JPH09248440A - Dispersant for aqueous fine particle dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To show sufficient dispersion stabilizing effect in small addition quantity by using a polyether compd. in combination with a specific sulfonic acid group-containing polymer and/or a salt thereof. SOLUTION: A polymer obtained by polymerizing a polymerizable aromatic sulfonic acid type monomer (a) and a monomer copolymerizable with the monomer (a) and containing the monomer (a) as an essential component, a sulfonated substance of a polymer obtained by polymerizing a polymerizable aromatic monomer (c) and a monomer copolymerizable with the monomer (c) and/or a salt thereof, a polyether compd., a sulfated substance thereof and a salt thereof are together used. This dispersant has excellent dispersing capacity and can relalize a highly conc. low viscosity aq. fine particle dispersant by a small use amt. and is excellent in stability with the elapse of day and can suppress a rise of viscosity even if allowed to stand for a long time after preparation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous fine particle dispersion which is widely used in various fields including the paper manufacturing industry, the paint industry, the agrochemical industry, and the like, and has excellent fluidity and excellent fluidity with respect to these dispersions. The present invention relates to a dispersant for an aqueous fine particle dispersion that imparts stability.

2. Description of the Related Art In an industry that uses various inorganic and organic pigments, dyes, disperse dyes, and atomized biocides for agrochemicals, such as the paper industry, pigment / paint industry, printing / ink industry, agrochemical industry, etc. Aqueous dispersions are widely used and usually have high concentration, low viscosity and high fluidity for good pumpability, and good stability during storage and transportation. It has been demanded. Conventionally, as dispersants for these aqueous dispersions, in addition to phosphoric acid-based soda salts such as sodium tripolyphosphate and sodium hexametaphosphate, organic polymer-based such as polyacrylic acid salts, naphthalene sulfonates and their formalin condensates. A dispersant is used. However, such a dispersant is not yet satisfactory in terms of dispersion effect such as high concentration performance and fluidization performance and stability over time. In order to solve these drawbacks, JP-A-1-104335 and JP-B-6-782.
No. 02 proposes to use a styrene sulfonate polymer as a dispersant. However, although a suitable improvement effect was found in the dispersion effect, it was still insufficient, and it was not at a satisfactory level in terms of stability over time.

[0002]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a dispersant for an aqueous fine particle dispersion, which shows a sufficient dispersion stabilizing effect in a small amount of addition to various aqueous fine particle dispersions. .

The present invention was made based on the finding that the above problem can be efficiently solved by using a polyether compound in combination with a specific sulfonic acid group-containing polymer and / or salt thereof. Of. That is, the present invention
(A) At least one sulfonic acid group-containing polymer and / or salt thereof selected from the following polymers (AI) and (A-II), and (B) polyether compound and its sulfated product. And a dispersant for an aqueous fine particle dispersion, which is used in combination with at least one compound selected from the group consisting of salts thereof. (AI): a polymer obtained by polymerizing at least one monomer selected from the group consisting of (a) a polymerizable aromatic sulfonic acid-based monomer and (b) a monomer copolymerizable with (a). And a polymer containing the monomer (a) as an essential component. (A-II): a polymer obtained by polymerizing at least one kind of monomer selected from (c) a polymerizable aromatic hydrocarbon monomer and (d) a monomer copolymerizable with (c). And a sulfonated product of a polymer containing the monomer (c) as an essential component.

[0003]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer of the component (A) of the present invention is
It is a polymer containing a sulfonic acid group and an aromatic hydrocarbon group in the molecule. Then, a polymer in which this sulfonic acid group is derived from a monomer, for example, a polymer obtained by polymerizing an aromatic hydrocarbon-based monomer having a sulfonic acid group alone or together with other monomers is the polymer (AI). . On the other hand, a polymer obtained by polymerizing a monomer having a sulfonation reaction point to obtain a polymer and then introducing a sulfonic acid group into the polymer by a sulfonation reaction is the polymer (A-II). (A-
In obtaining the polymer of I), the monomer composition ratio of the aromatic sulfonic acid monomer of (a) and the monomer of (b) is preferably mol%, and (a) / (b) = 40/60 to 100/0 is preferable. , And more preferably 50/50 to 100/0. The (a) group monomer is preferably an aromatic sulfonic acid monomer having 8 to 15 carbon atoms, and specific examples thereof include styrenesulfonic acid, α-methylstyrenesulfonic acid, vinyltoluenesulfonic acid, vinylnaphthalenesulfonic acid and the like. To be The (b) group monomer is preferably styrene, an unsaturated carboxylic acid monomer having 3 to 6 carbon atoms and its alkyl (having 1 to 22 carbon atoms) or a polyalkylene glycol ester, and specific examples thereof include acrylic acid, methacrylic acid, (Anhydrous) maleic acid, fumaric acid,
Examples thereof include itaconic acid and polyalkylene glycol esters thereof (polyethylene glycol [p = 1 to 30] ester). The polymer of (AI) is preferably water-soluble.

The polymerizable aromatic hydrocarbon monomer (c) constituting the polymer (A-II) has 8 to 8 carbon atoms.
Aromatic monomers of 15 are preferable, and specific examples thereof include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, indene and the like. Further, as the other monomer copolymerizable with the monomer (c) of (d), an aliphatic vinyl monomer having 3 to 12 carbon atoms is preferable, and specific examples thereof include butadiene, diisobutylene, cyclopentadiene, dicyclopentadiene. , Isoprene,
Acrylic acid, methacrylic acid, maleic acid (anhydrous), fumaric acid, itaconic acid and the like can be mentioned. In obtaining the polymer (A-II), the monomer composition ratio of the polymerizable aromatic hydrocarbon-based monomer (c) and the other monomer copolymerizable with the monomer (c) (d) is mol%, (C) /
(D) = 30/70 to 100/0 is suitable, preferably 40/60 to 100/0, and more preferably 50/50 to 100/0. By sulfonating such a polymer or further converting it into a salt (AI
A polymer of I) is obtained. The sulfonation can be carried out by using a sulfonating agent such as sulfuric anhydride, chlorosulfonic acid, sulfuric anhydride / Lewis base complex, and applying any sulfonation method. In the sulfonation of the polymer, the ratio of the units actually sulfonated to the total amount of units to be sulfonated is represented as a sulfonation rate,
The sulfonation rate of the polymer is preferably 70 to 100%, more preferably 80% to 100%.

The weight average molecular weight of the obtained sulfonic acid group-containing aromatic hydrocarbon polymer is preferably 1,000 to 200,000, and more preferably 1,000 to 100,000. In the present invention, these sulfonic acid group-containing polymers are used in the form of free acid or salt. As the salt in the component (A), as monovalent salts, alkali metal salts such as lithium, sodium and potassium, ammonium salts,
Or monoethanolamine, diethanolamine,
Organic amine salts such as triethanolamine, morpholine, ethylamine, butylamine, coconut oil amine and tallow amine; as divalent salts, alkaline earth metal salts such as calcium, magnesium and barium, and bifunctional organics such as ethylenediamine and hexamethylenediamine. Amine salts; trivalent salts include aluminum salts, trifunctional organic amine salts such as diethylenetriamine; and polyfunctional organic amine salts such as polyethyleneimine.

The polyether compound, its sulfated product and its salt used as the component (B) in the present invention may be produced by any method, and when the polymer sulfonated product (A-II) is produced, ( A-II) A raw material solution prepared by dissolving the polymer and the polyether compound is introduced with a sulfonating agent such as sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfuric anhydride, sulfuric anhydride / Lewis base complex, A sulfonation reaction may be carried out by applying the method, resulting in a mixture of the component (A) and the component (B). The component (B)
It is preferably water-soluble. Examples of the polyether compound include those represented by the formula (1).

[0007]

## STR00001 ## X ₁ --O-(R ₁ --O) n --X ₂ (1) (In the formula, X ₁ and X ₂ are independently hydrogen and carbon atoms 1
To an alkyl group having 1 to 30 carbon atoms, a phenyl group and an alkyl group having 1 to 9 carbon atoms as a substituent, R ₁ is an alkylene group having 2 to 4 carbon atoms, and n is 1 to 30. Represents the number of. At least _one of X ₁ and X ₂ is hydrogen. Examples of the polyether compound of the formula (1) include polyethylene glycols, polypropylene glycols, polyethylene / propylene glycols, polyoxyethylene alkyl ethers, and polyoxyethylene alkylphenyl ethers. Of these, polyethylene glycols are preferred. The sulfated compounds of these polyether compounds are sulfated compounds of these formulas (1), and their salts include alkali metal salts, alkaline earth metal salts, ammonium salts, various amine salts and the like. . In the dispersant for an aqueous fine particle dispersion of the present invention, the above-mentioned component (A) and component (B) can be used together in any ratio, but the weight ratio is 99.9 / 0.1 to 90 /.
It is desirable to use in the range of 10 and preferably 99.9
/0.1 to 95/5.

The dispersant of the present invention is generally applicable to all cases in which fine particles are dispersed in an aqueous medium. For example,
Inorganic pigments such as heavy and light calcium carbonate, kaolin, clay, satin white, titanium oxide and talc, inorganic fine particles such as cement, silica and ceramics, azo pigments such as disazo yellow and lake red C, phthalocyanine such as copper phthalocyanine blue -Based pigments, anthraquinone-based pigments, organic pigments such as carbon black, azo-based and anthraquinone-based disperse dyes, simazine [2-chloro-4,6-bis (ethylamino) -1,
3,5-triazine; herbicide], tsumaside [m-tolylmethylcarbamate; insecticide], daconyl (tetrachloroisophthalonitrile; fungicide), sappiran (p
-Chlorophenyl-p-chlorobenzene sulfonate;
It is possible to disperse biocides such as acaricide and organic fine particles such as coal, coke and carbon black. Further, the dispersant of the present invention, as an inorganic, organic pigment, a disperse dye, and a dispersion stabilizer for an aqueous fine particle dispersion such as a biocide, lowers the viscosity of the dispersion slurry to make the slurry more concentrated. It is also suitable for imparting long-term storage stability without increasing viscosity of the slurry due to aging. In the present invention, the concentration of fine particles in the dispersion slurry is 40 to 80% by weight (hereinafter,%
Abbreviated), preferably 55-75% is suitable,
In the case of organic fine particles, 10 to 80%, preferably 20
It is suitable to be 70%, more preferably 25-65%. The amount of dispersant used is 0.01 to 10%, preferably 0.05 to 7%, and more preferably 0.1 to 5%. When dispersing the disperse dye,
10% or more may be used.

When an aqueous fine particle dispersion is produced by adding the dispersant of the present invention, the dispersant may be added to the dispersoid fine particle powder as it is, or may be added as an aqueous solution having a concentration of about 5 to 50%. Alternatively, water can be added to obtain a desired concentration, and the dispersion can be obtained by stirring and mixing with a stirrer equipped with stirring blades such as paddle type blades and turbine blades, and a homomixer. . In addition, inorganic pigments, organic pigments, disperse dyes, dispersoids such as biocides, water, and after mixing the dispersants, by wet milling to a desired particle size with various mills such as a ball mill, a rod mill, and a sand grinder. It is also possible to obtain the dispersion. The order of adding the dispersoid, water and the dispersant can be appropriately changed depending on the circumstances.

EFFECT OF THE INVENTION The dispersant of the present invention has extremely excellent dispersibility in various inorganic and organic substances, and can be used to realize a high-concentration and low-viscosity aqueous fine particle dispersion by using a small amount, and The stability of the dispersion over time is excellent, and an increase in viscosity can be suppressed even when the dispersion is prepared and left standing for a long time. The dispersant of the present invention can also be used as a leveling agent for dyes, paint dispersion, color developer dispersion, microcapsule dispersion, and the like. Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0010]

【Example】

Synthesis Example 1 100 parts by weight of sodium p-styrenesulfonate was added to purified water 4
It was dissolved in 100 parts by weight. After substituting this with nitrogen,
0.8 parts by weight potassium persulfate and 1.5 parts ammonium persulfate
Parts by weight were added, and polymerization was carried out at 50 ° C. for 6 hours. The obtained polymer was neutralized with a 10% sodium hydroxide aqueous solution and then concentrated to obtain a polystyrene polystyrene sulfonate aqueous solution. The properties are shown in Table 1. Synthesis Examples 2 to 5 The total amount of the monomers shown in Table 1 (at the compounding ratio) is 100
Solution polymerization was carried out according to Synthesis Example 1 except that parts by weight, potassium persulfate and ammonium persulfate as initiators were used in appropriate amounts, and a neutralizing agent such as a salt shown in Table 1 was used. The properties of the obtained polystyrene sulfonate copolymer are shown in Table 1.

Synthesis Example 6 100 parts by weight of polystyrene was added to 1,2-dichloroethane 4
It was dissolved in 100 parts by weight to prepare a raw material solution. This raw material solution was continuously supplied to a sulfonation reactor equipped with a turbine-type stirrer together with sulfuric acid anhydride as a sulfonating agent,
The sulfonation reaction was carried out at ° C. In this case, the feed rate is
Raw material solution 24 g / min, sulfuric anhydride 4.07 g / min, molar ratio of sulfuric anhydride to styrene units in polystyrene is 1.1
0, and the reactor used had a jacket and a capacity of 400 ml. The obtained sulfonated product was neutralized with a 10% sodium hydroxide aqueous solution, and then separated and concentrated to obtain an aqueous polystyrene sulfonate Na solution. The properties are shown in Table 1. Synthetic Examples 7 to 12 100 parts by weight of the styrene-based polymer shown in Table 1 (by its compounding ratio) was used in total, and the molar ratio of sulfuric anhydride to styrene unit and isoprene unit in the styrene-based polymer was 1.
The sulfonation was carried out according to Synthesis Example 1 except that the neutralizing agent was 10 and the salt shown in Table 1 was used. The properties of the sulfonated styrene polymer thus obtained are shown in Table 1.

Synthesis Example 13 In addition to 100 parts by weight of polystyrene, 2 parts by weight of polyethylene glycol (molecular weight about 200) was added to 1,2-dichloroethane 4
Sulfonation was carried out in accordance with Synthesis Example 1 except that the starting material solution was prepared by dissolving in 100 parts by weight. The properties of the obtained polystyrene sulfonate Na are shown in Table 1. The weight average molecular weight and the sulfonation rate of the obtained polymer were measured as follows. (1) Weight average molecular weight of polymer Standard polystyrene sulfonate Na is used as a standard substance, and TSK-G3000SW manufactured by Tosoh Corporation is used as a separation column.
And G4000SW (7.5 mm ID x 30 cm) are used, and an ultraviolet ray detector (measurement wavelength 238 nm) is used for GP.
It was determined by the C method. (2) Sulfonation rate of polymer Sulfonation 1 based on the ratio of carbon atom and sulfur atom measured by an elemental analyzer (EA-1108 manufactured by Carlo Erba Co.)
The sulfonic acid group introduction rate per unit was calculated (when the water-soluble polymer contains a sulfur salt, its amount was quantified by ion chromatography, and the sulfur atom amount was subtracted from the sulfur atom amount obtained by an elemental analyzer). ).

[0013]

[Table 1] Table-1 Properties of component (A) Synthetic sun-monomer formation Poly-polymer formation (a) (b) (a) / (b) Weight average counterion Example name Molecular weight 1 A-1 Styrene sulfonic acid-100 / 0 10,000 Na 2 A- 2 styrenesulfonate ^{M-90G * 1 90/10 1,000 NH} 4 3 A-3 styrene sulfonic acid M-90G 50/50 1 million in NH _{4 4 A-4-styrene} sulfonate styrene 80/20 200,000 NH ₄ 5 A- 5 Styrene sulfonic acid Acrylic acid 40/60 100,000 K * 1; M-90G: Methoxy polyethylene glycol (p = 9) methacrylate

[0014]

[Table 2] Table-1 (continued)  Combined sun-monomer formation Combined formation pull (c) (d) (c) / (d) Weight average S-ized ratio Counterion Example name Molecular weight (%) 6 A-6 Styrene-100 / 0 20,000 90 Na 7 A-7 Styrene-100 / 0 1,500 90 NH_Four 8 A-8 Styrene Isoprene 80/20 10,000 80 NH_Four 9 A-9 Styrene Isoprene 50/50 200,000 70 Na 10 A-10 α-Methylstyrene Isoprene 60/40 100,000 80 Mg 11 A-11 α-Methylstyrene M-40G^{* 2} 40/60 50,000 90 K 12 A-12 Styrene Maleic anhydride 70/30 10,000 70 Na13 A-13 Styrene ^* 3-100 / 0 20,000 90 Na * 2; M-40G: methoxypolyethylene glycol (p = 4) methacrylate * 3; polyethylene glycol (Mw about 200) 1 wt% vs styrene added product (B) component is shown in Table-2.

[0015]

[Table 3] Table-2 No Species B-1 Na salt of diethylene glycol disulfate B-2 Polyethylene glycol (Mw = 200) B-3 Polyethylene glycol (Mw = 200) Na salt of monosulfate B-4 Polyethylene glycol (Mw = 800) Monosulfate K salt B-5 Nonylphenol ethylene oxide 5 mol adduct Na salt of sulfate

Example 1 Inorganic pigments shown in Table 3, water, and the polymer (A) and compound (B) shown in the synthesis example as a dispersant were charged in a container, and TK Auto manufactured by Tokushu Kika Kogyo Co., Ltd. 3000rp with Homo mixer
The mixture was stirred at m for 20 minutes to prepare 500 g of a pigment aqueous dispersion having the pigment concentration shown in Table-3. The total amount of the polymer (A) and the compound (B) in the dispersant is solid content with respect to the pigment.
It was added so as to be 0.5%. The viscosity of the thus-prepared aqueous pigment dispersion at 25 ° C. was measured with a B-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. Furthermore, in order to confirm the stability of the prepared aqueous pigment dispersion over time, the viscosity was measured under the same conditions after standing for 1 week. The results are shown in Table-4.

[0017]

[Table 4] Table-3 Pigment name Pigment concentration in pigment aqueous dispersion (wt%) Pigment 1 Light calcium carbonate (Average particle size 1 μm, Spindle type) 65 Pigment 2 Talc (Average particle size 6 μm, Plate crystal) 62

[0018]

[Table 5] Table-4 (Dispersion characteristics) Inorganic Pigment Polymer Compound (A) / (B) Inorganic Pigment Aqueous Dispersion Liquid Viscosity (cP) No (A) (B) (weight ratio) Initial 1 week later 1 1 A-1 B-3 99/1 85 90 2 1 A-2 B-4 99/1 110 120 120 3 1 A-3 B-5 99/1 120 135 4 1 A-3 B-5 93/7 150 180 5 1 A-4 B-1 99/1 135 150 6 1 A-5 B-2 99/1 140 160 7 1 A-6 B-3 99/1 75 80 8 1 A-6 B-3 96/4 100 105 95 9 1 A-7 B-4 99 / 1 90 100 10 1 A-8 B-5 98/2 80 90 90 11 1 A-9 B-1 98/3 125 125 140 12 1 A-10 B-2 98/2 140 155 13 1 A-11 B- 3 98/2 105 115 14 1 A-12 B-4 98/5 145 170 15 2 A-1 B-1 98/2 350 370 16 2 A-3 B-2 95/5 200 220 17 2 A-5 B-3 99/1 240 270 18 2 A-6 B-4 97/3 330 340 192 2 A -8 B-5 99/1 290 320 320 20 2 A-10 B-4 92/8 300 300 310 21 2 A-12 B-3 98/2 320 350 22 2 A-13 * 1 99/1 340 350 23 * 1 A-1-100 / 0 140 250 24 * 1-B-20 / 100 No slurry 25 * 1-B-40 / 100 No slurry 26 * 2 A-7-100 / 0 550 800 27 * 2-B-30 / 100 Not slurried * 1: Compound (B) equivalent compound at the time of A-13 synthesis In the table, 1 to 22 are products of the present invention, and 23 * to 27 * are comparative examples. .

Example 2 An organic pigment, water, and the polymer (A) and the compound (B) shown in the synthesis examples as the dispersant were used, the pigment concentration was 55%, and the dispersant was 2 in solid content based on the pigment. % To a container and use TK Auto Homo Mixer manufactured by Tokushu Kika Kogyo Co., Ltd.
The mixture was stirred at 3000 rpm for 20 minutes to prepare 500 g of an organic pigment aqueous dispersion. The following two types were used as the organic pigment. Organic Pigment 1: Benzidine Yellow (CI Pigment Yellow 14) (Average particle size 1.2 μm) Organic Pigment 2: Lake Red C (CI Pigment Red 53: 1) (Average particle size 0.7 μm) Organic prepared in this way 25 ° C of pigment-water slurry
Viscosity was measured by a B-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. Further, in order to confirm the stability of the prepared organic pigment-water slurry over time, the viscosity was measured under the same conditions after standing for 1 week. The results are shown in Table-5.

[0020]

[Table 6] Table-5 No. Organic Pigment Polymer Compound (A) / (B) Organic Pigment Aqueous Dispersion Liquid Viscosity (cP) (A) (B) (Weight ratio) Initial 1 week later 1 1 A-1 B-3 99/1 330 400 2 1 A-2 B-4 99/1 370 450 450 3 1 A-3 B-5 99/1 380 440 4 41 A-3 B-5 93/7 480 530 5 1 A-4 B-1 99 / 1 400 480 6 1 A-5 B-2 99/1 430 500 7 1 A-6 B-3 99/1 310 380 8 1 A-6 B-3 96/4 340 410 91 1 A-7 B-4 99/1 300 360 10 1 A-8 B-5 98/2 310 390 11 1 A-9 B-1 98/3 450 450 510 12 1 A-10 B-2 98/2 500 600 13 1 A-11 B -3 98/2 380 430 14 1 A-12 B-4 98/5 520 580 15 2 A-1 B-1 98/2 680 800 800 16 2 A-3 B-2 95/5 700 850 17 2 A-5 B-3 99/1 650 770 18 2 A-6 B-4 97/3 730 800 19 2 A-8 B-5 99/1 710 880 20 2 A-10 B-4 92/8 740 900 21 21 A-12 B-3 98/2 660 780 222 2 A-13 * 1 99 / 1 700 830 23 * 1 A-2- 100/0 640 1050 24 * 1-B-20 / 100 No slurry 25 * 1-B-40 / 100 No slurry 26 * 2 A-8- 100/0 1100 1850 27 * 2-B-30 / 100 Not slurried * 1: Compound (B) equivalent compound formulation at the time of A-13 synthesis In the table, 1 to 22 are products of the present invention, 23 * to 27 * Is a comparative example.

Example 3 An aqueous dispersion of disperse dye was prepared under the following conditions using a 1 / 4G batch type sand grinder manufactured by IMEX Co., Ltd. That is, the glass beads 20 having an average particle diameter of 1.6 mm
Disperse dye (CI Disperse Blue 79), water, and the polymer (A) and the compound (B) shown in the synthesis example as a dispersant were dispersed in a 800 ml container containing 0 ml at a dye concentration of 40%. The agent was charged so that the solid content was 25% with respect to the dye, and the mixture was pulverized and stirred while cooling at a rotation speed of 1500 rpm until the average particle diameter became 1 μm, to prepare 200 g of a disperse dye aqueous dispersion. The viscosity of the aqueous dispersion of the disperse dye thus prepared at 25 ° C. was measured with a B-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. Furthermore, in order to confirm the daily stability of the prepared aqueous dispersion of disperse dye, the viscosity was measured under the same conditions after standing for 1 week. The results are shown in Table-6.

[0022]

[Table 7] Table-6 No. Polymer Compound (A) / (B) Disperse dye aqueous dispersion viscosity (cP) (A) (B) (weight ratio) Initial period 1 week later 1 A-1 B-3 99/1 240 300 2 A -2 B-4 99/1 270 350 3 A-3 B-5 99/1 290 340 4 A-3 B-5 93/7 385 405 440 A-4 B-1 99/1 310 400 6 A-5 B-2 99/1 315 430 7 A-6 B-3 99/1 220 270 8 A-6 B-3 96/4 250 320 9 A-7 B-4 99/1 210 265 10 A-8 B- 5 98/2 225 300 11 A-9 B-1 98/3 370 450 12 A-10 B-2 98/2 380 470 13 A-11 B-3 98/2 280 330 330 14 A-12 B-4 98 / 5 360 455 15 A-13 * 1 99/1 220 280 16 * A- - 100/0 440 750 17 * A- 9 100/0 485 800 18 * - B-2 0/100 slurry without 19 * - B-4 0/100 not slurried * 1: When A-13 Synthesis Compound (B) equivalent product In the table, 1 to 15 are products of the present invention, and 16 * to 19 * are comparative examples.

Example 4 A biocide aqueous dispersion was prepared under the following conditions using a 1 / 4G batch type sand grinder manufactured by IMEX Co., Ltd. That is, 200 ml of glass beads having an average particle diameter of 1 mm
In a container of 800 ml, containing tsumaside, water, and the polymer (A) and the compound (B) shown in the synthesis examples as the dispersant, the tsumaside concentration was 50% by weight, and the dispersant was a solid content based on the tsumaside. Charge to 1.5%, cool down and rotate at 1000 rpm to give an average particle size of 0.6μ.
The mixture was pulverized and stirred until it became m to prepare 200 g of the aqueous dispersion of biocide. 2 of the aqueous dispersion of biocide thus prepared
The viscosity at 5 ° C. was measured with a B-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. Further, in order to confirm the daily stability of the prepared aqueous dispersion of biocide, the viscosity was measured under the same conditions after standing for 1 week. The results are shown in Table-7.

[0024]

[Table 8] Table-7 No. Polymer Compound (A) / (B) Viscosity of biocide dispersion (cP) (A) (B) (weight ratio) Initial period 1 week later 1 A-1 B-1 98/2 60 63 2 A -3 B-2 95/5 65 68 3 A-4 B-1 99/1 57 60 4 A-5 B-3 99/1 65 70 5 A-6 B-3 99/1 51 55 6 A-6 B-4 97/3 63 70 7 A-8 B-5 99/1 58 65 8 A-10 B-4 92/8 62 70 9 A-12 B-3 98/2 56 58 10 A-13 * 1 99/1 60 65 11 * A-5-100 / 0 115 225 12 * A-10-100 / 0 140 270 13 * -B-30 / 100 Not slurried * 1: Compound at the time of A-13 synthesis ( B) Equivalent product formulation In the table, 1 to 10 are products of the present invention, and 11 * to 13 * are comparative examples.

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Claims (1)

[Claims] 1. (A) At least one sulfonic acid group-containing polymer and / or salt thereof selected from the following polymers (AI) and (A-II); and (B) polyether. A dispersant for an aqueous fine particle dispersion, which is used in combination with at least one compound selected from the group consisting of a compound, its sulfated compound and its salt. (AI): a polymer obtained by polymerizing at least one monomer selected from the group consisting of (a) a polymerizable aromatic sulfonic acid-based monomer and (b) a monomer copolymerizable with (a). And a polymer containing the monomer (a) as an essential component. (A-II): a polymer obtained by polymerizing at least one kind of monomer selected from (c) a polymerizable aromatic hydrocarbon monomer and (d) a monomer copolymerizable with (c). And a sulfonated product of a polymer containing the monomer (c) as an essential component.