JP2756613B2 - Method for producing a developer dispersion for pressure-sensitive recording paper - Google Patents

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 coloring.

[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, UK Patent 2,140,449, US Patent 4,480052,
No. 4,436,920, JP-A-62-144,989
Details about the issue. In recent years, as a pressure-sensitive recording material, researches on property improvement such as (1) color density and color formation speed, (2) robustness of a color forming body, and (3) improvement of resistance under various use conditions have been earnestly conducted. The present inventors have found that for each of the electron-donating colorless dye, the electron-accepting compound and the additive, the oil solubility of the element, the solubility of Mizue, the distribution coefficient, the pKa, the polarity of the substituent, the position of the substituent, Focusing on properties such as change in crystallinity and solubility, the development of good recording material materials and recording materials has been pursued.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a pressure-sensitive recording paper developing sheet for a pressure-sensitive recording color sheet which has good color density and color developing speed and satisfies other conditions to be provided. An object of the present invention is to provide a method for producing a colorant dispersion.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal salt of a salicylic acid derivative having a total carbon number of 15 or more having a boiling point of 20 or less.
Dissolved in an organic solvent at 0 ° C. or lower, this developer solution was emulsified and dispersed in water containing a dispersant, and subsequently the organic solvent was removed from the resulting emulsified dispersion, followed by ether, ester, amide, urea. And a method for producing a developer dispersion for pressure-sensitive recording paper, characterized by adding and mixing a dispersion of an organic compound having at least one urethane bond. Among the salicylic acid derivatives having 15 or more carbon atoms according to the present invention, those represented by the following general formula (I) are preferable.

[0005]

Embedded image

In the formula, the groups represented by R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group.

In the above general formula (I), R ₁ , R ₂ , R ₃ and R ₄
The group represented by may be further substituted with an alkyl group, an alkenyl group, an aryl group, a hydrogen atom, an alkoxy group, an aryloxy group, an alkylthio group, a halogen atom, a nitro group, a cyano group, a hetero ring, or the like. Examples of the group represented by R ₁ , R ₂ , R ₃ and R ₄ include a hydrogen atom and a group having 1 to 1 carbon atoms.
An alkyl group of 20; an aralkyl group of 7 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms;
20 alkoxy groups and the like are preferable, and particularly, R ₁ and R ₃ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 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 acids, 3-alkyl-5-aralkylsalicylic acids, or 3-alkyl-5-alkylsalicylic acids And those having a total carbon number of 17 or more are preferred.

The metal salt of the salicylic acid derivative according to the present invention is preferably a zinc salt, an aluminum salt, a magnesium salt, a calcium salt, a sodium salt, a nickel salt, etc., and particularly preferably a zinc salt.

Specific examples of the salicylic acid derivative according to the present invention are shown below, but the present invention is not limited to these.
3,5-di-t-butylsalicylic acid, 3,5-di-t-
Octyl salicylic acid, 3,5-di-t-nonyl salicylic acid, 3,5-di-t-dodecyl salicylic acid, 3-methyl-5-t-dodecyl salicylic acid, 3-t-dodecyl salicylic acid, 3-isododecyl salicylic 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.

The organic solvent having a boiling point of 200 ° C. or lower according to the present invention includes halogenated hydrocarbons, aromatic hydrocarbons,
Esters, ketones, ethers, amides and nitriles are preferred. Among them, those having a solubility in water at room temperature of 5 or less are preferable. From the viewpoint of removal after dispersion, those azeotropic with water are preferred. Especially azeotropic point is 100 ° C
It is preferable from the viewpoint of handling that the amount of the solvent in the azeotropic composition becomes 5% by weight or more below. The amount of the organic solvent to be used is preferably 0.05 to 15 parts, more preferably 1 to 10 parts, per part of the zinc salt.
Specific examples of the organic solvent include toluene, xylene,
Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, carbon tetrachloride,
Examples thereof include dichloromethane, chloroform, and dimethylacetamide.

Among the organic compounds having at least one ether, ester, amide, urea or urethane bond according to the present invention, those represented by the following general formulas (II) to (VII) are preferred. Formulas (II) to (VII) R ₅ —O—R ₆ (II) R ₇ —COO—R ₈ (III) R ₉ —CONH—R ₁₀ (IV) R ₁₁ —NHCONH—R ₁₂ (V) R _{13 -NHCSNH-R 14 (VI)} R 15 R 5 ~R 16 in -NHCOO-R ₁₆ (VII) above general formula may be the same or different, represent a hydrogen atom, an aryl group or an alkyl group.

The group represented by R _{5 to} R ₁₆ may further have an ether, ester, amide, urea or urethane bond in the group. 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,
Allyl groups and the like. These substituents may further have a substituent. When the group represented by R _{5 to} R ₁₆ is an unsubstituted alkyl group, its structure may be linear or branched.

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

Next, ethers, esters, and the like according to the present invention,
Representative examples of organic compounds having at least one amide, urea, or urethane bond are shown. Ether, examples of ester derivatives p-dodecylphenyloctyl 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, -Dodecyl-1-phenoxybenzene, 2,4-bis-α-methylbenzyl-1-benzoyloxybenzene, 4-bis-
α, α-dimethylbenzyl-1-benzoyloxybenzene, octadecylbenzoate, dodecylphenoxyacetate, 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: stearic acid amide, methylol stearamide, ethylenebisstearic acid amide, behenic acid amide, stearic acid anilide, 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-hydroxy Benzoic 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 and the like.

Examples of urea derivatives 1-phenylurea, 1-decyl-3-phenylurea, 1-dodecyl-3-phenylurea, 1-tetradecyl-3-phenylurea, 1-hexadecyl-3-phenylurea, 1-phenylurea 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-
Methoxyphenylurea, 1-decyl-3-p-methylphenylurea, 1-dodecyl-3-p-methylphenylurea, 1-tetradecyl-3-p-methylphenylurea, 1-hexadecyl-3-p-methylphenyl Urea, 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-hexadecylurea, 1-octadecylurea, 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 and the like.

Examples of urethane derivatives N-phenylcarbamoyloxydecane, N-phenylcarbamoyloxidedecane, 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-octadecylcarbamoyloxidedecane, N-octadecylcarbamoyloxytetradecane, N- Octadecylcarbamoyloxyhexadecane, 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 and the like.

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-
Octyloxyphenylthiourea and the like.

Examples of compounds having a plurality of 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, 1,2,2
3-tris (phenoxyacetyloxy) benzene,
1,2,3-tris (stearoyloxy) benzene,
1,2,3-tris [2- (2,4-bis-t-amylphenoxy) butylcarbonyloxy] propane,
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-myristo-2,3-dicaprin, 2-stearo-1,3-dicaprin, 1-lauro-2,3-dipalmitin, 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,
Glycerin ester of an equimolar mixture of 3-dielaidin, tridecanoic acid, pentadecanoic acid, margaric acid, glycerin ester of an equimolar mixture of myristic acid, zomaric acid, oleic acid, glycerin of an equimolar mixture of myristic acid, stearic acid, oleic acid Glycerin ester of an equimolar mixture of ester, tridecanoic acid, pentadecanoic acid, heptadecenoic 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,
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-hexylcarbamoyl Aminobenzene, 1- [2- (2,4-bis-t-
Amylphenoxy) butylcarbonyloxy] -2-phenylcarbamoylaminoethane, and the like,
It is not limited to these.

In the color developer dispersion for pressure-sensitive recording according to the present invention, the well-known phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolak resins, which are well known in the present invention, are used. Alternatively, a metal-treated novolak resin, a metal complex, or the like may be used in combination. These examples are described in JP-B-40-9309 and JP-B-45-14039.
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-61-95988 and the like.

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

The electron-donating colorless dye is not particularly limited, but includes triphenylmethanephthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leucouramine compounds, rhodamine lactam compounds, and triphenyl compounds. Methane compounds, triazene compounds, spiropyran compounds, fluorene compounds and the like can be mentioned. Specific examples of phthalides are described in U.S. Patent Nos. 23,024, 3,491,111,
491,112, 3,491,116, 3,509,174, and specific examples of fluorans are described in U.S. Pat. Nos. 3,624,107 and 3,627,787.
No. 3,641,011, No. 3,462,82
No. 8, No. 3,681,390, No. 3,920,5
No. 3,959,571, specific examples of spirodipyrans are described in US Pat. No. 3,971,808, and pyridine and pyrazine compounds are described in US Pat. No. 3,775,4.
No. 24, No. 3,853,869, No. 4,246
No. 318, a specific example of a fluorene compound is disclosed in
No. 2,409,893 (JP-A-63-094878).

A specific method for producing the developer dispersion for pressure-sensitive recording according to the present invention will be described. Generally, a metal salt of a salicylic acid derivative according to the present invention and an organic solvent are mixed,
It is mechanically dispersed or emulsified in water containing a dispersant and other additives. Subsequently, the organic solvent is substantially removed from the obtained 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 the obtained dispersion and mixed. 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,
There are a method of mechanically dispersing with a dispersant, a method of dissolving in an organic solvent and emulsifying and dispersing with a dispersant, and a method of emulsifying and dispersing by heating in the presence of a dispersant as necessary. Further, the color developer dispersion for pressure-sensitive recording according to the present invention may contain additives such as pigments, antioxidants, and ultraviolet absorbers, if necessary. These additives, when dispersing the metal salt of the salicylic acid derivative, ether, ester, amide, urea,
When dispersing an organic compound having at least one urethane bond, or after mixing a dispersion of a metal salt of a salicylic acid derivative and a dispersion of an organic compound having at least one urethane bond with ether, ester, amide, urea, or Can be added.

In the process for producing a pressure-sensitive recording developer dispersion 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 provided. After mixing, it is preferable that the mixture is further processed by a disperser using a medium. At this time, it is important to control the volume average particle diameter, and by finely dispersing the particle diameter to 4 μm or less,
The performance such as the coloring speed is improved.

There are various types of dispersing machines using a medium, such as a sand mill, a dyno mill, an attritor, and a ball mill. Among them, a dispersing machine using a high-speed rotation such as a sand mill or a dyno mill and capable of continuous processing. However, it is advantageous in that the dispersion is continuously processed and directly sent to a coating machine tank or the like. Various media are used at the time of dispersion, but usually flint stone, Ottawa sand, steel balls, ceramics, hiana balls, zircon, glass beads and the like are used. Of these materials, spherical ones are easy to handle,
Excellent in maintainability. Further, it is preferable that the treatment with a dispersing machine is performed at 50 ° C. or lower in order to prevent aggregation of the dispersion.

The finally obtained dispersion is further added with a binder, an additive, and the like, if necessary, and applied to a support such as paper, a plastic sheet, or a resin-coated paper 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 to 0.5 with respect to the metal salt of the salicylic acid derivative having 15 or more total carbon atoms.
To 100% by weight, particularly 1 to 50% by weight.

As the dispersant used for dispersing the organic compound having at least one metal salt, ether, ester, amide, urea or urethane bond of the salicylic acid derivative having a total of 15 or more carbon atoms according to the present invention, water-soluble Preferred are water-soluble polymers or ionic or nonionic surfactants, and examples of water-soluble polymers include polyvinyl alcohol, alkyl-modified polyvinyl alcohol, cyanoethyl-modified polyvinyl alcohol, ether-modified polyvinyl alcohol, polyacrylamide, and polyacrylic acid.
Synthetic or natural polymers such as acrylamide / alkyl acrylate copolymer, sodium polystyrene sulfonate, maleic anhydride / isobutylene copolymer, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, starch, casein, gum arabic, gelatin and the like. . Examples of the ionic or nonionic surfactant include alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfonate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polycarboxylic acid. Soda salt of a type polymer, a polyhydric alcohol fatty acid ester and the like. Further, an ionic or nonionic surfactant may be used in combination with the water-soluble polymer.

Examples of the pigment 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. Of these, it is particularly preferable to use calcium carbonate having an average particle size of 5.0 μm or less, at 60% by weight or more of the total pigment. If the amount of calcium carbonate is less than 60% by weight, sufficient performance cannot be obtained with respect to the light fastness of the color former and the yellowing of the developed surface due to light. Unless calcium carbonate having an average particle size of 5.0 μm or less is used, sufficient color developing ability cannot be obtained.
Calcium carbonate having an average particle size of 5.0 μm or less is commercially available as, for example, Brilliant-15 or B
illiant-S15, Brilliant-3
0, PC, PCX, Unibur-70 and the like. The electron accepting compound and the pigment are preferably used in a weight ratio of 1: 5 to 1:15. If the use ratio of the pigment is higher or lower, sufficient color developing ability cannot be obtained. Examples of the binder of the coating solution include latexes such as styrene / butadiene copolymer latex and acrylate latex, polyvinyl alcohol, polyacrylic acid, maleic anhydride-styrene copolymer, starch, casein, gum arabic, gelatin, Synthetic or natural polymer substances such as carboxymethylcellulose and methylcellulose are used.

The amount of the electron accepting compound applied to the support is 0.1 to 2.0 g / m ² , preferably 0.2 to 1.0 g / m ² .
g / m ² 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 manufacturing method of the capsule, and other conditions, and may be appropriately selected according to the conditions. It is easy for those skilled in the art to determine this amount.

The performance of the developer sheet prepared using the 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 color former) Partial sodium salt of polyvinyl sulfonic acid (VERSA, TL500, manufactured by National Starch, average molecular weight 50)
(0.000) is added to 95 parts of hot water at about 80 ° C. while stirring, dissolved and cooled. The pH of the aqueous solution was 2-3, and a 20% by weight aqueous sodium hydroxide solution was added to adjust the pH to 4.0. On the other hand, 100 parts of diisopropylnaphthalene in which 2.5% of crystal violet lactone and 1.0% of benzoylleucomethylene blue are dissolved is emulsified and dispersed in 100 parts of a 5% aqueous solution of the above-mentioned sodium salt of polyvinyl benzene sulfonic acid to obtain an average diameter. 4.
An emulsion having a particle size of 5 μm was obtained. Separately, 6 parts of melamine and 11 parts of a 37% by weight aqueous formaldehyde solution were added to 60 parts.
After heating and stirring at 30 ° C. for 30 minutes, a transparent mixed aqueous solution of melamine and formaldehyde and a melamine-formaldehyde precondensate was obtained. The pH of this mixed aqueous solution was 6-8. Hereinafter, this mixed aqueous solution of melamine, formaldehyde and melamine-formaldehyde precondensate is referred to as a precondensate solution. The solution of the initial condensate obtained by the above method is added to the above-mentioned emulsion, mixed, and the pH is adjusted to 6.0 with a 3.6% by weight hydrochloric acid solution while stirring. Stirring continued for a minute. The capsule solution was cooled to room temperature, and pH 9.0 with a 20% by weight aqueous sodium hydroxide solution.
Was adjusted to 200 parts of a 10% by weight aqueous solution of polyvinyl alcohol and starch particles 5
0 parts were 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 applied to a 50 g / m ² base paper with an air knife coater so as to apply a solid content of 5 g / m ² , and dried to obtain a color capsule-containing microcapsule sheet. Examples will be shown below,
The present invention is not limited to this.

[0032]

EXAMPLE 1 Zinc 3,5-di- (α-methylbenzyl) salicylate 1
The developer solution was dissolved in 100 parts of xylene, and this developer solution was added to 500 parts of a 4% aqueous cyanoethylated polyvinyl alcohol solution containing 0.5% sodium dodecyl sulfate, and a homogenizer (Nippon Seiki, Model AM-7) was used. 120
The emulsion was emulsified at 00 rpm for 5 minutes to obtain a developer emulsion having an average particle size of 1.0 μm. The developer emulsion was heated to azeotropically remove xylene to prepare a developer dispersion having a solids concentration of 30%. Next, 1-phenyl-3-stearylurea 10
0 parts were mixed with 100 parts of xylene, and the solution was 0.5%
It is added to 500 parts of a 4% aqueous solution of cyanoethylated polyvinyl alcohol containing sodium dodecyl sulfate, and 12000 rpm using a homogenizer (Nippon Seiki, Model AM-7).
m to obtain an emulsion having 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 of 30%. Next, calcium carbonate (Shiraishi Kogyo, Bril
lient-15, average particle size 0.5 μm) 120 parts, activated clay 30 parts, zinc oxide 40 parts, 40% sodium hexametaphosphate aqueous solution 5 parts and water 230 parts, using a sand grinder to make the average particle size 3 μm. To obtain a pigment dispersion. 10% in 300 parts of this pigment dispersion
200 parts of an aqueous solution of PVA-117 (manufactured by Kuraray), 35 parts of the developer dispersion and 3.5 parts of the 1-phenyl-3-stearyl urea dispersion were added, and water was added so that the solid content concentration became 20%. Thus, a coating solution was obtained. 50 g of this coating solution
/ M ² base paper was coated with a bar so that a solid content of 5.0 g / m ² was applied 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 in place of 1-phenyl-3-stearylurea used in Example 1.

Example 3 A developer sheet was obtained in the same manner as in Example 1 except that anilide stearate was used instead of 1-phenyl-3-stearylurea used in Example 1.

Example 4 Zinc 3,5-di- (α-methylbenzyl) salicylate 1
00 parts were dissolved in 100 parts of xylene. This developer solution was added to 500 parts of a 4% aqueous cyanoethylated polyvinyl alcohol solution containing 0.5% sodium dodecyl sulfate, and emulsified at 12,000 rpm for 5 minutes using a homogenizer (Nippon Seiki, Model AM-7). Average particle size 1.0μ
m of a developer emulsion was obtained. This developer emulsion was heated to remove azeotropically xylene contained in the emulsion to prepare a developer dispersion having a solid content of 30%. Next, 120 parts of calcium carbonate (manufactured by Shiraishi Kogyo, Brilliant-15, average particle size 0.5 μm), 30 parts of activated clay, and 40 parts of zinc oxide
Parts, 1 part of 1-phenyl-3-stearyl urea, 2 parts of 2% aqueous solution of 2-ethylhexyl sulfosuccinate soda salt, 20 parts of 10% aqueous solution of PVA-117 (manufactured by Kuraray), 5 parts of 40% aqueous sodium hexametaphosphate Using 205 parts of water and water, the mixture was uniformly dispersed so as to have an average particle size of 3 μm by a sand grinder to obtain a pigment dispersion. To 300 parts of this pigment dispersion, 35 parts of the above-described developer dispersion was added, and the mixture was uniformly mixed by sand grinder treatment.
185 parts of an aqueous solution of A-117 (manufactured by Kuraray) was added, and water was prepared so that the solid content concentration became 20%, to obtain a coating solution.
The coating solution was applied to a 50 g / m ² base paper with a bar so as to apply a solid content of 5.0 g / m ² and dried to obtain a color developing sheet.

Example 5 A 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-stearylthiourea used in Example 4. .

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

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

Comparative Example 1 Zinc 3,5-di- (α-methylbenzyl) salicylate 1
00 parts were dissolved in 100 parts of xylene. This developer solution was added to 500 parts of a 4.5% aqueous solution of PVA-117 (manufactured by Kuraray Co., Ltd.) and emulsified at 12,000 rpm for 5 minutes using a homogenizer (Nippon Seiki, AM-7 type) to give an average particle size of 1. A developer emulsion of 0 μm was obtained. This developer emulsion was heated to remove azeotropically xylene contained in the emulsion to prepare a developer dispersion having a solid content of 30%. Next, 120 parts of calcium carbonate (manufactured by Shiroishi Kogyo, Brilliant-15, average particle size 0.5 μm), 30 parts of activated clay, 40 parts of zinc oxide, 40% sodium hexametaphosphate aqueous solution 5
And a part of water were uniformly dispersed by a sand grinder so as to have an average particle diameter of 3 μm to obtain a pigment dispersion.
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-described developer dispersion were added, and water was prepared so that the solid content concentration became 20% to obtain a coating solution. . 5.0 g of this coating solution was applied to 50 g / m ² base paper.
/ M ² , and dried with a bar so as to apply a solid content of / m ² to obtain a color developing sheet.

Each of the above-mentioned color developing sheets and the microca
Reputation as a pressure-sensitive recording sheet by combining
The value test was performed and the results are shown in Table 1. Note
The value test was performed by the following method. (Coloring speed and color density test) Includes color developing sheet and coloring agent
Heat the microcapsule sheet at 5 ° C and 35% RH
Stored in a moist chamber for over 1 hour. Next, in this constant temperature and humidity room
Microcapsules of microcapsule sheet containing color former
Layer on the color developing sheet, 300kg / cm ^TwoLoad
The color was developed over 1 second. Pressurized with Macbeth reflection densitometer
After 15 seconds, the concentration (D1) was measured. Then this color
The developed sheet is left at room temperature (25 ° C) for 24 hours.
After that, the density (D2) was measured with a Macbeth reflection densitometer.
The D1 / D2 ratio was defined as the color development speed, and D2 was defined as the color development density.

[0041]

[Table 1]

[0042]

As shown in Table 1, the color developing sheet prepared by using the color developing agent dispersion of the present invention is excellent in the color developing speed at a low temperature and extremely excellent in performance as compared with the color developing sheet for comparison. have.

Claims (3)

(57) [Claims] 1. A developer solution obtained by dissolving a metal salt of a salicylic acid derivative having a total carbon number of 15 or more in an organic solvent having a boiling point of 200 ° C. or less is emulsified and dispersed in water containing a dispersant, and subsequently obtained. Removing the organic solvent from the emulsified dispersion, and adding and mixing a dispersion of an organic compound having at least one ether, ester, amide, urea, or urethane bond, and mixing the resulting mixture. Liquid production method. 2. A method according to claim 1, wherein the developer for the pressure-sensitive recording paper according to claim 1 is treated with a disperser using a medium to obtain a dispersion having a volume average particle diameter of 4 μm or less. A method for producing a developer dispersion for pressure recording paper. 3. An ether, an ester, or a salt, based on the solid weight of a metal salt of a salicylic acid derivative having a total of 15 or more carbon atoms.
2. The method according to claim 1, wherein the solid weight of the organic compound having at least one amide, urea or urethane bond is 0.5 to 100% by weight. .