JPH04185482A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material producing a coloring image with high stability and satisfying essential conditions by employing a poly(1-allylvinyl-1- allylmethane) compound containing at least two frameworks in a molecule as an electron donative colorless dye. CONSTITUTION:An electron donative colorless dye containing at least two frameworks, shown by formula I, in a molecule is dissolved, solely or mixedly, into a solvent which is then contained in a microcapsule and applied onto a paper or the like to produce a coloring agent sheet. On the other hand, electron donative compound and additive are dispersed into a binder which is then applied, together with a pigment, onto a supporting material thus producing a color developing sheet. When a microcapsule sheet containing the electron donative colorless dye is laid on an electron acceptive compound sheet and applied with a load of 600kg/cm<2>, a blue green color emerges quickly and thus produced coloring image has high resistance against medicine, sunshine, and the like.

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. 6゜-123557.

As a recording material, in recent years (1) color density and color sensitivity (2)
) Research is being carried out to improve properties such as before use and the fastness of colored images.

Among these, in blue-light 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, and the light fastness of the colored image changes. The plasticizer properties are extremely poor.

The inventors have discovered that certain compounds may be useful in improving these properties.

(Object of the Invention) Therefore, an object of the present invention is to provide a recording material using a material that 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 (I). This was achieved using a recording material characterized by using a poly(I-arylvinyl-1-arylmethane) compound having at least two of the skeletons shown in the molecule.

In the above formula, A r + and A r x represent an aryl group or a heterocyclic group, R and -R represent a hydrogen atom or a monovalent group, and R4 represents a substituent that can be removed by contact with an electron-accepting compound; represents a group. However, at least one of Art, Art, and R1-R4 represents a divalent group.

When multiple skeletons represented by general formula (I) are bonded,
The bonding site may be any of Ar+ to Arz and R+ to R4, and is preferably bonded by a single bond or a divalent group.

As the divalent group, those represented by the following general formula (II) are preferred.

-(L6), (Ll)ili-(L2)("L3)
J'-(L4)e (L5), (L6ni-([
) In the above formula, Lo, Lz, La, La are -0-1
-NR, -1-NR, C0-1-CONR, -1-NR
, So, -1-3O! NR, -1-COO-1-OC
O-1-NR, C0NR, -1-0CONR, -1-N
R,COO-1-CHOH-1-3-1-SO-1-3
Ot-1-CO- (R represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group), L+, Lz,
Ls is alkylene, aralkylene, arylene, a
-g is an integer of 0 or l (however, b-c+de+f-g=
o) represents.

Each substituent of Art-R4 has 30 or less carbon atoms,
In particular, it is preferably 20 or less.

Furthermore, A r 1 , A r 2 has a heterocyclic group, 671) -/l, group having an amine residue, R4 or -XRI, -
PO(OR= ) 2 , CR7RI R1, -NR,
. RII, 5O2R1□ (X is an oxygen atom, a sulfur atom,
R5 to R+2 represent a hydrogen atom or a monovalent group. However, R
At least one of 7 to R represents an electron-withdrawing group).

Among the above-mentioned heterocycles, substituted indole, carbazole, virol, 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 aryol group are particularly preferred.

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, nitro group, cyano group, substituted carbamoyl group, substituted sulfamoyl group, substituted amino group, substituted oxycarbonyl group, substituted oxycarbonyl group, alkylthio group, or arylsulfonyl group.

More specifically, A r + and A r x are preferably substituents represented by the following general formula (■) or (IV).

In the above formula, among the substituents represented by RI3, NR8R,,
(R, , R11 represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group. Specifically, R11 and R11 represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms. , preferably an acyl group having 2 to 12 carbon atoms, and RII and RI may be bonded to each other and may contain a 5- to 8-membered heteroatom including the nitrogen atom to which they are bonded. rings, such as pyrrolidine, piperidine, morpholine, thiomorpholine, piperazine, and caprolactam rings, and may also include a benzene ring to form indoline and julolidine rings) are preferred.

R12 is a dimethylamino group, a diethylamino group,
Dipropylamino group, dibutylamino group, diarylamino group, diarylamino group, dioctylamino 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-tetrahydrofurfuryl Amino group, N-ethyl-N-tolylamino group, N-ethyl-N-methoxyphenylamino group, N-ethyl-N-benzylamino group,
Examples include N-ethyl-N-chlorobenzylamino group, pyrrolidino group, piperidino group, morpholino group, piperazino group, and acetylamino group.

R14, RI? Among the substituents represented by, hydrogen atoms,
Preferably, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group, a nitro group, a substituted amine group, a hydroxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and furthermore a hydrogen atom or number of carbon atoms. an alkyl group having 1 to 12 atoms, an alkoxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acyloxy group, an aryl group having 6 to 12 carbon atoms, an aryloxy group, an aryloxycarbonyl group having 7 to 12 carbon atoms; Hydroxy group, chlorine atom, bromine atom, fluorine atom, nitro group, cyano group, amino group, mono- or dialkylamino group having 1 to 12 carbon atoms, mono- or diarylamino group having 6 to 12 carbon atoms, number of carbon atoms 1 to 12 acylamino groups are preferred.

R14 and R17 are hydrogen atom, methyl group, ethyl group, propyl group, butyl group, octyl group, phenyl group, tolyl group, benzyl group, phenethyl group, methoxy group, nidoxy group, propokine group, butoxy group, octyloxy group , benzyloxy group, phenoxyethoxy group, phenoxy group, chlorine atom, bromine atom, fluorine atom, nitro group, cyan group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diarylamino group,
Diarylamino group, dioctylamino 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-methquinoethylamino group, N-ethyl-
N-β-ethoxyethylamino group, N-ethyl-N-β
-phenoxyethylamino group, N-methyl-N-β-anoethylamino group, N-methyl-N-β-chloroethylamino group, N-ethyl-N-cyclohekynylamino group, N-ethyl-N- pentylamino group, N-ethyl-N
-tetrahydrofurfurylamino group, N-ethyl-N-
hlylamino 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, and methoxycarbonyl group.

The preferred substitution position for R14 is the meta position relative to RI3.

m and n represent integers from 1 to 4.

Among the substituents represented by R+5 and R11, a hydrogen atom, an alkyl group, and an aryl group are preferred.

Furthermore, among the substituents represented by R15, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms are preferred.

RI8 is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-amyl group, isoamyl group, n-hexyl group, n
-hebutyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, n-octadecyl group, β-methoxyethyl group, β-ethoxyethyl group, γ-methoxypropyl group, γ-ethoxypropyl group, β -phenoxyethyl group, β-tolyloxyethyl group, β-chlorophenoxyethyl group, β-methoxyphenoxyethyl 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, methoxyphenyl group, benzyl group, phenethyl group, methylbenzyl group, chlorobenzyl group, methoxybenzyl group The basics are given.

Furthermore, among the substituents represented by R1, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferred.

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

Further, R1 to R+7 may be bonded to each other via a single bond or a divalent group represented by the general formula (I[).

Among the substituents represented by R3-R1, hydrogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, aryl groups, heterocyclic groups, aryloxy groups,
An arylthio group, an aryloxycarbonyl group, and a cyano group are preferable, and hydrogen atoms, alkyl groups, and groups of the general formula (I
II), (IV) or a substituent represented by the following general formula (V) is preferred.

In the above formula, R1° has the same meaning as RI4, and p is 1 to 5.
indicates an integer.

Among the substituents represented by R4, X R5, -P○(OR=)z, -CR7R,R,, -NR,, R,, -3ow R,
□ or preferred.

X is an oxygen atom, a sulfur atom, R6 is an alkyl group, an aryl group, a heterocyclic group, COR21,5OtRt2, N =
CRts R! 4, NR25R24 [R31
, Rts is a hydrogen atom, alkyl group, aryl group, heterocyclic group, R12, R24, R*5sR2a is a hydrogen atom, alkyl group, aryl group, heterocyclic group, COR27,5O2
R*-(R,!?, Rts represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group)].

R6 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Furthermore, R6 may be linked to each other to form a 4- to 12-membered ring structure that may contain a hetero atom.

R, , R, , R is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, halogen atom, cyano group, nitro group,
5OzR15, C0R2゜, NR representing R22 [R
29, R1° 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, N R31R2
, R31, R22, R, 23, and R24 are hydrogen atoms,
Alkyl group, aryl group, heterocyclic group, 5O2R,,C
OR3@ (Rs5, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group)]. Furthermore, R,? ,R-
may be connected to each other and contain a heteroatom 4-1
A two-membered ring structure may be formed.

Ro. , R1+ is a hydrogen atom, an alkyl group, an aryl group,
Heterocyclic group, 5OzRs7, COR1-, hydroxy group,
N R2* R4゜ [R27, R2t are hydrogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, heterocyclic groups, N R4+ R4t, R31, R
4゜, R41, R42 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, 5O2R-z, COR,4(R,1,
R44 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group]. Furthermore, R1° and R1 may be linked to each other to form a 4- to 12-membered ring structure that may contain a hetero atom.

R1ff1 represents an alkyl group, an aryl group, or a heterocyclic group.

Furthermore, R4 is -XRI,
-CR7R,R,, -NR10R1□ are preferred.

In particular, CR7R-R- is preferred from the viewpoint of stability of the leuco color former when used in recording materials.

R1 is a methoxy group, a nidoxy group, a propoxy group, a butquine group, a cyclohexyloxy group, an octyloxy group, a dodecyloxy group, an octadecyloxy group, a penzyluoquine group, a phenethyloxy group, a phenylbutyloquine group, 4-methylbenzyl Oxy group, 4-chlorobenzyloxy group, 4-methoxybenzyloxy group, β-phenoxyethoxy group, β-(4-methylphenoxy)ethoxy group, β-(3-methylphenoxy)nidoxy group,
β-(2-methylphenoxy)ethoxy group, β-(4-
methoxyphenoxy)ethoxy group, β-phenylthioethoxy group, β-phenylsulfonylethoxy group, β-naphthyloxyethoxy group, phenoxyethoxyethoxy group, pyridylmethoxy group, phenoxy group, naphthyloxy group, 4-chlorophenoxy group, 4 -Methylphenoxy 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)sulfonyl group, di(4-methoxyphenyl)phosphonyl group, di(4-nitrophenyl)phosphonyl group, di(4-cyanophenyl)phosphonyl group, di(naphthalene- 1-yl)phosphonyl group, di(naphthalen-2-yl)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-butoquinoanilino 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, sacunnylimide group, phthalimide group, acetylamino group, benzoylamino group, 2-methylbenzoylamino group, 4-
Methylbenzoylamino group, 4-chlorobenzoylamino group, phenylsulfonylamino group, 4-methylphenylsulfonylamino group, 4-chlorophenylsulfonylamino group, pyrrolidino group, piperidino group, morpholino group, piperazino group, phenylhydrazino group, N -Hydroquine-N-phenylsulfonylamino group, N-hydroxy-N-4-chlorophenylsulfonylamino group, benzoylhydrazino group, phenylsulfonylhydrazino group,
Benzoyloxy group, acetyloquine group, methylthio group, ethylthio group, phenylthio group, tolylthio group, hensylthio group, naphthylthio group, benzothiazole-2-
ylthio group, benzimidazol-2-ylthio group, benzoxazol-2-ylthio group, 1.1-diacetylmethyl group, 1,1-dicyanomethyl group, l-acetyl-1-benzoylmethyl group, 1.1-dimethoxy Carbonylmethyl group, 1.1-jethoxycarbonylmethyl group, 1.1-dipropoxycarbonylmethyl group, 1.1-
diphenyloxycarbonylmethyl group, l,1-di-n
-butoxycarbonylmethyl group, 1.1-di-isobutoxycarbonylmethyl group, I, l-di-t-butoxycarbonylmethyl group, 1. 1-Dibenzyloxycarbonylethyl group, 1.1-dihexyloxycarbonylmethyl group, 1. l-dibenzyloxycarbonylmethyl group,
1. ! -dioctyloxycarbonylmethyl group, 1.1
-didodecyloxycarbonylmethyl group, 1-phenoxycarbonyl-1-methoxycarbonylmethyl group, l-
Phenoxycarbonyl-1-ethquincarbonylmethyl group, 1-phenoxycarbonyl-1-butoxycarbonylmethyl group, 1-acetyl-1-methoxycarbonylmethyl group, 1-acetyl-1-ethquincarbonylmethyl group, l-acetyl- 1-isopropoxycarbonylmethyl group, l-acetyl-1-butoxycarbonylmethyl group, 1-acetyl-1-hexyloxycarbonylmethyl group, 1-acetyl-1-octyloxycarbonylmethyl group, ■-acetyl-1-benzyl Oxycarbonylmethyl group, l-acetyl-1-phenoxycarbonylmethyl group, 1-propionyl-1-methoxycarbonylmethyl group, 1-acetyl-1-ethoxycarbonylethyl group, 1.1-diacetylethyl group, 1-pivaloyl- 1-
Methoxycarbonylmethyl group, 1-cyano-1-ethoxycarbonylmethyl group, 1-benzoyl-1-ethoxycarbonylmethyl group, 1-acetyl-1-morpholinocarbonylmethyl group, 1-methoxysulfonyl-1-ethoxycarbonylmethyl group, I, 1-diphenylsulfonylmethyl group, 1-tolylsulfonyl-1-benzoylmethyl group, 1,1-di(trifluoromethylsulfonyl)
Methyl group, 1,1-dipivaloylmethyl group, l-furoyl-1-trifluoromethylcarbonylmethyl group, 1-
Chenyl sulfonyl-1-trifluoromethylcarbonylmethyl group, 1.1-dicarbamoylmethyl group, 1-acetyl-I-phenylcarbamoylmethyl group, 1.1-
Dibenzoylmethyl group, ■, l-dimethoxycarbonylethyl group, 1,1-jethoxycarbonylethyl group, ■
, ■-diphenyloxycarbonylethyl group, 1,1-
di-n-butoxycarbonylethyl group, 1. I-G-t
-butoxycarbonylethyl group, 1.1-dibenzyloxycarbonylethyl group, 1.1-dimethoxycarbonyl-n-propyl group, l, ]-dimethoxycarbonyl-
n-butyl group, α,α-dimethoxycarbonylbenzyl group, 1,1-dimethoxycarbonyl-1-methoxymethyl group, 1.1-jethoxycarbonyl-n-propyl group, 1.1-jethoxycarbonyl-n- pentyl group, 1
．． 1-shedkin carbonyl-n-butyl group, 1. I-
Jetoxycarbonyl-1-isopropylmethyl group, 1
．． 1-jethoxycarbonyl-1-t-butylmethyl 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.
1-jethoxycarbonyl-1-cyclopentylmethyl group, 1,1-jethoxycarbonyl-1-phthalimidomethyl group, 1.1-jethoxycarbonyl-2-ethoxycarbonylethyl group, 1,1,1. -) Jetoxycarbonylmethyl group, benzoylmethyl group, 4-chlorobenzoylmethyl group, 4-nitrobenzoylmethyl group, l
-Chloro-1-acetylmethyl group, 1-chloro-1-methoxycarbonylmethyl group, l-bromo-1-benzoylmethyl group, nitromethyl group, 1-nitroethyl group, methylsulfonyl group, ethylsulfonyl group, butyl group Rubonyl group, octylsulfonyl group, benzylsulfonyl group, phenethylsulfonyl group, phenylsulfonyl group, 4
-Tolylsulfonyl group, 3-tolylsulfonyl group, 2-
Tolylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-ethoxyphenylsulfonyl group, 4-propyloxyphenylsulfonyl group, 3-butoxyphenylsulfonyl group, 4-chlorophenylsulfonyl group, 4-nitrophenylsulfonyl group, 4-dodecyl group phenylsulfonyl group, 4-benzyloxyphenylsulfonyl group,
2.4-dimethoxyphenylsulfonyl group, naphthalen-1-ylsulfonyl group, naphthalen-2-ylsulfonyl group, 3.4-dichlorophenylsulfonyl group, 2.
Examples include 5-dichlorophenylsulfonyl group and 4-N,N-dimethylaminophenylsulfonyl group.

LI, Ll, and LI are preferably alkylene, aralkylene, or arylene having 1 to 30 carbon atoms.

LI, Ls, Li are -(CL)-, -(
CHri, -1(CHt)s-1-(CH6), -1-(
CHt)s-1-(CHri,-1~(CL)?-1-(
CHt)*-1-(CHri,-1-(C1(,),.-
1-(CH,CHCH6)-1-CHt-CH=CH-
Examples include CH, -.

Ra is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a heterocyclic group;
Examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, and a benzyl group.

Particularly preferred compounds of the present invention are represented by the following general formulas (VI) to (
It is shown in X[).

In the above formula, R1 to R1 have the meanings described above, and R represents a single bond or a divalent group represented by the general formula (I[).

Next, specific examples of the color former of the present invention will be shown, but the present invention is not limited thereto.

(l 2) In addition, these colorless dyes include well-known triphenylmethane phthalide compounds, fluoran compounds,
Recording materials can be used in combination with various compounds such as phenothiazine compounds, indolylphthalide compounds, leucoauramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds. It also comes with 8 to assemble.

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.

Concerning these, specific examples of phthalides are given in 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 subirodibilanes 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 Nos. 3,775,424, 3,853,869, and 4,246,318, and Japanese Patent Application No. 61-240989.

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. 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 or 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.

For use with pressure sensitive paper, U.S. Patent 2,505.470
No. 2,505,471, No. 2,505.489, No. 2,548,366, No. 2,712,507,
2,730.456, 2,730,457, 3,103,404, 3,418.250, 4
It can take a variety of forms, as described in prior patents such as No. 010,038. It most commonly consists of at least one pair of sheets containing separately 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 coacelvage 1 of a hydrophilic colloid sol described in British Patent No. 867.797, British Patent No. 950,443, British Patent No. 98
Examples include the interfacial polymerization method described in US Pat. No. 9.264 and US Pat. No. 1.091,076, and the method described in US Pat.

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 in a solvent (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl,
Synthesis of chlorinated paraffin, etc.: dissolved in cotton oil, castor oil, vegetable oil, animal oil, mineral oil, or mixtures thereof, and incorporated into microcapsules.
A color former sheet is obtained by coating 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 pigments described below to produce paper, plastic sheets, and resin-coated paper. A developer sheet is obtained by applying the color developer to a support.

The amounts of the electron-donating colorless dye and the electron-accepting compound to be used depend on the desired thickness of the casing, 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 for thermal paper, JP-A-62-144.989
No. 62-244,883, etc. Specifically, the electron-donating colorless dye and the electron-accepting compound are 10μ or less in the dispersion medium,
It is preferably used after being pulverized and dispersed to a particle size of 3 μm or less. As the dispersion medium, an aqueous polymer solution having a concentration of approximately 0.5 to 10% is generally used, 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. At that time, 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. The amount used is 20% or more and 300% or less by weight, particularly preferably 40% or more and 150% or less, based on the electron-accepting compound.

Additives may be added to the coating liquid thus obtained 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 addition to electron-donating colorless dyes and electron-accepting compounds that directly contribute to color development, thermofusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers,
Additives such as antifoaming agents, conductive agents, fluorescent 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 required. 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 or common, polyvinyl alcohol,
Hydroxyethylcellulose, hydroquinpropylcellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol modification Examples include polyacrylamide, starch derivatives, casein, and gelatin. Further, for the purpose of imparting water resistance to these binders, a water-resistant side 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,■.

2-di-m-tolyloxyethane, 1,2-diphenoxyethane, 1,4-diphenoxybutane, bis-[β-
(p-methoxyphenoxy)ethylfer, 1-phenoxy-2-p-ethylphenoxyethane, 1-p-methoxyphenoxy-2-phenoxypropane, 1-phenoxy-2-p-methoxyphenoxypropane, 1,2
-bis(p-methoxyphenoxy)propane, 1.3-
Bis(p-methoxyphenoxy)propane, 1-p-methoxyphenoxy-2-o-chlorophenoxyethane,
4-(p-methoxybenzylthio)anisole, l-phenoxy-2-p-methoxyphenylthioethane, 1.
2-bis(p-methoxyphenylthio)ethane, 1-p
- Ether compounds such as methylphenoxy-2-p-methoxyphenylthioethane, 4-(4-chlorobenzyloxy)ethoxybenzene, stearamide, methylene bisstearamide, stearanilide, behenic acid amide, stearanilide , stearyl urea, etc.

Pigments include kaolin, calcined kaolin, talc, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, lithopone, amorphous silica, colloidal silica, calcined gypsum, silica, magnesium carbonate, titanium oxide, Alumina, barium carbonate, barium sulfate, mica, microballoons, urea-formalin fillers, 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 waxes include paraffin wax, carboxy-modified paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax, polystyrene wax, higher fatty acid esters, amides, and the like.

The hindered phenol compound is preferably a phenol derivative in which at least one of the 2nd and 6th positions is substituted with a branched alkyl group. For example, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1°1,3-tris(2-ethyl-4-
Hydroxy-5-t-butylphenyl)butane, 1,1
．． 3-tris(3,5-di-t-butyl-4-hydroxyphenyl)butane, 1,1.3-tris(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-2,4,6-1lis(3,5-di-t-butyl-4
-hydroxybenzyl)benzene, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propinate] methane, 2,2,6.6-tetramethyl-4-piperidinyl sebacate etc. can be 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, sodium polystyrene sulfonate, sodium alginate, and styrene-maleic anhydride copolymer.
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, sulfosuccinic acid-based alkali metal salts, fluorine-containing surfactants, etc. are used. Specifically, G (
Sodium salts or ammonium salts such as n-hexyl)sulfosuccinic acid and di(2-ethylhexyl)sulfosuccinic acid are preferred, but anionic surfactants are 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 in which a conductive substance, an electron-donating colorless dye, and an electron-accepting compound are 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, and then a conductive layer is formed on the support. 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. 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. In general, photopolymerization initiators such as silver bromide, silver bromide, silver behenate, Michler's ketone, benzoin derivatives, and benzophenone derivatives, and crosslinking agents such as polyfunctional monomers such as polyallyl compounds, poly(meth)acrylates, and poly(meth)acrylamides It is encapsulated in a synthetic resin capsule 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 general formulas (XID, (XII[)) as raw materials, HXR,, HPO(OR*)!, HC
Rff R,R,,HNR,,R,,,H3O-R1*
Or it can be obtained by reacting with its salt.

In the above formula, Ar+ to Art, R+ to Rz have the above-mentioned meanings, and Z- represents an anion of an inorganic acid or nucleating acid necessary for forming a dye, for example, Cl-1Br-1F-1I
-1H3O, -1SO,'-1CHsSo, +, PO,
-1CIO, -1CH,COO-,Cg Hs Sow
-, p-CHx C+ Ha 5Oh-% BF-
-1PF-I can rank first.

The aforementioned HXRs, HPO(ORs)! , HCR7
The salts of R,R,, HNR10Rll, HS Ot R+2 are, for example, alkali metal salts, alkaline earth metal salts, ammonium salts or amine salts.

HXRs to use, HPO(ORg)! , H.C.R.
The amount of 7R-R-, HNRIORIISHSO2RIz or a salt thereof is preferably from 1 to 3 mol, particularly preferably from 1 to 1.5 mol, per mol of the compound of general formula (Xll) or (XfI+).

The above reaction is preferably carried out in an organic 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 10% or more, particularly 20% of the solid content.

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 100°C.
70°C is preferred.

It is also preferable to carry out the reaction in an atmosphere of an inert gas such as kiln or argon gas from the viewpoint of preventing coloring of the liquid.

(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 (2) which is an electron-donating colorless dye, bisphenol A which is an electron-accepting compound, and 4-(4-chlorobenzyloxy)ethoxybenzene which is a thermofusible substance , and 100 g of a 5% polyvinyl alcohol (furan PV Al05) aqueous solution were dispersed in a Pall mill overnight to make the volume average particle diameter 1.5 μm or less, thereby obtaining each dispersion. Further, 80 g of calcium carbonate was dispersed with 160 g of a 0.5% solution of sodium hexametaphosphate using a homogenizer to obtain a pigment dispersion.

Each dispersion prepared as above was mixed with 5gS of electron-donating colorless dye dispersion! Mix 10 g of a child-receptive 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 C for 1 minute, apply a super calender,
A thermosensitive recording paper was obtained.

The obtained thermal recording paper was free from fog during raw storage and had excellent stability over time.

Thermal recording paper is heated using a thermal head (KLT) manufactured by Kyocera Corporation.
-216-8MPDI) and 100kg just before the head
/cd in a thermal printing experimental device that produces a pressure roll, and prints with a pulse width of 1.0 while using the pressure roll under the conditions of a head voltage of 24 V and a pulse cycle of I Oms, a green-blue image is obtained. It was done. Moreover, the obtained colored image showed good resistance to chemicals, sunlight, etc.

(Example 2) Preparation of capsule sheet containing child-donating colorless dye from (1) 5 parts of a partial sodium salt of polyvinylbenzenesulfonic acid (manufactured by National Starch Co., Ltd., VER3A1TL500) are 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 16) 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 liquid temperature 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 coated on 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 to give an average particle size of 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 then further mixed with 100 parts of a 10% PVA aqueous solution and carboxylic acid as a binder. Modified SBR
10 parts of latex (as solid content) was added and water was added to the solid content to give a coating liquid (A).

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

Add 16 parts of 10% PVA aqueous solution and 1.0% PV to this dispersion.
Add 1'00 parts of A aqueous solution and 10 parts of carboxy-modified SBR latex (as solid content) to make the solid content concentration 20.
% to obtain a coating liquid (B).

Coating liquid (A) and coating liquid (B) were mixed at a ratio of 1:1 in terms of electron-accepting compound, and 5.0 g/m' was applied to base paper of 50 g/m'.
The mixture was coated using an air knife coater so that a solid fraction of 10% 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/d was applied, the color immediately developed into a greenish-blue color. Moreover, the obtained colored image showed good resistance to chemicals, sunlight, etc.

(Example 3) The following was used in place of the electron-accepting compound sheet of Example 2.

(2°) Adjustment of electron-accepting compound sheet Acidic clay 100
were dispersed in 400 parts of a 0.5% aqueous sodium hydroxide solution, followed by adding 20 parts of styrene-butadiene copolymer latex (solid content) and 40 parts of a 10% starch aqueous solution, and stirring and mixing thoroughly. A compound coating solution was obtained.

5. Apply the coating solution prepared in this way to a 50 g/m" base paper.
0g/m! The mixture 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 electron-donating colorless dye-containing microcapsule sheet of Example 2 was layered on this electron-accepting compound sheet for 600 kg.
When a load of g/al was applied, a blue color immediately developed. In addition, the obtained colored image had a high color density (color density = 0.32, measured with a Macbeth Co., Ltd. RD-918 type densitometer) and showed good resistance to chemicals, sunlight, etc.

(Example 4) Instead of the electron-donating colorless dye of Example 2, specific example (1
An electron-donating colorless dye-containing microcapsule sheet was obtained in the same manner as in Example 2 except that 7) was used. This sheet surface
Layered on the electron-accepting compound sheet of Example 3, 600 kg/
When a load of al was applied, a blue color developed. In addition, the color image obtained has a high color density (color density = 0.31
) It showed good resistance to chemicals, sunlight, etc.

(Example 5) In place of the electron-donating colorless dye of Example 2, specific example (6
An electron-donating colorless dye-containing microcapsule sheet was obtained in the same manner as in Example 2, except that the compound (2) was used. This sheet surface was stacked on the electron-accepting compound sheet of Example 3 for 600 minutes.
When a load of kg/cxl 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.

Claims (2)

[Claims] (1) In a recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, the electron-donating colorless dye contains at least two skeletons represented by the following general formula (I) in the molecule. A recording material characterized by using a poly(1-arylvinyl-1-arylmethane) compound having at least 1 ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (I) In the above formula, Ar_1 and Ar_2 are aryl groups, heterocycles, etc. The base,
R_1 to R_3 represent a hydrogen atom or a monovalent group, and R_4 represents a substituent that can be eliminated by contact with an electron-accepting compound. However, at least one of Ar_1, Ar_2, and R_1 to R_4 represents a divalent group. (2) In general formula (I), Ar_1 and Ar_2 are heterocyclic groups and aryl groups having an amine residue, and R_4 is -XR_5, -PO(OR_6)_2, -CR_7R_
8R_9, -NR_1_0R_1_1, -SO_2R_
1_2 (X is an oxygen atom, a sulfur atom, R_5 to R_1_
2 represents a hydrogen atom or a monovalent group. However, R_7~R_
At least one of 9 represents an electron-withdrawing group), and furthermore, the poly(1-arylvinyl-1-arylmethane) compound has a single bond or the following general formula ( Recording material characterized by using the compound according to claim 1, which is bonded with a divalent group represented by II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (II) In the above formula, L_0, L_2, L_4, L_6 are -O-, -
NR_a-, -NR_aCO-, -CONR_a-, -
NR_aSO_2-, -SO_2NR_a-, -COO
-, -OCO-, -NR_aCONR_a-, -OCO
NR_a-, -NR_aCOO-, -CHOH-, -S
-, -SO-, -SO_2-, -CO- (R_a represents a hydrogen atom, alkyl group, aryl group, heterocyclic group, acyl group), L_1, L_3, L_5 represent alkylene, aralkylene, arylene, a ~g represents an integer of 0 or 1 (b−c+de+f−g=0).