JP6708129B2 - Vinyl chloride resin composition and molded article - Google Patents

Description

Cross-reference of related applications

This application is an application which enjoys the benefit of the priority of Japanese Patent Application No. 2005-179794 (filing date: September 11, 2015), and the contents thereof are incorporated herein by reference in their entirety.

The present invention relates to a vinyl chloride resin composition.

Vinyl chloride resin is widely used as a general-purpose resin material for various molded products because it is excellent in chemical resistance, weather resistance, flame retardancy, electrical insulation, and the like and is inexpensive. In particular, it is widely used as a building material member in terms of thermal conductivity and cost.

A filler is used together with the resin for such a molded body for various purposes.
In recent years, from the viewpoints of environmental friendliness (reduction of petroleum-derived raw materials) and cost reduction, it is desired to reduce the amount of vinyl chloride resin in the resin composition and increase the amount of filler that is cheaper than vinyl chloride resin. There is.
However, when the amount of the filler in the resin composition is increased, the processability (gelling property), the productivity, the impact resistance, the appearance, etc. at the time of molding the molded product are deteriorated.
Therefore, in Patent Documents 1 and 2, polytetrafluoroethylene is added to the resin composition.

JP, 2007-326908, A JP, 2002-327124, A

However, the resin composition described in Patent Document 1 has insufficient dispersibility of polytetrafluoroethylene, and thus the appearance and physical properties of the molded body are likely to deteriorate.
In addition, the resin composition described in Patent Document 2 is liable to deteriorate in appearance, is likely to be insufficient in productivity, and is likely to impair the low heat shrinkability of the molded body.

An object of the present invention is to provide a vinyl chloride resin composition capable of obtaining a molded product having excellent productivity, low heat shrinkability, impact resistance, and excellent surface appearance of the molded product even when the amount of the filler added is increased. And to provide a molded product using the same.

The above object is achieved by the following inventions (1) to (12).
(1) Vinyl chloride resin (A),
Polytetrafluoroethylene (B),
Polymer (C) other than polytetrafluoroethylene and filler (D)
A vinyl chloride resin composition containing:
With respect to 100 parts by mass of the vinyl chloride resin (A),
0.001 to 3 parts by mass of the polytetrafluoroethylene (B),
A vinyl chloride resin composition containing 1 to 2000 parts by mass of the filler (D).
(2) The polymer (C) is at least one kind of monomer selected from the group consisting of (meth)acrylic acid ester-based monomers, aromatic vinyl-based monomers, and vinyl cyanide-based monomers. The vinyl chloride resin composition according to (1) above, containing 50% by mass or more of a constitutional unit derived from the body.
(3) The polymer (C) is at least one kind of monomer selected from the group consisting of (meth)acrylic acid ester-based monomers having an alkyl group having 1 to 12 carbon atoms at the ester site, styrene, and acrylonitrile. The vinyl chloride resin composition according to (1) or (2) above, which contains 50% by mass or more of a constitutional unit derived from the body.
(4) The polymer (C) contains 50% by mass or more of structural units derived from a (meth)acrylic acid ester-based monomer having an alkyl group having 1 to 12 carbon atoms at the ester portion, (1) The vinyl chloride resin composition according to any one of to (3).
(5) The polymer (C) contains 50% by mass or more of a structural unit derived from a (meth)acrylic acid ester-based monomer having an alkyl group having 1 to 5 carbon atoms at the ester portion, (1) The vinyl chloride resin composition according to any one of to (4).
(6) The vinyl chloride resin composition according to any one of (1) to (5), wherein the polymer (C) has a mass average molecular weight (Mw) of 10,000 to 1,500,000.
(7) The vinyl chloride resin composition according to any one of (1) to (6), wherein the polytetrafluoroethylene (B) has a number average molecular weight (Mn) of 5,000,000 to 20,000,000.
(8) The vinyl chloride resin composition according to (6), further including 0.1 to 10 parts by mass of an acrylic polymer having a mass average molecular weight (Mw) of 2 to 6 million.
(9) The vinyl chloride resin composition according to any one of (1) to (8), which contains 10 to 2000 parts by mass of the filler (D).
(10) The vinyl chloride resin composition according to any one of (1) to (9) above, which contains 0.001 to 1.5 parts by mass of the polytetrafluoroethylene (B).
(11) A resin molded product obtained by molding the vinyl chloride resin composition according to any one of (1) to (10).
(12) Mixing the polytetrafluoroethylene-containing powder (F) containing the polytetrafluoroethylene (B) and the polymer (C) with the vinyl chloride resin (A) and the filler (D). A method for producing the vinyl chloride resin composition according to any one of (1) to (10) above, which comprises:

The vinyl chloride resin composition of the present invention provides a vinyl chloride resin molded product having excellent low heat shrinkability, impact resistance, and molded product surface appearance with high productivity even when the amount of the filler added is increased. You can

The present invention is described in detail below.

Vinyl chloride resin (A)
The type of the vinyl chloride resin (A) used in the present invention is not particularly limited, and may be, for example, a vinyl chloride homopolymer, a post-chlorinated vinyl chloride polymer, a partially crosslinked vinyl chloride polymer or another vinyl compound. Examples thereof include copolymers with vinyl chloride, and mixtures thereof.

The above-mentioned other vinyl compounds are not particularly limited, but specific examples thereof include fatty acid vinyl esters such as vinyl acetate and vinyl propionate; methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate; ethyl acrylate and acryl. Acrylic acid alkyl esters such as butyl acid; α-olefins such as ethylene, propylene, and styrene; alkyl vinyl ethers such as vinyl methyl ether and vinyl butyl ether; and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride Alternatively, acid anhydrides thereof may be mentioned, and these may be used alone or in combination of two or more. When the copolymerization amount of the other vinyl compound is 30% by mass or less, the original characteristics of the vinyl chloride resin are not impaired, which is preferable.
Furthermore, these vinyl chloride resins may be used alone or in combination of two or more kinds.

The vinyl chloride resin (A) used in the present invention preferably has an average degree of polymerization of 300 to 5,000, more preferably 500 to 3,000. By setting the average degree of polymerization to 300 or more, the impact strength becomes good. Further, when the average degree of polymerization is 5,000 or less, the gelling property becomes good.

The method for producing the vinyl chloride resin (A) used in the present invention is not particularly limited, and those produced by various polymerization methods such as emulsion polymerization method, suspension polymerization method and bulk polymerization method can be used.

Polytetrafluoroethylene (B)
By using polytetrafluoroethylene (hereinafter referred to as "PTFE") (B), the gelling property of the vinyl chloride resin can be improved, and the lubricity can be imparted during the heat-melt kneading.

The number average molecular weight of PTFE (B) is not particularly limited, but is preferably 1,000,000 to 50,000,000, more preferably 1,000,000 to 30,000,000, further preferably 1.5,000,000 to 20,000,000, and 500. It is particularly preferable that it is from 10 to 20 million.

When the number average molecular weight of PTFE (B) is 1,000,000 or more, the effect of improving the gelling property when PTFE (B) is mixed with the vinyl chloride resin (A) becomes sufficient. Further, when the number average molecular weight of PTFE (B) is 50 million or less, the dispersibility of PTFE (B) when PTFE (B) is mixed with vinyl chloride resin (A) becomes good, and the obtained molded article is obtained. In addition to having an excellent surface appearance, the melt viscosity and melt tension are not excessive, so that the productivity improving effect of PTFE (B) is not hindered. Here, the number average molecular weight (Mn) of PTFE is the heat of crystallization ΔHc (cal/cal) using a differential scanning calorimeter (DSC) according to the method of Suwa et al. (Journal of Applied Polymer Science, 17, 3253 (1973)). g) is measured and calculated based on the following formula.
Mn=2.1×10̂10×ΔHĉ(−5.16)

PTFE (B) is obtained by emulsion-polymerizing a tetrafluoroethylene monomer using a fluorine-containing surfactant. In the emulsion polymerization, fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether as copolymerization components, and (meth), as long as the characteristics of PTFE are not impaired. (Meth)acrylic acid fluorine-containing alkyl ester such as acrylic acid perfluoroalkyl ester can be used. The other monomer that is copolymerized with tetrafluoroethylene can be used in a range that does not impair the gelling property improving effect of PTFE and properties such as lubricity, and is 10% by mass or less in 100% by mass of PTFE. Preferably.

In the resin composition, the PTFE (B) is added so as to be 0.001 to 3 parts by mass, and 0.001 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). Preferably 0.001 to 1.5 parts by mass, more preferably 0.001 to 1 part by mass, and further preferably 0.001 to 0.75. It is particularly preferable to add it so as to be in a mass part, it is particularly preferable to be added so as to be in a range of 0.05 to 0.5 mass part, and it is even more preferable to be in a range of 0.1 to 0.3 mass part. preferable.

When the amount of the PTFE component is 0.001 parts by mass or more, the gelling property improving effect is exhibited, the physical properties and appearance of the molded article are improved, and the lubricity of PTFE during heating, melt-kneading, and the productivity are improved. improves. Further, when the content of the PTFE component is 3 parts by mass or less, the lubricity at the time of heat-melt kneading does not become excessive, and in addition, excessive melt tension/melt viscosity does not appear, so that the productivity improving effect and gelation Good physical properties and a good appearance can be obtained without hindering the property improving effect.

Polymers other than polytetrafluoroethylene (C)
In the resin composition of the present invention, by allowing the polymer (C) to be present together with the PTFE (B), the dispersibility of the PTFE (B) in the vinyl chloride resin (A) can be improved, and the surface appearance of the molded article can be improved. It will be good.

The polymer (C) used in the present invention is not particularly limited, but for the purpose of improving the dispersibility of the PTFE (B) when blended with the vinyl chloride resin (A), a phase with the vinyl chloride resin is used. It is preferably highly compatible. Since the polymer (C) has excellent compatibility with the vinyl chloride resin (A), the dispersion of PTFE (B) in the molded product becomes good, and the surface appearance and impact strength of the resulting molded product are improved. Excel.

Specific examples of the monomer constituting the polymer (C) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid. (Meth)acrylate monomers such as 2-ethylhexyl, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, o-methoxystyrene, and α. -Aromatic vinyl monomers such as methylstyrene; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether: vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; ethylene, propylene, and Examples thereof include olefin-based monomers such as isobutylene; and diene-based monomers such as butadiene and isoprene. These monomers may be used alone or in combination of two or more depending on the purpose.
For example, the polymer may be a polymer composed of constitutional units derived from one or more of the above monomers.

Among them, the polymer (C) is a (meth)acrylic acid ester-based monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer in terms of compatibility with the vinyl chloride resin (A). It is preferable to contain 50% by mass or more of a structural unit derived from one or more kinds of monomers selected from the group consisting of a body. In addition, the structural unit derived from one or more kinds of monomers selected from the group consisting of (meth)acrylic acid ester-based monomers having an alkyl group having 1 to 12 carbon atoms at the ester site, styrene, and acrylonitrile is 50 It is more preferable that the content is at least mass %. Further, it is more preferable to contain 50% by mass or more of a structural unit derived from a (meth)acrylic acid ester-based monomer having an alkyl group having 1 to 12 carbon atoms at the ester portion. Further, it is particularly preferable to contain 50% by mass or more of a structural unit derived from a (meth)acrylic acid ester-based monomer having an alkyl group having 1 to 5 carbon atoms at the ester portion. The proportion of the structural unit in the polymer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.
Here, examples of the (meth)acrylic acid ester-based monomer having an alkyl group having 1 to 12 carbon atoms at the ester portion include methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, methyl acrylate. , Ethyl acrylate, and butyl acrylate.

50% by mass or more of structural units derived from one or more kinds of monomers selected from the group consisting of (meth)acrylic acid ester-based monomers, aromatic vinyl-based monomers, and vinyl cyanide-based monomers By containing it, the compatibility with the vinyl chloride resin (A) becomes good, and the dispersibility of PTFE (B) can be enhanced, so that the obtained molded article is excellent in the surface appearance and impact strength improving effect.

The mass average molecular weight (Mw) of the polymer (C) is preferably 10,000 to 1,500,000, more preferably 10,000 to 1,000,000, and particularly preferably 10,000 to 500,000. By setting Mw to 10,000 or more, the dispersibility of PTFE (B) when used as a PTFE-containing powder (F) can be increased, and by setting it to 1.5 million or less, the dispersibility of the polymer (C) can be increased. Can be increased. Here, Mw is a value obtained by measuring the tetrahydrofuran-soluble content of the polymer (C) by gel permeation chromatography (GPC).
As a method for adjusting the mass average molecular weight (Mw), a conventional method such as adjusting the amount of chain transfer agent or initiator used during polymerization and adjusting the polymerization temperature can be used.

The polymer (C) may be a non-rubber type thermoplastic resin.

Regarding the polymer (C), when 0.01 g of the polymer (C) is dispersed in 10 mL of tetrahydrofuran (THF), the ratio of dissolving in THF is 60% by mass or more based on 100% by mass of the polymer (C). Is more preferable, 75% by mass or more is more preferable, 90% by mass or more is particularly preferable, and 95% by mass or more is most preferable.

When the proportion of the polymer (C) dissolved in THF is 60% by mass or more based on 100% by mass of the polymer (C), the PTFE (B) is well dispersed in the molded product, and the resulting molded product is obtained. Excellent in improving the surface appearance and impact strength.

Various methods can be used for polymerizing the polymer (C), and examples of the polymerization method include emulsion polymerization, suspension polymerization, and solution polymerization. Among these polymerization methods, emulsion polymerization and soap-free emulsion polymerization are preferable, and emulsion polymerization is more preferable, because the production of the polytetrafluoroethylene-containing powder described later becomes easy.

The emulsifier that can be used when the emulsion polymerization method is applied is not particularly limited, and various emulsifiers can be used, and examples thereof include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonate salts, alkyl phosphate ester salts. , And anionic surfactants such as dialkyl sulfosuccinates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan acid fatty esters, and glycerin fatty acid esters; and cationic amines such as alkylamine salts Surfactants can be used. Further, these emulsifiers can be used alone or in combination.

Further, when the pH of the polymerization system is on the alkaline side depending on the type of emulsifier used, a suitable pH adjuster can be used to prevent hydrolysis of the alkyl methacrylate. Examples of the pH adjuster include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, potassium dihydrogen phosphate. Borax or disodium hydrogen phosphate-citric acid or the like or mixtures thereof can be used.

Further, the polymerization initiator may be a water-soluble, oil-soluble single type or redox type, for example, an inorganic initiator such as a usual persulfate is used alone, or sulfite, bisulfite, Alternatively, it can be used as a redox initiator in combination with thiosulfate or the like. Further, an organic peroxide such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, or lauroyl peroxide, or an azo compound or the like may be used alone or in combination with sodium formaldehyde sulfoxylate to start a redox system. Although it can be used as an agent, the present invention is not limited to these specific examples.

Examples of the chain transfer agent include alkyl mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan.
The amount of the chain transfer agent is not particularly limited, but is preferably 0 to 3 parts by mass, more preferably 0.01 to 3 parts by mass, and 0 with respect to 100 parts by mass of the polymer (C). It is more preferably 0.1 to 3 parts by mass.

In the resin composition, the polymer (C) is preferably added so as to be 0.001 to 30 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A), and 0.001 to 15 parts by mass. It is more preferable that it is added so as to be 0.001 to 12 parts by mass, further preferably 0.001 to 6 parts by mass, and particularly preferably 0.001 to 6 parts by mass. To 3 parts by mass is particularly preferred, 0.05 to 1.5 parts by mass is even more preferred, and 0.1 to 1 parts by mass is even more preferred. preferable.

When the amount of the polymer (C) is 0.001 part by mass or more, the dispersion of the PTFE (B) in the molded product becomes good, and the resulting molded product has excellent surface appearance and impact strength improving effect. Further, when the amount of the polymer (C) is 30 parts by mass or less, the decrease in impact strength can be suppressed.

Filler (D)
Examples of the filler (D) used in the present invention include metal powder, oxide, hydroxide, silicic acid and silicate, carbonate, silicon carbide, vegetable fiber, animal fiber, and synthetic fiber. Specific examples of the aluminum powder, copper powder, iron powder, alumina, natural wood, paper, calcium carbonate, talc, glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, aluminum hydroxide, Included are magnesium hydroxide, silica, clays, zeolites, acetate powders, silk powders, aramid fibers, azodicarbonamide, graphite, and reclaimed filler materials. These may be used alone or in combination of two or more.

When a filler is added for the purpose of improving flame retardancy, for example, metal hydroxide, bromine compound, triazine ring-containing compound, zinc compound, phosphorus compound, halogen compound, silicon compound, intumescent compound Alternatively, antimony oxide can be used. These can be used alone or in combination of two or more.

The amount of the filler (D) added is 1 to 2,000 parts by mass, preferably 6 to 2,000 parts by mass, more preferably 10 to 2,000 parts by mass, based on 100 parts by mass of the vinyl chloride resin (A). To 500 parts by mass are more preferred, 10 to 200 parts by mass are particularly preferred, and 20 to 150 parts by mass are even more preferred. By adjusting the amount to be 1 part by mass or more, it is possible to impart appropriate rigidity to the molded product and to expect the effect of increasing the amount of filler (reduction of petroleum-derived components, reduction of raw material cost). In addition, by increasing the amount of the filler added to 10 parts by mass or more, it is possible to meet the increasing demand for increasing the amount of the filler, and by increasing the amount of the filler added to 30 parts by mass or more, it is possible to meet the strong demand for increasing the amount of the filler. It is preferable that the amount of 40 parts by mass or more can meet a stronger demand for increasing the amount of the filler, and the amount of 50 parts by mass or more can satisfy a further demand for increasing the amount of the filler. Further, when the amount is 2000 parts by mass or less, it is possible to prevent deterioration of the smoothness of the appearance of the molded body.

Acrylic polymer (δ) or acrylic polymer powder (E)
The resin composition of the present invention may further contain an acrylic polymer (δ) or an acrylic polymer powder (E) for the purpose of imparting high gloss and further improving the gelling property.

The acrylic polymer powder (E) is a methacrylic acid alkyl ester (e-1) (hereinafter, referred to as a monomer (e-1)) in which the alkyl group of the alkyl ester portion is an alkyl group having 1 to 10 carbon atoms. Methacrylic acid alkyl ester copolymer obtained by polymerizing 10 to 100% by mass and 0 to 90% by mass of other copolymerizable monomer (e-2) (hereinafter referred to as monomer (e-2)). It is a polymer powder obtained by recovering a polymer (hereinafter referred to as polymer (δ)) in powder form.

Examples of the monomer (e-1) used in the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate. Be done. Among them, a methacrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, since the appearance-improving ability and the powder collecting ability of the molded article are improved, Butyl methacrylate and pentyl methacrylate are preferred.
These methacrylic acid alkyl esters may be used alone or in combination of two or more depending on the purpose.

The monomer (e-2) is not particularly limited as long as it is a monomer that can be copolymerized with the monomer (e-1), and for example, ethyl acrylate, butyl acrylate, acrylic acid-2- Acrylic esters such as ethylhexyl, benzyl acrylate, and phenyl acrylate; Aromatic methacrylic acid esters such as benzyl methacrylate and phenyl methacrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Acrylonitrile And vinyl cyanide compounds such as methacrylonitrile; vinyl esters such as vinyl acetate; and acid anhydrides such as maleic anhydride. These can be used alone or in combination of two or more.

The amount of the monomer (e-1) used is 10 to 100% by mass, preferably 30 to 100% by mass, based on 100% by mass of all the monomers as the raw material of the polymer (δ). %, more preferably 40 to 100% by mass, further preferably 50 to 100% by mass, particularly preferably 65 to 100% by mass, and most preferably 75 to 100% by mass. When the amount of the monomer (e-1) used is 10% by mass or more, the compatibility with the vinyl chloride resin becomes good, and the gloss and gelling property of the molded product can be improved.

The amount of the monomer (e-2) used is 0 to 90% by mass, preferably 0 to 70% by mass, based on 100% by mass of all the monomers as the raw material of the polymer (δ). It is more preferably 0 to 60% by mass, further preferably 0 to 50% by mass, particularly preferably 0 to 35% by mass, and most preferably 0 to 25% by mass. When the amount of the monomer (e-2) used is 90% by mass or less, the gelling property of the vinyl chloride resin composition is not hindered, and the appearance of the molded article becomes good.

As the monomer (e-2), a polyfunctional monomer such as divinylbenzene, allyl methacrylate, dimethacrylic acid-1,3-butylene glycol, or triallyl cyanurate may be used, but the monofunctional monomer may be used. The amount of the monomer used is preferably 0.1 to 2% by mass, and more preferably 0.2 to 1% by mass, based on 100% by mass of all the monomers as the raw material of the polymer (δ). It is preferable that the amount of the polyfunctional monomer used is 2% by mass or less, since it does not hinder a good molding appearance.

The mass average molecular weight (Mw) of the polymer (δ) is 2,000,000 to 6,000,000, preferably 2,000,000 to 5,000,000, more preferably 2,000,000 to 4.5,000,000, particularly preferably 2.5,000,000 to 4.5,000,000. When the Mw is 2,000,000 or more, the effect of improving the gloss of the molded article becomes good, and the effect of improving the gelling property is exhibited. Further, when the amount is 6 million or less, the dispersibility of the polymer (δ) in the molded product becomes good and the improvement of the appearance is not hindered. Here, Mw is a value obtained by measuring the tetrahydrofuran-soluble component of the polymer (δ) by gel permeation chromatography (GPC).
As a method for adjusting the mass average molecular weight (Mw), a conventional method such as adjusting the amount of chain transfer agent or initiator used during polymerization and adjusting the polymerization temperature can be used.

The polymer (δ) may be a non-rubber type thermoplastic resin.
Regarding the polymer (δ), when 0.01 g of the polymer (δ) is dispersed in 10 mL of tetrahydrofuran (THF), the ratio of dissolving in THF is 60% by mass or more based on 100% by mass of the polymer (δ). Is more preferable, 75% by mass or more is more preferable, 90% by mass or more is particularly preferable, and 95% by mass or more is most preferable.
When the proportion of the polymer (δ) dissolved in THF is 60% by mass or more based on 100% by mass of the polymer (δ), the dispersion of the polymer (δ) in the molded product becomes good, and the obtained molded product is obtained. Excellent body surface gloss and gelling properties.

Various methods can be used as the method for producing the polymer (δ), and examples of the polymerization method include emulsion polymerization, suspension polymerization, and solution polymerization. Furthermore, any method such as batch addition of monomers, dropping, and divided addition of monomers may be used, and methods such as random copolymerization or block copolymerization may be used. The random copolymer obtained by the method of adding all of

The emulsifier that can be used when applying the emulsion polymerization method is not particularly limited, and various emulsifiers can be used as in the polymerization of the polymer (C).

Further, when the pH of the polymerization system is on the alkaline side depending on the type of emulsifier used, a suitable pH adjuster can be used to prevent hydrolysis of the alkyl methacrylate.

Further, the polymerization initiator may be a water-soluble, oil-soluble single type or redox type, for example, an inorganic initiator such as a usual persulfate is used alone, or sulfite, bisulfite, Alternatively, it can be used as a redox initiator in combination with thiosulfate or the like. Further, an organic peroxide such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and lauroyl peroxide, and an azo compound or the like may be used alone or in combination with sodium formaldehyde sulfoxylate to start a redox system. Although it can be used as an agent, the present invention is not limited to these specific examples.

The method for recovering the polymer (δ) in powder form is not particularly limited, but in order to obtain a good molding appearance in the vinyl chloride resin composition, the obtained alkyl methacrylate ester-based polymer particle dispersion liquid is used. It is preferable to cool the dispersion, and to put the dispersion into hot water in which a coagulant is dissolved, and to powderize the dispersion by a coagulation method in which it is caused to undergo a segregation while stirring to be dried as a slurry, or a spray drying method.

Examples of the suspending agent used in the coagulation method include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid and acetic acid; and aluminum sulfate, magnesium sulfate, calcium acetate, calcium chloride, and Inorganic salts such as calcium sulfate can be used.
Further, the spray drying method refers to a drying method in which a particle dispersion liquid of the present polymer is sprayed in the form of fine droplets in a spray dryer and then hot air is applied.

Examples of the method of spraying the particle dispersion liquid of the present polymer in the form of fine droplets in a spray dryer include a rotating disk system, a pressure nozzle system, a two-fluid nozzle system, and a pressurized two-fluid nozzle system.
The capacity of the spray dryer may be any of a small capacity used in a laboratory and a large capacity used industrially.
The structure of the heating heating gas supply unit and the structure of the heating heating gas and dry powder discharge unit in the spray dryer may be appropriately selected according to the purpose.
The temperature of the heating gas for drying is preferably 200°C or lower, and more preferably 120 to 180°C.

Examples of the chain transfer agent include alkyl mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan.
The amount of the chain transfer agent is not particularly limited, but is preferably 0 to 2 parts by mass, more preferably 0 to 1 part by mass, and 0 to 100 parts by mass of the polymer (δ). It is more preferably 0.5 part by mass.

When the acrylic polymer (δ) is added, the addition amount is 0.1 to 10 parts by mass, preferably 0.1 to 7 parts by mass, with respect to 100 parts by mass of the vinyl chloride resin (A). 0.1 to 5 parts by mass is particularly preferable. When the amount is 0.1 part by mass or more, gloss can be imparted to the molded product, and in addition, the effect of improving the gelling property is exhibited. In addition, when the amount is 10 parts by mass or less, excessive load on the molding machine is suppressed and productivity is not impaired.

When the acrylic polymer powder (E) is added, the addition amount is 0.1 to 10 parts by mass, and 0.1 to 7 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). Preferably, 0.1 to 5 parts by mass is particularly preferable. When the amount is 0.1 part by mass or more, gloss can be imparted to the molded product, and in addition, the effect of improving the gelling property is exhibited. In addition, when the amount is 10 parts by mass or less, excessive load on the molding machine is suppressed and productivity is not impaired.

The vinyl chloride resin composition of the present invention may contain various additives such as a conventional stabilizer, a lubricant, or an impact resistance modifier, if necessary, as long as the effects of the present invention are not impaired. Can be added.

Examples of the stabilizer include lead stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate, potassium, magnesium, barium, zinc, cadmium, and lead. Metals: Metal soap stability derived from fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid and behenic acid Agents: Organotin stabilizers having an alkyl group, ester group, fatty acid group, maleic acid group, sulfide group, etc.; Ba-Zn type, Ca-Zn type, Ba-Ca-Sn type, Ca -Mg-Sn-based, Ca-Zn-Sn-based, Pb-Sn-based, and Pb-Ba-Ca-based complex metal soap-based stabilizers; metal groups such as barium and zinc; 2-ethylhexanoic acid, isodecane Acids, branched fatty acids such as trialkylacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid, and linoleic acid, alicyclic acids such as naphthenic acid, carboxylic acids, benzoic acid, salicylic acid, and aromatic acids such as substituted derivatives thereof. Metal salt stabilizers usually derived from two or more of such organic acids; these stabilizers are dissolved in an organic solvent such as petroleum hydrocarbon, alcohol, or glycerin derivative, and further phosphite ester, epoxy compound, color development Metal stabilizers such as a stabilizer, a transparency improver, a light stabilizer, an antioxidant, a bleed-out inhibitor, or a metal salt liquid stabilizer containing a stabilizing aid such as a lubricant; an epoxy resin; and Examples thereof include epoxy compounds such as epoxidized fatty acid alkyl ester, and non-metal stabilizers such as organic phosphite, and these are used alone or in combination of two or more.

The amount of the stabilizer added is not particularly limited, but is preferably 1 to 15 parts by mass, and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). When the amount is 1 part by mass or more, thermal decomposition at the time of processing can be suppressed, and when the amount is 15 parts by mass or less, the impact strength of the molded body can be prevented from lowering.
Examples of lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, and low molecular weight polyethylene; halogenated hydrocarbon lubricants, fatty acid lubricants such as higher fatty acids and oxyfatty acids. Fatty acid amides and fatty acid amide lubricants such as bis fatty acid amides; polyhydric alcohol esters of fatty acids such as lower alcohol esters and glycerides of fatty acids; polyglycol esters of fatty acids and esters of fatty alcohol esters (ester waxes) of fatty acids Lubricants: metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, and partial ester of fatty acid and polyglycol or polyglycerol. These are one kind. Alternatively, two or more kinds can be used in combination.

The amount of the lubricant added is not particularly limited, but is preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). When the amount is 0.1 parts by mass or more, the adhesion of the resin composition to the molding machine can be reduced, and when the amount is 15 parts by mass or less, the deterioration of the gelling property can be prevented.

Furthermore, when an impact modifier is added, for example, chlorinated polyethylene, polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, Acrylic core-shell type rubber such as methyl methacrylate-styrene-butadiene copolymer rubber and acrylic acid ester-methacrylic acid ester copolymer; silicone-acrylic acid ester-methacrylic acid ester copolymer and silicone-acrylic acid ester -Silicon core-shell type rubber such as acrylonitrile-styrene copolymer; styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-ethylene-butylene-styrene block copolymer rubber, Examples thereof include ethylene-propylene copolymer rubber and ethylene-propylene-diene copolymer rubber (EPDM). As the EPDM diene, 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene, or the like can be used. These impact modifiers may be used alone or in combination of two or more.

The amount of the impact resistance modifier added is not particularly limited, but is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the vinyl chloride resin (A). When the amount is 1 part by mass or more, the impact strength of the molded product can be improved, and when the amount is 20 parts by mass or less, deterioration of the molded appearance can be prevented.

In addition, a release agent, a fluidity improver, a colorant, an antistatic agent, a surfactant, an antifogging agent, an antibacterial agent, a plasticizer, a foaming agent, or the like may be used as long as the effects of the present invention are not impaired. It can be optionally blended.

The method for obtaining the vinyl chloride resin composition of the present invention is not particularly limited, and a generally known method can be used. For example, a predetermined amount of vinyl chloride resin (A) and PTFE (B), a polymer (C ), the filler (D) and, if necessary, the acrylic polymer (δ) or the acrylic polymer powder (E) are mixed by a Henschel mixer, a Banbury mixer, a V-type mixer, a ribbon blender or the like. ..

As a method for obtaining the vinyl chloride resin composition of the present invention, a polytetrafluoroethylene-containing powder (F) containing PTFE (B) and a polymer (C) is produced, which is then used as a vinyl chloride resin (A), It is preferable to mix with the filler (D) and, if necessary, the acrylic polymer (δ) or the acrylic polymer powder (E).
According to this method, the PTFE (B) is well dispersed in the molded article, and the resulting molded article is excellent in surface appearance and impact strength improving effect.

Polytetrafluoroethylene-containing powder (F)
The polytetrafluoroethylene-containing powder (F) used in the present invention contains PTFE (B) and a polymer (C) other than polytetrafluoroethylene.
The presence of the polymer (C) together with the PTFE (B) allows the PTFE-containing powder (F) to have good powder handling properties such as powder fluidity and powder bulk ratio.

In 100% by mass of the PTFE-containing powder (F) used in the present invention, the content of PTFE (B) is preferably 1 to 90% by mass, more preferably 5 to 85% by mass, and 10 to 10% by mass. It is more preferably 80% by mass, and particularly preferably 15 to 70% by mass. By setting the content of PTFE (B) to 1% by mass or more, the effect of improving the gelling property is enhanced, the physical properties and appearance of the molded article are improved, and the slipperiness during molding is imparted to improve the productivity. Become. Further, when the content of PTFE (B) is 90% by mass or less, the dispersibility of PTFE (B) in the molded product becomes good, and the appearance of the molded product becomes good.

Further, the content of the polymer (C) is preferably 10 to 99% by mass, more preferably 15 to 95% by mass, and more preferably 20 to 90% in 100% by mass of the PTFE-containing powder (F). The content is more preferably the mass%, and particularly preferably 30 to 85 mass%. When the content of the polymer (C) is 10% by mass or more, the powder handling property of the PTFE-containing powder (F) becomes good and the dispersibility of the PTFE (B) in the molded product becomes good. Therefore, the appearance of the molded body becomes good. When the content of the polymer (C) is 99% by mass or less, the effect of adding PTFE (B) is exhibited, and the physical properties, appearance and productivity of the molded product are improved.

The PTFE-containing powder (F) may contain additives, if necessary, in addition to the PTFE (B) and the polymer (C). Examples of the additives include powder fluidity modifiers such as inorganic salts and Aerosil.

The method for obtaining the aqueous dispersion of the PTFE-containing powder (F) is not particularly limited, but a method of mixing the aqueous dispersion of PTFE (B) and the aqueous dispersion of the polymer (C), and the method of mixing PTFE (B) A method of polymerizing a monomer constituting the polymer (C) in the presence of an aqueous dispersion, or an aqueous dispersion of an aqueous dispersion of PTFE (B) and a part of the monomer constituting the polymer (C). Examples thereof include a method of emulsion-polymerizing the remaining monomers constituting the polymer (C) in a dispersion obtained by mixing the liquids.

Examples of commercially available PTFE (B) aqueous dispersions include “Fluon AD911”, “Fluon AD912”, “Fluon AD915”, “Fluon AD938”, and “Fluon AD939” (trade name, manufactured by Asahi Glass Co., Ltd.), In addition, commercially available products (AD938E etc.) in which E or L follows the above product number can be mentioned.
As the aqueous dispersion of PTFE (B), one type may be used alone, or two or more types may be used in combination.

The method for recovering the PTFE-containing powder (F) is not particularly limited, but since the aggregation of PTFE (B) is suppressed, the aqueous dispersion thereof is introduced into hot water in which a coagulant is dissolved, It is preferable to powderize by a coagulation method in which the slurry is dried while stirring to cause a segregation or a spray drying method. Among these methods, the coagulation method is more preferable.

Examples of the suspending agent used in the coagulation method include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid and acetic acid; and aluminum sulfate, magnesium sulfate, calcium acetate, calcium chloride, and An inorganic salt such as calcium sulfate can be used.

The obtained vinyl chloride resin composition is applied to not only extrusion molding using a kneading extruder such as a single-screw extruder or a twin-screw extruder, but also known ordinary molding methods such as injection molding, blow molding, and roll processing. Thus, various desired molded bodies can be obtained.

The surface hardness (durometer D hardness) of the molded product obtained by molding the vinyl chloride resin composition of the present invention is preferably 65 or more, more preferably 70 or more, and particularly preferably 85 or more. ..
The durometer D hardness of 65 or more is suitable for use as a hard building member.
The surface hardness can be arbitrarily adjusted by a generally known method such as the amount of the plasticizer added, the type of the plasticizer, the degree of polymerization of the vinyl chloride resin, etc., as long as the effects of the present invention are not impaired.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.
In addition, in this Example, a comparative example, and a reference example, "part" shows a "mass part" and "phr" shows the "mass part with respect to 100 mass parts of vinyl chloride resin."

The vinyl chloride resin compositions obtained in the present Examples, Comparative Examples and Reference Examples and molded articles thereof were evaluated as follows.
(1) Using a tetrahydrofuran-soluble component of the mass average molecular weight polymer (C), acrylic polymer (δ) and acrylic polymer powder (E), the molecular weight is measured by gel permeation chromatography (GPC). did. The measurement conditions of GPC are as follows, and the mass average molecular weight was determined from the calibration curve of standard polystyrene.
Device: Tosoh Corporation "HLC8220"
Column: "TSKgel SuperMultipore HZ-H" manufactured by Tosoh Corporation (inner diameter 4.6 mm x length 15 cm x 2, exclusion limit 4 x 10^7 (estimated))
Eluent: THF
Eluent flow rate: 0.35 ml/min Measuring temperature: 40°C
Sample injection volume: 10 μl (sample concentration 0.1%)

(2) Evaluation of processability The vinyl chloride resin composition was filled in a Brabender Plasticorder (manufactured by Brabender) and the gelling property was evaluated to evaluate the processability.

The gelation time was the time required from the start of kneading after preheating to reaching the maximum torque. It can be said that the faster the gelling time is, the better the gelling property is, and the better the processability is.

(3) Productivity Evaluation When the vinyl chloride resin composition was melt-extruded, the extruded mass (discharging amount) of the molded product per hour was measured. At this time, it can be said that the larger the ejection amount, the better the productivity.

(4) Appearance evaluation The surface appearance was observed by visually observing the surface of the molded product obtained by melt-extruding the vinyl chloride resin composition.
++++: The surface of the molded product is smooth and has a high gloss. +++: The surface of the molded product is smooth ++: Some irregularities are seen on the surface of the molded product, and it is not smooth. +: Many irregularities are seen on the surface of the molded product. Not smooth

(5) Impact Strength Test A molded article obtained by melt-extruding a vinyl chloride resin composition was subjected to a Charpy impact strength test with a notch based on JIS K7111, and the impact strength at 23° C. was measured. The larger the value, the better the strength.

(6) Evaluation of Heat Shrinkability The molded product obtained by melt-extruding the vinyl chloride resin composition was allowed to stand for 1 hour in an atmosphere of 180° C., and the heat shrinkage rate was calculated based on the following formula.
{(L ₀ −L ₁ )/L ₀ }×100
L ₀ : Length of molded body before heating L ₁ : Length of molded body after heating Smaller value indicates lower heat shrinkage, which is considered to be good.

(Examples and comparative examples)
Manufacture of vinyl chloride resin composition In addition to a predetermined amount of various PTFE-containing powders (F) and an acrylic polymer (δ), a predetermined amount of calcium carbonate as a filler (D) (Hakutan CCR, manufactured by Shiraishi Calcium Co., Ltd.) , 100 parts of vinyl chloride resin (TK-1000, manufactured by Shin-Etsu Chemical Co., Ltd., average polymerization degree: 1050) as vinyl chloride resin (A), 3 parts of Ca-Zn composite stabilizer (manufactured by San Ace Co.) as a stabilizer, and glycerin as a lubricant. Fatty acid ester (Loxiol GH-4, manufactured by Emery Oleo) 1.0 part, polymer composite ester (Loxiol VPN963, manufactured by Emery Oleo) 0.6 part, Methyl methacrylate-butadiene-styrene as impact strength modifier 5.0 parts of the copolymer (Metablene C-223A, manufactured by Mitsubishi Rayon Co., Ltd., tetrahydrofuran-soluble content mass average molecular weight 840,000) was supplied to a Henschel mixer and uniformly mixed to obtain a vinyl chloride resin composition.

Production of Polytetrafluoroethylene-Containing Powder (F) As the PTFE-containing powder (F), the followings were used with the composition shown in Table 1.

[Production Example 1] Production of PTFE-containing powder (F-1) PTFE dispersion AD939E (manufactured by Asahi Glass Co., Ltd., number average molecular weight: 15 million, PTFE concentration: 60% by mass) 83.3 parts, distilled water 116.7 parts Was added to obtain a PTFE dispersion (B-1) having a PTFE concentration of 25.0% by mass.

On the other hand, in a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, 225 parts of distilled water, 80 parts of methyl methacrylate, 20 parts of -n-butyl acrylate, 0.2 parts of n-octyl mercaptan, dodecyl. 2.5 parts of sodium benzenesulfonate and 0.2 part of diisopropylbenzene hydroperoxide were charged and the atmosphere in the reaction vessel was replaced with nitrogen by passing a nitrogen stream. Then, when the temperature of the inside of the system was raised to 60°C and the temperature of the liquid inside reached 60°C, 0.0005 parts of iron (II) sulfate, 0.0015 parts of disodium ethylenediaminetetraacetate, and 0.3% of Rongalite salt were added. Part and 5 parts of distilled water were added to the mixture to initiate polymerization. Then, it hold|maintained at 80 degreeC for 90 minutes, superposition|polymerization was completed, and the polymer dispersion liquid (C-1) was obtained. The solid content concentration of this dispersion liquid (C-1) was 30.4%, and the mass average molecular weight (Mw) of the polymer contained in the dispersion liquid (C-1) was 120,000.

Then, 200 parts of the PTFE dispersion (B-1) prepared above (50 parts of polytetrafluoroethylene) was charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and the polymer was dispersed therein. 164.5 parts of the liquid (C-1) ((50 parts of polymer) was charged and heated and stirred until the internal liquid temperature reached 80° C. 1 hour while the internal liquid temperature reached 80° C. Stirring was continued to obtain a mixed solution of both dispersions, 100 parts of the obtained mixed solution of both dispersions was gradually added dropwise to 150 parts of a 4% by mass aqueous solution of aluminum sulfate while stirring to precipitate a solid matter. Next, this precipitate was separated, filtered, and dried to obtain PTFE-containing powder (F-1).

[Production Example 2] Production of PTFE-containing powder (F-2) Same as Production Example 1 except that the PTFE dispersion used was changed to AD915E (manufactured by Asahi Glass Co., Ltd., number average molecular weight: 3,000,000, PTFE concentration 60% by mass). Then, a PTFE-containing powder (F-2) was obtained.

[Production Example 3] Production of PTFE-containing powder (F-3) 2.0 parts of sodium dosylbenzenesulfonate and distilled water in a mixed solution of 70 parts of dodecyl methacrylate, 25 parts of methyl methacrylate and 5 parts of ethyl acrylate. After adding 300 parts of the mixed solution and stirring with a homomixer at 10000 rpm for 4 minutes, the mixture was passed through a homogenizer twice at a pressure of 300 kg/cm ² to obtain a stable dodecyl methacrylate/methyl methacrylate/ethyl acrylate predispersion liquid. Got This was charged into a reaction vessel equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet, 0.2 part of diisopropylbenzene hydroperoxide was added, and the atmosphere in the reaction vessel was replaced with nitrogen by passing a nitrogen stream. It was Then, when the temperature of the inside of the system was raised to 60°C and the temperature of the liquid inside reached 60°C, 0.0005 parts of iron (II) sulfate, 0.0015 parts of disodium ethylenediaminetetraacetate, and 0.3% of Rongalit salt Part and 5 parts of distilled water were added to the mixture to initiate polymerization. Then, it hold|maintained at 70 degreeC for 90 minutes, superposition|polymerization was completed, and the polymer dispersion liquid (C-3) was obtained. The solid content concentration of the polymer dispersion liquid (C-3) was 25.1% by mass.

Next, a PTFE stirrer AD939E (manufactured by Asahi Glass Co., Ltd.) 33.3 parts (PTFE concentration 60% by mass), a polymer dispersant (C-3) 239.0 parts, and sodium dosylbenzenesulfonate 0.5 part were stirred. A separable flask equipped with a condenser, a thermocouple, a nitrogen inlet, and a dropping funnel was charged, and the mixture was stirred at room temperature under a nitrogen stream for 1 hour. Then, the temperature of the system was raised to 80° C., and a mixed solution of 0.001 part of iron sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt, and 10 parts of distilled water was added, and then methacrylic acid was added. A mixed solution of 19 parts of methyl, 1 part of ethyl acrylate and 0.1 part of diisopropylbenzene hydroperoxide was added dropwise over 30 minutes, and after the addition was completed, the internal temperature was kept at 80° C. for 1 hour to complete the polymerization. .. Separation of solid content was not observed through a series of operations, and a uniform particle dispersion liquid was obtained. The solid content concentration of the particle dispersion was 28.5% by mass, and the mass average molecular weight (Mw) of the polymer contained in this dispersion was 450,000.

100 parts of the obtained dispersion was gradually added dropwise to 150 parts of a 7% by mass calcium acetate aqueous solution under stirring to precipitate a solid. Next, this precipitate was separated, filtered, and dried to obtain PTFE-containing powder (F-3).

[Production Example 4] Production of PTFE-containing powder (F-4) In a reaction vessel equipped with a stirring blade, condenser, thermocouple, and nitrogen inlet, 250 parts of distilled water, 1.0 part of dipotassium alkenylsuccinate, and iron sulfate. (II) 0.0005 parts, ethylenediaminetetraacetate disodium 0.0015 parts and Rongalite salt 0.12 parts were charged, and the atmosphere in the reaction vessel was replaced with nitrogen by passing a nitrogen stream. Then, the temperature of the system was raised to 60° C., and a mixed solution of 80 parts of styrene, 20 parts of acrylonitrile and 0.5 part of cumene hydroperoxide was added dropwise over 2 hours. After completion of the dropping, the polymerization was completed by maintaining the temperature at 60° C. for 90 minutes to obtain a polymer dispersion liquid (C-4). The solid content concentration of this dispersion liquid (C-4) was 28.8%, and the mass average molecular weight (Mw) of the polymer contained in the dispersion liquid (C-4) was 350,000.

Then, 200 parts of the PTFE dispersion (B-1) prepared above (50 parts of polytetrafluoroethylene) was charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and the polymer was dispersed therein. 173.6 parts of the liquid (C-4) ((50 parts of the polymer) was charged and heated and stirred until the internal liquid temperature reached 80° C. 1 hour while the internal liquid temperature reached 80° C. Stirring was continued to obtain a mixed solution of both dispersions, 100 parts of the obtained mixed solution of both dispersions was gradually added dropwise to 150 parts of a 4% by mass aqueous solution of aluminum sulfate while stirring to precipitate a solid matter. Next, this precipitate was separated, filtered, and dried to obtain PTFE-containing powder (F-4).

[Reference Example 1] PTFE-containing powder (F-5) containing no polymer (C)
As the PTFE containing no polymer (C), FLUON CD-1 (manufactured by Asahi Glass Co., Ltd., number average molecular weight: 3,000,000) was used.

The following was used as the acrylic polymer (δ).
[Production Example 5] Production of acrylic polymer (δ-1) 150 parts of ion-exchanged water was charged into a reaction vessel equipped with a stirrer and a reflux condenser, and 0.1 part of anhydrous sodium carbonate, 80 parts of methyl methacrylate and methacrylic acid were charged therein. 20 parts of acid-n-butyl was added, and the inside of the container was replaced with nitrogen. Then, 1.1 parts of sodium dodecyl sulfate was added, the reaction vessel was heated to 43° C. under stirring, 0.15 parts of potassium persulfate was charged to start the polymerization reaction, and then the mixture was heated and stirred for 2 hours to carry out polymerization. After that, an acrylic polymer (δ-1) was obtained. After cooling the resulting acrylic polymer (δ-1) particle dispersion, spray drying was performed under conditions of an inlet temperature of 150°C and an outlet temperature of 65°C to obtain a powdery acrylic polymer powder (E-1 ).
At this time, the polymerization rate was 99% or more, and the mass average molecular weight was 3.1 million.

The various PTFE-containing powders (F) and acrylic polymers (δ) obtained from the above production examples were added and mixed as shown in Table 2 below to obtain vinyl chloride resin compositions.

Each of the obtained compositions was filled in a Brabender Plasticorder (manufactured by Brabender Co., 160° C., preheating: 2 minutes, screw rotation speed: 30 rpm, filling amount: 65 g), and gelling property was evaluated.

In addition, each composition obtained was supplied to a 20 mm conical extruder (manufactured by Toyo Seiki Co., Ltd., C1-C2-C3-D=150-165-180-185° C., 60 rpm (feeder: 70 rpm)) and pelletized. Each vinyl chloride resin composition was obtained.

A 30 mm single screw extruder (GM Engineering Co., 100-150-170-180-180-180-180°C (C1-C2-C3-C4-C5-A- D) and the screw rotation speed: 20 rpm) were melt-extruded to obtain a rectangular rod-shaped vinyl chloride resin molded product having a width of 10 mm and a thickness of 4 mm.
The discharge amount of each vinyl chloride resin molded product was measured to evaluate the productivity.
The obtained molded body was cut into a length of 8 cm, and a test piece with a V-shaped notch having a depth of 2 mm was prepared and subjected to an impact strength test.
Further, the obtained molded body was cut into a length of 200 mm and subjected to heat shrinkage evaluation.

Table 2: Composition examples of vinyl chloride resin composition and properties of the obtained molded product

(Examples 1 to 7)
From the results of Table 2, since the PTFE-containing powder (F) is contained at a predetermined content, no PTFE-containing powder (Comparative Example 1) and PTFE containing no polymer (C) are contained in any of the Examples. Productivity (discharging amount), appearance of molded article, as compared with an example containing powder (F) (Comparative Example 2) and an example containing powder (F) containing PTFE in excess of a predetermined content (Comparative Example 3) It was found that the physical properties of the molded product were remarkably improved.
Further, it was found that in all the examples, the gelling property was remarkably improved, and the influence on the heat shrinkage rate was also small.

(Example 8)
By containing the PTFE-containing powder (F) in a predetermined content, the productivity (discharge amount), the appearance of the molded product, and the physical properties of the molded product are remarkably improved. In addition, by further containing an acrylic polymer, molding It was found that the body appearance had gloss.

(Comparative example 2)
Since the PTFE-containing powder (F) which does not contain the polymer (C) is added, the dispersibility of the PTFE-containing powder (F) becomes low, and the productivity (discharge amount), the appearance of the shaped article, and the physical properties of the shaped article are all decreased. It cannot be said that there is an improvement effect.

(Comparative example 3)
Although the gelling property and the appearance of the molded product are improved to some extent, when the PTFE component is added in excess of the predetermined content, the lubricity at the time of heat-melt kneading becomes excessive and the kneading level remarkably decreases. Moreover, not only the effect of improving productivity and the effect of improving physical properties of the molded article are not observed, but also the heat shrinkage rate is extremely large, which is not suitable for practical use at all.

(Comparative example 4)
Since it does not contain the PTFE-containing powder (F), it cannot be said that the productivity (discharge amount), the appearance of the molded product, and the physical properties of the molded product are all improved.

(Examples 9 to 12)
Even when the amount of the filler is increased with respect to Examples 1 to 7, if the PTFE-containing powder (F) is contained at a predetermined content, no PTFE-containing powder (Comparative Example 5) and polymer (C) are obtained. Productivity (discharging amount) as compared with an example containing a PTFE-containing powder (F) not containing it (Comparative Example 6) and an example containing a PTFE-containing powder (F) exceeding a predetermined content (Comparative Example 7) It can be seen that the appearance of the molded product and the physical properties of the molded product are remarkably improved.
Further, it is understood that in each of the examples, since the PTFE-containing powder (F) is contained in a predetermined content, the gelling property is remarkably improved and the influence on the heat shrinkage rate is small.

(Example 13)
By containing the PTFE-containing powder (F) in a predetermined content, the productivity (discharge amount), the appearance of the molded product, and the physical properties of the molded product are remarkably improved. In addition, by containing the acrylic polymer, It can be seen that the appearance of the molded article has gloss.

(Comparative example 6)
Since the PTFE-containing powder (F) which does not contain the polymer (C) is added, the dispersibility of the PTFE-containing powder (F) becomes low, and the productivity (discharge amount), the appearance of the shaped article, and the physical properties of the shaped article are all decreased. It cannot be said that there is an improvement effect.

(Comparative Example 7)
Although the gelling property and the appearance of the molded product are improved to some extent, the addition of the PTFE component in excess of the predetermined content causes an excessive slippage during heat-melt kneading, resulting in a significant decrease in the kneading level. Moreover, not only the effect of improving productivity and the effect of improving physical properties of the molded article are not observed, but also the heat shrinkage rate is extremely large, which is not suitable for practical use at all.

(Comparative Example 8)
Since it does not contain the PTFE-containing powder (F), it cannot be said that the productivity (discharge amount), the appearance of the molded product, and the physical properties of the molded product are all improved.

Claims (12)

Vinyl chloride resin (A),
Polytetrafluoroethylene (B),
Polymer (C) other than polytetrafluoroethylene and filler (D)
A vinyl chloride resin composition containing:
With respect to 100 parts by mass of the vinyl chloride resin (A),
0.001 to 3 parts by mass of the polytetrafluoroethylene (B),
A vinyl chloride resin composition containing 10 to 200 parts by mass of the filler (D). The polymer (C) is derived from at least one monomer selected from the group consisting of (meth)acrylic acid ester-based monomers, aromatic vinyl-based monomers, and vinyl cyanide-based monomers. The vinyl chloride resin composition according to claim 1, which comprises 50 mass% or more of the constituent unit. The polymer (C) is derived from at least one monomer selected from the group consisting of (meth)acrylic acid ester-based monomers having an alkyl group having 1 to 12 carbon atoms at the ester site, styrene, and acrylonitrile. The vinyl chloride resin composition according to claim 1 or 2, containing 50% by mass or more of the constituent unit. 4. The polymer (C) according to claim 1, wherein the polymer contains 50% by mass or more of a structural unit derived from a (meth)acrylic acid ester-based monomer having an alkyl group having 1 to 12 carbon atoms at the ester portion. The vinyl chloride resin composition according to item 1. Any of claims 1 to 4, wherein the polymer (C) contains 50% by mass or more of a structural unit derived from a (meth)acrylic acid ester-based monomer having an alkyl group having 1 to 5 carbon atoms at the ester site. The vinyl chloride resin composition according to item 1. The vinyl chloride resin composition according to any one of claims 1 to 5, wherein the polymer (C) has a mass average molecular weight (Mw) of 10,000 to 1,500,000. The vinyl chloride resin composition according to any one of claims 1 to 6, wherein the polytetrafluoroethylene (B) has a number average molecular weight (Mn) of 5,000,000 to 20,000,000. The vinyl chloride resin composition according to claim 6, further comprising 0.1 to 10 parts by mass of an acrylic polymer having a mass average molecular weight (Mw) of 2 to 6 million. The vinyl chloride resin composition according to any one of claims 1 to 8, which contains 10 to 2000 parts by mass of the filler (D). The vinyl chloride resin composition according to claim 1, comprising 0.001 to 1.5 parts by mass of the polytetrafluoroethylene (B). A resin molded product obtained by molding the vinyl chloride resin composition according to any one of claims 1 to 10. Mixing a polytetrafluoroethylene-containing powder (F) containing the polytetrafluoroethylene (B) and the polymer (C) with the vinyl chloride resin (A) and the filler (D). A method for producing the vinyl chloride resin composition according to claim 1.