JPS6362779A - Recording material - Google Patents

Abstract

PURPOSE:To provide a recording material having a good color forming property and good raw preservability and imparting a developed color image having good stability, by using a specific phthalide compound as an electron donating leuco dye forming a color upon the contact with an electron acceptive compound. CONSTITUTION:As an electron donative leuco dye, a phthalide compound having a part represented by Ar(XCnH2n)m- (wherein Ar is an aromatic ring, n and ma are in integer, X is -O-, -S- or -NR- and R is a hydrogen atom, an alkyl group, an acyl group or an aryl group) is used. As the phthalide compound, a triarylmethanephthalide forming a fluorane ring by heat-treatment at about 70-300 deg.C is pref. and, when an org. acid, an inorg. acid and a solid acid coexist at this time, a dye having the fluorance ring is formed and an image having depth due to the effect of Ar(XCnH2n)mOH separated at this time is obtained. In this phthalide compound, a compound having m.p. of 45-250 deg.C and solubility of 3 or less to hot water at 50 deg.C is especially pref.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and more particularly to a recording material with improved color development, shelf life, and stability of colored images.

(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/80μ≠ri, US patent 4c4c1
0012, same u4cJtW20, JP 60-23, Octopus λ, JP 7-/7P, rat, tO-123,
! rj&, same 6O-t23. Familiar with JJT etc.

The performance that a recording material should have is (1) sufficient color density and color development sensitivity, (2) no fogging, (3) sufficient fastness of the color material after color development, (
4) Appropriate color hue and suitability for copying machines, (57S
/N ratio should be high, and (6) the color former should have sufficient chemical resistance, but currently there is no product that completely satisfies these requirements.

Especially in recent years, as recording systems have become faster and demands have become more diverse,
Research into improving these characteristics is being carried out intensively.

The present inventors have discovered that the characteristics of the recording material can be greatly improved by incorporating a unique idea into the substituent portion of the colorless dye. In particular, as will be described later, its properties are significantly improved when used in combination with a specific ether compound.

(Object of the Invention) Therefore, the object of the present invention is to provide a recording material using a material that has good color development properties, shelf life, and stability of colored images, and also satisfies other necessary conditions.

(Structure of the Invention) An object of the present invention is to provide a recording material that utilizes the phenomenon in which a colorless dye is colored when it comes into contact with an electron-accepting compound.
This was achieved by developing a recording material characterized by using a phthalide compound having a moiety represented by XCn H2n )'m-.

In the formula, Ar represents an optionally substituted aromatic ring, and n represents an optionally substituted aromatic ring.

m represents an integer, and X represents 10-1-S-1 or -NR-. R represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.

Particularly preferred is the case where the above-mentioned phthalide compound is a triarylmethane phthalide compound which forms a fluoran ring by heat treatment at about 70°C to 3000°C. , in which case organic acids, inorganic acids,
Needless to say, if a solid acid is present, a dye with a fluorane ring will be formed. A who left at that time
An image with depth can be obtained due to the r(XCnH2n)mOH effect.

On the other hand, such a phenomenon is not observed when R2 and R4 are lower alkyl.

Among the above-mentioned phthalide compounds, those with a melting point of ur'c to 2
Compounds having a jf00C, preferably 7!0C to 2000C, and a jOoC solubility in hot water of 3 or less, preferably 1 or less, are particularly preferred.

In the above formula, n is preferably 6 or less, and m is particularly preferably λ or 3. Most preferably n is ko, 3 or hiro. X is preferably 10-. R is preferably an alkyl group or an acyl group. The number of carbon atoms is desirably less than or equal to it.

Ar is a substituted group such as a halogen atom, hydroxy group, alkyl group, alkoxy group, aryl group, acyl group, alkoxycarbonyl group, carboxyl group, alkylamino group, arylamino group, acylamino group, ureido group, urethane group, thiourido group, etc. It may have a plurality of substituents having a carbon number of IO or less, such as an optional amino group, a sulfo group, a cyano group, a carbamoyl group, and a sulfamoyl group.

The moiety represented by Ar(XCnzn)hl- is preferably bonded to the λ or 2'-position in the diarylphthalide colorless dye. - Preferred compounds are represented by the following general formula.

In the general formula, mA and B represent an aromatic ring which may have a hetero atom.

R□ is an amine residue, R3 represents a hydrogen atom, an alkyl group, a substituted amine group, an alkoxy group, or an atomyl group, and R1 and R3 may form a J-membered or t-membered term. R2, R4
is selected from a hydrogen atom, Ar(XCnH2n)m, an alkyl group, an alkoxy group, a hydroxy group, an acyloxy group, and an alkylthio group, and at least one of them is an Ar(XCnH2n)
H2n)m.

] As mA and B, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an indole ring, etc. are preferable.

These rings include alkyl groups, acyl groups, acylamino groups,
It may be substituted with one or more of an arylamino group, a halogen atom, a substituted carbamoyl group, a substituted sulfamoyl group, a hydroxyl group, an aryl group, a ureido group, an alkoxy group, an aryloxy group, an aryloxycarbonyl group, and the like.

A particularly preferred compound is represented by the general formula (2).

In the general formula (■), R5 and R are hydrogen atoms, alkyl groups,
Aryl groups such as ethyl group, inamyl group, phenoxyethyl group, butoxyethyl group, β-phenoxyethoxy group, furfurylmethyl group, isodutyl group, pyridylethyl group, dodecyl group, vinylbenzyl group, β-methacrylamidoethyl group, tolyl group Selected from the following. Y represents a carbon atom or a nitrogen atom.

Particularly preferred among these is the case where ring B is represented by the following formula.

R7,81 is selected from a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an aryloxy group, a substituted amino group, an acylamino group, an arylamino group, an alkoxy group, an acyl group, a carbamoyl group, a ureido group, and the like.

From the viewpoint of forming a recorded image of black phase, R7 is a group selected from an alkyl group, a halogen atom, and an aryl group, and R8
is a substituted amino group, such as a β-ethoxyethylamino group,
The case of β-chloroethylamino group and anilino group is preferred.

An example of the phthalide compound of the present invention is as follows. 0 j-(J-hydroxy-μm diethylaminophenyl) with emphasis on the case where X is 10-
-J-(J-β-phenoxyethoxy-μm diethylaminophenyl)phthalide, 3-(2-β-P-phenylphenoxyethyl≠-diethylaminophenyl)-J-
(Cortatilindole-3-yN)phthalide, 3-(
co-hydroxy-μm diethylaminophenyl)-j-
(2-β-phenoxyethoxy-≠-methylteranilinophenyl)fluoran, J-(J-hydroxy-≠
-N-ethyl-N-yneamylaminophenyl)-3-
<2-β-P-phenylphenoxyethoxy-μm methyl-t-anilinophenyl)fluoran,! -(2-ethoxy-μm dibutylaminophenyl)-j-(,2-
β-P-ethoxyphenoxyethoxy-butsu-chloro-yo-β-ethoxyethylaminophenyl) phthalide, J-
(,2-hydroxy-a-N-ethyl-N-toluidinoterphenyl-phenyl)-j-(,2-β-P-phenylphenoxypropoxy-μmchloro-y-β-chloroethylaminophenyl)phthalide , 3-(2-Hydroxy-Hiro-N-ethyl-N-isophthylaminophenyl)-3-(2-β-P-cyclohexylphenoxyethyloxyethoxyh-methyl-yo-anilinophenyl)phthalide , 3-(2-hydroxy-≠-N-ethyl-N-β-hyricylethylamino!-)uni/l/-
7enyl)-J-(J-β-phenoxypropoxy-methyl-j-anilinophenyl)-azaphthalide, and the like.

It is desirable to use two or more types of colorless dyes, and it is also possible to use two types of the above-mentioned compounds, or to use other colorless dyes, such as already known triphenylmethane phthalide compounds, fluoran compounds, and phenothiazine compounds. compounds, indolylphthalide compounds, leucoauramine compounds,
It can also be selected from various compounds such as rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, and spiropyran compounds.

Some examples include triarylmethane compounds,
3.3-bis(p-dimethylaminophenyl)-roudimethylaminophthalide, 3. j-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(/.

3-dimethylindol-3-yl)phthalide, 3-(
p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, etc., and examples of diphenylmethane compounds include Hiromu.

μ'-Histodimethylaminobe/Zhydrin benzyl ether, N-halophenyl-leucoolamine, N-'
I"#'-trichlorophenylleucoauramine, etc., and xanthine compounds include rhodamine-B
-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, 2-dibenzylamino-6-diethylaminofluorane, 2-anilino-6-diethylaminofluorane, co-anilino 3-methyl-6 -dinitylaminofluorane, coanilino 3-methyl-6-cyclohexylmethylaminofluorane, 2-o-chloroanilino-
t-diethylaminofluorane, λ-m-10roanilino-6-diethylaminofluorane, λ-('s”-dichloroanilino)-4-diethylaminofluorane, λ
-ogtylamino-6-diethylaminofluorane, cone hexylamino-6-diethylaminofluorane,
Coated IJ fluoromethylanilino-6-dinithylaminofluorane, λ-butylamino-3-chlorot
-diethylaminofluorane, coethoxyethylamino-3-chloro-6-diethylaminofluorane, 2-
p-10 Roanilino-3-methyl-6-dibutylaminofluorane, coanilino-3-methyl-6-thiocteraminofluorane, 2-anilino-3-chloro-6-
Diethylaminofluorane, 2-diphenylamino-6
-diethylaminofluorane, 2-anilino-3-methyl-6-diphenylaminofluorane, 2-phenyl-
6-diethylaminofluorane, co-anilino-3-methyl-4-N-ethyl-N-ynamylaminofluorane, 2-anilino-3-methyl-! -dichloro-6-dinithylaminofluorane λ-anilino 3-methyl-6
-Dinithylamino-7-methylfluorane, coanilino-3-methoxy-6-cyptylaminofluorane, 2
-,-chloroanilino-6-cyptylaminofluora 7
．． 2-p-chloroanilino-3-ethoxy-6-N-ethyl-N-isoamylaminofluorane, 2-o-chloroanilino-6-p-butylanilinofluorane, co-anilino 3-pentadecyl-6-diethylaminofluoran/ , 2-anilino-3-ethyl-t-dibutylaminofluorane, co-anilino 3-)f-μ′,! ′
-dichlorofluorane, co-o-toluidino 3-methyl-6-diitupropylamino p/, z/-
dimethylaminofluorane, λ-anilino-3-ethyl-AN-ethyl-N-isoamylaminofluorane,
Co-anilino 3-methyl-6-N-°ethyl-N-γ
-methoxypropylaminofluorane, co-anilino 3-chloro-4-N-ethyl-N-isoamylaminofluorane, etc. Thiazine compounds include penzoyl leucomethylene/blue, p-nitrobenzoyl leucomethylene blue, etc. As a spiro compound, 3
-Methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-cyclolosevirodinaphthopyran, 3-benzylspiro-dinaphthopyran,
Examples include 3-methyl-naphtho-(3-methoxy-benz)spiropyran and 3-propyl-spiro-dibenzopyran, with phthalide compounds, fluoran compounds, and triarylmethane compounds being particularly preferred. these are! It is used approximately 70% to 70% of the time.

Examples of electron-accepting compounds that impart color upon contact with colorless dyes include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, Nozerak resin, metal-treated novolak resin, μ-tert-butyl 3- Ethylphenol, μ-p-cyanophenylphenol, Co.

2-bis(4cm hydroxyphenyl)pro/en, 4
c, μ'-isopropylidene bis(3-methylphenol), /, l-bis-(3-chloro-Hiro-hydroxyphenyl)cyclohexane, /, /-bis(j-chloro-Hiro-hydroxyphenyl)-2 -ethylbutane, g
, l -secondary-isooctylidene diphenol,
μmtert-octylcochlorophenol, ≠, Hiro'-isobutylidenephenol, darkchlorophenylphenol, μ, μ'-inotylidenediphenol, p,≠'-methylcyclohexylidene diphenol, 4cllAl-dihydroxydiphenyl sulfide , i, a-bis-ψ'-hydroxy3'-carboxycumylbenzene: /, /, J-bis-≠'-hydroxycumylbenzene, ! , u'-thiobis(&-tert
-butyl-3-methylphenol), l, μ'-dihydroxydiphenylsulfone, hydroquinone monoindylethe) Lt, J, 4A-dihydroxy≠'-butoxybenzophenone, 2゜hiro-dihydroxybenzophenone, polyvinyl benzyloxyl Luponylphenol, 2. IA, 4L'-trihydroxybenzophenone, λ, 2', 4c.

μ′-tetrahydroxybenzophenone, μm dimethyl hydroxyphthalate, ≠-methyl hydroxybenzoate,
Co, 44.4t'-)lyhydroxydiphenylsulfone, l,! -bis-p-hydroxyphenylintane, I
, 6-bis-p-hydroxyphenoxyhexane, ≠-
Hydroxybenzoic e-tolyl, ≠-Hydroxybenzoic acid α
-Phenylbenzyl ester, μm phenylpropyl hydroxybenzoate, μm phenethyl hydroxybenzoate, p-chlorobenzyl hydroxybenzoate, μm
Hydroxybenzoic acid p-methoxybenzyl, Hiro-hydroxybenzoic acid benzyl ester, μ-hydroxybenzoic acid-m-phlolobenzyl ester, μm Hydroxybenzoic acid β-phenethyl ester, Hiro-hydroxy-2′
, lA'-dimethyldiphenylsulfone, β-phenethylorseinate, /-(≠-hydroxyphenyl)-
/-(-?-Carboxy μm hydroxyphenyl) Schift tube hexane zinc salt, cinnamyl orselinate, orselic acid-〇-chlorophenoxyethyl ester, 0-
Ethylphenoxyethyl orselinate, 0-phenylphenoxyethyl orselinate, m-phenylphenoxyethyl orselinate, 2,≠-dihydroxybenzoic acid-β-3/-t-butyl-μ'-hydroxyphenoxyethyl ester, /-i-butyl-≠-p-hydroxyphenylsulfonyloxybenzene, μ-N-
Benzylsulfamoylphenol, Co, Hiro-dihydrox7benzoic WR-p-methylbenzyl ester, λ.

France-cyhydroxybenzoic acid-β-phenoxyethyl ester, s, 4cm dihydroxy-6-mefbenzoic acid λ', t'-dimethoxybenzyl ester, bis-guhydroxyphenylacetate cy/namyl, ditolylthiourea, μ , tA/-diacetyldiphenylthiourea, 3
-Phenylsalicylic acid, t-p-α-methylbenzyl-
α-Methylbenzyl salicylic acid 1. t-p-methoxyphenoxyethyloxysalicylic acid,! -phenoxyethoxysalicylic acid, jp-benzyl-α-methylbenzyl salicylic acid, 3-xylyl-! -(α,α-dimethylbenzyl)salicylic acid, 3. ! - Aromatic carboxylic acids such as di(α-methylbenzyl)salicylic acid, co-hydroxyl-α-ethylbenzyl-3-naphthoic acid, 3.
j-di-cyclo is ntadienylsalicylic acid, para-phenylphenol-formalin m fat, /l/-bis(3-
carboxy-Hiro-hydroxyphenylcyclohexane)
, organic color developers such as phenolic resins such as para-butylphenol-acetylene resins, and salts of these organic color developers with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, etc. and hydrohalic acids such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, boric acid, silicic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid, and halides such as aluminum, zinc, nickel, tin, titanium, and boron. Inorganic acids such as acid clay, activated clay, achinolugite, bentonite, colloidal silica, aluminum silicate, magnesium silicate,
Inorganic color developers such as zinc silicate, tin silicate, zinc rhodan, zinc chloride, iron stearate, cobalt naphthenate, nickel peroxide, ammonium nitrate, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid, etc. Aliphatic carboxylic acid, benzoic acid, paratertiary butylbenzoic acid,
One or more types of phthalic acid, gallic acid, etc. may be used in combination.

When these colorless dyes and electron-accepting compounds are applied to recording materials, they are used in the form of fine dispersions or fine droplets.

When used with pressure sensitive paper, U.S. Patent No. λ, RIO! , 47
No. 0, same, 2. ! 0! , 4!7/issue, same co.

rot, 4Lry, same 2. ! 44F, No. 344,
same,! , 7/2. Jf07, same, 2,730,1Aj
No. 1, No. 2,730. μ! No. 7, same JIOJIAO≠
No. 3. Various forms are available as described in patents such as UTR, SJA, and UOt00Jr. Most commonly, they consist of a pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

A method of manufacturing capsules is described in a US patent.

A method using coacervation of a hydrophilic colloid sol described in the same issue J, Too, Tire, UK patent! f47,727, 930.4
c4! J issue, same t, 26≠ issue, same l.

Examples include the interfacial polymerization method described in U.S. Pat.

In general, electron-donating colorless dyes are used alone or in combination in solvents (alkylated naphthalene/, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl,
Synthetic oils such as chlorinated paraffin; Vegetable oils such as cotton oil and castor oil; Animal oils; Mineral oils and mixtures thereof)
After dissolving it in microcapsules,
A color forming agent sheet is obtained by coating a transparent or opaque smooth support such as paper, high-quality paper, plastic sheet, resin coated paper, etc.

In addition, an electron-accepting compound, alone or in combination, or together with other electron-accepting compounds, is dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol.
A developer sheet is obtained by coating a support such as resin-coated paper.

The amounts of the electron-donating colorless dye and the electron-accepting compound to be used depend on the desired coating thickness, the form of the pressure-sensitive copying paper, the capsule manufacturing method, and other conditions, and may be appropriately selected depending on the conditions. It is easy for one skilled in the art to determine this amount to use.

When used in thermal paper, the electron-donating colorless dye and the electron-accepting compound have a concentration in the dispersion medium of IOμ or less, preferably 3
It is used after being crushed and dispersed to a particle size of μ or less. A water-soluble polymer aqueous solution having a concentration of about 0.2 J to 10% is generally used as the dispersion medium, and dispersion is carried out using a ball mill, a sand mill, a horizontal sand mill attritor, a colloid mill, or the like.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably between l:10 and i'', o, and t, and particularly preferably between l:1 and 2=3. At that time, aromatic ether compounds such as JP-A No. 5-7
．． It is particularly preferable to use aromatic alkyl or substituted alkyl ethers disclosed in RIRY, 5ir-r7.0 and RI. Such ether compounds include phenoxyethyl biphenyl ether, phenethyloxybiphenyl, benzyloxynaphthalene, benzyloxybiphenyl, di-m-)lyloxyethane, β-phenoxyethoxyanisole, lniphenoxy-2-p-ethylphenoxyethane or bis- β-(p-methoxyphenoxy)ethoxymethane / -,2/-methylphenoxy-ethylphenoxyethane, l-tolyloxy-chole-methylphenoxyethane%'
1.2-diphenoxyethane, /, IA-diphenoxybutane, bis-β-(p-ethoxyphenoxy)ethyl ether, l-phenoxy-λ-p-chlorophenoxyethane, l-λ'-methylphenoxy Ethers such as co≠“-ethyloxyphenoxyethane, l-≠′-methylphenoxyco μ“-fluorophenoxyethane or l-phenoxyco p-naphthoxyphenylthioether %'1 cobi-p-methoxyphenylthioether, / + It is particularly preferable to use compounds such as +fluoroxy-col-methoxyphenylthioether, /, 2-bis-p-methoxyphenylthioethane, and the like. Furthermore, amides such as stearic acid anisidide, phenoxyacetylbenzylamide, p-chlorophenoxyacetylphenethylamide, and stearic acid amide can also be used in combination. These are used in finely dispersed form at the same time as a colorless dye or at the same time as an electron-accepting compound. In particular, it is preferable to disperse the colorless dye at the same time from the viewpoint of preventing fogging.

The amount of these to be used is added at a weight ratio of 10% or more and 300% or less, particularly preferably 4cO% or more/jO% or less, based on the electron-accepting compound.

Additives are further added to the coating liquid obtained by pressing in this manner to meet various requirements.

Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers in the binder in order to prevent the recording head from becoming dirty during recording, and also to improve releasability from the head. For this reason, fatty acids, metal stones, etc. are added. Therefore, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, hindered phenols, and surfactants are generally used. Additives such as these are coated on the support to form a recording material.

Specifically, pigments such as kaolin, calcined kaolin, talc, zinc oxide, aluminum oxide, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, carbonic acid Barium, barium sulfate, mica, microballoon, urea-formalin fizzy, polyethylene particles, cellulose filler, etc. particle size 0. / or l
! Selected from μ. Among these, at least one of them is preferably a solid acid or a solid base.

Examples of waxes include paraffin wax, carboxy-modified paraffin wax, cownaparow wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Examples of the metal soap include higher fatty acid polyvalent metal salts, ie, zinc stearate, aluminum stearate, calcium stearate, zinc oleate, and the like. As a hindered phenol, polybutylated cyclohexylidene diphenol, /, /,! ,-) Lisu j-t-
Examples include butyl-pi-hydroxy-6-methylphenylbutane.

These are dispersed and applied in a binder.

Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride. Examples include copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch conductors, casein, and gelatin. In addition, in order to impart water resistance to these binders, water-resistant agents (gelling agents, cross-linking agents) are added, or emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic resin emulsions, etc. You can also add

Furthermore, for the purpose of imparting chemical resistance to the surface of the coating layer, a gelatinizer (0, 2 to 2) consisting of a water-soluble polymer compound such as polyvinyl alcohol, hydroxyethyl starch, or epoxy-modified polyacrylamide and a gelling agent (hardening agent) is added. A layer of about 2μ can also be provided.

The coating fluid is most commonly applied onto base paper, fine abrasive or synthetic paper, preferably neutral paper.

Generally, the coating amount is 2~/Op/m2 as solid content.
Used to some extent.

When used for thermal paper, 0LS2ko21jtf/
No., same, l/10IJ”, Tokukosho!λ-20/442
Various embodiments are adopted such as those described in 5.

Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

For example, the electrically conductive thermal paper is published in Japanese Patent Publication No. 2003-110010.
-4ct No. 30 and the like. In general, a coating liquid in which a conductive substance, a basic dye mainly containing the fluoran derivative of the present invention, and an electron-accepting compound are dispersed together with a binder is applied to a support such as paper, or a conductive substance is coated on the support to conduct electricity. The electrically conductive thermal paper of the present invention is produced by forming a layer and applying thereon a coating liquid in which a colorless dye, an electron-accepting substance, and a binder are dispersed. Note that the sensitivity can also be improved by using the thermofusible substance described above in combination.

The photosensitive pressure sensitive paper is manufactured, for example, by the method described in Japanese Patent Application Laid-open No. 2003-120003. In general, a photopolymerization initiator such as silver iodobromide, silver bromide, silver behenate, Michler's ketone, henzin derivative, benzophenone derivative, etc. and a polyfunctional monomer such as a poly(V) compound, poly-(meth)acrylate, poly(meth)acrylamide, etc. A cross-linking agent such as polyether urethane, polyurea, etc. is encapsulated in a synthetic resin wall capsule such as polyether urethane, polyurea, etc. together with a colorless dye and optionally a solvent. After imagewise exposure, the colorless dye in the unexposed area is brought into contact with a color developer and colored, and was developed by the present inventors.

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

Example 1 (li) Preparation of sample 1 3 (2-hydroxy-φ-jethylaminophenyl)-
3-(2-β-phenoxyethoxy-￥-methyl-teranilinophenyl)phthalide Hiroshig12-anilino 3-
2 g of each methyl-6-dinithylaminofluorane was dispersed with a 2% aqueous polyvinyl alcohol solution using a sand mill to give an average particle size of μ.

On the other hand, p-hydroxybenzoic acid benzyl ester/O
p,β-p-ethoxyphenoxyethyl-p-hydroxybenzoate o,rg and/-phenoxy-2-p
- Ethyl phenoxyethane/lrg is dispersed with a 3% polyvinyl alcohol aqueous solution ROG in a ball mill overnight. Furthermore, /, /.

3-tris-2'-methyl-μ'-hydroxyt'-
t-Butylphenylbutane 0. /, 81! % polyvinyl alcohol aqueous solution overnight.

Mix this well, then add zinc oxide, 10. Add fine particle silica+, PV (disperse,
In addition, paraffin wax emul 93750% dispersion (
Middle East fat cellosol #≠21)≠,! I was added to prepare a coating liquid.

The coating liquid was applied onto neutral paper having a basis weight of rOp/m2 so that the solid content coating amount was A, 1777m2,
1. After drying at O'C for 1 minute, linear pressure AO kgW/crn
A coated paper was obtained by applying a super calender.

Coated paper is heated by facsimile with energy of 31 mJ/
When the color was developed by heating at m2 and the color density was determined, it showed 1.0 with a Macbeth reflection densitometer.

The obtained recording material had no fogging during raw storage and had excellent stability over time. On the other hand, the obtained colored image was clear black and showed good resistance to chemicals, sunlight, etc.

Example 2-anilino-3-methyl 2-anilino-3-methyl-6-dinithylaminofluorane was substituted for β-resorcinic acid-β-phenoxyethyl ester, p-hydroxybenzoic acid benzyl ester, in Example 1. -A-N ethyl-
A coating liquid was obtained in the same manner except that N-isoamylaminofluorane was used.

The coating solution was applied to high-quality paper coated with calcium carbonate on neutral paper so that the coating solution was applied to is jl/m2.
Dry as well.

When color was developed according to the method of Example 1, a clear black image was obtained, and the reflection density was 0. It was an octopus.

Example 3 3(2-Hydroxy-Hiro-diethylaminophenyl)-j-(λ-β-phenoxyethoxy-Hiro-nomethyl-anilinophenyl)phthalide of real mfl was converted to 3C2-hydroxy-≠-N-ethyl-N-yne. amylaminophenyl)-3-(2-β-p-ethoxyphenoxyethoxy-Hiro-methyl-yo-anilinophenyl)phthalide, /-phenoxy-λ-p-ethylphenoxyethane was used as l9.2-bis- m-methylphenoxyethane/.

A recording material was prepared in the same manner except that a 1:1 mixture of λ-bis-p-methoxyphenylthioethane was used.

When color was developed according to the method of Example 1, a black image was obtained. Fog during raw storage was extremely low (highly desirable as a recording material).

This black image was clear and showed excellent discoloration or fading even when exposed to oil or sunlight.

Claims (1)

[Claims] A recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, characterized by using a phthalide compound having a moiety represented by Ar(XCnH_2n)_m-. Recording materials. In the formula, Ar represents an aromatic ring, m represents an integer, and X represents -O-, -
It represents S- or -NR-, and R represents a hydrogen atom, an alkyl group, an acyl group, or an aryl group.