JPH08142502A - Pressure-sensitive recording material - Google Patents

Abstract

PURPOSE: To obtain excellent characteristics in the adaptation to OCR having a specific wavelength by using a zinc salt of a salicylic acid derivative as a coupler using at least one kind of a phenoxazine compd. represented by formula I as a basic dye and at least one kind of a phthalide compd. represented by formula II or III in combination. CONSTITUTION: When a phthalide compd. represented by formula II or III is contained in a phenoxazine compd. represented by formula I and a zinc salt of a salicylic acid derivative is used as a coupler, characteristics such as excellent color forming properties or the like are developed and excellent characteristics can be obtained in the adaptation to OCR having a reading wavelength of 650-700nm. In the formula I, R1 -R4 are respectively a 1-6C alkyl group and R5 is a hydrogen atom, a 1-4C alkyl group or a 1-4C alkoxy group and, in the formula II, R6 -R9 are respectively a 1-6C alkyl group and R10 and R11 are respectively a hydrogen atom or a 1-6C alkyl group but not a hydrogen atom at the same time and, in the formula III, R12 and R13 are a 1-8C alkyl group, R14 and R15 are respectively a methyl group or the like, R16 and R17 are respectively a 1-6C alkyl group and R18 is a hydrogen atom or the like.

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 utilizing a color-developing reaction between a colorless or light-colored basic dye and a coloring agent, and more particularly to an optical character reader having a reading wavelength of 650 to 700 nm. The present invention relates to a pressure-sensitive recording material that exhibits excellent properties when applied.

[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 is put into practical use as a copy set by combining upper paper, middle paper, and lower paper in this order. A self-coloring pressure-sensitive recording medium capable of pressure-sensitive recording with one sheet by coating a microcapsule containing a basic dye and a colorant on the same surface of the support is also a form of pressure-sensitive recording medium. Are known.

In recent years, office automation has been advanced along with the development of the information processing industry, and the rationalization of office work has been promoted. As one of the methods, OCR devices and OMR devices having a reading wavelength of 650 to 700 nm have become widespread. Various types of slips such as slips, sales slips, shipping slips, purchase slips, and input / output slips are becoming suitable for OCR and OMR devices.

By the way, in the case of the conventional pressure-sensitive recording material for OCR reading, although the color image has absorption at 650 to 700 nm, there are problems in light resistance, plasticizer resistance, long-term storability, etc. Improvements are strongly desired.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is 65
Excellent characteristics when applied to an optical character reading (OCR) device having a reading wavelength of 0 to 700 nm, that is, high density at the reading wavelength, and excellent light resistance, plasticizer resistance, long-term storage stability, etc. It is to provide a pressure-sensitive recording material that exhibits

[0006]

The present invention provides a pressure-sensitive recording material utilizing a color-forming 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 (1):
And at least one phenoxazine compound represented by
Use in combination with at least one phthalide compound represented by the following general formula (2) or the following general formula (3),
In addition, the pressure-sensitive recording material is characterized by using a zinc salt of a salicylic acid derivative as a coloring agent.

[0007]

[Chemical 4]

(Where R₁~ R_FourAre each C₁~ C₆
The alkyl group of R_FiveIs a hydrogen atom, C ₁~ C_FourThe archi
Group, C₁~ C_FourAlkoxyl group or halogen atom
Is shown. )

[0009]

Embedded image

(In the formula, R _{6 to} R ₉ are C _{1 to} C ₆ respectively.
R ₁₀ and R ₁₁ are each a hydrogen atom, C ₁
To C ₆ alkyl group or C _{1 to} C ₆ alkoxyl group. However, R ₁₀ and R ₁₁ are not hydrogen atoms at the same time. )

[0011]

[Chemical 6]

(In the formula, R ₁₂ and R ₁₃ are C _{1 to} C ₈ respectively.
R ₁₄ and R ₁₅ are each a methyl group, an ethyl group or a phenyl group, and R ₁₆ and R ₁₇ are each a C ₁ to
The C ₆ alkyl group, R ₁₈ represents a hydrogen atom, a C _{1 to} C ₆ alkyl group or a C _{1 to} C ₆ alkoxyl group. )

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the phenoxazine compound represented by the above general formula (1) used in the present invention include, for example, 3,7-bis (diethylamino) -10-benzoylphenoxazine and 3,7. -Bis (diethylamino) -10- (4-methylbenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3-methylbenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2 -Methylbenzoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(4-Ethylbenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-n-propylbenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-methoxybenzoyl) phenoxazine 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2-methoxybenzoyl) phenoxazine, 3,7-bis (diethylamino)- 10
-(4-ethoxybenzoyl) phenoxazine, 3,7
-Bis (diethylamino) -10- (3-ethoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2-ethoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4 -Isopropoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3-isopropoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-n-butoxybenzoyl) phenoxazine , 3,7-bis (diethylamino) -10-
(3-n-butoxybenzoyl) phenoxazine, 3,
7-bis (diethylamino) -10- (3,4-dimethoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3,5-dimethoxybenzoyl) phenoxazine, 3,7-bis (diethylamino)
-10- (2,6-dimethoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3,
4,5-trimethoxybenzoyl) phenoxazine,
3,7-bis (diethylamino) -10- (4-chlorobenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3-chlorobenzoyl) phenoxazine, 3,7-bis (diethylamino) -10 -(2-
Chlorobenzoyl) phenoxazine, 3,7-bis (dimethylamino) -10-benzoylphenoxazine,
3,7-bis (dimethylamino) -10- (4-methylbenzoyl) phenoxazine, 3,7-bis (dimethylamino) -10- (4-methoxybenzoyl) phenoxazine, 3,7-bis (dimethylamino) ) -10- (3
-Methoxybenzoyl) phenoxazine, 3,7-bis (dimethylamino) -10- (2-methoxybenzoyl) phenoxazine, 3,7-bis (dimethylamino)
-10- (4-ethoxybenzoyl) phenoxazine,
3,7-bis (dimethylamino) -10- (3-ethoxybenzoyl) phenoxazine, 3,7-bis (dimethylamino) -10- (4-isopropoxybenzoyl)
Phenoxazine, 3,7-bis (dimethylamino) -1
0- (3-isopropoxybenzoyl) phenoxazine, 3,7-bis (di-n-butylamino) -10-benzoylphenoxazine, 3,7-bis (di-n-butylamino) -10- (4 -Methylbenzoyl) phenoxazine, 3,7-bis (di-n-butylamino) -10
-(4-Methoxybenzoyl) phenoxazine, 3,7
-Bis (di-n-butylamino) -10- (3-methoxybenzoyl) phenoxazine, 3-diethylamino-
7-Dimethylamino-10-benzoylphenoxazine, 3-diethylamino-7-dimethylamino-10-
(4-Methylbenzoyl) phenoxazine, 3-dimethylamino-7-diethylamino-10- (4-methoxybenzoyl) phenoxazine, 3-dimethylamino-7
-Diethylamino-10- (3-methoxybenzoyl)
Phenoxazine, 3,7-bis (N-methyl-Nn-)
Propylamino) -10-benzoylphenoxazine,
3,7-bis (N-methyl-Nn-propylamino)
-10- (4-methylbenzoyl) phenoxazine,
3,7-bis (N-methyl-Nn-propylamino)
-10- (4-methoxybenzoyl) phenoxazine,
3,7-bis (N-methyl-Nn-propylamino)
-10- (3-methoxybenzoyl) phenoxazine,
3,7-bis (N-ethyl-N-isoamylamino)-
10-benzoylphenoxazine, 3,7-bis (N-
Ethyl-N-isoamylamino) -10- (4-methylbenzoyl) phenoxazine, 3,7-bis (N-ethyl-N-isoamylamino) -10- (4-methoxybenzoyl) phenoxazine, 3,7- Examples thereof include bis (N-ethyl-N-isoamylamino) -10- (3-methoxybenzoyl) phenoxazine.

The compound is not limited to these compounds, and any compound included in the general formula (1) can be used, and if necessary, two or more kinds of compounds can be used in combination. You can also

Specific examples of the phthalide compound represented by the above general formula (2) used in the present invention include, for example, 3,3-
Bis (4-dimethylamino-2-methylphenyl) -4
-Azaphthalide, 3,3-bis (4-dimethylamino-
2-Methoxyphenyl) -4-azaphthalide, 3,3-
Bis (4-dimethylamino-2-ethoxyphenyl)-
4-azaphthalide, 3,3-bis (4-diethylamino-2-methylphenyl) -4-azaphthalide, 3,3-
Bis (4-diethylamino-2-ethylphenyl) -4
-Azaphthalide, 3,3-bis (4-diethylamino-
2-isopropylphenyl) -4-azaphthalide, 3,
3-bis (4-diethylamino-2-methoxyphenyl) -4-azaphthalide, 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide,
3,3-bis (4-diethylamino-2-n-butoxyphenyl) -4-azaphthalide, 3,3-bis (4-diethylamino-2-n-hexyloxyphenyl) -4
-Azaphthalide, 3,3-bis (4-di-n-butylamino-2-ethoxyphenyl) -4-azaphthalide,
3,3-bis (4-di-n-pentylamino-2-ethoxyphenyl) -4-azaphthalide, 3,3-bis [4
-(N-ethyl-N-isoamylamino) -2-ethoxyphenyl) -4-azaphthalide, 3,3-bis [4-
(N-ethyl-Nn-hexylamino) -2-ethoxyphenyl) -4-azaphthalide, 3,3-bis [4-
(N-methyl-N-n-propylamino) -2-ethoxyphenyl) -4-azaphthalide, 3-dimethylaminophenyl-3- (4-diethylamino-2-methylphenyl) -4-azaphthalide, 3-dimethylamino Phenyl-3- (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 3-dimethylaminophenyl-3- (4-di-n-butylamino-2-ethoxyphenyl) -4-azaphthalide and the like can be mentioned. .

Among these compounds, 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-
Azaphthalide is particularly preferably used because it exhibits particularly excellent color developability, light resistance, plasticizer resistance, and the like. In addition,
The compound is not limited to these compounds, and any compound included in the general formula (2) can be used, and if necessary, two or more kinds can be used in combination.

Specific examples of the phthalide compound represented by the above general formula (3) used in the present invention include, for example, 3-
[2,2-bis (1-ethyl-2-methylindole-
3-yl) ethenyl] -3- (4-dimethylaminophenyl) phthalide, 3- [2,2-bis (1-ethyl-2)
-Methylindol-3-yl) ethenyl] -3- (4
-Diethylaminophenyl) phthalide, 3- [2,2-
Bis (1-ethyl-2-methylindol-3-yl)
Ethenyl] -3- (4-di-n-propylaminophenyl) phthalide, 3- [2,2-bis (1-ethyl-2-)
Methylindol-3-yl) ethenyl] -3- (4-
Di-n-butylaminophenyl) phthalide, 3- [2,
2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-dimethylamino-2-methylphenyl) phthalide, 3- [2,2-bis (1-ethyl-2-) Methylindol-3-yl) ethenyl] -3
-(4-Dimethylamino-2-methoxyphenyl) phthalide, 3- [2,2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylamino-2-methylphenyl ) Phthalide, 3- [2,2
-Bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylamino-2-methoxyphenyl) phthalide, 3- [2,2-bis (1-ethyl-2-methylindole) -3-yl) ethenyl]-
3- (4-diethylamino-2-ethoxyphenyl) phthalide, 3- [2,2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-di-n
-Butylamino-2-ethoxyphenyl) phthalide, 3
-[2,2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-di-n-pentylamino-2-ethoxyphenyl) phthalide, 3- [2,
2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- [4- (N-methyl-Nn-propylamino) -2-ethoxyphenyl] phthalide, 3
-[2,2-Bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- [4- (N-ethyl-N
-Isoamylamino) -2-ethoxyphenyl] phthalide, 3- [2,2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylamino-2-ethylphenyl) phthalide , 3- [2,2-
Bis (1-ethyl-2-methylindol-3-yl)
Ethenyl] -3- (4-diethylamino-2-n-propylphenyl) phthalide, 3- [2,2-bis (1-ethyl-2-methylindol-3-yl) ethenyl]-
3- (4-diethylamino-2-n-butylphenyl)
Phthalide, 3- [2,2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylamino-2-isopropoxyphenyl) phthalide,
3- [2,2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylamino-2-n-hexyloxyphenyl) phthalide, 3-
[2,2-bis (1,2-dimethylindol-3-yl) ethenyl] -3- (4-dimethylaminophenyl)
Phthalide, 3- [2,2-bis (1,2-dimethylindol-3-yl) ethenyl] -3- (4-diethylaminophenyl) phthalide, 3- [2,2-bis (1,2)
-Dimethylindol-3-yl) ethenyl] -3-
(4-di-n-propylaminophenyl) phthalide, 3
-[2,2-bis (1,2-dimethylindole-3-
Yl) ethenyl] -3- (4-di-n-butylaminophenyl) phthalide, 3- [2,2-bis (1,2-dimethylindol-3-yl) ethenyl] -3- (4-dimethylamino) -2-Methylphenyl) phthalide, 3-
[2,2-bis (1,2-dimethylindol-3-yl) ethenyl] -3- (4-dimethylamino-2-methoxyphenyl) phthalide, 3- [2,2-bis (1,2)
-Dimethylindol-3-yl) ethenyl] -3-
(4-Diethylamino-2-methylphenyl) phthalide, 3- [2,2-bis (1,2-dimethylindol-3-yl) ethenyl] -3- (4-diethylamino-
2-methoxyphenyl) phthalide, 3- [2,2-bis (1,2-dimethylindol-3-yl) ethenyl]
-3- (4-diethylamino-2-ethoxyphenyl)
Phthalide, 3- [2,2-bis (1,2-dimethylindol-3-yl) ethenyl] -3- (4-di-n-butylamino-2-ethoxyphenyl) phthalide, 3-
[2,2-bis (1,2-dimethylindol-3-yl) ethenyl] -3- (4-di-n-pentylamino-
2-ethoxyphenyl) phthalide, 3- [2,2-bis (1,2-dimethylindol-3-yl) ethenyl]
-3- [4- (N-methyl-N-n-propylamino)
2-Ethoxyphenyl] phthalide, 3- [2,2-bis (1,2-dimethylindol-3-yl) ethenyl] -3- [4- (N-ethyl-N-isoamylamino) -2-ethoxy Phenyl] phthalide, 3- [2,2
-Bis (1-n-butyl-2-methylindole-3-
Iyl) ethenyl] -3- (4-dimethylaminophenyl) phthalide, 3- [2,2-bis (1-n-butyl-
2-Methylindol-3-yl) ethenyl] -3-
(4-diethylaminophenyl) phthalide, 3- [2,
2-bis (1-n-butyl-2-methylindole-3
-Yl) ethenyl] -3- (4-di-n-propylaminophenyl) phthalide, 3- [2,2-bis (1-n-
Butyl-2-methylindol-3-yl) ethenyl]
-3- (4-di-n-butylaminophenyl) phthalide, 3- [2,2-bis (1-n-butyl-2-methylindol-3-yl) ethenyl] -3- (4-dimethylamino -2-methylphenyl) phthalide, 3- [2,
2-bis (1-n-butyl-2-methylindole-3
-Yl) ethenyl] -3- (4-dimethylamino-2-
Methoxyphenyl) phthalide, 3- [2,2-bis (1
-N-Butyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylamino-2-methylphenyl) phthalide, 3- [2,2-bis (1-n-butyl-
2-Methylindol-3-yl) ethenyl] -3-
(4-Diethylamino-2-methoxyphenyl) phthalide, 3- [2,2-bis (1-n-butyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylamino-2-ethoxyphenyl ) Phthalide, 3-
[2,2-bis (1-n-butyl-2-methylindol-3-yl) ethenyl] -3- (4-di-n-butylamino-2-ethoxyphenyl) phthalide, 3- [2,
2-bis (1-n-butyl-2-methylindole-3
-Yl) ethenyl] -3- (4-di-n-pentylamino-2-ethoxyphenyl) phthalide, 3- [2,2-
Bis (1-n-butyl-2-methylindol-3-yl) ethenyl] -3- [4- (N-methyl-Nn-propylamino) -2-ethoxyphenyl] phthalide, 3
-[2,2-bis (1-n-butyl-2-methylindol-3-yl) ethenyl] -3- [4- (N-ethyl-N-isoamylamino) -2-ethoxyphenyl] phthalide, 3 -[2,2-bis (1-methyl-2-phenylindol-3-yl) ethenyl] -3- (4-dimethylaminophenyl) phthalide, 3- [2,2-bis (1-methyl-2-) Phenylindol-3-yl) ethenyl] -3- (4-diethylaminophenyl) phthalide, 3- [2,2-bis (1-methyl-2-phenylindol-3-yl) ethenyl] -3- (4- The-n-
Propylaminophenyl) phthalide, 3- [2,2-bis (1-methyl-2-phenylindol-3-yl)
Ethenyl] -3- (4-di-n-butylaminophenyl) phthalide, 3- [2,2-bis (1-methyl-2-)
Phenylindol-3-yl) ethenyl] -3- (4
-Dimethylamino-2-methylphenyl) phthalide, 3
-[2,2-bis (1-methyl-2-phenylindol-3-yl) ethenyl] -3- (4-dimethylamino-2-methoxyphenyl) phthalide, 3- [2,2-bis (1- Methyl-2-phenylindol-3-yl)
Ethenyl] -3- (4-diethylamino-2-methylphenyl) phthalide, 3- [2,2-bis (1-methyl-
2-Phenylindol-3-yl) ethenyl] -3-
(4-Diethylamino-2-methoxyphenyl) phthalide, 3- [2,2-bis (1-methyl-2-phenylindol-3-yl) ethenyl] -3- (4-diethylamino-2-ethoxyphenyl) phthalide , 3- [2,
2-bis (1-methyl-2-phenylindole-3-
Iyl) ethenyl] -3- (4-di-n-butylamino-
2-Ethoxyphenyl) phthalide, 3- [2,2-bis (1-methyl-2-ferindol-3-yl) ethenyl] -3- (4-di-n-pentylamino-2-ethoxyphenyl) phthalide , 3- [2,2-bis (1-methyl-2-phenylindol-3-yl) ethenyl]
-3- [4- (N-methyl-N-n-propylamino)
2-Ethoxyphenyl] phthalide, 3- [2,2-bis (1-methyl-2-phenylindol-3-yl)
Ethenyl] -3- [4- (N-ethyl-N-isoamylamino) -2-ethoxyphenyl] phthalide, 3-
[2,2-bis (1-n-octyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylaminophenyl) phthalide, 3- [2,2-bis (1-n-
Octyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylamino-2-methylphenyl) phthalide, 3- [2,2-bis (1-n-octyl-2-methylindole-3-) (Il) ethenyl] -3-
(4-Diethylamino-2-ethoxyphenyl) phthalide, 3- [2,2-bis (1,2-diethylindol-3-yl) ethenyl] -3- (4-diethylaminophenyl) phthalide, 3- [2 2-bis (1,2-diethylindol-3-yl) ethenyl] -3- (4-diethylamino-2-methylphenyl) phthalide, 3-
[2,2-bis (1,2-diethylindol-3-yl) ethenyl] -3- (4-diethylamino-2-ethoxyphenyl) phthalide and the like can be mentioned.

Among these compounds, 3- [2,2
-Bis (1-n-butyl-2-methylindole-3-
Il) ethenyl] -3- (4-diethylaminophenyl) phthalide is particularly preferably used because it exhibits particularly excellent color developability, light resistance, plasticizer resistance, and the like. In addition,
The compound is not limited to these compounds, and any compound included in the general formula (3) can be used, and if necessary, two or more types can be used in combination.

In the present invention, the phenoxazine compound represented by the general formula (1) is used in an amount of 10 to 10 based on all dyes.
30% by weight is preferred. OCR if less than 10% by weight
There is a problem in readability, light resistance, plasticizer resistance, etc. If more than 30% by weight is used, the color of the capsule coated surface will become darker with time, causing problems such as long-term storage stability. Is.

The use ratio of the phenoxazine compound represented by the general formula (1) and at least one phthalide compound represented by the general formula (2) or (3) is not particularly limited. Is usually 1 by weight
It is preferably used in a ratio of 0:90 to 50:50.

In the present invention, known basic dyes within a range that does not impair the desired effects of the present invention, for example, triarylmethane compounds, diarylmethane compounds, fluorane compounds, phenothiazine compounds, rhodamine lactam compounds. It is also possible to use a spiropyran-based compound, a leuco auramine-based compound or the like together.

The basic dye used in the present invention is mixed with various known ultraviolet absorbers such as benzotriazole derivative, benzophenone derivative, cyanoacrylate derivative, salicylic acid derivative, cinnamic acid derivative, etc., if necessary, and then cottonseed oil, hydrogenated Terphenyl, hydrogenated terphenyl derivative,
Dissolved in a natural or synthetic hydrophobic medium such as dibasic acid ester such as alkylbiphenyl, alkylnaphthalene, diarylalkane, paraffin, naphthene oil, and phthalic acid ester, coacervation method, interfacial polymerization method, in-
It is encapsulated in microcapsules by a capsule manufacturing method such as an in situ polymerization method. The membrane material of the microcapsule is not particularly limited, but it does not generate color stains due to involuntary pressure or rubbing, and thus is made of a synthetic polymer such as aminoaldehyde resin, polyurea resin, polyurethane resin, or polyamide resin. Membrane materials are preferably used.

Aminoaldehyde resin wall membrane capsules include 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 are made of polyisocyanate and water, polyisocyanate and polyol, isothiocyanate and water, isothiocyanate and polyol, polyisocyanate and polyamine, isothiocyanate and polyamine, etc. 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 thus prepared containing the specific basic dye are used in the conventional manner, as well as adhesives such as polyvinyl alcohols, starches, carboxymethyl cellulose, and latexes, as well as stilts such as pulp powders and raw starch powders. Various auxiliaries such as agents are appropriately mixed and used as a capsule coating liquid for the production of upper paper, middle paper, self-coloring type pressure sensitive recording paper and the like.

In the present invention, a zinc salt of a salicylic acid derivative is selectively used as a color developing agent. By the way, when an inorganic compound such as activated clay or an acidic organic polymer such as p-phenylphenol novolac resin is used as a coloring agent, the color developability is low, and the image storability is particularly long-term light resistance and plastic resistance. There are problems that the formulation is inferior and the obtained pressure-sensitive recording material itself tends to yellow with time.

Specific examples of the salicylic acid derivative include, for example, 3-methyl-5- (α-methylbenzyl) salicylic acid, 3-methyl-5- (α, α-dimethylbenzyl) salicylic acid, and 3,5-di-tert. -Butylsalicylic acid, 3,5-di-tert-butyl-6-methylsalicylic acid, 3,5-di-tert-butyl-6-phenylsalicylic acid, 3,5-di-tert-amylsalicylic acid, 3,5-di -Cyclohexyl salicylic acid, 3-cyclohexyl-5
-(Α-methylbenzyl) salicylic acid, 3-dodecylsalicylic acid, 3-methyl-5-dodecylsalicylic acid, 3-
Dodecyl-6-methylsalicylic acid, 3-phenyl-5-
(Α-Methylbenzyl) salicylic acid, 3-phenyl-5
-(Α, α-Dimethylbenzyl) salicylic acid, 3- (α
-Methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5-methylsalicylic acid, 3- (α-methylbenzyl) -5-phenylsalicylic acid, 3- (α, 4-dimethylbenzyl) -5-methylsalicylic acid, 3- (α, α
-Dimethylbenzyl) -5-methylsalicylic acid, 3-
(Α, α-Dimethylbenzyl) -6-methylsalicylic acid, 3,5-di (α, α-dimethylbenzyl) salicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3
-(Α-Methylbenzyl) -5- (α, α-dimethylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5
-Bromo salicylic acid, 3- (α-methylbenzyl) -4
-Methylsalicylic acid, 3- (α-methylbenzyl) -6
-Methylsalicylic acid, 3-nonylsalicylic acid, 3,5-
Dinonylsalicylic acid, 3-nonyl-5-methylsalicylic acid, 3-nonyl-6-methylsalicylic acid, 3-nonyl-
Examples thereof include 5-phenylsalicylic acid, 3-methyl-5-nonylsalicylic acid, 5- (4-mesitylmethylbenzyl) salicylic acid, carboxylated terpene phenol resin, and benzylated styrenated salicylic acid. If necessary, two or more kinds may be used in combination.

Among these salicylic acid derivative zinc salts, the zinc salt of 3,5-di (α-methylbenzyl) salicylic acid, the zinc salt of carboxylated terpene phenol resin or the zinc salt of benzylated styrenated salicylic acid is excellent. The zinc salt of 3,5-di (α-methylbenzyl) salicylic acid is particularly preferable because it exhibits excellent performance and is particularly excellent in color developability and image storability.

The coloring agent coating liquid is usually prepared by a method in which a zinc salt of a salicylic acid derivative is dispersed 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, 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 an appropriate 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 or the like so that it will be about g / m ² .

[0031]

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] 20 parts of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid, 80 parts of kaolin, 1 part of magnesium oxide, carboxy-modified styrene-butadiene copolymer 20 parts (solid content) of latex and 1 part of sodium carboxymethyl cellulose were added to prepare a coloring agent coating liquid. [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 added to 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4- as a basic dye.
8 parts of azaphthalide and 3,7-bis (diethylamino)-
2 parts of 10- (4-methylbenzoyl) phenoxazine,
As a UV absorber, 2 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole are dissolved, and polymethylene polyphenyl isocyanate (trade name: Millionate MR400, manufactured by Nippon Polyurethane Industry Co., Ltd.) 5
Part and a trimer of hexamethylene diisocyanate having a burette bond (trade name: N-3200, manufactured by Sumitomo Bayer Co., Ltd.) as a capsule core substance in a solution obtained by dissolving 2 parts thereof in the above aqueous medium for capsule preparation, The emulsion was emulsified for 1 minute at 10000 rpm using a TK homomixer. To this emulsified dispersion liquid, 1 part of diethylenetriamine was added, and the mixture was stirred at room temperature for 30 minutes, then the temperature of the system was raised to 70 ° C. and reacted for 3 hours while continuing stirring, then the temperature was lowered to room temperature and the average particle size was increased. Of 5.5 μm of 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 microcapsule coating solution is applied to the opposite side of the lower sheet from the surface coated with the coloring agent by an air knife coater to a dry weight of 3.5 g / m ² and dried. To obtain a pressure sensitive recording medium paper.

Examples 2 to 16 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, 15 kinds of pressure-sensitive recording medium paper were obtained. -Example 2: 3- [2,2-bis (1-ethyl-2-
Methylindol-3-yl) ethenyl] -3- (4-
8 parts of diethylaminophenyl) phthalide and 3,7-bis (diethylamino) -10- (4-methylbenzoyl)
Phenoxazine 2 parts-Example 3: 3- [2,2-bis (1-n-butyl-
2-Methylindol-3-yl) ethenyl] -3-
8 parts of (4-diethylaminophenyl) phthalide and 3,7
-Bis (diethylamino) -10- (4-methylbenzoyl) phenoxazine 2 parts-Example 4: 3- [2,2-bis (1-ethyl-2-)
Methylindol-3-yl) ethenyl] -3- (4-
8 parts of diethylaminophenyl) phthalide and 3,7-bis (dimethylamino) -10- (4-methylbenzoyl)
Phenoxazine 2 parts-Example 5: 3- [2,2-bis (1-ethyl-2-)
Methylindol-3-yl) ethenyl] -3- (4-
Diethylaminophenyl) phthalide 8 parts and 3,7-bis (diethylamino) -10-benzoylphenoxazine 2 parts Example 6: 3- [2,2-bis (1-ethyl-2-)
Methylindol-3-yl) ethenyl] -3- (4-
Diethylaminophenyl) phthalide 8 parts and 3,7-bis (diethylamino) -10- (4-methoxybenzoyl) phenoxazine 2 parts Example 7: 3,3-bis (4-diethylamino-2)
-Ethoxyphenyl) -4-azaphthalide 8 parts and 3,7
-Bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine 2 parts-Example 8: 3- [2,2-bis (1-ethyl-2-)
Methylindol-3-yl) ethenyl] -3- (4-
Diethylaminophenyl) phthalide 8 parts and 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine 2 parts Example 9: 3,3-bis (4-diethylamino-2)
-Ethoxyphenyl) -4-azaphthalide 4 parts and 3-
[2,2-bis (1-ethyl-2-methylindole-
3-yl) ethenyl] -3- (4-diethylaminophenyl) phthalide 4 parts and 3,7-bis (diethylamino)
-10- (4-Methylbenzoyl) phenoxazine 2 parts-Example 10: 3,3-bis (4-diethylamino-)
2-ethoxyphenyl) -4-azaphthalide 4 parts and 3-
[2,2-bis (1-ethyl-2-methylindole-
3-yl) ethenyl] -3- (4-diethylaminophenyl) phthalide 4 parts and 3,7-bis (diethylamino)
-10- (3-Methoxybenzoyl) phenoxazine 2
Parts-Example 11: 3,3-bis (4-diethylamino-2)
-Ethoxyphenyl) -4-azaphthalide 4 parts and 3-
[2,2-bis (1-n-butyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylaminophenyl) phthalide 4 parts and 3,7-bis (diethylamino) -10- (4 -Methylbenzoyl) phenoxazine 2 parts Example 12: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 4 parts and 3,3-bis (4-diethylamino-2-ethoxyphenyl). -4
-4 parts of azaphthalide and 3,7-bis (diethylamino)
-10- (4-Methylbenzoyl) phenoxazine 2 parts Example 13: 3- (1-n-octyl-2-methylindolyl-3-yl) -3- (4-diethylamino-2)
-Ethoxyphenyl) -4-azaphthalide 4 parts and 3,3
-Bis (4-diethylamino-2-ethoxyphenyl)
-4-Azaphthalide 4 parts and 3,7-bis (diethylamino) -10- (4-methylbenzoyl) phenoxazine 2 parts Example 14: 3- (1-n-octyl-2-methylindolyl-3- Yl) -3- (4-diethylamino-2)
-Ethoxyphenyl) -4-azaphthalide 4 parts and 3,3
-Bis (4-diethylamino-2-ethoxyphenyl)
-4-azaphthalide 4 parts and 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine 2 parts Example 15: 3-diethylamino-6-methyl-7-
6 parts of anilinofluorane and 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide 2
Parts and 3,7-bis (diethylamino) -10- (4-methylbenzoyl) phenoxazine 2 parts. Example 16: 3-Diethylamino-6-methyl-7-
6 parts of anilinofluorane and 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide 2
Parts and 2 parts of 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine

Examples 17 to 18 In the preparation of the coloring agent coating liquid of Example 1, 3,5-di (α-
Two kinds of pressure-sensitive recording intermediate papers were obtained in the same manner as in Example 1 except that the following compound was used in place of the methylbenzyl) salicylic acid zinc salt. Example 17: Zinc salt of carboxylated terpene phenolic resin Example 18: Zinc salt of benzylated styrenated salicylic acid

Example 19 A pressure-sensitive recording medium paper 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.) and 8 parts of 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide as a basic dye and 3,7- An internal phase oil was obtained by dissolving 2 parts of bis (diethylamino) -10- (4-methylbenzoyl) phenoxazine and 2 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole as an ultraviolet absorber. .

Then, this internal phase oil was charged into the above-mentioned aqueous medium for capsule production, and was emulsified and dispersed for 1 minute at 10000 rpm with a TK homomixer, and then heated to 55 ° C. Separately, 15 parts of melamine was added to 45 parts of 37% aqueous formaldehyde solution 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 the mixture was further stirred before adding 0.1N-
After adjusting the pH to 5.3 with hydrochloric acid, the temperature was raised to 80 ° C. and kept at that temperature for 1 hour, the pH was lowered to 3.5 with 0.2N-hydrochloric acid, the temperature was kept for 3 hours, and then allowed to cool. Average particle size 5.3
Microcapsules consisting of a μm aminoaldehyde resin film were prepared.

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

Comparative Example 2 3,5-di (α-in the preparation of the coloring agent coating liquid of Example 1
A pressure-sensitive recording midleaf paper was obtained in the same manner as in Example 1 except that p-phenylphenol novolac resin was used in place of methylbenzyl) salicylic acid zinc salt.

Comparative Examples 3 to 5 Three kinds of pressure-sensitive recording medium paper were obtained in the same manner as in Example 1 except that the following compounds were used as dyes in the preparation of the microcapsule dispersion of Example 1. . Comparative Example 3: 3,3-bis (4-diethylamino-2-)
Ethoxyphenyl) -4-azaphthalide 10 parts Comparative Example 4: 3- [2,2-bis (1-ethyl-2-methylindol-3-yl) ethenyl] -3- (4-diethylaminophenyl) phthalide 10 parts Comparative Example 5: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 8 parts and 3,7-bis (diethylamino) -10- (4-methylbenzoyl)
2 parts phenoxazine

Using the thus obtained 24 kinds of pressure-sensitive recording medium paper, various performance comparison tests were conducted, and the results are shown in Table 1. [PCS Value] The PCS value is an index indicating the degree of OCR readability. The PCS value represents the relative density difference between the color print and the paper and is calculated by the following equation.

PCS = (Rw-Rp) / Rw Here, Rw represents the reflectance of the blank portion and Rp represents the reflectance of the printed portion. Therefore, the higher the PCS value, the clearer the identification of characters and the higher the readability. Generally, a PCS value of 0.70 or more is required.

[Measurement of PCS value at 670 nm] The prepared pressure-sensitive recording medium paper was overlaid so that the capsule-coated surface and the color-developing agent-coated surface faced each other, and printed with a dot printer. Immediately thereafter and 1 hour later, The blank part and the printing part are each set with a spectrophotometer (U-3300 made by Hitachi) 67
The reflectance at 0 nm was measured, and the PCS value was calculated from the measured value. [Lightfastness test] Colored surface of printing obtained above (coloring agent coated surface)
After being exposed to direct sunlight for 24 hours, the PCS value was similarly calculated and shown in Table 1. [Plasticizer resistance test] A vinyl chloride film was overlaid on the print color-developing surface (coloring agent-coated surface) obtained above and left at room temperature for 24 hours, and then the PCS value was similarly calculated and shown in Table 1.

[0046]

[Table 1]

[0047]

As is apparent from the results of Table 1, the pressure-sensitive recording material of the present invention exhibits excellent characteristics for an optical character reading (OCR) device having a reading wavelength of 670 nm. It was a body.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoko Kondo 4-3-1, Jokoji, Amakosaki City, Hyogo Prefecture Shin-Oji Paper Co., Ltd. Kanzaki Mill

Claims (2)

[Claims] 1. A colorless or light-colored basic dye and a coloring agent.
In a pressure-sensitive recording material using the color reaction of
As phenoxazine represented by the following general formula (1)
At least one compound and the following general formula (2) or
At least one of the phthalide compounds represented by the general formula (3)
Salicylic acid used in combination with seeds and as a coloring agent
A pressure-sensitive recording material comprising a zinc salt of a derivative. [Chemical 1](In the formula, R₁~ R_FourAre each C₁~ C₆Alkyl group of
To R_FiveIs a hydrogen atom, C ₁~ C_FourAlkyl group of C₁~
C_FourRepresents an alkoxyl group or a halogen atom. ) [Chemical 2](In the formula, R₆~ R₉Are each C₁~ C₆Alkyl group of
To R_Ten, R₁₁Are hydrogen atom and C respectively₁~ C₆Al
Kill group or C₁~ C₆Represents an alkoxyl group of. However
Then R_TenAnd R₁₁Are not hydrogen atoms at the same time. ) [Chemical 3](In the formula, R₁₂, R₁₃Are each C₁~ C₈Alkyl group of
To R₁₄, R_FifteenAre respectively methyl, ethyl or
Phenyl group, R₁₆, R₁₇Are each C₁~ C₆The archi
R group, R₁₈Is a hydrogen atom, C₁~ C₆The alkyl group of
Is C₁~ C₆Represents an alkoxyl group of. ) 2. The coloring agent is at least one of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid, zinc salt of carboxylated terpene phenol resin and zinc salt of benzylated styrenated salicylate. 1. The pressure-sensitive recording material according to 1.