di-tert-butyl) malonic acid-bis Hindered amine ultraviolet absorbers such as (1,2,2,6,6-pentamethyl-4-piperidyl) ester Such as 1,8-dihydroxy-2-acetyl-3-methyl-6-methoxynaphthalene and its related compounds can be exemplified.

The following can be illustrated as a fluorescent dye.
4,4′-bis [2-anilino-4- (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- (Hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2′-disulfonic acid disodium salt, 4,4′-bis [2-anilino-4- (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 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 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 Hexasodium salt, 4,4′-bis [2- (2,5-disulfoanilino) -4-formanilylamino-1,3,5-triazinyl-6-amino] stilbene-2,2′-disulfonic acid Sodium salt, 4,4′-bis [2- (2,5-disulfoanilino) -4-bis (hydroxyethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2′-disulfone Acid hexasodium salt etc.

  When the composition of the present invention is used for pressure-sensitive copying paper, it can be produced in the same manner as in the case of using a known image storage stabilizer, developer or sensitizer. For example, a coloring agent microencapsulated by a known method is dispersed with an appropriate dispersant and applied to paper to prepare a coloring agent sheet. Further, a developer sheet is prepared by applying a developer dispersion to paper. At that time, when the developer composition of the present invention is used as an image storage stabilizer, it may be used by being dispersed in either a color developer sheet or a developer sheet dispersion. A pressure-sensitive copying paper is produced by combining the two sheets thus produced. As pressure-sensitive copying paper, an upper paper having a microcapsule encapsulating an organic solvent solution of a chromophoric 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 the microcapsules and the developer are applied on the same paper surface.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
The abbreviations are as follows.
BPS: 4,4′-dihydroxydiphenylsulfone DCEE: bis (2-chloroethyl) ether

<Synthesis of developer composition>
[Reference Example (Comparative Example 1)]
1969 kg of BPS was added to 1309 kg of 49% NaOH aqueous solution, and dissolved by heating and stirring. Next, 500 kg of DCEE was added dropwise at 100 ° C., and the mixture was heated and stirred for 6 hours. Thereafter, 1952 kg of warm water was added dropwise, and the mixture was stirred at 90 to 100 ° C. for 90 minutes. After adding 2656 kg of methanol to the reaction solution and stirring, hydrochloric acid was added dropwise to adjust the pH to 5.5. The mixture was stirred for 1 hour and then cooled. The resulting product was filtered off and dried to obtain 1534 kg of composition.
The result of analyzing this by high performance liquid chromatography was as follows (however, the numerical values are relative area values).
BPS 3.2%
n = 1 44.7%
n = 2 22.8%
n = 3 12.8%
n = 4 7.5%
n = 5 2.7%
n = 6 1.5%
(Where n = 1 to 6 is n of the compound represented by formula (I))
The collapse point was 118.4 ° C.

[Example 1]
793.8 g of water, 61.2 g of 49% NaOH aqueous solution and 250 g of the reaction composition prepared in Reference Example were mixed, and heated and stirred at 94 to 99 ° C. for 2 hours. Subsequently, 800 ml of methanol was added, and the pH was adjusted to 5.5 with hydrochloric acid. After cooling, the resulting product was filtered off and dried to obtain 197.7 g of a composition.
The result of analyzing this by high performance liquid chromatography was as follows (however, the numerical values are relative area values).
BPS 0.9%
n = 1 45.6%
n = 2 22.4%
n = 3 12.8%
n = 4 8.0%
n = 5 3.1%
n = 6 1.6%
The collapse point was 119.8 ° C.

<DSC measurement>
The compositions of Example 1 and Comparative Example 1 were measured by DSC. The measurement conditions are as follows.
Apparatus: High sensitivity differential scanning calorimeter DSC8230 manufactured by Rigaku
Measurement environment: Under nitrogen atmosphere Sample: Approx. 3 mg (crushed in a mortar)
Temperature increase program: i) Temperature increase to 100 ° C. at 10 ° C./min→ii) Hold at 100 ° C. for 10 minutes → iii) Cool to 2 ° C./min to 60 ° C. → iv) Increase to 200 ° C. again at 10 ° C./min Warm

(DSC chart of Example 1)
It was shown in FIG.
The endotherm at 100 to 120 ° C. was 1.308 J / g, the endotherm at 100 ° C. or higher was 34.033 J / g, and the ratio of the endotherm at 100 to 120 ° C. with respect to the total endotherm was 3.8%. It was.
There was also an endothermic peak of crystal water having a peak at 89.7 ° C.

(DSC chart of Comparative Example 1)
It is shown in FIG.
The endotherm at 100 to 120 ° C. was 10.967 J / g, the endotherm at 100 ° C. or higher was 30.443 J / g, and the ratio of the endotherm at 100 to 120 ° C. with respect to the total endotherm was 35.6%. It was.
Moreover, there was no endothermic peak in 70-90 degreeC.

<Preparation of thermal recording paper>
[Example 2]
・ Dye dispersion (liquid A)
3-di-n-butylamino-6-methyl-7-anilinofluorane 16 parts polyvinyl alcohol 10% aqueous solution 84 parts developer developer (liquid B)
Reaction composition of Example 1 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 parts First, the mixture of each composition of liquids A to C is sufficiently ground with a sand grinder, and each component of liquids A to C is dispersed. The liquid was adjusted, and 1 part by mass of A liquid, 2 parts by mass of B liquid, and 4 parts by mass of C liquid were mixed to obtain a coating liquid. This coating solution was applied and dried on white paper using a wire rod (Webster, wire bar No. 12), and then subjected to a calendaring process to produce a thermal recording paper (the coating solution was in dry mass). About 5.5 g / m ² ).

[Comparative Example 2]
A thermal recording paper was prepared by the method described in Example 2 except that the reaction composition of Comparative Example 1 was used in place of the reaction composition of Example 1 in the developer dispersion liquid (B solution) of Example 2. Produced.

<Thermal evaluation test-background heat resistance test>
A part of the thermal recording paper prepared in Example 2 and Comparative Example 2 was cut out and held at a temperature of 90 ° C. and 100 ° C. for 24 hours in a thermostatic chamber (trade name: DK-400, manufactured by YAMATO), and then each test. The background density (Macbeth value) of the paper was measured. The results are shown in Table 1 below.
The smaller the Macbeth value, the closer to white, the better. The recording material of the present invention has a remarkable effect in the heat resistance test at 100 ° C. as shown in Table 1.

<Preparation of thermal recording paper 2 Combination of developer>
[Example 3]
・ Dye dispersion (liquid A)
3-di-n-butylamino-6-methyl-7-anilinofluorane 16 parts polyvinyl alcohol 10% aqueous solution 84 parts developer developer (liquid B)
Reaction composition of Example 1 16 parts Polyvinyl alcohol 10% aqueous solution 84 parts Developer dispersion (liquid C)
4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol 16 parts Polyvinyl alcohol 10% aqueous solution 84 parts Filler dispersion (liquid D)
Calcium carbonate 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 71 parts First, the mixture of each composition of liquids A to D is sufficiently ground with a sand grinder, and each component of liquids A to D is dispersed. The liquid was adjusted, and 1 part by mass of A liquid, 3 parts by mass of B liquid, 1 part by mass of C liquid, and 4 parts by mass of D liquid were mixed to obtain a coating liquid. This coating solution was applied and dried on white paper using a wire rod (Webster, wire bar No. 12), and then subjected to a calendaring process to produce a thermal recording paper (the coating solution was in dry mass). About 5.5 g / m ² ).

[Example 4]
A thermal paper was prepared by the method described in Example 3 except that the B liquid of Example 3 was changed to 2 parts by mass and the C liquid was changed to 2 parts by mass.

[Example 5]
Thermal paper was produced by the method described in Example 3 except that the B liquid of Example 3 was changed to 1 part by mass and the C liquid was changed to 3 parts by mass.

[Example 6]
In the liquid C of Example 3, except that 4-{[4- (1-allyloxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, A thermal paper was prepared by the method described in Example 3.

[Example 7]
In the liquid C of Example 3, 4-{[4- (1-allyloxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, and the liquid B was Thermal paper was produced by the method described in Example 3 except that 2 parts by mass and C liquid were changed to 2 parts by mass.

[Example 8]
In the liquid C of Example 3, 4-{[4- (1-allyloxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, and the liquid B was Thermal paper was produced by the method described in Example 3 except that 1 part by mass and C liquid were changed to 3 parts by mass.

[Example 9]
In the liquid C of Example 3, except that 4-{[4- (1-propoxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, A thermal paper was prepared by the method described in Example 3.

[Example 10]
In the liquid C of Example 3, 4-{[4- (1-propoxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, and the liquid B was Thermal paper was produced by the method described in Example 3 except that 2 parts by mass and C liquid were changed to 2 parts by mass.

[Example 11]
In the liquid C of Example 3, 4-{[4- (1-propoxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, and the liquid B was Thermal paper was produced by the method described in Example 3 except that 1 part by mass and C liquid were changed to 3 parts by mass.

[Comparative Example 3]
A thermal recording paper was prepared by the method described in Example 3 except that the reaction composition of Comparative Example 1 was used in place of the reaction composition of Example 1 in the developer dispersion liquid (B solution) of Example 3. Produced.

[Comparative Example 4]
A thermal paper was prepared by the method described in Comparative Example 3 except that the B liquid of Comparative Example 3 was changed to 2 parts by mass and the C liquid was changed to 2 parts by mass.

[Comparative Example 5]
A thermal paper was prepared by the method described in Comparative Example 3 except that the B liquid of Comparative Example 3 was changed to 1 part by mass and the C liquid was changed to 3 parts by mass.

[Comparative Example 6]
In the liquid C of Comparative Example 3, except that 4-{[4- (1-allyloxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, A thermal paper was prepared by the method described in Comparative Example 3.

[Comparative Example 7]
In the liquid C of Comparative Example 3, 4-{[4- (1-allyloxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, and the liquid B was A thermal paper was prepared by the method described in Comparative Example 3 except that 2 parts by mass and C liquid were changed to 2 parts by mass.

[Comparative Example 8]
In the liquid C of Comparative Example 3, 4-{[4- (1-allyloxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, and the liquid B was A thermal paper was produced by the method described in Comparative Example 3 except that 1 part by mass and C liquid were changed to 3 parts by mass.

[Comparative Example 9]
In the liquid C of Comparative Example 3, except that 4-{[4- (1-propoxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, A thermal paper was prepared by the method described in Comparative Example 3.

[Comparative Example 10]
In the liquid C of Comparative Example 3, 4-{[4- (1-propoxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, and the liquid B was A thermal paper was prepared by the method described in Comparative Example 3 except that 2 parts by mass and C liquid were changed to 2 parts by mass.

[Comparative Example 11]
In the liquid C of Comparative Example 3, 4-{[4- (1-propoxy) phenyl] sulfonyl} phenol was used instead of 4-{[4- (1-methoxyethoxy) phenyl] sulfonyl} phenol, and the liquid B was A thermal paper was produced by the method described in Comparative Example 3 except that 1 part by mass and C liquid were changed to 3 parts by mass.

<Thermal evaluation test 2-background heat resistance test>
A part of the heat-sensitive recording paper prepared in Examples 3 to 11 and Comparative Examples 3 to 11 was cut out and 24 at a temperature of 80 ° C., 90 ° C., and 100 ° C. in a thermostatic chamber (trade name: DK-400, manufactured by YAMATO). After holding for a time, the background density (Macbeth value) of each test paper was measured. The results are shown in Table 2 below.
The smaller the Macbeth value, the closer to white, the better. As shown in Table 2, the recording material of the present invention has a remarkable effect in a heat resistance test at a high temperature of 90 ° C. or higher.

<Preparation of thermal recording paper 3 Combination with sensitizer>
[Example 12]
・ Dye dispersion (liquid A)
3-di-n-butylamino-6-methyl-7-anilinofluorane 16 parts polyvinyl alcohol 10% aqueous solution 84 parts developer developer (liquid B)
Reaction composition of Example 1 16 parts polyvinyl alcohol 10% aqueous solution 84 parts Sensitizer dispersion (liquid C)
Oxalic acid di (4-methylbenzyl) 16 parts polyvinyl alcohol 10% aqueous solution 84 parts Filler dispersion (liquid D)
Calcium carbonate 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 71 parts First, the mixture of each composition of liquids A to D is sufficiently ground with a sand grinder, and each component of liquids A to D is dispersed. The liquid was adjusted, and 1 part by mass of A liquid, 2 parts by mass of B liquid, 1 part by mass of C liquid, and 4 parts by mass of D liquid were mixed to obtain a coating liquid. This coating solution was applied and dried on white paper using a wire rod (Webster, wire bar No. 12), and then subjected to a calendaring process to produce a thermal recording paper (the coating solution was in dry mass). About 5.5 g / m ² ).

[Example 13]
A thermal paper was prepared by the method described in Example 12 except that 1,2-bis (3-methylphenoxy) ethane was used in solution C of Example 12 instead of di (4-methylbenzyl) oxalate. did.

[Example 14]
A thermal paper was prepared by the method described in Example 12 except that 1,2-bis (phenoxymethyl) benzene was used in solution C of Example 12 instead of di (4-methylbenzyl) oxalate.

[Example 15]
A thermal paper was prepared by the method described in Example 12 except that diphenylsulfone was used instead of di (4-methylbenzyl) oxalate in the liquid C of Example 12.

<Thermal evaluation test 3-background heat resistance test>
A part of the heat-sensitive recording paper produced in Examples 12 to 15 was cut out and held at 80 ° C. and 90 ° C. for 24 hours in a thermostatic chamber (trade name: DK-400, manufactured by YAMATO), and then each test paper was The background density (Macbeth value) was measured. The results are shown in Table 3 below.

Claims (4)

Formula (I)
(Wherein n represents an integer of 1 to 6), and the content of n = 1 body is 5% by mass or more of the solid content of the whole composition. in the composition, DSC (differential scanning calorimetry) Ri der than 20% of the total heat quantity of 100 endothermic part heat is above 100 ° C. endothermic portion of the range of 120 ° C. from ° C. measurement, further, DSC (differential scanning calorimetry A composition having an endothermic peak from 70 ° C. to 90 ° C. of measurement . The composition according to claim 1, wherein the content of 4,4′-dihydroxydiphenylsulfone is 2% by mass or less. Formula (I) obtained by reaction of 4,4′-dihydroxydiphenylsulfone with bis (2-chloroethyl) ether
In the method for producing a reaction composition containing a mixture of compounds represented by the formula (wherein n represents an integer of 1 to 6), the content of 4,4′-dihydroxydiphenylsulfone is once 10 3. The method for producing a composition according to claim 1, wherein a heat treatment with an alkaline aqueous solution and a mixing treatment with an organic solvent are carried out again after producing a reaction composition having a mass% or less. Recording material comprising a composition according to claim 1 or 2.