JPH061061A - Method for storing aqueous dispersion of developer composition - Google Patents

Abstract

(57) [Abstract] [Purpose] Dissolve a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component in an organic solvent, and emulsify and disperse this solution in an aqueous solution with or without heating. Then, the aqueous dispersion obtained by removing the organic solvent from this dispersion,
Furthermore, the present invention provides a method for storing an aqueous dispersion obtained by wet pulverization. Composition: water containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component, wherein the aqueous dispersion is continuously stirred while maintaining the liquid temperature of the aqueous dispersion at 0 ° C to 25 ° C It is a method of storing a dispersion liquid. The temperature of the aqueous dispersion is 0 ° C to 40 ° C.
A method for storing an aqueous dispersion of a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component, characterized in that the aqueous dispersion is intermittently stirred while maintaining the above condition. The water dispersion contains an anionic or nonionic water-soluble polymer having an average molecular weight of 200 or more as a dispersion stabilizer, and the water dispersion is stirred while keeping the temperature of the water dispersion at 0 ° C to 40 ° C. A method for storing an aqueous dispersion of a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component, which is dissolved in an organic solvent, and this solution is emulsified in an aqueous solution with or without heating. The present invention relates to a method of dispersing an aqueous solution obtained by removing an organic solvent from the dispersion, and further wet-milling the resulting aqueous dispersion to store the obtained aqueous dispersion.

[0002]

2. Description of the Related Art Novolak type phenolic resins and polyvalent metal salts of nucleus-substituted salicylic acid are called organic developers, whereas activated clay is called inorganic developers, and are used for pressure-sensitive recording sheets. Has been widely put into practice (Japanese Patent Publication No. 42-201)
44, Japanese Patent Publication No. 51-25174). Then, these organic developers are usually finely pulverized or finely dispersed using water as a medium, and are mixed with an inorganic pigment, an adhesive, etc., and then applied to a sheet (Japanese Patent Publication No. 48-16341 and Japanese Patent Laid-Open No. 54-34341). −
143322).

By the way, when a novolac type phenol resin is used as a developer for a pressure-sensitive recording sheet (hereinafter, simply referred to as a developer), the coloring property is weaker than that of a polyvalent metal salt of nucleus-substituted salicylic acid. However, in order to obtain good color development, the amount used must be increased. Further, since a problem of yellowing due to NOx, SOx, sunlight, heat, etc. occurs, a polyvalent metal salt of nucleus-substituted salicylic acid is preferably used.

On the other hand, the polyvalent metal salt of the nucleus-substituted salicylic acid is
Usually, it is composed of an amorphous solid showing each softening point, and is generally applied to a sheet as an aqueous dispersion. It is desirable that the aqueous dispersion has a particle size for which a developer is desirable, has a high concentration, and is excellent in handleability and stability. However, when trying to finely pulverize the coarse particles of the color developer composition into a desired particle size with a ball mill or a sand mill in water containing a dispersant, etc., it is difficult to obtain fine particles, and the dispersion is It becomes remarkably thixotropic and has a poor fluidity and is difficult to handle. And, if it is desired to impart fluidity to this, it is necessary to reduce the concentration of the developer composition in the aqueous dispersion or to use a large amount of a dispersant such that foaming remarkably occurs. No, it is not preferable.

Japanese Unexamined Patent Publication Nos. 63-173680 and 6
No. 4-34782, a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component is dissolved in an organic solvent and emulsified and dispersed in an aqueous solution containing a dispersant by a strong dispersing means. It is disclosed that by heating this dispersion liquid to remove the organic solvent by distillation, an aqueous dispersion liquid of the developer composition having a desired particle size and high fluidity can be obtained even at a high concentration. Further, if this aqueous dispersion is used as it is as a coating liquid, the resulting color-developing sheet is liable to cause color stain due to the printing ink, so it is desirable to further finely pulverize the aqueous dispersion (JP-A-3-202388). ). However, it has been found that when the aqueous dispersion is subjected to wet pulverization, the storage stability thereof is significantly reduced. That is, the viscosity increases during storage, which makes handling of the aqueous dispersion extremely difficult, and a new problem occurs that storage for a long time cannot be performed.

[0006]

DISCLOSURE OF THE INVENTION In the present invention, a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component is dissolved in an organic solvent, and this solution is heated or unheated in an aqueous solution. Emulsified and dispersed in an aqueous dispersion, and then the aqueous dispersion obtained by removing the organic solvent from this dispersion is further subjected to a wet pulverization treatment to store the resulting aqueous dispersion, which significantly improves the storage stability. The purpose is to

[0007]

According to the present invention, a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component is dissolved in an organic solvent, and this solution is heated or unheated in an aqueous solution. In order to store the aqueous dispersion obtained by subjecting the resulting aqueous dispersion to emulsification and dispersion, and then removing the organic solvent from this dispersion, and further subjecting it to wet fine pulverization, the liquid temperature of the aqueous dispersion is set to 0. A method for storing an aqueous dispersion of a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component, which comprises continuously stirring the aqueous dispersion while maintaining the temperature at 25 ° C to 25 ° C.

Further, as a method for storing an aqueous dispersion obtained by a wet pulverization process as described above, the temperature of the aqueous dispersion is set to 0.
A method for storing an aqueous dispersion of a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component, which comprises intermittently stirring an aqueous dispersion while maintaining the temperature at 40 ° C to 40 ° C.

As a method for storing an aqueous dispersion obtained by wet pulverization in the same manner as described above, an anionic or nonionic water-soluble polymer having an average molecular weight of 200 or more as a dispersion stabilizer is added to the aqueous dispersion. And a developer composition water containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component, wherein the water dispersion is stirred while maintaining the temperature of the water dispersion at 0 ° C to 40 ° C. It is a method of storing a dispersion liquid.

[0010]

[Function] A developer composition containing a polyvalent metal salt of nucleus-substituted salicylic acid as a main component is dissolved in an organic solvent and emulsified and dispersed in an aqueous solution containing a dispersant by a strong dispersing means, and then this dispersion liquid is obtained. When the organic solvent is distilled off by heating, an aqueous dispersion having a desired particle size and good fluidity can be obtained even at a high concentration. However, when the aqueous dispersion is subjected to wet pulverization,
The storage stability of the aqueous dispersion is significantly reduced.

As a result of earnest studies to solve such a problem, the inventors of the present invention have probably performed a wet fine pulverization treatment on an aqueous dispersion to soften the surface of the developer particles.
It was presumed that the adhesiveness appeared and it was easy to aggregate.
The present inventors have set the storage temperature of the obtained aqueous dispersion at 0 to 25.
It was found that if the mixture is stirred in the temperature range of 0 ° C, the aggregation can be suppressed while maintaining the dispersed state. 2
If it exceeds 5 ° C, its aggregation cannot be suppressed, and if it becomes less than 0 ° C, it freezes. In addition, the developer composition will settle without stirring.

[0012] For stirring, a generally known stirring blade such as a paddle type, turbine type, or propeller type can be used, and the number and size of the stirring blades can be appropriately selected and used. Regarding the stirring speed, the stirring blade to be used, a device such as a tank, and the like, which is performed according to the concentration of the aqueous dispersion, cannot be generally stated, but excessive stirring tends to increase the viscosity of the aqueous dispersion, Also, from the viewpoint of energy efficiency, it is appropriately adjusted so that sedimentation does not occur. In addition, a surfactant, a dispersant, a water-soluble polymer or the like can be appropriately added and used as a dispersion stabilizer to the aqueous dispersion.

Further, as a result of repeated studies on stirring conditions, the present inventors have found that when intermittent stirring (discontinuous stirring) is carried out, agglomeration does not occur even in the storage temperature range of 0 to 40 ° C. Found. Intermittent agitation (discontinuous agitation) refers to agitation in which stirring is stopped for a certain period of time so that the time to perform the agitation is shorter or the same as the time to stop the agitation, as long as the aqueous dispersion does not sediment Is. In other words,
This is a stirring method that minimizes the stirring. The aqueous dispersion usually contains a surfactant as a dispersion stabilizer, a dispersant,
A water-soluble polymer or the like can be appropriately added and used.

The present inventors have further studied the dispersion stabilizer used in the aqueous dispersion. When an anionic or nonionic water-soluble polymer having an average molecular weight of 200 or more is used as the dispersion stabilizer among the dispersion stabilizers, the storage temperature of the aqueous dispersion is from 0 to 40 ° C. It was found that no trouble occurred even with continuous stirring.
It should be noted that when an anionic or nonionic water-soluble polymer having an average molecular weight of 200 or more is excessively used, bubbles tend to be formed, and when too small an amount is used, stability of the dispersion may be deteriorated. It is preferably used in the range of 0.05 to 4 parts by weight, and particularly preferably in the range of 0.1 to 2 parts by weight, based on 100 parts by weight of the developer composition containing a polyvalent metal salt as a main component. preferable.

Although it is time to add the water-soluble polymer, it is most effective to add it immediately before storage.
Immediately after forming the aqueous dispersion by removing the organic solvent in the dispersion state as it is from the developer composition emulsion containing the polyvalent metal salt of the nucleus-substituted salicylic acid containing the organic solvent, that is, wet pulverization It can be added before the treatment, and addition at this stage is preferable.

Generally, dispersion stabilizers which are excellent in long-term storage properties have a large foaming property, and when subjected to a wet pulverization treatment,
Although bubbles are severely generated and often become inoperable, the anionic or nonionic water-soluble polymer having an average molecular weight of 200 or more has extremely low bubbles despite its high storage stability. Therefore, it can be added before the wet pulverization process.

The anionic or nonionic water-soluble polymer having an average molecular weight of 200 or more is described in JP-A-62-1984.
92, JP-A-63-109084, JP-B-63-1
7635, JP-A-2-204083, JP-A-3-2
At least acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, itaconic acid, itaconic acid ester, maleic acid, maleic acid ester, acrylamide, isobutylene, α-methylstyrene, sulfone, etc. A copolymer composed of one kind of a monomer such as styrene or naphthalene sulfonic acid may be mentioned. Among them, a copolymer composed of methacrylic acid, an alkyl acrylate or an alkyl methacrylate, a copolymer composed of methacrylic acid, an alkyl methacrylate or acrylamide, and a copolymer composed of acrylamide or acrylic acid are preferable.

In the present invention, the above-mentioned anionic or nonionic water-soluble polymer having an average molecular weight of 200 or more is used as a dispersion stabilizer, and intermittent stirring (discontinuous stirring) is performed as a stirring condition to obtain an aqueous dispersion. Keeping at 0-40 ° C is the most preferred embodiment.

The polyvalent metal salt of the nucleus-substituted salicylic acid used in the developer composition of the present invention is, for example, JP-B-49-10.
856, JP-B-51-25174, JP-A-49-5.
5410, JP-A-3-227687, JP-A-3-21
5084, 3,5-di (α-
Methylbenzyl) salicylic acid, 3-α-benzylated phenylethylsalicylic acid, 3-α-methyl-α-ethylpentyl-5-α, α-dimethylbenzylsalicylic acid, 3
-Cumyl-5-isooctylsalicylic acid, 3-cumyl-
5-tert-butylsalicylic acid, 3-tert-butyl-5-
Cumylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-di-tert-octylsalicylic acid, 3,5-
Di-isononyl salicylic acid, 3,5-di-isododecyl salicylic acid, 3,5-di (methylcumyl) salicylic acid,
3,5-dicumylsalicylic acid, 3-α-methylbenzylated phenylethyl-6-methylsalicylic acid, 3-α-methyl-α-ethylpentyl-6-methylsalicylic acid,
3,5-di (α-benzylated phenylethyl) salicylic acid, 3,5-di (benzylated benzyl) salicylic acid,
3,5-di (α-methylbenzyl) -6-methylsalicylic acid, 3-α-tolylethyl-6-methylsalicylic acid,
3,5-di (α, α-dimethylbenzyl) -6-methylsalicylic acid, 3,5-di-tert-octyl-6-methylsalicylic acid, 3-α-dimethylphenylethyl-6-methylsalicylic acid, 3-α -Ethylphenylethyl-6-
Multivalent such as methyl salicylic acid, 3-α-isopropylphenylethyl-6-methylsalicylic acid, 3-α-benzylated benzylphenylethyl-6-methylsalicylic acid, 3-α-methyl-α-ethylpentyl-6-ethylsalicylic acid Metal salts may be mentioned. Here, the isononyl group, the isododecyl group, and the isopentadecyl group are collectively defined as the substituents produced by addition of propylene trimer, propylene tetramer or 1-butene trimer and propylene pentamer, respectively.

On the other hand, specific examples of the polyvalent metal include magnesium, calcium, zinc, aluminum, iron, cobalt, nickel and the like. Among them, zinc is most preferable. Further, the above various kinds of nucleus-substituted salicylic acids may be used not only alone but also in a mixture.

If the softening point of such a developer composition is too low, the developer composition is likely to permeate and migrate between the paper fibers during coating and drying on the paper surface, resulting in a color density. May decrease, or the aqueous dispersion of the developer composition may easily coagulate, resulting in lack of storage stability for a long time. Therefore, the softening point of the developer composition containing the polyvalent metal salt of the nucleus-substituted salicylic acid as the main component is preferably 40 ° C. or higher. However, if the softening point is extremely high, it hardly exhibits self-adhesion when it is applied and dried on the paper surface, so a large amount of adhesive must be used to fix it on the paper surface. In some cases, the adhesive forms a film on the developer composition, hinders the transfer of the color-dissolving agent-dissolved oil present in the microcapsules during recording, and the color-developing ability is slightly inferior. Therefore, the softening point of the developer composition containing the polyvalent metal salt of the nucleus-substituted salicylic acid as the main component is more preferably adjusted to about 40 to 85 ° C.

As a method for adjusting the color developer composition to a preferable softening point temperature, a method of mixing a polyvalent metal salt of a nucleus-substituted salicylic acid having a different softening point, and a softening point for lowering the softening point of the color developer Substances that reduce the amount of, for example, metal salts of fatty acids,
A method of adding trialkylphenol, triaralkylphenol, styrene oligomer, or the like, a substance such as polystyrene, poly-α-methylstyrene, or petroleum which increases the softening point to a polyvalent metal salt of a nucleus-substituted salicylic acid having a softening point that is too low. Examples include a method of adding a resin and the like. The mixing ratio is not particularly limited. The softening point referred to in the present invention means a softening temperature in a state in which the developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component contains equilibrium water in water, and usually in a dry state. The value is about 50 ° C lower than the softening point.

In the present invention, in order to obtain a developer composition having a desired particle size, an organic solvent is added to a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component to liquefy. Another method is to emulsify and disperse in a water containing a dispersant by a strong dispersing means, and then heat the dispersion to remove an organic solvent by distillation. This method emulsifies and disperses a developer composition containing a polyvalent metal salt of nucleus-substituted salicylic acid as a main component in an aqueous medium, so that it is usually necessary to include a dispersant in the aqueous medium. Examples of the dispersant include anionic surfactants such as alkali salts of alkyl sulfates, alkali salts of alkylbenzene sulfonic acids, alkali salts of alkylnaphthalene sulfonic acids, alkali salts of oleic acid amide sulfonic acids, and alkali salts of dialkyl sulfosuccinic acids. , Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester,
Natural high molecular substances such as gum arabic, sodium alginate, agar and gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethylated starch,
Semi-synthetic polymeric substances such as phosphorylated starch, sodium lignin sulfonate, methyl vinyl ether / maleic anhydride copolymer, ethylene / maleic anhydride copolymer, styrene / maleic anhydride copolymer, acrylic acid polymer, acrylic Alkali salts of polymers / copolymers such as acid / methyl methacrylate copolymers, acrylic acid / acrylamide copolymers, vinylbenzene sulfonic acid polymers, polyvinyl alcohol, polyacrylamide, vinyl carboxylic acid ester / acrylamide copolymers Synthetic polymer substances such as Among these, vinyl carboxylic acid ester / acrylamide copolymers are particularly preferable. Degree of polymerization is 10
An acrylamide copolymer having a copolymerization ratio of 0 or more and at least 70 to 96 mol% of acrylamide and an alkyl or alkoxyalkyl ester of acrylic acid, methacrylic acid, itaconic acid or maleic acid having 4 or less carbon atoms of 4 to 30 mol%. Is particularly preferable because it has a large protective colloid property and a small foaming property.

The amount of these dispersants used is appropriately adjusted according to the size of the target dispersed particles, etc., but is preferably in the proportion of about 1 to 30 parts by weight with respect to 100 parts by weight of the developer composition. Adjusted. These dispersants may be used alone or in combination of two or more. The emulsification and dispersion may be performed with or without heating.

As a disperser for further wet-dispersing the developer composition thus obtained, for example, a ball mill, a pebble mill, a sand mill (vertical type, a horizontal type), a cobol mill, an attritor, a dyno mill or the like is used. Various sand mill type crushers using media, 3 roll mill,
High-speed grinders such as high-speed impeller dispersers, high-speed stone mills, high-speed impact mills, etc. can be mentioned, but sand mill type crushers (vertical type, horizontal type), high-speed impellers considering the ease of setting processing conditions and crushing efficiency. A disperser is preferable, and a sand mill type crusher (vertical type, horizontal type) is more preferable.

The aqueous dispersion of the color developer composition is usually mixed with an inorganic pigment, an adhesive or the like, and then applied by a usual coating method such as an air knife coater, a blade coater, a roll coater, a size press coater, a curtain coater or a short dwell coater. It is coated on a support such as high-quality paper, coated paper, synthetic paper, film, etc. by a device so that the dry weight is about ² to 8 g / m ^2, and is used for pressure-sensitive recording bodies, light- and pressure-sensitive recording bodies, etc. Finished as a developer sheet. Further, a self-coloring type pressure-sensitive copying paper having a color developer layer and a color developer layer on the same surface of a support, or a mixed coating layer of a color developer coating liquid and a coating liquid containing an encapsulated color developing agent ( It can also be used for a so-called self-contained type).

[0027]

EXAMPLES Examples and comparative examples will be described below in order to further clarify the effects of the present invention, but the present invention is not limited to these. Further, "parts" and "%" in the examples represent "parts by weight" and "% by weight", respectively, unless otherwise specified.

Example 1 2000 g of water and 400 g of zinc sulfate (heptahydrate) were placed and dissolved in a cylindrical container made of stainless steel having an inner volume of 20000 ml equipped with a stirrer and a thermometer. To this, 8500 g of a 10% aqueous solution of sodium 3,5-di (α-methylbenzyl) salicylate is added with vigorous stirring. Due to the metathesis, the inside of the container immediately becomes a thixotropic drop. Here, a copolymer of α-methylstyrene and styrene (copolymerization ratio; 40:60
880 g of methyl isobutyl ketone (boiling point 116 ° C.) containing 150 g of mol%, average molecular weight; about 1500) are added in a short time. Since the fluidity of the thixotropic-dropped contents gradually improves, when it becomes easy to flow, the container is heated to 75 ° C. and left to stand still. Since the aqueous phase is separated into the upper layer and the oil phase is separated into the lower layer, the entire oil layer is taken out and transferred to a beaker made of hard glass having an internal volume of 5000 ml. This was further added with 600 g of water, 2.5 g of sodium carbonate, polyvinyl alcohol (saponification degree: 98
%, Polymerization degree about 1700) 500% 5% aqueous solution and copolymer of ethyl acrylate and acrylamide (copolymerization ratio; 1
3 to 87 mol%, degree of polymerization; about 400) 25% aqueous solution 60
g, and a homomixer (Model M, manufactured by Tokushu Kika Kogyo Co., Ltd.) at a temperature in the range of 35 ° C. to 40 ° C. and an emulsification operation for 20 minutes at a rotation speed of 8800 to 9000 rpm, for an oil-in-water emulsion. Is obtained. This is an internal volume of 10,000 ml with a stirrer, thermometer and distillation port.
Transfer to a hard glass three-necked flask and add water 2000
After adding g, heat the flask to a boil, stirring the contents slowly. When methyl isobutyl ketone and a part of water are taken out from the distillation port, the content is a water dispersion of a color developer composition containing 3,5-di (α-methylbenzyl) salicylate zinc as a main component and containing no methyl isobutyl ketone. A liquid is obtained. The average particle size is 1.2 μm.

Further, this aqueous dispersion was used in a sand mill (MODEL NO, OSG-8G, manufactured by Igarashi Kikai Co., Ltd.) to obtain 3,5-di (α- with a solid content of 38% and an average particle diameter of 1.1 μm. An aqueous dispersion of a developer composition containing zinc (methylbenzyl) salicylate as a main component was prepared. After that, a 38-% (solid content) 3,5-di (α-) was added to a stainless steel vat with a lid having an internal volume of 5 liters (the stirring port was inserted in the center).
2 kg of an aqueous dispersion of a developer composition containing methylbenzyl) salicylate as a main component is added. Next, attach a stirrer with a blade 5 cm long and 1 cm wide to a stainless steel vat, and stir continuously at a speed of 100 revolutions per minute for 15 minutes.
The viscosity of the B-type viscous form of the aqueous dispersion after immersion in a water bath controlled at a temperature of ℃ to 20 ℃ for 15 days (60
rpm) was measured.

Comparative Example 1 The same procedure as in Example 1 was carried out except that in Example 1, instead of being immersed in a water tank controlled at a temperature of 15 ° C. to 20 ° C., it was immersed in a water tank controlled at a temperature of 30 ° C. to 35 ° C. After 15 days, the viscosity of the B-type viscous form of the aqueous dispersion (60 rp
m) was measured.

Example 2 2000 g of water and 400 g of zinc sulfate (heptahydrate) were placed and dissolved in a cylindrical container made of stainless steel having an internal volume of 20000 ml equipped with a stirrer and a thermometer. To this, 8500 g of a 10% aqueous solution of sodium 3,5-diisononylsalicylate is added while vigorously stirring the contents. Due to the metathesis, the inside of the container immediately becomes a thixotropic drop. Here, 880 g of xylene (boiling point 139 ° C.) containing 150 g of a copolymer of α-methylstyrene and styrene (copolymerization ratio: 40:60 mol%, average molecular weight: about 1500) is added in a short time. Since the fluidity of the thixotropic-dropped contents gradually improves, when the contents become easy to flow, the container is heated to bring the temperature of the contents to 75 ° C and allowed to stand. Since the aqueous phase is separated into the upper layer and the oil phase is separated into the lower layer, the whole oil layer is taken out and transferred to a beaker made of hard glass having an internal volume of 5000 ml. This is further added with 600 g of water, 2.5 g of sodium carbonate, polyvinyl alcohol (saponification degree; 98%, polymerization degree of about 1700) 5
% Aqueous solution 500 g and copolymer of ethyl acrylate and acrylamide (copolymerization ratio; 13:87 mol%, degree of polymerization;
About 400) 60% of 25% aqueous solution was added, and the temperature was 35 ° C to 4 ° C.
A homomixer (Model M, manufactured by Tokushu Kika Kogyo Co., Ltd.) is emulsified for 20 minutes at a rotation speed of 8800 to 9000 rpm to obtain an oil-in-water emulsion. This is transferred to a hard glass three-necked flask with an internal volume of 10,000 ml equipped with a stirrer, a thermometer and a distillation port, 2000 g of water is further added, and the flask is heated to boil while slowly stirring the contents.
When xylene and a part of water are taken out from the distillation port, the content gives an aqueous dispersion of a developer composition containing xylene-free zinc 3,5-diisononylsalicylate as a main component and having a total solid content of 38%. . The average particle size is 0.9 μm.

Furthermore, this aqueous dispersion was used with a high-speed impeller disperser (MODEL LM-S manufactured by Tokushu Kika Kogyo Co., Ltd.)
An aqueous dispersion of a developer composition containing zinc 3,5-diisononylsalicylate having a solid content of 38% and an average particle diameter of 0.8 μm as a main component was prepared. After that, in a stainless steel vat with an internal volume of 5 liters (with a stirring bar insertion hole in the center), a color development containing 38% (solid content) of 3,5-di (isononyl) zinc salicylate as the main component Add 2 kg of an aqueous dispersion of the agent composition. Then add a stainless steel bat with a length of 5
15 minutes in a water tank controlled at a temperature of 30 ° C to 35 ° C, with a stirrer having a blade with a width of 1 cm and a width of 1 cm attached, stirring at a speed of 300 rpm for 10 minutes, and stopping for 50 minutes. The viscosity (60 rpm) of the B-type viscous form of the water dispersion after immersion was measured.

Example 3 Dispersion of the developer composition obtained in Example 1 containing 38% (solid content) of zinc 3,5-di (α-methylbenzyl) salicylate after sand milling as a main component in water After putting 3 kg of liquid into a stainless steel vat with a lid having an internal volume of 5 liters (the stirring port is inserted in the center), next, scrape with a blade of 5 cm in length and 1 cm in width on the stainless vat. Attach a mixer, stir at a speed of 300 rpm for 10 minutes, and stop for 50 minutes.
The viscosity (60 rpm) of the B-type viscous form of the aqueous dispersion after being immersed in a water bath controlled at a temperature of 5 ° C. for 15 days was measured.

Comparative Example 2 Similar to Example 2 except that instead of immersing in a water tank controlled at a temperature of 30 ° C. to 35 ° C. in Example 2, it is immersed in a water tank controlled at a temperature of 45 ° C. to 50 ° C. After 15 days, the viscosity of the B-type viscous form of the aqueous dispersion (60
rpm) was measured.

Example 4 Water dispersion of the developer composition obtained in Example 1 containing 38% (solid content) of zinc 3,5-di (α-methylbenzyl) salicylate after sand mill treatment as a main component After putting 3 kg of liquid into a stainless steel vat with a lid having an internal volume of 5 liters (the stirring port is inserted in the center), 20% is further added.
Acrylamide copolymer (the molar ratio of acrylamide, ethyl acrylate and butyl acrylate is 85:11:
Add 29 g of the aqueous solution of 4), then attach a stirrer having a blade of 5 cm in length and 1 cm in width to a stainless steel vat, and at 30 ° C. with continuous stirring at a speed of 100 rpm.
1 to 1 in a controlled water tank at a temperature of 35 to 35 ° C
Viscosity of B-type viscous form of water dispersion after immersion for 5 days (60 rp
m) was measured.

Example 5 Water dispersion of the developer composition obtained in Example 1 containing, as a main component, 38% (solid content) of zinc 3,5-di (α-methylbenzyl) salicylate after the sand mill treatment. After putting 3 kg of liquid into a stainless steel vat with a lid having an internal volume of 5 liters (the stirring port is inserted in the center), 20% is further added.
Methacrylic acid copolymer (the molar ratio of methacrylic acid, butyl methacrylate and methyl acrylate is 40: 30: 3).
86 g of the aqueous solution of 0) was added, and then a stainless steel vat was equipped with a stirrer having a blade with a length of 5 cm and a width of 1 cm, and with continuous stirring at a speed of 100 rpm, 30 ° C.
1 to 1 in a controlled water tank at a temperature of 35 to 35 ° C
The viscosity of the B-type viscous form of the aqueous dispersion after being immersed for 5 days (600
rpm) was measured.

Example 6 Water dispersion of the developer composition obtained in Example 1 containing, as a main component, 38% (solid content) of zinc 3,5-di (α-methylbenzyl) salicylate after the sand mill treatment. After putting 3 kg of liquid into a stainless steel vat with a lid having an internal volume of 5 liters (the stirring port is inserted in the center), 20% is further added.
Acrylamide copolymer (the molar ratio of acrylamide, ethyl acrylate and butyl acrylate is 85:11:
Add 4g of the aqueous solution of 4), then attach a stirrer with a blade of cm in length and 1 cm in width to a stainless steel vat, stir at a speed of 300 rpm for 10 minutes, and stop for 50 minutes. The viscosity (60 rpm) of the B-type viscous form of the aqueous dispersion after 15 days immersion in a water tank controlled at a temperature of 30 to 35 ° C. was measured repeatedly.

Comparative Example 3 The same as Example 4 except that in Example 4, instead of being immersed in a water tank controlled at a temperature of 30 ° C. to 35 ° C., it was immersed in a water tank controlled at a temperature of 45 ° C. to 50 ° C. After 15 days, the viscosity of the B-type viscous form of the aqueous dispersion (6
0 rpm) was measured.

Comparative Example 4 Instead of adding 120 g of an aqueous solution of 20% acrylamide copolymer (the molar ratio of acrylamide, ethyl acrylate and butyl acrylate is 85: 11: 4) in Example 4, 20% cationic dispersion. Agent (trade name: Chemistat 6
(300, Sanyo Kasei) 57 g was added, and the viscosity of the B-type viscous form of the aqueous dispersion after 15 days (60 rpm) was carried out in the same manner as in Example 4 except that it was immersed in a water tank controlled at a temperature of 30 ° C to 35 ° C. Was measured.

Comparative Example 5 Instead of being immersed in the water bath controlled at a temperature of 30 ° C. to 35 ° C. in Example 4, a water bath controlled at a temperature of 45 ° C. to 50 ° C. was used, and a speed of 300 revolutions per minute 1
Repeatedly stirring for 0 minutes and stopping for 50 minutes 15
The viscosity (60 rpm) of the B-type viscous form of the aqueous dispersion after 15 days was measured in the same manner as in Example 4 except that it was immersed for a day.

[Evaluation] Based on the viscosity of the initial dispersion, ⊚: viscosity after 15 days hardly changed ◯: viscosity after 15 days was within 2 times ×: dispersion was obtained within 15 days Breaks into cream

[0042]

[Table 1]

[0043]

As is apparent from the results shown in Table 1, the present invention is to dissolve a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component in an organic solvent, and to dissolve this solution in an aqueous solution. Emulsify and disperse under heating or without heating, and then remove the organic solvent from this dispersion to obtain an aqueous dispersion obtained by further wet pulverization, and store the dispersion very stably. be able to.

Claims (5)

[Claims] 1. A developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component is dissolved in an organic solvent, and this solution is emulsified and dispersed in an aqueous solution with or without heating. The water dispersion obtained by removing the organic solvent from the dispersion is subjected to a wet pulverization treatment to store the water dispersion, and the water temperature of the water dispersion is maintained at 0 ° C to 25 ° C. A method for storing an aqueous dispersion of a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component, which comprises stirring the dispersion. 2. A developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component is dissolved in an organic solvent, and this solution is emulsified and dispersed in an aqueous solution with or without heating. The water dispersion obtained by removing the organic solvent from the dispersion is further subjected to wet fine pulverization treatment to store the obtained water dispersion, and the water temperature of the water dispersion is maintained at 0 ° C to 40 ° C. A method for storing an aqueous dispersion of a developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component, which comprises stirring the dispersion intermittently. 3. A developer composition containing a polyvalent metal salt of a nucleus-substituted salicylic acid as a main component is dissolved in an organic solvent, and this solution is emulsified and dispersed in an aqueous solution with or without heating. An aqueous dispersion obtained by removing the organic solvent from the dispersion is further subjected to wet pulverization to store the resulting aqueous dispersion, and an anionic compound having an average molecular weight of 200 or more as a dispersion stabilizer is added to the aqueous dispersion. Alternatively, the main component is a polyvalent metal salt of a nucleus-substituted salicylic acid, which is characterized by containing a nonionic water-soluble polymer and stirring the aqueous dispersion while maintaining the temperature of the aqueous dispersion at 0 ° C to 40 ° C. And a method for storing an aqueous dispersion of the developer composition. 4. The developer according to claim 3, wherein 0.05 to 4.0 parts by weight of an anionic or nonionic water-soluble polymer having an average molecular weight of 200 or more is used with respect to 100 parts by weight of the developer composition. Method for storing aqueous dispersion of colorant composition. 5. The method for storing an aqueous dispersion of a developer composition according to claim 3, wherein the aqueous dispersion is intermittently stirred.