WO2010041620A1 - 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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- WO2010041620A1 WO2010041620A1 PCT/JP2009/067326 JP2009067326W WO2010041620A1 WO 2010041620 A1 WO2010041620 A1 WO 2010041620A1 JP 2009067326 W JP2009067326 W JP 2009067326W WO 2010041620 A1 WO2010041620 A1 WO 2010041620A1
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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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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, etc., and particularly relates to a polyvinyl chloride resin composition having good thermal stability and low coloration. It is.
- Polyvinyl chloride resin is molded and formulated with stabilizers such as Ca-Zn and Ba-Zn, and is widely used as a general molding material and as a material for products suitable for food and medical use. Yes. If only these stabilizers are blended, the ability to suppress the thermal degradation of the resulting molded product is inferior, so that the initial colorability of the molded product is impaired, and the thermal stability of the molded product is insufficient. For this reason, as a means for improving these defects, a polyvinyl chloride resin composition to which an antioxidant or a compound having a hydroxyl group is added has been proposed.
- stabilizers such as Ca-Zn and Ba-Zn
- 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 Composites, Vol. 11, p. 649 (2003)) describes polyvinyl chloride, zinc stearate-calcium stearate composite soap, a degree of polymerization of 500, and a degree of saponification 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.
- An object of the present invention is to provide a polyvinyl chloride resin composition having excellent thermal stability and little coloring.
- the inventors of the present invention have a viscosity average polymerization degree of 100 to 3000 and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 2.2 with respect to the polyvinyl chloride resin.
- PVA polyvinyl alcohol
- a zinc compound By adding a specific amount of polyvinyl alcohol of ⁇ 4.9 (hereinafter abbreviated as PVA) and a zinc compound, it is possible to sufficiently maintain the thermal stability at the time of molding and that the molded product is less colored.
- PVA polyvinyl alcohol of ⁇ 4.9
- the headline and the present invention were completed.
- the viscosity average polymerization degree is 100 to 3000 with respect to 100 parts by weight of the polyvinyl chloride resin, and the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is 2.2 to 4.
- 9 is a polyvinyl chloride resin composition containing 0.005 to 5 parts by weight of polyvinyl alcohol 9 and 0.01 to 5 parts by weight of a zinc compound. At this time, it is preferable that this polyvinyl alcohol is what saponifies the polyvinyl ester whose ratio of a vinyl-ester unit is 95 mol% or more.
- the polyvinyl alcohol is preferably formed by blending two or more kinds of polyvinyl alcohols having a viscosity average polymerization degree of 500 or more.
- the lubricant is preferably a fatty acid ester of polyol, and more preferably glycerin monostearate.
- the viscosity average degree of polymerization is 100 to 3000 with respect to 100 parts by weight of the polyvinyl chloride resin, and the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is 2.2 to 4.
- 9 is a method for producing a polyvinyl chloride resin composition in which 0.005 to 5 parts by weight of polyvinyl alcohol and 0.01 to 5 parts by weight of a zinc compound are added.
- the polyvinyl alcohol is preferably formed by blending two or more kinds of polyvinyl alcohols having a viscosity average polymerization degree of 500 or more.
- the polyvinyl chloride resin composition of the present invention is excellent in thermal stability and less colored. Therefore, the polyvinyl chloride resin composition can be melt-molded to obtain a molded product with less coloring, 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.
- the saponification degree of the PVA used in the present invention is preferably 40 to 99.9 mol%, more preferably 50 to 98.5 mol%, and particularly preferably 60 to 96 mol%. When the degree of saponification is less than 40 mol%, long-term thermal stability is lowered, which is not preferable.
- 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 3000 or less, preferably 2600 or less, particularly preferably 1700 or less. When the viscosity average polymerization degree is larger than 3000, long-term thermal stability is remarkably lowered. Further, the viscosity average degree of polymerization is 100 or more, preferably 150 or more, and more preferably 200 or more, from the viewpoint of production of PVA.
- the polymerization degree of each PVA or polyvinyl ester is also preferably within the above range.
- 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 ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn of the PVA is 2.2 to 4.9, preferably 2.4 to 4.7, and more preferably 2.6 to 4. 4.
- Mw / Mn of PVA is larger than 4.9, it is not preferable because long-term thermal stability is lowered.
- the number average molecular weight Mn and the weight average molecular weight Mw of PVA are the values measured according to the following method. That is, gel permeation chromatography (GPC) measurement was performed at 40 ° C.
- the method for adjusting the Mw / Mn of the PVA includes a method of blending PVA having different degrees of polymerization; a method of saponifying a blend of polyvinyl esters having different degrees of polymerization; and a vinyl ester monomer in producing a polyvinyl ester.
- the method of saponifying the obtained polyvinyl ester by adjusting the degree of polymerization at each stage and adjusting the polymerization rate of the vinyl ester monomer during the production of the polyvinyl ester And the method of saponifying the obtained polyvinyl ester is mentioned.
- the PVA is a vinyl ester polymer obtained by polymerizing a vinyl ester monomer by employing 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. It can be produced by saponifying. From the industrial viewpoint, 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. Examples of the vinyl ester monomer that can be used for polymerization include vinyl acetate, vinyl formate, vinyl propionate, vinyl caprylate, and vinyl versatate. Among these, vinyl acetate is preferable from an industrial viewpoint.
- the vinyl ester monomer When the vinyl ester monomer is polymerized, the vinyl ester monomer may be copolymerized with another monomer as long as the gist of the present invention is not impaired.
- the ratio is preferably 95 mol% or more from the viewpoint of long-term thermal stability.
- the ratio of the vinyl ester unit is more preferably 96 mol% or more, and still more preferably 98 mol% or more. It is particularly preferable that the polyvinyl ester is a homopolymer of a vinyl ester monomer.
- 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 high content of 1,2-glycol bonds 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 PVA is preferably formed by blending two or more types of PVA having a viscosity average degree of polymerization of 500 or more.
- the difference in viscosity average degree of polymerization of 500 or more means that the difference in viscosity average degree of polymerization between the lowest and highest viscosity average degree of polymerization of each blended PVA is 500 or more.
- the method for obtaining the blended PVA is not particularly limited, and the polyvinyl ester may be blended in advance before saponification, or the PVA may be blended after saponification. Usually, the viscosity average degree of polymerization of the polymer does not change before and after saponification. By doing in this way, PVA with which Mw / Mn was adjusted accurately can be obtained easily.
- the blending ratio of each PVA to be used for blending is not particularly limited, but the ratio of the PVA having the lowest viscosity average degree of polymerization is preferably 10 to 90% by weight, and 20 to 80% by weight. It is more preferable that Among each PVA, the one having the highest viscosity average degree of polymerization is preferably 10 to 90% by weight, and more preferably 20 to 80% by weight. When the blending ratio of each PVA is within the above range, the adjustment of Mw / Mn is facilitated. In addition to the two types of PVA, PVA having different viscosity average polymerization degrees may be further blended.
- 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, the resin composition is unfavorably colored.
- 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.
- 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.
- the content of the acid and / or metal salt thereof relative to PVA is less than 0.05 parts by weight, the long-term thermal stability is lowered, and when it exceeds 5 parts by weight, the polyvinyl chloride resin is unfavorably colored.
- 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; inorganic zinc salts such as zinc oxide and 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 polymerization.
- 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.
- the lubricant examples include hydrocarbon compounds such as liquid paraffin, natural paraffin, microwax and polyethylene wax, fatty acid compounds such as stearic acid and lauric acid, stearic acid amide, palmitic acid amide, methylene bisstearamide, ethylene bis Fatty acid amide compounds such as stearamide, lower alcohol esters of fatty acids such as butyl stearate, polyhydric alcohol esters of fatty acids such as hardened castor oil, fatty acid esters of polyols such as ethylene glycol monostearate and glycerin monostearate And ester compounds such as cetyl alcohol and stearyl alcohol.
- hydrocarbon compounds such as liquid paraffin, natural paraffin, microwax and polyethylene wax
- fatty acid compounds such as stearic acid and lauric acid
- stearic acid amide palmitic acid amide
- methylene bisstearamide ethylene bis Fatty acid amide compounds
- ethylene bis Fatty acid amide compounds such
- a fatty acid ester of polyol is preferable, and glycerin monostearate is more preferable as the fatty acid ester of polyol.
- 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.
- 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
- 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
- the polymerization degree of polyvinyl acetate A was measured as follows. That is, a part of a methanol solution of polyvinyl acetate A was taken and sodium hydroxide having a concentration of 10% so that the alkali molar ratio (molar ratio of alkali compound to vinyl acetate unit in polyvinyl acetate) was 0.5. A methanol solution was added and allowed to stand at 60 ° C. for 5 hours to allow saponification to proceed. After completion of saponification, Soxhlet extraction with methanol was carried out for 3 days, followed by drying under reduced pressure at 80 ° C. for 3 days to obtain purified polyvinyl alcohol. The degree of polymerization of this polyvinyl alcohol was 300 when measured according to JIS K6726 of the ordinary method. Thereby, it was found that the polymerization degree of the polyvinyl acetate A was 300.
- Polymerization was conducted in the same manner as described above using 2400 g of vinyl acetate, 600 g of methanol, 26.5 g of acetaldehyde, and 0.6 g of 2,2′-azobisisobutyronitrile, and polyvinyl acetate B having a polymerization degree of 1200 was obtained. Obtained.
- Polyvinyl acetate A having a polymerization degree of 300 and polyvinyl acetate B having a polymerization degree of 1200 produced as described above were blended at a weight ratio of 45/55.
- This polyvinyl acetate was dissolved in methanol to prepare a methanol solution of 55% concentration of polyvinyl acetate, 30% polyvinyl acetate, 1% water, 30% methyl acetate, and an alkali molar ratio of 0.02.
- saponification of polyvinyl acetate was carried out by adding water, methanol, methyl acetate and a methanol solution of sodium hydroxide having a concentration of 10%.
- the material gelled in about 5 minutes after the addition of alkali was pulverized with a pulverizer, allowed to stand at 40 ° C. for 1 hour, centrifuged to remove liquid, and then dried at 60 ° C. for 1 day in a dryer to obtain polyvinyl alcohol. .
- the polymerization degree and saponification degree of the polyvinyl alcohol were measured in accordance with JIS K6726, they were 740 and 72 mol%.
- the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight measured by the method described above was 3.1.
- the sodium acetate content measured by isotachophoresis (isotacophoresis) was 1.8%.
- 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 2 Manufacture of polyvinyl chloride resin
- PVC polyvinyl chloride resin
- Polyvinyl acetate C having a polymerization degree of 500 and polyvinyl acetate B having a polymerization degree of 1200 produced as described above were blended at a weight ratio of 60/40.
- This polyvinyl acetate was dissolved in methanol to prepare a methanol solution of 55% concentration of polyvinyl acetate, 30% polyvinyl acetate, 1% water, 30% methyl acetate, and an alkali molar ratio of 0.02.
- saponification of polyvinyl acetate was carried out by adding water, methanol, methyl acetate and a methanol solution of sodium hydroxide having a concentration of 10%.
- the material gelled in about 5 minutes after the addition of alkali was pulverized with a pulverizer, allowed to stand at 40 ° C. for 1 hour, centrifuged to remove liquid, and then dried at 60 ° C. for 1 day in a dryer to obtain polyvinyl alcohol. .
- the polymerization degree and saponification degree of the polyvinyl alcohol were measured according to JIS K6726, they were 750 and 72 mol%, respectively.
- the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight measured by the method described above was 2.4.
- the sodium acetate content measured by isotachophoresis (isotacophoresis) was 1.8%.
- Example 1 In the same manner as in Example 1, a resin composition sheet was prepared using the above PVA, and a thermal stability test and a colorability test were performed. The evaluation results are shown in Table 1.
- Example 3 Manufacture of polyvinyl chloride resin
- PVC polyvinyl chloride resin
- Polyvinyl acetate D having a polymerization degree of 230 and polyvinyl acetate E having a polymerization degree of 1550 produced as described above were blended at a weight ratio of 50/50.
- This polyvinyl acetate was dissolved in methanol to prepare a methanol solution of 55% concentration of polyvinyl acetate, 30% polyvinyl acetate, 1% water, 30% methyl acetate, and an alkali molar ratio of 0.02.
- saponification of polyvinyl acetate was carried out by adding water, methanol, methyl acetate and a methanol solution of sodium hydroxide having a concentration of 10%.
- the material gelled in about 5 minutes after the addition of alkali was pulverized with a pulverizer, allowed to stand at 40 ° C. for 1 hour, centrifuged to remove liquid, and then dried at 60 ° C. for 1 day in a dryer to obtain polyvinyl alcohol. .
- the polymerization degree and saponification degree of the polyvinyl alcohol were measured according to JIS K6726, they were 760 and 72 mol%.
- the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight measured by the above method was 4.4.
- the sodium acetate content measured by isotachophoresis (isotacophoresis) was 1.8%.
- Example 1 In the same manner as in Example 1, a resin composition sheet was prepared using the above PVA, and a thermal stability test and a colorability test were performed. The evaluation results are shown in Table 1.
- Example 4 Manufacture of polyvinyl chloride resin
- PVC polyvinyl chloride resin
- Polyvinyl acetate F having a polymerization degree of 700 produced above is dissolved in methanol to prepare a methanol solution of 55% concentration of polyvinyl acetate.
- Polyvinyl acetate is 30%, water is 1%, and methyl acetate is 30%.
- Polyvinyl acetate was saponified by adding water, methanol, methyl acetate and a methanol solution of sodium hydroxide having a concentration of 10% so that the alkali molar ratio was 0.02. The material gelled in about 5 minutes after the addition of alkali was pulverized with a pulverizer, allowed to stand at 40 ° C. for 1 hour, centrifuged to remove liquid, and then dried at 60 ° C.
- polyvinyl alcohol for 1 day in a dryer to obtain polyvinyl alcohol.
- polymerization degree and saponification degree of the polyvinyl alcohol were measured according to JIS K6726, they were 700 and 68 mol%, respectively.
- the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight measured by the method described above was 2.4.
- the sodium acetate content measured by isotachophoresis (isotacophoresis) was 1.8%.
- Example 5 Using the polyvinyl alcohol used in Example 1, an aqueous PVA solution was added to the polyvinyl chloride resin in the same manner as in Example 1 and dried. A sheet was prepared in the same manner as in Example 1 except that 0.5 parts by weight of glycerin monostearate was added as a lubricant to the polyvinyl chloride resin composition, and a thermal stability test and a colorability test were performed. . The results are shown in Table 1.
- Example 6 Using the polyvinyl alcohol used in Example 2, an aqueous PVA solution was added to the polyvinyl chloride resin and dried as in Example 2. A sheet was prepared in the same manner as in Example 2 except that 0.5 parts by weight of glycerin monostearate was added as a lubricant to the polyvinyl chloride resin composition, and a thermal stability test and a colorability test were performed. . The results are shown in Table 1.
- Example 7 Using the polyvinyl alcohol used in Example 3, the PVA aqueous solution was added to the polyvinyl chloride resin and dried as in Example 3. A sheet was prepared in the same manner as in Example 3 except that 0.5 parts by weight of glycerin monostearate was added as a lubricant to the polyvinyl chloride resin composition, and a thermal stability test and a colorability test were performed. . The results are shown in Table 1.
- Comparative Example 1 Using 100 parts by weight of PVA obtained in Example 4, 500 parts by weight of a methanol / methyl acetate mixed solvent (mixing ratio [wt] is 1: 1) is immersed at 50 ° C. for 1 hour and centrifuged off. The washing method was repeated 3 times. After washing, the polymerization degree and saponification degree of polyvinyl alcohol were measured in the same manner as in Example 4. As a result, they were 750 and 72 mol%. The ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight measured by the method described above was 1.9. The sodium acetate content measured by isotachophoresis (isotacophoresis) was 0.4%. Using the PVA, test pieces were prepared in the same manner as in Example 1, and long-term thermal stability and colorability were evaluated. The evaluation results are shown in Table 1. Long-term thermal stability was not sufficient
- the polyvinyl acetate G having a polymerization degree of 200 and the polyvinyl acetate H having a polymerization degree of 1770 produced as described above were blended at a weight ratio of 55/45.
- This polyvinyl acetate was dissolved in methanol to prepare a methanol solution of 55% concentration of polyvinyl acetate, 30% polyvinyl acetate, 1% water, 30% methyl acetate, and an alkali molar ratio of 0.02.
- saponification of polyvinyl acetate was carried out by adding water, methanol, methyl acetate and a methanol solution of sodium hydroxide having a concentration of 10%.
- the material gelled in about 5 minutes after the addition of alkali was pulverized with a pulverizer, allowed to stand at 40 ° C. for 1 hour, centrifuged to remove liquid, and then dried at 60 ° C. for 1 day in a dryer to obtain polyvinyl alcohol. .
- the polymerization degree and saponification degree of the polyvinyl alcohol were measured according to JIS K6726, they were 750 and 72 mol%, respectively.
- the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight measured by the method described above was 5.5.
- the sodium acetate content measured by isotachophoresis (isotacophoresis) was 1.8%.
- Example 1 In the same manner as in Example 1, a resin composition sheet was prepared using the above PVA, and a thermal stability test and a colorability test were performed. The evaluation results are shown in Table 1.
- Example 1 a test piece was prepared in the same manner as in Example 1 except that the blending amount of PVA with respect to polyvinyl chloride resin (PVC) was changed as shown in Table 1, and long-term thermal stability and colorability Evaluation was performed. The evaluation results are shown in Table 1. When there was too much PVA compounding quantity, it colored yellowish brown. When the amount is too small, long-term thermal stability is not sufficient.
- PVC polyvinyl chloride resin
- Example 5 test pieces were prepared in the same manner as in Example 1 except that PVA was not added to the polyvinyl chloride resin, and long-term thermal stability and colorability were evaluated. The evaluation results are shown in Table 1. Long-term thermal stability was not sufficient.
- Example 1 except that the addition amount of zinc stearate was changed as shown in Table 1, test pieces were prepared in the same manner as in Example 1, and long-term thermal stability and colorability were evaluated. The evaluation results are shown in Table 1. In all cases, the long-term thermal stability was insufficient.
- Comparative Example 8 Using the polyvinyl alcohol used in Comparative Example 1, an aqueous PVA solution was added to the polyvinyl chloride resin and dried as in Comparative Example 1. A sheet was prepared in the same manner as in Comparative Example 1 except that 0.5 parts by weight of glycerin monostearate was added as a lubricant to the polyvinyl chloride resin composition, and a thermal stability test and a colorability test were performed. . The results are shown in Table 1.
- Comparative Example 9 Using the polyvinyl alcohol used in Comparative Example 2, an aqueous PVA solution was added to the polyvinyl chloride resin and dried as in Comparative Example 2. A sheet was prepared in the same manner as in Comparative Example 2 except that 0.5 parts by weight of glycerin monostearate was added as a lubricant to the polyvinyl chloride resin composition, and a thermal stability test and a colorability test were performed. . The 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。
酢酸ビニル2400g、メタノール600g、アセトアルデヒド220gを反応器に仕込み、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、内温が60℃となったところで2,2’-アゾビスイソブチロニトリル0.6gを反応器に添加して重合を開始した。重合中は重合温度を60℃に維持した。重合開始から4.5時間後に該反応器を冷却して重合を停止した。この時点の重合率は50%であった。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、ポリ酢酸ビニルAのメタノール溶液(濃度60%)を得た。
ポリ塩化ビニル樹脂100重量部に対し、PVA1重量部になるように1%濃度のPVA水溶液を添加し、減圧乾燥機により50℃で8時間乾燥した。このポリ塩化ビニル樹脂組成物にステアリン酸亜鉛2重量部、ステアリン酸カルシウム1重量部、ジオクチルフタレート20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160℃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。
(ポリ塩化ビニル樹脂の製造)
実施例1と同様にしてポリ塩化ビニル樹脂(PVC)を得た。
酢酸ビニル2400g、メタノール600g、アセトアルデヒド98gを反応器に仕込み、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、内温が60℃となったところで2,2’-アゾビスイソブチロニトリル0.6gを反応器に添加して重合を開始した。重合中は重合温度を60℃に維持した。重合開始から4.5時間後に該反応器を冷却して重合を停止した。この時点の重合率は50%であった。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、ポリ酢酸ビニルCのメタノール溶液(濃度60%)を得た。実施例1と同様に重合度を測定した結果、500であった。
(ポリ塩化ビニル樹脂の製造)
実施例1と同様にしてポリ塩化ビニル樹脂(PVC)を得た。
酢酸ビニル2400g、メタノール600g、アセトアルデヒド245gを反応器に仕込み、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、内温が60℃となったところで2,2’-アゾビスイソブチロニトリル0.6gを反応器に添加して重合を開始した。重合中は重合温度を60℃に維持した。重合開始から4.5時間後に該反応器を冷却して重合を停止した。この時点の重合率は50%であった。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、ポリ酢酸ビニルDのメタノール溶液(濃度60%)を得た。実施例1と同様に重合度を測定した結果、230であった。
(ポリ塩化ビニル樹脂の製造)
実施例1と同様にしてポリ塩化ビニル樹脂(PVC)を得た。
酢酸ビニル2400g、メタノール600g、アセトアルデヒド45gを反応器に仕込み、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、内温が60℃となったところで2,2’-アゾビスイソブチロニトリル0.6gを反応器に添加して重合を開始した。重合中は重合温度を60℃に維持した。重合開始から7.0時間後に該反応器を冷却して重合を停止した。この時点の重合率は75%であった。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、ポリ酢酸ビニルFのメタノール溶液(濃度60%)を得た。実施例1と同様に重合度を測定した結果、700であった。
実施例1で用いたポリビニルアルコールを用い、実施例1と同様にPVA水溶液をポリ塩化ビニル樹脂に添加、乾燥させた。このポリ塩化ビニル樹脂組成物に、滑剤としてグリセリンモノステアレートを0.5重量部添加したこと以外は、実施例1と同様にしてシートを作成し、熱安定性試験および着色性試験を実施した。結果を表1に示す。
実施例2で用いたポリビニルアルコールを用い、実施例2と同様にPVA水溶液をポリ塩化ビニル樹脂に添加、乾燥させた。このポリ塩化ビニル樹脂組成物に、滑剤としてグリセリンモノステアレートを0.5重量部添加したこと以外は、実施例2と同様にしてシートを作成し、熱安定性試験および着色性試験を実施した。結果を表1に示す。
実施例3で用いたポリビニルアルコールを用い、実施例3と同様にPVA水溶液をポリ塩化ビニル樹脂に添加、乾燥させた。このポリ塩化ビニル樹脂組成物に、滑剤としてグリセリンモノステアレートを0.5重量部添加したこと以外は、実施例3と同様にしてシートを作成し、熱安定性試験および着色性試験を実施した。結果を表1に示す。
実施例4において得られたPVA100重量部に対して、メタノール/酢酸メチル混合溶媒(混合比率[wt]は1:1)500重量部を用いて、50℃にて1時間浸漬し、遠心脱する洗浄方法を3回繰り返した。洗浄後、実施例4と同様の方法でポリビニルアルコールの重合度およびけん化度を測定した結果、750および72モル%であった。前述の方法で測定した重量平均分子量Mwと数平均分子量との比Mw/Mnは1.9であった。等速電気泳動法(イソタコフォレシス)により測定した酢酸ナトリウム含有量は0.4%であった。該PVAを用いて、実施例1と同様にして試験片を作成し、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。長期の熱安定性が十分でなかった
(ポリ塩化ビニル樹脂の製造)
実施例1と同様にしてポリ塩化ビニル樹脂(PVC)を得た。
酢酸ビニル2400g、メタノール600g、アセトアルデヒド280gを反応器に仕込み、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、内温が60℃となったところで2,2’-アゾビスイソブチロニトリル0.6gを反応器に添加して重合を開始した。重合中は重合温度を60℃に維持した。重合開始から4.5時間後に該反応器を冷却して重合を停止した。この時点の重合率は50%であった。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、ポリ酢酸ビニルGのメタノール溶液(濃度60%)を得た。実施例1と同様に重合度を測定した結果、200であった。
実施例1において、PVAのポリ塩化ビニル樹脂(PVC)に対する配合量を表1に示すように変更した以外は実施例1と同様にして試験片を作成し、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。PVA配合量が多すぎる場合は黄褐色に着色した。また、少なすぎる場合は長期の熱安定性が十分でなかった。
実施例1において、ポリ塩化ビニル樹脂にPVAを添加しなかったこと以外は、実施例1と同様にして試験片を作成し、長期の熱安定性および着色性を評価した。評価結果を表1に示す。長期の熱安定性が十分ではなかった。
実施例1において、ステアリン酸亜鉛の添加量を表1に示すように変更した以外は、実施例1と同様にして試験片を作成し、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。いずれも長期の熱安定性が不十分であった。
比較例1で用いたポリビニルアルコールを用い、比較例1と同様にPVA水溶液をポリ塩化ビニル樹脂に添加、乾燥させた。このポリ塩化ビニル樹脂組成物に、滑剤としてグリセリンモノステアレートを0.5重量部添加したこと以外は、比較例1と同様にしてシートを作成し、熱安定性試験および着色性試験を実施した。結果を表1に示す。
比較例2で用いたポリビニルアルコールを用い、比較例2と同様にPVA水溶液をポリ塩化ビニル樹脂に添加、乾燥させた。このポリ塩化ビニル樹脂組成物に、滑剤としてグリセリンモノステアレートを0.5重量部添加したこと以外は、比較例2と同様にしてシートを作成し、熱安定性試験および着色性試験を実施した。結果を表1に示す。
Claims (7)
- ポリ塩化ビニル樹脂100重量部に対して、粘度平均重合度が100~3000であり、重量平均分子量Mwと数平均分子量Mnとの比Mw/Mnが2.2~4.9であるポリビニルアルコールを0.005~5重量部および亜鉛化合物を0.01~5重量部含有する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、ビニルエステル単位の割合が95モル%以上であるポリビニルエステルをけん化してなるものである請求項1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500以上異なる2種類以上のポリビニルアルコールをブレンドしてなる、請求項1または2記載のポリ塩化ビニル樹脂組成物。
- 前記ポリ塩化ビニル樹脂100重量部に対して、滑剤を0.001~10重量部含有する、請求項1~3のいずれか記載のポリ塩化ビニル樹脂組成物。
- 前記滑剤が、ポリオールの脂肪酸エステルである、請求項4記載のポリ塩化ビニル樹脂組成物。
- ポリ塩化ビニル樹脂100重量部に対して、粘度平均重合度が100~3000であり、重量平均分子量Mwと数平均分子量Mnとの比Mw/Mnが2.2~4.9であるポリビニルアルコール0.005~5重量部および亜鉛化合物0.01~5重量部を添加するポリ塩化ビニル樹脂組成物の製造方法。
- 前記ポリビニルアルコールが、粘度平均重合度が500以上異なる2種類以上のポリビニルアルコールをブレンドしてなる、請求項6記載のポリ塩化ビニル樹脂組成物の製造方法。
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US13/123,386 US8288465B2 (en) | 2008-10-08 | 2009-10-05 | Polyvinyl chloride resin compositions and manufacturing method therefor |
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US9751968B2 (en) | 2013-09-13 | 2017-09-05 | Kuraray Co., Ltd. | Vinyl alcohol polymer, thickening agent, stabilizer for emulsion polymerization, stabilizer for suspension polymerization, coating agent, coated article, sizing agent for fibers, sized yarn, and production method of textile |
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EP3848174B1 (en) * | 2018-09-07 | 2023-10-25 | Kuraray Co., Ltd. | Poly(vinyl alcohol) mold release film for artificial marble molding use, and method for producing artificial marble using same |
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JP5480150B2 (ja) | 2014-04-23 |
CN102245700B (zh) | 2013-11-20 |
EP2348070A4 (en) | 2012-03-21 |
ES2424458T3 (es) | 2013-10-02 |
EP2348070A1 (en) | 2011-07-27 |
TW201026767A (en) | 2010-07-16 |
KR101596685B1 (ko) | 2016-02-23 |
TWI466936B (zh) | 2015-01-01 |
US20110201737A1 (en) | 2011-08-18 |
KR20110079712A (ko) | 2011-07-07 |
JPWO2010041620A1 (ja) | 2012-03-08 |
CN102245700A (zh) | 2011-11-16 |
EP2348070B1 (en) | 2013-06-26 |
US8288465B2 (en) | 2012-10-16 |
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