JPH0732730A - Pressure-sensitive recording body - Google Patents

Abstract

(57) [Summary] [Object] To provide a pressure-sensitive recording material having excellent color forming properties and moisture resistance and light resistance of a color image, and having good desensitization suitability. A pressure-sensitive recording material utilizing a color reaction between a colorless or light-colored basic dye and a color-developing agent, wherein at least a diarylmethane compound represented by the following general formula [Chemical Formula 1] is used as the basic dye. A pressure-sensitive recording material comprising a combination of one type and at least one type of indole compound represented by the following general formula [Chemical formula 2]. [Chemical 1] [Chemical 2]

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 excellent color forming properties and moisture resistance and light resistance of a color image and having good desensitization suitability.

[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. In addition, a self-coloring pressure-sensitive recording medium capable of performing pressure-sensitive recording with one sheet by coating a microcapsule containing a basic dye and a coloring agent on the same surface of a support is also a pressure-sensitive recording medium. Known as the morphology.

The pressure-sensitive recording material should have the following properties: fast color development speed, sufficient color density, fastness of color image, especially light fastness and moisture fastness, and good reduction. It has the aptitude 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 high color development speed and exhibits a deep blue color, but has extremely poor light fastness of a color image.

Therefore, in order to improve the drawbacks of crystal violet lactone, tris such as bis (9-n-ethyl-carbazol-3-yl)-[4- (N-phenyl-N-methylamino) phenyl] methane are used. A method in which a reel methane compound or a leuco methylene blue compound such as benzoyl leuco methylene blue is used in combination with crystal violet lactone has been put to practical use and some effects have been obtained, but it is not always satisfactory in terms of light resistance. .

On the other hand, Japanese Patent Publication Nos. 442-189 and 44-2191 propose pressure-sensitive recording materials using diarylmethane compounds as basic dyes. However, the bis [4,4'-
Diarylmethane compounds such as bis (dimethylaminobenzhydryl)] ether and 4,4′-bis (dimethylaminobenzhydryl) benzyl-ether are robust to color images when used in combination with activated clay minerals. However, it has the drawback that the color tone of the image becomes reddish due to the influence of light or the like and that it is difficult to be desensitized with a conventional desensitizer.

[0007]

In view of the present situation, the present inventors have found that they have good desensitization suitability, and are excellent not only in color developability but also in light fastness and moisture fastness of a colored image, and further, in color tone at light fastness. As a result of intensive research to develop a pressure-sensitive recording material with further improved stability, the intended pressure-sensitive recording material can be obtained by using a specific diarylmethane compound and a specific indole compound together as a basic dye. This has led to the completion of the present invention.

[0008]

The present invention provides a pressure-sensitive recording material utilizing the color reaction between a colorless or light-colored basic dye and a color-forming agent, wherein the basic dye is represented by the following general formula: To at least one diarylmethane compound represented by [Chemical Formula 4],

[0009]

[Chemical 1]

[0010]

[Chemical 2]

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[Wherein R₁~ R_FourAre each C₁~ C_Five
Alkyl group of C₂~ C₆An alkoxyalkyl group of: C
_Five~ C₆Represents a cycloalkyl group or a benzyl group.
R_Five, R₆Are hydrogen atoms; C₁~ C_FiveThe alkyl
Group; C₁~ C_FiveThe alkoxyl group or halogen atom of
Although not shown, a hydrogen atom is not shown at the same time. In addition, R₁
And R₂, R₃And R_FourAre connected to each other and adjacent nitrogen atom
Together they can form a heterocycle. R₇Is C₁~ C₂₀
Alkyl group of C₂~ C₂₀An alkoxyalkyl group of: C
₁~ C_FourAlkyl group of C₁~ C_FourThe alkoxy alk
Group or benzyl group which may be substituted with halogen
You R₈~ R_TenAre hydrogen atoms; C₁~ C₂₀The al
Kill group; C₇~ C₂₀An alkyl group of: C₁~ C_FiveA
Rukiru group_,C₁~ C_FiveAlkoxyl group, halogen atom
A phenyl group which may be substituted with; C ₁~ C_FiveThe alkyl
Basis_,C₁~ C_FiveSubstituted with an alkoxyl group or halogen atom
Represents a naphthyl group which may be substituted. However, R₈And R₉Is the same
Sometimes it does not represent a hydrogen atom. In addition, R₈And R₉Are mutual
To form a heterocycle with the adjacent nitrogen atom.
You can R₁₁Is C₁~ C_TenAlkylene or the following formula
[Chemical 5]

[0014]

[Chemical 5]

(Here, X _{1 to} X ₈ are hydrogen atoms,
C ₁ -C ₄ alkyl group, an alkoxy group or a halogen atom C ₁ ~C _4, Z ₁ is directly bonded, -C -, - S
-, - an alkylene group or a C ₁ ~C ₆ - SO _2. ) Represents a group represented by. ] The following general formula [Chemical formula 6]-
A pressure-sensitive recording material comprising at least one of the indole compounds represented by [Chemical Formula 9].

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[In the formula, R ₁₂ and R ₁₃ are each C _{1 to} C ₅
An alkoxyalkyl group of C ₂ -C _6;; alkyl C
₅ shows a cycloalkyl group or a benzyl group -C _6.
R ₁₄ represents a hydrogen atom; a C ₁ -C ₁₂ alkyl group or a benzyl group. R ₁₅ represents a hydrogen atom; a C ₁ -C ₁₂ alkyl group or a phenyl group. R ₁₆ and R ₁₇ each represent a hydrogen atom; a C _{1 to} C ₅ alkyl group; a C _{1 to} C ₅ alkoxyl group or a halogen atom. R ₁₈ is a C _{1 to} C ₂₀ alkyl group; a C _{2 to} C ₂₀ alkoxyalkyl group; C ₁ to
A C ₄ alkyl group, a C ₁ -C ₄ alkoxyl group or a benzyl group which may be substituted with halogen is shown. R ₁₉ ~
R ₂₁ is each a hydrogen atom; a C ₁ -C ₂₀ alkyl group; C
Of ₇ -C ₂₀ aralkyl group, alkyl group of C ₁ -C _5,
C ₁ -C alkoxyl group _5, phenyl which may be substituted by a halogen atom group, alkyl group of C ₁ ~C _5, C ₁ ~
A C ₅ alkoxyl group and a naphthyl group which may be substituted with a halogen atom are shown. However, R ₁₉ and R ₂₀ do not represent hydrogen atoms at the same time. R ₁₉ and R ₂₀ can be linked to each other to form a heterocycle with the adjacent nitrogen atom. R ₂₂ is C ₁ -C ₁₀ alkylene or the following formula
0]

[0021]

[Chemical 10]

(Where X _{9 to} X ₁₆ are hydrogen atoms,
C ₁ -C ₄ alkyl group, an alkoxy group or a halogen atom C ₁ ~C _4, Z ₂ is a direct bonding, -C -, - S
-, - an alkylene group or a C ₁ ~C ₆ - SO _2. ) Represents a group represented by. ]

[0023]

The above-mentioned general formulas [Chemical formula 1] to [Chemical formula 4] used in the present invention
Specific examples of the diarylmethane compound represented by
For example: (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl ether, (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -ethyl ether, (4-dibutyl) Amino-2
-Methyl-4'-dimethylaminobenzhydryl) -n
-Propyl ether, (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -isobutyl ether, (4-dibutylamino-2-methyl-4 ')
-Dimethylaminobenzhydryl) -benzyl ether, (4-dibutylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -methyl ether, (4-
Dibutylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -n-octyl ether, (4-dibutylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -n-dodecyl ether, (4- Dibutylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -methoxypropyl ether, (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -ethoxypropyl ether, (4-dibutylamino) -2-methyl-4'-dimethylaminobenzhydryl) -4-methylbenzyl ether, (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -4-methylbenzyl ether, (4- Dibutylamino-3-methyl-4'-dimethylaminobenzhydryl) -methyl a , (4-dibutylamino-3-ethyl-4′-dimethylaminobenzhydryl) -n-propyl ether, (4-dibutylamino-2-methoxy-4′-dimethylaminobenzhydryl) -methyl ether, (4-dibutylamino-2-methoxy-4′-dimethylaminobenzhydryl) -benzyl ether,
(4-Dimethylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl ether, (4-dimethylamino-2-methoxy-4'-dimethylaminobenzhydryl) -methyl ether, (4-dimethyl Amino-
2-ethoxy-4'-dimethylaminobenzhydryl)
-Benzyl ether, (4-diethylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl ether, (4-diethylamino-2-methoxy-4'-
Dimethylaminobenzhydryl) -benzyl ether,
(4-Diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -ethyl ether, (4-dibutylamino-2-isobutoxy-4'-dimethylaminobenzhydryl) -methyl ether, (4-dibutylamino) -2-Chloro-4'-dimethylaminobenzhydryl) -ethyl ether, (4-dibutylamino-2-methyl-4'-diethylaminobenzhydryl) -methyl ether, (4-dibutylamino-2-methoxy-). 4 '
-Diethylaminobenzhydryl) -methyl ether,
(4-dibutylamino-2-ethoxy-4'-diethylaminobenzhydryl) -methyl ether, [4- (N
-Methyl-N-cyclohexylamino) -2-methoxy-4'-dimethylaminobenzhydryl] -methyl ether, [4- (N-ethyl-N-cyclohexylamino) -2-ethoxy-4'-dimethylaminobenz Hydryl] -methyl ether, [4- (N-methyl-N-ethoxypropyl) -2-methoxy-4′-dimethylaminobenzhydryl] -n-propyl ether, [4-
(N-Methyl-N-methoxypropyl) -2-ethoxy-4'-dimethylaminobenzhydryl] -benzyl ether, (4-diethylamino-2-ethoxy-4'-
Dibutylaminobenzhydryl) -methyl ether,
(4-dibenzylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl ether, [4,4 '
-Bis (diethylamino) -2,2'-dimethylbenzhydryl] -methyl ether, (4-diamylamino-
2-Methyl-4'-dimethylaminobenzhydryl)-
Methyl ether, bis (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -ether, bis (4-dibutylamino-2-methoxy-4'-
Dimethylaminobenzhydryl) -ether, bis (4
-Dimethylamino-2-methyl-4'-dimethylaminobenzhydryl) -ether, bis [4,4'-bis (dibutylamino) -2,2'-dimethylbenzhydryl) -ether, bis [4 4'-bis (diethylamino) -2,2'-dimethylbenzhydryl) -ether, N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine, N-
(4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-phenetidine, N- (4-
Dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-anisidine, N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -2-chloroaniline, N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -2-ethylaniline, N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl)
-Aniline, N- (4-dibutylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -o-toluidine, N- (4-dibutylamino-2-ethoxy-4 '
-Dimethylaminobenzhydryl) -2-chloroaniline, N- (4-dibutylamino-2-methoxy-4'-
Dimethylaminobenzhydryl) -o-toluidine, N
-(4-dibutylamino-2-methoxy-4'-dimethylaminobenzhydryl) -2-chloroaniline, N-
(4-Dimethylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine, N- (4-dimethylamino-2-methyl-4'-dimethylaminobenzhydryl) -2-chloroaniline , N- (4-Dimethylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -2-bromoaniline, N- (4-Dimethylamino-2-methoxy-4'-dimethylaminobenzhydryl)- p-toluidine, N- (4-diethylamino-2-methyl-4'-dimethylaminobenzhydryl)
-O-toluidine, N- (4-diamylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine, 4,4'-bis [(4-dibutylamino-2
-Methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane, 3,3'-dichloro-4,4 '
-Bis [(4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane, 3,3'-dimethyl-4,4'-bis [(4-dibutylamino-2-methyl- 4'-dimethylaminobenzhydryl) amino] diphenylmethane, 3,3'-dimethoxy-4,4'-bis [(4-dibutylamino-2-
Methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane, 2,2'-dichloro-4,4 '
-Bis [(4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane, N- [4,4'-bis (dibutylamino) -2,
2'-Dimethylbenzhydryl] -o-toluidine, N
-[4,4'-bis (dibutylamino) -2,2'-dimethoxybenzhydryl] -o-toluidine, 3,3 '
-Dichloro-4,4'-bis {[4,4'-bis (dibutylamino) -2,2'-dimethoxybenzhydryl]
Amino} diphenylmethane.

The compounds are not limited to the above specific examples, and any compound included in the above general formulas [Chemical formula 1] to [Chemical formula 4] can be used, and if necessary, 2
It is also possible to use two or more species together.

Among the above-mentioned diarylmethane compounds, the compounds represented by the following general formulas [Chemical formula 11] to [Chemical formula 14] are excellent in color forming property and light fastness of color image, and are used in the present invention. It is particularly preferably used because it is particularly excellent in color stability upon light resistance when combined with the indole compound described above, and the raw materials are easily available and easy to synthesize.

[0026]

[Chemical 11]

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[Wherein R_{twenty three}~ R₂₆Are each C₁~ C_Five
Represents an alkyl group of R,₂₇Is C₁~ C ₂An alkyl group of
C₁~ C₂The alkoxyl group or halogen atom of
You R₂₈Is C₁~ C_FourAlkyl group or benzyl group of
Show. R₂₉Is a hydrogen atom; C₁~ C ₂An alkyl group of
Indicates a halogen atom. ]

Further, the above general formulas [Chemical formula 11] to [Chemical formula 1]
4] among the compounds represented by 4], R ₂₃ and R ₂₄ are C ₄ to C.
_The compound in which the alkyl group of ₅ and R ₂₅ and R ₂₆ are methyl groups is most excellent in color stability when combined with the indole compound used in the present invention, and exhibits extremely excellent desensitization suitability. Therefore, it is particularly preferably used.

On the other hand, the above general formula [Chemical Formula 6] used in the present invention
Specific examples of the indole compound represented by the formulas [Chemical Formula 9] include the following. [(4-Dimethylaminophenyl)-(1-methyl-2
-Methylindol-3-yl) methyl] -methyl ether, [(4-dimethylaminophenyl)-(1-ethyl-2-ethylindol-3-yl) methyl] -methyl ether, [(4-dimethylaminophenyl) )-(1
-Methyl-2-phenylindol-3-yl) methyl] -methyl ether, [(4-dimethylaminophenyl)-(1-ethyl-2-methylindol-3-yl) methyl] -methyl ether, [(4 -Dimethylaminophenyl)-(1-octyl-2-methylindol-3-yl) methyl] -methyl ether, [(4-dimethylaminophenyl)-(1-benzyl-2-methylindol-3-yl) methyl ] -Methyl ether,
[(4-Dimethylaminophenyl)-(1-methyl-2
-Phenylindol-3-yl) methyl] -ethyl ether, [(4-dimethylaminophenyl)-(1-methyl-2-phenylindol-3-yl) methyl]-
n-Propyl ether, [(4-dimethylaminophenyl)-(1-methyl-2-phenylindol-3-yl) methyl] -benzyl ether, [(4-dimethylaminophenyl)-(1-ethyl-2- Methylindol-3-yl) methyl] -ethyl ether, [(4-dimethylaminophenyl)-(1-ethyl-2-methylindol-3-yl) methyl] -benzyl ether,
[(4-Diethylaminophenyl)-(1-methyl-2
-Phenylindol-3-yl) methyl] -methyl ether, [(4-dibutylaminophenyl)-(1-methyl-2-phenylindol-3-yl) methyl]-
Methyl ether, [(4-dimethylamino-2-methylphenyl)-(1-methyl-2-phenylindole-
3-yl) methyl] -methyl ether, [(4-dimethylamino-3-methylphenyl)-(1-methyl-2-
Phenylindol-3-yl) methyl] -methyl ether, [(4-dimethylamino-2-chlorophenyl)
-(1-Methyl-2-phenylindol-3-yl)
Methyl] -methyl ether, bis [(4-dimethylaminophenyl)-(1-methyl-2-phenylindol-3-yl) methyl] ether, bis [(4-dimethylaminophenyl)-(1-ethyl-2 -Methylindol-3-yl) methyl] ether, N-[(4-dimethylaminophenyl)-(1-ethyl-2-ethylindol-3-yl) methyl] -o-toluidine, N-
[(4-Dimethylaminophenyl)-(1-methyl-2
-Phenylindol-3-yl) methyl] -o-toluidine, N-[(4-dimethylaminophenyl)-(1
-Octyl-2-methylindol-3-yl) methyl] -o-toluidine, N-[(4-dimethylaminophenyl)-(1-ethyl-2-phenylindole-3)
-Yl) methyl] -o-toluidine, N-[(4-dimethylaminophenyl)-(1-ethyl-2-methylindol-3-yl) methyl] -o-phenetidine, N-
[(4-Dimethylaminophenyl)-(1-ethyl-2
-Methylindol-3-yl) methyl] -o-anisidine, N-[(4-dimethylaminophenyl)-(1-
Ethyl-2-methylindol-3-yl) methyl]-
2-ethylaniline, N-[(4-dimethylaminophenyl)-(1-methyl-2-phenylindole-3-
Il) methyl] -2-chloroaniline, N-[(4-dimethylamino-3-methylphenyl)-(1-methyl-
2-Phenylindol-3-yl) methyl] -2-chloroaniline, 4,4'-bis [(4-dimethylaminophenyl)-(1-methyl-2-phenylindole-
3-yl) methylamino] -diphenylmethane, 3,
3'-dichloro-4,4'-bis [(4-dimethylaminophenyl)-(1-methyl-2-phenylindol-3-yl) methylamino] -diphenylmethane, 3,
3'-Dimethyl-4,4'-bis [(4-dimethylaminophenyl)-(1-methyl-2-phenylindol-3-yl) methylamino] -diphenylmethane.

The compounds are not limited to the above specific examples, and any compounds included in the above general formulas [Chemical formula 6] to [Chemical formula 9] can be used, and if necessary, 2
It is also possible to use two or more species together.

Among the above-mentioned indole compounds, the compounds represented by the following general formulas [Chemical formula 15] to [Chemical formula 18] are
It is excellent in color developability and light resistance of a color image, and is particularly excellent in color stability during light resistance when combined with the diarylmethane compound used in the present invention, and the raw materials are easily available and easy to synthesize. Therefore, it is particularly preferably used.

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[Wherein R₃₀, R₃₁Are each C₁~ C_Five
Represents an alkyl group of R,₃₂Is C₁~ C ₈The alkyl group
Or benzyl group. R₃₃Is C₁~ C_FourAlkyl group of
Or a phenyl group is shown. R₃₄Is C₁~ C_FourThe alkyl
Represents a group or a benzyl group. R ₃₅Is a hydrogen atom; C₁~ C
₂ Represents an alkyl group or a halogen atom. ]

Further, the above general formulas [Chemical formula 15] to [Chemical formula 1]
Among the compounds represented by 8], the compound in which R ₃₀ and R ₃₁ are methyl groups is most excellent in color tone stability when combined with a diarylmethane compound, and is particularly preferably used.

In the present invention, the combined use ratio of the diarylmethane compounds represented by the general formulas [Chemical Formula 1] to [Chemical Formula 4] and the indole compounds represented by the general formulas [Chemical Formula 6] to [Chemical Formula 9] is particularly Although not limited thereto, it is desirable to use the indole compound in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 1 part by weight of the diarylmethane compound.

The present invention is characterized in that a specific diarylmethane compound and a specific indole compound are used in combination, but other known compounds can be used as long as the desired effects of the present invention are not impaired. Basic dyes such as triarylmethane compounds, triphenylmethanephthalide or azaphthalide compounds, indolylphthalide or azaphthalide compounds, fluorane compounds, fanothiazine compounds, rhodamine lactam compounds, triazene compounds, spiropyran compounds Compounds, leuco auramine compounds, ethylene phthalide compounds,
A styrylquinoline compound or the like can also be used in combination.

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,
It is dissolved in a natural or synthetic hydrophobic medium such as paraffin, naphthenic oil, and dibasic acid ester such as phthalic acid ester, and microcapsules are prepared by various capsule manufacturing methods such as coacervation method, interfacial polymerization method, in-situ polymerization method, etc. Encapsulated in a capsule. The film material of the microcapsule is not particularly limited, but since it does not cause color stains due to unintentional pressure or rubbing, it is a synthetic polymer film such as aminoaldehyde resin, polyurea resin, polyurethane resin, polyamide resin. Materials are preferably used.

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, para. It is produced by an in-situ polymerization method using at least one aldehyde such as formaldehyde, hexamethylenetetramine, glutaraldehyde, glyoxal and furfural, or an initial condensate obtained by condensing them.

Polyurethane resin and polyurea resin wall membrane capsules were prepared by using, for example, polyvalent isocyanate and water, polyvalent isocyanate and polyol, isothiocyanate and water, isothiocyanate and polyol, polyvalent isocyanate and polyamine, and isothiocyanate and polyamine. It is manufactured by an interfacial polymerization method. The polyamide resin wall membrane capsule is manufactured by, for example, an interfacial polymerization method of acid chloride and amine.

The microcapsules containing the specific basic dyes thus prepared are used in the conventional manner, in addition to adhesives such as polyvinyl alcohols, starches, carboxymethyl cellulose, and latexes, stilts such as pulp powders and raw starch powders. Various auxiliaries such as materials 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.

The colorant-containing layer or the colorant of the self-coloring type pressure-sensitive recording material, which is combined with the microcapsule coated surface such as the upper paper or the middle paper, includes phenol derivatives, salicylic acid derivatives, aromatic carboxylic acid derivatives and Those polyvalent metal salts, organic developers such as novolac phenol resin, acid clay, activated clay, active clay materials such as attapulgite, zeolite, bentonite and kaolin can be used.

Among these, the activated clay substance is preferable because a pressure-sensitive recording material having more excellent light resistance and moisture resistance can be obtained, and particularly, the content of silicon oxide (SiO ₂ ) is 65 to 80% by weight, preferably 65-75% by weight of activated clay material, especially activated clay, is preferably used.

The color developing agent coating liquid usually contains the above color developing agents.
It is prepared by a method such as dispersion in water 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, various inorganic pigments such as zinc oxide, magnesium sulfate, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium sulfate, and calcium sulfate, and various auxiliary agents known in the field of pressure-sensitive copying paper production may be used. Agents can also be added as appropriate.

The method of applying the coating liquid is not particularly limited, and for example, an on-machine or off-machine coater equipped with a suitable coating device such as an air knife coater, a roll coater, a blade coater, a rod plate coater, a curtain coater and a lip coater. And the dry weight is 2-10
It is applied to a support such as paper, synthetic paper, film, non-woven fabric, etc. so as to be about g / m ² .

[0051]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. 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] 100 parts of activated clay containing 72% of silicon oxide (SiO ₂ ), 1 part of magnesium oxide, 20 parts of carboxy-modified styrene-butadiene copolymer latex ( Solid content) and 1 part of sodium carboxymethyl cellulose were added to prepare a colorant coating liquid. [Manufacture of lower paper] The above color former 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, [(4-dimethylaminophenyl)-(1-methyl-2-phenylindol-3-yl) methyl]-as a basic dye was added to 100 parts of alkylnaphthalene (trade name: KMC oil, manufactured by Kureha Chemical Co., Ltd.). 5 parts of methyl ether and N- (4-dibutylamino-2-methyl-4'-
Dimethylaminobenzhydryl) -o-toluidine (5 parts) was dissolved, and further 5 parts of polymethylene polyphenylisocyanate (trade name: Millionate MR400, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-isocyanatoethyl-2,6.
-Diisocyanate hexaate (trade name: T-10
0, 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. 1 part of diethylenetriamine was added to this emulsified dispersion, and the mixture was stirred at room temperature for 30 minutes, then 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 to obtain a microcapsule dispersion liquid composed of a polyurea resin / polyurethane resin wall film having an average particle diameter of 5.6 μm and an average film thickness of 0.17 μm.

[Preparation of Microcapsule Coating Liquid] 70 parts of wheat starch powder and 20 parts of dissolved oxidized starch per 100 parts by weight (solid content) of the microcapsule dispersion liquid thus obtained.
Parts (solid content) were added to prepare a microcapsule coating solution. [Manufacture of Medium Paper] The microcapsule coating solution was applied to the surface of the lower paper obtained above opposite to the surface coated with the coloring agent with an air knife coater so that the dry weight was 4 g / m ² , and the pressure was applied. A medium paper for recording was obtained.

Examples 2 to 7 In the preparation of the microcapsule dispersion of Example 1, the basic dye [(4-dimethylaminophenyl)-
Six kinds of pressure-sensitive recording medium paper were prepared in the same manner as in Example 1 except that the compound shown below was used instead of (1-methyl-2-phenylindol-3-yl) methyl] -methyl ether. Obtained. The average particle size and the average film thickness of each of the prepared microcapsules were 5.4 to
The ranges were 5.8 μm and 0.15 to 0.19 μm. -Example 2: N-[(4-dimethylaminophenyl)-
(1-Methyl-2-phenylindol-3-yl) methyl] -o-toluidine Example 3: [(4-Dimethylaminophenyl)-(1
-Ethyl-2-methylindol-3-yl) methyl]
-Methyl ether-Example 4: N-[(4-dimethylaminophenyl)-
(1-Ethyl-2-methylindol-3-yl) methyl] -2-chloroaniline Example 5: [(4-dimethylaminophenyl)-(1
-Octyl-2-methylindol-3-yl) methyl] -methyl ether Example 6: [(4-Dimethylaminophenyl)-(1
-Methyl-2-phenylindol-3-yl) methyl] -n-propyl ether Example 7: [(4-diethylaminophenyl)-(1
-Methyl-2-phenylindol-3-yl) methyl] -methyl ether

Examples 8 to 13 In the preparation of the microcapsule dispersion of Example 1, N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine was used as the basic dye. Instead, six types of pressure-sensitive recording medium paper were obtained in the same manner as in Example 1 except that the compounds shown below were used.
The average particle size and the average film thickness of each of the prepared microcapsules were 5.4 to 5.8 μm and 0.
It was in the range of 15 to 0.19 μm. Example 8: (4-dibutylamino-2-methyl-4 '
-Dimethylaminobenzhydryl) -methyl ether Example 9: N- (4-dibutylamino-2-methoxy-4'-dimethylaminobenzhydryl) -o-toluidine Example 10: N- (4- Dibutylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -2-chloroaniline Example 11: 3,3'-dichloro-4,4'-bis (4
-Dibutylamino-2-methyl-4'-dimethylaminobenzhydrylamino) -diphenylmethane Example 12: N- (4-Diamylamino-2-methyl-
4'-Dimethylaminobenzhydryl) -o-toluidine Example 13: N- (4-dimethylamino-2-methyl-)
4'-diethylaminobenzhydryl) -o-toluidine

Examples 14 to 15 Two kinds of pressure-sensitive recording medium paper were prepared in the same manner as in Example 1 except that the following compounds were used as the basic dye in the preparation of the microcapsule dispersion of Example 1. Got The average particle size and the average film thickness of each of the prepared microcapsules were 5.4 to 5.8 μm and 0.1, respectively.
It was in the range of 5 to 0.19 μm. Example 14: [(4-Dimethylaminophenyl)-(1
-Methyl-2-phenylindol-3-yl) methyl] -methyl ether 4 parts, N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl)
4 parts of -o-toluidine and 2 parts of 3,6-di-methoxyfluorane Example 15: [(4-dimethylaminophenyl)-(1
-Methyl-2-phenylindol-3-yl) methyl] -methyl ether 4 parts, N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl)
4 parts of -o-toluidine and 2 parts of 2- (4-dodecyloxy-3-methoxystyryl) quinoline

Example 16 An intermediate paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that the microcapsule dispersion liquid 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 used as a basic dye [(4-dimethylaminophenyl)-(1-methyl-2).
-Phenylindol-3-yl) methyl] -methyl ether (5 parts) and N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine (5 parts) were dissolved to form an internal phase oil. Got

Then, this internal phase oil was charged into the above-mentioned aqueous medium for capsule production, and T. K. Using a homomixer, emulsify and disperse at 10000 rpm for 1 minute, then 55
The temperature was raised to ° C. Separately 37% formaldehyde aqueous solution 45
15 parts of melamine was added to each part and reacted at 60 ° C. for 15 minutes to prepare an aqueous prepolymer solution. This prepolymer aqueous solution was added dropwise to the emulsion and stirred, and then 0.1
After the pH was adjusted to 5.3 with N-hydrochloric acid, the temperature was raised to 80 ° C and kept at that temperature for 1 hour, and then the pH was adjusted to 3.5 with 0.2N-hydrochloric acid.
The average particle size is 5.
Microcapsules composed of an aminoaldehyde resin film having an average film thickness of 0.15 μm with a thickness of 3 μm were prepared.

Example 17 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 in place of the parts.

Comparative Example 1 In the preparation of the microcapsule dispersion of Example 1, the average particle size was 5.6 μm and the average film was the same as in Example 1 except that 10 parts of crystal violet lactone was used as the basic dye. Microcapsules having a thickness of 0.17 μm were prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Comparative Example 2 The average particle diameter was the same as in Example 1 except that 5 parts of crystal violet lactone and 5 parts of benzoyl leuco methylene blue were used as basic dyes in the preparation of the microcapsule dispersion of Example 1. Capsules having a thickness of 5.8 μm and an average film thickness of 0.16 μm were prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Comparative Example 3 In the preparation of the microcapsule dispersion of Example 1, N
5 parts of-(4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine and 5 parts of 3,3-bis (1-octyl-2-methyl-indol-3-yl) phthalide The average particle diameter was 5.7 μm and the average film thickness was 0.1 in the same manner as in Example 1 except that
8 μm capsules were prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Comparative Example 4 In the preparation of the microcapsule dispersion of Example 1, 5 parts of crystal violet lactone and [(4-dimethylaminophenyl)-(1-methyl-2-phenylindol-3-yl) methyl]- An average particle diameter of 5. was obtained in the same manner as in Example 1 except that 5 parts of methyl ether was used.
A capsule having a thickness of 7 μm and an average film thickness of 0.17 μm was prepared,
Thereafter, in the same manner as in Example 1, a pressure-sensitive recording medium paper was obtained.

Comparative Example 5 In the preparation of the microcapsule dispersion of Example 1,
5 parts of 4,4'-bis (dimethylaminobenzhydryl) -benzyl ether and [(4-dimethylaminophenyl)-(1-methyl-2-phenylindole-3-
Except that 5 parts of (yl) methyl] -methyl ether was used.
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 followed to obtain a pressure-sensitive recording medium paper.

Comparative Example 6 In the preparation of the microcapsule dispersion of Example 1, the basic dye [(4-dimethylaminophenyl)-
(1-Methyl-2-phenylindol-3-yl) methyl] -methyl ether was used in the same manner as in Example 1 except that the average particle diameter was 5.8 μm and the average film thickness was 0.16 μm. Capsules were prepared, and a pressure-sensitive recording intermediate paper was obtained in the same manner as in Example 1 below.

Comparative Example 7 In the preparation of the microcapsule dispersion of Example 1, 10 parts of N- (4-dibutylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine was used as the basic dye. Capsules having an average particle size of 5.7 μm and an average film thickness of 0.17 μm were prepared in the same manner as in Example 1 except that the capsules were prepared. .

Various performance comparison tests were carried out using the 24 kinds of pressure-sensitive recording medium paper thus obtained, and the results are shown in Table 1.

[Coloring Density] The prepared pressure-sensitive recording medium was overlaid so that the capsule-coated surface and the coloring agent-coated surface faced each other and printed with a dot printer, and then the color-developed density was measured by a Macbeth densitometer (Macbeth Co. (Manufactured by RD-914)) using a visual filter.

[Lightfastness Test] The printing color surface (coloring agent coated surface) obtained above was exposed to direct sunlight for 50 hours, and then the color density was measured again with a Macbeth densitometer.

[Lightfast Color Stability Test] The printing color-developing surface (coloring agent-coated surface) obtained above was exposed to direct sunlight for 10, 50 and 10
After the exposure for 0 hour, the color tone was visually judged according to the following evaluation criteria. (Evaluation Criteria) A: The color tone hardly changes even after exposure for 100 hours. ◯: The color tone hardly changes in the one exposed for 50 hours, but the color tone changes in the one exposed for 100 hours. Δ: The color tone hardly changes in the one exposed for 10 hours, but the color tone changes in the one exposed for 50 hours. X: A large change in color tone or decoloring is observed even after exposure for 10 hours.

[Humidity 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 (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. 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) ◎: Good desensitization for both 60 ° C and 90 ° C ○: Good for desensitization only for 60 ° C ×: Decrease for both 60 ° C and 90 ° C Poor aptitude

[0074]

[Table 1]

[0075]

As is clear from the results of Table 1, the pressure-sensitive recording material of the present invention in which a specific diarylmethane compound and a specific indole compound are used together as a basic dye has a sufficient color density and The pressure-sensitive recording material was extremely excellent in humidity resistance, light resistance, and color stability of light color of recorded images, and was also excellent in desensitization suitability.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 4, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4][In the formula, R₁~ R_FourAre each C₁~ C_FiveThe alkyl
Group; C₂~ C₆An alkoxyalkyl group of: C_Five~ C₆of
A cycloalkyl group or a benzyl group is shown. R_Five, R₆
Are hydrogen atoms; C₁~ C_FiveAlkyl group of C₁~
C_FiveThe alkoxyl group or halogen atom of
Sometimes it does not represent a hydrogen atom. In addition, R₁And R₂, R
₃And R_FourAre connected to each other and are heterocyclic with the adjacent nitrogen atom
Can be formed. R₇Is C₁~ C₂₀The alkyl
Group; C₂~ C₂₀An alkoxyalkyl group of: C₁~ C_Fourof
Alkyl group, C₁~ C_FourofAlkoxylGroup or halogen
Represents a benzyl group which may be substituted with benzene. R₈~ R_TenIs
Hydrogen atom; C₁~ C₂₀Alkyl group of C₇~ C
₂₀An alkyl group of: C₁~ C_FiveAlkyl group of_,C₁~
C_FiveAlkoxyl groups, may be substituted with halogen atoms
Phenyl group; C₁~ C _FiveAlkyl group of_,C₁~ C_Fiveof
Alkoxyl group, naphth which may be substituted with halogen atom
Indicates a chill group. However, R₈And R₉Are hydrogen atoms at the same time
There is nothing to do. In addition, R₈And R₉Are connected to each other
Heterocycles can be formed with nitrogen atoms. R₁₁
Is C₁~ C_TenAlkylene or the following formula

[Chemical 5] (Wherein X ₁ to X ₈ are each a hydrogen atom, a C ₁ -C ₄ alkyl group, alkoxy group or a halogen atom C ₁ ~C _4, Z ₁ is directly bonded, -C -, - S-, -SO ₂
- or an alkylene group of C ₁ -C _6. ) Represents a group represented by. ] A pressure-sensitive recording material comprising at least one indole compound represented by the following general formulas [Chemical formula 6] to [Chemical formula 9].

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9] [In the formula, R ₁₂ and R ₁₃ each represent a C _{1 to} C ₅ alkyl group; a C _{2 to} C ₆ alkoxyalkyl group; a C _{5 to} C ₆ cycloalkyl group or a benzyl group. R ₁₄ represents a hydrogen atom; a C ₁ -C ₁₂ alkyl group or a benzyl group. R ₁₅ represents a hydrogen atom; a C ₁ -C ₁₂ alkyl group or a phenyl group. R ₁₆ and R ₁₇ are each a hydrogen atom; C ₁
To C ₅ alkyl group; C _{1 to} C ₅ alkoxyl group or halogen atom. R ₁₈ is a C ₁ -C ₂₀ alkyl group; a C ₂ -C ₂₀ alkoxyalkyl group; a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxyl group or a benzyl group which may be substituted with halogen. Show. R _{19 to} R ₂₁ are each a hydrogen atom; a C _{1 to} C ₂₀ alkyl group; C _{7 to} C
₂₀ aralkyl groups; C _{1 to} C ₅ alkyl groups _, C ₁ to
Shows C ₁ -C ₅ alkyl _group, an alkoxyl group of C ₁ -C _5, a naphthyl group which may be substituted with a halogen atom; alkoxyl groups C _5, a phenyl group optionally substituted by a halogen atom. However, R ₁₉ and R ₂₀ do not represent hydrogen atoms at the same time. R ₁₉ and R ₂₀ can be linked to each other to form a heterocycle with the adjacent nitrogen atom. R ₂₂
Is C ₁ -C ₁₀ alkylene or the following formula

[Chemical 10] (Here, X _{9 to} X ₁₆ each represent a hydrogen atom, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group or a halogen atom, and Z ₂ represents a direct bond, —C—, —S—, -SO ₂
- or an alkylene group of C ₁ -C _6. ) Represents a group represented by. ]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

[Wherein R₁~ R_FourAre each C₁~ C_Five
Alkyl group of C₂~ C₆An alkoxyalkyl group of: C
_Five~ C₆Represents a cycloalkyl group or a benzyl group.
R_Five, R₆Are hydrogen atoms; C₁~ C_FiveThe alkyl
Group; C₁~ C_FiveThe alkoxyl group or halogen atom of
Although not shown, a hydrogen atom is not shown at the same time. In addition, R₁
And R₂, R₃And R_FourAre connected to each other and adjacent nitrogen atom
Together they can form a heterocycle. R₇Is C₁~ C₂₀
Alkyl group of C₂~ C₂₀An alkoxyalkyl group of: C
₁~ C_FourAlkyl group of C₁~ C_FourofAlkoxylBased
Or a benzyl group which may be substituted with halogen. R
₈~ R_TenAre hydrogen atoms; C₁~ C₂₀The alkyl
Group; C₇~ C₂₀An alkyl group of: C₁~ C_FiveThe archi
Ru basis_,C₁~ C_FiveWith the alkoxyl group and halogen atom
A phenyl group which may be replaced; C₁~ C _FiveAlkyl group of_,
C₁~ C_FiveSubstituted with a halogen atom
And optionally a naphthyl group. However, R₈And R₉At the same time
It does not represent a hydrogen atom. In addition, R₈And R₉Are each other
Can form a heterocycle with connecting and adjacent nitrogen atoms
it can. R₁₁Is C₁~ C_TenAlkylene or the following formula
5]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoto Arai 4-3-1, Jokoji Temple, Amagasaki City, Hyogo Prefecture Kanzaki Paper Manufacturing Co., Ltd. Kanzaki Mill

Claims (6)

[Claims] 1. A colorless or light-colored basic dye and a coloring agent.
In the pressure-sensitive recording material using the color reaction of
The dia compound represented by the following general formulas [Chemical formula 1] to [Chemical formula 4]
At least one reel methane compound, and[Chemical 2][Chemical 3][Chemical 4][In the formula, R₁~ R_FourAre each C₁~ C_FiveThe alkyl
Group; C₂~ C₆An alkoxyalkyl group of: C_Five~ C₆of
A cycloalkyl group or a benzyl group is shown. R_Five, R₆
Are hydrogen atoms; C₁~ C_FiveAlkyl group of C₁~
C_FiveThe alkoxyl group or halogen atom of
Sometimes it does not represent a hydrogen atom. In addition, R₁And R₂, R
₃And R_FourAre connected to each other and are heterocyclic with the adjacent nitrogen atom
Can be formed. R₇Is C₁~ C₂₀The alkyl
Group; C₂~ C₂₀An alkoxyalkyl group of: C₁~ C_Fourof
Alkyl group, C₁~ C_FourAn alkoxyalkyl group of
A benzyl group which may be substituted with halogen is shown. R₈~
R_TenAre hydrogen atoms; C₁~ C₂₀Alkyl group of C
₇~ C₂₀An alkyl group of: C₁~ C_FiveAlkyl group of_,
C₁~ C_FiveSubstituted with a halogen atom
Optionally a phenyl group; C ₁~ C_FiveAlkyl group of_,C₁~
C_FiveAlkoxyl groups, may be substituted with halogen atoms
Represents a naphthyl group. However, R₈And R₉Is hydrogen source at the same time
Never show a child. In addition, R₈And R₉Are connected to each other
Can form heterocycles with adjacent nitrogen atoms
It R₁₁Is C₁~ C_TenOf alkylene or the following formula [Chemical Formula 5](X here₁~ X₈Are hydrogen atom and C respectively₁~ C_Fourof
Alkyl group, C₁~ C_FourAlkoxy group or halogen source
Showing the child, Z₁Is a direct bond, -C-, -S-, -SO₂
-Or C₁~ C₆Is an alkylene group. )
Represents a group. ] Represented by the following general formulas [Chemical formula 6] to [Chemical formula 9]
That at least one of the indole compounds
Characteristic pressure-sensitive recording material. [Chemical 6][Chemical 7][Chemical 8][Chemical 9][In the formula, R₁₂, R₁₃Are each C₁~ C_FiveThe alkyl
Group; C₂~ C₆An alkoxyalkyl group of: C_Five~ C₆of
A cycloalkyl group or a benzyl group is shown. R₁₄Is hydrogen
Atom; C₁~ C₁₂Represents an alkyl group or a benzyl group of
You R₁₅Is a hydrogen atom; C₁~ C₁₂Alkyl group or
Represents a phenyl group. R₁₆, R₁₇Are hydrogen atoms; C₁
~ C_FiveAlkyl group of C₁~ C_FiveThe alkoxyl group of
Represents a halogen atom. R₁₈Is C₁~ C₂₀The alkyl
Group; C₂~ C₂₀An alkoxyalkyl group of: C₁~ C_Fourof
Alkyl group, C₁~ C_FourAlkoxyl or halogen
Represents a benzyl group which may be substituted with benzene. R₁₉~ R_{twenty one}Is
Hydrogen atom; C₁~ C₂₀Alkyl group of C₇~ C
₂₀An alkyl group of: C₁~ C_FiveAlkyl group of_,C₁~
C_FiveAlkoxyl groups, may be substituted with halogen atoms
Phenyl group; C₁~ C_FiveAlkyl group of_,C₁~ C_Fiveof
Alkoxyl group, naphth which may be substituted with halogen atom
Indicates a chill group. However, R₁₉And R₂₀Are hydrogen atoms at the same time
There is nothing to do. In addition, R₁₉And R₂₀Are connected to each other
Heterocycles can be formed with nitrogen atoms. R_{twenty two}
Is C₁~ C_TenAlkylene or the following formula:(X here₉~ X₁₆Are hydrogen atom and C respectively₁~ C_Fourof
Alkyl group, C₁~ C_FourAlkoxy group or halogen source
Showing the child, Z₂Is a direct bond, -C-, -S-, -SO₂
-Or C₁~ C₆Is an alkylene group. )
Represents a group. ] 2. A diarylmethane compound is represented by the following general formula:
A compound represented by [Chemical Formula 11] to [Chemical Formula 14].
1. The pressure-sensitive recording material according to 1. [Chemical 11][Chemical 12][Chemical 13][Chemical 14][In the formula, R_{twenty three}~ R₂₆Are each C₁~ C_FiveAlkyl group of
Indicates R₂₇Is C₁~ C ₂Alkyl group of C₁~ C₂of
An alkoxyl group or a halogen atom is shown. R₂₈Is C₁
~ C_FourRepresents an alkyl group or a benzyl group. R₂₉Is water
Elementary atom; C₁~ C ₂The alkyl group or halogen atom of
Show. ] 3. An indole compound is represented by the following general formula:
5] to [Chemical Formula 18], wherein the compound is
The pressure-sensitive recording material described. [Chemical 15][Chemical 16][Chemical 17][Chemical 18][In the formula, R₃₀, R₃₁Are each C₁~ C_FiveAlkyl group of
Indicates R₃₂Is C₁~ C ₈Alkyl group or benzyl
Indicates a group. R₃₃Is C₁~ C_FourAlkyl group or phenyl
Represents a radical. R₃₄Is C₁~ C_FourAlkyl group or benzene
Indicates a zir group. R ₃₅Is a hydrogen atom; C₁~ C₂ The alkyl
Indicates a group or a halogen atom. ] 4. R ₂₃ and R in the formulas [Chemical formula 11] to [Chemical formula 14]
The pressure-sensitive recording material according to claim 2, wherein a diarylmethane compound in which ₂₄ is a C ₄ -C ₅ alkyl group and R ₂₅ and R ₂₆ are methyl groups is used. 5. In the formulas [Chemical Formula 15] to [Chemical Formula 18], R ₃₀ and R
The pressure-sensitive recording material according to claim 3, wherein an indole compound in which ₃₁ is a methyl group is used. 6. The coloring agent is an activated clay material.
The pressure-sensitive recording material described.