JP3229735B2 - Polyvalent metal salt of salicylic acid resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvalent metal salt of a salicylic acid resin useful as a color developer for recording materials such as pressure-sensitive copying paper, and a method for producing the polyvalent metal salt of the resin. Further, the present invention relates to a color developing sheet using a polyvalent metal salt of the resin.

[0002]

2. Description of the Related Art Conventionally, metal salts of salicylic acid derivatives have been known to be useful as color developers for pressure-sensitive copying paper, and various salicylic acid derivatives and methods for producing and using the metal salts have been proposed. Have been. For example, a 3,5-disubstituted salicylic acid derivative is produced from a corresponding 2,4-disubstituted phenol derivative and carbon dioxide by utilizing the so-called Kolbe-Schmidt reaction (for example, Japanese Patent Publication No. 51-51).
25174). However, this method has drawbacks in the production equipment, such as that the production of the 3,5-disubstituted salicylic acid derivative is performed in two steps from phenol, and a special high-temperature and high-pressure apparatus is required for the reaction of carbon dioxide. . Further, when a metal salt of a 3,5-disubstituted salicylic acid derivative, for example, a zinc salt of 3,5-di (α-methylbenzyl) salicylic acid is used as a developer for pressure-sensitive copying paper, the color image becomes water. There is a problem such as disappearing with.

A method is disclosed in which a salicylic acid derivative and a styrene derivative are reacted at 50 to 150 ° C. in the presence of an acid catalyst, and then reacted with a metal salt of a fatty acid to produce a metal salt of a high molecular weight salicylic acid resin. (JP-A-63-11
No. 2537). However, there is a problem that the metal salt of salicylic acid resin produced by this method is often colored. Further, a metal salt (for example, a zinc salt) of a high molecular weight salicylic acid resin produced by this method.
When used as a color developer for pressure-sensitive copying paper, there are problems that it is difficult to form fine particles at the time of dispersion and that the dispersion liquid easily aggregates. Also disclosed is a method for producing a polyvalent metal salt of a salicylic acid resin in which a salicylic acid ester is reacted with a styrene to hydrolyze the obtained salicylic acid ester resin and then react with a polyvalent metal compound (Japanese Patent Application Laid-Open No. HEI 9-260,019). 1
-133780). For example, methyl salicylate is reacted with styrene in the presence of concentrated sulfuric acid to form a salicylic acid methyl ester resin, and after hydrolysis with an aqueous alkali solution, a polyvalent metal compound (eg, zinc sulfate) is allowed to act on the salicylic acid resin. A method for producing a polyvalent metal salt of is described. However, when a polyvalent metal salt of a salicylic acid resin (for example, a zinc salt) produced by this method is used as a color developer for pressure-sensitive copying paper, it is difficult to form fine particles at the time of dispersion, and the dispersion liquid is easily aggregated. There is a problem.

Further, salicylic acid and benzyl halides are converted to 20 to 160 in the presence of a Friedel-Crafts catalyst.
C., and the resulting salicylic acid resin is further reacted with a styrene derivative at 0 to 50 ° C. in the presence of a strong acid.
There is known a method of producing a polyvalent metal compound of a salicylic acid resin by acting with a polyvalent metal compound (Japanese Patent Laid-Open No. 2-1).
No. 60815). In this method, the reaction of salicylic acid with a benzyl halide and the reaction of a styrene derivative are separately performed in two steps. When a polyvalent metal salt of a salicylic acid resin (for example, a zinc salt) produced by this method is used as a developer for pressure-sensitive copying paper,
At the time of dispersion, there is a problem that it is difficult to form fine particles, and the dispersion liquid is easily aggregated. At present, there is a demand for a developer for pressure-sensitive copying paper which is easily formed into fine particles, has excellent storage stability of a dispersion, and has excellent storage stability (for example, water resistance) of a color image.

[0005]

An object of the present invention is to provide a polyvalent metal salt of a salicylic acid resin useful for pressure-sensitive copying paper, a method for producing the same, and a color developing sheet using the same.

[0006]

Means for Solving the Problems In order to meet the above-mentioned demands, the present inventors have intensively studied a polyvalent metal salt of a salicylic acid derivative, and have reached the present invention. That is,
In the present invention, a salicylic acid derivative represented by the general formula (1) (formula 4) is added to a benzyl halide derivative represented by the general formula (2) (formula 5) and a general formula (3) ( The present invention relates to a method for producing a polyvalent metal salt of a salicylic acid resin in which a styrene derivative represented by Chemical formula 6) is simultaneously reacted, and then reacted with a polyvalent metal compound.

[0007]

Embedded image (Wherein, R ₁ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and X ₁ and X ₂ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom)

[0008]

Embedded image (Wherein, R ₂ and R ₃ represent a hydrogen atom or an alkyl group, X ₃ represents a halogen atom, and X ₄ and X ₅ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom. Represent)

[0009]

Embedded image (Wherein, R ₄ , R ₅ and R ₆ represent a hydrogen atom or an alkyl group, and X ₆ and X ₇ represent a hydrogen atom, an alkyl group,
The present invention also relates to a polyvalent metal salt of a salicylic acid resin produced by the method, and a color developing sheet using the polyvalent metal salt of the salicylic acid resin.

In the general formula (1), R ₁ is a hydrogen atom,
It represents an alkyl group, an aralkyl group or an aryl group, preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. In the general formula (1), X ₁ and X
₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom, preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and 1 carbon atom.
An alkoxy group having 12 to 12 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a fluorine atom, a chlorine atom and a bromine atom.

Examples of the salicylic acid derivative represented by the general formula (1) include, for example, salicylic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-methylsalicylic acid,
-N-butylsalicylic acid, 6-ethylsalicylic acid, 5-
Isopropyl salicylic acid, 4-n-pentyl salicylic acid, 5-cyclohexyl salicylic acid, 5-n-octyl salicylic acid, 5-tert-octyl salicylic acid, 5-nonyl salicylic acid, 4-n-dodecyl salicylic acid, 4-methoxy salicylic acid, 6-methoxy salicylic acid , 5-ethoxysalicylic acid, 6-isopropoxysalicylic acid, 4-n
-Hexyloxysalicylic acid, 4-n-decyloxysalicylic acid, 3-benzylsalicylic acid, 5-benzylsalicylic acid, 3- (α-methylbenzyl) salicylic acid, 5-
(Α-methylbenzyl) 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, 4-phenylsalicylic acid, 5-phenylsalicylic 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,

Methyl salicylate, ethyl salicylate, n-propyl salicylate, isopropyl salicylate, n-butyl salicylate, isoamyl salicylate, tert-octyl salicylate, nonyl salicylate, dodecyl salicylate, cyclohexyl salicylate, benzyl salicylate, α-methyl salicylate Benzyl, phenyl salicylate, methyl 3-methylsalicylate, methyl 4-methylsalicylate, ethyl 4-methoxysalicylate, methyl 5-benzylsalicylate, 5- (α-methylbenzyl)
Methyl salicylate, 5- (α, α-dimethylbenzyl)
Methyl salicylate, ethyl 5-phenylsalicylate, 5
Examples include, but are not limited to, methyl-fluorosalicylate, methyl 3-chlorosalicylate, n-butyl 4-chlorosalicylate, and methyl 5-bromosalicylate. These salicylic acid derivatives are
It may be used alone or in combination. Preferred are salicylic acid or alkyl salicylate derivatives such as methyl salicylate and n-butyl salicylate.

In the general formula (2), R ₂ and R ₃ represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X ₃ represents a halogen atom, preferably a chlorine atom or a bromine atom. X ₄ and X _{5 each} represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom, preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Group, carbon number 7
An aralkyl group having 10 to 10, an aryl group having 6 to 10 carbon atoms,
They are a fluorine atom, a chlorine atom and a bromine atom. General formula (2)
Specific examples of the benzyl halide derivative represented by
For example, benzyl chloride, benzyl bromide, 2
-Methylbenzyl chloride, 3-methylbenzyl chloride, 4-methylbenzyl chloride, 3-ethylbenzyl chloride, 4-propylbenzyl chloride,
4-nonylbenzyl chloride, 2-phenylbenzyl fluoride, 4-cyclohexylbenzyl chloride, 4-benzylbenzyl chloride, 4- (α-methylbenzyl) benzyl chloride, 4- (α, α-dimethylbenzyl) benzyl chloride, 2 , 4-dimethylbenzyl chloride, 2,4-diethylbenzyl chloride, 3-methyl-4-ethylbenzyl chloride, 3
-(Α-methylbenzyl) -4-methylbenzyl chloride, 4- (2,5-dimethylbenzyl) benzyl chloride, α-methylbenzyl chloride, α-methylbenzyl bromide, 2-methyl-α-methylbenzyl chloride, 3 -Methyl-α-methylbenzyl chloride, 4-methyl-α-methylbenzyl chloride, 2-
Ethyl-α-methylbenzyl chloride, 4-ethyl-
α-methylbenzyl chloride, 4-isopropyl-α
-Methylbenzyl chloride, 4-n-hexyl-α-
Methylbenzyl chloride, 4-cyclohexyl-α-
Methylbenzyl chloride, 2,3-dimethyl-α-methylbenzyl chloride, 2,4-dimethyl-α-methylbenzyl chloride, 2,5-dimethyl-α-methylbenzyl chloride, 3,4-dimethyl-α-methylbenzyl Examples include, but are not limited to, chlorides. These benzyl halide derivatives may be used alone or in combination. Preferably,
Benzyl chloride or an alkyl-substituted benzyl halide derivative such as α-methylbenzyl chloride.

In the general formula (3), R ₄ , R ₅ and R ₆ represent a hydrogen atom or an alkyl group.
It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X ₆ and X _{7 each} represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, or a halogen atom, preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Group, carbon number 7-10
, An aryl group having 6 to 10 carbon atoms, a fluorine atom, a chlorine atom and a bromine atom. Examples of the styrene derivative represented by the general formula (3) include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 4-ethylstyrene, 3-isopropylstyrene, and 4-styrene. Isopropylstyrene, 4-
n-butylstyrene, 4-tert-butylstyrene, 4-
Cyclohexylstyrene, 4-n-octylstyrene,
4-n-decylstyrene, 2,4-dimethylstyrene,
2,5-dimethylstyrene, 3-methoxystyrene, 4
-Methoxystyrene, 4-ethoxystyrene, α-methylstyrene, α-ethylstyrene, α-n-butylstyrene, α-isobutylstyrene, α, β-dimethylstyrene, α, β-diethylstyrene, α-methyl-β -Isopropylstyrene, α-n-propyl-β-methylstyrene, 4- (α, α-dimethylbenzyl) styrene,
Examples thereof include, but are not limited to, 4-phenylstyrene, 4-fluorostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, and 4-bromostyrene. These styrene derivatives may be used alone or in combination of two or more. Preferred is styrene or an alkyl-substituted styrene derivative such as 4-methylstyrene and α-methylstyrene.

In the production method of the present invention, both a benzyl halide derivative represented by the general formula (2) and a styrene derivative represented by the general formula (3) are used. The ratio is not particularly limited, and any ratio can be used. Usually, the styrene derivative represented by the general formula (3) is used in an amount of about 0.05 to 20 times, more preferably 0.1 to 20 mol per mol of the benzyl halide derivative represented by the general formula (2). It is used in a ratio of about 10 moles. The total amount of the benzyl halide derivative represented by the general formula (2) and the styrene derivative represented by the general formula (3) is
Although not particularly limited, it is preferably about 1 to 10 moles, more preferably about 1.5 to 8 moles, per 1 mole of the salicylic acid derivative represented by the general formula (1). Particularly preferably, it is about 2 to 6 moles.

Examples of the acid used in the present invention include mineral acids such as hydrochloric acid, sulfuric acid, hydrogen bromide, hydrogen chloride, hydrogen fluoride, phosphoric acid and polyphosphoric acid, acetic acid, propionic acid, chloroacetic acid, trichloroacetic acid, and the like. Trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-
Organic acids such as toluenesulfonic acid, xylenesulfonic acid, p-chlorobenzenesulfonic acid, β-naphthalenesulfonic acid, stannic chloride, ferric chloride, zinc chloride, aluminum chloride, boron trifluoride, titanium tetrachloride, etc. Examples include, but are not limited to, Lewis acids and super-strong acids such as Nafion-H (trade name, manufactured by Dupont). These acids may be used alone or in combination of two or more. A particularly preferred acid is sulfuric acid. When sulfuric acid is used, sulfuric acid having a concentration of about 90% by weight or more is preferable, and fuming sulfuric acid may be used in combination.

The amount of the acid used is not particularly limited. The use of a large amount of acid does not adversely affect the properties of the product, but the use of a large amount itself only lowers the working efficiency, production efficiency and the like. Usually, the amount of the acid used is 5 to 100% by weight, more preferably 10 to 50% by weight, based on the weight of the salicylic acid derivative represented by the general formula (1).

The method of the present invention can be carried out in the absence of an organic solvent, but can also be carried out in the presence of an organic solvent. As the organic solvent, any organic solvent which is inert to the reaction can be used. For example, hexane, octane, decane, cyclohexane, benzene, toluene, hydrocarbon solvents such as xylene, dichloromethane, 1,2-dichloroethane, tetrachloromethane,
1,1-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, chlorobenzene,
o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o
Examples thereof include, but are not limited to, halogenated hydrocarbon solvents such as -chlorotoluene, m-chlorotoluene and p-chlorotoluene, and organic carboxylic acid solvents such as acetic acid and propionic acid. These solvents may be used alone or in combination of two or more. The usage capacity of the organic solvent is not particularly limited, but the use of a large amount of the organic solvent only lowers the working efficiency, production efficiency, and the like. Usually, the usage volume of the organic solvent is preferably 100 (volume / weight) or less times the weight of the salicylic acid derivative represented by the general formula (1).

In the production method of the present invention, in the presence of an acid,
When the benzyl halide derivative represented by the general formula (2) and the styrene derivative represented by the general formula (3) are supplied to the salicylic acid derivative represented by the general formula (1), the supply method is preferably This is a method of supplying a styrene derivative represented by the general formula (3) along with the supply of the benzyl halide derivative represented by the general formula (2). As the method, a method of continuously supplying the styrene derivative at a constant rate with the supply of the benzyl halide derivative, or a method of continuously or intermittently supplying the styrene derivative while changing the supply rate can be applied. The supply rate of the benzyl halide derivative represented by the general formula (2) depends on the supply rate of the styrene derivative represented by the general formula (3). 1
It is preferable to supply in about 50% of the time,
It is more preferable to supply in about 0% time, and 100%
It is particularly preferable to supply in about a time. That is, it is particularly preferable to supply the entire amount of the styrene derivative in the same amount of time as supplying the entire amount of the benzyl halide derivative.

In the production method of the present invention, there is no particular limitation on the operation method. As a general operation method, for example, an acid and a salicylic acid derivative represented by the general formula (1) and, if desired, an organic solvent are charged into a reaction vessel, and then the mixture is treated with a compound represented by the general formula (2). The method of supplying the styrene derivative represented by the general formula (3) while supplying the benzyl halide derivative is applied. In addition, a part of the styrene derivative is supplied to the mixture after supplying a part of the acid and the salicylic acid derivative and, if desired, an organic solvent to the reaction vessel, while supplying a part of the benzyl halide derivative to the mixture. Subsequently, a method of supplying the remaining amount of the styrene derivative to the mixture while supplying the remaining amount of the benzyl halide derivative, that is, a so-called split supply method can also be applied. Further, the benzyl halide derivative and the styrene derivative may be supplied separately or in advance as a mixture. Further, the benzyl halide derivative and the styrene derivative may be supplied neat, or may be dissolved in the above-mentioned organic solvent and supplied as an organic solvent solution. still,
As a method of supplying the benzyl halide derivative and the styrene derivative, a method of supplying continuously or intermittently in multiple stages by a known means and apparatus (for example, various dropping apparatuses and various metering pumps) can be applied. Of course, it goes without saying that other deformation methods that can be implemented in process engineering can also be applied. The supply rate of the benzyl halide derivative and the styrene derivative is not particularly limited, but is usually about 0.5 to about 15 hours, more preferably about 1 to about 10 hours.

[0021] The reaction temperature is preferably about -20 to about 150 ° C, more preferably about 0 to about 100 ° C. When sulfuric acid is used as the acid, the reaction temperature is about 0 to about 60.
C is preferred. The reaction can be carried out under atmospheric pressure, but can also be carried out under reduced pressure or under increased pressure.
The reaction time is generally about 1 to about 20 hours, more preferably about 2 to about 15 hours. Performing the reaction over a long period of time does not adversely affect the properties of the product. However, spending a long period of time only results in a decrease in work efficiency, production efficiency, and the like. The progress of the reaction was measured by a known analytical means such as a proton NMR spectrum and high performance liquid chromatography (HPLC) using the general formula (1).
The rate of change of the salicylic acid derivative represented by the following formula, the benzyl halide derivative represented by the general formula (2) and / or the styrene derivative represented by the general formula (3) can be monitored. Can be determined by the analysis means.

As described above, a resin obtained by simultaneously supplying and reacting a benzyl halide derivative and a styrene derivative with a salicylic acid derivative in the presence of an acid [hereinafter, in the general formula (1), R ₁ is a hydrogen atom A resin produced using a certain salicylic acid derivative is resin A, a resin produced using a salicylic acid ester derivative in which R ₁ is an alkyl group, an aralkyl group or an aryl group in the general formula (1), or a salicylic acid derivative and a salicylic acid ester derivative Abbreviated as resin B) can be taken out of the reaction system by a known method, or without being taken out of the reaction system, the reaction with the polyvalent metal compound or the hydrolysis Later, it can be used for a reaction with a polyvalent metal compound. The resin A and the resin B are made of a salicylic acid derivative represented by the general formula (1), a benzyl halide derivative represented by the general formula (2), a styrene derivative represented by the general formula (3), and the benzyl halide derivative. The reactive oligomer derived and / or the reactive oligomer derived from the styrene derivative is a resin of a complex composition consisting of various compounds reacted in a wide variety.

When the resin B is produced, hydrolysis is carried out prior to the reaction with the polyvalent metal compound. The hydrolysis of the resin B can be carried out by a known method, for example, using an acid or a base. The hydrolysis by acid is
Although the kind of the acid is not particularly limited, for example, a mineral acid such as hydrochloric acid or sulfuric acid is used, and the reaction is usually carried out in the presence of water. The hydrolysis with a base is performed, for example, using an alkali metal base such as lithium hydroxide, sodium hydroxide, or potassium hydroxide, or an organic base such as methylamine, ethylamine, or ammonia as a base, usually in the presence of water. I do. The ratio of the acid or the base to the water can be selected at an arbitrary ratio, but is usually 1: 100 to 100:
1, preferably in the range of 1:50 to 50: 1. The amount of the acid or base used for the hydrolysis is not particularly limited, and may be an amount sufficient to hydrolyze the ester group in the resin B into a carboxyl group. Usually, when hydrolysis is carried out using an acid with respect to 1 mol of the salicylic acid ester derivative used in producing the resin B, the amount of the acid used is usually about 0.05 to about 30 times the molar amount. ,
When the hydrolysis is carried out using a base, the amount of the base used is usually preferably about 1 to about 30 times mol.

The hydrolysis is usually carried out in the presence of water, but an organic solvent may be used in combination. Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, sulfolane, 1,3-dimethyl-2-
Aprotic polar solvents such as imidazolidinone, N-methyl-2-pyrrolidone, methanol, isopropanol,
Alcohol solvents such as ethylene glycol, 2-methoxyethanol and 2-ethoxyethanol can be exemplified. Further, n-hexane, n-octane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, 1,2
Water-immiscible organic solvents such as dichloroethane and 1,1,2-trichloroethane can also be used. It is sufficient that the used volume of the organic solvent is 0.5 to 10 (volume / weight) times the weight of the resin B. The hydrolysis may be carried out, for example, in the presence of a phase transfer catalyst such as a quaternary ammonium salt, a quaternary phosphonium salt, crown ether, cryptate, polyethylene glycols and the like.

The hydrolysis is usually carried out at about 20 to about 200 ° C.
Preferably, it is performed at about 50 to about 150 ° C. Also,
The hydrolysis can be carried out under atmospheric pressure, but can also be carried out under reduced pressure or under increased pressure. The hydrolysis is usually performed for about 0.5 to about 20 hours. The reaction taking a long time does not adversely affect the properties of the product, but spending a long time itself only lowers the working efficiency, the production efficiency and the like. The progress of the hydrolysis reaction can be monitored by known analytical means such as a proton NMR spectrum and high performance liquid chromatography (HPLC), and the reaction time can be determined by these analytical means. . After the hydrolysis, the salicylic acid resin (hereinafter, abbreviated as “resin C”) produced can be taken out of the reaction system by a known method, and can be continuously taken out from the reaction system without being taken out of the reaction system. Can also be used. The resin C is a resin obtained by hydrolyzing an ester group in the resin B, and like the resin B, is a resin having a complicated composition composed of various compounds.

The polyvalent metal salt of the salicylic acid resin of the present invention comprises:
Preferably, it is a poorly water-soluble or water-insoluble divalent, trivalent or tetravalent metal salt, and more preferably a divalent metal salt. Specific examples of divalent, trivalent or tetravalent metal salts include, for example, zinc, magnesium, calcium, barium, nickel, tin, copper, manganese, cobalt, titanium, aluminum and iron salts. However, the present invention is not limited to these. The metal salt may be a single kind or plural kinds. Particularly preferred are zinc salts. The polyvalent metal salt of the salicylic acid resin of the present invention can be produced by reacting the resin A or the resin C with a polyvalent metal compound. The production method is not particularly limited, and a known method can be applied. For example, resin A
A method in which the resin C and a polyvalent metal compound (for example, an oxide, hydroxide, carbonate, silicate, or organic carboxylate of a polyvalent metal) are melted to produce (melting method), or A water-soluble salt of resin A or resin C such as an alkali metal, amine salt or ammonium salt of resin A or resin C and a water-soluble polyvalent metal compound in the presence of water,
A method of producing by acting (double decomposition method) can be applied. This metathesis method is the preferred method.

When the polyvalent metal salt of the salicylic acid resin of the present invention is produced by a melting method, a general method is as follows: resin A or resin C and a polyvalent metal oxide, hydroxide, carbonate, silica, Acid salts, or polyvalent metal salts of organic carboxylic acids such as, for example, zinc acetate, zinc caproate, zinc stearate, zinc benzoate, at about 100 to about 180 ° C. for about 1 to about 5 hours, A method of melting can be given. At this time, heating and melting may be performed by adding a basic substance such as ammonium acetate, ammonium caproate, ammonium stearate, or ammonium benzoate. When the polyvalent metal salt of the salicylic acid resin of the present invention is produced by the metathesis method, a general method is to use an equivalent amount of an alkali metal compound (for example, hydroxide) with respect to the carboxyl group in the resin A or the resin C. Lithium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate) or an amine compound (for example, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, ethanolamine, isopropanolonamine,
Triethanolamine, 2-dimethylaminoethanol, morpholine, and ammonia) are allowed to act in an aqueous solution to prepare an alkali metal salt, an amine salt, or an ammonium salt of the resin A or the resin C. Then, a water-soluble polyvalent metal compound is removed. The compound is produced as a polyvalent metal salt of a salicylic acid resin which is hardly soluble in water or insoluble in water. At this time, the polyvalent metal compound may be added to the alkali metal salt of the resin A or the resin C, or the alkali metal salt of the resin A or the resin C may be added to the polyvalent metal compound. Further, heating may be performed, or an organic solvent may coexist.

As the water-soluble polyvalent metal compound, 2
Trivalent or trivalent metal compounds are preferred. As the polyvalent metal compound, for example, sulfates such as zinc sulfate, magnesium sulfate, calcium sulfate, and aluminum sulfate; zinc chloride, magnesium chloride, calcium chloride, barium chloride, nickel chloride, cobalt chloride, chlorides such as aluminum chloride; Acetates such as zinc acetate and manganese acetate are exemplified. These polyvalent metal compounds may be used alone or in combination. Further, these polyvalent metal compounds may be used in a solid state or as an aqueous solution. The amount of the polyvalent metal compound used is, for example, 0.8 to 1. 1 equivalent of the alkali metal salt of the resin A or the resin C.
5 equivalents, preferably 1.0 to 1.2 equivalents. still,
In this case, the equivalent weight means 0.5 mole of divalent metal compound (eg, zinc sulfate) per mole of alkali metal salt of resin A or resin C. Is one equivalent.

The polyvalent metal salt of the salicylic acid resin of the present invention produced by the above-mentioned method comprises a resin A or a resin C,
It is a resin obtained by reacting with a polyvalent metal compound, and its composition is more complicated than resin A or resin C.
The molecular weight of the polyvalent metal salt of the salicylic acid resin of the present invention is represented by the salicylic acid derivative represented by the general formula (1), the benzyl halide derivative represented by the general formula (2) or / and the general formula (3). It varies over a wide range depending on the amount of the styrene derivative used and further on the reaction conditions. When used as a developer for pressure-sensitive copying paper, the polyvalent metal salt of the salicylic acid resin of the present invention preferably has a weight average molecular weight of about 35.
0 to about 2000, more preferably about 400 to about 150
0. Usually, the softening point of the polyvalent metal salt of the salicylic acid resin of the present invention is from about 60 to about 150C.

The color developing sheet for pressure-sensitive copying paper using the polyvalent metal salt of salicylic acid resin of the present invention will be described below. When the polyvalent metal salt of the salicylic acid resin of the present invention is produced by a metathesis method, the polyvalent metal salt is generally produced within a short time,
Precipitates in aqueous media. The polyvalent metal salt can be easily filtered and isolated from the reaction system by a known means and device without using a special device. Dry after filtration,
A dispersion of a developer for pressure-sensitive copying paper can be prepared by performing dispersion treatment by a known means or method, or by performing dispersion treatment directly after filtration without performing a drying step. In the production of the color developing sheet of the present invention, the polyvalent metal salt of the salicylic acid resin of the present invention may be any other known color developing agent (for example, acid clay, as long as the desired effect of the present invention is not hindered).
Acid clay minerals such as activated clay, attapulgite, bentonite, etc., phenolic resins such as phenol-formaldehyde resin, phenol-salicylic acid-formaldehyde resin, phthalic acid, salicylic acid, 5-cyclohexylsalicylic acid, 5-tert-octylsalicylic acid, 5-nonylsalicylic acid , 3- (α-methylbenzyl) salicylic acid, 5
-(Α-methylbenzyl) salicylic acid, 5-phenylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (α, α-dimethylbenzyl) salicylic acid, 3,5-di-tert- Metal salts such as zinc salts of aromatic carboxylic acids such as butylsalicylic acid].

In preparing the developer dispersion, a known method can be applied as a method for dispersing the polyvalent metal salt of the salicylic acid resin of the present invention. For example, in the presence of binders, pigments, etc. in water, ball mills, attritors,
A method of pulverizing and dispersing to a particle size of usually 3 μm or less, preferably 2 μm or less by means such as a sand grinder can be applied. The binder is not particularly limited, for example, as a water-soluble binder, polyvinyl alcohol, casein, starch and derivatives thereof, methylcellulose, ethylcellulose,
Examples thereof include carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, and polyacrylamide. Further, for example, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene-acrylic copolymer, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyurethane, polyacrylic acid A synthetic rubber latex such as an ester or polybutyl methacrylate or a water-insoluble binder such as a synthetic rubber emulsion can be used if desired.

Examples of the pigment include zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, titanium oxide, talc, kaolin, diatomaceous earth, aluminum hydroxide, magnesium hydroxide, alumina, Silica can be mentioned. Further, in order to enhance the dispersibility of the dispersion, various known dispersants, for example, polymers such as polystyrene, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer An alkali metal salt, an alkaline earth metal salt, or an ammonium salt of a sulfonated product may be added. Furthermore, various additives (for example, an ultraviolet absorber, an antifoaming agent,
A surfactant, a pH adjuster, a viscosity adjuster, a plasticizer, and an organic polymer compound).

The dispersion thus prepared for preparing a color developing sheet can be prepared by a known method, for example, using an air knife coater, blade coater, roll coater, or the like.
Using a coating device such as a size press coater or a curtain coater, the developer is applied onto a support (for example, paper, a plastic sheet, synthetic paper, or a composite sheet obtained by combining these) to form a color developer layer, and the color developer sheet is formed. Can be made. Although the weight (coating amount) of the developer layer on the support is not particularly limited, it is usually 0.5% by dry weight.
g / m ² or more, preferably a 0.5 to 10 g / m ^2. The ratio of the polyvalent metal salt of the salicylic acid resin of the present invention in the developer layer is usually 5% by weight or more, preferably 5% by weight or more.
７０70% by weight. In the case where the support is paper, a method in which a polyvalent metal salt of the resin is added during papermaking can also be applied. Further, a method of preparing a coating solution in which the polyvalent metal salt of the salicylic acid resin is dissolved or suspended in an organic solvent, and applying the coating solution to a support can also be applied.

The form of the color developing sheet of the present invention is not particularly limited. For example, a microcapsule containing an electron-donating color-forming compound and a capsule oil may be combined with an upper sheet in which microcapsules are applied to the back surface of the sheet. The lower sheet to be used, inserted between the upper sheet and the lower sheet, and provided with a color developer layer on the surface of the sheet and a microcapsule layer on the back of the sheet to copy a plurality of sheets. In addition, there is an intermediate sheet, a single copy sheet in which both a microcapsule and a developer are applied to the same surface of the sheet. In a single copy sheet as one of the forms, the microcapsules are obtained by dissolving an electron-donating color-forming compound in capsule oil and subjecting the solution to, for example, a coacervation method, an interfacial polymerization method, an internal polymerization method, It can be produced by various known microencapsulation methods such as a separation method and an external polymerization method.
Examples of the electron-donating color-forming compound include a triarylmethane compound, a diarylmethane compound, a rhodamine-lactam compound, a fluoran compound, an indolylphthalide compound, a pyridine compound, a spiro compound, and a fluorene compound. And various known compounds such as phenothiazine compounds.

As the capsule oil, for example, cottonseed oil, castor oil, kerosene, paraffin, chlorinated paraffin,
Naphthenic oil, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, diarylalkane,
Various oils such as hydrogenated terphenyl and dialkyl phthalate can be mentioned. These capsule oils may be used alone or in combination.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
The weight average molecular weight was measured by GPC (gel permeation chromatography). The softening point is JI
It was measured by a ring and ball softening point measuring device according to SK-2548. Example 1 Salicylic acid 27.6 g (0.2 mol), 98% sulfuric acid 7 g
And 50 ml of 1,2-dichloroethane were charged into a glass reactor, and the solution was stirred at 30 ° C.
And 42.2 g of α-methylbenzyl chloride (0.3
Mol) and 31.2 g (0.3 mol) of styrene were supplied in advance using a dropping funnel over 6 hours. After the supply, the mixture was further stirred at the same temperature for 2 hours. 200 ml of water and 120 ml of 1,2-dichloroethane were added, and the mixture was neutralized with a 5 wt% aqueous sodium hydroxide solution. After separating the organic layer, 1,2-dichloroethane was distilled off. An aqueous solution of sodium hydroxide (8 g) (400 g) was added to the residue.
Then, an aqueous solution (200 ml) of zinc sulfate heptahydrate (29 g) was added dropwise to the solution at 40 ° C. over 1 hour. After further stirring at room temperature for 2 hours, filtration, washing with water,
After drying, 95 g of a colorless zinc salt of salicylic acid resin was obtained.
The weight average molecular weight was 580 and the softening point was 105 ° C.

Example 2 In Example 1, α-methylbenzyl chloride 4
2.2 g (0.3 mol) and 31.2 g (0.3
Mol), 14.1 g (0.1 mol) of α-methylbenzyl chloride, 52.0 g of styrene
(0.5 mol) and 23.6 g of 4-methylstyrene (0.
Colorless salicylic acid resin zinc salt was obtained according to the method described in Example 1 except that 2 mol) was used. The weight average molecular weight was 690, and the softening point was 105 ° C.

Example 3 In Example 1, α-methylbenzyl chloride 4
2.2 g (0.3 mol) and 31.2 g (0.3
Mol) instead of benzyl chloride.
7 g (0.1 mol), α-methylbenzyl chloride 2
8.2 g (0.2 mol) and styrene 72.8 g (0.7
Mol)), but according to the method described in Example 1,
A colorless zinc salt of salicylic acid resin was obtained. The weight average molecular weight was 800 and the softening point was 110 ° C.

Example 4 Salicylic acid 27.6 g (0.2 mol), 98% sulfuric acid 5 g
And 50 ml of 1,2-dichloroethane were charged into a glass reactor, and the solution was stirred at 30 ° C.
And 35.2 g of α-methylbenzyl chloride (0.2
5 mol) and 26.0 g (0.25 mol) of styrene were fed simultaneously using separate dropping funnels and at the same rate over 4 hours each. After the supply, the mixture was further stirred at the same temperature for 4 hours. After adding 400 ml of water and neutralizing with a 5 wt% aqueous solution of sodium hydroxide, 1,2-dichloroethane was distilled off. Sodium hydroxide (8
g) After the addition of an aqueous solution (100 ml), the solution was cooled at room temperature to an aqueous solution of zinc sulfate heptahydrate (29 g) (200 m
1) was added dropwise over 1 hour. After stirring at room temperature for 2 hours, the mixture was filtered, washed with water and dried to obtain 84 g of a zinc salt of a colorless salicylic acid resin. The weight average molecular weight was 450 and the softening point was 110 ° C.

Example 5 A glass reactor was charged with 13.8 g (0.1 mol) of salicylic acid, 15.2 g (0.1 mol) of methyl salicylate, 7 g of 98% sulfuric acid and 50 ml of 1,2-dichloroethane. While stirring the solution, add α
-Methylbenzyl chloride 42.2 g (0.3 mol)
And 31.2 g (0.3 mol) of styrene in advance were supplied over 4 hours using a dropping funnel.
After the supply, the mixture was further stirred at the same temperature for 2 hours. Water 400
Then, the mixture was neutralized with a 5 wt% aqueous sodium hydroxide solution, and 1,2-dichloroethane was distilled off. To the residue,
After adding aqueous sodium hydroxide (8 g) (100 ml), the mixture was stirred at 95 ° C. for 2 hours. The solution was added dropwise at 30 ° C. to an aqueous solution (200 ml) of zinc sulfate heptahydrate (29 g) over 1 hour. After stirring at room temperature for 2 hours, the mixture was filtered, washed with water, and dried to obtain a colorless zinc salt 95 of salicylic acid resin.
g was obtained. Weight average molecular weight: 560, softening point: 108 ° C
Met.

Example 6 In Example 5, α-methylbenzyl chloride 4
2.2 g (0.3 mol) and 31.2 g (0.3
Mol) instead of benzyl chloride.
7 g (0.1 mol), α-methylbenzyl chloride 2
8.1 g (0.2 mol) and α-methylstyrene 62.4
A colorless zinc salt of salicylic acid resin was obtained according to the method described in Example 5, except that g (0.6 mol) was used. The weight average molecular weight was 730 and the softening point was 105 ° C.

Example 7 A glass reaction vessel was charged with 30.4 g (0.2 mol) of methyl salicylate, 14 g of 98% sulfuric acid and 50 ml of 1,2-dichloroethane. While stirring the solution,
At 4 ° C., 42.2 g of α-methylbenzyl chloride (0.
3 mol), 41.6 g (0.4 mol) of styrene and 11.8 g (0.1 mol) of α-methylstyrene were previously mixed and supplied over 4 hours using a dropping funnel.
After the supply, the mixture was further stirred at the same temperature for 2 hours. Thereafter, 400 ml of water was added, and the mixture was neutralized with a 5 wt% aqueous solution of sodium hydroxide, and 1,2-dichloroethane was distilled off. An aqueous solution of sodium hydroxide (8 g) (100 ml) was added to the residue, and the mixture was stirred at 95 ° C. for 2 hours. The solution was added dropwise at room temperature to an aqueous solution (200 ml) of zinc sulfate heptahydrate (29 g) over 1 hour. After further stirring at room temperature for 2 hours, the mixture was filtered, washed with water, and dried to obtain a colorless zinc salt of salicylic acid resin 11
6 g were obtained. Weight average molecular weight is 630, softening point is 108
° C.

Example 8 22.1 g (0.16 mol) of salicylic acid, salicylic acid
7.8 g (0.04 mol) of n-butyl, 7 g of 98% sulfuric acid
And 50 ml of 1,2-dichloroethane were charged into a glass reaction vessel. While stirring the solution, at 30 ° C., α
-Methylbenzyl chloride 42.2 g (0.3 mol)
And 41.6 g (0.4 mol) of styrene were fed simultaneously and at the same rate over 4 hours using separate dropping funnels. After the supply, the mixture was stirred at the same temperature for 2 hours. Thereafter, 400 ml of water was added, and the mixture was neutralized with a 5 wt% aqueous sodium hydroxide solution, and 1,2-dichloroethane was distilled off. An aqueous solution of sodium hydroxide (8 g) (100 m
l) was added and the mixture was stirred at 90 ° C for 2 hours. The solution was added at room temperature to an aqueous solution of zinc sulfate heptahydrate (29 g) (200 m
1) was added dropwise over 1 hour. After stirring at room temperature for 2 hours, the mixture was filtered, washed with water and dried to obtain 105 g of a colorless zinc salt of salicylic acid resin. The weight average molecular weight was 600 and the softening point was 103 ° C.

Comparative Example 1 60 ml of chlorobenzene and 27.6 g of salicylic acid (0.
2 mol), and 62.4 g (0.6 mol) of styrene at about 50-60 ° C. Then 1
Stirring was performed at 30 ° C. for 3 hours. To this mixture at 50 ° C. was added 21.9 g of zinc acetate dihydrate. Thereafter, all solvents were removed by vacuum distillation to obtain 96.2 g of a zinc salt of a salicylic acid resin colored yellow. The softening point was 45 ° C. The zinc salt of this resin was colored and had a low softening point, and was of low practical value as a developer for pressure-sensitive copying paper.

Comparative Example 2 15.2 g (0.1 mol) of methyl salicylate, 3.7 g of 98% sulfuric acid and 50 ml of 1,2-dichloroethane were charged into a glass reactor, and the solution was stirred. At 0 DEG to 2 DEG C., 38.4 g of 4-methylstyrene (0.1 g).
(3 mol) was supplied over 6 hours using a dropping funnel.
After the supply, the mixture was further stirred at the same temperature for 3 hours. After neutralization with a 5 wt% aqueous sodium hydroxide solution, the mixture was heated and
2-Dichloroethane was distilled off. Further, an aqueous solution (100 ml) of sodium hydroxide (4 g) was added, and the mixture was added at 95 ° C for 6 hours.
Heating and stirring were performed for hours. To the solution, add water (300 ml)
, And at 25 ° C, zinc sulfate heptahydrate (14.5).
g) (200 ml) was added dropwise over 1 hour.
After further stirring at room temperature for 2 hours, filtration, washing with water, drying,
53 g of a zinc salt of salicylic acid resin was obtained. Softening point is 112
° C.

Comparative Example 3 Salicylic acid 27.6 g (0.2 mol) and zinc chloride 0.7
5 g (0.005 mol) and 42.2 g (0.3 mol) of α-methylbenzyl chloride were charged into a glass reaction vessel, and stirred at 70 to 100 ° C. for 3 hours. afterwards,
The reaction temperature was raised to 120 ° C, and the mixture was further stirred at the same temperature for 5 hours. Then, 1,2-dichloroethane 110m
and the mixture was cooled to 0-5 ° C. To the solution was added 7.2 g of 95% sulfuric acid, and with vigorous stirring,
At the same temperature, 31.6 g (0.3 mol) of styrene was added dropwise over 6 hours. The mixture was further stirred at the same temperature for 2 hours. Water (100 ml) was added to the reaction mixture, which was further adjusted to pH 6 with 28% aqueous ammonia. Thereafter, the lower organic layer was separated and heated, and 1,2-dichloroethane was distilled off. When the internal temperature reached 130 ° C., the mixture was degassed under reduced pressure for 30 minutes.
30.7 g (0.1 mol) of zinc benzoate was added to the residue,
The mixture was stirred at 145 ° C. for 30 minutes to obtain 101 g of a zinc salt of salicylic acid resin. The softening point was 78 ° C.

Examples 9 to 16 and Comparative Examples 4 to 6 Using the zinc salts of salicylic acid resins produced in Examples 1 to 8 and Comparative Examples 1 to 3, the following mixtures were prepared. A zinc salt of salicylic acid resin 50 g A sodium salt of sulfonated polystyrene 2 g Water 120 g The mixture having the above composition was subjected to a dispersion treatment at 25 ° C. with a sand grinder for 4 hours. The state of foaming during dispersion was visually observed. ○ indicates that foaming is small, and x indicates that foaming is extremely severe. Further, in order to examine the dispersion efficiency, the average particle size of the zinc salt of the salicylic acid resin after performing the dispersion treatment for 4 hours was measured. The average particle size was measured using a Coulter counter. Further, the dispersion state after the dispersion was allowed to stand at 50 ° C. for one week was visually observed. ○ indicates that a dispersed state that can be applied to the sheet is maintained, and X indicates that the particles are aggregated to such an extent that the sheet cannot be applied. The results are shown in Table 1 (Table 1). The zinc salts of salicylic acid resin used are as follows. In Example 9, zinc salt of salicylic acid resin manufactured in Example 1 In Example 10, zinc salt of salicylic acid resin manufactured in Example 2 In Example 11, zinc salt of salicylic acid resin manufactured in Example 3 In Example 12, the zinc salt of the salicylic acid resin produced in Example 4 In Example 13, the zinc salt of the salicylic acid resin produced in Example 5 In Example 14, the zinc salt of the salicylic acid resin produced in Example 6 In Example 16, the zinc salt of the salicylic acid resin manufactured in Example 8 In Comparative Example 4, the zinc salt of the salicylic acid resin manufactured in Comparative Example 1 was compared in Comparative Example 5. Zinc salt of salicylic acid resin produced in Example 2 In Comparative Example 6, zinc salt of salicylic acid resin produced in Comparative Example 3

[0048]

[Table 1] From the results shown in Table 1, it can be seen that the zinc salt of the salicylic acid resin of the present invention has little foaming at the time of dispersion and is easily micronized. In addition, it became clear that the dispersion liquid after dispersion was less likely to aggregate and had excellent storage stability.

Examples 17 to 24 and Comparative Example 7 The zinc salt of each salicylic acid resin and the zinc salt of 3,5-di (α-methylbenzyl) salicylic acid obtained in Examples 1 to 8 were used as developers. The developed color-sensitive sheet for pressure-sensitive copying paper was produced by the following method and evaluated by the following evaluation method. The performance evaluation results are shown in Table 2 (Table 2). Method for preparing a color developing sheet for pressure-sensitive copying paper A mixture having the following composition was dispersed with a sand grinder to prepare a dispersion (A). Developer 50 g Sodium salt of sulfonated polystyrene (Chemistat 6120, manufactured by Sanyo Chemical Industry Co., Ltd.) 2 g Water 120 g As the developer, in Example 17, the zinc salt of the salicylic acid resin produced in Example 1 was used. In Example 18, the zinc salt of the salicylic acid resin produced in Example 2 was used. In Example 19, the zinc salt of the salicylic acid resin produced in Example 3 was used. In Example 20, the zinc salt of the salicylic acid resin produced in Example 4 was used. In Example 21, the zinc salt of the salicylic acid resin manufactured in Example 5 was used. In Example 22, the zinc salt of the salicylic acid resin manufactured in Example 6 was used. In Example 23, the zinc salt of the salicylic acid resin was used. In Example 24, the zinc salt of the salicylic acid resin manufactured in Example 8 was used. In Comparative Example 7, the zinc salt of the salicylic acid resin was 3,5-di (α-methylbenzyl) salidium. The zinc salt of Le acid were used, respectively. Next, a dispersion having the following composition was prepared using the dispersion (A).

Dispersion (A) 8.0 g Heavy calcium carbonate (Super # 2000 manufactured by Maruo Calcium Co., Ltd.) 30.0 g Starch (Oji Ace B manufactured by Oji Cornstarch Co., Ltd.) 0.8 g Synthetic rubber latex (Mitsui Chemicals) Ltd. Porirakku 755) 0.8 g water 77.4g coating as the coating amount after drying is 5.0 g / m ² on a high-quality paper the dispersion (50 g / m ^2), dried, revelation A sheet (lower paper) was prepared.

Evaluation of a color developing sheet for pressure-sensitive copying paper (1) Measurement of color density The color density was measured in a constant temperature and humidity room at 20 ° C. and 65% RH. Crystal violet lactone (CV
L) as a main electron-donating color-forming compound and commercially available on which microcapsules are coated [Mitsubishi Paper Mills, Ltd.
N-40] and a color-developing sheet (lower paper) for pressure-sensitive copying paper obtained by the above method, with both coated surfaces facing each other, and striking with an electronic typewriter. The color was developed. After standing for 24 hours in the same environment after embossing, the color density was measured. The density of the color image is Σ−80
It was measured using a color difference meter and indicated as a Y value. The smaller the value, the deeper the color. (2) Water resistance test of color-developed image
The density of the color image after immersion in water for 24 hours was Δ-8
It measured using the 0 color difference meter, and indicated by Y value. The smaller the value and the smaller the difference from the value before the test, the better the water resistance of the color image. The results of visual observation of the color image after the water resistance test are also shown. O indicates that the color image before the test can be sufficiently identified, and X indicates that the color image has disappeared and the color image before the test cannot be identified.

[0052]

[Table 2] From the results shown in Table 2, it was found that the pressure-sensitive copying paper using the zinc salt of the salicylic acid resin of the present invention as a color developing sheet has excellent storage stability (water resistance) of a color image.

[0053]

According to the present invention, it has become possible to provide a method for producing a polyvalent metal salt of salicylic acid resin having excellent performance as a color developer for pressure-sensitive copying paper.

──────────────────────────────────────────────────の Continued on the front page (72) Inventor Masaru Wada Fukuoka Prefecture, Omuta-shi, 30 Asamuta-cho, Mitsui-Higashi Pressure Chemical Co., Ltd. Examiner Satoshi Morikawa, Inc. (56) References JP-A-6-135128 (JP, A) JP-A-1-133780 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/155 C08G 61/00-61/12

Claims (4)

(57) [Claims] 1. A salicylic acid derivative represented by the general formula (1) in the presence of an acid, (Wherein R ₁ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and X ₁ and X ₂ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom). 2) A benzyl halide derivative represented by (Chemical Formula 2) and a styrene derivative represented by General Formula (3) (Chemical Formula 3) are (Wherein, R ₂ and R ₃ represent a hydrogen atom or an alkyl group, X ₃ represents a halogen atom, and X ₄ and X ₅ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom. Represents) (Wherein, R ₄ , R ₅ and R ₆ represent a hydrogen atom or an alkyl group, and X ₆ and X ₇ represent a hydrogen atom, an alkyl group,
(Representing an alkoxy group, an aralkyl group, an aryl group or a halogen atom). A method for producing a polyvalent metal salt of a salicylic acid resin which is reacted simultaneously and then reacted with a polyvalent metal compound. 2. The production of a polyvalent metal salt of a salicylic acid resin according to claim 1, wherein a styrene derivative represented by the general formula (3) is supplied along with the supply of the benzyl halide derivative represented by the general formula (2). Method. 3. A polyvalent metal salt of a salicylic acid resin obtained by the method according to claim 1. 4. A color developing sheet using the polyvalent metal salt of salicylic acid resin according to claim 3.