WO2002079324A1 - Vinyl chloride-based paste sol composition - Google Patents

Abstract

A vinyl chloride-based paste sol composition which is sufficiently thixotropic without the need of containing a large amount of a thixotropic agent or solvent, which poses problems concerning productivity, cost, product quality, burden to the environment, etc. The composition comprises as essential ingredients a plasticizer and a vinyl chloride-based paste resin obtained by radical-polymerizing a vinyl chloride monomer in the presence of a specific compound having a thiocarbonylthio structure.

Description

 Specification

Shii-dani bull paste sol composition

Technical field

 The present invention relates to a vinyl chloride paste sol composition. More specifically, the present invention relates to a butyl chloride-based paste sol composition exhibiting remarkable thixotropic behavior under low viscosity, having less mold contamination during molding, and having a uniform molecular weight distribution.

Background art

Conventionally, dipping using a chloride chloride-based paste sol composition has been adopted for the molding of gloves made of vinyl chloride resin, caps for electrical components, coating materials such as hose fasteners, etc. . In this method, a mold such as gloves (porcelain, porcelain, or metal) is immersed in a chloride chlorinated paste sol composition, or a mold for electrical components or a hose made of fiber is immersed. By doing so, the sol adheres to the mold and the periphery of the hose, and then is heated and gelled, then cooled and peeled off from the mold, or the product is left as it is. Such immersion processing methods include a hot diving method in which the mold is preheated to a predetermined temperature and then immersed in the sol to adjust the amount of adhesion. There is known a cold diving method in which a sol is adhered and then gelled by heating. At present, the mainstream of the immersion processing method is the cold diving method, but in this case the amount of sol attached depends on the fluidity of the sol itself, and there is a conflicting relationship between the sol dripping and the attached amount. is there. It is known that a dripping sol has a problem in processability, and a method of adding a large amount of a thixotropic agent (thickener) to prevent dripping is known. However, a sol with a large amount of a thixotropic agent added is not seen. There was a problem that as a result of the increase in the viscosity and the increase in the amount of adhesion, only a thick material could be obtained. In addition, it is possible to adjust the amount of adhesion by adding a solvent, etc.Addition of a solvent not only increases the cost, but also causes a pinhole to be formed in the molded article due to the volatilization of the solvent during gelation. There were many problems, such as solvent vapor deteriorating the environment and causing fire. In addition, in the immersion processing method in which the mold is used repeatedly, the heat gel formation of the sol is repeatedly performed. In addition, there is a problem in that bleeding substances, especially sol compounding agents, especially stabilizers, adhere to and accumulate on the mold surface, resulting in mold fouling and the necessity of cleaning the mold, resulting in low productivity. Was.

 As a method for solving such a problem, a method of adding an organic sulfonic acid salt to a vinyl chloride paste sol composition is disclosed in Japanese Patent Publication No. 7-719, but is obtained by ordinary radical polymerization. In the prepared butyl chloride-based polymer, the uniform dispersibility of these organic sulfonates and other thixotropic agents is poor and the stability is low, so that the thixotropic behavior when the thixotropic agent is added is insufficient. There was a problem when the thickness of the molded product was not stable.

 On the other hand, in the production of vinyl copolymers, reversible addition-desorption chain transfer is possible because the molecular weight and molecular weight distribution can be controlled, a wide range of monomers and polymerization methods can be used, and it is suitable for the production of block products. (Reversible Ad dition—Fragmentation: hain Transfer: R

AFT) The polymerization method is excellent, for example, WO98 / 01478, WO99Z05099, WO99 / 31144, and Macromolecules 1998, 31 1, 5559-5562, and the reaction mechanism. The details are described, including However, for compositions containing a vinyl chloride paste resin as an essential component, application of the RAFT polymerization method has not been studied so far. The present invention relates to a composition containing a vinyl chloride paste resin produced by a RAFT polymerization method as an essential component.

Disclosure of the invention

 The problem to be solved by the present invention is to provide a thixotropic agent, which has problems in productivity, cost, product quality, environmental burden, etc. ゃ Biel chloride paste showing sufficient thixotropic behavior without the need to add a large amount of solvent It is to provide a sol composition.

The inventors of the present invention have been studying to solve the above problems, and (A) radical polymerization of a vinyl chloride monomer in the presence of a specific compound having a thiocarbonylthio structure. The present invention was found to be particularly effective in a vinyl chloride paste sol composition containing two components, a vinyl chloride paste resin and (B) a plasticizer, as essential components.

 Since the butyl chloride-based polymer produced by the RAFT polymerization method, which is the component (A) of the present invention, has a thiocarbonylthio structure at its terminal, various additives, particularly sulfonic acid salts, and other thixotroping agents are mixed. In this case, the uniform dispersibility is very good. For this reason, the vinyl chloride paste sol composition of the present invention shows a sufficient thixotropy behavior by adding a small amount of a thixotrope, and the like. And other additives can reduce the amount of additive. In addition, it is considered that the effects of hydrogen bonding and polarity involving the terminal thiocarboxy thio group also contribute to the development of thixotropic behavior. Further, in the Shiridani bull-based polymer produced by the RAFT polymerization method, the molecular weight, the molecular weight distribution, and the copolymer composition can be easily controlled. Therefore, when a composition suitable for an actual immersion processing method is added by adding a plasticizer or the like, it is possible to easily adjust the physical properties of the composition and the gelled product thereof.

 The vinyl chloride paste resin as the component (A) of the present invention has the general formula (1)

(In the formula, R ¹ is a p-valent organic group having 1 or more carbon atoms, and may include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom, and has a high molecular weight. Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom. When a plurality of Z ¹ are present, they may be the same or different, and p may be 1 or more. It is an integer. 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 may include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom, and has a high molecular weight. Z ² is an oxygen atom (when q = 2), a sulfur atom (when q = 2), a nitrogen atom (when q = 3), or a q-valent organic compound having 1 or more carbon atoms. R ² may be a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, or a high molecular weight compound, and R ² may be the same as or different from each other. Q is an integer of 2 or more.) A vinyl chloride monomer or a vinyl chloride monomer 50 in the presence of a compound having a thiocarbonylthio structure selected from the group consisting of compounds represented by Weight% or more, monomer copolymerizable with vinyl chloride monomer 50 weight. / ₀ is a vinyl chloride paste resin obtained by radical polymerization of less than / ₀ .

 The compound having a thiocarbolthio structure used in the present invention includes a compound represented by the general formula (3) in that a vinyl chloride polymer having a thiocarbolthio structure at both terminals can be easily produced.

(In the formula, R ³ is a divalent organic group having 1 or more carbon atoms, such as nitrogen atom, oxygen atom, sulfur It may contain atoms, halogen atoms, silicon atoms, phosphorus atoms, and metal atoms, and may be a high molecular weight compound. z ³ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and may include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a high molecular weight It may be a body. Z ³ may be the same or different. A compound having a thiocarbonylthio structure at both ends represented by

 In the vinyl chloride paste sol composition of the present invention, as a component other than the component (A) and the component (B), in order to exhibit a sufficient thixotropic behavior, the general formula (4)

(Wherein L ¹ is an alkali metal or ammonium group, and n is an integer of 1 to 20), and a compound represented by the general formula (5):

(Wherein, R ⁴ is a monovalent organic group having 1 or more carbon atoms, and L ² is an alkali metal or an ammonium group.) One or more sulfonates selected from the group consisting of compounds represented by the following formulas: Can be contained. These sulfonates act as thixotropic agents in the Shii-Dani Bull-based paste sol composition of the present invention.

Such sulfonates are not particularly limited, but include, for example, sodium isethionate, potassium isethionate, ammonium isethionate, sodium lauryl ethyl ester sulfonate, sodium myristyl ethyl ester sulfonate, and stearyl ethyl ester Examples include sodium sulfonic acid. You. These may be used alone or in combination of two or more. The salt-based paste resin used as the component (A) in the present invention exhibits a sufficient thixotropic behavior with a small amount of addition, since it has a very good uniform dispersion 1 "production with these sulfonates. The amount of the sulfonate used is not particularly limited but may be small, and is preferably 0.05 to 2 parts by weight, more preferably 0.02 to 100 parts by weight of the component (A). When the amount is less than 0.05 part by weight, the effect of improving the thixotropic behavior may not be clear, and when the amount is more than 2 parts by weight, the sol viscosity is too high, which is not practical.

In the compounds represented by the general formulas (1) and (2) having the thiocarbonylthio structure, R ¹ is not particularly limited, but from the viewpoint of availability, a benzyl group, a 1-phenyl / reethyl group, 2-phenyl-2-propyl, 1-acetoxityl, 11- (4-methoxyphenol) ethyl, ethoxycanolepolmethyl, 2-ethoxycarbonyl 2-propyl, 2-cyano 2 —Propyl group, t-butyl group, 1,1,3,3-tetramethylbutyl group, 2- (4-chlorophenyl) -12-propyl group, vinylbenzyl group, t-butylsulfide group, 2- Power / Repoxysilethyl group, carboxymethyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyano-2-butyl group, and general formula (6)

O CN O

— CH ₂ -CO-CH ₃ C-CH2CH2-CO-CH3

CH ₃

 O

II

CH ₂ CO "(cH ₂ CH

(Wherein, r represents an integer of 1 or more.). Also, R ² is not particularly limited, but in terms of availability, benzyl group, 1-phenylethyl group, 2-phenyl-2-propyl group, 1-acetoxethyl group, 1- (4-methoxyphenyl) ethyl Ethoxycanoleboninolemethyl group, 2-ethoxyethoxycarbonyl-2-propyl group, 2-cyano-2-propyl group, t-butyl group, 1,1, 3,3-tetramethylbutyl group, 2- (4-chlorophenol) 1-2-propyl group, vinylbenzyl group, t-butylsulfide group, 2-carboxyethyl group, carboxylmethyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyano-2-butyl group, and general formula on (7)

 0

 II

— CH ₂ CO-CH ₃ (7)

 CN

— C-CH ₂ CH ₂ -C0- (CH ₂ CH ₂ 0) -CH3

CH ₃ ^r

(Wherein, r represents an integer of 1 or more.). Also, Z ¹ is not particularly limited, but from the viewpoint of availability, phenyl, methyl, ethyl, benzyl, 4-chlorophenyl, 1-naphthyl, 2- Naphthyl group, diethoxyphosphinyl group, n-butyl group, t-butyl group, methoxy group, ethoxy group, thiomethyl group (methylsulfide), phenoxy group, thiophenyl group N, N-dimethylamino group, N, N-Getylamino group, N-phenyl-1-N-methylamino group, N-phenyl-1-N-ethylamino group, thiobenzinole group (benzylsnolefide), pentaphenylolef Enoxy group, and general formula (8)

CH ₃

— SC-COOCH ₂ CH ₃

Organic substituents represented by CH ₃ are preferred. Although not particularly limited as z ^2, in terms of the incoming hand property, phenyl group, methyl group, Echiru group, a benzyl group, 4 _ black port phenylene group, 1 _ naphthyl, 2 _ naphthyl group, di Ethoxyphosphinyl 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-getylamino, N-phenyl-1-N-methylamino, N-phenyl-N-ethylamino, thiobenzyl (benzylsulfide), pentafluorophenoxy, and the general formula (9)

The organic substituent represented by is preferred.

In the compound having a thiocarbolthio structure at both ends represented by the general formula (3), R ³ is not particularly limited, but from the viewpoint of availability, the compound represented by the general formula (10)

Is preferred. Although Z ³ is not particularly limited, phenyl, methyl, ethyl, benzyl, 4-chlorophenyl, 1-naphthyl, 2-naphthyl, diphenyl Ethoxyphosphinyl group, n-butyl group, t-butyl group, methoxy group, ethoxy group, thiomethyl group (methyl sulfide), phenoxy group, thiopheninole group (phenylsnosulfide), N, N-dimethylamido , N, N-Jethylamino, N-phenylN-methylamino, N-phenyl-N-ethylamino, thiobenzyl (benzylsulfido), pentafluorophenoxy, and the general formula ( ₇ ) 0

 II

CH ₂ CO-CH ₃ (7)

 CN O

II

— C- CH ₂ CH ₂ — CO; CH ₂ CH ₂ Oj "CH ₃

CH ₃ ^r

(Wherein, r represents an integer of 1 or more.).

Specific examples of the compound having a thiocarpenylthio structure described in any of the above and used in the present invention include a compound represented by the following general formula (11)

e (Π)

 S CN S

Ph— — S— CCH ₂ CH ₂ COOH Ph—C— S—CH ₂ COOH

 Me

 S

II

Ph— C-S-CH ₂ COO "(CH ₂ CH ₂ o)" Me

 S

Ph— C— S— CH _2. \ ■ CH ₂ -SC-Ph

 S S CN

II

Ph-CS-CH ₂ COOMe Ph-CS-CCH ₂ CH ₂ COOMe

Me

 s

 II

PhCH ₂ — S— C— S— CH ₂ Ph

(In the formula, Me represents a methyl group, E′t represents an ethyl group, Ph represents a phenyl group, Ac represents an acetyl group, and r represents an integer of 1 or more.) It is not limited to these.

 In the present invention, the method of radically polymerizing vinyl chloride monomer in the presence of a compound having a thiocarbonylthio structure is not particularly limited, and a vinyl chloride paste resin such as an emulsion polymerization method or a fine suspension polymerization method may be used. A conventionally known method used in the production can be used.

About polymerization initiator or polymerization initiation method when polymerizing vinyl chloride monomer Is not particularly limited, and a conventionally known polymerization initiator or a polymerization initiation method can be used. For example, cyclohexanone peroxide, 3,3,5-trimethinolecyclohexanone peroxide, methylcyclohexanone peroxide, 1,

1-bis (tert-butylperoxy) 1,3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyne 1,4,4-bis (tert-butylperoxy) Valerate, cumene hydroperoxide, 2,5-dimethylhexane-1,2,5-dihydridoperoxide, 1,3-bis (tert-butylpropyloxy) -mf-sopropyl) benzene, 2,5-dimethyl_2 , 5-di (tert-butylhydroxy) hexane, diisopropylpropylbenzeneperoxide, tert-butylcumylperoxide, decanoylperoxide, lauroylperoxide, benzoylbaroxide, 2, 4-dichlorobenzoyl peroxide, bis (tert-butyl / recyclohexynole) Oxydicarbonate, tert-butynoleha. Peroxide polymerization initiators such as monooxybenzoate, 2,5-dimethyl-1,2,5-di (benzoy ^^ propoxy) hexane; 2,2'-azobis (isobutyronitrile), 1,1 —Azobis (cyclohexane 1-force ^ / bonitolinole), azocumene, 2, 2 '—azobis (2-methylbutyronitrile), 2, 2'—azobisdimethinorevalero nitrile, 4, 4'-Azobis (4-cyanovaleric acid), 2- (tert-butylacetyl) -1-2-cyanopropane, 2, 2'-Azobis (2,4,4-trimethylpentane), 2,2,1-azobis Azo polymerization initiators such as (2-methylpropane) and dimethyl 2,2'-azobis (2-methylpropionate); inorganic peroxides such as potassium persulfate and sodium persulfate; styrene, etc. That generate radical species thermally, such as -Compounds that generate radical species by light, such as benzoin derivatives, benzophenone, asinolephosphinoxide, and photoredox systems; sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and sulfuric acid sulfate Iron is used as a reducing agent, and potassium peroxodisulfate, hydrogen peroxide, and t-butyl hydroperoxide are used as oxidizing agents. Redox-type polymerization initiators, but are not limited thereto. These polymerization initiators may be used alone or in combination of two or more. It is also possible to use a polymerization initiation system by electron beam irradiation, X-ray irradiation, radiation irradiation, or the like. Such a polymerization initiation method is described in Mo adand Sol omo nΓ he Chemistry of Free Radical P ol y mer rization ", Pergamon, London, 1995, pp. 53-95. 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 reduced in that a polymer having a small molecular weight distribution can be obtained. The amount of the compound having a thiocarbonylthio structure is preferably 1 equivalent or less, more preferably 0.5 equivalent or less, and the amount of the polymerization initiator used is controlled to control the amount of radical species generated during the polymerization. In addition, it is preferable to adjust the temperature in the case of a polymerization initiator that thermally dissociates, or to adjust the amount of irradiation energy in the case of a polymerization initiation system that generates radicals by light or electron beam.

In the present invention, when the vinyl monomer is subjected to emulsion polymerization or fine suspension polymerization, the emulsifier to be used is not particularly limited, and fatty acid soap, rosin acid soap, sodium naphthalenesulfonic acid sodium honoremarin condensate, Sodium alkylbenzenesnolephonate, ammonium alkyl sulfate, sodium alkyl sulfate, triethanolamine alkyl sulfate, sodium dialkyl sulfosuccinate, alkyl diphenyl ether disulfonate sodium, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkylphenyl Anionic surfactants such as sodium monoter sulfate; polyoxyethylene alkyl ether, polyoxyethylene higher alcohol ether, sorbitan fatty acid ester, polyoxy Nonionic surfactants such as Tylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkyl alkanolamide; alkyltrimethylammonium Cationic surfactant such as muchloride And the like. These emulsifiers may be used alone or in combination of two or more. If necessary, partially saponified polyacetic acid butyl, poly (vinyl alcohol), methyl / resenololose, phenolic methyl cellulose, gelatin, polyalkylene oxide, a combination of anionic surfactant and dispersing agent, etc. A conventionally known dispersant for suspension polymerization may be added. The amount of the emulsifier used is not particularly limited. For emulsification liquid (latex) stabilization, usually 0.01 to 3 parts by weight is used per 100 parts by weight of the monomer.

In the present invention, when a vinyl chloride monomer is polymerized in the presence of a compound having a thiocarbolthio structure, the method of adding the compound having a thiocarbolthio structure is not limited, but the polymerization behavior is stable. It is preferable that the structure of the vinyl chloride polymer is easily mixed with the vinyl chloride monomer in an aqueous dispersion or an aqueous emulsion and stirred in advance with a homogenizer or the like because the structure of the vinyl chloride polymer can be easily controlled. . In the present invention, when a vinyl chloride monomer is subjected to radical polymerization in the presence of a compound having a thiocarbonylthio structure, it is possible to copolymerize a monomer capable of undergoing radical copolymerization with a vinyl chloride monomer. . Such monomers are not particularly limited, but include, for example, styrene, α-methyl ^^ styrene, dibininolebenzene, ρ-hydroxystyrene, ρ-carboxystyrene, ρ-methoxystyrene, and acetylaminostyrene. Styrene compounds such as, ethinoleamino α-methinolestyrene, ρ-vinylinolebenzenesulfonic acid, ρ-vinylinolebenzenesnolephonate, and m, m_dimethyl / restyrene; ethylene, propylene, 1-butene, 1 —Aliphatic terminal olefin compounds such as heptene, 1-hexene, 1-octene, isobutylene, butadiene, and isoprene; halogen-containing olefins such as butyl fluoride, vinyl bromide, chloroprene, and vinylidene salt Compound; acrylic acid, methacrylic acid; acrylic acid Tyl, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, acrylate Decyl, dodecyl acrylate, phenyl acrylate, toluyl acrylate, Benzyl acrylate, Isobornyl acrylate, 2-Methoxyxyl acrylate, 3-Methoxybutyl acrylate, 2-Hydroxyshetinole acrylate, 2-Hydroxypropyl acrylate, Stearyl acrylate, Glycidyl acrylate, 2-Acrylo Inoleoxypropyl dimethoxymethylsilane, 2-acryloyloxypropyltrimethoxysilane, trifluoromethyl acrylate, pentaf / rheoloethyl acrylate, 2,2,2-trifluoroethyl acrylate, 3-dimethyla acrylate Minoethyl, isoptyl acrylate, 4-hydroxybutyl acrylate, t-butyl acrylate, alkyl-modified dipentaerythritol acrylate, ethylene oxide-modified bisphenol A diatalylate, acrylic acid Rubitol, E—Proprolactone modified dipentaerythritol acrylate, Proprolactone modified tetrahydrofurfuryl acrylate, Proprolactone modified hydroxypivalate neopentylglycol ester diacrylate, Ditrimethylolpropane tetraacrylate Dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, trimethylolpropane ethoxy tritalylate, trimethylolpropane Triatalylate, neopentyl glycol diacrylate, neopentyl dalicol hydroxybivalate diatalylate, 1,9-nonanediol acid, 1,4-butanediol acrylate, 2-propionic acid [2- [1,1,1-dimethyl-2-[((1-oxo-2-propenyl)] [Xin] ethinole] 1-5-ethyl-1, 3-dioxane-1 5-yl] methinoleestenole, 1,6-hexanediol acrylate, pentaerythritol triacrylate, 2-acryloyloxypropyl hydroxide Acrylates such as genphthalate, methyl 3-methacrylate, and aryl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-methacrylic acid Ethylhexyl, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate Metaku Benzyl acrylate, 2-hydroxyhexyl methacrylate, 2-hydroxypropyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-N-ethylaminoethyl methacrylate, glycidyl methacrylate, tetrahid methacrylate Furfuryl, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl methacrylate, Hexinyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate , Toluyl methacrylate, Isobol methacrylate, 2-Methoxyxetyl methacrylate, 3-Methoxybutyl methacrylate, 2-Aminoethyl methacrylate, Triethylene glycol methacrylate, 2-Methacryloyloxypropyl trimethoxysilane, 2-Methacryloyl Methacrylic acid esters such as oxypropyldimethoxymethylsilane, trif / reolomethyl methacrylate, pentaphenylenoethyl methacrylate, and 2,2,2-trifluoroethyl methacrylate; acrylamide, methacrylamide , N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-tert-butylacrylamide, N-t-butylmethacrylamide Mid, N—n—petit Acrylamide, N-n-butyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethylol acrylamide, N-ethylol methacrylamide, acrylonitrile, methacrylonitrile, N- Nitrogen-containing olefin compounds such as phenylenomaleimide, N-butylmaleimide, 4-vinylinolepyridine, N-vinylpyrrolidone, and N-butyl rubazole; P-vinylbenzoic acid, vinyl benzoate, itaconic acid, itaconic anhydride Carboxyl group-containing unsaturated compounds such as acid, α-methylbutylbenzoic acid, vinyl nitrate, vinyl butanoate, maleic anhydride, allylic acetate, and allyl benzoate; diarylammonium chloride, 1,6-heptadiene , 2, 6—Dicyan, 1, 6 Cyclobutadiene, and cyclopolymerizable compounds such as 2,4,4,6-tetrakis (ethoxycarbol) 1,6, -butadiene and other compounds with 1,6-heptadiene structure; dimethylbiphenyl Yulsilane, trimethylvinylsilane, dimethyinolepheny ^^ vinyla, dimethyoxymethy / rebiny / lehsilane, ethoxyphenyolebutyursilane, trimethoxyvinylinolesilane, pentamethylvinylinolesiloxane, trimethylarylsilane, trimethyoxyarylsilane , Dimethoxymethylarylsilane, heptamethylvinylcyclotetrasiloxane, and silicon-containing unsaturated compounds such as 1,1,3,3-tetramethyldivierdisiloxane; aryl-terminated polyethylene oxide, aryl-terminated polypropylene oxide, aryl-terminated Po Polyethylene oxide-polypropylene oxide copolymer, vinyl-terminated polyethylene oxide, vinyl-terminated polypropylene oxide, vinyl-terminated polyethylene oxide-polypropylene oxide copolymer, methallyl-terminated polypropylene oxide, bier-terminated polytetramethylene Oxide, acryloyl-terminated polyacrylic acid, methacryloyl-terminated polymethacrylic acid, acryloyl-terminated polyacrylic acid ester, acryloyl-terminated polymethacrylic acid ester, methacryloyl-terminated acrylic acid ester, methacryloyl-terminated methacrylic acid ester, vinyl-terminated polysiloxane, Bull-terminated polycarbonate, aryl-terminated polycarbonate, beer-terminated polyethylene terephthalate, vinyl-terminated polybutylene terephate Les one DOO, Bulle terminus force caprolactam, vinyl-terminated polyamide-de, and the like can be given unsaturated group-containing macromonomers such as vinyl terminus polyurethane, but is not limited thereto. The monomers used in the present invention may be used alone or in combination of two or more. Among these monomers, styrene, α-methylstyrene, butadiene, isoprene, chloroprene, ethylene, propylene, futonidani vinylonole, and bromide are useful in that the obtained polymer is useful. Vinylinole, vinylidene chloride, atalylic acid, methacrylic acid, acrylate ester, methacrylic acid ester, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, butyl acetate, vinyl butyrate, vinyl benzoate, maleic anhydride, Maleimide compounds, N-butylpyrrolidone, N-vinylcarbazole, fumaric acid esters, 1,6-heptadiene compounds, and diarylammonium salts are preferred, and styrene, butadiene, isoprene, More preferred are vinylidene chloride, acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, methacrylamide, acrylonitrile, and butyl acetate. When these monomers are copolymerized with a vinyl chloride monomer, a single monomer may be copolymerized, or a plurality of monomers may be combined and copolymerized. When the vinyl chloride monomer and the above monomer are copolymerized, a conventionally known form such as a random copolymer, a block copolymer, a graft copolymer, or a gradient copolymer may be used. it can. When copolymerizing these monomers and a vinyl chloride monomer as the (A) vinyl chloride paste resin of the present invention, the copolymer is copolymerized with 50% by weight or more of a vinyl chloride monomer.

 Further, the vinyl chloride paste resin of the present invention can be used by mixing a plurality of vinyl chloride paste resins having different number average molecular weights. When using a mixture of vinyl chloride-based resins, various physical properties such as viscosity, fluidity, thixotropy, genolization properties, heat resistance, weather resistance, hot water resistance, and light resistance are adjusted. It is preferable to mix vinyl chloride-based paste resins having different physical properties. For example, vinyl chloride-based paste resins whose number average molecular weights calculated by gel 'permeation' chromatography differ from each other by more than 300,000 are preferred. It is more preferable to mix vinyl chloride paste resins whose number average molecular weights are different from each other by 500 or more.

 Further, the chlorinated vinyl-based paste resin in the present invention preferably has a molecular weight distribution of 2 or less, more preferably 1.5 or less, as measured by gel permeation chromatography (GPC).

Further, the vinyl chloride paste resin in the present invention may be used as a chlorinated vinyl chloride polymer by polymerizing a vinyl chloride monomer and then partially chlorinating it. As a method of chlorinating a vinyl chloride resin, various conventionally known methods can be used. However, industrially, the water suspension chlorination method is preferred.

The plasticizer as the component (B) of the present invention is not particularly limited, and a conventionally known plasticizer can be used. Such plasticizers include, for example, dimethyl phthalate, di- / ethyl phthalate, di-n-butynole phthalate, diheptyl phthalate, di-2-ethyl phthalate hexyl, diisononyl phthalate, phthalic acid Disodecinole, ditridecyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, esterenole tetrahydrophthalate, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tri (2-chloroethynole) phosphate , Tris diclo mouth propionole phosphate, Tributoxyshetti phosphate, Tris — clo mouth propi / re) Phosphate, Triphenyl phosphate, Octyl diphenyl phosphate, Tris (Isopropi fenii) Nore) Phosphate, Cresi / Resiphenic Phosphate, Di-1-ethylhexyl adipate, Diisononyl adipate, Disodecyl adipate, Di-η-alkyl adipate, Dibutyldiglycol adipate, Bisazelate (2-Ethynole) Hexyl), dibutyl sebacate 4 ^, di-2-sechinolate hexinole, acetyl triethyl quenate, acetyl butyl citrate, dibutyl maleate, dibutyl maleate hexinole maleate, dibutyl fumarate, dibutyl fumarate, Examples include, but are not limited to, tris-2-ethylhexyl trimellitate, trialkyl trimellitate, polyester plasticizers, epoxy plasticizers, stearic plasticizers, and parabutyl chloride is not. These may be used alone or in combination of two or more. The amount of the plasticizer used in the present invention is not particularly limited. However, it is preferable to use 100 to 200 parts by weight based on 100 parts by weight of the vinyl chloride paste resin of the component (Α). , 50 to 100 parts by weight. If the amount is less than 100 parts by weight, the effect of plasticization may not be exhibited, and if it exceeds 2000 parts by weight, weather resistance and heat resistance may be adversely affected. In the butyl chloride-based paste sol composition of the present invention, an acidic compound, a hydrotalcite compound, and a zeolites are used for the purpose of improving the physical properties of the obtained butyl chloride-based resin. A compound selected from the group consisting of a light compound and a metal perchlorate can be contained. These may be used alone or in combination of two or more. The acidic compound used in the present invention is not particularly limited. For example, phosphoric acid, phosphorous acid, sodium hydrogen sulfate, potassium hydrogen sulfate, chromic acid, hydrochloric acid, sulfuric acid, sulfurous acid, thiosulfuric acid, nitric acid, nitrous acid, And inorganic acids such as iodic acid; acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, nicotinic acid, benzenes / lephonic 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, glycolic acid, gnoletamic acid, fumaric acid, maleic acid, malonic acid, lactic acid, oleic acid, salicylic acid, trimellitic acid, p-toluenesulfonic acid And organic acids such as strong acid ion exchange resins. These may be used alone or in combination of two or more. The hydrotalcite compound used in the present invention is not particularly limited. For example, natural hydrotasite; Japanese Patent Publication No. 46-22880, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. Synthetic hydrotalcite synthesized by the method described in, for example, Japanese Patent Publication No. 61-174702; hydrotalcite surface-treated with wax such as fatty acid ester; zinc-modified hydrotalcite; perchloric acid Hydrotalcite treated; hydrotalcite obtained by treating zinc-modified hydrotalcite with perchloric acid; and hydrotalcite dried. These may be used alone or in combination of two or more. The zeolite compound used in the present invention is not particularly limited, but zeolite 、, X-zeolite, Y-zeolite, P-zeolite, monodenite, arnassite, sodalite aluminokerate, clinopti mouth Examples include light, erionite, and chabazite. These may be used alone or in combination of two or more. The metal perchlorate used in the present invention is not particularly limited, and examples thereof include tin perchlorate, barium perchlorate, sodium perchlorate, and magnesium perchlorate. These may be used alone or in combination of two or more. In the vinyl chloride paste sol composition of the present invention, various conventionally known stabilizers, additives, fillers, and the like can be blended as components other than the above. Such stabilizers, additives, and fillers include, for example, cadmium stearate, zinc stearate, barium stearate, dibasic lead stearate, lead stearate, calcium stearate, and lead tribasic sulfate. , Dibutyltin diphosphoric acid ship, tris (noninolepheninole) phosphite, triphenylphosphite, and diphenylisodecyl phosphite, etc .; PVC stabilizers; di-n-octyltin bis (isooctylthioglycolic acid) Ester) Salt, di-n-octyltin maleate polymer, di-n-octyltin dilaurate, di-n-octynolesuzumaleate salt, di-n-butyltin bismaleate salt , Di-n-butyltin maleate polymer, g-n-butyltin bi Octylthioglycol ester salt, di-n-butyltin i3-mercaptopropionate polymer, di-n-butyltin dilaurate, di-n-methyltin bis (isooctylmercaptoacetate) salt, poly (thiobis-n) -Butyltin sulfide), monooctyltin tris (isooctylthioglycolate), di-n-butylinosuzumalate esterol carboxylate, and di-n-butyltin malate ester / mercaptide Organic tin stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic tin sulfite, dibasic lead phthalate, lead silicate, dibasic lead stearate, and lead stearate Lead-based stabilizer; power dome soap, zinc-based soap, barium-based soap, lead-based soap, composite metal stone 2,6-di-t-butyl-p-cresol, butylated hydroxydisole, 2,6-di-t-butyl, 4- and ethynolepheno-1 Le, stearinole-1- (3,5-di-butynole-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2,1-methylenebis (4-ethyl) 1, 6-t-butynolephenol), 4; 4, -thiobis (3-methynole-1-6-t-butynolephenol) 4, 4, 1-butylidenebis (3-methyl-6-t-butylenol), 3,9-bis [1,1-dimethinole-1- (β- (3-t-butynole-1-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-te Toloxaspiro [5.5] pentane, 1,3-tris (2-methynole-1-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-1,2,4,6-tris (3,5 —Di-t-butyl-4-hydroxybenzinole) benzene, tetrakis [methylene-1- (3 ′, 5, di-t-butynole-1,4-hydroxyphenyl) propionate] methane, bis [3 , 3'-bis- (4,1-hydroxy-1,3-t-butylphenyl) butylic acid] Glycol Estenole, 1,3,5-tris (3,, 5, di-tert-butyl-1 4 , One hydroxybenzinole)-

Phenolic antioxidants, such as 5-triazine-1,2,4,6- (1H, 3H, 5H) trione, and tocohues; dilauryl 3,3 '-^-dipropionate, dimyristyl 3, Sulfur-based antioxidants such as 3'-dithiopropionate and distearyl 3,3'-thiodipropionate; triphenylphosphite, diphenylisodecylphosphite, 4,4,1-butylidenebis (3-Methyl-6_t-butylphenylditridecyl) phosphite, cyclic neopentanetetraylbis (octadecyl phosphite), tris (noelfenenole) phosphite, tris (monononinolephenine) phosphite, Tris (diphenyl) phosphite, diisodecylpentaerythritol diphosphite 9,10-dihydro-9-oxa _10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t_butyl-1-4-hydroxybenzyl)-9,10 —Dihydro 9—oxa 10—Phosphafenanthrene 10—Oxide, 10—Desiloxy — 9,10—Dihydro 9—Oxa 10 0—Phosphaphenanthrene, Tris (2,4—G t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyltinole 4- methinorefue Ninore) phosphite and 2,2-methylenebis (4,

Phosphorus antioxidants such as 6-di-t-butylphenyl) octylphosphite; Salicylic acid-based ultraviolet absorbers such as phenyl salicylate, p-t-butylphenol-salicylate, and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-14-methoxybenzophene Non, 2-Hydroxy 4-hydroxybenzophenone, 2-Hydroxy_4-Dodecinoleoxybenzophenone, 2,2'-Dihydroxy_4-4-methoxybenzophenone, 2,2, Dihydroxy 1,4'-Dimethoxybenzophenone, 2-hydroxy-14-methoxy-5_sulfobenzophenone, and bis (2-methoxy-4-hydroxy-1-5-benzoylphenyl) methane Nzophenone UV absorber; 2- (2,1-hydroxy-5'-methylpheninole) benzotriazole, 2- (2'-hydroxy-1-5 , _T-Butylphenyl) benzotriazonole, 2- (2, -Hydroxy-1,3,, 5'-di-t-butylphenyl) benzotriazonole, 2-(2, -Hydroxy-1 3'-t —Bucinole 1-5, 1-Methinolephen-2-ole)-5 —Black benzotriazole, 2- (2, —Hydroxy-1,3,, 5,1-t-Bucinolefe) 1 5 _Black benzotriazole 1-5 , 2- (2, -hydroxy-1,3,, 5'-di-t-aminorefninole) benzotriazole, 2- (2'-hydroxy_4, octoxypheninole) benzotriazole, 2-[2,1-hydroxy-1,3-, (3 ", 4", 5 ", 6" -tetrahydrophthalimid-methyl) 1 5'-methinolepheninole] benzotriazole, 2,2-methylenebis [4- 1, 1, 3, 3-tetramethylbutyl) Zotriazole_2-yl) phenol], [2- (2'-hydroxy-5'-methacryloxyphenyl) -12H-benzotriazole], and [2,2'-methylenebis [4-1 ( 1,1-, 3-, 3-tetramethylbutyl) 16-[(2H-benzotriazole-2-yl) phenol]]] and other benzotriazole ultraviolet absorbers; 2-ethylhexyl-1-2 Cyanoacrylate-based ultraviolet absorbers such as cyano-3,3,1-diphenyl atalylate and ethyl-2—cyano-3,3′-diphenyl atalylate; nickel bis (octylphenyl) sulfide; [2,2 '—Chobis (4_t one-year-old tyl phenolate)] 1 n—Ptilamin Nickenore, Ecke Bis- (2,2,6,6) Eckenole-based UV stabilizers such as 1,3-di-tert-butyl-4-hydroxybenzyl-phosphate monoethylate and nickel ^ -dibutinoresitica canolebamate —Tetramethyl-1-piperidyl) Sebacate, Sanol LS—770 (manufactured by Sankyo), ADK STAB LA—77 (manufactured by Asahi Denka), Smithorpe 577 (manufactured by Sumitomo Chemical), BioSoap 04 (manufactured by Kyodo Yakuhin), Chima ssorb 944 LD (C iba S pecia 1 ty), Tinuvinl 44 (C iba S pecia 1 ty), ADK STAB LA—52 (Asahi Denki), ADK STAB LA—57 (Asahi Denka), ADK STAB LA—67 (Asahi Denka), ADK STAB LA—68 (Asahi Denka), ADK STAB LA—77 (Asahi Denka), ADK STAB LA—87 (Asahi Denka), and Go odrite UV-3034 (G hindered amine based light stability Agents (HAL S); nonionics such as poly (oxyethylene) alkylamine, poly (oxyethylene) alkylamide, poly (oxyethylene) alkyl ether, poly (oxyethylene) alkyl fuunyl ether, glycerin fatty acid ester, and sorbitan fatty acid ester Antistatic agent; anionic antistatic agents such as alkyl sulfonate, alkylbenzene sulfonate, anolequinolesanophosphate, and anolequinolephosphate; quaternary ammonium chloride, quaternary ammonium sulfate, and quaternary ammonium sulfate Antistatic agents such as high-grade ammonium nitrate; amphoteric antistatic agents such as alkyl betaine compounds, alkyl imidazoline compounds and alkyl alanine compounds; polyvinyl benzyl type Conductive compounds such as on-compounds and polyacrylic acid-type cationic compounds; tetrabromobisphenol A, 2,2-bis (4-hydroxy-1,3,5-dibromophenyl) prohane, hexane Bromobenzene, tris (2,3-dibromopropynole) isocyanurate, 2,2-bis (4-hydroxyethoxy-1,3,5-dibromophenyl) propane, decabromodiphenyl oxide, halogen-containing polyphosphate, etc. Ammonium phosphate, tricresyl phosphate, trietinole phosphate, tris (_chloroethinole) phosphate Phosphorus, trischloroethynolephosphate, tris-dichropropane phosphate, cresyl diphenyl phosphate, xylendiphenyl phosphate, acid-based phosphoric acid esters, and nitrogen-containing phosphorus compounds Flame retardants; inorganic flame retardants such as red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, and magnesium hydroxide; poly (dimethoxysiloxane), poly (diethoxysiloxane) ), Siloxane-based flame retardants such as poly (diphenoxysiloxane), poly (methoxyphenoxysiloxane), methyl silicate, ethyl silicate and phenyl silicate; powdery colorant, granular colorant, Liquid colorants and colorants such as master batches; Organic blowing agents such as carbonamide, azobisisobutyronitrile, Ν, Ν'-nitrosopentamethylenetetramine, ρ-toluenesolehoninolehydrazine, and ρ, ρ'-oxybis (benzenesulfohydrazide); liquid paraffin , Microcrystalline liposomes, natural paraffins, synthetic paraffins, polyolefin waxes, their partial oxides, their fluorides, and their chlorides, and other aliphatic hydrocarbon-based lubricants; animal oils such as tallow and fish oils, and coconut oil , Soybean oil, rapeseed oil, vegetable oils such as rice bran wax, their separated and purified products, and higher fatty alcohol and higher fatty acid lubricants such as montan wax; higher fatty acid amides and higher fatty acid bisamides such as bisamides System lubricant; steari Metal soap lubricants such as barium acid, calcium stearate, zinc stearate, aluminum stearate, magnesium stearate, zinc stearate / barium stearate complex, and zinc stearate / calcium stearate complex; Higher fatty acid esters of coal, higher fatty acid esters of polyhydric alcohols, higher fatty acid partial esters of polyhydric alcohols, long-chain esters of montan wax type, and partial hydrolysates of long-chain esters of montan wax type Sterilizing lubricants; protective agents such as binazine, preventol, and thiabendazole; 2,2,1-methylenebis (4,6-di-t-butylphenyl) phosphate sodium, bisphosphate (4-t —Butylphenyl) sodium, Bis (p-methyl Benzylidene) Sorbitol, alkyl-substituted dibenzylidene sorbitol, and crystal nucleating agents such as bis (p-ethylbenzylidene) sorbitol; hexamethylene teramine, n-butyl aldehyde aniline, 1,3-diphenylguanidine, diphenyl 1-o-tolylguanidine, 1-o-tolylbiguanide, dicatechol borate di-o-tolylguanidine salt, N, N, -diphenylthiourea, 2-mercaptoimidazoline, N, N'-getylthiourea, dibutylthio Urea, dilauryl thiourea, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, sodium salt of 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(4, one monorejo Nodithio) Benzothiazonole, N-cyclohexyl / le 2-benzothiazoli / resnolefenamide, N-cyclohexydiethylene-12-benzothiazolylsulfenamide, N-t_butyl-2-benzothia Zolylsulfenamide,

Tamethylene thiuram tetrasulfide, pentamethylene dithio-potassium pyrimidine salt, pipecolyl dithiocarbamic acid pipecoline salt, sodium dimethyl dithiocarbamate, sodium getyl dithiocarbamate, sodium dibutyl dithiocarbamate, Vulcanization accelerators such as zinc dimethyldithiocarbamate, zinc getyldithiocarbamate, zinc dibutyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, and telluride dimethyldithiocarbamate; Poly (2,2,4-trimethyl_1,2-dihydroquinoline), 6-ethoxy-1,2-dihydro-1,2,2,4-trimethylquinoline, 1- (N-phenylamino) -naphthalene, styrenated Diphenylamine, dialkyldiphenylamine, N, N'-Dipheninole p-Phenylenediamine, N-Pheninylene N'-Isopropyl-p-phenylenediamine, N, N'-G-2-naphthyl-p-Phenylenediamine, 2,6-Di-t- Butinole 4-methylinophenol, mono (α-methylbenzyl) phenol, di (α_methylbenzyl) phenol Tri (α-methylbenzyl) phenol, 2,2, -methylenebis (4-methyl-6-t-butynolephenol), 2,2,1-methylenebis (4-ethyl-6-t-butylphenol), 4,4 '—Butylidenebis (6-t-butynole-3-methylthiophene), 4,4,1-thiobis (6_t-butyl-3-methylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 2 , 5-dibutyltinolehydroquinone, 2,5-di-tert-amylhydroquinone, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimid Dazole, nickel dibutyldithiocarbamate, tris (noerphenyl) phosphite, dilauryl thiodipropionate, distear thiodipropionate Anti-aging agents such as Lil, Sunnock, Sunite, and Ozogard G; P-quinone dioxime, P, P, dibenzoylquinone dioxime, 4, 4'-dithiodimorpholine, poly p-dinitrosobenzene, 2-di-n-butylamino-1,4,6-dimercapto-1,3,5-triazine, 2,4,6-trimercapto s-triazine, Tatsukilol 201, Hitachi 2501,加 Vulcanizing agents such as brominated alkylphenol formaldehyde resins; anti-scorch agents such as N-ditrosodiphenylamine and phthalic anhydride; o, O'-dibenzamide diphenyl disulfide, 2-benzamide dothiophenol Zinc salts, and mastication accelerators such as Pepta S; Tatsukilol 101, Hitanol 1501, Modified alkylphenol formaldehyde Fats and tackifiers such as titanium 5501; latex coagulants such as hexylamine salt of acetic acid; processing aids such as Exton Kl and Exton L-2; Fillers such as calcium silicate, furnace black, channel black, thermal lamp black, gas black, oil black, acetylene black, calcium carbonate, clay, talc, titanium oxide, zinc oxide, diatomaceous earth, and barium sulfate However, the present invention is not limited to these. These may be used alone or in combination of two or more.

When producing the vinyl chloride paste sol composition of the present invention, a plasticizer and The method of adding the additive is not particularly limited, and may be kneaded with the vinyl chloride paste resin at the time of preparing the sol, may be added at the time of polymerization of the vinyl chloride paste resin, and may be added at the time of polymerization. It may be added to an aqueous dispersion or aqueous emulsion of the base paste resin, stirred and mixed, followed by spray drying, or a combination of these methods.

 Since the vinyl chloride polymer used in the present invention has a thiocarbonylthio structure at its terminal, it has very good uniform dispersibility when mixed with various additives, especially sulfonates and other thixotropic agents. Therefore, the vinyl chloride paste sol composition of the present invention exhibits a sufficient thixotropy behavior, and the amount of additive thixotrope and other additives can be reduced. In addition, it is considered that the effects of hydrogen bonding and polarity involving the terminal thiocarbonylthio group also contribute to the development of thixotropic behavior. Furthermore, since the vinyl chloride-based polymer used in the present invention can easily control the molecular weight, the molecular weight distribution, and the copolymer composition, the vinyl chloride-based paste sol composition and the gelled product thereof using the same can be easily controlled. Physical properties can be easily adjusted.

BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. The following method was used to evaluate the thixotropic behavior of the Biel chloride paste sol:

 (Determination of thixotropic index)

 When preparing the chlorinated butyl paste sol composition, a plasticizer, silicon dioxide powder, a solvent, etc. are added so that the sol viscosity becomes 4500 to 5000 centipoise (cps), and the temperature is adjusted to 35 ° C by Tokyo Keiki Co., Ltd. BM type viscometer using No. 3 rotor,

The viscosities at 6 rpm and 12 rpm were measured (referred to as V ₆ and V ₁₂ respectively). From this V _6, and V _12, it was calculated yield value and the number of thixotropy finger according to the following equation.

Yield value (dyn eZcm ² ) = (V ₆ — V ₁₂ ) X 1 2/100 Thixotropic index = yield value / corrected viscosity

However, corrected viscosity = 2V ₁₂ — V ₆

 (Example 1)

 In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 2,2'-azobisisobutylvaleroni trinole as a polymerization initiator, 500 g of sodium lauryl sulfate as an emulsifier, As a thixotropic agent, 300 g of sodium isethionate, and as a compound having a thiocarbolthio structure, a compound of the formula (12)

Was charged, and homogenized for 90 minutes using a homogenizer, followed by polymerization at 50 ° C. Obtained when the internal pressure of the reactor became LKG / cm ² lower than the saturated vapor pressure of the chloride Bulle monomer in 50 ° C, distilling off the unreacted monomers out of the reactor, a vinyl chloride polymer latex of Was. The molecular weight distribution of the vinyl chloride polymer determined by gel 'permeation' chromatography was 1.43.

 This latex was spray-dried, and 100 parts by weight of the obtained vinyl chloride paste resin, 100 parts by weight of dioctyl phthalate, 200 parts by weight of adipic acid polyester plasticizer, 0.5 parts by weight of silicon dioxide powder, and A salt-based paste sol was prepared by mixing 3 parts by weight of a zinc-based stabilizer. The thixotropy index of this butyl chloride-based paste sol was 0.33.

 (Example 2)

The same procedure as in Example 1 was repeated except that 700 g of sodium lauryl sulfate was used as an emulsifier, and sodium isethionate was not used as a thixotropic agent. Nyl paste sol was prepared. The thixotropic index of this vinyl chloride paste sol was 0.19.

 (Example 3)

 In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 2,2'-azobisisobutyl valeronitrile 500 g as a polymerization initiator, 400 g of sodium lauryl sulfate as an emulsifier, As a thixotropic agent, 300 g of sodium isethionate, and as a compound having a thiocarbolthio structure, a compound of the formula (13)

S

100 g of a compound represented by CH ₃ CH ₂₀ -C-S-CH ₂ CN (13) was charged, and homogenized using a homogenizer for 90 minutes, followed by polymerization at 50 ° C. When the internal pressure of the reactor became LKG cm ² lower than the saturated vapor pressure of vinyl chloride monomer in 50 ° C, distilling off the unreacted monomers out of the reactor, to obtain a chloride Bulle polymer latex . The molecular weight distribution of the vinyl chloride polymer determined by gel 'permeation' chromatography was 1.49.

 This latex was spray-dried, and 100 parts by weight of the obtained vinyl chloride paste resin, 100 parts by weight of dioctyl phthalate, 200 parts by weight of adipic acid polyester plasticizer, 0.5 parts by weight of silicon dioxide powder, and barium — 3 parts by weight of a zinc-based stabilizer were blended to prepare a butyl chloride-based paste sol. The thixotropic index of this vinyl chloride paste sol was 0.28.

 (Example 4)

The same procedure as in Example 3 was repeated except that 700 g of sodium lauryl sulfate was used as an emulsifier and sodium isethionate was not used as a thixotropic agent. Nyl paste sol was prepared. The thixotropy index of this butyl chloride paste sol was 0.19.

 (Example 5)

 In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 2,2'-azobisisobutyl valeroni trinole as a polymerization initiator, 500 g of sodium laurinole sulfate as an emulsifier 400 g, 300 g of sodium isethionate as a thixotropic agent, and a compound having a thiocarbolthio structure represented by the formula (14)

Was charged and homogenized for 90 minutes using a homogenizer, followed by polymerization at 50 ° C. When the internal pressure of the reactor became lk gZcm ² lower than the saturated vapor pressure of the chloride Bulle monomer in 50 ° C, distilling off the unreacted monomers out of the reactor, to obtain a vinyl chloride polymer latex . The molecular weight distribution of the vinyl chloride polymer determined by gel 'permeation' chromatography was 1.22.

 This latex was spray-dried, and 100 parts by weight of the obtained vinyl chloride paste resin, 100 parts by weight of dioctyl phthalate, 200 parts by weight of adipic acid polyester plasticizer, 0.5 parts by weight of silicon dioxide powder, and A salt-based paste sol was prepared by mixing 3 parts by weight of a zinc-based stabilizer. The thixotropic index of this vinyl chloride paste sol was 0.33.

 (Example 6)

In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 2, 2'-azobisisobutyl valeroni as a polymerization initiator Tolyl 500 g, sodium lauryl sulfate 400 g as an emulsifier, sodium isethionate 300 g as a thixotropic agent, and a compound having a thiocarbolthio structure represented by the formula (15)

( ¹⁵ )

Was charged, and homogenized using a homogenizer for 90 minutes, followed by polymerization at 50 ° C. When the internal pressure of the reactor became 1 kg / cm ² less than the saturated vapor pressure of vinyl chloride monomer in 50 ° C, distilling off the unreacted monomers out of the reactor, a vinyl chloride polymer latex of Obtained. The molecular weight distribution of the vinyl chloride polymer determined by gel 'permeation' chromatography was 1.67.

 This latex was spray-dried, and 100 parts by weight of octyl phthalate, 200 parts by weight of adipic acid polyester plasticizer, 0.5 parts by weight of silicon dioxide powder, and 100 parts by weight of barium chloride resin were obtained. A zinc chloride-based paste sol was prepared by mixing 3 parts by weight of a zinc-based stabilizer. The thixotropy index of this butyl chloride-based paste sol was 0.35.

 (Comparative 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'-azobisisobutylvaleronitrile as a polymerization initiator, and 400 g of sodium lauryl sulfate as an emulsifier After charging and homogenizing for 90 minutes using a homogenizer, polymerization was carried out at 50 ° C. When the internal pressure of the reactor than the saturated vapor pressure of the salt Ihibi alkenyl monomer in 50 ° C was l kgZcm ² low, distilling off the unreacted monomers out of the reactor, chloride Bulle polymer Ratetsu box I got The molecular weight distribution of the vinyl chloride polymer determined by gel permeation 'chromatography-1 was 2.30. This latex was spray-dried, and 100 parts by weight of the obtained vinyl chloride paste resin, 100 parts by weight of dioctyl phthalate, 200 parts by weight of adipic acid polyester plasticizer, 0.5 parts by weight of silicon dioxide powder, and A zinc chloride-based paste sol was prepared by mixing 3 parts by weight of a zinc-based stabilizer. The thixotropic index of this vinyl chloride paste sol was 0.10.

 (Comparative Example 2)

 A vinyl chloride paste sol was prepared in the same manner as in Comparative Example 1, using 300 g of sodium isethionate as a thixotropic agent. This thixotropic paste sol had a thixotropic index of 0.20.

 (Example 7)

 In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 100 kg of vinyl chloride monomer, 2,2'-azobisisobutylvaleroni trinole as a polymerization initiator, 500 g of sodium dodecylbenzenesulfonate as an emulsifier, 300 g As a thixotropic agent, sodium lauryl ester sulfonate (400 g), and a compound having a thiocarbolthio structure, a compound represented by the formula (14)

Was charged, and homogenized using a homogenizer for 90 minutes, followed by polymerization at 50 ° C. When the internal pressure of the reactor becomes 1 kg / cm ² lower than the saturated vapor pressure of vinyl chloride monomer at 50 ° C, unreacted monomers are distilled out of the reactor to obtain a vinyl chloride polymer latex. Was. The molecular weight distribution of the vinyl chloride polymer determined by gel 'permeation' chromatography was 1.38.

This latex is spray-dried, and the obtained vinyl chloride paste resin is 100 parts by weight. To 100 parts by weight of dioctyl phthalate, 200 parts by weight of adipic acid polyester plasticizer, 0.5 parts by weight of silicon dioxide powder, and 3 parts by weight of barium-zinc stabilizer The paste sol was prepared. The thixotropy index of this butyl chloride-based primary sol was 0.38.

 The obtained chlorinated butyl paste sol was dropped on a ferrule plate, heated at 230 ° C for 2 minutes to gel, and then peeled off 20 times. Was visually observed, but no mold contamination was observed.

 (Comparative Example 3)

 A butyl chloride-based paste sol was prepared in the same manner as in Example 7 without using a compound having a thiocarbonylthio structure. The thixotropic peak index of this butyl chloride paste sol was 0.19.

 The obtained chlorinated butyl-based paste sol was dropped on a top plate, heated at 230 ° C. for 2 minutes to gel, and then peeled off, repeating the operation 20 times to adhere the stain to the mold. When the degree was visually observed, mold contamination was observed.

 (Comparative 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′-azobisisobutyl valeronitrile as a polymerization initiator, Then, 1 kg of sodium dodecylbenzenesulfonate was charged as an emulsifier, homogenized using a homogenizer for 90 minutes, and then polymerized at 50 ° C. When the internal pressure of the reactor was 5 0 ° 1 kg Z cm ² lower than the saturated vapor pressure of vinyl chloride monomer in C, distilling off the unreacted monomers out of the reactor, vinyl chloride polymers Latex was obtained. The molecular weight distribution of the butyl chloride polymer was found to be 2.21 by gel permeation chromatography.

This latex was spray-dried, and based on 100 parts by weight of the obtained butyl chloride paste resin, 100 parts by weight of dioctyl phthalate, 200 parts by weight of an adipic acid polyester plasticizer, and 0.5 part of silicon dioxide powder. By weight, 3 parts by weight of a barium-zinc based stabilizer were blended to prepare a butyl chloride-based paste sol. This vinyl chloride type The thixotropic index of the stozol was 0.07.

 The obtained chlorinated butyl chloride paste sol was dropped onto a Hue mouth plate, heated at 230 ° C for 2 minutes to form a gel, and then peeled off 20 times. Was visually observed, and mold contamination was observed.

 (Example 8)

 In a 300 L stainless steel autoclave, 130 kg of ion-exchanged water, 90 kg of vinyl chloride monomer, 20 kg of atarilonitrile monomer, 2, 2'-azobisy as a polymerization initiator Sobutyl bale mouth-tolyl 500 g, sodium dodecylbenzene sulfonate 200 g as emulsifier, sodium lauryl ethyl ester sulfonate 500 g as thixotropic agent, and a compound having a thiocarbolthio structure (14 )

Was charged and homogenized for 90 minutes using a homogenizer, followed by polymerization at 50 ° C. When the internal pressure of the reactor was 5 0 ° 1 kg Z cm ² lower than the saturated vapor pressure of the chloride Bulle monomer in C, distilling off the unreacted monomers out of the reactor, chloride Bulle polymer Latex was obtained. ! Η NMR measurement confirmed that the copolymer was a vinyl chloride-acrylonitrile copolymer. The molecular weight distribution of the copolymer was determined by gel permeation chromatography to be 1.55.

This latex was spray-dried, and based on 100 parts by weight of the obtained butyl chloride-based paste resin, 100 parts by weight of octyl phthalate, 200 parts by weight of an adipic acid polyester-based plasticizer, and 0.5 part of silicon dioxide powder. By weight, 3 parts by weight of a barium-zinc-based stabilizer were blended to prepare a butyl chloride-based paste sol. The thixotropic index of this salt-based paste sol was 0.35. (Example 9)

 A vinyl chloride paste sol was prepared in the same manner as in Example 8, except that 700 g of sodium dodecylbenzenesulfonate was used as an emulsifier, and sodium lauryl ester sulfonate was not used as a thixotropic agent. . The thixotropic index of this vinyl chloride paste sol was 0.26.

 (Comparative Example 5)

 A hydrogenated paste paste sol was prepared in the same manner as in Example 8 without using a compound having a thiocarbolthio structure. The thixotopic peak index of this butyl chloride-based paste sol was 0.22.

 (Example 10)

 13 ◦ kg of ion-exchanged water, 70 kg of vinyl chloride monomer, 40 kg of vinyl acetate monomer, 500 g of 2,2, -azobisisobutylvaleronitrile as polymerization initiator in a 300 L stainless steel autoclave , 500 g of sodium dodecylbenzenesulfonate as an emulsifier, 200 g of sodium laurylethyl ester sulfonate as a thixotropic agent, and a compound having a thiocarbolthio structure represented by the formula (15)

Was charged, and homogenized using a homogenizer for 90 minutes, followed by polymerization at 50 ° C. When the internal pressure of the reactor became LkgZcm ² lower than the saturated vapor pressure of the salt Ihibiniru monomer in 50 ° C, distilling off the unreacted monomers out of the reactor, to obtain a chloride Bulle polymer latex . From NMR measurement, it was confirmed that the copolymer was a copolymer of vinyl chloride monobutyl acetate. The molecular weight distribution of this copolymer determined by gel permeation 'chromatography was 1.71. This latex was spray-dried, and based on 100 parts by weight of the obtained butyl chloride-based paste resin, 100 parts by weight of octyl phthalate, 200 parts by weight of an adipic acid polyester-based plasticizer, and 0.5 part of silicon dioxide powder. By weight, and 3 parts by weight of a barium-zinc-based stabilizer were blended to prepare a butyl chloride-based first sol. The thixotropy index of this butyl chloride-based paste sol was 0.28.

 (Example 11)

 A butyl chloride-based paste sol was prepared in the same manner as in Example 10 except that sodium lauryl ethyl sulfonate was not used as a thixotropic agent. The thixotropy index of the biel chloride paste sol was 0.17.

 (Comparative Example 6)

 A Bier chloride paste sol was prepared in the same manner as in Example 10 except that a compound having a thiocarpenylthio structure was not used. The thixotropic index of this vinyl chloride paste sol was 0.18.

 (Comparative Example 7)

 A butyl chloride-based paste sol was prepared in the same manner as in Example 10 except that a compound having a thiocarbolthio structure was not used, and sodium lauryl ethyl ester sulfonate as a thixotropic agent was not used. The thixotropy index of this Shii-Dani Bull type paste sol was 0.05.

Industrial applicability

 The butyl chloride-based paste sol composition of the present invention exhibits a high thixotropy behavior, so that the amount of the thixotrope agent to be added can be reduced, and a low-viscosity sol that does not easily drip can be easily obtained. Also, since there is almost no mold contamination during immersion processing, the number of mold washings is reduced, and productivity is improved. Furthermore, it is possible to easily obtain a vinyl chloride paste sol composition with controlled molecular weight, molecular weight distribution, etc., and to easily carry out copolymerization with vinyl monomers other than vinyl chloride monomer. Adjustments are possible.

Claims

The scope of the claims

 1. Vinyl chloride base sol composition containing the following two components (A) and (B) as essential components:

 (A) — General formula (1)

(In the formula, R ¹ is a p-valent organic group having 1 or more carbon atoms, and may include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom, and has a high molecular weight. Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom. When there are a plurality of Z ¹ , they may be the same or different, and p is an integer of 1 or more. , And general formula (2)

(In the formula, R ² is a monovalent organic group having 1 or more carbon atoms, and may include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom, and has a high molecular weight. Z ² is an oxygen atom (when q = 2) and a sulfur atom (q = 2 ), A nitrogen atom (when q = 3), or a q-valent organic group having 1 or more carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom. Or a high molecular weight compound. R ² may be the same or different. q is an integer of 2 or more. ) In the presence of a compound having a thiocarbolthio structure selected from the group consisting of compounds represented by the following formula: 50% by weight or more of vinyl chloride monomer or vinyl chloride monomer; 50 weight of copolymerizable monomer. / Vinyl chloride paste resin obtained by radical polymerization of less than / ₀ .

 (B) Plasticizer.

 2. The compound having a thiocarbonylthio structure is represented by the general formula (3)

(In the formula, R ³ is a divalent organic group having 1 or more carbon atoms, and may include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and a metal atom, and has a high molecular weight. Z 3 is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and includes a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom Z ³ may be the same as or different from each other.) The compound according to claim 1, wherein Z ³ is a compound represented by the following formula: -Based paste sol composition.

3. The monomers copolymerizable with vinyl chloride are styrene, butadiene, isoprene, chloroprene, vinylidene chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, and atalylonite. 3. The vinyl chloride paste sol composition according to claim 1, wherein the composition is at least one or more monomers selected from the group consisting of ril and vinyl acetate.

4. The vinyl chloride paste resin of component (A) has a molecular weight distribution measured by gel permeation chromatography (GPC) of 2 or less, wherein the molecular weight distribution is 2 or less. 4. The butyl chloride-based paste sol composition according to any one of 3.

5. The vinyl chloride paste resin of component (A) is characterized in that the molecular weight distribution measured by gel permeation 'chromatography (GPC) is 1.5 or less. 4. The chlorinated vinyl paste sol composition according to any one of the above-mentioned items.

 6) The vinyl chloride paste resin of component (A) is a mixture of multiple vinyl chloride paste resins that have a difference of 3000 or more in number average molecular weight determined by gel permeation and mouth chromatography (GPC) measurement. The butyl chloride-based paste sol composition according to any one of claims 1 to 5, wherein

7. As components other than component (A) and component (B), general formula (4)

(Wherein L ¹ is an alkali metal or an ammonium group, and n is an integer from 1 to 20), and a compound represented by the general formula (5)

0

 II

R ⁴ — C— 0— CH ₂ CH ₂ S0 ₃ L 2 (5)

(Wherein, R ⁴ is a monovalent organic group having 1 or more carbon atoms, and L ² is an alkali metal or an ammonium group.) One or more sulfonates selected from the group consisting of compounds represented by the following formulas: The vinyl chloride-based paste sol composition according to any one of claims 1 to 6, comprising:

8. Components other than component (A) and component (B) include acidic compounds and hydrotalcite. The paste sol composition according to any one of claims 1 to 7, wherein the paste sol composition contains a compound selected from the group consisting of a metal compound, a zeolite compound, and a metal perchlorate.