JPS63154390A - Recording material - Google Patents

Abstract

PURPOSE:To provide a recording material having favorable color forming properties, raw preservability and stability of developed color images and showing light absorption in near infrared region at a color-developed part, by incorporating a thiofluran derivative having a substd. amino group at 2-or 6-position and an electron-acceptive compound. CONSTITUTION:A thiofluran derivative having a substd. amino group at 2-or 6-position is preferably represented by general formula (I), wherein each of R<1> and R<2> is hydrogen, a 1-10C alkyl or aryl, each of R<3> and R<4> is hydrogen, a halogen, 1-8C alkyl, alkoxyl or aryl, each of R<5> and R<6> is hydrogen or a 1-10C alkyl, and A is an aromatic ring. An electron-acceptive compound is preferably one of compounds consisting of salicylic acid derivatives and metallic salts, particularly, a zinc salt. A recording material comprising these components shows light absorption in near infrared region at a color-developed part, has a sufficient developed color density, with a color-developed coloring matter being extremely stable, and is substantially free of discoloration or fading even under irradiation with light, heating or moistening for a long time, so that the recording material is particularly advantageous from the viewpoint of long- time preservation of records.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and in particular, a recording material having a color-forming portion absorbing light in the near-infrared region and having improved color-forming properties, shelf life, and stability of colored images. This invention relates to a recording material using an electron-donating colorless dye and an electron-accepting compound.

(Prior Art) Recording materials using an electron-donating colorless dye and an electron-accepting compound are already well known as pressure-sensitive paper, heat-sensitive paper, light-sensitive pressure-sensitive paper, electrically conductive heat-sensitive recording paper, and the like.

For example, British patent co/4t04t4su, U.S. patent Guru 10012, μ≠36taco0, Japanese Patent Publication No. 172-23, Tacoco, Japanese Patent Publication No. 7-172,13bu, same t0-/coj,
11bu, samebu 0-/23. ! I am familiar with 17 etc.

The properties that a recording material should have are (1) sufficient color density and color development sensitivity, (2) no capri, (3) sufficient fastness of the color body after color development, (
4) Appropriate color hue and suitability for copying machines, (5)
8/N ratio, and (6) sufficient chemical resistance of the color former, but currently no product has been obtained that completely satisfies these requirements.

In particular, heat-sensitive recording materials have the disadvantage that capri is caused by solvents and the like, and the color formers are discolored and faded by oils, fats, chemicals, and the like. Therefore, water-based ink pen, oil-based ink pen, fluorescent pen, ink, adhesive,
When it comes into contact with stationery and office supplies such as glue and diazo developer, or cosmetics such as hand cream and emulsion, the white part develops color and the colored part discolors and fades, resulting in a significant loss of product value. , the present inventors have determined that each of the electron-donating colorless dye electron-accepting compounds has its oil solubility,
We are pursuing the development of good materials for recording materials and recording materials by focusing on characteristics such as solubility in water, partition coefficient, polarity of pKa substituents, position of substitutional crystals, and changes in crystalline solubility when mixed. Ta. In recent years, there has been a desire to develop recording materials that absorb in the near-infrared region.

(Objective of the Invention) Therefore, the object of the present invention is to provide a recording material which has good coloring properties, shelf life, and stability of colored images, and in which the coloring portion absorbs light in the near-infrared region.

(Structure of the Invention) The object of the present invention is achieved by a recording material characterized by providing a coating layer containing a thiofluorane derivative having substituted amine groups at the 2- and 4-positions and an electron-accepting compound.

Among the thiofluorane derivatives according to the present invention, the following general formula (
Those represented by 1) are preferred.

(In the formula, R1 and B2 are a hydrogen atom, an alkyl group or an aryl group having a carbon number of up to IO, and R3 and R4 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group having a carbon number of up to t. The group is 几5, R6 is a hydrogen atom, the number of carbon atoms/
~ /Q alkyl group, human represents aromatic ring t-) In the above general formula (1) lc, Bl, 几2 and R8,B
The alkyl group represented by 6 may be bonded to each other to form a j to 7-membered ring, or may have a ring or a hetero atom or an unsaturated bond, and the alkyl group may be a halogen atom, an alkoxy may be substituted with a group, an aryloxy group, an aryl group, a nitro group, a cyano group, etc.

AFi may include foK child t-! A membered ring or a four-membered aromatic ring, specifically a be/zene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyran ring,
Preferred are a thiazole ring, an imidazole ring, an oxazole ring, a pyrrole ring, a thiophene ring, a furan ring, a benzofuran ring, a quinoline ring, a benzothiophene ring, and the like.

Examples of these colorless to light-colored electron-donating dye precursors include, but are not limited to, the following compounds.

(1) These can be used alone, but color vI4
! For the sake of uniformity and prevention of fading of colored images, two or more of them may be mixed.

These electron-donating colorless dyes include other triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucoolamine compounds, rhodamine lactam compounds, triphenylmethane compounds, and triazenes. It may be used in combination with Tanizashi's compounds such as fluorene-based compounds, fluorene-based compounds, and spiropyran-based compounds.

Specific examples of phthalides are given in U.S. Reissue Patent Specification Letter 23, O.
Co≠ No., U.S. Patent Specification Letter 3. ≠ri/.

No. 111, same No. 3. ≠ri/, ///- issue, same No. 3゜μri/
, 111 and 1it, J, 10? ,/7μ issue,
Specific examples of fluorans are given in U.S. Patent Specification Letter 3゜4J44.
．． No. 107, same number! , 1s27,717, same @j, t
4t/, 0//, U.S. Patent Specification Letter J, P-
〇、! No. 10, U.S. Patent Specification Letter 3. the law of nature! No. 177, specific examples of spirodipyra 7 are given in U.S. Patent Specification Letter 3. 7/, No. 101, and pyridi/pyridine-based and pyrazine-based color-forming compounds are described in U.S. Patent Specification Letter 3,771. ≠−μ No. and same No. J.

1rjJ, Itr, U.S. Pat.

No. 311, a specific example of Fluore 7 class is % Gansho 6/-coμo
It is described in the yry issue etc.

Among the electron-accepting compounds according to the present invention, the following general formula (n)
Those represented by ~(V) are preferred.

In the above general formula (II), R and R2 may be the same or different, and include a hydrogen atom, an alkyl group, an alkyl group,
An aryl group, an arylsulfonyl group, an alkoxycarmenyl group, R3 is a halogen atom, R3 is a hydrogen atom, and R3 is a group represented by the following general formula (Vl).

0H In the above formula ([), Bo and R2 are the same as 1 and R2 in the general formula (n), and R4 is a covalent group having a carbon atom number of 1 to /-. t-represent.

Among the compounds represented by the above general formula (II), R3eH
In the case where FLl and 几 are a hydrogen atom or an alkoxycarbonyl group, and when R3 is a group represented by the general formula ([), 8. is an alkyl group having 3 to 1 carbon atoms, a carbon atom
Preferred are a cycloalkylene group having j to 7 carbon atoms, an aralkylene group having rN/co carbon atoms, and SO□.

In the above general formula, the alkyl group represents a saturated or unsaturated alkyl group or a cycloalkyl group, which has a substituent such as an aryl group, an alkoxy group, an aryl group, a halogen atom, or a cyan group. Examples include phenylphenol, bisphenol sulfone, p-phenylsulfonylphenol, p-tolylsulfonylphenol, his(J-vinyluda-hydroxyphenyl)sulfone, co, cohis(3-vinyl- ≠-Hydrodiphenyl)pro/Hydrogen, bis-3-allyl-≠-Hydroxyphenylsulfo/
, hexflu≠-hydroxybenzoate, 2.2'-
In dihydro, Cibife macrol, Co, Corbis(4A-hydroxyphenyl)pro/Hetin, Hiro, ≠I-Inviridenebis(Cormeterphenol)%/l/-Bis(J-
chloro-≠-hydroxyphenyl) cyclohegosan, /
, /-bis(j-/Rolow≠-diphenyl in hydro)-
λ-Ethylbutane, l, μ'-Secondary inoctylidene diphenol, Hiroshi, 4A'-5ec-Butylidene diphenol, "-p-methyl 7-enylphenol, μI-Inpentylidene diphenol, lI, μ ′−
Methylcyclohexy+) f7 diphenol, France, μ-nodihydroxydiphenylsulfide)', /, 4&-bis-(Reference I-hydroxycumyl) be/zene, /,! -Bisu(4c/-hydroxycumyl)be/zene, #, 4t
'-fobis(butyl-J-methylphenol), ≠ 4c/-dihydroxydiphenylsulfone, hydroquinone monobenzyl ether, hydroxybenzophenone, ko-dihydroxybenzophenone, polyvinylbenzyloxycarbonylphenol, ko, g, e'-trihydroxybenzophenone, co,
J', 4A'-tetrahydroxybenzophenone,
Dimethyl hydroxyphthalate, methyl hydroxybenzoate, etc.

≠, trihydroxydiphenyl sulfone,! ,j
= bis-p-hydroxyphenylpentane, diphenoxyhexane in /lt-bis-hydro, ≠-tolyl hydroxybenzoate, hiro-hydroxybenzoic acid α-phenylbenzyl ester, phenylzorobyl p-hydroxybenzoate, dihydroxybenzoic acid Phenethyl, ≠-p-chlorobenzyl hydroxybenzoate, p-methoxybenzyl hydroxybenzoate, p-methoxybenzyl hydroxybenzoate, benzyl ester of benzoate, μm hydrobenzoic acid-m
-Chlorobe/dyl ester, μm hydroxybenzoic acid β
-7 enether ester, μm and doroki 2′, lA′
- Dimedel diphenyl sulfone, β-7enethyl orheptalineate, cinnamyl olicerinate, orceric acid -
〇-Chlorophe/=? Diethyl ester, diethyl orseinate in 〇-ethylphenol, 7 in O-phenylphenol ethylorcev*-to, 7 in m-phenylphenol
Ethyl orseinate, co9μm dihydro-cybenzoic acid-β-3'-t-7'thyl-μI-hydroxyphenoxyether ester, /-t-;/thi-μmp-hy)oxyphenylsulfonyl-cybenzoic acid, a -N-benzylsulfamoylphenol, co,4L-dihydroxybenzoic acid-p-methylbenzyl ester, -2hiro-dihydroxybenzoic acid-β-phenoxyethyl ester,
Tip 4A-Dihydromethylbenzoic acid benzyl ester, bis-methyl hydroxyphenylacetate,
etc. can be mentioned.

X In the above formula, Lij represents a hydrogen atom, an aryl group or an alkyl group, and X represents an alkyl group, alkoxy f! Alternatively, the halogen atom gold M represents a zero-valent metal atom, and n represents an integer of / to 3. R and X may be bonded to each other to form a ring.

Note that the alkyl group represents a saturated or unsaturated alkyl group or a cycloalkyl group, and these include an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an aclaramino group, an aminocarbonyl group, and a cyano group. The aryl group may have a substituent, and the aryl group represents a phenyl group, a naphthyl group, or a heteroaromatic ring group, and these include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, and a cyano group. , substituted carbamoyl group,
It may have a substituent such as a substituted sulfamoyl group, a substituted amino group, a substituted oxycarbonyl group, an Ilt-donating oxysulfonyl group, a thioalkoxy group, an arylsulfonyl group, or a phenyl group.

Among the substituents represented by the above formula sil, a hydrogen atom, a phenyl group, and an alkyl group having fi/~2 carbon atoms are preferable; among the substituents represented by X, an allyl group having fi/~2 carbon atoms, a carbon Preferred are alkoxy groups having an atomic number of 1 to 0, chlorine atoms, and fluorine atoms. Among the metal atoms represented by M, zinc, aluminum, magnesium, and calcium are preferred.

Among the substituents of the alkyl group and alkoxy group represented by An atom or an alkoxycarbonyl group is preferred.

From the viewpoint of water insolubility, the salicylic acid derivative according to the present invention preferably has a total number of carbon atoms of /4I or more, particularly preferably /4I or more. These may be used in the form of gold j14 clay, or they may be used, for example, by coexisting zinc oxide in the dispersion to cause salt formation, adsorption or double decomposition in the dispersion.

Next, a specific example will be shown.

≠-pentadecylsalicylic acid, 3-7 enylsa.

Lythyl fil, i-cyclohexylsalicylic acid, 3゜3
-di-t-butylsalicylic acid, 3. ! -didodecylsalicylic acid, 3-methyl-! -Benzylsalicylic acid, 3-
7enyl-j-(α,α-dimethylbenzyl) salicyl flll, J,! -C (α-methylbenzyl)
Salicylic acid! ,! -D-t-octylsalicylic acid,!
-Tetradecylsalicylic acid, J-hexadecylsalicylic acid,! -octadecyl salicic acid, z-α-(p-α-
Methylbenzylphenyl)ethylsalicylic acid, μm totecilyloxysalicylic acid, μmm teradecyloxysalicylic acid, ≠-hexadecyloxysalicylic acid, ≠-β-phenoxyethoxysalicylic acid, der β-p-tosylated oxysalicylic acid, Hiro-β-p- Edelpheno Life Ethoxysalicylic Acid β-p-Methoxyphenol Cisalicylic Acid, β-p-Ethoxyphenol Jetoxysalicylic Acid, β-m-Tolyloxyethoxysalicylic Acid, ≠-β-0-)Dyloxyeth medium cisalicylic acid, ≠-(r-phenoxyoctyloxy)salicylic acid, etc.

In the above formula, R represents a hydrogen atom, an aryl group, an alkyl group represents a halogen atom, X represents a hydrogen atom, an alkyl group, an alkoxy group represents a halogen atom, M represents a covalent metal,
n is 0. / or represents 2.

Specific examples include bis(co-hydroxy-!-butylphenyl) sulfone, bis(-1 and doro-go-shi!-phenylphenyl) sulfone, bis(2-hydroxy-!-octylphenyl) sulfone, bis(2-hydroxy-!-octylphenyl) sulfone, -!
-chlorophenyl) sulfone, bis(cohydroxy-3-chloro!-butylphenyl) sulfone, etc.
, nickel, magnesium salts, etc.

(Ru)2 Zn(A)2 (V) In the above formula, RF! , a monodentate or polydentate colorless organic ligand that is bonded to a lead ion through a heteroatom to form a complete complex,
A represents 5CNSα or a benzoic acid anion having an electron-withdrawing group.

Among the colorless organic ligands represented by 几, pyridine, imidazohequinoline, benzothiazole, benzimidazole or antipyrine ligands are preferred, and these include alkyl groups, cyano groups, alkoxy groups, phenyl groups, amino groups, formyl groups, etc. Specific examples include rhodan zinc imidazole complexes, cophenylimidazole complexes, picoline complexes, and pyridine/vinyl groups.
complex, λ-penzyli ξ dazole complex, penzimi f
/-h complex, 2, J-dimethyl-/-722-J-pyrazoline-! -o/complex, /-7enyl-comethyl-3-be/zyl-3-virazoline-! -on complex,
i-phenyl-coether-3-(coetherhegycil)-J-piazoline-! -one complex, /-7enyl-comethyl-3-isopropyl-3-pyrazoline-! −
on complex, /-phenyl-J,J-dibenzyl-pyrazoline-! -one complex, /-phenyl-λ-benzito-3
-Mesolupyrazoline-! -on complexes, etc. are rejected.

These may be used alone or in combination. Among these, electron-accepting compounds consisting of salicylic acid derivatives and metal salts are preferred, and zinc salts are particularly preferred.

The recording material according to the present invention has a color-forming part that absorbs light in the near-infrared region, has a sufficient color density, and is extremely stable, and hardly changes even with long-term light irradiation, heating, and humidification. Since it does not cause discoloration, it is particularly advantageous in terms of long-term preservation of records. In addition, when used as a heat-sensitive recording material, it is close to ideal as a recording material because it does not have the drawbacks that the uncolored part develops color and the color-forming body changes color or fades due to oils, fats, chemicals, etc. Has performance.

When used in thermal paper, the electron-donating colorless dye and the electron-accepting compound have a particle size of 10 μm or less, preferably 3 μm or less, in the dispersion medium.
The zero dispersion medium that is used after pulverization and dispersion to a particle size of μ or less is generally used as a zero dispersion medium. A water-soluble polymer water bath solution with a concentration of about J to 10% is used, and dispersion is carried out using a ball mill, sand mill,
This is done using a horizontal sand mill, attritor, colloid mill, etc.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably between 1:10 and 1:/, more preferably between 1:3 and 3:3 by weight. On the other hand, apart from the colorless colorless dye and the electron-accepting compound, calcium carbonate and/or zinc oxide are pulverized and dispersed in a dispersion medium. The amount of calcium carbonate and/or lead oxide used is 0 of the electron-accepting compound,! jN is preferably 20 times (weight ratio), particularly preferably /-10 times.In order to improve its thermal response, a thermofusible substance can be included in the thermosensitive coloring layer.

As an example of a preferable thermofusible substance, the following general formula (■) ~
()01) can be mentioned.

Ordinary, N) icON) 12 (X ) R, C0N) L- Ordinary 7 () 4)
In the formula, R-R is a phenyl group, pen!, respectively. Zyl group and these lower alkyl groups represent all halogen-substituted substances, R, and R are each an alkyl group having from 1 to 2 carbon atoms, and aryloxymethy' group 1, and 7 are hydrogen. or phenyl group.

In general formulas (■) to (XI), when the phenyl group or benzyl group represented by ~R4 is substituted with a lower alkyl group, the number of carbon atoms is / to r, preferably 7.
The above is 3 or less. When substituted with a halogen atom, fluorine is preferred. Also, formula (IX)
In, 几 and ′ represent hydrogen or a hydroxyl group.

x x' In the formula, A and B represent an oxygen atom or a sulfur atom, and R8 represents a covalent group, preferably an alkylene group, an alkylene group having a carbonyl group, an alkylene group having a halogen atom,
An alkylene group having an unsaturated bond, more preferably an alkylene group or an alkylene group having an ether bond. M9X%Y, Z.

X', Y', and Z' may be the same or different and represent a hydrogen atom, a halogen atom, an alkyloxycarbonyl group, and an aralkyloxycarbonyl group.

The compounds of the general formulas (■) to ('A) have a melting point of 70°C.
That’s 1! It is preferably below O@C, and more preferably above melting point to''c and below iso'c.Specifically, benzyl p-benzyloxybenzoate (mp
, / /ri0C), β-naphthylbenzyl ether (
mp, /□j”c), stearic acid amide (mp, 10
r'C), palmitic acid amide (mp, /03
°C), N-phenylairy/acid amide (mp, ri4
@C), N-stearylurea (mp, /10'C),
β-naphthoic acid phenyl ester (mp, taco@C),
/-HydroΦcyconaphthoate phenyl (mp, ri J
``C), β-naphthol (p-chloroy/sil) ether (mE), //j 'C), β-naphthol (p-methylbenzyl) ether (mp, PJ@C), α-naphthylbenzyl ether ( mp.

7bu@C), /, goobutanediol-p-methylphenyl ether (mp, RiJ'c), /, goupropanediol-p-methylphenyl ether (mp, 23
°C), stearic acid amide [mp, / 04~/
09 @C), / , 4C-purfudiol-p-isopropylphenyl ether (mp.

7ri'c), /, goubutanediol-p-t-octylphenyl ether (mp, Tata 0C], cophenoxy/-p-tolyl-oxy-ethane (mp, 10
≠@c), /-phenoxyco(≠-ethylphenoxy)ethane (mp, 104'C), t--y enoxy-
λ-(≠-chlorophenox)ethane (mp, 77°C
), /, Hiro-butanediol phenyl ether (mp,
PIrllC), diethylene glycol-bis(≠-methoxyphenyl)ether (mp, 10/''C),
p-z tylphenoxyacetic acid benzylamide (rnp, ri≠@C>, phenylacetic acid benzylamide (mp, /co≠
``C) etc.

The thermofusible substance may be used alone or in combination, and in order to obtain sufficient thermal responsiveness, it is preferable to use it in an amount of 70 to JOOt in the electron-accepting compound. The amount used is preferably 20 to 730% by weight.

Additives satisfying various requirements are further added to the coating liquid obtained by mixing the dispersion liquid thus obtained in an appropriate ratio.

Examples of additives include oil-absorbing substances such as inorganic pigments and polyurea fillers dispersed in the binder to prevent the recording head from becoming dirty during recording, and to improve the releasability of the head. Fatty acids, metal soap, etc. are added to increase the concentration. Therefore, in addition to colorless dyes and electron-accepting compounds that contribute to color development, pigments, waxes, @antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, surfactants, hindered phenols, etc. , additives such as benzoic acid derivatives are applied onto the support, and the recording material is constructed.

Specifically, pigments such as kaolin, calcined kaolin, Merck, diatomaceous earth, aluminum hydroxide, magnesium hydroxide, mineral richness, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, micro Balloon, urea-formalin filler, polyethylene particles, cellulose filler, etc. particle size O
1/ or l! Selected from μ. Examples of waxes include paraffin wax, carbo-oxidized norahin wax, carnauba wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Examples of the metal soap include polyvalent metal salts of higher fatty acids, such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate.

The hindered phenol is at least λ or 6
A phenol anchor conductor in which one or more of the positions is substituted with a branched alkyl group is preferred.

For example, /, l-bis(comethyl-≠-hydroxy-j-t-butylphenyl)buta/, ll/, j-)
Lis(J-methyl-hydroxy-j-1-7'tylphenyl)sita/, bis(=-hydroxy-1-t-butyl-!-methylphenyl)methane, bis(-monomethyl-hydro)7 -!-t-butylphenyl) sulfide, etc.

These are dispersed and applied in a binder.

Is it electron-withdrawing as a benzoic rR derivative? Metal salts of benzoic acid having: / or more are preferred, specifically halogen-substituted benzoic acid, nitrobenzoic acid, 7-anobenzoic acid, substituted sulfonylbenzoic acid, acylbenzoic acid, carbamoylbenzoic acid, alkoxycarbonylbenzoic acid, substituted sulfamoylbenzoic acid. Examples include zinc salts, aluminum salts, cadmium salts, magnesium salts, calcium salts, etc. of acids. Particularly preferred are zinc salts. These are also used as electron-accepting compounds and mixed with the aforementioned electron-accepting compounds'! Next, it is applied separately and dispersed. Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxyglobil cellulose,
Epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, inbutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivative, casein , gelatin, etc. In order to impart water resistance to Mayukon et al.'s binder, a water-resisting agent (gelling agent, cross-linking agent) was added, and an emulsion of a hydrophobic polymer, specifically styrene-
Butadiene rubber latex, acrylic resin emulsion, etc. can also be added. The coating liquid is coated on base paper, high quality paper, synthetic paper, plastic sheet or neutral paper.
/m2 is applied.

Furthermore, the resistance can be improved by providing a protective layer of about O2λ to 2μ consisting of a water-soluble or water-dispersible polymer compound such as polyvinyl alcohol, hydroxyethyldenbide/or epoxy-modified polyacrylamide, and a crosslinking agent on the coated surface layer. can.

In addition, when used for thermal paper, OL8.2-2tItI
No., same name / / Or! ≠, Tokko Akira! --The aspects of practice described in KoO7@2 etc. can be understood. Alternatively, all operations such as preheating, v4 moistening, and stretching of coated paper can be performed prior to printing.

(Examples of the Invention) Examples will be shown below, but the present invention is not limited only to these examples.

Example 1 Cordiethylamino-dibutylaminothiofluorane IO? which is an electron-donating colorless dye. and J-o-chloroanilino-bu-dibutylaminofluorane IO? , electron-accepting compound Roda/zinc J + j y
Methyl-7-phenyl-3-pyrazoline-! -one complex CoO21 thermofusible material Ruruichi benzilo-sinaphthalene 209 was dispersed in a ball mill overnight with 100 tons of 1% polyvinyl alcohol (CranPVA 1oz) aqueous solution to give a volume average particle size of 3μ. On the other hand, a mixture of calcium carbonate and zinc oxide was dispersed in a homogenizer together with 1 toy of a 003% solution of sodium hexametaphosphate.

Disperse each dispersion as described above, electron-donating colorless dye dispersion IP, NL electron-accepting table-accepting compound dispersion, fusible substance dispersion Jf, calcium carbonate and zinc oxide dispersion Coco? Then, 4tr of emulsion of zinc stearate and 2% aqueous solution of sodium sulfosuccinate!f! were added to obtain the entire coating liquid.This coating liquid had a basis weight of 109/ After drying, the mixture was coated on a high-quality paper with a wire spar to a coated amount of 477 m 2 , dried for 1 minute in a TO'C oven, and calendered to obtain a coated paper.

When colored using Fujitsu High Speed Facsimile pp=sooof, a green-black image was obtained. This colored image has light absorption in the near-infrared region, and when the filter paper is impregnated with ethanol and castor oil and superimposed on the colored side of the recording paper obtained by the above method, the white part is capri and colored. Discoloration (discoloration) of the parts is rarely observed.

Meanwhile, the obtained coated paper was heated to BO”C,JO%R)i)
Although the film was stored under conditions of high humidity (4Ao'c, %RH) for 2≠ hours, almost no fogging occurred.

Examples 2 to 4 Coated paper was obtained in the same manner as in Example 1 except that the following dyes were used in place of the electron-donating colorless dye in Example 1.

Example Co Co〇-octylamino-6-ethylaminothiofluoranchoQ? Example J 2-Piperidino-4-dibutylaminothiofluoran oy Example 4A Cordiethylamino-t-dimethylaminothiofluor 2nd 10f and 3. -bisdiederamino-J-diethylaminospiro(isobenzo7-l)
, 2'-Fluorene) 31-one IOf Examples 5 to 9 In place of the electron-accepting compound of Example 1, the following were used, and otherwise the same procedure as in Example 1 was carried out to obtain a cloth paper. t.

Example! 3-penzylco-methyl-7- of rhodan zinc
Phenyl-J-t'Lasoline! -On complex Example 6 Rodan zinc co(coethylhexyl)-
3-Methyl-/-phenyl-3-pyrazoline-! -one complex example 7 co,3-dibenzyl-7-phenyl-3-pyrazoli7-j-one complex example r of rhodan zinc co-inbropyruJ-methyl-/-phenyl-
3-Pyratholine! -one complex actual m%JP The colored images of the 3-phenyl-cometeru/-phenyl-J-piazolin-j-one complex of zinc rodan each have light absorption in the near-infrared region, and they exhibit psychokinesis. There was also less yellowtail.

Claims (1)

[Claims] A recording material characterized by containing a thiofluorane derivative having substituted amino groups at the 2- and 6-positions and an electron-accepting compound.