Halogenated resin composition

Abstract

To provide a halogenated resin composition having improved workability due to reduced slurry viscosity.SOLUTION: The present invention relates to a halogenated resin composition comprising a plasticizer, a polymeric dispersant, a basic inorganic filler, and a halogenated resin, wherein the polymeric dispersant contains a structural unit having a carboxy group and a structural unit having a hydrophobic group, the degree of neutralization of the polymeric dispersant is 30 mol% or less, and the weight-average molecular weight (Mw) of the polymeric dispersant is 4,000-200,000 inclusive.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to 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 composition comprising an inorganic solid on 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 on the surface, and a polymer containing a plasticizer. [Prior art documents] [Patent Documents]

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

[0006] The composition described in Patent Document 1 requires the surfactant to be dissolved in water by neutralizing it with an alkali in order to adsorb the surfactant onto the surface of an inorganic solid, and then the precipitate formed by settling the dispersion containing the surfactant and the inorganic solid is dried. Therefore, the composition described in Patent Document 1 has the problem that only surfactants that dissolve in water can be used, thus limiting the types of surfactants that can be used. This invention relates to a halogen-based resin composition in which processability is improved by reducing slurry viscosity. [Means for solving the problem]

[0007] The inventors have found that a halogen-based resin composition containing a plasticizer, a polymer dispersant, a basic inorganic filler, and a halogen-based resin can solve the above problems. In other words, the present invention relates to a halogen-based resin composition containing a plasticizer, a polymer dispersant, a basic inorganic filler, and a halogen-based resin, The polymer dispersant contains a structural unit having a carboxyl group and a structural unit having a hydrophobic group, The degree of neutralization of the polymer dispersant is 30 mol% or less. This invention relates to a halogenated resin composition having a weight-average molecular weight (Mw) of 4,000 or more and 200,000 or less. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a halogen-based resin composition with improved processability by reducing the slurry viscosity. [Modes for carrying out the invention]

[0009] [Halogenated resin composition] The halogenated resin composition of the present invention is a halogenated resin composition containing a plasticizer, a polymeric dispersant, a basic inorganic filler, and a halogenated resin, wherein the polymeric dispersant contains constituent units having a carboxyl group and constituent units having a hydrophobic group, the degree of neutralization of the polymeric dispersant is 30 mol% or less, and the weight-average molecular weight (Mw) is 4,000 or more and 200,000 or less. The halogen-based resin composition of the present invention exhibits the effect of low slurry viscosity and excellent processability. The reason for these effects 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. Here, the polymeric dispersant contained in the halogen-based resin composition of the present invention is thought to improve processability by adsorbing onto the surface of the basic inorganic filler and making the surface of the basic inorganic filler hydrophobic, thereby suppressing aggregation and network formation of the basic inorganic filler in the resin composition and reducing the slurry viscosity of the halogen-based resin composition. Furthermore, if the degree of neutralization of the polymeric dispersant is 50 mol% or less, the solubility of the polymeric dispersant in the plasticizer is improved, and adsorption to the basic inorganic filler becomes more uniform, which is thought to reduce the slurry viscosity. In addition, if the weight-average molecular weight of the polymeric dispersant is within a specific range, the surface hydrophobicization of the basic inorganic filler becomes more efficient. Specifically, if the weight-average molecular weight of the polymeric dispersant is 4,000 or more, it is thought that desorption is suppressed by multi-point adsorption. If the weight-average molecular weight of the polymeric dispersant is 200,000 or less, the solubility in the plasticizer is high, and the diffusion rate is also high, so when it acts on the basic inorganic filler, it can be adsorbed more uniformly, and the resulting halogen-based resin composition is thought to have excellent flexibility even at low temperatures. The slurry viscosity of the halogen-based resin composition of the present invention at 25°C 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 the halogen-based resin composition exhibiting excellent low-temperature flexibility and processability. The slurry viscosity is measured using the method shown in the examples. The shape of the halogen-based resin composition is not particularly limited, but may be, for example, a mixed powder, pellets, or paste.

[0010] [Polymer dispersant] In the present invention, the polymer dispersant contains a constituent unit having a carboxyl group, from the viewpoint of being easily adsorbed onto a basic inorganic filler, and a constituent unit having a hydrophobic group, from the viewpoint of being easily soluble or dispersed in a plasticizer. Examples of constituent units having a carboxyl group include constituent units derived from α,β-unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid, crotonic acid, and itaconic acid, preferably constituent units derived from (meth)acrylic acid, and more preferably constituent units derived 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 the above-mentioned α,β-unsaturated carboxylic acids, amides of the above-mentioned α,β-unsaturated carboxylic acids, styrene compounds, and linear or branched alkenes having 3 to 10 carbon atoms, from the viewpoint of being easily soluble or dispersed in plasticizers. 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 esters and amides of polycarboxylic acids shall constitute both structural units having an anionic group and structural units having a hydrophobic group.

[0011] 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 the low-temperature flexibility of the halogen-based resin composition and improving processability by reducing the slurry viscosity of the halogen-based 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 30 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 an 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 the low-temperature flexibility of the halogenated resin composition and improving processability by reducing the slurry viscosity of the halogenated resin composition.

[0012] Examples of the amide of an α,β-unsaturated carboxylic acid include amides of an α,β-unsaturated carboxylic acid and a linear or branched primary alkylamine from the viewpoint of easy introduction into the molecule. From the viewpoint of improving the compatibility with the plasticizer, the number of carbon atoms of the linear or branched primary alkylamine is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less in terms of the number of carbon atoms.

[0013] Examples of the styrene-based compound include styrene, α-methylstyrene, etc. from the viewpoint of easy availability. Examples of the linear or branched alkene having 3 to 10 carbon atoms include isoprene, butadiene, isobutylene, diisobutylene, etc. from the viewpoint of easy copolymerization with maleic anhydride.

[0014] Among the structural units having the hydrophobic group, from the viewpoint of further improving the low-temperature flexibility of the halogen-based resin composition and reducing the slurry viscosity of the halogen-based resin composition, 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 preferable.

[0015] From the viewpoint of adjusting the hydrophilic-hydrophobic balance, the polymer dispersant may contain a structural unit having a hydrophilic group. However, in the present invention, the structural unit having a hydrophilic group does not include a structural unit having a carboxy group. Examples of the structural unit having a hydrophilic group include structural units derived from compounds having acid groups such as sulfonic acid group, sulfinic acid group, sulfuric acid group, sulfurous acid group, phosphoric acid group, phosphorous acid group, (meth)acrylamide, dimethyl (meth)acrylamide, structural units derived from acrylonitrile, and structural units derived from α,β-unsaturated carboxylic acid alkyloxypolyalkylene glycol esters. The polymeric dispersant preferably contains constituent units derived from α,β-unsaturated alkyloxypolyalkylene glycol ester, more preferably from α,β-unsaturated alkyloxypolyethylene glycol and / or polypropylene glycol ester, and even more preferably from α,β-unsaturated alkyloxypolyethylene glycol ester, from the viewpoint of facilitating the design of a 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 monomethacrylate is preferred from the viewpoint of improving the low-temperature flexibility of the halogen-based resin composition and reducing the slurry viscosity of the halogen-based resin composition.

[0016] The content of carboxyl group-containing constituent units in the polymer dispersant 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 adsorbing onto the basic inorganic filler and reducing 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.

[0017] The weight-average molecular weight of the polymer dispersant 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 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.

[0018] The acid value of the polymer dispersant 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, and even more preferably 120 mg KOH / g or less. The acid value of a polymeric dispersant can be calculated from the mass ratio of its constituent monomers. Alternatively, it can be determined by titrating the polymeric dispersant after dissolving or swelling it in a suitable organic solvent (e.g., methyl ethyl ketone).

[0019] The polymeric dispersant is adsorbed onto the basic inorganic filler, and its degree of neutralization is 30 mol% or less, from the viewpoint of reducing the slurry viscosity of the halogenated resin composition. Preferably, the degree of neutralization of the polymeric dispersant is 25 mol% or less, more preferably 15 mol% or less, and even more preferably the polymeric dispersant is unneutralized.

[0020] Examples of neutralizing agents for polymer dispersants include alkali metal hydroxides, ammonia, and organic amines, from the viewpoint of their availability. 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.

[0021] In the halogenated resin composition of the present invention, the mass ratio of polymeric dispersant to the content of basic inorganic filler (polymeric dispersant / 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.

[0022] From the viewpoint of reducing the slurry viscosity of the halogenated resin composition, the content of the polymeric dispersant in the halogenated resin composition is preferably 0.001% by mass or more and 0.8% by mass or less relative to the halogenated resin composition.

[0023] (Method for manufacturing polymer dispersants) Polymeric dispersants can be produced by copolymerizing monomers such as compounds having anionic groups, hydrophobic groups, or 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.

[0024] From the viewpoint of easy adjustment of molecular weight, 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.

[0025] The preferred polymerization conditions vary depending on the type of polymerization initiator, monomer, and solvent used, but from the viewpoint of enabling polymerization with general-purpose equipment, the polymerization temperature is usually 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 a nitrogen gas atmosphere or argon.

[0026] [Halogen-based resins] In the present invention, halogenated resin means a monomer homopolymer, copolymer, or halogen-modified polymer containing a halogen. From the viewpoint of ease of availability, specifically, 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.

[0027] (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, as polymers other than vinyl chloride copolymers, any polymer that can graft copolymerize vinyl chloride is acceptable, 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 methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, and the like.

[0028] 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, 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.

[0029] [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.

[0030] The content of plasticizer in the halogen-based resin composition 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 the low-temperature flexibility resistance and processability of the halogen-based resin composition.

[0031] [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. Preferably, the basic inorganic filler contains calcium carbonate from an economic standpoint.

[0032] The content of the basic inorganic filler 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.

[0033] [Additives] The halogenated resin composition may optionally contain additives such as stabilizers, processing aids, colorants, antioxidants, UV absorbers, antistatic agents, and lubricants, to the extent that the effects of the present invention are not impaired.

[0034] 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 bis-butyl maleate, and dibutyl tin dilaurate; and antimony mercaptide compounds. The stabilizer content is 0.1 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0035] Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearate amide, ethylenebisstearate amide, butyl stearate, and calcium stearate. The content of the processing aid is 0.1 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0036] 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 colorant content is 1 to 100 parts by mass per 100 parts by mass of halogen-based resin.

[0037] 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 antioxidant content is 0.2 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0038] 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 UV absorber content is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0039] 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 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 content of the antistatic agent is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0040] 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 lubricant content is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0041] [Method for producing halogenated resin compositions] The method for producing the halogenated resin composition of the present invention includes the step of mixing a polymer dispersant, a plasticizer, a basic inorganic filler, and a halogenated resin. The polymer dispersant, plasticizer, basic inorganic filler, and halogenated resin may be added all at once, or each component may be mixed sequentially. Halogenated resin compositions can be prepared by mixing a polymer dispersant, a plasticizer, a basic inorganic filler, a halogenated resin, and various additives as needed using a stirrer such as a mortar mixer, Henschel mixer, Banbury mixer, or ribbon blender to obtain a mixed powder of halogenated resin compositions. Alternatively, halogenated resin compositions can be obtained in the form of mixed powder, pellets, or paste by melt molding using a kneader such as a conical twin-screw extruder, parallel twin-screw extruder, single-screw extruder, cone-type kneader, or roll kneader. The mixing and melt molding conditions can be any conditions used in a typical halogen-based resin composition manufacturing method.

[0042] In mixing the polymer dispersant, plasticizer, basic inorganic filler, and halogen-based resin, it is preferable to perform step 1 first, followed by steps 2 and 3, from the viewpoint of efficiently allowing the polymer dispersant to act on the basic inorganic filler. Steps 2 and 3 may be performed either first or simultaneously. Furthermore, it is preferable to mix the polymer dispersant, plasticizer, basic inorganic filler, and halogen-based resin by performing steps 1 to 3 sequentially. If the halogen-based resin composition includes additives, the additives may be mixed together with the halogen-based resin in step 3, or they may be mixed after step 3. Step 1: Mixing polymer dispersant and plasticizer. Step 2: Further mixing in basic inorganic fillers. Step 3: Further mixing in halogen-based resin.

[0043] Mixed powders or pellets of halogen-based resin compositions can be molded into desired shapes by known methods such as extrusion molding, injection molding, calendering, press molding, and blow molding. Furthermore, paste-like halogen-based resin compositions can be molded into desired shapes by known methods such as spread molding, dipping molding, gravure molding, and screen molding.

[0044] The halogen-based resin composition of the present invention is excellent in low-temperature flexibility and 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.

[0045] The present invention includes the following embodiments. <1> A halogen-based resin composition containing a plasticizer, a polymer dispersant, a basic inorganic filler, and a halogen-based resin, The polymer dispersant contains a structural unit having a carboxyl group and a structural unit having a hydrophobic group, The degree of neutralization of the polymer dispersant is 30 mol% or less. A halogen-based resin composition having a weight-average molecular weight (Mw) of 4,000 or more and 200,000 or less. <2> The polymer dispersant contains 2% by mass or more and 50% by mass or less of structural units having a carboxyl group, and contains 50% by mass or more and 98% by mass or less of structural units having a hydrophobic group, the above <1> The halogen-based resin composition described above. <3> The polymer dispersant contains 2% by mass or more and 30% by mass of constituent units having a carboxyl group, and contains 70% by mass or more and 98% by mass of constituent units having a hydrophobic group, the above <1> or <2> The halogen-based resin composition described above. <4> The polymer dispersant includes a constituent unit derived from methacrylic acid as a constituent unit having a carboxyl group, <1> ~ <3> A halogen-based resin composition as described in any of the following. <5> The polymer dispersant contains one or more constituent units having hydrophobic groups, selected 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. <1> ~ <4> A halogen-based resin composition as described in any of the following. <6> The polymer dispersant contains 5% to 20% by mass of methacrylic acid-derived constituent units as constituent units having a carboxyl group, and 10% to 70% by mass of stearyl (meth)acrylate-derived constituent units as constituent units having a hydrophobic group, <1> ~ <5> A halogen-based resin composition as described in any of the following. <7> The polymer dispersant contains 40% to 60% by mass of methacrylic acid-derived constituent units as carboxyl group constituent units, and 15% to 60% by mass of lauryl methacrylate-derived constituent units as hydrophobic group constituent units, <1> ~ <5> A halogen-based resin composition as described in any of the following. <8> The polymer dispersant contains, as constituent units having a carboxyl group, 5% to 20% by mass of constituent units derived from methacrylic acid, and as constituent units having a hydrophobic group, 80% to 95% by mass of constituent units derived from 2-ethylhexyloxypropylene glycol polyethylene glycol methacrylate, <1> ~ <5> A halogen-based resin composition as described in any of the following. <9> The polymer dispersant contains 5% to 20% by mass of methacrylic acid-derived constituent units as carboxyl group constituent units, and 80% to 95% by mass of lauroxy polyethylene glycol monomethacrylate-derived constituent units as hydrophobic group constituent units, <1> ~ <5> A halogen-based resin composition as described in any of the following. <10> The polymeric dispersant contains 10% to 20% by mass of methacrylic acid-derived constituent units as carboxyl group constituent units, and 80% to 90% by mass of 2-ethylhexyl methacrylate-derived constituent units as hydrophobic group constituent units, <1> ~ <5> A halogen-based resin composition as described in any of the following. <11> The polymer dispersant is not neutralized, <1> ~ <10> A halogen-based resin composition as described in any of the following. <12> The weight-average molecular weight of the polymer dispersant is 5,000 or more and 30,000 or less. <1> ~ <11> A halogen-based resin composition as described in any of the following. <13> The acid value of the polymer dispersant is 45 mg KOH / g or more and 120 mg KOH / g or less, as described above. <1> ~ <12> A halogen-based resin composition as described in any of the following. <14> The halogen-based resin is polyvinyl chloride resin, <1> ~ <13> A halogen-based resin composition as described in any of the following. <15> The basic inorganic filler contains calcium carbonate, <1> ~ <14> A halogen-based resin composition as described in any of the following. <16> The mass ratio of the polymeric dispersant to calcium carbonate (polymeric dispersant / calcium carbonate) is 0.0001 or more and 10 or less, as described above. <15> The halogen-based resin composition described above. <17> The mass ratio of the polymeric dispersant to calcium carbonate (polymeric dispersant / calcium carbonate) is 0.0001 or more and 0.01 or less, as described above. <15> or <16> The halogen-based resin composition described above. <18> The mass ratio of the polymeric dispersant to calcium carbonate (polymeric dispersant / calcium carbonate) is 0.002 or more and 0.01 or less, as described above. <15> ~ <17> A halogen-based resin composition as described in any of the following. <19> The plasticizer is a phthalate ester of an alcohol having 8 to 13 carbon atoms. <1> ~ <19> A halogen-based resin composition as described in any of the following. <20> The content of the 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 the halogen-based resin, <1> ~ <20> A halogen-based resin composition as described in any of the following. <21> The content of the basic inorganic filler is 5 parts by mass or more and 130 parts by mass or less per 100 parts by mass of the halogen-based resin. <1> ~ <21> A halogen-based resin composition as described in any of the following. <22> The basic inorganic filler contains calcium carbonate, and the calcium carbonate content is 5 parts by mass or more and 130 parts by mass or less per 100 parts by mass of halogen-based resin. <21> The halogen-based resin composition described above. <23> The content of the polymer dispersant in the halogen-based resin composition is 0.001% by mass or more and 0.8% by mass or less, as described above. <1> ~ <23> A halogen-based resin composition as described in any of the following. [Examples]

[0046] In the following manufacturing examples, embodiments, and comparative examples, "parts" and "%" refer to "parts by mass" and "mass%" unless otherwise specified.

[0047] [Measurement] [Method for Measuring Weight-Average Molecular Weight] The weight-average molecular weight of the polymer dispersant was measured using gel permeation chromatography (hereinafter also referred to as "GPC"). That is, the synthesized polymer dispersant was diluted with N,N-dimethylformamide to prepare a solution with a solid content concentration of 0.3% by mass as a sample solution, and 100 μL thereof 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 an eluent, and GPC [apparatus: "HLC-8320GPC" manufactured by Tosoh Corporation, detector: differential refractometer (attached to the apparatus), column: two "TSK-GEL α-M" columns manufactured by Tosoh Corporation, column temperature: 40 °C, eluent flow rate: 1 mL / min] was used for measurement. As standard substances, polystyrene (manufactured by Tosoh Corporation: molecular weights 5.26×10 2 , 1.02×10 5 , 8.42×10 6 ; manufactured by Nippon Seiro Co., Ltd.: molecular weights 4.0×10 3 , 3.0×10 4 , 9.0×10 5 ) were used.

[0048] [Method for Measuring Slurry Viscosity] The viscosity of the halogen-based resin composition, or the mixture of the polymer dispersant, plasticizer, and basic inorganic filler, was measured using a rheometer (manufactured by Anton Paar, product 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 the value of the viscosity at a shear rate of 1 s -1 .

[0049] [Measurement of Bleed-Out Rate] A 4 cm×4 cm test piece (1.7 g) was cut out 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 1The analysis was performed using 1H-NMR. The mass of polymer dispersants or surfactants in the heavy methanol solution was determined from the integral values ​​of the peaks derived from those contained in the halogenated resin composition. The amount of polymer dispersant or surfactant contained in 1.7g of the test specimen was calculated from the amount added to the halogenated resin composition, and the bleed-out rate was determined as a percentage (%) of that amount. With this measurement method, a bleed-out amount of 0.2 wt% is detectable, and those marked ND (Not Detected) indicate a bleed-out rate of less than 0.2 wt%.

[0050] [Measurement of solid content concentration] 10.0 parts of sodium sulfate, which had been weighed to a constant weight in a desiccator, were weighed into a 30 ml glass petri dish. Approximately 1.0 part of the sample was added and mixed. The mixture was then accurately weighed and maintained at 105°C for 2 hours to remove volatile components. After standing in the desiccator for another 15 minutes, the mass was measured. The mass of the sample after removal of volatile components was taken as the solid content, and the solid content concentration was obtained by dividing it by the mass of the added sample.

[0051] [Manufacturing of polymer dispersants] Manufacturing Example 1 (Manufacturing of Polymer Dispersant 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 shown as "dropwise added mixtures" 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 polymer dispersant 1. The weight-average molecular weight of the obtained polymer dispersant 1 was 27,000.

[0052] Manufacturing Example 2 (Manufacturing of Polymer Dispersant 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% by mass), 0.6 g of 4N sodium hydroxide solution was added and the mixture was stirred for 30 minutes to neutralize the carboxyl groups in polymer dispersant 1. The resulting polymer solution was dried under reduced pressure at 80°C for 3 hours to obtain polymer dispersant 2 (a 20% neutralized version of polymer dispersant 1).

[0053] Manufacturing Example 3 (Manufacturing of Polymer Dispersant 3) 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 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 80°C for 3 hours to obtain polymer dispersant 3. The weight-average molecular weight of the obtained polymer dispersant 3 was 5,800.

[0054] Manufacturing Example 4 (Manufacturing of Polymer Dispersant 4) 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 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 polymerization initiator and 50.9 g of toluene / ethanol mixture (mass ratio 50 / 50) was added dropwise separately over 120 minutes. After the 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 polymer dispersant 4. The weight-average molecular weight of the obtained polymer dispersant 4 was 166,000.

[0055] Manufacturing Example 5 (Manufacturing of Polymer Dispersant 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% by mass), 1.5 g of 4N sodium hydroxide solution was added and stirred for 30 minutes to neutralize the carboxyl groups in polymer dispersant 1. The resulting polymer solution was dried under reduced pressure at 80°C for 3 hours to obtain polymer dispersant 5 (50% neutralized polymer dispersant 1).

[0056] Manufacturing Example 6 (Manufacturing of Polymer Dispersant 6) 0.75 g of stearyl methacrylate, 0.75 g of methacrylic acid, 3.5 g of methoxypolyethylene glycol methacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name: NK Ester™-230G, average 23 molar addition of EO), and 11.7 g of ethanol were charged into a 1 L four-neck separable flask. 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 0.007 g of the polymerization initiator and 2.3 g of ethanol was added, and the resulting initial mixture was stirred for 10 minutes. Next, while maintaining the temperature, a mixed solution of 6.8 g of stearyl methacrylate, 6.8 g of methacrylic acid, 31.5 g of the above methoxypolyethylene glycol methacrylate, and 15.1 g of ethanol, and a mixed solution of 0.063 g of the above polymerization initiator and 20.9 g of ethanol were added dropwise separately over 180 minutes. After the addition was complete, the mixture was stirred at 80°C for 180 minutes and then cooled to room temperature. 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 polymer dispersant 6. The content of constituent units derived from unsaturated fatty acid α,β-unsaturated carboxylic acid in polymer dispersant 6 was 15.0%. The weight-average molecular weight of the obtained polymer dispersant 6 was 418,000.

[0057] Manufacturing Example 7 (Manufacturing of Polymer Dispersant 7) 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 polymer dispersant 7. The polymer dispersant 7 contained 15.0% of constituent units derived from α,β-unsaturated carboxylic acids and 60.0% of constituent units having hydrophobic groups. The weight-average molecular weight of the obtained polymer dispersant 7 was 14,300.

[0058] Manufacturing Example 8 (Manufacturing of Polymer Dispersant 8) A polymer dispersant 8 was obtained in the same manner as in Production Example 3, except that the amounts of each component were changed as shown in Table 1. The weight-average molecular weight of the obtained polymer dispersant 8 was 8,600.

[0059] Manufacturing Example 9 (Manufacturing of Polymer Dispersant 9) 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 perform 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 polymer dispersant 9. Since the obtained polymer dispersant 9 was insoluble in the GPC eluent, its weight-average molecular weight was calculated using the above GPC measurement values ​​to be 67,400.

[0060] Manufacturing Example 10 (Manufacturing of Polymer Dispersant 10) 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 polymer dispersant 10. The weight-average molecular weight of the obtained polymer dispersant 10 was 10,400.

[0061] Manufacturing Example 11 (Manufacturing of Polymer Dispersant 11) Polymeric dispersant 11 was obtained in the same manner as in Production Example 10, 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 polymer dispersant 11 was 7,700.

[0062] Manufacturing Example 12 (Manufacturing of Polymer Dispersant 12) Polymeric dispersant 12 was obtained in the same manner as in Production Example 10, except that 2-ethylhexyl methacrylate was replaced with 2-ethylhexyloxypolyethylene glycol polypropylene glycol methacrylate (manufactured by NOF Corporation, product name: Bremmer 50POEP-800B, average 8 moles of EO added, average 7 moles of PO added), and the blending amounts of each component were changed to the amounts shown in Table 1. The weight-average molecular weight of the obtained polymer dispersant 12 was 8,700.

[0063] Manufacturing Example 13 (Manufacturing of Polymer Dispersant 13) Polymeric dispersant 13 was obtained in the same manner as in Production Example 10, 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 polymer dispersant 13 was 16,400.

[0064] Manufacturing Example 14 (Manufacturing of Polymer Dispersant 14) Polymeric dispersant 14 was obtained in the same manner as in Production Example 10, 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 polymer dispersant 14 was 27,100.

[0065] Manufacturing Example 15 (Manufacturing of Polymer Dispersant 15) Polymeric dispersant 15 was obtained in the same manner as in Production Example 3, 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 as shown in Table 1. The weight-average molecular weight of the obtained polymer dispersant 15 was 17,400.

[0066] Manufacturing Example 16 (Manufacturing of Polymer Dispersant 16) A polymeric dispersant 15 was obtained in the same manner as in Production Example 3, except that stearyl acrylate was replaced with lauryl methacrylate and the amounts of each component were changed as shown in Table 1. The weight-average molecular weight of the obtained polymer dispersant 16 was 15,200.

[0067] Manufacturing Example 17 (Manufacturing of Polymer Dispersant 17) Polymeric dispersant 17 was obtained in the same manner as in Production Example 10, except that 2-ethylhexyl methacrylate was replaced with stearoxy polyethylene glycol methacrylate (manufactured by NOF Corporation, trade name: Bremmer PSE1300, average 30 moles of EO 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 polymer dispersant 17 was 13,900.

[0068] [Table 1]

[0069] Table 2 summarizes the content, weight-average molecular weight, acid value, and degree of neutralization of each constituent unit in polymer dispersants 1 to 17 produced in production examples 1 to 17.

[0070] [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). *6: Refers to stearoxy polyethylene glycol methacrylate (manufactured by NOF Corporation, product name: Bremmer PSE1300).

[0071] [Manufacturing of halogen-based resin compositions for slurry viscosity measurement] Example 1-1 0.2 g of polymer dispersant 3 (0.5% concentration relative to the mass of calcium carbonate), 55.0 g of plasticizer (bis(2-ethylhexyl) phthalate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 40.0 g of calcium carbonate (Shiraishi Calcium Co., Ltd., product name: Whiteon 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 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 obtain a halogen-based resin composition. The slurry viscosity of the halogen-based resin composition at 25°C was 13 Pa·s.

[0072] Comparative Example 1-1 A halogen-based resin composition was prepared in the same manner as in Example 1-1, except that polymer dispersant 3 was not used. The slurry viscosity of the halogen-based resin composition at 25°C was 36 Pa·s.

[0073] [Table 3]

[0074] As shown in Table 3, the results from Example 1-1 and Comparative Example 1-1 indicate that using a polymer dispersant reduces the slurry viscosity of the halogenated resin composition and improves its processability. Furthermore, in the production of the composition described in Patent Document 1, it is necessary to use an aqueous dispersion of the basic inorganic filler in order to cause precipitation with the neutralized surfactant. However, as shown in Example 1-1, in the production of the halogen-based resin composition of the present invention, the polymer dispersant, plasticizer, basic inorganic filler, and halogen-based resin can be mixed directly, thus resulting in high production efficiency.

[0075] [Measurement of slurry viscosity of mixture by single-component addition] Example 2-1 0.4 g of polymer dispersant 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., product 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 polymer dispersant 1, plasticizer, and calcium carbonate was obtained. The slurry viscosity of this mixture at 25°C was 10 Pa·s.

[0076] Examples 2-2 to 2-14 and Comparative Examples 2-1 to 2-2 The mixtures were prepared in the same manner as in Example 2-1, except that the type of polymer dispersant was changed as shown in Table 4, and the slurry viscosity of each mixture was measured at 25°C. The results are shown in Table 4.

[0077] Comparative Example 2-3 The mixture was prepared in the same manner as in Example 2-1, except that polymer dispersant 1 was not used, and the slurry viscosity of the mixture was measured at 25°C. The results are shown in Table 4.

[0078] [Table 4]

[0079] The results from Examples 1-1 and 2-1 to 2-14 show that when the slurry viscosity of the mixture of polymer dispersant, plasticizer, and basic inorganic filler is sufficiently low, the processability of the halogenated resin composition is improved. In Examples 2-1 to 2-14 and Comparative Examples 2-1 to 2-3, the calcium carbonate content is higher relative to the plasticizer, and the slurry viscosity tends to be higher compared to Examples 1-1 and Comparative Example 1-1. Furthermore, the reason why the slurry viscosity of the plasticizer and calcium carbonate mixture in Comparative Example 2-3 is significantly higher than that of the halogen-based resin composition in Comparative Example 1-1 is thought to be because the calcium carbonate content in the mixture of Comparative Example 2-3 is high, causing the calcium carbonate to form a network within the plasticizer, whereas the calcium carbonate content in the halogen-based resin composition of Comparative Example 1-1 is relatively low, preventing the formation of a calcium carbonate network to the extent that would significantly increase the slurry viscosity. The results from Example 2-2, which used polymer dispersant 2 with a degree of neutralization of 20 mol%, and Comparative Example 2-1, which used polymer dispersant 5 with a degree of neutralization of 50 mol%, show that polymer dispersants neutralized to a certain extent can reduce the slurry viscosity of halogenated resin compositions and improve processability. The surfactant described in Patent Document 1 has a degree of neutralization of 80 mol% or more, and therefore, similar to the results in Comparative Example 2-1, it is considered that it cannot sufficiently reduce the slurry viscosity of halogenated resin compositions. Furthermore, the surfactant described in Patent Document 1 is crosslinked and is considered to have a very large molecular weight. Comparative Example 2-2 of the present invention uses polymer dispersant 6 with a large weight-average molecular weight, and the slurry viscosity of the halogenated resin composition was not reduced. For this reason, it is considered that the surfactant in Patent Document 1 cannot reduce the slurry viscosity of halogenated resin compositions either.

[0080] Examples 2-3, 2-6, 2-8 to 2-12, and 2-14, which used the polymer dispersants in Production Examples 3, 8, 11-15, and 17, show that the slurry viscosity of the mixture is low, and it is considered that when used as a halogen-based resin composition, the bleed-out of the polymer dispersant is extremely small or does not occur.

[0081] [Low-temperature bending resistance test of halogen-based resin compositions] Example 3-1 (Manufacturing of halogen-based resin compositions) 0.1 g of polymer dispersant 3 (0.5% concentration relative to the mass of calcium carbonate) and plasticizer (manufactured by Kao Corporation, product name: Vinisizer 124N (dialkyl(C) phthalate)) 10 ~C 1260g of ))), 20g of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: Whiteon H), 100g of polyvinyl chloride resin (average degree of polymerization 1400, manufactured by Shin Daiichi Vinyl Chloride Co., Ltd., product name: ZEST1400), 2g of Ca / Mg / Zn-based stabilizer for polyvinyl chloride resin (manufactured by ADEKA Corporation, product name: ADEKA Stab RUP-103), and 0.5g of lubricant (manufactured by Kao Corporation, product name: Lunac S-70V) were mixed at room temperature using a stirring rod. Then, using a 4-inch open roll type kneader (manufactured by Nishimura Machinery Co., Ltd.), the mixture was mixed at a rotation speed of 17.5 rpm and 160°C to induce gelation, and mixing was continued for 10 minutes after gelation to obtain a halogen-based resin composition.

[0082] (Manufacturing of molded sheets) The halogen-based resin composition obtained above was preheated at 170°C for 5 minutes, then pressurized at a pressure of 20 MPa for 2 minutes to obtain a resin molded sheet with a thickness of 0.8 mm.

[0083] (Method for evaluating resistance to low-temperature bending) Six test specimens were prepared by punching out 6mm x 64mm molded sheets of the halogen-based resin composition obtained above, and a low-temperature bending resistance test was conducted using a Demacha bending tester (Ueshima Seisakusho Co., Ltd., product name: FT-1506). The test was conducted under the following conditions: test temperature -25°C, bending speed 300 times / min, grip distance 30mm, bending stroke 25mm. The device was stopped every 1000 times to check for breakage, and the number of bends until breakage of the six test specimens was measured. Table 5 shows the average value of four values ​​excluding the highest and lowest values ​​for the number of bends until breakage. A higher value indicates better low-temperature bending resistance.

[0084] Examples 3-2 to 3-4 Except for changing the type of polymer dispersant as shown in Table 5, molded sheets of halogen-based resin compositions were manufactured in the same manner as in Example 3-1, and their low-temperature flexibility was evaluated. The results are shown in Table 5.

[0085] Comparative Example 3-1 Molded sheets of halogen-based resin compositions were manufactured in the same manner as in Example 3-1, except that polymer dispersant 3 was not used, and their low-temperature flexibility was evaluated. The results are shown in Table 5.

[0086] [Table 5]

[0087] The results from Examples 3-1 to 3-4 and Comparative Example 3-1 show that the low-temperature flexibility of halogenated resin compositions can be improved by using a polymer dispersant.

[0088] [Measurement of slurry viscosity of mixture by single-component addition] Example 4-1 The mixture was prepared in the same manner as in Example 2-8, 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 6.

[0089] Example 4-2 The mixture was prepared in the same manner as in Example 2-10, 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 6.

[0090] Comparative Example 4-1 The mixture was prepared in the same manner as in Comparative Examples 2-3, 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 6.

[0091] [Table 6]

[0092] The results from Examples 4-1 to 4-2 and Comparative Example 4-1 show that even when trimellitic acid triester 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 4-1 and 4-2 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.

[0093] [Discoloration resistance test of halogen-based resin compositions] Example 5-1 (Manufacturing of molded sheets) The halogen-based resin compositions obtained in Examples 3-4 were preheated at 170°C for 5 minutes, then pressurized at a pressure of 20 MPa for 2 minutes to obtain a resin molded sheet with a thickness of 0.8 mm.

[0094] (Method for evaluating discoloration) The molded sheets of the halogen-based resin composition obtained above were subjected to L*a*b* measurement using a colorimeter (Videojet X-Rite Corporation, product name: eXact). Measurements were taken under conditions of illuminant D50 and standard observer 2°. A smaller absolute value of b* indicates a smaller hue shift towards yellow. The results are shown in Table 7.

[0095] Example 5-2 A halogen-based resin composition was prepared using the same method as in Example 3-4, except that the concentration of polymer dispersant 12 was changed as shown in Table 7. A molded sheet of the halogen-based resin composition was then produced using the same method as in Example 5-1, and the hue change towards yellow was evaluated. The results are shown in Table 7.

[0096] Comparative Example 5-1 A molded sheet of a halogen-based resin composition was manufactured in the same manner as in Example 5-1, except that the halogen-based resin composition obtained in Comparative Example 3-1 was used, and the hue change in the yellow direction was evaluated. The results are shown in Table 7.

[0097] [Table 7]

[0098] The results from Examples 5-1 to 5-2 and Comparative Example 5-1 show that the use of a polymer dispersant can suppress the yellowish hue change of halogenated resin compositions. Furthermore, the results from Examples 5-1 and 5-2 show that increasing the amount of polymer dispersant can further suppress the yellowish hue change of halogenated resin compositions.

Claims

1. A halogen-based resin composition containing a plasticizer, a polymer dispersant, a basic inorganic filler, and a halogen-based resin, wherein the polymer dispersant contains a structural unit having a carboxy group and a structural unit having a hydrophobic group, the degree of neutralization of the polymer dispersant is 30 mol% or less, and the weight average molecular weight (Mw) of the polymer dispersant is 4,000 or more and 200,000 or less. The halogen-based resin composition.

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

3. The halogen-based resin composition according to Claim 1 or 2, wherein the mass ratio of the polymer dispersant to the basic inorganic filler (polymer dispersant / basic inorganic filler) is 0.0001 or more and 10 or less.

4. The halogen-based resin composition according to Claim 3, wherein the mass ratio of the polymer dispersant to the content of the basic inorganic filler (polymer dispersant / basic inorganic filler) is 0.002 or more and 0.01 or less.

5. The halogen-based resin composition according to Claim 1 or 2, wherein the basic inorganic filler contains calcium carbonate.

6. The halogen-based resin composition according to Claim 1 or 2, wherein the polymer dispersant contains a structural unit derived from an α,β-unsaturated carboxylic acid as the structural unit having a carboxy group, and as the structural unit having a hydrophobic group, at least one selected from the group consisting of an ester of an α,β-unsaturated carboxylic acid, an amide of an α,β-unsaturated carboxylic acid, a styrenic compound, and a structural unit derived from a linear or branched alkene having 3 to 10 carbon atoms.

7. The content of the structural unit having a carboxy group in the polymer dispersant is 1% by mass or more and 50% by mass or less when the total structural units are 100%, and the content of the structural unit having a hydrophobic group in the polymer dispersant is 5% by mass or more and 98% by mass or less when the total structural units are 100% by mass. The halogen-based resin composition according to Claim 1 or 2.

8. The halogen-based resin composition according to claim 1 or 2, wherein the acid value of the polymer dispersant is 30 mgKOH / g or more and 150 mgKOH / g or less.

9. The halogen-based resin composition according to claim 1 or 2, wherein the content of the plasticizer 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 halogen-based resin composition according to claim 1 or 2, wherein the content 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.

11. The halogen-based resin composition according to claim 1 or 2, wherein the content of the polymer dispersant is 0.001% by mass or more and 0.8% by mass or less.

12. A polymer dispersant containing a structural unit having a carboxy group and a structural unit having a hydrophobic group, having a neutralization degree of 30 mol% or less, and having a weight average molecular weight (Mw) of 4,000 or more and 200,000 or less.

13. The structural unit having a carboxy group in the polymer dispersant includes a structural unit derived from an α,β-unsaturated carboxylic acid, and the structural unit having a hydrophobic group is an ester of an α,β-unsaturated carboxylic acid, an amide of an α,β-unsaturated carboxylic acid, a styrene-based compound, and a structural unit derived from a linear or branched alkene having 3 to 10 carbon atoms. The polymer dispersant according to claim 12, comprising at least one selected structural unit.

14. The content of the structural unit having a carboxy group in the polymer dispersant is 1% by mass or more and 50% by mass or less when the total structural units are 100%, and the content of the structural unit having a hydrophobic group in the polymer dispersant is 5% by mass or more and 98% by mass or less when the total structural units are 100% by mass. The halogen-based resin composition according to claim 12 or 13.

15. The halogen-based resin composition according to claim 12 or 13, having an acid value of 30 mgKOH / g or more and 150 mgKOH / g or less.