WO2010074139A1 - ポリ塩化ビニル樹脂組成物およびその製造方法 - Google Patents
ポリ塩化ビニル樹脂組成物およびその製造方法 Download PDFInfo
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- WO2010074139A1 WO2010074139A1 PCT/JP2009/071424 JP2009071424W WO2010074139A1 WO 2010074139 A1 WO2010074139 A1 WO 2010074139A1 JP 2009071424 W JP2009071424 W JP 2009071424W WO 2010074139 A1 WO2010074139 A1 WO 2010074139A1
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- polyvinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention relates to a polyvinyl chloride resin composition suitably used in the fields of food, medical use, daily necessities and the like.
- the present invention relates to a polyvinyl chloride resin composition having good thermal stability, little coloring, and easy melt processing.
- Polyvinyl chloride resin is molded by compounding stabilizers such as Ca-Zn and Ba-Zn, and is widely used as a general molding material and also as a material for products suitable for food and medical use. ing.
- stabilizers such as Ca-Zn and Ba-Zn
- the blending of these stabilizers is inferior in the ability to suppress the thermal deterioration of the molded product to be obtained, so that the initial colorability of the molded product is impaired and the thermal stability of the molded product is not sufficient. It was.
- a polyvinyl chloride resin composition to which an antioxidant or a compound having a hydroxyl group is added has been proposed.
- Patent Document 1 Japanese Patent Laid-Open No. 50-92947 discloses a method of adding calcium soap, zinc soap, polyhydric alcohol or derivative thereof, and neutral inorganic calcium salt to a chlorine-containing resin.
- Patent Document 2 Japanese Patent Laid-Open No. 54-81359 discloses a method of adding a water-soluble polymer to a chlorine-containing polymer.
- Patent Document 3 Japanese Patent Laid-Open No. 57-147552 discloses a method of adding a reaction condensate of dipentaerythritol and dicarboxylic acid, zinc oxide, zinc carbonate or fatty acid zinc, and hydrotalcite to a chlorine-containing resin. It is disclosed.
- Patent Document 4 Japanese Patent Laid-Open No. 60-238345 describes a saponified ethylene-vinyl acetate copolymer having a thermoplastic resin content of 20 to 50% ethylene units and a saponification degree of vinyl acetate units of 96% or more. And a method of adding a hydrotalcite compound.
- Patent Document 5 Japanese Patent Laid-Open No. 1-178543
- a halogen-containing thermoplastic resin has a copolymer composition with a metal soap and ethylene content of 20 to 75 mol% and a saponification degree of a vinyl acetate moiety of 50 mol% or more.
- a method of adding a saponified ethylene-vinyl acetate copolymer is disclosed.
- Patent Document 6 JP-A-6-287387 discloses a method of adding a metal salt of an organic acid and an acetalized product of polyvinyl alcohol to a vinyl chloride resin.
- Patent Document 7 Japanese Patent Application Laid-Open No. 9-32866 discloses a partially saponified polyvinyl chloride resin having a saponification degree of 70 to 95 mol%, an average polymerization degree of 300 to 2000, and having a mercapto group at the end of the molecular chain. A method of adding alcohol is disclosed.
- Patent Document 8 Japanese Patent Laid-Open No. 9-31281 discloses a method of adding a zinc compound, hydrotalcite, polyvinyl alcohol and polymethyl methacrylate to a vinyl chloride resin.
- Non-Patent Document 1 (Polymer Collection Vol. 47, No. 3, p. 197 (1990)) describes polyvinyl chloride, zinc stearate-calcium stearate composite soap, fully saponified polyvinyl having a polymerization degree of 600 or more. A method of adding alcohol is disclosed.
- Non-Patent Document 2 (Polymer Collection Vol. 47, No. 6, p. 509 (1990)) discloses that polyvinyl chloride, zinc stearate-calcium stearate composite soap and polymerization degree are 500, and saponification degree is 73. A method of adding 6 mol% partially saponified polyvinyl alcohol is disclosed.
- Non-Patent Document 3 Polymer Collection Vol. 50, No. 2, p. 65 (1993) shows that polyvinyl chloride, zinc stearate-calcium stearate composite soap and ethylene content of 29 mol% or more. A method for adding an ethylene-vinyl alcohol copolymer is disclosed.
- Non-Patent Document 4 (Polymers & Polymer Compositions, Vol. 11, p. 649 (2003)) describes polyvinyl chloride, zinc stearate-calcium stearate composite soap and a polymerization degree of 500, and a saponification degree of 98.5 mol. % Of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer having an ethylene content of 29 mol% or more are disclosed.
- Non-Patent Document 5 Journal of the Adhesion Society of Japan, Vol. 43, No. 2, p. 43 (2007) shows that polyvinyl chloride has a degree of polymerization of 500 and a degree of saponification of 88 mol% and a degree of polymerization of polyvinyl alcohol. 1700, a method of adding polyvinyl alcohol having a saponification degree of 78 mol% or more and polymethyl methacrylate is disclosed.
- Patent Documents 1 to 8 and Non-Patent Documents 1 to 5 have a problem that long-term thermal stability is not sufficient or coloring.
- the polyvinyl chloride molded product after melt processing has problems such as rough surface and lack of transparency.
- An object of the present invention is to provide a polyvinyl chloride resin composition having good thermal stability, little coloring, and less surface roughness after melting and lack of transparency.
- the present inventors have formulated polyvinyl alcohol having a specific structural unit (hereinafter sometimes abbreviated as PVA) and a specific amount of zinc compound with respect to the polyvinyl chloride resin at the time of molding.
- PVA polyvinyl alcohol having a specific structural unit
- zinc compound with respect to the polyvinyl chloride resin at the time of molding.
- the present inventors have found that the thermal stability of the resin can be sufficiently maintained, and that the molded product is less colored and the surface is less rough, and the present invention has been completed.
- the present invention relates to 0.005 to 5 parts by weight of polyvinyl alcohol having a structural unit represented by the formula (1) and 0.01 to 5 parts by weight of a zinc compound with respect to 100 parts by weight of the polyvinyl chloride resin. It is a polyvinyl chloride resin composition to contain.
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an acyl group.
- X represents a C 1 to C 3 alkylene group that may be through a single bond or an oxygen atom.
- the polyvinyl alcohol is preferably obtained by saponifying a copolymer of a vinyl ester monomer and a compound represented by the formula (2).
- Examples of the compound represented by the formula (2) include 3,4-dihydroxy-1-butene, 3,4-dialkoxy-1-butene, 3,4-diasiloxy-1-butene, 4,5-dihydroxy- 1-pentene, 4,5-dialkoxy-1-pentene, 4,5-diasiloxy-1-pentene, 5,6-dihydroxy-1-hexene, 5,6-dialkoxy-1-hexene, 5,6- At least one selected from the group consisting of diacyloxy-1-hexene, glycerol monoallyl ether, glycerol monovinyl ether, (2-hydroxy-3-alkoxy-propyl) allyl ether, (2-hydroxy-3-alkoxy-propyl) vinyl ether Preferably it is a seed.
- the polyvinyl alcohol preferably has a viscosity average polymerization degree of 800 or less and a saponification degree of 70 mol% or more. It is also preferable that the content of the structural unit represented by the formula (1) in the polyvinyl alcohol is 10 mol% or less.
- the present invention also provides 0.005 to 5 parts by weight of polyvinyl alcohol having a structural unit represented by the above formula (1) and 0.01 to 5 parts by weight of a zinc compound with respect to 100 parts by weight of the polyvinyl chloride resin. It is a manufacturing method of the polyvinyl chloride resin composition to add.
- the polyvinyl alcohol is preferably obtained by saponifying a copolymer of a vinyl ester monomer and a compound represented by the above formula (2).
- Examples of the compound represented by the formula (2) include 3,4-dihydroxy-1-butene, 3,4-dialkoxy-1-butene, 3,4-diasiloxy-1-butene, 4,5-dihydroxy- 1-pentene, 4,5-dialkoxy-1-pentene, 4,5-diasiloxy-1-pentene, 5,6-dihydroxy-1-hexene, 5,6-dialkoxy-1-hexene, 5,6- At least one selected from the group consisting of diacyloxy-1-hexene, glycerol monoallyl ether, glycerol monovinyl ether, (2-hydroxy-3-alkoxy-propyl) allyl ether, (2-hydroxy-3-alkoxy-propyl) vinyl ether Preferably it is a seed.
- the polyvinyl chloride resin composition of the present invention is characterized by excellent thermal stability, less coloration of the molded product and less surface roughness, and its industrial value is extremely high.
- the polyvinyl chloride resin used in the present invention may be a homopolymer of vinyl chloride or a copolymer of 50% by weight or more of vinyl chloride and a monomer copolymerizable therewith.
- Monomers copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylic esters such as methyl acrylate and ethyl acrylate; olefins such as ethylene and propylene; maleic anhydride Acrylonitrile; styrene; vinylidene chloride and the like.
- a method for producing the polyvinyl chloride resin using these monomers a method in which the monomers are subjected to suspension polymerization in the presence of a polymerization initiator can be suitably employed.
- dispersion stabilizers for example, water-soluble cellulose ethers such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, water-soluble polymers such as polyvinyl alcohol, gelatin; sorbitan monolaurate, Oil-soluble emulsifiers such as sorbitan trioleate, glycerin tristearate, and ethylene oxide propylene oxide block copolymer; water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, and sodium laurate are used.
- polyvinyl alcohol having a saponification degree of 65 to 99 mol% and a polymerization degree of 500 to 4000 is preferably used.
- the addition amount is preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of vinyl chloride.
- the dispersion stabilizer for suspension polymerization may be used alone, the polymerization degree is usually used in combination with suspension polymerization of vinyl compounds such as vinyl chloride in an aqueous medium, and the saponification degree is 30 to 4000.
- Up to 99 mol% of polyvinyl alcohol may be used in combination.
- the addition amount is not particularly limited, but is preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of vinyl compound such as vinyl chloride.
- oil-soluble or water-soluble polymerization initiators conventionally used for polymerization of vinyl chloride and the like can be used.
- oil-soluble polymerization initiator include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, t Perester compounds such as butyl peroxypivalate, t-hexylperoxypivalate, ⁇ -cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate Peroxides such as 3,5,5-trimethylhexanoyl peroxide and lauroyl peroxide; azobis (2,4-dimethylvaleronitrile), azobis (4-
- water-soluble polymerization initiator examples include potassium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, and the like. These oil-soluble or water-soluble polymerization initiators can be used alone or in combination of two or more.
- additives can be added to the polymerization reaction system as necessary.
- the additive include polymerization regulators such as aldehydes, halogenated hydrocarbons and mercaptans, and polymerization inhibitors such as phenol compounds, sulfur compounds and N-oxide compounds.
- a pH adjuster, a crosslinking agent, etc. can also be added arbitrarily.
- the polymerization temperature is not particularly limited. It can be adjusted to a high temperature exceeding 90 ° C. as well as a low temperature of about 20 ° C.
- a polymerization vessel with a reflux condenser In order to increase the heat removal efficiency of the polymerization reaction system, it is also one of preferred embodiments to use a polymerization vessel with a reflux condenser.
- conventionally used additives such as antiseptics, antifungal agents, antiblocking agents, antifoaming agents, antiscaling agents, and antistatic agents can be optionally used.
- the polyvinyl chloride resin composition of the present invention contains PVA having a structural unit represented by the formula (1). Thereby, the polyvinyl chloride resin composition is excellent in thermal stability, and a molded product with little coloring and surface roughness can be obtained.
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an acyl group.
- X represents a C 1 to C 3 alkylene group that may be through a single bond or an oxygen atom.
- the degree of saponification of the PVA used in the present invention is preferably 70 to 99.9 mol%.
- the lower limit of the saponification degree is more preferably 80 mol%. If the degree of saponification is less than 70 mol%, the long-term thermal stability may be reduced.
- the saponification degree of PVA is a value measured according to JIS K6726.
- the viscosity average degree of polymerization of the PVA (hereinafter sometimes simply referred to as the degree of polymerization) is preferably 800 or less, more preferably 700 or less, still more preferably 600 or less, and particularly preferably 550 or less.
- the viscosity average polymerization degree is larger than 800, the long-term thermal stability may be remarkably deteriorated, or the surface roughness of the molded product may become severe.
- the viscosity average degree of polymerization is preferably 100 or more, more preferably 150 or more, and further preferably 200 or more, from the viewpoint of production of PVA.
- the viscosity average degree of polymerization of PVA is a value measured according to JIS K6726. That is, it is a value obtained from the following formula from the intrinsic viscosity [ ⁇ ] measured in water at 30 ° C. after re-saponifying and purifying PVA to a saponification degree of 99.5 mol% or more.
- P ([ ⁇ ] ⁇ 1000 / 8.29) (1 / 0.62)
- the PVA having a structural unit represented by the formula (1) used in the present invention can be obtained by saponifying a copolymer of a vinyl ester monomer and a compound represented by the formula (2).
- Examples of the compound represented by the formula (2) include 3,4-dihydroxy-1-butene, 3,4-dialkoxy-1-butene, 3,4-diasiloxy-1-butene, 4,5-dihydroxy-1 -Pentene, 4,5-dialkoxy-1-pentene, 4,5-diacyloxy-1-pentene, 5,6-dihydroxy-1-hexene, 5,6-dialkoxy-1-hexene, 5,6-diacyloxy -1-hexene, glycerin monoallyl ether, glycerin monovinyl ether, (2-hydroxy-3-alkoxy-propyl) allyl ether, (2-hydroxy-3-alkoxy-propyl) vinyl ether, and the like. Of these, 3,4-diasiloxy-1-butene is preferred from the viewpoint of industrial productivity.
- the PVA employs a conventionally known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a dispersion polymerization method for the vinyl ester monomer and the compound represented by the formula (2).
- a conventionally known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a dispersion polymerization method for the vinyl ester monomer and the compound represented by the formula (2).
- preferred polymerization methods are solution polymerization, emulsion polymerization and dispersion polymerization. In the polymerization operation, any one of a batch method, a semi-batch method, and a continuous method can be employed.
- the vinyl ester monomer that can be used for polymerization include vinyl acetate, vinyl formate, vinyl propionate, vinyl
- the vinyl ester monomer may be copolymerized with another monomer as long as the gist of the present invention is not impaired.
- the content of the structural unit represented by the formula (1) in PVA is preferably 10 mol% or less.
- the content is more preferably 8 mol% or less.
- it is preferable that content is 1 mol% or more.
- the melting point of PVA is high, so that it is difficult to mold the resulting polyvinyl chloride resin composition at a temperature that does not cause thermal decomposition (usually 210 ° C. or less).
- thermal stability at the time of melt molding may fall.
- the melting point of PVA can be lowered and the amount of hydroxyl groups can be increased.
- the polyvinyl chloride resin composition can be molded in the vicinity of the melting point while maintaining good thermal stability, so that a molded product with little surface roughness and high transparency can be obtained.
- a chain transfer agent may be allowed to coexist for the purpose of adjusting the degree of polymerization of the obtained PVA.
- Chain transfer agents include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone and cyclohexanone; mercaptans such as 2-hydroxyethanethiol; halogens such as trichloroethylene and perchloroethylene Hydrocarbons are mentioned, among which aldehydes and ketones are preferably used.
- the addition amount of the chain transfer agent is determined according to the chain transfer constant of the added chain transfer agent and the degree of polymerization of the target PVA, but is generally 0.1 to 10% by weight based on the vinyl ester monomer. It is desirable to be.
- PVA having a large content of 1,2-glycol bonds in the main chain obtained by polymerizing a vinyl ester monomer under a temperature condition higher than usual, can also be used.
- the content of 1,2-glycol bond is preferably 1.9 mol% or more, more preferably 2.0 mol% or more, and further preferably 2.1 mol% or more.
- the saponification reaction of polyvinyl ester alcoholysis or hydrolysis reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or acidic catalyst such as p-toluenesulfonic acid is applied.
- a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or acidic catalyst such as p-toluenesulfonic acid
- the solvent used for the saponification reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene.
- the content of PVA in the polyvinyl chloride resin composition is 0.005 to 5 parts by weight, preferably 0.04 to 3 parts by weight, with respect to 100 parts by weight of the polyvinyl chloride resin. If it is less than 0.005 parts by weight, the long-term thermal stability of the obtained polyvinyl chloride resin composition is not sufficient, and if it exceeds 5 parts by weight, problems such as coloring and surface roughness of molded products made of the resin composition will occur. May occur.
- the method of containing PVA is not particularly limited. Although it may be added at the time of polymerization of vinyl chloride, a method of adding PVA to the polyvinyl chloride resin is preferable. In the method of adding the PVA at the time of polymerization of vinyl chloride, since the PVA acts as a dispersion stabilizer, it may affect the quality such as the average particle diameter and plasticizer absorbability of the obtained polyvinyl chloride resin, This is because sometimes there is a possibility of adverse effects.
- the content of PVA relative to 100 parts by weight of the polyvinyl chloride resin is 0.00. It is because it becomes less than 005 weight part and the effect as a heat stabilizer is not acquired.
- the PVA can be added to the polyvinyl chloride resin as a powder or dissolved in water or an organic solvent. When added as a powder, the smaller the particle size, the better the effect as a heat stabilizer may be, and a particle size of 12 to 200 mesh pass is usually used.
- the polyvinyl chloride resin composition of the present invention may contain an acid having a pKa at 25 ° C. of 3.5 to 5.5 and / or a metal salt thereof.
- an acetic acid pKa4.76), propionic acid (pKa4.87), butyric acid (pKa4.63), octanoic acid (pKa4.89), adipic acid (pKa5.03) ), Benzoic acid (pKa 4.00), formic acid (pKa 3.55), valeric acid (pKa 4.63), heptanoic acid (pKa 4.66), lactic acid (pKa 3.66), phenylacetic acid (pKa 4.10), isobutyric acid (PKa 4.63), cyclohexanecarboxylic acid (pKa 4.70), and the like.
- Acids that can be particularly preferably used are acetic acid, propionic acid, and lactic acid. Moreover, you may contain the metal salt of said acid. Although there is no restriction
- the content of an acid having a pKa of 3.5 to 5.5 and / or a metal salt thereof is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of PVA. Parts, more preferably 0.15 to 2 parts by weight. If the content of acid and / or metal salt thereof relative to PVA is less than 0.05 parts by weight, the long-term thermal stability may be reduced, and if it exceeds 5 parts by weight, the polyvinyl chloride resin may be colored. is there.
- the method of containing a predetermined amount of the acid and / or metal salt thereof is not particularly limited. Examples thereof include a method for adjusting the type and amount of an alkali catalyst used for saponification when producing PVA, and a method for adding or removing the acid and / or its metal salt after the production of PVA.
- Examples of the zinc compound used in the present invention include zinc aliphatic carboxylates such as zinc stearate, zinc laurate and zinc oleate, and aromatic carboxylic acids such as zinc benzoate and zinc p-tert-butylbenzoate.
- Examples thereof include zinc salts of organic acids such as zinc, amino acid zinc salts and phosphate ester zinc salts; zinc oxides; inorganic zinc salts such as zinc carbonate.
- the added amount of the zinc compound is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin.
- the zinc compound can be contained by adding the polyvinyl chloride resin to the polyvinyl chloride resin after the polyvinyl chloride resin is obtained by a polymerization reaction.
- the polyvinyl chloride resin composition of the present invention comprises a stabilizer, a phenolic antioxidant, a phosphorus antioxidant, a light stabilizer, an ultraviolet absorber, an antifogging agent, an antistatic agent, a flame retardant, a lubricant, It can contain modifiers, reinforcing agents, pigments, foaming agents, plasticizers and the like.
- the polyvinyl chloride resin composition of the present invention may be mixed with other resins as long as the mechanical properties are not impaired.
- alkaline earth metal soap such as calcium soap and barium soap, aluminum soap, organometallic salt such as organophosphate metal salt, metal oxidation Products, metal hydroxides, metal carbonates, inorganic metal salts such as inorganic composite metal salts such as zeolite, halogen oxyacid salts such as barium chlorate, barium perchlorate, sodium perchlorate, ⁇ -diketone, polyvalent Non-metal stabilizers such as alcohol and epoxy compounds can be mentioned.
- plasticizer examples include phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, and azelaic acid, and n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol.
- N-pentanol isopentanol, tert-pentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, n-
- esters of linear and branched alkyl alcohols such as decanol, isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, alone or in mixtures, and esters of butanediol and adipic acid.
- epoxy plasticizers such as reaction products
- phosphate plasticizers such as tricresyl phosphate, trixylenyl phosphate, monobutyldixylenyl phosphate, and trioctyl phosphate.
- the phenolic antioxidant is not particularly limited as long as it is usually used.
- the phosphorus-based antioxidant may be any of those usually used.
- trisnonylphenyl phosphite tris (2,4-ditertiarybutylphenyl) phosphite, tris [2-tertiarybutyl -4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite
- tridecyl phosphite tridecyl phosphite
- octyl diphenyl phosphite di (decyl) monophenyl phosphite
- di ( Tridecyl) pentaerythritol diphosphite distearyl pentaerythritol diphosphite
- di (nonylphenyl) pentaerythritol diphosphite bis (2,4-ditert-butylphenyl) pentaerythr
- ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).
- 2-hydroxybenzophenones such as 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2′-methylenebis ( 4-tert-octyl-6-benzotriazolyl) phenol, 2- (2- 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of droxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl- Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate and
- Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6, 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2, 2,6,6-pentamethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6, -Pentamethyl-4-hydroxybenzyl) malonate, 1- (2-hydroxye
- the lubricant examples include hydrocarbons such as liquid paraffin, natural paraffin, microwax and polyethylene wax; fatty acids such as stearic acid and lauric acid; stearic acid amide, palmitic acid amide, methylene bisstearamide, ethylene bisstearamide, etc. Fatty acid amides; fatty acid esters of monoalcohols such as butyl stearate; fatty acid esters of polyols such as hydrogenated castor oil, ethylene glycol monostearate and glycerin monostearate; alcohols such as cetyl alcohol and stearyl alcohol. Especially, when the fatty acid ester of polyol is used, the effect of the present invention may be further manifested.
- the amount of the above-mentioned lubricant added is preferably 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin.
- Examples of the processing method for the polyvinyl chloride resin composition of the present invention include extrusion processing, calendar processing, blow molding, press processing, powder molding, injection molding and the like.
- Example 1 Manufacture of polyvinyl chloride resin
- a dispersion stabilizer was prepared by dissolving polyvinyl alcohol having a polymerization degree of 850 and a saponification degree of 72 mol% in an amount corresponding to 600 ppm with respect to vinyl chloride in 40 parts of deionized water.
- the dispersion stabilizer thus obtained was charged into a glass-lined autoclave in which the scale adhesion inhibitor NOXOL WSW (CIRS) was applied to a solid content of 0.3 g / m 2 .
- NOXOL WSW scale adhesion inhibitor
- a methanol solution of this vinyl acetate copolymer (PVAc-1), methanol and distilled water were charged into a beaker, and the solution temperature was adjusted to 40 ° C.
- a methanol solution having a sodium hydroxide concentration of 9% by weight was added so that the alkali molar ratio (ratio of moles of sodium hydroxide to moles of vinyl acetate units in the vinyl acetate copolymer) was 0.0065.
- the saponification reaction was started.
- the amounts of methanol and distilled water added were adjusted so that the vinyl acetate copolymer concentration during the saponification reaction was 50% by weight and the water content of the saponification reaction system was 1.0% by weight.
- the gelled PVA was recovered and pulverized, and 1 hour after the addition of sodium hydroxide, the obtained PVA was immersed in methyl acetate and neutralized. After neutralization, the obtained PVA was dried at 60 ° C. for 1 day to obtain polyvinyl alcohol (PVA-1).
- seat obtained with the said test roll was cut into 50x70 mm, and it was set as the test piece. This test piece was put in a gear oven, and the time until it became completely black at a temperature of 180 ° C. was measured and used as an indicator of long-term thermal stability.
- Example 1 the sheet surface state was observed, and long-term thermal stability and colorability were evaluated in the same manner as in Example 1 except that the resin composition sheet was prepared by changing the amount of PVA-1 added. .
- the evaluation results are shown in Table 1.
- Example 1 Comparative Examples 4-5
- the resin composition sheet was prepared by changing the amount of zinc stearate added, the sheet surface state was observed, and the long-term thermal stability and colorability were evaluated. .
- the evaluation results are shown in Table 1.
- Examples 7-11 In the method for producing PVA of Example 1, vinyl acetate copolymers (PVAc-2 to PVAc-) were used in the same manner as in Example 1 except that the amount of vinyl acetate, methanol, 3,4-diacetoxy-1-butene, etc. was changed. 6) was obtained and saponified in the same manner to obtain polyvinyl alcohol (PVA-2 to PVA-6). Production conditions and various physical properties are shown in Table 2. Using the obtained PVA, the sheet surface state was observed, and long-term thermal stability and colorability were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
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Abstract
Description
P=([η]×1000/8.29)(1/0.62)
(ポリ塩化ビニル樹脂の製造)
塩化ビニルに対して600ppmに相当する量の重合度850、けん化度72モル%のポリビニルアルコールを、40部の脱イオン水に溶解させ、分散安定剤を調製した。このようにして得られた分散安定剤を、スケール付着防止剤NOXOL WSW(CIRS社製)が固形分として0.3g/m2になるように塗布されたグラスライニング製オートクレーブに仕込んだ。次いで、該グラスライニング製オートクレーブにジイソプロピルパーオキシジカーボネートの70%トルエン溶液0.04部を仕込み、オートクレーブ内の圧力が0.0067MPaとなるまで脱気して酸素を除いた後、塩化ビニル30部を仕込み、オートクレーブ内の内容物を57℃に昇温して撹拌下に重合を開始した。重合開始時におけるオートクレーブ内の圧力は0.83MPaであった。重合を開始してから7時間経過後、オートクレーブ内の圧力が0.44MPaとなった時点で重合を停止し、未反応の塩化ビニルを除去した後、重合反応物を取り出し、65℃にて一晩乾燥を行い、ポリ塩化ビニル樹脂(PVC)を得た。
還流冷却器、滴下漏斗、攪拌機を備えた反応器(6L)に、酢酸ビニル(VAM)1081g、メタノール(MeOH)2400g、3,4-ジアセトキシ-1-ブテン(コモノマー)137.98gを仕込み、窒素ガスのバブリングにより反応器内を窒素置換した。反応器の昇温を開始し、内温を60℃に保ちつつ、2,2'-アゾビスイソブチロニトリル(AIBN)7.8gをメタノール19gと共に反応器に添加して重合を開始した。重合中60℃を保ち、重合率が70%となった時点(固形分濃度23.7%)で、重合禁止剤としてソルビン酸10.7gをメタノール1000gと共に添加し重合を停止した。続いて30℃、減圧下にメタノールを時々添加しながら未反応酢酸ビニル単量体の除去を行い、さらにメタノールを加え減圧下で留去する操作を3回する操作を行い、酢酸ビニル共重合体(PVAc-1)のメタノール溶液を得た。
ポリ塩化ビニル樹脂100重量部に対し、ステアリン酸亜鉛1重量部、ステアリン酸カルシウム2重量部、PVA-1(16メッシュパス)0.4重量部を混合した。この塩化ビニル樹脂組成物をテストロールにより190℃で5分間混練し、厚さ0.45mmのシートを作成した。
上記テストロールで得られたシートの表面を目視観察し、以下の指標で評価した。
A:表面が滑らかで荒れがほとんどない。
B:わずかに表面が荒れている。
C:表面荒れが激しい。
上記テストロールで得られたシートを50×70mmにカットし、試験片とした。この試験片をギヤーオーブン中に入れ、180℃の温度で完全に黒色になるまでの時間を測定し、長期の熱安定性の指標とした。
上記テストロールで得られたシートを45×30mmにカットし、得られたシート片を数枚重ね合わせ、185℃で5分間プレスして厚さ5mmの試験片を作成し、目視により着色性を比較し、以下の基準に従って判定した。
A:着色がほとんどない。
B:わずかに着色が認められる。
C:黄褐色である。
実施例1において、PVA-1の添加量を変えて樹脂組成物シートを作成する以外は実施例1と同様にして、シート表面状態の観察、長期の熱安定性および着色性の評価を行った。評価結果を表1に示す。
実施例1において、ステアリン酸亜鉛の添加量を変えて樹脂組成物シートを作成する以外は実施例1と同様にして、シート表面状態の観察、長期の熱安定性および着色性の評価を行った。評価結果を表1に示す。
実施例1のPVAの製造方法において、酢酸ビニル、メタノール、3,4-ジアセトキシ-1-ブテンなどの仕込み量を変える以外は実施例1と同様に酢酸ビニル共重合体(PVAc-2~PVAc-6)を得、それを同様にけん化することによりポリビニルアルコール(PVA-2~PVA-6)を得た。製造条件と各種物性を表2に示す。得られたPVAを用い、実施例1と同様にして、シート表面状態の観察、長期の熱安定性および着色性の評価を行った。評価結果を表1に示す。
実施例1のPVA-1の代わりに、無変性PVA(PVA-7:重合度300、けん化度80.0モル%)を用いる以外は実施例1と同様にし、シート表面状態の観察、長期の熱安定性および着色性の評価を行った。評価結果を表1に示す。
Claims (8)
- 前記式(2)で表される化合物が、3,4-ジヒドロキシ-1-ブテン、3,4-ジアルコキシ-1-ブテン、3,4-ジアシロキシ-1-ブテン、4,5-ジヒドロキシ-1-ペンテン、4,5-ジアルコキシ-1-ペンテン、4,5-ジアシロキシ-1-ペンテン、5,6-ジヒドロキシ-1-ヘキセン、5,6-ジアルコキシ-1-ヘキセン、5,6-ジアシロキシ-1-ヘキセン、グリセリンモノアリルエーテル、グリセリンモノビニルエーテル、(2-ヒドロキシ-3-アルコキシ-プロピル)アリルエーテル、(2-ヒドロキシ-3-アルコキシ-プロピル)ビニルエーテルからなる群から選択される少なくとも1種である請求項2に記載のポリ塩化ビニル樹脂組成物。
- 前記ポリビニルアルコールが、粘度平均重合度が800以下、けん化度が70モル%以上である請求項1~3のいずれかに記載のポリ塩化ビニル樹脂組成物。
- 前記ポリビニルアルコール中の式(1)で表される構造単位の含有量が10モル%以下である請求項1~4のいずれかに記載のポリ塩化ビニル樹脂組成物。
- 前記式(2)で表される化合物が、3,4-ジヒドロキシ-1-ブテン、3,4-ジアルコキシ-1-ブテン、3,4-ジアシロキシ-1-ブテン、4,5-ジヒドロキシ-1-ペンテン、4,5-ジアルコキシ-1-ペンテン、4,5-ジアシロキシ-1-ペンテン、5,6-ジヒドロキシ-1-ヘキセン、5,6-ジアルコキシ-1-ヘキセン、5,6-ジアシロキシ-1-ヘキセン、グリセリンモノアリルエーテル、グリセリンモノビニルエーテル、(2-ヒドロキシ-3-アルコキシ-プロピル)アリルエーテル、(2-ヒドロキシ-3-アルコキシ-プロピル)ビニルエーテルからなる群から選択される少なくとも1種である請求項7に記載のポリ塩化ビニル樹脂組成物の製造方法。
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ES09834937.6T ES2551745T3 (es) | 2008-12-26 | 2009-12-24 | Composición de resina de cloruro de polivinilo y su método de fabricación |
EP09834937.6A EP2371899B1 (en) | 2008-12-26 | 2009-12-24 | Polyvinyl chloride resin composition and manufacturing method therefor |
US13/142,001 US20110319541A1 (en) | 2008-12-26 | 2009-12-24 | Polyvinyl chloride resin composition and manufacturing method therefor |
JP2010544119A JP5646347B2 (ja) | 2008-12-26 | 2009-12-24 | ポリ塩化ビニル樹脂組成物およびその製造方法 |
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FR2986003B1 (fr) * | 2012-01-24 | 2015-01-16 | Arkema France | Procede de preparation de polymeres halogenes |
KR102024141B1 (ko) | 2016-06-21 | 2019-09-23 | 주식회사 엘지화학 | 염화비닐계 중합체의 제조방법 |
WO2017222213A1 (ko) * | 2016-06-21 | 2017-12-28 | 주식회사 엘지화학 | 염화비닐계 중합체의 제조방법 |
EP3747976A4 (en) * | 2018-02-02 | 2021-11-10 | Adeka Corporation | COMPOSITION OF STABILIZER, COMPOSITION OF VINYL CHLORIDE RESIN CONTAINING IT, AND ARTICLE MOLDED THEREOF |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5092947A (ja) | 1973-12-22 | 1975-07-24 | ||
JPS5481359A (en) | 1977-12-12 | 1979-06-28 | Yoshizaki Kozo | Composition * film and coated structure of chlorinee containing polymer having good weatherability |
JPS57147552A (en) | 1981-03-09 | 1982-09-11 | Kyodo Yakuhin Kk | Stabilizing method of chlorine-containing resin |
JPS60238345A (ja) | 1984-05-10 | 1985-11-27 | Kuraray Co Ltd | 樹脂組成物 |
JPH01178543A (ja) | 1987-12-29 | 1989-07-14 | Nippon Synthetic Chem Ind Co Ltd:The | 含ハロゲン熱可塑性樹脂組成物 |
JPH06287387A (ja) | 1993-04-06 | 1994-10-11 | Sekisui Chem Co Ltd | 塩化ビニル系樹脂組成物 |
JPH093286A (ja) | 1995-06-20 | 1997-01-07 | Shin Etsu Chem Co Ltd | 塩化ビニル系樹脂組成物 |
JPH0931281A (ja) | 1995-07-21 | 1997-02-04 | Asahi Denka Kogyo Kk | 硬質塩化ビニル樹脂組成物 |
JP2006241448A (ja) * | 2005-02-02 | 2006-09-14 | Nippon Synthetic Chem Ind Co Ltd:The | ビニル系化合物の懸濁重合用分散安定剤 |
WO2008015739A1 (fr) * | 2006-08-01 | 2008-02-07 | The Nippon Synthetic Chemical Industry Co., Ltd. | Stabilisant de dispersion pour la polymérisation en suspension de composés vinyliques |
WO2009154178A1 (ja) * | 2008-06-16 | 2009-12-23 | 株式会社クラレ | ポリ塩化ビニル樹脂組成物およびその製造方法 |
WO2009154179A1 (ja) * | 2008-06-16 | 2009-12-23 | 株式会社クラレ | ポリ塩化ビニル樹脂組成物およびその製造方法 |
WO2009154176A1 (ja) * | 2008-06-18 | 2009-12-23 | 株式会社クラレ | ポリ塩化ビニル樹脂組成物およびその製造方法 |
WO2009157401A1 (ja) * | 2008-06-23 | 2009-12-30 | 株式会社クラレ | ポリ塩化ビニル樹脂組成物およびその製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1180019C (zh) * | 2000-09-01 | 2004-12-15 | 可乐丽股份有限公司 | 聚乙烯醇类树脂组合物和多层容器 |
WO2003072653A1 (fr) * | 2002-02-26 | 2003-09-04 | Kuraray Co., Ltd. | Composition de resine et structures multicouches |
-
2009
- 2009-12-24 CN CN200980157571.3A patent/CN102333817B/zh not_active Expired - Fee Related
- 2009-12-24 KR KR1020117017272A patent/KR20110110222A/ko not_active Application Discontinuation
- 2009-12-24 US US13/142,001 patent/US20110319541A1/en not_active Abandoned
- 2009-12-24 ES ES09834937.6T patent/ES2551745T3/es active Active
- 2009-12-24 JP JP2010544119A patent/JP5646347B2/ja not_active Expired - Fee Related
- 2009-12-24 WO PCT/JP2009/071424 patent/WO2010074139A1/ja active Application Filing
- 2009-12-24 EP EP09834937.6A patent/EP2371899B1/en not_active Not-in-force
- 2009-12-24 TW TW098144648A patent/TW201030079A/zh unknown
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5092947A (ja) | 1973-12-22 | 1975-07-24 | ||
JPS5481359A (en) | 1977-12-12 | 1979-06-28 | Yoshizaki Kozo | Composition * film and coated structure of chlorinee containing polymer having good weatherability |
JPS57147552A (en) | 1981-03-09 | 1982-09-11 | Kyodo Yakuhin Kk | Stabilizing method of chlorine-containing resin |
JPS60238345A (ja) | 1984-05-10 | 1985-11-27 | Kuraray Co Ltd | 樹脂組成物 |
JPH01178543A (ja) | 1987-12-29 | 1989-07-14 | Nippon Synthetic Chem Ind Co Ltd:The | 含ハロゲン熱可塑性樹脂組成物 |
JPH06287387A (ja) | 1993-04-06 | 1994-10-11 | Sekisui Chem Co Ltd | 塩化ビニル系樹脂組成物 |
JPH093286A (ja) | 1995-06-20 | 1997-01-07 | Shin Etsu Chem Co Ltd | 塩化ビニル系樹脂組成物 |
JPH0931281A (ja) | 1995-07-21 | 1997-02-04 | Asahi Denka Kogyo Kk | 硬質塩化ビニル樹脂組成物 |
JP2006241448A (ja) * | 2005-02-02 | 2006-09-14 | Nippon Synthetic Chem Ind Co Ltd:The | ビニル系化合物の懸濁重合用分散安定剤 |
WO2008015739A1 (fr) * | 2006-08-01 | 2008-02-07 | The Nippon Synthetic Chemical Industry Co., Ltd. | Stabilisant de dispersion pour la polymérisation en suspension de composés vinyliques |
WO2009154178A1 (ja) * | 2008-06-16 | 2009-12-23 | 株式会社クラレ | ポリ塩化ビニル樹脂組成物およびその製造方法 |
WO2009154179A1 (ja) * | 2008-06-16 | 2009-12-23 | 株式会社クラレ | ポリ塩化ビニル樹脂組成物およびその製造方法 |
WO2009154176A1 (ja) * | 2008-06-18 | 2009-12-23 | 株式会社クラレ | ポリ塩化ビニル樹脂組成物およびその製造方法 |
WO2009157401A1 (ja) * | 2008-06-23 | 2009-12-30 | 株式会社クラレ | ポリ塩化ビニル樹脂組成物およびその製造方法 |
Non-Patent Citations (6)
Title |
---|
JAPANESE JOURNAL OF POLYMER SCIENCE AND TECHNOLOGY, vol. 47, no. 3, 1990, pages 197 |
JAPANESE JOURNAL OF POLYMER SCIENCE AND TECHNOLOGY, vol. 47, no. 6, 1990, pages 509 |
JAPANESE JOURNAL OF POLYMER SCIENCE AND TECHNOLOGY, vol. 50, no. 2, 1993, pages 65 |
JOURNAL OF THE ADHESION SOCIETY OF JAPAN, vol. 43, no. 2, 2007, pages 43 |
POLYMERS & POLYMER COMPOSITES, vol. 11, 2003, pages 649 |
See also references of EP2371899A4 |
Cited By (1)
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---|---|---|---|---|
JP5755152B2 (ja) * | 2010-02-01 | 2015-07-29 | 株式会社クラレ | ポリ塩化ビニル用熱安定剤およびその製造方法 |
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EP2371899B1 (en) | 2015-08-12 |
ES2551745T3 (es) | 2015-11-23 |
EP2371899A4 (en) | 2012-04-25 |
US20110319541A1 (en) | 2011-12-29 |
EP2371899A1 (en) | 2011-10-05 |
JPWO2010074139A1 (ja) | 2012-06-21 |
TW201030079A (en) | 2010-08-16 |
JP5646347B2 (ja) | 2014-12-24 |
CN102333817A (zh) | 2012-01-25 |
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