JPH08207439A - Pressure sensitive recording body - Google Patents

Abstract

PURPOSE: To improve light resistance and plasticizer resistance by using a phenoxazine compound to be expressed by a specified formula in combination with a phthalide compound as a basic dye and using a zinc salt of salicylic acid derivative as a coloring agent, in a pressure sensitive recording body which utilizes a coloring reaction. CONSTITUTION: In a pressure sensitive recording body of a cutform to be used for an optical character read(OCR) device having a read wavelength of 650-700nm, at least one kind of a phenoxazine compound to be expressed by a formula I is used in combination with at least one kind of a phthalide compound to be expressed by a formula II, as a basic dye. As a coloring agent, a zinc salt of salicylic acid derivative is used. In the formula, R1 -R4 represent a 1-4C alkyl group respectively, R5 represents a hydrogen atom, a 1-4C alkyl group, R6 -R9 represent a hydrogen atom and a 1-6C alkyl group respectively, R10 represents a hydrogen atom or a 1-4C alkyl group, R11 represents a halogen atom, a 1-4C alkyl group, a nitro group, an amino group, and n is an integer of 0-4.

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-forming 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, the color image has absorption at 650 to 700 nm, but it is difficult to obtain a high reading density over the entire wavelength range of 650 to 700 nm, and the light resistance and resistance are high. Since there are problems with plasticizer properties, long-term storage stability, etc., improvement is strongly desired from a practical viewpoint.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is 65
It has excellent characteristics when applied to an optical character reading (OCR) device having a reading wavelength of 0 to 700 nm, that is, high reading density over a wide wavelength range in the near infrared region, light resistance, plasticizer resistance, and long-term It is an object of the present invention to provide a pressure-sensitive recording material exhibiting excellent performance such as storage stability.

[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
A pressure-sensitive recording material comprising a combination of at least one phthalide compound represented by the following general formula (2) and a zinc salt of a salicylic acid derivative as a coloring agent.

[0007]

Embedded image

(R₁~ R_FourAre each C₁~ C_FourAl
Kill group, R_FiveIs a hydrogen atom, C₁~ C _FourAn alkyl group of
C₁~ C_FourThe alkoxyl group or halogen atom of
You. )

[0009]

[Chemical 4]

[In the formula, R _{6 to} R ₉ are each a hydrogen atom,
Alkyl _{C 1 ~C 6, C 2 ~C} 6 alkoxyalkyl group, an aryl group of C ₆ -C _10, but showing a cycloalkyl group C ₇ -C ₁₀ aralkyl or C ₅ -C _8, R
Each of ₆ and R ₇ and R ₈ and R ₉ can also form a ring with the adjacent nitrogen atom. R ₁₀ is a hydrogen atom or a C ₁ -C ₄ alkyl group, R ₁₁ is a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxyl group, a nitro group, an amino group, a substituted amino group. Alternatively, it represents an alicyclic amino group. n shows the integer of 0-4. ]

[0011]

Specific examples of the phenoxazine compound represented by the above general formula (1) used in the present invention include 3,7
-Bis (diethylamino) -10- (1-naphthoyl)
Phenoxazine, 3,7-bis (diethylamino) -1
0- (2-naphthoyl) -phenoxazine, 3,7-bis (diethylamino) -10- (2-methyl-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-methyl-) 1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (8
-Methyl-1-naphthoyl) phenoxazine, 3,7-
Bis (diethylamino) -10- (4-ethyl-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (1-methyl-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(4-methyl-2-naphthoyl) phenoxazine, 3,
7-bis (diethylamino) -10- (6-methyl-2
-Naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-ethyl-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10
-(2-methoxy-1-naphthoyl) phenoxazine,
3,7-bis (diethylamino) -10- (4-methoxy-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (5-methoxy-1-naphthoyl) phenoxazine, 3,7- Bis (diethylamino) -10- (2-ethoxy-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(2-Isopropoxy-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (1-methoxy-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3- Methoxy-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (6-methoxy-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(3-ethoxy-2-naphthoyl) phenoxazine,
3,7-bis (diethylamino) -10- (3-isopropoxy-2-naphthoyl) phenoxazine, 3,7-
Bis (diethylamino) -10- (2-chloro-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-chloro-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(5-chloro-1-naphthoyl) phenoxazine, 3,
7-bis (diethylamino) -10- (8-chloro-1
-Naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-bromo-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10
-(2,4-Dichloro-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3-chloro-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- ( 5-chloro-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (8-chloro-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3
-Bromo-2-naphthoyl) phenoxazine, 3,7-
Bis (diethylamino) -10- (3,5-dichloro-
2-naphthoyl) phenoxazine, 3,7-bis (dimethylamino) -10- (1-naphthoyl) phenoxazine, 3,7-bis (dimethylamino) -10- (2-naphthoyl) -phenoxazine, 3, 7-bis (di-n-
Butylamino) -10- (1-naphthoyl) phenoxazine, 3,7-bis (di-n-butylamino) -10-
(2-naphthoyl) -phenoxazine, 3-dimethylamino-7-diethylamino-10- (1-naphthoyl)
Phenoxazine, 3-dimethylamino-7-diethylamino-10- (2-naphthoyl) -phenoxazine,
3,7-bis (N-methyl-Nn-propylamino)
-10- (1-naphthoyl) phenoxazine and the like can be mentioned. Among these compounds, 3,7-bis (diethylamino) -10- (1-naphthoyl) phenoxazine is particularly preferably used because it exhibits particularly excellent color developability, light resistance, plasticizer resistance and the like. The compounds are not limited to these compounds, and any compound included in the general formula (1) 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 (2) include, for example, 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) aminophenyl] ethylene-1-yl} -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) aminophenyl] 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-
Il} -6-diethylaminophthalide, 3- {2,2-
Bis [4- (N-ethyl-Nn-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-
Il] -6-dimethylaminophthalide, 3- [2,2-
Bis (4-di-n-butylaminophenyl) ethylene-
1-yl} -6-diethylaminophthalide, 3- {2,
2-bis [4- (N-ethyl-Nn-hexyl) aminophenyl] ethylene-1-yl} -6-dimethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-
N-n-hexyl) aminophenyl] ethylene-1-yl} -6-diethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-N-ethoxypropyl) aminophenyl] ethylene-1- Il} -6-dimethylaminophthalide, 3- {2,2-bis [4- (N-ethyl-N
-Ethoxypropyl) aminophenyl] ethylene-1-
Il} -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-
Il} -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-pyrrolidinophenyl) ethylene-1-yl] -6-pyrrolidinophthalide, 3- [2,2-bis (4-dimethyl) Aminophenyl) 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-
Il] -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-
Examples thereof include bis (N-ethyl-N-phenylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide. The compounds are 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. Among these compounds, 3-
[2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide is particularly preferably used because it exhibits particularly excellent performance.

In the present invention, the amount of the phenoxazine compound represented by the general formula (1) is 10 to 5 with respect to all dyes.
0% by weight is preferred. If it is less than 10% by weight, problems such as OCR readability, light resistance, and plasticizer resistance will occur. If it is used in excess of 50% by weight, the color of the capsule coated surface will become darker with time and This is because problems such as storability occur.

In the present invention, known basic dyes, such as triarylmethane compounds, diarylmethane compounds, fluorane compounds, phenothiazine compounds, rhodamine lactam compounds, within the range that does not impair the desired effects of the present invention. 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 cotton seed oil, hydrogenated Terphenyl, hydrogenated terphenyl derivative,
Dissolved in a natural or synthetic hydrophobic medium such as alkylbiphenyl, alkylnaphthalene, diarylalkane, paraffin, naphthene oil, dibasic acid ester such as phthalic acid ester, coacervation method, interfacial polymerization method, in
It is encapsulated in microcapsules by a capsule manufacturing method such as the 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, for example, at least one amine such as urea, thiourea, alkylurea, ethylene urea, 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 containing the specific basic dye thus prepared 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 such a 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-bromosalicylic 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-5-phenylsalicylic acid, 3-methyl-5
-Nonylsalicylic acid, 5- (4-mesitylmethylbenzyl) salicylic acid, carboxylated terpene phenol resin, benzylated styrenated salicylic acid and the like can be mentioned.
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 .

[0024]

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 vessel 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, 3- [2,2] as a basic dye was added to 100 parts of alkylnaphthalene (trade name: KMC oil, manufactured by Kureha Chemical Co., Ltd.).
-Bis (4-diethylaminophenyl) ethylene-1-
7-6 parts of 3,6-bis (diethylamino) -10- (1-naphthoyl) phenoxazine, and 2- (2′-hydroxy-5′-methylphenyl) as an ultraviolet absorber. ) Benzotriazole 2
And 5 parts of polymethylene polyphenyl isocyanate (trade name: Millionate MR400, manufactured by Nippon Polyurethane Industry Co., Ltd.) and hexamethylene diisocyanate trimer having a burette bond (trade name: N-32).
00, manufactured by Sumitomo Bayer Co., Ltd.), and a solution obtained by dissolving 2 parts thereof is used as a capsule core substance in the above-mentioned aqueous medium for capsule preparation, using a TK homomixer at 10000 rpm.
Emulsified for minutes. 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 prepare microcapsules composed of polyurea resin / polyurethane resin wall film having an average particle diameter of 5.5 μm.

[Preparation of Microcapsule Coating Liquid] 70 parts of wheat starch powder and 2 parts of aqueous solution of oxidized starch 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 with 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 7 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, six types of pressure-sensitive recording medium paper were obtained. Example 2: 3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide 7 parts and 3,7-bis (diethylamino) -10
-(2-naphthoyl) phenoxazine 3 parts-Example 3: 3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide 7 parts and 3,7-bis. (Dimethylamino) -10
-(1-naphthoyl) phenoxazine 3 parts-Example 4: 3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide 7 parts and 3,7-bis. (Dimethylamino) -10
-(2-naphthoyl) phenoxazine 3 parts-Example 5: 3- [2,2-bis (4-piperidinophenyl) ethylene-1-yl] -6-diethylaminophthalide 7 parts and 3,7- Bis (diethylamino) -10-
(1-naphthoyl) phenoxazine 3 parts Example 6: 3- [2,2-bis (4-dimethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide 7 parts and 3,7-bis (Diethylamino) -10
-(1-naphthoyl) phenoxazine 3 parts-Example 7: 3- [2,2-bis (4-dimethylamino-2-methoxyphenyl) ethylene-1-yl] -6-
7 parts of dimethylaminophthalide and 3,7-bis (diethylamino) -10- (1-naphthoyl) phenoxazine 3
Department

Examples 8 to 9 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 8: Zinc salt of carboxylated terpene phenolic resin Example 9: Zinc salt of benzylated styrenated salicylic acid

Example 10 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.) and 3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthali as a basic dye are used. 7 parts and 3,7-bis (diethylamino) -10- (1-naphthoyl) phenoxazine 3 parts, as an ultraviolet absorber 2-
An internal phase oil was obtained by dissolving 2 parts of (2'-hydroxy-5'-methylphenyl) benzotriazole.

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 In the preparation of the colorant 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 p-phenylphenol novolak resin was used in place of methylbenzyl) salicylic acid zinc salt.

Comparative Example 3 In the preparation of the microcapsule dispersion of Example 1, 10 parts of 3- [2,2-bis (4-diethylaminophenyl) ethylene-1-yl] -6-dimethylaminophthalide was used as a dye. An intermediate paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that it was used.

Comparative Example 4 In the preparation of the microcapsule dispersion of Example 1, 3,3-bis (p-dimethylaminophenyl) was used as the dye.
A pressure-sensitive recording medium paper was prepared in the same manner as in Example 1 except that 7 parts of 6-dimethylaminophthalide and 3 parts of 3,7-bis (diethylamino) -10- (1-naphthoyl) phenoxazine were used. Obtained.

Various performance comparison tests were carried out using the 14 kinds of pressure-sensitive recording medium paper thus obtained, and the results are shown in Table 1. The results were 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.

[P at 670 nm and 700 nm
Measurement of CS value] The prepared pressure-sensitive recording medium paper was overlaid so that the capsule-coated surface and the coloring agent-coated surface faced each other, and printed with a dot printer. Each is a spectrophotometer (U-33 manufactured by Hitachi
00) to measure the reflectance at 670 nm and 700 nm and calculate the PCS value at each wavelength from the measured values.
It was shown to. [Lightfastness test] Colored surface of printing obtained above (coloring agent coated surface)
After being exposed to direct sunlight for 24 hours, PCS values were calculated in the same manner and shown in Tables 1 and 2. [Plasticizer resistance test] After overlaying a vinyl chloride film on the color-developing surface (coloring agent-coated surface) obtained above and allowing it to stand at room temperature for 24 hours, PCS values were similarly calculated and shown in Tables 1 and 2. It was

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

As is clear from the results shown in Tables 1 and 2,
The pressure-sensitive recording material of the present invention is a pressure-sensitive recording material that exhibits excellent characteristics for an optical character reading (OCR) device having a reading wavelength of 670 to 700 nm.

[Procedure amendment]

[Submission date] March 23, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1](R₁~ R_FourAre each C₁~ C_FourThe alkyl group of R
_FiveIs a hydrogen atom, C₁~ C _FourAlkyl group of C₁~ C_Fourof
An alkoxyl group or a halogen atom is shown. )

Embedded image [In the formula, R _{6 to} R ₉ are each a hydrogen atom, a C _{1 to} C ₆ alkyl group, a C _{2 to} C ₆ alkoxyalkyl group, and a C ₆
To C ₁₀ aryl group, C _{7 to} C ₁₀ aralkyl group or C
₅ shows a cycloalkyl group -C ₈ but, R ₆ and R ₇ and R ₈ and R ₉ can also form a ring with each adjacent nitrogen atom. R ₁₀ is a hydrogen atom or C ₁ ~
A C ₄ alkyl group, R ₁₁ is a halogen atom, C _{1 to} C ₄
Is 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. n shows the integer of 0-4. ]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

Embedded image

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

[Chemical 4]

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B41M 5/12 108

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)
Represented by at least one compound and the following general formula (2)
Used in combination with at least one phthalide compound
And using a zinc salt of salicylic acid derivative as a colorant
A pressure-sensitive recording material characterized in that [Chemical 1](R₁~ R_FourAre each C₁~ C_FourThe alkyl group of R
_FiveIs a hydrogen atom, C₁~ C _FourAlkyl group of C₁~ C_Fourof
An alkoxyl group or a halogen atom is shown. ) [Chemical 2][In the formula, R₆~ R₉Are hydrogen atom and C respectively₁~ C₆of
Alkyl group, C₂~ C₆An alkoxyalkyl group of C₆
~ C_TenAryl group of C₇~ C_TenAralkyl group or C
_Five~ C₈The cycloalkyl group of₆And R₇And
And R₈And R₉Form a ring with each adjacent nitrogen atom
It can also be done. Also R_TenIs a hydrogen atom or C₁~
C_FourThe alkyl group of R₁₁Is a halogen atom, C₁~ C_Four
Alkyl group of C₁~ C_FourThe alkoxyl group of nitro
Group, amino group, substituted amino group or alicyclic amino group
You. n shows the integer of 0-4. ] 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.