JPH08169179A - Recording material - Google Patents

Abstract

PURPOSE: To obtain a sheet type recording material which develops color in high density by making the material contain crystal violet lactone as an electron donating color coupler and a mixture of vegetable oil containing a component having a fatty acid residue and a bisphenol compound as a solvent. CONSTITUTION: A recording material contains micro-capsules containing an electron donating color coupler dissolved in a solvent and an electron accepting developer. The color coupler is crystal violet lactone; the solvent contains 100 pts.wt. of vegetable oil with a fatty acid residue content of 10-60wt.% and 2-40 pts.wt. of a bisphenol compound expressed by a formula, where R<1> is -S-, etc.; R<2> -R<11> are hydrogen atom, 1-8 C alkyl, or hydroxyl group, respectively, and one or two of them are hydroxyl group.

Description

Detailed Description of the Invention

[0001]

The present invention has almost no odor,
The present invention relates to a sheet-shaped recording material having high biodegradability and capable of developing color at a high density.

[0002]

2. Description of the Related Art Microcapsules containing an electron-donating color former (hereinafter sometimes referred to as "color former") dissolved in a solvent and an electron-accepting developer (hereinafter referred to as "color former") The recording material utilizing the fact that a color-developed image is formed by the reaction between a color-developing agent and a color-developing agent has been known for a long time and is widely used.

Such recording materials are roughly classified into pressure sensitive recording materials and heat sensitive recording materials. The pressure-sensitive recording material is one in which a microcapsule containing a color-developing agent is destroyed by applying a pressure to this to form a color-developed image by reacting the color-developing agent with the color-developing agent. Coloring agent layer comprising microcapsules containing (hereinafter, "coloring agent layer"
And a developer layer containing a developer (hereinafter,
And a "color developer layer") are formed on the surfaces of separate supports or different surfaces of the same support, and the carbon-free paper is used by bringing the color developer layer and the developer layer into contact with each other. Type recording material, a so-called self-coloring type pressure-sensitive recording material (or press-type paper, self-developing) provided with a self-coloring layer containing a microcapsule containing a color-forming agent and a developer on the same surface of a support. There is something called a "contained paper".

In a carbonless paper type recording material, a color former layer is formed on one side of a support (generally paper) to form an upper sheet, and a color former layer is formed on one side of the support and on the opposite side. It is used by forming a developer layer to form a middle paper, forming a developer layer on one side of a support to form a lower paper, and contacting the color developer layer with the developer layer.

In addition, in the self-coloring type pressure-sensitive recording material, when pressure is applied to the surface on which the self-coloring layer is provided, the microcapsules are destroyed and the color-developing agent reacts with the color-developing agent to develop a color on the self-coloring layer. Since an image is formed, plain paper is placed on the self-coloring layer of the self-coloring type pressure-sensitive recording material, and an image such as letters is recorded on the plain paper with a writing instrument, type, etc. When forming a color image on the color-developing layer, OCR printing is performed when a color-developed image is formed by printing directly on the self-color-developing layer of the self-color-developing pressure-sensitive recording material without using an ink ribbon. It is used in some cases. Furthermore, when making multiple copies, a self-coloring type pressure-sensitive recording material in which a self-coloring layer is provided on one side of the support and a color-developing layer is formed on the opposite side is used to form a color on one side of the support. It may be used in combination with a medium sheet having a developer layer and a developer layer on the opposite side thereof or a lower sheet having a developer layer on one surface of a support. The self-coloring layer of the self-coloring type pressure-sensitive recording material includes a two-layer type in which a color-developing layer containing microcapsules containing a color-developing agent and a color-developing layer containing a color-developing agent are laminated, and in the same layer. There is a single-layer type including a color developer and a microcapsule containing a color developer.

On the other hand, a heat-sensitive recording material containing such microcapsules is disclosed in, for example, JP-A-63-2656.
No. 82 and JP-A-1-105782, there is a heat-sensitive recording material in which a heat-sensitive layer containing microcapsules containing a color former and a color developer is formed on a support. The heat-sensitive recording material containing the microcapsules is
It has the advantage that it can be designed for HP and can be designed as a multicolor thermal recording material.

The microcapsules contained in the recording material as described above contain a color former dissolved in a solvent. As the solvent, a substance capable of dissolving the color former used is used, and generally, kerosene, paraffin, naphthene oil, alkylated biphenyl, alkylated terphenyl,
Chlorinated paraffins, alkylated naphthalenes, diarylalkanes, phthalates and the like are used. However, many of these solvents generally have a bad or unpleasant odor, and also include an ecologically unfavorable one that may cause adverse effects on the human body during environmental pollution or during manufacture and use.

JP-A-50-90409 discloses that when a pressure-sensitive recording paper is manufactured by providing a microcapsule layer containing a color-forming agent solution on a support, the color-forming agent is added to 10
Disclosed is a method for producing a pressure-sensitive recording paper, which comprises dissolving in animal or vegetable oil heated to 5 to 260 ° C.

The animal oils and vegetable oils used in the above method are natural products and can be used for foods, have no offensive or unpleasant odor, are ecologically safe substances, and are relatively inexpensive. It is easily available and is a preferable solvent as the solvent of the color former solution in the microcapsules.

However, animal oils and vegetable oils have a small dissolving power for commonly used color formers, it is difficult to increase the concentration of the color former in the color former solution, and there is a problem that the color density of the recording material is low. . In the above method, the color former is dissolved in the animal oil or the vegetable oil at a high temperature such as 105 to 260 ° C. when the color developer solution is prepared, but when the animal oil or the vegetable oil is heated to a high temperature, it is easily oxidized and deteriorated. However, there is also a problem that an unpleasant odor or a bad odor may be generated. Further, depending on the coloring agent, the coloring property may be inhibited (desensitized).

The applicant of the present invention uses a glyceride such as the above vegetable oil and a specific fluoran compound or a specific indolyl phthalide or indolyl azaphthalide, which is soluble in the vegetable oil, as a recording material having improved color development using the above vegetable oil. A recording material composed of encapsulated microcapsules has already been filed (Japanese Patent Application No. 5-196132 and Japanese Patent Application No. 5196132).
187227).

However, it is necessary to make it possible to use a color former other than the above-mentioned color formers, which is difficult to dissolve in vegetable oil, in order to obtain a specific hue or to adjust the hue of the color, and it is easily available. It is of course desirable to use as many different color formers as possible. For example, when crystal violet lactone, which is widely used as a color-developing agent showing a blue color, is used, it cannot be sufficiently dissolved even if the above-mentioned vegetable oil is used as a solvent. Then, when such a color developer solution in an insufficiently dissolved state is microencapsulated, the capsule wall forming material that does not contribute to the formation of the capsule wall remains as a residue,
In addition to being disadvantageous in production, there is a problem that the recording material using the microcapsules thus obtained cannot obtain a high color density.

[0013]

DISCLOSURE OF THE INVENTION An object of the present invention is as a solvent for dissolving an electron-donating color developing agent that develops a color upon contact with an electron-accepting developer, a vegetable oil having no bad odor and having biodegradability. Is mainly used, and a recording material capable of obtaining a desired hue with a high color density is provided.

[0014]

The present invention is a recording material containing microcapsules containing an electron-donating color developing agent dissolved in a solvent, and an electron-accepting color developing agent. The agent is crystal violet lactone, and the solvent has an oleic acid residue content of 10 to 60.
It comprises a vegetable oil having a fatty acid residue composition of 1% by weight, and within the range of 2 to 40 parts by weight relative to 100 parts by weight of the vegetable oil, the following general formula (1):

[0015]

[Chemical 4] [However, R ¹ is -S-, -CR ¹² R ^13- (provided that R 1
¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or —SO ₂ —, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , R
⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, and R
^{One or two of 2} , R ³ , R ⁴ , R ⁵ , R ⁵ and R ⁶ and one or 2 of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ have a hydroxyl group; Represent. ] The recording material characterized by including the bisphenol compound represented by these.

The preferred embodiments of the present invention are as follows. 1) R ² and / or R ⁴ and R ⁷ and / or R ⁹ are
The above recording material having a hydroxyl group. 2) The above recording material wherein R ² and R ⁷ or R ⁴ and R ⁹ are hydroxyl groups. 3) The bisphenol compound has the following general formula (2):

[0017]

Embedded image [However, R ^{21 is, -S -, - CR 28 R} 29 - ( wherein, R
²⁸ and R ²⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or —SO ₂ —, and R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are respectively Independently, it represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] Or the following general formula (3):

[0018]

[Chemical 6] [However, R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] The above recording material which is a compound represented by

4) The recording material, wherein the solvent contains the bisphenol compound in an amount of 5 to 40 parts by weight (further 5 to 30 parts by weight) with respect to 100 parts by weight of vegetable oil. 5) The recording material, wherein 50% by weight or more of the electron-donating color former is crystal violet lactone. 6) The recording material as described above, wherein the electron-donating color former further contains at least one selected from the group consisting of benzoyl leuco methylene blue, fluorane compounds, indolyl phthalide compounds and indolyl azaphthalide compounds. 7) The recording material, wherein the electron-donating color former is dissolved in the solvent in an amount of 3 to 12% by weight. 8) The recording material as described above, wherein the walls of the microcapsules are polyurethane urea. 9) The above recording material which is a pressure sensitive recording material.

The form of the recording material of the present invention is not particularly limited as long as it contains the above-mentioned electron donating color former and developer. That is, the recording material of the present invention is a carbon-free paper-type pressure-sensitive recording material in which the above-mentioned color former layer and developer layer are formed on the surfaces of separate supports or different surfaces of the support. A self-coloring type pressure-sensitive recording material provided with a microcapsule containing a color former and a self-coloring layer containing a developer on the same surface of the body, and a microcapsule containing the color former and a developer It may be in any form of a heat-sensitive recording material having a heat-sensitive layer formed on a support. As described above, the recording material of the present invention is mainly characterized in that crystal violet lactone is mainly used as a color former contained in the microcapsules, and the solvent for dissolving the color former is limited to a vegetable oil containing a specific bisphenol compound. Is to have. Hereinafter, mainly the carbonless paper type pressure-sensitive recording material will be described in detail. It will be easily understood by those skilled in the art that similar effects can be obtained with other types of recording materials.

In the present invention, the solvent used for dissolving the color former comprises a vegetable oil having a fatty acid residue composition with an oleic acid residue content of 10 to 60% by weight, and 100% by weight of this vegetable oil. The specific bisphenol compound described later is contained in the range of 2 to 40 parts by weight with respect to parts.

Examples of the vegetable oil having a fatty acid residue composition having an oleic acid residue content of 10 to 60% by weight include soybean oil (oleic acid residue content in fatty acid residue composition (OA) = 20 to 35% by weight), corn oil (OA
= 25-45% by weight), rapeseed oil (OA = 10-35% by weight), cottonseed oil (OA = 15-30% by weight), sesame oil (OA = 35-46% by weight), peanut oil (OA = 35-35%)
60% by weight), sunflower oil (OA = 15-35% by weight)
Etc. can be mentioned. Above all, soybean oil, corn oil, rapeseed oil, cottonseed oil, etc. have a high solubility of the color former used (the ability to dissolve the color former (solubility)), and the color developability when reacted with the color developer. Is preferred, and it is industrially easily available. These vegetable oils may be used alone or in combination. Olive oil (OA =
70 to 85% by weight) and the like, vegetable oils having an oleic acid content in the fatty acid residue composition of more than 60% by weight have low solubility of the color former and are not preferred.

The solvent of the present invention comprises the above-mentioned vegetable oil, and contains the bisphenol compound represented by the following general formula (1) in the range of 2 to 40 parts by weight based on 100 parts by weight of the vegetable oil.

[0024]

[Chemical 7] [However, R ¹ is -S-, -CR ¹² R ^13- (provided that R 1
¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or —SO ₂ —, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , R
⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, and R
^{One or two of 2} , R ³ , R ⁴ , R ⁵ , R ⁵ and R ⁶ and 1 of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹
One or two are hydroxyl groups. ]

R ¹ is -S-, -CR ¹² R ^13-
(However, R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) or —SO
_2- is preferred. _{Furthermore, -S -, - SO 2 -} , methylene, isopropylidene or butylidene is preferred. R
² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰
And R ¹¹ are each independently a hydrogen atom or a carbon atom number 1 to
The alkyl group or hydroxyl group of 4 is preferable, and a hydrogen atom, methyl, ethyl or t-butyl is particularly preferable. Of the substituents R ^{2 to} R ¹¹ , R ² and / or R ⁴ and R ⁷ and / or R ⁹ are preferably hydroxyl groups, and particularly R ² and R ⁷ or R ⁴ and R ⁹ are hydroxyl groups. Is preferred.

The bisphenol compound is preferably a compound represented by the following general formula (2) or (3).

[0027]

Embedded image [However, R ^{21 is, -S -, - CR 28 R} 29 - ( wherein, R
²⁸ and R ²⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or —SO ₂ —, and R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are respectively Independently, it represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[0028]

[Chemical 9] [However, R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

In the general formula (2), R ²¹ is-
^{S -, - CR 28 R 29} - ( where an alkyl group of R ²⁸ and R ²⁹ each independently represent a hydrogen atom or a carbon atoms 1 to 4) or -SO ₂ - are preferred. Furthermore, -S-,
-SO ₂ -, methylene, isopropylidene or butylidene is preferred. R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷
As the above, a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, methyl and t-butyl are particularly preferable.

In the general formula (3), R ³¹ , R ³² , R ³³
As R ³⁴ and R ³⁴ , a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, ethyl and t-butyl are particularly preferable.

The above general formula (1) of the present invention (general formula (2)
Alternatively, as a preferred example of the bisphenol compound represented by (3)), 4,4′-methylenediphenol,
4,4'-isopropylidenediphenol, 4,4'-
Butylidene diphenol, 4,4'-methylenebis (3
-Methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), bis (4- Hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4,4′-thiobis (3-methyl-6-
t-butylphenol), 2,2'-methylenebis (4
-Methyl-6-t-butylphenol) and 2,2'-
Mention may be made of methylenebis (4-ethyl-6-t-butylphenol).

In the present invention, the solvent for dissolving the color former contains the bisphenol compound represented by the general formula (1) in the range of 2 to 40 parts by weight based on 100 parts by weight of the vegetable oil. 5 to 40 parts by weight is preferable, and further 1
It is preferably contained in an amount of 0 to 30% by weight. When the amount of the bisphenol compound exceeds 40% by weight, the color of the capsule dispersion liquid (coating liquid for forming the color developing agent layer), which is considered to be caused by the phenolic hydroxyl group, becomes large. This leads to a decrease in whiteness, and deviates from the viewpoint of using mainly vegetable oil having no bad odor and biodegradability, which is the object of the present invention.
On the other hand, if it is less than 2% by weight, a desired amount of a color forming agent such as crystal violet lactone having excellent color forming properties cannot be used.

In the present invention, together with the above-mentioned bisphenol compound and vegetable oil as a solvent, a conventionally used solvent is added in such an amount that does not give an unpleasant odor to the recording medium (generally, 30% by weight or less of the vegetable oil). Amount) may be used. Further, a benzophenone compound represented by the following general formula (4) or an aromatic carboxylic acid ester compound represented by the following general formula (5) or (6) may be used in combination with the bisphenol compound.

[0034]

[Chemical 10] (However, R ⁴¹ and R ⁴² represent a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group or an alkoxycarbonyl group having 1 to 12 carbon atoms, and R ⁴³ and R ⁴⁴ are hydrogen. Atom, hydroxyl group, 1 carbon atom
Represents an alkyl group having 12 to 12 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy). )

[0035]

[Chemical 11] (However, R ⁵¹ is an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a hydroxyl group, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, Or -CH ₂ COOR ⁵³ (R ⁵³ has 1 carbon atom
Represents an alkyl group having from 1 to 12 or a phenyl group), and R ⁵² represents an alkyl group having from 6 to 12 carbon atoms,
A cycloalkyl group having 5 to 8 carbon atoms, a hydroxyl group, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or R ⁵² is —CH ₂ COOR ⁵³ (R ⁵³ is 1 to 12 represents an alkyl group or a phenyl group)
Represents )

[0036]

[Chemical 12] (However, R ⁶¹ , R ^62, and R ⁶³ are each a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms.
Or an aralkyl group having 7 to 18 carbon atoms, and R ⁶⁴ represents an alkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms (eg, phenyl), or 7 to 7 carbon atoms. Aralkyl group having 10 carbon atoms, alkylaryl group having 7 to 18 carbon atoms or 7 to 1 carbon atoms
8 represents an alkoxyaryl group.

The color-developing agent used in the present invention is a color-developing agent containing crystal violet lactone, but any known color-developing agent other than crystal violet lactone can be used as long as it is soluble in a solvent containing the above-mentioned bisphenol compound and vegetable oil as a main component. Can be used. Examples of the color former of the present invention include triphenylmethanephthalide compounds other than crystal violet lactone, fluorane compounds,
Phenothiazine compounds, indolyl phthalide compounds, indolyl azaphthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds Can be used together. Among these, crystal violet lactone, benzoyl leuco methylene blue, fluorane compound, indolyl phthalide compound and indolyl azaphthalide compound are preferable. In the present invention, the content of crystal violet lactone is preferably 50% by weight or more of the total amount of the color former. Particularly, 60 to 100% by weight is preferable.

In producing the microcapsules containing the color former, the color former is dissolved in the mixture of the bisphenol compound and the vegetable oil as described above to prepare a color former solution, which is prepared by dissolving the color former in the vegetable oil. Temperature is 80-1
It is preferably 30 ° C. At a temperature lower than the above range, the color former is difficult to dissolve in the vegetable oil, and at a temperature higher than the above range, the vegetable oil may deteriorate. The concentration of the color former in the color former solution is preferably 3 to 12% by weight, and more preferably 3 to 10% by weight, based on the vegetable oil.

The microcapsules containing the color former can be produced by any method known per se, for example, interfacial polymerization method, internal polymerization method, phase separation method, external polymerization method, coacervation method and the like. it can. The wall material of the microcapsule is water-insoluble, which is conventionally used as the wall material of the color-forming agent-containing microcapsule of the pressure-sensitive recording material.
Any oil-insoluble polymer can be used without particular limitation, and examples thereof include a polyurethane urea wall, a melamine / formaldehyde wall, and a gelatin wall. The wall material of the microcapsules is particularly preferably a polyurethane urea resin because of its high resistance to thermal fog.

The polyurethane urea wall microcapsules encapsulating the color former as described above are prepared by dissolving a solution of a polyvalent isocyanate, a polyvalent hydroxy compound and the electron donating color former in a solvent such as the vegetable oil in a hydrophilic liquid. It can be prepared by emulsifying and dispersing in, and then adding a polyvalent amine into the emulsified dispersion and coating the hydrophobic droplets with a polyurethane urea film. The dispersion liquid containing the microcapsules thus obtained can be used as a coating liquid for forming a color former layer.

As the polyisocyanate used in the present invention, hydrogenated xylylene diisocyanate (generally called hydrogenated XDI) isocyanurate, isophorone diisocyanate (generally called IPDI) isocyanurate, 4,4 '. -Diphenylmethane diisocyanate, an adduct of hexamethylene diisocyanate and trimethylolpropane, biuret of hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, carbodiimide-modified diphenylmethane diisocyanate, tolylene diisocyanate and trimethylolpropane and Adduct of xylylene diisocyanate with trimethylol propane, Cyanurates, hydrogenated xylylene diisocyanate adducts with trimethylol propane, isophorone diisocyanate adducts with trimethylol propane, xylylene diisocyanate biuret and tris- (p-isocyanatophenyl) thiophosphite Etc. can be mentioned.

Of these, hydrogenated xylylene diisocyanate isocyanurates and isophorone diisocyanate isocyanurates are preferable because of their excellent solubility in vegetable oils. It is preferable to use a mixture of these two kinds of polyvalent isocyanate and aromatic polyvalent isocyanate, and the mixing ratio thereof is 8: 2 to 2: 8 by weight.
Is preferable (2 types: aromatic), and in particular, 7: 3 to 3:
A range of 7 is preferred.

The compound capable of polymerizing with a polyvalent isocyanate is
Water, a polyvalent hydroxy compound and / or a polyvalent amine. Specific examples of the above-mentioned polyhydric hydroxy compounds include aliphatic or aromatic polyhydric alcohols, hydroxypolyesters, hydroxypolyalkylene ethers, alkylene oxide adducts of polyvalent amines, and the like.

The above-mentioned polyvalent amine compound is a compound having two or more --NH-- groups or --NH ₂ groups in the molecule and soluble in a hydrophilic liquid. Specific examples of the polyvalent amine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,3-propylenediamine, hexamethylenediamine, phenylenediamine, diaminonaphthalene,
Examples include xylylenediamine and the like.

The dispersion liquid of the microcapsules prepared as described above is used as it is as a coating liquid for forming a color former layer, or a binder, a capsule protecting agent and the like are further added to this microcapsule dispersion liquid to form a color former layer. A coating liquid for formation is prepared, coated on a support by a method known per se, and dried to form a color former layer of a carbonless paper pressure-sensitive recording material. As the binder, a water-soluble binder, a latex binder or the like can be used, and as the capsule protecting agent, cellulose powder, starch particles, talc or the like can be used.

As the support, any support conventionally used as a support for pressure-sensitive recording materials and heat-sensitive recording materials, for example, paper from wood pulp, paper obtained by surface-treating this paper, plastics material Synthetic paper, plastics film, etc. from can be used.

The final coating amount of the color former to be coated on the support is
0.05-0.30 g / m ² , preferably 0.08-
0.20 g / m ² is suitable.

The color developer contained in the color developing layer of the carbonless pressure-sensitive recording material of the present invention includes acidic clay, activated clay, attapulgite, zeolite, bentonite, clay substances such as kaolin, and aromatic carvone. Acid (eg,
Examples thereof include metal salts of salicylic acid derivatives) and phenol formaldehyde resins. From the viewpoint of ecology, the developer is preferably a clay substance.

The coating liquid for forming the developer layer is
It can be prepared by a method known per se.For example, as a binder, styrene-butadiene copolymer latex, vinyl acetate latex, acrylic ester latex, polyvinyl alcohol, polyacrylic acid, It may contain synthetic or natural polymer substances such as maleic anhydride-styrene-copolymer, starch, casein, gum arabic, gelatin, carboxymethylcellulose, methylcellulose and the like.
The developer layer can be formed on the support as described above by a method known per se.

The final coating amount of the color developer applied to the support is
^{0.1g / m 2 ~4.0g / m 2} , preferably 0.2g
/ M ^{2 to} 3.0 g / m ² is suitable.

The carbon-free paper type pressure-sensitive recording material of the present invention has the same constitution as that of the conventionally known carbon-free paper type pressure-sensitive recording material except that the specific vegetable oil is used as a solvent for dissolving the color former. It can be manufactured in the same manner.

Although the recording material of the present invention has been described above with respect to the carbonless paper type pressure-sensitive recording material, the above-described specific microcapsules can be applied to the self-coloring type pressure-sensitive recording material and the heat-sensitive recording material. Other than the use, each can be configured and manufactured in the same manner as a conventionally known recording material.

[0053]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1] [Preparation of coating liquid for forming color former layer] As a color former, 9.0 g of crystal violet lactone was added to 4,4'-thiobis (3-methyl-6-t-butylphenol) 18.
A mixture of 0 g and 100 g of rapeseed oil was heated to 120 ° C. and dissolved. Hydrogenated XDI isocyanurate as polyvalent isocyanate was added to the obtained oily liquid (Takeda Pharmaceutical Co., Ltd.).
(Trade name "Takenate D-127N", 75 wt% ethyl acetate solution) 6.0 g and carbodiimide-modified diphenylmethane diisocyanate (manufactured by Mitsui Toatsu Chemicals, Inc., trade name "Cosmonate LK", solid content 100%) 6 0.0 g
Was dissolved in 30 g of ethyl acetate, and 3.0 g of ethylenediamine butylene oxide adduct (addition mole number of butylene oxide to ethylenediamine: 16.8 mol, molecular weight: 1267) was dissolved to prepare a primary solution.

Next, 10 g of polyvinyl alcohol and 5 g of carboxymethyl cellulose were heated and dissolved in 140 g of water in a stainless steel container to prepare a secondary solution. While vigorously stirring the secondary solution, the primary solution was poured into the secondary solution to form an oil-in-water emulsion. When the size of the oil droplet reached 6.0 μm, the stirring was weakened, and then 100 mL of water at 20 ° C. was added to this emulsion.
g and tetraethylenepentamine 2.0 g were added,
The temperature of the system is gradually raised to 80 ° C, and at this temperature 9
The capsule dispersion was prepared by maintaining for 0 minutes.

To the thus obtained capsule liquid, 80 g of a 15% aqueous solution of polyvinyl alcohol, 15 g of carboxy-modified SBR latex as a solid content and 40 g of starch particles (average particle diameter 15 μm) were added. Next, water was added to adjust the solid content concentration to 20% by weight to prepare a color developer layer-forming coating liquid (microcapsule dispersion liquid) containing microcapsules containing the color developer.

[Preparation of Coloring Agent Sheet] 5.0 g / m ² of the above coating solution for forming a coloring agent layer is coated on one side of a base paper of 50 g / m ^2.
The solid content of ² was applied using an air knife coater and dried to prepare a color former sheet.
This color former sheet had very little odor.

[Preparation of color developer sheet] [Preparation of coating liquid for forming color developer layer] To 100 g of water, 5 g of 20 wt% sodium hydroxide aqueous solution and 1 g of 10 wt% sodium hexametaphosphate were added. To the obtained solution, 2 g of magnesium oxide and 60 g of activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., trade name "Silton F-242") as a developer were added, and a homogenizer (AM-7, Nippon Seiki Co., Ltd.) was added. )
(Manufactured by Mitsui Chemicals Co., Ltd.) at 10,000 rpm for 5 minutes to obtain a color developer dispersion. An aqueous starch solution was prepared by dissolving 5 g of wheat flour in 100 g of a 1 wt% sodium hydroxide aqueous solution. To 100 g of the above-mentioned color developer dispersion, 35 g of starch aqueous solution, 15 g of SBR latex (solid content) and 4 g of additive (emulsion) were added, and water was further added to adjust the solid content concentration to 20% by weight. A coating liquid for forming a developer layer was prepared. 5
On one side of the base paper of 0 g / m ^2, the coating liquid for forming the developer layer is applied using a bar coater so that the solid content of 5.0 g / m ² is applied, dried, and developed. An agent sheet was prepared.

[Example 2] [Preparation of Coloring Agent Sheet] 4,4′-thiobis (3 used in the preparation of the coating solution for forming the coloring agent layer in Example 1
-Methyl-6-t-butylphenol) 18.0 g instead of 2,2'-methylenebis (3-ethyl-6-t-)
Butylphenol) 18 g. A color developer sheet was produced in the same manner as in Example 1 except that the coating liquid for forming a color developer layer prepared in the same manner as in Example 1 was used except that 0 was used. Further, a color developer sheet was prepared in the same manner as in Example 1.

Example 3 [Preparation of Coloring Agent Sheet] 100 g of corn oil was used instead of 100 g of rapeseed oil used in the preparation of the coating solution for forming the coloring agent layer in Example 1. A color former sheet was prepared in the same manner as in Example 1 by using the color developer layer forming coating solution prepared in the same manner as in Example 1. Further, a color developer sheet was prepared in the same manner as in Example 1.

Example 4 [Preparation of Coloring Agent Sheet] Except that 100 g of soybean oil was used instead of 100 g of rapeseed oil used in the preparation of the coating solution for forming the coloring agent layer in Example 1. A color former sheet was prepared in the same manner as in Example 1 by using the color developer layer forming coating solution prepared in the same manner as in Example 1. Further, a color developer sheet was prepared in the same manner as in Example 1.

Example 5 [Preparation of Coloring Agent Sheet] 4,4′-thiobis (3 used in the preparation of the coating solution for forming the coloring agent layer in Example 1
-Methyl-6-t-butylphenol) 18.0 g was replaced with 9.0 g of 4,4'-thiobis (3-methyl-6-t-butylphenol) and 9.0 g of 2-hydroxy-4-methoxybenzophenone. Other than using the coating liquid for forming a color former layer prepared in the same manner as in Example 1,
A color former sheet was prepared in the same manner as in Example 1. Also,
A color developer sheet was prepared in the same manner as in Example 1.

Example 6 [Preparation of Coloring Agent Sheet] 4,4′-thiobis (3) used in the preparation of the coating solution for forming the coloring agent layer in Example 1
Example 1 except that 12.0 g of 4,4′-thiobis (3-methyl-6-t-butylphenol) and 6.0 g of dicyclohexyl phthalate were used instead of 18.0 g of -methyl-6-t-butylphenol). A color developer sheet was prepared in the same manner as in Example 1, using the color developer layer forming coating solution prepared in the same manner as in (1). Further, a color developer sheet was prepared in the same manner as in Example 1.

Example 7 [Preparation of Coloring Agent Sheet] 4,4′-thiobis (3) used in the preparation of the coating solution for forming the coloring agent layer in Example 1
-Methyl-6-t-butylphenol) 18.0 g instead of 4,4'-thiobis (3-methyl-6-t-butylphenol) 9.0 g, 2-hydroxy-4-methoxybenzophenone 6.0 g and phthalic acid A color former sheet was prepared in the same manner as in Example 1 except that the coating liquid for forming a color former was prepared in the same manner as in Example 1 except that 6.0 g of dicyclohexyl was used. Further, a color developer sheet was prepared in the same manner as in Example 1.

[Comparative Example 1] [Preparation of Coloring Agent Sheet] 4,4′-thiobis (3) used in the preparation of the coating solution for forming the coloring agent layer in Example 1
-Methyl-6-t-butylphenol) was used in place of a mixture of 18.0 g of rapeseed oil and 100 g of rapeseed oil, and 118 g of rapeseed oil was used, and a coating liquid for forming a colorant layer prepared in the same manner as in Example 1 was used, A color former sheet was prepared in the same manner as in Example 1. Further, a color developer sheet was prepared in the same manner as in Example 1.

Comparative Example 2 [Preparation of Coloring Agent Sheet] 4,4′-thiobis (3 used in the preparation of the coating solution for forming the coloring agent layer in Example 1
-Methyl-6-t-butylphenol) 18.0 g and rapeseed oil 100 g instead of a mixture of corn oil 11
A color former sheet was prepared in the same manner as in Example 1 except that the coating liquid for forming a color former layer was prepared in the same manner as in Example 1 except that 8 g was used. Further, a color developer sheet was prepared in the same manner as in Example 1.

[Comparative Example 3] [Preparation of Coloring Agent Sheet] 4,4′-thiobis (3) used in the preparation of the coating solution for forming the coloring agent layer in Example 1
-Methyl-6-t-butylphenol) was used in place of a mixture of 18.0 g of rapeseed oil and 100 g of rapeseed oil, and 118 g of soybean oil was used, except that a coating solution for forming a color former was prepared in the same manner as in Example 1. A color former sheet was prepared in the same manner as in Example 1. Further, a color developer sheet was prepared in the same manner as in Example 1.

(1) The following tests were conducted on the color former solutions and the color developer layer forming coating solutions (microcapsule dispersions) obtained in the above Examples and Comparative Examples. a) Stability of color former solution The color former solution obtained by heating and dissolving at 120 ° C is gradually added to 5
After cooling to 0 ° C., the presence or absence of precipitate was visually observed. b) Residue in microcapsule dispersion liquid 1000 g of the obtained microcapsule dispersion liquid was filtered through a 250-mesh sieve, and the solid matter remaining on the sieve was dried at 100 ° C. for 1 hour, and its weight was measured.

(2) The following tests were carried out using the color-developing agent sheet and the color-developing agent sheet obtained in the above Examples and Comparative Examples. c) Coloring density test The color-developing sheet and the color-developing sheet prepared as described above are overlaid, and an electronic typewriter (IBM 6747 type) is used to continuously print by printing the lowercase letter m of the alphabet to develop the color on the color-developing layer. It was The obtained color image was allowed to stand at room temperature for 24 hours, and then the density (D) of the color developer in the developer layer was measured using a Macbeth reflection densitometer. The results are shown in Table 1.

[0070]

[Table 1] Table 1 ──────────────────────────────────── a) Coloring agent b) Capsule dispersion Solution c) Color density Solution stability Residue (mg) (D) ──────────────────────────────────── -Example 1 No precipitation 5.5 0.57 Example 2 No precipitation 7.5 0.56 Example 3 No precipitation 5.6 0.56 Example 4 No precipitation 5.2 0.57 Example 5 No precipitation 5.8 0.57 Example 6 No precipitation 6.4 0.56 Example 7 No precipitation 6.2 0.56 ────────────────────── ────────────── Comparative Example 1 Precipitation 398.2 0.50 Comparative Example 2 Precipitation 389.3 0.50 Comparative Example 3 Precipitation 386.7 0.51 ─── ───────── ───────────────────────

The color former solutions used for preparing the recording materials obtained in the examples were excellent in stability, and the capsule dispersions thereof had little residue. When the color former sheet obtained by using these coating solutions was used as a recording material in combination with the color developer sheet, it was possible to form a color-developed image with high color density on the color developer sheet. . On the other hand, as a solvent for dissolving the color former,
In Comparative Examples 1 to 3 in which the specific bisphenol compound of the present invention was not used, the stability of the color developer solution was poor and the residue of the capsule dispersion was large, and when used in combination with the color developer sheet. A color image having a sufficiently high color density could not be formed on the colorant sheet.

[0072]

The recording material of the present invention has no unpleasant odor or bad odor, has a high ecological safety, and uses a color-developing agent such as crystal violet lactone which is usually difficult to dissolve in vegetable oil, This is made possible by using a vegetable oil containing a small amount of a specific bisphenol compound as a solvent, and exhibits a remarkably excellent effect that a color image having a high color density can be formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B41M 5/30 5/28 B41M 5/18 101 C 103 110 112

Claims (3)

[Claims] 1. A recording material comprising microcapsules containing an electron-donating color former dissolved in a solvent and an electron-accepting developer, wherein the electron-donating color agent is crystal violet lactone. Then, the solvent is composed of a vegetable oil having a fatty acid residue composition with an oleic acid residue content of 10 to 60% by weight, and within the range of 2 to 40 parts by weight relative to 100 parts by weight of the vegetable oil, the following general formula (1 ): [Chemical 1] [However, R ¹ is -S-, -CR ¹² R ^13- (provided that R 1
¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or —SO ₂ —, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , R
⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, and R
^{One or two of 2} , R ³ , R ⁴ , R ⁵ , R ⁵ and R ⁶ and one or 2 of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ have a hydroxyl group; Represent. ] The recording material characterized by including the bisphenol compound represented by these. 2. A bisphenol compound has the following general formula (2): [However, R ^{21 is, -S -, - CR 28 R} 29 - ( wherein, R
²⁸ and R ²⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) or —SO ₂ —, and R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are respectively Independently, it represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] Or the following general formula (3): [However, R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] The recording material according to claim 1, which is a compound represented by the formula: 3. The recording material according to claim 1, wherein the amount of the bisphenol compound based on 100 parts by weight of the vegetable oil is 5 to 30 parts by weight.