JPH06227115A - Pressure-sensitive recording body - Google Patents

Abstract

PURPOSE:To obtain a pressure-sensitive recording body being excellent in the property of color development and the property of fastness of a colored image, free from a coloring stain and the like and also excellent in desensitization appropriateness, by using a specific diarylmethane compound in a state of being contained in a specific microcapsule and also by combining it with a specific coloring agent. CONSTITUTION:A pressure-sensitive recording body utilizes the color reaction of a colorless or light-colored basic material with a coloring agent. In this case, at least one kind of diarylmethane compound out of the ones expressed respectively by general formulas shown separately is used as a basic dyestuff. In each of the formulas, R1 to R4 denote alkyl groups of C1 to C5 or the like respectively, R5 and R6 hydrogen atoms or the like and R7 an alkoxy group of C1 to C4 or a benzyl group which may be replaced by a halogen atom, or the like, respectively. The basic dyestuff is contained in a synthetic macromolecular microcapsule of which the average particle size is 3 to 15mum and the average film thickness 0.1 to 0.7mum. As for the coloring agent, an active viscosity mineral containing a silicon oxide (SiO2) of 65 to 80wt.% is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive recording material, and more particularly to a pressure-sensitive recording material having a fast color image.

[0002]

2. Description of the Related Art A pressure-sensitive recording medium is prepared by applying a microcapsule composition containing microcapsules containing droplets of a basic dye or the like as a main component to one side of a support and a paper or one side of the support. Is a color-developing composition containing an electron-accepting color-developing agent (hereinafter simply referred to as a color-developing agent) as a main component, which is colored when contacted with a basic dye to form a color-developing layer on the opposite surface. Includes a middle paper coated with a microcapsule composition and a lower paper coated with a colorant composition on one side of a support to form a color layer. These three types of sheets are used as upper paper and lower paper, or It has been put into practical use as a copy set by combining upper paper, middle paper, and lower paper in this order. Further, there is also a self-coloring pressure-sensitive recording material in which a microcapsule containing a basic dye and a coloring agent are coated on a single surface of a support in a single layer or two layers to enable pressure-sensitive recording with one sheet. It is known as a form of pressure-sensitive recording material.

Performances required for the pressure-sensitive recording material include high speed of color development, sufficient color density, no stain, and sufficient fastness of color image. In recent years, due to diversification of quality requirements, there has been a strong demand for development of a pressure-sensitive recording material which is particularly excellent in fastness of a color image, for example, light resistance, water resistance, chemical resistance and the like.

Conventionally, triphenylmethane compounds, phthalide compounds, leucomethylene blue compounds and the like have been known as compounds which develop blue to blue violet, but pressure sensitive recording materials using these are still sufficiently satisfactory. A recording material having the quality that can be obtained has not been obtained. For example, 3,3
-Bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone) has a fast color-developing rate with respect to an organic colorant and exhibits a deep blue color, but is extremely fast in color image fastness. Inferior

On the other hand, Japanese Patent Publication Nos. 44189/1990 and 2191/1990 have proposed a pressure-sensitive recording material using a diarylmethane compound as a basic dye. However, the bis [4,4'-
Diarylmethane compounds such as bis (dimethylaminobenzhydryl)] ether and 4,4′-bis (dimethylaminobenzhydryl) benzyl-ether are robust to color images when used in combination with activated clay minerals. It has the advantage of being excellent in light, humidity,
It has the drawback that the color tone of the image turns red due to the influence of water, chemicals, etc., and it is difficult to desensitize with ordinary desensitizers.
These improvements are required. Further, in the system in which the diarylmethane compound and the activated clay mineral are combined as described above, the color density changes with the change of the writing pressure (printing pressure), or the undesired pressure or rubbing causes color stains. There is also a drawback that the defects peculiar to the pressure recording material appear more prominently, and improvement thereof is also demanded.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a pressure-sensitive recording material which is excellent in light fastness, water fastness, chemical resistance, etc. of a color image and which has the above-mentioned drawbacks when the diarylmethane compound is used. The purpose is to provide. The inventors of the present invention have conducted extensive studies in order to achieve such a subject, and as a result, use a specific diarylmethane compound as a basic dye, use it by encapsulating it in a specific microcapsule, and further specify. By combining the above colorants, the colored image is clear, and it has excellent light resistance, water resistance, and chemical resistance, and also has good desensitization aptitude, and there is no change in color tone, and there is little color stain. The inventors have found that a pressure recording material can be obtained, and completed the present invention.

[0007]

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: Alternatively, at least one kind of the diarylmethane compound represented by [Chemical Formula 2] is used, and the basic dye is a synthetic polymer microcapsule having an average particle diameter of 3 to 15 μm and an average film thickness of 0.1 to 0.7 μm. And the content of silicon oxide (SiO ₂ ) as a coloring agent is 65 to 80% by weight.
The pressure-sensitive recording material is characterized by using the activated clay mineral of.

[0008]

[Chemical 1]

[0009]

[Chemical 2]

[In the formula, R _{1 to} R ₄ are respectively C _{1 to} C ₅
Is an alkyl group or a benzyl group, wherein R ₅ and R ₆ are each a hydrogen atom, a C _{1 to} C ₅ alkyl group, and a C _{1 to} C ₅
Represents an alkoxyl group or a halogen atom. However, R
₅ and R ₆ do not represent a hydrogen atom at the same time. Also, R
₇ is an alkyl group of C ₁ -C _20; alkoxyalkyl groups C ₂ -C _20; or an alkyl group C ₁ ~C _4, C ₁ ~C
_{4 represents} an alkoxyl group of ₄ or a benzyl group which may be substituted with a halogen atom. ]

[0011]

The following are specific examples of the diarylmethane compound represented by the above general formula [Chemical formula 1] or [Chemical formula 2] used in the present invention. (4-diethylamino-2-methyl-4'-dimethylaminobenzhydryl)
-Methyl-ether, (4-diethylamino-2-methyl-4'-dimethylaminobenzhydryl) -ethyl-
Ether, (4-diethylamino-2-methyl-4'-
Dimethylaminobenzhydryl) -n-propyl-ether, (4-diethylamino-2-methyl-4'-dimethylaminobenzhydryl) -benzyl-ether,
(4-Diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -methyl-ether, (4-diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -n-propyl-ether, (4 -Diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -isopropyl-ether, (4-diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -n-octyl-ether, (4-diethylamino) -2-Ethoxy-4'-dimethylaminobenzhydryl) -n-dodecyl-ether, (4-diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -n-octadecyl-ether, (4-diethylamino) -2-Ethoxy-4'-dimethylaminobenzhydryl)-(meth Shipuropiru) - ether, (4-diethylamino-2-ethoxyphenyl-4'-dimethylamino-benzhydryl) - (ethoxy propyl) - ether,
(4-Diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl)-(ethoxytetradecyl)-
Ether, (4-diethylamino-2-ethoxy-4 '
-Dimethylaminobenzhydryl) -benzyl-ether, (4-diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl)-(4-methylbenzyl)
-Ether, (4-diethylamino-2-ethoxy-
4'-Dimethylaminobenzhydryl)-(4-chlorobenzyl) -ether, (4-diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl)-(4
-Methoxybenzyl) -ether, (4-diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl)-(4-n-propylbenzyl) -ether, (4
-Diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl)-(4-ethoxybenzyl) -ether, (4-diethylamino-2-methoxy-4'-dimethylaminobenzhydryl) -methyl-ether,
(4-Diethylamino-2-methoxy-4'-dimethylaminobenzhydryl) -benzyl-ether, (4-
Dimethylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl-ether, (4-dimethylamino-2-methyl-4'-dimethylaminobenzhydryl) -isopropyl-ether, (4-dimethylamino) -2-methyl-4'-dimethylaminobenzhydryl)
-Benzyl-ether, (4-dimethylamino-2-n
-Propyl-4'-dimethylaminobenzhydryl)-
Methyl-ether, (4-diethylamino-2-isopropoxy-4'-dimethylaminobenzhydryl) -methyl-ether, (4-dimethylamino-2-chloro-
4'-Dimethylaminobenzhydryl) -isopropyl-ether, (4-diethylamino-2-ethoxy-
4'-diethylaminobenzhydryl) -methyl-ether, (4-diethylamino-2-ethoxy-4'-diethylaminobenzhydryl) -benzyl-ether,
(4-diethylamino-2-ethoxy-4'-di-n-
Butylaminobenzhydryl) -methyl-ether,
(4-diethylamino-2-ethoxy-4'-di-n-
Butylaminobenzhydryl) -benzyl-ether,
[4-Diethylamino-2-methyl-4 ′-(N-methyl-Nn-propylamino) benzhydryl] -methyl-ether, (4-diethylamino-2-methyl-
4'-dibenzylaminobenzhydryl) -isopropyl-ether, [4,4'-bis (diethylamino)-
2,2'-Dimethylbenzhydryl] -methyl-ether, [4,4'-bis (diethylamino) -2,2'-
Dimethylbenzhydryl] -benzyl-ether,
[4,4'-bis (diethylamino) -2,2'-diethoxybenzhydryl] -methyl-ether, [4
4'-bis (diethylamino) -2,2'-diethoxybenzhydryl] -benzyl-ether, (4-dimethylamino-3-methyl-4'-dimethylaminobenzhydryl) -benzyl-ether, (4 -Di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -n-propyl-ether, (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) ) -Isopropyl-ether, (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -ethyl-ether, (4-di-n-butylamino-2-methyl-4 '). -Dimethylaminobenzhydryl) -methyl-ether, (4-di-n-butylamino-2-methoxy-4'-dimethylaminobenzhydryl) -n-propyi -Ether, (4-di-n-butylamino-2-methoxy-4'-dimethylaminobenzhydryl) -isopropyl-ether, (4-di-n-butylamino-2-methoxy-4'-dimethylamino) Benzhydryl) -ethyl-ether, (4-di-n-butylamino-2-methoxy-4'-dimethylaminobenzhydryl) -methyl-ether, (4-di-n-butylamino-2-ethoxy) -4'-Dimethylaminobenzhydryl) -n-propyl-ether, (4-di-n-butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -isopropyl-ether, (4-di- n
-Butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -ethyl-ether, (4-di-n-
Butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -methyl-ether, (4-di-n-amylamino-2-methyl-4'-dimethylaminobenzhydryl) -n-propyl-ether, (4-di-n-
Amylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl-ether, (4-di-n-amylamino-2-methoxy-4'-dimethylaminobenzhydryl) -ethyl-ether, (4- Di-n-amylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -methyl-ether, (4-di-n-butylamino-2-methyl-4'-diethylaminobenzhydryl) -n-propyl -Ether, (4-di-n-butylamino-2-methyl-4'-diethylaminobenzhydryl) -ethyl-ether, (4-di-n-butylamino-2-methyl-4'-diethylaminobenzhydri) Drill) -methyl-ether, bis (4-diethylamino-
2-Methyl-4'-dimethylaminobenzhydryl)-
Ether, bis (4-diethylamino-2-ethoxy-
4'-dimethylaminobenzhydryl) -ether, bis (4-diethylamino-2-methoxy-4'-dimethylaminobenzhydryl) -ether, bis (4-dimethylamino-2-methyl-4'-dimethylamino Benzhydryl) -ether, bis (4-dimethylamino-2)
-N-propyl-4'-dimethylaminobenzhydryl) -ether, bis (4-dimethylamino-2-tert)
-Butoxy-4'-dimethylaminobenzhydryl)-
Ether, bis (4-dimethylamino-2-chloro-
4'-Dimethylaminobenzhydryl) -ether, bis (4-diethylamino-2-ethoxy-4'-diethylaminobenzhydryl) -ether, bis [4-diethylamino-2-ethoxy-4 '-(N-methyl) -N-
n-propylamino) benzhydryl] -ether, bis (4-diethylamino-2-ethoxy-4′-dibenzylaminobenzhydryl) -ether, bis [4
4'-bis (dimethylamino) -2,2'-dimethylbenzhydryl] -ether, bis [4,4'-bis (diethylamino) -2,2'-dimethylbenzhydryl]
-Ether, bis (4-diethylamino-3-methyl-
4'-dimethylaminobenzhydryl) -ether, bis (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -ether, bis (4-
Di-n-butylamino-2-methoxy-4'-dimethylaminobenzhydryl) -ether, bis (4-di-n
-Butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -ether and the like.

The present invention is not limited to the above specific examples, and any compound included in the general formula [Chemical formula 1] or [Chemical formula 2] 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 formula [Chemical Formula 3] or [Chemical Formula 4] are particularly excellent in color developability and color image fastness, and the raw materials are easily available and synthesized. Since it is easy, it is particularly preferably used.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[Wherein R₈~ R₁₁Are each C₁~ C_Five
Represents an alkyl group of R,₁₂Is C₁~ C ₂An alkyl group of
C₁~ C₂The alkoxyl group or halogen atom of
And R₁₃Is C₁~ C_FourAlkyl group or benzyl group of
Show. ]

Further, among the compounds represented by the above general formula [Chemical Formula 3] or [Chemical Formula 4], the compounds in which R ₈ and R ₉ are each a C ₄ -C ₅ alkyl group are particularly excellent in desensitization. It is particularly preferably used because of its suitability.

In the pressure-sensitive recording material of the present invention, the amount of the diarylmethane compound used is appropriately selected according to the kind of the pressure-sensitive recording material such as upper paper, middle paper, self-coloring type, or desired quality. However, the coating amount (content) of the diarylmethane compound is 0.002 to 1 g / m ² , and preferably 0.00.
It is desirable to adjust it to be in the range of 5 to 0.3 g / m ² .

The present invention has the general formula [Chemical formula 1] or [Chemical formula 2]
It is characterized by using a diarylmethane compound represented by the formula (1), but other known basic dyes can be used in combination within a range that does not impair the desired effects of the present invention. Examples of such basic dyes include the following. 1,
1-bis [p- (N-methyl-N-phenyl) anilino] -1- (9-n-butylcarbazol-3-yl)
Triarylmethane compounds such as methane and leuco crystal violet, 3,3-bis (1-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethyl Triarylmethanelactone compounds such as aminophthalide, 3- (4-diethylamino-2-methylphenyl) -3- (4-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (N-ethyl-N) -Isoamyl) amino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-di-n-butylamino-6-methyl-7-anilinofluorane , 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane, 3-cyclohexylamino-6- Rorofuruoran, 3-diethylamino-benzo [2] fluoran, 3-diethylamino -7
-Chlorofluorane, 1,3-dimethyl-6-dimethylaminofluorane, 3,6-dimethoxyfluorane, 3
-(N-ethyl-p-toluidino) -7-N-methylanilinofluorane, 1-ethyl-8- (di-n-amylamino) -2,2,4-trimethyl-1,2-dihydrospiro [ 11H-chromeno [2,3-g] quinoline-1
1,3′-phthalide] and the like, 3,7
Phenothiazine compounds such as -bis (dimethylamino) -10-benzoylphenothiazine, 3,6-bis (diethylamino) fluorane-γ-anilinolactam, N
Rhodamine lactam compounds such as-(2-chlorophenyl) rhodamine-B-lactam, 3-methyl-di-β-
Spiropyran compounds such as naphthopiropyran, 3,3
-Bis [1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl] -4,5,6,7-tetrabromophthalide, 3,3-bis [1- (4-methoxyphenyl)-
1- (4-Dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide and other ethylenephthalide compounds, 2- (4-dodecyloxy-3)
-Methoxystyryl) quinoline and other thrylquinoline compounds, 3,3'-dichloro-4,4'-bis [4,4 '
-Bis (dimethylamino) benzhydryl] -diphenylmethane, bis (4-dimethylaminophenyl)-(p
-Diphenylmethane-based compounds such as -toluenesulfonyl) methane, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-n
-Octyl-2-methylindol-3-yl) phthalide and other indole compounds. Among these other known basic dyes, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide is preferable because it can be used in combination to obtain a pressure-sensitive recording material having more excellent color developability. .

In the present invention, when 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide is used in combination, the amount used is not particularly limited, but is usually [Chemical formula 1] or [Chemical formula 1] [Chemical Formula 2] is used in an amount of 20 to 1000 parts by weight, preferably 50 to 500 parts by weight, based on 100 parts by weight of the diarylmethane compound. By the way, if the amount used is less than 20 parts by weight, the combined effect will not be sufficiently exhibited, and if the amount used exceeds 1000 parts by weight, the storability of the color image may be deteriorated.

In the present invention, by specifying the wall film material of the microcapsules encapsulating the basic dye as a synthetic polymer material, the occurrence of color stains is suppressed and the average particle diameter is 3 to 15 μm. By restricting to, the unevenness and discontinuity of the color density due to the difference in writing pressure can be eliminated, and the contact stain caused by the unintended pressure can be significantly suppressed. Further, by specifying the average film thickness of the microcapsules to be 0.1 to 0.7 μm, the rubbing stain is further improved, and as a result, a sharp and clear print can be formed, and the pressure sensitive recording material having stable quality characteristics. Is what you get.

Incidentally, when a natural material is used as the wall film material of the microcapsules, it is impossible to prevent the generation of color stains. Even in the case of a microcapsule composed of a synthetic polymer-based wall film, when the average particle size of the capsule is less than 3 μm, the unevenness of the color density is promoted as the color density is lowered, resulting in a clear image. On the other hand, when the average particle size exceeds 15 μm, contact stains become noticeable. Therefore, it is necessary to adjust the average particle size of the capsule in the range of 3 to 15 μm, preferably 5 to 10 μm. Furthermore, when the average film thickness is less than 0.1 μm, the amount of rubbing stains increases, and when it exceeds 0.7 μm, the color developing sensitivity decreases.
The average film thickness of the capsule is adjusted in the range of 0.1 to 0.7 μm, preferably 0.1 to 0.4 μm.

The basic dye used in the present invention may be mixed with various known UV absorbers, if necessary, and then cottonseed oil, hydrogenated terphenyl, hydrogenated terphenyl derivative, alkylbiphenyl, alkylnaphthalene, diarylalkane,
Synthetic polymer-based wall membrane dissolved in a natural or synthetic hydrophobic medium such as paraffin, naphthenic oil, and dibasic acid ester such as phthalic acid ester, and by capsule manufacturing method such as interfacial polymerization method and in-situ polymerization method. It is encapsulated in microcapsules made of wood. Then, the encapsulation conditions at that time, for example, the amount of the wall membrane material used, the strength of the shear during emulsification,
By appropriately adjusting the emulsification time and the like, a capsule having the above-mentioned specific average particle diameter and average film thickness is prepared. Examples of the resin forming the wall film include aminoaldehyde resin, polyurea resin, polyurethane resin, polyamide resin and the like.

Aminoaldehyde resin wall membrane capsules include at least one amine such as urea, thiourea, alkylurea, ethyleneurea, acetoguanamine, benzoguanamine, melamine, guanidine, biuret, and cyanamide, and formaldehyde, acetaldehyde, para. In-si using at least one aldehyde such as formaldehyde, hexamethylenetetramine, glutaraldehyde, glyoxal and furfural, or an initial condensate obtained by condensing them as a wall film material
It is manufactured by the tu polymerization method.

Polyurethane resin and / or polyurea resin wall membrane capsules contain, for example, polyisocyanate and water, polyisocyanate and polyol, isothiocyanate and water, isothiocyanate and polyol, polyisocyanate and polyamine, isothiocyanate and polyamine, and the like. It is manufactured by the interfacial polymerization method used as a wall film material. The polyamide resin wall membrane capsule is manufactured by, for example, an interfacial polymerization method of acid chloride and amine.

The thus prepared microcapsules containing a specific basic dye and having a specific average particle diameter and average film thickness can be prepared by a conventional method from adhesive agents such as polyvinyl alcohols, starches, carboxymethyl cellulose and latexes. In addition, various auxiliary agents such as a tilting agent such as pulp powder and raw starch powder are appropriately blended to prepare a capsule coating solution, which is used for producing upper paper, middle paper, self-coloring pressure-sensitive recording material, etc. .

In the present invention, an activated clay mineral having a specific silicon oxide content is used as a colorant-containing layer combined with the microcapsule coated surface of the upper or middle paper or as a colorant of a self-coloring type pressure-sensitive recording material. There is also a feature in using. As the activated clay mineral, activated clay, attapulgite, zeolite, clay minerals such as bentonite, etc. are known, but in the present invention, from the viewpoint of colorability to the specific diarylmethane compound and fastness of the obtained image. Therefore, an activated clay mineral having a silicon oxide (SiO ₂ ) content of 65 to 80% by weight is selectively used. Further, among these, the activated clay which has been acid-treated so that the content of silicon oxide (SiO ₂ ) is 65% by weight to 75% by weight can provide a pressure-sensitive recording material having more excellent recorded image fastness. Therefore, it is more preferably used. Here, activated clay refers to acid clay activated by acid treatment. In addition,
In the present invention using a specific diarylmethane compound, when the active clay mineral used has a silicon oxide content of more than 80% by weight, only a pressure-sensitive recording material having extremely inferior image fastness, particularly light fastness, can be obtained. Absent.

In the pressure-sensitive recording material of the present invention, the amount of the specific activated clay mineral used is appropriately selected according to the type of the pressure-sensitive recording material such as the lower paper and the self-coloring type, or the desired quality. is intended to be, although not particularly limited, the coating amount of the active clay mineral (content) 1 to 15 g / m ^2, preferably it is desirable to adjust so that the range of 2 to 8 g / m ² .

As the coloring agent, various known organic coloring agents such as phenol derivatives, salicylic acid derivatives, aromatic carboxylic acid derivatives and their metal salts, and novolak resins are used in combination as long as the effects of the present invention are not impaired. It is also possible.

The coloring agent coating liquid is usually prepared by a method in which the above-mentioned specific activated clay mineral 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 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 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 to 20
It is applied to a support such as paper, synthetic paper, film or the like so that it will be about g / m ² .

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in an example show a weight part and weight%, respectively.

Example 1 [Preparation of Coloring Agent Coating Liquid] The content of silicon oxide (SiO ₂ ) was 7
2 parts by weight of activated clay 100 parts, magnesium oxide 1 part,
A coloring agent coating liquid was prepared by adding 20 parts (solid content) of carboxy-modified styrene / butadiene copolymer latex and 1 part of sodium carboxymethyl cellulose. [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.) and 10 parts of (4-diethylamino-2-methyl-4′-dimethylaminobenzhydryl) -n-propyl-ether as a basic dye. Dissolves and further polymethylene polyphenyl isocyanate (trade name:
Millionate MR400, made by Nippon Polyurethane Industry Co., Ltd.)
A solution obtained by dissolving 5 parts and a trimer of hexamethylene diisocyanate having a burette bond (trade name: N-3200, manufactured by Sumitomo Bayer Co., Ltd.) was used as a capsule core substance in the above aqueous medium for capsule preparation. , T. K. It was dispersed for 1 minute at 10000 rpm using a homomixer.

Diethylenetriamine 1 was added to this emulsion dispersion.
Parts and after stirring for 30 minutes at room temperature, the system temperature was adjusted to 7
The temperature was raised to 0 ° C. and the reaction was continued for 3 hours while stirring, then the temperature was lowered to room temperature and the average particle size was 5.6 μm.
Microcapsules composed of polyurea resin / polyurethane resin wall film having an average film thickness of 0.15 μm were prepared.

[Preparation of microcapsule coating solution] 70 parts of wheat starch powder and 2 parts of oxidized starch aqueous solution per 100 parts by weight (solid content) of the microcapsule dispersion thus obtained.
0 part (solid content) was added to prepare a microcapsule coating solution. [Manufacture of medium-sized paper] For pressure-sensitive recording, the microcapsule coating liquid is applied to the opposite side of the lower paper from the surface coated with the coloring agent by an air knife coater so as to have a dry weight of 4 g / m ² . I got the inside paper.

Examples 2 to 30 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, 29 kinds of pressure-sensitive recording medium paper were obtained. The average particle diameter and the average film thickness of each of the prepared microcapsules were 5.2 to 5.9 μm,
The average film thickness was in the range of 0.15 to 0.20 μm. -Example 2: (4-diethylamino-2-ethoxy-
4'-Dimethylaminobenzhydryl) -n-propyl-ether 10 parts-Example 3: (4-diethylamino-2-ethoxy-)
4'-Dimethylaminobenzhydryl) -benzyl-ether 10 parts Example 4: (4-Dimethylamino-2-methyl-4 ')
-Dimethylaminobenzhydryl) -isopropyl-ether 10 parts-Example 5: (4-diethylamino-2-ethoxy-
4'-di-n-butylaminobenzhydryl) -methyl-ether 10 parts-Example 6: (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl- Ether 10 parts-Example 7: (4-di-n-butylamino-2-methoxy-4'-dimethylaminobenzhydryl) -methyl-
Ether 10 parts-Example 8: (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -ethyl-ether 10 parts-Example 9: (4-di-n-butyl). Amino-2-methoxy-4'-dimethylaminobenzhydryl) -ethyl-
Ether 10 parts-Example 10: (4-di-n-butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -methyl-
Ether 10 parts-Example 11: (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -n-propyl-ether 10 parts-Example 12: (4-di-n -Amylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl-ether 10 parts-Example 13: [4,4'-bis (diethylamino)-
2,2'-Dimethylbenzhydryl] -methyl-ether 10 parts Example 14: Bis (4-diethylamino-2-methyl-)
4'-Dimethylaminobenzhydryl) -ether 1
0 part Example 15: Bis (4-diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -ether
10 parts-Example 16: Bis (4-diethylamino-2-methoxy-4'-dimethylaminobenzhydryl) -ether
10 parts-Example 17: Bis (4-dimethylamino-2-chloro-)
4'-Dimethylaminobenzhydryl) -ether 1
0 parts Example 18: Bis (4-diethylamino-2-ethoxy-4'-diethylaminobenzhydryl) -ether
10 parts-Example 19: Bis [4,4'-bis (dimethylamino)]
-2,2'-Dimethylbenzhydryl] -ether 1
Example 20: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts and (4-diethylamino-2-methyl-4'-dimethylaminobenzhydryl) -n- Propyl-ether 5 parts Example 21: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts and (4-diethylamino-2-ethoxy-4'-dimethylaminobenzhydryl). -N-propyl-ether 5 parts Example 22: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts and (4-diethylamino-2-methyl-4'-dimethylaminobenz). Hydryl) -benzyl-ether 5 parts Example 23: 5,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts and bis (4-)
Diethylamino-2-methyl-4′-dimethylaminobenzhydryl) -ether 5 parts Example 24: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts and bis (4-)
Diethylamino-2-ethoxy-4′-dimethylaminobenzhydryl) -ether 5 parts Example 25: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts and bis (4-)
Diethylamino-2-methoxy-4'-dimethylaminobenzhydryl) -ether 5 parts Example 26: 5,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts and (4-di) −
n-Butylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl-ether 5 parts Example 27: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts And (4-di-
n-Butylamino-2-ethoxy-4'-dimethylaminobenzhydryl) -methyl-ether 5 parts Example 28: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 5 parts And (4-di-
n-Butylamino-2-methyl-4'-dimethylaminobenzhydryl) -n-propyl-ether 5 parts Example 29: (4-di-n-butylamino-2-methyl-4'-dimethylamino) Benzhydryl) -methyl-ether 4 parts, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide 3 parts, and 2
-(4-dodecyloxy-3-methoxystyryl) quinoline 3 parts-Example 30: (4-di-n-butylamino-2-methyl-4'-dimethylaminobenzhydryl) -methyl-ether 4 parts, 3-diethylaminobenzo [2] fluorane 3 parts and 3,6-dimethoxyfluorane 3
Department

Example 31 In the preparation of the coloring agent coating solution of Example 1, 100 parts of activated clay having a silicon oxide content of 78% by weight was used in place of 100 parts of activated clay having a silicon oxide content of 72% by weight. A pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 except for the above.

Example 32 In the same manner as in Example 1, except that the emulsification time of the capsule core substance and the aqueous medium for capsule preparation was changed from 1 minute to 30 seconds in the preparation of the microcapsule dispersion of Example 1. Average particle size is 12.2μm and average film thickness is 0.30μ
m capsules were prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Example 33 An average particle size of 4. was obtained in the same manner as in Example 1 except that the amount of polymethylene polyphenyl isocyanate used was reduced from 5 parts to 3 parts in the preparation of the microcapsule dispersion of Example 1. A capsule having a thickness of 6 μm and an average film thickness of 0.11 μm was prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

Example 34 A pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 except that the microcapsule dispersion liquid was prepared as follows. [Preparation of Microcapsule Dispersion] In a stirring and mixing vessel equipped with a heating device, 200 parts of a 3% aqueous solution of an ethylene-maleic anhydride copolymer (trade name: EMA31, manufactured by Monsanto) was charged, and then 20% caustic soda was added. The aqueous solution was added dropwise to adjust the pH to 6.0 to obtain an aqueous medium for capsule production. Separately, 100 parts of alkylnaphthalene (trade name: KMC Oil, manufactured by Kureha Chemical Co., Ltd.) and 10 parts of (4-diethylamino-2-methyl-4′-dimethylaminobenzhydryl) -n-propyl-ether as a basic dye. Was dissolved to obtain an internal phase oil. Then, this internal phase oil was charged into the above-mentioned aqueous medium for capsule production, and T.I. K. Emulsify and disperse for 1 minute at 10000 rpm with a homomixer,
Then, the temperature was raised 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, then 0.2N. -P with hydrochloric acid
After H was lowered to 3.5 and the temperature was kept for another 3 hours, the mixture was allowed to cool to prepare microcapsules consisting of an aminoaldehyde resin film having an average particle diameter of 5.3 μm and an average film thickness of 0.15 μm.

Comparative Example 1 Preparation of the microcapsule dispersion of Example 1 was carried out except that 10 parts of 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide was used as the basic dye. Capsules having an average particle size of 5.7 μm and an average film thickness of 0.17 μm were prepared in the same manner as in Example 1, and the same procedure as in Example 1 was followed to obtain a pressure-sensitive recording medium paper.

Comparative Example 2 Example 1 was repeated except that 10 parts of 4,4'-bis (dimethylaminobenzhydryl) -benzyl-ether was used as the basic dye in the preparation of the microcapsule dispersion of Example 1. Capsules having an average particle diameter of 5.5 μm and an average film thickness of 0.16 μm were prepared in the same manner as in
In the same manner as above, a pressure-sensitive recording medium paper was obtained.

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

Comparative Example 4 In the preparation of the microcapsule dispersion of Example 1, the same procedure as in Example 1 was carried out except that the emulsification time of the capsule core substance and the aqueous medium for capsule production was changed from 1 minute to 15 seconds. A polyurea resin / polyurethane resin wall film capsule having a particle diameter of 18 μm and an average film thickness of 0.42 μm was prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 below.

Comparative Example 5 An average particle size of 5 was obtained in the same manner as in Example 1 except that the amount of polymethylene polyphenyl isocyanate used was reduced from 5 parts to 1 part in the preparation of the microcapsule dispersion of Example 1. A polyurea resin / polyurethane resin wall film capsule having a thickness of 0.3 μm and an average film thickness of 0.06 μm was prepared, and a pressure-sensitive recording medium paper was obtained in the same manner as in Example 1.

COMPARATIVE EXAMPLE 6 Preparation of the microcapsule dispersion of Example 1 except that the amount of polymethylene polyphenyl isocyanate used was increased from 5 parts to 10 parts and the emulsification time was changed from 1 minute to 15 seconds. As in Example 1, the average particle size was 20.
Prepare capsules with 3 μm and average thickness 0.81 μm,
Thereafter, in the same manner as in Example 1, a pressure-sensitive recording medium paper was obtained.

Comparative Example 7 In the preparation of the microcapsule dispersion of Example 1, the emulsification conditions of the capsule core substance and the aqueous medium for capsule preparation were changed from 1 minute at 10000 rpm to 2 minutes at 20000 rpm. Except for the above, capsules having an average particle diameter of 2.1 μm and an average film thickness of 0.14 μm were prepared in the same manner as in Example 1, and pressure-sensitive recording intermediate paper was obtained in the same manner as in the following examples.

Comparative Example 8 100 parts of alkyldiphenylethane and (4-diethylamino-2-methyl-4'-dimethylaminobenzhydryl) -n-propyl-ether 10 as a basic dye were used.
Parts were dissolved. Separately, 25 parts of pigskin gelatin having an isoelectric point of 8 and 25 parts of gum arabic as an encapsulating agent were dissolved in 300 parts of warm water (50 ° C.). To the gelatin-arabic gum mixed solution, the color-forming agent-containing oil was added while stirring to emulsify and disperse.

This emulsion was further diluted with 1000 parts of warm water, and acetic acid was gradually added to adjust the pH of the solution to 4 to 4.3. A capsule was produced. The capsule was cooled to about 10 ° C., 10 parts of a 25% aqueous solution of glutaraldehyde was added to cure the capsule, and the gelatin-based wall film having an average particle size of 6.2 μm and an average wall film thickness of 0.37 μm. Capsules were prepared, and a pressure-sensitive recording intermediate paper was obtained in the same manner as in Example 1 below.

Comparative Example 9 In the preparation of the coloring agent coating liquid of Example 1, 100 parts of activated clay having a silicon oxide content of 72% by weight was replaced with activated clay having a silicon oxide (SiO ₂ ) content of 85% by weight. A pressure-sensitive recording medium paper was obtained in the same manner as in Example 1 except that 100 parts were used.

Comparative Example 10 In the preparation of the coloring agent dispersion of Example 1, bentonite 100 having a silicon oxide (SiO ₂ ) content of 60% by weight was used instead of 100 parts of activated clay having a silicon oxide content of 72% by weight.
A pressure-sensitive recording medium sheet was obtained in the same manner as in Example 1 except that the parts were used.

Using the thus obtained 44 kinds of pressure-sensitive recording medium paper, various performance comparison tests were conducted, and the results are shown in Tables 1 and 2. [Printing Density] The prepared pressure-sensitive recording medium paper is overlaid so that the capsule coating surface and the coloring agent coating surface face each other and printed by a dot printer, and then the color density is measured by a Macbeth densitometer (Macbeth RD- 914 type) using a visual filter.

[Light resistance test] The printing color-developing surface (coloring agent-coated surface) obtained above was exposed to direct sunlight for 8 hours, and then the color-developing density was measured again with a Macbeth densitometer.

[Water resistance test] Printed medium paper in water 2
After being left for 4 hours, the color density was measured again with a Macbeth densitometer.

[Plasticizer resistance test] A vinyl chloride film was placed on the printed surface of the print and allowed to stand at 25 ° C. for 7 days, and then the developed color density was measured again with a Macbeth densitometer.

[Discoloration and Discoloration by Mending Tape] The discoloration and discoloration of the image was visually evaluated based on the following evaluation criteria after applying the mending tape on the printed surface and leaving it at 25 ° C. for 14 days. (Evaluation Criteria) ○: Almost no discoloration △: Some discoloration is observed, which is a problem depending on the quality grade ×: Significant discoloration, not practical

[Contact-Resistant Stain Test] The pressure-sensitive recording medium papers were superposed so that the capsule-coated surface and the coloring agent-coated surface faced each other, and a load of 20 kg / cm ² was applied for 1 minute, and then the coloring agent was coated. The degree of color stain on the surface was visually determined according to the following evaluation criteria. (Evaluation Criteria) ○: Almost no dirt △: A little dirt, which is a problem depending on the quality grade ×: Significantly dirty, not practical

[Scratch resistance test] After stacking the pressure-sensitive recording medium paper so that the capsule-coated surface and the coloring agent-coated surface face each other, after rubbing five times with a load of 4 kg / cm ² being applied. The degree of color stain on the surface coated with the color developing agent was visually determined according to the following evaluation criteria. (Evaluation Criteria) ○: Almost no dirt △: A little dirt, which is a problem depending on the quality grade ×: Significantly dirt, not practical

[Desensitization Suitability Test] Offset desensitizing ink (made by Teikoku Ink Co., N
o. 804) is printed so that the coating amount is 4 g / m ² and the desensitized ink coated surface is overlapped with the capsule coated surface of the medium paper on which the desensitized ink is not printed, and the result is printed by a dot printer. 1 at each room temperature and 90 ℃
After being left for a day, the desensitization suitability was visually judged according to the following evaluation criteria.

(Evaluation Criteria) ⊚: Desensitization suitability is good for both those treated at room temperature and 90 ° C. ◯: Desensitization suitability is good only for those treated at room temperature, which is a problem depending on the quality grade. Those treated at both room temperature and 90 ° C have poor desensitization suitability and are not practical

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

As is clear from the results of Table 1 and Table 2, the pressure-sensitive recording of the present invention in which a specific diarylmethane compound is used by being encapsulated in a specific microcapsule and a specific color-developing agent is further combined The body was a pressure-sensitive recording material excellent in color developability and color image fastness, and free from color stain and color tone change, and excellent in desensitization suitability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location 9221-2H B41M 5/12 112 (72) Inventor Koji Koga 4-3-1, Jokoji Amagasaki, Hyogo Prefecture No. Kanzaki Paper Manufacturing Co., Ltd. Kanzaki Mill

Claims (4)

[Claims] 1. A pressure-sensitive recording material utilizing a color reaction between a colorless or light-colored basic dye and a coloring agent, wherein the basic dye is represented by the following general formula [Chemical formula 1] or [Chemical formula 2]. At least one diarylmethane-based compound is used, and the basic dye has an average particle size of 3 to 15 μm and an average film thickness of 0.
A pressure-sensitive material characterized by using an active clay mineral contained in a synthetic polymer microcapsule of 1 to 0.7 μm and having a content of silicon oxide (SiO ₂ ) of 65 to 80% by weight as a coloring agent. Record body. [Chemical 1] [Chemical 2] [In the formula, R _{1 to} R ₄ each represent a C _{1 to} C ₅ alkyl group or a benzyl group, and R ₅ and R ₆ each represent a hydrogen atom, a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ An alkoxyl group or a halogen atom is shown. However, R ₅ and R ₆ do not represent hydrogen atoms at the same time. In addition, R ₇ is C _{1 to} C
An alkoxyalkyl group of C ₂ -C _{20; 20} alkyl group;
Alternatively, it represents a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxyl group or a benzyl group which may be substituted with a halogen atom. ] 2. A diarylmethane compound is represented by the following general formula:
The compound represented by [Chemical Formula 3] or [Chemical Formula 4].
The pressure-sensitive recording material described. [Chemical 3][Chemical 4][In the formula, R₈~ R₁₁Are each C₁~ C_FiveAlkyl group of
Indicates R₁₂Is C₁~ C ₂Alkyl group of C₁~ C₂of
R represents an alkoxyl group or a halogen atom, R₁₃Is C₁
~ C_FourRepresents an alkyl group or a benzyl group. ] 3. An activated clay having a silicon oxide (SiO ₂ ) content of 65 to 75% by weight is used as a color developing agent.
The pressure-sensitive recording material described. 4. The pressure-sensitive recording material according to claim 1, wherein 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide is used in combination as the basic dye.