JPH0796657A - Pressure-sensitive recording material - Google Patents

Abstract

PURPOSE:To enhance water resistance and plasticizer resistance, in a pressure- sensitive recording material utilizing the color forming reaction of a basic dye and a coupler, by jointly using a specific diarylmethane compd. and a specific phthalide compd. as the basic dye and using an active clay substance as the coupler. CONSTITUTION:One kind of a diarylmethane compd. represented by formula I (wherein R1-R4 are a 1-5C alkyl group and R5 and R6 are a hydrogen atom or a 1-5C alkyl group but are not a hydrogen atom at the same time and one kind of a phthalide compd. represented by formula II (wherein R12 is a halogen atom, R13 is a hydrogen atom or a 1-4C alkyl group, R12-R13 are a hydrogen atom or a 1-6C alkyl group, X and Y are a hydrogen atom or a 1-4C alkyl group and n is 0 or an integer of 1-4) are jointly used as a basic dye and an active clay substance is used as a coupler. By this constitution, a pressure- sensitive recording material capable of keeping sufficient reading aptitude even under a severe condition exposed to light, water or a plasticizer 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 exhibiting excellent suitability for an optical character reader (OCR) having a reading wavelength in the wavelength range of 600 to 800 nm. It is a thing.

[0002]

2. Description of the Related Art Pressure-sensitive recording materials (carbonless paper) are composed of colorless or light basic dyes such as crystal violet lactone and benzoyl leuco methylene blue (hereinafter referred to as basic dyes), activated clay, bentonite, phenolic resin and aroma. A recording material utilizing a color-forming reaction with a coloring agent such as a polyvalent metal salt of an aromatic carboxylic acid, and containing a basic dye prepared by a method such as a coacervation method, an interfacial polymerization method or an in-situ method. Overlay the top paper with the capsules applied to the back side of the base paper and the bottom paper with the coloring agent applied to the front side of the base paper so that the application surfaces face each other, and write the top surface of the top paper with a writing or typewriter. It is a recording body that is subjected to pressure printing to form a color image on a lower sheet.

When it is desired to copy a large number of sheets, the number of sheets of the middle paper coated with a coloring agent on the front surface of the base paper and microcapsules on the back surface is required between the upper paper and the lower paper. Just inserted. In addition, a microcapsule and a coloring agent,
A self-coloring paper formed on the same surface of a base paper as a laminated or mixed layer is also well known as one form of the pressure sensitive recording material. The demand for such pressure-sensitive recording materials has expanded remarkably over a wide range, mainly for general slips, contract documents, computer papers, etc., with the expansion of their applications.

On the other hand, office automation is advancing along with the development of the information processing industry, and the rationalization of office work is promoted. And as a rationalization method, 600-8
Optical character reader (OCR) and optical mark reader (OM) with reading wavelength in the near infrared region of 00 nm
R) has become widespread, and general companies need to use main orders such as order receiving slips, sales slips, shipping slips, purchasing slips, and input / output slips as slips suitable for OCR and OMR.

From such a background, there is an increasing demand for development of an OCR voucher using a pressure-sensitive recording material. However, for a general pressure-sensitive recording material, P in the near infrared region of 600 to 800 nm is used.
Since the CS value is 0.4 or less, there is a problem that reading becomes uncertain. The PCS value is an index indicating the degree of OCR readability, and indicates the degree of relative darkness between the color printing and the paper, and is represented by the following equation. PCS = (Rw-Rp) / Rw Here, Rw represents the reflectance of the white paper portion of the paper at the target wavelength, and Rp represents the reflectance of the printed portion. The higher the PCS value, the clearer the character identification becomes. Although the suitability becomes high, the read suitability becomes good when the PCS value is 0.6 or more in a general apparatus.

By the way, such a recording medium of 600-8 is used.
For the purpose of imparting OCR readability at 00 nm, JP-A-4-195047 and JP-A-4-212
No. 882, JP-A-4-251785 and the like propose a method using a basic dye having a color image of absorption at 600 to 800 nm. However, although using these basic dyes only has an initial OCR readability, the color image fades under the influence of, for example, water or a plasticizer, and as a result, OCR reading becomes impossible. There is.

[0007]

In view of the present situation, the present inventors have found that the OC in the wavelength region of 600 to 800 nm is used.
R A pressure-sensitive recording material excellent in readability, that is, a color image excellent in water resistance and plasticizer resistance as well as light resistance is obtained.
We have conducted intensive research to develop a pressure-sensitive recording medium that can maintain sufficient readability even when exposed to harsh conditions such as light, water, and a plasticizer. As a result, it was found that by using a specific diarylmethane compound and a specific phthalide compound together as a basic dye, and using an activated clay substance as a colorant, the desired pressure-sensitive recording material can be obtained. The invention was completed.

[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 of the diarylmethane compounds represented by [Chemical Formula 4] and at least one of the phthalide compounds represented by the following general formula [Chemical Formula 6], and using an active clay substance as a colorant It is a characteristic pressure-sensitive recording material.

[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~ C₆Or a benzyl group.
R_Five, R₆Are hydrogen atoms; C₁~ C_FiveThe alkyl
Group; C₁~ C_FiveAn alkoxyl group of; or a halogen atom
Although not shown, a hydrogen atom is not shown at the same time. R₇Is C₁
~ C₂₀Alkyl group of C₂~ C₂₀Alkoxyalkyl
Group; or C₁~ C_FourAlkyl group of C₁~ C_FourArco
Benzyl optionally substituted with a xyl group or a halogen atom
Represents a radical. R₈~ R_TenAre each a hydrogen atom; or C₁
~ C_FiveAlkyl group of C₁~ C_FiveThe alkoxyl group of
Represents a phenyl group which may be substituted with a halogen atom
But R₈And R₉Do not represent a hydrogen atom at the same time. R
₁₁Is C₁~ C ₁₂Or an alkylene group of
Show.

[0014]

[Chemical 5]

Here, X _{1 to} X ₈ are each a hydrogen atom; C
Alkoxyl groups C ₁ ~C _{4; 1} ~C ₄ alkyl group;
Or a halogen atom, Z is a direct bond; -O-; -S
-; - SO ₂ -; indicating or alkylene group of C ₁ -C _6. ]

[0016]

[Chemical 6]

[Wherein R ₁₂ is a halogen atom; C _{1 to} C ₄
An alkyl group; a C ₁ -C ₄ alkoxyl group; a nitro group; an amino group; a substituted amino group; or an alicyclic amino group, and R ₁₃ represents a hydrogen atom; or a C ₁ -C ₄ alkyl group. R _{14 to} R ₁₇ are each a hydrogen atom; C _{1 to} C ₆
An alkoxyalkyl group of C ₂ -C _6;; alkyl C
_{6 to} C ₁₀ aryl group; C _{7 to} C ₁₀ aralkyl group; or C _{5 to} C ₈ cycloalkyl group, wherein R ₁₄ and R ₁₅
And R ₁₆ and R ₁₇ can also form a heterocycle with the adjacent nitrogen atom. X and Y each represent a hydrogen atom; a C ₁ -C ₄ alkyl group; a C ₁ -C ₄ alkoxyl group; or a halogen atom. n represents 0 or an integer of 1 to 4. ]

[0018]

The above-mentioned general formulas [Chemical formula 1] to [Chemical formula 2] used in the present invention
Specific examples of the diarylmethane compound represented by
For example: (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl)
-Methyl-ether, (4-di-n-butylamino-2)
-Methyl-4'-dimethylaminobenzhydryl) -ethyl-ether, (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -n-propyl-ether, (4- Di-n-butylamino-2-
Methyl-4'-dimethylaminobenzhydryl) -isobutyl-ether, (4-di-n-butylamino-2-
Methyl-4'-dimethylaminobenzhydryl) -benzyl-ether, (4-di-n-butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -methyl-ether, (4-di-n -Butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -n-octyl-ether, (4-di-n-butylamino-2-
Ethoxy-4'-dimethylaminobenzhydryl) -n
-Dodecyl-ether, (4-di-n-butylamino-
2-ethoxy-4'-dimethylaminobenzhydryl)
-Methoxypropyl-ether, (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -ethoxypropyl-ether, (4-di-n-
Butylamino-2-methyl-4'-dimethylaminobenzhydryl) -4-methylbenzyl-ether, (4-
Di-n-butylamino-2-ethyl-4'-dimethylaminobenzhydryl) -4-methylbenzyl-ether, (4-di-n-butylamino-3-methyl-4'-
Dimethylaminobenzhydryl) -methyl-ether,
(4-di-n-butylamino-3-ethyl-4′-dimethylaminobenzhydryl) -n-propyl-ether, (4-di-n-butylamino-2-methoxy-4 ′)
-Dimethylaminobenzhydryl) -methyl-ether, (4-di-n-butylamino-2-methoxy-4 '
-Dimethylaminobenzhydryl) -benzyl-ether, (4-dimethylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl-ether, (4-
Dimethylamino-2-methoxy-4'-dimethylaminobenzhydryl) -methyl-ether, (4-dimethylamino-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-di-n-butylamino-2-isobutoxy-4'-dimethylaminobenzhydryl) -methyl-ether, (4-di-n-butyl) Amino-2-chloro-
4'-Dimethylaminobenzhydryl) -ethyl-ether, (4-di-n-butylamino-2-methyl-4 '
-Diethylaminobenzhydryl) -methyl-ether, (4-di-n-butylamino-2-methoxy-4 '
-Diethylaminobenzhydryl) -methyl-ether, (4-di-n-butylamino-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'-dimethylaminobenzhydryl] -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'-di-n-butylaminobenzhydryl) -methyl-ether, (4-dibenzylamino-2-methyl) -4'-Dimethylaminobenzhydryl)
-Methyl-ether, [4,4'-bis (diethylamino) -2,2'-dimethylbenzhydryl] -methyl-
Ether, (4-di-n-amylamino-2-methyl-
4'-Dimethylaminobenzhydryl) -methyl-ether, (4-di-n-amylamino-2-methyl-4 '
-Dimethylaminobenzhydryl) -benzyl-ether, bis (4-di-n-butylamino-2-methyl-
4'-dimethylaminobenzhydryl) -ether, bis (4-di-n-butylamino-2-methoxy-4'-
Dimethylaminobenzhydryl) -ether, bis (4
-Dimethylamino-2-methyl-4'-dimethylaminobenzhydryl) -ether, bis [4,4'-bis (di-n-butylamino) -2,2'-dimethylbenzhydryl) -ether, Bis [4,4'-bis (diethylamino) -2,2'-dimethylbenzhydryl) -ether and the like.

Specific examples of the diarylmethane compounds represented by the above general formulas [Chemical Formula 3] to [Chemical Formula 4] include the following. N- (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl)
-O-toluidine, N- (4-di-n-butylamino-)
2-Methyl-4'-dimethylaminobenzhydryl)-
o-phenetidine, N- (4-di-n-butylamino-
2-Methyl-4'-dimethylaminobenzhydryl)-
o-anisidine, N- (4-di-n-butylamino-2)
-Methyl-4'-dimethylaminobenzhydryl) -2
-Chloroaniline, N- (4-di-n-butylamino-)
2-Methyl-4'-dimethylaminobenzhydryl)-
2-ethylaniline, N- (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl)
-Aniline, N- (4-di-n-butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -o-
Toluidine, N- (4-di-n-butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -2-
Chloroaniline, N- (4-di-n-butylamino-2)
-Methoxy-4'-dimethylaminobenzhydryl)-
o-toluidine, N- (4-di-n-butylamino-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-di-n-amylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine, N-
[4,4'-bis (di-n-butylamino) -2,2 '
-Dimethylbenzhydryl] -o-toluidine, N-
[4,4'-bis (di-n-butylamino) -2,2 '
-Dimethoxybenzhydryl] -o-toluidine, 4,
4'-bis [(4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane, 3,3'-dichloro-4,4'-bis [(4-di -N-Butylamino-2-methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane, 3,3'-dimethyl-4,4'-bis [(4-di-
n-Butylamino-2-methyl-4′-dimethylaminobenzhydryl) amino] diphenylmethane, 3,3 ′
-Dimethoxy-4,4'-bis [(4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane, 2,2'-dichloro-4,4'-bis [(4-di-n-butylamino-2-
Methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane, 3,3'-dichloro-4,4 '
-Bis {[4,4'-bis (di-n-butylamino)-
2,2'-dimethoxybenzhydryl] amino} diphenylmethane and the like.

The compounds are not limited to the above specific examples, and any compounds 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 7] to [Chemical formula 10] are particularly excellent OCR when combined with the phthalide compound represented by [Chemical formula 6]. It is preferably used because it exhibits readability, and the raw materials are easily available and easy to synthesize.

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[Wherein R₁₈~ R_{twenty one}Are each C₁~ C_Five
Represents an alkyl group of R,_{twenty two}Is C₁~ C ₂An alkyl group of
C₁~ C₂An alkoxyl group of; or a halogen atom
You R_{twenty three}Is C₁~ C_FourAlkyl group; or benzyl group
Show. R_{twenty four}And R_{twenty five}Are hydrogen atoms; C₁~ C₂of
Alkyl group; C₁~ C_FourAlkoxyl group; or halogen
Represents a hydrogen atom. ]

Further, among the compounds represented by the general formulas [Chemical formula 7] to [Chemical formula 10], R ₁₈ and R ₁₉ are each a C _{4 to} C ₅ alkyl group, and R ₂₀ and R ₂₁ are each a chemical compound. The compound which is a methyl group has the best OCR readability when combined with a specific phthalide compound,
In addition, since it exhibits extremely excellent characteristics in terms of desensitization suitability, it is particularly preferably used.

On the other hand, specific examples of the phthalide compound represented by the general formula [Chemical Formula 6] used in the present invention include the following. 3- [2,2-bis (4-dimethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide, 3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl]- 6-Dimethylaminophthalide, 3- [2,2-bis (4-dimethylaminophenyl) ethylene-1-yl] -6-diethylaminophthalide, 3- [2,2-bis (4-diethylaminophenyl) ethylene -1-yl] -6-diethylaminophthalide, 3- [2- (4-dimethylaminophenyl) -2- (4-diethylaminophenyl) ethylene-
1-yl] -6-dimethylaminophthalide, 3- [2-
(4-Dimethylaminophenyl) -2- (4-diethylaminophenyl) ethylene-1-yl] -6-diethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-N-isoamyl) amino Phenyl] ethylene-1-
Il} -6-dimethylaminophthalide, 3- {2,2-
Bis [4- (N-ethyl-N-isoamyl) aminophenyl] ethylene-1-yl} -6-diethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-N-cyclohexyl) amino] Phenyl] ethylene-1-yl}
-6-Dimethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-N-cyclohexyl) aminophenyl] ethylene-1-yl} -6-diethylaminophthalide, 3- {2,2 -Bis [4- (N-ethyl-p-toluidino) phenyl] ethylene-1-yl} -6-dimethylaminophthalide, 3- {2,2-bis [4- (N-
Ethyl-p-toluidino) phenyl] ethylene-1-yl} -6-diethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-N-isobutyl) aminophenyl] ethylene-1-yl} -6-Dimethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-N-isobutyl) aminophenyl] ethylene-1-yl} -6-
Diethylaminophthalide, 3- {2,2-bis [4-
(N-Ethyl-N-n-propyl) aminophenyl] ethylene-1-yl} -6-dimethylaminophthalide, 3
-{2,2-bis [4- (N-ethyl-N-n-propyl) aminophenyl] ethylene-1-yl} -6-diethylaminophthalide, 3- [2,2-bis (4-di-) n
-Butylaminophenyl) ethylene-1-yl] -6-
Dimethylaminophthalide, 3- [2,2-bis (4-di-n-butylaminophenyl) ethylene-1-yl}-
6-diethylaminophthalide, 3- {2,2-bis [4
-(N-ethyl-N-n-hexyl) aminophenyl]
Ethylene-1-yl} -6-dimethylaminophthalide,
3- {2,2-bis [4- (N-ethyl-Nn-hexyl) aminophenyl] ethylene-1-yl} -6-diethylaminophthalide, 3- {2,2-bis [4- ( N
-Ethyl-N-ethoxypropyl) aminophenyl] ethylene-1-yl} -6-dimethylaminophthalide, 3
-{2,2-bis [4- (N-ethyl-N-ethoxypropyl) aminophenyl] ethylene-1-yl} -6-
Diethylaminophthalide, 3- {2,2-bis [4-
(N-Methyl-N-ethoxypropyl) aminophenyl] ethylene-1-yl} -6-dimethylaminophthalide, 3- {2,2-bis [4- (N-methyl-N-ethoxypropyl) aminophenyl ] Ethylene-1-yl}
-6-Diethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-N-cyclopentyl) aminophenyl] ethylene-1-yl} -6-dimethylaminophthalide, 3- {2,2 -Bis [4- (N-ethyl-N-cyclopentyl) aminophenyl] ethylene-1-yl}
-6-Diethylaminophthalide, 3- [2,2-bis (4-pyrrolidinophenyl) ethylene-1-yl} -6
-Dimethylaminophthalide, 3- [2,2-bis (4-
Pyrrolidinophenyl) ethylene-1-yl} -6-diethylaminophthalide, 3- [2,2-bis (4-piperidinophenyl) ethylene-1-yl} -6-dimethylaminophthalide, 3- [ 2,2-bis (4-piperidinophenyl) ethylene-1-yl} -6-diethylaminophthalide, 3- [1,1-bis (4-dimethylaminophenyl) -1-propen-2-yl] -6-Dimethylaminophthalide, 3- [2,2-bis (4-dimethylaminophenyl) ethylene-1-yl] -6-pyrrolidinophthalide, 3- [2,2-bis (4-pyrrolidino) Phenyl)
Ethylene-1-yl] -6-pyrrolidinophthalide, 3-
[2,2-bis (4-dimethylaminophenyl) ethylene-1-yl] phthalide, 3- [2,2-bis (4-dimethylaminophenyl) ethylene-1-yl] -6-chlorophthalide, 3- [ 2,2-bis (4-pyrrolidinophenyl) ethylene-1-yl] -5-chlorophthalide,
3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -4,5,6,7-tetrachlorophthalide, 3- [2,2-bis (4-diethylaminophenyl) ethylene- 1-yl] -4,5,6,7-tetrabromophthalide, 3- [2,2-bis (4-dimethylaminophenyl) ethylene-1-yl] -5-methoxyphthalide, 3- [2 , 2-bis (4-dimethylaminophenyl) ethylene-1-yl] -5-nitrophthalide, 3
-[2,2-bis (2-methoxy-4-dimethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide, 3- [2,2-bis (2-methyl-4-diethylaminophenyl) Ethylene-1-yl] -6-dimethylaminophthalide, 3- [2,2-bis (2-chloro-4-diethylaminophenyl) ethylene-1-yl]
-6-Dimethylaminophthalide, 3- [2,2-bis (N-ethyl-N-benzylaminophenyl) ethylene-1-yl] phthalide, 3- [2,2-bis (N-ethyl-N-) Phenylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide and the like. Of course, it is not limited to these, and two or more kinds may be used in combination as required.

In the pressure-sensitive recording material of the present invention, the use ratio of the specific diarylmethane compound and the specific phthalide compound is not particularly limited, but generally, the phthalide compound is added to 100 parts by weight of the diarylmethane compound. 20-500 parts by weight, preferably 30-300
It is desirable to adjust the content to be in the range of parts by weight.

The present invention is characterized in that a specific diarylmethane compound and a specific phthalide compound are used in combination, but other known basic dyes can be used as long as the desired effects of the present invention are not impaired. , For example, triarylmethane compounds, triphenylmethanephthalide or azaphthalide compounds, indolylphthalide or azaphthalide compounds, fluorane compounds, phenothiazine compounds, rhodamine lactam compounds, triazene compounds, spiropyran compounds, leuco An auramine-based compound, an ethylenephthalide-based compound, a styrylquinoline-based compound and the like can be used in combination.

In the present invention, the basic dye is mixed with various known ultraviolet absorbers as necessary, and cotton seed oil, hydrogenated terphenyl, hydrogenated terphenyl derivative, alkylbiphenyl, alkylnaphthalene, diarylalkane,
It is dissolved in a natural or synthetic hydrophobic medium such as paraffin, naphthenic oil, or dibasic acid ester such as phthalic acid ester, and microcapsulated by various encapsulation methods such as coacervation method, interfacial polymerization method and in-situ polymerization method. Encapsulated in a capsule. The film material of the microcapsule is not particularly limited, but since it is difficult to cause color stain due to inadvertent pressure or rubbing, it is made of synthetic polymer such as aminoaldehyde resin, polyurea and / or polyurethane resin, polyamide resin. Membrane materials are preferably used.

The aminoaldehyde resin wall membrane capsule is formed of at least one amine such as urea, thiourea, alkylurea, ethyleneurea, acetoguanamine, benzoguanamine, melamine, guanidine, biuret and cyanamide, and formaldehyde, acetaldehyde, para. By in-situ polymerization using a combination with at least one aldehyde such as formaldehyde, hexamethylenetetramine, glutaraldehyde, glyoxal, furfural, etc., or an initial condensate obtained by condensing these as a wall film material. Manufactured.

Polyurethane and / or polyurea resin wall membrane capsules are prepared, for example, from polyisocyanate and water, polyisocyanate and polyol, isothiocyanate and water,
It is produced by an interfacial polymerization method using isothiocyanate and polyol, polyvalent isocyanate and polyamine, isothiocyanate and polyamine and the like as a wall film material. The polyamide resin wall membrane capsule is manufactured by an interfacial polymerization method using, for example, acid chloride and amine as a wall membrane material.

The particle size and film thickness of the microcapsules are not particularly limited, but color stains due to involuntary pressure and rubbing are prevented, and unevenness of color density due to difference in writing pressure is prevented. In order to prevent the generation, the average particle diameter of the microcapsules is 3 to 15 μm, preferably 5
-10 μm, and the average film thickness is 0.1 to 0.7 μm, preferably 0.1 to 0.4 μm, so that the encapsulation conditions (for example, the amount of the wall film material used and the shear strength during emulsification) ，
It is desirable to adjust the emulsification time).

The microcapsules containing the specific basic dyes thus prepared are used in a 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 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.

In the pressure-sensitive recording material of the present invention, as a color-forming agent-containing layer or a color-developing agent for a self-coloring type pressure-sensitive recording material, which is combined with a microcapsule coated surface such as upper paper or middle paper,
Characterized by the use of activated clay materials. Examples of such activated clay substances include acid clay, activated clay, attapulgite, zeolite, bentonite, kaolin and the like. Among these, activated clay having a silicon oxide (SiO ₂ ) content of 65 to 80% by weight, particularly 65 to 75% by weight, is particularly preferably used because it exhibits excellent properties.

The coloring agent coating liquid contains the above-mentioned coloring agent,
It is prepared by a method of dispersing 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 oxide, 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 coater or an off-machine 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. It is applied to a support such as paper, synthetic paper, film and non-woven fabric by a coater so that the dry weight is about ² to 10 g / m ² .

[0039]

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 having a silicon oxide (SiO ₂ ) content of 72%, 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 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 Liquid] To 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.) and N- (4-
5 parts di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -o-toluidine and 3-
[2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide (5 parts) was dissolved, and polymethylene polyphenyl isocyanate (trade name: Millionate MR400, manufactured by Nippon Polyurethane Industry Co., Ltd.) A solution obtained by dissolving 5 parts and 2 parts of a hexamethylene diisocyanate trimer having a burette bond (trade name: N-3200, manufactured by Sumitomo Bayer Co., Ltd.) was used as a capsule core substance in the above-mentioned aqueous medium for capsule preparation. 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-polyurethane resin wall film having an average particle diameter of 5.7 μm and an average film thickness of 0.16 μm.

[Preparation of microcapsule coating liquid] 70 parts of wheat starch powder and aqueous solution of oxidized starch 2 per 100 parts by weight (solid content) of the thus obtained microcapsule dispersion liquid
0 part (solid content) was 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 N- (4-di-n-butylamino-2-) was used as the basic dye in the preparation of the microcapsule dispersion of Example 1.
Methyl-4'-dimethylaminobenzhydryl) -o-
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 instead of toluidine. The average particle size and the average film thickness of each of the prepared microcapsules were 5.4 to 5.8 μm,
It was in the range of 0.15 to 0.19 μm. Example 2: N- (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl-ether Example 3: N- (4-di-n-butylamino) -2-methoxy-4'-dimethylaminobenzhydryl) -o-
Toluidine Example 4: N- (4-di-n-butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -2-
Chloroaniline Example 5: 3,3'-dichloro-4,4'-bis [(4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) amino] diphenylmethane Example 6: (4-di-n-amylamino-2-methyl-4'-dimethylaminobenzhydryl) -benzyl-
Ether Example 7: Bis (4-dimethylamino-2-methyl-)
4'-Dimethylaminobenzhydryl) -ether

Examples 8-10 In the preparation of the microcapsule dispersion of Example 1, 3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalic acid was used as the basic dye. Three kinds of pressure-sensitive recording medium paper were obtained in the same manner as in Example 1 except that the compounds shown below were used in place of the dots. The average particle size and the average film thickness of each of the prepared microcapsules were 5.3 to 5.7 μm, respectively.
m, and the range was 0.16 to 0.19 μm. Example 8: 3- [2,2-bis (4-piperidinophenyl) ethylene-1-yl] -6-diethylaminophthalide Example 9: 3- [2,2-bis (4-dimethyl) Aminophenyl) ethylene-1-yl] -6-dimethylaminophthalide Example 10: 3- [2,2-bis (4-dimethylamino-2-methoxyphenyl) ethylene-1-yl] -6-
Dimethylaminophthalide

Example 11 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 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.
Dimethylaminobenzhydryl) -o-toluidine (5 parts) and 3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide (5 parts) were dissolved to give an internal phase oil. Obtained. 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, 15 parts of melamine was added to 45 parts of 37% aqueous formaldehyde solution, and the mixture was 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 0.1N
-After adjusting the pH to 5.3 with hydrochloric acid, the temperature was raised to 80 ° C and maintained at that temperature for 1 hour, and then the pH was adjusted to 3. with 0.2N hydrochloric acid.
The temperature was lowered to 5 and held for 3 hours, and then allowed to cool to obtain a microcapsule dispersion liquid comprising an aminoaldehyde resin wall film having an average particle size of 5.4 μm and an average film thickness of 0.16 μm.

Comparative Example 1 In the preparation of the microcapsule dispersion of Example 1, the average particle diameter was 5.5 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 0.18 μm were prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Comparative Example 2 The procedure of Example 1 was repeated except that 5 parts of crystal violet lactone and 5 parts of benzoyl leuco methylene blue were used as the basic dye in the preparation of the microcapsule dispersion of Example 1, and the average particle size was Prepare microcapsules of 5.8 μm and average thickness of 0.15 μm,
Thereafter, in the same manner as in Example 1, a pressure-sensitive recording medium paper was obtained.

Comparative Example 3 In the preparation of the microcapsule dispersion of Example 1, 3
An average particle diameter of 5.7 μm was averaged in the same manner as in Example 1 except that 10 parts of-[2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide was used. Microcapsules having a film thickness of 0.17 μm were prepared, and then the same procedure as in Example 1 was carried out to obtain an intermediate paper for pressure-sensitive recording.

Comparative Example 4 In the preparation of the microcapsule dispersion of Example 1, 5 parts of crystal violet lactone and 3- [2,2
-Bis (4-diethylaminophenyl) ethylene-1-
[Ill] -6-dimethylaminophthalide was used in the same manner as in Example 1 to prepare microcapsules having an average particle diameter of 5.7 μm and an average film thickness of 0.17 μm. In the same manner as described above, 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 3- [2,2-bis (4-
Diethylaminophenyl) ethylene-1-yl] -6-
In the same manner as in Example 1 except that 5 parts of dimethylaminophthalide was used, the average particle size was 5.8 μm and the average film thickness was 0.1.
18 μm microcapsules were prepared, and then the same procedure as in Example 1 was carried out to obtain a pressure-sensitive recording medium paper.

Comparative Example 6 In the preparation of the microcapsule dispersion of Example 1, N- (4-di-n-butylamino-2-) was used as the basic dye.
Methyl-4'-dimethylaminobenzhydryl) -o-
An average particle diameter of 5.7 μm and an average film thickness of 0.17 μm were obtained in the same manner as in Example 1 except that 10 parts of toluidine was used.
The microcapsules of Example 1 were prepared and the same procedure as in Example 1 was performed to obtain a pressure-sensitive recording medium paper.

Comparative Example 7 In the preparation of the microcapsule dispersion of Example 1, 3,3-bis (4-diethylamino-2) was used as the basic dye.
-Ethoxyphenyl) -4-azaphthalide was used in the same manner as in Example 1 except that 10 parts were used, and the average particle size was 5.8 μm.
Microcapsules having an average 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 8 1-Ethyl-8- (di-n-butylamino) -2,2,4-trimethyl-1,2-dihydro was used as the basic dye in the preparation of the microcapsule dispersion of Example 1. Spiro [11H-chromeno [2,3g] quinoline-11.
3'-phthalide] was used in the same manner as in Example 1 except that 10 parts were used and the average particle size was 5.7 μm and the average film thickness was 0.17.
Microcapsules of μm were prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Using the 19 kinds of pressure-sensitive recording medium paper thus obtained, various performance comparison tests were conducted, and the results are shown in Table 1.

[Unprocessed] A slip was prepared by using four sheets of each of the pressure-sensitive recording medium papers prepared in Examples and Comparative Examples as one set, printed with a dot printer, and then printed with respect to the fourth slip. Of 660 nm and 740 nm in the blank and blank areas were measured using a spectrophotometer (UVIDEC 505, manufactured by JASCO Corporation), and the values were used to measure PCS.
Values were calculated and the results are shown in Table 1.

[Lightfastness Test] A slip was prepared by using four sheets of each of the pressure-sensitive recording medium sheets prepared in Examples and Comparative Examples as a set, and after printing with a dot printer, the fourth printed color surface After the (coloring agent coated surface) was exposed to direct sunlight for 8 hours, the PCS value was calculated in the same manner as above, and the results are shown in Table 1.

[Water resistance test] A slip was prepared by using four sheets of each of the pressure-sensitive recording medium sheets prepared in Examples and Comparative Examples as one set, and after printing with a dot printer, the fourth medium sheet was printed. After soaking in water for 24 hours, PC as above
The S value was calculated, and the results are shown in Table 1.

[Plasticizer Resistance Test] A slip was prepared by using four sheets of each of the pressure-sensitive recording medium sheets prepared in Examples and Comparative Examples as one set, and after printing with a dot printer, color development of the fourth sheet A vinyl chloride film was placed on the surface (coloring agent-coated surface) and left in an environment of 40 ° C. for 16 hours, and then the PCS value was calculated in the same manner as above, and the results are shown in Table 1.

[Desensitization Suitability Test] Letterpress desensitizing ink (manufactured by Kanzaki Paper Co., Ltd.) was applied on the surface of the pressure-sensitive recording medium paper prepared in Examples and Comparative Examples so as to have a coating amount of 3 g / m ^2. The desensitizing ink coated surface obtained by printing on the above and the capsule coated surface of the medium paper on which the desensitizing ink is not printed are overlapped and printed by a dot printer, and the printing is performed at 60 ° C and 90 ° C in each environment. After being left for a day, the desensitization suitability was visually judged according to the following evaluation criteria. (Evaluation Criteria) A: Good desensitization suitability for both 60 ° C. and 90 ° C. ○: Good desensitization suitability only for 60 ° C. ×: Treatment at either 60 ° C. or 90 ° C. Is poor in desensitization

[0061]

[Table 1]

[0062]

As is clear from the results shown in Table 1, the pressure-sensitive recording material of the present invention is extremely excellent in OCR readability not only after being affected by light but also by water and a plasticizer, and further, it is reduced in readability. It was an excellent pressure-sensitive recording material with good aptitude.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location 6956-2H B41M 5/12 107 (72) Inventor Naoto Arai 4-3-1, Jokoji Amagasaki, Hyogo Prefecture No. Kanzaki Paper Manufacturing Co., Ltd. Kanzaki Mill

Claims (2)

[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 the following general formula
At least one of the phthalide compounds represented by [Chemical Formula 6]
That they were used in combination and that an activated clay substance was used as a coloring agent.
Characteristic pressure-sensitive recording material. [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_FiveOr an halogen atom,
Sometimes it does not represent a hydrogen atom. R₇Is C₁~ C₂₀A
Rukiru group; C₂~ C₂₀An alkoxyalkyl group of: or C
₁~ C_FourAlkyl group of C₁~ C_FourThe alkoxyl group
Or a benzyl group which may be substituted with a halogen atom.
You R₈~ R_TenAre each a hydrogen atom; or C₁~ C_Fiveof
Alkyl group, C₁~ C_FiveAlkoxyl or halogen
Represents a phenyl group which may be substituted with a hydrogen atom,₈When
R₉Do not represent a hydrogen atom at the same time. R₁₁Is C₁~
C ₁₂Or an alkylene group of the following formula: [Chemical 5]Where X₁~ X₈Are hydrogen atoms; C₁~ C_FourA
Rukiru group; C₁~ C_FourAlkoxyl group; or halogen
Represents an atom, Z is a direct bond; -O-; -S-; -SO₂
-; Or C₁~ C₆Is an alkylene group. ] [Chemical 6][In the formula, R₁₂Is a halogen atom; C₁~ C_FourThe alkyl
Group; C₁~ C_FourAlkoxyl group; nitro group; amino
A group; a substituted amino group; or an alicyclic amino group, R₁₃Is
Hydrogen atom; or C₁~ C_FourIs an alkyl group. Also,
R₁₄~ R₁₇Are hydrogen atoms; C₁~ C₆The alkyl
Group; C₂~ C₆An alkoxyalkyl group of: C₆~ C_Tenof
Aryl group; C₇~ C_TenAn aralkyl group of: or C_Five~ C
₈The cycloalkyl group of₁₄And R₁₅And R₁₆When
R₁₇Form a heterocycle with each adjacent nitrogen atom
You can also do it. X and Y are each a hydrogen atom; C₁~
C_FourAlkyl group of C₁~ C_FourAn alkoxyl group of;
Indicates a halogen atom. n is 0 or an integer of 1 to 4
You ] 2. A diarylmethane compound is represented by the following general formula:
At least one of the compounds represented by [Chemical formula 7] to [Chemical formula 10]
The pressure-sensitive recording material according to claim 1. [Chemical 7][Chemical 8][Chemical 9][Chemical 10][In the formula, R₁₈~ R_{twenty one}Are each C₁~ C_FiveAlkyl group of
Indicates R_{twenty two}Is C₁~ C ₂Alkyl group of C₁~ C₂of
An alkoxyl group; or a halogen atom. R_{twenty three}Is C₁
~ C_FourOr an benzyl group. R_{twenty four}as well as
R_{twenty five}Are hydrogen atoms; C₁~ C₂Alkyl group of C
₁~ C_FourAn alkoxyl group of; or a halogen atom
You ]