JPS6335382A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material having favorable color forming properties, raw preservability and stability of developed color images, by using a specified compound as an electron-donative colorless dye. CONSTITUTION:A compound of formula (I), where in each of R and R' is an alkyl, R1 is an aralkyl, each of R2 and R3 is an alkyl or aryl, and each of X, Y and Z is hydrogen, an alkyl, alkoxyl, aryloxyl, halogen or substd. amino, is used as an electron-donative colorless dye in a recording material using the electron-donative colorless dye and an electron-acceptive compound. The dye is rapidly developed into a color upon making contact with the electron- acceptive compound. A coloring matter thus color developed is extremely stable, and is substantially insusceptible to discoloration or fading. In addition, stability of the color former is also excellent, so that deterioration or coloring will not occur even after long-time preservation. Accordingly, the color former has an almost ideal performance as a color former for recording materials.

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 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 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 21 IAOIA Ko2, U.S. patent Hirohiro 100 ter, 1s6ri λQ1 special public Shobo-23, octopus λ, % Kaishoj7-/7ri, ni36, AO-/23. !
! &, 1.0-/23. ! ! I am familiar with 7 etc.

The characteristics that the recording material should have are (1) sufficient color development resistance and color development sensitivity, (2) no turning IJ' and (3) sufficient fastness of the color material after color development. (4) Appropriate color hue and suitability for copying machines;
5) It has a high S/N ratio, (6) The color former has sufficient chemical resistance, and (7) It is easily soluble in organic solvents, but currently there is no material that completely satisfies these requirements. Not obtained.

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.

BACKGROUND ART Fujidinylmethane compounds, triphenylmethane compounds, phthalide compounds, leucomethylene blue compounds, and the like are conventionally known as compounds that develop a blue to bluish-purple color. However, each of these compounds has drawbacks.

For example, 3,5-bis-(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e., crystal violet lactone, CVL) develops quickly and exhibits a plaster-colored color, but the light resistance of the colored image is extremely poor. be. Furthermore, 3,7-bis(dimethylamino)10-benzoylphenothiazine (i.e., benzoylleucomethylene blue, BLMB), which is one of the seven leucomethylene blue-based compounds, has extremely excellent light resistance in its color image, but its 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 bath property, water solubility, partition coefficient, pKa, polarity of substituents, position of substituents, and research on the colorless electron-donating dye and 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 product which has good color development properties, shelf life, and stability of colored images, and has good solubility in aromatic bath additives and rough-in bath additives, as well as in other products. It is an object of the present invention to provide recording materials using materials titrated to mechanically compatible conditions.

(Structure of the Invention) The object of the present invention is to produce an electron-donating colorless dye of the following general formula (
Compound shown in 1)? This was achieved by a recording material characterized by the use of

In the above formula, R and R' are alkyl groups.%R1 is an aralkyl group.
%R2, R3 is an alkyl group, aryl group, X%Y, Z
represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, or a substituted amine group.

The aryl group represents a phenyl group, a naphthyl group, or a heteroaromatic ring group, and these include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group,
Substituents such as substituted amine group, substituted Ogin carbonyl group or @-substituted oxysulfonyl group! may have. 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, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.

Among the @ substituents represented by R or R' in the above formula, alkyl groups having 1 to 10 carbon atoms, alkoxyalkyl groups, halogen atom-substituted alkyl groups, and aryloxyalxy groups are preferred, even if they are the same or different. Yo(,R
Among the substituents represented by , aralkyl groups having 7 to 2 carbon atoms are preferred. Among the substituents represented by R2, an aryl group having 7 to 1λ carbon atoms, an alkyl group which may have an aryloxy group, an alkoxy group, an aryloxy group or a halogen atom as a substituent, and an alkyl group having 6 to IO carbon atoms; A phenyl group which may have an alkoxy group or a halogen atom as a substituent is preferable, and among the islands and substituents represented by R3, an alkyl group having carbon atoms/~j and a phenyl group having 6 to 10 carbon atoms are preferable. Preferably, X%Y
, the number of hydrogen atoms and carbon atoms among the substituents represented by Z/
-40 full: Ixy group, aryloxy group having 6 to IO carbon atoms, chlorine atom and fluorine atom, number of carbon atoms /-/
The alkyl group and substituted amino group of 2 are preferred.

The electron-donating colorless dye according to the present invention is a colorless or light-colored crystal, and has a 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 dye is extremely stable compared to dyes produced from existing coloring agents, and hardly changes color or fades even when exposed to light, heat, or humidification for long periods of time, making it especially advantageous in terms of long-term preservation of records. The coloring agent has excellent stability, does not change in quality or discoloration even after long-term storage, has sufficient coloring ability, and has near-ideal performance as a coloring agent for recording materials such as pressure-sensitive paper and thermal paper. Shoulder.

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

/)j-(≠-diethylamino-2-benzyloxyphenyl)-J-(/-ethyl-2-methylindole-
3-yl)phthalide λ)j-(4C-diethylamino-
λ-(≠-methylbenzyloxy)phenyl J-j-(
/-dithyl-comethylindol-3-yl)7talido J)
-Methylindol-3-yl)phthalide) )j-(Hiro-diethylamino-2-(v-methoxydibenzyloxy)phenylJ-j-(/-ethyl-2-methylin)--ruj-yl)phthalide6)j-(&-dibutylamino-2-(v-methoxydibenzyloxy)phthalide) )-1-pencyloxyphenyl)-j-(/-ethyl-λ-menalindol-3-yl)7thallide 7) J-(44-diethylamino-
λ-benzyloxyphenyl)-J-(/,λ-dimethylindol-3-yl)phthalide 1) j-(4L-diethylamino-λ-benzyloxyphenyl)-J-(/-ethyl-λ-phenylindole 3-yl)phthalidota) 3-Cμmdiethylamine-2-(β-phenethyloxy)phenyl 3-
j-(/-ethyl-2-methylindol-3-yl)
Phthalide 10) J-(Hiro-diethylamino-(α-7enethyloxy)phenylJ-j-(/-ethyl-2-methylindol-3-yl)phthalide//)j-(≠-diethylamino)-- 2-(β-phenethyloxy)phenyl J-j-(/-ethyl-J-i
so-- <methyl indole 3-year) phthalide These colorless dyes are also known triphenylmethane phthalide compounds, fluoran compounds,
Recording materials can also be assembled in combination with various compounds such as phenothiazine compounds, intriazalphthalide compounds, leucoauramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, and spiropyran compounds. can.

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 of the colorless dyes used in combination like that? For example, as a triarylmethane compound, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (f
fU (crystal violet lactone), J, j-bis(p-dimethylaminophenyl) phthalide, J-(p
-dimethyla is nophenyl) -j-(/,j-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-J-(2-methylindole-3-
diphenylmethane-based compounds include Hiro, Hiro'-bis-dimethylaminobenzhydrin (endyl ether, N-halophenyl-leuko,
Fmin, N-2゜hiro, t-t+)chlorophenylleukoolamine, etc., and life-santhene compounds include rhodamine-B-anilinolactam, rhodamine(p-nitroanilino)lactam, rhodamine B(p- Chlorani υ)) Lactam, codibenzylamino 6-dinithylaminofluorane, -monoanilino 6-diethyl ξ
nofluorane, 2-anilino-3-methyl-6-dinithylaminofluorane, λ-anilino-3-methyl-6-
Cyclomethylaminofluorane, 2-O-chloroanilino-6-dinithylazunofluorane, λ-m-
Chloroanilino-6-dinithylaminofluorane, -1(3,Hiro-dichloroanilino)-6-dinithylaminofluorane, -1octylamino-6-dinithylaminofluorane, 2-dihexylamino-6- Diethylaminofluorane, 2-m-trifluoromethylanilino-6-
Dinithylaminofluoran, λ-butylamino-3-chloro-6-dinithylaminofluoran, 2-ethobyldiethylamino-3-chloro-6-dinithylaminofluoran, up-p-chloroanilino-3-methyl-6 -dimethylaminofluorane, 2-anilino-3-methyl-6-
Cyoctylaminofluorane, co-anilino 3-chloro-6-dinithylaminofluorane, co-phenylamino-6-diethylaminofluoran, co-anilino 3-methyl-6-diphenylabanofluorane, co-anilino 3-chloro-6-dinithylaminofluorane , co-anilino 3-methyl-b-N-ethyl-N-ynamylaminofluorane, co-anilino 3-methyl-yo-chloro-
6-dinitylaminofluorane, co-anilino 3-methyl-6-dinitylamino-7-methylfluorane, λ
-anilino 3-methoxy 6-cyptylano ξnofluorane, λ-〇-chloroanilino-6-cyptylaminofluorane, col-10 loanilino 3-ethoxy-4
-N-ethyl-N-ynamylaminofluorane, λ-
0-/loloanilino 6-p-butylanilinofluorane, co-anilino 3-tertatecyl-6-diethylaminofluorane, λ-anilino 3-ethyl-6-cyptylaminofluoran, λ-anilino 3-methyl≠
',j'-dichlorofluorane, co-0-toluidino-3-methyl-6-diinpropylamino-Hiroshi1. j／
-dimethylaminofluorane, λ-anilino 3-ethyl-6-N-ethyl-N-ynamylaminofluorane, co-anilino 3-methyl-6-N-ethyl η
-methoxypropylainofluorane, λ-anilino-3-chloro-6-N-ethyl-N-ynamylaminofluorane, etc. Thiazine compounds include benzoylleucomethylene blue, p-nitrobenzoylleucomethylene blue, etc. As a system compound, 3
-Methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran,! ,! '-Cyclolosespiro-dinaphthopyran, 3-indylspiro-dinaphthopyran,
Examples include 3-methyl-naphtho-(3-methoxy-benz)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 cast conductor, bricylic acid derivative, metal salt of aromatic carboxylic acid, acid clay, bentonite, tumelac resin, metal-treated novolac resin, Hiro-tertiary-butylphenol, Hiro-phenylphenol, Hiro-hydroxydiphenoxide, α-naphthol, β-naphthol, hexyl-hiro-hydroxybenzoate, 2.2
'-dihydroxybiphenyl, 2,2-bis(≠-hydroxyphenyl)propane (hisphenol A), μ
, v'-inpropylidene bis(2-methylphenol), /, /-bis-(J-chloro-Hiro-hydroxyphenyl)cyclohexane, /, /-his(3-chloro-Hiro-hydroxyphenyl)-co ethylbutane, g, 1-
Sekanguryin octylidene diphenol, Hiro-te
rt-octylphenol, μ, Hiro'-5ec-butylidene diphenol, 4C-p-methylphenylphenol, 4C,4u-impentylidene diphenol <4
, μ′-methylcyclohexylidene diphenol, 4
clμ'-dihydroxydiphenyl sulfide%/1
μm bis-Hiro'-hydroxycumylbenzene, l,3-
Dicumylbenzene in bisuzhen'-hydro, 4c, 44'
-thiobis(4-tert-butyl-3-methylphenol),! , µ'-dihydro-phenyl sulfone quinone monobenzyl ether, µm hydroxybenzoenone, 2. Dibenzophenone in μm dihydro, dicarbonylphenol in polyvinylbenzylhydro,'
e”+”h! J Hydroxybenzophenone,'
t ” 1 ” eμ! -tetrahydroxybenzophenone, dimethyl l-hydroxyphthalate, methyl hydroxybenzoate, λ+ ” * ” ' -) lyhydroxydiphenyl sulfone, 1. j-bis-hydro-diphenylintane, /, A-bis-hydro-diphenol hexane, tolyl hydroxybenzoate, hydroxybenzoic acid α-phenylbenzyl ester, phenylpropyl dihydroxybenzoate, hydroxybenzoate 7-enethyl hydroxybenzoate, Hiro-hydroxybenzoate-p-chlorobenzyl, Hiro-hydro a=? Shian J1m-
p-methoxybenzyl, infant-hydroxybenzoic acid ester, ≠-hydroxybenzyl, 1-ht-m-chlorobenzyl ester, hydroxybenzoic acid β-phenethyl ester, hydroxy-21,4CI-dimethyldiphenyl sulfone, β-7enethyl orselinate, cinnamyl orselinate, orselic acid-〇-chlorophenoxyethyl ester, 〇-ethylphenoxyethyl orselinate, O-phenylphenoxyethyl orselinate, m-phenylphenoxyethyl orselinate nate, λ, 4C-dihydroxybenzoic acid-β-37t
-butyl-benz'-hydro-diphenol diethyl ester, /-t-butyl-hiro-p-hydroxyphenylsulfonyloxybenzene, μ-N-benzylsul 7-ammoylphenol, co, 4A-dihydroxybenzoic fli-p
-Methylbenzyl ester, λ,tA-dihydroxybenzoic acid-β-phenoxyethyl ester, Y.

μm dihydroxy-rumethylbenzoic acid benzyl ester, bis-μm hydrobovine diphenylacetate methyl, ditolylthiourea, <C, <CI-diacetyldiphenylthiourea, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3. j-di-tert-butylsalicylic acid, 3. j-di-dodecylsalicylic acid, 3-methyl-yo-benzylsalicylic acid, 3-phenyl-yo-(α, α-
dimethylbenzyl)salicylic acid, 3. Aromatic carboxylic acids such as j-di(α-methylbenzyl)salicylic acid, cohydroxy-7-benzyl-3-naphthoic acid, 3. j
- Di-cyclo is an organic color developer such as 7-enol resin such as ntadienylsalicylic acid, para-phenylphenol-formalin resin, norabutylphenol-acetylene resin, and in combination with these organic color developers, such as zinc magnesium, aluminum or nium, Salts with polyvalent metals such as calcium, titanium, manganese, tin, and 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, amenol guide, bentonite, colloidal silica, aluminum silicate, Magnesium silicate, zinc silicate, tin silicate, zinc rhodan, zinc chloride, iron stearate, cobalt naphthenate, nickel peroxide, ammonium nitrate, and other non-isolated color developers, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid,
One or more types of aliphatic carboxylic acids such as stearic acid, benzoic acid, paratertiary butylbenzoic acid, phthalic 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. 2. jO, Hiro7
No. 0, same! 01, Hiroshi 7/issue, same λ.

rot, ary issue, same 2. ! at, No. 344, same, 7
1λ, No. 507, same, 730. Hiroj No. 6, Hiroj No. 2, 7
30.4! ! No. 7, No. J/ No. 0JltO4A, No. J
, A11,230, A140/0031, and other prior patents. Most commonly they consist of a 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.

100.44j No. 7, same J, too, uzt'sv
c. A method using coacervation of a hydrophilic colloid sol described in British Patent No. 167.797, ibid. jO
No. 91, same as J, 26≠, same as L.

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

In general, electron-donating colorless dyes are used singly 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 a bath and incorporating it into microcapsules,
A color forming agent sheet is obtained by coating it on a support such as paper, paper, plastic sheet, or resin coated paper.

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. Those skilled in the art will use this! It is easy to determine #.

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
The dispersion medium used for pulverizing and dispersing particles to a particle size of μ or less is generally a water-soluble polymer aqueous solution with grooves of about 0,j to 10 g.
This is done using a horizontal sand mill, attritor, colloid mill, etc.

The ratio by weight of the electron-donating colorless dye and the electron-accepting compound used is preferably between /:lO and l:l, and even l:! % to 3 is preferred. At that time, fatty acid amide, acetoacetanilide, diphenylamine,
Nitrogen-containing organic compounds or compounds like penzamide, carbazole, etc.

J-di-m-tolylbutane, 0-fluorobenzoyldurene, chlorobenzoylmesitylene, Hiromu.

Hiro'-dimethylbiphenyl, or carminic acid esters such as dimeflLt inphthalate, diphenyl phthalate, dimethyl terephthalate, methacryloxybiphenyl, etc., or polyether compounds such as di-m-tolyloxyethane, β-phenoquinethane, cyaninol, l- Phenoxy-λ-p-ethylphenoxyethane, bis-β-(p-methoxyphenoxy)ethoxymethane, /-1'-methylphenoxy7-λ-≠'L
Ethylphenoxyethane, l-tolylox7-2-p-
Methylphenoxyethane, 1,2-diphenoxyethane, /, tA-diphenoxybutane, bis-β-(p-ethoxyphenoxy)ethyl ether, /-phinoxyJ-p-chlorophenoxye fi7, / It is preferable to use a compound having a melting point of 7j0C to /30°C such as -λ'-methylphenoxycoμ"-ethyloxyphenoxyethane and /-4C'-methylphenoxycoμ"-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. These usage amounts are added at a weight ratio of 2Q% or more and 300% or less with respect to the electron-accepting compound.
It is preferably at least r-44o% and at most izo%.

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

Examples of additives include oil-absorbing substances such as inorganic pigments and polyurea fillers that are dispersed in the binder in order to prevent the recording head from becoming dirty during recording. Fatty acids, metal soaps, etc. are added to enhance the coloring.Therefore, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, Additives such as a conductive agent, a fluorescent dye, and a surfactant are applied onto the support to form a recording material.

Specifically, pigments such as kaolin, calcined kaolin, talc, waxite, geriatric earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, ME gypsum, 7 Lika, magnesium carbonate, titanium oxide, alumina, barium carbonate, Barium sulfate, mica, microballoon, urea-formalin filler, polyethylene particles, cellulose filler, etc. particle size 0. / or l! Selected barrels from μ's. Examples of the waxes include morphine wax, carboxy-modified paraffin wax, cownaparow wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Examples of metal phosphorus include polyvalent metal salts of higher fatty acids, ie, zinc stearate, albanium stearate, calcium stearate, and olein h'Jl lead'4.

These are dispersed and applied in a binder.

Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, dipropyl cellulose in hydrochloride, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and imbutylene-maleic anhydride copolymer. Examples include maleic anhydride copolymer, 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, or emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic resin emulsions, etc. You can also add

The coating liquid is applied onto base paper, high quality paper, plastic snack sheet, synthetic paper or neutral paper at a thickness of about λ~109/m2.

Furthermore, a protective layer of about 0.λ to 2 μm consisting of a water-soluble or water-dispersible polymer compound such as polyvinyl alcohol, hydroxyethyldenbane, 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, OLSλ, Zfsri
No. 211011 Hiro, Tokko Akira! 2-207 Hiroki et al. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

The electrically conductive thermal paper is manufactured, for example, by the method described in Japanese Patent Application Laid-open No. 2-/3IItμ and to-er PJO. Generally, a coating liquid in which a conductive substance, a basic dye mainly composed 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 paper, or
The electrically conductive thermal paper of the present invention is produced by coating a support with a conductive substance to form a conductive layer, and then coating thereon a coating liquid in which a colorless dye, an electron-accepting substance, and a binder are dispersed. In addition, using the thermofusible substance mentioned earlier,
Sensitivity can also be improved.

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, benzoin derivatives,
A photopolymerization initiator such as a benzophenone derivative and a crosslinking agent such as a polyfunctional monomer such as a polyallylated compound, poly(meth)acrylate, or poly(meth)acrylamide are used together with a colorless dye and optionally a solvent to produce polyether urethane,
A synthetic resin wall, such as polyurea, is encapsulated within 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, in the presence of a condensing agent such as acetic anhydride or phosphorus oxychloride, the corresponding carboxybenzoic acid or benzoylpyridinecarboxylic acid and an indole, or the corresponding carboxybenzoylindole or carboxypyridine carboxylic acid and an aniline derivative are combined. , using the necessary volatile organic inert solvents such as chloroform, benzene, and benzene chloride, and
After reacting for 20 minutes at a temperature corresponding to C, the reaction product was placed in ice water to hydrolyze the condensing agent, the above volatile organic inert solvent was added, and the solvent was made alkaline with an aqueous sodium hydroxide solution. It is obtained by separating the layers 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 70 parts of the color developer shown in Table 1 were dissolved in 20 parts of t/-impropylphenyl-2-phenylethane by heating in an evaporator at 00C. This was mixed with 2% polyvinyl alcohol (PVA-
/ / 7) Added to 30 parts of aqueous solution (manufactured by Kuraray), and further added 7 parts of 10% dodecylbenzenesulfonic acid triethanolamine salt water bath solution kO as a surfactant, and emulsified with a homogenizer so that the average particle size of the emulsion was 3μ. A liquid was prepared.

Next, a dispersion of 10 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water was prepared using a Keddy mill, and after the above emulsion was mixed, 10% PVA-/ / 7 (manufactured by Kuraray) aqueous solution ioo part tocarfoxy modified SBR latex (SN-307, Sumitomo Nogatux H) 10 parts (
(as a solid content) was added and adjusted by adding water so that the solid content concentration was 20%, to obtain a coating liquid (AJ).

Next, using 70 parts of the color developer, 20 parts of Jilton clay, 60 parts of calcium carbonate, 20 parts of zinc oxide, 7 parts of sodium hexametaphosphate, and 200 parts of water, the particles were uniformly ground to an average particle size of 3 μm using a sand grinder. Dispersed.

First, 6 parts of a 70% PVA-to3 (manufactured by Kuraray) aqueous solution was added to the obtained dispersion, and then Vc10% PVA-/i 7
(ri5VtJ) water mW/00HA5 and 10 parts of calxoxy-modified SBR latex (SN-3o7 manufactured by Sumitomo Naugatux) (added as solid content, solid content concentration is 2
Water was adjusted to 0% to obtain a coating liquid (B).

Coating liquid (A) and coating liquid (I3) in terms of color developer A/B==j
Mix with O/J O and apply to 60g7m of base paper.
Q,! It was coated with an air knife coater so that the solid content of il/rfL2 was coated and dried to obtain a color developer sheet. ■ Preparation of color developer-containing capsule sheet ■ Part of melamine/formaldehyde resin capsule polyvinylbenzenesulfonic acid R parts of sodium salt (National Starch Company a, VER8A, TL!OO 1 average molecule Hsoo, ooo) were added to 23 parts of hot water at about ro 0 C with stirring and dissolved. After dissolving for about 30 minutes, it is cooled. The pH of the aqueous solution is 2 to 3, which is VC20
Add heavy U% sodium hydroxide water bath solution p) 4g, 0
And so. On the other hand, the color forming agent shown in Table 7 was emulsified and dispersed in 100 parts of diimpropylnaphthalene dissolved at 7% in 100 parts of a j% aqueous solution of a partial sodium salt of the polyvinylbenzenesulfonic acid, and the average diameter was 100 parts. An emulsion with particle size was obtained. Separately, 6 parts of melamine, 37 weight ft
% formaldehyde aqueous solution 1 part, water 30 parts bc 0
After 30 minutes of CVC heating and stirring, a transparent mixed aqueous solution of melamine, formaldehyde and initial condensate of melamine-formaldehyde was obtained.

Is the pH of this mixed aqueous solution 6~? Met. Hereinafter, this mixed bath 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 the mixture was poured with 3.61 parts of phosphoric acid solution while stirring.
H1A was adjusted to 0, the liquid temperature was raised to ¥47'C, and stirring was continued for 340 minutes. This capsule liquid was cooled to room temperature and diluted with 20 kg of sodium hydroxide to adjust the concentration to Q.

To this capsule dispersion, 200 parts of a 10% by weight polyvinyl alcohol aqueous solution and 50 parts of starch particles were added, and water was added to adjust the solid content concentration to 20% to prepare a coating liquid of the microcapsule dispersion.

This coating liquid was applied to a 30ji/m2 base paper using an air knife coater so that the solid content was 39/rn2.
After drying, a capsule sheet containing a coloring agent used in the present invention was obtained.

■ Polyvalent incyanate compound (tolylene diincyanate 3
A 7th solution was prepared by mixing 1 g of a polyvalent hydroxy compound (ethylenediamine-brobylene-ox-cyto adduct)/1 lfr' at a temperature below 200C.

Next, 3g of 200C water ginseng 9VC polyvinyl alcohol
and carboxymethyl cellulose sodium [/-j
F'2 bath was dissolved. Further, funnel oil (emulsifier) o and ip were added to prepare a secondary solution.

While vigorously stirring the secondary solution, the primary solution was poured into the secondary solution to form an oil-in-water emulsion. When the size of the oil droplets reached 1,000 μm, the stirring was weakened, and then 100 C of water was added to the emulsion.
The temperature of the system is gradually raised to 7j0C, and at this temperature 6
I kept Q minutes.

To the turnip upper layer liquid obtained in this way, a lj% aqueous solution of polyvinyl alcohol (coj9) and a modified SBR latex in calic acid (7%) were added to the solid content of λy% starch particles (average particle size/μ).
), 2Cg were added.

Then, water was added to adjust the solid content concentration to 2 g% to prepare a coating solution.

Apply this coating solution to a dry weight of 397 m2!
Coat it on Ofi/m2 base paper using an air knife coater and dry to obtain a microcapsule sheet.

■ Gelatin Capsules 20 parts of acid-treated gelatin having an isoelectric point t, O and 20 parts of gum arabic were dissolved in 720 parts of Hiro O0C water, and 0.1 part of sodium alkylbenzenesulfonate was added as an emulsifier. 200 parts of diimpropylnaphthalene in which J and j% of the coloring agent shown in J and J are dissolved are added with vigorous stirring and emulsified to μ and jμ, then uooC
200 parts of water was added to suppress the progress of emulsification.

While continuing to stir, add 300C Mizuhiro λO part, -
The pH of the system was adjusted to μ, H by adding 2C% acetic acid. The liquid was further cooled to t0C while stirring, and then 37%
7.0 parts formaldehyde and 20% glutaraldehyde 1. js was added.

Subsequently, 60 parts of a 10% calyti-j dimethyl cellulose bath solution was poured and then λ! The pH was lowered by dropping an iced sodium hydroxide solution, and after adjusting the temperature to 00C, microcapsules with hardened walls were obtained. To this capsule dispersion, 200 parts of IQ% polyvinyl alcohol aqueous solution and 30 parts of starch particles were added, and the solid content &! 1
Water was added to adjust the concentration to 12Q%, and a coating liquid of the microcapsule dispersion was prepared.

This coating solution was coated with an air knife coater so that the solid content of 309 parts m2 of base paper was coated and dried to obtain a color former-containing capsule sheet to be used for comparison.

The color developer sheet and color former-containing capsule sheet obtained as described above were combined to make a pressure-sensitive recording sheet v 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 1.

[Colored material lightfastness test]

The colored material was irradiated with light of 32,000 lux for 10 hours, and the color density before and after irradiation was compared to determine the residual rate.

In addition, the coloring agent of the present invention has a negative effect on aromatic bath additives.
The solubility was measured at The results are shown in Table λ.

From the results in Table 2, it can be seen that the recording material of the present invention is clearly excellent in light resistance and solubility in organic solvents.

Example 9 j-(4m-diethylamino-penzyloxyphenyl)-j-(/-dithyl-co-methylindole-3
-30 parts of phthalide was mixed and ground for 2 hours using 1 ton of 70% polyvinyl alcohol water bath solution and 70 parts of water for 2 hours to create a dispersion! It was adjusted. The particle size after milling was approximately i, s6 croons. (Component A) 70% polyvinyl alcohol aqueous solution of 30 parts of ≠-β-(p-methoxyphenoxy)ethoxysalicylic acid zinc, 30 parts of 1-penzyloxinenaphthalene 1ron, on the other hand;
Then, the mixture was mixed and pulverized with J part of water using a sand mill to prepare a dispersion TY4. The particle size of the unbathed product after pulverization was approximately 2 microns. (Component B) Next, component A in part J and component B in part O were mixed, applied to paper, and dried to obtain thermal paper.

When this thermal paper was heated with heat in, it developed a blue color.The resulting color image was very stable against light, and even when the image was irradiated with an ultraviolet lamp for 1 hour, there was almost no change in 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. Materials ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) In the above formula, R and R' are alkyl groups, R_1 is aralkyl groups, R_2 and R_3 are alkyl groups and aryl groups,
Y and Z represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom or a substituted amino group.