JP2011006621A - Flow modifier for inorganic particle slurry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flow modifier that gives excellent flow characteristics even in an inorganic particle slurry, in which polyvalent metal ions exist, and maintains the flow characteristics.SOLUTION: The flow modifier comprises a copolymer (A) containing an ethylenic unsaturated carboxylic acid (a1), an ethylenic unsaturated carboxylic acid salt (a2) and an alkoxy polyoxyalkylene glycol ethylenic unsaturated carboxylic acid ester (a3) as essential constituent monomers in which the content of the unit (a1) is 9.9-79.9 mol%, the content of the unit (a2) is 0.1-40 mol% and the content of the unit (a3) is 20-90 mol% based on the molar numbers of the unit (a1), the unit (a2) and the unit (a3).

Description

  The present invention relates to a fluidity improver for an inorganic particle slurry.

  Conventionally, a polycarboxylic acid salt-based drug has been used for dispersing inorganic particles in an aqueous medium to form a slurry (Patent Document 1).

JP-A-8-188986

However, the conventional polycarboxylate-based drug has a problem that the slurry is remarkably thickened in the inorganic particle slurry in which polyvalent metal ions are present.
An object of the present invention is to provide a fluidity improver that can impart excellent fluidity and maintain fluidity even in an inorganic particle slurry in which polyvalent metal ions are present.

  The fluidity improver for inorganic particle slurry of the present invention is characterized by ethylenically unsaturated carboxylic acid (a1) unit, ethylenically unsaturated carboxylic acid salt (a2) unit and ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester. (A3) Based on the number of moles of the unit, the content of the ethylenically unsaturated carboxylic acid (a1) unit is 9.9 to 79.9 mol%, and the content of the ethylenically unsaturated carboxylate (a2) unit is The gist is that the content of an ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3) unit is 0.1 to 40 mol% and 20 to 90 mol%.

  The fluidizing agent for inorganic particle slurry of the present invention can impart excellent fluidity even in a slurry in which polyvalent metal ions are present.

  Examples of the ethylenically unsaturated carboxylic acid (a1) include ethylenically unsaturated monocarboxylic acid and ethylenically unsaturated dicarboxylic acid.

  As the ethylenically unsaturated monocarboxylic acid, aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like can be used.

Aliphatic monocarboxylic acids include (meth) acrylic acid, crotonic acid, 3-butenoic acid, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, 3-methyl-2-butenoic acid, 3-methyl- 3-butenoic acid, 2-methyl-3-butenoic acid, 2-methyl-2-butenoic acid, 2-ethyl-2-propenoic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-methyl- 2-pentenoic acid, 2-heptenoic acid, 4,4-dimethyl-2-pentenoic acid, 2-octenoic acid, 3-methyl-2-heptenoic acid, 2-nonenoic acid, 3-methyl-2-octenoic acid, 2 -Decenoic acid, 2-hydroxypropenoic acid, etc. are mentioned.
"(Meth) acryl ..." means metacri ..., cri ... (the same shall apply hereinafter).

  Examples of the alicyclic monocarboxylic acid include 1-cyclopentenecarboxylic acid, 3-cyclopentenecarboxylic acid, 4-cyclopentenecarboxylic acid, 1-cyclohexenecarboxylic acid, 3-cyclohexenecarboxylic acid, 4-cyclohexenecarboxylic acid, and 1-cycloheptene. Carboxylic acid, 3-cycloheptenecarboxylic acid, 4-cycloheptenecarboxylic acid, 5-cycloheptenecarboxylic acid, 1-cyclooctenecarboxylic acid, 3-cyclooctenecarboxylic acid, 4-cyclooctenecarboxylic acid, 5- Cyclooctenecarboxylic acid, 1-cyclononenecarboxylic acid, 3-cyclononenecarboxylic acid, 4-cyclononenecarboxylic acid, 5-cyclononenecarboxylic acid, 1-cyclodecenecarboxylic acid, 3-cyclodecenecarboxylic acid, 4-cyclo Dekencarboxylic acid and 5-cyclodekaenka Bonn acid and the like.

  As aromatic monocarboxylic acids, o-styrene carboxylic acid, p-styrene carboxylic acid, cinnamic acid, atropic acid, 5-vinyl-1-naphthalene carboxylic acid, 4-vinyl-1-naphthalene carboxylic acid and 4-vinyl- Examples include 1-anthraquinone carboxylic acid.

  Examples of unsaturated dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and intramolecular acid anhydrides thereof.

  Examples of aliphatic dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, butenedioic acid, 2-pentenedioic acid, 3-pentenoic acid, 4-pentenoic acid, 2-methyl-2-butene Acid, 2-ethyl-2-propenoic acid, 2-hexenedioic acid, 2-heptenedioic acid, 2-octenoic acid, 3-methyl-2-heptenedioic acid, 2-nonenedioic acid, 2-decenedioic acid and Examples include 2-hydroxyptenelodioic acid.

  Examples of the alicyclic dicarboxylic acid include 1,2-cyclopentene dicarboxylic acid, 1,3-cyclopentene dicarboxylic acid, 1,4-cyclopentene dicarboxylic acid, 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid, 4-cyclohexene dicarboxylic acid, 1,2-cycloheptene dicarboxylic acid, 1,3-cycloheptene dicarboxylic acid, 1,4-cycloheptene dicarboxylic acid, 1,5-cycloheptene dicarboxylic acid, 1,2- Cyclooctene dicarboxylic acid, 1,3-cyclooctene dicarboxylic acid, 1,4-cyclooctene dicarboxylic acid, 1,5-cyclooctene dicarboxylic acid, 1,2-cyclononene dicarboxylic acid, 1,3-cyclononene dicarboxylic acid, 1,4-cyclononene dicarboxylic acid, 1,5-cyclononene dicarboxylic acid, 1,2-cyclodecenedicarboxylic acid, 1,3-cyclodecenedicarboxylic acid, 1,4-cyclodecenedicarboxylic acid, 1,5-cyclodecenedicarboxylic acid and the like can be mentioned.

  Examples of the aromatic dicarboxylic acid include o, p-styrene dicarboxylic acid, o, p-styrene dicarboxylic acid, 4-vinyl-1,2-naphthalenedicarboxylic acid and 4-vinyl-1,3-anthraquinone dicarboxylic acid. .

  Examples of intramolecular acid anhydrides of unsaturated dicarboxylic acids include maleic anhydride, itaconic anhydride, and citraconic anhydride.

  Of these ethylenically unsaturated carboxylic acids, aliphatic monocarboxylic acids and aliphatic dicarboxylic acids are preferable from the viewpoint of flow characteristics and the like, more preferably (meth) acrylic acid and maleic anhydride, particularly preferably (meth). Acrylic acid.

Examples of the ethylenically unsaturated carboxylate (a2) include alkali metal salts, alkaline earth metal salts, amine salts, ammonium salts and / or quaternary organic ammonium salts of the ethylenically unsaturated carboxylic acid (a1). It is.
The ethylenically unsaturated carboxylic acid includes the ethylenically unsaturated monocarboxylic acid and ethylenically unsaturated dicarboxylic acid described for the ethylenically unsaturated carboxylic acid (a1), and the preferred range is the same as above.

Examples of the alkali metal salt include lithium, potassium and sodium salts.
Examples of the alkaline earth metal salt include salts such as calcium or magnesium.
As the amine salt, a salt such as an aliphatic amine having 2 to 6 carbon atoms, an alicyclic amine having 3 to 6 carbon atoms, or an aromatic amine having 6 to 8 carbon atoms can be used.

  Examples of the aliphatic amine include ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, dimethylethanolamine, diethylethanolamine, and ethylenediamine.

  Examples of alicyclic amines include cyclopropylamine, cyclobutylamine, cyclopentylamine, and cyclohexylamine.

  Examples of the aromatic amine include aniline, pyridine, piperidine, benzylamine, and phenylenediamine.

  As the quaternary organic ammonium salt, an organic ammonium salt having 4 to 8 carbon atoms can be used, such as tetramethylammonium salt, tetraethylammonium salt, trimethylethylammonium salt, N-methylpyridinium salt and N-methylimidazolium salt. Is mentioned.

  Of these salts, alkali metal salts, amine salts and quaternary organic ammonium salts are preferable, lithium salts, potassium salts, sodium salts and quaternary organic ammonium salts are more preferable, and sodium salts and quaternary salts are particularly preferable. Organic ammonium salt.

  That is, among the ethylenically unsaturated carboxylates (a2), aliphatic monocarboxylic acids or aliphatic dicarboxylic acid alkali metal salts, amine salts and / or quaternary organic ammonium salts are preferred, and (meth) is more preferred. Alkali metal salts, amine salts and / or quaternary organic ammonium salts of acrylic acid or maleic acid, particularly preferably sodium salt or quaternary organic ammonium salt of (meth) acrylic acid acrylic acid.

  Examples of the ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3) include ethylenically unsaturated monocarboxylic acid alkoxyalkylene ester, ethylenically unsaturated dicarboxylic acid alkoxypolyoxyalkylene ester, and mixtures thereof.

  Examples of oxyalkylene include oxyalkylene having 2 to 4 carbon atoms (oxyethylene, oxypropylene and oxybutylene).

  The polyoxyalkylene may be composed of one kind of oxyalkylene or may be composed of two or more kinds of oxyalkylene. When composed of two or more oxyalkylenes, the bonding mode may be block, random, or a mixture thereof.

  The degree of polymerization of the polyoxyalkylene group is preferably 2 to 90, more preferably 4 to 60, and particularly preferably 10 to 40 from the viewpoint of improving fluidity.

  As an alkoxy group, a C1-C30 hydrocarbon group etc. are contained and a linear alkyloxy group, a branched alkyloxy group, etc. can be used.

  Linear alkyl alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy , Hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, icosyloxy, henicosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, heptacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy And triaconyloxy and the like.

  Examples of branched alkylalkoxy groups include isopropyloxy, isobutyloxy, t-butyloxy, isopentyloxy, neopentyloxy, isohexyloxy, 2-ethylhexyloxy, isotridecyloxy, isooctadecyloxy, and isotriaconcyloxy Is mentioned.

  Among these alkoxy groups, a linear alkyloxy group is preferable from the viewpoint of improving fluidity, and a linear alkyloxy group having 1 to 18 carbon atoms is more preferable, and methoxy, ethoxy and octadecyloxy are particularly preferable.

  The copolymer (A) is composed of an ethylenically unsaturated carboxylic acid (a1), an ethylenically unsaturated carboxylic acid salt (a2), and an ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3). An unsaturated monomer (a4) can be included as a constituent monomer.

  Other ethylenically unsaturated monomers (a4) include ethylenically unsaturated carboxylic acid (a1), ethylenically unsaturated carboxylic acid salt (a2), and ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3). If it can be copolymerized with olefin, there will be no restriction | limiting, and an olefin, an ethylenically unsaturated nitrile, an ethylenically unsaturated amide, etc. are mentioned.

  Examples of the olefin include α-olefins having 2 to 20 carbon atoms (ethylene, propylene, butylene, hexylene, octylene, undecylene, tetradecylene, and nonadecylene), diisobutylene, butadiene, piperylene, chloroprene, pinene, limonene, indene, and cyclopentadiene. , Bicyclopentadiene, ethylidene norbornene and the like.

  Examples of the ethylenically unsaturated nitrile include (meth) acrylonitrile, cyanopropene and cyanopentene.

  Examples of the ethylenically unsaturated amide include (meth) acrylamide, N-methyl (meth) acrylamide, N-2-hydroxymethyl (meth) acrylamide, N- (2-aminoethyl) (meth) acrylamide and N- (2- And dimethylaminoethyl) (meth) acrylamide.

  The content (mol%) of the ethylenically unsaturated carboxylic acid (a1) unit is such that the ethylenically unsaturated carboxylic acid (a1) unit, the ethylenically unsaturated carboxylic acid salt (a2) unit, and the ethylenically unsaturated carboxylic acid alkoxy poly Based on the number of moles of the oxyalkylene ester (a3) unit, 9.9 to 79.9 is preferable, more preferably 20 to 69.5, particularly preferably 30 to 59, and most preferably 35 to 50. Within this range, the fluidity is further improved.

  The content (mol%) of the ethylenically unsaturated carboxylate (a2) unit is determined by the ethylenically unsaturated carboxylic acid (a1) unit, the ethylenically unsaturated carboxylate (a2) unit, and the ethylenically unsaturated carboxylate alkoxy. Based on the number of moles of the polyoxyalkylene ester (a3) unit, 0.1 to 40 is preferable, more preferably 0.5 to 35, particularly preferably 1 to 30, and most preferably 5 to 20. Within this range, the fluidity is further improved.

  The content (mol%) of the ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3) unit is determined based on the ethylenically unsaturated carboxylic acid (a1) unit, the ethylenically unsaturated carboxylic acid salt (a2) unit, and the ethylenically unsaturated group. Based on the number of moles of the saturated carboxylic acid alkoxypolyoxyalkylene ester (a3) unit, 20 to 90 are preferable, more preferably 30 to 79.5, particularly preferably 40 to 69, and most preferably 45 to 60. . Within this range, the fluidity is further improved.

  When other ethylenically unsaturated monomer (a4) is included, the content (mol%) of other ethylenically unsaturated monomer (a4) is ethylenically unsaturated carboxylic acid (a1) unit, ethylenic. Based on the number of moles of the unsaturated carboxylate (a2) unit and the ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3) unit, 0.1 to 40 is preferable, more preferably 0.5 to 25, and particularly Preferably it is 1-10, but it is most preferable not to contain another ethylenically unsaturated monomer (a4).

The weight average molecular weight (Mw) of the copolymer (A) is preferably 5,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 15,000 to 70, from the viewpoint of fluidity. 20,000, most preferably 20,000 to 50,000.
Within this range, the fluidity is remarkably excellent and the fluidity can be maintained over a long period of time.

  The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) method using (poly) ethylene glycol of known molecular weight as a standard substance (column temperature 40 ° C., eluent methanol: ion-exchanged water: Sodium acetate = 800: 1200: 15 (weight ratio), flow rate 0.8 ml / min, sample concentration: 0.4 wt% eluent solution.).

  The copolymer (A) can be obtained by using an ordinary vinyl monomer polymerization method. As the polymerization method, suspension polymerization, bulk polymerization, solution polymerization and the like can be applied. From the viewpoint of productivity, solution polymerization is possible. Is preferred.

  The copolymer (A) is composed of an ethylenically unsaturated carboxylic acid (a1), an ethylenically unsaturated carboxylic acid salt (a2), an ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3), and other ethylenically if necessary. Method of producing unsaturated monomer (a4) by copolymerization (Method 1); ethylenically unsaturated carboxylic acid (a1), ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3), and other if necessary A method of preparing an ethylenically unsaturated monomer (a4) by copolymerization and then neutralizing with a base (such as an alkali metal hydroxide or ammonia) (Method 2); and (Method 1) and ( It can be obtained by a method (method 3) or the like using method 2) in combination.

  A polymerization catalyst can be used for the polymerization. As the polymerization catalyst, an ordinary polymerization catalyst or the like is used, and azo compounds, persulfates, inorganic peroxides, redox catalysts, organic peroxides, and the like are included. Examples of the azo compound include 2,2′-azobisisobutyronitrile, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis (4-methoxy-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], 1,1'-azobis (1-acetoxy-1-phenylethane) and the like. Examples of the salt include ammonium persulfate, potassium persulfate, sodium persulfate, etc. Examples of the inorganic peroxide include perborate and hydrogen peroxide. Examples of the redox catalyst include ascorbic acid-hydrogen peroxide, etc. Examples of the organic peroxide include benzoyl peroxide, etc. These polymerization catalysts may be used alone or in combination. Of these, persulfates and azo compounds are preferred, more preferred are persulfates and 2,2′-azobisisobutyronitrile, and particularly preferred are ammonium persulfate, potassium persulfate, and sodium persulfate.

  When the polymerization catalyst is used, the amount (% by weight) of the polymerization catalyst is preferably 3 to 100, more preferably 8 to 80, and particularly preferably 10 to 60, based on the weight of the constituent monomer.

  Moreover, you may use the chain transfer agent for radical polymerization as needed. Examples of chain transfer agents include thiocarboxylic acids (n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, etc.), thiolic acids (thioglycolic acid, thiomalic acid, etc.), secondary alcohols (isopropanol, etc.), amines (dibutylamine, etc.). ), Hypophosphites (sodium hypophosphite, etc.) and the like.

  When the chain transfer agent is used, the amount (% by weight) of the chain transfer agent is preferably 0.01 to 10, more preferably 0.05 to 5, particularly preferably based on the weight of the constituent monomer. 0.1-1.

In the case of solution polymerization and suspension polymerization, the solvent includes water (tap water, ion exchange water, industrial water, etc.), alcohol solvent (methanol, ethanol, isopropyl alcohol, etc.) and / or aromatic solvent (toluene, xylene, etc.). Etc. can be used. Among these, water, a mixed solvent of water and an alcohol solvent are preferable, a mixed solvent of water and alcohol is more preferable, and a mixed solvent of ion-exchanged water and isopropyl alcohol is particularly preferable.
When a solvent is used, the amount (% by weight) used is preferably 50 to 900, more preferably 60 to 800, and particularly preferably 100 to 600, based on the total weight of the constituent monomers.

  The polymerization reaction temperature is preferably about 40 to 130 ° C., and the polymerization reaction time is preferably about 1 to 15 hours.

  In addition, you may superpose | polymerize, dripping the whole quantity or one part of a structural monomer. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a polymerization catalyst. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a solvent with a structural monomer or a polymerization catalyst. On the other hand, the entire amount of the solvent may be charged in a polymerization tank and polymerization may be performed while removing the solvent. Among these, from the viewpoint of productivity and the like, the method of dropping the whole amount of the constituent monomer and the polymerization catalyst and the method of dropping a part of the solvent together with the constituent monomer or the polymerization catalyst are preferable, and more preferably the constituent unit. In this method, the entire amount of the monomer and the polymerization catalyst is dropped together with a part of the solvent.

The form of the copolymer (A) is not particularly limited, and may be liquid or solid.
When the copolymer (A) is in a liquid state, it means a state in which the copolymer (A) is dissolved or dispersed in an aqueous solvent. In this case, the copolymer (A) may be obtained by suspension polymerization or solution polymerization without removing all of the solvent, or the copolymer (A) obtained by bulk polymerization or the like may be dissolved in an aqueous solvent. Alternatively, it may be obtained by dispersing.
Examples of the aqueous solvent include water, alcohols having 1 to 6 carbon atoms (such as ethyl alcohol, methyl alcohol, ethylene glycol and diethylene glycol), and ketones having 1 to 6 carbon atoms (such as methyl isobutyl ketone and acetone). You may use individually or in mixture.

On the other hand, when the copolymer (A) is solid, it may be a solid made of the copolymer (A) or may be a powder in which the liquid copolymer (A) is supported on a powder. .
In the case of a solid comprising the copolymer (A), it may be obtained by bulk polymerization, or after the solution or dispersion containing the copolymer (A) is obtained by suspension polymerization or solution polymerization, the solvent is removed. May be obtained.
As a method for removing the solvent from the solution or dispersion containing the copolymer (A), known methods such as a dry pulverization method, a freeze pulverization method, a spray dryer method, and a drum dryer method can be used. Of these, the dry pulverization method and the spray dryer method are preferred.
The size (mm; maximum length) of the solid copolymer (A) is preferably 0.01 to 5, more preferably 0.05 to 3 from the viewpoint of the solubility of the fluidizing agent of the present invention. Especially preferably, it is 0.08-1.
When the liquid copolymer (A) is supported on a powder, examples of the powder include activated carbon, calcium carbonate, silica, zeolite, shirasu balloon, and bentonite.
As a method for supporting the liquid copolymer (A) on these powders, the powder and the liquid copolymer (A) can be obtained by using a known stirring mixer (such as a ribbon mixer and a Henschel mixer). A method of stirring and mixing can be applied.
Among the forms of the copolymer (A), a liquid form is preferable, and a state where the copolymer (A) is dissolved in an aqueous solvent is more preferable.

The fluidity improver for inorganic particle slurry of the present invention further includes a polyoxyalkylene compound (B1) represented by the general formula (1) and / or a polyoxyalkylene compound (B2 represented by the general formula (2)). ) May be contained.
First, the polyoxyalkylene compound (B1) represented by the general formula (1) will be described.

{R ^1- (OA-) ni} m Q (1)

Q is a reaction residue obtained by removing a hydrogen atom from m primary hydroxyl groups of non-reducing di- or trisaccharides, OA is an oxyalkylene group having 2 to 4 carbon atoms, and R ¹ is an alkyl group having 1 to 3 carbon atoms. Represents a propenylene group and / or a hydrogen atom, m R ¹ and m (OA) ni may be the same or different, ni is an integer of 0 to 100, m is an integer of 2 to 4, i Represents an integer of 1 to m, and m ni may be the same or different, but at least one is 1 or more, and the total number of OA (Σni × m) is 10 to 100.

R ^2- (OA-) p OH (2)

R ² represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and p represents an integer of 1 to 100.

  Examples of di- or trisaccharides that can constitute a reaction residue (Q) obtained by removing a hydrogen atom from m primary hydroxyl groups of non-reducing di- or trisaccharides include sucrose, trehalose, isotrehalose, Examples include isosaccharose, gentianose, raffinose, meretitol and planteose. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of fluidity and the like, more preferably trehalose and sucrose, and particularly preferably sucrose from the viewpoint of supply and cost. These may be used alone or in combination.

  m is preferably an integer of 2 to 4, more preferably 3 or 4, and particularly preferably 3. Within this range, the fluidity is further improved. This m corresponds to the number of primary hydroxyl groups of the non-reducing di- or trisaccharide.

ni is preferably an integer of 0 to 100, more preferably an integer of 2 to 98, particularly preferably an integer of 5 to 95, and most preferably an integer of 7 to 90. Within this range, the fluidity is further improved.
i represents an integer of 1 to m, and m ni may be the same value or different values, but at least one is 1 or more.

  The total number of OA (Σni × m) is preferably 10 to 100, more preferably 25 to 95, particularly preferably 30 to 90, and most preferably 35 to 85. Within this range, the fluidity is further improved.

Examples of the oxyalkylene group (OA) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Among these, from the viewpoint of fluidity, oxyethylene, a mixture containing oxyethylene and oxypropylene are preferable, and a mixture containing oxyethylene is more preferable.
The ni OA may be the same or different, and the m (OA) ni may be the same or different.

  When plural kinds of oxyalkylene groups are contained in OA, there is no limitation on the bonding order (block shape, random shape and combinations thereof) and content ratio of these oxyalkylene groups, but the block shape or block shape and random shape It is preferable to include the combination of these. In this case, oxyethylene is preferably included, and the content ratio (% by weight) of oxyethylene is preferably 2 to 30, more preferably 3 to 27, and particularly preferably based on the total weight of the oxyalkylene group. 4-23, most preferably 5-20.

  When OA contains an oxyethylene group and an oxypropylene group and / or oxybutylene group, it is preferable that the oxypropylene and / or oxybutylene is located away from the reaction residue (Q). That is, it is preferable that an oxyethylene group is directly bonded to the reaction residue (Q).

Among the alkyl group having 1 to 3 carbon atoms, the propenylene group and / or the hydrogen atom (R ¹ ), examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl and iso-propyl. In addition, examples of the propenylene group include 2-propenyl and 1-propenyl. Of these, methyl, ethyl, iso-propenyl and 2-propenyl are preferable, methyl, ethyl and 2-propenyl are more preferable, and methyl and ethyl are particularly preferable.
The m R ^{1 s} may be the same or different.

During the m R ^1, when containing an alkyl group and / or an alkenyl group, of all the R ^1, the number of hydrogen atoms, 0-3 preferably when m is 4, more preferably 0 to 2, Particularly preferably 0 or 1, when m is 3, 0 to 3 is preferable, more preferably 0 or 1, and when m is 2, 0 or 1 is preferable.

  The polyoxyalkylene compound (B1) represented by the general formula (1) includes a non-reducing di- or trisaccharide (b1), an alkylene oxide (b2) having 2 to 4 carbon atoms, and optionally 1 to 3 carbon atoms. Those having a structure that can be produced by a chemical reaction of the monohalogenated hydrocarbon (b3). That is, the polyoxyalkylene compound (B1) having a structure that can be produced by such a chemical reaction may cause distribution in the oxyalkylene group. In this case, strictly speaking, a plurality of types of polyoxyalkylene compounds (B1) In this mixture, the polyoxyalkylene compound (B1) represented by the general formula (1) is contained. Even in this case, the manufacturing method is not limited.

And as usage-amount (mol part) of alkylene oxide (b2), 10-100 are preferable with respect to 1 mol part of non-reducing di- or trisaccharide (b1), More preferably, it is 25-95, Most preferably Is 30-90, most preferably 35-85. Within this range, the fluidity is further improved.
Moreover, when using C1-C3 monohalogenated hydrocarbon (b3), as usage-amount (mol part) of (b3), with respect to 1 mol part of non-reducing di- or trisaccharide units, 1-4 are preferable, More preferably, it is 1.2-3.7, Most preferably, it is 1.4-3.3, Most preferably, it is 1.5-3.0. Within this range, the fluidity is further improved.

  As the non-reducing di- or trisaccharide (b1), the same disaccharide or trisaccharide that can constitute the reaction residue (Q) in the general formula (1) can be used, and the preferred range is also the same.

Examples of the alkylene oxide (b2) include alkylene oxides having 2 to 4 carbon atoms, ethylene oxide (EO), propylene oxide (PO), butylene oxide (1,2-butylene oxide, etc.) (BO), and mixtures thereof. Etc. Among these, from the viewpoint of fluidity and the like, EO, a mixture containing EO and PO are preferable, and more preferably a mixture containing EO.
Moreover, when using multiple types of alkylene oxide, although it does not restrict | limit to the order (block shape, random shape, and these combination) and the usage rate to make it react, it is preferable to include a block shape or the combination of block shape and random shape. In this case, it is preferable to contain EO, and the use ratio (% by weight) of EO is preferably 2 to 30, more preferably 3 to 27, particularly preferably 4 to 4, based on the total weight of the alkylene oxide. 23, most preferably 5-20. When EO and PO or / and BO are included, it is preferable to react PO and / or BO after the reaction of EO.

As the monohalogenated hydrocarbon (b3), monohalogenated alkyl having 1 to 3 carbon atoms, monohalogenated propene and the like can be used. Examples of the monohalogenated alkyl include monochloromethane, monobromomethane, monochloroethane, monobromoethane, 2-bromopropane, 1-chloropropane and 2-chloropropane.
Examples of the monohalogenated propene include 1-chloropropene, 1-bromopropene, 2-bromopropene and 2-chloropropene.
Of these, monochloromethane, monobromomethane, monochloroethane, monobromoethane, 2-bromopropane, 2-chloropropane, 1-chloropropene and 1-bromopropene are preferable, and monochloromethane, monobromomethane, mono Chloroethane, monobromoethane, 1-chloropropene and 1-bromopropene, particularly preferably monochloromethane, monobromomethane, monochloroethane and monobromoethane.
These may be used alone or in combination.

  The polyoxyalkylene compound (B1) can be obtained by a known alkylene oxide addition reaction and Williamson synthesis reaction (International Publication WO 2004/101103 pamphlet, etc.).

Next, the polyoxyalkylene compound (B2) represented by the general formula (2) will be described.
Among hydrogen atoms, alkyl groups having 1 to 30 carbon atoms or alkenyl groups having 2 to 30 carbon atoms (R ² ), linear alkyl groups and branched alkyl groups are used as the alkyl groups having 1 to 30 carbon atoms. it can.

  Linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl , Tricosyl, tetracosyl, heptacosyl, hexaxyl, heptacosyl, octacosyl, nonacosyl and triaconsil.

  Examples of the branched alkyl group include isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, isohexyl, 2-ethylhexyl, isotridecyl, isotetradecyl, isooctadecyl, isotriaconyl, 2-ethylhexyl, 2-propylheptyl, 2-propyl Examples include butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexyl, 2-dodecylhexadecyl, 3,5,5-trimethylhexyl, and 3,7,11-trimethyldodecyl. It is done.

Furthermore, (R ^2), examples of the alkenyl group having 2 to 30 carbon atoms, such as a linear alkenyl group and branched alkenyl groups can be used.

  Linear alkenyl groups include vinyl, allyl, propenyl, butenyl, pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, hexocenyl, , Tetracosenyl, heptacosenyl, hexaxenyl, heptacosenyl, octacocenyl, nonacosenyl, triaconenyl and the like.

  Examples of the branched alkenyl group include isobutenyl, isopentenyl, neopentenyl, isohexenyl, isotridecenyl, isooctadecenyl, and isotriacontenyl.

  Among these, from the viewpoint of fluidity, a hydrogen atom, a linear alkyl group and a branched alkyl group are preferable, more preferably a hydrogen atom and a branched alkyl group, particularly preferably a branched alkyl group having 4 to 18 carbon atoms, and most preferably. Are 2-ethylhexyl, 2-butyloctyl and 2-octyldodecyl.

The oxyalkylene group (OA) having 2 to 4 carbon atoms is the same as in the general formula (1). Of these, oxyethylene and oxypropylene are preferred.
OA may contain two or more oxyalkylene groups. When two or more kinds of oxyalkylene groups are contained, any of block, random and a mixture thereof may be used, but a block of oxyethylene and oxypropylene is preferable.

  p represents an integer of 1 to 100, preferably an integer of 2 to 50, more preferably an integer of 4 to 20, and particularly preferably an integer of 6 to 15.

  The polyoxyalkylene compound (B2) may be a single compound having one kind of p or a mixture having a distribution (a compound having a distribution is preferable from the viewpoint of ease of production). Moreover, the mixture of the compounds from which the kind of alkyl group or alkenyl group differs may be sufficient.

  The polyoxyalkylene compound (B2) can be obtained by a known alkylene oxide addition reaction (Japanese Patent Laid-Open No. 2005-054128).

The polyoxyalkylene compound (B2) can be easily obtained from the market, and examples thereof include the following products.
PEG series (PEG200, PEG600, PEG1000, PEG2000, PEG4000S, etc.) {manufactured by Sanyo Chemical Industries, Ltd.}
Narrow Acty (registered trademark) series (CL-40, CL-70, CL-100, CL-120, CL-140, CL-160, ID-40, ID-60, ID-70, FD-80, FD- 140 etc.) {Sanyo Chemical Industries, Ltd.}
New Paul (registered trademark) series (LB-285, LB-1715, 50HB-100, 50HB-260, 50HB-400, PP-200, PP-1000, PP-4000, PE-61, PE-71, PE- 75 etc.) {Sanyo Chemical Industries, Ltd.}
Sannonic (registered trademark) series (SS-70, SS-90, SS-120, etc.) {manufactured by Sanyo Chemical Industries Ltd.}

  When the polyoxyalkylene compound (B1) and / or (B2) is contained, the content (% by weight) of the polyalkylene compound (B1) and / or (B2) depends on the copolymer (A), the polyalkylene compound ( Based on the total weight of B1) and (B2), 0.1-40 are preferable, More preferably, it is 0.2-30, Most preferably, it is 0.5-20. Within this range, the fluidity is further improved.

  When the polyoxyalkylene compounds (B1) and (B2) are contained, the content (% by weight) of the polyoxyalkylene compound (B1) is 0 based on the weight of the polyoxyalkylene compounds (B1) and (B2). 1 to 60 is preferable, 1 to 50 is more preferable, and 10 to 30 is particularly preferable. In this case, the content (% by weight) of the polyoxyalkylene compound (B2) is preferably 40 to 99.9, more preferably 50 based on the weight of the polyoxyalkylene compounds (B1) and (B2). ˜99, particularly preferably 70˜90.

  When the polyoxyalkylene compound (B1) and / or (B2) is contained, the content (% by weight) of the copolymer (A) is the copolymer (A), polyalkylene compounds (B1) and (B2). 60 to 99.9 is preferable, 70 to 99.8 is more preferable, and 80 to 99.5 is particularly preferable. Within this range, the fluidity is further improved.

The fluidizing agent of the present invention may contain other components (such as a surfactant and / or an aqueous solvent) in addition to the copolymer (A) and the polyoxyalkylene compounds (B1) and (B2). Good.
As the surfactant, nonionic, cationic, anionic or amphoteric surfactants can be used.

  Nonionic surfactants include alkylphenol alkylene oxide (alkylene oxide having 2 to 4 carbon atoms unless otherwise specified) adduct, higher fatty acid alkylene oxide adduct, polyhydric alcohol fatty acid ester, higher alkyl amine alkylene oxide. Examples include adducts, alkylene oxide adducts of higher fatty acid amides, alkylene oxide adducts of acetylene glycol, and polyoxyalkylene-modified silicones (polyether-modified silicones).

  Examples of cationic surfactants include higher alkylamine salts, higher alkylamine alkylene oxide adducts, solomin A type cationic surfactants, sapamin A type cationic surfactants, Arcobel A type cationic surfactants, and imidazoline type cationic surfactants. Agents, higher alkyltrimethylammonium salts, higher alkyldimethylbenzylammonium salts, sapamine-type quaternary ammonium salts and pyridinium salts.

  Examples of the anionic surfactant include fatty acid salts, α-olefin sulfonates, alkylbenzene sulfonic acids and salts thereof, alkyl sulfate esters, alkyl ether sulfates, N-acyl alkyl taurates, and alkyl sulfosuccinates. It is done.

  Examples of amphoteric surfactants include higher alkylaminopropionates and higher alkyldimethylbetaines.

  When the surfactant is contained, the content (% by weight) is 0.1 to 20 based on the weight of the copolymer (A), the polyoxyalkylene compound (B1) and the polyoxyalkylene compound (B2). Is preferable, more preferably 0.5 to 10, and particularly preferably 1 to 5. Within this range, the fluidity is further improved.

Examples of the aqueous solvent include those described above.
When the aqueous solvent is contained, the content (% by weight) is preferably 10 to 1000 based on the weight of the copolymer (A), the polyoxyalkylene compound (B1) and the polyoxyalkylene compound (B2). More preferably, it is 50-900, Most preferably, it is 100-600.

  When the fluidity improver for inorganic particle slurry of the present invention contains the polyoxyalkylene compound (B1), polyoxyalkylene compound (B2) and / or other components, the fluidity improvement for inorganic particle slurry of the present invention The agent is obtained by uniformly mixing (uniformly dissolving or uniformly dispersing) the copolymer (A) with the polyoxyalkylene compound (B1), the polyoxyalkylene compound (B2) and / or other components.

  For example, when the copolymer (A) is in a liquid state, the polyoxyalkylene compound (B1) and / or the polyoxyalkylene compound (B2) is uniformly mixed with the copolymer (A) together with the aqueous solvent (uniform dissolution or uniform dispersion). )

  When the copolymer (A) is solid, the copolymer (A) is uniformly mixed (uniformly dissolved or uniformly dispersed) with the polyoxyalkylene compound (B1) and / or the polyoxyalkylene compound (B2). May be. Moreover, the fluidity improver of the present invention supports a liquid in which a liquid copolymer (A) and a polyoxyalkylene compound (B1) and / or a polyoxyalkylene compound (B2) are uniformly mixed, supported on a powder. Powder may be sufficient.

  The fluidizing agent of the present invention is suitable as a fluidizing agent for inorganic particle slurry. When the fluidity improver of the present invention is added, the slurry fluidity of the article to be added is greatly improved, and the workability is very good.

  Examples of the inorganic particles include metal oxides, metal hydroxides, metal carbonates, metal sulfates, metal silicates, metal nitrides and metal powders, and mixtures and composites thereof.

  Metal oxides include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, copper oxide, manganese oxide, cobalt oxide, vanadium oxide, molybdenum oxide, yttrium oxide and antimony oxide. Etc.

  Examples of the metal hydroxide include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

  Examples of the metal carbonate include calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, and hydrotalcite.

  Examples of the metal sulfate include calcium sulfate and barium sulfate.

  Examples of the metal silicate include calcium silicate, clay (montmorillonite, bentonite, activated clay, etc.), talc, mica, sepiolite, imogolite, sericite, and glass.

  Examples of the metal nitride include aluminum nitride, boron nitride, and silicon nitride.

  Examples of the metal powder include gold, silver, copper, titanium, chromium, barium, platinum, rhodium and tin.

EXAMPLES Next, although an Example demonstrates this invention further, this invention is not limited to this. Hereinafter, unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
<Example 1>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 500 parts of ion-exchanged water, 200 parts of isopropyl alcohol and 3 parts of 2-mercaptanol are added, and 50 parts of acrylic acid and methoxypolyoxy acrylate are stirred. Ethylene (oxyethylene: 2 mol) ester [Blemmer AE-90, manufactured by NOF Corporation; “Blemmer” is a registered trademark of the same company. ] 1000 parts and 100 parts of 40% sodium persulfate aqueous solution were reacted in a sealed state while dropping at a constant rate over 2 hours from separate dropping lines. The reaction temperature was maintained at 80-100 ° C. After the completion of dropping, the mixture was kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol was removed under reduced pressure while dropping 150 parts of ion-exchanged water (hydrolysis), then cooled to 30 ° C. and kept at 40 ° C. or lower with stirring. Then, gradually, 0.6 part of a 48% aqueous sodium hydroxide solution (special grade reagent, manufactured by Kanto Chemical Co., Inc.) was added in portions. Then, by adding water to adjust the concentration to 40%, the fluidity improver (1) of the present invention [acrylic acid (9.9 mol% -acrylic acid sodium salt (0.1 mol%)-methoxy polyoxyacrylate] Ethylene (oxyethylene: 2 mol) ester (90 mol%) copolymer] was obtained, and the weight average molecular weight was 5,000.

<Example 2>
"200 parts of isopropyl alcohol, 3 parts of 2-mercaptanol, 50 parts of acrylic acid and 1000 parts of methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester and 0.6 part of 48% aqueous sodium hydroxide" Isopropyl alcohol 0 part, 2-mercaptanol 1 part, methacrylic acid 50 parts, methacrylic acid methoxypolyoxyethylene (oxyethylene: 90 mol) ester [Blenmer PME-4000, manufactured by NOF Corporation] 583 parts and 28% The fluidity improver (2) [methacrylic acid (79.9 mol) of the present invention was the same as in Example 1, except that the aqueous ammonia solution [reagent special grade, manufactured by Nacalai Tesque Co., Ltd.] 0.04 part] was used. %)-Ammonium methacrylate (0.1 mol%)-Methoxypolyoxyethylene methacrylate (O Xylethylene: 90 mol) ester (20 mol%) copolymer] was obtained. The weight average molecular weight was 20,000.

<Example 3>
"200 parts of isopropyl alcohol, 3 parts of 2-mercaptanol, 50 parts of acrylic acid and 1000 parts of methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester and 0.6 part of 48% aqueous sodium hydroxide" Isopropyl alcohol 0 part, 2-mercaptanol 0.5 part, maleic anhydride 50.0 part, methacrylate octadecyloxypolyoxyethylene (oxyethylene: 30 mol) ester [Blenmer PSE-1300, manufactured by NOF Corporation ] The fluidity improver of the present invention in the same manner as in Example 1 except that it was changed to 845.9 parts and 50% aqueous potassium hydroxide solution [reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.] 28.6 parts. (3) [maleic acid (25 mol%)-potassium maleate (25 mol%)-octadecyloxypolymethacrylate Oxyethylene (oxyethylene 30 mol) ester (50 mol%)] was obtained. The weight average molecular weight was 50,000.

<Example 4>
"200 parts of isopropyl alcohol, 3 parts of 2-mercaptanol, 50 parts of acrylic acid and 1000 parts of methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester and 0.6 part of 48% aqueous sodium hydroxide" Isopropyl alcohol 0 part, 2-mercaptanol 0.1 part, acrylic acid 50 parts, acrylic acid methoxypolyoxyethylene (oxyethylene: 2 mol) ester 74.1 parts and 48% sodium hydroxide aqueous solution 38.6 parts " The fluidity improver of the present invention (4) [acrylic acid (20 mol%-sodium acrylate (40 mol%)-methoxypolyoxyethylene acrylate] (oxy) Ethylene: 2 mol) ester (40 mol%) copolymer] was obtained, and the weight average molecular weight was 10 , It was 000.

<Example 5>
"200 parts of isopropyl alcohol, 3 parts of 2-mercaptanol, 50 parts of acrylic acid and 1000 parts of methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester and 0.6 part of 48% aqueous sodium hydroxide" Isopropyl alcohol 0 part, 2-mercaptanol 1.5 parts, methacrylic acid 50 parts, methacrylic acid methoxypolyoxyethylene (oxyethylene: 23 mol) ester [Blenmer PME-1000, manufactured by NOF Corporation] 958.6 The fluidity improver (5) [methacrylic acid (30 mol%)-ammonium methacrylate (10 mol) of the present invention was the same as in Example 1 except that the amount was changed to 8.7 parts by weight and 8.7 parts by weight 28% aqueous ammonia solution. %)-Methoxypolyoxyethylene methacrylate (oxyethylene: 23 mol) ester (6 0 mol%) copolymer]. The weight average molecular weight was 30,000.

<Example 6>
"200 parts of isopropyl alcohol, 3 parts of 2-mercaptanol, 50 parts of acrylic acid and 1000 parts of methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester and 0.6 part of 48% aqueous sodium hydroxide" Isopropyl alcohol 0 part, 2-mercaptanol 0.5 part, maleic anhydride 50 parts, methoxypolyoxyethylene methacrylate (oxyethylene: 90 mol) ester [Blenmer PME-4000, NOF Corporation] 2531. The fluidizing agent (6) [maleic acid (40 mol%)-ammonium maleate (5 mol) of the present invention was the same as in Example 1 except that the amount was changed to 7 parts and 3.4 parts of 28% ammonia aqueous solution. %)-Methoxypolyoxyethylene methacrylate (oxyethylene: 90 mol) ester (55 mol) %) Copolymer]. The weight average molecular weight was 40,000.

<Example 7>
Fluidizing agent (1) obtained in Example 1 [acrylic acid (9.9 mol% -acrylic acid sodium salt (0.1 mol%)-acrylic acid methoxypolyoxyethylene (oxyethylene: 2 mol) ester (90 Mol%) copolymer] 99 parts and polyoxyalkylene compound (B1-1) [sucrose / propylene oxide 35 mol adduct / methyl 2 mol etherified product] 1 part were heated to 40 ° C. while stirring. The fluidity improver (8) of the present invention was obtained by uniformly stirring and mixing at this temperature.

The polyoxyalkylene compound (B1-1) was obtained as follows.
While uniformly mixing 342 parts (1 mole part) of purified granulated sugar and 800 parts of N-methylpyrrolidone, using nitrogen gas, pressurize with nitrogen (pressurize to 0.4 MPa with gauge pressure until 0.02 MPa) The operation of discharging was repeated 3 times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 2030 parts (35 mole parts) of propylene oxide was added dropwise at the same temperature over 6 hours, and stirring was continued at the same temperature for 4 hours to react the remaining propylene oxide. It was. Thereafter, N-methylpyrrolidone was distilled off under reduced pressure at 120 ° C. and 666 to 13332 Pa, and then 88 parts (2.2 parts by mole) of sodium hydroxide was added at 50 ° C. or less. The temperature was raised to 80 ° C. while stirring under reduced pressure, and the pressure was returned to atmospheric pressure, and 101 parts (2 mole parts) of methyl chloride was introduced over 4 hours at the same temperature with stirring. The mixture was further stirred at the same temperature for 2 hours and then cooled to 40 ° C. 500 parts of the obtained reaction mixture is taken in a separatory funnel, 500 parts of ion-exchanged water and 500 parts of n-hexane {special grade reagent, manufactured by Sigma Co., Ltd.} are added and shaken, and then left to stand for separation. To obtain an n-hexane layer. After removing n-hexane from this n-hexane layer under reduced pressure at 100 ° C. and 666-13332 Pa, at 90 ° C., 85 parts of ion-exchanged water was added to the crude polyoxyalkylene compound and mixed uniformly. , KYOWARD 700 {manufactured by Kyowa Chemical Industry Co., Ltd.}, 200 parts, and stirred uniformly for 1 hour at the same temperature. Filtered using 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove Kyoward 700, and further dehydrated at 120 ° C. under reduced pressure of 1333 to 2666 Pa for 1 hour to obtain polyoxyalkylene compound (B1-1) [sucrose -Propylene oxide 35 mol adduct-Methyl 2-mol etherified product] was obtained.

<Example 8>
Fluidizing agent (2) obtained in Example 2 [methacrylic acid (79.9 mol%)-ammonium methacrylate (0.1 mol%)-methacrylic acid methoxypolyoxyethylene (oxyethylene: 90 mol) ester (20 Mol%) copolymer] 90 parts, polyoxyalkylene compound (B1-2) [sucrose / propylene oxide 13 mol / propylene oxide / ethylene oxide 5 mol random / propylene oxide 40 mol adduct] 5 parts, and polyoxy The temperature of the alkylene compound (B2-1) [butanol / propylene oxide 50 mol / ethylene oxide 50 mol adduct] 5 parts was raised to 40 ° C. with stirring, and the mixture was uniformly stirred and mixed at this temperature to obtain the fluidity of the present invention. An improving agent (8) was obtained.

The polyoxyalkylene compound (B1-2) and the polyoxyalkylene compound (B2-1) were obtained as follows.
Sanix polyol RP-410A {manufactured by Sanyo Chemical Industries, Ltd., 13 mol adduct of sucrose with propylene oxide; "Sanix" is a registered trademark of the company. } 1095 parts (1 mol part) and potassium hydroxide {reagent special grade (active ingredient 85%), the same shall apply hereinafter) 10 parts (the amount of the active ingredient with reduced water content, the same shall apply hereinafter) After dehydrating for 1 hour under a reduced pressure of 2666 Pa, a mixture of 290 parts (5 parts by mole) of propylene oxide and 220 parts (5 parts by weight) of ethylene oxide was added dropwise at 100 to 120 ° C. in about 2 hours under the same reduced pressure. Then, 2320 parts (40 mol parts) of propylene oxide was added dropwise at 100 to 120 ° C. over about 6 hours, and the remaining propylene oxide was reacted at the same temperature for about 4 hours to obtain a crude polyoxyalkylene compound.
Next, in the same manner as in Example 7, it was treated with 200 parts of Kyoward 700 to obtain polyoxyalkylene compound (B1-2) [sucrose / propylene oxide 13 mol / propylene oxide / ethylene oxide 5 mol random / propylene oxide. 40 mol adduct].

  74 parts of butanol {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} (1 mole part) and potassium hydroxide {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} 0.5 parts are uniformly mixed and replaced with pressurized nitrogen. The temperature was raised to 100 ° C. while dehydrating for 1 hour under reduced pressure (0.013 MPa or less). Next, the temperature was raised to 150 ° C., and 2900 parts (50 mole parts) of propylene oxide was continuously added dropwise at this temperature (0.1 to 1 MPa), and the temperature was maintained at the same temperature for 2 hours. Thereafter, the temperature was adjusted to 130 ° C., and 2200 parts (50 mole parts) of ethylene oxide was continuously dropped at this temperature (0.1 to 1 MPa), and the temperature was further maintained for 3 hours. Then, 200 parts of magnesium silicate (Kyoward 600, Kyowa Chemical Co., Ltd.) was added to the reaction product, and the mixture was stirred uniformly for 1 hour at the same temperature. Using 2 filter papers {manufactured by Toyo Filter Paper Co., Ltd.}, the Kyoward 600 was removed to obtain a polyoxyalkylene compound (B2-1) [butanol / propylene oxide 50 mol / ethylene oxide 50 mol adduct].

<Example 9>
Fluidizing agent (3) obtained in Example 3 [maleic acid (25 mol%)-potassium maleate (25 mol%)-octadecyloxypolyoxyethylene methacrylate (oxyethylene: 30 mol) ester (50 mol%) ] 80 parts and 20 parts of polyoxyalkylene compound (B1-3) [10-mole adduct of trehalose / ethylene oxide] were heated to 40 ° C. with stirring, and uniformly stirred and mixed at this temperature. A fluidity improver (9) was obtained.

The polyoxyalkylene compound (B1-3) was obtained as follows.
Trehalose {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} 342 parts (1 mole part) and DMF {dimethylformamide; manufactured by Mitsubishi Gas Chemical Co., Ltd., water content 0.005%, the same below} 2000 parts uniformly While mixing, pressurized nitrogen substitution (operation to pressurize until the gauge pressure became 0.4 MPa and discharge until 0.02 MPa) was repeated three times using nitrogen gas. Thereafter, the temperature was raised to 100 ° C. while stirring, 440 parts (10 mole parts) of ethylene oxide was added dropwise at the same temperature over 12 hours, and stirring was continued at the same temperature for 4 hours to react the remaining ethylene oxide. Next, DMF was removed under reduced pressure of 1333 to 13332 Pa at 120 ° C., and further treated with 200 parts of Kyoward 700 in the same manner as in Example 7 to obtain a polyoxyalkylene compound (B1-3) [trehalose / ethylene oxide. 10 mol adduct].

<Example 10>
Fluidizing agent (4) obtained in Example 4 [acrylic acid (20 mol% -acrylic acid sodium salt (40 mol%)-acrylic acid methoxypolyoxyethylene (oxyethylene: 2 mol) ester (40 mol%) Polymer] 70 parts, polyoxyalkylene compound (B1-4) [raffinose / ethylene oxide 100 mol addition] 15 parts, polyoxyalkylene compound (B2-2) [triacontanol / ethylene oxide 1 mol addition product] 15 parts The mixture was heated to 40 ° C. with stirring and uniformly stirred and mixed at this temperature to obtain the fluidity improver (10) of the present invention.

The polyoxyalkylene compound (B1-4) and the polyoxyalkylene compound (B2-2) were obtained as follows.
Example except that “trehalose 342 parts and ethylene oxide 440 parts” were changed to “raffinose {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} 504 parts (1 mole part) and ethylene oxide 4400 parts (100 mole parts)” In the same manner as in Example 9, a polyoxyalkylene compound (B1-4) [raffinose / ethylene oxide 100 mol adduct] was obtained.

  438 parts of triacontanol {purity 96% or more, manufactured by Aldrich Co.} (1 mol part) potassium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} 0.5 part while homogeneously mixing and replacing with pressurized nitrogen After raising the temperature to 100 ° C., dehydration was performed under reduced pressure (0.013 MPa or less) for 1 hour. Subsequently, the temperature was raised to 150 ° C., and 44 parts (1 mole part) of ethylene oxide was continuously dropped at this temperature (0.1 to 1 MPa), and the temperature was kept at the same temperature for another 2 hours. Then, 200 parts of magnesium silicate (Kyoward 600, Kyowa Chemical Co., Ltd.) was added to the reaction product, and the mixture was stirred uniformly for 1 hour at the same temperature. Using 2 filter papers {manufactured by Toyo Filter Paper Co., Ltd.}, Kyoword 600 was removed to obtain a polyoxyalkylene compound (B2-2) [triacontanol / ethylene oxide 1 mol adduct].

<Example 11>
Fluidizing agent (5) obtained in Example 5 [methacrylic acid (30 mol%)-ammonium methacrylate (10 mol%)-methacrylic acid methoxypolyoxyethylene (oxyethylene: 23 mol) ester (60 mol%) Polymer] 60 parts and 40 parts of polyoxyalkylene compound (B2-3) [tridecyl alcohol / ethylene oxide 5 mol adduct] were heated to 40 ° C. with stirring, and stirred uniformly at this temperature. The fluidity improver (11) of the present invention was obtained.

The polyoxyalkylene compound (B2-3) was obtained as follows.
Implemented except that "Triaconsanol 438 parts and ethylene oxide 44 parts" were changed to "Tridecanol 200 parts {reagent special grade, Wako Pure Chemical Industries, Ltd.} (1 mol part) and ethylene oxide 220 parts (5 mol part)". In the same manner as in Example 10, a polyoxyalkylene compound (B2-3) [tridecyl alcohol / ethylene oxide 5-mol adduct] was obtained.

<Example 12>
Fluidizing agent (6) obtained in Example 6 [maleic acid (40 mol%)-ammonium maleate (5 mol%)-methacrylic acid methoxypolyoxyethylene (oxyethylene: 90 mol) ester (55 mol%) Polymer] Heated to 40 ° C. while stirring 99 parts and 1 part of polyoxyalkylene compound (B2-4) [polyoxyethylene glycol (ethylene oxide 45 mol adduct), PEG 2000, Sanyo Chemical Industries, Ltd.] The fluidity improver (12) of the present invention was obtained by uniformly stirring and mixing at this temperature.

<Comparative Example 1>
Into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, 300 parts of ion-exchanged water and 300 parts of isopropyl alcohol are added, and 50 parts of acrylic acid and 100 parts of 40% sodium persulfate aqueous solution are added separately under stirring. The reaction was conducted in a sealed state while dropping at a constant rate over 3 hours. The reaction temperature was maintained at 80-100 ° C. After the completion of dropping, the mixture was kept at 95 to 100 ° C. for 3 hours, and then isopropyl alcohol was removed under reduced pressure while dropping 150 parts of ion-exchanged water (hydrolysis), then cooled to 30 ° C. and kept at 40 ° C. or lower with stirring. Then, 57.3 parts of a 48% aqueous sodium hydroxide solution (special grade reagent, manufactured by Kanto Chemical Co., Inc.) was gradually added in portions. Then, the concentration was adjusted to 40% by adding water to obtain a comparative fluidity improver (13) [acrylic acid (1 mol%)-acrylic acid sodium salt (99 mol%) copolymer]. The weight average molecular weight was 20,000.

<Comparative Example 2>
"200 parts of isopropyl alcohol, 3 parts of 2-mercaptanol, 50 parts of acrylic acid and 1000 parts of methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester and 0.6 part of 48% aqueous sodium hydroxide" Isopropyl alcohol 0 part, 2-mercaptanol 1 part, methacrylic acid 50 parts, methacrylic acid methoxypolyoxyethylene (oxyethylene: 90 mol) ester [Blenmer PME-4000, manufactured by NOF Corporation] 411.8 parts and A fluidity improver for comparison (14) [methacrylic acid (11 mol%)-ammonium methacrylate (50 mol%), in the same manner as in Example 1, except that it was changed to “28% ammonia aqueous solution 28.7 parts”. -Methoxypolyoxyethylene methacrylate (oxyethylene: 15 mol) ester (3 9 mol%) copolymer]. The weight average molecular weight was 20,000.

<Comparative Example 3>
"200 parts of isopropyl alcohol, 3 parts of 2-mercaptanol, 50 parts of acrylic acid and 1000 parts of methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester and 0.6 part of 48% aqueous sodium hydroxide" 0 parts isopropyl alcohol, 0.05 parts 2-mercaptanol, 50 parts acrylic acid, methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester [Blenmer AE-4000, manufactured by NOF Corporation] 1000 parts and A fluidity improver for comparison (15) [acrylic acid (9 mol%)-sodium acrylate (1 mol) in the same manner as in Example 1 except that the amount was changed to 5.8 parts of a 48% sodium hydroxide aqueous solution. %)-Methoxypolyoxyethylene acrylate (oxyethylene: 2 mol) ester (90 mol%) copolymer Combined] was obtained. The weight average molecular weight was 150,000.

  Using the fluidity improvers (1) to (15) obtained in the examples and comparative examples, a fluidity test was performed on the alumina slurry, and the results are shown below.

<Preparation 1 of polyvalent metal ion aqueous solution>
In a stainless steel beaker, 1.44 parts of calcium chloride dihydrate [reagent special grade, manufactured by Kanto Chemical Co., Ltd.] and magnesium chloride hexahydrate [reagent special grade, manufactured by Kanto Chemical Co., Ltd.] 1.64 parts and ion-exchanged water After adding 1000 parts, it stirred until it melt | dissolved completely and obtained polyvalent metal ion aqueous solution (C-1).

<Preparation 2 of polyvalent metal ion aqueous solution>
A stainless beaker was charged with 1 part of aluminum chloride hexahydrate [reagent grade, manufactured by Kanto Chemical Co., Ltd.] and 1000 parts of ion-exchanged water, and then stirred until it was completely dissolved. )

<Fluidity test method 1>
Into a stainless steel beaker having a capacity of 500 ml, 92 g of the polyvalent metal ion aqueous solution (C-1) prepared above was added, and 7 g of a fluidity improver and an antifoaming agent made into a 40 wt% aqueous solution (Nopco NXZ: manufactured by San Nopco) 2g was added. Subsequently, a homomixer [T. K. While stirring at 1,000 rpm with HOMO MIXER MARKII, manufactured by Tokushu Kika Kogyo Co., Ltd., 308 g of calcium carbonate [Escalon # 2000, manufactured by Sankyo Seimitsu Co., Ltd.] was added, and then at 3,000 rpm for 10 minutes. Stirring was performed to prepare a slurry having a concentration of 77% by weight. The temperature of the obtained slurry was adjusted to 25 ° C., and the viscosity of the slurry was immediately measured using an E-type viscometer [CAP-2000L, manufactured by Brookfield] at a rotation speed of 5 rpm. The slurry after viscosity measurement was allowed to stand at 25 ° C. for 1 month under sealing, and then the presence or absence of a hard cake was confirmed using a glass rod. Only the material without a hard cake was shaken up and down 30 times, and then the viscosity was measured under the same conditions as immediately after slurry preparation.
A blank slurry was prepared in the same manner as described above except that the fluidity improver was not used, and the viscosity was measured in the same manner.
These results are shown in Table 1. A smaller numerical value means higher fluidity and is preferable.

（注）表中の「×」は、ハードケーキが発生し、粘度測定ができなかったことを意味する。
「スラリー作成不可」は、多価金属イオン水溶液と無機粒子とを均一に混合することすらできないため、スラリー化もできなかった（以下同じ）。

(Note) “X” in the table means that a hard cake was generated and the viscosity could not be measured.
“Slurry cannot be prepared” was not able to evenly mix the polyvalent metal ion aqueous solution and the inorganic particles, and therefore could not be slurried (the same applies hereinafter).

<Fluidity test method 2>
Into a stainless steel beaker having a capacity of 500 ml, 120 g of the polyvalent metal ion aqueous solution (C-2) prepared above was charged, and 7 g of a fluidity improver and an antifoaming agent made into a 40 wt% aqueous solution (Nopco NXZ: manufactured by San Nopco) 2g was added. Subsequently, a homomixer [T. K. 280 g of titanium oxide [GTR-100, manufactured by Sakai Chemical Industry Co., Ltd.] was added while stirring at 1,000 rpm with HOMO MIXER MARKII, manufactured by Tokushu Kika Kogyo Co., Ltd., and then at 3,000 rpm for 10 minutes. Stirring was performed to prepare a slurry having a concentration of 70% by weight.
Moreover, the slurry for blanks was prepared like the above except not having used a fluid improvement agent.
For these slurries, the viscosity was measured in the same manner as in <Flowability Test Method 1>, and the results are shown in Table 2. A smaller numerical value means higher fluidity and is preferable.

（注）表中の×は、ハードケーキが発生し、粘度測定ができなかったことを意味する。

(Note) “X” in the table means that a hard cake was generated and the viscosity could not be measured.

<Fluidity test method 3>
Into a stainless steel beaker having a capacity of 500 ml, 120 g of the polyvalent metal ion aqueous solution (C-1) prepared above was added, and 7 g of a fluidity improver and an antifoaming agent made into a 40 wt% aqueous solution (Nopco NXZ: manufactured by San Nopco) 2g was added. Subsequently, a homomixer [T. K. 280 g of alumina [AES-11, manufactured by Sumitomo Chemical Co., Ltd.] was added while stirring at 1,000 rpm with HOMO MIXER MARKII, manufactured by Tokushu Kika Kogyo Co., Ltd., followed by stirring at 3,000 rpm for 10 minutes. And a slurry with a concentration of 70% by weight was prepared.
Moreover, the slurry for blanks was prepared like the above except not having used a fluid improvement agent.
For these slurries, the viscosity was measured in the same manner as in <Flowability Test Method 1>, and the results are shown in Table 3. A smaller numerical value means higher fluidity and is preferable.

（注）表中の×は、ハードケーキが発生し、粘度測定ができなかったことを意味する。

(Note) “X” in the table means that a hard cake was generated and the viscosity could not be measured.

  The slurry using the fluidity improver of the present invention exhibits high fluidity even in a slurry in which a large amount of polyvalent metal ions are present, compared to a slurry using a comparative fluidity improver, And it was excellent in long-term dispersion stability.

  The fluidizing agent of the present invention contains inorganic particles in which polyvalent metal ions are present (metal oxide, metal hydroxide, metal carbonate, metal sulfate, metal silicate, metal nitride, metal powder, etc.) Suitable for slurry.

Claims (6)

A copolymer (A) comprising an ethylenically unsaturated carboxylic acid (a1), an ethylenically unsaturated carboxylic acid salt (a2) and an ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3) as essential constituent monomers Containing
Based on the number of moles of the ethylenically unsaturated carboxylic acid (a1) unit, the ethylenically unsaturated carboxylic acid salt (a2) unit and the ethylenically unsaturated carboxylic acid alkoxypolyoxyalkylene ester (a3) unit, the ethylenically unsaturated carboxylic acid The content of the acid (a1) unit is 9.9 to 79.9 mol%, the content of the ethylenically unsaturated carboxylate (a2) unit is 0.1 to 40 mol%, and the ethylenically unsaturated carboxylic acid alkoxypoly A fluidity improver for an inorganic particle slurry, wherein the content of the oxyalkylene ester (a3) unit is 20 to 90 mol%. The fluidity improver according to claim 1, wherein the copolymer (A) has a weight average molecular weight (Mw) of 5,000 to 100,000. The polyoxyalkylene compound (B1) represented by the general formula (1) and / or the polyoxyalkylene compound (B2) represented by the general formula (2) is further contained according to claim 1 or 2. Fluidity improver.

{R ^1- (OA-) ni} m Q (1)

Q is a reaction residue obtained by removing a hydrogen atom from m primary hydroxyl groups of non-reducing di- or trisaccharides, OA is an oxyalkylene group having 2 to 4 carbon atoms, and R ¹ is an alkyl group having 1 to 3 carbon atoms. Represents a propenylene group and / or a hydrogen atom, m R ¹ and m (OA) ni may be the same or different, ni is an integer of 0 to 100, m is an integer of 2 to 4, i Represents an integer of 1 to m, and m ni may be the same or different, but at least one is 1 or more, and the total number of OA (Σni × m) is 10 to 100.

R ^2- (OA-) p OH (2)

R ² represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and p represents an integer of 1 to 100. Based on the total weight of the copolymer (A), the polyoxyalkylene compound (B1) and the polyoxyalkylene compound (B2), the content of the copolymer (A) is 60 to 99.9% by weight, polyoxyalkylene The fluidity improver according to any one of claims 1 to 3, wherein the total content of the compound (B1) and the polyoxyalkylene compound (B2) is 0.1 to 40% by weight. The fluidity improver according to any one of claims 1 to 4, wherein the inorganic particles are metal oxides. A slurry of inorganic particles comprising the fluidity improver according to any one of claims 1 to 5, inorganic particles, and an aqueous medium.