Method for producing halogenated resin composition

Abstract

To provide a method for producing a halogenated resin composition that achieves improved workability through reduction in slurry viscosity during the production of the halogenated resin composition.SOLUTION: The present invention relates to a method for producing a resin composition containing chlorine atoms, the method comprising the following steps 1-3, wherein step 1 is carried out first. Step 1: a step for mixing an anionic polymer and a plasticizer. Step 2: a step for further mixing with a basic inorganic filler. Step 3: a step for further mixing with a halogenated resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a halogen-based resin composition. [Background technology]

[0002] Halogen-containing resins such as polyvinyl chloride (PVC) are important general-purpose polymers used in a variety of fields, including home interiors such as wallpaper, general-purpose products such as toys, and automotive materials such as sealants. When a halogen-based resin is used, for example, a halogen-based resin composition is prepared by blending a resin powder of the halogen-based resin with a plasticizer, a diluent, a viscosity reducer, a filler such as calcium carbonate, a pigment, a flame retardant, a foaming agent, a stabilizer, etc. However, many halogen-based resin compositions have high viscosity, and are often difficult or impossible to process.

[0003] Conventionally, methods for reducing the viscosity of halogen-based resin compositions have involved the use of diluents or viscosity reducers such as hydrocarbon solvents such as mineral spirits, alkylbenzenes, and paraffins, anionic surfactants, polyoxyethylene alkylphenol ethers, polyethylene glycols, and glycerin alkyl esters. These diluents and viscosity reducers are added after the production of the halogen-based resin or when preparing the halogen-based resin composition, but their viscosity reducing effect is not sufficient, and the viscosity reduction is insufficient particularly when a filler such as calcium carbonate is blended.

[0004] Patent Document 1 discloses a method for reducing the viscosity of a halogen-based resin composition, which comprises a vinyl chloride resin and one or more additives selected from the group consisting of an ester of a fatty acid and an aliphatic alcohol and a (poly)alkylene glycol mono- or dialkyl ether, one or more additives selected from the group consisting of a polyoxyalkylene alkyl ether and a polyoxyalkylene alkyl ether carboxylate, a plasticizer, and a filler, each in a specific amount. Furthermore, Patent Document 2 discloses a method for producing a resin composition, in which a surfactant characterized by a plurality of addition polymer chains, each chain having an average of at least 0.5 adsorptive or chemically adsorptive groups, at least one polyether residue, and at least one divalent polyether residue between the chains, is adsorbed onto an inorganic solid in water, followed by filtering and drying to produce a dispersible inorganic solid, which is then redispersed in a mixture of a plasticizer and a PVC resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-335696 [Patent Document 2] Special Publication No. 7-504846 Summary of the Invention [Problem to be solved by the invention]

[0006] In the resin composition described in Patent Document 1, additives are adsorbed and desorbed from the filler, so a large amount of additives is required to reduce the viscosity of the resin composition, and there is a problem in that the additives bleed out from the resin molded product after molding processing. Furthermore, the manufacturing method described in Patent Document 2 requires complicated steps of neutralizing an anionic polymer with an alkali to dissolve it in water, contacting the neutralized anionic polymer with an inorganic solid, removing the water by filtration and drying to obtain an anionic polymer-adsorbed inorganic solid, and then mixing it with a vinyl chloride resin and a plasticizer. The present invention relates to a method for producing a halogen-based resin composition, which improves processability by reducing the slurry viscosity during production of the halogen-based resin composition. [Means for solving the problem]

[0007] The present inventors have found that the above-mentioned problems can be solved by a simple method, without using water, by mixing an anionic polymer and a plasticizer, and then mixing a basic inorganic filler and a halogen-containing resin. That is, the present invention relates to a method for producing a halogen-based resin composition, which comprises the following steps 1 to 3, in which step 1 is carried out first. Step 1: Mixing anionic polymer and plasticizer Step 2: Further mixing of a basic inorganic filler Step 3: Further mixing with halogen-based resin [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a method for producing a halogen-based resin composition in which the processability is improved by reducing the slurry viscosity during production of the halogen-based resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Method of manufacturing halogen-based resin composition] The method for producing a halogen-based resin composition of the present invention (hereinafter also simply referred to as "the production method of the present invention") includes a step of mixing an anionic polymer and a plasticizer (step 1), a step of further mixing a basic inorganic filler (step 2), and a step of further mixing a halogen-based resin (step 3), with step 1 being carried out first. Steps 2 and 3 may be carried out simultaneously, or step 2 may be carried out first, or step 3 may be carried out first. However, from the viewpoint of improving production efficiency, it is preferable to carry out step 2 first.

[0010] From the viewpoint of improving production efficiency, in step 1, the water content is preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, based on the anionic polymer, and even more preferably substantially free of water. From the viewpoint of improving production efficiency, in step 2, the water content is preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, relative to the basic inorganic filler, and even more preferably substantially free of water. From the viewpoint of improving production efficiency, it is preferable that steps 1, 2, and 3 do not include an operation for removing water. From the viewpoint of improving production efficiency, the anionic polymer may be dissolved in an organic solvent and mixed with the plasticizer in step 1. When an organic solvent is contained, it is preferable to carry out a step of removing the organic solvent after step 1, step 2, or step 3.

[0011] According to the present invention, it is possible to provide a method for producing a halogen-based resin composition in which the processability is improved by reducing the slurry viscosity during the production of the halogen-based resin composition. The reason for this effect is not clear, but is thought to be as follows. In a halogen-based resin composition containing a plasticizer, the basic inorganic filler is hydrophilic and therefore stabilizes by aggregating and forming a network in the plasticizer. However, the aggregated basic inorganic filler that forms a network increases the viscosity of the halogen-based resin composition. Therefore, it is believed that by adsorbing an anionic polymer onto the surface of a basic inorganic filler and rendering the surface of the basic inorganic filler hydrophobic, aggregation and network formation of the basic inorganic filler in the resin composition can be suppressed, thereby reducing the slurry viscosity of the halogen-based resin composition. However, unlike low-molecular-weight surfactants, high-molecular-weight anionic polymers adsorb at multiple points on the surface of the basic inorganic filler and do not desorb. Therefore, if they are unevenly adsorbed on the surface of the basic inorganic filler, it is difficult to ensure that they are uniformly present. Furthermore, if high-molecular-weight anionic polymers are unevenly adsorbed on the surface of the basic inorganic filler, the basic inorganic filler will still aggregate and form a network, thereby increasing the viscosity of the halogen-based resin composition. In the method for producing a halogen-based resin composition of the present invention, it is believed that by mixing an anionic polymer and a plasticizer in step 1, the anionic polymer is uniformly dissolved and dispersed in the plasticizer, and by mixing a basic inorganic filler with an anionic polymer and a plasticizer in step 2, the anionic polymer acts uniformly on the surface of the basic inorganic filler. Therefore, the anionic polymer is uniformly adsorbed onto the surface of the basic inorganic filler, making the surface of the basic inorganic filler uniformly hydrophobic, thereby more effectively suppressing aggregation and network formation of the basic inorganic filler and reducing the viscosity of the slurry obtained in step 2. Furthermore, when a halogen-based resin is mixed in step 3, it is believed that the aggregation and network formation of the basic inorganic filler in the resin composition is more effectively suppressed, reducing the slurry viscosity of the halogen-based resin composition, thereby improving processability.

[0012] When an additive is contained in the halogen-based resin composition, the additive may be mixed together with the halogen-based resin in step 3, or may be mixed after step 3. By mixing the anionic polymer uniformly in the plasticizer first, the anionic polymer can be more uniformly adsorbed onto the basic inorganic filler.

[0013] When the components are mixed sequentially, the mixing in step 1 may be performed using a magnetic stirrer, a laboratory mixer, or the like, and the mixing in steps 2 and 3 may be performed using a stirrer or kneader. Examples of the stirrer include a laboratory mixer, a mortar mixer, a Henschel mixer, a Banbury mixer, and a ribbon blender, and examples of the kneader include a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a co-kneader-type kneader, and a roll kneader. The mixing conditions in step 1 are preferably 150 rpm or more, more preferably 200 rpm or more, and even more preferably 250 rpm or more from the viewpoint of thoroughly mixing the anionic polymer and the plasticizer, and are preferably 4,500 rpm or less, more preferably 4,000 rpm or less, and even more preferably 3,500 rpm or less from the viewpoint of suppressing a rise in temperature. The mixing time in step 1 is preferably 1 minute 30 seconds or more, more preferably 2 minutes or more, and even more preferably 2 minutes 30 seconds or more from the viewpoint of thoroughly mixing the anionic polymer and the plasticizer, and is preferably 5 minutes or less, more preferably 4 minutes or less, and even more preferably 3 minutes 30 seconds or less from the viewpoint of improving production efficiency. Alternatively, in step 1, the anionic polymer dissolved in the organic solvent may be mixed with the plasticizer. In this case, the mixing conditions are preferably 100 rpm or higher, more preferably 150 rpm or higher, and even more preferably 180 rpm or higher to thoroughly mix the anionic polymer and the plasticizer, and preferably 4,500 rpm or lower, more preferably 4,000 rpm or lower, and even more preferably 3,500 rpm or lower to suppress temperature rise. The organic solvent is preferably removed simultaneously with or after mixing, and from the viewpoint of production efficiency, removal simultaneously with mixing is preferred. When the organic solvent is removed simultaneously with mixing, the mixing time is preferably 10 minutes or longer, more preferably 30 minutes or longer, even more preferably 45 minutes or longer, and preferably 3 hours or shorter, more preferably 2 hours or shorter, and even more preferably 1 hour 30 minutes or shorter. The organic solvent is preferably removed by heating, and the heating temperature is preferably 120°C or higher, more preferably 140°C or higher, even more preferably 150°C or higher, and preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower.

[0014] The mixing conditions in step 2 are preferably 2,000 rpm or more, more preferably 2,500 rpm or more, and even more preferably 3,000 rpm or more from the viewpoint of allowing the anionic polymer to act sufficiently on the basic inorganic filler, and are preferably 8,000 rpm or less, more preferably 7,500 rpm or less, and even more preferably 7,000 rpm or less from the viewpoint of suppressing a temperature rise. The mixing time in step 2 is preferably 1 minute 30 seconds or more, more preferably 2 minutes or more, and even more preferably 2 minutes 30 seconds or more from the viewpoint of allowing the anionic polymer to act sufficiently on the basic inorganic filler, and is preferably 5 minutes or less, more preferably 4 minutes or less, and even more preferably 3 minutes 30 seconds or less from the viewpoint of improving production efficiency.

[0015] When step 2 is carried out after step 1, the slurry viscosity of the mixture of the anionic polymer, the plasticizer, and the basic inorganic filler at a temperature of 25°C after completion of step 2 is preferably 60 Pa s or less, more preferably 30 Pa s or less, and even more preferably 10 Pa s or less, from the viewpoint of reducing the slurry viscosity of the halogen-based resin composition produced by the production method of the present invention and improving production efficiency. The slurry viscosity is measured by the method shown in the examples.

[0016] The mixing conditions in step 3 may be those used in a typical method for producing a halogen-based resin composition. By performing the mixing in step 3 using a stirrer, a mixed powder of the halogen-based resin composition can be obtained. Furthermore, by melt-molding the mixture in step 3 using a kneader, a mixed powder, pellet-like, or paste-like halogen-based resin composition can be obtained.

[0017] When steps 1, 2, and 3 are carried out sequentially in this order, the slurry viscosity at 25°C of the mixture of the anionic polymer, the plasticizer, the basic inorganic filler, and the halogen-based resin after completion of step 3 is preferably 23 Pa s or less, more preferably 20 Pa s or less, and even more preferably 17 Pa s or less, from the viewpoint of improving the processability of the halogen-based resin composition produced by the production method of the present invention.

[0018] [Anionic polymer] In the present invention, an anionic polymer is a polymer having one or more anionic groups in the molecule. From the viewpoint of ease of adsorption to a basic inorganic filler, examples of the anionic group include those having a carboxy group, a sulfonic acid group, a sulfinic acid group, a sulfate group, a sulfite group, a phosphate group, a phosphite group, etc., and preferably those having a carboxy group or a sulfonic acid group, and more preferably those having a carboxy group.

[0019] The anionic polymer is preferably a polymer containing a structural unit having an anionic group and a structural unit having a hydrophobic group. From the viewpoint of ease of dissolving or dispersing in a plasticizer, examples of structural units having an anionic group include structural units derived from α,β-unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid, crotonic acid, and itaconic acid, and structural units derived from styrene-based compounds substituted with the above-mentioned anionic groups. Of these, structural units derived from α,β-unsaturated carboxylic acids are preferred, structural units derived from (meth)acrylic acid are more preferred, and structural units derived from methacrylic acid are even more preferred. 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. From the viewpoint of ease of dissolving or dispersing in a plasticizer, examples of structural units having a hydrophobic group include structural units derived from esters of α,β-unsaturated carboxylic acids, amides of α,β-unsaturated carboxylic acids, styrene-based compounds, and linear or branched alkenes having 3 to 10 carbon atoms, of which esters of α,β-unsaturated carboxylic acids, amides of α,β-unsaturated carboxylic acids, and linear or branched alkenes are preferred, and esters of α,β-unsaturated carboxylic acids are more preferred. In addition, when the ester of an α,β-unsaturated carboxylic acid and the amide of an α,β-unsaturated carboxylic acid are, respectively, an ester and an amide of a polycarboxylic acid and have at least one carboxy group, the ester and amide of the polycarboxylic acid constitute both a structural unit having an anionic group and a structural unit having a hydrophobic group.

[0020] From the viewpoint of easy availability, examples of esters of α,β-unsaturated carboxylic acids include esters of α,β-unsaturated carboxylic acids and linear or branched alkyl alcohols. From the viewpoint of improving compatibility with plasticizers, the number of carbon atoms in the linear or branched alkyl alcohol is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and is preferably 30 or less, more preferably 25 or less, even more preferably 20 or less. As the ester of the α,β-unsaturated carboxylic acid and a linear or branched alkyl alcohol, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate are preferred from the viewpoints of improving production efficiency due to the solubility of the anionic polymer in the plasticizer and improving processability due to a reduction in the slurry viscosity of the halogen-based resin composition. Furthermore, from the viewpoint of further improving solubility in plasticizers, the ester of α,β-unsaturated carboxylic acid may be an ester of α,β-unsaturated carboxylic acid and a polyalkylene glycol having a medium- or long-chain alkyl group at one end and a repeating number of 1 to 40. From the viewpoint of improving compatibility with plasticizers, the carbon number of the medium- or long-chain alkyl group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and is preferably 24 or less, more preferably 18 or less, even more preferably 16 or less. As the ester of polyalkylene glycol and α,β-unsaturated carboxylic acid, stearoxy polyethylene glycol mono(meth)acrylate, lauroxy polyethylene glycol mono(meth)acrylate, and 2-ethylhexyloxypropylene glycol polyethylene glycol (meth)acrylate are preferred from the viewpoints of improving production efficiency due to the solubility of the anionic polymer in the plasticizer and improving processability due to a reduction in the slurry viscosity of the halogen-based resin composition.

[0021] Examples of amides of α,β-unsaturated carboxylic acids include amides of α,β-unsaturated carboxylic acids and linear or branched primary alkylamines, which are easily incorporated into molecules. The number of carbon atoms in the linear or branched primary alkylamine is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more, and is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less, from the viewpoint of improving compatibility with plasticizers.

[0022] As the styrene-based compound, for example, styrene, α-methylstyrene, etc. can be mentioned from the viewpoint of easy availability. Examples of the linear or branched alkenes having 3 to 10 carbon atoms include isoprene, butadiene, isobutylene, and diisobutylene, from the viewpoint of ease of copolymerization with maleic anhydride.

[0023] Among the above-mentioned structural units having a hydrophobic group, structural units derived from one or more selected from stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearoxypolyethylene glycol mono(meth)acrylate, lauroxypolyethylene glycol (meth)acrylate, 2-ethylhexyloxypolypropylene glycol polyethylene glycol (meth)acrylate, and diisobutylene are preferred, from the viewpoints of further improving production efficiency due to the solubility of the anionic polymer in the plasticizer and further improving processability due to the reduced slurry viscosity of the halogen-based resin composition.

[0024] The anionic polymer may contain a structural unit having a hydrophilic group from the viewpoint of adjusting the hydrophilic-hydrophobic balance. However, in the present invention, the structural unit having a hydrophilic group does not include a structural unit having an anionic group. Examples of the structural unit having a hydrophilic group include a structural unit derived from (meth)acrylamide, dimethyl(meth)acrylamide, or acrylonitrile, and a structural unit derived from an α,β-unsaturated carboxylic acid alkyloxy polyalkylene glycol ester. From the viewpoint of facilitating the design of the hydrophilic / hydrophobic balance, the anionic polymer preferably contains a constituent unit derived from an α,β-unsaturated carboxylic acid alkyloxy polyalkylene glycol ester, more preferably a constituent unit derived from an α,β-unsaturated carboxylic acid alkyloxy polyethylene glycol and / or polypropylene glycol ester, and even more preferably a constituent unit derived from an α,β-unsaturated carboxylic acid alkyloxy polyethylene glycol ester. The number of repeating alkylene glycol moieties in the structural units derived from an α,β-unsaturated carboxylic acid alkyloxy polyalkylene glycol ester is preferably 2 or more, more preferably 4 or more, even more preferably 9 or more, from the viewpoint of adsorption to the basic inorganic filler and reducing the slurry viscosity of the halogen-based resin composition, and is preferably 60 or less, more preferably 55 or less, even more preferably 45 or less. As the structural unit derived from the α,β-unsaturated carboxylic acid alkyloxy polyalkylene glycol ester, methoxypolyethylene glycol mono(meth)acrylate is preferred from the viewpoint of improving processability by adsorbing to a basic inorganic filler and reducing the slurry viscosity of the halogen-based resin composition.

[0025] The content of the structural units derived from α,β-unsaturated carboxylic acid in the anionic polymer, when all structural units are taken as 100% by mass, is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and still more preferably 5% by mass or more, from the viewpoint of being adsorbed to the basic inorganic filler and reducing the slurry viscosity of the halogen-based resin composition, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and still more preferably 20% by mass or less, from the viewpoint of improving compatibility with the plasticizer. The content of the structural unit having a hydrophobic group, when all structural units are taken as 100% by mass, is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 13% by mass or more from the viewpoint of improving compatibility with plasticizers, and is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 93% by mass or less from the viewpoint of not interfering with adsorption to basic inorganic fillers.

[0026] The weight average molecular weight of the anionic polymer is preferably 4,000 or more, more preferably 4,500 or more, and even more preferably 5,000 or more, from the viewpoint of suppressing detachment from the basic inorganic filler, and is preferably 200,000 or less, more preferably 180,000 or less, even more preferably 170,000 or less, still more preferably 150,000 or less, still more preferably 120,000 or less, still more preferably 100,000 or less, still more preferably 70,000 or less, still more preferably 50,000 or less, still more preferably 30,000 or less, and still more preferably 20,000 or less, from the viewpoint of efficient adsorption to the basic inorganic filler. The weight average molecular weight is measured by the method shown in the examples.

[0027] The acid value of the anionic polymer is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, and even more preferably 45 mgKOH / g or more, from the viewpoint of adsorbing to the basic inorganic filler and reducing the slurry viscosity of the halogen-based resin composition, and is preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less, even more preferably 120 mgKOH / g or less, and still more preferably 100 mgKOH / g or less, from the viewpoint of improving compatibility with the plasticizer. The acid value of the anionic polymer can be calculated from the mass ratio of the constituent monomers, or can be determined by dissolving or swelling the anionic polymer in an appropriate organic solvent (e.g., methyl ethyl ketone) and titrating the resultant.

[0028] The anionic polymer may be neutralized to increase the degree of freedom in molecular design. When a halogen-based resin composition is produced by sequentially performing steps 1 to 3, the effects of the present invention can be achieved regardless of the degree of neutralization. On the other hand, the slurry viscosity of a halogen-based resin composition produced by simultaneously mixing a neutralized anionic polymer, a plasticizer, a basic inorganic filler, and a halogen-based resin is higher than that of a halogen-based resin composition produced by the production method of the present invention. This is thought to be because, by sequentially performing steps 1 to 3, the anionic polymer and the basic inorganic filler are mixed before the basic inorganic filler and the halogen-based resin are mixed, making the surface of the basic inorganic filler more hydrophobic due to the anionic polymer than when they are added all at once. The degree of neutralization herein means the molar equivalent of the neutralizing agent divided by the molar amount of the anionic groups in the polymer.

[0029] The anionic polymer may be neutralized, but from the viewpoints of improving production efficiency by increasing the solubility in a plasticizer and improving processability by reducing the slurry viscosity of the halogen-based resin composition, it is preferable that the degree of neutralization of the anionic polymer is 0 mol %, i.e., that the anionic polymer is unneutralized.

[0030] Examples of neutralizing agents for anionic polymers include alkali metal hydroxides, ammonia, organic amines, etc., which are readily available. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. Examples of organic amines include trimethylamine, ethylamine, diethylamine, triethylamine, and triethanolamine.

[0031] In the production method of the present invention, the mass ratio of the anionic polymer to the content of the basic inorganic filler (anionic polymer / basic inorganic filler) is, from the viewpoint of adsorption to the basic inorganic filler, reducing the slurry viscosity of the halogen-based resin composition, and improving processability, preferably 0.0001 or more, more preferably 0.0005 or more, even more preferably 0.001 or more, still more preferably 0.002 or more, and is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, still more preferably 0.5 or less, still more preferably 0.1 or less, still more preferably 0.05 or less, still more preferably 0.03 or less, still more preferably 0.01 or less.

[0032] In the manufacturing method of the present invention, the amount of the anionic polymer in the halogen-based resin composition is preferably 0.001% by mass or more and 1.0% by mass or less relative to the halogen-based resin composition, from the viewpoint of improving processability by reducing the slurry viscosity of the halogen-based resin composition.

[0033] (Method for producing anionic polymer) The anionic polymer can be produced by copolymerizing monomers such as a compound having an anionic group, a compound having a hydrophobic group, a compound having a hydrophilic group, etc., by a known polymerization method. As the polymerization method, a solution polymerization method is preferred from the viewpoint that the polymer can be produced using general-purpose equipment. The solvent used in the solution polymerization method is not limited as long as it dissolves the monomer, but is preferably an aromatic solvent such as toluene or xylene, or a polar solvent such as an aliphatic alcohol, ketones, ethers, or esters, more preferably toluene, methanol, ethanol, acetone, or methyl ethyl ketone, and even more preferably toluene or ethanol. One type of solvent may be used alone, or two or more types of solvents may be mixed and used. During the polymerization, a polymerization initiator and a chain transfer agent can be used. As the polymerization initiator, from the viewpoint of enabling stable polymerization at the boiling point of the solvent, known radical polymerization initiators such as azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile), and organic peroxides such as t-butyl peroxyoctoate and benzoyl peroxide can be used. The amount of the radical polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, per 100 parts by mass of the monomer mixture. As the chain transfer agent, known chain transfer agents such as mercaptans such as octyl mercaptan, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, and mercaptopropionic acid, and thiuram disulfides can be used from the viewpoint of ease of molecular weight adjustment. There is no limitation on the chain mode of polymerization of the monomers, and any of the polymerization modes such as random, block, and graft may be used.

[0034] The monomer may contain a compound (crosslinking agent) containing two or more radically polymerizable carbon-carbon double bonds. When the monomer contains a crosslinking agent, the content of the crosslinking agent in the total monomers is preferably 3 mol % or less to prevent gelation of the reaction system. The content of the crosslinking agent in the monomer mixture is preferably 2 mol % or less, more preferably 1 mol % or less, and even more preferably 0.5 mol % or less.

[0035] From the viewpoint of enabling polymerization using general-purpose equipment, preferred polymerization conditions vary depending on the types of polymerization initiator, monomer, solvent, etc. used, but typically the polymerization temperature is preferably 30° C. or higher, more preferably 50° C. or higher, and preferably 95° C. or lower, more preferably 80° C. or lower. The polymerization time is preferably 1 hour or longer, more preferably 2 hours or longer, and preferably 20 hours or shorter, more preferably 10 hours or shorter. The polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.

[0036] [Halogen-based resin] In the present invention, the halogen-based resin means a homopolymer or copolymer of a halogen-containing monomer, or a polymer modified with a halogen. Specific examples thereof include, from the viewpoint of easy availability, one or more resins selected from vinyl chloride resin, vinylidene chloride resin, chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, chloroprene rubber, etc. Preferably, the halogen-based resin composition of the present invention contains one or more resins selected from vinyl chloride resin, vinylidene chloride resin, and chloroprene rubber.

[0037] (Vinyl chloride resin) Examples of vinyl chloride resins include vinyl chloride homopolymers, copolymers of vinyl chloride with monomers copolymerizable with vinyl chloride (hereinafter also referred to as "vinyl chloride copolymers"), and graft copolymers in which vinyl chloride is graft-copolymerized onto polymers other than the vinyl chloride copolymers. The monomer copolymerizable with vinyl chloride may be any monomer having a reactive double bond in the molecule, from the viewpoint of ease of copolymerization, and examples thereof include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and phenyl (meth)acrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. As polymers other than vinyl chloride copolymers, any polymer that can be graft-copolymerized with vinyl chloride may be used, and from the viewpoint of ease of availability, examples include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl acrylate-carbon monoxide copolymer, ethylene-methyl (meth)acrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, etc.

[0038] Among the above halogen-based resins, from the viewpoint of flexibility and the like, one or more selected from vinyl chloride resins such as vinyl chloride resins, ethylene-vinyl chloride copolymers, vinyl acetate-vinyl chloride copolymers, and polyurethane-grafted polyvinyl chloride copolymers, vinylidene chloride resins, and chloroprene rubbers are preferred, one or more selected from vinyl chloride resins, vinylidene chloride resins, and chloroprene rubbers are more preferred, and vinyl chloride resins are even more preferred.

[0039] [Plasticizer] In the present invention, the plasticizer may be a compound that is normally used as a plasticizer for halogen-based resins. From the viewpoint of high compatibility with halogen-based resins, such plasticizers have an SP value of preferably 7.5 or more, more preferably 8 or more, even more preferably 8.5 or more, and preferably 11.5 or less, more preferably 11 or less, even more preferably 10.5 or less. Examples of plasticizers that have high compatibility with halogen-based resins include dioctyl phthalate (DOP) and diisononyl phthalate (DINP), as well as phthalate esters of alcohols having 1 to 13 carbon atoms such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and diundecyl phthalate; trimellitate esters of alcohols having 6 to 10 carbon atoms such as tris(2-ethylhexyl) trimellitate, trioctyl trimellitate, and tridecyl trimellitate; adipate, azelaate, sebate, phosphate, polyester, epoxy, fatty acid ester, and pyromellitate plasticizers. One type of plasticizer may be used alone, or two or more types may be mixed and used. From the viewpoint of high compatibility with halogen-based resins, the plasticizer is preferably a phthalate ester or trimellitate ester of an alcohol having 1 to 20 carbon atoms, more preferably a phthalate ester or trimellitate ester of an alcohol having 5 to 18 carbon atoms, and even more preferably a phthalate ester or trimellitate ester of an alcohol having 8 to 13 carbon atoms.

[0040] The amount of plasticizer in the halogen-based resin composition in the production method of the present invention is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, per 100 parts by mass of the halogen-based resin, from the viewpoint of exhibiting the plasticizing effect of the halogen-based resin composition, and is preferably 170 parts by mass or less, more preferably 160 parts by mass or less, and even more preferably 150 parts by mass or less, from the viewpoint of improving processability.

[0041] [Basic inorganic filler] Examples of the basic inorganic filler used in the present invention include calcium carbonate, talc, calcium silicate, alumina, etc. One basic inorganic filler may be used alone, or two or more basic inorganic fillers may be used in combination. From the viewpoint of economic efficiency, the basic inorganic filler preferably contains calcium carbonate, and more preferably is calcium carbonate.

[0042] In the production method of the present invention, the amount of the basic inorganic filler to be blended is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and is preferably 150 parts by mass or less, more preferably 140 parts by mass or less, even more preferably 130 parts by mass or less, per 100 parts by mass of the halogen-based resin, from the viewpoint of reducing the cost of the halogen-based resin composition.

[0043] [Additives] In the production method of the present invention, additives such as stabilizers, processing aids, colorants, antioxidants, ultraviolet absorbers, antistatic agents, and lubricants may be blended as needed within the range that does not impair the effects of the present invention.

[0044] Examples of stabilizers 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-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, and dibutyltin dilaurate, and antimony mercaptide compounds. The amount of stabilizer blended is 0.1 to 20 parts by mass per 100 parts by mass of the halogen-based resin.

[0045] Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bisstearic acid amide, butyl stearate, calcium stearate, etc. The amount of processing aid to be added is 0.1 to 20 parts by mass per 100 parts by mass of the halogen-based resin.

[0046] Examples of colorants include carbon black, lead sulfide, white carbon, titanium white, lithopone, red iron oxide, antimony sulfide, chrome yellow, chrome green, cobalt blue, molybdenum orange, etc. The amount of colorant to be added is 1 to 100 parts by mass per 100 parts by mass of the halogen-based resin.

[0047] Examples of antioxidants include phenolic compounds such as 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, and 2-hydroxy-4-methoxybenzophenone; sulfur compounds such as alkyl disulfides, thiodipropionic acid esters, and benzothiazole; phosphoric acid compounds such as trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite; and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. The amount of antioxidant blended is 0.2 to 20 parts by mass per 100 parts by mass of the halogen-based resin.

[0048] Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone, benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, and cyanoacrylate compounds. The amount of the ultraviolet absorber to be added is 0.1 to 10 parts by mass per 100 parts by mass of the halogen-based resin.

[0049] Examples of antistatic agents include anionic antistatic agents of the alkyl sulfonate type, alkyl ether carboxylic acid type, or dialkyl sulfosuccinate type, nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives, cationic antistatic agents such as quaternary ammonium salts of the alkylamidoamine type, alkyldimethylbenzyl type, and alkylpyridinium type organic acid salts or hydrochlorides, and amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. The blending amount of the antistatic agent is 0.1 to 10 parts by mass per 100 parts by mass of the halogen-based resin.

[0050] Examples of lubricants include silicone, liquid paraffin, paraffin wax, fatty acids such as stearic acid and lauric acid and their metal salts, fatty acid amides, fatty acid wax, higher fatty acid wax, etc. The amount of lubricant blended is 0.1 to 10 parts by mass per 100 parts by mass of the halogen-based resin.

[0051] [Halogen-based resin composition] The halogen-based resin composition obtained by the production method of the present invention is a halogen-based resin composition containing a plasticizer, an anionic polymer, a basic inorganic filler, and a halogen-based resin, and is characterized by a low slurry viscosity. From the viewpoint of exhibiting excellent processability, the slurry viscosity of the halogen-based resin composition is preferably 23 Pa s or less, more preferably 20 Pa s or less, and even more preferably 17 Pa s or less. The slurry viscosity is measured by the method shown in the examples.

[0052] The mixed powder or pellets of the halogen-based resin composition obtained by the production method of the present invention can be molded into a desired shape by known methods such as extrusion molding, injection molding, calendar molding, press molding, blow molding, etc. Furthermore, the paste-like halogen-based resin composition obtained by the production method of the present invention can be molded into a desired shape by known methods such as spread molding, dipping molding, gravure molding, screen processing, etc. The halogen-based resin composition produced by the production method of the present invention has excellent processability and is therefore useful as adhesives, sealants, paints, plastisols, foams, synthetic leather, pipes such as water pipes, building materials, wallpaper, flooring, floor covering materials, heat insulation materials, roofing membrane materials and other residential interior products; packaging materials such as food packaging films; agricultural materials such as agricultural films; automotive materials such as sealants and undercoats; base protection materials, fabric coating materials, electric wire coating materials, various types of leather, various foam products, general hoses, gaskets, packings, boots, toys, food packaging materials, and medical supplies such as tubes and blood bags.

[0053] The present invention includes the following aspects. <1> A method for producing a halogen-based resin composition, comprising the following steps 1 to 3, in which step 1 is carried out first. Step 1: Mixing anionic polymer and plasticizer Step 2: Further mixing of a basic inorganic filler Step 3: Further mixing with halogen-based resin <2> The steps 1 to 3 are carried out sequentially. <1> 1. A method for producing the halogen-based resin composition according to claim 1. <3> The mixing conditions in step 1 are 250 rpm or more and 3,500 rpm or less. <1> , or the above <2> 1. A method for producing the halogen-based resin composition according to claim 1. <4> The mixing time in step 1 is 2 minutes 30 seconds or more and 3 minutes 30 seconds or less. <1> ~ <3> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <5> The mixing conditions in step 2 are 3,000 rpm or more and 7,000 rpm or less. <1> ~ <4> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <6> The mixing time in step 2 is 2 minutes 30 seconds or more and 3 minutes 30 seconds or less. <1> ~ <5> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <7> After step 2, the mixture of the anionic polymer, the plasticizer, and the basic inorganic filler has a slurry viscosity of 10 Pa·s or less at a temperature of 25°C. <1> ~ <6> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <8> After the step 3 is completed, the mixture of the anionic polymer, the plasticizer, the basic inorganic filler, and the halogen-based resin has a slurry viscosity of 17 Pa·s or less at a temperature of 25°C. <1> ~ <7> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <9> The anionic polymer contains a structural unit having an anionic group and a structural unit having a hydrophobic group. <1> ~ <8> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <10> The structural unit having an anionic group is a structural unit having a carboxy group. <9> 1. A method for producing the halogen-based resin composition according to claim 1. <11> The structural unit having a carboxy group is a structural unit derived from (meth)acrylic acid. <10> 1. A method for producing the halogen-based resin composition according to claim 1. <12> The structural unit having a hydrophobic group is at least one selected from the group consisting of structural units derived from stearyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearoxy polyethylene glycol mono(meth)acrylate, lauroxy polyethylene glycol mono(meth)acrylate, and 2-ethylhexyloxypropylene glycol polyethylene glycol (meth)acrylate. <9> ~ <11> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <13> the structural unit having an anionic group is a structural unit derived from methacrylic acid, the structural unit having a hydrophobic group is a structural unit derived from stearyl (meth)acrylate, the structural units derived from methacrylic acid account for 5% by mass or more and 20% by mass or less of all structural units in the anionic polymer, and the structural units derived from stearyl (meth)acrylate account for 15% by mass or more and 60% by mass or less of all structural units in the anionic polymer; <9> ~ <12> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <14> the structural unit having an anionic group is a structural unit derived from methacrylic acid, the structural unit having a hydrophobic group is a structural unit derived from lauryl methacrylate, the structural units derived from methacrylic acid account for 40% by mass or more and 60% by mass or less of all structural units in the anionic polymer, and the structural units derived from lauryl methacrylate account for 15% by mass or more and 60% by mass or less of all structural units in the anionic polymer; <9> ~ <12> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <15> the structural unit having an anionic group is a structural unit derived from methacrylic acid, and the structural units derived from methacrylic acid account for 5% by mass or more and 20% by mass or less of all structural units in the anionic polymer; the structural unit having a hydrophobic group is a structural unit derived from 2-ethylhexyloxypropylene glycol polyethylene glycol methacrylate, and the structural units derived from 2-ethylhexyloxypropylene glycol polyethylene glycol methacrylate account for 80% by mass or more and 95% by mass or less of all structural units in the anionic polymer; <9> ~ <12> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <16> the structural unit having an anionic group is a structural unit derived from methacrylic acid, and the structural unit derived from methacrylic acid accounts for 5% by mass or more and 20% by mass or less of all structural units in the anionic polymer; the structural unit having a hydrophobic group is a structural unit derived from lauroxypolyethylene glycol monomethacrylate, and the structural unit derived from lauroxypolyethylene glycol monomethacrylate accounts for 80% by mass or more and 95% by mass or less of all structural units in the anionic polymer; <9> ~ <12> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <17> the structural units having an anionic group are structural units derived from methacrylic acid, and the structural units derived from methacrylic acid account for 10% by mass or more and 20% by mass or less of all structural units in the anionic polymer; the structural units having a hydrophobic group are structural units derived from 2-ethylhexyl methacrylate, and the structural units derived from 2-ethylhexyl methacrylate account for 80% by mass or more and 90% by mass or less of all structural units in the anionic polymer; <9> ~ <12> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <18> The weight average molecular weight of the anionic polymer is 4,000 or more and 200,000 or less. <1> ~ <17> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <19> The weight average molecular weight of the anionic polymer is 5,000 or more and 20,000 or less. <1> ~ <17> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <20> the anionic polymer is unneutralized; <1> ~ <19> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <21> The acid value of the anionic polymer is 45 mgKOH / g or more and 100 mgKOH / g or less. <1> ~ <20> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <22> the mass ratio of the anionic polymer to the basic inorganic filler (anionic polymer / basic inorganic filler) is 0.0001 or more and 10 or less; <1> ~ <21> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <23> the mass ratio of the anionic polymer to the basic inorganic filler (anionic polymer / basic inorganic filler) is 0.002 or more and 0.01 or less; <1> ~ <22> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <24> The basic inorganic filler includes calcium carbonate. <1> ~ <23> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <25> The halogen-based resin is a vinyl chloride resin. <1> ~ <24> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <26> The plasticizer is a phthalate ester of an alcohol having 8 to 13 carbon atoms. <1> ~ <25> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <27> The amount of the plasticizer in the halogen-based resin composition is 30 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the halogen-based resin. <1> ~ <26> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <28> The amount of the basic inorganic filler in the halogen-based resin composition is 5 parts by mass or more and 130 parts by mass or less with respect to 100 parts by mass of the halogen-based resin. <1> ~ <27> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. <29> The amount of the anionic polymer in the halogen-based resin composition is 0.001% by mass or more and 1.0% by mass or less. <1> ~ <28> 1. A method for producing the halogen-based resin composition according to any one of claims 1 to 9. [Example]

[0054] In the following Production Examples, Examples and Comparative Examples, "parts" and "%" are "parts by mass" and "% by mass" unless otherwise specified.

[0055] [measurement] [Method for measuring weight average molecular weight] The weight average molecular weight of the anionic polymer was measured by gel permeation chromatography (hereinafter also referred to as "GPC") method. The synthesized anionic polymer was diluted with N,N-dimethylformamide to prepare a solution with a solids concentration of 0.3% by mass. 100 μL of this solution was used for the measurement. The eluent was a solution of 60 mmol / L phosphoric acid and 50 mmol / L lithium bromide dissolved in N,N-dimethylformamide. The gel permeation was measured using a Tosoh HLC-8320GPC system (with a differential refractometer attached), two Tosoh TSK-GEL α-M columns, at a column temperature of 40°C and a flow rate of 1 mL / min. The standard material was polystyrene (manufactured by Tosoh Corporation: molecular weight 5.26 × 10 2 , 1.02 × 10 5 , 8.42 × 10 6 Nishio Kogyo Co., Ltd.: molecular weight 4.0 x 10 3 , 3.0×10 4 , 9.0×10 5 ) was used.

[0056] [Method for measuring slurry viscosity] The viscosity of the halogen-based resin composition obtained by the manufacturing method of the present invention, or the mixture of the anionic polymer, plasticizer, and basic inorganic filler obtained in step 2 of the manufacturing method of the present invention, was measured using a rheometer (manufactured by Anton Paar, product name: MCR302). The jig used was a 25 mm diameter parallel plate, and the viscosity was measured at 25°C for 0.1 s. -1 From 10s -1 The shear rate was swept up to 1 s. The slurry viscosity was -1 The viscosity value was used.

[0057] [Measurement of bleed-out rate] A 4 cm x 4 cm test piece (1.7 g) was cut from a molded sheet of the halogen-based resin composition. One surface of this test piece was washed with 2 g of deuterated methanol containing 0.1 wt% TMS, and the deuterated methanol solution was 1 Analysis was performed by H-NMR measurement. The mass of the anionic polymer or surfactant blended into the halogen-based resin composition in the deuterated methanol solution was determined from the integrated value of the peak derived from the polymer or surfactant. The amount of the anionic polymer or surfactant blended into a 1.7 g test piece was calculated from the amount charged to the halogen-based resin composition, and the bleed-out rate was calculated as a percentage (%) of that amount. With this measurement method, a bleed-out amount of 0.2 wt% is detectable, and ND (Not Detected) indicates a bleed-out rate of less than 0.2 wt%.

[0058] [Measurement of solids concentration] 10.0 parts of sodium sulfate, brought to a constant weight in a desiccator, was weighed into a 30 ml glass Petri dish, and approximately 1.0 part of the sample was added thereto and mixed. The mixture was then accurately weighed, maintained at 105°C for 2 hours to remove volatiles, and then left in the desiccator for 15 minutes, after which the mass was measured. The mass of the sample after volatiles removal was taken as the solid content, and divided by the mass of the added sample to obtain the solid content concentration.

[0059] [Production of Anionic Polymer 1] Production Example 1 (Production of Anionic Polymer 1) A 1 L four-neck separable flask was charged with 7.9 g of stearyl methacrylate (Shinnakamura Chemical Co., Ltd., trade name: NK Ester S), 7.9 g of methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.), 36.7 g of methoxypolyethylene glycol methacrylate (Shinnakamura Chemical Co., Ltd., trade name: NK Ester TM-230G, average 23 moles of EO added), and 26.0 g of ethanol. The flask was equipped with two dropping funnels, a reflux condenser, a thermometer, and a stirrer. After purging with nitrogen, the reaction system was heated to 80 °C with stirring. A mixed solution of 1.6 g of polymerization initiator (Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-65B) and 8.9 g of ethanol was added, and the resulting initial mixture was stirred for 10 minutes. Next, while maintaining the temperature, a mixed solution of 31.5 g of stearyl methacrylate, 31.5 g of methacrylic acid, 148.8 g of the above methoxypolyethylene glycol methacrylate, and 104.2 g of ethanol, and a mixed solution of 6.3 g of polymerization initiator and 35.6 g of ethanol were separately added dropwise over 180 minutes (hereinafter, these mixed solutions are referred to as "dropping mixtures" in Table 1). After completion of the addition, the mixture was stirred at 80°C for 180 minutes and then cooled to room temperature. The solids concentration of the resulting polymer solution was 60.1%. 10.0 g of the resulting polymer solution was weighed into a glass Petri dish and dried under reduced pressure at 80°C for 3 hours to obtain anionic polymer 1. The weight average molecular weight of the resulting anionic polymer 1 was 27,000.

[0060] Production Example 2 (Production of Anionic Polymer 2) To 10.0 g of the polymer solution produced in Production Example 1 (solid content: 6.0 g, content of structural units derived from methacrylic acid: 14.9%), 0.3 g of 4N sodium hydroxide solution was added and stirred for 30 minutes to neutralize the carboxyl groups in Anionic Polymer 1. The resulting polymer solution was dried under reduced pressure at 80°C for 3 hours to obtain Anionic Polymer 2 (10% neutralized form of Anionic Polymer 1).

[0061] Production Example 3 (Production of Anionic Polymer 3) To 10.0 g of the polymer solution produced in Production Example 1 (solid content: 6.0 g, content of structural units derived from methacrylic acid: 14.9%), 0.6 g of 4N sodium hydroxide solution was added and stirred for 30 minutes to neutralize the carboxyl groups in Anionic Polymer 1. The resulting polymer solution was dried under reduced pressure at 80°C for 3 hours to obtain Anionic Polymer 3 (20% neutralized form of Anionic Polymer 1).

[0062] Production Example 4 (Production of Anionic Polymer 4) To 10.0 g of the polymer solution produced in Production Example 1 (solid content: 6.0 g, content of structural units derived from methacrylic acid: 14.9%), 1.5 g of 4N sodium hydroxide solution was added and stirred for 30 minutes to neutralize the carboxyl groups in Anionic Polymer 1. The resulting polymer solution was dried under reduced pressure at 80°C for 3 hours to obtain Anionic Polymer 4 (50% neutralized form of Anionic Polymer 1).

[0063] Production Example 5 (Production of Anionic Polymer 5) To 10.0 g of the polymer solution produced in Production Example 1 (solid content: 6.0 g, content of structural units derived from methacrylic acid: 14.9%), 3.0 g of 4N sodium hydroxide solution was added and stirred for 30 minutes to neutralize the carboxy groups in Anionic Polymer 1. The resulting polymer solution was dried under reduced pressure at 80°C for 3 hours to obtain Anionic Polymer 5 (a 100% neutralized form of Anionic Polymer 1).

[0064] Production Example 6 (Production of Anionic Polymer 6) A 1L four-neck separable flask was charged with 20.3g of stearyl acrylate, 6.8g of methacrylic acid, 18.0g of methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester TM-230G, average 23 moles of EO added), 1.8g of mercaptopropanediol (chain transfer agent: Fujifilm Wako Pure Chemical Industries, Ltd.), and 27.0g of ethanol, and was equipped with two dropping funnels, a reflux condenser, a thermometer, and a stirrer. After replacing the atmosphere with nitrogen, the reaction system was heated to 80°C with stirring, and a mixed solution of 1.4g of the above polymerization initiator and 11.3g of ethanol was added. The resulting initial mixture was stirred for 10 minutes. Next, while maintaining the temperature, a mixed solution of 182.3 g of stearyl acrylate, 60.8 g of methacrylic acid, 162.0 g of the above methoxypolyethylene glycol methacrylate, 16.2 g of mercaptopropanediol, and 143.0 g of ethanol, and a mixed solution of 12.2 g of the above polymerization initiator and 100.0 g of ethanol were separately added dropwise over 180 minutes. After completion of the dropwise addition, the mixture was stirred at 80°C for 180 minutes and then cooled to room temperature. Next, 556.3 g of toluene and 275.3 g of ethanol were added to adjust the solids concentration to 30.4%. 10.0 g of the resulting polymer solution was weighed into a glass Petri dish and dried under reduced pressure at 100°C for 5 hours to obtain anionic polymer 6. The weight average molecular weight of the resulting anionic polymer 6 was 5,800.

[0065] Production Example 7 (Production of Anionic Polymer 7) A 1L four-neck separable flask was charged with 4.5g of stearyl methacrylate, 1.5g of methacrylic acid, 4.0g of methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester TM-230G, average 23 moles of EO added), and 24.7g of a toluene / ethanol mixture (50 / 50 by mass), and was equipped with two dropping funnels, a reflux condenser, a thermometer, and a stirrer. After replacing the atmosphere with nitrogen, the reaction system was heated to 80°C with stirring, and a mixed solution of 0.02g of the above polymerization initiator and 5.7g of a toluene / ethanol mixture (50 / 50 by mass) was added, and stirring was continued for 10 minutes. Next, while maintaining the temperature, a mixed solution of 40.5 g of stearyl methacrylate, 13.5 g of methacrylic acid, 36.0 g of the above methoxypolyethylene glycol methacrylate, and 42.1 g of a toluene / ethanol mixed solution (50 / 50 by mass), and a mixed solution of 0.15 g of the above polymerization initiator and 50.9 g of a toluene / ethanol mixed solution (50 / 50 by mass), were separately added dropwise over 120 minutes. After completion of the dropwise addition, the mixture was stirred at 80°C for 120 minutes and then cooled. The solids concentration of the resulting polymer solution was 45.2% by mass. 10.0 g of the resulting polymer solution was weighed into a glass Petri dish and dried under reduced pressure at 100°C for 5 hours to obtain anionic polymer 7. The weight average molecular weight of the resulting anionic polymer 7 was 166,000.

[0066] Production Example 8 (Production of Anionic Polymer 8) A 1L four-neck separable flask was pre-charged with 100.0 g of a toluene / ethanol mixture (50 / 50 by mass) and equipped with two dropping funnels, a reflux condenser, a thermometer, and a stirrer. After purging the reaction system with nitrogen, the temperature was raised to 80 °C while stirring. While maintaining the temperature, a mixed solution of 300.0 g of stearyl methacrylate, 75.0 g of methacrylic acid, 125.0 g of methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester M-450G, average 45 moles of EO added), 4.9 g of mercaptopropanediol, and 350.4 g of a toluene / ethanol mixture (50 / 50 by mass), and a mixed solution of 6.8 g of the above polymerization initiator and 49.6 g of a toluene / ethanol mixture (50 / 50 by mass), were separately added dropwise over 120 minutes. After the dropwise addition, the mixture was stirred at 80 °C for 60 minutes and then cooled to room temperature. The solids concentration of the obtained polymer solution was 49.7%. 10.0 g of the obtained polymer solution was weighed into a glass petri dish and dried under reduced pressure at 100°C for 5 hours to obtain anionic polymer 8. The content of structural units derived from α,β-unsaturated carboxylic acid in anionic polymer 8 was 15.0%. The weight average molecular weight of the resulting anionic polymer 8 was 14,300.

[0067] Production Example 9 (Production of Anionic Polymer 9) Anionic polymer 9 was obtained in the same manner as in Production Example 6, except that stearyl acrylate was changed to stearyl methacrylate and the amounts of each component were changed as shown in Table 1. The weight average molecular weight of the resulting anionic polymer 9 was 8,600.

[0068] Production Example 10 (Production of Anionic Polymer 10) A 1L four-neck separable flask was charged with 450.0 g of toluene, 224.0 g of diisobutylene (Fujifilm Wako Pure Chemical Industries, Ltd.), 198.0 g of maleic anhydride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 13.3 g of benzoyl peroxide (polymerization initiator: Tokyo Chemical Industry Co., Ltd.), and equipped with a reflux condenser, thermometer, and stirrer. After purging the reaction system with nitrogen, the temperature was raised to 83°C while stirring, and the reaction was allowed to proceed for 240 minutes while maintaining the temperature. The mixture was then transferred to a Teflon (registered trademark)-coated tray and dried under reduced pressure at 100°C for 5 hours. The weight-average molecular weight of the resulting polymer was 28,600. A 1L four-neck separable flask was charged with 136.0 g of methyl isobutyl ketone and 24.8 g of the solid obtained above (containing 0.12 mol of components derived from maleic anhydride). The reaction system was purged with nitrogen, and then the mixture was dissolved at room temperature for 2 hours with stirring. The mixture was then heated to 72°C with stirring, and 32.0 g (0.12 mol) of stearylamine (Kao Corporation, trade name: Farmin 80) pre-melted at 80°C was added. The mixture was stirred at 72°C for 120 minutes to carry out amidation, and then cooled to room temperature. The solids concentration of the resulting polymer solution was 30.1%. 10.0 g of the resulting polymer solution was weighed into a glass Petri dish and dried under reduced pressure at 100°C for 5 hours to obtain anionic polymer 10. The resulting anionic polymer 10 was insoluble in the eluent for GPC, and therefore the weight average molecular weight was calculated using the above GPC measurement values ​​to be 67,400.

[0069] Production Example 11 (Production of Anionic Polymer 11) A 1L four-neck separable flask was charged with 8.5g of 2-ethylhexyl methacrylate, 1.5g of methacrylic acid, 0.13g of mercaptopropanediol, and 22.1g of a toluene / ethanol mixture (50 / 50 by mass), and was equipped with two dropping funnels, a reflux condenser, a thermometer, and a stirrer. After the reaction system was purged with nitrogen, the temperature was raised to 80°C with stirring, and a mixed solution of 0.12g of the above polymerization initiator and 5.9g of the toluene / ethanol mixture (50 / 50 by mass) was added, and the resulting initial mixture was stirred for 10 minutes. Next, while maintaining the temperature, a mixed solution of 76.5 g of 2-ethylhexyl methacrylate, 13.5 g of methacrylic acid, 1.2 g of mercaptopropanediol, and 19.2 g of a toluene / ethanol mixture (50 / 50 by mass), and a mixed solution of 0.11 g of the above polymerization initiator and 52.8 g of a toluene / ethanol mixture (50 / 50 by mass), were separately added dropwise over 120 minutes. After the addition was completed, the mixture was stirred at 80°C for 120 minutes and then cooled to room temperature. 10.0 g of the resulting polymer solution was weighed into a glass Petri dish and dried under reduced pressure at 100°C for 5 hours to obtain anionic polymer 11. The weight average molecular weight of the resulting anionic polymer 11 was 10,400.

[0070] Production Example 12 (Production of Anionic Polymer 12) Anionic polymer 12 was obtained in the same manner as in Production Example 11, except that 2-ethylhexyl methacrylate was changed to 2-ethylhexyloxypolyethylene glycol polypropylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer 50POEP-800B, with an average of 8 moles of EO added and an average of 7 moles of PO added), the solvent was changed to ethanol, and the amounts of each component were changed to those shown in Table 1. The weight average molecular weight of the resulting anionic polymer 12 was 7,700.

[0071] Production Example 13 (Production of Anionic Polymer 13) To 10.0 g of the polymer solution produced in Production Example 12 (solid content: 4.0 g, content of structural units derived from methacrylic acid: 15%), 2.00 g of 4N sodium hydroxide solution was added and stirred to neutralize the carboxyl groups in anionic polymer 12. The resulting polymer solution was dried under reduced pressure at 80°C to obtain anionic polymer 13 (a 100% neutralized form of anionic polymer 12).

[0072] Production Example 14 (Production of Anionic Polymer 14) Anionic polymer 14 was obtained in the same manner as in Production Example 11, except that 2-ethylhexyl methacrylate was changed to 2-ethylhexyloxypolyethylene glycol polypropylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer 50POEP-800B, with an average of 8 moles of EO and 7 moles of PO added), the solvent was changed to ethanol, and the amounts of each component were changed to those shown in Table 1. The weight average molecular weight of the resulting anionic polymer 14 was 8,700.

[0073] Production Example 15 (Production of Anionic Polymer 15) Anionic polymer 15 was obtained in the same manner as in Production Example 11, except that 2-ethylhexyl methacrylate was changed to lauroxy polyethylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer PLE200, with an average of 4 moles of EO added) and the amounts of each component were changed to those shown in Table 1. The weight average molecular weight of the resulting anionic polymer 15 was 16,400.

[0074] Production Example 16 (Production of Anionic Polymer 16) Anionic polymer 16 was obtained in the same manner as in Production Example 11, except that 2-ethylhexyl methacrylate was changed to 2-ethylhexyloxypolyethylene glycol polypropylene glycol methacrylate (manufactured by NOF Corporation, trade name: Blemmer 50POEP-800B, with an average of 8 moles of EO and 7 moles of PO added), the solvent was changed to ethanol, and the amounts of each component were changed to those shown in Table 1. The weight average molecular weight of the resulting anionic polymer 16 was 27,100.

[0075] Production Example 17 (Production of Anionic Polymer 17) Anionic polymer 17 was obtained in the same manner as in Production Example 6, except that stearyl acrylate was changed to lauryl methacrylate, the solvent was changed to a toluene / ethanol mixed liquid (mass ratio 50 / 50), and the amounts of each component were changed to those shown in Table 1. The weight average molecular weight of the resulting anionic polymer 17 was 17,400.

[0076] Production Example 18 (Production of Anionic Polymer 18) Anionic polymer 18 was obtained in the same manner as in Production Example 6, except that stearyl acrylate was changed to lauryl methacrylate and the amounts of each component were changed as shown in Table 1. The resulting anionic polymer 18 had a weight average molecular weight of 15,200.

[0077] [Table 1] Table 2 shows the raw material monomers used in Production Examples 1 to 18, as well as the weight average molecular weights, acid values, and degrees of neutralization of the produced anionic polymers 1 to 18.

[0078] [Table 2-1] [Table 2-2] *1: This refers to methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: NK Ester TM-230G, with an average of 23 moles of EO added). *2: This refers to methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: NK Ester TM-450G, with an average of 45 moles of EO added). *3: 2-ethylhexyl methacrylate. *4: Lauroxy polyethylene glycol methacrylate (manufactured by NOF Corporation, product name: Blenmar PLE200). *5: 2-ethylhexyloxypolypropylene glycol polyethylene glycol methacrylate (manufactured by NOF Corporation, product name: Blemmer 50POEP-800B).

[0079] [Production of halogen-based resin composition for slurry viscosity measurement] Example 1-1 0.2 g of anionic polymer 2 (0.5% concentration relative to the mass of calcium carbonate) and 55.0 g of plasticizer (bis(2-ethylhexyl) phthalate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed for 3 minutes at 300 rpm using a magnetic stirrer. The resulting mixture and 40.0 g of calcium carbonate (Whiten H, manufactured by Shiraishi Calcium Co., Ltd.) were placed in a 500 mL plastic cup and mixed at 5,000 rpm using a laboratory mixer. 40.0 g of vinyl chloride resin (average degree of polymerization: 800, manufactured by Kaneka Corporation, product name: PSL-675) was added to the resulting mixture of anionic polymer 2, plasticizer, and calcium carbonate and mixed uniformly with a spatula. The mixture was then mixed at 5,000 rpm using a laboratory mixer for 3 minutes. The mixture was then allowed to stand at room temperature under reduced pressure for 10 minutes and degassed to obtain a halogen-based resin composition. The slurry viscosity of the halogen-based resin composition at 25°C was 14 Pa·s.

[0080] Examples 1-2 to 1-6 Halogen-based resin compositions were produced in the same manner as in Example 1-1, except that the concentrations of the anionic polymer and the anionic polymer relative to calcium carbonate were changed as shown in Table 3. The slurry viscosities of the halogen-based resin compositions at 25°C are shown in Table 3.

[0081] Examples 1-7 An ethanol solution of anionic polymer 9 was prepared using the same method as in Preparation Example 9, except that vacuum drying was not performed. 0.33 g of anionic polymer 9 solution (solids concentration 61.3%, equivalent to 0.5% anionic polymer by mass relative to calcium carbonate) and 55.0 g of plasticizer (bis(2-ethylhexyl) phthalate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a 1 L four-neck flask. The mixture was stirred at 200 rpm while nitrogen gas was blown in. The pressure was reduced to 160 °C and 6 torr or less for 1 hour to remove the solvent. The resulting mixture, 40.0 g of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: Whiten H), and 40.0 g of polyvinyl chloride resin (average degree of polymerization 800, manufactured by Kaneka Corporation, product name: PSL-675) were placed in a 500 mL plastic cup, in this order, and mixed uniformly with a spatula. The mixture was then mixed in a laboratory mixer at 5,000 rpm for 3 minutes. The mixture was then left to stand at room temperature under reduced pressure for 10 minutes to degas, yielding a halogen-based resin composition. The slurry viscosity of the halogen-based resin composition at 25°C was 12 Pa·s. The results are shown in Table 3.

[0082] Examples 1-8 An ethanol mixed solution of anionic polymer 12 was produced in the same manner as in Production Example 12, except that drying under reduced pressure was not performed. A halogen-based resin composition was produced in the same manner as in Example 1-7, except that the solution of anionic polymer 9 was changed to 0.50 g of a solution of anionic polymer 12 (solids concentration 40.4%, equivalent to a concentration of anionic polymer of 0.5% relative to the mass of calcium carbonate). The slurry viscosity of the halogen-based resin composition at 25°C was 13 Pa s. The results are shown in Table 3.

[0083] Examples 1-9 A toluene / ethanol mixed solution of anionic polymer 15 was produced in the same manner as in Production Example 15, except that drying under reduced pressure was not performed. A halogen-based resin composition was produced in the same manner as in Example 1-7, except that the amount of anionic polymer 15 solution was changed to 0.33 g (solids concentration 59.9%, equivalent to a concentration of anionic polymer of 0.5% relative to the mass of calcium carbonate). The slurry viscosity of the halogen-based resin composition at 25°C was 14 Pa s. The results are shown in Table 3.

[0084] Comparative Example 1-1 A halogen-based resin composition was produced in the same manner as in Example 1-1, except for not using anionic polymer 2. The slurry viscosity of the halogen-based resin composition at 25°C was 36 Pa·s.

[0085] Comparative Examples 1-2 to 1-4 Halogen-based resin compositions were produced in the same manner as in Example 1-1, except that anionic polymer 2 was changed to a surfactant (manufactured by Kao Corporation, trade name: Excel S-95, glycerin monostearyl) and the concentration relative to calcium carbonate was changed as shown in Table 3. The slurry viscosity of the halogen-based resin composition at 25°C is shown in Table 3.

[0086] [Table 3]

[0087] [Production of halogen-based resin composition for measuring bleed-out rate] Example 2-1 (Production of halogen-based resin composition) 0.1 g of anionic polymer 2 (0.5% concentration relative to the mass of calcium carbonate) and 60 g of plasticizer (bis(2-ethylhexyl) phthalate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed for 3 minutes at 300 rpm using a magnetic stirrer. The resulting mixture and 20 g of calcium carbonate (Whiten H, manufactured by Shiraishi Calcium Co., Ltd.) were mixed for 3 minutes at 5000 rpm using a laboratory mixer. The resulting mixture of anionic polymer 2, plasticizer, and calcium carbonate was mixed with 100 g of vinyl chloride resin (average degree of polymerization: 1400, manufactured by Shin-Dai-Ichi Vinyl Corporation, product name: ZEST1400), 2 g of a Ca / Mg / Zn-based vinyl chloride resin stabilizer (ADEKA Corporation, product name: Adeka Stab RUP-103), and 0.5 g of a lubricant (Kao Corporation, product name: Lunac S-70V) using a stirring rod at room temperature. Thereafter, the mixture was mixed using a 4-inch open roll kneader (manufactured by Nishimura Machinery Co., Ltd.) at a rotation speed of 17.5 rpm at 160° C. to gel, and mixing was continued for 10 minutes after gelation to obtain a halogen-based resin composition. (Molded sheet manufacturing) The halogen-based resin composition obtained above was pressed at 175°C and a pressure of 0.5 MPa for 5 minutes, then at 20 MPa for 2 minutes, and again at 15°C and a pressure of 0.5 MPa for 2 minutes to obtain a 0.8 mm thick molded resin sheet. No bleeding of anionic polymer 2 was detected from the obtained molded resin sheet. The results are shown in Table 4.

[0088] Examples 2-2 to 2-6 Molded sheets of halogen-based resin compositions were obtained in the same manner as in Example 2-1, except that the anionic polymer and the concentration of the anionic polymer relative to calcium carbonate were changed as shown in Table 4. No bleeding of the anionic polymer from the obtained molded resin sheet was detected. The results are shown in Table 4.

[0089] Comparative Examples 2-1 to 2-3 A resin molded sheet was produced in the same manner as in Example 2-1, except that anionic polymer 2 was replaced with a surfactant (manufactured by Kao Corporation, trade name: Excel S-95, glycerin monostearyl) and the concentration relative to calcium carbonate was changed as shown in Table 4. The bleed-out rate of the surfactant was calculated. The results are shown in Table 4.

[0090] [Table 4]

[0091] As shown in Table 3, the results of Examples 1-1 to 1-9 and Comparative Example 1-1 show that the use of an anionic polymer reduces the slurry viscosity of the halogen-based resin composition, improving processability. Furthermore, as shown in Tables 3 and 4, the results of Examples 1-1 to 1-9 and 2-1 to 2-6 and Comparative Examples 1-2 to 1-4 and 2-1 to 2-3 indicate that surfactants such as glycerin monostearyl, which do not have an anionic group, reduce the slurry viscosity of the halogen-based resin composition to some extent, but do not reduce the slurry viscosity sufficiently to improve processability. Furthermore, it was found that when the concentration of glycerin monostearyl relative to calcium carbonate exceeds a certain level, glycerin monostearyl bleeds out from the halogen-based resin composition. This is thought to be due to the insufficient adsorption of glycerin monostearyl to calcium carbonate, which is a basic inorganic filler. The results of Examples 1-4 and 1-8 show that the slurry viscosity of the halogen-based resin composition is almost the same whether step 1 is followed by steps 2 and 3 in sequence or step 1 is followed by steps 2 and 3 simultaneously. Furthermore, from the results of Examples 1-1, 1-2, and 1-6, it was found that even when a neutralized anionic polymer was used, the slurry viscosity of the halogen-based resin was reduced by producing a halogen-based resin composition by sequential addition. From this, it is considered that the method for producing a halogen-based resin composition by sequential addition makes it possible to use both unneutralized anionic polymers and neutralized anionic polymers, and to produce a halogen-based resin composition using a wider variety of anionic polymers. Furthermore, as shown in Examples 1-1 to 1-6, according to the production method of the present invention, calcium carbonate as a basic inorganic filler is added to a mixture of a plasticizer and an anionic polymer, thereby rendering the surface of the basic inorganic filler uniformly hydrophobic, and then a halogen-based resin is added, thereby enabling the production of a halogen-based resin composition in a short process. In the example of Patent Document 2, the slurry is dried at 105°C for 24 hours to obtain calcium carbonate powder coated with an anionic polymer. In contrast, the production method of the present invention, compared to the production method described in Patent Document 2, has high production efficiency because it does not require the basic inorganic filler to be made into an aqueous dispersion to cause precipitation with the neutralized surfactant, and it does not require filtering and drying the aqueous dispersion of the basic inorganic filler to produce a halogen-based resin composition.

[0092] [Measurement of Slurry Viscosity of Mixture] Example 3-1 0.4 g of anionic polymer 1 (0.5% concentration relative to the mass of calcium carbonate) and 40.0 g of plasticizer were mixed for 3 minutes at 300 rpm using a magnetic stirrer. The resulting mixture was mixed with 85.0 g of calcium carbonate (Shiraishi Calcium Co., Ltd., product name: Whiten H) using a laboratory mixer at 5000 rpm for 3 minutes. The mixture was then left to stand at room temperature under reduced pressure for 10 minutes and degassed to obtain a mixture of anionic polymer 1, plasticizer, and calcium carbonate. The slurry viscosity of this mixture at 25°C was 9.0 Pa·s.

[0093] Examples 3-2 to 3-17 and Comparative Examples 3-1 to 3-3 Mixtures were prepared in the same manner as in Example 3-1, except that the type of anionic polymer or surfactant and its concentration relative to calcium carbonate were changed as shown in Table 5, and the slurry viscosity of the mixtures was measured at 25°C. The results are shown in Table 5.

[0094] Comparative Example 3-4 A mixture of a plasticizer and calcium carbonate was obtained in the same manner as in Example 3-1, except for not using anionic polymer 1. The slurry viscosity of the mixture at 25°C was 104.0 Pa·s.

[0095] [Table 5]

[0096] From the results of Examples 1-1 to 1-6 and Examples 3-1 to 3-17, it is considered that the processability of the halogen-based resin composition is improved when the slurry viscosity of the mixture of the anionic polymer, the plasticizer, and the basic inorganic filler is sufficiently low. Note that in Examples 3-1 to 3-17 and Comparative Examples 3-1 to 3-4, the amount of calcium carbonate blended relative to the plasticizer is high, and the slurry viscosity tends to be higher than in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4. Furthermore, the reason why the slurry viscosity of the mixture of plasticizer and calcium carbonate in Comparative Example 3-4 was significantly higher than that of the halogen-based resin composition in Comparative Example 1-1 is thought to be that the calcium carbonate content was high in the mixture in Comparative Example 3-4, causing the calcium carbonate to form a network, whereas the calcium carbonate content in the halogen-based resin composition in Comparative Example 1-1 was relatively low, preventing the formation of a calcium carbonate network to the extent that would significantly increase the slurry viscosity.

[0097] Measurement of Slurry Viscosity of Mixtures with Neutralized Anionic Polymers Examples 4-1 to 4-5 Mixtures were prepared in the same manner as in Example 3-1, except that the type of anionic polymer and its concentration relative to calcium carbonate were changed as shown in Table 6, and the slurry viscosity of the mixtures was measured at 25° C. The results are shown in Table 6.

[0098] Comparative Example 4-1 0.4 g of anionic polymer 3 (20% neutralized anionic polymer 1) (0.5% concentration relative to the mass of calcium carbonate), 40 g of plasticizer (bis(2-ethylhexyl) phthalate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 85 g of calcium carbonate (Whiten H, manufactured by Shiraishi Calcium Co., Ltd.) were placed in a 500 mL plastic cup and mixed uniformly with a spatula. The mixture was then mixed at 5,000 rpm for 3 minutes using a laboratory mixer. The mixture was then allowed to stand at room temperature under reduced pressure for 10 minutes and degassed to obtain a mixture of anionic polymer 3, plasticizer, and calcium carbonate. The slurry viscosity of this mixture at 25 °C was 52 Pa·s. The results are shown in Table 6.

[0099] Comparative Example 4-2 A mixture was prepared in the same manner as in Comparative Example 4-1, except that anionic polymer 3 was replaced with anionic polymer 5 (a 100% neutralized form of anionic polymer 1), to obtain a mixture of anionic polymer 5, a plasticizer, and calcium carbonate. The slurry viscosity of this mixture at 25°C was 119 Pa s. The results are shown in Table 6.

[0100] [Table 6]

[0101] The results of Examples 4-1 to 4-5 show that even when a neutralized anionic polymer is used, the sequential addition of the anionic polymer, plasticizer, and basic inorganic filler reduces the slurry viscosity of the mixture. Furthermore, from the results of Examples 4-1 to 4-5 and Comparative Examples 4-1 and 4-2, it was found that when a neutralized anionic polymer is used, the method for producing a halogen-based resin composition in which the polymer is added sequentially after step 1 reduces the slurry viscosity of the halogen-based resin composition more than the method for producing a halogen-based resin composition in which the polymer is added all at once.

[0102] [Measurement of Slurry Viscosity of Mixture] Example 5-1 A mixture was prepared in the same manner as in Example 3-11, except that the plasticizer was changed to trimellitate (tris(2-ethylhexyl) trimellitate, manufactured by Tokyo Chemical Industry Co., Ltd.), and the slurry viscosity of the mixture was measured at 25° C. The results are shown in Table 7.

[0103] Example 5-2 A mixture was prepared in the same manner as in Example 3-14, except that the plasticizer was changed to the trimellitate, and the slurry viscosity of the mixture was measured at 25° C. The results are shown in Table 7.

[0104] Comparative Example 5-1 A mixture was prepared in the same manner as in Comparative Example 3-1, except that the plasticizer was changed to the trimellitate, and the slurry viscosity of the mixture was measured at 25° C. The results are shown in Table 7.

[0105] [Table 7]

[0106] From the results of Examples 5-1 to 5-2 and Comparative Example 5-1, it was found that even when trimellitate was used as a plasticizer, the slurry viscosity of the mixture of the polymer dispersant, the plasticizer, and the basic inorganic filler could be reduced, and the processability of the halogen-based resin composition was improved. The reason why the slurry viscosity of the mixtures of Examples 5-1 and 5-2 is higher than that of the mixtures of Examples 3-11 and 3-14 is thought to be because the viscosity of the plasticizer trimellitate is higher than that of bis(2-ethylhexyl) phthalate.

Claims

1. A method for producing a halogen-based resin composition, comprising the following steps 1 to 3, with step 1 being carried out first. Step 1: A step of mixing an anionic polymer and a plasticizer Step 2: A step of further mixing a basic inorganic filler Step 3: A step of further mixing a halogen-based resin

2. The method for producing a halogen-based resin composition according to claim 1, wherein the steps 1 to 3 are carried out sequentially.

3. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein the anionic polymer has a carboxyl group.

4. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein the weight average molecular weight of the anionic polymer is 4,000 or more and 200,000 or less.

5. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein the mass ratio of the anionic polymer to the content of the basic inorganic filler after mixing (anionic polymer / basic inorganic filler) is 0.0001 or more and 10 or less.

6. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein the basic inorganic filler contains calcium carbonate.

7. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein the halogen-based resin contains one or more selected from the group consisting of vinyl chloride resin, vinylidene chloride resin, and chloroprene rubber.

8. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein the mass ratio of the anionic polymer to the content of the basic inorganic filler (anionic polymer / basic inorganic filler) is 0.0001 or more and 10 or less.

9. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein the blending amount of the plasticizer in the halogen-based resin composition is 10 parts by mass or more and 170 parts by mass or less with respect to 100 parts by mass of the halogen-based resin.

10. The mixing amount of the basic inorganic filler is 1 part by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the halogen-based resin, the method for producing a halogen-based resin composition according to Claim 1 or 2.

11. The content of the anionic polymer in the halogen-based resin composition is 0.001% by mass or more and 1.0% by mass or less, the method for producing a halogen-based resin composition according to Claim 1 or 2.

12. The anionic polymer contains a structural unit derived from an α,β-unsaturated carboxylic acid, the method for producing a halogen-based resin composition according to Claim 1 or 2.

13. The content of the structural unit derived from an α,β-unsaturated carboxylic acid in the anionic polymer is 1% by mass or more and 50% by mass or less, the method for producing a halogen-based resin composition according to Claim 12.

14. The anionic polymer contains one or more structural units selected from a structural unit derived from an ester of an α,β-unsaturated carboxylic acid, a structural unit derived from an amide of an α,β-unsaturated carboxylic acid, a structural unit derived from a styrenic compound, and a structural unit derived from a linear or branched alkene having 3 to 10 carbon atoms, the method for producing a halogen-based resin composition according to Claim 1 or 2.

15. The weight average molecular weight of the anionic polymer is 5,000 or more and 20,000 or less, the method for producing a halogen-based resin composition according to Claim 1 or 2.