JPS6362778A - Recording material - Google Patents

Abstract

PURPOSE:To provide a recording material having good color developability and preservability, imparting a stable developed color image and containing a specific dye having good solubility, by using a specific compound as an electron donative leuco dye. CONSTITUTION:An electron donative leuco dye is represented by formula (I) (wherein R1-R10 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a substituted amino group or an aryl group and R7 and R8, and R9 and R10 may be bonded to each other to form a ring. R is a 1-20C divalent group and Ar is an aryl group which may be substituted). This electron donative leuco dye is a colorless or light-colored crystal and has high solubility to an org. solvent and, further, forms a blue color upon the contact with an electron acceptive substance. The developed dye is stable and generates almost no discoloration and facing even under long-time light irradiation, heating and humidifying conditions and recording can be preserved over a long period of time.

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 that uses a secondary electron-donating colorless dye and an electron-accepting compound to improve color development, shelf life, and stability of colored images. related to recorded materials.

(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, UK patent 27μO≠Tata, US patent μ≠100
92, same μ≠3t octopus 01 special public show to-23, ri22,
Unexamined Japanese Patent Publication No. 17-17-7, r36, tO-/23, 1j &
, 1.0-/23, ! I am familiar with 17 etc.

Performance U that the recording material should have: (11) the color density and sensitivity should be sufficient, (2) no fogging should occur, (3) the fastness of the coloring material after coloring should be sufficient, (
4) Appropriate color hue and suitability for copying machine, +518
/N ratio is high, (6) the color former has sufficient chemical resistance, and (7) it is easily soluble in the patented organic solvent, but currently no product has been obtained that satisfies these requirements. .

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. ! -Bis(p-dimethylaminophenyl)-A-dimethylaminophthalide (i.e., crystal violet lactone) 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., penzoyl leucomethylene blue), which is one of the seven leucomethylene blue compounds, has an excellent color image and has good light resistance, but the color development is very slow. However, it has drawbacks such as very poor color development with organic color developers.

The present inventors investigated the oil solubility, water solubility, partition coefficient, pKa1 polarity of the substituent, position of the substituent, and changes in crystallinity and solubility for each of the electron-donating colorless dye and the electron-accepting compound. We have continued to pursue the development of good recording material materials and recording materials, with a focus on properties such as .

(Objective of the Invention) Therefore, the object of the present invention is to provide a material that has good color development properties, raw shelf life, and stability of colored images, and has good solubility in aromatic solvents and paraffinic solvents, and also meets other necessary conditions. Our goal is to provide recording materials using the following materials.

(Structure of the Invention) The object of the present invention is to produce an electron-donating colorless dye with the following general formula +
This was achieved by a recording material characterized by using the compound shown in No. 11.

In the above formula, R1 to RIO are hydrogen atoms, hydrogen atoms, alkyl groups, alkoxy groups, substituted amino groups, or aryl groups.
! ”, R7 and R8 and R9 and RIO are groups that may be combined with each other to form a ring, and R is the number of carbon atoms/to 2 of U.
The valent groups e and Ar represent an optionally substituted aryl group.

In addition, 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 norogen group, a nitro group,
The cyano group, substituted carbamoyl group, substituted sulfamoyl group, substituted amino group, and substituted oxycarbonyl group may carry a substituent such as a substituted oxysulfonyl group. The alkyl group represents a saturated or unsaturated alkyl group, and the cycloalkyl group represents a cycloalkyl group, which is a substituent group such as an aryl group, an alkoxy group, an aryloxy group, or a cyano group. You may do so.

Among the substituents represented by n1XR3 and R4 in the above formula, a hydrogen atom, an alkyl group having 1 to 1 carbon atoms, or an aryl group are preferred; may be substituted with a group such as a cyano group, a pyridyl group, or a furfuryl group.

R3 and 14ri combine with each other! Negative to j-negative rings such as piperidine, morpholine, pyrrolidine, piperazine, hexamethyleneimine, indole and the like may be formed.

Among the substituents represented by R2 and R5, hydrogen atoms, alkoxy groups with carbon atoms/-4, aryl groups with carbon atoms a6 to IQ, aryloxy groups, chlorine atoms and fluorine atoms, carbon atoms/-/2 Alkyl groups and substituted amine groups are preferred.

R2 is particularly preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

R7 and R8, R9 and RIO may be bonded to each other to form a ring, in which case the heteroatom may be an aromatic compound that may contain one or more of an oxygen atom, a nitrogen atom, or a sulfur atom. A ring is preferred. The aromatic ring may carry a substituent as mentioned above for R1 or R2, an N-substituted rubamoyl group, an alkoxycarbonyl group, etc.

% is preferred in the case of a benzene ring and a pyridine ring which may be directly substituted.

Among the substituents represented by R, alkylene, alkenylene,
Arylene and the like are particularly preferred, especially -cnH2m-X-cn
The one represented by Hzrrl-+y-CnHzm+B- is preferred. Here, n and m are integers from 1 to 20, and m does not exceed kon. The integer Y in p t'i represents an oxygen atom, a sulfur atom, an arylene or -N-.

R11 represents an alkyl group, an aryl group, or an acyl group. Further, the alkylene or arylene group may have a substituent.

Particularly preferable examples of R include /, 2-ethylene, /, 3 or /, λ-propylene, l, ≠ or 2゜3-butylene,
3-oxabenchrene, methylene, phenylene, 5-N
-acetyl-azaventhrene, xylylene, phenylethylene, λ, coco-methylpropylene, cyclohexylidene, etc.

The general formula of a preferred compound is as follows.

R12XR13 represents the substituent described for R5, and X represents a carbon atom or a nitrogen atom.

Among these, particularly preferred compounds are those in which Ar is represented by the following formula.

The electron-donating colorless dye according to the present invention has the advantage of being colorless to light-colored crystals, having high solubility in organic solvents, and quickly developing a blue color when it comes into contact with an electron-accepting substance. The color-forming dye is extremely stable compared to dyes produced from existing color-forming agents, and hardly changes color or fades even after long-term light irradiation, heating, or humidification, making it especially advantageous from the perspective of long-term preservation of records. be. In addition, the coloring agent has excellent stability, does not cause deterioration or layer coloring even after long-term storage, and has sufficient coloring ability, making it ideal as a coloring agent for recording materials such as pressure-sensitive paper and thermal paper. Responsible for performance.

Representative examples of the electron-donating colorless dye according to the present invention include:
The following compounds are mentioned.

Ethylenebis3-(≠-diethylaminocooxyphenyl)-j-1/-ethyl-2-methylindole-
3-yl) phthalide, butylene bis 3-(l/--ethylamino-cooxyphenyl 1-J-(/-ether-2-methylindol-3-yl) phthalide, 3-oxabenchrene/.

! -bis3-(Hiro-diethylamino-oxyphenyl)-j-(/-ethyl-λ-methylindole3-
yl) phthalide, l,2-propylenebis3-[≠-diethylamine-2-oxy)phenyl]-1-(/-phenyl-comethylindol-3-yl)phthalide,
3-Oxabenchrene-l,! -bis1-(ti-diethylamino-4-oxyphenyl)-j-(/-butyl-comethylindol-3-yl)phthalide, /.

≠-Butylenebis-3-[Hiro-dietheramino-λ-oxyphenyl)-J-(/-broby-co-methyl-indol-3-yl)phthalide, ethylenebis-3-[
≠-diethylamino-cooxyphenyl: 1-s-(
/-Benzyluromethylindol-3-yl)phthalide, 3-oxapentele-/, J-bis-3-(Hiro-diphthylamino-2-oxyphenyl)-J-17-
7enethyl-λ-methylindol-3-yl) phthalide, ethylenebis3-(≠-diethylamino-λ-oxyphenyl)-j-(/, 2-'))f-ruindol-3-yl)phthalide, and the like.

In addition, these colorless dyes are already well-known triphenylmethane phthalide compounds, fluoran compounds,
Recording materials can be produced in combination with various compounds such as phenothiazine compounds, intriazalphthalide compounds, leucoauramine compounds, rhodami/lactam compounds, )IJ7 dinylene methane compounds, triazene compounds, and spiropyran compounds. It can also be assembled.

In this case, it is preferable to use the colorless dye in an amount of 60% or more in order to improve the properties. Some examples of such colorless dyes used in combination include triarylmethane compounds such as 3.3-bis(p-dimethylaminophenyl)-6-cyphthylamino 7-thallide (i.e., crystal violet lactone); −Bis(
p-dimethylaminophenyl) 7thalide, J (p-
dimethylaminophenyl)-J-(/, J-Schiff fk indol-3-yl) phthalide, 3-(p-dimethylaminophenyl)-7-(J-methylindol-3-yl)7thalide, etc. Examples of the 7-engineered dilumethane compounds include p,4c'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoolamine, and N-2゜≠I! xanthine-based compounds include rhodamine-B-anilinolactam, rhodamine(p-nitroanilino)lactam, and rhodamine B(p-nitroanilino)lactam.
chloroanilino)lactam, λ-dibe/dylamino-6
-ethylaminofluorane, rhoanilino 6-diethylaminofluorane, λ-anilino 3-methyl-6
-dietheraminofluorane, 4-anilino-3-methyl-6-cyclohexylmethylaminofluorane, -2
0-chloroanilino-6-diethylaminofluorane,
2-m-chloroanilino-6-diethylaminofluorane, λ-(3,Hiro-dichloroanilino)-6-diethylaminofluorane, λ-octylamino-6-dinithylaminofluorane, λ-dihexylamino-6- Diethylaminofluorane, m-trifluoromethylanilino-t-diethylaminofluorane, coptylamino-3-chloro-6-diethylaminofluoran, 2-ethoxyethylamino-3-chloro-t-diethylaminofluorane, λ -p-chloroanilino 3-, 7'thyl-6-dibutylaminofluorane, λ-anilino 3-
Methyl-6-dioctylaminofluorane, noanilino-3-chloro-bu-diethylaminofluoran, Korgphenylamino-t-diethylaminofluoran, rhoanilino-3-methyl-6-diphenylaminofluorane, rhophenyl-6-diethylaminofluoran fluorane,
λ-anilino 3-methyl-&-N-ethyl-N-ynamylaminofluorane, rhoanilino 3-methyl-
Yo-1 chloro-6-ethylaminofluoran, no-anilino-3-methyl-6-ethylamino-6-ethylaminofluoran, low-anilino-3-methoxy7-/;-dibutylaminofluoran, j-o-chloroanilino-6 -dibutylaminofluorane, col-chloroanilino-3
-Ethoxy-&-N-ethyl-N-yne'mylaminofluorane, λ-0-chloroanilino 6-p-butylanilinofluorane, rhoanilino 3-bentadenyl-6-diethylaminofluorane, rhoanilino 3
-Ethyl-6-cyptylaminofluorane, λ-anilino 3-methyl-p/, r/-dichlorofluoran, λ-o-toluidino 3-methyl-ot-diinpropylamino-≠'! ' -dimethylaminofluorane, rhoanilino 3-ethyl-A -N -f-N-i:/amylaminofluorane, λ-anilino 3-methyl-AN-ethyl-N-coumethoxypropylaminofluorane, co-anilino 3- Kuroro Otsu-
N-ethyl-N-ynamylaminofluorane, etc.; thiazine compounds include benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene flu, etc.; spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3.3'-cyclospirodinaphthopyran,
Examples include 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)spiropyran, and 3-propyl-spiro-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 resins, metal-treated novolac resins, ≠-tert-butylphenol, Hiro-phenylphenol, ≠-hydroxydiphenoxide, α-naphthol, β- Naphthol, hexyl-≠-hydroxyinzoate, λ, λ
'-dihydroxybiphenyl, co, 2-bis(μm hydroxyphenyl)furopane (bisphenol A), ≠
, Hiro'-inpropylidene bis(2-methylphenol), /, /-bis-(3-chloro-μm hydroxyphenyl)cyclohexane, /, l-bis(3-chloro-
Hiro-hydroxyphenyl)-coethylbutane, Hiro, ≠
′-Secondary isooctylidene diphenol, ≠-
ter t-octylphenol, ≠, ≠'-5ec-
Butylidene diphenol, ≠-p-methylphenylphenol, ≠, 4t'-inpentylidene diphenol,! ,! ' -Methylcyclohexylitine diphenol, ≠, Hiro' -dihydroxydiphenyl sulfide, /, ≠-bis-≠'-hydroxycumylbenzene, l
, 3-bis≠′-hydroxycumylbenzene, Hiroshi, 3-bis′-thiobis<b-tert-butyl-3-methylphenol), ≠, 4A′-dihydroxydiphenylsulfone, hydroquinone monobenzyl ether, ≠-hydroxybenzophenone, 2. ≠-dihydroxybenzophenone, polyvinylbenzyloxyphenol, λ, e, e'-trihydroxybenzophenone,
'e'e≠, 3'-detrahydroxybenzophenone,
≠-Hydroxyphthalate 1fl dimethyl, Hiroshi-methyl hydroxybenzoate, λ, 44.4A' -) IJ hydroxydiphenyl sulfone, l,! -bis-p-hydroxyphenylpentane, l,6-bis-p-hydroxyphenoxyhexane, tolyl hydroxybenzoate, α-phenylbenzyl hydroxybenzoate, phenylpropyl hydroxybenzoate, hydroxybenzoic acid Phenethyl, ≠-hydroxybenzoic acid-p-
Chlorobenzyl, ≠-hydroxybenzoic acid-p-methoxy be/zyl, ≠-hydroxybenzoic acid benzyl ester, ≠-hydroxybenzoic acid-m-chlorobenzyl ester, ≠-hydroxybenzoic acid β-phenethyl ester,
≠-Hydroxy-λ', Hiro'-dimethyldiphenylsulfone, β-7enethyl orseinate, shicinamyl orseinate, orselic acid-o-chlorophenoxyethyl ester, 0-ethylphenoxyethyl orseline), o-7 dinylphenoxyethyl orcelinate,
m-Phenylphenoxyethyl orcelinate, 2,4
cm dihydroxybenzoic acid-β-3'-1-butyl-μ
'-Hydroxyphenoxyether ester, 1-t-butyl-≠-p-hydroxyphenylsulfonyloxybenzene, Hiro-N-benzylsulfamoylphenol,
λ, ≠-dihydroxybenzoic [-p-)f-rubenzyl ester, λ, Hiro-dihydroxybenzoic acid-β-phenoxyethyl ester, λ.

Hiro-dihydroxy-6-methylbenzoic acid benzyl ester, bis-μm methyl hydroxyphenylacetate, ditolylthiourea, Hiro, 4L'-diacetyldiphenylthiourea, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3. ! - tertiary butylsalicylic acid, 3. ! -didodecylsalicylic acid, 3-methyl-!
-Benzylsalicylic acid, 3-phenyl-j-(α, α-
(dimethylbenzyl)salicylic acid, 3. Aromatic carboxylic acids such as r-di(α-methylbenzyl)salicylic acid and λ-hydroxy-7-benzyl-3-su7toic acid; 3. !
- Organic color developers such as phenolic resins such as dicyclopentagenyl salicylic acid, para-phenylphenol-formalin resin, and para-dutylphenol-acetylene resin. Salts with polyvalent metals such as titanium, manganese, tin, nickel, and hydrogen chloride,
Hydrohalic acids such as hydrogen bromide and hydrogen iodide, boric acid,
Inorganic acids such as halides such as silicic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid, aluminum, zinc, nickel, tin, titanium, boron, etc., acid clay, activated clay, attapulgide, bentonite, colloidal silica, aluminum silicate, Magnesium silicate, zinc silicate, tin silicate, p-danzinc, zinc chloride, iron stearate, cobalt naphthenate, nickel oxide, inorganic color developer such as ammonium nitrate, oxalic acid, maleic acid, tartaric acid, Que'L succinic acid, One or more types of aliphatic carboxylic acids such as stearic acid, benzoic acid, g-laterbutylbenzoic acid, heptalic acid, gallic acid, etc. 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. λ, jO! , Hiro 7
No. 0, same λ, rot, Hiroshi 71, same co.

rot, 4cry issue, same 2. ．． ! r4#, Ett issue, same co, 7/ko, j07 issue, same J, 730, ≠! No. 2,730. ≠! No. 7, 31031 ILO Hiroshi No. 3, No. 3. Various forms are possible as described in prior patents such as No. II/1,2!0 and No. Aoioozr. Most commonly they consist of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

A method for manufacturing capsules is described in US Patent λ.

No. 100.1117, same? , 100, 'A method using coacervation of a subhydrophilic colloid sol described in Art No., British Patent No. ff67.727, same!
0, #4Zj No. t, same No. 26μ, same No. 1.

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

In general, electron-donating colorless dyes are used alone or in combination as solvents (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, alkylated terphenyl, etc.).
Chlorinated paraffin-rich synthetic oils; 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 it on a support such as paper, high quality paper, plastic sheet, resin coated paper, etc.

Neutral paper is particularly preferred as the support.

The electron-accepting compounds described below, alone or in combination, or together with other electron-accepting compounds, are dispersed in a binder such as butadiene latex, polyvinyl 7/l/coal, and the pigments described below are dispersed in paper, plastics, etc. A developer sheet is obtained by coating a support such as a sheet or 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 use fn.

When used in thermal paper, the electron-donating colorless dye and the electron-accepting compound have a molecular weight of less than ioμ, preferably 3
It is used after being crushed and dispersed to a particle size of μ or less. As a dispersion medium, a water-soluble polymer aqueous solution with a concentration of about Q, 0 to 10 is generally used, and dispersion is carried out by ball mill, sand mill,
This is done using a horizontal sand mill, attritor, colloid mill, etc.

The ratio of the electron-donating colorless dye used to the electron-accepting compound is preferably between l:lO and l:/, and even l:! The period between 3 and 3 is particularly preferable. At that time, fatty acid amide, acetoacetate 27 dilide, diphenylamine,
For nitrogen-containing M-like compounds 1 such as penzamide, carbazole, etc.

3-sheet m-t! jLuzotan, 0-fluorobenzoyldurene, chlorobenzoylmesitylene, ≠.

μ′-dimethylbiphenyl, or carboxylic acid esters such as dimethyl isophthalate, diphenyl phthalate, dimethyl terephthalate, methacryloxybiphenyl, etc., or polyether compounds such as di-m
-) Ryloxyethane, β-phenoxyethoxyanisole, /-phenoxy-J-p-ethylphenoxyethane, bis-β-(p-methoxyphenoxy)ethoxymethane, /-λ'-methylphenoxy J-4! '-ethylphenoxyethane, /-tolyloxy-2-p-methylphenoxyethane, l, cordiphenoxyethane, /
, 4cm diphenoxybutane, bis-β-(p-ethoxyphenoxy)ethyl ether, l-phenoxy-J-
p-chlorophenoxyethane, /-J'-methylphenoxyethane≠“-ethyloxyphenoxyethane, l
It is preferable to use a compound having a melting point of 7j0C to 130oC, such as -≠'-methylphenoxyco≠"-fluorophenoxyethane. These are used in finely dispersed form at the same time as the colorless dye or at the same time as the 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 20% to 300% with respect to the electron-accepting compound, and preferably %≠OCS to 1zocs.

Additives are further added to the coating liquid thus obtained in order to meet various requirements.

Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers 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 enhance the quality. Therefore, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, additives such as pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, and surfactants are used. is applied onto the support to constitute the recording material.

Specifically, pigments such as kaolin, calcined kaolin, talc, waxite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, and sulfuric acid are used as pigments. It is selected from barium, mica, microballoons, urea-formalin fillers, polyethylene particles, cellulose fillers, etc. with a particle size of 0.1 mm/jμ. Examples of waxes include /g rough-in wax, carboxy-modified paraffin wax, cowna wax, microcrystal 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 oleic acid, and the like.

These are dispersed and applied in a binder.

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

The coating liquid is applied onto base paper, high-quality paper, plastic sheet, synthetic paper, or neutral paper in an amount of about λ to IOf/m2.

Furthermore, a protective layer of about 0.2 to 2 μm consisting of a water-soluble or water-dispersible polymer chill 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 it.

When used for thermal paper, 0Llz cocotjri issue, same 2/10r! Hiroshi, special public Akira! Various embodiments described in Coco O/41c etc. can be taken. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

For example, electric thermal paper is manufactured by Kokai Akihiroter//J4A≠, same J
It is manufactured by the method described in O-≠t230. 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. form a layer, on top of which
The electrically conductive thermal paper of the present invention is produced by applying 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 JP-A-17-72136. Generally silver iodobromide, silver bromide, silver behenate, Michler's ketone, bency/derivatives,
A photopolymerization initiator such as a benzophenone derivative and a polyfunctional polymer such as a crosslinking agent such as a polyallylated compound, poly(meth)acrylate, or poly(meth)acrylamide are used together with a colorless dye and optionally a solvent to form polyether urethane,
A synthetic resin wall, such as polyurea, is encapsulated within the capsule. After the image area is exposed to light, the colorless dye in the unexposed area is brought into contact with a color developer and colored.

The electron-donating colorless dye according to the present invention is synthesized by the following 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 volatile organic inert solvents such as Rava chloroform, benzene, and benzene chloride,! After reacting for 10 to 8 days at a corresponding temperature of O~/≠o0C, the reactants were placed in ice water to hydrolyze the condensing agent, the above volatile organic inert solvent was added, and the mixture was made alkaline with an aqueous sodium hydroxide solution. It is obtained by separating the solvent layer and distilling off the solvent under reduced pressure.

Preferred is a method in which a bis-type aniline derivative obtained by reacting m-dialkylamine phenol with civalide or ditosylate is reacted with carboxybenzoylindole or carboxypyridinecarbonylindole.

For the reaction method, known methods can be applied, for example, as disclosed in JP-A-Sho t/-
No./614414 also discloses reaction conditions.

Synthesis Example 1 Synthesis of 3-oxatylene-l,j-bisJ-(p-ethylamino-cooxyphenyl)-j-(/-ethyl-2-phenylindol-3-yl)7thalide m-diethylamino Phenol 001 mol, diethylene glycol ditosylate o, oar mol, potassium carbonate 0
．． Weigh 1 mole of sulfolane in a flask equipped with a stirrer. Add O- and stir while heating.

When you pour it into water/! -Bis-m-diethylaminophenoxy-3-oxaintane is obtained as a liquid. 0.01 mole of this aniline derivative and 0005 mole of 3-0-carboxybenzoyl-7-ethyl-2-methylindole obtained by reacting l-ethyl-methylindole with phthalic anhydride are placed in a flask and placed in a weighing vessel. Add acetic anhydride and heat. The reaction proceeds immediately and the system becomes blue-purple. After pouring the reaction product into water, it is separated by column chromatography using chloroform-ethyl acetate as a solvent. The desired product is obtained as white crystals, melting point /l-≠0C.

Synthesis example λ t, 1A--f tyrenebis-3-(p-diethylamine-2-oxy)phenyl]-3-(/-ethyl-methylindol-3-yl)7talide diethylene glycol ditosylate of synthesis example 1 The reaction was carried out in the same manner except that /1 μm butanediol ditosylate was used instead.

The melting point of the crude product was l≠7-/60°C, and it appeared as a bright purple color on silica gel.

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

Examples and Comparative Examples ■ Preparation of color developer sheet 3. 3-bis-α-methylbenzylsalicylic acid zinc salt 1
0 parts/-inpropylphenyl-! -Phenylethane-0 part was added to the mixture and dissolved by heating at 0°C. Add this to polyvinyl alcohol (PVA-/17 Kuraray all)
Added to the aqueous solution JO part, and further added 10S as a surfactant.
A milky ζ solution was prepared by adding 7 parts of dodecylbenzenesulfonic acid triethanolamine salt aqueous solution using a homogenizer so that the average particle size of the emulsion was 3 μm.

Next, a dispersion of 10 parts of calcium carbonate, 20 parts of zinc oxide, 200 parts of sodium hexametaphosphate and 200 parts of water was prepared using a Keddy Mill, and after mixing the above emulsion,
As a binder, 10% PVA-//7 (manufactured by Kuraray)
100 parts of aqueous solution Tocarfoxy-modified SDR latex (S
N-307, manufactured by Sumitomo Naugatux Co., Ltd.) 70 parts (as solid content) were added thereto and water was added to adjust the solid content concentration to 2+17% to obtain a coating liquid (A).

Next, using 10 parts of the color developer, 20 parts of silt/clay, 40 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water, use a sand grinder to uniformly obtain an average particle size of 3 μm. dispersed into

First, add 10 pieces of PVA-10! to the resulting dispersion. (Manufactured by Kuraray) 74 parts of an aqueous solution were added, and then 10% PVA-//7 (Ioo parts of aqueous solution) and Io parts of carboxy-modified SBR latex (SN-307 made by Sumitomo Nogatatsu) (
As a solid content), add water and adjust the water so that the solid content concentration is 20%, and apply liquid (B).

Coating liquid (A) and coating liquid (B) t - A/B = z in terms of color developer
Mix with o / z o to make j Of / m2 base paper! , Of/rrL2 solid content was coated using an air knife coater and dried to obtain a color developer sheet.

■ Preparation of capsule sheet containing color former Melamine/formaldehyde resin capsule Partial sodium salt of polyvinylbenzenesulfonic acid (manufactured by National Starch Co., Ltd., VER8A1 TLjoo, average molecular weight zo
o, ooo) z parts were added to 1 part of hot water at about to 'C with stirring and dissolved. After dissolving for about 30 minutes, it is cooled. The pH of the aqueous solution was 2 to 3, and an aqueous solution of sodium hydroxide mixed with CO was added thereto to adjust the pH to 44.0. On the other hand, add 7700 parts of diimpropyl naphthalene in which the following color forming agent is dissolved in J and 1% to a portion of the sodium salt of the polyvinylbenzenesulfonic acid. Emulsified and dispersed in 700 parts of aqueous solution and average diameter ≠,! An emulsion with a particle size of μ was obtained. Separately, 1 part of melamine, 37 parts by weight of formaldehyde aqueous solution, and 30 parts of water were heated and stirred at 6z'C, and after 30 minutes, a transparent mixed aqueous solution of melamine, formaldehyde, and melamine formaldehyde precondensate was obtained. The pH of this mixed aqueous solution was Jr. Hereinafter, this mixed aqueous solution 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 added and mixed to the above emulsion, and while stirring, the pH was adjusted to t, o with a 3.6% by weight glue/acid solution, and the liquid temperature was raised to 6z'C. Continue stirring for 360 minutes. The capsule liquid was cooled to room temperature and the pH was adjusted to OK with 20% sodium hydroxide.

10 for this capsule dispersion! 200 parts of i% polyvinyl alcohol aqueous solution and starch particles! A coating solution of a microcapsule dispersion was prepared by adding 0 part of the microcapsule dispersion and adding water to give a solid content concentration of 20 g.

Is this coating liquid IO? / j f on the base paper of 7FL2
The mixture was coated with an air knife coater so that a solid content of 2/yl 2 was coated and dried to obtain a color former-containing capsule sheet used in the present invention.

When a pressure-sensitive recording sheet was prepared by combining the color developer sheet obtained as described above and a color former-containing capsule sheet and was colored, extremely clear images with good light resistance were obtained.

The color forming agent used is as follows.

Example 1 3-Oxaventhrene-1, terbis-3-(≠-diethylamino-cooxyphenyl)-3-(/-ethyl-comethylindol-3-yl)phthalide, Example cophthalide of Example 1 A 7/3 (weight ratio) mixture of crystal violet lactone and -(g-diethylamine-(α-7enethyloxy)phenyl)-j-
(weight ratio) mixture of (/-ethyl-2-methylindol-3-yl) phthalide Example ≠ Example / phthalide and 3-[dardiethylamino)-co(β-7enethyloxy)phenyl]- j/2 (weight ratio) mixture with J-(/-ethyl-2-anthylin)'A/-3-yl)azaphthalide

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 general formula (I), R_1 to R_1_0 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a substituted amino group, or an aryl group, and R_7, R_8, and R_9 and R_1_0 may be combined with each other to form a ring. R represents a divalent group having 1 to 20 carbon atoms, and Ar represents an optionally substituted aryl group.