JPH08244339A - Pressure-resistant recording developer composition and pressure-resistant recording sheet - Google Patents

Abstract

PURPOSE: To obtain pressure-sensitive recording developer composition having an excellent color developing velocity by preparing a composition containing a developer which contains a polyvalent metallic salt of a salicylic acid derivative as a main ingredient and a compound represented by a specific general formula. CONSTITUTION: This developer composition containing a polyvalent metallic salt of salicylic acid derivative as an ingredient is mixed with a compound represented by the general formula (X1 and X2 are each hydrogen, an aralkyl group, or an aryl group, Y is an oxygen atom, or a sulfur atom, and m and n are each 1 or 2) to prepare a pressure-sensitive recording developer composition. A water dispersion fluid containing the composition is prepared, and a support is coated with the fluid to manufacture a pressure-sensitive recording sheet. The embodiment of the polyvalent of the derivative includes, for example, magnesium or zinc salt of salicylic acid, or 3-methylsalicylic acid. The embodiment of the compound represented by the general formula includes, for example, oxydiglycolic acid, or diethyloxydiglycolate.

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 color developer composition and a pressure-sensitive recording sheet obtained by coating a support with an aqueous dispersion containing the composition.

[0002]

2. Description of the Related Art Conventionally, as a pressure-sensitive recording sheet, for example, a microcapsule composition mainly containing a capsule containing an oily substance in which an electron-donating color-forming compound or the like is dissolved is coated on one side of a support. A developer composition containing an electron-accepting color developer as a main component, which is colored when it comes into contact with the electron-donating color-forming compound, is applied to one surface of the upper sheet and the support, and the microcapsule composition is applied to the other surface. There is an intermediate sheet coated with the product, and a lower sheet coated with the developer composition on one surface of the support, and generally, an upper sheet-lower sheet, or an upper sheet-middle sheet-lower. It is used in a combination of sheets. There is also a single copying sheet in which the above-mentioned microcapsule composition and the electron-accepting color developer composition are coated on the same surface of a support to enable copying in one sheet. Further, conventionally, it is obtained by reacting a salicylic acid derivative, for example, a polyvalent metal salt of a 3,5-di-substituted salicylic acid derivative (for example, Japanese Patent Publication No. 51-25174), or a salicylic acid ester with styrene. A polyvalent metal salt of a salicylic acid resin obtained by allowing a polyvalent metal compound to act after hydrolyzing a salicylic acid ester resin (JP-A-1-133780) is useful as an electron-accepting developer for a pressure-sensitive recording sheet. Known to be. However, the pressure-sensitive recording sheet using a polyvalent metal salt of these salicylic acid derivatives as an electron-accepting developer has a slow color development speed, particularly in a low temperature environment, and provides an image of practically sufficient color density. However, there is a drawback that it takes a long time. At present, a pressure-sensitive recording sheet having a high coloring speed is desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color-developing composition for pressure-sensitive recording having an excellent color development rate, and a pressure-sensitive recording sheet obtained by coating an aqueous dispersion containing the composition. Is to provide.

[0004]

Means for Solving the Problems In order to meet the above-mentioned demands, the present inventors have made earnest studies on a developer composition for pressure-sensitive recording and a pressure-sensitive recording sheet, and as a result, have completed the present invention. It was That is, the present invention provides a color developer composition containing a polyvalent metal salt of a salicylic acid derivative as a component and a compound represented by the general formula (1) or (Chemical Formula 2). The present invention relates to an aqueous dispersion containing a developer composition, and a pressure-sensitive recording sheet obtained by coating the support with the aqueous dispersion.

[0005]

Embedded image (In the formula, X ₁ and X ₂ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, Y represents an oxygen atom or a sulfur atom, and m and n represent 1 or 2.) of the salicylic acid derivative according to the present invention As a polyvalent metal salt,
Preferred examples include polyvalent metal salts of salicylic acid derivatives represented by the general formulas (2) and (Chemical Formula 3).

[0006]

Embedded image (In the formula, R _{1 to} R ₄ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom, and, in R _{1 to} R ₄ , two adjacent groups are bonded to each other to form a ring. In the general formula (2), R _{1 to} R ₄ each represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom, and among R _{1 to} R ₄ , they are adjacent to each other. The two groups described above may combine to form a ring. Preferably, it has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent. And an aryl group having 6 to 20 carbon atoms, a fluorine atom, a chlorine atom, or a bromine atom.

Specific examples of the polyvalent metal salt of salicylic acid derivative according to the present invention include, for example, salicylic acid, 3-methylsalicylic acid, 6-ethylsalicylic acid, 5-isopropylsalicylic acid, 5-sec-butylsalicylic acid and 5-tert-
Butyl salicylic acid, 5-tert-amyl salicylic acid, 5-
Cyclohexyl salicylic acid, 5-n-octyl salicylic acid, 5-tert-octyl salicylic acid, 5-isononyl salicylic acid, 3-isododecyl salicylic acid, 5-isododecyl salicylic acid, 5-isopentadecyl salicylic acid, 4
-Methoxysalicylic acid, 6-methoxysalicylic acid, 5-
Ethoxysalicylic acid, 6-isopropoxysalicylic acid,
4-n-hexyloxysalicylic acid, 4-n-decyloxysalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-di-tert-octylsalicylic acid, 3,5-
Diisononyl salicylic acid, 3,5-diisododecyl salicylic acid, 3-methyl-5-tert-nonyl salicylic acid, 3
-Tert-butyl-5-isononylsalicylic acid, 3-isononyl-5-tert-butylsalicylic acid, 3-isododecyl-5-tert-butylsalicylic acid, 3-isononyl-5
-Tert-amyl salicylic acid, 3-isononyl-5-tert
-Octylsalicylic acid, 3-isononyl-6-methylsalicylic acid, 3-isododecyl-6-methylsalicylic acid,
3-sec-octyl-5-methylsalicylic acid, 3-isononyl-5-phenylsalicylic acid, 3-phenyl-5-
Isononyl salicylic acid, 3-methyl-5- (α-methylbenzyl) salicylic acid, 3-methyl-5- (α, α-dimethylbenzyl) salicylic acid, 3-isononyl-5-
(Α-Methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5-tert-butylsalicylic acid, 3-benzylsalicylic acid, 5-benzylsalicylic acid, 3- (α-methylbenzyl) salicylic acid, 5- (α-methyl Benzyl) salicylic acid, 3- (α, α-dimethylbenzyl) salicylic acid, 4- (α, α-dimethylbenzyl) salicylic acid, 5- (α, α-dimethylbenzyl) salicylic acid,
3,5-di (α-methylbenzyl) salicylic acid, 3,5
-Di (α, α-dimethylbenzyl) salicylic acid, 3-
(Α-Methylbenzyl) -5- (α, α-dimethylbenzyl) salicylic acid, 3- (1 ′, 3′-diphenylbutyl) salicylic acid, 5- (1 ′, 3′-diphenylbutyl) salicylic acid, 3- [ α-methyl-4 ′-(α′-methylbenzyl) benzyl] salicylic acid, 5- [α-methyl-4 ′-(α′-methylbenzyl) benzyl] salicylic acid, 3- (α-methylbenzyl) -5- (1 ', 3'
-Diphenylbutyl) salicylic acid, 3- (1 ', 3'-
Diphenylbutyl) -5- (α-methylbenzyl) salicylic acid, 3-phenylsalicylic acid, 5-phenylsalicylic acid, 3- (α-methylbenzyl) -5-phenylsalicylic acid, 3- (α, α-dimethylbenzyl) -5 -Phenyl salicylic acid,

3-Phenyl-5- (α-methylbenzyl) salicylic acid, 5- (4'-methylphenyl) salicylic acid, 5- (4'-methoxyphenyl) salicylic acid, 5
-Fluorosalicylic acid, 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 5-bromosalicylic acid, 3-chloro-5- (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5-chloro Salicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, 2-hydroxy-3- (α, α-dimethylbenzyl) -1-naphthoic acid, 3-hydroxy-7- (α, α
-Dimethylbenzyl) -2-naphthoic acid, and further, for example, a carboxy-modified terpene phenol resin described in JP-A-62-19486, JP-A-63-11253.
7, JP-A-63-186729, JP-A-1
Examples thereof include polyvalent metal salts such as polystyrene-modified salicylic acid resin derivatives described in JP-A-133780 and polybenzylated styrenated salicylic acid resin derivatives described in JP-A-2-160815.

In the above salicylic acid derivative, propylene trimer, propylene tetramer or 1-butene trimer and propylene pentamer are added to the isononyl group, isododecyl group and isopentadecyl group, respectively. It is a general term for the resulting substituents. Some of the above salicylic acid derivatives are commercially available, and can be obtained, for example, from phenol derivatives by Kolbe-Schmidt reaction. Specific examples of the polyvalent metal include magnesium, zinc, nickel, aluminum and calcium, and zinc is particularly preferable. These polyvalent metal salts of salicylic acid derivatives may be used alone or in combination. Further, it may be a polyvalent metal salt of a mixed salicylic acid derivative obtained by chlorinating a polyvalent metal using plural kinds of salicylic acid derivatives.

The method for producing the polyvalent metal salt of the salicylic acid derivative according to the present invention is not particularly limited,
Known methods can be applied. For example, one or more salicylic acid derivatives and a polyvalent metal compound (eg, polyvalent metal oxides, hydroxides, carbonates, silicates, organic carboxylates).
And a method for producing (melting method), or a salt of a water-soluble salicylic acid derivative such as an alkali metal salt, an amine salt or an ammonium salt of one or more salicylic acid derivatives, and a water-soluble polyvalent metal compound (for example, Sulfates such as zinc sulfate, magnesium sulfate, aluminum sulfate,
And a chloride (such as zinc chloride, magnesium chloride, calcium chloride, nickel chloride, aluminum chloride, or an acetate such as zinc acetate) in the presence of water to produce the compound (double decomposition method).

The color developer according to the present invention contains a polyvalent metal salt of a salicylic acid derivative as a component, and if desired, a known color developer (for example, acidic clay, activated clay, attapulgite, bentonite, and other acidic developer) can be used. Clay minerals, phenols-
Formaldehyde condensate, phenols-salicylic acid-formaldehyde condensate, or polyvalent metal salts of these condensates). In this case, the proportion of the polyvalent metal salt of the salicylic acid derivative in the color developer is generally preferably adjusted to 60% by weight or more, more preferably 80% by weight or more.

In the compound represented by the general formula (1) according to the present invention, X ₁ and X ₂ are a hydrogen atom, an alkyl group,
It represents an aralkyl group or an aryl group, and preferably has a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an aralkyl group having a total of 7 to 14 carbon atoms which may have a substituent or a substituent. It is a good aryl group having 6 to 14 carbon atoms. In the compound represented by the general formula (1), Y represents an oxygen atom or a sulfur atom, more preferably a sulfur atom, and m and n represent 1 or 2. Specific examples of the compound represented by the general formula (1) include, for example, oxydiglycolic acid, diethyloxydiglycolate,
Diisopentyloxydiglycolate, di- (2-ethylhexyl) oxydiglycolate, di-n-decyloxydiglycolate, di-n-dodecyloxydiglycolate, di-n-octadecyloxydiglycolate,
Dibenzyloxydiglycolate, diphenyloxydiglycolate, mono-n-hexyloxydiglycolate, mono-n-decyloxydiglycolate, mono-n
-Tetradecyloxydiglycolate, oxydipropionic acid, diethyloxydipropionate, di-n-butyloxydipropionate, dicyclohexyloxydipropionate, di- (2-ethylhexyl) oxydipropionate, di-n -Dodecyloxydipropionate, di-n-tetradecyloxydipropionate, di-n-hexadecyloxydipropionate, di-n-octadecyloxydipropionate, dibenzyloxydipropionate, diphenethyloxydipropionate Pionate, diphenyloxydipropionate, mono-n-dodecyloxydipropionate, mono-n-octadecyloxydipropionate, monophenyloxydipropionate,

Thiodiglycolic acid, di-n-butylthiodiglycolate, di-n-hexylthiodiglycolate, di- (2-ethylhexyl) glycolate, di-n
-Decyl glycolate, di-n-dodecyl glycolate, di-n-tetradecyl glycolate, di-n-octadecyl glycolate, dibenzylthiodiglycolate, diphenylthiodiglycolate, monoethylthiodiglycolate, Monopentylthiodiglycolate, monocyclohexylthiodiglycolate, mono-n-octylthiodiglycolate, mono-n-decylthiodiglycolate, mono-n-hexadecylthiodiglycolate,
Monophenylthiodiglycolate,

Thiodipropionic acid, dimethylthiodipropionate, diethylthiodipropionate, diisopropylthiodipropionate, di-n-butylthiodipropionate, diisobutylthiodipropionate, di-sec-butylthiodipropionate , Di-n-pentylthiodipropionate, diisopentylthiodipropionate, di-n-hexylthiodipropionate, dicyclohexylthiodipropionate, di-n-octylthiodipropionate, di- (2 -Ethylhexyl)
Thiodipropionate, di-n-decylthiodipropionate, di-n-dodecylthiodipropionate, di-
n-tetradecylthiodipropionate, di-n-hexadecylthiodipropionate, di-n-octadecylthiodipropionate, dibenzylthiodipropionate, diphenethylthiodipropionate, di (4-methylbenzyl) ) Thiodipropionate, di (4-chlorobenzyl) thiodipropionate, diphenylthiodipropionate, di (4-methylphenyl) thiodipropionate, di (4-tert-butylphenyl) thiodipropionate, Di (4-methoxyphenyl) thiodipropionate, di (3-ethoxyphenyl) thiodipropionate, di (4-chlorophenyl) thiodipropionate,

Monoisobutylthiodipropionate, mono- (2-ethylhexyl) thiodipropionate, mono-n-decylthiodipropionate, mono-n-dodecylthiodipropionate, mono-n-tetradecylthiodipropionate Examples thereof include pionate, mono-n-octadecylthiodipropionate, monobenzylthiodipropionate, monophenylthiodipropionate, and the like, but are not limited thereto. These may be used alone or in combination. Some of the compounds represented by the general formula (1) according to the present invention are commercially available. Furthermore, the thio or oxydialkyl carboxylic acid ester derivative can be produced by a known method, for example, a method of reacting a thio or oxydialkyl carboxylic acid with an alcohol derivative or the like.

The developer composition for pressure-sensitive recording of the present invention is a developer composition containing a developer containing a polyvalent metal salt of a salicylic acid derivative as a component and a compound represented by the general formula (1). The composition is not particularly limited, but usually,
With respect to 100 parts by weight of the color developer containing the polyvalent metal salt of salicylic acid derivative, the compound represented by the general formula (1) is 1 to 10 parts.
It is about 0 parts by weight, more preferably about 3 to 50 parts by weight. In addition, in the developer composition for pressure-sensitive recording of the present invention, in addition to a developer containing a polyvalent metal salt of a salicylic acid derivative as a component, a compound represented by the general formula (1), styrene Derivative oligomers, preferably 2 of styrene derivatives
The inclusion of about 20 to 20 mer oligomers
In some cases, it is possible to obtain a developer composition having a further improved color development speed in a low temperature environment, which is preferable. The oligomer is a chain oligomer (for example, 1,3-diphenyl-1-butene which is a chain dimer of styrene) or a cyclic oligomer (for example, a cyclic dimer of styrene 1-
Methyl-3-phenylindane) or a mixture thereof. In this case, the amount of the styrene derivative oligomer is 100% by weight of the compound represented by the general formula (1).
It is preferable that the amount is adjusted to about 1000 parts by weight or less, more preferably about 800 parts by weight or less with respect to parts by weight.

The developer composition for pressure-sensitive recording of the present invention is usually used as an aqueous dispersion and coated on a support to form a developer layer. As the preparation method, a method in which a developer containing a polyvalent metal salt of a salicylic acid derivative and a compound represented by the general formula (1) are dispersed together in an aqueous medium,
Alternatively, a method of separately dispersing and then mixing can be applied. For example, a developer containing a polyvalent metal salt of a salicylic acid derivative and a compound represented by the general formula (1) can be used as a disperser in an aqueous medium. , For example, ball mill, attritor, sand grinder, pebble mill, cobol mill, dyno mill, high speed impeller disperser, high speed stone mill,
Using an annular mill or the like, a method of pulverizing and dispersing to obtain an aqueous dispersion, a developer containing a polyvalent metal salt of a salicylic acid derivative and a compound represented by the general formula (1) are dissolved in an organic solvent, In an aqueous medium, for example, an ultrasonic dispersion machine, a homogenizer, a homomixer, a line homomixer or the like may be used to carry out an emulsification dispersion treatment and remove the organic solvent to obtain an aqueous dispersion. Usually, the developer composition for pressure-sensitive recording is pulverized and dispersed to an average particle size of 3 μm or less, preferably 2 μm or less.

A dispersant may be used when dispersing in an aqueous medium. The dispersant used is preferably an ionic or nonionic surfactant, and examples thereof include polyvinyl alcohol, alkyl-modified polyvinyl alcohol, cyanoethyl-modified polyvinyl alcohol, ether-modified polyvinyl alcohol, polyacrylamide, polyacrylic acid, acrylamide / alkyl acrylate. Copolymer,
Polystyrenesulfonic acid alkali metal salt, maleic anhydride / isobutylene copolymer, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, starch and its derivatives, casein, gum arabic, agar, synthetic or natural polymer compounds such as gelatin, alkylbenzene sulfone Acid alkali metal salt, alkylnaphthalene sulfonic acid alkali metal salt, dialkylsulfosuccinic acid alkali metal salt, alkylsulfonic acid alkali metal salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyhydric alcohol fatty acid Examples thereof include esters. Even if these dispersants are used alone,
Alternatively, a plurality may be used in combination. The amount of the dispersant used is not particularly limited, but is usually 1 to 3 parts by weight with respect to 100 parts by weight of the color developer containing the polyvalent metal salt of the salicylic acid derivative.
It is about 0 parts by weight.

In the above method, the organic solvent used is preferably one having a low solubility in water, a high solubility of the color developer and a relatively low boiling point. Examples of the organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, 1-methylnaphthalene, dichloromethane, chloroform, tetrachloroethylene, 1,2-dichloroethane, 1,1,1-
Trichloroethane, 1,1,2-trichloroethane,
1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p
-Dichlorobenzene, o-chlorotoluene, m-chlorotoluene, halogenated hydrocarbon solvents such as p-chlorotoluene, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, ethyl acetate, butyl acetate, amyl acetate, etc. Examples thereof include ester solvents, alcohol solvents such as butanol, pentanol, hexanol, cyclohexanol and the like. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but is usually about 5 to 500 parts by weight, more preferably 20 to 300 parts by weight with respect to 100 parts by weight of the color developer containing the polyvalent metal salt of the salicylic acid derivative. It is about part by weight. In this case, the emulsification dispersion treatment is carried out at a temperature equal to or lower than the boiling point of the organic solvent, and is carried out under atmospheric pressure or under pressure. After the dispersion treatment, the organic solvent is distilled off to obtain an aqueous dispersion of the developer composition for pressure-sensitive recording. As a method for distilling off the organic solvent, the organic solvent can be distilled off under atmospheric pressure or under reduced pressure by heating to a temperature above the boiling point of the organic solvent. The aqueous dispersion thus obtained can be further subjected to a dispersion treatment using the above-mentioned disperser (for example, a sand grinder or an annular mill), if desired.

The aqueous dispersion of the developer composition for pressure-sensitive recording of the present invention further contains a binder, a pigment and the like in addition to the developer composition for pressure-sensitive recording obtained as described above. The solid content may be about 10 to 50% by weight, preferably about 20 to 40% by weight. The binder is not particularly limited, and examples thereof include polyvinyl alcohol, casein, starch and derivatives thereof, gum arabic, methyl cellulose, carboxymethyl cellulose, polyacrylic acid, styrene / butadiene copolymer latex, acrylate latex. Synthetic or natural polymer compounds such as latexes. The amount of the binder used is not particularly limited, but it is generally adjusted so as to be about 5 to 40% by weight, preferably about 10 to 30% by weight of the total solid content of the aqueous dispersion. Examples of the pigment include zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate,
Barium carbonate, magnesium sulfate, barium sulfate, titanium oxide, talc, kaolin, activated clay, diatomaceous earth, zinc hydroxide, aluminum hydroxide, magnesium hydroxide,
Examples thereof include inorganic pigments such as alumina and silica, organic pigments such as styrene microballs, nylon particles, urea-formalin fillers, polyethylene particles, cellulose fillers and starch particles. The amount of the pigment used is not particularly limited, but is generally 5% of the total solid content of the aqueous dispersion.
To about 90% by weight, preferably about 10 to 80% by weight. Furthermore, if desired, various additives (for example, an ultraviolet absorber, an antifoaming agent, a pH adjusting agent, a viscosity adjusting agent, a plasticizer, an organic polymer compound, etc.) may be added to this aqueous dispersion.

The aqueous dispersion of the developer composition for pressure-sensitive recording prepared in this manner can be prepared by a known method, for example, an air knife coater, a blade coater, a roll coater, a size press coater, a curtain coater, or a short coat. -A coating device such as a dwell coater is used to coat a support (for example, paper, plastic sheet, synthetic paper, or a composite sheet combining these) to form a color developer layer, thereby producing a pressure-sensitive recording sheet. can do. The weight (that is, the coating amount) of the developer layer on the support is not particularly limited, but it is usually 0.5 g / m 2 in terms of dry weight.
^{It is 2} or more, preferably 0.5 to 10 g / m ² .

The form of the pressure-sensitive recording sheet of the present invention is as follows.
Although not particularly limited, for example, a lower sheet used in combination with an upper sheet in which microcapsules containing an electron-donating color forming compound and a capsule oil are applied to the back surface of the sheet, multiple sheets are copied. For the purpose of inserting the intermediate sheet between the upper sheet and the lower sheet, the developer sheet is provided on the front surface of the sheet and the microcapsule layer is provided on the back surface of the sheet, and further, the microsheet is formed on the same surface of the sheet. There is a single copy sheet coated with both the capsule and the color developer. The above-mentioned microcapsules are prepared by dissolving an electron-donating color-forming compound in capsule oil, and subjecting the solution to known methods such as coacervation method, interfacial polymerization method, internal polymerization method, phase separation method, and external polymerization method. It can be produced by processing by various microencapsulation methods. Examples of the electron-donating color-forming compound include triarylmethane compounds, diarylmethane compounds, rhodamine-lactam compounds, fluorane compounds, indolylphthalide compounds, pyridine compounds, spiro compounds, and fluorene compounds. , Various known compounds such as phenothiazine compounds. As the capsule oil, for example,
Examples include various oils such as cottonseed oil, castor oil, kerosene, paraffin, chlorinated paraffin, naphthene oil, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, diarylalkane, hydrogenated terphenyl, and dialkyl phthalate. These capsule oils may be used alone or in combination.

[0023]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following,% means% by weight. Example 1 Zinc 3,5-di (α-methylbenzyl) salicylate 20
A mixture of g, 4 g of di-n-octylthiodipropionate, 120 g of calcium carbonate and 200 g of water was atomized and dispersed by a sand grinder to an average particle diameter of 1.5 μm to obtain a dispersion liquid. A 100% aqueous solution of 10% polyvinyl alcohol (PVA-117, manufactured by Kuraray) was added to this dispersion.
g and 50% carboxy modified SBR latex (SN
(-307, manufactured by Sumitomo Nogatac) was added, and water was added so that the solid content concentration became 20% to obtain an aqueous dispersion of the developer composition. An aqueous dispersion of this developer composition was applied to woodfree paper (50 g / m ² ) so that the coating amount (weight of the developer layer) at the time of drying would be 5.0 g / m ^2, and dried. A pressure-sensitive recording sheet (lower sheet) was produced.

Example 2 In Example 1, 3,5-di (α-methylbenzyl)
Instead of using 20 g of zinc salicylate, 20 g of a zinc salt of a polystyrene salicylate resin produced by the method shown in the following Reference Example was used, and the average particle diameter was 1.6 μm by the method described in Example 1. An aqueous dispersion of the color developer composition of Example 1 was obtained, and a pressure-sensitive recording sheet was prepared.

Reference Example Methyl salicylate (152 g), 98% sulfuric acid (37 g) and 1,2-dichloroethane (500 ml) were placed in a glass reaction vessel, and the solution was stirred at 0 to 2 ° C.
Then, using a dropping funnel with 384 g of 4-methylstyrene,
It was supplied over 6 hours. After the supply, the mixture was further stirred at the same temperature for 3 hours. After neutralizing with a 5 wt% sodium hydroxide aqueous solution, the mixture was heated to distill away 1,2-dichloroethane. Further, an aqueous solution prepared by dissolving 40 g of sodium hydroxide in 1000 g of water was added, and the mixture was heated and stirred at 95 ° C. for 6 hours. After adding 3000 g of water to the solution, at 25 ° C.,
An aqueous solution of 145 g of zinc sulfate heptahydrate dissolved in 2000 g of water was added dropwise over 1 hour. The mixture was further stirred at room temperature for 2 hours, filtered, washed with water and dried to obtain 530 g of a colorless polystyrene salt of a zinc salicylate resin. Softening point is 112
° C.

Example 3 75 g of 3,5-di (α-methylbenzyl) salicylic acid,
A mixture of 25 g of 3- (α-methylbenzyl) -5- (1,3-diphenylbutyl) salicylic acid was dissolved at 30 ° C. in an aqueous solution in which 11 g of sodium hydroxide was dissolved in 500 g of water, and zinc sulfate 7 was added to the aqueous solution. 39.3 g of hydrate was added to 2 parts of water
An aqueous solution dissolved in 00 g was added dropwise over 30 minutes. After dropping 3
After stirring for 0 minutes, 100 g of toluene was added to the aqueous solution in which the mixed zinc salt of the salicylic acid derivative was deposited, and after stirring, the toluene layer was separated. The temperature of the toluene solution was raised to 50 ° C., 10 g of di-n-decylthiodipropionate was added, and 5% polyvinyl alcohol (PVA-11 was added.
(7, made by Kuraray), 500 g of an aqueous solution was added, and a homomixer [AM-7 type, manufactured by Nippon Seiki Co., Ltd.] was used for 10000 minutes per minute.
The emulsion was emulsified for 10 minutes at the number of revolutions to obtain an oil-in-water emulsion. The emulsion was heated to distill off toluene and a part of water to obtain a dispersion liquid (solid content concentration 30%) having an average particle size of the developer dispersion particles of 1.3 μm. Next, 120 g of calcium carbonate, 30 g of activated clay, 40 g of zinc oxide, 5 g of 40% sodium hexametaphosphate aqueous solution and 230 g of water were dispersed by a sand grinder so as to have an average particle diameter of 2 μm to obtain a pigment dispersion liquid. To 50 g of this pigment dispersion,
40 g of a 10% aqueous polyvinyl alcohol solution and the above dispersion liquid were added, and further water was added so that the solid content concentration was 20% to obtain an aqueous dispersion coating liquid of the developer composition. An aqueous dispersion of this developer composition was applied to woodfree paper (50 g / m ² ) so that the coating amount (weight of the developer layer) at the time of drying would be 5.0 g / m ^2, and dried. A pressure sensitive recording sheet was prepared.

Example 4 In Example 3, except that 10 g of di-n-decylthiodipropionate was used instead of 10 g of di-n-decylthiodipropionate, 8 g of di-n-dodecylthiodipropionate and 5 g of diethylthiopropionate were used. By the method described in Example 3,
An aqueous dispersion of the developer composition having an average particle diameter of 1.2 μm was obtained, and a pressure-sensitive recording sheet was prepared.

Example 5 In Example 3, 6 g of di-n-tetradecyl thiodipropionate and 4 g of dibenzylthiodipropionate were used instead of 10 g of di-n-decylthiodipropionate. In accordance with the method described in Example 3, an aqueous dispersion of the developer composition having an average particle diameter of 1.2 μm was obtained, and a pressure sensitive recording sheet was prepared.

Example 6 Instead of using 10 g of di-n-decylthiodipropionate in Example 3, 8 g of di-n-tetradecyloxydipropionate and 4 g of di-n-octadecyloxydipropionate were used. Example 3 except that it was used
By the method described in 1., an aqueous dispersion of the developer composition having an average particle diameter of 1.2 μm was obtained, and a pressure sensitive recording sheet was prepared.

Example 7 The method described in Example 3 except that 8 g of mono-n-dodecylthiodipropionate was used in place of 10 g of di-n-decylthiodipropionate in Example 3. Thus, an aqueous dispersion of the color developer composition having an average particle diameter of 1.2 μm was obtained, and a pressure sensitive recording sheet was prepared.

Example 8 Instead of using 10 g of di-n-decylthiodipropionate in Example 3, 7 g of thiodiglycolic acid was used.
And 4 g of mono- (2-ethylhexyl) thiodipropionate were used, and by the method described in Example 3, an aqueous dispersion of a color developer composition having an average particle size of 1.2 μm was obtained, and the feeling was further improved. A pressure recording sheet was prepared.

Example 9 Instead of using 10 g of di-n-decylthiodipropionate in Example 3, 7 g of thiodipropionic acid was used.
And 5 g of di-n-decylthiodiglycolate were used, but an aqueous dispersion of a developer composition having an average particle size of 1.2 μm was obtained by the method described in Example 3, and the pressure-sensitive recording was performed. A sheet was prepared.

Example 10 Instead of using 10 g of di-n-decylthiodipropionate in Example 3, 8 g of di-n-octadecylthiodipropionate and 1,3 which is a chain dimer of styrene. By the method described in Example 3, except that 5 g of -diphenyl-1-butene was used, the average particle size was 1.
An aqueous dispersion of a 2 μm color developer composition was obtained, and a pressure-sensitive recording sheet was prepared.

Example 11 100 g of a zinc salt of a polystyrene-modified salicylic acid resin prepared in Reference Example, 10 g of diphenylthiodipropionate,
1,3-diphenyl-1-which is a chain dimer of styrene
A xylene solution was prepared by dissolving 4 g of butene and 3 g of 1-methyl-3-phenylindane, which is a cyclic dimer of styrene, in 100 g of xylene. 0.2 g of sodium carbonate and 1 g of acrylamide / ethyl acrylate copolymer (weight average molecular weight 2500) were added to the xylene solution.
A homomixer was added to 80 g of water containing 2 g of polyvinyl alcohol while rotating the homomixer at a rotation speed of 8000 rpm to obtain an emulsion. After adding 150 g of water to this emulsion, the emulsion is heated to distill off xylene and a part of water to obtain a dispersion having an average particle size of 1.2 μm (solid content concentration 3
0%). Next, 120 g of calcium carbonate, 30 g of activated clay, 40 g of zinc oxide, 5 g of 40% sodium hexametaphosphate aqueous solution and 230 g of water were dispersed by a sand grinder so as to have an average particle diameter of 2 μm to obtain a pigment dispersion liquid. To 50 g of this pigment dispersion, 40 g of a 10% aqueous solution of polyvinyl alcohol and the above dispersion were added, and further,
Water was added so that the solid content concentration was 20% to obtain an aqueous dispersion of the developer composition. An aqueous dispersion of this developer composition was applied to woodfree paper (50 g / m ² ) so that the coating amount (weight of the developer layer) at the time of drying would be 5.0 g / m ^2, and dried. A pressure sensitive recording sheet was prepared.

Comparative Example 1 A developer composition having an average particle diameter of 1.5 μm was obtained by the method described in Example 1 except that di-n-octylthiodipropionate was not used. An aqueous dispersion of was obtained, and a pressure-sensitive recording sheet was prepared.

Comparative Example 2 In Example 11, 10 g of diphenylthiodipropionate, 4 g of 1,3-diphenyl-1-butene, which is a chain dimer of styrene, and 1-methyl-, which is a cyclic dimer of styrene, are used. By the method described in Example 11 except that 3 g of 3-phenylindane was not used, an aqueous dispersion of a developer composition having an average particle size of 1.2 μm was obtained, and a pressure-sensitive recording sheet was prepared. .

The pressure-sensitive recording sheet (lower sheet) produced as described above was evaluated by the following methods. -Evaluation of pressure-sensitive recording sheet (low temperature color development test) Each pressure-sensitive recording sheet (lower sheet) prepared, and crystal violet lactone (CV)
A commercially available blue coloring upper sheet [N-40, manufactured by Mitsubishi Paper Mills, Ltd.] coated with microcapsules containing L) as a main electron-donating color-forming compound is at 5 ° C. and 30% R.
It was stored in a room of constant temperature and humidity of H for 5 hours. Next, in this constant temperature and constant humidity chamber, the application sheets of the upper sheet and the lower sheet were overlapped with each other facing each other, and a color was developed by applying a load pressure of 300 kg / cm ² for 1 second. The color density after 30 seconds from the pressurization was measured using a Macbeth reflection densitometer. Further, the color-developed lower sheet was stored in the same environment for 24 hours, and then the color density was measured in the same manner. The results are shown in Table 1. As for the color density, the larger the value, the deeper the color is developed.

[0038]

[Table 1] From the results shown in Table 1, since the pressure-sensitive recording sheet obtained by applying the color developer composition of the present invention develops a deep color in a short time under a low temperature environment, it has excellent initial color development at low temperature. It turned out that

[0039]

According to the present invention, it is possible to provide a developer composition for pressure-sensitive recording excellent in low-temperature color development and a pressure-sensitive recording sheet obtained by applying the composition.

Claims (3)

[Claims] 1. A developer composition for pressure-sensitive recording containing a developer containing a polyvalent metal salt of a salicylic acid derivative as a component and a compound represented by the general formula (1) (formula 1). Embedded image (In the formula, X ₁ and X ₂ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, Y represents an oxygen atom or a sulfur atom, and m and n represent 1 or 2.) 2. An aqueous dispersion containing the developer composition for pressure-sensitive recording according to claim 1. 3. A pressure-sensitive recording sheet obtained by applying the aqueous dispersion according to claim 2 on a support.