JP2000212371A - Pigment dispersant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersant excellent in both the lowering of the initial viscosity of an inorganic pigment slurry and the agebased stability of the viscosity of an inorganic pigment slurry. SOLUTION: This pigment dispersant comprises a neutralized (co)polymer A having 50-100 mol.%. α,β-unsaturated carboxylic acid unit and 0-50 mol.% other monomer unit as structural units. The acid radical of the (co)polymer A comprises 18.8-99.9 mol.% alkali metal salt or alkaline earth metal (except magnesium) salt, 0.1-1.2 mol.% magnesium salt and 0-80 mol.% free acid radical.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pigment dispersant, particularly a dispersant useful for inorganic pigments.

[0002]

Conventionally, as a dispersant, alkali metal salts of polyacrylic acid (such as sodium and lithium), alkaline earth metal salts, and quaternary ammonium salts have been known (for example, JP-A-54-82416). JP, JP-A-7-3
No. 08563).

[0003]

However, these dispersants are still unsatisfactory in the reduction of the initial viscosity of the obtained inorganic pigment slurry and the stability with time of the viscosity of the inorganic pigment slurry. When preparing a slurry, there is a problem that the initial viscosity is high and the viscosity increases significantly with time. Further, there is a problem that it is extremely difficult to increase the concentration and to make fine particles in the wet grinding of calcium carbonate.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and have reached the present invention. That is, the present invention comprises a neutralized product of a (co) polymer (A) comprising 50 to 100 mol% of α, β-unsaturated carboxylic acid and 0 to 50 mol% of another monomer as constituent units. A)
18.8 to 99.9 mol% of the acid groups in the alkaline earth metal salt except the alkali metal or magnesium salt,
0.1 to 1.2 mol% is a magnesium salt;
A pigment dispersant, wherein 0 mol% is a free acid group.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the α, β-unsaturated carboxylic acid which is a constitutional unit of the (co) polymer (A) includes, for example, (meth) acrylic acid, maleic acid, maleic anhydride, Fumaric acid, itaconic acid, itaconic anhydride,
Citraconic acid, citraconic anhydride, maleic acid half-ester (monobutyl maleate, monoethyl carbitol maleate, etc.), fumaric acid half-ester (monobutyl fumarate, monoethyl carbitol fumarate, etc.) α, β-unsaturated carboxylic acids or anhydrides thereof; and combinations thereof. Of these, preferred are (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, maleic acid half ester and fumaric acid half ester, and particularly preferred is (meth) acrylic acid.

Other copolymerizable monomers can be used as the structural unit of the (co) polymer (A). Examples of other monomers include, but are not limited to, the following. (A) Aromatic ethylenically unsaturated monomer: styrene, α-
Styrenes such as methylstyrene, vinyltoluene and hydroxystyrene, halogen-substituted styrenes such as dichlorostyrene, vinylnaphthalenes and the like; (b) aliphatic ethylenically unsaturated monomers having 2 to 20 carbon atoms: ethylene Propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene and the like; (c) an alicyclic ethylenically unsaturated monomer having 5 to 15 carbon atoms: cyclopentadiene, pinene, Limonene, indene, bicyclopentadiene, ethylidene norbornene and the like; (d) alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms: methyl (meth) acrylate;
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc. (E) hydroxyl group-containing (meth) acrylate: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc .; (f) amide-containing ethylenically unsaturated monomer: (meth) acrylamide, N-methylol (meth) ) Acrylamide and the like; (g) polyalkylene glycol chain (molecular weight of 44 to 20)
Ethylenically unsaturated monomers having (00): polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) mono (meth) acrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl Alcohol ethylene oxide 30 mol adduct (meth)
Acrylate and the like;

(H) Sulfone group-containing monomers: vinyl sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-
3- (meth) allyloxypropanesulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, sulfopropyl (meth) acrylate, 2-hydroxy-3-
(Meth) acryloxypropanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 3- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfone Acid, 2- (meth) acrylamide-
2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) (meth) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene mono (meth) Sulfate ester of acrylate (the oxyalkylene is an oxyalkylene having 2 to 4 carbon atoms and may be single, random or block) [for example, poly (n = 5 to 1)
5) Oxypropylene monomethacrylate sulfate ester etc.] and the following other general formulas (I), (II),
Compounds represented by (III) and the like.

[0008]

Embedded image

(Wherein, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different; It may be a block, Ar represents a benzene ring, and n represents an integer of 1 to 50.)

[0010]

Embedded image

(Wherein, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different; It may be a block, Ar represents a benzene ring, and n represents an integer of 1 to 50.)

[0012]

Embedded image

(In the formula, R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted by a fluorine atom.)

Of these, (a), (b), and
(D), (e), (g) and (h), particularly preferably (a), (d) and (h). In the present invention,
The acid group is usually a carboxylic acid group, but when (h) is used as a copolymerization component, it is a carboxylic acid group or a sulfonic acid group. The acid group as a monomer may be neutralized with an alkali metal, an alkaline earth metal, or an organic amine.

In the copolymer (A), the content of α, β-unsaturated carboxylic acid as a constitutional unit is usually 50 to 50.
100 mol%, preferably 70 to 100 mol%,
The content of the other monomer is usually 0 to 50 mol%, preferably 0 to 30 mol%.

The copolymer (A) can be obtained by subjecting the above monomer to radical polymerization. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (2-methylbutyronitrile) , 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile Azo compounds such as 1,1'-azobis (1-acetoxy-1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, benzoyl peroxide Organic peroxides such as lauric, lauroyl peroxide, persuccinic acid; inorganic peroxides such as persulfate, perborate, hydrogen peroxide, etc. it can. Further, a redox-based initiator combined with a reducing agent can be used. Examples of the reducing agent used for the redox initiator include ascorbic acid (salt), Rongalit, hypophosphorous acid (salt), sulfurous acid (salt), bisulfite (salt), ferrous salt and the like.
These may be used in combination of two or more. The amount of the radical polymerization initiator is usually 0.01 to 20% by weight based on the monomer,
Preferably it is 0.05 to 5% by weight.

Examples of the chain transfer agent include lauryl mercaptan, thioglycolic acid, mercaptoethanol,
Triethylene glycol dimercaptan, tris (polyoxypropylene-2-hydroxy-3-thiolpropane) alkyl ether and the like. The amount of the chain transfer agent is usually 0.01 mol% to 10 mol%, preferably 0.05 to 3 mol%, based on the monomer.

The polymerization methods include solution polymerization, emulsion polymerization,
Any of suspension polymerization and bulk polymerization may be used, but solution polymerization, emulsion polymerization and suspension polymerization are preferred, and solution polymerization is particularly preferred. Solvents for solution polymerization include water, alcohols (eg, methanol, ethanol, isopropanol), ketones (eg, acetone, methyl isobutyl ketone), ethers (eg, tetrahydrofuran), and aliphatic hydrocarbons (eg, hexane, heptane, etc.). ), Aromatic hydrocarbons (eg, toluene, xylene), halogenated solvents (eg, ethylene dichloride), and mixtures thereof. Particularly preferred are isopropanol and a mixed solvent of isopropanol and water.

The polymerization temperature is usually from 20 to 200 ° C.
Preferably it is 60-150 degreeC. Examples of the temperature include a temperature lower than the boiling point of the polymerization solution under normal pressure, a boiling point of the polymerization solution under normal pressure, and a temperature higher than the boiling point of the polymerization solution under pressure. Preferably, the polymerization is carried out at a temperature higher than the boiling point of the polymerization solution under pressure. When an emulsifier, a dispersant, or the like is used, there is no particular limitation, and known ones can be used.

The weight average molecular weight of the (co) polymer (A) is usually from 1,000 to 100,000. Preferably,
5,000 to 30,000, and the molecular weight distribution is usually 1.10 to 4.50, preferably 1.1 to 2.5.
It is.

In the present invention, 18.8 to 99.9 mol%, preferably 25 to 9%, of the acid groups in the (co) polymer (A) is used.
9.9 mol% is an alkaline earth metal salt excluding an alkali metal or magnesium salt, and 0.1 to 1.2 of an acid group.
Mole%, preferably 0.6-1.1 mol%, is a magnesium salt and 0-80 mol% of the acid groups are free acid groups. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include calcium and barium.

Examples of the organic amine include aliphatic (primary, secondary, and tertiary) amines, alicyclic amines, aromatic amines, alkylene oxide adducts of the primary or secondary amines, and (poly) alkylene polyamines. Can be Examples of the aliphatic amine include an alkylamine having an alkyl group having 1 to 20 carbon atoms. Examples of the primary amine include methylamine, ethylamine, n-butylamine, octylamine, decylamine, dodecylamine, tetradecylamine, and hexadecyl. Examples include amine, octadecylamine, palm alkylamine, tallowalkylamine, hardened tallowalkylamine, oleylamine, and soybean alkylamine. As secondary amines, dimethylamine, diethylamine, dibutylamine, dioctylamine, didecylamine, didodecylamine, ditetradecylamine,
Examples include dihexadecylamine, dioctadecylamine, dioleylamine, dicocoalkylamine, and di-hardened tallowalkylamine. Examples of the tertiary amine include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diethyl-1-propylamine, octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, and hexadecyldimethyl. Amines and octadecyldimethylamine. As the alicyclic amine,
Examples include cycloalkylamines having a cycloalkyl group, and specific examples include cyclopentylamine, cyclohexylamine, pyrrolidine, purine, dicyclohexylamine, cyclohexylmethylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine,
N-ethylpiperidine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, N-methylmorpholine, N-butylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8- Diazabicyclo [5,4,0] -7-undecene and the like. As aromatic amines, aniline, benzylamine, toluidine, benzidine, pyrimidine, N, N dimethylaniline, phenylenediamine (o, m, p), pyridine,
4-methylbenzimidazole, quinoline, 4,4'-
Dipyridyl and the like. Examples of the alkylene oxide of the alkylene oxide adduct of the primary or secondary amine include ethylene oxide, propylene oxide and butylene oxide. These additional moles are usually
1 to 5 mol per active hydrogen, preferably 1 to 2 mol
Is a mole. Specific examples include cyclohexylamine adduct of 2 mol of propylene oxide, dioctylamine adduct of 1 mol of propylene oxide and the like. (Poly)
Examples of the alkylene polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and alkylated products thereof. Of the organic amines, preferred are aliphatic or alicyclic amines or their alkylene oxide adducts.

The method for obtaining the copolymer salt of the present invention includes:
18.8 to 99.9 mol% of the acid groups in the (co) polymer (A) is an alkaline earth metal salt excluding an alkali metal or a magnesium salt, and 0.1 to 1.2 mol% of a magnesium salt. Yes, so that 0 to 80 mol% becomes free acid groups,
The (co) polymer (A) is treated with an aqueous solution of an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) or an alkaline earth metal hydroxide excluding magnesium (barium hydroxide, calcium hydroxide, etc.). After the addition, it can be obtained by neutralizing with magnesium hydroxide. An aqueous solution of the (co) polymer (A), an aqueous solution of an alkali metal salt of the (co) polymer (A) or an aqueous solution of an alkaline earth metal salt excluding magnesium, and an aqueous solution of a magnesium salt of the (co) polymer (A) It can also be obtained by blending.

The dispersant of the present invention is useful for dispersing inorganic substances, and is particularly effective as a dispersant for inorganic pigments. In the present invention, as the target inorganic substance, calcium carbonate, calcium phosphate, zinc phosphate, clay, bentonite, satin white, zinc white, red iron, ferrite, titanium oxide, talc, white carbon, cement, gypsum, carbon black, Various silicates and the like can be mentioned, and calcium carbonate is preferable. Specifically, it is effective as a dispersant for wet grinding of calcium carbonate, for a light calcium carbonate production process, and for paper coating paint. A pigment dispersion composition can be obtained by dispersing a pigment powder in an aqueous solvent using the dispersant of the present invention. The aqueous solvent is water, water and a water-soluble organic solvent (for example,
Mixed solution with methyl alcohol, ethyl alcohol, ethylene glycol, etc.). Preferably it is water. The amount of the dispersant used per solid is usually 0.001.
10 to 10% by weight, preferably 0.05 to 5% by weight,
The amount of the aqueous solvent used is 10 to 70% by weight based on the solid content of the pigment.
It is.

The method for obtaining the pigment dispersion composition using the dispersant of the present invention may be a conventional dispersion method, for example, by adding pigment powder to an aqueous solvent in which the dispersant of the present invention is dissolved. Stirring and mixing methods may be mentioned. For this stirring and mixing, a commonly used stirring device such as a high-speed disper, a homomixer, and a ball mill can be used. As another method, there is a method in which, when the raw ore or coarse particles of the powder are wet-pulverized, the dispersant of the present invention is simultaneously added to obtain a dispersion composition.

[0026]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In Examples and Comparative Examples,% and parts represent% by weight and parts by weight. The measurement of the molecular weight by GPC is as follows. The molecular weight is a value assuming complete neutralization with sodium hydroxide. << GPC measurement conditions >> Model: Waters 510 (manufactured by Nippon Waters Limited) Column: TSK gel G5000pwXL TSK gel G3000pwXL (both manufactured by Tosoh Corporation) Column temperature: 40 ° C. Detector: RI solvent: 0.5% sodium acetate・ Water / methanol (volume ratio 70/30) Flow rate: 1.0 ml / min Sample concentration: 0.25% by weight Injection volume: 200 μl Standard: polyoxyethylene glycol (manufactured by Tosoh Corporation; TSK STANDARD POLYETHYLENE OXIDE) Data processing Apparatus: SC-8010 (manufactured by Tosoh Corporation)

Example 1 420 parts of isopropyl alcohol and 1 part of water were placed in a pressure-resistant reaction vessel.
20 parts were charged, and the flask was replaced with nitrogen, sealed, and heated to 100 ° C. With stirring, 305 parts of acrylic acid and sodium persulfate 4
% Aqueous solution was dropped from separate containers over 3 hours. After completion of the dropping, a 35% aqueous hydrogen peroxide solution 3
Then, the mixture was maintained at the same temperature for 1 hour to obtain a polymer (a) having a conversion of 99.8%. Its weight-average molecular weight measured by GPC was 9,200 and the molecular weight distribution was 1.25. The mixture was neutralized with 559 parts of a 30% aqueous sodium hydroxide solution and 2.47 parts of magnesium hydroxide, and isopropyl alcohol was distilled off to obtain a polyacrylic acid mixed salt aqueous solution.

Examples 2 to 5 The same as Example 1 except that the neutralized salt and the degree of neutralization were changed as shown in Table 1 using the polymer (a).

Example 6 370 parts of isopropyl alcohol and 1 part of water were placed in a pressure-resistant reaction vessel.
70 parts were charged, and the flask was replaced with nitrogen, sealed, and heated to 100 ° C. Under stirring, 264.9 parts of acrylic acid, 40.1 parts of 2-acrylamido-2-methylpropanesulfonic acid, and 80 parts of a 4% aqueous solution of sodium persulfate were added dropwise from separate containers over 3 hours. After the completion of the dropwise addition, 3 parts of a 35% aqueous hydrogen peroxide solution were added, and the mixture was maintained at the same temperature for 1 hour to obtain a polymerization rate of 9%.
9.9% of copolymer (b) was obtained. Its weight average molecular weight was 8,000 by GPC, and the molecular weight distribution was 1.45.
Met. After the isopropyl alcohol was distilled off, the mixture was neutralized with 511.2 parts of a 30% aqueous solution of sodium hydroxide and 1.81 parts of magnesium hydroxide to obtain an aqueous solution of a mixed salt of polyacrylic acid.

Example 7 The same as Example 6 except that the neutralized salt and the degree of neutralization were changed as shown in Table 1 using the polymer (b).

Comparative Examples 1 to 3 The same as Example 1 except that the neutralized salt and the degree of neutralization were changed as shown in Table 1 using the polymer (a).

Comparative Examples 4 and 5 The same as Example 6 except that the polymer (b) was used and the neutralization salt and the degree of neutralization were changed as shown in Table 1.

[0033]

[Table 1]

Test Example 1 (Wet pulverization dispersion of calcium carbonate) 25 parts of water and the dispersant of Examples 1 to 7 and Comparative Examples 1 to 5
To each aqueous solution in which 38 parts (solid content) were uniformly dissolved, 75 parts of coarse ore of calcium carbonate was added, and the mixture was stirred and dispersed using a sand grinder for 30 minutes. Immediately after the production of the obtained 75% by weight aqueous calcium carbonate slurry, and 25
The viscosity after standing at 7 ° C. for 7 days was measured using a BL viscometer at 25 ° C.
The measurement was performed under the condition of 60 rpm. Table 2 shows the test results.

[0035]

[Table 2]

[0036]

The dispersant of the present invention, when used for inorganic pigments, makes it possible to obtain a dispersant having a lower viscosity and a better stability over time than conventional dispersants.

Claims (7)

[Claims] 1. A neutralized product of a (co) polymer (A) comprising 50 to 100 mol% of α, β-unsaturated carboxylic acid and 0 to 50 mol% of other monomers as constituent units. (A)
18.8 to 99.9 mol% of the acid groups in the alkaline earth metal salt except the alkali metal or magnesium salt,
0.1 to 1.2 mol% is a magnesium salt;
A pigment dispersant, wherein 0 mol% is a free acid group. 2. The α, β-unsaturated carboxylic acid is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, maleic acid half ester and fumaric acid half ester. 2. The dispersant according to 1. 3. The dispersant according to claim 1, wherein the α, β-unsaturated carboxylic acid is (meth) acrylic acid. 4. The weight average molecular weight of (A) is from 1,000 to 1,000.
The dispersant according to any one of claims 1 to 3, which is 100,000. 5. The dispersant according to claim 1, which is used for an inorganic pigment. 6. The dispersant according to claim 5, wherein the inorganic pigment is calcium carbonate. 7. The dispersant according to any one of claims 1 to 6,
A pigment dispersion composition for coated paper comprising water and an inorganic pigment.