Method for producing halogen-based resin compositions

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] This invention relates to a method for producing halogen-based resin compositions. [Background technology]

[0002] Halogenated resins such as polyvinyl chloride (PVC) are important general-purpose polymers used in a wide range of fields. For example, PVC is used in various applications such as interior furnishings like wallpaper, general-purpose products like toys, and automotive materials such as sealants. When using halogen-based resins, for example, a halogen-based resin composition is prepared by blending a halogen-based resin powder with plasticizers, diluents, viscosity reducers, fillers such as calcium carbonate, pigments, flame retardants, foaming agents, stabilizers, etc. However, halogen-based resin compositions are often highly viscous, making processing difficult or impossible.

[0003] Conventionally, methods for reducing the viscosity of halogenated resin compositions have involved using hydrocarbon solvents such as mineral spirits, alkylbenzenes, and paraffins, as well as anionic surfactants, polyoxyethylene alkylphenol ethers, polyethylene glycol, and glycerin alkyl esters, as diluents or viscosity reducers. These diluents and viscosity reducers are added after the manufacture of halogenated resins or when preparing halogenated resin compositions, but their viscosity reduction effect is not sufficient, and viscosity reduction is particularly inadequate when fillers such as calcium carbonate are included.

[0004] Patent Document 1 discloses a resin composition containing, in addition to a vinyl chloride resin, a specific amount of one or more additives selected from the group consisting of esters made of fatty acids and aliphatic alcohols and (poly)alkylene glycol mono or dialkyl ethers, one or more additives selected from the group consisting of polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl ether carboxylates, a plasticizer, and a filler. Furthermore, Patent Document 2 discloses a method for producing a resin composition in which a surfactant characterized by a plurality of addition polymer chains, an average of at least 0.5 adsorbent or chemisorbent groups per chain, at least one polyether residue, and at least one divalent polyether residue between chains is adsorbed onto an inorganic solid in water, then filtered and dried to produce a dispersible inorganic solid, and further redispersed in a mixture of a plasticizer and a PVC resin. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2001-335696 [Patent Document 2] Special Publication No. 7-504846 [Overview of the project] [Problems that the invention aims to solve]

[0006] The resin composition described in Patent Document 1 has the problem that, because the additive is adsorbed and desorbed from the filler, a large amount of additive is required to reduce the viscosity of the resin composition, and the additive bleeds out of the molded resin product after molding. Furthermore, the manufacturing method described in Patent Document 2 required a complicated process in which the anionic polymer was neutralized with an alkali to dissolve it in water, the neutralized anionic polymer was brought into contact with an inorganic solid, the water was removed by filtration and drying to obtain an anionic polymer-adsorbed inorganic solid, and then mixed with PVC resin and a plasticizer. The present invention relates to a method for producing a halogen-based resin composition in which processability is improved by reducing the slurry viscosity during the production of the halogen-based resin composition. [Means for solving the problem]

[0007] The inventors have found that the above problem can be solved by mixing an anionic polymer and a plasticizer in a simple manner without the use of water, and further mixing a basic inorganic filler with a halogen-based resin. In other words, the present invention relates to a method for producing a halogen-based resin composition comprising the following steps 1 to 3, wherein step 1 is performed first. Step 1: Mixing the anionic polymer with the plasticizer. Step 2: Further mixing in basic inorganic fillers. Step 3: Further mixing in halogen-based resin. [Effects of the Invention]

[0008] According to the present invention, a method for producing a halogen-based resin composition is provided in which processability is improved by reducing the slurry viscosity during the production of the halogen-based resin composition. [Modes for carrying out the invention]

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

[0010] From the viewpoint of improving manufacturing efficiency, in step 1, the water content is preferably 1% by mass or less relative to the anionic polymer, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and even more preferably substantially water-free. From the viewpoint of improving manufacturing efficiency, in step 2, the water content is preferably 1% by mass or less relative to the basic inorganic filler, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and even more preferably substantially water-free. From the viewpoint of improving manufacturing efficiency, it is preferable that steps 1, 2, and 3 do not include the operation of removing water. From the viewpoint of improving manufacturing efficiency, the anionic polymer can also be mixed with the plasticizer in step 1 while dissolved in an organic solvent. If an organic solvent is present, it is preferable to remove the organic solvent at one of the following points: after step 1, after step 2, or after step 3.

[0011] According to the present invention, a method for producing a halogen-based resin composition is provided in which processability is improved by reducing the slurry viscosity during the production of the halogen-based resin composition. The reason for this effect is not entirely clear, but it is thought to be as follows. In halogenated resin compositions containing plasticizers, basic inorganic fillers are hydrophilic and therefore stabilized by aggregating and forming a network within the plasticizer. However, the aggregated and networked basic inorganic fillers thicken the halogenated resin composition. Therefore, it is thought that by adsorbing anionic polymers onto the surface of basic inorganic fillers and making the surface of the basic inorganic fillers hydrophobic, aggregation and network formation of the basic inorganic fillers 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 are adsorbed at multiple points onto the surface of basic inorganic fillers, so desorption does not occur, and if they are adsorbed unevenly onto the surface of the basic inorganic fillers, it is difficult to ensure uniform distribution. Furthermore, if high-molecular-weight anionic polymers are adsorbed unevenly onto the surface of basic inorganic fillers, the basic inorganic fillers still aggregate and form networks, thereby increasing the viscosity of the halogen-based resin composition. In the method for producing the halogen-based resin composition of the present invention, the anionic polymer is uniformly dissolved and dispersed in the plasticizer by mixing the anionic polymer and the plasticizer in step 1, and the anionic polymer is uniformly acted upon the surface of the basic inorganic filler by mixing the basic inorganic filler, the anionic polymer, and the plasticizer in step 2. 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, which more strongly suppresses aggregation and network formation of the basic inorganic filler, and reduces the viscosity of the slurry obtained in step 2. Furthermore, when the halogen-based resin is mixed in step 3, it is believed that aggregation and network formation of the basic inorganic filler in the resin composition are more strongly suppressed, and the processability is improved by reducing the viscosity of the slurry of the halogen-based resin composition.

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

[0013] When mixing each component sequentially, the mixing in step 1 may be performed using a magnetic stirrer or a lab mixer, and the mixing in steps 2 and 3 may be performed using an agitator or kneader. Examples of agitators include lab mixers, mortar mixers, Henschel mixers, Banbury mixers, and ribbon blenders, while examples of kneaders include conical twin-screw extruders, parallel twin-screw extruders, single-screw extruders, cone-type kneaders, and roll kneaders. In Step 1, the mixing conditions are preferably 150 rpm or more, more preferably 200 rpm or more, still more preferably 250 rpm or more, from the viewpoint of sufficiently mixing the anionic polymer and the plasticizer, and preferably 4,500 rpm or less, more preferably 4,000 rpm or less, still more preferably 3,500 rpm or less, from the viewpoint of suppressing temperature rise. The mixing time in Step 1 is preferably 1 minute 30 seconds or more, more preferably 2 minutes or more, still more preferably 2 minutes 30 seconds or more, from the viewpoint of sufficiently mixing the anionic polymer and the plasticizer, and preferably 5 minutes or less, more preferably 4 minutes or less, still more preferably 3 minutes 30 seconds or less, from the viewpoint of improving production efficiency. Also, in Step 1, the anionic polymer dissolved in an organic solvent may be mixed with the plasticizer. In this case, the mixing conditions are preferably 100 rpm or more, more preferably 150 rpm or more, still more preferably 180 rpm or more, from the viewpoint of sufficiently mixing the anionic polymer and the plasticizer, and preferably 4,500 rpm or less, more preferably 4,000 rpm or less, still more preferably 3,500 rpm or less, from the viewpoint of suppressing temperature rise. The organic solvent is preferably removed simultaneously with or after mixing, and from the viewpoint of production efficiency, it is preferably removed simultaneously with mixing. When the organic solvent is removed simultaneously with mixing, the mixing time is preferably 10 minutes or more, more preferably 30 minutes or more, still more preferably 45 minutes or more, and preferably 3 hours or less, more preferably 2 hours or less, still more preferably 1 hour 30 minutes or less. The removal of the organic solvent is preferably carried out by heating, and the heating temperature is preferably 120°C or more, more preferably 140°C or more, still more preferably 150°C or more, and preferably 200°C or less, more preferably 180°C or less, still more preferably 170°C or less.

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

[0015] When Step 2 is carried out after Step 1, the slurry viscosity at 25°C of the mixture of the anionic polymer, the plasticizer, and the basic inorganic filler after the completion of Step 2 is preferably 60 Pa·s or lower, more preferably 30 Pa·s or lower, and still more preferably 10 Pa·s or lower, 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 the production efficiency. The method for measuring the slurry viscosity is measured by the method shown in the examples.

[0016] The mixing conditions in Step 3 may be any conditions used in a normal production method of a halogen-based resin composition. By carrying out the mixing in Step 3 using a stirrer, a mixed powder of the halogen-based resin composition can be obtained. Further, by melt-molding the mixing in Step 3 using a kneader, a mixed powder, pellet-shaped, or paste-shaped halogen-based resin composition can be obtained.

[0017] When Steps 1, 2, and 3 are sequentially carried out 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 the completion of Step 3 is preferably 23 Pa·s or lower, more preferably 20 Pa·s or lower, and still more preferably 17 Pa·s or lower, from the viewpoint of improving the processability of the halogen-based resin composition produced by the production method of the present invention.

[0018] [Anionic polymers] In the present invention, an anionic polymer is a polymer having one or more anionic groups in its molecule. Examples of anionic groups from the viewpoint of their ease of adsorption to basic inorganic fillers include carboxyl groups, sulfonic acid groups, sulfinic acid groups, sulfate groups, sulfite groups, phosphoric acid groups, and phosphite groups. Preferably, the polymer has carboxyl groups and sulfonic acid groups, and more preferably, it has carboxyl groups.

[0019] The anionic polymer is preferably a polymer that contains structural units having anionic groups and structural units having hydrophobic groups. Examples of structural units having anionic groups 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 compounds substituted with the above-mentioned anionic groups, from the viewpoint of ease of dissolution or dispersion in plasticizers. Preferably, the structural units are derived from α,β-unsaturated carboxylic acids, more preferably from (meth)acrylic acid, and even more preferably from methacrylic acid. 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. Examples of constituent units having hydrophobic groups include those derived from esters of α,β-unsaturated carboxylic acids, amides of α,β-unsaturated carboxylic acids, styrene compounds, and linear or branched alkenes having 3 to 10 carbon atoms, from the viewpoint of ease of dissolution or dispersion in plasticizers. Preferably, these are esters of α,β-unsaturated carboxylic acids, amides of α,β-unsaturated carboxylic acids, and linear or branched alkenes, and more preferably esters of α,β-unsaturated carboxylic acids. Furthermore, if the ester of an α,β-unsaturated carboxylic acid and the amide of an α,β-unsaturated carboxylic acid are, respectively, esters and amides of polycarboxylic acids and have at least one carboxyl group, then the ester and amide of the polycarboxylic acid shall constitute both a structural unit having an anionic group and a structural unit having a hydrophobic group.

[0020] Examples of esters of α,β-unsaturated carboxylic acids that are readily available include esters of α,β-unsaturated carboxylic acids with 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 preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less. As the ester of the α,β-unsaturated carboxylic acid with a linear or branched alkyl alcohol, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate are preferred from the viewpoint of improving manufacturing efficiency by increasing the solubility of the anionic polymer in the plasticizer and improving processability by reducing the slurry viscosity of the halogenated resin composition. Furthermore, the ester of the α,β-unsaturated carboxylic acid may be an ester of a polyalkylene glycol having a medium-chain or long-chain alkyl group at one end and a repeating number of 1 to 40 or less, from the viewpoint of further improving solubility with plasticizers. From the viewpoint of improving compatibility with plasticizers, the number of carbon atoms in the medium-chain or long-chain alkyl group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 24 or less, more preferably 18 or less, and even more preferably 16 or less. As the ester of the polyalkylene glycol with the 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 viewpoint of improving manufacturing efficiency by increasing the solubility of the anionic polymer in the plasticizer and improving processability by reducing the slurry viscosity of the halogenated 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, from the viewpoint of ease of introduction into the molecule. From the viewpoint of improving compatibility with plasticizers, the number of carbon atoms in the linear or branched primary alkylamine is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0022] Examples of styrene-based compounds that are readily available include styrene and α-methylstyrene. Examples of linear or branched alkenes having 3 to 10 carbon atoms include isoprene, butadiene, isobutylene, and diisobutylene, from the viewpoint of easy copolymerization with maleic anhydride.

[0023] Among the above-mentioned hydrophobic structural units, structural units derived from one or more selected from stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearoxy polyethylene glycol mono (meth)acrylate, lauroxy polyethylene glycol (meth)acrylate, 2-ethylhexyloxy polypropylene glycol polyethylene glycol (meth)acrylate, and diisobutylene are preferred because they allow for improved manufacturing efficiency due to the solubility of the anionic polymer in the plasticizer and improved processability due to the reduction in slurry viscosity of the halogenated resin composition.

[0024] Anionic polymers may contain hydrophilic units from the viewpoint of adjusting the hydrophilic-hydrophobic balance. However, in the present invention, hydrophilic units do not include anionic units. Examples of hydrophilic units include (meth)acrylamide, dimethyl(meth)acrylamide, units derived from acrylonitrile, and units derived from α,β-unsaturated carboxylate alkyloxypolyalkylene glycol esters. The anionic polymer preferably contains constituent units derived from α,β-unsaturated alkyloxypolyalkylene glycol esters, more preferably from α,β-unsaturated alkyloxypolyethylene glycol and / or polypropylene glycol esters, and even more preferably from α,β-unsaturated alkyloxypolyethylene glycol esters, from the viewpoint of ease of designing the hydrophilic-hydrophobic balance. The number of repeating alkylene glycol portions in the constituent units derived from α,β-unsaturated carboxylate alkyloxypolyalkylene glycol esters is preferably 2 or more, more preferably 4 or more, even more preferably 9 or more, and preferably 60 or less, more preferably 55 or less, and even more preferably 45 or less, from the viewpoint of adsorption onto the basic inorganic filler and reduction of the slurry viscosity of the halogen-based resin composition. As the constituent unit derived from the α,β-unsaturated carboxylate alkyloxypolyalkylene glycol ester, methoxypolyethylene glycol mono(meth)acrylate is preferred from the viewpoint of adsorption onto the basic inorganic filler and improvement of processability by reducing the slurry viscosity of the halogen-based resin composition.

[0025] The content of constituent units derived from α,β-unsaturated carboxylic acids in the anionic polymer is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of adsorption to the basic inorganic filler and reduction of the slurry viscosity of the halogen-based resin composition, when the total constituent units are considered to be 100% by mass. From the viewpoint of improving compatibility with plasticizers, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 20% by mass or less. The content of hydrophobic constituent units is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 13% by mass or more, when the total constituent units are considered to be 100% by mass, from the viewpoint of improving compatibility with plasticizers, and 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 hindering 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 desorption with the basic inorganic filler, and from the viewpoint of efficiently adsorbing to the basic inorganic filler, it is preferably 200,000 or less, more preferably 180,000 or less, even more preferably 170,000 or less, even more preferably 150,000 or less, even more preferably 120,000 or less, even more preferably 100,000 or less, even more preferably 70,000 or less, even more preferably 50,000 or less, even more preferably 30,000 or less, and even more preferably 20,000 or less. 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 mg KOH / g or more, more preferably 40 mg KOH / g or more, and even more preferably 45 mg KOH / g or more, from the viewpoint of adsorption to the basic inorganic filler and reduction of the slurry viscosity of the halogen-based resin composition, and from the viewpoint of improving compatibility with the plasticizer, it is preferably 150 mg KOH / g or less, more preferably 130 mg KOH / g or less, even more preferably 120 mg KOH / g or less, and even more preferably 100 mg KOH / g or less. The acid value of an anionic polymer can be calculated from the mass ratio of its constituent monomers. Alternatively, it can be determined by titrating the anionic polymer after dissolving or swelling it in a suitable organic solvent (e.g., methyl ethyl ketone).

[0028] The anionic polymer may be neutralized to increase the degree of freedom in molecular design. By sequentially performing steps 1 to 3, the halogen-based resin composition can be manufactured, and 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 manufactured by mixing a neutralized anionic polymer, a plasticizer, a basic inorganic filler, and a halogen-based resin all at once is greater than the slurry viscosity of a halogen-based resin composition manufactured by the manufacturing 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 halogen-based resin are mixed, making the surface of the basic inorganic filler more hydrophobic due to the anionic polymer compared to when they are added all at once. Here, the degree of neutralization is calculated by dividing the molar equivalent of the neutralizing agent by the molar amount of the anionic groups of the polymer.

[0029] The anionic polymer may be neutralized, but from the viewpoint of improving manufacturing efficiency by increasing solubility in plasticizers 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 be 0 mol%, i.e., unneutralized.

[0030] Examples of neutralizing agents for anionic polymers, from the standpoint of ease of availability, include alkali metal hydroxides, ammonia, and organic amines. 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 manufacturing 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 preferably 0.0001 or more, more preferably 0.0005 or more, even more preferably 0.001 or more, even more preferably 0.002 or more, and 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, and even more preferably 0.01 or less.

[0032] In the manufacturing method of the present invention, the amount of anionic polymer blended 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 polymers) Anionic polymers can be produced by copolymerizing monomers such as compounds having anionic groups, compounds having hydrophobic groups, and compounds having hydrophilic groups using known polymerization methods. From the viewpoint of being able to be produced using general-purpose equipment, solution polymerization is preferred as the polymerization method. The solvent used in solution polymerization is not limited as long as the monomer is soluble, but aromatic solvents such as toluene and xylene, and polar solvents such as aliphatic alcohols, ketones, ethers, and esters are preferred, with toluene, methanol, ethanol, acetone, and methyl ethyl ketone being more preferred, and toluene and ethanol being even more preferred. One type of solvent may be used alone, or two or more types of solvents may be used in mixture form. Polymerization initiators and chain transfer agents can be used during polymerization. As polymerization initiators, known radical polymerization initiators such as azo compounds like 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile), or organic peroxides like t-butylperoxyoctoate and benzoyl peroxide can be used, from the viewpoint of enabling stable polymerization below the boiling point of the above-mentioned solvent. The amount of 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. From the viewpoint of ease of adjusting molecular weight, known chain transfer agents such as octyl mercaptan, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, mercaptopropionic acid, mercaptans, thiuram disulfides, etc. can be used as chain transfer agents. Furthermore, there are no restrictions on the mode of polymerization chain of monomers; any polymerization mode such as random, block, or graft is acceptable.

[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, from the viewpoint of preventing gelation of the reaction system, the content of the crosslinking agent in the total monomer 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, and even more preferably 0.5 mol% or less.

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

[0036] [Halogen-based resins] In the present invention, halogenated resin means a monomer homopolymer, copolymer, or halogen-modified polymer containing a halogen. Specifically, from the viewpoint of ease of availability, this includes one or more selected from vinyl chloride resin, vinylidene chloride resin, chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, chloroprene rubber, etc. Preferably, the halogenated resin composition of the present invention contains one or more 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 copolymerizable monomers (hereinafter also referred to as "vinyl chloride copolymers"), and graft copolymers obtained by graft copolymerizing vinyl chloride with polymers other than said vinyl chloride copolymers. The monomers copolymerizable with vinyl chloride mentioned above can be any monomer having a reactive double bond in its molecule, from the viewpoint of ease of copolymerization. Examples 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; esters of (meth)acrylic acid 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. Furthermore, polymers other than vinyl chloride copolymers can be any polymer capable of graft copolymerization with vinyl chloride, and from the viewpoint of being readily available, 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 halogen-based resins mentioned above, from the viewpoint of flexibility and other factors, one or more selected from vinyl chloride resins such as vinyl chloride resin, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, polyurethane grafted polyvinyl chloride copolymer, vinylidene chloride resin, and chloroprene rubber are preferred, one or more selected from vinyl chloride resin, vinylidene chloride resin, and chloroprene rubber are more preferred, and vinyl chloride resin is even more preferred.

[0039] [Plasticizer] In the present invention, the plasticizer can be a compound that is commonly used as a plasticizer for halogen-based resins. From the viewpoint of high compatibility with halogen-based resins, such plasticizers include those with an SP value of preferably 7.5 or higher, more preferably 8 or higher, even more preferably 8.5 or higher, and preferably 11.5 or lower, more preferably 11 or lower, and even more preferably 10.5 or lower. Examples of plasticizers that have high compatibility with halogenated resins include dioctyl phthalate (DOP) and diisononyl phthalate (DINP), as well as phthalate esters of C1-C13 alcohols such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and diundecyl phthalate; trimellitic acid esters of C6-C10 alcohols such as tris(2-ethylhexyl) trimellitic acid, trioctyl trimellitic acid, and tridecyl trimellitic acid; and adipic acid esters, azelaic acid esters, sebatic acid esters, phosphate esters, polyesters, epoxys, fatty acid esters, and pyromellitic acid ester plasticizers. Plasticizers may be used individually or in mixtures of two or more types. From the viewpoint of high compatibility with halogenated resins, the plasticizer is preferably a phthalate or trimellitic ester of an alcohol having 1 to 20 carbon atoms, more preferably a phthalate or trimellitic ester of an alcohol having 5 to 18 carbon atoms, and even more preferably a phthalate or trimellitic ester of an alcohol having 8 to 13 carbon atoms.

[0040] The amount of plasticizer blended in the halogen-based resin composition in the manufacturing 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 halogen-based resin, from the viewpoint of exhibiting the plasticizing effect of the halogen-based resin composition, and 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 basic inorganic fillers used in the present invention include calcium carbonate, talc, calcium silicate, and alumina. A single basic inorganic filler may be used, or two or more may be used in combination. From an economic standpoint, the basic inorganic filler preferably contains calcium carbonate, and more preferably calcium carbonate.

[0042] The amount of basic inorganic filler blended in the manufacturing method of the present invention 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 preferably 150 parts by mass or less, more preferably 140 parts by mass or less, and even more preferably 130 parts by mass or less, from the viewpoint of reducing the cost of the halogen-based resin composition, per 100 parts by mass of halogen-based resin.

[0043] [Additives] In the manufacturing method of the present invention, additives such as stabilizers, processing aids, colorants, antioxidants, ultraviolet absorbers, antistatic agents, and lubricants may be added as needed, provided that the effects of the present invention are not impaired.

[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 dimethyl tin bis-2-ethylhexyl thioglycolate, dibutyl tin maleate, dibutyl tin bisbutyl maleate, and dibutyl tin dilaurate; and antimony mercaptide compounds. The amount of stabilizer added is 0.1 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0045] Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearate amide, ethylenebisstearate amide, butyl stearate, and calcium stearate. The amount of processing aid added is 0.1 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0046] Examples of colorants include carbon black, lead sulfide, white carbon, titanium white, lithopone, red iron oxide, antimony sulfide, chromium yellow, chromium green, cobalt blue, and molybdenum orange. The amount of colorant added is 1 to 100 parts by mass per 100 parts by mass of 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; sulfuric compounds such as alkyl disulfides, thiodipropionates, and benzothiazoles; 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 added is 0.2 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0048] Examples of UV absorbers 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 UV absorber to be blended is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0049] Examples of antistatic agents include anionic antistatic agents of the alkyl sulfonate, alkyl ether carboxylic acid, 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 and alkyldimethylbenzyl type, and organic acid salts or hydrochlorides of the alkylpyridinium type; and amphoteric antistatic agents such as alkyl betaine type and alkylimidazoline type. The amount of antistatic agent to be blended is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0050] Examples of lubricants include silicones, liquid paraffins, paraffin waxes, 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 amount of lubricant added is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0051] [Halogenated resin composition] The halogenated resin composition obtained by the manufacturing method of the present invention is a halogenated resin composition containing a plasticizer, an anionic polymer, a basic inorganic filler, and a halogenated resin, and is characterized by low slurry viscosity. From the viewpoint of achieving excellent processability, the slurry viscosity of the halogenated 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 manufacturing method of the present invention can be molded into a desired shape by known methods such as extrusion molding, injection molding, calendering, press molding, and blow molding. Furthermore, the paste-like halogen-based resin composition obtained by the manufacturing method of the present invention can be molded into a desired shape by known methods such as spread molding, dipping molding, gravure molding, and screen processing. The halogen-based resin composition produced by the manufacturing method of the present invention has excellent processability and is therefore useful as an adhesive, sealant, paint, plastisol, foam, synthetic leather, pipes such as water pipes, building materials, wallpaper, flooring, floor coverings, insulation materials, roofing membranes and other interior building materials; packaging materials such as food packaging films; agricultural materials such as agricultural films; automotive materials such as sealing materials and undercoat materials; substrate protection materials, fabric covering materials, wire covering 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 embodiments. <1> A method for producing a halogen-based resin composition, comprising the following steps 1 to 3, wherein step 1 is performed first. Step 1: Mixing the anionic polymer with the plasticizer. Step 2: Further mixing in basic inorganic fillers. Step 3: Further mixing in halogen-based resin. <2> Steps 1 to 3 described above are performed in order. <1> A method for producing the halogen-based resin composition described above. <3> The mixing conditions in step 1 are 250 rpm or more and 3,500 rpm or less, <1> , or the above <2> A method for producing the halogen-based resin composition described above. <4> The mixing time in step 1 is 2 minutes 30 seconds or more and 3 minutes 30 seconds or less. <1> ~ <3> A method for producing a halogen-based resin composition as described in any of the following. <5> The mixing conditions in step 2 are 3,000 rpm or more and 7,000 rpm or less, <1> ~ <4> A method for producing a halogen-based resin composition as described in any of the following. <6> The mixing time in step 2 is 2 minutes 30 seconds or more and 3 minutes 30 seconds or less. <1> ~ <5> A method for producing a halogen-based resin composition as described in any of the following. <7> The slurry viscosity of the mixture of the anionic polymer, the plasticizer, and the basic inorganic filler after step 2 at a temperature of 25°C is 10 Pa·s or less. <1> ~ <6> A method for producing a halogen-based resin composition as described in any of the following. <8> The slurry viscosity of the mixture of the anionic polymer, the plasticizer, the basic inorganic filler, and the halogen-based resin at a temperature of 25°C after the completion of step 3 is 17 Pa·s or less. <1> ~ <7> A method for producing a halogen-based resin composition as described in any of the following. <9> The anionic polymer contains a structural unit having an anionic group and a structural unit having a hydrophobic group, <1> ~ <8> A method for producing a halogen-based resin composition as described in any of the following. <10> The aforementioned structural unit having an anionic group is a structural unit having a carboxyl group. <9> A method for producing the halogen-based resin composition described above. <11> The aforementioned structural unit having a carboxyl group is a structural unit derived from (meth)acrylic acid. <10> A method for producing the halogen-based resin composition described above. <12> The hydrophobic constituent unit is one or more selected from constituent 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> A method for producing a halogen-based resin composition as described in any of the following. <13> The constituent units having an anionic group are derived from methacrylic acid, the constituent units having a hydrophobic group are derived from stearyl (meth)acrylate, the constituent units derived from methacrylic acid make up 5% to 20% by mass of the total constituent units in the anionic polymer, and the constituent units derived from stearyl (meth)acrylate make up 15% to 60% by mass of the total constituent units in the anionic polymer. <9> ~ <12> A method for producing a halogen-based resin composition as described in any of the following. <14> The constituent units having an anionic group are derived from methacrylic acid, the constituent units having a hydrophobic group are derived from lauryl methacrylate, the constituent units derived from methacrylic acid constitute 40% to 60% by mass of the total constituent units in the anionic polymer, and the constituent units derived from lauryl methacrylate constitute 15% to 60% by mass of the total constituent units in the anionic polymer. <9> ~ <12> A method for producing a halogen-based resin composition as described in any of the following. <15> The constituent units having an anionic group are derived from methacrylic acid, and the amount of methacrylic acid-derived constituent units in the anionic polymer is 5% by mass or more and 20% by mass or less, and the constituent units having a hydrophobic group are derived from 2-ethylhexyloxypropylene glycol polyethylene glycol methacrylate, and the amount of 2-ethylhexyloxypropylene glycol polyethylene glycol methacrylate-derived constituent units in the anionic polymer is 80% by mass or more and 95% by mass or less, <9> ~ <12> A method for producing a halogen-based resin composition as described in any of the following. <16> The constituent units having an anionic group are derived from methacrylic acid, and the amount of methacrylic acid-derived constituent units in the anionic polymer is 5% by mass or more and 20% by mass or less, and the constituent units having a hydrophobic group are derived from lauroxy polyethylene glycol monomethacrylate, and the amount of lauroxy polyethylene glycol monomethacrylate-derived constituent units in the anionic polymer is 80% by mass or more and 95% by mass or less, <9> ~ <12> A method for producing a halogen-based resin composition as described in any of the following. <17> The constituent units having an anionic group are derived from methacrylic acid, and the amount of methacrylic acid-derived constituent units in the anionic polymer is 10% by mass or more and 20% by mass or less, and the constituent units having a hydrophobic group are derived from 2-ethylhexyl methacrylate, and the amount of 2-ethylhexyl methacrylate-derived constituent units in the anionic polymer is 80% by mass or more and 90% by mass or less, <9> ~ <12> A method for producing a halogen-based resin composition as described in any of the following. <18> The weight-average molecular weight of the anionic polymer is 4,000 or more and 200,000 or less. <1> ~ <17> A method for producing a halogen-based resin composition as described in any of the following. <19> The weight-average molecular weight of the anionic polymer is 5,000 or more and 20,000 or less. <1> ~ <17> A method for producing a halogen-based resin composition as described in any of the following. <20> The anionic polymer is unneutralized, <1> ~ <19> A method for producing a halogen-based resin composition as described in any of the following. <21> The acid value of the anionic polymer is 45 mg KOH / g or more and 100 mg KOH / g or less. <1> ~ <20> A method for producing a halogen-based resin composition as described in any of the following. <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> A method for producing a halogen-based resin composition as described in any of the following. <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> A method for producing a halogen-based resin composition as described in any of the following. <24> The basic inorganic filler contains calcium carbonate, <1> ~ <23> A method for producing a halogen-based resin composition as described in any of the following. <25> The halogen-based resin is a vinyl chloride resin. <1> ~ <24> A method for producing a halogen-based resin composition as described in any of the following. <26> The plasticizer is a phthalate ester of an alcohol having 8 or more carbon atoms and 13 or fewer carbon atoms. <1> ~ <25> A method for producing a halogen-based resin composition as described in any of the following. <27> The amount of plasticizer in the halogen-based resin composition is 30 parts by mass or more and 150 parts by mass or less per 100 parts by mass of halogen-based resin. <1> ~ <26> A method for producing a halogen-based resin composition as described in any of the following. <28> The amount of basic inorganic filler in the halogen-based resin composition is 5 parts by mass or more and 130 parts by mass or less per 100 parts by mass of halogen-based resin. <1> ~ <27> A method for producing a halogen-based resin composition as described in any of the following. <29> The amount of anionic polymer in the halogen-based resin composition is 0.001% by mass or more and 1.0% by mass or less. <1> ~ <28> A method for producing a halogen-based resin composition as described in any of the following. [Examples]

[0054] In the following manufacturing examples, embodiments, and comparative examples, "parts" and "%" refer to "parts by mass" and "mass%" unless otherwise specified.

[0055] [measurement] [Method for measuring weight-average molecular weight] The weight-average molecular weight of the anionic polymer was measured using gel permeation chromatography (hereinafter also referred to as "GPC"). Specifically, the synthesized anionic polymer was diluted with N,N-dimethylformamide to prepare a sample solution with a solid content concentration of 0.3% by mass, and 100 μL of this solution was used for measurement. A solution prepared by dissolving phosphoric acid and lithium bromide in N,N-dimethylformamide at concentrations of 60 mmol / L and 50 mmol / L, respectively, was used as the eluent, and the sample was measured using GPC [instrument: Tosoh Corporation "HLC-8320GPC", detector: differential refractometer (attached to the instrument), column: Tosoh Corporation "TSK-GEL α-M" x 2, column temperature: 40°C, eluent flow rate: 1 mL / min]. As a standard material, polystyrene (manufactured by Tosoh Corporation: molecular weight 5.26 × 10⁻¹⁶) is used. 2 , 1.02 × 10 5 , 8.42×10 6 Nishio Kogyo Co., Ltd.: Molecular weight 4.0 × 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 production method of the present invention, or the mixture of the anionic polymer obtained in Step 2 of the production method of the present invention, a plasticizer, and a basic inorganic filler, was measured using a rheometer (manufactured by Anton Paar, trade name: MCR302). A 25 mmΦ parallel plate was used as the jig, and the shear rate was swept from 0.1 s -1 to 10 s -1 at 25°C. The slurry viscosity was determined using the viscosity value at a shear rate of 1 s -1 .

[0057] [Measurement of bleed-out rate] A 4 cm × 4 cm test piece (1.7 g) was cut from the molded sheet of the halogen-based resin composition. One surface of this test piece was washed with 2 g of heavy methanol containing 0.1 wt% of TMS, and the heavy methanol solution was 1 analyzed by 1H-NMR measurement. The masses of the anionic polymer or surfactant derived from the peaks in the heavy methanol solution were determined from the integral values of the peaks, and the amount of the anionic polymer or surfactant incorporated into the 1.7 g test piece was calculated from the amount charged into the halogen-based resin composition. The bleed-out rate was determined as the ratio (%) with respect to this amount. In this measurement method, a bleed-out amount of 0.2 wt% can be detected, and those described as ND (not detected) indicate a bleed-out rate of less than 0.2 wt%.

[0058] [Measurement of solid content concentration] Weighed 10.0 parts of sodium sulfate that had been made constant in a desiccator into a 30 ml glass petri dish, added approximately 1.0 part of the sample thereto, mixed it, weighed it accurately, maintained it at 105°C for 2 hours to remove the volatile components, left it in the desiccator for 15 minutes, and measured the mass. The mass of the sample after removing the volatile components 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) In a 1L four-necked separable flask, 7.9g of stearyl methacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: NK Ester S), 7.9g of methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 36.7g of methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: NK Ester TM-230G, average 23 molar addition of EO), and 26.0g of ethanol were charged. Two dropping funnels, a reflux condenser, a thermometer, and a stirrer were attached. After purging the reaction system with nitrogen, the temperature was raised to 80°C while stirring. A mixed solution of polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-65B) 1.6g and ethanol 8.9g 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-mentioned 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 added dropwise separately over 180 minutes (these mixed solutions are hereafter referred to as "dropwise mixtures" and shown in Table 1). After the dropwise addition was complete, the mixture was stirred at 80°C for 180 minutes and then cooled to room temperature. The solid content concentration of the obtained polymer solution was 60.1%. 10.0 g of the obtained 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 obtained anionic polymer 1 was 27,000.

[0060] Manufacturing Example 2 (Manufacturing of Anionic Polymer 2) To 10.0 g of the polymer solution prepared in Production Example 1 (solids: 6.0 g, content of constituent units derived from methacrylic acid: 14.9%), 0.3 g of 4N sodium hydroxide solution was added and the mixture was 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 product of anionic polymer 1).

[0061] Manufacturing Example 3 (Manufacturing of Anionic Polymer 3) To 10.0 g of the polymer solution prepared in Production Example 1 (solids: 6.0 g, content of constituent units derived from methacrylic acid: 14.9%), 0.6 g of 4N sodium hydroxide solution was added and the mixture was 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 (a 20% neutralized product of anionic polymer 1).

[0062] Manufacturing Example 4 (Manufacturing of Anionic Polymer 4) To 10.0 g of the polymer solution prepared in Production Example 1 (solids: 6.0 g, content of constituent units derived from methacrylic acid: 14.9%), 1.5 g of 4N sodium hydroxide solution was added and the mixture was 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] Manufacturing Example 5 (Manufacturing of Anionic Polymer 5) To 10.0 g of the polymer solution prepared in Production Example 1 (solids: 6.0 g, content of constituent units derived from methacrylic acid: 14.9%), 3.0 g of 4N sodium hydroxide solution was added and the mixture was 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 5 (100% neutralized product of anionic polymer 1).

[0064] Manufacturing Example 6 (Manufacturing of Anionic Polymer 6) In a 1L four-necked separable flask, 20.3g of stearyl acrylate, 6.8g of methacrylic acid, 18.0g of methoxypolyethylene glycol methacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name: NK Ester™-230G, average 23 moles of EO added), 1.8g of mercaptopropanediol (chain transfer agent: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 27.0g of ethanol were charged. Two dropping funnels, a reflux condenser, a thermometer, and a stirrer were attached. After purging the reaction system with nitrogen, the temperature was raised to 80°C while stirring. A mixed solution of 1.4g of the polymerization initiator and 11.3g of ethanol was added, and 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 added dropwise separately over 180 minutes. After the dropwise addition was complete, 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 solid content concentration to 30.4%. 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 6. The weight-average molecular weight of the obtained anionic polymer 6 was 5,800.

[0065] Manufacturing Example 7 (Manufacturing of Anionic Polymer 7) In a 1L four-necked separable flask, 4.5g of stearyl methacrylate, 1.5g of methacrylic acid, 4.0g of methoxypolyethylene glycol methacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name: NK Ester™-230G, average 23 moles of EO added), and 24.7g of toluene / ethanol mixture (mass ratio 50 / 50) were charged. Two dropping funnels, a reflux condenser, a thermometer, and a stirrer were attached. After purging the reaction system with nitrogen, the temperature was raised to 80°C while stirring. A mixture of 0.02g of the polymerization initiator and 5.7g of toluene / ethanol mixture (mass ratio 50 / 50) 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-mentioned methoxypolyethylene glycol methacrylate, and 42.1 g of toluene / ethanol mixture (mass ratio 50 / 50) was added dropwise, and a mixed solution of 0.15 g of the above-mentioned polymerization initiator and 50.9 g of toluene / ethanol mixture (mass ratio 50 / 50) was added dropwise separately over 120 minutes. After the dropwise addition was complete, the mixture was stirred at 80°C for 120 minutes and then cooled. The solid content concentration of the obtained polymer solution was 45.2% by mass. 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 7. The weight-average molecular weight of the obtained anionic polymer 7 was 166,000.

[0066] Manufacturing Example 8 (Manufacturing of Anionic Polymer 8) 100.0g of toluene / ethanol mixture (mass ratio 50 / 50) was pre-loaded into a 1L four-neck separable flask, and two dropping funnels, a reflux condenser, a thermometer, and a stirrer were attached. After purging the reaction system with nitrogen, the temperature was raised to 80°C while stirring, and while maintaining the temperature, a mixed solution of 300.0g of stearyl methacrylate, 75.0g of methacrylic acid, 125.0g of methoxypolyethylene glycol methacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name: NK Ester M-450G, average 45 moles of EO added), 4.9g of mercaptopropanediol, and 350.4g of toluene / ethanol mixture (mass ratio 50 / 50) and a mixed solution of 6.8g of the above polymerization initiator and 49.6g of toluene / ethanol mixture (mass ratio 50 / 50) were added separately over 120 minutes. After the addition was complete, the mixture was stirred at 80°C for 60 minutes, and then cooled to room temperature. The solid content 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 constituent units derived from α,β-unsaturated carboxylic acids in anionic polymer 8 was 15.0%. The weight-average molecular weight of the obtained anionic polymer 8 was 14,300.

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

[0068] Manufacturing Example 10 (Manufacturing of Anionic Polymer 10) 450.0g of toluene, 224.0g of diisobutylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 198.0g of maleic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 13.3g of benzoyl peroxide (polymerization initiator: manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a 1L four-neck separable flask. A reflux condenser, thermometer, and stirrer were attached. After purging the reaction system with nitrogen, the temperature was raised to 83°C while stirring, and the reaction was carried out for 240 minutes while maintaining the temperature. The mixture was then transferred to a Teflon®-coated vat and dried under reduced pressure at 100°C for 5 hours. The weight-average molecular weight of the obtained polymer was 28600. 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) were charged into a 1 L four-necked separable flask. After purging the reaction system with nitrogen, the mixture was dissolved at room temperature for 2 hours while stirring. Next, the temperature was raised to 72°C while stirring, and 32.0 g (0.12 mol) of stearylamine (manufactured by Kao Corporation, product name: Farmin 80), which had been melted at 80°C beforehand, was added. The mixture was stirred at 72°C for 120 minutes to carry out 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 petri dish and dried under reduced pressure at 100°C for 5 hours to obtain anionic polymer 10. Since the obtained anionic polymer 10 was insoluble in the GPC eluent, its weight-average molecular weight was calculated to be 67,400 using the above GPC measurement values.

[0069] Manufacturing Example 11 (Manufacturing of Anionic Polymer 11) 8.5 g of 2-ethylhexyl methacrylate, 1.5 g of methacrylic acid, 0.13 g of mercaptopropanediol, and 22.1 g of toluene / ethanol mixture (mass ratio 50 / 50) were placed in a 1 L four-neck separable flask, and two dropping funnels, a reflux condenser, a thermometer, and a stirrer were attached. After purging the reaction system with nitrogen, the temperature was raised to 80°C while stirring, and a mixed solution of 0.12 g of the polymerization initiator and 5.9 g of toluene / ethanol mixture (mass ratio 50 / 50) 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 toluene / ethanol mixture (mass ratio 50 / 50) and a mixed solution of 0.11 g of the polymerization initiator and 52.8 g of toluene / ethanol mixture (mass ratio 50 / 50) were added dropwise separately over 120 minutes. After the addition was complete, 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 obtained anionic polymer 11 was 10,400.

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

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

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

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

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

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

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

[0077] [Table 1] Table 2 summarizes the weight-average molecular weight, acid value, and degree of neutralization of the raw material monomers used in Production Examples 1 to 18, as well as the anionic polymers 1 to 18 produced.

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

[0079] [Manufacturing of halogen-based resin compositions 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 with a magnetic stirrer at 300 rpm for 3 minutes. The resulting mixture and 40.0 g of calcium carbonate (Shiraishi Calcium Co., Ltd., trade name: Whiteon H) were placed in a 500 mL poly cup and mixed with a lab mixer at 5,000 rpm for 3 minutes. 40.0 g of vinyl chloride resin (average degree of polymerization 800, manufactured by Kaneka Corporation, trade name: PSL-675) was added to the resulting mixture of anionic polymer 2, plasticizer, and calcium carbonate and mixed uniformly with a spatula. Then, the mixture was mixed with a lab mixer at 5,000 rpm for 3 minutes. Next, it was allowed to stand at room temperature under reduced pressure for 10 minutes to degas, and a halogenated resin composition was obtained. The slurry viscosity of the halogen-based resin composition at 25°C was 14 Pa·s.

[0080] Examples 1-2 to 1-6 A halogen-based resin composition was prepared in the same manner as in Example 1-1, except that the anionic polymer and the concentration of the anionic polymer relative to calcium carbonate were changed as shown in Table 3. The slurry viscosity of the halogen-based resin composition at 25°C is shown in Table 3.

[0081] Examples 1-7 Except for not performing vacuum drying, the ethanol solution of anionic polymer 9 was prepared using the same method as in Production Example 9. 0.33 g of the anionic polymer 9 solution (solids concentration 61.3%, corresponding to 0.5% of the anionic polymer 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 placed in a 1 L four-necked flask. Desolventing was performed by stirring at 200 rpm while blowing in nitrogen gas at 160°C, under a reduced pressure of 6 torr or less for 1 hour. The resulting mixture was then placed in a 500 mL poly cup in the following order: 40.0 g of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiteon H) and 40.0 g of polyvinyl chloride resin (average degree of polymerization 800, manufactured by Kaneka Corporation, trade name: PSL-675), and mixed uniformly with a spatula. Subsequently, the mixture was mixed using a lab mixer at a rotation speed of 5,000 rpm for 3 minutes. Next, the mixture was allowed to stand at room temperature under reduced pressure for 10 minutes to remove air bubbles and obtain 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 Except for not performing vacuum drying, the ethanol-mixed solution of the anionic polymer 12 was prepared in the same manner as in Production Example 12. The halogen-based resin composition was prepared in the same manner as in Examples 1-7, except that the solution of the anionic polymer 9 was replaced with 0.50 g of the solution of the anionic polymer 12 (solid content concentration 40.4%, where the concentration of the anionic polymer relative to the mass of calcium carbonate is 0.5%). 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 Except for not performing vacuum drying, the toluene / ethanol mixed solution of the anionic polymer 15 was prepared in the same manner as in Production Example 15. The halogenated resin composition was prepared in the same manner as in Examples 1-7, except that the amount of solution of the anionic polymer 15 was changed to 0.33 g (solid content concentration 59.9%, where the concentration of the anionic polymer relative to the mass of calcium carbonate is 0.5%). The slurry viscosity of the halogenated 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 prepared in the same manner as in Example 1-1, except that anionic polymer 2 was not used. The slurry viscosity of the halogen-based resin composition at 25°C was 36 Pa·s.

[0085] Comparative Examples 1-2 to 1-4 A halogen-based resin composition was prepared in the same manner as in Example 1-1, except that the anionic polymer 2 was replaced with a surfactant (Kao Corporation, product 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] [Manufacturing of halogen-based resin compositions for measuring bleed-out rates] Example 2-1 (Manufacturing of halogen-based resin compositions) 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 with a magnetic stirrer at 300 rpm for 3 minutes. The resulting mixture and 20 g of calcium carbonate (Shiraishi Calcium Co., Ltd., product name: Whiteon H) were mixed with a lab mixer at 5000 rpm for 3 minutes. To the resulting mixture of anionic polymer 2, plasticizer, and calcium carbonate, 100 g of polyvinyl chloride resin (average degree of polymerization 1400, manufactured by Shin-Daiichi Vinyl Chloride Co., Ltd., product name: ZEST1400), 2 g of Ca / Mg / Zn-based polyvinyl chloride resin stabilizer (ADEKA Corporation, product name: ADEKA Stab RUP-103), and 0.5 g of lubricant (Kao Corporation, product name: Lunac S-70V) were mixed at room temperature using a stirring rod. Subsequently, the mixture was mixed using a 4-inch open-roll type kneader (manufactured by Nishimura Machinery Co., Ltd.) at a rotation speed of 17.5 rpm and 160°C to induce gelation. Mixing was continued for 10 minutes after gelation to obtain a halogen-based resin composition. (Manufacturing of molded sheets) The halogen-based resin composition obtained above was pressurized at 175°C and 0.5 MPa for 5 minutes, then at 20 MPa for 2 minutes, and finally at 15°C and 0.5 MPa for 2 minutes to obtain a resin molded sheet with a thickness of 0.8 mm. No bleed-out of anionic polymer 2 was detected from the obtained resin molded sheet. The results are shown in Table 4.

[0088] Examples 2-2 to 2-6 Molded sheets of halogenated 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 bleed-out of the anionic polymer was detected from the obtained resin molded sheets. The results are shown in Table 4.

[0089] Comparative Examples 2-1 to 2-3 A resin molded sheet was manufactured in the same manner as in Example 2-1, except that the anionic polymer 2 was replaced with a surfactant (Kao Corporation, product 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 then calculated. The results are shown in Table 4.

[0090] [Table 4]

[0091] As shown in Table 3, the results from Examples 1-1 to 1-9 and Comparative Example 1-1 indicate that using anionic polymers reduces the slurry viscosity of halogen-based resin compositions and improves processability. Furthermore, as shown in Tables 3 and 4, the results from Examples 1-1 to 1-9, Examples 2-1 to 2-6, and Comparative Examples 1-2 to 1-4 and Comparative Examples 2-1 to 2-3 indicate that surfactants such as glycerin monostearyl, which do not have anionic groups, reduce the slurry viscosity of halogenated resin compositions to some extent, but do not reduce the slurry viscosity sufficiently to improve processability. It was also found that when the concentration of glycerin monostearyl relative to calcium carbonate exceeds a certain level, glycerin monostearyl bleeds out from the halogenated resin composition. This is thought to be because glycerin monostearyl is not sufficiently adsorbed onto calcium carbonate, which is a basic inorganic filler. The results from Examples 1-4 and 1-8 showed that the slurry viscosity of the halogen-based resin composition was almost the same whether steps 2 and 3 were performed sequentially after step 1, or whether steps 2 and 3 were performed simultaneously after step 1. Furthermore, the results from Examples 1-1, 1-2, and 1-6 showed that even when using neutralized anionic polymers, sequential addition of halogenated resins reduces the viscosity of the halogenated resin slurry. Therefore, it is believed that the sequential addition method for producing halogenated resin compositions allows the use of both unneutralized and neutralized anionic polymers, enabling the production of halogenated resin compositions using a wider variety of anionic polymers. Furthermore, as shown in Examples 1-1 to 1-6, the manufacturing method of the present invention allows for the production of a halogen-based resin composition in a short number of steps by adding calcium carbonate as a basic inorganic filler to a mixture of a plasticizer and anionic polymer to make the surface of the basic inorganic filler uniformly hydrophobic, and then adding a halogen-based resin. In the example of Patent Document 2, the slurry is dried at 105°C for 24 hours to obtain calcium carbonate powder coated with anionic polymer. In contrast, the manufacturing method of the present invention has high manufacturing efficiency because, compared to the manufacturing method described in Patent Document 2, it is not necessary to make the basic inorganic filler an aqueous dispersion to cause precipitation with the neutralized surfactant, nor is it necessary to filter and dry the aqueous dispersion of the basic inorganic filler to produce the halogen-based resin composition.

[0092] [Measurement of slurry viscosity of mixtures] 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 using a magnetic stirrer at 300 rpm for 3 minutes. The resulting mixture and 85.0 g of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiteon H) were mixed using a lab mixer at 5000 rpm for 3 minutes. The mixture was then allowed to stand at room temperature under reduced pressure for 10 minutes to remove air bubbles, yielding 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 The mixture was 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 this mixture at 25°C was measured. The results are shown in Table 5.

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

[0095] [Table 5]

[0096] The results from Examples 1-1 to 1-6 and Examples 3-1 to 3-17 suggest that the processability of halogenated resin compositions improves when the slurry viscosity of the mixture of anionic polymer, plasticizer, and basic inorganic filler is sufficiently low. In Examples 3-1 to 3-17 and Comparative Examples 3-1 to 3-4, the amount of calcium carbonate relative to the plasticizer was higher, resulting in a tendency for higher slurry viscosity compared to Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4. Furthermore, the reason why the slurry viscosity of the plasticizer and calcium carbonate mixture in Comparative Example 3-4 is significantly higher than that of the halogen-based resin composition in Comparative Example 1-1 is that the calcium carbonate content in the mixture of Comparative Example 3-4 is high, causing the calcium carbonate to form a network, whereas in the halogen-based resin composition of Comparative Example 1-1, the calcium carbonate content in the composition is relatively low, and a calcium carbonate network was not formed to the extent that it significantly increased the slurry viscosity.

[0097] [Measurement of slurry viscosity of mixtures using neutralized anionic polymers] Examples 4-1 to 4-5 The mixture was 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. The slurry viscosity of this mixture at 25°C was then measured. The results are shown in Table 6.

[0098] Comparative Example 4-1 0.4 g of anionic polymer 3 (20% neutralized form of 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 (Shiraishi Calcium Co., Ltd., trade name: Whiteon H) were placed in a 500 mL poly cup in that order and mixed uniformly with a spatula. Then, the mixture was mixed using a lab mixer at a rotation speed of 5,000 rpm for 3 minutes. Next, it was allowed to stand at room temperature under reduced pressure for 10 minutes to degas, and a mixture of anionic polymer 3, plasticizer, and calcium carbonate was obtained. 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 from Examples 4-1 to 4-5 show that even when using a neutralized anionic polymer, sequential addition reduces the viscosity of the slurry of the mixture of the anionic polymer, plasticizer, and basic inorganic filler. Furthermore, from the results of Examples 4-1 to 4-5 and Comparative Examples 4-1 and 4-2, it was found that when using neutralized anionic polymers, the method of producing halogen-based resin compositions by sequentially adding the polymers after step 1 reduces the slurry viscosity of the halogen-based resin composition more effectively than the method of producing halogen-based resin compositions by adding the polymers all at once.

[0102] [Measurement of slurry viscosity of mixtures] Example 5-1 The 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 at 25°C was measured. The results are shown in Table 7.

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

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

[0105] [Table 7]

[0106] The results from Examples 5-1 to 5-2 and Comparative Example 5-1 show that even when trimelite is used as a plasticizer, the viscosity of the slurry of the mixture of polymer dispersant, plasticizer, and basic inorganic filler can be reduced, improving the processability of the halogenated resin composition. The reason why the slurry viscosity of the mixtures in Examples 5-1 and 5-2 is higher than that of the mixtures in 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, wherein step 1 is performed first. Step 1: Mixing the anionic polymer with the plasticizer. Step 2: Further mixing in a basic inorganic filler. Step 3: Further mixing in halogen-based resin.

2. A method for producing a halogen-based resin composition according to claim 1, comprising performing steps 1 to 3 in order.

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

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

8. A 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 amount of the plasticizer in the halogen-based resin composition is 10 parts by mass or more and 170 parts by mass or less per 100 parts by mass of the halogen-based resin.

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

11. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein 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.

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

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

14. The method for producing a halogen-based resin composition according to claim 1 or 2, wherein the anionic polymer comprises one or more structural units selected from structural units derived from esters of α,β-unsaturated carboxylic acids, structural units derived from amides of α,β-unsaturated carboxylic acids, structural units derived from styrene compounds, and structural units derived from linear or branched alkenes having 3 to 10 carbon atoms.

15. 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 5,000 or more and 20,000 or less.

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