WO2002079324A1 - Composition sol pateuse a base de chlorure de vinyle - Google Patents

Composition sol pateuse a base de chlorure de vinyle Download PDF

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Publication number
WO2002079324A1
WO2002079324A1 PCT/JP2002/002218 JP0202218W WO02079324A1 WO 2002079324 A1 WO2002079324 A1 WO 2002079324A1 JP 0202218 W JP0202218 W JP 0202218W WO 02079324 A1 WO02079324 A1 WO 02079324A1
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atom
vinyl chloride
group
compound
acid
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PCT/JP2002/002218
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English (en)
Japanese (ja)
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Ryotaro Tsuji
Tomoki Hiiro
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Kaneka Corporation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates

Definitions

  • 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.
  • 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. .
  • 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.
  • 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.
  • a cold diving method in which a sol is adhered and then gelled by heating.
  • 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.
  • 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.
  • 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.
  • 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.
  • the thickness of the molded product was not stable.
  • 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.
  • 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. ⁇ 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.
  • 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.
  • 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)
  • 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.
  • p may be 1 or more. It is an integer.
  • 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.
  • 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.
  • / 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.
  • 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
  • the general formula (4) As a component other than the component (A) and the component (B), in order to exhibit a sufficient thixotropic behavior, the general formula (4)
  • R 4 is a monovalent organic group having 1 or more carbon atoms, and L 2 is an alkali metal or an ammonium group.
  • 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).
  • 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.
  • 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)
  • 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)
  • 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)
  • 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.
  • R 3 is not particularly limited, but from the viewpoint of availability, the compound represented by the general formula (10)
  • 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
  • r represents an integer of 1 or more.
  • Me represents a methyl group
  • E′t represents an ethyl group
  • Ph represents a phenyl group
  • Ac represents an acetyl group
  • r represents an integer of 1 or more. It is not limited to these.
  • 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.
  • 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.
  • a conventionally known polymerization initiator or a polymerization initiation method can be used.
  • 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.
  • a polymerization initiation system by electron beam irradiation, X-ray irradiation, radiation irradiation, or the like.
  • a polymerization initiation method is described in Mo adand Sol omo n ⁇ 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.
  • 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
  • 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.
  • 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. .
  • a vinyl chloride monomer when 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, ⁇ -methyl ⁇ styrene, dibininolebenzene, ⁇ -hydroxystyrene, ⁇ -carboxystyrene, ⁇ -methoxystyrene, and acetylaminostyrene.
  • Styrene compounds such as, ethinoleamino ⁇ -methinolestyrene, ⁇ -vinylinolebenzenesulfonic acid, ⁇ -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-ethylhexy
  • the monomers used in the present invention may be used alone or in combination of two or more.
  • styrene, ⁇ -methylstyrene, butadiene, isoprene, chloroprene, ethylene, propylene, futonidani vinylonole, and bromide are useful in that the obtained polymer is useful.
  • a single monomer may be copolymerized, or a plurality of monomers may be combined and 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.
  • the copolymer is copolymerized with 50% by weight or more of a vinyl chloride monomer.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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
  • 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 ( ⁇ ). , 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.
  • 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
  • hydrotalcite compound used in the present invention is not particularly limited.
  • 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.
  • 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 (iso
  • 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, diisode
  • 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
  • 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.
  • 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.
  • 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.
  • 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,
  • V 6 and V 12 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.
  • 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.
  • 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 3 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.
  • 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.
  • 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.
  • 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.
  • This latex is spray-dried, and the obtained vinyl chloride paste resin is 100 parts by weight.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

Abstract

La présente invention concerne une composition sol pâteuse à base de chlorure de vinyle qui est suffisamment thixotrope pour ne pas avoir besoin d'une grande quantité d'agent thixotrope ou de solvant, ce qui permet d'éviter les problèmes de productivité, de coût, de qualité de produit et d'incidence sur l'environnement, etc. Les principaux ingrédients de cette composition sont un plastifiant et une résine pâteuse à base de chlorure de vinyle, obtenue par polymérisation radicalaire d'un monomère de chlorure de vinyle, en présence d'un composé spécifique présentant une structure thiocarbonylthio.
PCT/JP2002/002218 2001-03-28 2002-03-08 Composition sol pateuse a base de chlorure de vinyle WO2002079324A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2004003042A1 (fr) * 2002-06-28 2004-01-08 Kaneka Corporation Resine de copolymere de chlorure de vinyle pour adhesifs, composition, et procede de fabrication de cette resine

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Publication number Priority date Publication date Assignee Title
KR20160066530A (ko) * 2014-12-02 2016-06-10 한화케미칼 주식회사 염화비닐계 페이스트 수지 및 이의 제조방법
KR101841356B1 (ko) 2015-09-14 2018-03-22 주식회사 엘지화학 염화비닐-비닐아세테이트 공중합체 및 이의 제조방법

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Publication number Priority date Publication date Assignee Title
JPS59197449A (ja) * 1983-04-26 1984-11-09 Asahi Chem Ind Co Ltd 被覆用ゾル組成物
JPH03217406A (ja) * 1990-01-22 1991-09-25 Mitsubishi Kasei Vinyl Co 塩化ビニル系重合体の製造方法

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
JPS59197449A (ja) * 1983-04-26 1984-11-09 Asahi Chem Ind Co Ltd 被覆用ゾル組成物
JPH03217406A (ja) * 1990-01-22 1991-09-25 Mitsubishi Kasei Vinyl Co 塩化ビニル系重合体の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004003042A1 (fr) * 2002-06-28 2004-01-08 Kaneka Corporation Resine de copolymere de chlorure de vinyle pour adhesifs, composition, et procede de fabrication de cette resine
US7354970B2 (en) 2002-06-28 2008-04-08 Kaneka Corporation Polyvinyl chloride copolymer paste resin, composition thereof, and method for making the resin
KR101014584B1 (ko) 2002-06-28 2011-02-16 카네카 코포레이션 페이스트용 염화비닐계 공중합 수지, 조성물 및 수지의 제조 방법
KR101015077B1 (ko) 2002-06-28 2011-02-16 카네카 코포레이션 페이스트용 염화비닐계 공중합 수지, 조성물 및 수지의제조 방법

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