WO2012023408A1 - 塩化ビニル系樹脂組成物 - Google Patents
塩化ビニル系樹脂組成物 Download PDFInfo
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- WO2012023408A1 WO2012023408A1 PCT/JP2011/067412 JP2011067412W WO2012023408A1 WO 2012023408 A1 WO2012023408 A1 WO 2012023408A1 JP 2011067412 W JP2011067412 W JP 2011067412W WO 2012023408 A1 WO2012023408 A1 WO 2012023408A1
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- vinyl chloride
- chloride resin
- resin composition
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
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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
- C08K5/09—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Definitions
- the present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition having excellent resistance to warm water whitening.
- Chlorine-containing resins such as vinyl chloride resins are excellent in flame resistance and chemical resistance, and are used for various applications.
- chlorine-containing resins have the disadvantage that they are thermally decomposed to cause dehydrochlorination, resulting in a decrease in mechanical strength and coloration, thereby impairing commercial properties.
- Patent Document 1 discloses that a hard or semi-hard chlorine-containing polymer in which foaming during processing is suppressed by combining magnesium hydroxide and a zinc hydrotalcite compound is disclosed.
- the vinyl chloride resin composition has a problem of so-called warm water whitening in which turbidity occurs after being immersed in warm water, and transparency that should be originally maintained is impaired.
- the combination of the agents was insufficient in improving the hot water whitening resistance.
- a hard vinyl chloride resin that uses little or no plasticizer has a problem in hot water whitening resistance.
- Patent Document 1 does not describe at all the use of a zinc hydrotalcite compound and a specific processing aid in combination and improvement of resistance to warm water whitening.
- an object of the present invention is to provide a vinyl chloride resin composition having improved resistance to warm water whitening.
- the vinyl chloride resin composition of the present invention comprises (a) 0.01 to 10 parts by mass of zinc-modified hydrotalcite and (b) a weight average molecular weight of 200,000 to 7 million with respect to 100 parts by mass of the vinyl chloride resin.
- the acrylic processing aid is contained in an amount of 0.01 to 10 parts by mass.
- the (a) zinc-modified hydrotalcite is preferably a compound represented by the following general formula (I).
- x1 and x2 each represent a number satisfying the condition represented by the following formula, and m represents a real number.
- the refractive index of the (a) zinc-modified hydrotalcite is preferably 1.52 to 1.56.
- the weight average molecular weight of the (b) acrylic processing aid is preferably 200,000 to 2,000,000.
- the vinyl chloride resin composition of the present invention preferably contains 0 to 10 parts by mass of a plasticizer component with respect to 100 parts by mass of the vinyl chloride resin.
- the vinyl chloride resin composition of the present invention has excellent hot water whitening resistance, and can be suitably used for applications such as films, bottles, trays, plates, packages, pipes, and sheets.
- the vinyl chloride resin composition of the present invention comprises (a) 0.01 to 10 parts by mass of zinc-modified hydrotalcite and (b) an acrylic having a weight average molecular weight of 200,000 to 7 million with respect to 100 parts by mass of the vinyl chloride resin. It contains 0.01 to 10 parts by mass of a system processing aid.
- the vinyl chloride resin used in the present invention is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
- the zinc-modified hydrotalcite which is the component (a) used in the present invention is a carbonate and double carbonate compound of zinc and aluminum, preferably a compound represented by the following general formula (I). Also, a zinc-modified hydrotalcite having a refractive index of 1.52 to 1.56 is preferable because a vinyl chloride resin composition having excellent transparency can be obtained.
- the refractive index can be measured according to JIS K0062.
- the zinc-modified hydrotalcite has a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate, and a higher fatty acid amide.
- a higher fatty acid such as stearic acid
- a higher fatty acid metal salt such as an alkali metal oleate
- an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate
- Those coated with higher fatty acid esters or waxes can also be used.
- the amount of the zinc-modified hydrotalcite added is 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Part.
- the acrylic processing aid as component (b) used in the present invention is a polymer or copolymer composed of acrylic acid and its ester, methacrylic acid and its ester, and is a resin such as vinyl chloride resin.
- the weight average molecular weight of the acrylic processing aid according to the present invention is 200,000 to 7,000,000, and preferably 200,000 to 2,000,000 because foaming of the molded product is reduced.
- Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and the like.
- Examples of the methacrylate ester include methyl methacrylate, Examples thereof include ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and cyclohexyl methacrylate. Of these, methyl methacrylate and butyl methacrylate are preferred.
- the acrylic processing aid may be a single polymer or a copolymer of two or more of the above acrylic acid and its ester, or methacrylic acid and its ester.
- acrylic processing aids include, for example, Metablene P type manufactured by Mitsubishi Rayon, Kaneace PA series manufactured by Kaneka Chemical Industry (Kaneka), Paraloid K series manufactured by Rohm and Haas, and the like.
- Specific examples of acrylic processing aids having a weight average molecular weight of 200,000 to 2,000,000 include Metablene P-570A, Metabrene P-551A manufactured by Mitsubishi Rayon, Kaneace PA-10 manufactured by Kaneka Chemical Industry (Kaneka), and the like. Can be mentioned.
- These acrylic processing aids having a weight average molecular weight of 200,000 to 2,000,000 are preferable because they can be used for vinyl chloride resins to obtain molded products with small foaming and excellent color resistance.
- the amount of the acrylic processing aid added is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
- the vinyl chloride resin composition of the present invention includes other additives usually used in vinyl chloride resin compositions such as plasticizers, organic acid metal salts, zeolite compounds, ⁇ -diketone compounds, perchloric acid. Salts, epoxy compounds, polyhydric alcohols, phosphorus-based, phenol-based and sulfur-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, fillers, lubricants, and the like can be added.
- plasticizer examples include phthalate plasticizers such as dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; dioctyl adipate, diisononyl adipate, Adipate plasticizers such as diisodecyl adipate and di (butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri ( Butoxyethyl) phosphate, octyl diphen
- Sulfate plasticizer polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5 -Hexanediol, 1,6-hexanediol, neopentyl glycol, etc.
- dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, Polyester plasticizer using isophthalic acid, terephthalic acid, etc., and monohydric alcohol or monocarboxylic acid as a stopper if necessary; tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, Stearic acid plasticizer, citric acid Plasticizers, trimellitic acid plasticizers, pyromellitic acid plasticizers biphenyltetracarboxylic acid ester plasticizer, and a chlorinated plasticizer.
- the amount of the plasticizer to be used is appropriately adjusted according to the application, but it is a so-called hard vinyl chloride resin composition that is 0 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. This is preferable because the effect is more exhibited.
- organic acid metal salt examples include metal (sodium, potassium, calcium, barium, aluminum, zinc) salts of organic carboxylic acids, phenols and organic phosphoric acids.
- organic carboxylic acid examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid, lauric acid, and tridecanoic acid.
- phenols examples include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2 -Ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofuxylphenol, methyltertiaryoctylphenol and the like.
- organic phosphoric acids examples include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, and phosphonic acid stearyl ester. Etc.
- the metal salts of the above organic carboxylic acids, phenols, and organic phosphoric acids are acidic, neutral salts, basic salts, or overbased complexes obtained by neutralizing a part or all of basic salt bases with carbonic acid. It may be.
- the zeolite compound is an aluminosilicate of alkali metal or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and representative examples thereof include A-type, X-type, Y-type and P-type zeolite, monodenite, Analite, sodalite group aluminosilicate, clinobutyrolite, erionite, and chabazite can be mentioned, and water-containing substances having crystal water (so-called zeolite water) of these zeolite compounds or anhydrous water from which crystal water has been removed Any of those may be used, and those having a particle size of 0.1 to 50 ⁇ m can be used, and those having a particle size of 0.5 to 10 ⁇ m are particularly preferable.
- ⁇ -diketone compound examples include dehydroacetic acid, dibenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, and the like, and metal salts thereof are also useful.
- perchlorates include metal perchlorate, ammonium perchlorate, perchloric acid-treated hydrotalcite, and perchloric acid-treated silicate.
- metal constituting the metal salt include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum.
- the perchloric acid metal salt may be an anhydride or a hydrated salt, and may be one dissolved in an alcohol or ester solvent such as butyl diglycol or butyl diglycol adipate or a dehydrate thereof.
- epoxy compound examples include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil.
- polyhydric alcohol examples include pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or stearic acid partial ester of dipentaerythritol, bis (dipentaerythritol) adipate,
- examples include glycerin, diglycerin, and tris (2-hydroxyethyl) isocyanurate.
- Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono-, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tri
- phenolic antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide] 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6) Tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-ter
- sulfur-based antioxidant examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and ⁇ -alkyl mercapto of polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate).
- dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl
- ⁇ -alkyl mercapto of polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate).
- propionic acid esters examples include propionic acid esters.
- 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 (2-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5 Chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole 2- (2'-hydroxy-3'.5'-dicumylphenyl) 2- (2'-) such as benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybut
- hindered amine light stabilizer examples 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, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-ditert-butyl-4- Hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl) 4-piperidyl) -2-butyl-2- (3,5-ditert-butyl)
- filler examples include calcium carbonate, silica, clay, glass beads, mica, sericite, glass flake, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonotlite, MOS, phosphate fiber, and glass fiber. , Carbonate fiber, aramid fiber and the like.
- the lubricant examples include hydrocarbons such as natural paraffin and low molecular weight polyethylene, fatty acids such as stearic acid, lauric acid, and erucic acid, aliphatic alcohols such as cetyl alcohol and stearyl alcohol, stearic acid amide, and methylene bis.
- hydrocarbons such as natural paraffin and low molecular weight polyethylene
- fatty acids such as stearic acid, lauric acid, and erucic acid
- aliphatic alcohols such as cetyl alcohol and stearyl alcohol
- stearic acid amide examples include fatty acid amides such as stearamide, lower alcohol esters of fatty acids such as butyl stearate, higher alcohol esters of higher fatty acids such as glycerol monostearate, and the like.
- the vinyl chloride resin composition of the present invention includes additives that are usually used in vinyl chloride resins as necessary, for example, crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents, surface treatments.
- additives for example, crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents, surface treatments.
- Agents, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, mold release agents, processing aids, and the like can be blended.
- the vinyl chloride resin composition of the present invention can be processed by a conventionally known vinyl chloride resin processing method, for example, calendar processing, roll processing, extrusion processing, melt rolling method, injection molding. It can be suitably processed and molded by processing, pressure molding processing, paste processing, powder molding processing, foam molding processing and the like.
- the vinyl chloride resin composition of the present invention can be suitably used for applications such as films, bottles, trays, plates, packages, pipes and sheets.
- building materials such as wall materials, floor materials, window frames, wall materials, corrugated plates, gutters; automotive interior and exterior materials; fish food packaging materials; used as miscellaneous goods such as packing, gaskets, hoses, joints, toys be able to.
- Examples 1-1 to 1-4, Comparative Examples 1-1 to 1-3 The compound shown in the following compounding example 1 was blended with a 10 L Henschel mixer, and a twin-screw extruder (cylinder 1: 160 ° C., cylinder 2: 170 ° C., cylinder 3: 180 ° C., die: 190 ° C., screw rotation speed: 15 rpm) ) To prepare a sheet-like sample. (transparency) The sheet-like sample obtained above was pressed at 190 ° C. for 5 minutes to produce a 0.5 mm-thick press plate, and the haze value (transparency) was measured with a haze meter.
- Zinc-modified hydrotalcite compositional formula: Mg 3.5 Zn 1 Al 2 (OH) 12 ⁇ CO 3 ⁇ 3H 2 O), refractive index: 1.54 * 2: Hydrotalcite (compositional formula: Mg 4.5 Al 2 (OH) 12 ⁇ CO 3 ⁇ 3H 2 O), refractive index: 1.50 * 3: Metablen P-570A (Mitsubishi Rayon Co., Ltd., weight average molecular weight 260,000) * 4: Metablen P-551A (Mitsubishi Rayon Co., Ltd., weight average molecular weight 1.46 million) * 5: Kane Ace PA-40 (manufactured by Kaneka Corporation, weight average molecular weight 5 million) * 6: Paraloid K-130 (Rohm and Haas, weight average molecular weight 3.1 million) * 7: Kane Ace PA-60 (manufactured by Kaneka Corporation, weight average molecular weight 8 million)
- Examples 2-1 to 2-8, Comparative examples 2-1 to 2-2 The blend shown in the following blending example 2 was blended with a 10 L Henschel mixer, and a twin-screw extruder (cylinder 1: 160 ° C., cylinder 2: 170 ° C., cylinder 3: 180 ° C., die: 190 ° C., screw rotation speed: 15 rpm) ) To prepare a sheet-like sample. (Initial coloring) The yellowness (YI) of the sheet-like sample obtained above was measured with a color difference meter (TC-8600A manufactured by Tokyo Denshoku).
- a combination of zinc-modified hydrotalcite and an acrylic processing aid having a weight average molecular weight of 200,000 to 7 million can provide a material having excellent transparency and resistance to hot water whitening.
- an acrylic processing aid having a weight average molecular weight of 200 to 2,000,000 it is possible to improve the extrusion productivity with excellent initial colorability, excellent gloss, and less foaming during processing.
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Abstract
Description
なお、特許文献1には、亜鉛ハイドロタルサイト化合物と特定の加工助剤とを併用する事、および、耐温水白化性の改善に関しては全く記載されていない。
Mgx1Znx2Al2(OH)2(X1+X2)+4・CO3・mH2O (I)
(式中、x1およびx2は各々下記式で表される条件を満たす数を示し、mは実数を示す。0.1≦x2/x1<10,2≦x1+x2<20)
(式中、x1およびx2は各々下記式で表される条件を満たす数を示し、mは実数を示す。0.1≦x2/x1<10,2≦x1+x2<20)
上記アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸n-ブチル、アクリル酸イソブチル、アクリル酸2-エチルヘキシル、アクリル酸シクロヘキシル等が挙げられ、上記メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-ブチル、メタクリル酸イソブチル、メタクリル酸2-エチルヘキシル、メタクリル酸シクロヘキシル等が挙げられる。これらのうち、メタクリル酸メチル、メタクリル酸ブチルが好ましい。アクリル系加工助剤は、上記のアクリル酸およびそのエステルや、メタクリル酸およびそのエステルそれぞれの単独の重合体であっても2種以上の共重合体であってもよい。上記アクリル系加工助剤の市販品としては、例えば、三菱レイヨン製のメタブレンPタイプ、鐘淵化学工業(カネカ)製カネエースPAシリーズ、ローム・アンド・ハース社製パラロイドKシリーズ等が挙げられ、特に、重量平均分子量が20万~200万のアクリル系加工助剤の具体例としては、三菱レイヨン製のメタブレンP-570A、メタブレンP-551A、鐘淵化学工業(カネカ)製カネエースPA-10等が挙げられる。これら重量平均分子量が20万~200万のアクリル系加工助剤は、塩化ビニル系樹脂に使用することによって、発泡が小さく耐着色性に優れた成形品が得られるため好ましい。
ここで金属塩を構成する金属としては、リチウム、ナトリウム、カリウム、カルシウム、マグネシウム、ストロンチウム、バリウム、亜鉛、カドミウム、鉛、アルミニウムなどが例示できる。上記過塩素酸金属塩は、無水物でも含水塩でもよく、また、ブチルジグリコール、ブチルジグリコールアジペート等のアルコール系およびエステル系の溶剤に溶かしたものおよびその脱水物でもよい。
下記配合例1に示した配合物を10Lヘンシェルミキサーでブレンドし、二軸押出成型機(シリンダー1:160℃、シリンダー2:170℃、シリンダー3:180℃、ダイ:190℃、スクリュー回転数15rpm)でシート状サンプルを作成した。
(透明性)
上記で得られたシート状サンプルを190℃で5分間プレス加工し、0.5mm厚のプレス板を作成し、ヘーズメーターでヘーズ値(透明性)を測定した。
(耐温水白化性)
該プレス板を85℃の温水に30分間浸漬した後、室温で3日間乾燥し、再度透明性を測定した。温水浸漬前後のヘーズ値の差(ΔHaze)を算出し耐温水白化性を評価した。得られた結果を下記表1に示す。
塩化ビニル樹脂(新第一塩ビ(株)製ZEST1000Z、重合度1050) 100
LoxiolG-72(エメリー社製滑剤) 0.5
テトラキス〔メチレン-3-(3,5-ジ第三ブチル- 0.1
4-ヒドロキシフェニル)プロピオネート〕メタン
ラウリン酸亜鉛 0.3
ステアロイルベンゾイルメタン 0.5
試験化合物 表1に記載
*2:ハイドロタルサイト(組成式:Mg4.5Al2(OH)12・CO3・3H2O)、屈折率:1.50
*3:メタブレンP-570A(三菱レイヨン株式会社製、重量平均分子量26万)
*4:メタブレンP-551A(三菱レイヨン株式会社製、重量平均分子量146万)
*5:カネエースPA-40(株式会社カネカ製、重量平均分子量500万)
*6:パラロイドK-130(ローム・アンド・ハース社製、重量平均分子量310万)
*7:カネエースPA-60(株式会社カネカ製、重量平均分子量800万)
下記配合例2に示した配合物を10Lヘンシェルミキサーでブレンドし、二軸押出成型機(シリンダー1:160℃、シリンダー2:170℃、シリンダー3:180℃、ダイ:190℃、スクリュー回転数15rpm)でシート状サンプルを作成した。
(初期着色)
上記で得られたシート状サンプルの黄色度(Y.I.)を、色差計(東京電色製TC-8600A)で測定した。
(グロス)
また、該シート状サンプルの光沢度(グロス)をグロスメーター(測定角度60℃)で測定した。
(透明性)
また、該シート状サンプルを190℃で5分間プレス加工し、1mm厚プレス板を作成し、目視により透明性を評価した。評価基準は、◎:非常にクリア、○:にごりがほとんど見られない、△:にごりが見られる、×:にごりが大きい、とした。
(発泡)
また、目視にて該プレス板の発泡の有無を評価した。
(押出機負荷)
また、押出成型時のトルクから押出機への負荷を評価した。加工助剤未添加(比較例2-1)を負荷小とし、小から大に分類した。さらに、押出成型時、1分間にダイスから出てくる樹脂量(g/min)を測定した。
得られた結果を下記表2に示す。
塩化ビニル樹脂(新第一塩ビ(株)製ZEST1000Z、重合度1050) 100
エポキシ化大豆油 1
ジステアリルペンタエリスリトールジホスファイト 0.25
トリス(2ーヒドロキシエチル)イソシアヌレート 0.5
テトラキス〔メチレン-3-(3,5-ジ第三ブチル- 0.1
4-ヒドロキシフェニル)プロピオネート〕メタン
ラウリン酸亜鉛 0.3
ステアロイルベンゾイルメタン 0.5
LoxiolG-60(エメリー社製滑剤) 1.0
試験化合物 表2に記載
*4:メタブレンP-551A(三菱レイヨン株式会社製、重量平均分子量146万)
*8:カネエースPA-10(株式会社カネカ製、重量平均分子量80万)
*9:メタブレンP-530A(三菱レイヨン株式会社製、重量平均分子量310万)
Claims (5)
- 塩化ビニル系樹脂100質量部に対し、(a)亜鉛変性ハイドロタルサイト0.01~10質量部及び(b)重量平均分子量20万~700万のアクリル系加工助剤0.01~10質量部を含有することを特徴とする塩化ビニル系樹脂組成物。
- 前記(a)亜鉛変性ハイドロタルサイトが下記一般式(I)で表される化合物である請求項1記載の塩化ビニル系樹脂組成物。
Mgx1Znx2Al2(OH)2(X1+X2)+4・CO3・mH2O(I)
(式中、x1およびx2は各々下記式で表される条件を満たす数を示し、mは実数を示す。0.1≦x2/x1<10,2≦x1+x2<20) - 前記(a)亜鉛変性ハイドロタルサイトの屈折率が1.52~1.56である請求項1記載の塩化ビニル系樹脂組成物。
- 前記(b)アクリル系加工助剤の重量平均分子量が20万~200万である請求項1記載の塩化ビニル系樹脂組成物。
- 前記塩化ビニル系樹脂100質量部に対し、可塑剤成分を0~10質量部含有する請求項1記載の塩化ビニル系樹脂組成物。
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EP11818051.2A EP2607423B1 (en) | 2010-08-20 | 2011-07-29 | Vinyl chloride resin composition |
US13/817,663 US9187615B2 (en) | 2010-08-20 | 2011-07-29 | Vinyl chloride resin composition |
KR1020187003369A KR20180016626A (ko) | 2010-08-20 | 2011-07-29 | 염화 비닐계 수지 조성물 |
KR1020137007062A KR20130106824A (ko) | 2010-08-20 | 2011-07-29 | 염화 비닐계 수지 조성물 |
CN201180039760.8A CN103068902B (zh) | 2010-08-20 | 2011-07-29 | 氯乙烯系树脂组合物 |
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CN105295271B (zh) * | 2014-06-11 | 2017-08-25 | 中国石油化工股份有限公司 | 一种耐热高透明cpvc组合物 |
KR102006716B1 (ko) * | 2015-09-16 | 2019-08-02 | 주식회사 엘지화학 | 아크릴계 가공조제 및 이를 포함하는 염화비닐계 수지 조성물 |
TWI753895B (zh) * | 2016-04-20 | 2022-02-01 | 美商羅門哈斯公司 | 用於製備定向聚氯乙烯的方法 |
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Also Published As
Publication number | Publication date |
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CN103068902A (zh) | 2013-04-24 |
JP5709246B2 (ja) | 2015-04-30 |
US20130150513A1 (en) | 2013-06-13 |
EP2607423B1 (en) | 2016-07-20 |
EP2607423A4 (en) | 2014-11-05 |
KR20180016626A (ko) | 2018-02-14 |
KR20130106824A (ko) | 2013-09-30 |
US9187615B2 (en) | 2015-11-17 |
CN103068902B (zh) | 2015-08-05 |
JP2012041484A (ja) | 2012-03-01 |
EP2607423A1 (en) | 2013-06-26 |
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