KR100318857B1 - Polyvalent metal salts of salicylic acid resin and processes for the preparation thereof - Google Patents

Abstract

The present invention comprises a step of reacting salicylic acid or a derivative thereof and styrene or a derivative thereof at 50 to 200 ° C. under an organic carboxylic acid zincide or a polyvalent metal compound or a mixture thereof, and then reacting the obtained reaction product with the polyvalent metal compound. Manufacturing method of polyvalent metal salt of salicylic acid resin; An aqueous dispersion in which the polyvalent metal salt of the resin is dispersed in water; And a developing sheet using a polyvalent metal salt of salicylic acid resin.

Description

Polyvalent metal salts of salicylic acid resin and processes for the preparation etc

The present invention relates to a method for preparing a polyvalent metal salt of salicylic acid resin useful as a colorant for recording materials such as depressurized copying paper, and to a polyvalent metal salt of salicylic acid resin prepared by the method, and to an aqueous dispersion prepared from the polyvalent metal salt of salicylic acid resin. Contains a color sheet.

Metal salts of salicylic acid derivatives are known to be useful as colorants for pressure sensitive copying, and various preparation methods and methods of use have been proposed. E.g,

(1) 3,5-disubstituted salicylic acid derivatives prepared from the 2,4-disubstituted phenol derivatives and carbon dioxide using the so-called Kolbe-Schmitt reaction have been known (Japanese Patent Publication No. 76-25174 And US Patent No. 3983292). However, this method requires two steps to prepare a 3,5-disubstituted salicylic acid derivative from phenol, and requires a high temperature and high pressure device for the reaction of carbon dioxide. In addition, in the case of metal salts of 3,5-disubstituted salicylic acid derivatives, for example, zinc salts of 3,5-di (?-Methylbenzyl) salicylic acid, there is a problem that the color image is lost by water.

(2) It is known to react 1 mole of salicylic acid with at least 2 moles of phenylethanol derivatives to produce 4- [α-methylbenzyl (α-methylbenzyl)] salicylic acid derivatives (Japanese Patent Publication No. 93-61110 and United States). Patent 4754063).

(3) 1 mole of salicylic acid is reacted with at least 2 moles of styrene derivatives in the presence of aromatic sulfonic acid and the reaction product is reacted with a polyvalent metal salt of an inorganic acid or a lower aliphatic carboxylic acid to give 3,5-di (α-methylbenzyl) There has been known a method for preparing polyvalent metal salts of salicylic acid derivatives and polyvalent metal salts of 4- [α-methylbenzyl (α-methylbenzyl)] salicylic acid derivatives (Japanese Patent Publication Nos. 93-75736 and US 474745959). . However, when a polyvalent metal salt of 4- [α-methylbenzyl (α-methylbenzyl)] salicylic acid (for example, zinc salt) prepared by these methods is used as a developer of a pressure-sensitive copy paper, the color image is obtained when contacted with water. There is a problem that is lost.

(4) It has been known to prepare 3,5-di (α-methylbenzyl) salicylic acid derivatives by reacting salicylic acid with a styrene compound in the presence of aliphatic carboxylic acid using an eutectic acid or an inorganic acid as a catalyst (Japanese Patent) Publication 90-91043). However, in the case of polyvalent metal salts of 3,5-di (α-methylbenzyl) salicylic acid (eg, zinc salts) produced by these methods, there is a problem that the color image disappears as above when contacted with water.

(5) A method of producing a metal salt of a salicylic acid polymer by reacting a salicylic acid derivative with a styrene derivative at 40-170 ° C. in the presence of an acid catalyst and reacting the obtained reaction product with a fatty acid metal salt (Japanese Patent Publication No. 88-112537 and the United States) Patent 4929710). However, the metal salt of the salicylic acid resin formed by this method has a problem that it is sometimes colored, and the dispersion obtained because it is difficult to be granulated during dispersion is easy to aggregate.

(6) A method for producing polyvalent metal salts of salicylic acid resins is disclosed, which reacts salicylic acid esters with styrene, and then hydrolyzes and reacts with polyvalent metal compounds (Japanese Patent Application Laid-Open No. 89-133780 and U.S. Patent No. 4952648). . However, there is a problem that the polyvalent metal salt (eg, zinc salt) of the salicylic acid resin obtained by this method does not become fine particles at the time of dispersion, so that the obtained dispersion is easy to aggregate.

(7) A method for producing a polyvalent metal salt of salicylic acid resin has been known, which comprises a step of reacting salicylic acid or a derivative thereof and styrene or a derivative thereof at -20 to 40 ° C. in the presence of sulfuric acid followed by reaction with a polyvalent metal compound (Japanese Patent Publication 95-228042 and US Pat. No. 55,25686.). Although the physical properties of the colorant obtained by this method have been greatly improved, there are problems that the reaction process is complicated and productivity is lowered due to the large discharge of environmental pollutants and low yield. In addition, the average particle diameter in the preparation of the aqueous dispersion stays about 1.5㎛.

As described above, the performance of the product obtained by the reaction of the salicylic acid derivative and the styrene derivative and the polyvalent metal salt of the product may be different in physical properties depending on the given reaction conditions (for example, catalyst, solvent, reaction temperature, etc.). . Therefore, the physical properties of the salicylic acid resin and its polyvalent metal salt cannot be determined by the theoretical method, and it is very difficult to infer these according to experiments. At present, the performance and physical properties are expected to be set by the experimental fixation.

In recent years, a colorant which is easy to be granulated, has excellent storage stability of the dispersion liquid, and has excellent storage stability (e.g., water resistance) of a color image when forming a reduced pressure copying colored sheet, and has excellent wear resistance.

Therefore, the present inventors have made a number of studies to solve the problems of the prior art as described above, as well as the production of the polyvalent metal salt of salicylic acid resin in a high yield in the presence of a specific catalyst and a specific temperature, not the acid catalyst, the product The present invention was completed by discovering the excellent physical properties.

Accordingly, an object of the present invention is to provide a method for producing a polyvalent metal salt of salicylic acid resin.

It is also an object of the present invention to provide a polyvalent metal salt of salicylic acid resin prepared by the above production method.

It is also an object of the present invention to provide an aqueous dispersion of the polyvalent metal salt of salicylic acid resin prepared by the above production method.

It is also an object of the present invention to provide a color sheet excellent in storage stability, water resistance and abrasion resistance of the color density of a color image prepared by the polyvalent metal salt of salicylic acid resin prepared by the above method.

The present invention is to react the salicylic acid or its derivatives of the formula (1) and styrene or its derivatives of the formula (2) at 50 to 200 ℃ in the presence of an organic carboxylic acid zincide or polyvalent metal compound or a mixture thereof, and then The present invention relates to a method for producing a polyvalent metal salt of salicylic acid resin comprising reacting with a polyvalent metal compound.

[ Formula 1 ]

[ Formula 2 ]

In the above formula, X 'and X ₂ are each a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, R ₁ , R ₂ and R ₃ are each a hydrogen atom or an alkyl group, X ₃ and X ₄ are each a hydrogen atom, an alkyl group, It is an alkoxy group, an aralkyl group, an aryl group, or a halogen atom.

The compound of the formula (1) used in the preparation method of the present invention is preferably X X and X ₂ are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a bromine atom. In particular, X 'and X ₂ are particularly preferably hydrogen atoms.

That is, specific examples of Formula 1 include salicylic acid, 3-methyl salicylic acid, 4-methyl salicylic acid, 5-methyl salicylic acid, 3-n-butyl salicylic acid, 6-methyl salicylic acid, 6-ethyl salicylic acid, 5-isopropyl salicylic acid, 4 -n-pentylsalicylic acid, 5-cyclohexylsalicylic acid, 5-n-octylsalicylic acid, 5-t-octylsalicylic acid, 4-nonylsalicylic acid, 5-nonylsalicylic acid, 4-n-dodecylsalicylic acid, 4-methoxysalicylic acid, 6-methoxysalicylic acid, 5-ethoxysalicylic acid, 4-n-hexyloxysalicylic acid, 5-fluorosalicylic acid, 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid and 5-bromosalicylic acid, It is not limited to this.

These salicylic acid derivatives can be used individually or in combination of 2 or more. Of these, alkyl-substituted salicylic acid derivatives such as salicylic acid or 3-methylsalicylic acid are preferred, and salicylic acid is particularly preferred.

Compounds of the formula (2) used in the production method of the present invention, X ₃ and X ₄ are each a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an aralkyl group of 1 to 10 carbon atoms, 6 to 10 carbon atoms Is preferably an aryl group, a fluorine atom, a chlorine atom or a bromine atom, of which X ₃ and X ₄ are most preferably hydrogen atoms. In addition, R ₁ , R ₂ and R ₃ are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.

That is, examples of the compound of Formula 2 include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 4-ethylstyrene, 3-isopropylstyrene, 4-isopropylstyrene, 4 -n-butylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-n-octylstyrene, 4-n-decylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3-meth Oxystyrene, 4-methoxystyrene, 4-ethoxystyrene, α-methylstyrene, α-ethylstyrene, α-n-butylstyrene, α-isobutylstyrene, α, β-dimethylstyrene, α, β-di Ethyl styrene, α-methyl-β-isopropylstyrene, α-n-propyl-β-methylstyrene, 4- (α, α-dimethylbenzyl) styrene, 4-phenylstyrene, 4-fluorostyrene, 2-chloro Styrene, 3-chlorostyrene, 4-chlorostyrene and 4-bromostyrene, but is not limited thereto.

These styrene derivatives may be used alone or in combination of two or more. Of these, alkyl-substituted styrene derivatives such as styrene or 4-methylstyrene and α-methylstyrene are preferred, and styrene is most preferred.

Referring to the manufacturing method of the present invention step by step.

Reaction A : reacting a compound of Formula 1 with a compound of Formula 2

The reaction amount of the compound of formula 2 is 1-9 moles, preferably 1.5-7 moles, most preferably 1.6-6 moles per 1 mole of the compound of formula 1.

Reaction A is carried out in the presence of an organic carboxylic acid zincide or a polyvalent metal compound or a mixture thereof, and there is no particular limitation on the type and the amount of the organic carboxylic acid zincide and the polyvalent metal compound, but the use of a large amount adversely affects the properties of the product. In addition, heavy use may impair work efficiency and production efficiency.

Therefore, the amount of the organic carboxylic acid zincide and the polyvalent metal compound is 0.05% by weight or more, preferably 0.5-50% by weight based on the weight of the compound of formula (1). The higher the purity of the organic carboxylic acid zincide and the polyvalent metal compound used, the better. The types of the organic carboxylic acid zincide include zinc benzoate, zinc caprylate, zinc stearate, zinc acetate, and the like. Examples of the metal compound include water-soluble or insoluble divalent, trivalent, and tetravalent metal compounds. Representative examples of the polyvalent metal compounds include sulfates such as zinc sulfate, magnesium sulfate, calcium sulfate and aluminum sulfate, zinc chloride, magnesium chloride, calcium chloride, barium chloride, nickel chloride, chlorides such as cobalt chloride and aluminum chloride, zinc acetate and manganese acetate. Nitrates such as acetates and zinc nitrate, oxides such as zinc oxide, and hydroxides such as zinc hydroxide.

There is no particular limitation on the operation of the reaction A, and the method of adding the compound of the formula (2) to the mixture obtained after charging the organic carboxylic acid zincide or polyvalent metal compound or a mixture thereof and the compound of the formula (1) to the reaction vessel Can be. In another method, a method of charging an organic carboxylic acid zincide or a polyvalent metal compound or a mixture thereof, a part of the compound of Formula 1, or a compound of Formula 2 into a reactor, and adding the balance of the compound of Formula 2 to the mixture, or It is also possible to use all the above mentioned substances at once.

As a supply method for adding the remainder of the compound of formula (2), it is possible to apply a method of supplying the compound of formula (2) in multiple stages continuously or intermittently by known means and devices (e.g., dropping device and metering pump). . Of course, other methods that can be implemented in process engineering can also be applied.

There is no particular limitation regarding the feed rate of the compound of formula 2, but it is generally about 0.5-13 hours, preferably about 1-9 hours.

In order to improve reaction efficiency, it is preferable to perform reaction A, stirring. There is no particular limitation on the stirring method and the stirring device, but in general, it is preferable to use a stirring device having a stirring force that allows the reaction to proceed efficiently. Examples of the reaction apparatus include a propeller stirrer, a turbine stirrer, a paddle stirrer, a homogenizer, a homomixer, a line mixer or a line type mixer with a stirrer such as a line homomixer, and the reaction A is a batch method or This can be done by a continuous method.

In carrying out the production method of the present invention, the reaction temperature of reaction A is 50 to 200 ° C, and 120 to 180 ° C is preferable.

The reaction time is longer than the feed time when the compound of Formula 2 is added dropwise, and the solution may be left after the supply of the compound of Formula 2 or stirred at 50 to 200 ° C. for an arbitrary time. Usually, reaction is performed for 0.5 to 20 hours, preferably about 1 to 12 hours.

Generally, reaction A is performed under atmospheric pressure, and it can carry out under reduced pressure or pressure_pressure as needed. For example, the reaction can be carried out in the atmosphere, but can be carried out in the presence of an inert gas (for example, a gas such as nitrogen, helium or argon).

The resin prepared by reaction A (hereinafter referred to as resin A) can be used by continuous reaction with a polyvalent metal compound (reaction B), unlike the conventional method.

Resin A is a resin having a complex compound composed of various compounds formed by various reactions of reactive oligomers.

Reaction B : reacting the reaction product obtained in reaction A with a polyvalent metal compound

The polyvalent metal salt of the salicylic acid resin of the present invention can be prepared by reacting Resin A with a polyvalent metal compound. There is no restriction | limiting in particular in the manufacturing method, A well-known method can be used. For example, a method of melting resin A and a polyvalent metal compound (for example, an oxide, hydroxide, carbonate, silicate, or organic carboxylate) of a polyvalent metal (melting method), an alkali metal salt, an amine salt of resin A, or A method (metathesis) in which a salt of a resin A such as an ammonium salt is reacted with a polyvalent metal compound in water can be used. Preferably, the polyvalent metal salt of the salicylic acid resin of the present invention is prepared by the melting method.

When the reaction B is carried out by the melting method, as a conventional method, a polyvalent metal salt of an organic carboxylic acid such as an oxide, hydroxide, carbonate or silicate of zinc A, zinc caproate, zinc stearate, zinc benzoate, etc. It carries out by the method of heat-melting for 1 to 10 hours at 50-200 degreeC. In this case, basic substances, such as ammonium acetate, ammonium caproate, ammonium stearate, or ammonium benzoate, can also be added.

Examples of the polyvalent metal compound include water-soluble or insoluble divalent, trivalent, and tetravalent metal compounds. Representative examples of the polyvalent metal compounds include sulfates such as zinc sulfate, magnesium sulfate, calcium sulfate and aluminum sulfate, zinc chloride, magnesium chloride, calcium chloride, barium chloride, nickel chloride, chlorides such as cobalt chloride and aluminum chloride, zinc acetate and manganese acetate. Nitrates such as acetate and zinc nitrate; oxides such as zinc oxide; and hydroxides such as zinc hydroxide. These polyvalent metal compounds may be used alone or in combination of two or more thereof.

The polyvalent metal compound can be used in the form of a solid or an aqueous solution.

The amount of the polyvalent metal compound used is 0.6 to 1.6 equivalents, preferably 0.8 to 1.2 equivalents, per equivalent of Resin A. Here, when the polyvalent metal compound is, for example, a divalent metal compound (eg, zinc oxide), one equivalent of the polyvalent metal compound means 0.5 mole of the divalent metal compound with respect to 1 mole of the resin A.

Another method for preparing a polyvalent metal salt of salicylic acid resin according to the present invention is a mixture of a polyvalent metal compound or a polyvalent metal compound and an organic carboxylic acid zincide in the salicylic acid of Formula 1 or a derivative thereof and styrene or a derivative thereof of Formula 2 The reaction at 50-200 degreeC in presence is also possible. However, the usage-amount of all the materials is as above-mentioned.

The polyvalent metal salt of the salicylic acid resin of the present invention prepared as described above is a resin obtained by reacting the resin A with the polyvalent metal compound, and the composition of the salt thus obtained is much more complicated than that of the resin A.

The molecular weight of the polyvalent metal salt of the salicylic acid resin of the present invention largely depends on the amount of use of the compound of the general formula (1) and / or the compound of the general formula (2), and the reaction conditions. 300-2,000 are preferable and 400-1,300 are more preferable.

Generally, the softening point of the polyvalent metal salt of the salicylic acid resin of this invention is 50-130 degreeC.

The present invention includes an aqueous dispersion in which the polyvalent metal salt of salicylic acid resin prepared as described above is dispersed in water.

In another aspect, the present invention includes a color sheet prepared from the polyvalent metal salt of the salicylic acid resin.

Hereinafter, the pressure-reduced color development sheet using the water dispersion of the polyvalent metal salt of the salicylic acid resin of this invention and the polyvalent metal salt of the salicylic acid resin as a developing agent is demonstrated.

As a method of obtaining an aqueous dispersion,

(1) A method of obtaining a predetermined aqueous dispersion by polishing and dispersing a polyvalent metal salt of salicylic acid resin in an aqueous medium using a disperser such as a bowl mill, sand grinder, dynomill, high speed impeller disperser, or annular mill,

(2) Dissolve the polyvalent metal salt of salicylic acid resin in an organic solvent, emulsify and disperse it in an aqueous medium using, for example, an ultrasonic dispersion machine, a homogenizer, a homomixer or a line homomixer, and then remove a predetermined aqueous dispersion by removing the organic solvent. How to get there,

(3) A method in which an emulsifying dispersant is directly added to a polyvalent metal salt of salicylic acid resin to obtain a predetermined aqueous dispersion through high speed stirring.

Emulsifying and dispersing agents which can be used in the aqueous medium at the time of dispersion are ionic or nonionic surfactants. Examples of the emulsifying dispersant include polyvinyl alcohol, alkyl modified polyvinyl alcohol, cyanoethyl modified polyvinyl alcohol, ether modified polyvinyl alcohol, polyacrylamide, polyacrylic acid, acrylamide-alkyl acrylate copolymer, and alkali metal salts of polystyrene sulfonic acid. , Synthetic or natural polymers such as maleic anhydride-isobutylene copolymer, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, starch and derivatives thereof, casein, gum arabic, agar and gelatin, alkylbenzene And alkali metal salts of sulfonic acid, alkali metal salts of alkylnaphthalene sulfonic acid, alkali metal salts of dialkyl sulfosuccinic acid, alkali metal salts of alkyl sulfonic acids, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyhydric alcohol fatty acid esters. These emulsion dispersants may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount of an emulsifying dispersant, Usually, it is 0.5-25 weight part with respect to 100 weight part of polyvalent metal salts of a salicylic acid resin.

There is no particular limitation on the amount of water used in the preparation of the aqueous dispersion, but the amount of the developer to be in the range of 10 to 60% by weight, more preferably 20 to 50% by weight in the aqueous dispersion.

When using the aqueous dispersion of the developer thus obtained as a coating liquid for forming the developer layer on a support, a binder, a pigment, etc. can be mix | blended normally.

There is no particular limitation on the type of binder, but examples of the binder that can be used include polyvinyl alcohol, casein, starch and derivatives thereof, gum arabic, methyl cellulose, carboxymethyl cellulose, polyacrylic acid, styrene-butadiene copolymer latex; Synthetic and natural polymer compounds such as latex such as acrylate ester latex.

Although there is no restriction | limiting in particular in the usage-amount of a binder, Usually, 5-40 weight% of the total solid amount of a developer coating liquid, Preferably it is 10-30 weight%.

Examples of pigments that can be used in the present invention include zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, titanium oxide, talc, kaolin, activated china clay, diatomaceous earth, zinc hydroxide, aluminum hydroxide, Inorganic pigments such as magnesium hydroxide, alumina and silica, and organic pigments such as styrene microol, nylon particles, urea formaldehyde fillers, polyethylene particles, cellulose fillers and starch particles.

There is no particular limitation on the amount of the pigment used, but in general, the color development is adjusted to be in the range of 30 to 90% by weight of the total solid content of the coating solution.

Moreover, various additives (for example, a ultraviolet absorber, an antifoamer, a pH adjuster, a viscosity adjuster, a plasticizer, an organic polymer compound, etc.) can be added to the coating liquid of the said developer layer as needed.

The coating solution prepared as described above may be a support (for example, a plastic sheet, a synthetic sheet or a composite sheet including a combination thereof) by a known method, for example, an air knife coater, a blade coater, a roll coater, a size press coater, a curtain. A developer sheet can be manufactured by apply | coating using an applicator or a shot duwell applicator etc., and forming a developer layer.

There is no particular limitation on the weight (coating amount) of the developer layer on the support, but the drying weight is 0.5 g / m 2 or more, preferably 0.5 to 10 g / m 2. Moreover, the content of the polyvalent metal salt of the salicylic acid resin according to the present invention in the developer layer is usually 5% by weight or more, and preferably 5 to 70% by weight.

Further, in the production of the developing sheet of the present invention, the polyvalent metal salt of the salicylic acid resin according to the present invention may be prepared using other developing agents (e.g., ashic china clay, activated china clay, atepal) as long as the predetermined effect of the present invention is not impaired. Phenolic resins such as acidic clayminerals such as zite and bendonite, phenol-formaldehyde resins, phenol-salicylic acid formaldehyde resins, phthalic acid, salicylic acid, 5-cyclohexylsalicylic acid, 5-t-octylsalicylic acid, 5-nonylsalicylic acid , 3,5-dinonylsalicylic acid, 3- (α-methylbenzyl) salicylic acid, 5- (α-dimethylbenzyl) salicylic acid, 5-phenylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5 Metal salts of zinc salts of aromatic carboxylic acids such as di (α, α-dimethylbenzyl) salicylic acid and 3,5-di-t-butylsalicylic acid].

The form of the developing sheet according to the present invention is not particularly limited, but for example,

(1) CF sheet which can be used in combination with CB sheet coated with back surface with microcapsules containing electron-donating chromogenic compound and capsule oil

(2) A CF / CB sheet provided with a developer layer on the surface of the sheet inserted between the CB sheet and the CF sheet to obtain a plurality of copies, and a macrocapsule layer on the back of the sheet.

(3) There is a single copy sheet in which both microcapsules and developer are applied to one side of the sheet.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1

204 g of salicylic acid, 20 g of zinc acetate (dihydrate), 20 g of zinc stearate and 100 g of styrene were charged into a glass reaction vessel. The mixture was heated to 140 ° C. while stirring. 287 g of styrene was added dropwise thereto over 3 hours, followed by further stirring at the same temperature for 2 hours. The temperature of the reactant was lowered to 115 ° C. and 60 g of zinc oxide was added, followed by further reaction at the same temperature for 2 hours to obtain 655 g of zinc salt of salicylic acid resin (yield: 94.8%, softening point: 98 ° C., average molecular weight: 670).

30 g of polyvinyl alcohol, 3 g of sodium dodecylbenzenesulfonate, and 840 g of purified water were continuously added to the obtained resin, followed by emulsification and dispersion. As a result, an aqueous dispersion having a solid content of 45% and an average particle diameter of 0.38 μm was obtained.

Example 2

68 g of salicylic acid, 0.8 g of zinc oxide, and 128 g of styrene were charged into a glass reaction vessel. The mixture was heated to 155 ° C. with stirring for 2-3 hours, 19.3 g of zinc oxide was added at 150 ° C., and reacted at 140-155 ° C. for 2 hours to obtain 204 g of zinc salt of salicylic acid resin. (Yield: 94.4%, Softening Point: 98 ° C, Average Molecular Weight 690)

The resulting resin was emulsified and dispersed using 10 g of polyvinyl alcohol and 262 g of purified water to obtain 476 g of an aqueous dispersion having a solid content of 45% and an average particle diameter of 0.41 µm.

Example 3

640 g of zinc salt of salicylic acid resin was obtained in the same manner as in Example 1, except that 387 g of styrene was replaced with 400 g and 20 g of zinc stearate was replaced with 30 g of zinc acetate. (Yield: 92.2%, Softening Point: 99 ° C, Average Molecular Weight: 715)

Example 4

In Example 1, the amount of styrene loaded was reduced from 100 g to 120 g, and the dropping amount was adjusted from 287 g to 267 g, and zinc salt of salicylic acid resin 656 g was obtained in the same manner except that 20 g of zinc acetate was replaced with 30 g of zinc stearate. (Yield: 96.3%, Softening Point: 110 ℃, Average Molecular Weight: 730)

Example 5

A zinc salt of salicylic acid resin 632 g was obtained in the same manner as in Example 1, except that zinc caprylate was replaced with 15 g of zinc acetate and zinc stearate. (Yield 94.9%, Softening Point: 96 ℃, Average Molecular Weight: 680)

Example 6

A 657 g of zinc salt of salicylic acid resin was obtained in the same manner except that 204 g of salicylic acid was replaced with 184 g of salicylic acid and 22.5 g of 4-methylsalicylic acid in Example 1. (Yield: 94.7%, Softening Point: 112 ° C, Average Molecular Weight: 705)

Example 7

A zinc salt of salicylic acid resin 658 g was obtained in the same manner except that 287 g of styrene dropped in Example 1 was replaced with 256 g of styrene and 35 g of 4-methylstyrene. (Yield: 94.7%, Softening Point: 113 ° C, Average Molecular Weight: 710)

Example 8

204 g of salicylic acid, 30 g of zinc acetate, and 387 g of styrene were added to the glass reaction vessel. After stirring at 150 ° C. for 3 hours, 60 g of zinc oxide was added at 135 ° C. and reacted for 2 hours to obtain 635 g of zinc salt of salicylic acid resin. (Yield 93.2%, Softening Point 99 ℃, Average Molecular Weight 685)

Example 9

129 g of styrene, 36 g of zinc oxide, and 80 g of salicylic acid were added to a glass reactor, and the temperature was raised to 157 ° C. and stirred for 5 hours to give 245 g of zinc salt of salicylic acid resin (yield: 85%, softening point: 114 ° C., average molecular weight). 803)

Example 10 Preparation of Pressure Sensitive Copy Color Sheet

Using the aqueous dispersion obtained in Example 1 as the developer, a developer's developed pressure-sensitive developer developed a color sheet according to the following method.

※ The mixture of the following compositions was disperse | distributed and the dispersion liquid (A) was obtained. At this time, the pH was adjusted to 7.5.

105.8 g of water

24g wonder

Clay 49g

Starch Oxide (20%) 22.2g

Latex (48%) 11.6 g

Dispersant (40%) 6.8 g

Lubricant (50%) 4.5g

Ammonia Water Required

2.61 g of the developer obtained in Example 1 was mixed with 22.4 g of the dispersion (A), and then the solution was applied to the upper limb (50 g / m 2) so that the coating amount at the time of drying was 5.0 g / m 2 to prepare a developer sheet.

The production method of the present invention can effectively prepare the polyvalent metal salt of salicylic acid resin without secondary treatment (washing, dehydration, desolvent) without using an acid catalyst, which can simplify the reaction process and reduce the environmental degradation factor, The polyvalent metal salt of salicylic acid resin can be prepared in yield. In addition, the polyvalent metal salt of the salicylic acid resin prepared according to the production method of the present invention can be made into an ultra-fine particle, unlike the conventional manufacturing method, can be prepared as an aqueous dispersion having excellent storage stability, and the storage stability of the color density of the coloring image, water resistance, etc. The color development sheet which is excellent and excellent in abrasion resistance can be manufactured.

Claims (7)

The salicylic acid or a derivative thereof and the styrene or a derivative thereof are reacted at 50 to 200 ° C. in the presence of an organic carboxylic acid zincide or a polyvalent metal compound or a mixture thereof, and then the obtained reaction product is a polyvalent metal compound. Method for preparing a polyvalent metal salt of salicylic acid resin comprising reacting with: 1 2 In the above formula, X 'and X ₂ are each a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, R ₁ , R ₂ and R ₃ are each a hydrogen atom or an alkyl group, and X ₃ and X ₄ are each a hydrogen atom, an alkyl group, It is an alkoxy group, an aralkyl group, an aryl group, or a halogen atom. Salicylic acid comprising reacting salicylic acid or a derivative thereof according to claim 1 with styrene or a derivative thereof and having a mixture of a polyvalent metal compound or a polyvalent metal compound and an organic carboxylic acid zincide at 50 to 200 ° C. Method for producing polyvalent metal salt of resin. The method for producing a polyvalent metal salt of salicylic acid resin according to claim 1 or 2, wherein the organic carboxylic acid zincide is at least one selected from the group consisting of zinc benzoate, zinc caprylate, zinc stearate, and zinc acetate. . The polyvalent metal compound according to claim 1 or 2, wherein the polyvalent metal compound is zinc sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, zinc chloride, magnesium chloride, calcium chloride, barium chloride, nickel chloride, cobalt chloride, aluminum chloride, zinc acetate, acetic acid. A method for producing a polyvalent metal salt of salicylic acid resin, characterized in that at least one selected from the group consisting of manganese, zinc nitrate, zinc oxide and zinc hydroxide. A polyvalent metal salt of salicylic acid resin prepared by the process according to claim 1 or 2. An aqueous dispersion, wherein the polyvalent metal salt of salicylic acid resin according to claim 5 is dispersed in water. A color sheet made of a polyvalent metal salt of salicylic acid resin according to claim 5.