JP2001087640A - Dispersant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant useful especially for an inorganic pigment, cement, an agricultural chemical granule, a scale dispersion, a detergent builder or a dredged sludge. SOLUTION: The dispersant is a (co)polymer produced by polymerizing an α, β unsaturated carboxylic acid (salt) as a monomer using a radical polymerization initiator and a chain shifting agent for radical polymerization having a general formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dispersant, especially a dispersant useful for inorganic pigments, cement, pesticides, scale dispersion, detergent builders or drilling mud.

[0002]

2. Description of the Related Art Conventionally, as a dispersant, salts of polyacrylic acid, salts of a copolymer of acrylic acid and another copolymerizable monomer (for example, polyoxyalkylene mono (meth) acrylate) and the like are known. (See, for example,
193126).

[0003]

However, the polymer obtained by ordinary radical polymerization contains a large amount of low molecular weight substances and high molecular weight substances which deteriorate the dispersing performance, and these dispersing agents are used for inorganic pigments. For muddy water, cement,
In the case of drilling mud, it is still unsatisfactory in the effect of lowering the viscosity of the obtained slurry and the effect of giving the viscosity of the slurry with time, and has a problem that the amount of addition is large, and in the case of pesticide granules, The problem is that the water disintegration spreadability (dispersibility) is insufficient, the scale dispersion performance is insufficient for scale dispersion, and the mud stain dispersibility is insufficient for detergent builders. Have.

[0004]

Means for Solving the Problems The present inventors have developed a GPC.
The peak top molecular weight is in a specific range, and the dispersant having a low molecular weight and a high molecular weight content of a specific value or less solves the above-described problem, and also uses a specific chain transfer agent and radical polymerization. The present inventors have found that the (co) polymer obtained by the above can solve the above-mentioned problems, and have reached the present invention. That is, the present invention is obtained by polymerization using an α, β-unsaturated carboxylic acid (salt) as a structural unit and a radical polymerization initiator and a chain transfer agent for radical polymerization represented by the following general formula (1). The dispersant is characterized by comprising a (co) polymer obtained. General formula [Wherein Q is a polyvalent organic group, X ¹ is a carbonyl group or-
CONH—, A ¹ and A ² are divalent organic groups, X ² is an oxygen atom,
A sulfur atom or an NH group, Z is a chain transfer group, p, q, r,
x is any of the following cases 1) to 7), and m is 1 to
An integer of 50, n represents an integer of 2 to 100. The values in [] and the values in Δ when m is 2 to 50 may be the same or different. 1) When p is 0, x is 0, q is 0, and r is 0, 2) When p is 1, x is 0, q is 0, and r is 0, 3) p is 0 and x is 1 , Q is 1, r is 0, 4) p is 0, x is 1, q is 0, r is 0, 5) p is 0, x is 0, q is 1, and r is 0 6) When p is 1, x is 0, q is 1, and r is 0, 7) When p is 1, x is 0, q is 0, and r is 1.

In the present invention, examples of the α, β-unsaturated carboxylic acid (salt) include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. Α, β- such as citraconic acid, maleic acid half-ester (monobutyl maleate, monoethyl carbitol maleate, etc.), fumaric acid half-ester (monobutyl fumarate, monoethyl carbitol fumarate, etc.) Unsaturated carboxylic acids or their anhydrides;
Alkali metal (lithium, sodium, potassium, etc.) salt, alkaline earth metal (calcium, magnesium, etc.) salt, ammonium (ammonium, tetraoctylammonium, etc.) salt, organic amine ｛alkanolamine, polyalkylenepolyamine Or a derivative thereof (alkylated product, alkylene oxide adduct), a salt such as a lower alkylamine, or a combination of two or more of these. Of these, preferred are (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, alkali metal salts, alkaline earth metal salts or ammonium salts thereof, and combinations of two or more thereof.

[0006] Other copolymerizable monomers include, for example, the following, but are not limited thereto.

(A) Aromatic ethylenically unsaturated monomers: styrenes such as styrene, α-methylstyrene, vinyltoluene and hydroxystyrene, halogen-substituted styrenes such as vinylnaphthalenes and dichlorostyrene, etc.
(B) an aliphatic ethylenically unsaturated monomer having 2 to 20 carbon atoms: ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, etc. (c)
Alicyclic ethylenically unsaturated monomer having 5 to 15 carbon atoms: (d) alkyl (meth) having an alkyl group having 1 to 50 carbon atoms, such as cyclopentadiene, pinene, limonene, indene, bicyclopentadiene, and ethylidene norbornene; Acrylate: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) (E) hydroxyl group-containing (meth) acrylates such as acrylate and eicosyl (meth) acrylate:
(F) Amide-containing ethylenically unsaturated monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate: (meth) acrylamide, N-methylol (meth) acrylamide, and (g) polyalkylene glycol chains ( Ethylenically unsaturated monomer having a molecular weight of 44 to 2000): polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth)
Acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.

(H) Sulfone group-containing monomers: vinylsulfonic acid (salt), (meth) allylsulfonic acid (salt), 2-
Hydroxy-3- (meth) allyloxypropanesulfonic acid (salt), styrenesulfonic acid (salt), α-methylstyrenesulfonic acid (salt), sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acrylic Roxypropanesulfonic acid (salt), 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid (salt), 3-
(Meth) acryloyloxyethanesulfonic acid (salt),
3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid (salt), 2- (meth) acrylamide-
2-methylpropanesulfonic acid (salt), 3- (meth) acrylamide-2-hydroxypropanesulfonic acid (salt), alkyl (3 to 18 carbon atoms) (meth) allylsulfosuccinic acid (salt), poly (n = 2 To 30) oxyalkylene (ethylene, propylene, butylene: single, random, or block) mono (meth) acrylate sulfate (salt) [poly (n = 5 to 15) oxypropylene monomethacrylate sulfate (salt) )
Etc.], polyoxyethylene polycyclic phenyl ether sulfate (salt) [styrenated (degree of substitution 2) phenol polyethylene oxide (35 mol) sulfate ammonium salt, etc.], and other general formulas (I) and (II) below:
Compounds represented by (III) and the like. (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, and when they are different, they may be random or block. X represents an alkali metal, an alkaline earth metal, ammonium, or an amine cation, Ar represents a benzene ring, and n represents an integer of 1 to 50.) (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, and when they are different, they may be random or block. X represents an alkali metal, an alkaline earth metal, ammonium, or an amine cation, Ar represents a benzene ring, and n represents an integer of 1 to 50.) (In the formula, R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted by a fluorine atom, and X represents an alkali metal, an alkaline earth metal, ammonium, or an amine cation.)

[0009] Of these, preferably (a), (b),
(D), (e), (g) and (h).

In the copolymer, the content of the monomer other than the α, β-unsaturated carboxylic acid (salt) is usually 0 to 90%, preferably 0 to 60% by weight.

In the general formula (1), examples of the polyvalent organic group for Q include a residue obtained by removing OH from a polyhydric alcohol or a polyhydric phenol, a residue obtained by removing COOH from a polyvalent carboxylic acid, and the like. As a polyhydric alcohol, a compound having 2 to 2 carbon atoms
8 alkylene glycols (ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.) and diols having 5 to 10 carbon atoms having a cyclic group. Polyhydric alcohols; trihydric alcohols having 3 to 12 carbon atoms such as glycerin, trimethylolpropane, trimethylolethane, and hexanetriol; tetrahydric alcohols having 4 to 20 carbon atoms such as pentaerythritol, methylglycoside, and diglycerin; and higher Alcohols having a functional group (pentavalent or higher), such as pentitol (adonitol, arabitol, xylitol, etc.), hexitol (sorbitol, mannitol, iditol, talitol, dulcitol, etc.), saccharides [sucrose, monosaccharide (Glucose, mannose, fructose, sorbose, etc.), oligosaccharides (crehalose, lactose, raffinose, etc.), etc .; glucosides [eg glucosides of polyols (alkane polyols such as glycol, glycerin, trimethylolpropane, hexanetriol)]; polyalkanes Polyols (eg, polyglycerin such as triglycerin and tetraglycerin); polypentaerythritol (such as dipentaerythritol and tripentaerythritol); and cycloalkane polyols (such as tetrakis (hydroxymethyl) cyclohexanol). Further, polyvinyl alcohol having a degree of polymerization of up to 100 can be used.

Di- and triethanolamines; alkylamines having 2 to 20 carbon atoms;
Alkylene diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, polyalkylenepolyamines such as aliphatic amines such as diethylenetriamine and triethylenetetramine, and fragrances such as aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline and diphenyletherdiamine And alkylene oxide adducts such as alicyclic amines such as aromatic amines, isophoronediamine, cyclohexylenediamine and dicyclohexylmethanediamine, and heterocyclic amines such as aminoethylpiperazine.

Examples of polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensates of phenol and formaldehyde (novolak); and polyphenols.

Examples of polyvalent carboxylic acids include divalent carboxylic acids [(1) aliphatic dicarboxylic acids having 2 to 20 carbon atoms (maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, (2) an alicyclic dicarboxylic acid having 8 to 20 carbon atoms (such as cyclohexanedicarboxylic acid and methylmedic acid); and (3) an aromatic dicarboxylic acid having 8 to 20 carbon atoms (phthalic acid). Acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, etc.);
(4) Alkyl or alkenyl succinic acids having a hydrocarbon group having 4 to 35 carbon atoms in the side chain (such as isododecenyl succinic acid and n-dodecenyl succinic acid)], trivalent or higher carboxylic acids [(1) carbon number 7-20 aliphatic polycarboxylic acids (1,2,4-butanetricarboxylic acid, 1,2,5
-Hexanetricarboxylic acid, 1,3-dicarboxyl-
2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, etc.); (2) carbon number 9-20
Alicyclic polycarboxylic acids (e.g., 1,2,4-cyclohexanetricarboxylic acid); (3) aromatic polycarboxylic acids having 9 to 20 carbon atoms (1,2,4-benzenetricarboxylic acid, 1,2,5 -Benzenetricarboxylic acid, 2,5,7
-Naphthalenetricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, etc.)]. Further, a polymer of an unsaturated polycarboxylic acid having a degree of polymerization of up to 100 can be mentioned.

In the general formula (1), the divalent organic groups represented by A ¹ and A ² include an alkylene group of 1 to 8 and a carbon number substituted with a hydroxyl group, a phenyl group, an alkylphenyl group or a phenylalkyl group. And 1-8 alkylene groups. Preferred are alkylene groups of 1-4, -CH
_{(OH) -CH (CH 3)} - is a group.

In the general formula (1), Z is SH,
SR, SSR, CX ₃ (R is an alkyl, aryl, aralkyl, alkoxy, aryloxy or cycloalkyl group having 1 to 20 carbon atoms, which may be substituted with a halogen atom, an alkyl group, a cyano group, or a nitro group. Represents a chlorine atom, a bromine atom.) And the like. Of these, SH is preferred.

In the general formula (1), when Q is a polyhydric alcohol or polyhydric phenol residue, p is 0;
P is 1 in the case of a polyvalent carboxylic acid residue. When p is 0, preferably r is 0. When p is 1, x is preferably 0. Particularly preferably, p, q, r and s are 0.

In the general formula (1), n is an integer of 2 to 100, preferably 2 to 8. M is 0 or 1 to 1
An integer of 50 and 0 or 1 to 30 are preferred.

The chain transfer agent represented by the general formula (1)
Is SH, for example, it can be manufactured by the following method. Chain transfer agent 1 (when p is 0, x is 0, q is 0, and r is 0) After adding a cyclic ether to ω-mercapto-alkyl alcohol, it is etherified with a polyhydric alcohol. Alternatively, a cyclic ether is added to a polyhydric alcohol, and the terminal is chlorinated with thionyl chloride or the like, and then reacted with an alkali hydrosulfide. Alternatively, a method of reacting a polyhydric alcohol with epihalohydrin (e.g., epichlorohydrin), and further reacting hydrogen sulfide with a terminal cyclic ether may be mentioned. Specific examples of the chain transfer agent include polyoxyethylene glycol-di-2-mercaptoethyl ether,
Ethylene glycol-di-2-hydroxy-3-mercaptopropyl ether, tris (polyoxypropylene-2-hydroxy-3-thiolpropane) propyl ether (addition of 1 to 15 mol of oxypropylene), tris (polyoxypropylene-2- Hydroxy-3-thiolpropane) hexyl ether (oxypropylene 1
15 mol addition).

Chain transfer agent 2 (p is 1, x is 0, q is 0,
when r is 0) ω-mercapto-alkyl alcohol to cyclic ether,
After addition of the cyclic sulfide or cyclic imine, it is esterified with a polycarboxylic acid.

Chain transfer agent 3 (p = 0, x = 1, q = 1,
(When r is 0) After adding a cyclic lactone or a cyclic lactam to the polyhydric alcohol, esterification (amidation) is performed with ω-mercapto-carboxylic acid. Specific examples of the chain transfer agent include triethanolamine-ε-caprolactone adduct-tri-3.
-Mercaptopropionate and the like.

Chain transfer agent 4 (p = 0, x = 1, q = 0,
(When r is 0) After adding a cyclic lactone or cyclic lactam to the polyhydric alcohol, it is etherified (aminated) with ω-mercapto-halogenide. Specific examples of the chain transfer agent include triethanolamine-ε-caprolactone adduct-tri-2.
-Mercaptoethyl ether and the like.

Chain transfer agent 5 (p is 0, x is 0, q is 1,
(When r is 0) After adding a cyclic ether, a cyclic sulfide or a cyclic imine to the polyhydric alcohol, esterification, thioesterification or amidation with ω-mercapto-carboxylic acid is performed. Specific examples of the chain transfer agent that can be produced by this method include the following. (1) Alkylene oxide (ethylene oxide, propylene glycol, etc.) is mixed with alkylene oxide (ethylene oxide, propylene oxide, etc.) from 1 to 10
A product obtained by adding 0 mol and diestering the terminal with 3-mercaptopropionic acid. Polyoxyethylene glycol (number average molecular weight 630) di-3-mercaptopropionate, polyoxypropylene glycol (number average molecular weight 600) di-3-mercaptopropionate, and the like. (2) A compound obtained by adding 1 to 150 moles of an alkylene oxide to a trihydric or higher polyhydric alcohol (glycerin, pentaerythritol, sho, etc.), and diestering the terminal with 3-mercaptopropionic acid. Pentaerythritol ethylene oxide 20 mol adduct tetra-3-mercaptopropionate; (3) polyvinyl acetate (for example, a weight average molecular weight of 50,0
(00, degree of saponification 10%) esterified with 2-mercaptoacetic acid.

Chain transfer agent 6 (p is 1, x is 0, q is 1,
(When r is 0) After adding a cyclic ether, a cyclic sulfide, or a cyclic imine to the polyvalent carboxylic acid, esterification, thioesterification, or amidation with ω-mercapto-carboxylic acid is performed. Specific examples of the chain transfer agent include adipate propylene oxide 4 mol adduct-di-2-mercaptoacetic acid ester and the like.

Chain transfer agent 7 (p is 1, x is 0, q is 0,
(When r is 1) After adding a cyclic lactone or a cyclic lactam to the polyvalent carboxylic acid, esterification is performed with ω-mercapto-alcohol.

Among the above exemplified chain transfer agents, preferred are chain transfer agents 1 to 4, more preferred are chain transfer agents 1 and 2, and particularly preferred is chain transfer agent 1.

In the production of the above compound, for example, a cyclic ether and a cyclic lactone can be co-added, and when co-addition, either random co-addition or block co-addition may be used. In the above compounds, examples of the cyclic ether include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, and styrene oxide. Examples of the cyclic thioether include episulfide, and examples of the cyclic imine include ethylene imine. These can be co-added, and when co-added, either random co-addition or block co-addition may be used. Of these, preferred are cyclic ethers, and more preferred are ethylene oxide, propylene oxide and mixtures thereof.

In the above compounds, cyclic lactones include ε-caprolactone and δ-valerolactone, and cyclic lactams include ε-caprolactam. These can be co-added, and when co-added, either random co-addition or block co-addition may be used.

The gist of the chain transfer agent of the present invention resides in the presence of a plurality of chain transfer groups.
The present invention enables the production of a polymer having a desired peak top molecular weight in a specific range and having a low content of low molecular weight substances and high molecular weight substances.

As long as the above conditions are satisfied, the structure of the polymer can be arbitrarily selected depending on the desired properties of the polymer. In the case of the water-soluble dispersant of the present invention, a water-soluble one is preferable as the chain transfer agent.

The amount of the chain transfer agent used in the production method of the present invention is usually 0.001 to 50% by weight based on the monomer,
It is preferably 0.01 to 30% by weight, particularly preferably 0.1 to 30% by weight.
1 to 15% by weight.

The radical polymerization initiator is of the type that generates free radicals to initiate polymerization, for example, 2,2 ′
-Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1- Albonitrile), 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; Organic peroxides such as benzoyl peroxide, lauroyl peroxide and persuccinic acid; persulfates,
Inorganic peroxides such as perborate and hydrogen peroxide can be used. 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, preferably 0.02% by weight, based on the monomer.
5 to 5% by weight.

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 neutralizing salt of the (co) polymer includes alkali metal salts (such as lithium, sodium and potassium), alkaline earth metal salts (such as calcium and magnesium), and ammonium salts (such as ammonium and tetraalkylammonium). And mixtures of two or more of these.

The peak top molecular weight (M) of the (co) polymer in GPC is preferably from 3,000 to 20,000.
0, more preferably 5,000 to 15,000.
Peak top molecular weight less than 3,000 and 20,000
If it is 0 or more, the dispersing agent has poor dispersing performance. In the case where the peak top molecular weight is 5,000 to 15,000,
The content of a low molecular weight substance of M × 0.2 or less and a high molecular weight substance of M × 2.0 or more are 0.8% or less and 3.5% or less, respectively, in an area on a GPC chart, preferably They are respectively 0.7% or less and 3.0% or less, and more preferably 0.6% or less and 2.8% or less, respectively.
The content of the low molecular weight substance of M × 0.2 or less and the content of high molecular weight substance of M × 2.0 or more are 0.8% or more and 3, respectively.
If it is 5% or more, the dispersibility is insufficient.

The dispersant of the present invention is useful for dispersing inorganic substances, and is particularly effective as a dispersant for inorganic pigments, cement, pesticides, scale dispersion, detergent builders or drilling mud dispersion. Demonstrate. In the present invention, as the target inorganic substance, calcium carbonate, calcium phosphate, zinc phosphate, clay, bentonite, satin white, zinc white, red iron oxide, ferrite, titanium oxide, talc, white carbon, cement, gypsum, carbon black, And various silicates. Specifically, it is effective as a dispersant for calcium carbonate wet grinding, light calcium carbonate production process, ferrite production process, paper coating paint, water paint, mortar, concrete, drilling mud and the like. When the powder is dispersed in an aqueous solvent using the dispersant of the present invention, the amount of the dispersant to be used per solid is usually 0.001 to 10% by weight, preferably 0.05% by weight, based on the powder. ~ 5% by weight. If it is less than 0.0005%, the dispersing effect is insufficient, and if it exceeds 10% by weight, a cohesive action is exhibited and the viscosity of a high-concentration aqueous slurry increases. In particular, when an inorganic pigment such as calcium carbonate or titanium oxide is dispersed in water using the dispersant of the present invention, the amount of the dispersant used per solid content is usually 0 based on the weight of the dispersion composition. 0.01 to 5% by weight, preferably 0.05 to 1% by weight. If it is less than 0.0001%, the dispersing effect is insufficient, and if it exceeds 5% by weight, an aggregating action is exhibited and the viscosity increases. The amount of the inorganic pigment is 60 to 80% by weight.

The aqueous dispersion of the powder can be obtained by using the dispersant of the present invention by a conventional dispersion method. For example, the powder is added to an aqueous solution in which the dispersant of the present invention is dissolved. Stirring and mixing. As the aqueous solution, water, water and a water-soluble organic solvent (for example, methyl alcohol,
Ethyl alcohol, ethylene glycol, etc.). For this stirring and mixing, a commonly used stirring device such as a high-speed disperser, a homomixer, a ball mill, and a concrete mixer can be used. As another method, there is a method in which the dispersant of the present invention is added at the same time when the raw ore or coarse particles of the powder are wet-pulverized to obtain a dispersion.

In the present invention, pesticides used in the case of a dispersant for pesticide granules include insecticides, fungicides, acaricides, herbicides, and the like, and examples thereof include the following. As insecticides, o, o-dimethyl-s-
Fungicides such as (N-methylcarbamoylmethyl) dithiophosphate (dimethoate) and 3,5-xylyl-N-methylcarbamate (XMC) include 3-allyloxy-1,2-benzoylthiazole-1,1-dioxide ( Probenazole), etc .;
Examples include, but are not limited to, 4,6-trichlorophenyl-4-nitrophenol (generic name CNP), 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) acetanilide (butachlor) is not. These pesticides can be used alone or in combination of two or more. The dispersant of the present invention is used as a dispersant for a pesticide granule composition containing the above-described pesticide and inorganic mineral fine powder as constituent components. Examples of the inorganic mineral fine powder include bentonite, clay, talc, kaolin, calcium carbonate, and diatomaceous earth.

In addition to the above (co) polymer, the dispersant of the present invention includes, for example, a granulation improver (eg, a monovalent salt of carboxymethyl cellulose), a binder (eg, sodium ligninsulfonate, polyethylene glycol), and a penetrant (eg, Other dispersants (such as polyoxyethylene alkylphenyl ether) and the like can be added. Dioctylsulfosuccinic acid sodium salt, polyoxyethylene alkylphenyl ether sulfate sodium salt, and the like can be added. The dispersant is usually 0.2-10% based on the weight of the pesticide granule composition,
Preferably it is 1 to 5%. The amount of the inorganic mineral fine powder is usually 99 to 60%, preferably 96 to 75%. Pesticide is usually 1 to 15%, preferably 3 to 10%. The method for producing the pesticidal granule composition may be the same as the conventional method.For example, after adding an inorganic mineral fine powder and, if necessary, an auxiliary agent to a slurry containing a pesticide and a dispersant, kneading the mixture, extruding the mixture from a screen. It is molded and dried by a granulator, and a pesticide granule composition having a desired particle size is obtained by sieving with a shifter or the like. The pesticide granule composition is applied to fields and the like as it is.

As a method for obtaining a scale dispersing effect using the dispersant of the present invention, the dispersant may be used alone or in combination with various anticorrosive agents, slime control agents, etc., in water for boiler or water for cooling, continuously with a metering pump. , Or intermittently, or only when the concentration ratio is high. The scale dispersant may be injected neat or diluted with water to the appropriate concentration. The scale dispersant of the present invention is generally added in an amount of 1 to 50 ppm, preferably 2 to 20 ppm in terms of pure content.

The dispersant of the present invention is mixed with a surfactant, an alkali agent, an enzyme, a fluorescent agent, a bleaching agent, and other builders, and used as a detergent for clothing and the like. Examples of the surfactant include anionic surfactants (alkyl benzene sulfonate, α-olefin sulfonate, alkane sulfonate, alkyl sulfate, polyethylene glycol alkyl ether sulfate, sulfo fatty acid ester, fatty acid salt, etc.). Nonionic surfactants (polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyethylene glycol sorbitan fatty acid ester, coconut oil fatty acid diethanolamide, etc.); cationic surfactants (alkyltrimethylammonium chloride) , Dialkyldimethylammonium chloride, etc.); amphoteric surfactants (eg, alkyldimethylaminoacetate betaine) And the like.

Other builders (sodium tripolyphosphate, sodium metasilicate, sodium aluminosilicate, nitrilotriacetate, citrate, laurate, triethanolamine hydrochloride, etc.); inorganic compounds (nitrate, urea, etc.) Alkali (caustic soda, sodium carbonate, sodium silicate, triethanolamine, etc.); acid (hydrochloric acid, citric acid, etc.); solvent (ethanol, isopropyl alcohol, butyl alcohol, ethylene glycol, etc.); water; oxidizing agent (hydrogen peroxide, A reducing agent (such as sodium bisulfite); a chelating agent (such as ethylenediaminetetraacetate); a re-staining agent (such as carboxymethylcellulose); an abrasive (such as talc and finely divided silica); a turbidity agent; Colorants; preservatives; foaming agents; foam stabilizers; Ingredients such as an agent, an enzyme, a fluorescent dye, and a hydrotope agent can be blended.

When the dispersant of the present invention is used as a detergent builder, the amount of the dispersant is based on the weight of the detergent composition.
Usually, it is 0.05 to 50%, preferably 1 to 15%.
If the amount of the builder is less than this range, the ability to soften hard water and the ability to prevent re-contamination are insufficient, and the detergency is reduced. Exceeding the upper limit is uneconomical. The amount of the surfactant is usually 3 to 60%, preferably 10 to 40%, based on the weight of the detergent composition, and the amount of the other component is usually 30 to 90.
%, Preferably 50 to 70%. The detergent composition using the dispersant of the present invention can be prepared into a solid, powder, liquid, paste, slurry, etc. by a usual method.

The method of using the detergent composition using the dispersant of the present invention is not particularly limited.
It is used after being diluted about 0 times.

The detergent composition using the dispersant of the present invention can be preferably used as a detergent for textile products. Textile products include natural fibers such as cotton, wool, and silk;
Reproduced fibers such as rayon, semi-synthetic fibers such as acetate, synthetic fibers such as nylon, acrylic, polyester, and polypropylene, and knitted and woven fabrics made of various fibers mixed with these, especially household fiber products (underwear, Diapers, lingerie, sweaters, etc.). As a method of applying to textiles, for example, there is a method of diluting in water to adjust a washing bath, immersing, stirring, rinsing, and then squeezing and drying the textiles.

When the dispersant of the present invention is used as a dispersant for drilling mud, the drilling mud to be used is an inorganic clay mud such as bentonite, attapulgite, sepiolite, sericite, and carboxymethyl cellulose (salt). Polymer mud having a water-soluble polymer as a skeleton.

The amount (pure amount) of the dispersant of the present invention in the drilling mud is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight, based on the total weight of the drilling mud composition. . If it is less than 0.01% by weight, the effect of preventing deterioration of muddy water performance is low due to seawater, cement and other electrolytes.
%, The effect of mixing is not obtained, which is uneconomical.

In mixing the dispersant of the present invention into the drilling mud, the following method can be used. (1) A method in which an inorganic clay, a water-soluble polymer, and the additive of the present invention are simultaneously charged into kneading water. (2) An inorganic clay, a water-soluble polymer, and the like are previously charged in kneading water, and swelling thereof is performed. Method of adding the additive of the present invention later

An example of the method using the dispersant of the present invention is as follows. First, a muddy water composition is prepared by mixing the dispersant of the present invention, an inorganic clay, a water-soluble polymer and the like into water, and the ground is excavated using an excavator while circulating or retaining the muddy water composition in an excavation part. In this case, the muddy composition always fills the inside of the excavation part, absorbs frictional heat, releases heat, performs operations such as lubrication, and carries out excavated earth and sand to the ground to advance excavation and form an impermeable mud wall. Prevents the collapse of the borehole wall. After the predetermined excavation is completed, the concrete is filled in the excavation part and the pile or the wall is constructed while the concrete is put in from the bottom and the muddy water is collected from the excavation groove while the rebar frame is usually put. The drilling mud replaced with concrete is returned to the tank again and reused.

In addition to the dispersant of the present invention, a deterioration inhibitor, a putrefaction inhibitor, a dissolution promoter (ethylene glycol, diethylene glycol, polyethylene glycol, etc.), and a disintegrating agent (sodium nitrohumate, tannic acid, lignic acid, lignin) Sulfonic acid, condensed phosphate, etc.) may be used in combination.

[0052]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In Examples and Comparative Examples,% and parts represent% by weight and parts by weight. The method of measuring the peak top molecular weight by GPC and calculating the contents of low molecular weight substances and high molecular weight substances is as follows. The content of the peak top molecular weight, the low molecular weight substance and the high molecular weight substance are all values 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)

<< Method for Calculating Content of Low-Molecular-Weight Substance and High-Molecular-Weight Substance >> Based on the peak top molecular weight M, the following method was used to calculate (see FIG. 1). Low molecular weight compound: The ratio (%) of the area of the portion having a molecular weight of M × 0.2 or less to the total peak area (retention time, for example, a peak appearing by 20 minutes in FIG. 1) is calculated using a data processing device. did. High molecular weight substance: the molecular weight is M × 2.
The ratio (%) of the area of 0 or more portions was calculated using a data processing device. The GPC chart is based on the retention time.

<< Preparation Conditions by GPC >> Dispersants of Examples and Comparative Examples were obtained by fractionation or blending of fractionated products using the following apparatus. The peak top molecular weight, the content of low molecular weight substances and the content of high molecular weight substances were measured by the GPC. Model: Flep C-type liquid chromatographic preparative apparatus (manufactured by Soken Chemical Co., Ltd.) Column: TSK gel G3000pw TSK gel G5000pw (all manufactured by Tosoh Corporation) Column temperature: 20-30 ° C. Detector: RI solvent: 0. 5% sodium acetate / water / methanol (volume ratio 70/30) Flow rate: 30 ml / min Sample concentration: 2% by weight Injection amount: 50 ml Standard: polyoxyethylene glycol (Tosoh Corporation; TSK STANDARD POLYETHYLENE OXIDE)

[0055]

EXAMPLES Chain transfer agents (A) used in the following Examples
(G) and a chain transfer agent (H) used in Comparative Examples,
(I) used a compound having the structure shown in Table 1.

[0056]

[Table 1]

Example 1 370 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, 77 parts of acrylic acid, 228 parts of acrylic acid, 4 parts of chain transfer agent (A), 2 parts of sodium hypophosphite (dihydrate), and 0.7 parts of ferrous chloride (tetrahydrate) And 50 parts of a 6% aqueous solution of sodium persulfate from separate containers for 3 hours, 1 hour and 2 hours, respectively.
It was added dropwise over 5 hours. After the completion of the dropwise addition, 3 parts of a 35% aqueous hydrogen peroxide solution were added thereto, and the mixture was maintained at the same temperature for 1 hour.
After confirming 9 or more, sodium hydroxide 48% aqueous solution 3
Neutralize with 50 parts, distill off isopropyl alcohol,
An aqueous solution of sodium polyacrylate was obtained. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 2 370 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. With stirring, a uniform mixture of 102 parts of acrylic acid, 204 parts of acrylic acid, 4 parts of a chain transfer agent (A), 6 parts of sodium hypophosphite (dihydrate), and 70 parts of a 4% aqueous solution of sodium persulfate. Was added dropwise from separate containers over 3 hours, 1 hour after, 2 hours and 3.5 hours. After completion of the dropwise addition, 3 parts of a 35% aqueous hydrogen peroxide solution were added, the mixture was maintained at the same temperature for 1 hour, and after a polymerization rate of 99.9 or more was confirmed, the mixture was neutralized with 350 parts of a 48% aqueous sodium hydroxide solution and isopropyl alcohol was distilled off. After that, an aqueous solution of sodium polyacrylate was obtained. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 3 An aqueous sodium polyacrylate solution was obtained in the same manner as in Example 2, except that 8 parts of the chain transfer agent (B) was used instead of 4 parts of the chain transfer agent (A). Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 4 Chain transfer agent (C) 16 instead of 4 parts of chain transfer agent (A)
A sodium polyacrylate aqueous solution was obtained in the same manner as in Example 2 except that the parts were used. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 5 An aqueous sodium polyacrylate solution was obtained in the same manner as in Example 2 except that 5 parts of the chain transfer agent (D) was used instead of 4 parts of the chain transfer agent (A). Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 6 An aqueous sodium polyacrylate solution was obtained in the same manner as in Example 2 except that 9 parts of the chain transfer agent (E) was used instead of 4 parts of the chain transfer agent (A). Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 7 Chain transfer agent (F) 15 instead of 4 parts of chain transfer agent (A)
A sodium polyacrylate aqueous solution was obtained in the same manner as in Example 2 except that the parts were used. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 8 Chain transfer agent (G) 20 instead of 4 parts of chain transfer agent (A)
A sodium polyacrylate aqueous solution was obtained in the same manner as in Example 2 except that the parts were used. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 9 370 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. A homogeneous mixture of 102 parts of acrylic acid, 204 parts of acrylic acid, 6 parts of a chain transfer agent (A) and 15 parts of sodium hypophosphite (dihydrate) under stirring, and 4% of sodium persulfate
An aqueous solution (70 parts) was added dropwise from separate containers over 4.5 hours, 1 hour, 3.5 hours, and 5 hours.
After completion of the dropwise addition, 3 parts of a 35% aqueous hydrogen peroxide solution were added, the mixture was maintained at the same temperature for 1 hour, and after a polymerization rate of 99.9 or more was confirmed, the mixture was neutralized with 350 parts of a 48% aqueous sodium hydroxide solution and isopropyl alcohol was distilled off. After that, an aqueous solution of sodium polyacrylate was obtained. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 10 370 parts of isopropyl alcohol and 1 part of water were placed in a pressure-resistant reaction vessel.
70 parts were charged, sealed after nitrogen replacement, and heated to 110 ° C. Under stirring, 102 parts of acrylic acid, 204 parts of acrylic acid, 10 parts of chain transfer agent (D) and sodium hypophosphite (2
Hydrate) and 70 parts of a 5% aqueous solution of hydrogen peroxide in separate containers for 4.5 hours each.
After 3.5 hours, the solution was added dropwise over 3.5 hours and 5 hours. After the completion of the dropping, 3 parts of a 35% aqueous hydrogen peroxide solution were charged, and the mixture was heated at the same temperature for 1 hour.
After holding for a time and confirming a polymerization rate of 99.9 or more, the mixture was neutralized with 350 parts of a 48% aqueous sodium hydroxide solution, and isopropyl alcohol was distilled off to obtain an aqueous sodium polyacrylate solution. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 11 A partially neutralized aqueous solution of sodium polyacrylate was obtained in the same manner as in Example 2 except that neutralization was performed using 210 parts of a 48% aqueous sodium hydroxide solution. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of sodium polyacrylate.

Example 12 Instead of acrylic acid, acrylic acid / methacrylic acid = 5
A sodium salt aqueous solution of a copolymer of acrylic acid and methacrylic acid was obtained in the same manner as in Example 2 except that 0/50 (molar ratio) was used and 322 parts of a 48% aqueous sodium hydroxide solution was used. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

Example 13 Acrylic acid / hydroxyethyl methacrylate = 85/15 (molar ratio) was used instead of acrylic acid.
A sodium salt aqueous solution of a copolymer of acrylic acid and hydroxyethyl methacrylate was obtained in the same manner as in Example 5, except that 124 parts of an aqueous sodium hydroxide solution was used. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

Examples 14 to 18 From sodium polyacrylate obtained by polymerization according to a conventional method, various peak top molecular weights were measured using preparative GPC.
In addition, a fraction having a low content of a low molecular weight substance and a high molecular weight substance was obtained. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

Examples 19 to 23 Acrylic acid / methacrylic acid obtained by polymerization according to a conventional method =
From the sodium salt of the 50/50 (molar ratio) copolymer, fractions having various peak top molecular weights and low contents of low molecular weight substances and high molecular weight substances were obtained using preparative GPC. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

Examples 24 to 28 Various peak top molecular weights from sodium salt of an acrylic acid / hydroxyethyl methacrylate = 85/15 (molar ratio) copolymer obtained by polymerization according to a conventional method using preparative GPC. Thus, a fraction having a low molecular weight and a low molecular weight was obtained. Table 2 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

[0073]

[Table 2]

Comparative Examples 1 to 11 Polymers (Comparative Examples 1 to 11) were obtained in the same manner as in Examples 1 to 11, except that (H) was used as the chain transfer agent. Table 3 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

Comparative Examples 12 to 22 Polymers (Comparative Examples 12 to 22) were obtained in the same manner as in Examples 1 to 11, except that (I) was used as the chain transfer agent. Table 3 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

Comparative Examples 23 to 33 Polymers (Comparative Examples 23 to 33) were obtained in the same manner as in Examples 1 to 11 except that no chain transfer agent was used. Table 3 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

[0077]

[Table 3]

Comparative Examples 34 to 40 A fraction obtained using preparative GPC was blended from sodium polyacrylate obtained by polymerization according to a conventional method.
Polymers having various peak top molecular weights and high contents of low molecular weight substances and high molecular weight substances were obtained. Table 4 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

Comparative Examples 41-47 Acrylic acid / methacrylic acid obtained by polymerization according to a conventional method =
Fractions obtained by preparative GPC from the sodium salt of a 50/50 (molar ratio) copolymer are blended to obtain a polymer having various peak top molecular weights and a large content of low molecular weight and high molecular weight substances. A coalescence was obtained. Table 4 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

Comparative Examples 48 to 54 Acrylic acid / hydroxyethyl methacrylate = 85/15 (molar ratio) obtained by polymerization according to a conventional method was blended with a fraction obtained using preparative GPC from a sodium salt. As a result, polymers having various peak top molecular weights and high contents of low molecular weight substances and high molecular weight substances were obtained. Table 4 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

Comparative Example 55 A commercially available product of sodium polyacrylate “Cariblon L-
400 ". Table 4 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the polymer.

Comparative Example 56 A sodium salt of a copolymer of acrylic acid and methacrylic acid was obtained in the same manner as in Example 12 except that the chain transfer agent (H) was used instead of the chain transfer agent (A). Table 4 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

Comparative Example 57 A sodium salt of a copolymer of acrylic acid and hydroxymethacrylate was obtained in the same manner as in Example 13 except that the chain transfer agent (H) was used instead of the chain transfer agent (D).
Peak top molecular weight of the copolymer, low molecular weight content,
The high molecular weight content is shown in Table 4.

Comparative Example 58 A sodium salt of a copolymer of acrylic acid and methacrylic acid was obtained in the same manner as in Example 12 except that the chain transfer agent (I) was used instead of the chain transfer agent (A). Table 4 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

Comparative Example 59 A sodium salt of a copolymer of acrylic acid and hydroxymethacrylate was obtained in the same manner as in Example 13 except that the chain transfer agent (I) was used instead of the chain transfer agent (D).
Peak top molecular weight of the copolymer, low molecular weight content,
The high molecular weight content is shown in Table 4.

Comparative Example 60 A sodium salt of a copolymer of acrylic acid and methacrylic acid was obtained in the same manner as in Example 12 without using the chain transfer agent (A). Table 4 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

Comparative Example 61 A sodium salt of a copolymer of acrylic acid and hydroxymethacrylate was obtained in the same manner as in Example 13 without using the chain transfer agent (D). Table 4 shows the peak top molecular weight, low molecular weight content, and high molecular weight content of the copolymer.

[0088]

[Table 4]

The dispersants obtained in Examples and Comparative Examples were evaluated by the following test methods. Test Example 1 (Dispersion of heavy calcium carbonate powder) 30 parts of water, Examples 1 to 10, 14 to 18, Comparative Examples 1 to
5,10,23,24,35,36,38,55 and 0.2 parts (solid content) of dispersant was uniformly dissolved in each aqueous solution to obtain a powder of heavy calcium carbonate (Escalon 2000; manufactured by Sankyo Milling). 70 parts were added, and the mixture was stirred and dispersed at 3,000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo). Immediately after and after standing at 25 ° C. for 7 days, the viscosity was measured using a BL viscometer at 25 ° C. and 60 rpm. Table 5 shows the test results.

[0090]

[Table 5]

Test Example 2 (Wet grinding and dispersion of heavy calcium carbonate) 25 parts of water, Examples 1 to 11, 14 to 18, Comparative Example 1,
2, 6, 7 to 11, 14, 15, 22, 25, 26, 3
To each aqueous solution in which 0.6 part (solid content) of 3, 35, 36 to 38, and 55 dispersants are uniformly dissolved, 75 parts of coarse ore of calcium bicarbonate is added, and the mixture is stirred using a sand grinder for 30 minutes. Dispersed. The viscosities of the resulting 75% by weight calcium carbonate aqueous slurry immediately after production and after standing at 25 ° C. for 7 days were measured at 25 ° C. and 60 rpm using a BL viscometer.
It measured on condition of. Table 6 shows the test results.

[0092]

[Table 6]

Test Example 3 (Dispersion of Satin White) Examples 8 to 10, 15 to 18, Comparative Examples 8 to 10, 34 to
Using 40 dispersants, 1.74 g of a 50% aqueous solution of a dispersant (solid content) was added to 200 g of satin white cake containing 71% water, and the mixture was uniformly dispersed.
The viscosity of the slurry was measured at 5 ° C. and 60 rpm.
Table 7 shows the test results.

[0094]

[Table 7]

Test Example 4 (Dispersion of Concrete) A concrete mixture was prepared using the dispersants of Examples 2 to 8 and Comparative Examples 24 to 30, and a dispersion was obtained using a concrete mixer. The concrete was mixed at a unit cement amount of 320 kg / m ³ , a water / cement ratio of 55%, and a fine aggregate ratio of 46%. The test was performed with a dispersant (solid content) of 1% based on the cement. Table 8 shows the test results of the concrete dispersion at 25 ° C. (the dispersibility is represented by slump, and the larger the value of slump, the better the dispersibility).

[0096]

[Table 8]

Test Example 5 (Dispersant for pesticide granule) 25 parts of bentonite as a carrier (fine inorganic mineral powder)
5 parts of white carbon and 63 parts of talc, 5 parts of dimethoate as an insecticide, Examples 14 to 18 and Comparative Example 34
Composition 100 containing 1.5 parts of each of -38 dispersants
20 parts of water was added to each part and kneaded, granules having a diameter of 0.9 mm were prepared with a granulator, and used in the following water disintegration spreadability (dispersibility) test. Table 9 shows the results. (1) Underwater disintegration spreadability test method A 3 degree hard water is placed in a 10 cm diameter petri dish so as to have a depth of 1 cm, and the temperature is maintained at 20 ° C. One granule (particle diameter: 0.9 mm, length: 2 mm) is gently dropped in the center of the Petri dish, and after 30 minutes, the area of the underwater disintegration spread of the granule (c)
m ² ) was measured. The larger the area of the expansion, the better the dispersibility.

[0098]

[Table 9]

Test Example 6 (Scale Dispersion for Boiler) Examples 4, 5, 9, 10, 16 to 18 and Comparative Example 1
Using 3, 14, 20, 21, 38 to 40 dispersants, the scale dispersion effect on the calcium carbonate scale was evaluated. Scale dispersion evaluation method: 0.2% in 250 ml of deionized water.
50 ml of a 29% aqueous calcium chloride solution, 50 ml of a 0.44% aqueous sodium hydrogen carbonate solution,
ppm dispersant aqueous solution 50ml (10p
pm), adjust the pH to 8.5 with 0.1 N sodium hydroxide, and add deionized water to add 5
The solution was made up to 00 ml to prepare a 5 times supersaturated aqueous solution of calcium carbonate at 25 ° C. In the same manner, solutions were prepared in which the amount of the scale dispersant added was changed to 5 ppm, 7.5 ppm, 10 ppm, and 20 ppm. 300 ml of these solutions are placed in a glass bottle, sealed and sealed at 60 ° C. for 24 hours.
After standing for a while, the amount of precipitated calcium carbonate was observed. Table 10 shows the results.

[0100]

[Table 10]

Test Example 7 (Dispersion of scale for cooling water) Examples 13, 24 to 28 and Comparative Examples 48 to 54, 5
The scale dispersing effect on calcium phosphate was evaluated using 7, 59 and 61 dispersants. Scale dispersion evaluation method: 0.2% in 250 ml of deionized water.
30 ml of 29% aqueous solution of calcium chloride, 8 ml of 0.16% aqueous solution of sodium phosphate monobasic, 30 ml of aqueous solution of 0.44% sodium hydrogen carbonate, dispersant (solid content) 10
50 ml of a 0 ppm aqueous solution (corresponding to 10 ppm addition) was mixed, the pH was adjusted to 8.5 with 0.1 N sodium hydroxide, and then deionized water was added to 500 ml. In the same manner, the amount of the scale dispersant added was 5 ppm and 2 ppm.
A solution changed to 0 ppm was also prepared. These solutions 3
00 ml was placed in a glass bottle, sealed and allowed to stand at 60 ° C. for 24 hours to observe the amount of precipitated calcium phosphate. Table 11 shows the results.

[0102]

[Table 11]

Test Example 8 (for detergent builder) Examples 1, 6 to 10, 15 to 17 and Comparative Examples 12, 1
A detergency test was performed using the dispersants 7 to 21, 38, and 39 as builders. (1) Detergency test A powder detergent composition and a liquid detergent composition having the following composition were obtained using the builder of the present invention. Powder detergent composition Builder of the present invention: 15 parts LAS: 20 parts Sodium silicate: 10 parts Sodium carbonate: 6 parts Bow nitrate: 48 parts Carboxymethyl cellulose: 1 part Liquid detergent composition Builder of the present invention: 5 parts C12 _{/ 13} sec. Alcohol ethanol oxide 9 mol adduct: 25 parts C12 / ₁₃ aliphatic alcohol ethylene oxide 3 mol adduct sulfate salt sodium salt: 15 parts Ethanol 3 parts Water 52 parts

The detergent composition was tested for detergency by the following test method. Table 12 shows the test results. Preparation of Artificial Soil Artificial soil was prepared by mixing the following organic soil components, calcined clay, and carbon black at 69.7: 29.8: 0.5 (weight ratio). Organic soil components Oleic acid: 28.3 Triolein: 15.6 Cholesterol oleate: 12.2 Liquid paraffin: 2.5 Squalene: 2.5 Cholesterol: 1.6 Gelatin: 7.0 Washing This artificial soil is used. A contaminated cloth was prepared by an aqueous solvent-based wet method, cut into 5 cm × 5 cm, and the reflectance was 41 ± 2.
% Were subjected to the test. In the test, washing was performed under the following conditions using 10 pieces of the contaminated cloth and 3 pieces of cotton knitted cloth to which 60 mg of organic soil was adhered. Thereafter, the surface reflectance of the cloth before and after washing was measured, and the washing power was determined from the following equation. Detergency = [(K / S of dirty cloth−K / S of cleaning cloth)
) / (K / S of dirty cloth-K / S of clean cloth)]
× 100 K / S (n) = (1−R _n ) ² / 2R _n (Kube
lka-Munk formula) wherein R _n is the surface reflectance of the fabric showing the (%) / 100].

[0105]

[Table 12]

Test Example 9 (Dispersion for drilling mud) Examples 12, 19 to 23 and Comparative Examples 41 to 47, 5
Table 13 shows the test results of drilling mud using the dispersants of Nos. 6 and 58.
~ 16. The preparation and evaluation methods for the test solution are as follows. Preparation of test solution 100 parts of water and 6 parts of bentonite (Kunimine VI, manufactured by Kunimine Industries Co., Ltd.) were charged into a juicer mixer and stirred for 2 minutes. After standing for one day, the amounts of the (co) polymer salt and sodium aluminate shown in Table 1 were added, and the mixture was further stirred for 2 minutes to obtain a stable liquid composition.

Evaluation method (1) Funnel viscosity (FV): Measured with a 500 ml funnel viscometer. The unit is seconds. (2) 10 minutes gel strength (10 Gel): measured with a fan VG meter. The unit is lb / ft ² . (3) Dehydration amount: 3 kg using a filter according to API standards
The amount of dehydration after 30 minutes under a pressure of / cm ² was measured. The unit is m
l. (4) Stability to be mixed with cement: 1 and 3 parts of Portland cement were added to 100 parts of the stabilizing solution and mixed well.
After a lapse of one day, the stability liquid performance of the above (1) to (3) was measured. (5) Stability against seawater mixing: 0.4 and 1.2 parts of "Aquamarine S" (artificial seawater manufactured by Yasushi Pharmaceutical Co., Ltd.) were added to 100 parts of the stabilizing solution, mixed well, and after one day had passed. The performances of the above-mentioned stable liquids (1) to (3) were measured.

[0108]

[Table 13]

[0109]

[Table 14]

[0110]

[Table 15]

[0111]

[Table 16]

[0112]

According to the present invention, when the dispersant of the present invention is used for inorganic pigments and cements, it is possible to obtain a dispersion having a lower viscosity and a better aging stability than conventional dispersants. I do. Moreover, when used for pesticide granules, it is possible to obtain granules excellent in disintegration spreadability (dispersibility) in water. Further, by using the dispersant of the present invention for scale dispersion,
Boilers, cooling water for cooling towers (circulating water), seawater desalination equipment, etc. can be prevented from generating scale.
A decrease in thermal efficiency due to scale adhesion can be prevented. further,
When the dispersant of the present invention is used for a detergent builder, it has good compatibility with surfactants and mixing stability, and exhibits a good detergency-enhancing effect in washing textiles. In addition, since it is water-soluble, there is no fear that the powder adheres to the clothes after washing and becomes dusty, and there is no problem of eutrophication of rivers and lakes like polyphosphate. In addition, when the dispersant of the present invention is used as a dispersant for drilling mud, it can be used repeatedly because the physical properties of liquid (dispersion stability, dehydration amount) hardly change even when cement or seawater is mixed. Since the amount of dewatering is small, it is excellent in mud wall forming properties, that is, in the excavation hole collapse prevention performance. In addition, the dispersant of the present invention can obtain excellent performance as compared with the conventional one with a small amount of addition.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a GPC chart in <Method for calculating low molecular weight substance and high molecular weight substance> and is a diagram for explaining a peak top and peaks of low molecular weight substance and high molecular weight substance.
The horizontal axis indicates the retention time, the left vertical axis indicates the peak intensity (millivolt) by GPC, the right vertical axis indicates the logarithm of the molecular weight, and the broken line indicates the standard calibration curve.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C04B 24/26 C04B 24/26 FHG DZ A C08F 2/06 C08F 2/06 2/38 2/38 20 / 04 20/04 20/06 20/06 22/02 22/02 22/16 22/16 C09D 17/00 C09D 17/00 C09K 7/02 C09K 7/02 C C11D 3/37 C11D 3/37 // C04B 103: 40 C04B 103: 40 (31) Priority claim number Japanese Patent Application No. 7-209029 (32) Priority date July 24, 1995 (July 24, 1995) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-215227 (32) Priority date July 31, 1995 (July 31, 1995) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-215228 (32) Priority Date July 31, 1995 (July 31, 1995) (33) Countries claiming priority Japan (JP) (31) Priority claim number Japanese Patent Application Hei 7-216684 ( 32) Priority date August 1, 1995 (August 1995) (33) Priority country Japan (JP) (31) Priority number (2) Priority Date August 1, 1995 (August 1, 1995) (33) Priority Country Japan (JP) (72) Inventor Nao Yamauchi 11-Hitohashi Nohoncho, Higashiyama-ku, Kyoto-shi (1) Sanyo Kasei Kogyo Co., Ltd. (72) Inventor Taikao Saito 11-1, Nobashinohoncho, Higashiyama-ku, Kyoto Sanyo Kasei Kogyo Co., Ltd.

Claims (12)

[Claims] 1. A radical polymerization initiator comprising an α, β-unsaturated carboxylic acid (salt) as a constitutional unit and the following general formula (1):
A dispersant comprising a (co) polymer obtained by polymerization using a chain transfer agent for radical polymerization represented by the formula: General formula [Wherein Q is a polyvalent organic group, X ¹ is a carbonyl group or-
CONH—, A ¹ and A ² are divalent organic groups, X ² is an oxygen atom,
A sulfur atom or an NH group, Z is a chain transfer group, p, q, r,
x is any of the following cases 1) to 7), and m is 1 to
An integer of 50, n represents an integer of 2 to 100. The values in [] and the values in Δ when m is 2 to 50 may be the same or different. 1) When p is 0, x is 0, q is 0, and r is 0, 2) When p is 1, x is 0, q is 0, and r is 0, 3) p is 0 and x is 1 , Q is 1, r is 0, 4) p is 0, x is 1, q is 0, r is 0, 5) p is 0, x is 0, q is 1, and r is 0 6) When p is 1, x is 0, q is 1, and r is 0, 7) When p is 1, x is 0, q is 0, and r is 1. 2. An α, β-unsaturated carboxylic acid (salt) comprising (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid,
The dispersant according to claim 1, which is at least one compound selected from the group consisting of maleic acid half ester, fumaric acid half ester, and alkali metal salts, alkaline earth metal salts or ammonium salts thereof. 3. The (co) polymer further comprises an aromatic ethylenically unsaturated monomer, an aliphatic ethylenically unsaturated monomer having 2 to 20 carbon atoms, and an alicyclic having 5 to 15 carbon atoms. Ethylenically unsaturated monomer, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms, hydroxyl group-containing (meth) acrylate, amide-containing ethylenically unsaturated monomer, ethylenic having a polyalkylene glycol chain 3. The dispersant according to claim 1, wherein the dispersant is a copolymer obtained by copolymerizing at least one member selected from the group consisting of an unsaturated monomer and a sulfone group-containing monomer. 4. The dispersant according to claim 1, wherein in formula (1), the chain transfer group Z is SH. 5. The dispersant according to claim 1, wherein said polymer is obtained by solution polymerization, emulsion polymerization or suspension polymerization. 6. The dispersant according to claim 5, wherein the polymer is obtained by solution polymerization. 7. The dispersant according to claim 6, wherein the polymer is obtained by solution polymerization carried out in a solvent containing isopropanol as a constituent. 8. The (co) polymer whose GPC has a peak top molecular weight (M) of 5,000 to 15,000,
The content of a low molecular weight substance of × 0.2 or less and a high molecular weight substance of M × 2.0 or more are 0.8% or less and 3.5% or less, respectively, in an area on a GPC chart. The dispersant according to any one of claims 1 to 7, wherein 9. The dispersant according to claim 1, which is used for an inorganic pigment, a cement, or a pesticide granule. 10. The dispersant according to claim 1, which is used for scale dispersion. 11. The dispersant according to claim 1, which is for a detergent builder. 12. The dispersant according to claim 1, which is used for dispersing drilling mud.