JPH04151285A - Recording material - Google Patents

Abstract

PURPOSE:To improve stability of coloring image by using a specific compound as an electron donating colorless dye. CONSTITUTION:A compound shown in a formula (1.) is used as an electron donating colorless dye making use of a coloring caused by a contact of the electron donating colorless dye and an electron accepting compound. In the formula (I), Ar1 and Ar2 represent allyl group comprising heterocyclic group and substituent, Ar3 represents allyl group which may comprise the heterocyclic group and the substituent, R1 and R2 represent hydrogen atom and univalent group, R3 represents -XR4, -PO(OR5)2, -CR6R7R8, -NR9R10, X represents oxygen atom and sulfur atom, and R4-R10 represent hydrogen atom or univalent group. However, at least one out of R6-R8 represents electron attractive group, and the substituents in the Ar1-Ar4 are respectively preferable to be of carbon atomicity at 30 or less, and particularly 20 or less is desirable.

Description

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

(Prior Art) Recording materials using electron-donating colorless dyes and electron-accepting compounds are already well known as pressure-sensitive paper, thermal paper, light-sensitive pressure-sensitive paper, electrically conductive thermal recording paper, thermal transfer paper, and the like. For example, British Patent No. 2140449, U.S. Patent No. 4480052, U.S. Pat.
For details, see No. 60-123557.

As a recording material, in recent years (11 color density and color sensitivity (2)
) For improving properties such as before use and color image fastness,
A lot of research is being carried out.

Among these, in blue color recording materials, especially (2)
There is a strong demand for

For example, the blue coloring agent 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e., crystal violet lactone) develops quickly and exhibits a deep blue color, but the light fastness of the colored image Plasticizer properties are extremely poor. Alternatively, although the fastness of the colored image (light fastness, plasticizer resistance) is good, it has drawbacks such as low solubility in the encapsulation solvent, already colored blue by itself, and low color density.

The present inventors have discovered that specific compounds are effective in improving these properties.

(Objective of the Invention) Therefore, an object of the present invention is to provide a recording material using a material which has good stability of a colored image and satisfies other requirements.

(Structure of the Invention) An object of the present invention is to provide a recording material that utilizes color development through contact between an electron-donating colorless dye and an electron-accepting compound, in which the electron-donating colorless dye is represented by the following general formula (1). This was achieved using a recording material characterized by the use of a compound that

In the above formula, Ar+, Arz represent a heterocyclic group, an aryl group which carries a substituent, Ar8 represents a heterocyclic group, an aryl group which may carry a substituent, R,, Rt represent a hydrogen atom, a -valent group. group, R3 is XR, -PO(ORs')! , -CR,Rt R,, -NR,R (X represents an oxygen atom or a sulfur atom, R4-R1゜ represents a hydrogen atom or a -valent group. However, at least one of R, ~R1 is an electron-withdrawing (represents a sexual group).

In addition, an alkyl group, an aryl group, and a heterocyclic group further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group,
It may have a substituent such as a halogen atom, a nitro group, a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group, a substituted amino group, a substituted oxycarbonyl group, a substituted oxysulfonyl group, an alkylthio group, or an arylsulfonyl group.

Each of the substituents of Ar l-Ra preferably has 30 or less carbon atoms, particularly preferably 20 or less carbon atoms.

Among the above-mentioned heterocycles, from the viewpoint of synthetic handling, substituted indole, carbazole, role, indolenine,
Quinoline, thiophene, benzothiazole, benzoxazole, benzimidazole residues, etc. are preferred, and indole and carbazole residues in which the nitrogen atom is substituted with an alkyl group or an aryl group are particularly preferred.

More specifically, Ar+ and Art are represented by the following general formula (■) or (
The substituent represented by I[), Ar3, is represented by the following general formula (II[
) or (IV) is preferred.

In the above formula, among the substituents represented by R11, an alkyl group,
Aryl group, alkoxy group, aryloxy group, cyano group, nitro group, hydroxy group, halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, alkoxy group, NY, Yl (Y, , Y is a hydrogen atom, an alkyl group, R1 is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an alkoxy group, or an alkoxy group having 6 to 12 carbon atoms. Aryl group, aryloxy group, aryloxycarbonyl group having 7 to 12 carbon atoms, hydroxy group, chlorine atom, bromine atom, fluorine atom, nitro group, cyano group, NY, Yt (
Yl , Yl represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, and furthermore, YI and Y are bonded to each other, 5 including those bonded nitrogen atoms
Rings which may contain 8- to 8-membered heteroatoms, such as pyrrolidine, piperidine, morpholine, thiomorpholine, piperazine, and caprolactam rings, may also include benzene rings to form indoline and julolidine rings. RII is preferably an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthetic handling;
Alkoxy group, chlorine atom, bromine atom, fluorine atom, NY.

Yt (Y,,Y, means the above) is preferable, especially N
Y, Y, are preferred.

RII includes methyl group, ethyl group, propyl group, butyl group, octyl group, phenyl group, tolyl group, benzyl group, phenethyl group, methoxy group, nidoxy group, propoxy group, butoxy group, octyloxy group, and benzyloxy group. group, phenoxyethoxy group, phenoxy group, chlorine atom, bromine atom, fluorine atom, nitro group, cyano group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diethylamino group, diethylamino group, dioctylamino group group, diphenylamino group, ditolylamino group, dibenzylamino group, N-methyl-N-ditylamino group, N-methyl-N-butylamino group, N-ethyl-N-butylamino group, N-ethyl-N-β -methoxyethylamino group, N-ethyl-N-β-ethoxyethylamino group, N-ethyl-N-β-phenoxyethylamino group, N-methyl-N-β-cyanoethylamino group, N-methyl-N- β-chloroethylamino group, N-ethyl-N-cyclohexylamino group, N-ethyl-N-
Pentylamino group, N-ethyl-N-tetrahydrofurfurylamino group, N-ethyl-N-tolylamino group, N
-Ethyl-N-methoxyphenylamino group, N-ethyl-N-benzylamino group, N-ethyl-N-chlorobenzylamino group, pyrrolidino group, piperidino group, morpholino group, piperazino group, acetylamino group, acetyloxy group , methoxycarbonyl group.

RI! , RIs to R+7 are preferably a hydrogen atom or a group represented by Rll, and p, q, and r are preferably integers from 0 to 4.

RIfsR+7 is preferably in the meta position relative to RHHlRIa.

Among the substituents represented by R+s and R14, a hydrogen atom, an alkyl group, and an aryl group are preferred.

Further, among the substituents represented by R+s, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms are preferred.

R+s is a hydrogen atom, methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 1so
-butyl group, n-amyl group, 1so-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, n-octadecyl group,
β-methoxyethyl group, β-2ndoxyethyl group, γ-methoxypropyl group, γ-ethoxypropyl group, β-phenoxyethyl group, β-tolyloxyethyl group, β-chlorophenoxyethyl group, β-methoxyphenoxyethyl group group, β-ethylphenoxyethyl group, β-phenoxyprobyl group, β-cyanoethyl group, β-chloroethyl group,
β-hydroxyethyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, chlorophenyl group,
Examples include methoxyphenyl group, hensyl group, phenethyl group, methylbenzyl group, chlorobenzyl group, and methoxybenzyl group.

Further, among the substituents represented by Rt4, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable.

Examples of R14 include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, and a tolyl group.

Among the substituents represented by R+ and Rt, a hydrogen atom-valent group is preferable, and furthermore, R,, R1 is a hydrogen atom, an alkyl group,
Alkoxy group, alkylthio group, alkoxycarbonyl group, aryl group, aryloxy group, arylthio group,
Preferably, it is an aryloxycarbonyl group or a cyano group.

R and R are hydrogen atoms, methyl groups, ethyl groups, propyl groups, butyl groups, amyl groups, hexyl groups, octyl groups, methoxypropyl groups, ethoxypropyl groups, phenoxoethyl groups, cyclopentyl groups, cyclohexyl groups,
Examples include benzyl group and phenethyl group, and hydrogen atom is particularly preferred.

Among the substituents represented by R1, -XR,, PO(OR+)t, -CR,R,R,,~NR,R is preferred.

X represents an oxygen atom or a sulfur atom, and R4-R1° represents a hydrogen atom or a -valent group. However, if R,, Rt, and R1 are small (
One of them represents an electron-withdrawing group.

More specifically, R4 is an alkyl group, an aryl group, a heterocyclic group, COR+, 5OtR1*, N=CR,.

Rll, N RttR! 2 [R8, Ro represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, R1°, R
t+, R22, R22 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, CoRI4, SO2RlS (R14
, R□ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group].

R5 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Furthermore, R3 may be linked to each other to form a 4- to 12-membered ring structure that may contain a hetero atom.

Rt, Rt, Rt are hydrogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups,
Arylthio group, halogen atom, cyano group, nitro group,
5OxRts, CoRID, NR2sRts (R
t-1Rt7 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxy group, NR. R21
, R21, R21, R20, R21 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, 5O1R, , COR
33 (R-1R33 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group)]. Furthermore, R= and R7 may be linked to each other to form a 4- to 12-membered ring structure that may contain a heteroatom.

R,,R,. is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, 5O1R, , C0Rss, a hydroxy group, N
Rs = R! t [R24, Rls is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heterocyclic group, N Rs -Rs, R11
, R27, R31, Rss are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, So! R,6,COR,l(R,
.

, R61 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group]. Furthermore, R,,R,. may be linked to each other to form a 4- to 12-membered ring structure which may contain a hetero atom.

Furthermore, R2 is -XR,,C
RsR? R=, -NR,R,.

Or preferable.

In particular, from the viewpoint of the stability of the leuco color former when used in recording materials, -CRs RT R is preferred.

R1 is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a cyclohexyloxy group, an octyloxy group, a dodecyl oxine group, an octadecyloxy group, a benzyloxy group, a phenethyloxy group, a phenylbutyl oxine group, 4-methylbenzyl Oxy group, 4-chlorobenzyloquine group, 4-methoxybenzyloquine group, β-phenoxyethoxy group, β-(4-methylphenoxy)ethoxy group, β-(3-methylphenoxy)ethoxy group, β
-(2-methylphenoxy)nidoxy group β-(4-methoxyphenoquine)ethkyne group, β-phenylthioethoxo group, β-phenylsulfonylethoxy group, β-naphthylokynethoxy group, phenoxyethoxyethoxy group,
Pyridylmethoxy group, phenoxy group, naphthyloxy group, 4-chlorophenoxy group, 4-methylphenoquine group 3
-methylphenoxy group, 2-methylphenoxy group, 4-
Ethylphenoxy group, 2,4-dichlorophenoxy group,
Methyliminooxy group, dimethyliminooxy group, phenyliminooxy group, diethylphosphonyl group, dibutylphosphonyl group, diphenylphosphonyl group, di(4-tolyl)phosphonyl group, di(4-chlorophenyl)phosphonyl group di(4 -methoxyphenyl)phosphonyl group, di(4
-nitrophenyl)phosphonyl group, di(4-cyanophenyl)phosphonyl group, di(naphthalenl-yl)phosphonyl group, di(naphthalen-2yl)phosphonyl group, di(
2,4-dichlorophenyl)phosphonyl group, di(4-chloro-3-methylphenyl)phosphonyl group, anilino group, 2-chloroanilino group, 2-methoxycarbonylanilino group, 2-nitroanilino group, 2-methoxyanilino group , 3-ethylanilino group, 4-fluoroanilino group,
4-butoxyanilino group, 2,4-dichloroanilino group, 2,5-dimethylanilino group, β-naphthylamino group, N-methylanilino group, N-butylanilino group, N-
Acetylanilino group, pyridylamino group, quinolyl amino group, cyclohexylamino group, indol-1-yl group, carbazol-1-yl group, succinylimide group,
Phthalimide group, acetylamino group, benzoylamino group, 2-methylbenzoylamino group, 4-methylbenzoylamino group, 4-chlorobenzoylamino group, phenylsulfonylamino group, 4-methylphenylsulfonylamino group, 4-chlorophenylsulfonylamino group group, pyrrolidino group, piperidino group, morpholino group, piperazino group, phenylhydrazino group, N-hydroxy-N-phenylsulfonylamino group, N-hydroxy-N-4-chlorophenylsulfonylamino group, benzoylhydrazino group, phenylsulfonylamino group dino group, benzoyloxy group, acetyloxy group, methylthio group, ethylthio group, phenylthio group, tolylthio group, benzylthio group, naphthylthio group, benzothiazol-2-ylthio group, benzimidazol-2-ylthio group, benzoxazol-2-ylthio group group, 1.1-diacetylmethyl group, l,
1-dicyanomethyl group, 1-acetyl-1-benzoylmethyl group, 1. 1-dimethoxycarbonylmethyl group,
! , l-jethoxycarbonylmethyl group, 1,1-dipropoxycarbonylmethyl group, l,1-diphenyloxycarbonylmethyl group, 1,1-di-n-butoxycarbonylmethyl group, 1,1-di-1so-butoxy Carbonylmethyl group, 1.1-di-t-butoxycarbonylmethyl group, 1.1-dipentyloxyluponylmethyl group, 1.1-dihexyloxyluponylmethyl group, 1.
1-dibenzyloxycarbonylmethyl group, 1.1-dioctyloxycarbonylmethyl group, 1.1-didodecyloxycarbonylmethyl group, l-phenoxycarbonyl-1-methoxycarbonylmethyl group,! -phenoxycarbonyl-1-ethoxycarbonylmethyl group, l-phenoxycarbonyl-1-butoxycarbonylmethyl group, l-acetyl-1-methoxycarbonylmethyl group, l
-acetyl-1-ethoxycarbonylmethyl group, l-acetyl-1-iso-propoxycarbonylmethyl group,
l-acetyl-1-butoxycarbonylmethyl group, 1-
Acetyl-l-hexyloxycarbonylmethyl group, l
-acetyl-1-octyloxycarbonylmethyl group,
l-acetyl-1-benzyloxycarbonylmethyl group, 1-acetyl-1-phenoxycarbonylmethyl group,
1-propionyl-1-methoxycarbonylmethyl group,
1-acetyl-1-ethoxycarbonylethyl group, 1,
1-diacetylethyl group, 1-pivaloyl-1-methoxycarbonylmethyl group, l-cyano-1-ethoxycarbonylmethyl group, l-benzoyl-1-ethoxycarbonylmethyl group, 1-acetyl-1-morpholinocarbonylmethyl group, l-methoxycarbonyl-1-ethoxycarbonylmethyl group, 1.1-diphenylsulfonylmethyl group, 1-tolylsulfonyl-1-benzoylmethyl group, 1.1-di(trifluoromethylcarbonyl)methyl group, 1.1- dipivaloylmethyl group, l-furoyl-1
-1-lifluoromethylcarbonylmethyl group, l-thienylcarbonyl-l-trifluoromethylcarbonylmethyl group, 1.1-dicarbamoylmethyl group, 1-acetyl-1-phenylcarbamoylmethyl group, 1.1-dibenzoylmethyl group, 1,1-dimethoxycarbonylethyl group, l,1-jethoxycarbonylethyl group, 1.1-
diphenyloxycarbonylethyl group, 1,1-di-n
-butoxycarbonylethyl group, l,1-di-t-butoxycarbonylethyl group, t,t-dibenzyloxycarbonylethyl group, l,1-dimethoxycarbonyl-n
-propyl group, 1,1-dimethoxycarbonyl-n-butyl group, α,α-dimethoxycarbonylbenzyl group, 1
．． l-dimethoxycarbonyl-■-methoxymethyl group,
! , 1-jethoxycarbonyl-n-propyl group, 1.
1-jethoxycarbonyl-1so-propyl group, 1.
1-jethoxycarbonyl-n-butyl group, 1.1-jethoxycarbonyl-1so-butyl group, 1.1-jethoxycarbonyl-tert-butyl group, α, α-jethoxycarbonylbenzyl group, β, β -Jethoxycarbonylphenethyl group, 1.1-jethoxycarbonyl-
1-allylmethyl group, 1.1-jethoxycarbonyl-
1-acetaminomethyl group 1.1-jethoxycarbonyl-1-chloromethyl group, 1. ! -jethoxycarbonyl-1-cyclopentylmethyl group, 1.1-jethoxycarbonyl-1-phthalimidomethyl group, 1.1-jethoxycarbonyl-2-ethoxycarbonylethyl group,
I, 1. I, -triethoxycarbonylmethyl group, benzoylmethyl group, 4-chlorobenzoylmethyl group, 4-
Nitrobenzoylmethyl group l-chloro-1-acetylmethyl group,! Examples include -chloro-1-methoxycarbonylmethyl group, l-bromo-1-benzoylmethyl group, nitromethyl group, and l-nitroethyl group.

Particularly preferred compounds of the present invention are represented by the following formulas (V) to (X
).

K121p In the above formula, R, ~RIT, p, q, and rt have the above meanings.

Next, we will show specific examples of the coloring agent of the present invention (the present invention is not limited to these).In addition, these colorless dyes include well-known triphenylmethane phthalide compounds. , fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leucoolamine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, fluorene compounds, and various other compounds. They can also be used together to assemble recording materials.

In this case, it is preferable to use the above-mentioned colorless dye in an amount of 30% or more from the viewpoint of improving properties.

Regarding these, for example, specific examples of phthalides are U.S. Reissue Patent No. 23,024 and U.S. Patent No. 3°491.111.
No. 3,491.112, No. 3,491.116, and No. 3,509.174, and specific examples of fluorans are U.S. Pat.
No. 7, No. 3゜641.011, No. 3,462.828
No. 3,681.390, No. 3,920,510, No. 3,959.571, specific examples of spirodipyrans are US Pat. No. 3,971.808, and pyridine and pyrazine compounds are US Pat. Specific examples of fluorene compounds are described in Japanese Patent No. 3,775.424, Japanese Patent No. 3,853.869, Japanese Patent No. 4246.318, and Japanese Patent Application No. 61-240989.

Examples of electron-accepting compounds that impart color upon contact with colorless dyes include common compounds such as phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins, and metal complexes. are used, and these may be used in combination. Examples of these are Tokuko No. 9309, No. 40-9309, and Tokuko No. 4
5-14039, JP 52-140483, JP 48-51510, JP 57-210886,
JP-A-58-87089, JP-A-59-11286, JP-A-60-176795, JP-A-61-9598
No. 8, U.S. Patent No. 3,767°449, U.S. Patent No. 4,219,
No. 219, No. 4,269.893, No. 4,374,6
No. 71, No. 4゜687.869, etc.

Especially salicylic acid derivatives, phenol derivatives, metal complexes,
A combination with acid clay and bentonite is preferred. When these are applied to recording materials, they are used in the form of fine dispersions or fine droplets, or in the form of films.

Furthermore, in this case, various additives well known in the fields of recording materials and polymer resins, such as pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, and fluorescent agents, are used. Additives such as dyes and surfactants are used.

When used for pressure sensitive paper, U.S. Patent No. 2.505470, U.S. Pat.
No. 2,548,366, No. 2712.507, No. 2
, No. 730,456, No. 2,730.457, No. 3,
103.404, 3,418.250, 4.0
It takes various forms as described in prior patents such as No. 10,038. Most commonly it 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 described in U.S. Pat. No. 2.800.
457, a method using coacervation of a hydrophilic colloid sol described in British Patent No. 867.797, British Patent No. 950,443, British Patent No. 98
Examples include interfacial polymerization methods described in US Pat. No. 9,264 and US Pat. No. 1091.076, and methods described in US Pat. No. 3,103,404.

The capsule wall material is preferably a synthetic resin-based wall material, for example, a polyurethane and/or polyurea-based material, or a melamine resin-based material.

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.).
Synthetic oils such as chlorinated paraffin; Vegetable oils such as cotton oil and castor oil; Animal oils.

A coloring agent sheet is obtained by dissolving the coloring agent in mineral oil or a mixture thereof, encapsulating it in microcapsules, and applying it to paper, high-quality paper, plastic sheet, resin-coated paper, etc.

In addition to the electron-donating colorless dye, ultraviolet absorbers, antioxidants, and the like may be added as additives to the microcapsules. In particular, from the viewpoint of improving the stability of the electron-donating colorless dye in the capsule before use and the coloring of the capsule, benzotriazole-based ultraviolet absorbers, hindered amine-based antioxidants, hindered phenol-based antioxidants, aniline-based oxidants, etc. It is preferable to add an inhibitor, a quinoline antioxidant, etc.

In addition, an electron-accepting compound and optionally additives may be dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and used together with the pigment described below to produce paper, plastic sheets, resin-coated paper, etc. A developer sheet is obtained by coating the support.

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 recording paper, the capsule manufacturing method, and other conditions, and may be appropriately selected depending on the conditions. This amount can be easily determined by one skilled in the art.

When used in thermal paper, it takes the form as described in Japanese Patent Application Laid-open No. 144989/1989, Japanese Patent Application No. 244,883/1983, and the like. Specifically, the electron-donating colorless dye and the electron-accepting compound are used after being pulverized and dispersed in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less. Generally, an aqueous polymer solution having a concentration of about 0.5 to 10% is used as the dispersion medium, and dispersion is carried out using a ball mill, sand mill, horizontal sand mill, attritor, colloidal mill, or the like.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably between 1:10 and 1:1 by weight, and particularly preferably between 1:5 and 2=3. In this case, it is preferable to use a thermofusible substance in combination. These are used in finely dispersed form at the same time as the electron-donating colorless dye or simultaneously with the electron-accepting compound. These are added at a weight ratio of 20% or more and 300% or less, particularly preferably 40% or more and 150% or less, based on the electron-accepting compound.

Additives may be added to the coating liquid obtained in step 6 as necessary to meet various requirements. Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers in the binder in order to prevent the recording head from becoming dirty during recording, and also to improve releasability from the head. For this reason, fatty acids, metal soaps, etc. are added. Therefore, in general, in addition to electron-donating colorless dyes and electron-accepting compounds that directly contribute to color development, thermofusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, and fluorescent materials are used. Additives such as dyes and surfactants are coated onto the support to form the recording material.

Furthermore, a protective layer may be provided on the surface of the heat-sensitive recording layer, if necessary. Two or more protective layers may be laminated as necessary. Further, a coating liquid similar to that of a protective layer may be applied to the back surface in order to correct the curl balance of the support or to improve chemical resistance from the back surface. An adhesive may be applied to the back side and a release paper may be further added to form a label.

Usually, the electron-donating colorless dye and the electron-accepting compound are dispersed in a binder and applied. As a binder,
Water-soluble ones are common, such as polyvinyl alcohol,
Hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyamide Examples include acrylamide, starch derivatives, casein, and gelatin. Further, for the purpose of imparting water resistance to these binders, a water resistance agent may be added, or an emulsion of a hydrophobic polymer, specifically, styrene-butadiene rubber latex, acrylic resin emulsion, etc. may be added. Coating liquid can be used on base paper, high quality paper, synthetic paper,
Coated onto plastic sheets, resin-coated paper, or acid-free paper.

Examples of thermofusible substances are disclosed in JP-A-58-57989 and JP-A-58-87094. Examples of such compounds include 2-benzyloxynaphthalene, 4-
Benzyl biphenyl, 1゜2-di-m-tolyloxyethane, 1.2-diphenoxyethane, 1.4-difenoquinbutane, bis-[β-(p-methquinphenoquine)
ethyl]ether, ■-phenoxy-2-p-ethylphenoxyethane, 1-p-methoxyphenoxy-2-phenoquinepropane, l-phenoxy-2-p-methquinephenoxypropane, 1,2-bis(p- Methoxyphenoquino)propane, 1,3-bis(p-methoxyphenoxy)propane, I-p-methoxyphenoquino 2-o
-chlorophenoxyethane, 4-(p-methoxybenzylthio)anisole, 1-phenoxy-2-p-methquinphenylthioethane, 1,2-bis(p-methoxydiphenylthio)ethane, 1-p-methylphenoxy -2-
Ether compounds such as p-methoxyphenylthioethane, 4-(4-chlorobenzyloxy)ethoxybenzene, stearamide, methylene bisstearamide,
Examples include stearic acid anilide, behenic acid amide, stearic acid aniside, and stearyl urea.

Pigments include kaolin, calcined kaolin, talc, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, lithopone, amorphous silica, colloidal silica, calcined stone wax, silica, magnesium carbonate, titanium oxide, Alumina, barium carbonate, barium sulfate, mica, microballoons, urea-formalin filler polyester particles, cellulose fillers, etc. are used.

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

Examples of wax chips include paraffin wax, carboxy-modified paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax, polystyrene wax, higher fatty acid esters, amides, and the like.

As the hindered phenol compound, a phenol derivative substituted with a branched alkyl group at at least one of the 2nd and 6th positions is preferred. For example 1,1.3-)lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, l.

1.3-tris(2-ethyl-4-hydroxy-5-t
-butylphenyl)butane, 1. l,3-tris(3,
5-di-t-butyl-4-hydroxyphenyl)butane, 1,1.3-)lis(2-methyl-4-hydroxy-
5-t-butylphenyl)propane, 4.4-butylidenebis(6-t-butyl-3-methylphenol, 4.
4-thiobis(3-methyl-6-t-butylphenol) 2.2-methylenebis(6-t-butyl-4-methylphenol), 2.2-methylenebis(6-t-butyl-4-ethylphenol), Octadecyl-3-(3,
5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-)lis(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis [Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propinate comethane, 2,2.6.6-tetramethyl-4-piperidinyl sebacate, etc. are mentioned.

The amount of the hindered phenol compound to be used is preferably 1 to 200% by weight, more preferably 5 to 100% by weight, based on the electron accepting compound.

As ultraviolet absorbers, cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives, etc.
For example, butyl α-cyano-β-phenylcinnamate, 0
-benzotriazolylphenol, 0-benzotriazolyl-p-chlorophenol, 0-benzotriazolyl-p-methylphenol, 0-benzotriazolyl-2
, 4-di-t-butylphenol, and 0-benzotriazolyl-2,4-di-t-octylphenol.

Water-resistant agents include water-soluble initial condensates such as N-methylol urea, N-methylol melamine, and urea-formalin;
Examples include blend heat treatment of dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic crosslinking agents such as boric acid and borax, polyacrylic acid, methyl vinyl ether-maleic acid copolymer, isobutylene-maleic anhydride copolymer, etc. .

Materials used for the protective layer include polyvinyl alcohol,
Carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, gelatins, gum arabic, casein, styrene-maleic acid copolymer hydrolyzate, Water-soluble polymers such as styrene-maleic acid copolymer half ester hydrolyzate, isobutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivatives, polyvinylpyrrolidone, polystyrene sodium sulfonate, sodium alginate, and styrene-
Water-insoluble polymers such as butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion are used.

In addition, pigments, metal soaps, waxes, waterproofing agents, etc. may be added to the protective layer for the purpose of improving matching properties with the thermal head.

Further, when coating the protective layer on the thermosensitive coloring layer, a surfactant may be added in order to obtain a uniform protective layer. As the surfactant, a sulfosuccinic acid-based alkali metal salt, a fluorine-containing surfactant, etc. are used. Specifically, G (
Sodium salts or ammonium salts such as n-hexyl)sulfosuccinic acid and di(2-ethylhexyl)sulfosuccinic acid are preferred, or anionic surfactants may be effective.

The electrically conductive thermal paper is manufactured by the method described in, for example, Japanese Patent Application Laid-open No. 49-11344 and Japanese Patent Application Laid-Open No. 50-48930. Generally, a coating liquid containing a conductive substance, an electron-donating colorless dye, and an electron-accepting compound dispersed together with a binder is applied to a support such as paper, or a conductive substance is applied to the support to form a conductive layer. The electrically conductive thermal paper is manufactured by applying a coating liquid in which an electron-donating colorless dye, an electron-accepting compound, and a binder are dispersed thereon. Note that the sensitivity can also be improved by using the thermofusible substance described above in combination.

The photosensitive pressure sensitive paper is manufactured by the method described in, for example, Japanese Patent Application Laid-open No. 179836/1983. Generally, crosslinking of photopolymerization initiators such as silver bromide, silver bromide, silver behenate, Michler's ketone, benzoin derivatives, and benzophenone derivatives with polyfunctional monomers such as polyallyl compounds, poly(meth)acrylates, poly(meth)acrylamides, etc. The agent is encapsulated in a capsule of synthetic resin such as polyether urethane or polyurea together with an electron-donating colorless dye and, if necessary, a solvent. After imagewise exposure, the unexposed area is colored by contacting with an electron-accepting compound using an electron-donating colorless dye.

The electron-donating colorless dye according to the present invention can be produced using, for example, the following formula (XI) or (Xl[) as a raw material, HXR,, HPO(CH2)1, HCR
,R,R,,HNR,R,. Or it can be obtained by reacting with its salt.

In the above formula, Art ~A r! , R+ to Rlo have the above-mentioned meanings, and Z- represents an anion of an inorganic acid or nucleating acid necessary for forming a pigment, for example, CI-BrF-l-
1H3○=-, SO4'-CH35O, -P○, -%
C10,-1CHs co○, Cs Hs SO*
-p-CHs -Cs Hs SO Coco-BF4- and the like.

The aforementioned HXR, , HPO(ORs), , HCR, R
, R, , HNR, R, are, for example, alkali metal salts, alkaline earth metal salts, ammonium salts or amine salts.

HXR,, HPO(CHs)*, HCR,R, used
R,,HNR,R,. or the amount of its salt is represented by general formula (XI)
Or, preferably from 1 to 3 mol, particularly preferably from 1 to 1.5 mol, per 1 mol of the compound (X[I).

The above reaction is preferably carried out in a *a solvent, such as alcohols, ethers, esters, aromatic hydrocarbons, halogenated hydrocarbons, etc. Specific examples include methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, dioxane, ethyl acetate, toluene, xylene, methylene chloride, and the like. Among these, polar organic solvents are particularly preferred.

The amount of organic solvent used is preferably such that the solid content concentration is 10% or more, particularly 20%.

0. As a catalyst, an acidic catalyst such as an aliphatic carboxylic acid such as formic acid or acetic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or perchloric acid may be added.

The reaction temperature is preferably 10 to 100°C, particularly 20 to 7°C.
0°C is preferred.

It is also preferable to carry out the reaction under an atmosphere of an inert gas such as nitrogen or argon gas from the viewpoint of preventing coloration of the liquid.

(Synthesis Example-1) The compound of Specific Example (9) was placed in a three-necked flask equipped with a stirrer, and 0.15 mol of 4-NN-dimethylaminobenzaldehyde and 1.1-
0.15 mol of bis(4-N,N-dimethylaminophenyl)ethylene and 100 mol of acetic anhydride are weighed out, and 0.15 mol of 70% perchloric acid is added dropwise at room temperature while stirring. After the addition is complete, raise the internal temperature to 70°C and stir for 2 hours. Cool the reaction mixture and add cold water. The precipitated crystals were filtered, washed with water and ethanol, and the following compound (
X[[D was obtained.

In a separate three-necked flask with a stirrer, 0.011 mol of sodium hydride and 40 rI of tetrahydrofuran.
Weigh out Ll and add 0 acetylacetone while stirring.
．． 0105 mol was added dropwise. After stirring at room temperature for 5 minutes, compound (H[[) 0. Gradually add 0.1 mOl and stir at room temperature for 2 hours. The reaction mixture was poured into water, filtered, dried, and recrystallized from ethyl acetate to obtain white crystals (point #i: 165-7°C).

(Synthesis Example-2) In a three-bottle flask equipped with a stirrer, phosphorus oxychloride 6 was added to the compound of Example (31).
0-11. 2-dimethylindole 0゜2 mol
Weigh out and add anhydrous vinegar while stirring at 80℃. ! 0.
Drop 102 mol. After dropping, lower the internal temperature to 10
Bring to 0°C and stir for 1 hour. Cool the reaction mixture;
After adding ice water, make alkaline with 10% caustic soda water. The precipitated crystals were filtered, washed with water, and washed with ethyl acetate.1.
l-bis(l,2-dimethylindol-3-yl)ethylene was obtained.

This 1,1-bis(1,2-dimethylindole-3-
yl) ethylene 0.15 mol, 4-N.

N-dimethylaminobenzaldehyde 0.15mof,
Weigh out 100% of acetic anhydride and boil it at room temperature without stirring.
0.15 mol of 2% fluoroboric acid is added dropwise. After the addition is complete, raise the internal temperature to 70°C and stir for 2 hours. Cool the reaction mixture and add cold water. The precipitated crystals were filtered, washed with water, and separated from the ether in a three-bottle flask equipped with a stirrer with 0.0% sodium hydride. 011 mo11 Tetrahydrofuran 40- is weighed out and 0.0105 mol of dimethyl malonate is added dropwise while stirring. After stirring for 5 minutes at room temperature, compound (Shoulder V) 0. 01
mol gradually and stir at room temperature for 2 hours. The reaction mixture was poured into water, filtered, dried, and recrystallized from ethyl acetate to obtain white crystals (melting point: 97-9°C).

(Examples of the Invention) Examples are shown below, but the present invention is not limited thereto. % represents weight % unless otherwise specified.

(Example 1) 20 g each of the compound of Example (10), bisphenol A which is an electron accepting compound, and 4-(4-chlorobenzyloxy)ethoxybenzene which is a thermofusible substance was
g of 5% polyvinyl alcohol (furan PVA 105
) Each dispersion liquid was obtained by dispersing with an aqueous solution in a ball mill for one day and night to reduce the volume average particle size to 1.5 μm or less. In addition, 80 g of calcium carbonate was added to 0.0 g of sodium hexametaphosphate.
Disperse with 160g of 5% solution using a homogenizer,
A pigment dispersion was obtained.

Each of the dispersions prepared as described above was mixed in a ratio of 5 g of an electron-donating colorless dye dispersion, 10 g of an electron-accepting compound dispersion, 10 g of a thermofusible substance dispersion, and 15 g of a pigment dispersion,
Further, 3 g of a 21% zinc stearate emulsion was added to obtain a heat-sensitive coating liquid. This coating liquid was applied to high-quality paper using a coating bar so that the dry weight of the coating layer was 5 g/m'', and after drying at 50°C for 1 minute, a super calender was applied to heat-sensitive recording paper. I got it.

The obtained thermal recording paper had no fog during raw storage and had excellent stability over time.

Thermal recording paper was heated using a thermal head manufactured by Kyocera Corporation (KLT-
216-8MPDI) and 100kg/just before the head.
A blue image was obtained by printing with a pulse width of IO while using a pressure roll with a head voltage of 24 V and a pulse cycle of 10 ms in a thermal printing experimental apparatus having a cof pressure roll. In addition, the obtained colored image is
It showed good resistance to chemicals and sunlight.

(Examples 2 to 3) In place of the electron-donating colorless dye and electron-accepting compound of Example 1, the following were used, respectively. A coated paper was obtained in the same manner as in Example 1 in other respects.

Example 2 Electron-donating colorless dye: Compound 10g1 of specific example (9)
Crystal violet lactone IOg Electron-accepting compound: 5 g of 4-hydroxyphenyl-4-isopropoxyphenylsulfone, 15 g of rhodan zinc benzimidazole complex Example 3 Electron-donating colorless dye: 10 g of the compound of specific example (31),
3-(1-n-cutyl-2-methylindol-3-yl)-3-(4-N,N-diethylamino-2
-ethoxyphenyl)phthalide lg Electron-accepting compound: l, 1-bis(4-hydroxyphenyl)cyclohexane 8g, 4-β-p-methoxyphenoxyethoxyethoxysalicylate zinc 8g, rhodan zinc 1-
4 g of phenyl-2,3-dimethyl-3-pyrazolin-5-one complex The colored images obtained in all of Examples 2 to 3 showed good resistance to chemicals, sunlight, etc.

(Example 4) (1) Preparation of capsule sheet containing electron-donating colorless dye 5 parts of a partial sodium salt of polyvinylbenzenesulfonic acid (manufactured by National Starch, VER3A, TL500) is dissolved in 95 parts of hot water and then cooled. . A sodium hydroxide aqueous solution was added to this to adjust the pH to 40. On the other hand, a specific example (
100 parts of diisopropylnaphthalene in which 3.5% of the compound of 10) was dissolved was emulsified and dispersed in 100 parts of a 5% aqueous solution of a partial sodium salt of the polyvinylbenzenesulfonic acid to obtain an emulsion having a particle size of 4.0 μm in diameter. Ta. Separately, 6 parts of melamine, 11 parts of a 37% by weight formaldehyde aqueous solution, and 30 parts of water were heated and stirred at 60°C, and after 30 minutes, a transparent aqueous solution of a melamine-formaldehyde prepolymer was obtained.

This aqueous solution was mixed with the above emulsion. While stirring, the pH was adjusted to 6.0 with a 2M phosphoric acid solution, the temperature of the solution was raised to 65°C, and stirring was continued for 6 hours. This capsule liquid was cooled to room temperature and adjusted to pH 9.0 with an aqueous sodium hydroxide solution.

To this 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 prepare a solution of a microcapsule dispersion with a solid content concentration of 20%.

This coating liquid was applied to a 50 g/m'' base paper using an air knife coater so that a solid content of 5 g/m'' was applied, and dried to obtain a capsule sheet containing an electron-donating colorless dye.

(2) Preparation of electron-accepting compound sheet 3.5-bis-α-methylbenzylsalicylic acid zinc salt 1
0 part was added to 20 parts of 1-isopropylphenyl-2-phenylethane and dissolved. This was mixed with 50 parts of a 2% polyvinyl alcohol aqueous solution and 0.1 part of a 10% dodecylbenzenesulfonic acid triethanolamine salt aqueous solution and emulsified so that the average particle size was 3 μm.

Next, a dispersion consisting of 80 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water was mixed with the above emulsion, and 100 parts of a 10% PVA aqueous solution as a binder and carboxy-modified SBR
10 parts of latex (as solid content) was added and water was added so that the solid content concentration was 20% to obtain a coating liquid (A).

Next, 10 parts of the electron-accepting compound, 20 parts of Jilton clay
A dispersion liquid consisting of 200 parts of water, 60 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water was dispersed using a sand grinder so that the average particle size was 3 μm.

Add 16 parts of 10% PVA aqueous solution and 10% PVA to this dispersion.
100 parts of an aqueous solution and 10 parts of carboxy-modified SBR latex (as solid content) were added, and water was added so that the solid content concentration was 20% to obtain a coating liquid (B).

Coating liquid (A) and coating liquid (B) were mixed 1:1 in terms of electron-accepting compound, and 5.0 g/m was applied to 50 g/m' base paper.
It was coated using an air knife coater so that a solid content of 100% was coated and dried to obtain an electron-accepting compound sheet.

The surface of the microcapsule sheet containing an electron-donating colorless dye is
When the electron-accepting compound sheet was stacked and a load of 600 kg/aIr was applied, a blue color immediately developed. Moreover, the obtained colored image showed good resistance to chemicals, sunlight, etc.

(Example 5) The following was used instead of the electron-accepting compound sheet of Example 4.

(2') Preparation of electron-accepting compound sheet Acidic clay 100
were dispersed in 400 parts of a 0.5% aqueous sodium hydroxide solution, and then 20 parts of styrene-butadiene copolymer latex (solid content) and 40 parts of a 10% starch aqueous solution were added, thoroughly stirred and mixed, and the electron accepting A compound coating solution was obtained.

5. Apply the coating solution prepared in this way to 50 g/m' base paper.
It was coated using an air knife coater so that a solid content of 0 g/m'' was coated and dried to obtain an electron-accepting compound sheet.

On this electron-accepting compound sheet, the surface of the electron-donating colorless dye-containing microcapsule sheet of Example 4 was layered for 600 kg.
When a load of g/cd was applied, a blue color immediately developed. Further, the obtained colored image had a high color density (color density = 0.31: measured with Macbeth Co., Ltd. RD-918 type densitometer) and showed good resistance to chemicals, sunlight, etc.

(Example 6) In place of the electron-donating colorless dye of Example 4, specific example (1
An electron-donating colorless dye-containing microcapsule sheet was obtained in the same manner as in Example 4, except that the compound 1) was used. This sheet surface was stacked on the electron-accepting compound sheet of Example 5 for 60 minutes.
When a load of 0 kg/a11 was applied, a blue color developed. Furthermore, the obtained colored image had a high color density (color density = 0.31) and showed good resistance to chemicals, sunlight, etc.

(Example 7) In place of the electron-donating colorless dye of Example 4, specific example (3
An electron-donating colorless dye-containing microcapsule sheet was obtained in the same manner as in Example 4, except that the compound 2) was used. This sheet surface was stacked on the electron-accepting compound sheet of Example 5 for 60 minutes.
When a load of 0 kg/al was applied, a blue color developed.

In addition, the color image obtained has a high color density (color density =
0.30) Good resistance to chemicals, sunlight, etc.

(Example 8) In place of the electron-donating colorless dye of Example 4, specific example (3
An electron-donating colorless dye-containing microcapsule sheet was obtained in the same manner as in Example 4 except that the compound 9) was used. This sheet surface was stacked on the electron-accepting compound sheet of Example 5 for 60 minutes.
When a load of 0 kg/Ci was applied, a blue color developed.

In addition, the color image obtained has a high color density (color density =
0.31) Good resistance to chemicals, sunlight, etc.

(Example 9) In place of the electron-donating colorless dye of Example 4, specific example (4
An electron-donating colorless dye-containing microcapsule sheet was obtained in the same manner as in Example 4, except that the compound 6) was used. This sheet surface was stacked on the electron-accepting compound sheet of Example 5 for 60 minutes.
When a load of 0 kg/al was applied, a blue color developed.

In addition, the color image obtained has a high color density (color density =
0.30) Good resistance to chemicals, sunlight, etc.

(Comparative Example) A microcapsule sheet containing an electron-donating colorless dye was obtained in the same manner as in Example 4, except that the following compound was used instead of the electron-donating colorless dye of Example 4. The surface of this sheet was tinted blue. When this sheet surface was stacked on the electron-accepting compound sheet of Example 5 and a load of 600 kg/cnf was applied, a blue color developed, but the color density of the obtained colored image was low (color density = 0. 23).

Claims (2)

[Claims] (1) 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 electron-donating colorless dye. Recording materials ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (I) In the above formula, Ar_1 and Ar_2 are a heterocyclic group or an aryl group having a substituent, and Ar_3 is a heterocyclic group or an aryl group that may have a substituent. Aryl group, R_1, R_2 are hydrogen atoms, monovalent groups, R_3 is -XR_4, -PO(OR_5)_2, -CR_6R_7R_8, -NR_9R_1_0 (X is oxygen atom, sulfur atom, R_4 to R_1_0 are hydrogen atoms or represents a monovalent group (provided that at least one of R_6 to R_8 represents an electron-withdrawing group). (2) In general formula (I), Ar_1 and Ar_2 represent the following general formula (II) or (III), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( III) Ar_3 represents the general formula (III) or the following general formula (IV), ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) R_1 to R_2 are hydrogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, aryl groups, aryloxy groups, arylthio groups, aryloxycarbonyl groups, cyano groups , wherein R_2 represents -XR_4, -PO(OR_5)_2, -CR_6R_7R_8, -NR_9R_1_0. [In the above formula, R_1_1 is an alkyl group, an aryl group, an alkoxy group. , aryloxy group, cyano group, nitro group, hydroxy group, halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, NY_1
Y_2 (Y_1, Y_2 represent a hydrogen atom, an alkyl group, an aryl group, an acyl group), R_1_2, R_1_5
~R_1_7 is a hydrogen atom or a group represented by R_1_1, p, q, r are integers from 0 to 4, R_1_3, R_1
_4 represents a hydrogen atom, an alkyl group, or an aryl group. X is an oxygen atom, a sulfur atom, R_4 is an alkyl group, an aryl group, a heterocyclic group, COR_1_8, SO_2R_1_
9, N=CR_2_0R_2_1, NR_2_2R_2
_3 [R_1_8, R_1_9 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, R_2_0, R_2
_1, R_2_2, R_2_3 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, COR_2_4, SO_2R
_2_5 (R_2_4 and R_2_5 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group)]. R_5
represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Furthermore, R_5 may be linked to each other to form a 4- to 12-membered ring structure that may contain a hetero atom. R_6
, R_7, R_8 are hydrogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups,
Arylthio group, halogen atom, cyano group, nitro group,
SO_2R_2_6, COR_2_7, NR_2_8R
Represents _2_9 [R_2_6, R_2_7 are hydrogen atoms,
Alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, hydroxy group, NR_3_0R_3_1, R_2_8,
R_2_9, R_3_0, R_3_1 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, SO_2R_3_2,
COR_3_3 (R_3_2, R_3_3 are hydrogen atoms,
represents an alkyl group, aryl group, or heterocyclic group]. Further, R_6 and R_7 may be linked to each other to form a 4- to 12-membered ring structure that may contain a hetero atom. R_
9, R_1_0 is a hydrogen atom, an alkyl group, an aryl group,
Represents a heterocyclic group, SO_2R_3_4, COR_3_5, hydroxy group, NR_3_6R_3_7 [R_3_4
, R_3_5 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heterocyclic group, NR_3_
8R_3_9, R_3_6, R_3_7, R_3_8
, R_3_9 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, SO_2R_4_0, COR_4_1 (R_4
_0 and R_4_1 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group]. Furthermore, R_9, R_1_0
may be connected to each other and contain a heteroatom 4-1
A two-membered ring structure may be formed. ]