Polymer dispersant

Abstract

The present invention pertains to a polymer dispersant for a non-aqueous solvent, the polymer dispersant containing a structural unit derived from a monomer represented by general formula (1) and a structural unit derived from a monomer having a hydroxyl group. (In general formula (1), R1, R2, and R3 are each selected from hydrogen element and methyl group, X1 represents oxygen element, ester group, amide group, or-CH2O-, Y1 represents repeating units of alkylene glycol having 2-4 carbon atoms, R4 represents hydrogen element or alkyl group having 1-20 carbon atoms, and n represents the number of repeating units of alkylene glycol) # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polymer dispersant, an oil dispersion containing the polymer dispersant, and a halogen-based resin composition containing the polymer dispersant. Background Art

[0002] Conventionally, in order to obtain an oil dispersion containing a filler such as a metal oxide, an aromatic solvent has been used as a solvent. However, in view of the environmental impact, in recent years, it has gradually become less compatible with aromatic solvents and a highly polar non-aromatic organic solvent is used.

[0003] Chlorine-containing resins such as vinyl chloride resin (PVC) are important resins used in various fields as general polymers. For example, PVC can be used for various purposes such as interior decorations in houses such as wallpapers; general products such as toys; and automotive-related materials such as sealing materials.

[0004] In the case of using a chlorine-containing resin, for example, a plasticizer, a diluent, a viscosity reducer, a filler such as calcium carbonate, a pigment, a flame retardant, a foaming agent, a stabilizer, etc. are blended into the resin powder of the chlorine-containing resin to prepare a halogen-based resin composition. However, most halogen-based resin compositions containing a filler have a high viscosity, and it is often found that they are difficult to process or cannot be processed. In addition, there is a problem that the processed product of the halogen-based resin composition containing a filler is liable to break due to flexural fatigue at low temperatures.

[0005] As a method for reducing the viscosity of an oil dispersion and a halogen-based resin composition, heretofore, as a diluent or a viscosity reducer, hydrocarbon solvents such as mineral spirits, alkylbenzenes, and paraffins, anionic surfactants, polyoxyethylene alkylphenol ethers, polyethylene glycols, glycerol alkyl esters, etc. have been used. These diluents and viscosity reducers are added when preparing an oil dispersion or after the production of a chlorine-containing resin when preparing a halogen-based resin composition, but the viscosity reduction effect cannot be said to be sufficient. In particular, when an inorganic filler is blended, the viscosity reduction is insufficient. In addition, these diluents and viscosity reducers cannot suppress the breakage caused by flexural fatigue of the processed product of the halogen-based resin composition when an inorganic filler such as calcium carbonate is blended.

[0006] Japanese Patent Application Laid-Open No. 2009-138115 (Patent Document 1) discloses an oil dispersion composition for electronic materials, which contains: at least one dispersant selected from amidates or esters of copolymers of olefins and unsaturated dibasic acids, and having an amidation rate or an esterification rate of 10 to 60 mol% with respect to the unsaturated dibasic acid; and a non-aromatic organic solvent having a solubility parameter of 8.5 to 22 (cal / cm 3 ) 1 / 2 ).

[0007] In Japanese Patent Laid-Open No. 2001-335696 (Patent Document 2), as a method for reducing the viscosity of a halogen-based resin composition, a resin composition is disclosed which contains, in specific amounts relative to a vinyl chloride-based resin, one or more additives selected from esters formed from fatty acids and fatty alcohols and (poly)alkylene glycol mono- or dialkyl ethers, one or more additives selected from polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl ether carboxylates, a plasticizer, and a filler. SUMMARY OF THE INVENTION

[0008] The present invention relates to a polymer dispersant containing structural units derived from a monomer having a specific structure and structural units derived from a monomer having a hydroxyl group. DETAILED DESCRIPTION OF THE INVENTION

[0009] Although the oil-in-dispersion described in the above Patent Document 1 has achieved low viscosity, there is still room for improvement in the coatability and moldability of the oil-in-dispersion.

[0010] In the resin composition described in the above Patent Document 2, since the additives are adsorbed and desorbed from the filler, a large amount of additives is required to reduce the viscosity of the resin composition, and there is a problem that the additives ooze out from the resin molded article after molding. In addition, there is a problem that the processed product of the halogen-based resin composition using the resin composition described in the above Patent Document 2 cannot suppress breakage due to flexural fatigue.

[0011] The present invention relates to a polymer dispersant capable of improving coatability and moldability by reducing the slurry viscosity of an oil-in-dispersion, and capable of improving the processability and low-temperature flexural properties of a halogen-based resin composition.

[0012] The present inventors have found that a specific polymer dispersant, an oil-in-dispersion containing the polymer dispersant, and a halogen-based resin composition containing the polymer dispersant and a halogen-based resin can solve the above problems.

[0013] That is, the present invention relates to the following [1] to

[18] .

[0014] [1] A polymer dispersant containing structural units derived from a monomer represented by the following general formula (1) and structural units derived from a monomer having a hydroxyl group.

[0015]

[0016] (In the general formula (1), R 1 , R 2 and R 3 are each independently selected from a hydrogen element and a methyl group, X 1 represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1 represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R4 represents a hydrogen element or an alkyl group having 1 to 20 carbon atoms. n represents the number of repeating units of the above-mentioned alkylene glycol.)

[0017] [2] The polymer dispersant according to [1], wherein the polymer dispersant is any one of the following polymer dispersants A to C.

[0018] Polymer dispersant A: A compound containing 20% by mass or more and 65% by mass or less of a structural unit derived from a monomer (a) represented by the following general formula (1a) having a molecular weight of 400 or more and 2000 or less, 5% by mass or more and 50% by mass or less of a structural unit derived from a monomer (b) having a hydroxyl group with a molecular weight of less than 400, and 30% by mass or more and 75% by mass or less of a structural unit derived from a monomer (c) having a hydrophobic group with a molecular weight of less than 400

[0019]

[0020] (In the general formula (1a), R 1a , R 2a and R 3a are each independently selected from a hydrogen element and a methyl group, X 1a represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1a represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4a represents a hydrogen element or an alkyl group having 1 to 4 carbon atoms. n1 represents the number of repeating units of the above-mentioned alkylene glycol.)

[0021] Polymer dispersant B: A compound containing 45% by mass or more and 95% by mass or less of a structural unit derived from a monomer (d) represented by the following general formula (1b) having a molecular weight of 300 or more and 2000 or less, 5% by mass or more and 40% by mass or less of a structural unit derived from a monomer (b) having a hydroxyl group with a molecular weight of less than 400, and 0% by mass or more and 20% by mass or less of a structural unit derived from a monomer (c) having a hydrophobic group with a molecular weight of less than 400

[0022]

[0023] (In the general formula (1b), R 1b , R 2b and R 3b are each independently selected from a hydrogen element and a methyl group, X 1b represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1b represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4b represents a hydrocarbon group having 6 to 18 carbon atoms. n2 represents the number of repeating units of the above-mentioned alkylene glycol.)

[0024] Polymer dispersant C: a compound comprising 10% by mass or more and 40% by mass or less of structural units derived from a monomer (d) represented by the general formula (1b) having a molecular weight of 300 or more and 2000 or less, 5% by mass or more and 20% by mass or less of structural units derived from a monomer (b) having a hydroxyl group and a molecular weight of less than 400, and 60% by mass or more and 80% by mass or less of structural units derived from a macromonomer, wherein the macromonomer includes a structural unit derived from a monomer (c) having a hydrophobic group and a molecular weight of less than 400.

[0025] [3] The polymer dispersant according to [1] or [2], which has a weight average molecular weight of 5,000 to 120,000.

[0026] [4] The polymer dispersant according to any one of [1] to [3], wherein the number n of repeating units of the alkylene glycol is 2 or more and 60 or less.

[0027] [5] A dispersion in oil comprising the polymer dispersant according to any one of [1] to [4], an inorganic filler, and a compound having no group that dissociates into hydrogen ions.

[0028] [6] The dispersion in oil according to [5], wherein the compound having no group that dissociates into hydrogen ions is selected from toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

[0029] [7] The dispersion in oil according to [5] or [6], wherein the content of the inorganic filler is 10% by mass or more and 80% by mass or less.

[0030] [8] A halogen-based resin composition comprising: the polymer dispersant according to any one of [1] to [4], an inorganic filler, a compound having no group that dissociates hydrogen ions, and a halogen-based resin.

[0031] [9] The halogen-based resin composition according to [8], wherein the SP value of the compound having no group that dissociates hydrogen ions as determined by the Fedors method is 7.5 (cal / cm 3 ) 1 / 2 Above and 11.5 (cal / cm 3 ) 1 / 2 the following.

[0032]

[10] The halogen-based resin composition according to [8] or [9], wherein the compound having no group that dissociates a hydrogen ion is selected from dialkyl phthalate and trialkyl trimellitate.

[0033]

[11] The halogen-based resin composition according to any one of [8] to

[10] , wherein the content of the inorganic filler is 1 part by mass or more and 150 parts by mass or less relative to 100 parts by mass of the halogen-based resin.

[0034]

[12] A method for producing an oil dispersion, which includes a step of mixing the polymer dispersant according to any one of [1] to [4], an inorganic filler, and a compound that does not have a group capable of dissociating a hydrogen ion.

[0035]

[13] A method for producing a halogen-based resin composition, which includes a step of mixing the polymer dispersant according to any one of [1] to [4], an inorganic filler, a compound that does not have a group capable of dissociating a hydrogen ion, and a halogen-based resin.

[0036]

[14] Use of compound (I) as a dispersant, wherein the compound (I) contains a structural unit derived from a monomer having a hydroxyl group and a structural unit derived from a monomer represented by the following general formula (1).

[0037]

[0038] (In general formula (1), R 1 , R 2 and R 3 are each independently selected from a hydrogen element and a methyl group, X 1 represents an oxygen element, an ester group, an amide group, or -CH2O-, Y 1 represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, and R 4 represents a hydrogen element or an alkyl group having 1 to 20 carbon atoms. n represents the number of repeating units of the alkylene glycol.)

[0039]

[15] The use according to

[14] , wherein the compound (I) is any one of the following compounds A to C.

[0040] Compound A: A compound containing 20% by mass or more and 65% by mass or less of a structural unit derived from a monomer (a) represented by the following general formula (1a) having a molecular weight of 400 or more and 2000 or less, 5% by mass or more and 50% by mass or less of a structural unit derived from a monomer (b) having a hydroxyl group and a molecular weight of less than 400, and 30% by mass or more and 75% by mass or less of a structural unit derived from a monomer (c) having a hydrophobic group and a molecular weight of less than 400

[0041]

[0042] (In general formula (1a), R 1a , R 2a and R 3a are each independently selected from a hydrogen element and a methyl group, X1a represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1a represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4a represents a hydrogen element or an alkyl group having 1 to 4 carbon atoms. n1 represents the number of repeating units of the above alkylene glycol.)

[0043] Compound B: A compound containing 45% by mass or more and 95% by mass or less of structural units derived from a monomer (d) represented by the following general formula (1b) having a molecular weight of 300 or more and 2000 or less, 5% by mass or more and 40% by mass or less of structural units derived from a monomer (b) having a hydroxyl group with a molecular weight of less than 400, and 0% by mass or more and 20% by mass or less of structural units derived from a monomer (c) having a hydrophobic group with a molecular weight of less than 400

[0044]

[0045] (In the general formula (1b), R 1b , R 2b and R 3b are each independently selected from a hydrogen element and a methyl group, X 1b represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1b represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4b represents a hydrocarbon group having 6 to 18 carbon atoms. n2 represents the number of repeating units of the above alkylene glycol.)

[0046] Compound C: A compound containing 10% by mass or more and 40% by mass or less of structural units derived from a monomer (d) represented by the above general formula (1b) having a molecular weight of 300 or more and 2000 or less, 5% by mass or more and 20% by mass or less of structural units derived from a monomer (b) having a hydroxyl group with a molecular weight of less than 400, and 60% by mass or more and 80% by mass or less of structural units derived from a macromonomer, the macromonomer containing structural units derived from a monomer (c) having a hydrophobic group with a molecular weight of less than 400.

[0047]

[16] The use according to

[15] , which is used for dispersing an inorganic filler in a compound that does not have a group capable of dissociating hydrogen ions.

[0048]

[17] The use of the polymer dispersant according to any one of [1] to [4] for producing a dispersion in oil.

[0049]

[18] The use of the polymer dispersant according to any one of [1] to [4] for producing a halogen-based resin composition.

[0050] According to the present invention, for an oil dispersion, a polymer dispersant capable of improving coatability and moldability by reducing the viscosity of a slurry, and an oil dispersion having improved coatability and moldability due to a reduced slurry viscosity can be provided.

[0051] Furthermore, for a halogen-based resin composition, a polymer dispersant capable of improving processability and low-temperature flex resistance by reducing the viscosity of a slurry of the halogen-based resin composition, and a halogen-based resin composition having improved processability and low-temperature flex resistance due to a reduced slurry viscosity can be provided.

[0052] [Polymer Dispersant]

[0053] The polymer dispersant of the present invention is a compound (I) composed of a copolymer containing a structural unit derived from a monomer represented by the following general formula (1) and a structural unit derived from a monomer having a hydroxyl group.

[0054]

[0055] In the general formula (1), R 1 , R 2 and R 3 are each independently selected from a hydrogen element and a methyl group, X 1 represents an oxygen element, an ester group, an amide group, or -CH2O-, Y 1 represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, and R 4 represents a hydrogen element or an alkyl group having 1 to 20 carbon atoms. n represents the number of repeating units of the alkylene glycol.

[0056] (Monomer Represented by General Formula (1))

[0057] In the polymer dispersant, the structural unit derived from the monomer represented by formula (1) functions to adjust the hydrophilic-hydrophobic balance of the polymer dispersant and improve dispersibility by steric repulsion.

[0058] From the viewpoints of easy availability and easy production of the polymer dispersant, R 1 , R 2 and R 3 are preferably R 1 and R 2 are hydrogen elements, and R 3 is a hydrogen element or a methyl group.

[0059] When X 1 is an oxygen element, the monomer represented by the general formula (1) is a substituted or unsubstituted vinyl ether. When X 1 is an ester group or an amide group, the monomer represented by the general formula (1) is an ester or amide derived from (meth)acrylic acid. When X 1When it is -CH2O-, the monomer represented by the general formula (1) is a substituted or unsubstituted allyl ether. Among them, from the viewpoints of easy availability and easy production of the polymer dispersant, X 1 is preferably an ester group.

[0060] It should be noted that in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid, and "(meth)acrylate" means at least one selected from acrylate and methacrylate.

[0061] Y 1 represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, (Y 1 ). n represents a polyalkylene glycol composed of a repeating unit of an alkylene glycol having 2 to 4 carbon atoms. The alkylene glycol can be a linear alkylene glycol such as ethylene glycol, trimethylene glycol, or tetramethylene glycol, or a branched alkylene glycol such as propylene glycol or butylene glycol. Y 1 can be a repeating unit derived from one type of alkylene glycol, or a combination of repeating units derived from two or more types of alkylene glycols.

[0062] n represents the number of repeating units of the above alkylene glycol. From the viewpoints of improving the coatability and moldability of the oil-in-dispersion, as well as improving the processability and low-temperature flexural resistance of the halogen-based resin composition, it is preferably 1 or more, and furthermore preferably 100 or less.

[0063] R 4 The hydrocarbon group having 1 to 20 carbon atoms represented, for example, includes a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and an aromatic group having 6 to 18 carbon atoms.

[0064] Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, lauryl, stearyl, eicosyl, etc.

[0065] Examples of the linear or branched alkenyl group having 1 to 20 carbon atoms include an alkenyl group having a carbon-carbon double bond in the straight chain, and may have multiple carbon-carbon double bonds. In addition, the geometric isomer of the carbon-carbon double bond can be cis or trans.

[0066] Examples of the aromatic group having 1 to 20 carbon atoms include phenyl, naphthyl, etc.

[0067] (Monomer having a hydroxyl group)

[0068] The monomers having a hydroxyl group are monomers that impart hydrophilicity to the polymer dispersant. From the viewpoints of improving the coatability and moldability of the dispersion in oil, as well as improving the processability of the halogen-based resin composition and improving the low-temperature flexural properties, examples include esters of α,β-unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid, etc. and polyhydric alcohols having two or more hydroxyl groups, amides of α,β-unsaturated carboxylic acids and amino alcohols having one or more hydroxyl groups, hydroxyl-substituted styrene compounds, hydroxyl-substituted linear or branched olefins, etc.

[0069] When the α,β-unsaturated carboxylic acid is a polycarboxylic acid, the monomer having a hydroxyl group may have the following structure: one or more carboxyl groups are esters with polyhydric alcohols, and the other carboxyl groups are unsubstituted alkyl esters and / or unsubstituted alkyl amides; it may also have the following structure: one or more carboxyl groups are amides with amino alcohols, and the other carboxyl groups are unsubstituted alkyl esters and / or unsubstituted alkyl amides; it may also have the following structure: one or more carboxyl groups are esters with polyhydric alcohols, one or more carboxyl groups are amides with amino alcohols, and the other carboxyl groups are unsubstituted alkyl esters and / or unsubstituted alkyl amides; it may also have the following structure: all carboxyl groups are esters with polyhydric alcohols and / or amides with amino alcohols.

[0070] As the esters of α,β-unsaturated carboxylic acids and polyhydric alcohols, from the viewpoint of easy introduction into the molecule, examples include esters of α,β-unsaturated carboxylic acids and polyhydric alcohols having 2 to 6 carbon atoms and polyalkylene glycols. As the polyhydric alcohols having 2 to 6 carbon atoms, examples include linear diols such as 1,2-ethanediol (ethylene glycol), 1,3-propanediol (trimethylene glycol), 1,4-butanediol (tetramethylene glycol), 1,5-pentanediol, 1,6-hexanediol, etc.; branched diols such as 1,2-propanediol (propylene glycol), 1,2-butanediol (butanediol), 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol, 1,3-hexanediol, etc.; trihydroxymethylethane, trimethylolpropane, and sugar alcohols such as glycerol, erythritol, xylitol, and sorbitol. As the polyalkylene glycols, for example, the polyalkylene glycols shown as (Y 1 ). n in the general formula (1).

[0071] As the styrene compounds having a substituted hydroxyl group, examples include vinylphenol and isopropenylphenol.

[0072] As the hydroxyl-substituted linear or branched olefins, from the viewpoint of easy preparation of the polymer dispersant, examples include hydroxyl-substituted olefins having 6 to 20 carbon atoms. Among them, from the viewpoint of easy introduction into the molecule, linear olefins having a double bond at one end and a hydroxyl group at the other end are preferred.

[0073] (Monomer having a hydrophobic group)

[0074] The polymer dispersant may include a structural unit derived from a monomer having a hydrophobic group that imparts hydrophobicity to the polymer dispersant. As the monomer having a hydrophobic group, from the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flexural resistance of the halogen-based resin composition, for example, esters and amides of α,β-unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid, etc., styrene-based compounds, linear or branched olefins, etc. can be cited.

[0075] In addition, when the α,β-unsaturated carboxylic acid is a polycarboxylic acid, the monomer having a hydrophobic group may have a structure in which all carboxyl groups are esters, may have a structure in which all carboxyl groups are amides, or may have a structure containing esters and amides.

[0076] As the ester of the α,β-unsaturated carboxylic acid, from the viewpoint of easy availability, for example, esters of α,β-unsaturated carboxylic acids and linear or branched alkyl alcohols can be cited. From the perspective of improving the compatibility with the halogen-based resin and / or a compound having no group that dissociates a hydrogen ion, the carbon number of the linear or branched alkyl alcohol is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, preferably 30 or less, more preferably 25 or less, and further preferably 20 or less. From the same viewpoint, the carbon number of the linear or branched alkyl alcohol is preferably from 1 to 30, more preferably from 2 to 25, and further preferably from 3 to 20.

[0077] As the amide of the α,β-unsaturated carboxylic acid, from the viewpoint of easy introduction into the molecule, for example, amides of α,β-unsaturated carboxylic acids and linear or branched primary alkylamines can be cited. From the perspective of improving the compatibility with the halogen-based resin and / or a compound having no group that dissociates a hydrogen ion, the carbon number of the linear or branched primary alkylamine is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, preferably 22 or less, more preferably 20 or less, and further preferably 18 or less. From the same viewpoint, the carbon number of the linear or branched primary alkylamine is preferably from 4 to 22, more preferably from 6 to 20, and further preferably from 8 to 18.

[0078] As the styrene-based compound, from the viewpoint of easy availability, for example, styrene, α-methylstyrene, etc. can be cited.

[0079] As the linear or branched olefin, from the viewpoint of easy preparation of the polymer dispersant, for example, olefins having 6 to 25 carbon atoms can be cited. Among them, from the viewpoint of easy introduction into the molecule, a linear olefin having a double bond at one end is preferred.

[0080] The polymer dispersant of the present invention is used in oil dispersions to reduce the slurry viscosity of the oil dispersions, thereby improving coatability and moldability. In addition, when used in halogen-based resin compositions, it reduces the slurry viscosity of the halogen-based resin compositions, thereby improving processability and achieving the effect of enhancing low-temperature flexural properties. The reason for achieving such effects is not yet determined, but is considered as follows.

[0081] The oil dispersion of the present invention contains the polymer dispersant of the present invention, an inorganic filler, and a compound that does not have a group capable of dissociating hydrogen ions. Therefore, it is considered that in the compound that does not have a group capable of dissociating hydrogen ions, the polymer dispersant is uniformly adsorbed on the surface of the inorganic filler, thereby making the surface of the inorganic filler uniformly hydrophobic, and thus more strongly inhibiting the aggregation and network formation of the inorganic filler. Therefore, it is considered that the oil dispersion containing the above polymer dispersant, inorganic filler, and compound that does not have a group capable of dissociating hydrogen ions has a low viscosity, and the oil dispersion has excellent coatability and moldability.

[0082] In addition, in the halogen-based resin composition, since the inorganic filler is hydrophilic, it is stabilized by aggregating and forming a network in the halogen-based resin composition. However, the aggregated and network-formed inorganic filler increases the viscosity of the halogen-based resin composition.

[0083] Here, the polymer dispersant of the present invention is adsorbed on the surface of the inorganic filler to make its surface hydrophobic. Thus, the aggregation and network formation of the inorganic filler in the halogen-based resin composition are inhibited, the slurry viscosity of the halogen-based resin composition is reduced, and it has excellent processability.

[0084] In addition, the inventors of the present invention found that the fracture of the halogen-based resin composition occurs on the surface of the inorganic filler. As described above, it is considered that the halogen-based resin composition of the present invention inhibits the fracture of the halogen-based resin composition generated from the surface of the inorganic filler by adsorbing the polymer dispersant of the present invention on the surface of the inorganic filler and making the surface hydrophobic, and has excellent low-temperature flexural properties.

[0085] Since the polymer dispersant of the present invention has an excellent balance of hydrophilicity and hydrophobicity, it exhibits excellent dispersibility when used in a compound that does not have a group capable of dissociating hydrogen ions described later.

[0086] From the viewpoints of improving the coatability and moldability of the oil dispersion and improving the processability and low-temperature flexural properties of the halogen-based resin composition, the polymer dispersant of the present invention is preferably any one of polymer dispersant A, polymer dispersant B, and polymer dispersant C.

[0087] 〔Polymer Dispersant A〕

[0088] The polymer dispersant A is a compound (A) composed of the following copolymers among the above polymer dispersants. Among them, the structural unit derived from the monomer represented by the general formula (1) is the structural unit derived from the monomer (a) represented by the following general formula (1a) with a molecular weight of 400 or more and 2000 or less. The structural unit derived from the monomer having a hydroxyl group is the structural unit derived from the monomer (b) having a hydroxyl group with a molecular weight of less than 400. And, as the structural unit derived from the monomer having a hydrophobic group, it includes the structural unit derived from the monomer (c) having a hydrophobic group with a molecular weight of less than 400.

[0089] (Monomer (a))

[0090] The monomer (a) is a monomer represented by the following general formula (1a) with a molecular weight of 400 or more and 2000 or less, which regulates the hydrophilic-lipophilic balance of the polymer dispersant A.

[0091]

[0092] In the general formula (1a), R 1a , R 2a , R 3a and X 1a are the same as R 1 , R 2 , R 3 and X 1 in the general formula (1), and the preferred ranges are also the same.

[0093] In the general formula (1a), Y 1a represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, and (Y 1a ) n1 represents a polyalkylene glycol composed of a repeating unit of an alkylene glycol having 2 to 4 carbon atoms. Examples of the alkylene glycol include the same alkylene glycol as Y in the general formula (1). Among them, Y 1a is preferably ethylene glycol.

[0094] In the general formula (1a), n1 represents the number of repeating units of the alkylene glycol represented by Y 1a . From the viewpoints of improving the coating property and moldability of the oil-in-dispersion, as well as improving the processability and low-temperature flexural resistance of the halogen-based resin composition, it is preferably 2 or more, more preferably 5 or more, further preferably 10 or more, still more preferably 15 or more. In addition, it is preferably 40 or less, more preferably 35 or less, further preferably 30 or less. From the same viewpoints, n1 is preferably 2 or more and 40 or less, more preferably 5 or more and 35 or less, further preferably 10 or more and 30 or less, still more preferably 15 or more and 30 or less.

[0095] In the general formula (1a), R 4ais an alkyl group having 1 to 4 carbon atoms, which is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and isobutyl, and methyl is preferred.

[0096] As the structural unit derived from monomer (a) contained in the polymer dispersant A, from the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flex resistance of the halogen-based resin composition, the structural unit derived from methoxypolyethylene glycol (meth)acrylate is preferred.

[0097] In the polymer dispersant A, the content of the structural unit derived from monomer (a) is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, further more preferably 37% by mass or more, and in addition, it is 65% by mass or less, preferably 55% by mass or less, more preferably 45% by mass or less. In the polymer dispersant A, the content of the structural unit derived from monomer (a) is 20% to 65% by weight, preferably 25% to 65% by weight, more preferably 30% to 55% by weight, still more preferably 35% to 45% by weight, still more preferably 37% to 45% by weight.

[0098] (Monomer (b))

[0099] Monomer (b) is a monomer having a hydroxyl group with a molecular weight of less than 400, which imparts hydrophilicity to the polymer dispersant A. As monomer (b), for example, a monomer having a molecular weight of less than 400, which is the monomer having a hydroxyl group mentioned in the above polymer dispersant, can be cited.

[0100] When monomer (b) is an ester of an α,β-unsaturated carboxylic acid and a polyol, and the polyol is a polyalkylene glycol, the number of repeating units of the alkylene glycol in the polyalkylene glycol is preferably 2 or more and 8 or less, more preferably 4 or more and 6 or less. Among them, from the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flex resistance of the halogen-based resin composition, a polyol having hydroxyl groups at both ends is preferred, and 1,2-ethylene glycol, glycerol, and polypropylene glycol are more preferred.

[0101] As the structural unit derived from monomer (b) contained in the polymer dispersant A, from the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flex resistance of the halogen-based resin composition, the structural unit derived from 1,2-hydroxyethyl mono(meth)acrylate, the structural unit derived from glycerol mono(meth)acrylate, and the structural unit derived from polypropylene glycol mono(meth)acrylate are preferred, and the structural unit derived from glycerol mono(meth)acrylate is more preferred.

[0102] In the polymer dispersant A, the content of the structural unit derived from monomer (b) is 5% by mass or more, preferably 10% by mass or more, more preferably 13% by mass or more, and further preferably 20% by mass or less, in addition, it is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. In the polymer dispersant A, the content of the structural unit derived from monomer (b) is 5% to 50% by weight, preferably 10% to 40% by weight, more preferably 10% to 30% by weight, and further preferably 13% to 20% by weight.

[0103] (Monomer (c))

[0104] Monomer (c) is a monomer having a hydrophobic group with a molecular weight of less than 400, which imparts hydrophobicity to the polymer dispersant A. As monomer (c), for example, a monomer having a hydrophobic group and a molecular weight of less than 400 can be cited, as described in the above polymer dispersant.

[0105] As the structural unit derived from monomer (c) contained in the polymer dispersant A, from the viewpoints of improving the coatability and moldability of the dispersion in oil, and improving the processability and low-temperature flexural resistance of the halogen-based resin composition, the structural unit derived from stearyl (meth)acrylate is preferred.

[0106] In the polymer dispersant A, the content of the structural unit derived from monomer (c) is 30% by mass or more, preferably 35% by mass or more, more preferably 38% by mass or more, and further preferably 50% by mass or less, in addition, it is 75% by mass or less, preferably 65% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less. In the polymer dispersant A, the content of the structural unit derived from monomer (c) is 30% to 75% by weight, preferably 35% to 65% by weight, more preferably 35% to 55% by weight, and further preferably 38% to 50% by weight.

[0107] From the viewpoint of suppressing the desorption of the polymer dispersant A from the inorganic filler, the weight-average molecular weight of the polymer dispersant A is preferably 5000 or more, more preferably 10000 or more, further preferably 15000 or more, and further more preferably 20000 or more. In addition, from the viewpoint of effectively adsorbing to the inorganic filler, the weight-average molecular weight of the polymer dispersant A is preferably 120000 or less, more preferably 100000 or less, further preferably 50000 or less, and further more preferably 30000 or less. From the same viewpoint, the weight-average molecular weight of the polymer dispersant A is preferably 5000 or more and 120000 or less, more preferably 10000 or more and 100000 or less, further preferably 15000 or more and 50000 or less, and even more preferably 20000 or more and 30000 or less.

[0108] The weight-average molecular weight is measured by the method shown in the examples.

[0109] [Polymeric Dispersant B]

[0110] The polymeric dispersant B is a compound (B) composed of the following copolymer among the above polymeric dispersants. Among them, the structural unit derived from the monomer represented by the general formula (1) is the structural unit derived from the monomer (d) represented by the following general formula (1b) having a molecular weight of 300 or more and 2000 or less, and the structural unit derived from the monomer having a hydroxyl group is the structural unit derived from the monomer (b) having a hydroxyl group with a molecular weight of less than 400. The compound (B) as the polymeric dispersant B may also contain the structural unit derived from the monomer (c) having a hydrophobic group with a molecular weight of less than 400.

[0111] (Monomer (d))

[0112] The monomer (d) is the monomer represented by the following general formula (1b) having a molecular weight of 300 or more and 2000 or less, which adjusts the hydrophilic-lipophilic balance of the polymeric dispersant B.

[0113]

[0114] In the general formula (1b), R 1b , R 2b , R 3b and X 1b are the same as R 1 , R 2 , R 3 and X 1 in the general formula (1), and the preferred ranges are also the same.

[0115] In the general formula (1b), Y 1b represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, and (Y 1b ) n2 represents a polyalkylene glycol composed of a repeating unit of an alkylene glycol having 2 to 4 carbon atoms. Examples of the alkylene glycol include the same alkylene glycol as Y in the general formula (1). Among them, Y 1b is more preferably polyethylene glycol, polypropylene glycol, and a combination thereof.

[0116] In the general formula (1b), n2 represents the number of repeating units of the alkylene glycol represented by Y 1b . From the viewpoints of improving the coatability and moldability of the oil-based dispersion, as well as improving the processability and low-temperature flex resistance of the halogen-based resin composition, it is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, and in addition, preferably 50 or less, more preferably 40 or less, further preferably 35 or less. From the same viewpoints, n2 is preferably 2 or more and 50 or less, more preferably 3 or more and 40 or less, further preferably 4 or more and 35 or less.

[0117] In general formula (1b), R 4b is a hydrocarbon group having 6 to 18 carbon atoms, and examples thereof include linear or branched alkyl groups having 6 to 18 carbon atoms, linear or branched alkenyl groups having 6 to 18 carbon atoms, and aromatic groups having 6 to 18 carbon atoms. Among them, linear or branched alkyl groups having 6 to 18 carbon atoms and linear or branched alkenyl groups having 6 to 18 carbon atoms are preferred, and linear or branched alkyl groups having 6 to 18 carbon atoms are more preferred.

[0118] Examples of the linear or branched alkyl group having 6 to 18 carbon atoms include hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, lauryl, stearyl and the like.

[0119] Examples of the linear or branched alkenyl group having 6 to 18 carbon atoms include alkenyl groups having a carbon-carbon double bond in the straight chain, and may have a plurality of carbon-carbon double bonds. In addition, the geometric isomers of the carbon-carbon double bond can be cis or trans.

[0120] Examples of the aromatic group having 6 to 18 carbon atoms include phenyl and naphthyl.

[0121] As the structural unit derived from monomer (d) contained in the polymer dispersant B, from the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flexural resistance of the halogen-based resin composition, the structural unit derived from lauryloxy polyethylene glycol (meth)acrylate, the structural unit derived from 2-ethylhexyloxy polypropylene glycol polyethylene glycol (meth)acrylate, the structural unit derived from 2-ethylhexyloxy polyethylene glycol (meth)acrylate, and the structural unit derived from stearyloxy polyethylene glycol (meth)acrylate are preferred.

[0122] When the polymer dispersant B does not contain the structural unit derived from monomer (c), the content of the structural unit derived from monomer (d) is 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and further 95% by mass or less, preferably 93% by mass or less, more preferably 90% by mass or less. When the polymer dispersant B does not contain the structural unit derived from monomer (c), the content of the structural unit derived from monomer (d) is 60% to 95% by weight, preferably 70% to 93% by weight, more preferably 80% to 90% by weight.

[0123] When the polymer dispersant B contains a structural unit derived from monomer (c), the content of the structural unit derived from monomer (d) is 45% by weight or more, preferably 50% by weight or more, more preferably 55% by weight or more, more preferably 60% by weight or more, more preferably 70% by weight or more, more preferably 75% by weight or more, more preferably 80% by weight or more, and further less than 95% by weight, preferably 90% by weight or less, more preferably 88% by weight or less. When the polymer dispersant B contains a structural unit derived from monomer (c), the content of the structural unit derived from monomer (d) is 45% by weight or more and less than 95% by weight, preferably 50% by weight or more and 90% by weight or less, more preferably 55% by weight or more and 90% by weight or less, further preferably 60% by weight or more and 90% by weight or less, further preferably 70% by weight or more and 88% by weight or less, further preferably 75% by weight or more and 88% by weight or less, further preferably 80% by weight or more and 88% by weight or less.

[0124] (Monomer (b))

[0125] Monomer (b) is a monomer having a hydroxyl group with a molecular weight of less than 400, which imparts hydrophilicity to the polymer dispersant B. As monomer (b), the monomers exemplified in the above polymer dispersant A can be similarly cited.

[0126] From the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flexural resistance of the halogen-based resin composition, monomer (b) is preferably a structural unit derived from 2-hydroxyethyl (meth)acrylate, a structural unit derived from glycerol mono(meth)acrylate, or a structural unit derived from polypropylene glycol mono(meth)acrylate.

[0127] When the polymer dispersant B does not contain a structural unit derived from monomer (c), the content of the structural unit derived from monomer (b) is 5% by mass or more, preferably 10% by mass or more, and further 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. When the polymer dispersant B does not contain a structural unit derived from monomer (c), the content of the structural unit derived from monomer (b) is 5% to 40% by weight, preferably 5% to 35% by weight, more preferably 10% to 30% by weight, and still more preferably 10% to 25% by weight.

[0128] When the polymer dispersant B contains a structural unit derived from monomer (c), the content of the structural unit derived from monomer (b) is 5% by weight or more, preferably 7% by weight or more, more preferably 8% by weight or more, and further 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, more preferably 15% by weight or less, and still more preferably 12% by weight or less. When the polymer dispersant B contains a structural unit derived from monomer (c), the content of the structural unit derived from monomer (b) is 5% by weight to 40% by weight, preferably 5% by weight to 35% by weight, more preferably 7% by weight to 30% by weight, still more preferably 7% by weight to 20% by weight, still more preferably 8% by weight to 15% by weight, and still more preferably 8% by weight to 12% by weight.

[0129] (Monomer (c))

[0130] Monomer (c) is a monomer having a hydrophobic group with a molecular weight of less than 400, and imparts hydrophobicity to the polymer dispersant B as needed. As monomer (c), the monomers exemplified in the above polymer dispersant A can be similarly cited.

[0131] As the structural unit derived from monomer (c) contained in the polymer dispersant B, from the viewpoints of improving the coatability and moldability of the oil-in-dispersion, and improving the processability and low-temperature flexural resistance of the halogen-based resin composition, the structural unit derived from 2-ethylhexyl (meth)acrylate is preferred.

[0132] The polymer dispersant B may not contain (the content is 0% by mass) the structural unit derived from monomer (c). When it contains the structural unit derived from monomer (c), the content of the structural unit derived from monomer (c) is more than 0% by mass, preferably 2% by mass or more, more preferably 4% by mass or more, and further 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less. When the polymer dispersant B contains the structural unit derived from monomer (c), the content of the structural unit derived from monomer (c) is more than 0% by weight and 20% by weight or less, preferably 2% by weight to 15% by weight, more preferably 2% by weight to 10% by weight, still more preferably 4% by weight to 8% by weight.

[0133] From the viewpoint of suppressing the desorption of the polymer dispersant B from the inorganic filler, the weight-average molecular weight of the polymer dispersant B is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, still more preferably 12,000 or more, still more preferably 14,000 or more. In addition, from the viewpoint of effectively adsorbing onto the inorganic filler, the weight-average molecular weight of the polymer dispersant B is preferably 120,000 or less, more preferably 115,000 or less, still more preferably 110,000 or less, still more preferably 100,000 or less, still more preferably 90,000 or less, still more preferably 80,000 or less, still more preferably 70,000 or less, still more preferably 60,000 or less, still more preferably 50,000 or less, still more preferably 40,000 or less, still more preferably 30,000 or less, still more preferably 20,000 or less, still more preferably 17,000 or less. From the same viewpoint, the weight-average molecular weight of the molecular dispersant B is preferably 5,000 or more and 120,000 or less, more preferably 5,000 or more and 115,000 or less, still more preferably 8,000 or more and 110,000 or less, still more preferably 8,000 or more and 100,000 or less, still more preferably 8,000 or more and 90,000 or less, still more preferably 10,000 or more and 80,000 or less, still more preferably 10,000 or more and 70,000 or less, still more preferably 10,000 or more and 60,000 or less, still more preferably 12,000 or more and 50,000 or less, still more preferably 12,000 or more and 40,000 or less, still more preferably 12,000 or more and 30,000 or less, still more preferably 14,000 or more and 20,000 or less, still more preferably 14,000 or more and 17,000 or less.

[0134] The weight-average molecular weight is measured by the method shown in the examples.

[0135] [Polymer Dispersant C]

[0136] The polymer dispersant C is a compound (C) composed of the following copolymer among the above polymer dispersants. Among them, the structural unit derived from the monomer represented by the general formula (1) is the structural unit derived from the monomer (d) represented by the general formula (1b) having a molecular weight of 300 or more and 2,000 or less, the structural unit derived from the monomer having a hydroxyl group is the structural unit derived from the monomer (b) having a hydroxyl group with a molecular weight of less than 400, and the structural unit derived from the monomer having a hydrophobic group contains the structural unit derived from the monomer (c) having a hydrophobic group with a molecular weight of less than 400.

[0137] (Monomer (d))

[0138] The monomer (d) is a monomer represented by the following general formula (1b) with a molecular weight of 300 or more and 2000 or less, which regulates the hydrophilic-lipophilic balance of the polymer dispersant C. As the monomer (d), the monomers exemplified in the monomer (d) cited in the polymer dispersant B can be similarly cited.

[0139]

[0140] As the structural unit derived from the monomer (d) contained in the polymer dispersant C, from the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flexural resistance of the halogen-based resin composition, the structural unit derived from 2-ethylhexoxy polyethylene glycol (meth)acrylate is preferred.

[0141] In the polymer dispersant C, the content of the structural unit derived from the monomer (d) is 10% by mass or more, preferably 12% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and further less than 40% by mass, preferably 35% by mass or less, more preferably 30% by mass or less. In the polymer dispersant C, the content of the structural unit derived from the monomer (d) is 10% by mass or more and less than 40% by mass, preferably 12% by mass or more and 35% by mass or less, more preferably 15% by mass or more, and further preferably 20% by mass or more and 30% by mass or less.

[0142] (Monomer (b))

[0143] The monomer (b) is a monomer (b) with a hydroxyl group and a molecular weight of less than 400, which imparts hydrophilicity to the polymer dispersant C. As the monomer (b), the monomers exemplified in the above polymer dispersant A can be similarly cited.

[0144] From the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flexural resistance of the halogen-based resin composition, the monomer (b) is preferably a structural unit derived from 2-hydroxyethyl (meth)acrylate, a structural unit derived from glycerol mono(meth)acrylate, or a structural unit derived from polypropylene glycol mono(meth)acrylate.

[0145] In the polymer dispersant C, the content of the structural unit derived from the monomer (b) is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, and further 20% by mass or less, preferably 18% by mass or less, more preferably 15% by mass or less. In the polymer dispersant C, the content of the structural unit derived from the monomer (b) is 5% to 20% by weight, preferably 6% to 18% by weight, more preferably 7% to 15% by weight.

[0146] (Macromonomer containing a structural unit derived from monomer (c))

[0147] The macromonomer containing a structural unit derived from monomer (c) is a copolymer containing monomer (c) having a hydrophobic group with a molecular weight of less than 400 as a structural unit, and imparts hydrophobicity to the polymer dispersant C.

[0148] Examples of monomer (c) constituting the macromonomer include the same ones as those exemplified above for polymer dispersant A.

[0149] The weight-average molecular weight of the macromonomer containing a structural unit derived from monomer (c) is preferably 3000 or more and 20000 or less.

[0150] As the structural unit of the macromonomer containing a structural unit derived from monomer (c) contained in the polymer dispersant C, from the viewpoints of improving the coatability and moldability of the dispersion in oil and improving the processability and low-temperature flexural resistance of the halogen-based resin composition, the structural unit of the macromonomer derived from the structural unit containing isobutyl (meth)acrylate and the structural unit of the macromonomer derived from the structural unit containing styrene are preferred, and the structural unit of the macromonomer derived from the structural unit containing isobutyl (meth)acrylate is more preferred.

[0151] In the polymer dispersant C, the content of the structural unit of the macromonomer containing a structural unit derived from monomer (c) is more than 60% by mass, preferably 62% by mass or more, more preferably 65% by mass or more, and further 80% by mass or less, preferably 77% by mass or less, more preferably 75% by mass or less. In the polymer dispersant C, the content of the structural unit of the macromonomer (including the structural unit derived from monomer (c)) is more than 60% by mass and 80% by mass or less, preferably 62% by mass or more and 77% by mass or less, more preferably 65% by mass or more and 75% by mass or less.

[0152] From the viewpoint of suppressing the desorption of the polymer dispersant C from the inorganic filler, the weight-average molecular weight of the polymer dispersant C is preferably 30,000 or more, more preferably 40,000 or more, furthermore preferably 50,000 or more. In addition, from the viewpoint of effectively adsorbing to the inorganic filler, the weight-average molecular weight of the polymer dispersant C is preferably 120,000 or less, more preferably 115,000 or less, more preferably 110,000 or less, more preferably 100,000 or less, more preferably 90,000 or less, more preferably 80,000 or less, more preferably 70,000 or less, and furthermore preferably 65,000 or less. From the same viewpoint, the weight-average molecular weight of the polymer dispersant C is preferably 30,000 or more and 120,000 or less, more preferably 30,000 or more and 115,000 or less, further preferably 30,000 or more and 110,000 or less, still further preferably 40,000 or more and 100,000 or less, still further preferably 40,000 or more and 90,000 or less, still further preferably 40,000 or more and 80,000 or less, still further preferably 50,000 or more and 70,000 or less, still further preferably 50,000 or more and 65,000 or less.

[0153] The weight-average molecular weight is measured by the method shown in the examples.

[0154] (Method for producing polymer dispersant)

[0155] As a method for producing the polymer dispersant, a method of copolymerizing a monomer mixture containing a monomer represented by the general formula (1), a monomer having a hydroxyl group, and, if necessary, a monomer having a hydrophobic group by a known polymerization method can be mentioned. For example, as a method for producing the polymer dispersant A, a method of copolymerizing a monomer mixture containing monomer (a), monomer (b), and monomer (c) by a known polymerization method can be mentioned. As a method for producing the polymer dispersant B, a method of copolymerizing a monomer mixture containing monomer (d), monomer (b), and, if necessary, monomer (c) by a known polymerization method can be mentioned. As a method for producing the polymer dispersant C, a method of copolymerizing a monomer mixture containing a macromonomer having structural units derived from monomer (a), monomer (b), and monomer (c) by a known polymerization method can be mentioned. As the polymerization method, from the viewpoint of being able to be produced with general equipment, the solution polymerization method is preferred.

[0156] The solvent used in the solution polymerization method is not limited as long as it can dissolve monomers (a) to (d), and aromatic solvents such as toluene and xylene, ketones such as aliphatic alcohols, acetone, and methyl ethyl ketone, ethers, and polar solvents such as esters are preferred, and toluene, methanol, ethanol, acetone, methyl ethyl ketone, etc. are more preferred, and toluene and ethanol are further preferred. The solvent can be used alone or in combination of two or more solvents.

[0157] During polymerization, a polymerization initiator or a chain transfer agent can be used.

[0158] As the polymerization initiator, from the viewpoint of being able to stably polymerize at the boiling point of the above-mentioned solvent, known radical polymerization initiators such as azo compounds like 2,2'-azobis(isobutyronitrile dimethyl ester), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), organic peroxides such as tert-butyl octanoate peroxide and benzoyl peroxide can be used. The amount of the radical polymerization initiator is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, further preferably 5 parts by mass or less, and even more preferably 4 parts by mass or less with respect to 100 parts by mass of the monomer mixture. Moreover, with respect to 100 parts by mass of the monomer mixture, the amount of the radical polymerization initiator is preferably 0.1 part by mass or more and 5 parts by mass or less, more preferably 0.3 part by mass or more and 4 parts by mass or less.

[0159] As the chain transfer agent, from the viewpoint of easily adjusting the molecular weight, known chain transfer agents such as thiols like octyl mercaptan, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, mercaptopropionic acid, and thiuram disulfides can be used.

[0160] In addition, the mode of the polymer chain of the monomer polymerization is not limited and can be any one of random, block, graft, etc. polymerization modes.

[0161] The monomer mixture may also contain a compound having two or more radical-polymerizable carbon-carbon double bonds (crosslinking agent). When the monomer mixture contains a crosslinking agent, from the viewpoint of preventing gelation of the reaction system, the content of the crosslinking agent in the mixture containing the crosslinking agent is preferably 3 mol% or less. The content of the crosslinking agent in the monomer mixture is preferably 2 mol% or less, more preferably 1 mol% or less.

[0162] The preferred polymerization conditions vary depending on the types of the polymerization initiator, monomer, solvent, etc. From the viewpoint of being able to perform polymerization with general equipment, usually, the polymerization temperature is preferably 30°C or higher, more preferably 50°C or higher, further preferably 95°C or lower, and even more preferably 90°C or lower. The polymerization temperature is preferably from 30°C to 95°C, more preferably from 50°C to 90°C. The polymerization time is preferably 1 hour or more, more preferably 2 hours or more, further preferably 20 hours or less, and even more preferably 10 hours or less. The polymerization time is preferably 1 hour or more and 20 hours or less, more preferably 2 hours or more and 10 hours or less. In addition, the polymerization atmosphere is preferably an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere.

[0163] In the production of the polymer dispersant of the present invention, since the conversion rate of the monomer mixture is approximately 100%, the content of each monomer used in the polymerization is approximately equal to the content of the structural units derived from each monomer in each polymer dispersant.

[0164] [Dispersion in oil]

[0165] The dispersion in oil of the present invention contains the above polymer dispersant, an inorganic filler, and a compound that does not have a group that dissociates hydrogen ions. The polymer dispersant contained in the dispersion in oil is preferably any one of polymer dispersant A, polymer dispersant B, and polymer dispersant C.

[0166] [Inorganic filler]

[0167] Examples of the inorganic filler contained in the dispersion in oil of the present invention include calcium carbonate, talc, calcium silicate, alumina (bauxite), titanium oxide, magnesium oxide, etc. The inorganic filler can be used alone or in combination of two or more. From the viewpoints of improving the coatability and moldability of the dispersion in oil and economy, the inorganic filler is preferably alumina.

[0168] From the viewpoint of improving the coatability and moldability of the dispersion in oil, the median particle size of the inorganic filler in the dispersion in oil of the present invention is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and preferably 2 μm or less, more preferably 1.5 μm or less, further preferably 1 μm or less. From the same viewpoint, the median particle size of the inorganic filler is preferably 0.01 μm or more and 2 μm or less, more preferably 0.05 μm or more and 1.5 μm or less, further preferably 0.1 μm or more and 1 μm or less.

[0169] From the viewpoint of improving the coatability and moldability of the dispersion in oil, the content of the inorganic filler in the dispersion in oil of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 73% by mass or less. From the same viewpoint, the content of the inorganic filler in the dispersion in oil is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 75% by mass or less, further preferably 20% by mass or more and 73% by mass or less.

[0170] From the viewpoint of improving the coatability and moldability of the oil dispersion, the mass ratio of the polymer dispersant to the inorganic filler (polymer dispersant / inorganic filler) in the oil dispersion of the present invention is preferably 0.0001 or more, more preferably 0.0005 or more, further preferably 0.001 or more, still further preferably 0.002 or more, and furthermore preferably 10 or less, more preferably 5 or less, further preferably 1 or less, still further preferably 0.5 or less, still further preferably 0.1 or less, still further preferably 0.05 or less, still further preferably 0.03 or less, still further preferably 0.01 or less. From the same viewpoint, the mass ratio of the polymer dispersant to the inorganic filler (polymer dispersant / inorganic filler) is preferably from 0.0001 to 10, more preferably from 0.0001 to 5, still more preferably from 0.0005 to 1, still more preferably from 0.0005 to 0.5, still more preferably from 0.001 to 0.1, still more preferably from 0.001 to 0.05, still more preferably from 0.002 to 0.03, still more preferably from 0.002 to 0.01.

[0171] Compound having no group dissociating hydrogen ions

[0172] The compound having no group dissociating hydrogen ions may be any compound as long as it becomes a slurry state by mixing with the polymer dispersant and the inorganic filler.

[0173] Examples of the group dissociating hydrogen ions include, but are not limited to, hydroxyl group, amino group, carboxyl group, and carbonyl group having a hydrogen atom which is easily deprotonated (strong acidity) at the α-position such as enol generated by tautomerization by mixing with an inorganic filler.

[0174] Examples of the compound having no group dissociating hydrogen ions in the oil dispersion of the present invention include non-aqueous solvents such as aromatic compounds such as toluene, xylene, mesitylene, ethylbenzene, anisole; ketone compounds such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone; ester compounds such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate.

[0175] The SP value of the compound having no group dissociating hydrogen ions measured by the Fedors method is preferably 7.5 (cal / cm 3 ) 1 / 2 or more, more preferably 7.8 (cal / cm 3 ) 1 / 2 or more, further preferably 8 (cal / cm 3 ) 1 / 2 or more, and furthermore preferably 12 (cal / cm 3 ) 1 / 2 or less, more preferably 11.5 (cal / cm 3 )1 / 2 Hereinafter, it is further preferably 11 (cal / cm 3 ). 1 / 2 Hereinafter, the SP value of a compound having no group dissociating hydrogen ions, measured by the Fedors method, is preferably 7.5 (cal / cm 3 ). 1 / 2 or more and 12 (cal / cm 3 ). 1 / 2 Hereinafter, it is more preferably 7.8 (cal / cm 3 ). 1 / 2 or more and 11.5 (cal / cm 3 ). 1 / 2 Hereinafter, it is further preferably 8 (cal / cm 3 ). 1 / 2 or more and 11 (cal / cm 3 ). 1 / 2 Hereinafter.

[0176] A compound having no group dissociating hydrogen ions may be used alone or in combination of two or more. From the viewpoint of further improving the coatability and moldability of the dispersion in oil, the compound having no group dissociating hydrogen ions is preferably toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, and more preferably cyclohexanone and propylene glycol monomethyl ether acetate.

[0177] From the viewpoint of improving the coatability and moldability of the dispersion in oil, the content of the compound having no group dissociating hydrogen ions is preferably 19% by mass or more, more preferably 24% by mass or more, and further preferably 26% by mass or more. In addition, it is preferably 89% by mass or less, more preferably 84% by mass or less, and further preferably 79% by mass or less. From the same viewpoint, the content of the compound having no group dissociating hydrogen ions is preferably 19% to 89% by weight, more preferably 24% to 84% by weight, and further preferably 26% to 79% by weight.

[0178] [Additive]

[0179] The dispersion in oil may contain, as needed, the same additives as those contained in the halogen-based resin composition described below, within the range not impairing the effects of the present invention.

[0180] (Method for producing dispersion in oil)

[0181] The method for producing the dispersion in oil of the present invention includes a step of mixing a polymer dispersant, an inorganic filler, and a compound having no group dissociating hydrogen ions (non-aqueous solvent).

[0182] The oil-in-dispersion can be obtained by mixing a polymer dispersant, an inorganic filler, and a compound having no group capable of dissociating hydrogen ions using a stirrer such as a mortar mixer, a Henschel mixer, a Banbury mixer, a belt blender, etc., and dispersing the polymer dispersant and the inorganic filler in the compound having no group capable of dissociating hydrogen ions.

[0183] [Halogen-based resin composition]

[0184] The halogen-based resin composition of the present invention contains the above polymer dispersant, inorganic filler, compound having no group capable of dissociating hydrogen ions, and halogen-based resin. The polymer dispersant contained in the halogen-based resin composition is preferably any one of polymer dispersant A, polymer dispersant B, and polymer dispersant C.

[0185] [Halogen-based resin]

[0186] In the present invention, the halogen-based resin refers to a homopolymer, copolymer, or halogen-modified polymer of a monomer containing halogen. From the viewpoint of easy availability, specifically, one or more selected from vinyl chloride resin, vinylidene chloride resin, chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, chloroprene rubber, etc. are exemplified. Preferably, the halogen-based resin composition of the present invention contains one or more selected from vinyl chloride resin, vinylidene chloride resin, and chloroprene rubber.

[0187] [Vinyl chloride resin]

[0188] As the vinyl chloride resin, for example, a vinyl chloride homopolymer, a copolymer of vinyl chloride and a copolymerizable monomer, hereinafter also referred to as "vinyl chloride copolymer", "graft copolymer in which vinyl chloride is grafted onto a polymer other than the vinyl chloride copolymer", etc. can be exemplified.

[0189] As the above monomer copolymerizable with vinyl chloride, from the viewpoint of easy copolymerization, any monomer having a reactive double bond in the molecule can be used. For example, α-olefins such as ethylene, propylene, and butene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; esters of (meth)acrylic acid such as (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, and (meth)acrylic acid phenyl ester; aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, etc. can be exemplified.

[0190] In addition, as a polymer other than the vinyl chloride copolymer, from the viewpoint of easy availability, any polymer capable of graft copolymerizing vinyl chloride may be used. Examples thereof include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, and the like.

[0191] Among the above-mentioned halogen-based resins, from the viewpoint of improving the low-temperature bendability of the halogen-based resin composition, it is preferably at least one selected from vinyl chloride resins, ethylene-vinyl chloride copolymers, vinyl acetate-vinyl chloride copolymers, polyurethane-grafted polyvinyl chloride copolymers and other vinyl chloride-based resins, vinylidene chloride, and chloroprene rubber. More preferably, it is at least one selected from vinyl chloride resins, vinylidene chloride resins, and chloroprene rubber. Further preferably, it is a vinyl chloride resin.

[0192] From the viewpoints of improving the processability and low-temperature bendability of the halogen-based resin composition, the content of the polymer dispersant in the halogen-based resin composition is preferably 0.001 part by mass or more and 0.8 part by mass or less relative to 100 parts by mass of the halogen-based resin.

[0193] 〔Inorganic filler〕

[0194] As the inorganic filler contained in the halogen-based resin composition of the present invention, the same inorganic fillers as those exemplified in the oil dispersion can be cited. From the viewpoint of economy, the inorganic filler is preferably calcium carbonate.

[0195] The median particle diameter of the inorganic filler in the halogen-based resin composition of the present invention is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less from the viewpoints of improving the processability and low-temperature bendability of the halogen-based resin composition. From the same viewpoints, the median particle diameter of the inorganic filler in the halogen-based resin composition is preferably 0.01 μm or more and 20 μm or less, more preferably 0.05 μm or more and 15 μm or less, further preferably 0.1 μm or more and 10 μm or less.

[0196] From the viewpoint of reducing the cost of the halogen-based resin composition, the inorganic filler in the halogen-based resin composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and further preferably 150 parts by mass or less, more preferably 140 parts by mass or less, still more preferably 130 parts by mass or less, based on 100 parts by mass of the halogen-based resin. From the same viewpoint, the inorganic filler in the halogen-based resin composition is preferably 1 part by mass or more and 150 parts by mass or less, more preferably 3 parts by mass or more and 140 parts by mass or less, still more preferably 5 parts by mass or more and 130 parts by mass or less, based on 100 parts by mass of the halogen-based resin.

[0197] From the viewpoints of improving the processability of the halogen-based resin composition and improving the low-temperature flexural properties, the mass ratio of the polymer dispersant to the inorganic filler (polymer dispersant / inorganic filler) in the halogen-based resin composition is preferably 0.0001 or more, more preferably 0.0005 or more, still more preferably 0.001 or more, even more preferably 0.002 or more, and further preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, even more preferably 0.5 or less, even more preferably 0.1 or less, even more preferably 0.05 or less, even more preferably 0.03 or less, even more preferably 0.01 or less. From the same viewpoints, the mass ratio of the polymer dispersant to the inorganic filler (polymer dispersant / inorganic filler) in the halogen-based resin composition is preferably from 0.0001 to 10, more preferably from 0.0001 to 5, still more preferably from 0.0005 to 1, still more preferably from 0.0005 to 0.5, still more preferably from 0.001 to 0.1, still more preferably from 0.001 to 0.05, still more preferably from 0.002 to 0.03, still more preferably from 0.002 to 0.01.

[0198] [Compound without a group dissociating hydrogen ions]

[0199] In the halogen-based resin composition of the present invention, examples of the compound without a group dissociating hydrogen ions include compounds generally used as plasticizers for halogen-based resins.

[0200] As compounds commonly used as plasticizers for halogen-based resins, for example, in addition to dioctyl phthalate (DOP) and diisononyl phthalate (DINP), phthalate esters of alcohols having 1 to 13 carbon atoms such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and heneicosyl phthalate can also be cited; trimellitate esters of alcohols having 6 to 10 carbon atoms such as tris(2-ethylhexyl) trimellitate, trioctyl trimellitate, and tridecyl trimellitate; adipate esters, azelate esters, sebacate esters, phosphate esters, polyester esters, epoxy esters, fatty acid esters, pyromellitate esters, and other plasticizers.

[0201] From the viewpoint of high compatibility between compounds that do not have a group capable of dissociating hydrogen ions and halogen-based resins, the SP value obtained by the Fedors method is preferably 7.5 (cal / cm 3 ). 1 / 2 or more, more preferably 7.8 (cal / cm 3 ). 1 / 2 or more, further preferably 8 (cal / cm 3 ). 1 / 2 or more, and further preferably 11.5 (cal / cm 3 ). 1 / 2 or less, more preferably 10.5 (cal / cm 3 ). 1 / 2 or less, further preferably 10 (cal / cm 3 ). 1 / 2 or less. From the same viewpoint, the SP value of a compound that does not have a group capable of dissociating hydrogen ions measured by the Fedors method is preferably 7.5 (cal / cm 3 ). 1 / 2 or more and 11.5 (cal / cm 3 ). 1 / 2 or less, more preferably 7.8 (cal / cm 3 ). 1 / 2 or more and 10.5 (cal / cm 3 ). 1 / 2 or less, further preferably 8 (cal / cm 3 ). 1 / 2 or more and 10 (cal / cm 3 ). 1 / 2 or less.

[0202] Compounds that do not have a group capable of dissociating hydrogen ions can be used alone or in combination of two or more. From the viewpoints of improving the processability of the halogen-based resin composition and improving the low-temperature flexural properties, the compounds that do not have a group capable of dissociating hydrogen ions are preferably dialkyl phthalates and trialkyl trimellitates, and more preferably bis(2-ethylhexyl) phthalate and tris(2-ethylhexyl) trimellitate.

[0203] From the viewpoint of exhibiting the plasticizing effect of the halogen-based resin composition, the content of the compound that does not have a group capable of dissociating hydrogen ions in the halogen-based resin composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more, based on 100 parts by mass of the halogen-based resin. From the viewpoints of improving the processability of the halogen-based resin composition and improving the low-temperature flexural properties, it is preferably 170 parts by mass or less, more preferably 160 parts by mass or less, and further preferably 150 parts by mass or less. From the same viewpoints, based on 100 parts by mass of the halogen-based resin, the content of the compound that does not have a group capable of dissociating hydrogen ions in the halogen-based resin composition is preferably 5 parts by mass or more and 170 parts by mass or less, more preferably 10 parts by mass or more and 160 parts by mass or less, and further preferably 15 parts by mass or more and 150 parts by mass or less.

[0204] 〔Additives〕

[0205] The halogen-based resin composition may contain additives such as stabilizers, processing aids, colorants, antioxidants, ultraviolet absorbers, antistatic agents, and lubricants, as needed, within the range that does not impair the effects of the present invention.

[0206] Examples of the stabilizer include metal soap compounds such as lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octoate, zinc laurate, zinc ricinoleate, and zinc stearate; organotin compounds such as dimethyltin bis(2-ethylhexyl) thioglycolate, dibutyltin maleate, dibutyltin bis(butyl maleate), and dibutyltin dilaurate; and antimony mercaptan compounds. The content of the stabilizer is 0.1 to 20 parts by mass based on 100 parts by mass of the halogen-based resin.

[0207] Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearamide, ethylene bisstearamide, butyl stearate, and calcium stearate. The content of the processing aid is 0.1 to 20 parts by mass based on 100 parts by mass of the halogen-based resin.

[0208] Examples of the colorant include carbon black, lead sulfide, silica white, titanium white, lithopone, iron oxide red, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange. The content of the colorant is 1 to 100 parts by mass based on 100 parts by mass of the halogen-based resin.

[0209] Examples of the antioxidant include phenolic compounds such as 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and 2-hydroxy-4-methoxybenzophenone; sulfur compounds such as alkyldisulfides, thiodipropionates, and benzothiazoles; phosphoric acid compounds such as trinonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and tris(2,4-di-tert-butylphenyl) phosphite; and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. The content of the antioxidant is 0.2 to 20 parts by mass with respect to 100 parts by mass of the halogen-based resin.

[0210] Examples of the ultraviolet absorber include salicylic acid esters such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone compounds such as 2-hydroxy-4-n-octyloxybenzophenone and 2-hydroxy-4-methoxybenzophenone; benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole; and cyanoacrylate compounds. The content of the ultraviolet absorber is 0.1 to 10 parts by mass with respect to 100 parts by mass of the halogen-based resin.

[0211] Examples of the antistatic agent include anionic antistatic agents such as alkyl sulfonate type, alkyl ether carboxylate type, or dialkyl sulfosuccinate type; nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives; quaternary ammonium salts such as alkylamide amine type and alkyldimethylbenzyl type; and cationic antistatic agents such as alkylpyridinium type organic acid salts or hydrochlorides. The content of the antistatic agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the halogen-based resin.

[0212] Examples of the lubricant include silicone, liquid paraffin, fatty acids such as stearic acid and lauric acid and their metal salts, fatty acid amides, fatty acid waxes, and higher fatty acid waxes. The content of the lubricant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the halogen-based resin.

[0213] (Method for producing the halogen-based resin composition)

[0214] The method for producing the halogen-based resin composition of the present invention includes, for example, a step of mixing a polymer dispersant, an inorganic filler, a compound having no group capable of dissociating a hydrogen ion, and a halogen-based resin.

[0215] A halogen-based resin composition can be prepared by mixing a polymer dispersant, an inorganic filler, a compound having no group dissociating a hydrogen ion, a halogen-based resin, and optionally various additives using a blender such as a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender to prepare a slurry of the halogen-based resin composition. Further, by melt molding using a kneader such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a co-kneading type kneader, a roll kneader, etc., a halogen-based resin composition in a mixed powder, granular, or paste form can be obtained.

[0216] The conditions for mixing and melt molding can be any conditions for a method for producing a conventional halogen-based resin composition.

[0217] Further, a method for producing a halogen-based resin composition can include, for example, a step of mixing a polymer dispersant, an inorganic filler, a slurry composition containing a compound having no group dissociating a hydrogen ion, a halogen-based resin, and various additives as needed. The mixing of the slurry composition and the halogen-based resin can be performed using the above blender to prepare a slurry of the halogen-based resin composition. Further, a halogen-based resin composition in a mixed powder, granular, or paste form can be obtained by melt molding using the above kneader.

[0218] The mixed powder or granules of the halogen-based resin composition can be formed into a desired shape by known methods such as extrusion molding, injection molding, calendering molding, compression molding, blow molding, etc. Further, the paste-like halogen-based resin composition can be formed into a desired shape by known methods such as spreading molding, dipping molding, gravure molding, screen processing, etc.

[0219] (Use as a dispersant)

[0220] As described above, the compound (I) constituting the polymer dispersant can be used as a dispersant. The compound (I) can be preferably used to disperse an inorganic filler in a compound having no group dissociating a hydrogen ion. Examples of the compound having no group dissociating an inorganic filler and a hydrogen ion include the inorganic fillers and the compounds having no group dissociating a hydrogen ion (non-aqueous solvents) exemplified in the oil dispersion and the halogen-based resin composition. As the compound (I), from the viewpoint of effectively dispersing an inorganic filler in a compound having no group dissociating a hydrogen ion, any one of the compound A constituting the polymer dispersant A, the compound B constituting the polymer dispersant B, and the compound C constituting the polymer dispersant C is preferred.

[0221] (Use of the polymer dispersant for manufacturing an oil dispersion and a halogen-based resin composition)

[0222] As described above, the polymer dispersant of the present invention can be used to produce dispersions in oil and halogen-based resin compositions. As the use of the polymer dispersant for producing dispersions in oil and halogen-based resin compositions, for example, the uses exemplified in the above methods for producing dispersions in oil and halogen-based resin compositions can be cited. The polymer dispersant used in the production methods of dispersions in oil and halogen-based resin compositions is preferably any one of polymer dispersant A, polymer dispersant B, and polymer dispersant C.

[0223] The present invention includes the following aspects.

[0224] <1> A polymer dispersant A, which contains structural units derived from a monomer (a) having a hydrophobic group with a molecular weight of less than 400 in an amount of 30% by mass or more and 75% by mass or less, structural units derived from a monomer (b) represented by the following general formula (1) with a molecular weight of 400 or more and 2000 or less in an amount of 20% by mass or more and 65% by mass or less, and structural units derived from a monomer (c) having a hydroxyl group with a molecular weight of less than 400 in an amount of 5% by mass or more and 50% by mass or less.

[0225]

[0226] (In the general formula (1), R 1 , R 2 and R 3 are each independently selected from a hydrogen element and a methyl group, X 1 represents an oxygen element, an ester group, an amide group, or -CH2O-, Y 1 represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4 represents a hydrogen element or an alkyl group having 1 to 4 carbon atoms. n1 represents the number of repeating units of the above alkylene glycol.)

[0227] <2> A polymer dispersant, which contains structural units derived from a monomer represented by the following general formula (1) and structural units derived from a monomer having a hydroxyl group.

[0228]

[0229] (In the general formula (1), R 1 , R 2 and R 3 are each independently selected from a hydrogen element and a methyl group, X 1 represents an oxygen element, an ester group, an amide group, or -CH2O-, Y 1 represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4 represents a hydrogen element or a hydrocarbon group having 1 to 20 carbon atoms. n represents the number of repeating units of the above alkylene glycol.)

[0230] <3>Polymeric dispersant A, which contains structural units derived from monomer (a) represented by the following general formula (1a) with a molecular weight of 400 or more and 2000 or less, in an amount of 20% by mass or more and 65% by mass or less, structural units derived from monomer (b) with a hydroxyl group and a molecular weight of less than 400, in an amount of 5% by mass or more and 50% by mass or less, and structural units derived from monomer (c) with a hydrophobic group and a molecular weight of less than 400, in an amount of 30% by mass or more and 75% by mass or less.

[0231]

[0232] (In the general formula (1a), R 1a , R 2a and R 3a are each independently selected from a hydrogen element and a methyl group, X 1a represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1a represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, and R 4a represents a hydrogen element or an alkyl group having 1 to 4 carbon atoms. n1 represents the number of repeating units of the above alkylene glycol.)

[0233] <4>The polymeric dispersant A according to <3> above, wherein it contains structural units derived from monomer (a) in an amount of 30% by mass or more and 45% by mass or less, structural units derived from monomer (b) in an amount of 13% by mass or more and 30% by mass or less, and structural units derived from monomer (c) in an amount of 38% by mass or more and 50% by mass or less.

[0234] <5>The polymeric dispersant A according to <3> or <4> above, wherein the structural units derived from monomer (a) are structural units derived from methoxypolyethylene glycol (meth)acrylate, the structural units derived from monomer (b) are structural units derived from glycerol mono(meth)acrylate, and the structural units derived from monomer (c) are structural units derived from stearyl (meth)acrylate.

[0235] <6>The polymeric dispersant A according to any one of <3> to <5> above, wherein it contains structural units derived from monomer (b) in an amount of 37% by mass or more and 45% by mass or less, structural units derived from monomer (a) in an amount of 13% by mass or more and 20% by mass or less, and structural units derived from monomer (c) in an amount of 38% by mass or more and 50% by mass or less. The structural units derived from monomer (a) are structural units derived from methoxypolyethylene glycol (meth)acrylate, the structural units derived from monomer (b) are structural units derived from glycerol mono(meth)acrylate, and the structural units derived from monomer (c) are structural units derived from stearyl (meth)acrylate.

[0236] <7> The polymer dispersant A according to any one of <3> to <6> above, wherein the weight-average molecular weight of the polymer dispersant A is 20,000 or more and 30,000 or less.

[0237] <8> The polymer dispersant A according to any one of <3> to <7> above, wherein the number of repeating units n1 of the alkylene glycol is 15 or more and 30 or less.

[0238] <9> A polymer dispersant B, which contains structural units derived from monomer (d) represented by the following general formula (1B) having a molecular weight of 300 or more and 2,000 or less in an amount of 45% by mass or more and 95% by mass or less, structural units derived from a monomer (b) having a hydroxyl group and a molecular weight of less than 400 in an amount of 5% by mass or more and 40% by mass or less, and structural units derived from a monomer (c) having a hydrophobic group and a molecular weight of less than 400 in an amount of 0% by mass or more and 20% by mass or less.

[0239]

[0240] (In the general formula (1b), R 5 , R 6 and R 7 are each independently selected from a hydrogen element and a methyl group, X 2 represents an oxygen element, an ester group, an amide group or -CH2O-, Y 2 represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, and R 8 represents a hydrocarbon group having 6 to 18 carbon atoms. n2 represents the number of repeating units of the alkylene glycol.)

[0241] <10> The polymer dispersant B according to <9> above, wherein it contains structural units derived from monomer (d) in an amount of 60% by mass or more and 88% by mass or less, structural units derived from monomer (b) in an amount of 12% by mass or more and 40% by mass or less, and does not contain structural units derived from monomer (c).

[0242] <11> The polymer dispersant B according to <9> or <10> above, wherein, as the structural units derived from monomer (d), it contains structural units derived from lauryl polyoxyethylene (meth)acrylate in an amount of 75% by mass or more and 88% by mass or less, and as the structural units derived from monomer (b), it contains structural units derived from glycerol mono(meth)acrylate or (meth)acrylic acid 2-hydroxyethyl ester in an amount of 12% by mass or more and 25% by mass or less.

[0243] <12>According to the polymeric dispersant B described in any one of <9> to <11> above, wherein, as the structural unit derived from monomer (d), it contains 80% by mass or more and 88% by mass or less of the structural unit derived from lauryloxy polyethylene glycol (meth)acrylate, and as the structural unit derived from monomer (b), it contains 12% by mass or more and 20% by mass or less of the structural unit derived from 2-hydroxyethyl (meth)acrylate.

[0244] <13>According to the polymeric dispersant B described in <9> or <10> above, wherein, as the structural unit derived from monomer (b), it contains 12% by mass or more and 25% by mass or less of the structural unit derived from glycerol mono(meth)acrylate, and as the structural unit derived from monomer (d), it contains 75% by mass or more and 88% by mass or less of the structural unit derived from stearyloxy polyethylene glycol (meth)acrylate.

[0245] <14>According to the polymeric dispersant B described in any one of <9> or <10> above, wherein, as the structural unit derived from monomer (d), it contains 75% by mass or more and 88% by mass or less of the structural unit derived from 2-ethylhexoxy polypropylene glycol polyethylene glycol (meth)acrylate, and as the structural unit derived from monomer (b), it contains 12% by mass or more and 25% by mass or less of the structural unit derived from glycerol mono(meth)acrylate.

[0246] <15>According to the polymeric dispersant B described in <9> above, wherein it contains 55% by mass or more and 88% by mass or less of the structural unit derived from monomer (d), 8% by mass or more and 12% by mass or less of the structural unit derived from monomer (b), and 4% by mass or more and 8% by mass or less of the structural unit derived from monomer (c).

[0247] <16>According to the polymeric dispersant B described in <9> or <15> above, wherein the structural unit derived from monomer (d) is the structural unit derived from stearyloxy polyethylene glycol (meth)acrylate, the structural unit derived from monomer (b) is the structural unit derived from 2-hydroxyethyl (meth)acrylate, and the structural unit derived from monomer (c) is the structural unit derived from 2-ethylhexyl (meth)acrylate.

[0248] <17>According to the polymeric dispersant B described in any one of <9> to <16> above, its weight-average molecular weight is 10,000 or more and 110,000 or less.

[0249] <18>The polymeric dispersant B according to any one of <9> to <11> above, wherein, as the structural unit derived from monomer (d), it contains a structural unit derived from lauryloxy polyethylene glycol (meth)acrylate of 80% by mass or more and 88% by mass or less, and as the structural unit derived from monomer (b), it contains a structural unit derived from glycerol mono(meth)acrylate of 12% by mass or more and 20% by mass or less, and the weight average molecular weight is 14,000 or more and 17,000 or less.

[0250] <19>The polymeric dispersant B according to any one of <9> to <18> above, wherein the repeating unit number n2 of the alkylene glycol is 4 or more and 35 or less.

[0251] <20>A polymeric dispersant C, which contains a structural unit derived from monomer (d) of the general formula (1b) shown above with a molecular weight of 300 or more and 2000 or less of 10% by mass or more and 40% by mass or less, a structural unit derived from a monomer (b) with a hydroxyl group and a molecular weight less than 400 of 5% by mass or more and 20% by mass or less, and a structural unit derived from a macromonomer of 60% by mass or more and 80% by mass or less, and the macromonomer contains a structural unit derived from monomer (c) with a hydrophobic group and a molecular weight less than 400.

[0252]

[0253] (In the general formula (1b), R 1b , R 2b and R 3b are each independently selected from a hydrogen element and a methyl group, X 1b represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1b represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, and R 4b represents a hydrocarbon group having 6 to 18 carbon atoms. n2 represents the repeating unit number of the above alkylene glycol.)

[0254] <21>The polymeric dispersant C according to <20> above, wherein it contains a structural unit derived from monomer (d) of 15% by mass or more and 30% by mass or less, a structural unit derived from monomer (b) of 7% by mass or more and 15% by mass or less, and a structural unit derived from monomer (c) of 65% by mass or more and 75% by mass or less.

[0255] <22>The polymeric dispersant C according to <20> or <21> above, wherein the structural unit derived from monomer (d) is a structural unit derived from 2-ethylhexoxy polyethylene glycol methacrylate, the structural unit derived from monomer (b) is a structural unit derived from 2-hydroxyethyl methacrylate, and the structural unit derived from monomer (c) is a structural unit derived from a polystyrene macromonomer.

[0256] <23>According to the polymer dispersant C described in any one of <20> to <22> above, wherein the polymer dispersant C contains 15% by weight or more and 30% by weight or less of structural units derived from 2-ethylhexoxy polyethylene glycol methacrylate as structural units derived from monomer (d), 7% by weight or more and 15% by weight or less of structural units derived from 2-hydroxyethyl methacrylate as structural units derived from monomer (b), and 65% by weight or more and 75% by weight or less of structural units derived from polystyrene macromonomer as structural units derived from monomer (c).

[0257] <24>According to the polymer dispersant described in <20> or <21> above, wherein the structural units derived from monomer (d) are structural units derived from 2-ethylhexoxy polyethylene glycol methacrylate, the structural units derived from monomer (b) are structural units derived from 2-hydroxyethyl methacrylate, and the structural units derived from monomer (c) are structural units derived from polyisobutyl acrylate macromonomer.

[0258] <25>According to the polymer dispersant C described in any one of <20> to <21> or <24> above, wherein, as the structural units derived from monomer (d), it contains 15% by weight or more and 30% by weight or less of structural units derived from 2-ethylhexoxy polyethylene glycol methacrylate, as the structural units derived from monomer (b), it contains 7% by weight or more and 15% by weight or less of structural units derived from 2-hydroxyethyl methacrylate, and as the structural units derived from monomer (c), it contains 65% by weight or more and 75% by weight or less of structural units of polyisobutyl methacrylate macromonomer.

[0259] <26>According to the polymer dispersant C described in any one of <20> to <25> above, its weight-average molecular weight is 50,000 or more and 65,000 or less.

[0260] <27>According to the polymer dispersant C described in any one of <20> to <23> or <26> above, wherein, as the structural units derived from monomer (d), it contains 15% by mass or more and 30% by mass or less of structural units derived from 2-ethylhexoxy polyethylene glycol methacrylate, as the structural units derived from monomer (b), it contains 7% by mass or more and 15% by mass or less of structural units derived from 2-hydroxyethyl methacrylate, as the structural units derived from monomer (c), it contains 65% by mass or more and 75% by mass or less of structural units derived from polystyrene macromonomer, and the weight-average molecular weight is 50,000 or more and 65,000 or less.

[0261] <28>According to the polymer dispersant C described in any one of <20> to <21> or <24> to <26> above, wherein, as the structural unit derived from monomer (d), it contains a structural unit derived from 2-ethylhexoxy polyethylene glycol methacrylate of 15% by weight or more and 30% by weight or less, as the structural unit derived from monomer (b), it contains a structural unit derived from 2-hydroxyethyl methacrylate of 7% by weight or more and 15% by weight or less, as the structural unit derived from monomer (c), it contains a structural unit of polyisobutyl methacrylate macromonomer of 65% by weight or more and 75% by weight or less, and the weight average molecular weight is 50,000 or more and 65,000 or less.

[0262] <29>According to the polymer dispersant C described in any one of <20> to <28> above, wherein the repeating unit number n2 of the above-mentioned alkylene glycol is 4 or more and 35 or less.

[0263] <30>According to the polymer dispersant described in any one of <1> to <29> above, it is used for a compound that does not have a group that dissociates hydrogen ions.

[0264] <31>According to the polymer dispersant described in <30> above, wherein the compound that does not have a group that dissociates hydrogen ions is selected from cyclohexanone and propylene glycol monomethyl ether acetate.

[0265] <32>According to the polymer dispersant described in <31> above, wherein the compound that does not have a group that dissociates hydrogen ions is cyclohexanone.

[0266] <33>According to the polymer dispersant described in <31> above, wherein the compound that does not have a group that dissociates hydrogen ions is propylene glycol monomethyl ether acetate.

[0267] <34>According to the polymer dispersant described in <30> above, wherein the compound that does not have a group that dissociates hydrogen ions is dialkyl phthalate.

[0268] <35>According to the polymer dispersant described in <30> above, wherein the compound that does not have a group that dissociates hydrogen ions is trialkyl trimellitate.

[0269] <36>An oil dispersion, which contains the polymer dispersant described in any one of <1> to <29> above, an inorganic filler, and a compound that does not have a group that dissociates hydrogen ions.

[0270] <37>According to the oil dispersion described in <36> above, wherein the compound that does not have a group that dissociates hydrogen ions is selected from toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate.

[0271] <38>The oil dispersion according to <37> above, wherein the compound not having a hydrogen ion-dissociating group is selected from cyclohexanone and propylene glycol methyl ether acetate.

[0272] <39>The oil dispersion according to any one of <36> to <38> above, wherein the compound not having a hydrogen ion-dissociating group is cyclohexanone.

[0273] <40>The oil dispersion according to any one of <36> to <38> above, wherein the compound not having a hydrogen ion-dissociating group is propylene glycol methyl ether acetate.

[0274] <41>The oil dispersion according to any one of <36> to <38> above, wherein the compound not having a hydrogen ion-dissociating group is dialkyl phthalate.

[0275] <42>The oil dispersion according to any one of <36> to <38> above, wherein the compound not having a hydrogen ion-dissociating group is trialkyl trimellitate.

[0276] <43>The oil dispersion according to any one of <36> to <42> above, wherein the inorganic filler is alumina.

[0277] <44>The oil dispersion according to any one of <36> to <42> above, wherein the inorganic filler is calcium carbonate.

[0278] <45>The oil dispersion according to any one of <36> to <44> above, wherein the content of the inorganic filler is 10% by mass or more and 80% by mass or less.

[0279] <46>The oil dispersion according to any one of <36> to <45> above, wherein the mass ratio of the polymer dispersant to the inorganic filler (polymer dispersant / inorganic filler) is 0.002 or more and 0.01 or less.

[0280] <47>A halogen-based resin composition comprising the polymer dispersant according to any one of <1> to <35> above, an inorganic filler, a compound not having a hydrogen ion-dissociating group, and a halogen-based resin.

[0281] <48>The halogen-based resin composition according to <47> above, wherein the SP value of the compound not having a hydrogen ion-dissociating group determined by the Fedors method is 7.5 (cal / cm 3 ) 1 / 2 or more and 11.5 (cal / cm 3 ) 1 / 2 or less.

[0282] <49>The halogen-based resin composition according to <47> or <48> above, wherein the compound having no group capable of dissociating hydrogen ions is selected from dialkyl phthalates and trialkyl trimellitates.

[0283] <50>The halogen-based resin composition according to <49> above, wherein the compound having no group capable of dissociating hydrogen ions is selected from bis(2-ethylhexyl) phthalate and tris(2-ethylhexyl) trimellitate.

[0284] <51>The halogen-based resin composition according to any one of <47> to <50> above, wherein the inorganic filler is calcium carbonate.

[0285] <52>The halogen-based resin composition according to any one of <47> to <51> above, wherein the content of the calcium carbonate is 1 part by mass or more and 150 parts by mass or less relative to 100 parts by mass of the halogen-based resin.

[0286] <53>The halogen-based resin composition according to any one of <47> to <52> above, wherein the mass ratio of the polymer dispersant to the calcium carbonate (polymer dispersant / inorganic filler) is from 0.002 to 0.01.

[0287] <54>An oil dispersion comprising a polymer dispersant A, alumina as an inorganic filler, and cyclohexanone as a compound having no group capable of dissociating hydrogen ions, wherein the polymer dispersant A comprises a structural unit derived from monomer (a) in an amount of 37% by mass or more and 45% by mass or less, a structural unit derived from monomer (b) in an amount of 13% by mass or more and 20% by mass or less, and a structural unit derived from monomer (c) in an amount of 38% by mass or more and 50% by mass or less. The structural unit derived from monomer (a) is a structural unit derived from methoxypolyethylene glycol (meth)acrylate, the structural unit derived from monomer (b) is a structural unit derived from glycerol mono(meth)acrylate, and the structural unit derived from monomer (c) is a structural unit derived from stearyl (meth)acrylate.

[0288] <55>An oil dispersion comprising a polymer dispersant B, alumina as an inorganic filler, and propylene glycol methyl ether acetate as a compound having no group that dissociates hydrogen ions, wherein the polymer dispersant B contains 55% by mass or more and 88% by mass or less of structural units derived from monomer (d), 8% by mass or more and 12% by mass or less of structural units derived from monomer (b), and 4% by mass or more and 8% by mass or less of structural units derived from monomer (c). The structural units derived from monomer (b) are structural units derived from 2-hydroxyethyl (meth)acrylate, the structural units derived from monomer (d) are structural units derived from stearyloxy polyethylene glycol (meth)acrylate, and the structural units derived from monomer (c) are structural units derived from 2-ethylhexyl (meth)acrylate.

[0289] <56>An oil dispersion comprising a polymer dispersant C, alumina as an inorganic filler, and propylene glycol methyl ether acetate as a compound having no group that dissociates hydrogen ions, wherein the polymer dispersant C contains 15% by mass or more and 30% by mass or less of structural units derived from 2-ethylhexoxy polyethylene glycol methacrylate as structural units derived from monomer (d), 7% by mass or more and 15% by mass or less of structural units derived from 2-hydroxyethyl methacrylate as structural units derived from monomer (b), and 65% by mass or more and 75% by mass or less of structural units derived from a polystyrene macromonomer as structural units derived from monomer (c), and the weight-average molecular weight is 50,000 or more and 65,000 or less.

[0290] <57>An oil dispersion comprising a polymer dispersant C, alumina as an inorganic filler, and propylene glycol methyl ether acetate as a compound having no group that dissociates hydrogen ions, wherein the polymer dispersant C contains 15% by mass or more and 30% by mass or less of structural units derived from 2-ethylhexoxy polyethylene glycol methacrylate as structural units derived from monomer (d), 7% by mass or more and 15% by mass or less of structural units derived from 2-hydroxyethyl methacrylate as structural units derived from monomer (b), and 65% by mass or more and 75% by mass or less of structural units of polyisobutyl methacrylate macromonomer as structural units derived from monomer (c), and the weight-average molecular weight is 50,000 or more and 65,000 or less.

[0291] <58>A slurry mixture comprising a polymer dispersant B, calcium carbonate as an inorganic filler, and a dialkyl phthalate as a compound having no group that dissociates hydrogen ions. In the above polymer dispersant B, as a structural unit derived from monomer (d), it contains 80% by mass or more and 88% by mass or less of a structural unit derived from lauryloxy polyethylene glycol (meth)acrylate, and as a structural unit derived from monomer (b), it contains 12% by mass or more and 20% by mass or less of a structural unit derived from glycerol mono(meth)acrylate. The weight-average molecular weight of the above polymer dispersant B is 14,000 or more and 17,000 or less.

[0292] <59>A slurry mixture comprising: a polymer dispersant C, wherein the polymer dispersant C contains 15% by weight or more and 30% by weight or less of a structural unit derived from 2-ethylhexoxy polyethylene glycol methacrylate as a structural unit derived from monomer (d), contains 7% by weight or more and 15% by weight or less of a structural unit derived from 2-hydroxyethyl methacrylate as a structural unit derived from monomer (b), contains 65% by weight or more and 75% by weight or less of a structural unit derived from a polystyrene macromonomer as a structural unit derived from monomer (c), and the weight-average molecular weight of the above polymer dispersant C is 50,000 or more and 65,000 or less; calcium carbonate as an inorganic filler; and a dialkyl phthalate as a compound having no group that dissociates hydrogen ions.

[0293] <60>A slurry mixture comprising a polymer dispersant C, calcium carbonate as an inorganic filler, and a dialkyl phthalate as a compound having no group that dissociates hydrogen ions. The above polymer dispersant C contains 15% by mass or more and 30% by mass or less of a structural unit derived from 2-ethylhexoxy polyethylene glycol methacrylate as a structural unit derived from monomer (d), contains 7% by mass or more and 15% by mass or less of a structural unit derived from 2-hydroxyethyl methacrylate as a structural unit derived from monomer (b), contains 65% by mass or more and 75% by mass or less of a structural unit of polyisobutyl methacrylate macromonomer as a structural unit derived from monomer (c), and the weight-average molecular weight is 50,000 or more and 65,000 or less.

[0294] <61>A slurry mixture comprising a polymer dispersant B, calcium carbonate as an inorganic filler, and a trialkyl trimellitate as a compound having no group that dissociates hydrogen ions. The above polymer dispersant B contains 80% by mass or more and 88% by mass or less of a structural unit derived from lauryloxy polyethylene glycol (meth)acrylate as a structural unit derived from monomer (d), and contains 12% by mass or more and 20% by mass or less of a structural unit derived from 2-hydroxyethyl (meth)acrylate as a structural unit derived from monomer (b).

[0295] <62>A halogen-based resin composition comprising a polymer dispersant B, calcium carbonate as an inorganic filler, a dialkyl phthalate as a compound having no group capable of dissociating hydrogen ions, and a halogen-based resin. In the polymer dispersant B, as the structural unit derived from monomer (d), it contains 80% by mass or more and 88% by mass or less of the structural unit derived from lauryloxy polyethylene glycol (meth)acrylate, and as the structural unit derived from monomer (b), it contains 12% by mass or more and 20% by mass or less of the structural unit derived from glycerol mono(meth)acrylate. The weight-average molecular weight of the polymer dispersant B is 14,000 or more and 17,000 or less.

[0296] <63>A halogen-based resin composition comprising a polymer dispersant C, calcium carbonate as an inorganic filler, a dialkyl phthalate as a compound having no group capable of dissociating hydrogen ions, and a halogen-based resin. The polymer dispersant C contains 15% by mass or more and 30% by mass or less of the structural unit derived from 2-ethylhexoxy polyethylene glycol methacrylate as the structural unit derived from monomer (d), 7% by mass or more and 15% by mass or less of the structural unit derived from 2-hydroxyethyl methacrylate as the structural unit derived from monomer (b), and 65% by mass or more and 75% by mass or less of the structural unit derived from polystyrene macromonomer as the structural unit derived from monomer (c), and the weight-average molecular weight is 50,000 or more and 65,000 or less.

[0297] <64>A method for producing an oil-in-dispersion, which includes a step of mixing the polymer dispersant according to any one of <1> to <29> above, an inorganic filler, and a compound having no group capable of dissociating hydrogen ions.

[0298] <65>A method for producing a halogen-based resin composition, which includes a step of mixing the polymer dispersant according to any one of <1> to <29> above, an inorganic filler, a compound having no group capable of dissociating hydrogen ions, and a halogen-based resin.

[0299] <66>The use of compound (I) as a dispersant, wherein compound (I) contains a structural unit derived from a monomer having a hydroxyl group and a structural unit derived from a monomer represented by the following general formula (1).

[0300]

[0301] (In general formula (1), R 1 , R 2 and R 3 are each independently selected from a hydrogen element and a methyl group, X 1 represents an oxygen element, an ester group, an amide group, or -CH2O-, and Y 1Represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4 Represents a hydrogen element or a hydrocarbon group having 1 to 20 carbon atoms. n represents the number of repeating units of the above alkylene glycol.)

[0302] <67>The use of the dispersant of <66> above for dispersing inorganic fillers in a compound that does not have a group capable of dissociating hydrogen ions.

[0303] <68>The use of the polymer dispersant according to any one of <1> to <29> above for producing a dispersion in oil.

[0304] <69>The use of the polymer dispersant according to any one of <1> to <29> above for preparing a halogen-based resin composition.

[0305] Examples

[0306] In the following examples and comparative examples, unless otherwise specified, "parts" and "%" are "parts by mass" and "% by mass".

[0307] [Measurement]

[0308] [Method for measuring the weight-average molecular weight of polymer dispersant A (Compound A)]

[0309] The weight-average molecular weight of polymer dispersant A was measured using gel permeation chromatography, hereinafter also referred to as the "GPC" method.

[0310] That is, the synthesized polymer dispersant was diluted with a tetrahydrofuran / methanol mixture (volume ratio: 85 / 15) to prepare a sample solution with a solid content concentration of 0.01% by mass as the sample solution, and 2 μL of it was used for the measurement. A solution prepared by dissolving acetic acid in a tetrahydrofuran / methanol mixture (volume ratio: 85 / 15) was used as the eluent, and the measurement was carried out using GPC [apparatus: "HLC-8320GPC" manufactured by Tosoh Corporation, detector: differential refractometer (attached to the apparatus), column: "TSKgel SuperHM-L" manufactured by Tosoh Corporation, column temperature: 45°C, eluent flow rate: 0.5 mL / min].[[]END]]

[0311] As the standard substance, polystyrene was used (manufactured by Tosoh Corporation: molecular weights 5.26×102, 1.02×105, 8.42×106; manufactured by Nissei Industry Co., Ltd.: molecular weights 4.0×103, 3.0×104, 9.0×105).

[0312] [Method for measuring the weight-average molecular weight of polymer dispersant B (Compound B)]

[0313] Under the following conditions, the weight-average molecular weight of polymer dispersant B was measured using the GPC method.

[0314] That is, the synthesized polymer dispersant B was diluted with N,N-dimethylformamide to prepare a sample solution with a solid component concentration of 0.3 mass%, and 100 μL thereof was used for the measurement. A solution in which phosphoric acid and lithium bromide were dissolved in N,N-dimethylformamide to concentrations of 60 mmol / L and 50 mmol / L, respectively, was used as the eluent, and measurement was carried out using GPC [apparatus: "HLC-8320GPC" manufactured by Tosoh Corporation, detector: differential refractometer (attached to the apparatus), column: two "TSK-GEL α-M" manufactured by Tosoh Corporation, column temperature: 40 °C, eluent flow rate: 1 mL / min].

[0315] As the standard substances, polystyrene (manufactured by Tosoh Corporation: molecular weights 5.26×102, 1.02×105, 8.42×106; manufactured by Nishio Kogyo Co., Ltd.: molecular weights 4.0×103, 3.0×104, 9.0×105) was used.

[0316] [Method for measuring slurry viscosity]

[0317] Measurement was carried out using a rheometer (manufactured by antonpal, trade name: MCR 3 02). A 25 mmΦ parallel plate was used as the fixture, and a shear rate sweep was carried out from 0.1 s-1 to 10 s-1 at 25 °C. The slurry viscosity was the value of the viscosity at a shear rate of 1 s-1.

[0318] [Determination of solid component concentration]

[0319] 10.0 parts of sodium sulfate that had been constant-weighted in a desiccator was measured into a 30 mL glass dish, and about 1.0 part of the sample was added thereto. After mixing, it was accurately weighed, maintained at 105 °C for 2 hours to remove volatile components, and further placed in a desiccator for 15 minutes, and the mass was measured. The mass of the sample after removing volatile components was taken as the solid component, and divided by the mass of the added sample to obtain the solid component concentration.

[0320] [Manufacture of polymer dispersant]

[0321] [Production of Polymer Dispersant A-1 in Example 1-1]

[0322] Into a 1 L four-necked detachable flask, 4.5 g of stearyl methacrylate, 4.0 g of methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK EsterTM-230G, average EO addition of 23 moles), 1.5 g of glycerol monomethacrylate (manufactured by NOF Corporation, trade name: blemmerGLM), 0.085 g of 3-mercapto-1,2-propanediol (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Corporation), and 15.4 g of a toluene / ethanol mixture (mass ratio 50 / 50) were added to prepare an initial mixture. Two dropping funnels, a reflux condenser, a thermometer, and a stirring device were installed in the above four-necked detachable flask. After purging the reaction system with nitrogen, the temperature was raised to 80 °C with stirring, and an initial additive of a mixed solution of 0.065 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator: manufactured by Fujifilm Wako Pure Chemical Corporation, trade name: V-65B) and 3.2 g of a toluene / ethanol mixture (mass ratio 50 / 50) was added, and the resulting mixture was stirred for 10 minutes.

[0323] Then, while maintaining the temperature, a dropping mixture 1 of a mixed solution of 40.5 g of stearyl methacrylate, 36.0 g of methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK EsterTM-230G, average EO addition of 23 moles), 13.5 g of glycerol monomethacrylate (manufactured by NOF Corporation, trade name: blemmerGLM), 0.765 g of 3-mercapto-1,2-propanediol (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Corporation), and 19.3 g of a toluene / ethanol mixture (mass ratio 50 / 50) and a dropping mixture 2 of a mixed solution of 0.590 g of the above polymerization initiator and 28.7 g of a toluene / ethanol mixture (mass ratio 50 / 50) were added dropwise over 120 minutes respectively. After the dropping was completed, the mixture was stirred at 80 °C for 30 minutes, and an additive 1 of a mixed solution of 0.100 g of the above polymerization initiator and 4.8 g of a toluene / ethanol mixture (mass ratio 50 / 50) was added. Further, the mixture was stirred at 80 °C for 60 minutes, and an additive 2 of a mixed solution of 0.100 g of the above polymerization initiator and 4.8 g of a toluene / ethanol mixture (mass ratio 50 / 50) was added. Then, the mixture was stirred at 80 °C for 30 minutes and then cooled to room temperature. The resulting polymer solution was dried under reduced pressure at 100 °C for 5 hours to obtain a polymer dispersant A-1.

[0324] The weight-average molecular weight of the polymer dispersant A-1 obtained by the above method was measured, and as a result, the weight-average molecular weight of the dispersant A-1 was 27,800.

[0325] Example 1-2 (Manufacture of Polymer Dispersant A-2)

[0326] A polymer dispersant A-2 was obtained in the same manner as in Example 1-1, except that the compounding amounts of the respective components were changed to the amounts shown in Table 1.

[0327] The weight-average molecular weight of the polymer dispersant A-2 measured by the above method was 25,700 as a result.

[0328] Example 1-3 (Production of Dispersant B-1)

[0329] 1.5 g of glycerol monomethacrylate (manufactured by NOF Corporation, trade name: Blemmer GLM), 8.5 g of lauryloxy polyethylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer PLE200, average EO addition 4 moles), 0.094 g of 3-mercapto-1,2-propanediol (chain transfer agent: manufactured by FUJIFILM Wako Pure Chemical Corporation), and 15.1 g of a toluene / ethanol mixed solution (mass ratio 50 / 50) were placed in a 1 L four-necked detachable flask as an initial mixture. Two dropping funnels, a reflux condenser, a thermometer, and a stirring device were installed in the above four-necked detachable flask. After purging the reaction system with nitrogen, the temperature was raised to 80 °C with stirring, and an initial additive of a mixed solution of 0.072 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator: manufactured by FUJIFILM Wako Pure Chemical Corporation, trade name: V-65B) and 3.5 g of a toluene / ethanol mixed solution (mass ratio 50 / 50) was added, and the resulting mixture was stirred for 10 minutes.

[0330] Next, while maintaining the temperature, a dropping mixture 1 of a mixed solution containing 13.5 g of glycerol monomethacrylate (manufactured by NOF Corporation, trade name: Blemmer GLM), 76.5 g of lauryl polyoxyethylene methacrylate (manufactured by NOF Corporation, trade name: Blemmer PLE200, average EO addition 4 moles), 0.846 g of 3-mercapto-1,2-propanediol (chain transfer agent: manufactured by FUJIFILM Wako Pure Chemical Corporation), and 16.1 g of a toluene / ethanol mixed solution (mass ratio 50 / 50) was added dropwise over 120 minutes, and a dropping mixture 2 of a mixed solution containing 0.648 g of the above polymerization initiator and 31.9 g of a toluene / ethanol mixed solution (mass ratio 50 / 50) was added dropwise. After the addition was completed, the mixture was stirred at 80°C for 30 minutes, and additive 1, which is a mixed solution containing 0.110 g of the above polymerization initiator and 5.3 g of a toluene / ethanol mixed solution (mass ratio 50 / 50), was added. Then, the mixture was stirred at 80°C for 60 minutes, and additive 2, which is a mixed solution containing 0.110 g of the above polymerization initiator and 5.3 g of a toluene / ethanol mixed solution (mass ratio 50 / 50), was added. Next, the mixture was stirred at 80°C for 30 minutes and then cooled to room temperature. The resulting polymer solution was dried under reduced pressure at 100°C for 5 hours to obtain dispersant B-1.

[0331] The weight-average molecular weight of the obtained dispersant B-1 was measured by the above method, and as a result, the weight-average molecular weight of dispersant B-1 was 15,600.

[0332] Examples 1-4 to 1-12 (Preparation of Polymer Dispersants B-2 to B-10)

[0333] Except for changing the components and compounding amounts as shown in Table 1, polymer dispersants B-2 to B-10 were obtained in the same manner as in Example 1-3.

[0334] The weight-average molecular weights of the obtained polymer dispersants B-2 to B-10 were measured by the above method. The results are shown in Table 2.

[0335] [Table 1]

[0336]

[0337] * In Table 1, unless otherwise specified, the values of the respective components refer to mass (g).

[0338] *1: Methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NKEsterTM-230G, average EO addition 23 moles).

[0339] *2: Polypropylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer PP-1000, average PO addition 4 - 6 moles).

[0340] *3: Lauroyloxy polyethylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer PLE-200, average EO addition 4 moles).

[0341] *4: 2-Ethylhexoxy polypropylene glycol polyethylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer 50 POEP-800B, average EO addition 8 moles, average PO addition 7 moles).

[0342] *5: 2-Ethylhexoxy polyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: EH-4E, average EO addition 4 moles).

[0343] *6: Stearoyloxy polyethylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer PSE-1300, average EO addition 30 moles).

[0344] *7: 2,2'-Azobis(2,4-dimethylvaleronitrile) (polymerization initiator: manufactured by FUJIFILM Wako Pure Chemical Corporation, trade name: V-65B).

[0345] *8: Dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator: manufactured by FUJIFILM Wako Pure Chemical Corporation, trade name: V-601).

[0346] *9: Refers to the content (mass %) of each monomer in the total mass of monomers (a) to (d).

[0347] [Table 2]

[0348]

[0349] *In Table 2, the values of each structural unit refer to the content (mass %) of the structural unit derived from each monomer in the total mass of the structural units derived from monomers (a) to (d).

[0350] *1 to *6 are the same as *1 to *6 in Table 1.

[0351] Example 1-13 (Preparation of Polymer Dispersant C-1)

[0352] In a 1 L four-necked detachable flask, 0.8 g of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation), 7.0 g of polystyrene macromonomer (manufactured by Toagosei Co., Ltd., trade name: AS-6), 2.2 g of 2-ethylhexoxy polyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name EH-4E, average addition of 4 moles of EO), 0.043 g of 3-mercapto-1,2-propanediol (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Corporation), and 20.1 g of toluene were added to prepare an initial mixture. Two dropping funnels, a reflux condenser, a thermometer, and a stirring device were installed in the above-mentioned four-necked detachable flask. After replacing the reaction system with nitrogen, the temperature was raised to 80 °C while stirring, and an initial additive, which was a mixed solution of 0.046 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator: manufactured by Fujifilm Wako Pure Chemical Corporation, trade name: V-601) and 4.5 g of toluene, was added, and the resulting mixture was stirred for 10 minutes.

[0353] Next, while maintaining the temperature, a mixed solution of 7.2 g of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation), 63.0 g of polystyrene macromonomer (manufactured by Toagosei Co., Ltd., trade name: AS-6), 19.8 g of 2-ethylhexoxy polyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name EH-4E, average addition of 4 moles of EO), 0.387 g of 3-mercapto-1,2-propanediol (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Corporation), and 63.0 g of toluene, i.e., dropping mixture 1, and a mixed solution of 0.414 g of the above polymerization initiator and 40.6 g of toluene, i.e., dropping mixture 2, were respectively added dropwise over 120 minutes. After the dropping was completed, the mixture was stirred at 80 °C for 30 minutes, and additive 1, which was a mixed solution of 0.06 g of the above polymerization initiator and 6.0 g of toluene, was added. Further, the mixture was stirred at 80 °C for 60 minutes, and additive 2, which was a mixed solution of 0.06 g of the above polymerization initiator and 6.0 g of toluene, was added. Then, the mixture was stirred at 80 °C for 30 minutes and then cooled to room temperature. The obtained polymer solution was dried under reduced pressure at 100 °C for 5 hours to obtain dispersant C-1.

[0354] The weight-average molecular weight of the obtained dispersant C-1 was measured in the same manner as the above polymer dispersant B (compound B), and as a result, the weight-average molecular weight of dispersant C-1 was 51,900.

[0355] Example 1-14 (Preparation of Polymer Dispersant C-2)

[0356] (Preparation of Poly(isobutyl methacrylate) Macromonomer Solution)

[0357] In a 1 L four-necked detachable flask, 20.0 g of isobutyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation), 0.425 g of 3-mercaptopropionic acid (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Corporation), and 49.5 g of propylene glycol methyl ether acetate (manufactured by Fujifilm Wako Pure Chemical Corporation) were added to prepare an initial mixture. Two dropping funnels, a reflux condenser, a thermometer, and a stirring device were installed in the above four-necked detachable flask. After purging the reaction system with nitrogen, the temperature was raised to 94 °C while stirring, and an initial additive, which was a mixed solution of 0.167 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator: manufactured by Fujifilm Wako Pure Chemical Corporation, trade name: V-601) and 6.5 g of propylene glycol methyl ether acetate, was added. The resulting mixture was stirred for 10 minutes.

[0358] Next, while maintaining the temperature, a dropping mixture 1, which was a mixed solution of 180 g of isobutyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation), 3.825 g of 3-mercaptopropionic acid (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Corporation), and 85.6 g of propylene glycol methyl ether acetate (manufactured by Fujifilm Wako Pure Chemical Corporation), and a dropping mixture 2, which was a mixed solution of 1.503 g of the above polymerization initiator and 58.4 g of propylene glycol methyl ether acetate, were added dropwise over 120 minutes, respectively.

[0359] After the dropping was completed, the dropping funnels were removed, a capillary for air blowing was set up, and air bubbling was started with a pump. While maintaining the temperature inside the system at 92 - 93 °C and continuing the bubbling, 0.20 g of p-methoxyphenol (polymerization inhibitor: manufactured by Fujifilm Wako Pure Chemical Corporation) and 3.87 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Corporation) were added. Then, 6.83 g of glycidyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation) was added, and the mixture was maintained for 9 hours. Then, it was cooled to room temperature to obtain a polyisobutyl acrylate macromonomer solution. The effective component of the obtained polyisobutyl methacrylate macromonomer solution was 46.5% by weight, and as a result of measuring the weight-average molecular weight of the polyisobutyl methacrylate macromonomer using the same method as that for the above polymer dispersant B (Compound B), the weight-average molecular weight of the polyisobutyl methacrylate macromonomer was 8690.

[0360] (Manufacture of Polymer Dispersant C-2)

[0361] In a 1 L four-necked detachable flask, 0.4 g of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation), 7.5 g of the above-prepared polyisobutyl methacrylate macromonomer solution, 1.1 g of 2-ethylhexoxy polyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name EH-4E, average addition of 4 moles of EO), 0.021 g of 3-mercapto-1,2-propanediol (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Corporation), and 5.2 g of ethanol were added to prepare an initial mixture. Two dropping funnels, a reflux condenser, a thermometer, and a stirring device were installed in the above four-necked detachable flask. After purging the reaction system with nitrogen, the temperature was raised to 80 °C while stirring, and an initial additive, which was a mixed solution of 0.015 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator: manufactured by Fujifilm Wako Pure Chemical Corporation, trade name: V-601) and 4.3 g of ethanol, was added, and the resulting mixture was stirred for 10 minutes.

[0362] Next, while maintaining the temperature, a dropping mixture 1, which was a mixed solution of 3.6 g of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation), 67.7 g of the above-prepared polyisobutyl methacrylate macromonomer solution, 9.9 g of 2-ethylhexoxy polyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name EH-4E, average addition of 4 moles of EO), 0.19 g of 3-mercapto-1,2-propanediol (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Corporation), and 1.6 g of ethanol, and a dropping mixture 2, which was a mixed solution of 0.14 g of the above polymerization initiator and 38.9 g of ethanol, were respectively added dropwise over 120 minutes. After the dropping was completed, the mixture was stirred at 80 °C for 30 minutes, and an additive 1, which was a mixed solution of 0.03 g of the above polymerization initiator and 8.2 g of ethanol, was added. Further, the mixture was stirred at 80 °C for 60 minutes, and an additive 2, which was a mixed solution of 0.03 g of the above polymerization initiator and 8.2 g of ethanol, was added. Then, the mixture was stirred at 80 °C for 30 minutes and then cooled to room temperature. The resulting polymer solution was dried under reduced pressure at 120 °C for 5 hours to obtain dispersant C-2.

[0363] The weight-average molecular weight of the obtained dispersant C-2 was measured in the same manner as the above polymer dispersant B (compound B), and as a result, the weight-average molecular weight of dispersant C-2 was 61,800.

[0364] [Table 3]

[0365]

[0366] *5, *8, and *9 are the same as *5, *8, and *9 in Table 1.

[0367] *10: refers to a macromonomer containing structural units derived from monomer (c).

[0368] Comparative Example 1-1 (Production of Polymer Dispersant D-1)

[0369] Into a 1 L four-necked detachable flask, 450.0 g of toluene, 224.0 g of diisobutylene (manufactured by Fujifilm Wako Pure Chemical Corporation), 198.0 g of maleic anhydride (manufactured by Fujifilm Wako Pure Chemical Corporation), and 13.3 g of benzoyl peroxide (polymerization initiator: manufactured by Tokyo Chemical Industry Co., Ltd.) were charged, and a reflux condenser, a thermometer, and a stirring device were installed. After purging the reaction system with nitrogen, the temperature was raised to 83 °C with stirring, and the reaction was carried out for 240 minutes while maintaining the temperature. Then, it was transferred to a container coated with Teflon (registered trademark), and dried under reduced pressure at 100 °C for 5 hours. Using the method for measuring the weight-average molecular weight of polymer dispersant B, the weight-average molecular weight of the obtained polymer was measured, and the result was 28,600.

[0370] In a 1 L four-necked detachable flask, 136.0 g of methyl isobutyl ketone and 24.8 g of the above-obtained polymer (containing 0.12 mol of a constituent component derived from maleic anhydride) were added. After purging the reaction system with nitrogen, it was dissolved at room temperature with stirring for 2 hours. Then, while stirring, the temperature was raised to 72 °C, and 32.0 g (0.12 mol) of oleylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) pre-melted at 80 °C was added. Stirring was carried out at 72 °C for 120 minutes for amidation, and then cooled to room temperature. The solid content concentration of the obtained polymer solution was 30.1%. 10.0 g of the obtained polymer solution was weighed into a glass dish and dried under reduced pressure at 100 °C for 5 hours to obtain polymer dispersant D-1.

[0371] Since polymer dispersant D-1 is insoluble in the eluent of GPC, the weight-average molecular weight was calculated to be 65,500 using the above measurement values of GPC.

[0372] 〔Measurement of Slurry Viscosity of Dispersion in Oil (1)〕

[0373] Example 2-1

[0374] 0.4 g of polymer dispersant A-1 (concentration based on the mass of alumina: 0.5%), 40 g of cyclohexanone, and 85 g of alumina (manufactured by Sumitomo Chemical Co., Ltd., trade name: Alumina AES-12, median particle size 0.44 μm) were sequentially added to 500 mL of polycarbonate, and uniformly mixed with a powder. Then, using a laboratory mixer, it was mixed at a rotation speed of 1500 rpm for 1 minute to obtain a dispersion in oil containing polymer dispersant A-1, cyclohexanone, and alumina. The slurry viscosity of this mixture at 25 °C was 16.8 Pa·s.

[0375] Example 2-2 and Comparative Examples 2-1 to 2-2

[0376] An oil dispersion was prepared in the same manner as in Example 2-1, except that the type of the polymer dispersant was changed as shown in Table 4, and the slurry viscosity of each oil dispersion at 25 °C was measured. The results are shown in Table 4.

[0377] Comparative Example 2-3

[0378] An oil dispersion was prepared in the same manner as in Example 2-1, except that the polymer dispersant A-1 was not used, and the slurry viscosity of the oil dispersion at 25 °C was measured. The results are shown in Table 4.

[0379] [Table 4]

[0380]

[0381] 〔Measurement of the slurry viscosity of the oil dispersion (2)〕

[0382] Example 3-1

[0383] 0.4 g of the polymer dispersant B-1 (concentration based on the mass of alumina: 0.5%), 40 g of propylene glycol monomethyl ether acetate (manufactured by Fujifilm Wako Pure Chemical Corporation), and 85 g of alumina (manufactured by Sumitomo Chemical Co., Ltd., trade name: Alumina AES-12, median particle size 0.44 μm) were successively added to 500 mL of polycarbonate and mixed uniformly with a powder. Then, using a laboratory mixer, the mixture was mixed at a rotation speed of 1500 rpm for 1 minute to obtain an oil dispersion containing the polymer dispersant B-1, propylene glycol monomethyl ether acetate, and alumina. At 25 °C, the slurry viscosity of the mixture was 24.1 Pa·s.

[0384] Examples 3-2 to 3-6 and Comparative Examples 3-1 to 3-2

[0385] An oil dispersion was prepared in the same manner as in Example 3-1, except that the type of the polymer dispersant was changed as shown in Table 5, and the slurry viscosity of each oil dispersion at 25 °C was measured. The results are shown in Table 5.

[0386] Comparative Example 3-3

[0387] An oil dispersion was prepared in the same manner as in Example 3-1, except that the polymer dispersant B-1 was not used, and the slurry viscosity of the oil dispersion at 25 °C was measured. The results are shown in Table 5.

[0388] [Table 5]

[0389]

[0390] As shown in Table 4, compared with the slurry viscosities of the oil dispersions containing glyceryl monostearate as a dispersant instead of the polymer dispersant A, the oil dispersions containing the polymer dispersant D-1 as a dispersant instead of the polymer dispersant A, and the slurry of the oil dispersion containing alumina and cyclohexanone without using a dispersant, the slurry viscosity of the oil dispersion containing the polymer dispersant A of the present invention, alumina as an inorganic filler, and cyclohexanone as a compound having no group dissociating hydrogen ions is sufficiently reduced.

[0391] Similarly, as shown in Table 5, compared with the slurry viscosities of the oil dispersions containing glyceryl monostearate as a dispersant to replace the polymer dispersant B or C, the oil dispersions containing the polymer dispersant D-1 as a dispersant to replace the polymer dispersant B or C, and the slurry of the oil dispersion containing alumina and propylene glycol methyl ether acetate without using a dispersant, the slurry viscosity of the oil dispersion containing the polymer dispersant B or C of the present invention, alumina as an inorganic filler, and propylene glycol methyl ether acetate as a compound having no group dissociating hydrogen ions is sufficiently reduced.

[0392] In addition, from the results of Tables 4 and 5, it can be considered that the polymer dispersant of the present invention can reduce the slurry viscosity of the oil dispersion and improve its coatability and moldability even when a highly polar non-aromatic organic solvent is used instead of the aromatic solvent conventionally used in the oil dispersion.

[0393] Furthermore, from the results of Comparative Examples 2-2 and 3-2, it is considered that the polymer dispersant D-1 has a high solubility in the solvent, so the effect as a dispersant is insufficient and the slurry viscosity of the oil dispersion cannot be reduced.

[0394] [Measurement of Slurry Viscosity of Halogen-Based Resin Composition]

[0395] Example 4-1

[0396] Using a stir bar, 0.1 g (at a concentration of 0.5% relative to the mass of calcium carbonate), 60 g of bis(2-ethylhexyl) phthalate, 20 g of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: whiten H), 100 g of vinyl chloride resin (average degree of polymerization 1400, manufactured by Shin-Etsu Vinyl Chloride Co., Ltd., trade name: ZEST1400), 2 g of a Ca / Mg / Zn-based stabilizer for vinyl chloride resin (manufactured by Adeka Corporation, trade name: ADK STARUP-103), and 0.5 g of a lubricant (manufactured by Kao Corporation, trade name: LUNAS-70V) were mixed at room temperature. Then, using a laboratory mixer, the mixture was mixed at a rotational speed of 5000 rpm for 3 minutes. Next, it was left to stand at room temperature under reduced pressure for 10 minutes to remove air bubbles, obtaining a halogen-based resin composition. The slurry viscosity of this halogen-based resin composition at 25°C was 13 Pa·s.

[0397] Example 4-2

[0398] Except for changing the type of the polymer dispersant as shown in Table 6, a halogen-based resin composition was prepared in the same manner as in Example 4-1, and the slurry viscosity of the halogen-based resin composition at 25°C was measured. The results are shown in Table 6.

[0399] Comparative Example 4-1

[0400] Except for not using the polymer dispersant B-1, a halogen-based resin composition was prepared in the same manner as in Example 4-1, and the slurry viscosity of the halogen-based resin composition at 25°C was measured. The results are shown in Table 6.

[0401] [Table 6]

[0402]

[0403] As shown in Table 6, from the results of the examples and comparative examples, it can be seen that by using the polymer dispersant of the present invention, the slurry viscosity of the halogen-based resin composition is reduced and the processability of the halogen-based resin composition is improved.

[0404] [Measurement of the Slurry Viscosity of the Mixture (1)]

[0405] Example 5-1

[0406] Polymeric dispersant A-1 was added in an amount of 0.4 g (concentration relative to the mass of calcium carbonate was 0.5%), 40 g of bis(2-ethylhexyl) phthalate (manufactured by Fujifilm Wako Pure Chemical Corporation), and 85 g of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: whitelonH) were successively added to a 500 mL polycarbonate cup and mixed uniformly with a medicine spatula. Then, using a laboratory mixer, it was mixed at a rotation speed of 5000 rpm for 3 minutes. Next, it was left to stand for 10 minutes at room temperature under reduced pressure for defoaming to obtain a mixture of polymeric dispersant A-1, bis(2-ethylhexyl) phthalate, and calcium carbonate. At 25 °C, the slurry viscosity of the mixture was 4.4 Pa·s.

[0407] Examples 5-2 to 5-10 and Comparative Examples 5-1 to 5-3

[0408] Except for changing the type of polymeric dispersant as shown in Table 7, mixtures were prepared in the same manner as in Example 5-1, and the slurry viscosities of the respective mixtures at 25 °C were measured. The results are shown in Table 7.

[0409] Comparative Example 5-4

[0410] Except for not using polymeric dispersant A-1, a mixture was prepared in the same manner as in Example 5-1, and the slurry viscosity of the mixture at 25 °C was measured. The results are shown in Table 7.

[0411] [Table 7]

[0412]

[0413] From the results of Examples 4-1 and 4-2 and Examples 5-2 and 5-4, it was found that when the slurry viscosity of the mixture of the polymeric dispersant, inorganic filler, and compound not having a group that dissociates hydrogen ions of the present invention is sufficiently low, the slurry viscosity of the halogen-based resin composition containing the polymeric dispersant, inorganic filler, compound not having a group that dissociates hydrogen ions, and halogen-based resin of the present invention can be reduced, and the processability is improved. Therefore, based on the results of Examples 5-1 to 5-10, it is considered that since the slurry viscosity of the mixture of the polymeric dispersant, inorganic filler, and compound not having a group that dissociates hydrogen ions of the present invention is sufficiently low, for the slurry viscosity of the halogen-based resin composition containing the polymeric dispersant, inorganic filler, compound not having a group that dissociates hydrogen ions, and halogen-based resin of the present invention, the slurry viscosity is low and the processability is improved.

[0414] On the other hand, as shown in Comparative Examples 5-1 to 5-3, surfactants such as glyceryl monostearate reduced the slurry viscosity of the surfactant, inorganic filler, and compound not having a group that dissociates hydrogen ions to some extent, but the slurry viscosity was not sufficiently reduced.

[0415] 〔Measurement of Slurry Viscosity of Mixture (2)〕

[0416] Examples 6-1 and 6-2

[0417] A mixture was prepared in the same manner as in Example 5-1, except that the type of dispersant was changed as described in Table 8 and bis(2-ethylhexyl) phthalate was changed to trimellitate (manufactured by Tokyo Chemical Industry Co., Ltd., tris(2-ethylhexyl) trimellitate). The slurry viscosity of the mixture at 25 °C was measured. The results are shown in Table 8.

[0418] Comparative Example 6-1

[0419] A mixture was prepared in the same manner as in Comparative Example 5-4, except that bis(2-ethylhexyl) phthalate was changed to the above trimellitate. The slurry viscosity of the mixture at 25 °C was measured. The results are shown in Table 8.

[0420] [Table 8]

[0421]

[0422] From the results of Examples 6-1 and 6-2 and Comparative Example 6-1, it can be seen that even when trimellitate is used as a compound having no group that dissociates hydrogen ions, the slurry viscosity of the mixture of the polymer dispersant, the compound having no group that dissociates hydrogen ions, and the inorganic filler of the present invention can be reduced, and the processability of the halogen-based resin composition containing them is improved.

[0423] It should be noted that the reason why the slurry viscosity of the mixtures of Examples 6-1 and 6-2 is higher than that of the mixtures of Examples 5-3 and 5-4 is considered to be that the viscosity of trimellitate is higher than that of bis(2-ethylhexyl) phthalate.

[0424] [Low Temperature Bending Test of Halogen-Based Resin Composition]

[0425] Example 7-1

[0426] (Manufacture of Halogen-Based Resin Composition)

[0427] Using a stir bar at room temperature, 0.1 g (at a concentration of 0.5% based on the mass of calcium carbonate), dialkyl phthalate (C10-C12) (manufactured by Kao Corporation, trade name: vinsizeR 160 g of 2,4,6 - tribromophenol (24N), 20 g of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: whiten H), 100 g of vinyl chloride resin (average degree of polymerization 1400, manufactured by Shin Nippon Vinyl Co., Ltd., trade name: ZEST1400), 2 g of Ca / Mg / Zn - based stabilizer for vinyl chloride resin (manufactured by Adeka Corporation, trade name: ADK STARUP - 103), and 0.5 g of lubricant (manufactured by Kao Corporation, trade name: Lunac S - 70V) were mixed. Then, using a 4 - inch open - roll kneader (manufactured by Nishimura Co., Ltd.), they were mixed at a rotation speed of 17.5 rpm and 160 °C to cause gelation, and after gelation, mixing was continued for 10 minutes to obtain a halogen - based resin composition.

[0428] (Manufacture of molding sheet)

[0429] The halogen - based resin composition obtained above was preheated at 170 °C for 5 minutes and then pressed at a pressure of 20 MPa for 2 minutes to obtain a resin molding sheet with a thickness of 0.8 mm.

[0430] (Evaluation of low - temperature bending resistance)

[0431] The molding sheet of the halogen - based resin composition obtained above was punched into pieces of 6 mm × 64 mm to prepare test pieces. Using 6 test pieces each, a low - temperature bending test was carried out with a Texas West Asia bending test machine (manufactured by Ueshima Seisakusho Co., Ltd., trade name: FT - 1506). The test was carried out under the conditions of a test temperature of - 25 °C, a bending speed of 300 times / minute, a distance between jigs of 30 mm, and a bending stroke of 25 mm. The stop device was stopped every 1000 times to confirm whether there was fracture, and the number of bending times until 6 test pieces were fractured was measured. Table 9 shows the average value of 4 values after removing the maximum and minimum values of the number of bending times until fracture. The larger this value, the more excellent the low - temperature bending resistance.

[0432] Examples 7 - 2 to 7 - 5

[0433] Except that the polymer dispersant B - 1 was changed to dispersants B - 5, B - 9, B - 10, and C - 1, the molding sheet of the halogen - based resin composition was manufactured in the same manner as in Example 7 - 1, and the low - temperature bending resistance was evaluated. The results are shown in Table 9.

[0434] Comparative Example 7 - 1

[0435] Except that the polymer dispersant B - 1 was not used, the molding sheet of the halogen - based resin composition was manufactured in the same manner as in Example 7 - 1, and the low - temperature bending resistance was evaluated. The results are shown in Table 9.

[0436] [Table 9]

[0437]

[0438] From the results of Examples 7-1 to 7-5 and Comparative Example 7-1, it was found that the low-temperature flexural properties of the halogen-based resin composition were improved by using the polymer dispersant of the present invention.

[0439] Industrial availability

[0440] The oil dispersion of the present invention can be used as a micro-ceramic for electromagnetic and optical components after being coated or molded and sintered at a high temperature. Since the coating property and moldability of the oil dispersion of the present invention are excellent, it can be used as fine ceramics such as IC packages, wiring boards, insulators, sensors, electrodes, magnetic materials, semiconductors, capacitors, and optical fibers.

[0441] In addition, since the halogen-based resin composition of the present invention has excellent processability and low-temperature bending properties, examples thereof include adhesives, sealants, coatings, plastisols, foams, synthetic leathers, pipes such as water pipes, building materials, wallpaper materials, floor covering materials, heat insulating materials, roof membrane materials, etc. for interior decoration of houses; packaging materials such as films for food packaging; agricultural materials such as agricultural films; automobile-related materials such as sealing materials and primer materials; useful as substrate protection materials, fabric covering materials, wire covering materials, various leather products, various foamed products, ordinary hoses, gaskets, seals, boots, toys, food packaging materials, medical supplies such as tubes or blood bags.

Claims

1. A polymer dispersant, which comprises a structural unit derived from a monomer represented by the following general formula (1) and a structural unit derived from a monomer having a hydroxyl group. In general formula (1), R 1 , R 2 and R 3 are each independently selected from a hydrogen element and a methyl group, X 1 represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1 represents a repeating unit of an alkylene diol having 2 to 4 carbon atoms, R 4 represents a hydrogen element or a hydrocarbon group having 1 to 20 carbon atoms, and n represents the number of repeating units of the alkylene diol.

2. The polymer dispersant according to claim 1, wherein The polymer dispersant is any one of the following polymer dispersants A to C. Polymer dispersant A: A compound comprising a structural unit derived from a monomer (a) represented by the following general formula (1a) having a molecular weight of 400 or more and 2000 or less in an amount of 20% by mass or more and 65% by mass or less, a structural unit derived from a monomer (b) having a hydroxyl group with a molecular weight of less than 400 in an amount of 5% by mass or more and 50% by mass or less, and a structural unit derived from a monomer (c) having a hydrophobic group with a molecular weight of less than 400 in an amount of 30% by mass or more and 75% by mass or less. In general formula (1a), R 1a , R 2a and R 3a are each independently selected from a hydrogen atom and a methyl group, X 1a represents an oxygen atom, an ester group, an amide group or -CH2O-, Y 1a represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 represents the number of repeating units of the alkylene glycol. Polymer dispersant B: A compound comprising a structural unit derived from a monomer (d) represented by the following general formula (1b) having a molecular weight of 300 or more and 2000 or less in an amount of 45% by mass or more and 95% by mass or less, a structural unit derived from a monomer (b) having a hydroxyl group with a molecular weight of less than 400 in an amount of 5% by mass or more and 40% by mass or less, and a structural unit derived from a monomer (c) having a hydrophobic group with a molecular weight of less than 400 in an amount of 0% by mass or more and 20% by mass or less. In general formula (1b), R 1b , R 2b and R 3b are each independently selected from a hydrogen element and a methyl group, X 1b represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1b represents a repeating unit of an alkylene diol having 2 to 4 carbon atoms, R 4b represents a hydrocarbon group having 6 to 18 carbon atoms, and n2 represents the number of repeating units of the alkylene diol. Polymer dispersant C: A compound comprising a structural unit derived from a monomer (d) represented by the general formula (1b) having a molecular weight of 300 or more and 2000 or less in an amount of 10% by mass or more and 40% by mass or less, a structural unit derived from a monomer (b) having a hydroxyl group with a molecular weight of less than 400 in an amount of 5% by mass or more and 20% by mass or less, and a structural unit derived from a macromonomer in an amount of 60% by mass or more and 80% by mass or less. The macromonomer comprises a structural unit derived from a monomer (c) having a hydrophobic group with a molecular weight of less than 400.

3. The polymer dispersant according to claim 1 or 2, having a weight-average molecular weight of 5000 or more and 120000 or less.

4. The polymeric dispersant according to any one of claims 1 to 3, wherein The number of repeating units n of the alkylene glycol is 2 or more and 40 or less.

5. An oil dispersion, which comprises the polymer dispersant according to any one of claims 1 to 4, an inorganic filler, and a compound not having a group capable of dissociating a hydrogen ion.

6. The oil dispersion according to claim 5, wherein, The compound not having a group capable of dissociating a hydrogen ion is selected from toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate.

7. The oil dispersion according to claim 5 or 6, wherein The content of the inorganic filler is 10% by mass or more and 80% by mass or less.

8. A halogen-based resin composition, which comprises: the polymer dispersant according to any one of claims 1 to 4, an inorganic filler, a compound not having a group capable of dissociating a hydrogen ion, and a halogen-based resin.

9. The halogen-based resin composition according to claim 8, wherein The SP value of the compound without a hydrogen ion-dissociating group, determined by the Fedose method, is 7.5 (cal / cm 3 ) 1 / 2 or more and 11.5 (cal / cm 3 ) 1 / 2 or less.

10. The halogen-based resin composition according to claim 8 or 9, wherein The compound not having a group capable of dissociating a hydrogen ion is selected from dialkyl phthalates and trialkyl trimellitates.

11. The halogen-based resin composition according to any one of claims 8 to 10, wherein, The content of the inorganic filler is 1 part by mass or more and 150 parts by mass or less relative to 100 parts by mass of the halogen-based resin.

12. A method for producing an oil dispersion, which comprises a step of mixing the polymer dispersant according to any one of claims 1 to 4, an inorganic filler, and a compound not having a group capable of dissociating a hydrogen ion.

13. A method for manufacturing a halogen-based resin composition, which includes a step of mixing the polymer dispersant according to any one of claims 1 to 4, an inorganic filler, a compound having no group capable of dissociating a hydrogen ion, and a halogen-based resin.

14. Use of compound (I) as a dispersant, wherein compound (I) contains a structural unit derived from a monomer having a hydroxyl group and a structural unit derived from a monomer represented by the following general formula (1). In general formula (1), R 1 , R 2 , and R 3 are each independently selected from a hydrogen atom and a methyl group, X 1 represents an oxygen atom, an ester group, an amide group, or -CH2O-, Y 1 represents a repeating unit of an alkylene glycol having 2 to 4 carbon atoms, R 4 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n represents the number of repeating units of the alkylene glycol.

15. The use according to claim 14, wherein Compound (I) is any one of the following compounds A to C. Compound A: A compound containing 20% by mass or more and 65% by mass or less of a structural unit derived from monomer (a) represented by the following general formula (1) having a molecular weight of 400 or more and 2000 or less, 5% by mass or more and 50% by mass or less of a structural unit derived from a monomer (b) having a hydroxyl group and a molecular weight of less than 400, and 30% by mass or more and 75% by mass or less of a structural unit derived from a monomer (c) having a hydrophobic group and a molecular weight of less than 400. In general formula (1a), R 1a , R 2a and R 3a are each independently selected from a hydrogen element and a methyl group, X 1a represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1a represents a repeating unit of an alkylene diol having 2 to 4 carbon atoms, R 4a represents a hydrogen element or an alkyl group having 1 to 4 carbon atoms, and n1 represents the number of repeating units of the alkylene diol. Compound B: A compound containing 45% by mass or more and 95% by mass or less of a structural unit derived from monomer (d) represented by the following general formula (1b) having a molecular weight of 300 or more and 2000 or less, 5% by mass or more and 40% by mass or less of a structural unit derived from a monomer (b) having a hydroxyl group and a molecular weight of less than 400, and 0% by mass or more and 20% by mass or less of a structural unit derived from a monomer (c) having a hydrophobic group and a molecular weight of less than 400. In general formula (1b), R 1b , R 2b and R 3b are each independently selected from a hydrogen element and a methyl group, X 1b represents an oxygen element, an ester group, an amide group or -CH2O-, Y 1b represents a repeating unit of an alkylene diol having 2 to 4 carbon atoms, R 4b represents a hydrocarbon group having 6 to 18 carbon atoms, and n2 represents the number of repeating units of the alkylene diol. Compound C: A compound containing 10% by mass or more and 40% by mass or less of a structural unit derived from monomer (d) represented by the following general formula (1b) having a molecular weight of 300 or more and 2000 or less, 5% by mass or more and 20% by mass or less of a structural unit derived from a monomer (b) having a hydroxyl group and a molecular weight of less than 400, and 60% by mass or more and 80% by mass or less of a structural unit derived from a macromonomer, the macromonomer containing a structural unit derived from a monomer (c) having a hydrophobic group and a molecular weight of less than 400.

16. The use according to claim 15, which is used for dispersing an inorganic filler in a compound having no group capable of dissociating a hydrogen ion.

17. Use of the polymer dispersant according to any one of claims 1 to 4 for preparing a dispersion in oil.

18. Use of the polymer dispersant according to any one of claims 1 to 4 for preparing a halogen-based resin composition.

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