JP2002363362A - Vinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride-based resin composition which gives a molded article excellent in fracture toughness strength and long-term durability. SOLUTION: The vinyl chloride-based resin composition comprises (A) a vinyl chloride-based resin and (B) a surface modifier. The vinyl chloride-based resin composition is obtained by radical-polymerizing a monomer mainly composed of a vinyl chloride monomer in the presence of a compound having a specific thiocarbonylthio structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition. More specifically, for pipes and fittings,
The present invention relates to a vinyl chloride resin composition useful for molded articles requiring fracture toughness.

[0002]

2. Description of the Related Art Extruded products utilizing a vinyl chloride resin are widely used in the fields of pipes, flat plates, sheets and the like. When manufacturing an extruded product using such a vinyl chloride resin, a method of adding an inorganic filler such as calcium carbonate for the purpose of improving strength and reducing raw material costs is generally performed. I have. However, there is a problem in that the long-term durability and the fracture toughness of the molded product are deteriorated because the affinity between the inorganic filler and the vinyl chloride resin is low and the interfacial adhesion between the two is poor.

In order to increase the affinity between the inorganic filler and the vinyl chloride resin, a technique of blending a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent with the vinyl chloride resin has been proposed. JP 200
It is disclosed in Japanese Patent Publication No. 0-302931. According to this method, it is possible to improve the fracture toughness of the vinyl chloride resin, but since the coupling agent and the vinyl chloride resin have poor compatibility, the effect of improving the fracture toughness is sufficiently satisfactory. I couldn't do it. In order to solve these problems, it is not enough to devise additives and compounding agents anymore, and a method of controlling the polymer structure and functional groups of the vinyl chloride resin itself is strongly desired.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a vinyl chloride resin composition capable of obtaining a molded article having excellent fracture toughness and long-term durability. It is to provide things.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied the control of the polymer structure of the vinyl chloride resin and the introduction of functional groups, and completed the present invention.

[0006] The vinyl chloride resin composition of the present invention comprises:
A vinyl chloride-based resin composition containing (A) a vinyl chloride-based resin and (B) a surface modifier; The compound having a thiocarbonylthio structure is obtained by radical polymerization of a monomer having a monomer as a main component;

[0007]

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Wherein R ¹ is a p-valent organic group having 1 or more carbon atoms, wherein the p-valent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, Z ¹ may include at least one of metal atoms and may be a high molecular weight compound; Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms;
The monovalent organic group, nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and at least one of the phosphorus atoms may include, may be a high molecular weight; is Z ¹ And when there are a plurality thereof, they may be the same or different; and p is an integer of 1 or more), and a compound represented by the general formula (2):

[0009]

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Wherein R ² is a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, It may contain at least one of the metal atoms and may be of high molecular weight; Z ² is an oxygen atom (q =
2), a sulfur atom (when q = 2), a nitrogen atom (q
= 3) or a q-valent organic group having 1 or more carbon atoms, wherein the q-valent organic group is at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom. R ² may be the same or different from each other; and q is an integer of 2 or more. At least one selected from the group
Is a seed.

In a preferred embodiment, the surface modifier is at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.

In a preferred embodiment, the surface modifier is added in an amount of 0.1 to 100 parts by weight of the vinyl chloride resin.
It is contained at a ratio of 01 to 5 parts by weight.

In a preferred embodiment, the compound having the thiocarbonylthio structure is represented by the following general formula (3):

[0014]

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(Wherein R ³ is a divalent organic group having 1 or more carbon atoms, and the divalent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, It may contain at least one of the metal atoms, may be a high molecular weight substance, and Z ³ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms,
The monovalent organic group, nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and may comprise at least one of the phosphorus atoms may be a high molecular weight, Z ³ is May be the same or different from each other).

In a preferred embodiment, the vinyl chloride resin is a copolymer of a vinyl chloride monomer and another vinyl monomer, and the vinyl monomer is styrene, butadiene, At least one selected from the group consisting of isoprene, chloroprene, vinylidene chloride, acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, methacrylamide, acrylonitrile, and vinyl acetate; The body contains at least 50% by weight of the total monomers.

In a preferred embodiment, the vinyl chloride resin has a molecular weight distribution (Mw / Mw) determined by gel permeation chromatography (GPC).
n) is 2 or less.

In a preferred embodiment, the composition of the present invention further comprises a plasticizer, a thixotropic improver, a heat resistance improver, a stabilizer, an antioxidant, a UV absorber, a hindered amine light stabilizer (HALS), Inhibitors, flame retardants, coloring agents, foaming agents, lubricants, fungicides, crystal nucleating agents, vulcanization accelerators, anti-aging agents, vulcanizing agents, scorch inhibitors, mastication accelerators, tackifiers, latex coagulation And at least one additive selected from the group consisting of an agent, a processing aid, and an inorganic filler.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin composition of the present invention contains (A) a vinyl chloride resin and (B) a surface modifier. This vinyl chloride-based resin (hereinafter sometimes referred to as vinyl chloride-based resin (A)) radically polymerizes a monomer containing a vinyl chloride monomer as a main component in the presence of a compound having a thiocarbonylthio structure. It is obtained by doing. Hereinafter, the components contained in the composition of the present invention and the composition of the present invention will be sequentially described.

[Compound having a thiocarbonylthio structure]
The compound having a thiocarbonylthio structure used for producing the vinyl chloride resin (A) contained in the composition of the present invention is represented by the following general formula (1):

[0021]

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(Wherein, R ¹ is a p-valent organic group having 1 or more carbon atoms, and the p-valent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, Z ¹ may include at least one of metal atoms and may be a high molecular weight compound; Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms;
The monovalent organic group, nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and at least one of the phosphorus atoms may include, may be a high molecular weight; is Z ¹ When there are a plurality of compounds, they may be the same or different; and p is an integer of 1 or more (hereinafter, “compound (1) having a thiocarbonylthio structure”) Or simply referred to as “compound (1)”) and general formula (2):

[0023]

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(Wherein, R ² is a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, It may contain at least one of the metal atoms and may be of high molecular weight; Z ² is an oxygen atom (q =
2), a sulfur atom (when q = 2), a nitrogen atom (q
= 3) or a q-valent organic group having 1 or more carbon atoms, wherein the q-valent organic group is at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom. One or more of which may be a high molecular weight compound; two or more R ^{2 s} may be the same as or different from each other; and q is an integer of 2 or more (hereinafter, a compound represented by the following formula: , "Compound (2) having a thiocarbonylthio structure" or simply "compound (2)".

In the structure of the compound (1) having a thiocarbonylthio structure, R ¹ is not particularly limited.
From the viewpoint of the availability of the compound, R ¹ preferably has ^{1 to 1} carbon atom.
20 and p is 6 or less. Examples of R ¹ include an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, a divalent or higher valent aliphatic hydrocarbon group, a divalent or higher valent aromatic hydrocarbon group, and a divalent or higher valent aliphatic having an aromatic ring. Aromatic hydrocarbon group, divalent or higher aromatic hydrocarbon group having an aliphatic group,
Examples thereof include a divalent or higher valent aliphatic hydrocarbon group containing a hetero atom, and a divalent or higher aromatic substituted hydrocarbon group containing a hetero atom. In terms of the availability of the compound, R ¹ is preferably the following groups: benzyl group, 1-phenylethyl group, 2-phenyl-2-propyl group, 1-acetoxyethyl group, 1-
(4-methoxyphenyl) ethyl group, ethoxycarbonylmethyl group, 2-ethoxycarbonyl-2-propyl group, 2-cyano-2-propyl group, t-butyl group,
1,3,3-tetramethylbutyl group, 2- (4-chlorophenyl) -2-propyl group, vinylbenzyl group, t-
Butyl sulfide group, 2-carboxylethyl group, carboxymethyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyano-2-butyl group, and organic groups represented by the following general formula:

[0026]

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(Wherein, r represents an integer of 0 or more, and n represents 1
Or an integer greater than or equal to). R and n in the above formula are preferably 500 or less from the viewpoint of availability of the compound.

Further, as described above, R ¹ may be a polymer having a high molecular weight, and examples thereof include the following groups: a hydrocarbon group having a polyethylene oxide structure and a hydrocarbon group having a polypropylene oxide structure. Group, a hydrocarbon group having a polytetramethylene oxide structure, a hydrocarbon group having a polyethylene terephthalate structure, a hydrocarbon group having a polybutylene terephthalate structure, a hydrocarbon group having a polydimethylsiloxane structure, a hydrocarbon group having a polycarbonate structure, Hydrocarbon groups having a polyethylene structure, hydrocarbon groups having a polypropylene structure, hydrocarbon groups having a polyacrylonitrile structure, and the like. These hydrocarbon groups may include at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and may include a cyano group, an alkoxy group, and the like. These molecular weights are usually 500 or more. Hereinafter, the high molecular weight group in the present invention refers to the above groups.

In the above compound (1), Z ¹ is not particularly limited. However, in view of the availability of the compound, when Z ¹ is an organic group, the number of carbon atoms thereof is preferably 1 to 20. Examples thereof include alkyl groups, substituted alkyl groups, alkoxy groups, aryloxy groups, aryl groups, substituted aryl groups, aralkyl groups, substituted aralkyl groups, N-aryl-N-alkylamino groups, N, N-diarylamino groups. , N, N-dialkylamino group, thioalkyl group, dialkylphosphinyl group and the like. From the viewpoint of availability of the compound, the following groups are preferable as Z ¹ : phenyl, methyl, ethyl, benzyl, 4-chlorophenyl, 1-naphthyl, 2-naphthyl, diethoxyphosphinyl Group, n-butyl group, t-butyl group, methoxy group, ethoxy group, thiomethyl group (methyl sulfide),
Phenoxy group, thiophenyl group (phenyl sulfide), N, N-dimethylamino group, N, N-diethylamino group, N-phenyl-N-methylamino group, N-phenyl-N-ethylamino group, thiobenzyl group (benzyl sulfide ), A pentafluorophenoxy group, and an organic group represented by the following general formula:

[0030]

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In the structure of the compound (2) having a thiocarbonylthio structure, R ² is not particularly limited.
From the viewpoint of availability of the compound, R ² preferably has 1 to 1 carbon atom.
20. Examples of R ² include alkyl group, substituted alkyl group, an aralkyl group, and the like substituted aralkyl group.
In terms of the availability of the compound, R ² is preferably the following groups: benzyl group, 1-phenylethyl group, 2-phenyl-2-propyl group, 1-acetoxyethyl group, 1- (4
-Methoxyphenyl) ethyl group, ethoxycarbonylmethyl group, 2-ethoxycarbonyl-2-propyl group, 2
-Cyano-2-propyl group, t-butyl group, 1,1,
3,3-tetramethylbutyl group, 2- (4-chlorophenyl) -2-propyl group, vinylbenzyl group, t-butylsulfide group, 2-carboxylethyl group, carboxylmethyl group, cyanomethyl group, 1-cyanoethyl group,
2-cyano-2-butyl group and an organic group represented by the following general formula:

[0032]

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(Wherein, r represents an integer of 0 or more, and n represents 1
Or an integer greater than or equal to). R and n in the above formula are preferably 500 or less from the viewpoint of availability of the compound.

In the above compound (2), Z ² is not particularly limited. However, from the viewpoint of availability of the compound, when Z ² is an organic group, it preferably has 1 to 20 carbon atoms, and q Is 6 or less. Examples thereof include a divalent or higher valent aliphatic hydrocarbon group, a divalent or higher valent aromatic hydrocarbon group, a divalent or higher valent aliphatic hydrocarbon group having an aromatic ring, and a divalent or higher valent aromatic group having an aliphatic group. Examples thereof include a hydrocarbon group, a divalent or higher aliphatic hydrocarbon group containing a hetero atom, and a divalent or higher aromatic substituted hydrocarbon group containing a hetero atom. In terms of the availability of the compound, Z ² includes, for example, an organic group represented by the following general formula:

[0035]

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As the compound having a thiocarbonylthio structure used in the present invention, both compounds having a thiocarbonylthio structure represented by the following general formula (3) are highly effective in improving physical properties by adding a surface modifier. A compound having a terminal (hereinafter sometimes referred to as a compound (3) having a thiocarbonylthio structure at both terminals, or simply as a compound (3)) is preferable:

[0037]

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(In the formula, R ³ is a divalent organic group having 1 or more carbon atoms. From the viewpoint of availability of the compound, R ³ preferably has 1 to 20 carbon atoms. Groups are nitrogen, oxygen, sulfur, halogen, silicon,
It may contain at least one of a phosphorus atom and a metal atom, and may be a high molecular weight substance. Z ³ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, the monovalent organic group, nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and may comprise at least one of the phosphorus atoms may be a high molecular weight, Z ³ is May be identical to each other,
May be different).

In the structure of the compound (3) having a thiocarbonylthio structure at both terminals, R ³ is not particularly limited, but from the viewpoint of availability of the compound, a structure represented by the following general formula is preferable.

[0040]

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Z of compound (3)³Is particularly limited
However, in view of the availability of compounds, Z ³Where is an organic radical
In this case, the number of carbon atoms is preferably 1 to 20. That
Examples include alkyl groups, substituted alkyl groups, alkoxy
Group, aryloxy group, aryl group, substituted aryl group,
Aralkyl group, substituted aralkyl group, N-aryl-N-
Alkylamino group, N, N-diarylamino group, N,
N-dialkylamino group, thioalkyl group, dialkyl
And a phosphinyl group. In terms of compound availability, Z
³Are preferably the following groups: a phenyl group, a methyl group,
Ethyl group, benzyl group, 4-chlorophenyl group, 1-na
Futyl group, 2-naphthyl group, diethoxyphosphinyl
Group, n-butyl group, t-butyl group, methoxy group, ethoxy group
Si group, thiomethyl group (methyl sulfide), phenoxy
Group, thiophenyl group (phenyl sulfide), N, N-
Dimethylamino group, N, N-diethylamino group, N-phenyl
Phenyl-N-methylamino group, N-phenyl-N-ethyl
Amino group, thiobenzyl group (benzyl sulfide),
A pentafluorophenoxy group, and represented by the following general formula:
Organic groups:

[0042]

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(Wherein, r represents an integer of 0 or more, and n represents 1
Or an integer greater than or equal to). R and n in the above formula are preferably 500 or less from the viewpoint of availability of the compound.

Specific examples of the compound having a thiocarbonylthio structure described in any of the above include, but are not limited to, a compound represented by the following general formula:

[0045]

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[0046]

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[0047]

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[0048]

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(In the above formula, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, Ac represents an acetyl group, and r represents
Is an integer greater than or equal to 0, and s is an integer greater than or equal to 1). R and s in the above formula are preferably 500 or less from the viewpoint of the availability of the compound.

[Monomer Constituting Vinyl Chloride Resin] The vinyl chloride resin contained in the composition of the present invention is prepared from a monomer having a vinyl chloride monomer as a main component. "A monomer having a vinyl chloride monomer as a main component" means a vinyl monomer having a vinyl chloride monomer as a main component and, if necessary, a radical copolymerizable with the vinyl chloride monomer. It contains.

The vinyl monomers which can be radically copolymerized with the vinyl chloride monomer include, but are not limited to, the following compounds: styrene, α-methylstyrene, divinylbenzene, p-hydroxystyrene , P
Styrene compounds such as carboxystyrene, p-methoxystyrene, diethylaminostyrene, diethylamino α-methylstyrene, p-vinylbenzenesulfonic acid, sodium p-vinylbenzenesulfonate, m, m-dimethylstyrene; ethylene, propylene, Aliphatic terminal olefin compounds such as butene, 1-heptene, 1-hexene, 1-octene, isobutylene, butadiene, and isoprene; halogen-containing olefin compounds such as vinyl fluoride, vinyl bromide, chloroprene, and vinylidene chloride; acrylic acid; Methacrylic acid: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, a Octyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, acrylic 2-hydroxypropyl acid, stearyl acrylate, glycidyl acrylate, 2-acryloyloxypropyldimethoxymethylsilane, 2-acryloyloxypropyltrimethoxysilane, trifluoromethyl acrylate, pentafluoroethyl acrylate, acrylate 2,2 2-trifluoroethyl, 3-dimethylaminoethyl acrylate, isobutyl acrylate, 4-hydroxybutyl acrylate, t-butyl acrylate, lauryl acrylate, alkyl-modified dipen Taerythritol acrylate, ethylene oxide-modified bisphenol A diacrylate, carbitol acrylate, ε-caprolactone-modified dipentaerythritol acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, ditrimethylolpropane Tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, trimethylolpropaneethoxy triacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate Acrylate Neopentyl glycol hydroxypivalic acid ester diacrylate, acrylic acid 1,9
Nonanediol, 1,4-butanediol acrylate,
2-propenoic acid [2- [1,1-dimethyl-2-[(1-oxo-2-propenyl) oxy] ethyl] -5-ethyl-1,3-dioxan-5-yl] methyl ester, 1,6-hexanediol acrylate,
Acrylates such as pentaerythritol triacrylate, 2-acryloyloxypropyl hydrogen phthalate, methyl 3-methoxyacrylate, allyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid t-butyl, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol methacrylate, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, Dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate,
3-methoxybutyl methacrylate, 2-aminoethyl methacrylate, triethylene glycol methacrylate, 2
-Methacryloyloxypropyltrimethoxysilane,
Methacrylic esters such as 2-methacryloyloxypropyldimethoxymethylsilane, trifluoromethyl methacrylate, pentafluoroethyl methacrylate, 2,2,2-trifluoroethyl methacrylate; acrylamide, methacrylamide, N-methylacrylamide, N- Methyl methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N
-T-butylacrylamide, Nt-butylmethacrylamide, Nn-butylacrylamide, Nn-butylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylolacrylamide, N-ethylol Nitrogen-containing olefin compounds such as methacrylamide, acrylonitrile, methacrylonitrile, N-phenylmaleimide, N-butylmaleimide, 4-vinylpyridine, N-vinylpyrrolidone, and N-vinylcarbazole; p-vinylbenzoic acid;
Carboxyl group-containing unsaturated compounds such as vinyl benzoate, itaconic acid, itaconic anhydride, α-methylvinylbenzoic acid, vinyl acetate, vinyl butanoate, maleic anhydride, allyl acetate, allyl benzoate; diallyl ammonium chloride, 1, 6-heptadiene, 2,6-dicyano-
Cyclopolymerizable compounds such as 1,6-heptadiene and compounds having a 1,6-heptadiene structure such as 2,4,4,6-tetrakis (ethoxycarbonyl) -1,6-heptadiene; dimethylvinylsilane; Trimethylvinylsilane, dimethylphenylvinylsilane, dimethoxymethylvinylsilane, diethoxyphenylvinylsilane, trimethoxyvinylsilane, pentamethylvinyldisiloxane, trimethylallylsilane, trimethoxyallylsilane, dimethoxymethylallylsilane, heptamethylvinylcyclotetrasiloxane, 1,1,
Silicon-containing unsaturated compounds such as 3,3-tetramethyldivinyldisiloxane; allyl-terminated polyethylene oxide, allyl-terminated polypropylene oxide, allyl-terminated polyethylene oxide-polypropylene oxide copolymer, vinyl-terminated polyethylene oxide, vinyl-terminated polypropylene oxide, vinyl-terminated Polyethylene oxide-polypropylene oxide copolymer, methallyl-terminated polypropylene oxide, vinyl-terminated polytetramethylene oxide, acryloyl-terminated polyacrylic acid, methacryloyl-terminated polymethacrylic acid, acryloyl-terminated polyacrylic ester, acryloyl-terminated polymethacrylic ester, methacryloyl-terminated acrylic Acid ester, methacryloyl-terminated methacrylate, vinyl-terminated poly Rokisan, vinyl-terminated polycarbonate, allyl-terminated polycarbonate, vinyl-terminated polyethylene terephthalate, vinyl-terminated polybutylene terephthalate, vinyl terminated caprolactam, vinyl-terminated polyamide, and unsaturated group-containing macromonomers such as vinyl terminated polyurethane. These may be used alone,
A plurality of them may be used in combination.

Among these vinyl monomers, the following compounds are preferred because they are easily available and the obtained copolymer is useful: styrene, α-methylstyrene, butadiene, isoprene, chloroprene , Ethylene, propylene, vinyl fluoride, vinyl bromide, vinylidene chloride,
Acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl butanoate, vinyl benzoate, maleic anhydride, maleimide compound, N-vinylpyrrolidone, N- Vinyl carbazole, fumaric acid ester, 1,6-heptadiene compound, and diallylammonium salt. Among them, styrene, butadiene, isoprene, chloroprene, vinylidene chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, acrylonitrile, and vinyl acetate are more preferable.

In the present invention, when the vinyl monomer is copolymerized with a vinyl chloride monomer, the composition ratio of the two is not particularly limited. In terms of balance between physical properties and cost,
The weight ratio of the monomers is preferably at least 50% by weight of the vinyl chloride monomer, and at least 60% by weight of the vinyl chloride monomer.
More preferably, it is the above.

[Polymerization Method for Production of Vinyl Chloride Resin (A), Solvents Used for Polymerization Reaction, Initiator, etc.] The above vinyl chloride monomer for preparing vinyl chloride resin (A) The type of radical polymerization using a monomer having as a main component is not particularly limited. Bulk polymerization,
It is possible to apply a method usually used in this field, such as solution polymerization, emulsion polymerization, suspension polymerization, and fine suspension polymerization.

Solvents used in the solution polymerization of the above monomers include, but are not limited to, the following solvents: hydrocarbon solvents such as heptane, octane and mineral spirit; ethyl acetate, acetic acid ester solvents such as n-butyl, isobutyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; methanol, ethanol, isopropanol, n-butanol,
alcohol solvents such as sec-butanol and isobutanol; ether solvents such as tetrahydrofuran, n-butyl ether, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether; toluene, xylene, swazol 310 (manufactured by Cosmo Oil), swazol 1000 ( Aromatic petroleum solvents such as Cosmo Oil Co., Ltd. and Swazol 1500 (Cosmo Oil Co., Ltd.). These may be used alone or in combination of two or more. Regarding the type and amount of the solvent to be used, the solubility of the monomer to be used, the solubility of the obtained polymer, the concentration of the polymerization initiator and the monomer concentration appropriate for achieving a sufficient reaction rate, the thiocarbonylthio structure May be determined in consideration of the solubility of the compound having, the effect on the human body and environment, the availability, the price, and the like, and are not particularly limited.

When the above monomers are subjected to emulsion polymerization or fine suspension polymerization, the emulsifiers used include, but are not limited to, fatty acid soaps, rosin acid soaps, and sodium naphthalene sulfonate. Formalin condensate, sodium alkyl benzene sulfonate, sodium alkyl sulfate (eg, sodium lauryl sulfate), ammonium alkyl sulfate, triethanolamine alkyl sulfate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulfonate, sodium polyoxyethylene alkyl ether sulfate, poly Anionic surfactants such as sodium oxyethylene alkylphenyl ether sulfate; polyoxyethylene alkyl ether, polyoxyethylene higher alcohol Le, sorbitan fatty acid esters,
Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester,
Nonionic surfactants such as polyoxyethylene alkylamines and alkylalkanolamides; cationic surfactants such as alkyltrimethylammonium chloride. These emulsifiers may be used alone or in combination of two or more. If necessary, a cationic surfactant such as an alkylamine hydrochloride may be used, and a dispersant for suspension polymerization described below may be added. The amount of the emulsifier used is not particularly limited, but is usually 100
It is 0.1 to 20 parts by weight based on parts by weight.

In the case where the above-mentioned monomer having a vinyl chloride monomer as a main component is subjected to suspension polymerization, any of the dispersants commonly used in the art can be used as the dispersant. It is. Examples include, but are not limited to, the following dispersants: partially saponified polyvinyl acetate, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, gelatin, polyalkylene oxide, a combination of an anionic surfactant and a dispersing aid, and the like. These may be used alone or in combination of two or more. If necessary, an emulsifier used in the above emulsion polymerization may be used in combination. The amount of the dispersant used is not particularly limited, but is usually 0.1 to 20 parts by weight based on 100 parts by weight of the monomer used.

Among the above polymerization methods, aqueous polymerization such as suspension polymerization, fine suspension polymerization, and emulsion polymerization is preferred from the viewpoint of safety and obtaining a vinyl chloride resin having a uniform particle diameter.

The polymerization initiator or the polymerization initiation method used in the above radical polymerization is not particularly limited, and a polymerization initiator or a polymerization initiation method usually used in the art can be used. For example, polymerization initiators include, but are not limited to, the following compounds: methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, isobutyryl peroxide, 3,5,5-trimethyl Hexanoyl peroxide, lauroyl peroxide,
Benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butylperoxide Oxide, t-butyl-α-cumyl peroxide, di-α-
Cumyl peroxide, 1,4-bis [(t-butylperoxy) isopropyl] benzene, 1,3-bis [(t-butylperoxy) isopropyl] benzene,
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-
Butylperoxy) -3-hexyne, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, t-butyl Peroxyacetate, t-
Butylperoxyisobutyrate, t-butylperoxyoctoate, t-butylperoxypivalate, t
-Butyl peroxy neodecanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-
Butylperoxybenzoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (2-ethylhexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di- sec-butyl peroxydicarbonate, di-n-propylperoxydicarbonate, bis (3-methoxybutyl) peroxydicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, bis (4-t-butylcyclohexyl) ) Peroxide-based polymerization initiators such as peroxydicarbonate, Ot-butyl-O-isopropylperoxycarbonate and succinic peroxide; 2,2′-azobis-
(2-amidinopropane) dihydrochloride, dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-
Azobis (isobutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (isobutylvaleronitrile) ), 2,2′-azobis- (2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), 2- (t-butylazo) -2-cyanopropane,
Azo-based polymerization initiators such as 2,2'-azobis (2,4,4-trimethylpentane) and 2,2'-azobis (2-methylpropane); inorganic peroxides such as potassium persulfate and sodium persulfate A vinyl monomer which generates radical species thermally, such as styrene; a compound which generates radical species by light, such as a benzoin derivative, benzophenone, acylphosphine oxide, or photoredox system;
Sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid,
Redox-type polymerization initiators using ferrous sulfate or the like as a reducing agent and oxidizing agents such as potassium peroxodisulfate, hydrogen peroxide or t-butyl hydroperoxide. These polymerization initiators may be used alone or in combination of two or more. In addition, it is also possible to use a polymerization initiation system by electron beam irradiation, X-ray irradiation, radiation irradiation, or the like. Regarding such a polymerization initiation method, see Mod a
nd Solomon "The Chemistry
of Free Radical Polymeriz
ation ", Pergamon, London, 19
The method described on pages 95, 53-95 can be used.

The amount of the polymerization initiator used in the practice of the present invention is not particularly limited, but the amount of the radical species generated during the polymerization is limited to the thiocarbonylthio structure in that a polymer having a small molecular weight distribution is obtained. Is preferably 1 mol or less, more preferably 0.5 mol or less, per 1 mol of the thiocarbonylthio group of the compound having the formula: In addition, in order to control the amount of radical species generated during the polymerization, in conjunction with the amount of the polymerization initiator used, in the case of a thermally dissociated polymerization initiator, the temperature is adjusted, and light or an electron beam is used. In the case of a polymerization initiation system that generates radicals, it is preferable to adjust the amount of energy to be irradiated.

[Production of Vinyl Chloride Resin (A)] In the presence of the compound having a thiocarbonylthio structure, a vinyl chloride monomer is radically polymerized to give a vinyl chloride resin. (A) is obtained. The type of radical polymerization is not particularly limited as described above. Methods generally used in the art, such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and fine suspension polymerization, can be applied. When a vinyl chloride monomer and the above-mentioned vinyl monomer are copolymerized, a random copolymer, a block copolymer, a graft copolymer, a gradient copolymer, and a form usually used in the art. can do.

The compound having a thiocarbonylthio structure may be present in the reaction system at the time of polymerization. However, in the case of solution polymerization, the polymerization behavior and the structure of the vinyl chloride polymer can be easily controlled. It is preferred to dissolve in the solution before starting. In the case of aqueous polymerization, a method in which a small amount of an organic solvent or a vinyl chloride monomer is mixed in advance with an aqueous dispersion or an aqueous emulsion and the mixture is stirred in advance with a homogenizer or the like is preferable.

In the polymerization reaction using a monomer having a vinyl chloride monomer as a main component, reversible addition-elimination chain transfer (RAFT) polymerization occurs using a compound having a thiocarbonylthio structure as a chain transfer agent. A vinyl chloride resin is formed. When the compound (1) having a thiocarbonylthio structure is used, for example, when a vinyl chloride monomer (X) is reacted, the vinyl chloride resin (4) shown below becomes a compound having a thiocarbonylthio structure. When (2) is used, a vinyl chloride resin (5) is formed.

[0064]

Embedded image

In the above formula, n is the number of monomers bonded.
Is shown. Z¹, R¹, P, Z², R ², And q are
Specified in the section of compounds having a thiocarbonylthio structure described above
As you did. Branching when p or q is 3 or more
A vinyl chloride resin is formed.

It is also possible to radically polymerize the monomer containing the above-mentioned vinyl chloride monomer as a main component and then partially chlorinate it to obtain a chlorinated vinyl chloride polymer. Such a polymer has high heat resistance. As a chlorination method, various methods usually used in the art can be used, but from an industrial viewpoint, a water suspension chlorination method is preferable.

The molecular weight of the vinyl chloride resin (A) obtained above is not particularly limited, but the number average determined by gel permeation chromatography (GPC) in terms of strength, heat resistance, moldability and the like. Molecular weight is 30
It is preferably in the range of 00 to 500,000, and 50
More preferably, it is in the range of 00 to 300,000.
If the number average molecular weight is too low, heat resistance may be poor, and if it is too high, moldability may decrease. The ratio (Mw / Mn; molecular weight distribution) between the weight average molecular weight and the number average molecular weight of the vinyl chloride resin (A) determined by (GPC) is preferably 2 or less. The vinyl chloride resin (A) having such a molecular weight distribution is preferable in strength, heat resistance, and gelling characteristics. In the present invention, since the compound having a thiocarbonylthio structure having the above specific structure is used as a chain transfer agent, such a vinyl chloride resin having a molecular weight distribution of 2 or less can be easily prepared.

Since the vinyl chloride resin (A) is produced using a compound having a specific thiocarbonylthio structure, it has a thiocarbonylthio structure in the molecule. Therefore, when the resin and the coupling agent are mixed, the compatibility is good, and a high fracture toughness is obtained.

The vinyl chloride resin (A) may be a mixture of a plurality of vinyl chloride resins having different number average molecular weights. When using a mixture of vinyl chloride resins,
In order to adjust various physical properties such as viscosity, fluidity, thixotropic behavior, gelling properties, heat resistance, weather resistance, hot water resistance, and light resistance, it is preferable to mix vinyl chloride resins having different physical properties. For example, it is preferable to use a mixture of vinyl chloride paste resins whose number average molecular weights calculated by gel permeation chromatography differ from each other by 3,000 or more, and use a mixture of vinyl chloride paste resins whose number average molecular weights differ from each other by 5,000 or more. Is more preferable. Even when mixing vinyl chloride resins having different molecular weights as described above, if the molecular weight distribution (Mw / Mn) is 2 or less as described above, it is easy to control the physical properties of the obtained vinyl chloride resin mixture. There are advantages.

[Surface Modifier] The surface modifier contained in the vinyl chloride resin composition of the present invention (hereinafter referred to as the surface modifier (B))
), Various conventionally used modifiers can be used without particular limitation. It is preferable to use a modifier selected from the group consisting of a silane-based coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent in that the effect of improving the fracture toughness is high.

The silane coupling agent includes, but is not limited to, the following compounds: γ-
Chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane Such.

The titanate-based coupling agents include, but are not limited to, the following compounds: isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate,
Isopropyl tris (dioctyl pyrophosphate)
Titanate, tetraisopropylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, titanium stearate, Bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-amidoethylaminoethyl) titanate, dicumyl Phenyloxyacetate titanate, diisostearoylethylene titanate and the like.

Examples of the aluminum-based coupling agent include, but are not limited to, acetoalkoxyaluminum diisopropylate.

The above surface modifiers may be used alone or in combination of two or more. Among these surface modifiers, titanate-based coupling agents are preferred because of their high effect of improving fracture toughness.

The content of the surface modifier (B) used in the present invention is not particularly limited, but is preferably 0.1 to 100 parts by weight of the vinyl chloride resin (A) in view of the balance between physical properties and cost.
It is preferably contained in the composition in a proportion of from 01 to 5 parts by weight, more preferably from 0.1 to 4 parts by weight.

[Additives] In addition to the vinyl chloride resin (A) and the surface modifier (B), one or more vinyl chloride resin compositions of the present invention may be used for adjusting various physical properties, if necessary. Additives can be blended. As additives,
(i) plasticizer, (ii) thixotropic improver, (iii) heat resistance improver, (iv) stabilizer, (v) antioxidant, (vi) ultraviolet absorber, (vii) hindered amine light stabilizer ( HALS),
(viii) antistatic agent, (ix) flame retardant, (x) coloring agent, (xi) foaming agent, (xii) lubricant, (xiii) fungicide, (xiv) crystal nucleating agent, (xv)
Vulcanization accelerator, (xvi) antioxidant, (xvii) vulcanizing agent, (xviii)
Scorch inhibitor, (xix) mastication accelerator, (xx) tackifier,
(xi) a latex coagulant, (xii) a processing aid, (xxiii) an inorganic filler and the like.

Examples of the plasticizer (i) include, but are not limited to, the following compounds: dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, diheptyl phthalate, di-phthalic phthalate. 2-ethylhexyl, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, tetrahydrophthalate, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, trisdichloropropylphosphate, tributoxyethylphosphate, tris (β-chloropropyl) phosphate, triphenylphosphate, octyldiphenylphosphate, Scan (isopropylphenyl) phosphate, cresyl diphenyl phosphate, di-2-ethylhexyl adipate, diisononyl adipate,
Diisodecyl adipate, di-n-alkyl adipate, dibutyl diglycol adipate, bis (2-ethylhexyl) azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, acetyl triethyl citrate, acetyl tributyl citrate, maleic acid Dibutyl, di-2-ethylhexyl maleate, dibutyl fumarate, tris-2-ethylhexyl trimellitate,
Trialkyl trimellitate, polyester plasticizer,
Epoxy plasticizer, stearic plasticizer, chlorinated paraffin, etc. These may be used alone or in combination of two or more.

The thixotropic improver of the above (ii) includes, but is not limited to, the following compounds: sodium isethionate, potassium isethionate,
Sulfonates such as ammonium isethionate, sodium salt of 2-sulfoethyl laurate, sodium salt of 2-sulfoethyl myristate, and sodium salt of 2-sulfoethyl stearate. These may be used alone or in combination of two or more.

The heat resistance improver of the above (iii) includes, but is not limited to, the following compounds: phosphoric acid, phosphorous acid, sodium hydrogen sulfate, potassium hydrogen sulfate, chromic acid, hydrochloric acid, sulfuric acid, Sulfurous acid, thiosulfuric acid, nitric acid,
Nitrous acid, iodic acid, acetic acid, chloroacetic acid, dichloroacetic acid,
Trichloroacetic acid, nicotinic acid, benzenesulfonic acid, benzoic acid, tartaric acid, malic acid, formic acid, butyric acid, citric acid, succinic acid, oxalic acid, picric acid, picolinic acid, phthalic acid, sulfamic acid, sulfamic acid, aspartic acid, glycol Acidic compounds such as acid, glutamic acid, fumaric acid, maleic acid, malonic acid, lactic acid, oleic acid, salicylic acid, trimellitic acid, p-toluenesulfonic acid, and strongly acidic ion exchange resin; natural hydrotalcite, JP-B-46-2280 JP-B, JP-B-50-30039, JP-B-61-174270, etc., synthetic hydrotalcite, hydrotalcite surface-treated with a wax such as a fatty acid ester, and zinc-modified hydrotalcite , Perchloric acid treated hydrotalcite, zinc modified Hydrotalcite compounds such as modified hydrotalcite obtained by treating idrotalcite with perchloric acid and dried hydrotalcite obtained by drying treatment; A-type zeolite, X-type zeolite, Y-type zeolite, P-type zeolite, monodenite, alunacite ,
Zeolite compounds such as sodalite aluminosilicates, clinobutyrolite, erionite and chabazite; metal perchlorates such as tin perchlorate, barium perchlorate, sodium perchlorate and magnesium perchlorate . These may be used alone or in combination of two or more.

The stabilizers of (iv) above include, but are not limited to, the following compounds: cadmium stearate, zinc stearate, barium stearate,
Stabilizers for vinyl chloride such as calcium stearate, lead dibutyltin dilaurate, tris (nonylphenyl) phosphite, triphenylphosphite, diphenylisodecylphosphite; di-n-octyltin bis (isooctylthioglycolate) Salt, di-n
-Octyltin maleate polymer, di-n-octyltin dilaurate, di-n-octyltin maleate, di-n-butyltin bismaleate, di-n-butyltin maleate polymer , Di-n-butyltin bisoctylthioglycol ester salt, di-n-butyltin β-mercaptopropionate polymer, di-n-butyltin dilaurate, di-n-
Methyl tin bis (isooctyl mercapto acetate)
Salt, poly (thiobis-n-butyltin sulfide),
Monooctyltin tris (isooctylthioglycolate), di-n-butyltin malate ester
Organotin stabilizers such as carboxylate, di-n-butyltin malate ester / mercaptide; tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, dibasic lead phthalate, lead silicate , Lead stabilizers such as dibasic lead stearate and lead stearate; metal soap stabilizers such as cadmium soap, zinc soap, barium soap, lead soap, composite metal soap and calcium stearate. These may be used alone or in combination of two or more.

The antioxidant of the above (v) includes, but is not limited to, the following compounds: 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6- Di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4
-Hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-
Butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 3,
9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5. 5] undecane, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t -Butyl-4-hydroxybenzyl)
Benzene, tetrakis- [methylene-3- (3 ', 5'
-Di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3 , 5-Tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H,
5H) Phenolic antioxidants such as trione and tocopherols; sulfur such as dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate Antioxidant; triphenyl phosphite, diphenyl isodecyl phosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl ditridecyl)
Phosphite, cyclic neopentanetetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9 , 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-
Di-tert-butyl-4-hydroxybenzyl) -9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-
Dihydro-9-oxa-10-phosphaphenanthrene, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, Cyclic neopentanetetraylbis (2,6-di-
t-butyl-4-methylphenyl) phosphite, 2,
2-methylenebis (4,6-di-t-butylphenyl)
Phosphorus antioxidants such as octyl phosphite. These may be used alone or in combination of two or more.

Examples of the ultraviolet absorber (vi) include, but are not limited to, the following compounds: phenyl salicylate, pt-butylphenyl salicylate,
salicylic acid-based ultraviolet absorbers such as p-octylphenyl salicylate; 2,4-dihydroxybenzophenone;
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-
Dihydroxy-4-methoxybenzophenone, 2,2 ′
-Dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-
Benzophenone-based ultraviolet absorbers such as benzoylphenyl) methane; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole,
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3',
5′-di-t-amylphenyl) benzotriazole,
2- (2'-hydroxy-4'-octoxyphenyl)
Benzotriazole, 2- [2'-hydroxy-3'-
(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 -(2H-benzotriazol-2-yl) phenol], [2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole], [2,2'-methylenebis [4- (1,
Benzotriazole ultraviolet absorbers such as 1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]]]; 2-ethylhexyl-2-cyano-3,3′- Diphenyl acrylate,
Cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3'-diphenylacrylate; nickel bis (octylphenyl) sulfide, [2,2'-
Thiobis (4-t-octylphenolate)]-n-butylamine nickel, nickel complex-3,5
Nickel-based ultraviolet stabilizers such as -di-t-butyl-4-hydroxybenzyl-phosphate monoethylate and nickel-dibutyldithiocarbamate; These may be used alone or in combination of two or more.

The hindered amine light stabilizer (HALS) of the above (vii) includes, but is not limited to, the following compounds: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate , SanolLS-
770 (manufactured by Sankyo), ADK STAB LA-77 (manufactured by Asahi Denka), Sumithorpe 577 (manufactured by Sumitomo Chemical), Biosorb 04 (manufactured by Kyodo Yakuhin), Chimassorb 944LD
(Manufactured by Ciba Specialty), Tinuvin
144 (made by Ciba Specialty), ADK STAB LA-52 (made by Asahi Denka), ADK STAB LA-57
(Made by Asahi Denka), ADK STAB LA-67 (made by Asahi Denka),
ADK STAB LA-68 (made by Asahi Denka), ADK STAB L
A-77 (manufactured by Asahi Denka), ADK STAB LA-87 (manufactured by Asahi Denka), GoodriteUV-3034 (Gooddr)
ich). These may be used alone or in combination of two or more.

Examples of the antistatic agent (viii) include, but are not limited to, the following compounds: poly (oxyethylene) alkylamine, poly (oxyethylene) alkylamide, poly (oxyethylene) alkyl ether Nonionic antistatic agents such as poly (oxyethylene) alkylphenyl ether, glycerin fatty acid ester and sorbitan fatty acid ester; anionic antistatic agents such as alkyl sulfonate, alkylbenzene sulfonate, alkyl sulfate and alkyl phosphate; quaternary ammonium chloride , Quaternary ammonium sulfate, quaternary ammonium nitrate and other cationic antistatic agents; amphoteric antistatic agents such as alkyl betaine compounds, alkyl imidazoline compounds and alkyl alanine compounds Agent; polyvinyl benzyl type cation compound, such as a conductive resin antistatic agent such as polyacrylic acid type cation compound. These may be used alone or in combination of two or more.

The flame retardant of the above (ix) includes, but is not limited to, the following compounds: tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,
5-dibromophenyl) propane, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-3,5
-Dibromophenyl) propane, decabromodiphenyl oxide, halogen-containing polyphosphates and other halogen-based flame retardants; ammonium phosphate, tricresyl phosphate, triethyl phosphate, tris (β-chloroethyl) phosphate, trischloroethyl phosphate, trisdichloro Phosphorus flame retardants such as propyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, acidic phosphate esters, and nitrogen-containing phosphorus compounds; red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, and hydroxide Inorganic flame retardants such as aluminum and magnesium hydroxide; poly (dimethoxysiloxane), poly (diethoxysiloxane), poly (diphenoxysiloxane), poly (methoxyphenoxysilo) Sun), methyl silicate, ethyl silicate, etc. siloxane-based flame retardant such as phenyl silicates. These may be used alone or in combination of two or more.

Examples of the colorant (x) include, but are not limited to, a powdery colorant, a granular colorant, a liquid colorant, and a colorant such as a masterbatch containing the colorant. . These may be used alone or in combination of two or more.

As the foaming agent (xi), azodicarbonamide, azobisisobutyronitrile, N, N'-nitrosopentamethylenetetramine, p-toluenesulfonylhydrazine, p, p'-oxybis (benzenesulfo Organic blowing agents such as hydrazide), but are not limited thereto. These may be used alone or in combination of two or more.

The lubricant of (xii) above includes, but is not limited to, the following materials: liquid paraffin,
Aliphatic hydrocarbon lubricants such as microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, their partial oxides, their fluorides and their chlorides; animal oils such as tallow, fish oil, coconut oil, soybean oil Rapeseed oil, vegetable oils such as rice bran wax, their separated refined products, higher fatty alcohols and higher fatty acid lubricants such as montan wax; fatty acid amide lubricants such as higher fatty acid amides and higher fatty acid bisamides; barium stearate Metal soap-based lubricants such as calcium stearate, zinc stearate, aluminum stearate, magnesium stearate, zinc stearate / barium stearate complex, zinc stearate / calcium stearate complex; higher fatty acid of monohydric alcohol Ether, higher fatty acid esters of polyhydric alcohols, higher fatty acid partial esters of polyhydric alcohols, long chain esters of montan wax type, such as fatty acid ester lubricant, such as partially hydrolyzed product of long chain esters of montan wax type. These may be used alone or in combination of two or more.

Examples of the fungicide (xiii) include, but are not limited to, binazine, preventol, and thiabendazole. These may be used alone or in combination of two or more.

Examples of the crystal nucleating agent (xiv) include sodium 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, sodium bis (4-t-butylphenyl) phosphate, (P-methylbenzylidene) sorbitol, alkyl-substituted dibenzylidene sorbitol,
Examples include, but are not limited to, bis (p-ethylbenzylidene) sorbitol. These may be used alone or in combination of two or more.

The vulcanization accelerator of the above (xv) includes, but is not limited to, the following compounds: hexamethylenetetramine, n-butyraldehydeaniline,
3-diphenylguanidine, di-o-tolyl guanidine, 1-o-tolyl biguanide, di-o-tolyl guanidine salt of dicatechol borate, N, N'-diphenylthiourea, 2-mercaptoimidazoline, N, N'- Diethylthiourea, dibutylthiourea, dilaurylthiourea, 2-mercaptobenzothiazole, dibenzothiazyldisulfide, sodium salt of 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (4′-morpholinodithio) benzothiazole, N-cyclohexyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, Nt-butyl-2-benzothiazolylsulfen A , Tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, pentamethylenedithiocarbamic acid piperidine salt, pipecolyldithiocarbamic acid pipecoline salt, dimethyldithiocarbamate sodium, diethyl Sodium dithiocarbamate, sodium dibutyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, tellurium diethyldithiocarbamate and the like. These may be used alone or in combination of two or more.

The antioxidants of the above (xvi) include, but are not limited to, the following compounds: poly (2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-1 , 2-Dihydro-2,2,4-
Trimethylquinoline, 1- (N-phenylamino) -naphthalene, styrenated diphenylamine, dialkyldiphenylamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-
Phenylenediamine, N, N'-di-2-naphthyl-p
-Phenylenediamine, 2,6-di-t-butyl-4-
Methylphenol, mono (α-methylbenzyl) phenol, di (α-methylbenzyl) phenol, tri (α
-Methylbenzyl) phenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (6-t-butyl-3-methylphenol), 4,4'-thiobis (6-
t-butyl-3-methylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,5-
Di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-
Mercaptomethylbenzimidazole, nickel dibutyldithiocarbamate, tris (nonylphenyl) phosphite, dilauryl thiodipropionate, distearyl thiodipropionate, Sannock (Ouchi Shinko Chemical), Suntight (Seiko Chemical), Ozogard G (manufactured by Kawaguchi Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

The vulcanizing agents of the above (xvii) include, but are not limited to, the following compounds: p-quinonedioxime, p, p'-dibenzoylquinonedioxime,
4,4'-dithiodimorpholine, poly p-dinitrosobenzene, 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine, 2,4,6-trimercapto-s- Triazine, tacky roll 201 (manufactured by Taoka Chemical Co., Ltd.), hitanol 2501 (manufactured by Hitachi Chemical Co., Ltd.), brominated alkylphenol formaldehyde resin, and the like. These may be used alone or in combination of two or more.

As the scorch inhibitor of the above (xviii),
Examples include, but are not limited to, N-nitrosodiphenylamine, phthalic anhydride, and the like. These may be used alone or in combination of two or more.

Examples of the above-mentioned mastication accelerator (xix) include O,
Examples thereof include, but are not limited to, O'-dibenzamide diphenyl disulfide, zinc salt of 2-benzamide thiophenol, Pepter 3S (manufactured by Kawaguchi Chemical Co., Ltd.). These may be used alone or in combination of two or more.

Examples of the tackifier (xx) include Tackilol 101 (manufactured by Taoka Chemical Co., Ltd.), Hitanol 1501 (manufactured by Hitachi Chemical Co., Ltd.), modified alkylphenol formaldehyde resin, and Hitanol 5501 (manufactured by Hitachi Chemical Co., Ltd.) Can, but is not limited to. These may be used alone or in combination of two or more.

As the latex coagulant of the above (xxi),
Examples include, but are not limited to, cyclohexylamine salts of acetic acid. Latex coagulants may be used alone or in combination of two or more.

Examples of the processing aid (xxii) include, but are not limited to, Exton K1 and Exton L-2 (all manufactured by Kawaguchi Chemical Co., Ltd.). These may be used alone or in combination of two or more.

The inorganic filler of the above (xxiii) includes, but is not limited to, the following materials: hydrous finely divided silica, calcium silicate, furnace black, channel black, thermal lamp black, gas black, Oil black, acetylene black, calcium carbonate, clay, talc, titanium oxide, zinc white, diatomaceous earth, and barium sulfate. These may be used alone or in combination of two or more.

[Vinyl chloride resin composition] The vinyl chloride resin composition of the present invention contains a vinyl chloride resin (A), a surface modifier (B), and various additives as required. Each of these components can be blended,
By heating and kneading, a desired molded product is obtained. The vinyl chloride resin composition of the present invention can be used as various molded products such as pipes, joints, flat plates, corrugated sheets, sheets, films, wall materials, floor materials, toys, grips, shoe soles, window frames, doors, and the like. .

[0101]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

In this example, the fracture toughness was determined by S.I.
Hashemi and J.M. G. FIG. Polymer Engineeri, invented by Williams
ngand Science, 1986, Vol. 26,
No. 11, pages 760-767. In this method, a force is applied to the notched test piece, and the length of the resulting crack is determined by
The applied force (energy required to cause a crack) was plotted, and the slope of the obtained straight line was defined as the fracture toughness. The greater the inclination, the more energy is required to grow the crack, indicating that the fracture toughness is large.

The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). In the GPC measurement, a polystyrene gel column was used, and tetrahydrofuran (THF) was used as an eluate.

(Production Example 1) In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 500 g of 2,2'-azobis (isobutylvaleronitrile) as a polymerization initiator, and 400 g of sodium lauryl sulfate as an emulsifier And a compound having a thiocarbonylthio structure represented by the formula (6)

[0105]

Embedded image

108 g of the compound shown in the above was charged, and homogenized using a homogenizer for 90 minutes.
The polymerization was carried out. After heating and stirring at 50 ° C for 20 hours,
Unreacted monomers were distilled out of the reactor to obtain a vinyl chloride latex. Gel of vinyl chloride polymer in the latex
The number average molecular weight (Mn) of the vinyl chloride polymer was determined by permeation chromatography.
97600, weight average molecular weight (Mw) = 129800,
The molecular weight distribution (Mw / Mn) was 1.33.

The latex was spray-dried to obtain a vinyl chloride resin (A-1).

(Production Example 2) In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 500 g of 2,2'-azobis (isobutylvaleronitrile) as a polymerization initiator, and 400 g of sodium lauryl sulfate as an emulsifier And a compound having a thiocarbonylthio structure represented by the formula (7)

[0109]

Embedded image

100 g of the compound represented by the following formula was charged and homogenized using a homogenizer for 90 minutes.
The polymerization was carried out. After heating and stirring at 50 ° C for 20 hours,
Unreacted monomers were distilled out of the reactor to obtain a vinyl chloride latex. Gel of vinyl chloride polymer in the latex
The number average molecular weight (Mn) of the vinyl chloride polymer was determined by permeation chromatography.
93500, weight average molecular weight (Mw) = 129000,
The molecular weight distribution (Mw / Mn) was 1.38.

This latex was spray-dried to obtain a vinyl chloride resin (A-2).

(Production Example 3) In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 500 g of 2,2'-azobis (isobutylvaleronitrile) as a polymerization initiator, 400 g of sodium lauryl sulfate as an emulsifier, And a compound having a thiocarbonylthio structure represented by the formula (8)

[0113]

Embedded image

110 g of the compound represented by the following formula was charged and homogenized using a homogenizer for 90 minutes.
The polymerization was carried out. After heating and stirring at 50 ° C for 20 hours,
Unreacted monomers were distilled out of the reactor to obtain a vinyl chloride latex. According to the gel permeation chromatography measurement of the vinyl chloride polymer, the number average molecular weight (M
n) = 72,500, weight average molecular weight (Mw) = 8830
0, molecular weight distribution (Mw / Mn) = 1.22.

The latex was spray-dried to obtain a vinyl chloride resin (A-3).

Production Example 4 In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 500 g of 2,2′-azobis (isobutylvaleronitrile) as a polymerization initiator, 400 g of sodium lauryl sulfate as an emulsifier, And a compound having a thiocarbonylthio structure represented by the formula (9)

[0117]

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170 g of the compound shown in the following was charged and homogenized for 90 minutes using a homogenizer.
The polymerization was carried out. After heating and stirring at 50 ° C. for 24 hours,
Unreacted monomers were distilled out of the reactor to obtain a vinyl chloride latex. Gel of vinyl chloride polymer in the latex
The number average molecular weight (Mn) of the vinyl chloride polymer was determined by permeation chromatography.
120600, weight average molecular weight (Mw) = 18210
0, molecular weight distribution (Mw / Mn) = 1.51.

The latex was spray-dried to obtain a vinyl chloride resin (A-4).

Comparative Production Example 1 In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 500 g of 2,2'-azobis (isobutylvaleronitrile) as a polymerization initiator, and sodium lauryl sulfate as an emulsifier After charging 400 g and homogenizing for 90 minutes using a homogenizer,
Polymerization was carried out at ° C. When the internal pressure of the reactor became 1 kg / cm ² lower than the saturated vapor pressure of the vinyl chloride monomer at 50 ° C., unreacted monomers were distilled out of the reactor to obtain vinyl chloride latex. When gel permeation chromatography of the vinyl chloride polymer in the latex was measured, the number average molecular weight (Mn) of the vinyl chloride polymer was 98,000 and the weight average molecular weight (Mw) was 2
25600, molecular weight distribution (Mw / Mn) = 2.30.

This latex was spray-dried to obtain a vinyl chloride resin (A′-1).

Example 1 A vinyl chloride resin (A-1) was used as the vinyl chloride resin. With respect to 100 parts by weight of the vinyl chloride resin, titanium stearate S151 (manufactured by Nippon Soda Co., Ltd.)
-1) 0.1 part by weight, di-n as a tin-based stabilizer
0.5 parts by weight of octyltin laurate, zinc stearate / calcium stearate complex as lubricant 0.1.
9 parts by weight and 3.0 parts by weight of calcium carbonate CCR (manufactured by Shiraishi Industry Co., Ltd.) were blended to obtain a resin blend (vinyl chloride resin composition).

This resin blend is kneaded and extruded,
An 8-inch roll (outer diameter of about 2
0cm) H0S-2103 (manufactured by Nippon Roll Co., Ltd.)
A roll sheet having a thickness of about 1 mm was prepared. Twenty of these roll sheets are stacked, and using a Sindho SF-type hydraulic press (manufactured by Shinto Metal Industry Co., Ltd.), 190 ° C., 50 kg /
Pressing was performed for 15 minutes under the condition of cm ² to obtain a test plate having a thickness of 10 mm. The test plate was cut to form a test piece, and the fracture toughness was measured. Table 1 shows the results.
Shown in Table 1 also shows the results of Examples 2 to 14 and Comparative Examples 1 to 8 described below.

(Examples 2 to 14) The same procedures as in Example 1 were carried out except that the kinds and amounts of the compounds shown in Table 1 were used as the vinyl chloride resin and the surface modifier. In Table 1, (B-2) is N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane KBM603
(Shin-Etsu Chemical Co., Ltd.) and (B-3) are acetoalkoxy aluminum diisopropylates (Ajinomoto Co., Inc.)
Manufactured).

(Comparative Examples 1 to 8) The same as in Example 1 except that the vinyl chloride resin and the compounds of the types and amounts shown in Table 1 were used as the surface modifier.

[0126]

[Table 1]

As shown in Table 1, the vinyl chloride resin (A
When the vinyl chloride resin composition of the present invention containing -1) to (A-4) and a surface modifier is used, a sufficiently high fracture toughness is obtained. Comparative Examples 1 to 3 are examples in which a surface modifier was added to a resin obtained by polymerizing a vinyl chloride monomer without using a compound having a thiocarbonylthio structure. Comparison of Comparative Example 1 with Examples 3, 6, 9, and 12, Comparison of Comparative Example 2 with Examples 4, 7, 10, and 13, Comparative Example 3 with Examples 5, 8, 11, and 14. It can be seen from the comparison with that that each comparative example is inferior in fracture toughness. Comparative Examples 4 to 8 show the breaking strength of the vinyl chloride resin alone. Comparison between Comparative Example 4 and Examples 1 to 5, Comparison between Comparative Example 5 and Examples 6 to 8, Comparative Example 6 and Examples 9 to 11
By comparison with Comparative Example 7, and Comparative Example 7 with Examples 12 to 14, it is recognized that the surface modifier effectively functions in the present invention. From the comparison between Comparative Examples 4 to 7 and Comparative Example 8, the vinyl chloride resin obtained in the presence of the compound having a thiocarbonylthio structure has a higher fracture toughness than the vinyl chloride resin obtained by an ordinary method. It turns out that it is excellent.

[0128]

According to the present invention, as described above, a vinyl chloride resin obtained by using a compound having a specific thiocarbonylthio structure as a chain transfer agent and a vinyl chloride resin composition having a surface modifier Is obtained. When this vinyl chloride resin composition is used, a molded article having excellent mechanical strength, particularly excellent fracture toughness, and long-term durability can be obtained. Therefore, the composition of the present invention can be used in many fields, including molded articles requiring fracture toughness such as pipes and joints.

Continued on front page F term (reference) 4J002 BD051 DJ009 EC076 EF039 EF049 EF069 EG019 EG049 EH098 EH108 EH148 EV007 EV256 EV257 EW046 EW048 EW066 EX006 EX016 EX026 EX066 EX076 FD028 FD039 FD050 FD100 FD090 FD100 FD090 FD100 FD090 FD100 FD090 FD090 FD100 FD090 FD090 FD090 FD100 AC06 BA06 DA01 DA03 DB04 DB12 DB26 JA06 JA07 JA08 JA11 KA04 KA08 KA10 KA13 KB02 KB29 NA26

Claims (7)

[Claims] 1. A vinyl chloride resin composition containing (A) a vinyl chloride resin and (B) a surface modifier, wherein the vinyl chloride resin is in the presence of a compound having a thiocarbonylthio structure. Wherein the compound having a thiocarbonylthio structure is obtained by radical polymerization of a monomer having a vinyl chloride monomer as a main component, and is represented by the following general formula (1): (Wherein, R ¹ is a p-valent organic group having 1 or more carbon atoms, and the p-valent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, Z ¹ may be a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group may include at least one of them and may be a high molecular weight compound. , nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and may comprise at least one of the phosphorus atoms may be a high molecular weight substance; when Z ¹ is present in plurality And they may be the same or different from each other; and p is an integer of 1 or more), and a compound represented by the general formula (2): (In the formula, R ² is a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom. Z ² may include at least one of them and may be a high molecular weight substance; Z ² is an oxygen atom (when q = 2), a sulfur atom (when q = 2), a nitrogen atom (when q = 3) Case),
Or a q-valent organic group having 1 or more carbon atoms, wherein the q-valent organic group contains at least one of a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom. And may be of high molecular weight;
Two or more R ^{2 s} may be the same or different from each other; and q is an integer of 2 or more), and is at least one selected from the group consisting of compounds represented by the following formula: . 2. The chloride according to claim 1, wherein the surface modifier is at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent. Vinyl-based resin composition. 3. The vinyl chloride resin composition according to claim 1, wherein the surface modifier is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. object. 4. The compound having a thiocarbonylthio structure is represented by the following general formula (3): (Wherein, R ³ is a divalent organic group having 1 or more carbon atoms, and the divalent organic group is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, Z ³ may be a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and the monovalent organic group may include at least one of them and may be a high molecular weight substance. , A nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom, may be a high molecular weight substance, and Z ³ may be the same as or different from each other. The vinyl chloride resin composition according to any one of claims 1 to 3, which is a compound represented by the formula: 5. The vinyl chloride resin is a copolymer of a vinyl chloride monomer and another vinyl monomer, wherein the vinyl monomer is styrene, butadiene, isoprene, chloroprene, At least one selected from the group consisting of vinylidene, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, acrylonitrile, and vinyl acetate; The vinyl chloride resin composition according to any one of claims 1 to 4, which is contained in a proportion of 50% by weight or more of the body. 6. The method according to claim 1, wherein the vinyl chloride resin has a molecular weight distribution (Mw / Mn) of 2 or less determined by gel permeation chromatography (GPC). Vinyl chloride resin composition. 7. A plasticizer, a thixotropy improver, a heat resistance improver, a stabilizer, an antioxidant, an ultraviolet absorber, a hindered amine light stabilizer (HALS), an antistatic agent, a flame retardant, a colorant, and a foam. Agents, lubricants, fungicides, crystal nucleating agents, vulcanization accelerators, antioxidants, vulcanizing agents, anti-scorch agents, mastication accelerators, tackifiers, latex coagulants, processing aids, and inorganic fillers The vinyl chloride resin composition according to any one of claims 1 to 6, further comprising at least one additive selected from the group consisting of agents.