JPH06247039A - Pressure sensitive recording body - Google Patents

Abstract

PURPOSE:To obtain a pressure sensitive recording body wherein a color development image is clear and light resistance, water resistance and chemical resistance are improved, by a method wherein a pressure sensitive color development layer containing a specific basic dyes and specific activated clay mineral of a coloration agent is provided on a substrate. CONSTITUTION:A micro-capsule is prepared which encapsulates a compound represented by a formula I(R1-R4 represent C1-C5 alkyl group, R5 represents C1-C5 alkoxyl group, R6 represents a halogen atom and R7 represents C1-C12 alkylene group), a formula II(R8-R11 represent C1-C5 alkyl group, R13 represents C1-C5 alkoxyl group, R14 represents hydrogen atom and R12 represents a phenyl group) and a formula III(R15-R18 represent C1-C5 benzyl group R19 represents the halogen atom and R20 represents hydrogen atom), and has a mean particle diameter of 3-15mum and a mean film thickness of 0.1-0.7mum. The micro-capsule is dispersed into a water dispersion liquid of activated clay mineral having contents of 65-80wt.% SiO2 the dispersion liquid is applied onto a substrate for drying, a pressure sensitive color development layer is provided and a pressure sensitive recording body is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive recording material, and more particularly to a pressure-sensitive recording material having a fast color image.

[0002]

2. Description of the Related Art A pressure-sensitive recording medium is prepared by applying a microcapsule composition containing microcapsules containing droplets of a basic dye or the like as a main component to one side of a support and a paper or one side of the support. Is a color-developing composition containing an electron-accepting color-developing agent (hereinafter simply referred to as a color-developing agent) as a main component, which is colored when contacted with a basic dye to form a color-developing layer on the opposite surface. Includes a middle paper coated with a microcapsule composition and a lower paper coated with a colorant composition on one side of a support to form a color layer. These three types of sheets are used as upper paper and lower paper, or It has been put into practical use as a copy set by combining upper paper, middle paper, and lower paper in this order. Further, there is also a self-coloring pressure-sensitive recording material in which a microcapsule containing a basic dye and a coloring agent are coated on a single surface of a support in a single layer or two layers to enable pressure-sensitive recording with one sheet. It is known as a form of pressure-sensitive recording material.

Performances required for the pressure-sensitive recording material include high speed of color development, sufficient color density, no stain, and sufficient fastness of color image. In recent years, due to diversification of quality requirements, there has been a strong demand for development of a pressure-sensitive recording material which is particularly excellent in fastness of a color image, for example, light resistance, water resistance, chemical resistance and the like.

Conventionally, triphenylmethane compounds, phthalide compounds, leucomethylene blue compounds and the like have been known as compounds which develop blue to blue violet, but pressure sensitive recording materials using these are still sufficiently satisfactory. A recording material having the quality that can be obtained has not been obtained. For example, 3,3
-Bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone) has a fast color-developing rate with respect to an organic colorant and exhibits a deep blue color, but is extremely fast in color image fastness. Inferior

On the other hand, when a diarylmethane compound is used in combination with an activated clay mineral, a pressure-sensitive recording material having excellent fastness of a color image can be obtained, but since such a compound has a sublimation property, it is stored during storage. It is easy to cause spontaneous color development due to transfer, and in addition, the color density changes with a change in writing pressure (printing pressure), or color defects occur due to unintentional pressure or rubbing. Since the system in which a methane compound and an activated clay mineral are combined is more prominent, improvement of these is required. In addition, in a system in which a diarylmethane compound and an activated clay mineral are combined, the color tone of the color-developed image turns red due to the influence of light, humidity, water, or chemicals, and it is difficult to desensitize with an ordinary desensitizer. There are drawbacks, and these improvements are required.

[0006]

DISCLOSURE OF THE INVENTION The object of the present invention is to obtain a pressure-sensitive recording in which a color image is excellent in light resistance, water resistance and chemical resistance, and in which the properties peculiar to the pressure-sensitive recording medium are improved. To provide the body. The present inventors have conducted extensive studies in order to achieve such an object, and as a result, use a specific diarylmethane-based compound as a basic dye, use it by encapsulating it in a specific microcapsule, and further specify. By combining the above colorants, the color image is clear, the light resistance, water resistance and chemical resistance are excellent, and the desensitization suitability is good, and there is no change in color tone, and there is little color stain. Finding that a pressure-sensitive recording material can be obtained,
The present invention has been completed.

[0007]

The present invention provides a pressure-sensitive recording material utilizing a color reaction between a colorless or light-colored basic dye and a color-developing agent, wherein the basic dye is represented by the following general formula: , [Chemical Formula 2] or [Chemical Formula 3], and the basic dye has an average particle diameter of 3 to 15 μm and an average film thickness of 0.1 to 0.7 μm.
m encapsulated in synthetic polymer microcapsules,
In addition, the content of silicon oxide (SiO ₂ ) as a coloring agent is 65 to
The pressure-sensitive recording material is characterized by using 80% by weight of activated clay mineral.

[0008]

[Chemical 1]

[In the formula, R _{1 to} R ₄ are respectively C _{1 to} C ₅
Is an alkyl group or a benzyl group, and R ₅ is C ₁ -C
_{5 represents} an alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom, R ₆ represents a hydrogen atom, a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom, and R ₇ Represents a C ₁ -C ₁₂ alkylene group or a group represented by [Chemical Formula 4].

[0010]

[Chemical 4]

Here, X _{1 to} X ₈ are hydrogen atoms,
C ₁ -C ₄ alkyl group, an alkoxyl group or a halogen atom C ₁ -C _4, Z is a direct bond, -O -, -
S -, - an alkylene group or a C ₁ ~C ₆ - SO _2. ]

[0012]

[Chemical 2]

[In the formula, R _{8 to} R ₁₁ are each C _{1 to} C ₅
Is an alkyl group or a benzyl group, and R ₁₃ is C ₁ -C
_{5 represents} an alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom, R ₁₄ represents a hydrogen atom, a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom, and R ₁₂ Represents a phenyl group or a C ₃ -C ₇ alkoxycarbonylalkyl group. The phenyl group is C
_{1 to} C ₄ alkyl group, C _{1 to} C ₄ alkoxyl group,
It may be substituted with a halogen atom or a hydroxymethyl group. ]

[0014]

[Chemical 3]

[In the formula, R _{15 to} R ₁₈ are each C _{1 to} C ₅
Is an alkyl group or a benzyl group, and R ₁₉ is C ₁ -C
_{5 represents} an alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom, R ₂₀ represents a hydrogen atom, a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom,

[0016]

[Chemical 5]

Represents a saturated or unsaturated heterocycle having a 5- or 6-membered ring. ]

[0018]

The specific examples of the diarylmethane compound represented by the above general formula [Formula 1] used in the present invention include the following. 4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-dichloro-
4,4'-bis [(4-diethylamino-2-methyl-
4'-dimethylamino) diphenylmethylamino] diphenylmethane, 2,2'-dichloro-4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane,
2,2 ', 5,5'-tetrachloro-4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane,
3,3 ', 5,5'-tetrachloro-4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane,
3,3'-dimethoxy-4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 2,2'-dimethyl-4,4'-bis [( 4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-dimethyl-4,4 '
-Bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-diethyl-4,4'-bis [(4-diethylamino-2-methyl-4'- Dimethylamino) diphenylmethylamino] diphenylmethane, 3,3′-
Di-tert-butyl-4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3 ', 5,5'
-Tetra-tert-butyl-4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 2,2-bis [4-{(4-diethylamino-2 -Methyl-4'-dimethylamino) diphenylmethylamino} phenyl] propane, 2,2-bis [4-{(4-diethylamino-
2-Methyl-4'-dimethylamino) diphenylmethylamino} phenyl] -4-methyl-pentane, N, N '
-Bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethyl] benzidine, 4,
4'-bis [(4-diethylamino-2-methyl-4 '
-Dimethylamino) diphenylmethylamino] diphenyl ether, 4,4'-bis [(4-diethylamino-
2-Methyl-4'-dimethylamino) diphenylmethylamino] diphenylthioether, 4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylsulfone, 1,2- Bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] ethane, 1,6-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino]
Hexane, 3,3'-dichloro-4,4'-bis [(4
-Diethylamino-2-ethoxy-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 4,
4'-bis [(4-diethylamino-2-ethoxy-
4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-dimethyl-4,4'-bis [(4-diethylamino-2-ethoxy-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3 ′ -Dichloro-4,4′-bis [(4-dimethylamino-3-methyl-4′-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3′-dimethyl-4,4′-bis [(4- Dimethylamino-3-
Methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-dichloro-4,4 '
-Bis [(4-di-n-butylamino-2-methyl-
4'-di-n-butylamino) diphenylmethylamino] diphenylmethane, 3-chloro-4,4'-bis [(4-dimethylamino-2-chloro-4'-dimethylamino) diphenylmethylamino] diphenylmethane,
3-chloro-4,4'-bis [(4-di-n-butylamino-2-methoxy-4'-di-n-butylamino) diphenylmethylamino] diphenylmethane, 3,3'-
Dichloro-4,4'-bis [(4-dibenzylamino-
2-Methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-dichloro-4,
4'-bis [{4- (N-isopropyl-N-methyl)
Amino-2-ethoxy-4'-dimethylamino} diphenylmethylamino] diphenylmethane, 3,3'-dichloro-4,3'-bis [bis (4-dimethylamino-2)
-Methylphenyl) methylamino] diphenylmethane,
3,3'-dichloro-4,4'-bis [bis (4-dimethylamino-2-methoxyphenyl) methylamino] diphenylmethane, 3,3'-dichloro-4,4'-bis [(4-diethylamino- 2-methyl-4'-di-n-
Butylamino) diphenylmethylamino] diphenylmethane, 3,3'-dichloro-4,4'-bis [(4-diethylamino-2-ethoxy-4'-dibenzylamino) diphenylmethylamino] diphenylmethane, 4,
4'-bis [(4-di-n-amylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 4,4'-bis [(4-di-n-butylamino-2-methyl) -4'-Dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-dichloro-4,4'-bis [(4-di-n-butylamino-
2-Methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 2,2'-dichloro-4,
4'-bis [(4-di-n-butylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 4,4'-bis [(4-di-n-butylamino-2- Methoxy-4′-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3′-dichloro-4,4′-bis [(4-di-n-butylamino-2-methoxy-4′-dimethylamino) diphenylmethyl Amino] diphenylmethane, 3,3′-dimethyl-
4,4'-bis [(4-di-n-butylamino-2-methoxy-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 4,4'-bis [(4-di-n
-Butylamino-2-ethoxy-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,
3'-dichloro-4,4'-bis [(4-di-n-butylamino-2-ethoxy-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-dimethyl-4,4'- Bis [(4-di-n-butylamino-2-ethoxy-4'-dimethylamino) diphenylmethylamino] diphenylmethane, 3,3'-dimethyl-
4,4'-bis [(4-di-n-butylamino-2-ethoxy-4'-diethylamino) diphenylmethylamino] diphenylmethane, 1,2-bis [(4-di-n-
Butylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] ethane, 1,6-bis [(4-
Di-n-butylamino-2-ethoxy-4'-dimethylamino) diphenylmethylamino] hexane and the like.

Specific examples of the diarylmethane compound represented by the general formula [Formula 2] include the following. N- (4-diethylamino-2-methyl-
4'-dimethylamino) diphenylmethyl-2-methylaniline, N- (4-diethylamino-2-methyl-
4'-dimethylamino) diphenylmethyl-3-methylaniline, N- (4-diethylamino-2-methyl-
4'-Dimethylamino) diphenylmethyl-3-ethylaniline, N- (4-diethylamino-2-methyl-
4'-dimethylamino) diphenylmethylaniline, N
-(4-Diethylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-methoxyaniline, N
-(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-isopropoxyaniline, N- (4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethyl-4-methoxyaniline, N- (4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-chloroaniline, N- (4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethyl-4-chloroaniline, N- (4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2,4-dichloroaniline, N- (4-diethylamino-3-methyl-4 '
-Dimethylamino) diphenylmethyl-2,6-dichloroaniline, N- (4-diethylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-2-methylaniline, N- (4-diethylamino-2-ethoxy- 4'-Dimethylamino) diphenylmethyl-2-chloroaniline, N- (4-dimethylamino-2-chloro-
4'-dimethylamino) diphenylmethyl-2-methylaniline, N- (4-dimethylamino-2-chloro-
4′-dimethylamino) diphenylmethyl-2-chloroaniline, N- (4-dimethylamino-2-methyl-)
4'-dimethylamino) diphenylmethyl-2-methylaniline, N- (4-dimethylamino-2-methyl-)
4'-dimethylamino) diphenylmethyl-2-chloroaniline, N- (4-dimethylamino-3-methyl-
4'-dimethylamino) diphenylmethylaniline, N
-(4-Diethylamino-2-methyl-4'-di-n-
Butylamino) diphenylmethyl-2-chloroaniline, N- [4-diethylamino-2-methyl-4′-
(N-methyl-N-n-propyl) amino] diphenylmethyl-2-methylaniline, N- [4-diethylamino-2-ethoxy-4 '-(N-ethyl-N-benzyl) amino] diphenylmethyl-2 -Chloroaniline,
N-bis (4-dimethylamino-2-methylphenyl)
Methyl-2-chloroaniline, N-bis (4-diethylamino-2-ethoxyphenyl) methyl-2-chloroaniline, N- (4-diethylamino-2-ethoxy-
4'-Dimethylamino) diphenylmethyl-glycine methyl ester, N- (4-diethylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-glycine ethyl ester, N- (4-di-n-butylamino-
2-Methyl-4'-dimethylamino) diphenylmethyl-aniline, N- (4-di-n-butylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-
Methylaniline, N- (4-di-n-butylamino-2)
-Methyl-4'-dimethylamino) diphenylmethyl-
2-chloroaniline, N- (4-di-n-butylamino-2-methoxy-4'-dimethylamino) diphenylmethyl-aniline, N- (4-di-n-butylamino-2)
-Methoxy-4'-dimethylamino) diphenylmethyl-2-methylaniline, N- (4-di-n-butylamino-2-methoxy-4'-dimethylamino) diphenylmethyl-2-chloroaniline, N- ( 4-di-n-butylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-aniline, N- (4-di-n-butylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-2 -Methylaniline, N- (4-di-n-butylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-2-chloroaniline, N- (4-di-
n-Butylamino-2-methoxy-4'-diethylamino) diphenylmethyl-aniline, N- (4-di-n-
Butylamino-2-methoxy-4'-diethylamino)
Diphenylmethyl-2-methylaniline, N- (4-di-n-butylamino-2-methoxy-4'-diethylamino) diphenylmethyl-2-chloroaniline, N-
(4-di-n-amylamino-2-methyl-4′-dimethylamino) diphenylmethyl-2-methylaniline,
N- (4-di-n-amylamino-2-methoxy-4 '
-Dimethylamino) diphenylmethyl-2-chloroaniline, N- (4-di-n-amylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-2-methylaniline and the like.

In addition, in the diarylmethane compound represented by the general formula [Chemical Formula 3],
Alternatively, the 6-membered saturated or unsaturated heterocycle includes a benzotriazinyl group, a pyrazolyl group, a 3,5-dimethylpyrazolyl group, an indolyl group, a pyrrolyl group, and 2-methyl-2.
-Imidazolinyl group, 9-carbazolyl group, pyrrolidyl group, piperidyl group, morpholyl group, benzimidazolyl group and imidazolyl group are preferable, and benzotriazinyl group, pyrrolidyl group, piperidyl group, morpholyl group and imidazolyl group are more preferable. Specific examples of the diarylmethane compounds having these heterocyclic groups include the following. (4-Diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -benzotriazinylmethane, (4-diethylamino-2-
Methylphenyl)-(4-dimethylaminophenyl)-
Pyrazolylmethane, (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -3,5
-Dimethylpyrazolylmethane, (4-diethylamino-
2-Methylphenyl)-(4-dimethylaminophenyl) -indolylmethane, (4-diethylamino-2-
Methylphenyl)-(4-dimethylaminophenyl)-
Pyrrolylmethane, (4-diethylamino-2-ethoxyphenyl)-(4-dimethylaminophenyl) -pyrrolidylmethane, (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl)-(2-methyl-2 -Imidazolinyl) methane, (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -9-carbazolylmethane, (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl)- Pyrrolidyl methane, bis (4-diethylamino-
2-Methylphenyl) -imidazolylmethane, (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -morpholylmethane, (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -benzimidazolyl Methane, (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -imidazolylmethane, (4-dimethylamino-2-ethoxyphenyl)-(4-dimethylaminophenyl) -pyrazolylmethane, (4- Dimethylamino-2-ethoxyphenyl)-(4-dimethylaminophenyl) -indolylmethane, (4-dimethylamino-3)
-Ethoxyphenyl)-(4-dimethylaminophenyl) -indolylmethane, (4-dimethylamino-3-)
Methylphenyl)-(4-dimethylaminophenyl)-
Indolylmethane, (4-diethylamino-2-chlorophenyl)-(4-diethylaminophenyl) -benzotriazinylmethane, (4-diethylamino-3-chlorophenyl)-(4-diethylaminophenyl) -benzotriazylmethane, ( 4-dimethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -morpholylmethane, (4-diethylamino-2-ethoxyphenyl)-(4-dimethylaminophenyl) -imidazolylmethane, (4-diethylamino-2- Methylphenyl)-(4-dibenzylaminophenyl) -morpholylmethane, [4- (Nn-amyl-N-methylamino)
2-Methylphenyl]-(4-di-n-butylaminophenyl) -indolylmethane, (4-di-n-butylamino-2-methylphenyl)-(4-dimethylaminophenyl) -indolylmethane , (4-Di-n-butylamino-2-methylphenyl)-(4-dimethylaminophenyl) -pyrrolidylmethane, (4-di-n-butylamino-2-methylphenyl)-(4-dimethylamino Phenyl) -piperidyl methane, (4-di-n-butylamino-2-methoxyphenyl)-(4-dimethylaminophenyl) -indolylmethane, (4-di-n-butylamino-2-methoxyphenyl)- (4-Dimethylaminophenyl) -pyrrolidylmethane, (4-di-n-butylamino-2-ethoxyphenyl)-(4-dimethylaminophenyl) Pylori Jill such as methane.

In the present invention, at least one kind of the above-mentioned diarylmethane compounds is used as the basic dye, and of course, two or more kinds may be used in combination if necessary. The compounds are not limited to the above specific examples, and any compound included in the general formula can be used. The compounds represented by the following general formulas [Chemical formula 6] to [Chemical formula 8] are It is more preferably used because it is excellent in color developability and fastness of a color image, and the raw materials for its synthesis are easily available and easy to synthesize.

[0022]

[Chemical 6]

[In the formula, R _{21 to} R ₂₄ are respectively C _{1 to} C ₅
R ₂₅ is a C ₁ -C ₂ alkyl group,
C ₁ -C ₂ alkoxyl group or halogen atom is shown, R ₂₆ is a hydrogen atom, C ₁ -C ₂ alkyl group, C _1-
A C ₄ alkoxyl group or a halogen atom is shown. ]

[0024]

[Chemical 7]

[In the formula, R _{27 to} R ₃₀ are respectively C _{1 to} C ₅
R ₃₁ is a C ₁ -C ₂ alkyl group,
C ₁ -C shows _two alkoxyl groups or a halogen atom, R ₃₂ is a hydrogen atom, an alkyl group of C ₁ ~C _2, C ₁ ~
A C ₄ alkoxyl group or a halogen atom is shown. ]

[0026]

[Chemical 8]

[In the formula, R _{33 to} R ₃₆ are respectively C _{1 to} C ₅
R ₃₇ is a C ₁ -C ₂ alkyl group,
Represents a C ₁ -C ₂ alkoxyl group or a halogen atom,

[0028]

[Chemical 9]

Is a benzotriazinyl group, a pyrazolyl group, a 3,5-dimethylpyrazolyl group, an indolyl group, a pyrrolyl group, a 2-methyl-2-imidazolinyl group, a 9-carbazolyl group, a pyrrolidyl group, a piperidyl group, a morpholyl group. , A benzimidazolyl group or an imidazolyl group. ]

Further, among the diarylmethane compounds represented by the above general formulas [Chemical formula 6] to [Chemical formula 8], R ₂₁ ,
A compound in which R ₂₂ , R ₂₇ , R ₂₈ , R ₃₃ , and R ₃₄ are each a C _{4 to} C ₅ alkyl group is more preferably used because a pressure-sensitive recording material excellent in desensitization is obtained.

In the pressure-sensitive recording material of the present invention, the amount of the diarylmethane compound used is appropriately selected according to the kind of the pressure-sensitive recording material such as upper paper, middle paper, self-coloring type or the desired quality. However, the coating amount (content) of the diarylmethane compound is 0.002 to 1 g / m ² , and preferably 0.00.
It is desirable to adjust it to be in the range of 5 to 0.3 g / m ² .

In the present invention, other known basic dyes may be used in combination within a range that does not impair the desired effects of the present invention. Examples of such basic dyes include the following. Azaphthalide compounds represented by the following general formula [Chemical Formula 10], leuco crystal violet, triarylmethane type compounds such as compounds represented by the following general formula [Chemical Formula 11], 3,3-bis (1-butyl-2) -Methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3-
(4-Diethylamino-2-methylphenyl) -3-
Triarylmethane lactone compounds such as (4-dimethylaminophenyl) -6-dimethylaminophthalide, 3
-(N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane, 3-diethylamino-6-
Methyl-7-anilinofluorane, 3-di-n-butylamino-6-methyl-7-anilinofluorane, 3-
(N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylaminobenzo [2] fluorane, 3-diethylamino-7-chlorofluor Oran, 1,3-dimethyl-6-dimethylaminofluorane, 3,6-dimethoxyfluorane, 3- (N-ethyl-p-toluidino) -7-N-methylanilinofluorane, 1-ethyl-8 -(Di-n-amylamino)-
2,2,4-Trimethyl-1,2-dihydrospiro [1
1H-chromeno [2,3-g] quinoline-11,3'-
Phthalide] and other fluorane compounds, 3,7-bis (dimethylamino) -10-benzoylphenothiazine and other phenothiazine compounds, 3,6-bis (diethylamino) fluorane-γ-anilinolactam, N- (2-chlorophenyl) ) Rhodamine lactam compounds such as rhodamine-B-lactam, spiropyran compounds such as 3-methyl-di-β-naphthospiropyran, 3,3-bis [1,1-bis (4-pyrrolidinophenyl) ethylene-
2-yl] -4,5,6,7-tetrabromophthalide,
3,3-bis [1- (4-methoxyphenyl) -1-
(4-Dimethylaminophenyl) ethylene-2-yl]
Ethylene phthalide compounds such as 4,5,6,7-tetrachlorophthalide, thrylquinoline compounds such as 2- (4-dodecyloxy-3-methoxystyryl) quinoline, 3,3'-dichloro-4 , 4'-bis [4,4'-
Bis (dimethylamino) benzhydryl] -diphenylmethane, bis (4-dimethylaminophenyl)-(p-
Diphenylmethane compounds such as toluenesulfonyl) methane, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-n-)
Indole compounds such as octyl-2-methylindol-3-yl) phthalide.

[0033]

[Chemical 10]

[Wherein R ₃₇ and R ₃₈ are each C _{1 to} C ₄
, Which may be bonded to each other to form a heterocycle with the adjacent nitrogen atom. R ₃₉ is C _{1 to} C ₆
Is an alkyl group or a C ₁ -C ₆ alkoxyl group, R ₄₀ is a hydrogen atom, a C ₁ -C ₈ alkyl group or a benzyl group, and R ₄₁ is a hydrogen atom, a C ₁ -C ₄ alkyl group or Indicates a phenyl group. ]

[0035]

[Chemical 11]

[Wherein R₄₂Is a hydrogen atom, C₁~ C₈A
Represents a rukyl group or a benzyl group, R ₄₃, R₄₄Is that
Hydrogen atom, C₁~ C_FourAlkyl group, benzyl group of
Represents a phenyl group. The phenyl group is C₁~ C_FourA
Rukiru group, C₁~ C_FourAlkoxyl group, benzyl group,
It may be substituted with a benzyloxy group or a halogen atom.
Yes. n shows the integer of 1-3. ]

Among the other known basic dyes as mentioned above,
The azaphthalide compound represented by the general formula [Chemical Formula 10] is a preferred embodiment because a pressure-sensitive recording material excellent in color developability, light resistance and humidity resistance can be obtained by using it together with the specific diarylmethane compound. one of. Specific examples of such azaphthalide compounds include the following.

3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-dimethylamino-2-ethoxyphenyl) -3- (2-Methyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-dibutylamino-2-ethoxyphenyl) -3- (2-methyl-1-octylindole-3)
-Yl) -4-azaphthalide, 3- (4-piperidino-
2-ethoxyphenyl) -3- (2-methyl-1-octylindol-3-yl) -4-azaphthalide, 3-
(4-Pyrrolidino-2-ethoxyphenyl) -3- (2
-Methyl-1-octylindol-3-yl) -4-
Azaphthalide, 3- (4-diethylamino-2-methoxyphenyl) -3- (2-methyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-dimethylamino-2-methoxyphenyl)- 3- (2-Methyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-ethyl-1-octylindole-
3-yl) -4-azaphthalide, 3- (4-dimethylamino-2-ethoxyphenyl) -3- (2-ethyl-1)
-Octylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-ethylindole-3-
Yl) -4-azaphthalide, 3- (4-dimethylamino-2-ethoxyphenyl) -3- (2-methyl-1-ethylindol-3-yl) -4-azaphthalide, 3-
(4-diethylamino-2-hexyloxyphenyl)
-3- (2-Methyl-1-ethylindol-3-yl) -4-azaphthalide, 3- (4-dimethylamino-
2-hexyloxyphenyl) -3- (2-methyl-1)
-Ethylindol-3-yl) -4-azaphthalide,
3- (4-diethylamino-2-ethoxyphenyl)-
3- (2-phenyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-
2-Ethoxyphenyl) -3- (2-methyl-1-benzylindol-3-yl) -4-azaphthalide, 3-
(4-Diethylamino-2-methylphenyl) -3-
(2-Methyl-1-ethylindol-3-yl) -4
-Azaphthalide, 3- (4-dimethylamino-2-methylphenyl) -3- (2-methyl-1-ethylindol-3-yl) -4-azaphthalide, 3- (4-dibutylamino-2-methylphenyl) ) -3- (2-Methyl-
1-ethylindol-3-yl) -4-azaphthalide, 3- (4-piperidino-2-methylphenyl) -3
-(2-Methyl-1-ethylindol-3-yl)-
4-azaphthalide, 3- (4-pyrrolidino-2-methylphenyl) -3- (2-methyl-1-ethylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethylphenyl) -3- (2-methyl-1
-Ethylindol-3-yl) -4-azaphthalide,
3- (4-dimethylamino-2-ethylphenyl) -3
-(2-Methyl-1-ethylindol-3-yl)-
4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (2-ethyl-1-ethylindol-3-yl) -4-azaphthalide, 3- (4-dimethylamino-2-methylphenyl) ) -3- (2-Ethyl-1-ethylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenyl)
-3- (2-Phenyl-1-ethylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-
2-Methylphenyl) -3- (2-phenyl-1-methylindol-3-yl) -4-azaphthalide, 3-
(4-Dimethylamino-2-methylphenyl) -3-
(2-Phenyl-1-methylindol-3-yl)-
4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (2-methyl-1-benzylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (2-Methyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (2-methyl-1-hexylindole-3
-Yl) -4-azaphthalide and the like. The dyes are not limited to these dyes, and two or more kinds of dyes may be used in combination if necessary.

Among the azaphthalide compounds as described above, 3- (4-diethylamino-2-methylphenyl)-
3- (2-methyl-1-ethylindol-3-yl)
-4-azaphthalide, 3- (4-diethylamino-2-
Methylphenyl) -3- (2-phenyl-1-methylindol-3-yl) -4-azaphthalide, 3- (4-
Diethylamino-2-ethoxyphenyl) -3- (2-
Methyl-1-octylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-ethylindol-3-yl) -4-azaphthalide and 3- (4-diethylamino-2-hexyloxyphenyl) -3- (2-
Methyl-1-ethylindol-3-yl) -4-azaphthalide is more preferably used because the effect of improving the color developability by the combined use thereof is particularly remarkable.

The amount of the azaphthalide compound used in combination should be kept within a range that does not impair the desired effects of the present invention.
10 to 1000 parts by weight of azaphthalide compound relative to parts by weight
It is desirable to appropriately adjust the amount by weight, preferably 20 to 500 parts by weight. By the way, if the amount of the azaphthalide compound used is less than 10 parts by weight, a sufficient combined effect cannot be exhibited, and if it exceeds 1000 parts by weight, there is a possibility that the storability of the color image may be deteriorated.

Further, the triarylmethane compound represented by the above general formula [Chemical Formula 11] can be used in combination to obtain a pressure-sensitive recording material having more excellent color developability and image storability. Is one. Specific examples of such triarylmethane compounds include the following. (Carbazol-3-yl) -bis (4-dimethylaminophenyl) methane, (9-methyl-carbazol-3-yl) -bis (4-dimethylaminophenyl) methane, (9-ethyl-carbazol-3-yl) ) -Bis (4-dimethylaminophenyl) methane, (9-n-butyl-carbazol-3-yl) -bis (4-dimethylaminophenyl) methane, (9-n-butyl-carbazol-3-yl)- Bis (4-diethylaminophenyl) methane, (9-n-butyl-carbazol-3-yl) -bis (4-di-n-butylaminophenyl) methane, (9-methyl-carbazol-3-yl) -bis [4- (N-benzyl-N-methylamino) phenyl]
Methane, (9-ethyl-carbazol-3-yl) -bis [4- (N-phenyl-N-methylamino) phenyl] methane, (9-n-butyl-carbazol-3-yl) -bis [4- (N-phenyl-N-methylamino)
Phenyl] methane, (9-n-octyl-carbazol-3-yl) -bis [4- (N-phenyl-N-methylamino) phenyl] methane, (9-ethyl-carbazol-3-yl) -bis [ 4- (N-methyl-N-p-methoxyphenylamino) phenyl] methane, (9-ethyl-carbazol-3-yl) -bis [4- (N-methyl-N-p-benzyloxyphenylamino) phenyl ] Methane, (9-n-butyl-carbazol-3-yl) -bis [4- (N-methyl-N-p-benzyloxyphenylamino) phenyl] methane, bis (9-ethyl-carbazol-3-yl) )-(4-Dimethylaminophenyl) methane, bis (9-n-butyl-carbazol-3-yl)-(4-diethylaminophenyl) methane, bis (9-ethyl) - carbazol-3-yl) -
[4- (N-phenyl-N-methylamino) phenyl]
Methane, bis (9-n-butyl-carbazol-3-yl)-[4- (N-phenyl-N-methylamino) phenyl] methane, bis (9-n-octyl-carbazol-3-yl)-[ 4- (N-phenyl-N-methylamino) phenyl] methane, bis (9-benzyl-carbazol-3-yl)-[4- (N-phenyl-N-methylamino) phenyl] methane, bis (9- Ethyl-carbazol-3-yl)-[4- (N-methyl-Np-methoxyphenylamino) phenyl] methane, tris (9
-Ethyl-carbazol-3-yl) methane, tris (9-n-butyl-carbazol-3-yl) methane,
Tris (9-n-octyl-carbazol-3-yl)
Methane, etc. The dyes are not limited to these dyes, and two or more kinds of dyes may be used in combination if necessary.

In the present invention, when the above-mentioned triarylmethane compound is used in combination, the amount thereof is 10 to 3 with respect to 100 parts by weight of the specific diarylmethane compound.
It is desirable to use together in an amount of 00 parts by weight, preferably 50 to 200 parts by weight. By the way, if the amount of the triarylmethane compound used is less than 10 parts by weight, a sufficient combined effect cannot be exhibited, and if it is used in excess of 300 parts by weight, there is a possibility that a problem may occur in the initial color development of printing.

Further, among the above-mentioned other basic dyes, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide can be used in combination to obtain a pressure-sensitive recording material having further excellent color developability. Therefore, such combination is also one of the preferable embodiments. The amount of 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide used is 20 to 1000 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the specific diarylmethane compound.
It is desirable to adjust in the range of 500 parts by weight. By the way,
If the amount used is less than 20 parts by weight, the combined effect will not be sufficiently exerted, whereas if the amount used exceeds 1000 parts by weight, there is a risk that the storability of the color image may be deteriorated.

In the present invention, the wall film agent of the microcapsules encapsulating the basic dye is specified as a synthetic polymer material to suppress the generation of rubbing stains, and further to make the average particle diameter 3 to 15 μm. By limiting, the unevenness and discontinuity of the color density due to the difference in writing pressure are eliminated, and the contact stain caused by the unintended pressure is significantly suppressed. The average film thickness of the microcapsules is 0.1
It is possible to obtain a pressure-sensitive recording material having a stable quality characteristic, by which the rubbing stain can be further improved by specifying the particle size to be 0.7 μm, and as a result, sharp and clear printing can be formed.

Incidentally, when a natural material is used as the wall film agent for the microcapsules, it is impossible to prevent the generation of color stains. Even in the case of microcapsules made of synthetic polymer wall film, when the average particle size of the capsules is less than 3 μm, the color density is lowered and the sharpness of the print is lowered, while when it exceeds 15 μm, the contact stain is remarkable. Therefore, the average particle size of the capsules is 3 to 15 μm, preferably 5 to 1
It is necessary to adjust in the range of 0 μm. Furthermore, when the average film thickness is less than 0.1 μm, unnecessary rubbing stains increase,
When it exceeds 0.7 μm, the color development sensitivity is lowered.
It is adjusted in the range of up to 0.4 μm.

The basic dye used in the present invention may be mixed with various known UV absorbers, if necessary, and then cottonseed oil, hydrogenated terphenyl, hydrogenated terphenyl derivative, alkylbiphenyl, alkylnaphthalene, diarylalkane,
Synthetic polymer-based wall membrane dissolved in a natural or synthetic hydrophobic medium such as paraffin, naphthenic oil, and dibasic acid ester such as phthalic acid ester, and by capsule manufacturing method such as interfacial polymerization method and in-situ polymerization method. Are encapsulated in microcapsules. And the encapsulation conditions at that time,
For example, a capsule having a specific average particle size and average film thickness as described above can be prepared by appropriately adjusting the amount of the wall membrane agent used, the shear strength during emulsification, and further the emulsification time. Examples of the resin forming the wall film include aminoaldehyde resin, polyurea resin, polyurethane resin, polyamide resin and the like.

Polyurethane resin and polyurea resin wall membrane capsules are, for example, polyvalent isocyanate and water, polyvalent isocyanate and polyol, isothiocyanate and water, isothiocyanate and polyol, polyvalent isocyanate and polyamine, isothiocyanate and polyamine, and the like. It is produced by the interfacial polymerization method used as an agent. Also,
Aminoaldehyde resin wall membrane capsules include, for example, at least one amine such as urea, thiourea, alkylurea, ethyleneurea, acetoguanamine, benzoguanamine, melamine, guanidine, biuret, and cyanamide, and formaldehyde, acetaldehyde, paraformaldehyde, and hexaform. It is produced by an in-situ polymerization method using at least one aldehyde such as methylenetetramine, glutaraldehyde, glyoxal and furfural, or an initial condensate obtained by condensing them as a wall film agent. Furthermore, the polyamide resin wall membrane capsule is manufactured by, for example, an interfacial polymerization method of acid chloride and amine.

Microcapsules containing the specific basic dye thus prepared and having a specific average particle diameter and average film thickness can be prepared by a conventional method from adhesive agents such as polyvinyl alcohols, starches, carboxymethyl cellulose and latexes. Various materials such as a tilting agent such as pulp powder and raw starch powder are appropriately blended to prepare a capsule coating solution, which is used for producing upper paper, middle paper, self-coloring type pressure-sensitive recording material and the like.

In the present invention, an activated clay mineral having a specific silicon oxide content is used as a colorant-containing layer or a colorant of a self-coloring type pressure-sensitive recording material which is combined with the microcapsule coated surface of the upper or middle paper. There is a significant feature in using. As the activated clay mineral, activated clay, attapulgite, zeolite, and clay minerals such as bentonite are known, but in the present invention, the coloring ability for the specific diarylmethane compound and the fastness of the obtained image are considered. Therefore, the content of silicon oxide (SiO ₂ ) is 65-80.
This is to selectively use the active clay mineral in a weight percentage. Further, among these, the activated clay which has been acid-treated so that the content of silicon oxide (SiO ₂ ) is 65% by weight to 75% by weight can provide a pressure-sensitive recording material having more excellent recorded image fastness. Therefore, it is more preferably used. Here, activated clay refers to acid clay activated by acid treatment.
In the present invention using a specific diarylmethane compound, the active clay mineral used has a silicon oxide content of 8%.
If it exceeds 0% by weight, only a pressure-sensitive recording material having extremely poor image fastness, particularly light resistance, can be obtained.

In the pressure-sensitive recording material of the present invention, the amount of the specific activated clay mineral used is appropriately selected according to the type of the pressure-sensitive recording material such as the lower paper and the self-coloring type, or the desired quality. is intended to be, although not particularly limited, the coating amount of the active clay mineral (content) 1 to 15 g / m ^2, preferably it is desirable to adjust so that the range of 2 to 8 g / m ² .

As the coloring agent, various known organic coloring agents such as phenol derivatives, salicylic acid derivatives, aromatic carboxylic acid derivatives and their metal salts, and novolac resins are used in combination as long as the effects of the present invention are not impaired. It is also possible.

The coloring agent coating liquid is usually prepared by a method of dispersing the above-mentioned specific activated clay mineral in water together with an adhesive. Examples of the adhesive include starch, casein, gum arabic, carboxymethyl cellulose, polyvinyl alcohol, styrene / butadiene copolymer latex, vinyl acetate latex and the like. In addition, in the coating liquid, if necessary, inorganic pigments such as zinc oxide, magnesium oxide, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium sulfate, and calcium sulfate, and various auxiliaries known in the production of pressure-sensitive copying paper may be added. It can also be added as appropriate.

The method of applying the capsule coating liquid and the color developing agent coating liquid is not particularly limited, and for example, an appropriate coating device such as an air knife coater, roll coater, blade coater, rod coater, curtain coater, lip coater, etc. is provided. An on-machine or off-machine coater is used to apply a dry weight of about ² to 20 g / m ² to a support such as paper, synthetic paper or film.

[0054]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, unless otherwise indicated, the part and% in an example show a weight part and weight%, respectively.

Example 1 [Preparation of Coloring Agent Coating Liquid] The content of silicon oxide (SiO ₂ ) was 7
2 parts by weight of activated clay 100 parts, magnesium oxide 1 part,
A coloring agent coating liquid was prepared by adding 20 parts (solid content) of carboxy-modified styrene / butadiene copolymer latex and 1 part of sodium carboxymethyl cellulose. [Manufacture of lower paper] The above color developing agent coating liquid is applied to a base paper of 40 g / m ^{2 by} an air knife coater so that the dry weight is 5 g / m ² , dried, and calendered to prepare a lower paper for pressure-sensitive recording. It was created.

[Preparation of Microcapsule Dispersion] In a stirring and mixing container equipped with a heating device, 150 parts of a 3% aqueous solution of polyvinyl alcohol (trade name: PVA-117, manufactured by Kuraray Co., Ltd.) was added to prepare an aqueous medium for capsule production. And Separately, 100 parts of alkylnaphthalene (trade name: KMC oil, manufactured by Kureha Chemical Co., Ltd.) was used as a basic dye, 3,3′-dichloro-4,4′-bis [(4-diethylamino-2-
Methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane (10 parts) was dissolved, and further, 5 parts of polymethylene polyphenylisocyanate (trade name: Millionate MR400, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 3 of hexamethylene diisocyanate having a buret bond were dissolved. Quantum (product name: N-3200, Sumitomo Bayer) 2
Part of the solution obtained by dissolving the same was used as a capsule core substance in the above-mentioned aqueous medium for capsule preparation. K. It was dispersed for 1 minute at 10000 rpm using a homomixer. To this emulsified dispersion was added 1 part of diethylenetriamine, and the mixture was stirred at room temperature for 30 minutes.
After stirring for 1 minute, the temperature of the system was raised to 70 ° C. and the reaction was continued for 3 hours while continuing stirring. Then, the temperature was lowered to room temperature and the average particle size was 5.7 μm and the average film thickness was 0.17 μm.
Microcapsules consisting of the polyurea resin / polyurethane resin wall film were prepared.

[Preparation of microcapsule coating solution] 70 parts of wheat starch powder and 2 parts of oxidized starch aqueous solution per 100 parts by weight (solid content) of the microcapsule dispersion thus obtained.
0 part (solid content) was added to prepare a microcapsule coating solution. [Manufacture of Medium Paper] The above microcapsule coating solution is applied to the opposite side of the color developing agent-coated surface of the lower sheet with an air knife coater so as to have a dry weight of 4 g / m ² , and is dried for pressure-sensitive recording. I got the paper.

Examples 2 to 30 Example 1 was repeated except that the following compounds were used as the basic dye in the preparation of the microcapsule dispersion of Example 1.
In the same manner as above, 29 kinds of pressure-sensitive recording medium paper were obtained. The prepared microcapsules had an average particle size of 5.
2 to 5.8 μm, the average film thickness is 0.15 to 0.20 μm
Was in the range. Example 2: 3,3'-dichloro-4,4'-bis [(4-diethylamino-2-ethoxy-4'-dimethylamino) diphenylmethylamino] diphenylmethane 10 parts Example 3: 3,3 '-Dimethyl-4,4'-bis[(4-diethylamino-2-ethoxy-4'-dimethylamino) diphenylmethylamino] diphenylmethane 10 parts-Example 4: 3,3'-dichloro-4,4'-bis [Bis (4-dimethylamino-2-methylphenyl) methylamino] diphenylmethane 10 parts Example 5: 3,3'-dichloro-4,4'-bis [(4-diethylamino-2-ethoxy-4'- Dibenzylamino) diphenylmethylamino] diphenylmethane 10 parts Example 6: 3,3'-dichloro-4,4'-bis [(4-diethylamino-2 Methyl-4'-di -n-
Butylamino) diphenylmethylamino] diphenylmethane 10 parts Example 7: 3,3'-dimethoxy-4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane
10 parts-Example 8: N- (4-diethylamino-2-methyl-
4'-Dimethylamino) diphenylmethyl-2-methylaniline 10 parts Example 9: N- (4-dimethylamino-2-chloro-
4'-Dimethylamino) diphenylmethyl-2-methylaniline 10 parts-Example 10: N- (4-dimethylamino-2-methyl-)
4'-Dimethylamino) diphenylmethyl-2-chloroaniline 10 parts-Example 11: N- (4-diethylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-2-methylaniline 10 parts-Example 12 : N-bis (4-dimethylamino-2-methylphenyl) methyl-2-chloroaniline 10 parts Example 13: (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -benzotriazide Nylmethane 10 parts-Example 14: (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -pyrrolidylmethane 10 parts-Example 15: (4-diethylamino-2-ethoxyphenyl)-( 4-Dimethylaminophenyl) -imidazolylmethane 10 parts-Example 16: (4-dimethylamino-2-methylphenyl) Nyl)-(4-dimethylaminophenyl) -morpholylmethane 10 parts-Example 17: 3,3'-dichloro-4,4'-bis [(4-di-n-butylamino-2-methyl-4'- Dimethylamino) diphenylmethylamino] diphenylmethane 10 parts Example 18: 3,3'-Dimethyl-4,4'-bis [(4-di-n-butylamino-2-methoxy-4'-
Dimethylamino) diphenylmethylamino] diphenylmethane 10 parts Example 19: N- (4-di-n-butylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-
Chloroaniline 10 parts Example 20: N- (4-di-n-butylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-
Methylaniline 10 parts Example 21: N- (4-di-n-amylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-2
-Methylaniline 10 parts-Example 22: (4-di-n-butylamino-2-methylphenyl)-(4-dimethylaminophenyl) -pyrrolidylmethane 10 parts-Example 23: 3,3'-dichloro -4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane 5
Parts and (9-n-butyl-carbazol-3-yl) -bis [4- (N-phenyl-N-methylamino) phenyl] methane 5 parts Example 24: 3,3'-dichloro-4,4 ′ -Bis [(4-diethylamino-2-methyl-4′-dimethylamino) diphenylmethylamino] diphenylmethane 5
Parts and bis (9-ethyl-carbazol-3-yl)-
[4- (N-phenyl-N-methylamino) phenyl]
Methane 5 parts Example 25: N- (4-diethylamino-2-methyl-
4'-Dimethylamino) diphenylmethyl-2-methylaniline 5 parts and (9-n-butyl-carbazole-3
-Yl) -bis [4- (N-phenyl-N-methylamino) phenyl] methane 5 parts Example 26: N- (4-dimethylamino-2-methyl-)
4'-Dimethylamino) diphenylmethyl-2-chloroaniline 5 parts and (9-n-butyl-carbazole-3
-Yl) -bis [4- (N-phenyl-N-methylamino) phenyl] methane 5 parts-Example 27: N- (4-diethylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-2- 5 parts of methylaniline and (9-n-butyl-carbazole-
3-yl) -bis [4- (N-phenyl-N-methylamino) phenyl] methane 5 parts Example 28: (4-diethylamino-2-methylphenyl)-(4-dimethylaminophenyl) -pyrrolidyl 5 parts of methane and (9-n-butyl-carbazol-3-yl) -bis [4- (N-phenyl-N-methylamino)
Phenyl] methane 5 parts Example 29: N- (4-di-n-butylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-
Methylaniline 4 parts, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide 3 parts,
And 2- (4-dodecyloxy-3-methoxystyryl) quinoline 3 parts Example 30: N- (4-di-n-butylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-
Methylaniline 4 parts, 3-diethylaminobenzo [2] fluorane, and 3,6-dimethoxyfluorane 3 parts

Example 31 In the preparation of the color developing agent coating solution of Example 1, 100 parts of activated clay having a silicon oxide content of 78% by weight was used in place of 100 parts of activated clay having a silicon oxide content of 72% by weight. A pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 except for the above.

Example 32 In the same manner as in Example 1, except that the emulsification time of the capsule core substance and the aqueous medium for capsule preparation was changed from 1 minute to 30 seconds in the preparation of the microcapsule dispersion of Example 1. Average particle size is 12.3μm and average film thickness is 0.29μ
m capsules were prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Example 33 An average particle size of 4. was obtained in the same manner as in Example 1 except that the amount of polymethylene polyphenyl isocyanate used was reduced from 5 parts to 3 parts in the preparation of the microcapsule dispersion of Example 1. A capsule having a thickness of 6 μm and an average film thickness of 0.13 μm was prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Example 34 A pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 except that the microcapsule dispersion was prepared as follows. [Preparation of Microcapsule Dispersion] In a stirring and mixing vessel equipped with a heating device, 200 parts of a 3% aqueous solution of an ethylene-maleic anhydride copolymer (trade name: EMA31, manufactured by Monsanto) was charged, and then 20% caustic soda was added. The aqueous solution was added dropwise to adjust the pH to 6.0 to obtain an aqueous medium for capsule production. Separately, 100 parts of alkylnaphthalene (trade name: KMC oil, manufactured by Kureha Chemical Co., Ltd.) was added to N- (4-di-n-butylamino-2-methyl-4′-) as a basic dye.
An internal phase oil was obtained by dissolving 10 parts of dimethylamino) diphenylmethyl-2-methylaniline. Then, this internal phase oil was charged into the above-mentioned aqueous medium for capsule production, and T.I. K.
The mixture was emulsified and dispersed at 10000 rpm for 1 minute using a homomixer, and then heated to 55 ° C. Separately, add 15 parts of melamine to 45 parts of 37% formaldehyde aqueous solution, and add 60 ° C.
Was reacted for 15 minutes to prepare an aqueous prepolymer solution.
This prepolymer aqueous solution was dropped into the emulsion, and the mixture was further stirred and then adjusted to pH 5.3 with 0.1N-hydrochloric acid.
After raising the temperature to 80 ° C and keeping it at that temperature for 1 hour, 0.2N-
After the pH was lowered to 3.5 with hydrochloric acid and the temperature was kept for 3 hours, the mixture was allowed to cool to prepare microcapsules consisting of an aminoaldehyde resin film having an average particle diameter of 5.3 μm and an average film thickness of 0.15 μm.

Comparative Example 1 Preparation of the microcapsule dispersion of Example 1, except that 10 parts of 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide was used as the basic dye. Capsules having an average particle diameter of 5.8 μm and an average film thickness of 0.18 μm were prepared in the same manner as in Example 1, and the same procedure as in Example 1 was performed to obtain a pressure-sensitive recording medium paper.

Comparative Example 2 In the preparation of the microcapsule dispersion of Example 1, 10 parts of 1,2-bis [4,4'-bis (dimethylamino) diphenylmethylamino] ethane was used as the basic dye. Has an average particle diameter of 5.5 as in Example 1.
A capsule having a thickness of 0.16 μm and an average film thickness of 0.16 μm was prepared, and the same procedure as in Example 1 was performed to obtain a pressure-sensitive recording medium paper.

Comparative Example 3 In the preparation of the coloring agent coating liquid of Example 1, 100 parts of activated clay was used.
A pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 except that 20 parts of 3,5-bis (α-methylbenzyl) salicylic acid zinc salt and 80 parts of kaolin were used instead of the parts.

Comparative Example 4 In the preparation of the microcapsule dispersion of Example 1, the same procedure as in Example 1 was carried out except that the emulsification time of the capsule core substance and the aqueous medium for capsule production was changed from 1 minute to 15 seconds. A polyurea resin / polyurethane resin wall film capsule having a particle diameter of 17 μm and an average film thickness of 0.43 μm was prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 below.

Comparative Example 5 An average particle size of 5 was obtained in the same manner as in Example 1 except that the amount of polymethylene polyphenyl isocyanate used was reduced from 5 parts to 1 part in the preparation of the microcapsule dispersion of Example 1. A polyurea resin / polyurethane resin wall film capsule having a thickness of 0.2 μm and an average film thickness of 0.07 μm was prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Comparative Example 6 In the preparation of the microcapsule dispersion of Example 1, the procedure was repeated except that the amount of polymethylene polyphenyl isocyanate used was increased from 5 parts to 10 parts and the emulsification time was changed from 1 minute to 15 seconds. As in Example 1, the average particle size was 20.
Prepare capsules with an average film thickness of 2 μm and 0.85 μm,
Thereafter, in the same manner as in Example 1, a pressure-sensitive recording medium paper was obtained.

Comparative Example 7 In the preparation of the microcapsule dispersion of Example 1, the emulsification conditions of the capsule core substance and the aqueous medium for capsule preparation were changed from 1 minute at 10000 rpm to 2 minutes at 20000 rpm. Except for this, capsules having an average particle size of 2.0 μm and an average film thickness of 0.14 μm were prepared in the same manner as in Example 1, and the following pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Comparative Example 8 3,3'-dichloro-4,4'-bis [(4-diethylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] as a basic dye was added to 100 parts of alkyldiphenylethane. 10 parts of diphenylmethane was dissolved. Separately, 25 parts of pigskin gelatin having an isoelectric point of 8 and 25 parts of gum arabic as an encapsulating agent were dissolved in 300 parts of warm water at 50 ° C. To the gelatin-gum arabic mixed solution was added the above-mentioned color-forming agent-containing oil with stirring to emulsify and disperse.

This emulsion was further diluted with 1000 parts of warm water, and acetic acid was gradually added to adjust the pH of the solution to 4 to 4.3. A capsule was produced. The capsule was cooled to about 10 ° C. and 10 parts of a 25% aqueous solution of glutaraldehyde was added to harden the capsule. Capsules were prepared, and a pressure-sensitive recording intermediate paper was obtained in the same manner as in Example 1 below.

Comparative Example 9 In the preparation of the coloring agent coating liquid of Example 1, 100 parts of activated clay having a silicon oxide content of 72% by weight was replaced with activated clay having a silicon oxide (SiO ₂ ) content of 85% by weight. A pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 except that 100 parts were used.

Comparative Example 10 In the preparation of the colorant dispersion of Example 1, bentonite having a silicon oxide (SiO ₂ ) content of 60% by weight was replaced with 100 parts of activated clay having a silicon oxide content of 72% by weight. An intermediate paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that it was used.

Using the thus obtained 44 kinds of pressure-sensitive recording medium paper, various performance comparison tests were conducted, and the results are shown in Tables 1 and 2. [Printing Density] The prepared pressure-sensitive recording medium paper is overlaid so that the capsule-coated surface and the coloring agent-coated surface face each other and printed by a dot printer. 914 type) using a visual filter.

[Light resistance test] The print color-developing surface (coloring agent-coated surface) obtained above was exposed to direct sunlight for 8 hours, and then the color-developing density was measured again with a Macbeth densitometer.

[Water resistance test] Printed medium paper in water 2
After being left for 4 hours, the color density was measured again with a Macbeth densitometer.

[Plasticizer resistance test] A vinyl chloride film was placed on the printed surface of the print and allowed to stand at 25 ° C for 7 days, and then the color density was measured again with a Macbeth densitometer.

[Discoloration and Discoloration by Mending Tape] After the mending tape was applied to the printed color surface and left at 25 ° C. for 14 days, the degree of discoloration of the image was visually judged by the following evaluation criteria. (Evaluation Criteria) ○: Almost no discoloration △: Some discoloration is observed, which is a problem depending on the quality grade ×: Significant discoloration, not practical

[Contact-Resistant Staining Test] Pressure-sensitive recording medium papers were superposed so that the capsule-coated surface and the color-developing agent-coated surface faced each other, and a load of 20 kg / cm ² was applied for 1 minute, and then the color-developing agent was applied. The degree of color stain on the surface was visually determined according to the following evaluation criteria. (Evaluation Criteria) ○: Almost no dirt △: A little dirt, which is a problem depending on the quality grade ×: Significantly dirt, not practical

[Scratch Resistance Test] After stacking the pressure-sensitive recording medium sheets so that the capsule-coated surface and the coloring agent-coated surface face each other, after rubbing 5 times with a load of 4 kg / cm ² being applied. The degree of color stain on the surface coated with the color developing agent was visually determined according to the following evaluation criteria. (Evaluation Criteria) ○: Almost no dirt △: A little dirt, which is a problem depending on the quality grade ×: Significantly dirt, not practical

[Desensitization Suitability Test] Offset desensitizing ink (manufactured by Teikoku Ink Co., N
o. 804) is printed so that the coating amount is 4 g / m ² and the desensitized ink coated surface is overlapped with the capsule coated surface of the medium paper on which the desensitized ink is not printed, and the result is printed by a dot printer. 1 at each room temperature and 90 ℃
After being left for a day, the desensitization suitability was visually judged according to the following evaluation criteria.

(Evaluation Criteria) ⊚: Desensitization suitability is good for both the ones treated at room temperature and 90 ° C. ◯: Only those treated at room temperature have good desensitization suitability, which is a problem depending on the quality grade. Those treated at both room temperature and 90 ° C have poor desensitization suitability and are not practical

[0083]

[Table 1]

[0084]

[Table 2]

Example 35 An intermediate paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that the microcapsule dispersion liquid prepared by the following method was used. [Preparation of Microcapsule Dispersion] In a stirring and mixing container equipped with a heating device, polyvinyl alcohol (trade name: PV
150 parts of a 3% aqueous solution (A-117, manufactured by Kuraray Co., Ltd.) was added to prepare an aqueous medium for capsule production. Separately, alkylnaphthalene (trade name: KMC oil, Kureha Chemical Co., Ltd.) 1
To 00 parts, 5 parts of 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-octylindol-3-yl) -4-azaphthalide as a basic dye and N- (4-dimethyl) Amino-2-methyl-4'-
Dimethylamino) diphenylmethyl-2-methylaniline (5 parts) was dissolved, and further, polymethylene polyphenylisocyanate (trade name: Millionate MR400, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 5 parts of 2-isocyanatoethyl-
2,6-Diisocyanate hexaate (trade name: T-
100 parts, manufactured by Toray Industries, Inc.) was used as a capsule core substance to prepare a solution of T.
K. It was dispersed for 1 minute at 10000 rpm using a homomixer. To this emulsified dispersion was added 1 part of diethylenetriamine, and the mixture was stirred at room temperature for 30 minutes, then the system temperature was adjusted to 70
The temperature was raised to ° C and the reaction was continued for 3 hours while continuing stirring. Then, the temperature was lowered to room temperature to obtain a microcapsule dispersion liquid composed of a polyurea resin / polyurethane resin wall film having an average particle diameter of 5.7 μm and an average film thickness of 0.16 μm.

Examples 36 to 41 In the preparation of the microcapsule dispersion of Example 35,
In the same manner as in Example 35 except that the compound shown below was used in place of N- (4-dimethylamino-2-methyl-4′-dimethylamino) diphenylmethyl-2-methylaniline as the basic dye. Six types of pressure-sensitive recording medium paper were obtained. The average particle size and the average film thickness of the prepared microcapsules were 5.4 to 5.8 μm, respectively.
m, and the range was 0.15 to 0.19 μm. Example 36: N- (4-diethylamino-2-methyl-
4′-dimethylamino) diphenylmethyl-2-methylaniline Example 37: N- (4-di-n-butylamino-2-methyl-4′-dimethylamino) diphenylmethyl-2-
Methylaniline Example 38: N- (4-di-n-butylamino-2-ethoxy-4'-dimethylamino) diphenylmethyl-2
-Chloroaniline Example 39: N- (4-di-n-butylamino-2-methyl-4'-diethylamino) diphenylmethyl-2-
Methylaniline Example 40: N- (4-di-n-amylamino-2-methyl-4'-dimethylamino) diphenylmethyl-2-
Methylaniline Example 41: 3,3'-dichloro-4,4'-bis [(4-di-n-butylamino-2-methyl-4'-dimethylamino) diphenylmethylamino] diphenylmethane

Examples 42 to 45 In the preparation of the microcapsule dispersion of Example 35,
Instead of 3- (4-diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-octylindol-3-yl) -4-azaphthalide as a basic dye, the following compounds were used. In the same manner as in Example 35, four types of pressure-sensitive recording medium paper were obtained. The average particle size and average film thickness of each of the prepared microcapsules are
5.4 to 5.8 μm and 0.15 to 0.19 μm, respectively
Was in the range. Example 42: 3- (4-Diethylamino-2-ethoxyphenyl) -3- (2-methyl-1-ethylindol-3-yl) -4-azaphthalide Example 43: 3- (4-Diethylamino- 2-hexyloxyphenyl) -3- (2-methyl-1-ethylindol-3-yl) -4-azaphthalide Example 44: 3- (4-diethylamino-2-methylphenyl) -3- (2- Methyl-1-ethylindole-
3-yl) -4-azaphthalide Example 45: 3- (4-diethylamino-2-methylphenyl) -3- (2-phenyl-1-methylindol-3-yl) -4-azaphthalide

Using the thus obtained 11 kinds of pressure-sensitive recording medium paper, various performance comparison tests were conducted, and the results are shown in Table 3.

[Printing Density] The prepared medium pressure-sensitive recording medium is superposed such that the capsule-coated surface and the coloring agent-coated surface face each other and printed by a dot printer. (Manufactured by RD-914)) using a visual filter.

[Light Resistance Test] The print color surface (coloring agent coated surface) obtained above was exposed to direct sunlight for 20 hours, and then the color density was measured again with a Macbeth densitometer.

[Moisture resistance test]
After leaving for 7 days in an environment of 90% RH, the color density was measured again with a Macbeth densitometer.

[Desensitization Suitability Test] Offset desensitizing ink (made by Teikoku Ink Co., N
o. 804) is printed so that the coating amount is 4 g / m ² and the desensitized ink coated surface is overlapped with the capsule coated surface of the medium paper on which the desensitized ink is not printed, and the result is printed by a dot printer. After being left in each of the environments of 60 ° C. and 90 ° C. for 1 day, the desensitizing suitability thereof was visually judged according to the following evaluation criteria.

(Evaluation Criteria) A: Desensitization suitability is good for both 60 ° C. and 90 ° C. ○: Only desensitization suitability is good for those treated at 60 ° C.
Depends on the quality grade. ×: Those treated at both 60 ° C and 90 ° C have poor desensitization suitability and are not practical.

[0094]

[Table 3]

[0095]

As is clear from the results of Tables 1 to 3,
The pressure-sensitive recording material of the present invention in which a specific diarylmethane compound is used by being encapsulated in a specific microcapsule and further combined with a specific color-imparting agent is excellent in storage stability of a recorded image and causes stains or color change of color. The pressure-sensitive recording material had no fading and was excellent in desensitization suitability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location B41M 5/165 9221-2H B41M 5/12 107 9221-2H 112 (72) Inventor Masato Tanaka Hyogo 4-3-1, Jokoji, Amagasaki City Kanzaki Paper Manufacturing Co., Ltd. Kanzaki Mill

Claims (6)

[Claims] 1. A pressure-sensitive recording material utilizing a color reaction between a colorless or light-colored basic dye and a coloring agent, wherein the basic dye is represented by the following general formula [Chemical formula 1], [Chemical formula 2] or [Chemical formula 2] 3] is used, and the basic dye is contained in a synthetic polymer microcapsule having an average particle diameter of 3 to 15 μm and an average film thickness of 0.1 to 0.7 μm. And silicon oxide (S
A pressure-sensitive recording material comprising an activated clay mineral having an iO ₂ ) content of 65 to 80% by weight. [Chemical 1] [In the formula, R _{1 to} R ₄ each represent a C _{1 to} C ₅ alkyl group or a benzyl group, and R ₅ represents a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom. , R ₆ is a hydrogen atom, a C ₁ -C ₅ alkyl group, C ₁
To C ₅ alkoxyl group or halogen atom, R
₇ represents a C _{1 to} C ₁₂ alkylene group or a group represented by [Chemical Formula 4]. [Chemical 4] Here, X ₁ to X ₈ are each a hydrogen atom, C ₁ -C ₄ alkyl group, an alkoxyl group or a halogen atom C ₁ -C _4, Z is a direct bond, -O -, - S -, - SO
₂ - or an alkylene group of C ₁ -C _6. ] [Chemical 2] [In the formula, R _{8 to} R ₁₁ each represent a C _{1 to} C ₅ alkyl group or a benzyl group, and R ₁₃ represents a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom. , R ₁₄ is a hydrogen atom, a C ₁ -C ₅ alkyl group, C ₁
To C ₅ alkoxyl group or halogen atom, R
₁₂ represents a phenyl group or a C ₃ -C ₇ alkoxycarbonylalkyl group. Note phenyl group is an alkyl group of C ₁ -C _4, alkoxy group of C ₁ -C _4, it may be substituted by a halogen atom or a hydroxymethyl group. ] [Chemical 3] [In the formula, R _{15 to} R ₁₈ each represent a C _{1 to} C ₅ alkyl group or a benzyl group, and R ₁₉ represents a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxyl group or a halogen atom. , R ₂₀ is a hydrogen atom, a C ₁ -C ₅ alkyl group, C ₁
To C ₅ alkoxyl groups or halogen atoms, Represents a 5- or 6-membered saturated or unsaturated heterocycle. ] 2. The pressure-sensitive recording material according to claim 1, wherein the diarylmethane compound is a compound represented by the following general formula [Chemical formula 6], [Chemical formula 7] or [Chemical formula 8]. [Chemical 6] [Wherein R _{21 to} R ₂₄ each represent a C _{1 to} C ₅ alkyl group, R ₂₅ represents a C _{1 to} C ₂ alkyl group, a C _{1 to} C ₂ alkoxyl group or a halogen atom, and R ₂₆ Represents a hydrogen atom, a C ₁ -C ₂ alkyl group, a C ₁ -C ₄ alkoxyl group or a halogen atom. ] [Chemical 7] [Wherein, R _{27 to} R ₃₀ each represent a C _{1 to} C ₅ alkyl group, R ₃₁ represents a C _{1 to} C ₂ alkyl group, a C _{1 to} C ₂ alkoxyl group or a halogen atom, and R ₃₂ Represents a hydrogen atom, a C ₁ -C ₂ alkyl group, a C ₁ -C ₄ alkoxyl group or a halogen atom. ] [Chemical 8] [In the formula, R _{33 to} R ₃₆ each represent a C _{1 to} C ₅ alkyl group, R ₃₇ represents a C _{1 to} C ₂ alkyl group, a C _{1 to} C ₂ alkoxyl group or a halogen atom; 9] Is a benzotriazinyl group, a pyrazolyl group, a 3,5-dimethylpyrazolyl group, an indolyl group, a pyrrolyl group, 2-
Methyl-2-imidazolinyl group, 9-carbazolyl group,
A pyrrolidyl group, piperidyl group, morpholyl group, benzimidazolyl group or imidazolyl group is shown. ] 3. In the general formulas [Chemical formula 6] to [Chemical formula 8],
R ₂₁ , R ₂₂ , R ₂₇ , R ₂₈ , R ₃₃ , and R ₃₄ are each C ₄ to.
The pressure-sensitive recording material according to claim 2, which is a C ₅ alkyl group. 4. The pressure-sensitive recording material according to claim 1, wherein at least one azaphthalide compound represented by the following general formula [Chemical Formula 10] is used in combination as the basic dye. [Chemical 10] [In the formula, R ₃₇ and R ₃₈ each represent a C _{1 to} C ₄ alkyl group, but they may be bonded to each other to form a heterocycle with the adjacent nitrogen atom. R ₃₉ represents a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxyl group, R ₄₀ represents a hydrogen atom, a C ₁ -C ₈ alkyl group or a benzyl group, and R ₄₁ represents a hydrogen atom, C an alkyl group or a phenyl group of ₁ -C _4. ] 5. The azaphthalide compound is 3- (4-diethylamino-2-methylphenyl) -3- (2-methyl-1-ethylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino). -2-methylphenyl)
-3- (2-phenyl-1-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-
2-Ethoxyphenyl) -3- (2-methyl-1-octylindol-3-yl) -4-azaphthalide, 3-
(4-Diethylamino-2-ethoxyphenyl) -3-
(2-Methyl-1-ethylindol-3-yl) -4
-Azaphthalide or 3- (4-diethylamino-2-
The pressure-sensitive recording material according to claim 4, which is hexyloxyphenyl) -3- (2-methyl-1-ethylindol-3-yl) -4-azaphthalide. 6. The pressure-sensitive recording material according to claim 1, wherein activated clay having a silicon oxide (SiO ₂ ) content of 65 to 75% by weight is used as a color developing agent.