JPH04282283A - Pressure-sensitive recording sheet - Google Patents

Abstract

PURPOSE:To obtain a pressure-sensitive recording sheet forming a color at a high speed with a sufficient coloring density by a method wherein a color- forming layer consisting of a substantially colorless electron donative dye made of a specific compound, a crystal violet lactone, and the like and an electron accepting color developer is formed on a substrate. CONSTITUTION:Coating liquid is prepared by dissolving a substantially colorless electron donative dye and an electron accepting color developer in a solvent: the former is made of one or more compounds shown by formulas I and II [R1-R4 are H, alkyl, and aryl; R5-R11 are H or a monovalent group; (m) and (n) are integers 1-4; and R12 is -XR13, -PO(OR14)2, -CR15R16R17, -NR18R19, or -SO2R20 (X is O or S; R13-R20 are H or a monovalent group; and one or more of R15-R17 are an electron attractive group)], a crystal violet lactone, a p-substd. aminophenyl indolyl phthalide compound, and the like. This coating liquid is applied on a substrate and dried to form a color forming layer for obtaining a pressure-sensitive sheet.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to pressure-sensitive recording sheets. More specifically, the present invention relates to a pressure-sensitive recording sheet that obtains a colored image by a reaction between a nearly colorless electron-donating dye (hereinafter referred to as a color former) and an electron-accepting color developer (hereinafter referred to as a color developer).

0002

[Prior Art] Pressure-sensitive recording sheets are made by dissolving a coloring agent in a suitable solvent and coating a support with a microcapsule layer containing microcapsules encapsulating oil droplets. It consists of a combination of a lower sheet paper with a color developer layer containing it coated on another support, and in some cases a middle sheet paper with a microcapsule layer coated on one side of the support and a color developer layer coated on the other side. The above-mentioned capsules and color developer are contained on the same side of the support, or the support contains one of the capsules or the color developer and the other is coated. be.

[0003] Performance that a pressure-sensitive recording sheet should have is as follows:
1) The coloring speed is fast and the coloring density is sufficient. 2) No fogging should occur. 3) The coloring material has excellent light resistance. 4) The color forming body has excellent chemical resistance and plasticizer resistance. etc. can be mentioned. As a coloring agent for pressure-sensitive recording sheets,
Triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, indolyl azaphthalide compounds, leucoolamine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazenes Compounds such as spiropyran compounds and the like have been conventionally known.

0004

[Problem to be solved by the invention] However, pressure-sensitive recording sheets using these color formers do not have sufficient performance in terms of the light resistance, chemical resistance, and plasticizer resistance of the color formers. It wasn't. Accordingly, an object of the present invention is to provide a pressure-sensitive recording sheet in which the color former has excellent light resistance, chemical resistance, and plasticizer resistance, has a fast color development rate, and has sufficient color density.

[0005]

[Means for Solving the Problems] The above objects have been achieved by the present invention described below. That is, the present invention provides a pressure-sensitive recording sheet that obtains a colored image by a reaction between a nearly colorless electron-donating dye and an electron-accepting color developer, in which (a) the following general formula [1] and the general formula (1) are used as the electron-donating dye. At least one compound represented by formula [2] and (b) crystal violet lactone, (c) p-substituted aminophenylindolylphthalide compound, or (d) p-substituted aminophenylindolyl azaphthalyl compound This is a pressure-sensitive recording sheet characterized by containing at least one of the following.

General formula [1]

[Chemical formula 3] General formula [2]

embedded image In the above formula, R1 to R4 are a hydrogen atom, an alkyl group, or an aryl group, and R5 to R11 are a hydrogen atom or a monovalent group,
m and n are integers of 1 to 4, R12 is -XR13, -PO(OR14)2, -CR15R1
6R17, -NR18R19, -SO2 R20 (X represents an oxygen atom or a sulfur atom, R13 to R20 represent a hydrogen atom or a monovalent group. However, at least one of R15 to R17 represents an electron-withdrawing group) represent. Also, R5
~R9 may be linked to each other to form an alicyclic 4- to 12-membered ring which may contain a hetero atom.

The present invention will be explained in detail below. Preferred substituents of the compounds represented by formulas [1] and [2] used in the present invention are shown below. R1 to R4 are hydrogen atoms,
Alkyl group, aryl group, R5 to R9 are hydrogen atoms, alkyl group, alkoxy group, alkylthio group, alkoxycarbonyl group, aryl group, aryloxy group, arylthio group, aryloxycarbonyl group, cyano group, R10 and R11 are Hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, cyano group, nitro group, substituted amino group, hydroxy group, halogen atom,
an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, m and n are integers of 1 to 4, R12
-XR13, -PO(OR14)2, -CR15R
16R17, -NR18R19, -SO2 R20. Furthermore, R5 to R9 may be linked to each other to form an alicyclic 4- to 12-membered ring which may contain a hetero atom.

In the above formula, X represents an oxygen atom, a sulfur atom, and R1
3 is an alkyl group, an aryl group, a heterocyclic group, COR21,
SO2 R22, N=CR23R24, NR25R26
[R21, R22 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, R23, R24, R25, R26 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, COR
27, SO2 R28 (R27 and R28 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group)]. R
14 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Furthermore, R14 may be linked to each other to form a 4- to 12-membered ring structure that may contain a hetero atom. R15
, R16 and R17 represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a cyano group, a nitro group, SO2 R29, COR30, NR31R32 [R29 and R30 are Hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, hydroxy group, NR33
R34, R31, R32, R33, R34 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, SO2 R3
5, COR36 (R35 and R36 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group)]. Further R
15 and R16 may be linked to each other to form a 4- to 12-membered ring structure that may contain a hetero atom.

R18 and R19 are hydrogen atoms, alkyl groups,
Aryl group, heterocyclic group, SO2 R37, COR38
, represents a hydroxy group, NR39R40 [R37, R3
8 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heterocyclic group, NR41R42,
R39, R40, R41, R42 are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, SO2 R43, COR
44, (R43 and R44 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group)]. Furthermore, R18, R1
4 to 9 may be connected to each other and contain a heteroatom
A 12-membered ring structure may be formed. R20 is an alkyl group,
Represents an aryl group or a heterocyclic group. In addition, an alkyl group and an aryl group further include an alkyl group, an alkoxy group, an aryl group,
Containing substituents such as aryloxy group, halogen atom, nitro group, cyano group, substituted carbamoyl group, substituted sulfamoyl group, substituted amino group, substituted oxycarbonyl group, substituted oxysulfonyl group, alkylthio group, arylsulfonyl group, hydroxy group, etc. You may do so.

More specifically, among the substituents represented by R1 to R4, hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and aryl groups having 6 to 12 carbon atoms are preferred. R1 ~
R4 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
-heptyl 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-cyanoethyl group, β-chloroethyl group, β-hydroxyethyl group, cyclopentyl group, cyclohexyl group, tetrahydrofurfuryl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, benzyl group, phenethyl group, Examples include methylbenzyl group, chlorobenzyl group, and methoxybenzyl group.

Preferably, R1 to R4 are not hydrogen atoms at the same time. R1 and R2, R3 and R4 are bonded to each other to form a ring which may contain a 5- to 8-membered heteroatom including the nitrogen atom to which they are bonded, such as pyrrolidine, piperidine, morpholine, thiomorpholine, Piperazine may form a caprolactam ring. In addition, R1 to R4 are bonded to the benzene ring carbon at the ortho position of the nitrogen atom to which they are bonded, and are 5 to 5, respectively.
It may also form an 8-membered ring, such as an indoline ring, a 1,2,3,4-tetrahydroquinoline ring, or a julolidine ring. Among the substituents represented by R5 to R9, hydrogen atoms,
Alkyl group having 1 to 18 carbon atoms, alkoxy group, alkylthio group, alkoxycarbonyl group, having 6 carbon atoms
to 12 aryl groups, aryloxy groups, arylthio groups, aryloxycarbonyl groups or cyano groups are preferred.

More specifically, R5 to R9 include hydrogen atom, methyl group, ethyl group, propyl group, butyl group,
amyl group, hexyl group, octyl group, octadecyl group,
Methoxypropyl group, ethoxypropyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, allyl group, benzyl group, phenethyl group, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4- Methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-N,N-dimethylaminophenyl group, 3-N,N-dimethylaminophenyl group, 2-N,N-dimethylaminophenyl group, 4 −
N,N-diethylaminophenyl group, 1,2-dimethylindol-3-yl group, 1-butyl-2-methylindol-3-yl group, 1-ethyl-2-phenylindol-3-yl group, cyano group , methoxycarbonyl group,
Examples include ethoxycarbonyl group and methylthio group.

Furthermore, R5 to R9 may be linked to each other to form an alicyclic 4- to 12-membered ring structure which may contain a hetero atom, and it is particularly preferable to form a 5- to 8-membered ring structure. preferable. Furthermore, this ring may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Especially R6 and R
It is preferable that 8 are connected. Among the substituents represented by R10 and R11, hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, alkoxy groups, alkoxycarbonyl groups having 2 to 12 carbon atoms, acyloxy groups, and 6 to 12 carbon atoms;
12 aryl group, aryloxy group, aryloxycarbonyl group having 7 to 12 carbon atoms, hydroxy group,
Chlorine atom, bromine atom, fluorine atom, nitro group, cyano group,
An amino group, a mono- or dialkylamino group having 1 to 12 carbon atoms, a mono- or diarylamino group having 6 to 12 carbon atoms, and an acylamino group having 1 to 12 carbon atoms are preferred.

R10 and R11 are hydrogen atom, methyl group, ethyl group, propyl group, butyl group, octyl group, phenyl group, tolyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, propoxy group, butoxy group, oxytyloxy group, benzyloxy group, phenoxyethoxy group, phenoxy group, chlorine atom, bromine atom, fluorine atom, nitro group, cyano group, hydroxy group, dimethylamino group,
Examples include diethylamino group, acetylamino group, acetyloxy group, and methoxycarbonyl group. R10, R1
1 is -NR1 R2 , -NR3 R from the point of view of coloring wavelength
4, the meta position is preferred.

Among the substituents represented by R12, those having 20 or less carbon atoms are preferred. Furthermore, from the viewpoint of synthetic handling, R12 is -XR13, -CR15R16R17, -NR18R1
9, -SO2 R20 is preferred. As R12, methoxy group, ethoxy group, propoxy group, butoxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group, octadecyloxy group, benzyloxy group, phenethyloxy group, phenylbutyloxy group, 4-methylbenzyloxy group basis,
4-chlorobenzyloxy group, 4-methoxybenzyloxy group, β-phenoxyethoxy group, β-(4-methylphenoxy)ethoxy group, β-(3-methylphenoxy)ethoxy 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)phosphonyl group, di(4-methoxyphenyl)phosphonyl group, di(4-nitrophenyl)phosphonyl group, di(4-cyanophenyl)phosphonyl group, di(naphthalen-1-yl)phosphonyl group, di(naphthalene-1-yl)
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-butoxyanilino group, 2,4-dichloroanilino group, 2,5-dimethylanilino group, β-naphthyl Amino group, N-methylanilino group, N-butylanilino group, N-acetylanilino group, pyridylamino group, quinolylamino group, cyclohexylamino group, indol-1-yl group, carbazole-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, pyrrolidino group, piperidino group, morpholino group, piperazino group, phenylhydrazino group, N-hydroxy-N-phenylsulfonylamino group, N-hydroxy-N-4 -chlorophenylsulfonylamino group, benzoylhydrazino group, phenylsulfonylhydrazino group, benzoyloxy group, acetyloxy group, methylthio group, ethylthio group, phenylthio group, tolylthio group, benzylthio group, naphthylthio group, benzothiazol-2-ylthio group , benzimidazole-2
-ylthio group, benzoxazol-2-ylthio group,
1,1-diacetylmethyl group, 1,1-dicyanomethyl group, 1-acetyl-1-benzoylmethyl group, 1,1-
Dimethoxycarbonylmethyl group, 1,1-diethoxycarbonylmethyl group, 1,1-dipropoxycarbonylmethyl group, 1,1-diphenyloxycarbonylmethyl group, 1,1-di-n-butoxycarbonylmethyl group, 1,
1-di-isobutoxycarbonylmethyl group, 1,1-di-t-butoxycarbonylmethyl group, 1,1-dipentyloxycarbonylmethyl group, 1,1-dihexyloxycarbonylmethyl group, 1,1-dibenzyloxy Carbonylmethyl group, 1,1-dioctyloxycarbonylmethyl group, 1,1-didodecyloxycarbonylmethyl group, 1-phenoxycarbonyl-1-methoxycarbonylmethyl group, 1-phenoxycarbonyl-1-ethoxycarbonylmethyl group, 1 -phenoxycarbonyl-1-
Butoxycarbonylmethyl group, 1-acetyl-1-methoxycarbonylmethyl group, 1-acetyl-1-ethoxycarbonylmethyl group, 1-acetyl-1-isopropoxycarbonylmethyl group, 1-acetyl-1-butoxycarbonylmethyl group, 1-acetyl-1-hexyloxycarbonylmethyl group, 1-acetyl-1-octyloxycarbonylmethyl group, 1-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, 1-cyano-1-ethoxycarbonylmethyl group, 1-benzoyl-1-ethoxycarbonylmethyl group, 1-acetyl-
1-morpholinocarbonylmethyl group, 1-methoxycarbonyl-1-ethoxycarbonylmethyl group, 1,1-diphenylsulfonylmethyl group, 1-tolylsulfonyl-1
-benzoylmethyl group, 1,1-di(trifluoromethylcarbonyl)methyl group, 1,1-dipivaloylmethyl group, 1-furoyl-1-trifluoromethylcarbonylmethyl group, 1-thienylcarbonyl-1- Trifluoromethylcarbonylmethyl group, 1,1-dicarbamoylmethyl group, 1-acetyl-1-phenylcarbamoylmethyl group, 1,1-dibenzoylmethyl group, 1,1-dimethoxycarbonylethyl group, 1,1-dicarbamoylmethyl group, Ethoxycarbonylethyl group, 1,1-diphenyloxycarbonylethyl group, 1,1-di-n-butoxycarbonylethyl group,
1,1-di-t-butoxycarbonylethyl group, 1,1
-dibenzyloxycarbonyl ethyl group, 1,1-dimethoxycarbonyl-n-propyl group, 1,1-dimethoxycarbonyl-n-butyl group, α,α-dimethoxycarbonylbenzyl group, 1,1-dimethoxycarbonyl-1
-Methoxymethyl group, 1,1-diethoxycarbonyl-
n-propyl group, 1,1-diethoxycarbonyl-n-
Pentyl group, 1,1-diethoxycarbonyl-n-butyl group, 1,1-diethoxycarbonyl-1-isopropylmethyl group, 1,1-diethoxycarbonyl-1-t-
Butylmethyl group, α,α-diethoxycarbonylbenzyl group, β,β-diethoxycarbonylphenethyl group, 1
, 1-diethoxycarbonyl-1-allylmethyl group, 1
, 1-diethoxycarbonyl-1-acetaminomethyl group, 1,1-diethoxycarbonyl-1-chloromethyl group, 1,1-diethoxycarbonyl-1-cyclopentylmethyl group, 1,1-diethoxycarbonyl- 1-phthalimidomethyl group, 1,1-diethoxycarbonyl-2
-Ethoxycarbonylethyl group, 1,1,1,-triethoxycarbonylmethyl group, benzoylmethyl group, 4-
Chlorobenzoylmethyl group, 4-nitrobenzoylmethyl group, 1-chloro-1-acetylmethyl group, 1-chloro-1-methoxycarbonylmethyl group, 1-bromo-1-
Benzoylmethyl group, nitromethyl group, 1-nitroethyl group, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, benzylsulfonyl group, phenethylsulfonyl group, phenylsulfonyl group, 4-tolylsulfonyl group, 3-tolylsulfonyl group group, 2-tolylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-ethoxyphenylsulfonyl group, 4-
Propyloxyphenylsulfonyl group, 3-butoxyphenylsulfonyl group, 4-chlorophenylsulfonyl group, 4-nitrophenylsulfonyl group, 4-dodecylphenylsulfonyl group, 4-benzyloxyphenylsulfonyl group, 2,4-dimethoxyphenylsulfonyl group, Naphthalen-1-ylsulfonyl group, naphthalen-2-ylsulfonyl group, 3,4-dichlorophenylsulfonyl group, 2,5-dichlorophenylsulfonyl group, 4-N,N
-dimethylaminophenylsulfonyl group.

Next, specific examples of the compounds represented by the general formulas [1] and [2] will be shown.

[C5]

[C6]

[0017]

[C7]

[Chemical formula 8]

[0018]

[Chemical formula 9]

[Chemical formula 10]

[0019]

[Chemical formula 11]

[Chemical formula 12]

[0020]

[Chemical formula 13]

[Chemical formula 14]

[0021]

[Chemical formula 15]

[Chemical formula 16]

[0022]

[Chemical formula 17]

[Chemical formula 18]

[0023]

[Chemical formula 19]

[C20]

[0024]

[C21]

[C22]

[0025]

[C23]

[C24]

[0026]

[C25]

[C26]

[0027]

[C27]

[C28]

[0028]

[C29]

[C30]

As the color former electron-donating dye of the present invention, (
When using a) at least one of the compounds represented by the general formulas [1] and [2] and (b) crystal violet lactone, the ratio of their combined use is (a)/(b) by weight.
(b)=20/80 to 90/10 is preferable, 30/7
More preferably 0 to 80/20. General formula [1] or [2]
] If the amount of the compound represented by is too small, the light resistance, chemical resistance and plasticizer resistance of the color former will be insufficient, and if the amount of crystal violet lactone used is too small, the color development rate will be insufficient. Compound (a
As the (c) p-substituted aminophenylindolphthalide compound used with ), those represented by the following general formula are preferred.

[0030]

[Chemical Formula 31] In the above formula, X, Y, and Z are a hydrogen atom, a halogen atom, a C1 to C8 alkyl group, a C1 to C12 alkoxy group, a C6 to C18 aryloxy group, or a C7 to C18 aralkyloxy group. group, W represents a hydrogen atom or a halogen atom, R1 represents a hydrogen atom or 1
Represents an alkyl group having up to 2 carbon atoms, unsubstituted or substituted with a halogen atom, a hydroxyl group, a cyano group, or a lower alkoxy group, R2 is a hydrogen atom, a C1 to C8 alkyl group, or a C6 to C1
2, R3 and R4 are each independently a hydrogen atom or an alkyl group having up to 12 carbon atoms, unsubstituted or substituted with a halogen atom, a hydroxyl group, a cyano group, or a lower alkoxy group, C5
-C7 represents a cycloalkyl group, benzyl group, or phenyl group, and -NR3 R4 may further form a pyrrolidinyl group. The p-substituted aminophenylindolyl azaphthalide compound used as the color former of the present invention is preferably one represented by the following general formula.

[0031]

In the above formula, one of X and Y represents -N=, the other represents -CH=, and Z is a hydrogen atom, a halogen atom, a C1
~C8 alkyl group, C1 ~C12 alkoxy group, C6 ~C18 aryloxy group, or C7 ~
C18 aralkyloxy group, W represents a hydrogen atom or a halogen atom, and R1 is a hydrogen atom or an alkyl group having up to 12 carbon atoms, unsubstituted or substituted with a halogen atom, a hydroxyl group, a cyano group, or a lower alkoxy group. represents a group, R2 is a hydrogen atom, C1
~C8 alkyl group or C6 ~C12 aryl group, R3 and R4 are each independently a hydrogen atom or 1
represents an alkyl group, unsubstituted or substituted by a halogen atom, a hydroxyl group, a cyano group, or a lower alkoxy group, a C5-C7 cycloalkyl group, a benzyl group, or a phenyl group having up to 2 carbon atoms, and - A pyrrolidinyl group may be formed as NR3 R4.

As the coloring agent of the present invention, (a) the general formula [1
] and or [2] and (c) P-substituted aminophenylindolphthalide compound, for the same reason, the combined ratio of (a) by weight is
/(c)=20/80 to 90/10 is preferable, and 30/
More preferably 70 to 80/20. When using (a) the compound represented by the general formula [1] or [2] and (d) the P-substituted aminophenylindolyl azaphthalide compound as the coloring agent of the present invention, for the same reason, the ratio of their combined use is The weight ratio is (a)/(d) = 20/80 to 90/1.
0 is preferable, and 30/70 to 80/20 is more preferable. Color formers other than those mentioned above may be used in combination for the purpose of hue adjustment and the like. In this case, it is desirable that the amount of color formers other than those mentioned above be 20% by weight or less of the total amount of color formers.

The coloring agent used in the present invention is dissolved in a solvent, encapsulated, and applied to a support. As a solvent, natural or synthetic oils can be used alone or in combination. Examples of solvents include kerosene, paraffin, naphthenic oil, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes, diarylalkane, phthalate esters, and the like. Methods for producing color former-containing microcapsules include interfacial polymerization,
An internal polymerization method, a phase separation method, an external polymerization method, a coacervation method, etc. are used. In preparing a coating solution containing microcapsules containing a color former, a water-soluble binder or a latex binder is generally used. Furthermore, a capsule protectant such as cellulose powder, starch particles, talc, etc. is added to obtain a color former-containing microcapsule coating solution.

Examples of the color developer that reacts with the color forming agent used in the pressure-sensitive recording sheet of the present invention include clay materials such as acid clay, activated clay, attapulgite, zeolite, bentonite, and kaolin, and metals of aromatic carboxylic acids. Examples include salts, phenol formaldehyde resins, and the like. The performance of the pressure-sensitive recording sheet of the present invention was tested using the following color developer sheet.

[Adjustment of color developer sheet] 200 g of activated clay
, 8 g of magnesium oxide, 1 g of sodium hexametaphosphate, 20 g of 20% sodium hydroxide, and 500 g of water were dispersed in a Keddy mill. To this, 40 g (as solid content) and 10 g of carboxy-modified SBR latex were added.
% starch aqueous solution was added to obtain a coating solution. This coating liquid was applied to a 50 g/m2 base paper using an air knife coater so that the solid content was 6 g/m2 and dried to obtain a color developer sheet.

[0036]

[Examples] The pressure-sensitive recording sheet of the present invention will be specifically explained below with reference to Examples, but the invention is not limited to these Examples. Example 1 Specific examples of compounds represented by general formula [1] as color formers (
Dissolve 5.0 g of 1-1) and 2.5 g of crystal violet lactone in 100 g of diisopropylnaphthalene. In this oily liquid, add 10 g of carbodiimide-modified diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name "Millionate MTL"), 5 g of isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate EH"), and butylene oxide of ethylenediamine. A primary solution was prepared by dissolving 3.0 g of an adduct (number of moles added of butylene oxide to ethylene diamine: 16.8 moles, molecular weight: 1267).

Next, add 1 part polyvinyl alcohol to 140 g of water.
A secondary solution was prepared by dissolving 0 g and 5 g of carboxymethylcellulose. Step 1 above while stirring the secondary solution vigorously.
The solution was then poured to form an oil-in-water emulsion. When the size of the oil droplets reached 50μ, the stirring was weakened, and then 10g of water at 20°C was added to the emulsion.
and 1.6 g of tetraethylenepentamine, the temperature of the system was gradually raised to 75° C. and maintained at this temperature for 90 minutes. To the capsule liquid thus obtained, 80 g of a 15% aqueous solution of polyvinyl alcohol, carboxy-modified S
30 g of BR latex in terms of solid content and 60 g of starch particles (average particle size 15 μm) were added. Next, water was added to adjust the solid content concentration to 20% to prepare a coating solution. Apply this coating solution to a dry weight of 4.0 g/m2.
g/m2 on base paper using an air knife coater and drying to obtain a color former-containing microcapsule sheet.

Example 2 Specific examples of compounds represented by general formula [1] as color formers (
A color former-containing microcapsule sheet was obtained in the same manner as in Example 1, except that 5.0 g of 1-7) and 2.5 g of crystal violet lactone were used.

Example 3 Specific examples of compounds represented by general formula [2] as color formers (
A color former-containing microcapsule sheet was obtained in the same manner as in Example 1, except that 5.0 g of 2-1) and 2.5 g of crystal violet lactone were used. Example 4 Specific examples of compounds represented by general formula [2] as color formers (
A color former-containing microcapsule sheet was obtained in the same manner as in Example 1, except that 5.0 g of 2-5) and 2.5 g of crystal violet lactone were used.

Comparative Example 1 7.5 g of crystal violet lactone as a coloring agent
A color former-containing microcapsule sheet was obtained in the same manner as in Example 1 except that . Comparative Example 2 Specific example of a compound represented by general formula [1] as a coloring agent (
1-1) A color former-containing microcapsule sheet was obtained in the same manner as in Example 1 except that 7.5 g was used. Comparative Example 3 Specific example of a compound represented by general formula [1] as a coloring agent (
2-5) A color former-containing microcapsule sheet was obtained in the same manner as in Example 1 except that 7.5 g was used.

Example 5 Specific examples of compounds represented by general formula [1] as color formers (
1-2) and 4.0 g of 3-[4-(diethylamino)-
4.0 g of 2-ethoxyphenyl]-3-(2-methyl-1-octyl-3-indolyl) phthalide is dissolved in 80 g of 1-phenyl-1-xylylethane and 20 g of isoparaffin. Add 8 g of polymethylene polyphenyl polyisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name "Millionate MR200") and a biuret form of hexamethylene diisocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd.) to this oily liquid.
A primary solution was prepared by dissolving 8 g of Sumidur N3200 (trade name).

Next, add 1 part polyvinyl alcohol to 140 g of water.
A secondary solution was prepared by dissolving 0 g and 5 g of carboxymethylcellulose. Step 1 above while stirring the secondary solution vigorously.
The solution was then poured to form an oil-in-water emulsion. When the size of the oil droplets reached 8.0μ, the stirring was weakened, and then 100% of water at 20°C was added to the emulsion.
After adding g and 1.6 g of diethylenetriamine, the temperature of the system was gradually increased to 85° C. and maintained at this temperature for 60 minutes. 80 g of a 15% aqueous solution of polyvinyl alcohol and carboxy-modified SB were added to the capsule liquid thus obtained.
30 g of solid content of R latex and 60 g of starch particles (average particle size 15 μm) were added. Next, water was added to adjust the solid content concentration to 20% to prepare a coating solution. Apply 40g of this coating solution to a dry weight of 4.0g/m2.
/m2 coated on base paper with an air knife coater and dried.
A microcapsule sheet containing a coloring agent was obtained.

Example 6 Specific examples of compounds represented by general formula [1] as color formers (
1-16) and 4.0 g of 3-[4-(diethylamino)
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5, except that 4.0 g of -2-ethoxyphenyl]-3-(2-methyl-1-octyl-3-indolyl) phthalide was used. Example 7 Specific examples of compounds represented by general formula [2] as color formers (
2-8) and 4.0 g of 3-[4-(diethylamino)-
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5, except that 4.0 g of 2-ethoxyphenyl]-3-(2-methyl-1-octyl-3-indolyl) phthalide was used. Comparative Example 4 3-[4-(diethylamino)-2-ethoxyphenyl]-3-(2-methyl-1-octyl-3
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5, except that 8.0 g of -indolyl) phthalide was used.

Comparative Example 5 Specific examples of compounds represented by general formula [1] as color formers (
1-2) A color former-containing microcapsule sheet was obtained in the same manner as in Example 5 except that 8.0 g was used. Comparative Example 6 Specific example of a compound represented by general formula [1] as a color former (
1-16) A color former-containing microcapsule sheet was obtained in the same manner as in Example 5, except that 8.0 g was used.

Example 8 Specific examples of compounds represented by general formula [1] as color formers (
1-3) and 3.0 g of 3-[4-(diethylamino)-
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5, except that 5.0 g of 2-ethoxyphenyl]-3-(2-methyl-1-octyl-3-indolyl)-4-azaphthalide was used. Example 9 Specific examples of compounds represented by general formula [1] as color formers (
1-47) and 3.0 g of 3-[4-(diethylamino)
-2-ethoxyphenyl]-3-(2-methyl-1-octyl-3-indolyl)-4-azaphthalide 5.0 g
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5 except that .

Example 10 Specific examples of compounds represented by general formula [2] as color formers (
2-13) and 3.0 g of 3-[4-(diethylamino)
-2-ethoxyphenyl]-3-(2-methyl-1-octyl-3-indolyl)-4-azaphthalide 5.0 g
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5 except that . Comparative Example 7 3-[4-(diethylamino)-2-ethoxyphenyl]-3-(2-methyl-1-octyl-3
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5, except that 8.0 g of -indolyl)-4-azaphthalide was used.

Comparative Example 8 A specific example of a compound represented by the general formula [1] as a coloring agent (
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5, except that 8.0 g of 1-47) was used. Comparative Example 9 Specific example of a compound represented by general formula [2] as a color former (
A color former-containing microcapsule sheet was obtained in the same manner as in Example 5, except that 8.0 g of 2-13) was used.

[0048] An evaluation test was carried out on the combination of the color developer sheet and the color former-containing microcapsule sheet as a pressure-sensitive recording sheet, and the results are shown in Table 1. The evaluation test was conducted using the following method.

(1) Color development speed and color density test The color developer sheet and each color former-containing microcapsule sheet are stacked and IB
The lowercase letter m of the alphabet was printed continuously using an M6747 electronic typewriter to develop color. The density (D1) after 1 minute has passed after color development using a Macbeth reflection densitometer,
The density (D2) was measured 24 hours after color development. The D1/D2 ratio was defined as the color development rate, and D2 was defined as the color development density.

(2) Light resistance test of coloring body The coloring body obtained in (1) after being left for 24 hours was irradiated for 24 hours with a “xenon fade meter (FAL-25AX-HC type)” (manufactured by Suga Test Instruments). The reflection density of the color former was measured after irradiation (density DL after irradiation). Further, a value indicating light resistance (light resistance value) was calculated using the following formula. *The larger the lightfastness value, the better the lightfastness of the coloring material.

(3) Plasticizer resistance test of colored body After leaving it for 24 hours obtained in (1), a soft polyvinyl chloride sheet (thickness 0.5 mm, 15% of dibutyl phthalate as a plasticizer was placed on top of the colored body obtained in (1). % by weight and 7% by weight of dioctyl phthalate) in an atmosphere of 50°C and 20% RH.
After applying a load of 0 g/cm2 and leaving it for one week, the reflection density of the colored body was measured (Dp). Further, a value indicating light resistance (light resistance value) was calculated using the following formula. *The larger the plasticizer resistance value, the better the plasticizer resistance of the colored body.

(4) Chemical resistance test of colored body After standing for 24 hours obtained in (1), stick glue was applied on the colored body, and decolorization of the colored body was visually observed.

[Table 1]

[0053]

[Effects of the Invention] As shown in Table 1, the pressure-sensitive recording sheet of the present invention has excellent light resistance, plasticizer resistance, and chemical resistance, and has sufficient color development speed compared to the comparative pressure-sensitive recording sheet. , has extremely good performance.

Claims (1)

[Claims] Claim 1: In a pressure-sensitive recording sheet that obtains a colored image by the reaction of a nearly colorless electron-donating dye and an electron-accepting color developer, the electron-donating dyes include (a) general formula [1] and general formula [ 2] and at least one compound represented by (b
) crystal violet lactone, (c) p-substituted aminophenylindolyl phthalide compound, or (d)
A pressure-sensitive recording sheet comprising at least one P-substituted aminophenylindolyl azaphthalyl compound. General formula [1] [Chemical formula 1] General formula [2] [Chemical formula 2] In the above formula, R1 to R4 are hydrogen atoms, alkyl groups, and aryl groups, R5 to R11 are hydrogen atoms or monovalent groups,
m and n are integers of 1 to 4, R12 is -XR13, -PO(OR14)2, -CR15R1
6R17, -NR18R19, -SO2 R20 (X represents an oxygen atom or a sulfur atom, R13 to R20 represent a hydrogen atom or a monovalent group. However, at least one of R15 to R17 represents an electron-withdrawing group) represents, also, R5
~R9 may be linked to each other to form an alicyclic 4- to 12-membered ring which may contain a hetero atom.