JPH04298386A - Manufacture of developer dispersion for thermal recording paper - Google Patents

Abstract

PURPOSE:To provide a developer dispersion for thermal recording having high color-developing speed, particularly high color-developing speed under the conditions of a low temperature. CONSTITUTION:The metallic salt of a salicylic acid derivative having total number of carbon atom of 17 of more is dissolved in an organic solvent having the boiling point of 200 deg.C or lower, the developer solution is emulsified and dispersed in water containing a separating agent, the organic solvent is removed from an emulsified dispersion obtained, and the dispersion of an organic compound having at least one or more of ether, amine, urea and urethane bonds is added and mixed.

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 color-developing sheet for pressure-sensitive recording with improved color development.

0002

2. Description of the Related Art Recording materials using an electron-donating colorless dye (hereinafter referred to as a color former) and an electron-accepting compound (hereinafter referred to as a color developer) are already well known. For example, British Patent No. 2,140,449, US Patent No. 4,480052,
No. 4,436,920, JP-A-62-144,989
Familiar with issues etc. In recent years, as a pressure-sensitive recording material, intensive research has been carried out to improve properties such as (1) color development density and color development speed, (2) fastness of the color former, and (3) improvement of durability under various usage conditions. The present inventors have investigated the basic oil solubility, solubility of Mizuki, partition coefficient, pKa, polarity of substituent, position of substituent, and compatibility with each of electron-donating colorless dyes, electron-accepting compounds, and additives. Focusing on characteristics such as changes in crystallinity and solubility, we have pursued the development of good materials for recording materials and recording materials.

0003

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a developer for pressure-sensitive recording paper for a color-developing sheet for pressure-sensitive recording, which has good color development density and color development speed, and satisfies other requirements. An object of the present invention is to provide a method for producing a colorant dispersion.

0004

[Means for Solving the Problem] An object of the present invention is to prepare a metal salt of a salicylic acid derivative having a total number of carbon atoms of 17 or more.
After dissolving in an organic solvent at 0°C or less, emulsifying and dispersing this developer solution in water containing a dispersant, and removing the organic solvent from the resulting emulsified dispersion, ether, ester, amide, urea The problem was solved by a method for producing a color developer dispersion for pressure-sensitive recording paper, which comprises adding and mixing a dispersion of an organic compound having at least one urethane bond. Among the salicylic acid derivatives having 17 or more carbon atoms according to the present invention, those represented by the following general formula (I) are preferred.

[0005]

[Chemical formula 1]

In the formula, the groups represented by R1, R2, R3 and R4 represent a hydrogen atom, an alkyl group or an aryl group.

The groups represented by R1, R2, R3 and R4 in the above general formula (I) further include alkyl groups, alkenyl groups, aryl groups, hydrogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, halogen atoms, nitro It may be substituted with a group, a cyano group, a heterocycle, etc. R1, R2, R
The groups represented by 3 and R4 include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a aryl group having 1 to 20 carbon atoms. An alkoxy group such as R1 and R3 is preferred, and particularly preferred is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

Among the salicylic acid derivatives represented by the above general formula (I), 3,5-bisaralkylsalicylic acid derivatives, 3-alkylsalicylic acid, 3-alkyl-5-aralkylsalicylic acid, or 3-alkyl-5-alkylsalicylic acid is preferable, and those having a total carbon number of 17 or more are preferable.

Preferred metal salts of salicylic acid derivatives according to the present invention include zinc salts, aluminum salts, magnesium salts, calcium salts, sodium salts, and nickel salts, with zinc salts being particularly preferred.

[0010] Specific examples of salicylic acid derivatives according to the present invention are shown below, but the present invention is not limited thereto. 3,5-di-t-butylsalicylic acid, 3,5-di-t-
Octylsalicylic acid, 3,5-di-t-nonylsalicylic acid, 3,5-di-t-dodecylsalicylic acid, 3-methyl-5-t-dodecylsalicylic acid, 3-t-dodecylsalicylic acid, 3-isododecylsalicylic acid, 3 -decylsalicylic acid, 5-cyclohexylcyclohexylsalicylic acid, 3,5-bis(α-methylbenzyl)salicylic acid, 3
, 5-bis(α,α-dimethylbenzyl)salicylic acid,
3-methyl-5-(α-methylbenzyl)salicylic acid,
3-(α,α-dimethylbenzyl)-6-methylsalicylic acid, 3-(α-methylbenzyl)-5-(α,α-dimethylbenzyl)salicylic acid, 3-(α,α-dimethylbenzyl)-6- Ethylsalicylic acid, 3-phenyl-5
-(α,α-dimethylbenzyl)salicylic acid, 3-(α
-methylbenzyl)-5-t-butylsalicylic acid, 3-
(α-Methylbenzyl)-5-t-octylsalicylic acid, 3-(α-methylbenzyl)-5-t-octylsalicylic acid, 3-α-benzylated phenylethylsalicylic acid, 3-α-methyl-α-ethylpentyl -5-α, α-
Dimethylbenzylsalicylic acid, 3-cumyl-5-t-octylsalicylic acid, 3-cumyl-5-t-butylsalicylic acid, 3-t-butyl-5-cumylsalicylic acid, 3,5
-bis(methylcumyl)salicylic acid, 3-(α-methylbenzyl)-6-methylsalicylic acid, 3-α-benzylated phenylethyl-6-methylsalicylic acid, 3-α-methyl-α-ethylpentyl-6-methylsalicylic acid ,3
, 5-bis(-α-benzylated phenylethyl)salicylic acid, 3,5-bis(benzylated benzyl)salicylic acid, 3,5-bis(α-methylbenzyl)-6-methylsalicylic acid, 3-α-triethyl- 6-methylsalicylic acid, 3,5-di-t-octyl-6-methylsalicylic acid,
3-α-dimethylphenylethyl-6-methylsalicylic acid, 3-α-ethylphenylethyl-6-methylsalicylic acid, 3-α-isopropylphenylethyl-6-methylsalicylic acid, 3-α-benzylated benzylphenylethyl-6 -methylsalicylic acid, 3-α-methyl-α-ethylpentyl-6-ethylsalicylic acid, and the like.

[0011] The organic solvent with a boiling point of 200°C or less according to the present invention includes halogenated hydrocarbons, aromatic hydrocarbons,
Preferred are esters, ketones, ethers, amides, and nitriles. Among these, those having a solubility in water at room temperature of 5 or less are preferred. Also, from the viewpoint of removal after dispersion, those that are azeotropic with water are preferred. Especially when the azeotropic point is 100°C
It is preferable for handling that the amount of solvent in the azeotropic composition is 5% by weight or more. The amount of these organic solvents to be used is preferably 0.05 to 15 parts, particularly preferably 1 to 10 parts, per 1 part of the zinc salt. Specific examples of organic solvents include toluene, xylene,
Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, carbon tetrachloride,
Dichloromethane, chloroform, dimethylacetamide, etc. can be mentioned.

Among the organic compounds according to the present invention having at least one ether, ester, amide, urea, or urethane bond, those represented by the following general formulas (II) to (VII) are preferred. General formulas (II) to (VII) R5-O-R6 (II) R7-C
OO-R8 (III) R9-CONH
-R10 (IV)R11-NHCONH-
R12 (V)R13-NHCSNH-R14
(VI) R15-NHCOO-R16 (VI
I) In the above general formula, R5 to R16 may be the same or different and represent a hydrogen atom, an aryl group or an alkyl group.

The groups represented by R5 to R16 may further have an ether, ester, amide, urea, or urethane bond in the group. Further, it may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an aryloxy group, a halogen atom, an alkoxy group, a hydroxy group, an allyl group, and the like. These substituents may further have a substituent. When the group represented by R5 to R16 is an unsubstituted alkyl group, its structure may be linear or branched.

The organic compound according to the present invention having at least one ether, ester, amide, urea or urethane bond preferably has a molecular weight of 250 or more, particularly preferably 300 or more. Further, the organic compound having at least one ether, ester, amide, urea, or urethane bond according to the present invention is
Preferably, it is liquid at room temperature or has a melting point of 150°C or less.

Next, the ether, ester,
Representative examples of organic compounds having at least one amide, urea, or urethane bond are shown below. Examples of ether and ester derivatives p-dodecyl phenyl octyl ether,
p-benzyloxyphenyl dodecyl ether, 2,4
-bis-α-methylbenzyl-1-octyloxybenzene, 2,4-bis-α-methylbenzyl-1-benzyloxybenzene, 2,4-bis-α-methylbenzyl-1-phenoxyethyloxybenzene, 4 -dodecyl-1-phenoxybenzene, 2,4-bis-α-methylbenzyl-1-benzoyloxybenzene, 4-bis-
α,α-dimethylbenzyl-1-benzoyloxybenzene, octadecylbenzoate, dodecylphenoxy acetate, 1-dodecyloxycarbonyl-2-(2
, 4-di-t-amylphenoxy)butane, 1-benzyloxycarbonyl-2-(2,4-di-t-amylphenoxy)butane, and the like.

Examples of amide derivatives: stearamide, methylolstearamide, ethylene bisstearamide, behenic acid amide, stearanilide, stearic acid-p-chloroanilide,
Stearic acid p-anisidide, stearic acid p-toluidide, stearic acid m-toluidide, stearic acid o-toluidide, stearic acid p-ethoxyanilide, behenic acid anilide, stearic acid methylamide,
Stearic acid benzylamide, stearic acid butylamide, stearic acid octylamide, stearic acid dodecylamide, stearic acid octadecylamide, phenoxyacetic acid dodecylamide, phenoxyacetic acid octadecylamide, phenylacetic acid dodecylamide, phenylacetic acid octadecylamide, phenoxyacetic acid hexadecylamide,
Benzoic acid octylamide, benzoic acid decylamide, benzoic acid dodecylamide, benzoic acid tetradecylamide, benzoic acid hexadecylamide, benzoic acid octadecylamide, benzoic acid-(3-dodecyloxypropyl)amide, benzoic acid-(3-tetra) decyloxypropyl)amide, p-methylbenzoic acid octadecylamide, p-methoxybenzoic acid octadecylamide, p-chlorobenzoic acid octadecylamide, 4-hydroxybenzoic acid dodecylamide, 4-hydroxybenzoic acid tetradecylamide,
4-hydroxybenzoic acid octadecylamide, 4-hydroxybenzoic acid eicosylamide, 4-hydroxybenzoic acid (3-(2-ethylhexyloxy)propyl)amide, 4-hydroxybenzoic acid (3-tetradecyloxypropyl)amide, 4-hydroxybenzoic acid (2-(
2,5-bis-t-amylphenoxy)butyl)amide, 1,5-bis(4-hydroxybenzoylamino)-
3-oxapentane etc.

Examples of urea derivatives 1-Phenylurea, 1-decyl-3-phenylurea, 1-dodecyl-3-phenylurea, 1-tetradecyl-3-phenylurea, 1-hexadecyl-3-phenylurea, 1- octadecyl-3-phenylurea,
1-decyl-3-p-chlorophenylurea, 1-dodecyl-3-p-chlorophenylurea, 1-tetradecyl-3-p-chlorophenylurea, 1-hexadecyl-3-p-chlorophenylurea, 1-octadecyl-
3-p-chlorophenylurea, 1-decyl-3-p-
Methoxyphenylurea, 1-dodecyl-3-p-methoxyphenylurea, 1-tetradecyl-3-p-methoxyphenylurea, 1-hexadecyl-3-p-methoxyphenylurea, 1-octadecyl-3-p-methoxyphenyl Urea, 1-decyl-3-p-methylphenylurea, 1-dodecyl-3-p-methylphenylurea, 1-tetradecyl-3-p-methylphenylurea, 1-hexadecyl-3-p-methylphenylurea, 1-octadecyl-3-p-methylphenylurea,
1-phenyl-3-p-dodecyloxyphenylurea, 1-phenyl-3-p-stearyloxyphenylurea, 1-decyl-3-benzylurea, 1-dodecyl-3-benzylurea, 1-hexadecyl-3- Benzylurea, 1-octadecyl-3-benzylurea, 1
-hexadecyl urea, 1-octadecyl urea, 1-
phenyl-3-(3-decyloxypropyl)urea,
1-phenyl-3-(3-dodecyloxypropyl)urea, 1-phenyl-3-(3-tetradecyloxypropyl)urea, 1-phenyl-3-(3-(2-ethylhexyloxy)propyl)urea, etc. .

Examples of urethane derivatives N-phenylcarbamoyloxydecane, N-phenylcarbamoyloxydodecane, N-phenylcarbamoyloxytetradecane, N-phenylcarbamoyloxyhexadecane, N-phenylcarbamoyloxytetradecane, N-phenylcarbamoyloxyeicosane, N-phenylcarbamoyloxymethylbenzene, N
-phenylcarbamoyloxyethylbenzene, (2-
(N-phenylcarbamoyloxy)ethoxy)benzene, N-octadecylcarbamoyloxymethane, N-
Octadecylcarbamoyloxyethane, N-octadecylcarbamoyloxybutane, N-octadecylcarbamoyloxyhexane, N-octadecylcarbamoyloxyoctane, N-octadecylcarbamoyloxydecane, N-octadecylcarbamoyloxydodecane, N-octadecylcarbamoyloxytetradecane, N-octadecyl carbamoyloxyhexadecane,
N-octadecylcarbamoyloxyoctadecane, N
-octadecylcarbamoyloxybenzene, N-octadecylcarbamoyloxy-p-methylbenzene, N
-octadecylcarbamoyloxy-p-ethylbenzene, N-octadecylcarbamoyloxy-p-methoxybenzene, N-octadecylcarbamoyloxy-p
-ethoxybenzene, N-octadecylcarbamoyloxy-p-chlorobenzene, N-octadecylcarbamoyloxy-m-methylbenzene, N-octadecylcarbamoyloxy-o-methylbenzene, etc.

Examples of thiourea derivatives N-phenyl-N'-dodecylthiourea, N-phenyl-N'-tetradecylthiourea, N-phenyl-N
'-hexadecylthiourea, N-phenyl-N'-octadecylthiourea, N-phenyl-N'-(3-decyloxypropyl)thiourea, N-phenyl-N'
-(3-dodecyloxypropyl)thiourea, N-phenyl-N'-(3-tetradecyloxypropyl)thiourea, N-phenyl-N'-(3-hexadecyloxypropyl)thiourea, N-phenyl-N' −(3
-octadecyloxypropyl)thiourea, N-phenyl-N'-(3-(2-ethylhexyloxy)propyl)thiourea, N-phenyl-N'-p-amylphenylthiourea, N-phenyl-N'-p-octyl Oxyphenylthiourea etc.

Examples of compounds having multiple functional groups α, α-
Bis(1-methyl-2-phenoxyethoxycarbonylamino)-m-xylene, α,α-bis(tetradecyloxycarbonylamino)-m-xylene, α,α-bis(hexadecyloxycarbonylamino)-m- Xylene, α,α-bis(octadecyloxycarbonylamino)-m-xylene, α,α-bis(isopropylbenzyloxycarbonylamino)-m-xylene, α,
α-bis[(2,4-bis-α-methylbenzylphenoxy)carbonylamino]-m-xylene, bis(4-
hexadecyloxycarbonylaminophenyl)methane, 1,6-bis(1-methyl-2-phenoxyethoxycarbonylamino)hexane, 1,3-bis(octadecylcarbamoyloxy)benzene, 2,2-bis(4
-octadecylcarbamoyloxyphenyl)propane, 1,1-bis(4-phenylcarbamoyloxyphenyl)-2-ethylhexane, 1,10-bis(4-phenylcarbamoyloxy)decane, 1,3-bis(myristoyloxy) Benzene, 1,3-bis[2-(2
, 4-bis-t-amylphenoxy)butylcarbonyloxy]benzene, 1,1-bis(4-phenoxyacetyloxyphenyl)-2-ethylhexane, 1,1-
Bis(4-phenylacetyloxyphenyl)-2-ethylhexane, 1,4-bis[2-(2,4-bis-t
-amylphenoxy)butylcarbonyloxy]butane, bis[(2,4-bis-α-methylbenzylphenoxy)carbonyl], bis[(2,4-bis-α-methylbenzylphenoxy)carbonyl]ethane, bis(4 −
dodecylphenoxycarbonyl), 1,2,3-tris[2-(2,4-bis-t-amylphenoxy)butylcarbonyloxy]benzene, 1,2,3-tris(phenoxyacetyloxy)benzene, 1,2 , 3-tris(stearoyloxy)benzene, 1,2,3-tris[2-(2,4-bis-t-amylphenoxy)butylcarbonyloxy]propane, 1,2,3-tris(
phenoxyacetyloxy)propane, 1,2,3-tris[2-(2,4-bis-t-amylphenoxy)butylcarbonyloxy]-2-methylpropane, tricaprin, trilaurin, triolein, trimyristin, tripalmitin , tristearin, 1-myrist-2
, 3-dicaprin, 2-stearo-1,3-dicaprine, 1-lauro-2,3-dipalmitine, 1-oleo-2
, 3-distearin, 1-stearo-2,3-dipalmitin, 1-myristo-2-capryl-3-stearin,
1-Myristo-2-palmito-3-stearin, 2-oleo-1,3-dipalmitin, 2-lauro-1,3-distearin, 1-myristo-2,3-dielaydine, tridecanoic acid, pentadecanoic acid, margarine Glycerin esters of equimolar mixtures of acids, myristic acid, zomarinic acid, glycerin esters of equimolar mixtures of oleic acids,
Glycerin ester of an equimolar mixture of myristic acid, stearic acid, oleic acid, glycerin ester of an equimolar mixture of tridecanoic acid, pentadecanoic acid, heptadenoic acid, α,α-bis[(2,4-bis-α-methylbenzylphenoxy) ) acetylamino]-m-xylene, α,
α-bis[(2,4-bis-t-amylphenoxy)butylcarbonylamino]-m-xylene, 1,4-bis[2-(2,4-bis-t-amylphenoxy)butylcarbonylamino]butane , 1,2-bis[3-(2,
4-bis-t-amylphenoxy)propylcarbamoyl]benzene, 1,4-bis[3-(2,4-bis-t
-amylphenoxy)propylcarbamoyl]butane,
3-[2-(2,4-bis-t-amylphenoxy)butylcarbonyloxy]-1-phenylcarbamoylaminobenzene, 3-[2-(2,4-bis-α-methylbenzylphenoxy)acetyloxy] -1-phenylcarbamoylaminobenzene, 3-[2-(2,4-bis-t-amylphenoxy)butylcarbonyloxy]
-1-hexylcarbamoylaminobenzene, 1-[2
Examples include, but are not limited to, -(2,4-bis-t-amylphenoxy)butylcarbonyloxy]-2-phenylcarbamoylaminoethane.

In the color developer dispersion for pressure-sensitive recording according to the present invention, well-known compounds other than the present invention such as phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, and novolak resins can be used. , metal-treated novolak resin, metal complex, etc. may be used in combination. Examples of these are Special Publication No. 40-9309 and Special Publication No. 14039 of 1972.
No., JP-A-52-140483, JP-A-48-515
No. 10, JP-A-57-210886, JP-A-58-8
No. 7089, JP-A-59-11286, JP-A-60-
No. 176795, JP-A No. 61-95988, etc.

[0022] A pressure-sensitive recording material using a color developer sheet prepared using the color developer dispersion for pressure-sensitive recording according to the present invention is as follows:
U.S. Patent Nos. 2,505,470, 2,505489, 2,550,471, 2,548,366,
As described in prior patents such as No. 2,730,457, No. 3,418,250, JP-A-49-28,411, and JP-A-50-44,09, various forms are available. Possible. Most commonly it consists of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

Electron-donating colorless dyes are not particularly limited, but include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leucoauramine compounds, rhodamine lactam compounds, and triphenyl phthalide compounds. Examples include methane compounds, triazene compounds, spiropyran compounds, and fluorene compounds. Specific examples of phthalides are given in U.S. Patent No. 2.
No. 3,024, No. 3,491,111, No. 3,4
No. 91,112, No. 3,491,116, No. 3,
No. 509,174, specific examples of fluorans are U.S. Pat. No. 3,624,107, U.S. Pat.
, 641,011, 3,462,828, 3,681,390, 3,920,510, 3,959,571, and specific examples of spirodipyrans are disclosed in U.S. patents. No. 3,971,808, U.S. Patent No. 3,775,424 for pyridine and pyrazine compounds, U.S. Patent No. 3,853,869, U.S. Pat. No. 4,246,318, specific examples of fluorene compounds Patent application 1986-240989
It is stated in the number etc.

A specific method for producing the color developer dispersion for pressure-sensitive recording according to the present invention will be described. Generally, the metal salt of the salicylic acid derivative according to the present invention and an organic solvent are mixed,
Mechanical or emulsifying dispersion in water containing dispersants and other additives. Subsequently, the organic solvent is substantially removed from the resulting dispersion under normal pressure or reduced pressure. Thereafter, a dispersion of an organic compound having at least one ether, ester, amide, urea, or urethane bond is added to and mixed with the obtained dispersion. The method for preparing a dispersion of an organic compound having at least one ether, ester, amide, urea, or urethane bond is not particularly limited, but may include mechanical dispersion together with a dispersant, dissolution in an organic solvent, and emulsification dispersion together with a dispersant. There are methods such as a method of emulsifying and dispersing by heating if necessary in the presence of a dispersant. Further, the color developer dispersion for pressure-sensitive recording according to the present invention may contain pigments,
Additives such as antioxidants and ultraviolet absorbers can be added. These additives are used when dispersing a metal salt of a salicylic acid derivative, when dispersing an organic compound having at least one ether, ester, amide, urea, or urethane bond, or when dispersing a dispersion of a metal salt of a salicylic acid derivative with an ether or ester. It can be added after mixing a dispersion of an organic compound having at least one, amide, urea, or urethane bond.

In the method for producing a color developer dispersion for pressure-sensitive recording according to the present invention, a dispersion of a metal salt of a salicylic acid derivative and a dispersion of an organic compound having at least one ether, ester, amide, urea, or urethane bond are used. After mixing, it is preferable to further perform a dispersion treatment using a media. At this time, it is important to control the volume average particle size.
By finely dispersing the particle size to 4 μm or less, performances such as color developing ability and color development speed are improved.

There are various types of dispersion machines that use media, such as sand mills, dyno mills, attritors, and ball mills, but among these, there are those that use high-speed rotation to disperse and can perform continuous processing, such as sand mills and dyno mills. However, it is advantageous in that the dispersion can be continuously processed and sent as is to a coating machine tank or the like. Various media are used during dispersion, but usually flint stones, Otsutawa sand, steel balls, ceramics, hyana balls, zircon, glass beads, etc. are used. Among these materials, spherical ones are superior in handling and maintainability. Further, it is preferable to perform the treatment with a dispersion machine at a temperature of 50° C. or lower in order to prevent agglomeration of the dispersion.

[0027] The finally obtained dispersion is further added with binders, additives, etc. as necessary, and is applied to a support such as paper, plastic sheet, resin-coated paper, etc. to form a color developing sheet. . The amount of the organic compound having at least one ether, ester, amide, urea, or urethane bond according to the present invention is 0.5% based on the metal salt of a salicylic acid derivative having a total number of carbon atoms of 17 or more.
-100% by weight, particularly 1-50% by weight.

The dispersant used in dispersing the organic compound having at least one metal salt, ether, ester, amide, urea, or urethane bond of a salicylic acid derivative having 17 or more carbon atoms in total according to the present invention may be a water-soluble one. Polymers or ionic or nonionic surfactants are preferred, and examples of water-soluble polymers include polyvinyl alcohol, alkyl-modified polyvinyl alcohol, cyanoethyl-modified polyvinyl alcohol, ether-modified polyvinyl alcohol, polyacrylamide, polyacrylic acid, and acrylamide. /alkyl acrylate copolymer, polystyrene sodium sulfonate, maleic anhydride/isobutylene copolymer, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, starch, casein, gum arabic, gelatin, and other synthetic or natural polymers. Examples of ionic or nonionic surfactants include alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polycarboxylic acids. Examples include soda salts of type polymers, polyhydric alcohol fatty acid esters, and the like. Further, a water-soluble polymer and an ionic or nonionic surfactant may be used in combination.

Examples of the pigments to be added include titanium oxide, zinc oxide, aluminum hydroxide, magnesium carbonate, magnesium oxide, barium sulfate, silicon oxide, calcium carbonate, kaolin, activated clay, and talc. Among these, it is particularly preferable to use calcium carbonate having an average particle size of 5.0 μm or less in an amount of 60% by weight or more of the total pigment. If the amount of calcium carbonate used is less than 60% by weight, sufficient performance in terms of light resistance of the color former and yellowing of the color developing surface due to light cannot be obtained. Further, unless calcium carbonate with an average particle size of 5.0 μm or less is used, sufficient color developing ability cannot be obtained. Calcium carbonate with an average particle size of 5.0 μm or less is commercially available, such as Brilliant-15 and B manufactured by Shiraishi Kogyo.
rilliant-S15, Brilliant-30
, PC, PCX, Unibur-70, etc. The electron-accepting compound and the pigment are preferably used in a weight ratio of 1:5 to 1:15. If the ratio of pigment used is higher or lower than this, sufficient color developing ability cannot be obtained. Binders for the coating solution include latexes such as styrene/butadiene copolymer latex and acrylic acid ester latex, polyvinyl alcohol, polyacrylic acid, maleic anhydride-styrene copolymer, starch, casein, gum arabic, gelatin, carboxymethyl cellulose,
Synthetic or natural polymeric materials such as methylcellulose are used.

[0030] The amount of electron-accepting compound applied to the support is 0.1 to 2.0 g/m2, preferably 0.2 to 1.0 g/m2.
g/m2 is appropriate. The amount of the electron-donating colorless dye to be used depends on the desired coating thickness, the form of the pressure-sensitive recording paper, the capsule manufacturing method, and other conditions, and may be appropriately selected depending on the conditions. It is easy for one skilled in the art to determine this amount to use.

The performance of a color developer sheet prepared using the color developer dispersion for pressure-sensitive recording according to the present invention was tested using the following microcapsule sheet containing an electron-donating colorless dye. (Preparation of microcapsule sheet containing coloring agent) Partial sodium salt of polyvinyl sulfonic acid (manufactured by National Starch Co., Ltd., VERSA, TL500, average molecular weight 50
0,000) was added to 95 parts of hot water at about 80° C. with stirring, dissolved, and then cooled. The pH of the aqueous solution was 2 to 3, and a 20% by weight aqueous sodium hydroxide solution was added thereto to adjust the pH to 4.0. On the other hand, 100 parts of diisopropylnaphthalene in which 2.5% crystal violet lactone and 1.0% benzoyl leucomethylene blue were dissolved was emulsified and dispersed in 100 parts of a 5% aqueous solution of a partial sodium salt of the polyvinylbenzenesulfonic acid, and the average diameter 4.
An emulsion with a particle size of 5 μm was obtained. Separately, add 6 parts of melamine and 11 parts of a 37% by weight formaldehyde aqueous solution to 60 parts.
Thirty minutes after heating and stirring at <RTIgt;C,</RTI> a transparent mixed aqueous solution of melamine, formaldehyde, and melamine-formaldehyde initial condensate was obtained. The pH of this mixed aqueous solution was 6-8. Hereinafter, this mixed aqueous solution of melamine, formaldehyde, and melamine-formaldehyde initial condensate will be referred to as an initial condensate solution. The initial condensate solution obtained by the above method was added to and mixed with the above emulsion, the pH was adjusted to 6.0 with 3.6% by weight hydrochloric acid solution while stirring, and the liquid temperature was raised to 65°C. I kept stirring. This capsule liquid was cooled to room temperature and added with a 20% by weight aqueous sodium hydroxide solution to pH 9.0.
It was adjusted to 200 parts of a 10% by weight polyvinyl alcohol aqueous solution and 5 parts of starch particles based on this capsule dispersion.
0 part was added, and water was added to adjust the solid content concentration to 20% to prepare a color former-containing microcapsule coating solution. This coating solution was coated on a 50 g/m2 base paper using an air knife coater so that the solid content was 5 g/m2, and dried to obtain a color former-containing microcapsule sheet. Examples will be shown below, but the present invention is not limited thereto.

[0032]

[Example] Example 1 Zinc 3,5-di-(α-methylbenzyl)salicylate 1
00 parts was dissolved in 100 parts of xylene, and this developer solution was added to 500 parts of a 4% cyanoethylated polyvinyl alcohol aqueous solution containing 0.5% sodium dodecyl sulfate, using a homogenizer (Nippon Seiki, Model AM-7). Te120
Emulsification was carried out at 00 rpm for 5 minutes to obtain a developer emulsion having an average particle size of 1.0 μm. This color developer emulsion was heated to azeotropically remove xylene to prepare a color developer dispersion having a solid content concentration of 30%. Next, 1-phenyl-3-stearylurea 10
Mix 0 parts with 100 parts of xylene and make this solution 0.5%
It was added to 500 parts of a 4% cyanoethylated polyvinyl alcohol aqueous solution containing sodium dodecyl sulfate, and heated at 12,000 rp using a homogenizer (Nippon Seiki, Model AM-7).
Emulsification was performed at m to obtain an emulsion with an average particle size of 1.0 μm. This emulsion was heated to azeotropically remove xylene to prepare a 1-phenyl-3-stearylurea dispersion having a solid content concentration of 30%. Next, calcium carbonate (manufactured by Shiraishi Kogyo, Bril)
Using 120 parts of liant-15 (average particle size 0.5 μm), 30 parts of activated clay, 40 parts of zinc oxide, 5 parts of 40% sodium hexametaphosphate aqueous solution and 230 parts of water, use a sand grinder to obtain an average particle size of 3 μm. to obtain a pigment dispersion. 10% to 300 parts of this pigment dispersion
Add 200 parts of PVA-117 (manufactured by Kuraray) aqueous solution, 35 parts of the above color developer dispersion, and 3.5 parts of the above 1-phenyl-3-stearylurea dispersion, and adjust with water so that the solid content concentration is 20%. A coating solution was obtained. 50g of this coating liquid
/m2 base paper was coated with a bar so that the solid content was 5.0 g/m2, and dried to obtain a color developing sheet.

Example 2 A color developing sheet was obtained in the same manner as in Example 1 except that tristearin was used instead of 1-phenyl-3-stearylurea used in Example 1.

Example 3 A color developing sheet was obtained in the same manner as in Example 1 except that stearic acid anilide was used instead of 1-phenyl-3-stearylurea used in Example 1.

Example 4 Zinc 3,5-di-(α-methylbenzyl)salicylate 1
00 parts was dissolved in 100 parts of xylene. This developer solution was added to 500 parts of a 4% cyanoethylated polyvinyl alcohol aqueous solution containing 0.5% sodium dodecyl sulfate, and 1
Emulsify at 2000 rpm for 5 minutes, average particle size 1.0 μm
A developer emulsion was obtained. This color developer emulsion is heated to azeotropically remove the xylene contained in the emulsion, and the solid content concentration is 3.
A 0% developer dispersion was prepared. Next, calcium carbonate (
Manufactured by Shiraishi Kogyo, Brilliant-15, average particle size 0.
5μm) 120 parts, activated clay 30 parts, zinc oxide 40 parts,
1-phenyl-3-stearylurea 2 parts, 2% sulfosuccinic acid 2-ethylhexyl ester soda salt aqueous solution 0
．． 2 parts, 10% PVA-117 (manufactured by Kuraray) aqueous solution 20
1 part, 5 parts of a 40% sodium hexametaphosphate aqueous solution and 205 parts of water, and the average particle size was 3 μm using a sand grinder.
A pigment dispersion liquid was obtained by uniformly dispersing the pigment so as to have a pigment dispersion of m.m. Add 35 parts of the above color developer dispersion to 300 parts of this pigment dispersion, process with a sand grinder, mix uniformly, and add 10% PVA-
185 parts of an aqueous solution of 117 (manufactured by Kuraray) were added to the mixture, and water was added so that the solid content concentration was 20% to obtain a coating liquid. This coating solution was coated on a 50 g/m 2 base paper with a bar so that the solid content was 5.0 g/m 2 and dried to obtain a color developing sheet.

Example 5 A color developing sheet was obtained in the same manner as in Example 4, except that 1-phenyl-3-stearylthiourea was used instead of 1-phenyl-3-stearylurea used in Example 4. .

Example 6 Zinc 3,5-di-(α-methylbenzyl)salicylate 1
00 parts was dissolved in 100 parts of xylene. This color developer solution was added to 500 parts of a 4.5% PVA-117 (manufactured by Kuraray) aqueous solution, and emulsified for 5 minutes at 12,000 rpm using a homogenizer (Nippon Seiki, Model AM-7), with an average particle size of 1.
．． A developer emulsion of 0 μm was obtained. This color developer emulsion was heated to azeotropically remove xylene contained in the emulsion to prepare a color developer dispersion having a solid content concentration of 30%. Next, using 120 parts of calcium carbonate (manufactured by Shiraishi Kogyo, Brilliant-15, average particle size 0.5 μm), 30 parts of activated clay, 40 parts of zinc oxide, 5 parts of a 40% aqueous solution of sodium hexametaphosphate, and 230 parts of water, a sand grinder was used. A pigment dispersion liquid was obtained by uniformly dispersing the particles to have an average particle size of 3 μm. Next, 50 parts of water, 50 parts of a 10% PVA105 (manufactured by Kuraray) aqueous solution, 1 part of a 2% 2-ethylhexyl sulfosuccinic acid 2-ethylhexyl ester sodium salt aqueous solution, and 40 parts of 1-phenyl-3-hexadecylurea were treated with a Dynomill to obtain an average particle size. Diameter 3μm
A 1-phenyl-3-hexadecylurea dispersion was prepared. 10% PVA-117 in 300 parts of the above pigment dispersion
(manufactured by Kuraray) 200 parts of the aqueous solution, 35 parts of the above color developer dispersion, and 6 parts of the 1-phenyl-3-hexadecylurea dispersion were added, and water was added so that the solid content concentration was 20% to obtain a coating solution. Ta. Apply 5.0g of this coating liquid to 50g/m2 base paper.
A color developing sheet was obtained by bar coating and drying so that a solid content of /m2 was coated.

Example 7 A color developing sheet was obtained in the same manner as in Example 6, except that stearic acid anilide was used instead of 1-phenyl-3-hexadecylurea.

Comparative Example 3,5-di-(α-methylbenzyl)zinc salicylate 1
00 parts was dissolved in 100 parts of xylene. This color developer solution was added to 500 parts of a 4.5% PVA-117 (manufactured by Kuraray) aqueous solution, and emulsified for 5 minutes at 12,000 rpm using a homogenizer (Nippon Seiki, Model AM-7), with an average particle size of 1.
．． A developer emulsion of 0 μm was obtained. This color developer emulsion was heated to azeotropically remove xylene contained in the emulsion to prepare a color developer dispersion having a solid content concentration of 30%. Next, using 120 parts of calcium carbonate (manufactured by Shiraishi Kogyo, Brilliant-15, average particle size 0.5 μm), 30 parts of activated clay, 40 parts of zinc oxide, 5 parts of a 40% aqueous solution of sodium hexametaphosphate, and 230 parts of water, a sand grinder was used. A pigment dispersion liquid was obtained by uniformly dispersing the particles to have an average particle size of 3 μm. To 300 parts of this pigment dispersion, 200 parts of a 10% PVA-117 (manufactured by Kuraray) aqueous solution and 35 parts of the above color developer dispersion were added, and water was added so that the solid content concentration was 20% to obtain a coating liquid. . Apply 5.0 g/m of this coating liquid to 50 g/m2 base paper.
Apply a bar so that a solid content of m2 is applied and dry.
A color developing sheet was obtained.

[0040]Evaluation tests were carried out on the combination of each of the above color developing sheets and the color former-containing microcapsule sheets as pressure-sensitive recording sheets, and the results are shown in Table 1. The evaluation test was conducted using the following method. (Color development speed and color development density test) The color developer sheet and the color developer-containing microcapsule sheet were stored in a constant temperature and humidity room at 5°C and RH 35% for over 1 hour. Next, in this constant temperature and humidity chamber, the microcapsule layer of the color former-containing microcapsule sheet was placed on the color developing sheet, and a load pressure of 300 kg/cm 2 was applied for 1 second to develop color. The density (D1) was measured 15 seconds after pressurization using a Macbeth reflection densitometer. Thereafter, this color developing sheet was left at room temperature (25° C.) for 24 hours, and then the density (D2) was measured using a Macbeth reflection densitometer. The D1/D2 ratio was defined as the color development rate, and D2 was defined as the color development density.

[0041]

[Table 1]

[0042]

[Effects of the Invention] As shown in Table 1, the color developer sheet prepared using the color developer dispersion of the present invention has excellent color development speed at low temperatures and extremely good performance compared to the comparative color developer sheet. have.

Claims (3)

[Claims] Claim 1: A color developer solution in which a metal salt of a salicylic acid derivative having a total number of carbon atoms of 17 or more is dissolved in an organic solvent with a boiling point of 200°C or less is emulsified and dispersed in water containing a dispersant, and then obtained. A color developer dispersion for pressure-sensitive recording paper, characterized in that after removing an organic solvent from an emulsified dispersion, a dispersion of an organic compound having at least one ether, ester, amide, urea, or urethane bond is added and mixed. Method of manufacturing liquid. 2. A color developer dispersion for pressure-sensitive recording paper according to claim 1, which is further processed in a dispersion machine using media to obtain a dispersion having a volume average particle diameter of 4 μm or less. A method for producing a color developer dispersion for pressure recording paper. 3. The solid weight of the organic compound having at least one ether, ester, amide, urea, or urethane bond is 0.5 to 0.5 to the solid weight of the metal salt of a salicylic acid derivative having a total number of carbon atoms of 17 or more. 2. The method for producing a color developer dispersion for pressure-sensitive recording paper according to claim 1, wherein the color developer dispersion is 100% by weight.