JPH02653A - Aqueous suspension - Google Patents

Abstract

PURPOSE:To obtain the above suspension improved in hue, storage stability and dispersion stability and useful as the material for pressure-sensitive copying paper by dispersing a polyvalent metal salt of a salicylic acid resin in water in the presence of an anionic water-soluble polymer. CONSTITUTION:The subject aqueous suspension is prepared by dispersing a salt of a polyvalent metal (particularly preferably Zn) with a salicylic acid resin of a weight-average MW of 500-10000, preferably, 500-5000, comprising 60-95mol% structural salicylic acid units having bonding positions of 3 and 5 of formula I and 60-95mol% structural benzyl derivative units having 0-3 bonding positions in the benzene ring and having a bonding position in the alpha-carbon atom of the benzene ring of, e.g., formula II (wherein R1 and R2 are each H or a 1-4C alkyl) in water in the presence of an anionic water-soluble polymer (e.g., a saponificate of a sulfonated vinyl acetate/styrene copolymer or a polystyrenesulfonate).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to an aqueous suspension of a polyvalent metal compound of a salicylic acid resin having a novel composition, particularly a novel oil-soluble salicylic acid suspension used as a material for pressure-sensitive copying paper. The present invention relates to an aqueous suspension of a resin polyvalent metal compound.

More specifically, the present invention relates to an aqueous suspension of a polyvalent metal compound of a salicylic acid resin for pressure-sensitive copying paper, which has significantly improved hue, storage stability of the dispersion, and dispersion stability of the coating material for coating base paper.

[Conventional technology]

In general, pressure-sensitive copying paper contains a sheet (CB paper) coated with microcapsules of a non-volatile organic solvent containing an electron-donating organic compound (so-called pressure-sensitive dye) and an electron-accepting color developer. Sheet coated with water-based paint composition (C
F paper), with each coated side facing each other, and the pressure-sensitive dye solution, which breaks the microcapsules and flows out using the printing pressure of a ballpoint pen, typewriter, etc., comes into contact with a color developer and develops a color. This is what I did. therefore,
By changing the combination of the microcapsule layer containing the pressure-sensitive dye and the color developer layer, it is possible to make multiple copies, and it is also possible to produce pressure-sensitive copying paper (SC paper) that develops color with a single sheet. be.

Colorless or light-colored dye precursors used in such pressure-sensitive copying papers include (1) triarylmethane phthalide compounds such as crystal violet lactone, (2) 3-dibutylamino-6-methyl-7- One or more selected from fluoran compounds such as anilinofluorane (3) pyridyl phthalide compounds (4) phenothiazine compounds (5) leukoolamine compounds, etc. are dissolved in a hydrophobic high boiling point solvent, and Used in microencapsulation.

On the other hand, electron-accepting color developers have conventionally been used as (1) inorganic solid acids such as acid clay and activated clay, (2) oil-soluble phenol-formaldehyde condensates and their polyvalent metal modified products, or (3) substituted salicylic acids. polyvalent metal salts are used. However, these color developers lack image stability, cause colored images to discolor and fade during storage, and have insufficient water resistance stability or solvent resistance stability.

The present inventors discovered a new polyvalent metal compound of salicylic acid resin as a color developer that solved these problems, and filed a patent application (Japanese Patent Application No. 82-019873.62-1122).
97, 82-278377).

Generally, in order to produce pressure-sensitive copying paper using a color developer, the color developer is wet-pulverized in the presence of a surfactant, with a particle diameter of 1.
A dispersant is used to form an aqueous suspension of ~ioILm into fine particles.

[Problem to be solved by the invention]

However, the selection of a combination of particles to be dispersed and a dispersant to obtain a good dispersion system is mostly based on experience, and there are no general rules. Furthermore, when selecting a dispersant, it is necessary to consider not only the dispersibility but also the influence it has on the interaction with the particles to be dispersed.

Therefore, by combining the polyvalent metallized salicylic acid resin and a dispersant compatible with it, the dispersibility can be improved.

It is not easy to create an aqueous suspension with good performance in various aspects such as stability and color development. For example, p-phenylphenol/formaldehyde polymers, p-octylphenol, and formaldehyde polymers, which are currently used as color developers for pressure-sensitive copying paper, are usually treated with polycarboxylic acid-type anionic polymeric surfactants, specific Typically, sodium salts of maleic anhydride/diisobutylene copolymers are used as dispersants, but when these are used as dispersants to form an aqueous suspension of the polyvalent metal compound of the salicylic acid resin, polyvalent Unfavorable complex formations occur between metals and carboxylates. As a result, dispersion performance and dispersion stability are significantly reduced, foams that are difficult to defoam are formed, and the physical properties of the color developer are changed due to deterioration of the polyvalent metal compound of the salicylic acid resin, which is the substance to be dispersed. It is not possible to obtain an aqueous suspension that

In addition, some salts of formaldehyde condensates of naphthalene sulfonic acid and salts of lignin sulfonic acid, which were once used in phenol-formaldehyde condensation color developers, have dispersion performance for the polyvalent metal compound of the salicylic acid resin. However, when used in pressure-sensitive copying paper, it is extremely impractical due to coloration of the paper surface or photoyellowing caused by the dispersant itself.

The present invention has been made to solve the above-mentioned problems, and its first main purpose is to provide excellent dispersibility, stability, etc., and to provide an extremely convenient method for producing pressure-sensitive copying paper. The objective is to provide an available aqueous suspension. The second
1 is an aqueous suspension that enables the production of high-quality pressure-sensitive copying paper that has high image stability, water-resistance stability, and solvent-resistance stability, and that does not cause discoloration or yellowing of the paper surface or cause discoloration of the colored image during storage. The objective is to provide a cloudy liquid.

[Means to solve the problem]

The above objects can be achieved by the present invention as described below. That is, the present invention provides the following formulas: (representing an alkyl group of numbers 1 to 4), and the structural unit (I) is 5 to 4.
40 mol%, structural unit (II) accounts for 60 to 95 mol%, the structural unit (I) is bonded to the structural unit (II) through the α carbon, and the structural unit (II) is bonded to the structural unit (II) through the α carbon. ) A polyvalent metal compound of salicylic acid resin (a) or formula (m) (IV) (V) ( In the formula, R1 and R2 are hydrogen atoms or have 1 to 12 carbon atoms.
R3 and R6 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 and R3 are a hydrogen atom or a methyl group. ), the structural unit (m) is 5 to 35 mol%, the structural unit (I
10 to 85 mol% of one or more of V), one of the structural units (V)
The above is 4 to 85 mol%, the structural unit (III) is bonded via the α carbon of the structural unit (TV), and the structural unit (I
V) can also be bonded to the benzene ring of the structural unit (TV) via the α carbon;
) and/or (V) is bonded to the benzene ring via the α carbon, and has a weight average molecular weight of 500 to 10.0
00 polyvalent metallized salicylic acid resin (b), (A) an anionic water-soluble polymer consisting of a polyvinyl alcohol derivative or a salt thereof having a sulfonic acid group in the molecule, and/or (B) -format (Vl ) (wherein, R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M is an alkali metal or ammonium ion) This is an aqueous suspension of a polyvalent metal compound of salicylic acid resin dispersed in the presence of.

The aqueous suspension of the present invention is made by aqueous suspension of a polyvalent metallized salicylic acid resin having good color development performance using a dispersant that is particularly compatible with the metallized product and has excellent properties. It can be suitably used in the production of pressure-sensitive copying paper, and the pressure-sensitive copying paper produced therefrom also exhibits good performance, with improved coloring performance and the like.

The present invention will be explained in more detail below.

First, in the present invention, (A) and (B) act as dispersants.
) Anionic water-soluble polymers are described below.

The 7-ionic water-soluble polymer (A) is an anionic water-soluble polymer made of a polyvinyl alcohol derivative or a salt thereof having a sulfonic acid group in the molecule, and has a degree of polymerization of 200 to 5000, preferably 300. ~2000
It is.

In group (A) polymers, the sulfonic acid groups are generally alkali metals (Na'', K'', Li'', Cs''Rh).
", Fr") or NH4+ salt.

The method for producing the anionic water-soluble polymer (A) is as follows: (1) Vinyl acetate and α containing a sulfonic acid group in the molecule.
(2) A method of reacting polyvinyl alcohol with concentrated sulfuric acid (3) A method of oxidizing polyvinyl alcohol with bromine, iodine, etc., and then reacting it with acidic sodium sulfite. Method (4) includes a method in which an aldehyde compound having a sulfonic acid group is reacted with polyvinyl alcohol in the presence of an acid catalyst to form a sulfoacetal.

Among these, method (1) is preferred.

Specific examples of α,β-unsaturated heptanomers having sulfonic acid groups include (1) sulfoalkyl acrylates, such as sulfoethyl acrylate, sulfoethyl methacrylate (2) vinylsulfonic acid, styrenesulfonic acid, allylsulfonic acid (3) ) maleimido-N-alkanesulfonic acid, (4
) 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, etc. are exemplified, and generally 0.0.
After copolymerizing at a ratio of 5 to 20 moles, preferably 1 to 10 moles, the vinyl acetate group can be obtained by saponifying (50 to 100%) under alkaline conditions by a conventional method.

The anionic water-soluble polymer (A) can be obtained by sulfonating a copolymer of vinyl acetate and an aromatic α,β-unionized polymer such as styrene, and then saponifying the copolymer, and Vinyl acetate and α and β containing sulfonic acid groups in the molecule
In addition to -unsaturated-unsaturated-tumer, it can also be obtained by copolymerizing α,β-unsaturated heptanomers, and these are also included as the anionic water-soluble polymer of (A).

A typical example of the 7-ionic water-soluble polymer (B) represented by the above formula is a polymer having styrene sulfonic acid or a derivative unit thereof in the molecule. Among them, polystyrene sulfonate with an average degree of polymerization of 5 to tooo, polyα
-Methylstyrene sulfonate is mentioned as a suitable example.

Such homopolymers may be synthesized in any way. That is, a salt of a polystyrene sulfonic acid derivative may be synthesized by sulfonating polystyrene, or may be synthesized by polymerizing styrene sulfonic acid (or a salt thereof).

Polymerization may be carried out by known methods. For example, radical polymerization and ionic polymerization at 0 to 150°C.

Specific examples where the anionic water-soluble polymer (B) is a copolymer include a salt of a copolymer of styrene sulfonic acid and maleic anhydride, a sulfonated salt of a styrene-maleic acid copolymer, and a salt of a sulfonated styrene-maleic acid copolymer. Examples include salts of copolymers of other vinylic compounds, and salts of sulfonated copolymers of styrene and other vinylic monomers.

Although these may be synthesized in any manner, they can be synthesized by conventional methods such as ionic polymerization and radical polymerization.

The properties of the polymers (A) and (B) used as dispersants in the present invention are as follows.

Unlike general fully saponified or partially saponified polyvinyl alcohol, the anionic water-soluble polymer (A) having a sulfonic acid group has high solubility in water, dissolves easily, and has a wide pH range. The viscosity varies little over the range and is virtually colorless or very pale in color. Therefore, it does not color the aqueous suspension of polyvalent metallized salicylic acid resin obtained using it, and therefore does not color the pressure-sensitive copying paper (CF paper) produced using the aqueous suspension. Polyvinyl alcohol derivatives with sulfonic acid groups in their molecules have the property of not deteriorating or discoloring themselves under harsh environmental conditions, but also have excellent dispersion performance for polyvalent metallized salicylic acid resins. The present invention provides a thermally, mechanically, and chemically stable aqueous suspension of a salicylic acid resin polyvalent metal compound.

Furthermore, the anionic water-soluble polymer (A) used as a dispersant in the present invention is generally used completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, or polyvinyl alcohol modified with carboxyl groups, etc. Unlike others, it has low foaming properties and excellent self-defoaming properties, so it can eliminate troubles caused by foam during dispersion work.

Further, the anionic water-soluble polymer (B) used in the present invention also provides a stable aqueous solution over a wide pH range and is extremely pale in color.

In this way, in the present invention, (
The water-soluble anionic polymers A) and (B) each have an extremely excellent dispersion ability for polyvalent metallized salicylic acid resins, and the aqueous suspension of the present invention has a stable, high concentration and low viscosity. Become something. Furthermore, problems such as significant foaming or difficulty in defoaming do not occur, unlike when using general polyvinyl alcohol.

In addition, the 7-ionic water-soluble polymer (A) used in the present invention has not only anionic properties but also nonionic properties, and has excellent dispersion performance and excellent protective colloid ability, so that the resulting aqueous suspension has significantly better mechanical and thermal stability than aqueous suspensions using other dispersants.

Next, the polyvalent metal compound of salicylic acid resin used in the present invention will be explained. The polyvalent metal compound of the salicylic acid resin of the present invention refers to the polyvalent metal compound formed between the carboxyl group within the molecule of the salicylic acid resin or between the salicylic acid resin molecule and the polyvalent metal ion, or the polyvalent metal compound formed between the carboxyl group and the polyvalent metal ion. Any of the molten mixtures containing salt.

First, the method for producing salicylic acid resin, which is the polyvalent metal compound (a) of salicylic acid resin, will be described. This resin is composed of salicylic acid and the general formula (VII) [wherein R2 and R2 are hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, aralkyl groups, aryl groups, or cycloalkyl groups, and R3 is hydrogen atoms or 1 to 4 carbon atoms] at least one benzyl derivative represented by It is obtained by condensing these in the presence of an acid catalyst.

As a benzyl derivative represented by formula (■).

For example, the following 1) to 4) may be mentioned.

1) Benzyl methyl ether, benzyl ethyl ether, p-methylhensyl methyl ether, m-methylbenzyl ethyl ether, 〇-ethylbenzyl isopropyl ether, 2,3-dimethylbenzyl methyl ether, α-methylbenzyl methyl ether, α -Methylbenzyl isopropyl ether, α-ethylbenzyl methyl ether, P-methyl-α-methylbenzyl methyl ether, 0-ethyl-α-methylbenzyl methyl ether, 2,3-dimethyl-α-methylbenzyl methyl ether, dibenzyl Ether, di(p-methylbenzyl)
Ether, di(α-methylbenzyl)ether, di(p
-Benzyl ethers such as -methyl-α-methylbenzyl) ether.

2) Benzyl alcohol, p-methylbenzyl alcohol, α-methylbenzyl alcohol, dimethyl-α
- Benzyl alcohols such as methylbenzyl alcohol.

3) Mixtures of benzyl ethers and benzyl alcohols.

4) Pencil chloride, p-methylbenzyl chloride, α-methylbenzyl chloride, dimethyl-α
-Benzyl halides such as methylbenzyl chloride.

The amount of these benzyl derivatives used is 2 to 30 mol, preferably 2 to 10 mol, based on the benzyl group contained per 1 mol of salicylic acid. The weight average molecular weight of the salicylic acid resin produced using this amount is in the range of 500 to 10,000, preferably 500 to 5,000, and the salicylic acid content in the resin composition is 3 to 70% by weight, preferably 5 to 50%. It suffices if it is % by weight.

Catalysts used in the reaction include, for example, mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; Friedelkraft acids such as ferric chloride, zinc chloride, aluminum chloride, tin chloride, titanium tetrachloride, and boron trifluoride; Examples include strong acid catalysts such as methane sulfonic acid and trifluoromethanesulfonic acid.

The salicylic acid resin used in the present invention as the polyvalent total compound (b) of the salicylic acid resin is obtained by condensing salicylic acid and at least one benzyl derivative represented by the above-mentioned formula (■) in the presence of an acid catalyst. The resulting resin is further reacted with a styrene derivative represented by the formula (■) H et al. (wherein R4, R5 and R6 have the same meanings as in formula (V)) in the presence of an acid catalyst. It will be done.

Styrene derivatives used in this reaction include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene,
-Methylstyrene, 0-ethylstyrene, p-ethylstyrene, 0-isopropylstyrene, m-isopropylstyrene, P-isopropylstyrene, p-tert-
Examples include, but are not limited to, butylstyrene, α-methylstyrene, β-methylstyrene, and the like.

From a commercial standpoint, styrene is preferred because it is inexpensive.

The amount of this styrene derivative used is 0.2 to 20 mol, preferably 0.5 to 10 mol, per 1 mol of salicylic acid in the resin obtained in the first stage reaction.

The weight average molecular weight of resins produced in this range of usage ranges from 500 to 10,000.

The catalyst used in the reaction is the same as in the previous example.

Several known methods can be applied to produce a polyvalent metal salt from the salicylic acid resin. For example, it can be produced by reacting an alkali metal salt of the present resin with a water-soluble polyvalent metal salt in water or a solvent in which both are soluble. That is, after reacting an alkali metal hydroxide, carbonate, or alkoxide with salicylic acid resin to obtain an alkali metal salt of salicylic acid resin or an aqueous solution, alcohol solution, or water-alcohol mixed solution thereof, a water-soluble There is a method of producing it by reacting polyvalent metal salts.

Alternatively, the resin after the condensation can be neutralized without being separated from the reaction mixture, and the polyvalent metal chloride used as a free sol fluorine catalyst can be reacted with the resin to obtain a metalized resin.

To obtain a molten mixture containing polyvalent metal salts of salicylic acid resin, salicylic acid resin can be mixed with formic acid, acetic acid, propionic acid,
It can be produced by mixing with a polyvalent metal salt of an organic carboxylic acid such as valeric acid, caproic acid, stearic acid or benzoic acid, causing a heating melting reaction, and then cooling. In some cases, a basic substance such as ammonium carbonate, ammonium bicarbonate, ammonium acetate, or ammonium benzoate may be further added to carry out a heating melting reaction.

Furthermore, salicylic acid resin and polyvalent metal carbonates, oxides,
It can be produced by heating and melting reaction of hydroxide with basic substances such as ammonium organic carboxylates such as ammonium formate, ammonium acetate, ammonium caproate, ammonium stearate, and ammonium benzoate, followed by cooling.

Preferred polyvalent metals include calcium, magnesium,
aluminum, copper, zinc, tin, barium, cobalt,
Examples include nickel, and zinc is particularly preferred.

The polyvalent metallized salicylic acid resin obtained in this way was tested by the ring and ball softening point measurement method based on JIS-2548 (
All softening points described hereinafter are based on this method).Those having a softening point of 50°C to 120°C are generally used.

The polyvalent metallized salicylic acid resin produced as described above has the drawbacks of the conventionally known aromatic carboxylic acid metal salts as a color developer. This can improve problems such as (b) insufficient compatibility with color oils, (c) some dissolution in water, (c) disappearance of colored images by light, and (ii) high cost. That is, when these polyvalent metal compounds of salicylic acid function as color developers, C8
It has excellent compatibility with oil in paper microcapsules, and the rate of color development, especially at low temperatures, is significantly improved compared to conventional products, and it has no solubility in water. Therefore, the polyvalent metallized salicylic acid used in the present invention has color development properties at low temperatures, stability of colored images against light and water,
It is a more useful color developer that has improved durability and is cheaper.

Next, a method for preparing the aqueous suspension of the present invention from the anionic water-soluble polymers (A) and (B) above and the polyvalent metallized salicylic acid resin (a) or (b) will be described.

Both of the anionic water-soluble polymers (A) and (B) are generally obtained as a white powder that is easily soluble in water or as an aqueous solution, so if necessary, they are dissolved in water in advance. Then, the pH is adjusted to a range of 4 to IO, preferably 6 to 9.

Powder of the polyvalent metallized salicylic acid resin is charged into the polymer aqueous solution prepared in this way, and after stirring and forming into a slurry, the powder is mixed with a wet pulverizer, such as a ball mill, an attritor, or a slurry.
The average particle size is 1 to 20 g using a wet pulverization device using a spherical pulverization measure such as a sand grinder.
78 type to obtain an aqueous suspension. Such wet pulverization can be performed by either a patch method or a continuous processing method, and the work is completed after pulverizing the particles to the desired particle size. If the polyvalent metal compound of salicylic acid resin has a low softening point and easily liquefies below the boiling point of water, emulsify the polyvalent metal compound of salicylic acid resin in water by stirring at high speed in warm to hot water. An aqueous suspension can be obtained upon cooling.

In the aqueous suspension of the present invention, (A) and/or (
The amount of the anionic water-soluble polymer used in B) varies depending on the substance to be dispersed (salicylic acid resin polyvalent metal compound) and the physical properties of the intended aqueous suspension (tR degree, particle size of the substance to be dispersed, etc.). Although not limited, to obtain a practical aqueous suspension (average particle size 1 to 10 pm), at least 0.5 part by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the salicylic acid resin polyvalent metal compound. Parts by weight. The content of the salicyl-resistant resin polyvalent metal compound/aqueous suspension YJ solution is preferably 30 to 60% by weight.

As the dispersant used in the present invention, either polymer (A) or (B) may be used, but it is preferable to use them in combination.By using both together, when used alone when forming an aqueous suspension. It becomes possible to further reduce the amount of the dispersant used, and it is possible to obtain a more stable aqueous suspension of the polyvalent metal compound of the salicylic acid resin than when the dispersant is used alone.

When the anionic water-soluble polymers (A) and (B) are used in combination, an extremely stable aqueous suspension can be obtained at 10 parts by weight or less per 1100 ff of salicylic acid resin polyvalent metal compound. Furthermore, other anionic or nonionic surfactants, water-soluble polymers, etc. can also be used in combination to adjust the viscosity-rheological properties of the aqueous suspension.

Aqueous9. The average particle size of the polyvalent metallized salicylic acid resin in the liquid m is 10 microns or less, preferably in the range of 0.5 to 5 microns. If there are many particles larger than 10 microns, there will be a lot of sediment when the aqueous suspension is stored stationary, and the coloring performance of the pressure-sensitive copying paper, especially the density immediately after coloring, will be reduced. On the other hand, if there are many particles less than 0.5 microns, the aqueous suspension exhibits thickening behavior, making it difficult to increase the concentration and handle the aqueous suspension.

When producing pressure-sensitive copying paper using the aqueous suspension of the present invention prepared as described above, first, in order to adjust the paper surface characteristics of the pressure-sensitive copying paper, (1) inorganic or organic pigments, (2) pigment dispersant, (3) coating binder,
(4) Mix other various additives to prepare a water-based paint according to the coating method. This water-based paint is then applied to base paper and dried to produce pressure-sensitive copying paper.

(1) Inorganic or organic pigments used here include:
Sumo phosphorus, calcined kaolin, bentonite, talc, calcium carbonate, barium sulfate, aluminum oxide (alumina), silicon oxide (silica), satin white, titanium oxide, polystyrene emulsion, etc. (2) As a pigment dispersant, metaphosphoric acid Phosphate salts such as soda, sodium hexametaphosphate, and sodium tripolyphosphate, and polycarboxylate salts such as polyacrylic acid sorter (3
) Coating binders include modified starches such as oxidized starch, enzymatic starch, urea phosphate starch, and alkylated starch, water-soluble proteins such as casein and gelatin, styrene-butadiene latex (SBR), and methyl methacrylate. Butadiene latex (MBR)
, vinyl acetate polymer emulsion, polyvinyl alcohol, carboxymethyl cellulose, ethyl cellulose, methyl cellulose, and other synthetic and semi-synthetic binders; (4) Other various additives include fluorescent brighteners, antifoaming agents, and viscosity modifiers. , anti-dusting agents, lubricants, waterproofing agents, etc. are used.

The water-based paint prepared by mixing and dispersing the water-soluble suspension of the polyvalent metal compound of the salicylic acid resin of the present invention and the various components described above can be applied to an air knife coater, a blade coater, a brush coater, a roll coater, a bar coater, a gravure coater, etc. It is coated onto base paper and dried to form a pressure-sensitive copying paper developer sheet.

Generally, the coating amount of the water-based paint is 0.5 g/m or more, preferably 1 to Log/m' in terms of dry weight. The color development performance of a sheet coated with a water-based paint is mainly controlled by the concentration of the salicylic acid resin polyvalent metal compound in the water-based paint.
A coating amount exceeding '' is not effective in improving coloring performance and is also economically disadvantageous.

The suitability of the aqueous suspension of the present invention for producing pressure-sensitive copying paper is specifically recognized in the following points. For example, since the aqueous suspension of the present invention has little tendency to increase in viscosity, it significantly improves workability when applying aqueous paints containing it as a main component.

In addition, if the air knife coating method, which uses a low viscosity coating liquid during coating, is used to apply these water-based paints,
This is advantageous because foaming during circulation of the aqueous coating liquid is significantly suppressed.

The aqueous suspension of the present invention may also contain other components commonly used in preparing aqueous coatings for use in pressure-sensitive copying paper.
For example, there is no tendency for thickening (shock) when mixed with white inorganic pigments such as kaolin clay and calcium carbonate.

Furthermore, these aqueous suspensions have a high solids content and excellent thermal stability, and water-based paints using them have excellent thermal and mechanical stability. It can be suitably applied to a coating machine that uses a water-repellent paint.

Furthermore, the novel color developer sheet for pressure-sensitive copying paper produced using the aqueous suspension of the present invention is superior to the color developer sheet using an inorganic solid acid or p-phenylphenol novolank resin. It has the same or better color development properties, and has greatly improved resistance to yellowing due to sunlight exposure, making it extremely convenient for handling and storage.

〔Example〕

Hereinafter, the present invention will be specifically described in detail with reference to Examples and Comparative Examples.

The various sex test methods are shown below.

A) Properties of the aqueous suspension (I) Hue The aqueous suspension was deposited on a Mayer bar on a fine paper by dry weight of 5.
Four sheets (aqueous suspension coated sheets) coated so that g/rrr' are stacked on top of each other, and the reflectance is determined using a blue filter with a TSS model Hunter colorimeter (manufactured by Toyo Seiki). The whiteness (whiteness) of the aqueous suspension coated sheet is expressed as reflectance (A).

The higher the reflectance (A), the whiter the aqueous suspension;
If the difference is about 1 point (%), it is possible to distinguish superiority or inferiority at the southern limit.

(II) Viscosity After adjusting the solid content of the aqueous suspension obtained by atomization to 40% by weight, it was measured at 25°C using a B-type viscometer, Nol rotor, 60 rpm.
It is expressed as a number measured under the following conditions (unit: cp).

([) Pour 2 kg of high-temperature storage-stable aqueous suspension into a stainless steel beaker with an internal volume of 3 cm, and use a glass stirring blade (Ikari type, diameter 100 mm).
The sample was stored at 40°C for one week while stirring at 100 rpm, and the filtration performance before and after storage was compared using the filtration time (sea) through a 200-mesh sieve with a diameter of 7.5 cm. In a dispersion with poor high-temperature storage stability, the polyvalent metal compound particles of the salicyl ugly resin aggregate in the aqueous suspension, and the sieve filtration performance decreases as the particle size grows.

B) Properties of aqueous coating liquid Using the aqueous suspensions of Examples and Comparative Examples, an aqueous coating liquid for pressure-sensitive copying paper blade coating (solid content 50%) having the following composition was prepared in A. The properties were determined as Jl+.

Ingredients 1 part (a) Aqueous suspension (as salicylic acid 18 resin polyvalent metal compound in liquid) (b) Light calcium carbonate 100 (
C) Styrene-butadiene latte 6(d
) Oxidized starch 6 (e) Sodium polyacrylate 0.5 (pigment dispersant) (I) Viscosity Check for thickening using a B-type viscometer (No., 30-ter, 6o rpa+). Preferred viscosity is 300-1oooc
It is ps.

(II) Mechanical stability” JIS K-6 using a 50% solids water-based paint
The amount of aggregates produced is measured using a Maron mechanical stability tester according to 392 (Test method for NBR synthetic latex), and is used as a measure of the mechanical stability of the water-based paint.

Jllll constant conditions, sample 100g, looOrp
m, 10m1n, load 20kg. After the test, it is filtered through a 200 mesh sieve and the amount of aggregates (after completely dry) is weighed. The display is expressed in aggregate production rate (%).

Water-based paints that show a large rate of aggregate formation according to this test method may be used during high-speed coating, such as blade coating or gate roll coating, where strong shearing forces are applied, resulting in destruction of the dispersion state of the water-based coating liquid and the formation of solid components. Coating problems due to agglomeration etc. are likely to occur.

C) Performance as pressure-sensitive copying paper The water-based paint that has undergone the mechanical and thermal stability tests using the homomixer described in the previous section was applied to high-quality paper at a dry coating amount of 6 g/
The mixture was coated with a Meyer parser so as to form a solid color and dried to obtain a bileaf type pressure-sensitive copying paper (CF) paper.

CI) Color density and speed For biplane pressure-sensitive copying paper, reprinted CB with crystal violet lactone (CVL) as the main pressure-sensitive dye
Place the coated sides of the paper (NW-407 manufactured by Jujo Paper Industries) and CF paper facing each other, and place one piece of high-quality paper on the top and bottom, and then! I-leaf type pressure-sensitive copying paper is made of high-quality paper on the top and bottom, and can be used with an electric typewriter.
Develop a color to Konokuruto blue, and measure the reflectance using a TSS type/\intercolorimeter with an Ann/Kuichi filter.

Measurement of color density It 1 minute after the striking force is generated, 20 hours after color development Time axis 1, X Performed, before color development, 1 minute after color development 1 20 hours after color development
■Reflectance of time. , ■1, and ■2. The difference between the initial color development rate and the final color development rate is very small,
It is preferable that the achieved color development rate is high in terms of both color development speed and density.

(TI) Whiteness of Color Developing (CF) Paper Layer four sheets of CF paper coated and dried using the method described above, and using a blue filter with a Hunter colorimeter, 1. % to find the reflectance. The whiteness (whiteness) of CF paper is expressed as reflectance [F], and the larger [F] is, the whiter the CF paper is, and the difference can be determined within a range of about 0.5 points.

(III) Light resistance Yellowing CF paper that has not developed color is irradiated with sunlight for 10 hours, and the reflectance before and after irradiation is measured as 1, K2 (using a Hunter colorimeter and blue filter). The difference between 1 and 2 is based on the photooxidative yellowing of the polyvalent metal compound of the salicylic acid resin and the photoyellowing of the dispersant.
F indicates the degree of yellowing of paper.

The degree of photoyellowing is expressed as ΔK = K, -K2, and Δ
The smaller K is, the less photo-yellowing of CF paper is.

(JV) Reconversion by NOx Based on JIS L-1055 [Test method for nitrogen oxide gas fastness of dyed products and dyes], CF paper was tested with NaN0□ (
The sample was stored for 1 hour in a sealed container in an atmosphere of NOx gas generated by the reaction between sodium nitrite), H, and PO4 (phosphoric acid), and the degree of yellowing was examined.

The reflectance is measured using a Hunter colorimeter (using a blue filter) before and 1 hour after the N0w gas treatment.

Difference ΔL between reflectance L1 before treatment and reflectance L2 after treatment
= L, the smaller -L2, the NO of CF paper! Indicates less yellowing.

Next, a synthesis example of a salicylic acid resin polyvalent metal compound used in Examples and Comparative Examples will be shown.

Synthesis Example a-1 27.6 g (0.2 mol) of salicylic acid, 253.2 g (2 mol) of benzyl chloride, and 1.5 g of anhydrous zinc chloride as a catalyst were placed in a glass reactor, and nitrogen gas was bubbled through the vessel to adjust the temperature. Linearization was carried out at 70-90°C for 3 hours.

Thereafter, the temperature was raised to 120°C, and aging was performed at the same temperature for 5 hours to complete the reaction. Next, 200 ffl of toluene and 80 g of water were added to the reaction solution with stirring, and the mixture was left to separate. The weight average molecular weight of the obtained resin was 15
It was 50. The upper solvent layer was charged into another glass reactor, and 20 g of 28% ammonia water and 8.0 g of zinc oxide were added thereto.
1 g (0.1 mol) was added and stirred at room temperature for 1 hour.

Thereafter, the solvent was distilled off by heating.

After raising the internal temperature to 150'O and aging for 2 hours,
The product was devolatilized for 30 minutes under a vacuum of 20 mmHg and taken out to obtain 212 g of a reddish-brown transparent zincated salicylic acid resin (yield quantitative).

The softening point of this resin zincide was 86°C. This is referred to as salicylic acid resin polyvalent metal compound [a-1].

Synthesis example a-2 27.8 g (0.2 mol) of salicylic acid, p-methyl-
123.7 g (0.8 mol) of α-methylbenzyl chloride, 100 mJ1 of monochlorobenzene, and Nafion H (trade name, manufactured by Du'Pont) as a catalyst 5
．． 8 g was charged into the reactor and reacted for 5 hours under reflux of the solvent.

After the reaction, 300 mJ1 of warm water was added and stirred at 90°C or higher for 20 minutes to remove the upper water layer. The weight average molecular weight of the produced resin was 850. To this was added 1500 ml of water, and further 36 g (0.4 mol) of a 45% aqueous solution of caustic soda was added dropwise. Then, the temperature is raised to co-distill the solvent,
A slightly cloudy aqueous solution was obtained. This was cooled to 40°C and 29g of zinc sulfate heptahydrate (0,1
An aqueous solution prepared by dissolving mol) in 200 ffi of water was added dropwise. A white precipitate was deposited, which was filtered, washed with water, and vacuum dried to obtain 126 g of salicylic acid resin zinc salt.The zinc content according to zero elemental analysis was 5.05%. This is referred to as salicylic acid resin polyvalent metal compound [a-21].

Synthesis Example a-3 27.8 g (0.2 mol) of salicylic acid, 74 g (0.4 mol) of α-methylbenzyl bromide, and 15.2 g of zinc chloride as a catalyst were charged into a reactor, and nitrogen gas was bubbled through the reactor. Linearization was carried out at a temperature of 60 to 90°C for 5 hours. Thereafter, the temperature was raised to 135°C and the reaction was continued for 2 hours.

The weight average molecular weight of the condensed resin produced was 550.

150 mL of toluene was added to this reaction composition and dissolved. Next, dilute ammonia water was added dropwise at a temperature of 70 to 80°C to adjust the pH to 6. After this, 8.1g of zinc oxide (0,
1 mol) was added thereto and stirred for 1 hour at a temperature of 70 to 80°C to complete the reaction. After the reaction is complete, remove the lower aqueous layer,
Heat the organic layer. The molten resin was then taken out, cooled, and pulverized to obtain 75 g of powder of a zinc-modified salicylic acid resin. The softening point of this galvanized material is 110°C
Met. This was converted into salicylic acid resin polyvalent metal compound [a-3
].

Synthesis example a-4 Salicylic acid 6.9g (0.05 mol), anhydrous zinc chloride 0
．． 2 g and 10 ml of acetic acid were placed in a reactor, and then 48.1 g (0.2 mol) of α-methylbenzylbenzyl chloride was added in portions over 5 hours at an internal temperature of 90 to 95°C. After the addition was completed, the temperature was raised and the reaction was carried out for 3 hours under reflux of acetic acid to complete the reaction. Subsequently, 8.3 g (0,025 mol) of nickel acetate was added to this reaction solution, and acetic acid was distilled off while increasing the temperature. When the temperature reached 150'0, it was evacuated, and this was continued for 1 hour. The softening point of this salicylic acid resin nickelide was 102°C. This is salicylic acid resin polyvalent metal compound [a-4]
shall be.

Synthesis Example a-5 i) Synthesis of salicylic acid resin 27.8 g (0.2 mol) of salicylic acid, 109 g (0.8 mol) of benzyl ethyl ether, and 1.3 g of p-toluenesulfonic acid as a catalyst were charged into a glass reactor. After linearization was carried out at 160 to 170°C for 3 hours per reactor, the temperature was further raised to 180°C and the reaction was carried out for 2 hours.

During this time, 34 g of ethanol was distilled out. Next, the mixture was immediately poured into a shallow dish made of enamel at the same temperature and allowed to stand to solidify the resinous product, yielding 95 g of a reddish-brown transparent resin. The softening point of the obtained resin was 52°C.

(100) Synthesis of polyvalent metal compound of salicylic acid resin Above resin 1
Pour 0g into a flask and heat to 150-160°C.
It was melted at a temperature of Then, while stirring, a mixture of 3 g of zinc benzoate and 2 gtm of ammonium bicarbonate was gradually added to the molten resin over 30 minutes. Thereafter, the mixture was stirred at a temperature of 155 to 165° C. for 1 hour to complete the reaction. After the reaction was completed, the molten resin was taken out, cooled, and then pulverized to obtain 120 g of powder of modified salicylic acid resin and zinc fragrant. The softening point of this zincide is 79°
It was C. This was converted into salicylic acid resin polyvalent metal compound [a-
5].

Synthesis Example a-8 (1) Synthesis of salicylic acid resin Salicylic acid 27.8g (0.2 mol), 3.5-dimethylbenzylethyl ether 83g (0.5 mol)
And 0.75 g of anhydrous zinc chloride as a catalyst was sent to a glass reactor, and after linearization was carried out at a temperature of 150 to 160°C for 4 hours, the temperature was further raised to 170°C and a reaction was carried out for 2 hours. Next, cool the internal temperature to 100°C and add 200ml of toluene.
After dissolving, add 500ml of warm water and heat to 85~100°.
Stir for 20 minutes at C and remove the aqueous layer. This hot water washing and liquid separation operation was repeated two more times to remove unreacted salicylic acid. Then, the solvent was distilled off and the condensate was cooled to obtain 68 g of a reddish-brown transparent resin. The softening point was 58°C.

(11) Synthesis of salicylic acid resin polyvalent metal compound The above resin l
og was dispersed in 0.85 g of caustic soda and 100 g of water. This dispersion was heated to 70°C while stirring to dissolve it. Then, anhydrous zinc chloride (purity 90%) was added in advance while stirring while maintaining the temperature of the solution at 45-50°C.
A solution of 1.2 g dissolved in 30 ml of water was added dropwise over 30 minutes.

A white precipitate was deposited, and after continued stirring at the same temperature for 2 hours, it was filtered, washed with water, and dried to obtain 9.8 g of a white powder. This is referred to as a salicylic acid resin polyvalent metal compound [a-Eil.

Synthesis Example a-7 i) Synthesis of salicylic acid resin 27.6 g (0.2 mol) of salicylic acid, 54 g (0.5 mol) of benzyl alcohol, and 0.8 g of anhydrous zinc chloride and 0.8 g of P-)luenesulfonic acid as a catalyst.
were charged into a glass reactor and aligned at a temperature of 130 to 140°C for 4 hours, and then further heated to 160°C for 2 hours.
Allowed time to react. Next, the internal temperature was cooled to 200°C, 200mM of toluene was added and dissolved, 500mM of warm water was added, and the mixture was stirred at 95-100°C for 20 minutes and the aqueous layer was removed.

This hot water washing and liquid separation operation was repeated two more times to remove unreacted salicylic acid. Then, the solvent was distilled off and the condensate was cooled to obtain 70 g of a light brown transparent resin. Softening point is 46°C
Met.

(II) Synthesis of salicylic acid resin polyvalent metal compound Above resin 1
0g was dispersed in 0.8g of caustic soda and 100g of water and heated to 70°C with stirring to dissolve. Next, while maintaining the temperature of the solution at 45 to 50°C, 1.7 g of anhydrous zinc chloride (90% purity) was added to 30 ml of water while stirring.
A solution dissolved in M was added dropwise over 30 minutes.

A white precipitate was deposited, and after continued stirring at the same temperature for 2 hours, it was filtered, washed with water, and dried to obtain 10.5 g of a white powder.

This is referred to as salicylic acid resin polyvalent metal compound [a-7].

Synthesis Example a-8 (1) Synthesis of salicylic acid resin 27.8 g (0.2 mol) of salicylic m, 24.4 g (0.2 mol) of α-methylbenzyl alcohol, and 3.0 g of P-1 luenesulfonic acid as a catalyst. Pour into a glass reactor and pass nitrogen gas through it to a temperature of 150 to 160°.
After linearization at C for 3 hours, 48.8 g (0.4 mol) of α-methylbenzyl alcohol was added dropwise to the colander over 5 hours at the same temperature. Then, the temperature was raised to 170-180°C and aged for 3 hours. Next, the mixture was immediately poured into an enamel shallow dish at the same temperature and allowed to stand to solidify the resinous product, yielding 88 g of a pale yellow transparent resin. The weight average molecular weight of the obtained resin was 750, and the softening point was 54°C.

(11) Synthesis of polyvalent metal compound of salicylic acid resin 25g of the resin was placed in a flask and heated to a temperature of 150 to 160%.
Melted at a temperature of °C. Then, while stirring, add 20 g of ammonium, 8.8 g of zinc fragrant, and 4 g of ammonium l'fX acid.
g was gradually added to the molten resin over a period of 30 minutes. Thereafter, the mixture was stirred at a temperature of 155 to 165° C. for 1 hour to complete the reaction. After the reaction was completed, the molten resin was discharged, cooled, and then pulverized to obtain 27 g of a powder of zinc benzoate modified salicylic acid resin. The softening point of this galvanized material was 78°C.

This is referred to as salicylic acid resin polyvalent metal compound [a-8].

Synthesis Example a-9 48g of 20% by weight aqueous sodium carbonate solution (0%
, 09 mol) and 21.3 g (0.1 mol) of 2,4-dimethyl-α-methylbenzyl bromide were charged, and the reaction was carried out at +00°C for 200 hours. After the reaction was completed, the mixture was cooled and left to stand to separate into two layers. The lower aqueous layer was removed to obtain an upper organic layer. The yield was 14.5 g, and the composition determined by gas chromatography was as follows.

Others 0. [i wt % then
Using this benzyl compound, a salicylic acid cocondensation resin and a metal compound were produced by the following method. In a reactor, 3.45 g (0,025 mol) of salicylic acid, 14.5 g of the above benzyl compound, and 0.0 aluminum chloride as a catalyst were added.
9 g was charged, and the temperature was raised while blowing nitrogen gas. 1
Distillation of water started at 20°C, and the temperature was further raised and maintained at 150°C while distilling the distilled water out of the system. The reaction was carried out at the same temperature for 7 hours to complete the cocondensation reaction. Immediately after completion of the reaction, the mixture was discharged to obtain 18.2 g of a salicylic acid cocondensation resin. The average molecular weight was 780. Next, this co-condensation resin was poured into a solution of 1.38 g (0,013 mol) of sodium carbonate dissolved in 100 mJ1 of water, and the mixture was heated to 70°C.
The mixture was heated and stirred until dissolved. Then, after lowering the temperature of the solution to 30"C, a solution prepared by dissolving 4.3 g (0,015 mol) of zinc sulfate heptahydrate in 30 aJJ of water was added dropwise over 30 minutes. A white precipitate was deposited. After stirring at the same temperature for 2 hours, the mixture was filtered, washed with water, and dried to obtain 16.5 g of a white powder.This is referred to as salicylic acid resin polyvalent metal compound [a-9].

Synthesis Example b-1 27.8 g (0.2 mol) of salicylic acid, 48.8 g (0.4 mol) of benzyl methyl ether, and 0.78 g of p-toluenesulfonic acid and 0.78 g of anhydrous zinc chloride as a catalyst.
7Ei g was charged into a glass reactor, and nitrogen gas was passed through the reactor for linearization at a temperature of 125 to 135°C for 3 hours. Thereafter, the reaction temperature was raised to 145°C and the reaction was continued for 2 hours. Next, cool the internal temperature to 70°C, add 1,
150 IIll of 2-dichloroethane was charged and cooled to room temperature. Then, 7.5 g of 88% sulfuric acid was charged, and 83.2 g (0.8 mol) of styrene was added dropwise at 20 to 30° C. over 5 hours while stirring vigorously. Thereafter, the reaction was completed by aging at the same temperature for 5 hours. Next, 80 g of water was added to the reaction solution while stirring, and the mixture was allowed to stand still for liquid separation. The weight average molecular weight of the resin obtained here was 1380. The lower solvent layer was charged into another glass reactor, and 20 g of 28% ammonia water and 8.1 g of zinc oxide (
0.1 mol) was added thereto, and the mixture was stirred at room temperature for 1 hour. . Thereafter, the temperature was raised and the reaction was carried out at 60 to 70°C for 1 hour, and then the solvent was distilled off by heating. After raising the internal temperature to 150°C, it was degassed and discharged under a vacuum of 20 mmHg for 30 minutes, and 156 g of a reddish-brown transparent salicylic acid resin zincide was obtained.
was obtained (yield quantitative).

The softening point of this resin was 85°C. This is referred to as salicylic acid resin polyvalent metal compound [b-1].

Synthesis example b-2 27.8 g (0.2 mol) of salicylic acid, p-methyl-
A reactor was charged with 40.8 g (0.3 mol) of α-methylbenzyl alcohol, 100 ml of monochlorobenzene, and 0.7 g of anhydrous zinc chloride as a catalyst, and reacted for 5 hours under reflux of the solvent, followed by distillation in the middle. Water was removed using an ice separator. After the reaction, add 300ml of warm water and heat at 90'C or higher for 2 hours.
Stir for 0 minutes and remove the upper aqueous layer. This hot water washing and liquid separation operation was repeated two more times to remove unreacted salicylic acid. Next, 10 g of concentrated sulfuric acid was added to the monochrome 0-benzene solution cooled to 5°C, and 31.2 g of styrene was added.
(0.3 mol) was added dropwise over 7 hours at a temperature of 5 to 10°C, and after the reaction, it was aged at the same temperature for 3 hours. The weight average molecular weight of the resin at this time was 1150. Water 1500 for this
Add mJ1 and add 38g of 45% caustic soda aqueous solution.
(0.4 mol) was added dropwise. Then, the temperature was raised and the solvent was azeotropically distilled off to obtain a slightly cloudy aqueous solution. This is 40
Cool to °C and pre-mix 29 g of zinc sulfate heptahydrate.
An aqueous solution of (0.1 mol) dissolved in 200 mM water was added dropwise. A white precipitate is precipitated from 1~, which is filtered and washed with water,
Vacuum drying yielded 92 g of salicylic acid resin zinc salt. The zinc content by elemental analysis was 6.78%. This is referred to as salicylic acid resin polyvalent metal compound [b-2].

Synthesis example b-3 Same mole of benzyl alcohol instead of benzyl methyl ether, 83.2 g (0.8 mole) of styrene
172 g of a pale reddish-brown zincated salicylic acid cocondensation resin was obtained in the same manner as in Synthesis Example b-t, except that 104 g (1.0 mol) of styrene was used instead of styrene. The softening point of this resin is 58° C., and this is designated as salicylic acid resin polyvalent metal compound To-3].

Examples and Comparative Examples Example a-1 2-acrylamido-2-methylpropanesulfonic acid N
25 g of a 20% aqueous solution of polyvinyl alcohol (average degree of polymerization 300, degree of saponification 90%) containing 5 mol% a unit and water
135.7 g of the polyvalent metal compound of salicylic acid resin obtained in Synthesis Example a-1 [a-II] was added to an aqueous solution whose pH was adjusted to 8.0, and stirred to form a slurry. After that, it was treated with a sand grinder using glass beads with a diameter of 1 mm for 3 hours until the average particle diameter was 2.5 mm.
4 g m of a white aqueous suspension (solids content 40% by weight) was obtained.

Example a-2 An ethylene sulfonic acid-vinyl acetate copolymer with an ethylene sulfonic acid content of 3 mol% was saponified with caustic soda,
Polyvinyl alcohol containing 3 mol% of sulfonic acid groups and 1 mol% of acetyl groups (average degree of polymerization 30
0) was obtained.

20 of this polyvinyl alcohol having sulfonic acid groups
% aqueous solution 50 [and water! 100 g of the salicylic acid resin polyvalent metal compound [a-2] obtained in Synthesis Example a-2 was charged into an aqueous solution (pH 8,4) in which 90 g was mixed in advance and stirred to form a slurry. , using a zirconium measure with a diameter of 5 mm) for 5 hours under water cooling to obtain a white aqueous suspension (solid content: 45
% by weight, average particle diameter of 2.3 square meters) was obtained.

Example a-3 Polyvinyl alcohol was added to 80% sulfuric acid (kept at 0°C) and reacted, followed by neutralization and purification. 25 g of a 20% aqueous solution of sulfono 1 (and containing 10 mol% of acetyl groups) corresponding to mol% and water 8
A pre-mixed aqueous solution of 5g was heated to 90°C,
Salicylic acid resin polyvalent metal compound obtained in Synthesis Example a-3 [a-
3] Add long and homomixer (manufactured by Tokushu Kikako)
After high-speed emulsification and dispersion, it was cooled to room temperature to form a white aqueous suspension with a solid content of 50% by weight (average particle size 2.1 m).
) was obtained.

Example a-4 15 g of a 20% aqueous solution of polyvinyl alcohol containing 5 mol% of ethylene sulfonic acid (average degree of polymerization 250, degree of saponification 88%), sodium salt of polystyrene sulfonic acid 3
100 g of fine powder of the salicylic acid resin polyvalent metal compound [a-4] obtained in Synthesis Example a-4 was added to an aqueous solution prepared by mixing 6.7 g of a 0% aqueous solution with 140.8 g of water and stirred to form a slurry. A white aqueous suspension (solid content: 40
% by weight, average particle size 2.4 μm).

Example a-5 Polystyrene sulfonic acid sodium salt (molecular weight 1000
0, degree of sulfonation 70%) and 135.7 g of water were mixed in advance and the pH was adjusted to 8.0. A white aqueous suspension (solid content: 40 g) was charged in the same manner as in Example a-1.
ff1) for weight % and average particle diameter of 2.1 was obtained.

Example a-8 Salicylic acid obtained in Synthesis Example a-2 was added to a mixture of 30 g of a 30% aqueous solution and 8 L g of water (adjusted to pH 8.5 with dilute ammonia water). Resin polyvalent metal compound [a
-2] was charged and stirred to form a slurry, followed by dispersion treatment in the same manner as in Example a-2 to obtain a white essential suspension (solid content 45% by weight, average particle size 1.9 mm). ) was obtained.

Example a-7 10 g of a 20% aqueous solution of polyvinyl alcohol containing 5 mol% of ethylene sulfonic acid (average degree of polymerization 250, degree of saponification 88%), 3 g of polystyrene sulfonic acid sodium salt
Fine powder 1 of salicylic acid resin polyvalent metal compound [a-3] obtained in Synthesis Example a-3 was added to an aqueous solution in which 5 g of 0% aqueous solution (Nippon Gosei OKS-33713) was mixed with 112.1 g of water.
A closed type sand grinder (Dyn.

ml) for 1.5 hours, and the average particle size was 2.4.
A white aqueous 2% liquid (solid content: 48% by weight) of p-111 was obtained.

Example a-8 13.3 g of 30% aqueous solution of sulfonated sodium styrene-maleic acid copolymer @ (Area S-9MA-IQQQ) and 11% of water. , 8 g of the salicylic acid resin polyvalent metal compound obtained in Synthesis Example a-4 [a-4
]100g is charged and the diameter is 1. Processed for 2 hours in a horizontal sand mill using OI glass beads as a measure to reduce the average particle size to 2.
．． 3 ml of a white aqueous suspension (solids content 45% by weight) was obtained.

Example a-9 Same as Example a-1 except that salicylic acid resin polyvalent metal compound [a-5] was used instead of salicylic acid resin polyvalent metal compound [a-1], except that the average particle diameter was 2. 5 gm of a white aqueous suspension (solids content 40% by weight) was obtained.

Example a-10 The same procedure as Example a-2 was carried out except that the salicylic acid resin polyvalent metal compound [a-8] was used instead of the salicylic acid resin polyvalent metal compound [a-2], so that the average particle diameter was 2. A white aqueous suspension (solids content: 45% by weight) of 4 ml was obtained.

Example a-11 Same as Example a-3 except that salicylic acid resin polyvalent metal compound [a-2] was used instead of salicylic acid resin polyvalent metal compound [a-3] +'-VU stirring and slurry. A white aqueous suspension (solid content: 40% by weight) with an average particle size of 2.5 μm was obtained by dispersion treatment in the same manner as in Example a-1.

Example a-12 The same procedure as Example a-3 was carried out except that the salicylic acid resin polyvalent metal compound [a-9] was used instead of the salicylic acid resin polyvalent metal compound [a-3], with an average particle size of 2. A white aqueous suspension (solids content: 50% by weight) of 1 Rue was obtained.

Example a-13 A white aqueous suspension was prepared in the same manner as in Example a-5 except that salicylic acid resin polyvalent metal compound (a-11 was replaced with salicylic acid resin polyvalent metal compound [a-7]). (Solid content 4
0% by weight and an average particle size of 2.1 gm).

Example a-14 Instead of salicylic acid resin polyvalent metal compound [a-2],
A white aqueous suspension (solid content: 45% by weight, average particle size: 19 μm) was obtained in the same manner as in Example a-6, except that the salicylic acid resin polyvalent metal compound [a-8] was used.

Example a-15 Instead of the salicylic acid resin polyvalent metal compound [a-4], a salicylic acid resin polyvalent metal compound (average particle diameter 2.3 μm was prepared in the same manner as in Example a-8 except that the a-th one was used) A white aqueous suspension (solids content: 45% by weight) was obtained.

Example a-18 Instead of salicylic acid resin polyvalent metal compound [a-4],
Except for using the salicylic acid resin polyvalent metal compound [a-8], it was stirred and slurried in the same manner as in Example a-4, and then dispersed in the same manner as in Example a-1 to obtain a coat for an average particle size of 2.1. A white aqueous suspension (solids content: 40% by weight) was obtained.

Example a-17 2-acrylamido-2-methylpropanesulfonic acid N
20 g of a 20% aqueous solution of polyvinyl alcohol (average degree of polymerization 300, degree of saponification 90%) containing 5 mol% a units and 3.3 g of a 30% aqueous solution of sodium salt of a sulfonated styrene cocondensation resin were added to 157 g of wood. The salicylic acid condensation resin polyvalent gold compound obtained in Synthesis Example a-5 [a-
5] was charged, stirred and slurried, and then processed for 2 hours in the horizontal sand mill used in Example a-8 to obtain a white aqueous suspension (solid content) with an average particle size of 2.2 gm. 40
% by weight) was obtained.

Examples a to 18 The average particle size was 2.2 in the same manner as in Example a-7 except that salicylic acid resin polyvalent metal compound [a-9] was used instead of salicylic acid resin polyvalent metal compound [a-3]. A white aqueous suspension (solids content: 48% by weight) was obtained.

Example a-19 12 g of a 20% aqueous solution of sulfonated polyvinyl alcohol (containing sulfonic groups corresponding to 5 mol% of the total monomer units and 10 mol% of acetyl groups), 30% aqueous solution of styrene-maleic acid copolymer sodium salt 10g to 11 parts water
100 g of the salicylic acid resin polyvalent metal compound [a-2] obtained in Synthesis Example a-2 was added to the aqueous solution mixed with 4 g, stirred,
After slurrying, it was dispersed for 5 hours under water cooling using the attritor used in Examples a to 2 to obtain a white aqueous suspension (solid content 45% by weight, average particle size 2.6 m). Ta.

Comparative Example a-1 Sulfone M2. A brown aqueous suspension with an average particle size of 2.8 gm was prepared in the same manner as in Example a-1, except that the same amount of the sodium salt of the formaldehyde condensate of naphthalene sulfonic acid was used in place of the polyvinyl alcohol having H. I got the liquid.

Comparative Example a-2 Partially saponified polyvinyl alcohol (Clary, Poval) was used instead of polyvinyl alcohol having a sulfonic acid group.
An aqueous suspension was prepared in the same manner as in Examples d to 1, except that the same amount of 117) was used. Significant foaming occurred during stirring and slurrying before sand grinder treatment, and during sand grinder treatment, and it took a day and night for the foam to disappear even after treatment, resulting in a markedly poor working efficiency. The resulting aqueous suspension was a viscous white aqueous suspension with an average particle size of 2.6 μm.

Comparative Example a-3 Salicylic acid resin polyvalent metal compound obtained in Synthesis Example a-2 (a-
Example a-
Treat with a sand grinder in the same manner as in 1 to obtain a brown aqueous suspension (solid content 47.8% by weight, average particle size 2.5 m)
I got it.

Comparative Example a-4 Salicylic acid resin polyvalent metal compound [a
-II instead of salicylic acid resin polyvalent metallization [a
A brown aqueous suspension having an average particle size of 2.8 g tn was obtained in the same manner as in Comparative Example a-1 except that -57 was used.

Comparative Example a-5 Salicylic acid resin polyvalent metal compound [a
-II instead of salicylic acid resin polyvalent metallization [a
-5] Aqueous suspension formation was carried out in the same manner as in Comparative Example a-2 except that Comparative Example a-2 was used. Significant foaming occurred during stirring and slurrying before the sand grinder treatment and before the sand grinder treatment, and it took a day and night for the foam to disappear even after the treatment, resulting in a markedly poor working efficiency. The resulting aqueous suspension was a viscous white aqueous suspension with an average particle size of 2.6 μm.

Comparative Example a-8 A brown aqueous suspension was prepared in the same manner as Comparative Example a-3, except that salicylic acid resin polyvalent metal compound [a-8] was used instead of salicylic acid resin polyvalent metal compound [a-2]. (Solid content 47
．． 8% by weight and an average particle size of 2.5 m).

Comparative Example a-7 In Comparative Example a-5, polycarboxylic acid sodium salt (CS
Sodium salt of copolymer of distillate and maleic anhydride...
-Nippon Zeon Quinflow 540) When treated using the same ox, the dispersion state was poor and the whole became a hard paste, and could not be taken out as an aqueous suspension.

Comparative Example a-8 170 g of p-phenylphenol, 22.5 g of 80% paraformaldehyde, 2.0 g of P-toluenesulfonic acid
Then, 200 g of benzene was placed in a glass reactor, heated while stirring, and reacted at 70 to 80° C. for 2 hours while water produced by the reaction was distilled out of the system along with the benzene. After reaction 10% aqueous sodium hydroxide solution 3
20 g was added, and benzene was distilled off by water vapor distillation.

Next, after cooling, dilute sulfuric acid was added dropwise, and the precipitated p-phenylphenol formaldehyde polymer was collected by filtration, washed with water, and dried to obtain 176 g of white powder.

100 g of this p-phenylphenol formaldehyde polymer powder was dispersed into a slurry in 160 g of water in which 12 g of a 25% aqueous solution of polycarboxylic acid sodium salt (NOF Polystar OM) was dissolved. A white aqueous suspension (solid content 39.6% by weight, average particle size 2.5 gm) was obtained by processing with a grinder.

The above Example a-1-a-19 and Comparative Examples a-1 to a-
The properties of the aqueous suspension and water-based paint and the performance of the pressure-sensitive copying paper obtained in step 8 are summarized in Table 1.

Example b-1 Salicylic acid resin polyvalent metal compound obtained in Synthesis Example b-1 [b-
100 g of T powder of No. 11 was mixed with polystyrene sulfonic acid sodium salt (molecular weight: 5000, degree of sulfonation: 65%).
Mix 25 g of 0% aqueous solution and 137.5 g of water in advance and
) It was charged into an aqueous solution whose I was adjusted to 8.0, stirred and made into a slurry, and then processed for 3 hours with a sand grinder using glass beads with a diameter of 1111 II+ as a measure, so that the average particle diameter was 2.5 mm. white aqueous suspension (solids content 40
% by weight) was obtained.

Example b-2 A white aqueous suspension ( A solid content of 50% by weight and an average particle diameter of 2.4 Bl!l) was obtained.

Example b-3 Salicylic acid resin polyvalent metal compound obtained in Synthesis Example b-2 [b-
100 g of fine powder of No. 21 was mixed with sodium salt of sulfonated styrene maleic anhydride copolymer (ARCOChew,
S-9MA3000) 130g of water dissolved in 5g
After slurrying, the mixture was treated with a sand grinder in the same manner as in Example b-1 to obtain a white aqueous suspension. (Solid content 44.7% by weight, average particle size 3.4 lm
) Example b-4 Same as Example b-3 except that a sodium salt of sulfonated styrene cocondensation resin (Kanebo NSC, NARLEX-D82) was used instead of the sodium salt of styrene/maleic anhydride copolymer sulfonate. In the same manner, a white aqueous suspension (solid content: 50% by weight, 1% by weight, average particle size: 2.71% by weight) was obtained.

Example b-5 The mixture obtained in Synthesis Example b-1 was added to an aqueous solution prepared by mixing 50 g of a 20% aqueous solution of polyvinyl alcohol (average degree of polymerization 250, degree of saponification 88%) with an ethylene sulfonic acid content of 5 mol % and 135 g of water. 100 g of fine powder of salicylic acid resin polyvalent metal compound [b-11] was charged, stirred to form a slurry, and then dispersed in the same manner as in Example b-1 to form a white aqueous suspension with an average particle size of 2.3 m. A cloudy liquid (solid content 40% by weight) was obtained.

Example b-e Sodium salt of sulfonated styrene cocondensation resin (Kanebo NSC, NARLEX-082) 30% aqueous solution 13
．． The salicylic acid resin polyvalent metal compound obtained in Synthesis Example b-2 [b-211
A white aqueous suspension (solid content 50% by weight) with an average particle size of 2.5 pI11 was obtained by processing for 2 hours in a horizontal sand mill using glass beads with a diameter of 1.0 ml11.
) was obtained.

Example b-7 20 g of a 20% aqueous solution of 15 mol% polyvinyl alcohol containing ethylene sulfonic acid (average degree of polymerization 250, degree of saponification 88%) and 3.3 g of a 30% aqueous solution of polystyrene sulfonic acid ammonium salt were mixed in 110 g of water. The salicylic acid resin polyvalent metal compound obtained in Synthesis Example b-t [b
-1] was charged and treated with the sand grinder used in Example a-7 for 1.5 hours, with an average particle size of 2.
．． A white aqueous suspension (solid content: 45% by weight) of Gin was obtained.

Example b-8 The average particle size was 2.8 p in the same manner as in Example a-1 except that the salicylic acid resin polyvalent metal compound [b-1] was used instead of the salicylic acid resin polyvalent metal compound [a-11]. -rm white aqueous suspension (solid content 40% by weight) was obtained.

Example kl-s A white aqueous ASJ liquid ( Solid content 45
% by weight, average particle size 2.8 pm).

Example b-10 Same as Example a-3 except that salicylic acid resin polyvalent metal compound [b-3] was used instead of salicylic acid resin polyvalent metal compound [a-3], solid content 50% by weight. A white aqueous suspension (average particle size: 2.1 pm) was obtained.

Example b-11 25 g of a 20% aqueous solution of polyvinyl alcohol containing 5 mol% of ethylene sulfonic acid (average degree of polymerization 250, degree of saponification 88%), sodium salt of polystyrene sulfonic acid 3
The salicylic acid resin polyvalent metal compound obtained in Synthesis Example b-1 [b-1
After charging 100 g of fine powder from No. 1 and stirring to form a slurry, grind No. 2 using a sand mill using glass beads with a diameter of 1 mm as a measure.
A white aqueous suspension (solid content: 40% by weight, average particle size: 2.2 μm) was obtained after treatment for a period of time.

Example b-12 The average particle diameter was 2.1 in the same manner as in Example a-17 except that salicylic acid resin polyvalent metal compound [b-2] was used instead of salicylic acid resin polyvalent metal compound [a-5]. A white aqueous suspension of ILm (solids content 40% by weight) was obtained.

Example b-13 20 g of a 20% aqueous solution of polyvinyl alcohol containing 3 mol% of ethylene sulfonic acid (average degree of polymerization 300, degree of saponification 88%) and sodium salt of polystyrene sulfonate (molecules 310,000, degree of sulfonation 94%) 100 g of salicylic acid resin polyvalent metal compound [b-3] was added to an aqueous solution prepared by mixing 5 g of a 30% aqueous solution with 139 g of water, stirred to form a slurry, and the average particle size was 2.1 in the same manner as in Example b-1.
A white aqueous suspension (solids content 40% by weight) of gm was obtained.

Example b-14 20 g of a 20% aqueous solution of sulfonated polyvinyl alcohol (containing sulfonic groups corresponding to 5 mol % of the total monomer units and 10 mol % acetyl groups) and polystyrene sulfonic acid sodium salt (molecular weight 5000, degree of sulfonation 90)
%) was mixed with 139 g of water, and the salicylic acid resin polyvalent metal compound obtained in Synthesis Example b-2 [
After charging 100 g of [b-2] and stirring to form a slurry,
A white aqueous suspension (solid content 40% by weight, average particle size 2.1 m) was obtained by processing in the same manner as in Example a-8.

Example b-15 Polystyrene sulfonic acid sodium salt (molecular weight 3000
A white aqueous suspension (solid content: 45% by weight) having an average particle size of 2.0 gm was obtained by processing in the same manner as in Example b-7, except that a sulfonation degree of 60%) was used.

Comparative Example b-1 The average particle size was 2.8 p in the same manner as Comparative Example a-1 except that salicylic acid resin polyvalent metal compound [b-11] was used instead of salicylic acid resin polyvalent metal compound [a-1]. A brown aqueous suspension of -m was obtained.

Comparative Example b-2 An aqueous suspension was prepared in the same manner as Comparative Example a-2 except that salicylic acid resin polyvalent metal compound [b-11] was used instead of salicylic acid resin polyvalent metal compound [a-1]. . Significant foaming occurred during stirring and slurrying before sand grinder treatment and during sand grinder treatment, and it took a day and night for the foam to disappear even after treatment, resulting in a markedly poor working efficiency. The resulting aqueous suspension has an average particle size of 2.7
It was a viscous, white aqueous suspension of I.

Comparative Example b-3 A brown aqueous suspension was prepared in the same manner as Comparative Example a-3 except that salicylic acid resin polyvalent metal compound [b-21] was used instead of salicylic acid resin polyvalent metal compound [a-2]. (Solid content 47
．． 8% by weight, average particle size 3.0 lm).

The properties of the aqueous suspensions and water-based paints and the performance of the pressure-sensitive copying papers obtained in Examples b-t to b-15 and Comparative Examples b-1 to b-3 are summarized in Table 2.

〔Effect of the invention〕

As is clear from the above, according to the present invention, by using the anionic water-soluble polymer of the present invention as a dispersant when obtaining an aqueous suspension of a polyvalent metal compound of a salicylic acid resin, (+) coloring is reduced. It is highly white in color, (2) is extremely stably dispersed, exhibiting low agglomeration and sedimentation even during long-term storage at high temperatures, and (3) provides an aqueous suspended PA solution that is stable over a wide pH range, and (4) Less thickening and foaming during aqueous suspension work; (5) Water-based paint for pressure-sensitive copying paper production. (mixed with other water-based paint components) has excellent natural and mechanical stability; (6) there is little foaming during preparation and application of the water-based paint;
It has excellent properties such as excellent coating workability and (7) providing excellent pressure-sensitive copying paper that does not deteriorate in quality due to the dispersant itself yellowing when exposed to light or during storage. It has become possible to produce an aqueous suspension of a polyvalent metal compound of salicylic acid resin.

Claims (1)

[Claims] (1) Formulas (I), (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups with 1 to 12 carbon atoms, aralkyl groups , an aryl group or a cycloalkyl group, R_3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and the structural unit (I) is 5
The structural unit (II) is 60 to 95 mol%, the structural unit (I) is bonded to the structural unit (II) through the α carbon, and the structural unit (II) is bonded to the structural unit (II) via the α carbon. Polyvalent metallized salicylic acid resin (a) that can be bonded to the benzene ring of II) via the α carbon and has a weight average molecular weight of 500 to 10,000, or formula (III), (IV), ( V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and/or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V
) (In the formula, R_1 and R_2 are hydrogen atoms or carbon atoms 1 to 1
It represents an alkyl group, an aralkyl group, an aryl group or a cycloalkyl group up to 2, R_3 and R_6 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R_4 and R_5 represent a hydrogen atom or a methyl group. ), the structural unit (III) is 5 to 35 mol%, the structural unit (IV) is 10 to 85 mol%, and the structural unit (V) is 4 to 8 mol%.
5 mol%, and the structural unit (m) is α of the structural unit (IV).
Bonded through carbon, structural unit (IV) is structural unit (IV)
The structural unit (V) can also be bonded to the benzene ring of the structural unit (IV) and/or (V) via the α carbon, and the weight average molecular weight polyvalent metallized salicylic acid resin (b) having a sulfonic acid group of 500 to 10,000, (A) an anionic water-soluble polymer consisting of a polyvinyl alcohol derivative or a salt thereof having a sulfonic acid group in the molecule, and/or (B ) General formula (VI) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (VI) (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M represents an alkali metal or ammonium ion.) An aqueous suspension of a polyvalent metal compound of salicylic acid resin dispersed in the presence of an anionic water-soluble polymer made of a homopolymer or copolymer containing the compound as an essential component.