WO2009154178A1 - 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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- WO2009154178A1 WO2009154178A1 PCT/JP2009/060894 JP2009060894W WO2009154178A1 WO 2009154178 A1 WO2009154178 A1 WO 2009154178A1 JP 2009060894 W JP2009060894 W JP 2009060894W WO 2009154178 A1 WO2009154178 A1 WO 2009154178A1
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—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
- 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 more specifically, a polyvinyl chloride resin composition having good thermal stability and little coloring. It is about.
- Polyvinyl chloride resin is molded by blending calcium-zinc and barium-zinc stabilizers, and the molded products are widely used for general use, and for food and medical use. ing.
- Patent Document 1 Japanese Patent Laid-Open No. 50-92947 discloses a method of adding calcium soap, zinc soap, polyhydric alcohol or a derivative thereof, and a neutral inorganic calcium salt to a chlorine-containing resin. ing.
- 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. Has been.
- Patent Document 5 Japanese Patent Application Laid-Open No. 1-178543 discloses a halogen-containing thermoplastic resin, a metal soap, and a copolymer having an 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 having a composition 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 alcohol having a saponification degree of 70 to 95 mol%, an average polymerization degree of 300 to 2000, and a mercapto group at the molecular chain terminal. A method of adding is disclosed.
- Patent Document 8 Japanese Patent Laid-Open No. 9-31281 discloses a method of adding a zinc compound, hydrotalcites, polyvinyl alcohol, and polymethyl methacrylate to a vinyl chloride resin.
- Non-Patent Document 1 (Polymer Collection Vol. 47, No. 3, 197 (1990)) includes polyvinyl chloride, zinc stearate-calcium stearate composite soap, and fully saponified polyvinyl alcohol having a polymerization degree of 600 or more. A method of adding is disclosed.
- Non-Patent Document 4 Polymers & Polymer Compositions, Vol. 11, 649 (2003)), polyvinyl chloride, a zinc stearate-calcium stearate composite soap, a polyvinyl alcohol having a polymerization degree of 500 and a saponification degree of 98.5 mol%, and an ethylene content of 29 mol% or more.
- a method for adding an ethylene-vinyl alcohol copolymer is disclosed.
- Non-Patent Document 5 Journal of the Adhesion Society of Japan Vol.43 No. 2, 43 (2007), polyvinyl chloride having a polymerization degree of 500 and a saponification degree of 88 mol%, a polyvinyl alcohol having a polymerization degree of 1700, a saponification degree of 78 mol% or more, and polymethyl methacrylate. A method of adding is disclosed.
- An object of the present invention is to provide a vinyl chloride resin composition that is excellent in thermal stability at the time of molding and can obtain a molded product with less coloring.
- a vinyl alcohol polymer (hereinafter referred to as PVA) having a saponification degree of 75 to 99.9 mol% and a viscosity average polymerization degree of 450 or less with respect to the polyvinyl chloride resin. )
- PVA vinyl alcohol polymer
- a stabilizer composed of a zinc compound is added to the polyvinyl chloride resin composition, the thermal stability during molding can be sufficiently retained, and the molded body is less colored. As a result, the present invention has been completed.
- the above problem is that 0.005 to 5 wt.% Of a vinyl alcohol polymer having a saponification degree of 75 to 99.9 mol% and a viscosity average polymerization degree of 450 or less with respect to 100 parts by weight of the polyvinyl chloride resin. And a polyvinyl chloride resin composition containing 0.01 to 5 parts by weight of a zinc compound.
- the vinyl alcohol polymer is a polymer obtained by polymerizing a vinyl ester monomer alone.
- the lubricant is preferably a fatty acid ester of polyol, and particularly preferably glycerin monostearate.
- the above problem is that 0.005 to 5 parts by weight of a vinyl alcohol polymer having a saponification degree of 75 to 99.9 mol% and a viscosity average polymerization degree of 450 or less with respect to 100 parts by weight of the polyvinyl chloride resin.
- a method for producing a polyvinyl chloride resin composition in which 0.01 to 5 parts by weight of a zinc compound is added to the polyvinyl chloride resin. At this time, it is preferable to add 0.001 to 10 parts by weight of a lubricant with respect to 100 parts by weight of the polyvinyl chloride resin.
- a vinyl chloride monomer as a main component and a mixture thereof with a copolymerizable monomer (single vinyl chloride)
- the body is 50% by weight or more.
- monomers copolymerized with this vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters or methacrylic esters such as methyl acrylate and ethyl acrylate, ethylene, Examples include olefins such as propylene, maleic anhydride, acrylonitrile, styrene, and vinylidene chloride.
- a method for producing the polyvinyl chloride resin using these monomers a method of suspension polymerization of the monomers in the presence of a polymerization initiator can be suitably employed.
- dispersion stabilizers for example, water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, water-soluble polymers such as polyvinyl alcohol, gelatin; sorbitan monolaurate, sorbitan trio.
- Oil-soluble emulsifiers such as rate, glycerin tristearate, ethylene oxide propylene oxide block copolymer; water-soluble emulsification such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, sodium laurate Among them, polyvinyl alcohol having a saponification degree of 65 to 99 mol% and a polymerization degree of 500 to 4000 is preferably used, and the addition amount is 0.01 to 2.0 parts by weight per 100 parts by weight of vinyl chloride. preferable.
- 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.
- the polymerization temperature is not particularly limited, and can be adjusted to a high temperature exceeding 90 ° C. as well as a low temperature of about 20 ° C.
- additives such as preservatives, antifungal agents, anti-blocking agents, antifoaming agents, anti-scale agents, antistatic agents and the like that are usually used for polymerization can be optionally added as necessary.
- the PVA contained in the polyvinyl chloride resin composition of the present invention can be contained, for example, by polymerizing a polyvinyl chloride resin and then adding it to the polyvinyl chloride resin.
- the PVA can be added to the polyvinyl chloride resin as a powder or dissolved in water or an organic solvent. If the PVA is added during polymerization of the polyvinyl chloride resin, since the PVA acts as a dispersant for the polyvinyl chloride resin, the resulting polyvinyl chloride resin has an adverse effect on the quality such as the average particle diameter and plasticizer absorbability. Sometimes.
- the degree of saponification of PVA added to the polyvinyl chloride resin is 75 to 99.9 mol%, preferably 78 to 98.5 mol%, particularly preferably 80 to 96 mol%. When the degree of saponification is less than 75 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 PVA has a viscosity average degree of polymerization (hereinafter sometimes simply referred to as a degree of polymerization) of 450 or less, preferably 430 or less, and particularly preferably 410 or less.
- a degree of polymerization a viscosity average degree of polymerization
- 50 or more are preferable and 100 or more are more preferable.
- a viscosity average degree of polymerization of greater than 450 is not preferred because long-term thermal stability is significantly reduced.
- the viscosity average degree of polymerization of PVA is a value measured according to JIS K6726.
- the vinyl ester monomer When the vinyl ester monomer is polymerized, the vinyl ester monomer may be copolymerized with other monomers as long as the gist of the present invention is not impaired. It is preferable to polymerize alone.
- 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, benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone, cyclohexanone; mercaptans such as 2-hydroxyethanethiol; thiocarboxylic acids such as thioacetic acid; trichloroethylene And halogenated hydrocarbons such as perchlorethylene, among which aldehydes and ketones are preferably used.
- the saponification reaction of vinyl ester polymers alcoholysis or hydrolysis using conventionally known basic catalysts such as sodium hydroxide, potassium hydroxide and sodium methoxide, or acidic catalysts such as p-toluenesulfonic acid.
- Decomposition reaction can be applied.
- 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 is not sufficient, and if it exceeds 5 parts by weight, the polyvinyl chloride resin is unfavorably colored.
- the PVA used in the present invention When the PVA used in the present invention is added during polymerization of the polyvinyl chloride resin, the PVA is almost removed by washing the resin after the production of the polyvinyl chloride resin, so the PVA content in the polyvinyl chloride resin composition
- the amount is less than 0.005 parts by weight, and the effect as a heat aid is not obtained.
- PVA may contain an acid having a pKa of 3.5 to 5.5 at 25 ° C. and / or a metal salt thereof.
- an acid having a pKa of 3.5 to 5.5 at 25 ° C. and / or a metal salt thereof there are no particular limitations on the type of acid, and specific examples thereof include acetic acid (pKa4.76), propionic acid (pKa4.87), butyric acid ( ⁇ pKa4.63), octanoic acid (pKa4.89), and 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
- Acids that can be particularly preferably used are acetic acid, propionic acid and lactic acid.
- the metal salt of said acid can also be used.
- alkali metal salts such as sodium, potassium, magnesium, calcium, are used.
- the content of the 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. More preferably, it is 0.15 to 2 parts by weight. If 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 if it exceeds 5 parts by weight, the polyvinyl chloride resin may be colored.
- Examples of the zinc compound used in the present invention include zinc aliphatic carboxylates such as zinc stearate, zinc laurate and zinc oleate, and zinc aromatic carboxylates such as zinc benzoate and zinc p-tert-butylbenzoate. And zinc salts of organic acids such as amino acid zinc salts and phosphate zinc salts, and inorganic zinc salts such as zinc oxide and zinc carbonate.
- the amount of the zinc compound added is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.
- 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, A modifier, a reinforcing agent, a pigment, a foaming agent, a plasticizer, and the like can be used in combination.
- 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 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, glycerin monostearate, triethylene glycol di-2-ethylhexanoate; cetyl alcohol and Examples include alcohols such as stearyl alcohol.
- hydrocarbons such as liquid paraffin, natural paraffin, microwax and polyethylene wax
- fatty acids such as stearic acid and lauric acid
- the fatty acid ester of polyol when used, the effect of the present invention is further exhibited.
- it is preferable that it is a fatty acid monoester of a polyol, and it is also preferable that it is a fatty acid ester of glycerol.
- the fatty acid ester preferably has 8 to 22 carbon atoms, more preferably a stearic acid ester.
- glycerol monostearate is particularly preferable.
- the amount of the 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 soaps such as calcium soap and barium soap, aluminum soaps, organometallic salts such as organophosphate metal salts, metal oxidation Metal hydroxides, metal carbonates, inorganic metal salts such as inorganic composite metal salts such as zeolite, barium chlorate, barium perchlorate, halogen peroxyacid salts such as sodium perchlorate, ⁇ -diketone, polyvalent Non-metal stabilizers such as alcohol and epoxy compounds can be mentioned.
- plasticizer examples include acids such as 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-decanol Of straight-chain and branched alkyl alcohols such as isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, alone or as a mixture, or esters of
- 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-3 Benzoates such as 1,5-ditert-butyl-4-hydroxybenzoate, he
- 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, tetrates (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-hydroxyethyl
- 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 deionized water in an amount corresponding to 600 ppm with respect to vinyl chloride.
- 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
- Examples 2-7 PVA shown in Table 1 was obtained in the same manner as in Example 1 except that the weights of vinyl acetate and methanol were changed during polymerization and the alkali molar ratio was changed during saponification. The thermal stability and colorability were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
- Example 8 PVA shown in Table 1 was obtained in the same manner except that sodium acetate was additionally added to 100 parts by weight of PVA obtained in Example 1 so that the sodium acetate content was 2 parts by weight.
- the thermal stability and colorability were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
- Example 9 PVA shown in Table 1 was obtained in the same manner except that sodium acetate was additionally added so that the sodium acetate content was 5 parts by weight with respect to 100 parts by weight of PVA obtained in Example 1. The thermal stability and colorability were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
- Example 10 (Production of terminal SH-PVA) A 6 L reactor equipped with a stirrer, nitrogen inlet, additive inlet, and initiator inlet was charged with 2450 g of vinyl acetate and 1050 g of methanol, heated to 60 ° C., and then purged with nitrogen by nitrogen bubbling for 30 minutes. . A 5% concentration solution in which thioacetic acid was dissolved in methanol was prepared as a chain transfer agent, and nitrogen substitution was performed by bubbling with nitrogen gas. The temperature inside the reaction vessel was adjusted to 60 ° C., 9.6 g of the previously prepared methanol solution of thioacetic acid was added, and then 2.0 g of 2,2′-azobis (isobutyronitrile) was added to perform polymerization.
- 2,2′-azobis isobutyronitrile
- PVAc polyvinyl acetate
- the PVAc solution adjusted to 30% was saponified by adding NaOH methanol solution (10% concentration) so that the alkali molar ratio (number of moles of NaOH / number of moles of vinyl ester units in PVAc) was 0.01. The obtained PVA was washed with methanol.
- terminal SH-PVA having a polymerization degree of 400 and a saponification degree of 93 mol% was obtained.
- the sodium acetate content measured by isotachophoresis (isotacophoresis) was 0.5%.
- Comparative Examples 8 and 9 Thermal stability and colorability were evaluated in the same manner as in Example 1 except that the blending amount of zinc stearate was changed as shown in Table 1. The evaluation results are shown in Table 1. In either case, the thermal stability was insufficient and the sheet was colored.
- Comparative Examples 10-12 In this example, 0.5 part by weight of glycerin monostearate as a lubricant is added to 100 parts by weight of vinyl chloride resin.
- the formulations as shown in Table 1 were mixed in the same manner as in Example 1, and the thermal stability and colorability were evaluated. The evaluation results are shown in Table 1.
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Abstract
Description
& Polymer Composites, Vol.11, 649 (2003))には、ポリ塩化ビニルに、ステアリン酸亜鉛-ステアリン酸カルシウム複合石けん、重合度が500、けん化度が98.5モル%のポリビニルアルコールやエチレン含有量が29モル%以上のエチレン-ビニルアルコール共重合体を添加する方法が開示されている。
No.2,43(2007))には、ポリ塩化ビニルに、重合度が500、けん化度が88モル%のポリビニルアルコールや重合度が1700、けん化度が78モル%以上のポリビニルアルコール、ポリメタクリル酸メチルを添加する方法が開示されている。
P=([η]×1000/8.29)(1/0.62)
(ポリ塩化ビニル樹脂の製造)
重合度850、けん化度72モル%のポリビニルアルコールを塩化ビニルに対して600ppmに相当する量で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、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。
撹拌機、窒素導入口、添加剤導入口および開始剤添加口を備えた6L反応槽に酢酸ビニル2450g、メタノール1050gを仕込み、60℃に昇温した後30分間窒素バブリングにより系中を窒素置換した。連鎖移動剤として2-メルカプトエタノール(以下、2-MEと記載する)をメタノールに溶解した濃度20%溶液を調製し、窒素ガスによるバブリングを行って窒素置換した。上記の反応槽内温を60℃に調整し、2-ME0.2gを添加した後に、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)1.2gを加えて重合を開始した。重合中は重合温度を60℃に維持し、2-MEの20%メタノール溶液を5.0mL/hrで連続添加した。4時間後に重合率が60%に達したところで冷却して重合を停止した。次いで、減圧下にて未反応の酢酸ビニルを除去し、ポリ酢酸ビニル(PVAc)のメタノール溶液を得た。30%に調整したPVAc溶液にアルカリモル比(NaOHのモル数/PVAc中のビニルエステル単位のモル数)が0.01となるようにNaOHメタノール溶液(10%濃度)を添加してけん化した。得られたPVAはメタノールで洗浄した。以上の操作により重合度400、けん化度93モル%のPVAを得た。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0.5%であった。
ポリ塩化ビニル樹脂100重量部に対し、1%濃度のPVA水溶液を用いて表1に示す量になるように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。このポリ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。このシートを50×70mmにカットした。このシート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、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、以下の基準にしたがって判定した。
A:着色がほとんどない。
B:わずかに着色が認められる。
C:黄色である。
D:黄褐色である。
実施例1において、重合時に酢酸ビニルとメタノールの仕込み重量を変更し、けん化時にアルカリモル比を変更した以外は同様の方法で、表1に示すPVAを得た。実施例1と同様にして熱安定性、着色性の評価を行った。評価結果を表1に示す。
実施例1で得られたPVA100重量部に対して、酢酸ナトリウム含有量が2重量部になるように酢酸ナトリウムを追加で添加した以外は同様の方法で、表1に示すPVAを得た。実施例1と同様にして熱安定性、着色性の評価を行った。評価結果を表1に示す。
実施例1で得られたPVA100重量部に対して、酢酸ナトリウム含有量が5重量部になるように酢酸ナトリウムを追加で添加した以外は同様の方法で、表1に示すPVAを得た。実施例1と同様にして熱安定性、着色性の評価を行った。評価結果を表1に示す。
(末端SH化PVAの製造)
撹拌機、窒素導入口、添加剤導入口および開始剤添加口を備えた6L反応槽に酢酸ビニル2450g、メタノール1050gを仕込み、60℃に昇温した後30分間窒素バブリングにより系中を窒素置換した。連鎖移動剤としてチオ酢酸をメタノールに溶解した濃度5%溶液を調製し、窒素ガスによるバブリングを行って窒素置換した。上記の反応槽内温を60℃に調整し、先に調整したチオ酢酸のメタノール溶液9.6gを添加した後に、2,2’-アゾビス(イソブチロニトリル)2.0gを加えて重合を開始した。重合中は重合温度を60℃に維持し、チオ酢酸の5%メタノール溶液を23.2mL/hrで連続添加した。4時間後に重合率が60%に達したところで冷却して重合を停止した。次いで、減圧下にて未反応の酢酸ビニルを除去し、ポリ酢酸ビニル(PVAc)のメタノール溶液を得た。30%に調整したPVAc溶液にアルカリモル比(NaOHのモル数/PVAc中のビニルエステル単位のモル数)が0.01となるようにNaOHメタノール溶液(10%濃度)を添加してけん化した。得られたPVAはメタノールで洗浄した。以上の操作により重合度400、けん化度93モル%の末端SH化PVAを得た。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0.5%であった。この変性PVAを重水に溶解し、核磁気共鳴分析を行ったところ、分子の片末端にSH基が存在していることが確認された。
滑剤としてグリセリンモノステアレートを、塩化ビニル樹脂100重量部に対して0.5重量部添加した例である。表1に示すような処方で実施例1と同様に混合して、熱安定性、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、重合時に酢酸ビニルとメタノールの仕込み重量を変更し、けん化時にアルカリモル比を変更した以外は同様の方法で、表1に示すPVAを得た。実施例1と同様にして熱安定性、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十分でなかった。けん化度が70モル%と低い比較例4では、黄色に着色した。
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と同様の方法で、熱安定性、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色に着色し、少なすぎる場合は長期の熱安定性が十分でなかった。
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と同様にして熱安定性、着色性の評価を行った。評価結果を表1に示す。熱安定性が十分ではなかった。
ステアリン酸亜鉛の配合量を表1に示すように変更した以外は実施例1と同様にして、熱安定性、着色性の評価を行った。評価結果を表1に示す。いずれも熱安定性が不十分であり、シートが着色した。
滑剤としてグリセリンモノステアレートを、塩化ビニル樹脂100重量部に対して0.5重量部添加した例である。表1に示すような処方で実施例1と同様に混合して、熱安定性、着色性の評価を行った。評価結果を表1に示す。
Claims (8)
- ポリ塩化ビニル樹脂100重量部に対して、けん化度が75~99.9モル%であり粘度平均重合度が450以下であるビニルアルコール系重合体を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。
- ビニルアルコール系重合体および亜鉛化合物を、ポリ塩化ビニル樹脂に添加することによって含有させた請求項1に記載のポリ塩化ビニル樹脂組成物。
- ビニルアルコール系重合体が、ビニルエステル系単量体を単独で重合したものである請求項1に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重量部に対して滑剤を0.001~10重量部含有する、請求項1~3のいずれか1項に記載のポリ塩化ビニル樹脂組成物。
- 滑剤がポリオールの脂肪酸エステルである、請求項4に記載のポリ塩化ビニル樹脂組成物。
- ポリオールの脂肪酸エステルがグリセリンモノステアレートである、請求項5に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、けん化度が75~99.9モル%であり粘度平均重合度が450以下であるビニルアルコール系重合体0.005~5重量部、および亜鉛化合物0.01~5重量部をポリ塩化ビニル樹脂に添加するポリ塩化ビニル樹脂組成物の製造方法。
- ポリ塩化ビニル樹脂100重量部に対して滑剤0.001~10重量部を添加する、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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JP2011219546A (ja) * | 2010-04-06 | 2011-11-04 | Kuraray Co Ltd | ポリ塩化ビニル樹脂組成物およびその製造方法 |
JP2011246555A (ja) * | 2010-05-25 | 2011-12-08 | Kuraray Co Ltd | ポリ塩化ビニル樹脂組成物およびその製造方法 |
US9163138B2 (en) * | 2011-09-22 | 2015-10-20 | Kuraray Co., Ltd. | Halogen-containing resin composition, production process therefor and molded article therefrom |
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US8288465B2 (en) * | 2008-10-08 | 2012-10-16 | Kuraray Co., Ltd. | Polyvinyl chloride resin compositions and manufacturing method therefor |
TWI586742B (zh) * | 2011-09-28 | 2017-06-11 | 可樂麗股份有限公司 | 含有鹵原子之樹脂組成物、其製造方法及包含其之成形品 |
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