JPH0952439A - Pressure sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make an optical reader having a specific read wavelength exhibit excellent characteristics by a method wherein at least one kind of phenoxazine compound expressed by the formula as a basic dye is used by a specified amount, and zinc salt of salicylic acid derivative is used as a color developing agent. SOLUTION: In a pressure sensitive recording material wherein color development reaction of a colorless or light-colored basic dye with a color developing agent is used, at least one kind of phenoxazine compound expressed by the formula as the basic dye is used by 10-50wt.% to the total dye, and zine salt derived from salicylic acid is used as the color developing agent. In the formula, R1 -R4 are respectively alkyl group of C1 -C4 . R5 is alkoxyl group or benzyloxy group of C1 -C6 . m is an integer of 1-3. Thereby, the pressure sensitive recording materials can exhibit excellent characteristics by being applied to an optical character reader having a read wavelength of 650-700nm.

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.

Various proposals have heretofore been made as pressure-sensitive recording materials for OCR reading. In each case, although the color image has absorption at 650 to 700 nm, the light resistance and plasticizer resistance of the printed portion, Since there is a problem in the long-term storability of the non-printed portion, improvement thereof is strongly demanded.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems and to exert excellent characteristics when applied to an optical character reading (OCR) device having a reading wavelength of 650 to 700 nm. It is to provide a recording body.

[0006]

[Means for solving the problems] As a result of earnest research,
A pressure-sensitive recording material utilizing a color reaction between a colorless or light-colored basic dye and a coloring agent, wherein at least one of the specific phenoxazine compounds represented by the following general formula (1) is used as the basic dye. It was found that a pressure-sensitive recording material exhibiting excellent properties can be obtained by using 10 to 50% by weight, and by using a zinc salt of a salicylic acid derivative as a colorant.

[0007]

Embedded image

(R _{1 to} R ₄ are each a C _{1 to} C ₄ alkyl group, R ₅ is a C _{1 to} C ₆ alkoxyl group or a benzyloxy group, and m is an integer of 1 to 3.)

[0009]

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-
(3-Methoxybenzoyl) phenoxazine, 3,7-
Bis (diethylamino) -10- (3-ethoxybenzoyl) -phenoxazine, 3,7-bis (diethylamino) -10- (3-isopropoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(3-n-butoxybenzoyl) phenoxazine, 3,
7-bis (diethylamino) -10- (3-n-heptyloxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3-n-hexyloxybenzoyl) phenoxazine, 3,7-bis ( Diethylamino) -10- (3-benzyloxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10
-(4-Methoxybenzoyl) phenoxazine, 3,7
-Bis (diethylamino) -10- (4-ethoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-isopropoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(4-n-butoxybenzoyl) phenoxazine, 3,
7-bis (diethylamino) -10- (4-benzyloxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2-methoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(2-Ethoxybenzoyl) phenoxazine, 3,7-
Bis (diethylamino) -10- (2-isopropoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2-n-butoxybenzoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(2-benzyloxybenzoyl) phenoxazine,
3,7-bis (dimethylamino) -10- (3-methoxybenzoyl) phenoxazine, 3,7-bis (dimethylamino) -10- (3-ethoxybenzoyl) phenoxazine, 3,7-bis (dimethylamino) ) -10-
(4-Methoxybenzoyl) phenoxazine, 3,7-
Bis (dimethylamino) -10- (4-ethoxybenzoyl) phenoxazine, 3,7-bis (dimethylamino) -10- (2-methoxybenzoyl) phenoxazine, 3,7-bis (dimethylamino) -10- (2-Ethoxybenzoyl) phenoxazine, 3,7-bis (di-n-butylamino) -10- (3-methoxybenzoyl) phenoxazine, 3,7-bis (di-n-butylamino) -10- (4-Methoxybenzoyl) phenoxazine, 3,7-bis (di-n-butylamino) -10-
(2-Methoxybenzoyl) phenoxazine, 3-dimethylamino-7-diethylamino-10- (3-methoxybenzoyl) phenoxazine, 3-dimethylamino-
7-diethylamino-10- (4-methoxybenzoyl) phenoxazine, 3-dimethylamino-7-diethylamino-10- (2-methoxybenzoyl) phenoxazine, 3,7-bis (N-methyl-Nn-propyl) Amino) -10- (3-methoxybenzoyl) phenoxazine, 3,7-bis (N-methyl-Nn-propylamino) -10- (4-methoxybenzoyl) phenoxazine, 3,7-bis (N -Methyl-Nn-propylamino) -10- (2-methoxybenzoyl) 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)
Examples include phenoxazine 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.

Among these compounds, the compound represented by the following general formula (3) has not only OCR readability but also stability of non-printed portion when exposed to light for a long time and desensitization suitability. It is particularly preferably used because it has excellent properties.

[0011]

Embedded image

(R _{1 to} R ₄ each represent a C _{1 to} C ₄ alkyl group, and R ₅ represents a C _{1 to} C ₆ alkoxyl group or a benzyloxy group.)

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.
Specified as 0% by weight, but if less than 10% by weight O
Problems such as CR readability, light resistance, and plasticizer resistance may occur, and if more than 50% by weight is used,
The capsule-coated surface is colored over time, which causes problems in practical use, and causes problems in OCR reading suitability and desensitization suitability.

In the present invention, the basic dye used in combination with the specific phenoxazine compound is a known basic dye within a range that does not impair the desired effects of the present invention, such as triarylmethane compounds and diarylmethane compounds. ,
Fluoran compounds, phenothiazine compounds, rhodamine lactam compounds, spiropyran compounds, leuco auramine compounds and the like are used. Among these basic dyes, when at least one of the fluorane compounds represented by the following general formula (2) is used in combination, the color tone is clear and black, and the image of light resistance, plasticizer resistance, etc. It is preferable because a pressure-sensitive recording material having excellent storability can be obtained.

[0015]

[Chemical 6]

(R ₆ and R ₇ are each a C ₁ -C ₆ alkyl group, an ethoxypropyl group or a p-tolyl group, R ₈ is a hydrogen atom or a methyl group, and R ₉ is a methyl group, a chlorine atom or a triatomic group. Represents a fluoromethyl group, and n represents an integer of 0 to 2.)

Specific examples of the fluorane compound represented by the general formula (2) include 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane and 3-diethylamino-6. -Methyl-7-anilinofluorane, 3-di-n-butylamino-6-methyl-7
-Anilinofluorane, 3-di-n-pentylamino-
6-methyl-7-anilinofluorane, 3-diethylamino-7- (m-trifluoromethylanilino) fluorane, 3- (N-ethyl-N-isobutyl) amino-6
-Methyl-7-anilinofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-ethoxypropyl) amino-6-methyl -7-anilinofluorane, 3-diethylamino-6-methyl-7- (2,4-xylidino) fluorane, 3-diethylamino-6-methyl-7-
(2,6-Xylidino) fluorane, 3-di-n-butylamino-6-methyl-7- (2,6-xylidino) fluorane, 3-di-n-butylamino-7- (o-chloroanilino) fluorane , 3- (N-ethyl-N-isoamyl) -7- (o-chloroanilino) fluorane and the like. The compound is not limited to these compounds, and any compound included in the general formula (2) can be used, and if necessary, 2
It is also possible to use two or more species 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 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, 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 such salicylic acid derivatives 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-5-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 zinc salts of salicylic acid derivatives, 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 coating method of 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, roll coater, blade coater, rod plate coater, curtain coater, lip coater and the like. 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 .

[0027]

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.) as a basic dye, 7 parts of 3-diethylamino-6-methyl-7-anilinofluorane and 3,7-bis (diethylamino) -10. 3 parts of-(3-methoxybenzoyl) phenoxazine and 2 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole as an ultraviolet absorber were dissolved, and further polymethylene polyphenyl isocyanate (trade name: Millionate MR4
00, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2 parts of hexamethylene diisocyanate trimer having a burette bond (trade name: N-3200, manufactured by Sumitomo Bayer Co., Ltd.) as a capsule core substance. 1 minute per minute using TK homomixer in the above aqueous medium for capsule preparation
The emulsion was emulsified at 0000 rpm for 1 minute. 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 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 4 g / m ² , and then dried. A medium pressure recording paper was obtained.

Examples 2 to 4 In the preparation of the microcapsule dispersion of Example 1,
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 instead of 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine. .

Example 2: 3,7-bis (dimethylamino) -10- (3-methoxybenzoyl) phenoxazine Example 3: 3,7-bis (diethylamino) -10-
(3-Ethoxybenzoyl) phenoxazine Example 4: 3,7-bis (diethylamino) -10-
(4-Methoxybenzoyl) phenoxazine

Examples 5-7 In the preparation of the microcapsule dispersion of Example 1, 3
Three kinds of pressure-sensitive recording intermediate papers were obtained in the same manner as in Example 1 except that the following compounds were used instead of -diethylamino-6-methyl-7-anilinofluorane. -Example 5: 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane-Example 6: 3-diethylamino-6-methyl-7-
(2,6-Xylidino) fluorane Example 7: 3-Diethylamino-7- (m-trifluoromethylanilino) fluorane

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 7 parts of 3-diethylamino-6-methyl-7-anilinofluorane as a basic dye and 3,7-bis (diethylamino)- 10-
An internal phase oil was obtained by dissolving 3 parts of (3-methoxybenzoyl) phenoxazine and 2 parts of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole as an ultraviolet absorber. Next, this internal phase oil was charged into the above-mentioned aqueous medium for capsule production, and 100 minutes per minute using a TK homomixer.
It was emulsified and dispersed at 00 rotations for 1 minute, 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, adjusted to pH 5.3 with 0.1N-hydrochloric acid, heated to 80 ° C., and kept at that temperature for 1 hour.
After the temperature was kept for 2 hours, the pH was lowered to 3.5 with 0.2N-hydrochloric acid, the temperature was kept for 3 hours, and then allowed to cool to prepare microcapsules consisting of an aminoaldehyde resin film having an average particle diameter of 5.3 μm.

Examples 11 to 12 In the preparation of the microcapsule dispersion of Example 1, 3
-Diethylamino-6-methyl-7-anilinofluorane 7 parts and 3,7-bis (diethylamino) -10- (3
-Methoxybenzoyl) phenoxazine 2 was prepared in the same manner as in Example 1 except that the following compound was used instead of 3 parts.
Two kinds of pressure sensitive recording medium paper were obtained.

Example 11: 3-diethylamino-6-
Methyl-7-anilinofluorane 8 parts and 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine 2 parts Example 12: 3-diethylamino-6-methyl-7-
6 parts of anilinofluorane and 4 parts of 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine

Comparative Example 1 In the preparation of the microcapsule dispersion of Example 1, 3-diethylamino-6-methyl-7 was used as the basic dye.
A pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 except that 10 parts of anilinofluoran was used.

Comparative Examples 2-3 In the preparation of the microcapsule dispersion of Example 1,
An intermediate paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that the following dye was used instead of 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine. Comparative Example 2: 3,3-bis (4-diethylamino-2-)
Ethoxyphenyl) -4-azaphthalide-Comparative Example 3: 3,7-bis (diethylamino) -10-
(4-methylbenzoyl) phenoxazine

Comparative Example 4 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 Examples 5-6 In the preparation of the microcapsule dispersion of Example 1, 3
-Diethylamino-6-methyl-7-anilinofluorane 7 parts and 3,7-bis (diethylamino) -10- (3
-Methoxybenzoyl) phenoxazine 2 was prepared in the same manner as in Example 1 except that the following compound was used instead of 3 parts.
Two kinds of pressure sensitive recording medium paper were obtained.

Comparative Example 5: 9.5 parts of 3-diethylamino-6-methyl-7-anilinofluorane and 0.5 parts of 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine. Comparative Example 6: 3-diethylamino-6-methyl-7-anilinofluorane 4 parts and 3,7-bis (diethylamino) -10- (3-methoxybenzoyl) phenoxazine 6 parts

Using the 18 kinds of pressure-sensitive recording medium paper thus obtained, 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 coloring agent-coated surface faced each other, and printed with a dot printer. The reflectance at 670 nm was measured by a spectrophotometer (U-3300 manufactured by Hitachi), and the PCS value was calculated from the measured reflectance. [Lightfastness test] After the printing color-developing surface (coloring agent-coated surface) of the pressure-sensitive recording material obtained above was exposed to direct sunlight for 24 hours, it was similarly subjected to P
The CS value was calculated and shown in Table 1. Further, the degree of coloring of the non-printed portion was visually observed and judged according to the following criteria.

◯: No problem in practical use Δ: No problem in practical use although some coloration is observed X: Significant coloration and problems in practical use [Plasticizer resistance test] Printed surface of the pressure-sensitive recording material obtained above Overlay a vinyl chloride film on (coloring agent coated surface) 40 ° C
After leaving it for 24 hours at room temperature, the PCS value was calculated in the same manner and shown in Table 1.

[Desensitization Suitability] Offset desensitizing ink (manufactured by Teikoku Ink, No.
804) is applied at a coating amount of 3 g / m ² and the desensitized ink application surface is overlapped with the capsule application surface of the medium paper on which the desensitization ink is not printed, and after printing with a dot printer, room temperature and 50 ° C. After being stored for 72 hours under the condition of relative humidity of 90%, the desensitization suitability was visually observed and judged according to the following criteria.

◯: Good desensitization suitability without any problems at room temperature and 50 ° C., 90% relative humidity Δ: Good at room temperature, but slightly desensitization suitability at 50 ° C., 90% relative humidity Poor and may cause problems depending on the quality grade, but usually no problem x: Poor desensitization under both room temperature, 50 ° C, and 90% relative humidity

[0050]

[Table 1]

[0051]

As is clear from the results shown in Table 1, the pressure-sensitive recording material of the present invention in which a specific phenoxazine compound and a specific color-developing agent are combined is an optical character reading (OCR) having a reading wavelength of 670 nm. ) It is a pressure-sensitive recording material which exhibits excellent properties for the apparatus and is also excellent in light resistance, coloring of the non-printed portion, and suitability for desensitization.

Claims (4)

[Claims] 1. A pressure-sensitive recording material utilizing a color-developing reaction between a colorless or light-colored basic dye and a coloring agent, wherein the basic dye is at least one of phenoxazine compounds represented by the following general formula (1). Is used in an amount of 10 to 50% by weight with respect to all dyes, and a zinc salt of a salicylic acid derivative is used as a coloring agent. Embedded image (R _{1 to} R ₄ are each a C _{1 to} C ₄ alkyl group,
₅ represents a C ₁ -C ₆ alkoxyl group or a benzyloxy group. m shows the integer of 1-3. ) 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. 3. The pressure-sensitive recording material according to claim 1, wherein at least one fluoran compound represented by the following general formula (2) is used in combination as the basic dye. Embedded image (R ₆ and R ₇ are each a C ₁ -C ₆ alkyl group,
An ethoxypropyl group or a p-tolyl group, R ₈ represents a hydrogen atom or a methyl group, and R ₉ represents a methyl group, a chlorine atom or a trifluoromethyl group. n shows the integer of 0-2. ) 4. A phenoxazine compound represented by the following general formula (3):
The pressure-sensitive recording material according to claim 1, which is a compound represented by: Embedded image (R _{1 to} R ₄ are each a C _{1 to} C ₄ alkyl group,
₅ represents a C ₁ -C ₆ alkoxyl group or a benzyloxy group. )