JPS6331787A - Recording material - Google Patents

Abstract

PURPOSE:To provide a recording material having favorable color forming property, raw preservability and stability of developed color images and having favorable solubility in aromatic solvents and paraffinic solvents, by using a specified compound as a colorless dye in a recording material utilizing color formation by the contact of an electron-donative colorless dye and an electron- acceptive compound. CONSTITUTION:A compound of the formula, wherein each of R and R' is an alkyl, R1 is an alkoxy-or aryloxy-substd. alkyl, each of R2 and R3 is an alkyl or aryl, and each of X, Y and Z is H, an alkyl, alkoxyl, aryloxyl, halogen or substd. amino, is used as an electron-donative colorless dye. The dye is a colorless or light-colored crystal, is highly soluble in organic solvents, and is rapidly developed into a blue color upon making contact with an electron- acceptive substance. The color-developed coloring matter is extremely stable as compared with a coloring matter formed from an existing color former, and is substantially unsusceptible to discoloration or fading even under long-time light irradiation, heating or humidifying, so that a record obtained can be preserved for a long time. In addition, the color former has excellent stability, and deterioration or coloring will not occur even after long-time preservation.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and in particular to a recording material using an electron-donating colorless dye and an electron-accepting compound that have improved color development, shelf life, and stability of colored images. related to recorded materials.

(Prior Art) Recording materials using electron-donating colorless dyes and electron-accepting compounds include pressure-sensitive paper, thermal paper, and photosensitive pressure-sensitive paper.

It is already well known as electrically conductive thermal recording paper.

For example, British patent 5ittoa≠9. U.S. Patent Hiroμro
o9ko, same≠≠3bu9ko0, special public Akiotsu 0~43.922
．． % Kaisho jt7-/79, 13t-same≦0-/23.
! ! All of them are familiar with 60-/j, 3.367, 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 development and suitability for copying machines - (51S
/N ratio is high, (6) the color former has sufficient chemical resistance, and (7) it is easily soluble in organic solvents, but currently there is no product that completely satisfies these requirements. stomach.

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

Conventionally, diphenylmethane compounds, triphenylmethane compounds, phthalide compounds, leucomethylene blue compounds, and the like have been known as compounds that develop a blue to blue-purple color. However, each of these compounds has drawbacks.

For example, -3,3-bis-(p-dimethylaminephenyl 1-J-dimethylaminophthalide (i.e., crystal violet lactone, CVL)) develops quickly and exhibits a deep blue color, but the light resistance of the colored image is extremely poor. In addition, 3,7-bis(
(dimethylamino)-10 benzoylphenothiazine (i.e., benzoyl leucomethylene blue, BLMBl has excellent light fastness in its color image Fi, but the color development is very slow and the color development with organic coloring agents is very poor. There are drawbacks.

The present inventors have investigated the oil solubility, water solubility, partition coefficient p-pKa, substituent ratio, substituent position, crystallization in short circumference for each of the electron-donating colorless dye and the electron-accepting compound. We have pursued the development of good materials for recording materials and recording materials, focusing on characteristics such as changes in solubility.

(Objective of the Invention) Therefore, the object of the present invention is to provide a material that has good color development, shelf life, and stability of colored images, and has good solubility in aromatic solvents and paraffinic solvents, and also meets other requirements. The aim is to provide mental recording materials using materials that are satisfactory.

(Structure of the Invention) The object of the present invention has been achieved by a recording material characterized in that a compound represented by the following general formula (I) is used as an electron-donating colorless dye.

In the above formula, R-R' is an alkyl group, R1 is an alkoxy or aryloxy-substituted alkyl group, -R2-R3 is an alkyl group, -X is an aryl group, Y-Z is a hydrogen atom, an alkyl group, Represents an alkoxy group, aryloxy group, halogen atom or substituted amine group.

The aryl group represents a phenyl group, a naphthyl group, or a heteroaromatic group; residual sulfamoyl group,
It may have a substituent such as a substituted amine 7 group, a substituted oxycarbonyl group, or a substituted oxysulfonyl group. Further, the alkyl group represents a saturated or unsaturated alkyl group or a cycloalkyl group, which may have a substituent such as an -aryl group-alkoxy group, an aryloxy group, a halogen atom, or a cyano group.

Among the substituents represented by R-4 or R' in the above formula, carbon W
An alkyl group-alkoxyalkyl group, a halogen atom-substituted alkyl group, and an aryloxyalkyl group with child number/~IO are preferred, and these may be the same or different, and the number of carbon atoms among the substituents represented by R1 is λ~/ The alfkydialkyl group of 2 - an aryloxyalkyl group having 7 to 7 carbon atoms is preferred. Among the substituents represented by R2, an aryl group having carbon atoms/~2, an alkyl group which may have a halogen atom as a substituent, an alkoxy group, an aryloxy group, and a carbon atom a+~10
R3 is preferably an alkyl group, an alkoxy group, or a phenyl group which may have a halogen atom as a substituent.
Among the substituents represented by, an alkyl group having a carbon atom number/~r and a phenyl group having a carbon atom number t~IO are preferable,
X.

Among the substituents represented by Y-Z, hydrogen atoms, alkoxy groups with carbon atoms of l to O, aryloxy groups with carbon atoms of 2 to IO, chlorine atoms and fluorine atoms, carbon atoms / to /
An alkyl group-substituted amine group is preferred.

The electron-donating colorless dye according to the present invention is a colorless or light-colored crystal, has high solubility in organic solvents, and has the advantage of quickly developing a blue color when it comes into contact with an electron-accepting substance. The developed pigment is extremely stable compared to pigments produced from existing color formers, and hardly changes color or fades even after prolonged exposure to light, heating, or humidification, making it especially advantageous in terms of long-term preservation of records. . In addition, the stability of the coloring agent is excellent, and it has sufficient coloring ability without causing deterioration or discoloration even after long-term storage, making it almost ideal as a coloring agent for recording materials such as pressure-sensitive paper and thermal paper. Has performance.

As a representative example of the electron-donating colorless dye according to the present invention, 1
The following compounds are mentioned.

/1 3-(≠-diethylamino-2-(α-methoxypropoxy)-phenyl]-3-I/-ethyl-comethylindol-3-yl)phthalide x) J-C≠-diethylamino-co(r- methoxypropoxy)-phenyl]-J-17-n-7'thyl-comethylindol-3-yl)phthalide 3) 3-[≠-diethylamino-λ-(γ-methoxypropoxy)-phenyl)-3-(/ -1so --<phthyl-comethylindol-3-yl)phthalide II) 3-[Hiro-diethylamino-λ-(β-methoxyethoxy)-phenyl]-J-(/-ethyl-comethyl-indole-3 -yl)phthalide 5) 3-[a-diethylamino-(β-ethoxyethoxy)-phenyl)-J-(t-ethyl-comethyl-indol-3-yl)phthalide J)J-[μmdiethylamino- j-(r-ethoxypropoxy)-phenyl: ]-J-(/-ethyl-λ-methylindol-3-yl)phthalide 7) 3-[μm di-n-butylamino-Cγ-ethoxypropoxy)-phenyl ]-J-(/-ethyl-comethylindol-3-yl)phthalide, r)J-C≠-diethylamino-2-(γ-ethoxypropoxy)-phenyl)-3-17-benzyl-λ-
methylindol-3-yl)phthalidota)3-[≠-N-ethylN-n-butylaminoco-(r-ethoxypropoxy)-phenyl]-3-(/
-Ethyl-co-methylindol-3-yl)phthalide 10) 3-Chiro-diethylaminol-(r-ethoxypropoxy)-phenyl]-J-(/-ethyl-co-phenylindol-3-yl)phthalide// ) J-4 μm diethylamino-λ-(β-phenoxyethoxy)-phenyl]-J-(/-ethyl-λ-methylindol-3-yl)phthalide l co)3-[≠-diethylamino-(β- μm chlorophenoxyethoxy)-phenyl]-J-(l-ethyl-λ-methylindol-3-yl)phthalide/3)3-[μm diethylamino-λ-(β-Koichimethylphenoxyethoxy)phenyl]-3- (t-ethyl-co-methylin)'-ru-3-yl)phthalide/≠13-C≠-diethylamino-λ-(β-≠-methoxyphenoxyethoxy)phenyl]-J-(l-ethyl-co- Examples include methylindol-3-yl) phthalide.

These may be used alone or in combination.

1 However, these colorless dyes are already well known (known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indriazalphthalide compounds, leuco auramine compounds, rhodamine lactam compounds, It is also possible to assemble recording materials by using it in combination with various compounds such as phenylmethane compounds, triazene compounds, and spiropyran compounds.

In this case, it is preferable to use the above-mentioned colorless dye in an amount of tocs or more from the viewpoint of improving properties. Some examples of such colorless dyes used in combination are -triarylmethane compounds.

J, J-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e. crystal violet lactone), J, J-bis(p-dimethylaminophenyl) phthalide, 3-(p-dimethylaminophenyl) -J
-(/,!-dimethylindol-3-yl)phthalide, J-(1)-dimethylaminophenyl)-3-(2-
methylin)”-ni-J-yl)phthalide, etc.
As a diphenylmethane compound, ≠, Hiro'-bis-
Dimethylaminobenzhydrin benzyl ether.

N-Hasephenylleucoauramine, N-2゜≠,z
-Trichlorophenylleucoolamine, etc., and xanthine compounds include monorhodamine-B-anilinolactam-rhodamine (p-nitroanilino)lactam,
Rhodamine B (p-chloroanilino)lactam, 2-di(ndylamino-j-diethylaminofluoran-coanilino 6-diethylaminofluorane, λ-anilino 3-methyl-6-dinithylaminofluoran).

λ-Anilino-3-methyl-2-cyclohexylmethylaminofluorane-〇-chloroanilino-2-diethylaminofluorane, λ-m-chloroanilino-
Di-diethylaminofluorane 2-(J, Hiro-dichloroanilino)-6-diethylaminofluorane, no-octylamino-t-diethylaminofluorane, colahexylamino-6-diethylaminofluorane, 2-m
-) Reflow methylanilino-6-diethylaminofluoran, coptylamino-3-chloro-4-diethylaminofluoran, λ-ethoxyethylamino-3-chloro-t-diethylaminofluoran++2-1)-chloroanilino- 3-Methyl-t-dibutylaminofluoran, 2-anilino-3-methyl-t-dioctylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, no-diphenylamino-6-diethylaminofluoran. Coanilino 3-methyl-6
-Siphenylaminofluorane, Cophenyl-6-diethylaminofluorane, Coanilino 3-methyl-
A-N-ethyl-N-isoamylaminofluorane, λ
-anilino-3-methyl-chloro-6-dinithylaminofluorane, 2-anilino-3-methyl-4-diethylamino-7-methylfluorane, 2-anilino-3
-Methoxy-bu-dibutylaminofluorane +2-0-
Chloroanilino-t-dibutylaminofluorane-λ-
p-chloroanilino 3-ethoxy-A, -N-ethyl-N-isoamylaminofluorane, no-0-chloroanilino A-p-butylanilinofluoran, co-anilino 3-bentatecyl-6-diethylaminofluorane, λ -anilino 3-ethyl-t-dibutylaminofluorane-λ-anilino 3-methyl-Hiro',j'-dichlorofluoran-u-Q-toluidino-3-methyl-
t-Diimpropylamino-≠′,! '-dimethylaminofluorane, 2-anilino-3-ethyl-J-N-ethyl-N-isoamylaminofluoran-coanilino-3-methyl-AN-ethyl-N-η-methoxypropylaminofluoran .

Coanilino 3-chloro-A-N-ethyl-N-isoamylaminofluorane, etc.; thiazine compounds include benzoylleucomethylene blue-p-nitrobenzoylleucomethylene blue; and spiro compounds include 3-methyl -spiro-dinaphthopyran-3
-ethyl-spiro-dinaphthopyran, 3,3'-cyclolosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-
Examples include benzo) spiropyran 4j-#d biruspiro dibenzopyran.

Electron-accepting compounds that provide color upon contact with colorless dyes include inorganic and organic Lewis and Brønsted acids. Phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite-novolac resin, metal-treated novolac resin-l-tert-butylphenol, Hiro-phenylphenol + l-human σ-oxydiphenoxide-α-naphthol-β -Naphthol, hexyl-≠-hydroxybenzoate.

u,J'-dihydroxybiphenyl-2,u-bis(
a-Hydroxyphenyl) flonogun (bisphenol Al μ, μ′-isopropylidene bis(2-methylphenol)-/, /-bis-(J-chloro-Hiro-hydroxyphenyl)cyclohexane, /, /-bis( 3-Chloro-[mu]mhydroxyphenyl)-coethylbutane, ≠, ≠'-Secondary-inoctylidene diphenol.

p-tert-octylphenol, ≠, ≠'-5ec
-butylidene diphenol, ≠-p-methylphenylphenol-4t, IA'-isopentylidene diphenol, μ, 4t'-methylcyclohexylidene diphenol, ≠, 4L'-dihydroxydiphenyl sulfide, /1μm bisuhiro'- Hydroxycumylbenzene, 1
．． 3-bis≠'-hydroxycumylbenzene-≠, μ
'-Thiobis(1,-tert-butyl-3-methylphenol), g,4t'-dihydroxydiphenylsulfone.

Hydroquinone monobenzyl ether, Hiro-hydroxybenzophenone, 2. v-dihydroxybenzophenone,
polyvinylbenzyloxylponylphenol,
Buddha, Hiro'-trihydroxybenzophenone + -, +2
', ≠, ≠'-tetrahydroxybenzophenone,
≠-dimethyl hydroxyphthalate-methyl l-hydroxybenzoate 1.2゜≠, ≠'-trihydroxydiphenylsulfone, 1,j-bis-p-hydroxyphenyl methane/, hubis-p-hydroxyphenoxyhexane-μm hydroxybenzoate 8m trill, ≠-hydroki'
4-AIF acid α-phenylbenzyl ester, l-hydroxybenzoic acid phenylpropyl-4cm hydroxybenzoic acid phenethyl-≠-hydroxybenzoic acid-p-chlorobenzyl, 4t-hydroxybenzoic acid p-methoxybenzyl-1I- Hydroxybenzoic acid benzyl ester, Hiro-hydroxybenzoic acid em-chlorobenzyl ester, ≠-hydroxybenzoic acid β-phenethyl ester,
≠-Hydroxy-λ', μ'-dimethyldiphenylsulfone, β-phenethyl orselinate, cinnamyl orselinate, orselic acid-〇-chlorophenoxyethyl ester, 0-ethylphenogyethyl orselinate-o-phenyl Phenoxyethyl orcelinate-m
-Phenylphenoxyethyl orcelinate, 2. ≠−
Dihydroxybenzoic acid-β-3'-t-butyl-μ'-
Hydroxyphenoxyethyl ester-/-t-butyl-μmp-hydroxyphenylsulfonyloxybenzene, ≠-N-benzylsulfamoylphenol, λ,
≠-dihydroxybenzoic acid-p-methylbenzyl ester-9≠-dihydroxybenzoic acid-β-phenoxyethyl ester, 2,4L-,)hydroxy-2-methylbenzoic acid benzyl ester-bis-μm methyl hydroxyphenylacetate- Ditolylthiourea, ≠'-diacetyldiphenylthiourea, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3. j-di-tert-butylsalicylic acid, 3. j-di-dodecylsalicylic acid, 3-methyl-! -Benzylsalicylic acid, 3-phenyl-j-(α,α-dimethylbenzyl)salicylic acid, 3
．． ! - Aromatic carboxylic acids such as di(α-methylbenzyl)salicylic acid -2-hydroxy-nobenzyl-3-naphthoic acid -3, J'-di-cyclo is ntazidinylsalicylic acid, para-phenylphenol - formalin resin ,
Organic color developers such as phenolic resins such as para-butylphenol-acetylene resins, and combinations of these organic color developers such as zinc magnesium-aluminum, calcium,
Salts with polyvalent metals such as titanium, manganese, tin, and nickel; and hydrohalic acids such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, boric acid-silicic acid-phosphoric acid, sulfuric acid, nitric acid, and perchloric acid. - Aluminum - Zinc - Inorganic acids such as halides such as nickel, tin, titanium, boron, acid clay.

Activated clay - attapulgide, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, zinc rhodan, zinc chloride, iron stearate, cobalt naphthenate, nickel chisel oxide - inorganic color developer such as ammonium nitrate, shu Acids - maleic acid, tartaric acid,
Aliphatic carboxylic acids such as citric acid, conolic acid, and stearic acid, benzoic acid-paratertiary butylbenzoic acid, and phthalic acid.

One or more types of gallic acid are used.

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.

For use with pressure sensitive paper, U.S. Patent No. 2. ! O! , Hiro 7
No. 0, same co., 60j, 447/no. - same co.

! O! , Guri No. - Same Ko, O4.3 At No., Same λ, 7/
Ko,! No. 07-Same, No. 730.4 Alt.

Same No. λ, 730, 4Aj No. 7 - Same No. j, 103. μO≠ No. j, IA/r, No. 210, a, oio.

It can take various forms as described in prior patents such as No. 031. Most common? - consists of at least one pair of sheets separately containing an electron-donating colorless dye and an electron-accepting compound.

A method of manufacturing capsules is disclosed in a United States patent.

: 1'00, 1tj No. 7, a method using coacervation of a hydrophilic colloid sol described in s, too, art, British Patent rA7,727, 910. !
eJ issue, same? l'? , 2t' No. 7゜0?1,07
No. 6 etc. describes the following interfacial polymerization method or US patent! ,
103. There are methods such as those described in the Hiroo Hiro issue.

In general, one-electron-donating colorless dyes are used alone or in combination as 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,
The color former sheet is produced by coating it on a support such as paper, high-quality paper, plastic sheet, resin-coated paper, or the like.

Neutral paper is particularly preferred as the support.

In addition, the electron-accepting compounds described below, alone or in combination, or together with other electron-accepting compounds, are dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and the pigments described below are used to produce paper, plastic sheets, and resin-coated paper. A developer sheet is obtained by coating a support such as the following.

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 particle size of 70 μm or less, preferably 3 μm, in the dispersion medium.
It is used after being crushed and dispersed to a particle size of μ or less. As a dispersion medium, generally 0. A water-soluble polymer aqueous solution with a concentration of about 2 to 10 ml is used.

For dispersion, ball mills, sand mills, and horizontal sand mills are used.

This is done using an attritor colloid mill or the like.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably between /:10 and l:/, and even l:! and Koni 3 are particularly preferred. At that time, fatty acid amide-acetoacetanilide-diphenylamine,
Nitrogen-containing organic compounds such as penzamide, carbazole, etc.'-! Or 2゜J-Gm-) Lylbutane-
Fluoropenzoyldurene, chlorobenzoylmesitylene, ≠.

≠'-Dimethylbiphenyl, carboxylic acid esters such as dimethyl isophthalate, diphenyl phthalate, dimethyl terephthalate, methacryloxybiphenyl, etc., or polyether compounds such as di-m
-tolyloxyethane, β-phenoxyethoxyanisole, /-phenoxy-2-p-ethylphenoxyethane-bis-β-(,-methoxyphenoxy)ethoxymethane.

/-2'-methylphenoxy-coke"-ethylphenoxyethane, /-tolyloxy-rp-methylphenoxyethane, /,-1diphenoxyethane, /,≠-diphenoxybutane, bis-β-(p -ethoxyphenoxy)ethyl ether, /-phenoxy-J-p-chlorophenoxyethane-/-j'-methylphenoxy-λ-
≠ -ethyloxyphenogyethane, /-μ′-methylphenoxy! - It is preferable to use a compound having a melting point of 7.00 to 7300 C, such as fluorophenoxyethane. 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 used is - for a child-accepting compound, -Q factor or more, 30
It is added at a weight ratio of 04 or less, and the special VCu is added at a weight ratio of 04 or more.
4 or less is preferable.

In addition, additives are added to the coating liquids obtained in this way in order 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 purpose, fatty acids, metal soaps, etc. are added. Therefore, in general, in addition to the colorless dye-electron-accepting compound that directly contributes to color development, additives such as pigment-wax-antistatic agent, ultraviolet absorber-antifoaming agent, conductive agent, fluorescent dye, surfactant, etc. is coated on a support to form a recording material.

Specifically, kaolin as a pigment, calcined kaolin, talc-dollite, cane earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined silica, magnesium carbonate, r9. titanium chloride/, alumina barium carbonate, barium sulfate-mica microballoon,
Urea-formalin filler, polyethylene Nauticule cellulose filler, etc. particle size 0. /Naishi/! Selected from μ. Examples of waxes include paraffin wax, carboxy-modified paraffin wax, cowna wax, microcrystalline wax to 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.

These are dispersed and applied in a binder.

The binder is generally water-soluble.

polyvinyl alcohol, hydroxyethyl cellulose,
Hydroxypropylcellulose, epichlorohydrin-modified polyamide ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer-isobutylene-maleic anhydride copolymer, polyacrylic acid-polyacrylamide-methylol-modified polyacrylamide-starch derivative , casein, gelatin, etc. In addition, in order to impart water resistance to these binders, water-resistant agents (gelling agents, cross-linking agents) are added, and emulsions of hydrophobic polymers, such as niha-styrene-phtadiene rubber latex, acrylic resin emulsions, etc. are added. You can also do that. The coating liquid is applied to base paper, high-quality paper, plastic sheet, synthetic paper or neutral paper at a thickness of about 2 to 10 l/7712.

Furthermore, a protective layer of about 0.2 to 2 μm consisting of a water-soluble polymer compound such as polyvinyl alcohol, hydroxyethyl starch, or epoxy-modified polyacrylamide and a crosslinking agent is provided on the surface of the coating layer to improve resistance. You can also do that.

When used for thermal paper, also 0LS2 here tJ-rI
No., same, 211013-41, Tokko Akira! ,! -207 Kou 2, etc., various n-types are taken. Alternatively, operations such as preheating/humidity conditioning or stretching of the cloth paper may be added prior to recording.

For example, the electrically conductive thermal paper is published in Japanese Patent Application Publication No. 2003-120003.

Same 60-≠? It is manufactured by the method described in No. 30. Generally, a coating liquid in which a conductive substance, a basic dye mainly consisting of 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 gold 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 mentioned above in combination.

For example, the photosensitive and pressure sensitive paper is made by Tokkai Sho! It is manufactured by the method described in t7-/7rit3t and the like. Generally silver iodobromide - silver bromide, silver behenate, Michler's ketone.

A photopolymerization initiator such as a benzoin derivative or a benzophenone derivative and a crosslinking agent such as a polyfunctional septamer such as a polyallylated product - poly(meth)acrylate or poly(meth)acrylamide are used together with a colorless dye and optionally a solvent to produce polyether urethane, polyurea, etc. A synthetic resin wall is encapsulated in the capsule. After imagewise exposure, the colorless dye in the unexposed area is brought into contact with a color developer to be colored.

The electron-donating colorless dye according to the present invention is synthesized by a known method. For example, the corresponding benzoylbenzoic acid or benzoylpyridinecarboxylic acid and the indole, or the corresponding carboxybenzoylindole or carboxypyridinecarbonylindole and the aniline derivative are combined in the presence of a condensing agent such as acetic anhydride or phosphorus oxychloride, as required. Using a volatile organic inert solvent such as chloroform, benzene, or benzene chloride,
After reacting for 10 minutes at a temperature corresponding to C, one reactant was placed in ice water to hydrolyze the condensing agent.

It is obtained by adding the above volatile organic inert solvent, making it alkaline with an aqueous sodium hydroxide solution, separating one solvent layer, and distilling off the solvent under reduced pressure.

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

Examples and Comparative Examples (2) Preparation of Color Developer Sheet 10 parts of the color developer shown in Table 1 were added to 20 parts of /-isoprobylphenyl-co-phenylethane and dissolved by heating at 0°C. This was mixed with polyvinyl alcohol (PVA-
t/7 (manufactured by Kuraray) aqueous solution JO part, and 0.0% of 104 dodecylbenzenesulfonic acid triethanolamine salt aqueous solution was added as a surfactant to a part. An emulsion was prepared using a homogenizer so that the average particle size of the emulsion was 3 μm.

Next, 10 parts of calcium carbonate and 20 parts of zinc oxide.

Prepare a dispersion of 1 part of sodium hexametaphosphate and 200 parts of water using a Keddy Mill, and add -10C6PVA-//7 as a binder after mixing the above emulsion.
(manufactured by Kuraray) aqueous solution ioo part and carboxy-modified SBR
Latex (SN-3oy, manufactured by Sumitomo Naugatax) 7
0 parts (as solid content) was added and water was added to adjust the solid content concentration to 20% to obtain a coating liquid (A).

Next, 10 parts of the color developer, θ parts of Silton Clayco, zO parts of calcium carbonate, 0 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water were used.

Use a sand grinder to uniformly disperse the particles to an average particle size of 3μ.

To the resulting dispersion was added 1 part of PVA-103C (manufactured by Kuraray) aqueous solution;
7 (manufactured by Ri5v) 100 parts of aqueous solution and Calr6xy modified S
BR latex (SN-3o7 manufactured by Sumitomo Naugatux)
Add 10 parts (as solid content) to make the solid content concentration ko4
Water was added to obtain coating liquid rB3.

Coating liquid (A) and coating liquid (B) in terms of developer: A, / B =
! 0/! j, Oe to 13097m2 of base paper
A developer sheet was obtained by coating with an air knife coater so that a solid content of 1/m2 was coated and drying.

■ Preparation of capsule sheet containing coloring agent ■ Melamine/formaldehyde resin capsule One part of polyvinylbenzenesulfonic acid (IJum Salt C, manufactured by National Starch Co., Ltd., VER8A-TL, average molecular weight: zoo, ooo), about 1 part to ' C hot water 9! 1 part and dissolved while stirring. After dissolving for about 30 minutes, it is cooled. The pH of the aqueous solution is 2 to 3;
A heavy sodium tetrahydroxide solution was added to adjust the pH to μ, O. On the other hand, use the coloring agent shown in Table 1 in 3. ! 100 parts of the dissolved diisopropylnaphthalene was emulsified and dispersed in 100 parts of a j% aqueous solution of the partial sodium salt of polyvinylbenzenesulfonic acid to obtain an emulsion having a particle size of average diameter≠jμ. Separately, 2 parts of 1 melamine, 37 parts by weight of formaldehyde aqueous solution, and 30 parts of water were heated and stirred to 0C, and after 30 minutes, a transparent mixed aqueous solution of melamine, formaldehyde, and melamine-formaldehyde initial condensate was obtained.

The pH of this mixed aqueous solution is t~! Met. Hereinafter, the six liquid mixtures of melamine, formaldehyde, and melamine-formaldehyde initial condensate will be referred to as an initial condensate solution. The initial condensate solution obtained by the above method was mixed with the above emulsified liquid pressure, and while stirring, a phosphoric acid solution with a width of 7.4 weight was added.
H was adjusted to 1.0, the temperature of one liquid was raised to 0C, and stirring was continued for JAO minutes. The capsule liquid was cooled to room temperature and the pH was adjusted to 20% by weight of hydroxide.

10 parts by weight of polyvinyl alcohol aqueous solution JOO and starch particles for this capsule dispersion! A coating solution of a microcapsule dispersion was prepared by adding O parts and adding water to adjust the solid content concentration to 20%.

Apply this coating liquid to JO? Coated using an air knife coater so that 397 m2 of solid content was coated on 7 m2 of raw sand.
After drying, a capsule sheet containing a coloring agent used in the present invention was obtained.

■ Polyurethane urea capsule diisopropyl naphthalene 30? Add the color former shown in Table 1 to 3. ! A polyvalent incyanate compound (tolylene diisocyanate 37/1 mole trimethylolpropane adduct), r? and a polyhydric hydroxy compound (C ethylene diamine-propylene oxide adduct)/n at a temperature below -o'C.
The following solution was prepared.

Next, 2000 water≠l? Sodium salt of polyvinyl alcohol 32 and carboxymethylcellulose/, j7
was dissolved. Further, tertiary oil (emulsifier) o and it were added to prepare a primary solution.

While vigorously stirring the secondary solution, the seventh solution was poured to form an oil-in-water emulsion. When the size of the oil droplet reaches 1.0 m, the stirring is weakened.Next, 1 oor of 200C water is added to this emulsion, and the temperature of the system is gradually raised to 7.0C. I kept it.

Polyvinyl alcohol is added to the capsule liquid thus obtained. Winter ice aqueous solution 239-carboxy-modified SBR latex in solid content ≠ 2? , starch particles (average particle size/j
μm20f was added.

Then, water was added to adjust the solid content concentration to 2t)4,
A coating solution was prepared.

The dry weight of this coating liquid was 27 m2.
Coat on f/m2 base paper using an air knife coater and dry.
A microcapsule sheet was obtained.

■ Gelatin Capsules 20 parts of acid-treated gelatin having isoelectric points r, o and 20 parts of gum arabic are dissolved in 120 parts of Hiroshi 00C water, and 0.0% of sodium alkylbenzenesulfonate is added as an emulsifier. 3. Add the coloring agent shown in Table 1 to this. ! Add 7,200 parts of dissolved diisoprobyl naphthalene with vigorous stirring and emulsify. When the temperature reached μ, 200 parts of water at ≠0°C was added to suppress the progress of emulsification.

While continuing to stir, add 300C of Mizuhiro Co.
The pH of the system was adjusted to ≠ by adding 0% acetic acid. The solution was cooled to r'C with continuous stirring, and then 37% formaldehyde/0 parts and 0% glutaraldehyde/0 parts were added.

Continuing - 104 carboxymethyl cellulose aqueous solution z
Pour part O and then 2! Add sodium hydroxide solution dropwise to adjust the pH to 9. ! After adjusting the liquid temperature to 3o0C, microcapsules with hardened walls were obtained. To this capsule dispersion, JOO parts of a 104 polyvinyl alcohol aqueous solution and 10 parts of starch particles were added, and water was added to adjust the solid content concentration to 204 to prepare a coating liquid of a microcapsule dispersion.

Is this coating liquid jO? 3 for /m2 base paper? Coat and dry with an air knife coater so that a solid content of /m2 is coated,
A capsule sheet containing a coloring agent was obtained for comparison.

A pressure-sensitive recording sheet was prepared by combining the color developer sheet and color former-containing capsule sheet obtained as described above as shown in Table 7, and the performance of each combination was compared.

A light fastness test was conducted by placing each color developer sheet and color former-containing sheet facing each other to develop color. The results are shown in Table/.

[Coloring body lightfastness test]

The coloring body was irradiated with light of 32,000 lux for io hours, and the color density before and after one irradiation was compared to determine the survival rate.

Furthermore, the 2r'C of the color former of the present invention for aromatic solvents is
The solubility was measured at The results are shown in Table 2.

The results in Table 1.2 show that the recording material of the present invention clearly has excellent light resistance and solubility in organic solvents.

Example 9 A solution of 30 parts of 3-[≠-diethylamino-J-(r-methoxypropoxy)phenyl]-5-(t-ethyl-comethylindol-3-yl)phthalide in an aqueous solution of 750 parts of 70-width polyvinyl alcohol and 70 parts of A dispersion liquid was prepared by mixing and pulverizing the mixture with water for 1 hour using a ball mill. The particle size after milling was approximately 1.1 microns. (Ingredients) On the other hand, 30 parts of zinc ≠-β-(p-methoxyphenoxy)ethoxysalicylate, 30 parts of cobenzyloxynaphthalene ljO parts of a 104 polyvinyl alcohol aqueous solution, and 35 parts of water were mixed and ground using a sand mill. A dispersion liquid was prepared. The particle size of the insoluble material after pulverization was approximately comicron. (Component B) Next, mix K1 part of Component A and 4cO part of Component B.

Thermal paper was obtained by coating on abrasive and drying.

This thermal paper developed a blue color when heated with heat in or the like. The color image obtained was very stable against light, and even when the image was irradiated with an ultraviolet lamp for one hour, there was almost no change in either hue or density.

Claims (1)

[Scope of Claims] A recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, characterized in that a compound represented by the following general formula (I) is used as the colorless dye. material. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the above formula, R and R' are alkyl groups, R_1 is alkoxy or aryloxy-substituted alkyl groups, R_2, R_
3 represents an alkyl group-aryl group, and X, Y, and Z represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, or a substituted amino group.