WO2014141608A1 - 透明製品用塩化ビニル系樹脂組成物 - Google Patents
透明製品用塩化ビニル系樹脂組成物 Download PDFInfo
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- WO2014141608A1 WO2014141608A1 PCT/JP2014/001056 JP2014001056W WO2014141608A1 WO 2014141608 A1 WO2014141608 A1 WO 2014141608A1 JP 2014001056 W JP2014001056 W JP 2014001056W WO 2014141608 A1 WO2014141608 A1 WO 2014141608A1
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- vinyl chloride
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
- 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
- C08K2003/267—Magnesium carbonate
Definitions
- the present invention relates to a vinyl chloride resin composition suitable for transparent product applications, and particularly to a vinyl chloride resin composition for transparent products that does not require the use of a heavy metal stabilizer containing a heavy metal such as tin.
- vinyl chloride resin can easily adjust the hardness by adding a plasticizer, it can be used for various applications.
- a hard vinyl chloride resin composition containing no plasticizer or a semi-rigid vinyl chloride resin composition containing a small amount of plasticizer is widely used for building materials and the like because of its excellent rigidity. Therefore, in the case of a hard vinyl chloride resin composition containing no plasticizer or a semi-rigid vinyl chloride resin composition containing only a small amount of plasticizer, not only during processing exposed to high temperature and high pressure, but also as a molded product. Higher performance is also required in terms of thermal stability and weather resistance.
- hard transparent molded products obtained from rigid vinyl chloride resin compositions formulated for transparent molded products include a wide range of containers, industrial plates, decorative plates, films and sheets that require glass-like transparent products. Used in products.
- vinyl chloride resin has insufficient stability to light and heat, and has a drawback that it is liable to cause decomposition mainly due to dehydrohalogenation during thermoforming and product use. ing.
- various stabilizers such as metal salts of organic acids, organic tin compounds, organic phosphite compounds, epoxy compounds, ⁇ -diketone compounds, antioxidants and ultraviolet absorbers have been conventionally used. Attempts have been made to improve the stability of vinyl chloride-based resins by blending with.
- heavy metal stabilizers such as lead and cadmium have been used as the stabilizer from the viewpoint of cost advantage, etc.
- interest in environmental problems has increased, and toxicity and environment of heavy metals etc.
- barium-zinc composite stabilizers tend to be used.
- the environmental impact of barium has begun to be a concern, and further replacement with a low-toxicity calcium-zinc, magnesium-zinc or calcium-magnesium-zinc composite stabilizer is desired.
- Patent Document 1 organic acid calcium salt, organic acid zinc salt, basic phosphite and hydrotalcite compound
- Patent Document 2 organic acid alkaline earth metal salt, organic acid
- Patent Document 2 organic acid alkaline earth metal salt, organic acid
- Patent Document 3 a vinyl chloride-based foamable resin composition for foamed molded articles, to which an inorganic filler, a zinc compound, a zinc-modified hydrotalcite-based compound, and a pyrolytic organic foaming agent are added, and adipic acid
- Patent Document 4 a polyvinyl chloride resin composition for food packaging (Patent Document 4) containing an ester plasticizer, a calcium salt of an organic carboxylic acid, and a zinc-modified hydrotalcite compound.
- tin-based stabilizers have been proposed as stabilizers that can increase transparency (Patent Documents 5 and 6).
- tin is also not preferable from the viewpoint of environmental impact and toxicity.
- tin-based stabilizers are in a liquid state, when they are used, not only the lubricity of the molten resin during the molding process is lowered, but also the thermal deformation temperature (softening point) of the molded body is lowered. There was a problem.
- a stabilizer such as calcium-zinc, magnesium-zinc or calcium-magnesium-zinc
- the colorability often becomes a problem.
- a vinyl chloride resin composition that not only does not adversely affect the environment but also can provide a molded product excellent in coloring resistance and transparency has not been known yet.
- a first object of the present invention is to provide a vinyl chloride resin composition for transparent products that is excellent in transparency, thermal stability, and color resistance without using heavy metal stabilizers such as lead, tin, and barium. Is to provide.
- the second object of the present invention is to provide a transparent molded product obtained by molding a vinyl chloride resin composition that is not only highly transparent but also excellent in thermal stability, color resistance and environmental compatibility. There is.
- the present inventors have found that specific amounts of an organic acid zinc salt, a zinc-modified hydrotalcite compound, and a phosphite compound are contained in a vinyl chloride resin composition. It was found that good results can be obtained when it is contained in the present invention, and the present invention has been achieved.
- (C) At least one phosphite compound At least one phosphite compound.
- the organic acid zinc salt of the component (A) is preferably a salt of an organic carboxylic acid having 6 to 18 carbon atoms, and the component (C) is a phosphite having 12 to 32 carbon atoms. It is preferable that it is an acid ester compound.
- the component (B) is preferably a zinc-modified hydrotalcite compound represented by the following general formula (I), and particularly preferably does not contain an organotin compound; M y1 Zn y2 Al x (OH) 2 (CO 3 ) x / 2 ⁇ mH 2 O (I)
- M in the above formula represents magnesium or magnesium and calcium
- x, y1 and y2 are 0 ⁇ x ⁇ 0.5
- y1 + y2 1 ⁇ x, y1 ⁇ y2, 0.3 ⁇ y1 ⁇ , respectively.
- 1, a number satisfying the condition represented by the expression 0 ⁇ y2 ⁇ 0.5, m represents 0 or an arbitrary positive number.
- the vinyl chloride resin composition for transparent products of the present invention (hereinafter simply abbreviated as “resin composition of the present invention”) is excellent in transparency, thermal stability, and coloration resistance.
- a molded product obtained by molding the resin composition is also highly transparent, and excellent in thermal stability and coloring resistance.
- organic acid constituting the organic acid zinc salt that is the component (A) used in the present invention include carboxylic acid, organic phosphoric acid, and phenols.
- the organic acid zinc salt may be any of an acid salt, a basic salt, or an overbased salt.
- carboxylic acid examples include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid.
- Acid chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linolenic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids, tallow fatty acid, coconut oil fatty acid Natural acid mixtures such as tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, p-toluic acid, o-toluyl Acid, m-toluic acid, xylic acid, salicylic acid 5-tert-octyl salicylic acid, naphthenic acid, and cyclohexane carboxylic acid.
- organic phosphoric acid 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, phosphonic acid stearyl ester, and the like.
- phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, and dodecylphenol.
- the organic acid zinc salt used as the component (A) may be used alone or in combination of two or more.
- a zinc salt of an organic carboxylic acid particularly a zinc salt of an organic carboxylic acid having 6 to 18 carbon atoms.
- a zinc salt of an organic carboxylic acid having 6 to 14 carbon atoms Specifically, zinc stearate, zinc laurate, zinc benzoate, zinc p-toluate, and zinc oleate can be mentioned as preferred organic acid zinc salts.
- the content of the organic acid zinc salt used as the component (A) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
- the content is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, Most preferably, it is 0.1 to 1.0 part by mass.
- the content is less than 0.01 parts by mass, the color resistance of the resin composition of the present invention is insufficient, and when it exceeds 10 parts by mass, the transparency and thermal stability of the resin composition are lowered.
- the zinc-modified hydrotalcite compound used as the component (B) used in the present invention is a double salt compound containing magnesium, zinc and aluminum as metal components, or magnesium, calcium, zinc and aluminum as metal components. It is a double salt compound. In the present invention, it is preferable to use a double salt compound containing magnesium, zinc and aluminum as metal components, particularly from the viewpoint of transparency.
- the above-mentioned double salt compound is obtained by treating a hydrotalcite compound with a zinc compound by an ordinary method.
- the treatment may be a zinc-modified hydrotalcite compound obtained by treatment with a zinc compound during the synthesis of the hydrotalcite compound or by treatment after the synthesis.
- These zinc-modified hydrotalcite compounds include, for example, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 47-32198, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 48-29477 and Japanese Patent Publication No. 51-29129. It is described in the gazette. Naturally, a commercial item can also be used in this invention.
- the zinc-modified hydrotalcite compound as the component (B) those represented by the following general formula (I) are used. It is preferable to do.
- M in the formula (I) represents magnesium or magnesium and calcium
- magnesium is particularly preferable from the viewpoint of transparency in the resin composition of the present invention.
- zinc-modified hydrotalcite compound used in the present invention include the following compounds.
- Alkamizer 4 Alkamizer P-93: trade name manufactured by Kyowa Chemical Industry.
- Alkamizer P-93 Alkamizer P-93.
- only one type of these zinc-modified hydrotalcite compounds may be used, but two or more types may be used in combination.
- the refractive index of the zinc-modified hydrotalcite compound used as the component (B) in the present invention is preferably 1.52 to 1.56 from the viewpoint of transparency.
- the surface of the zinc-modified hydrotalcite compound is coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, or an organic sulfonic acid metal such as an alkali metal dodecylbenzenesulfonate.
- Zinc-modified hydrotalcite compounds coated with salts, higher fatty acid amides, higher fatty acid esters or waxes can also be used.
- the amount of the zinc-modified hydrotalcite compound used as the component (B) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
- the amount used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, from the viewpoints of transparency, thermal stability and color resistance of the resin composition of the present invention.
- the amount used is less than 0.01 parts by mass, the thermal stability of the resin composition of the present invention is insufficient, and when it exceeds 10 parts by mass, the coloration resistance of the resin composition of the present invention decreases. A decrease occurs.
- Phosphite compounds that can be used in the present invention include trialkyl phosphite, dialkyl phosphite, dialkyl allyl phosphite, alkyl allyl phosphite, alkyl diallyl phosphite, Examples thereof include diallyl phosphite ester and triallyl phosphite ester.
- a triester or a diester can be used, but it is preferable to use a triester from the viewpoints of transparency and color resistance of the resin composition of the present invention.
- Thioesters can also be used.
- phosphite compound examples include triphenyl phosphite, tricresyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonyl).
- Phenyl) phosphite tris (mono- and di-mixed nonylphenyl) phosphite, diphenyl phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite, diphenyldecyl phosphite, diphenyl (2-ethylhexyl) phosphite, diphenyl tridecyl phosphite, diphenyl (C 12 ⁇ C 15 mixed alkyl) phosphite, phenyl diisodecyl phosphite, phenyl bis (isotridecyl) phosphite, triethyl phosphite, tributyl phosphite Tris (2-ethylhexyl) phosphite, tris (decyl) phosphit
- the phosphite compound used as the component (C) may be used alone or in combination of two or more. From the viewpoint of thermal stability, transparency, and color resistance of the resin composition of the present invention, it is preferable to use a phosphite compound having 12 to 32 carbon atoms, and phosphorous acid having 18 to 28 carbon atoms. It is more preferable to use an ester compound.
- the amount of the phosphite compound used as the component (C) used in the present invention is 0.01 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, but the resin composition of the present invention is transparent. From the viewpoints of heat resistance, thermal stability and color resistance, it is preferably used in an amount of 0.05 to 2 parts by weight, particularly preferably 0.2 to 1.5 parts by weight. When the amount used is less than 0.01 parts by mass, the transparency and color resistance of the resin composition of the present invention are insufficient, and when it exceeds 3 parts by mass, the transparency and color resistance of the resin composition of the present invention are insufficient. Degradation of the performance occurs.
- the resin composition of the present invention preferably further contains a lubricant from the viewpoint of processability.
- the lubricant can be appropriately selected from known lubricants.
- the known lubricant include hydrocarbon lubricants such as low molecular wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, and fluorocarbon; natural wax lubricants such as carnauba wax and candelilla wax; lauric acid and stearic acid , Fatty acid-based lubricants such as higher fatty acids such as behenic acid, or oxyfatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, oleylamide or methylenebisstearylamide, ethylenebisstearylamide Aliphatic amide-based lubricants such as alkylenebisaliphatic amides; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, distearyl phthal
- a fatty acid alcohol ester-based lubricant such as a monovalent fatty acid and / or a complex ester compound of a polybasic organic acid and a polyhydric alcohol, particularly from the viewpoint of transparency.
- the content thereof is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. It is preferable that When the content of the lubricant is less than 0.01 parts by mass, the processability of the resin composition of the present invention may be insufficient, and when it exceeds 10 parts by mass, there is a decrease in performance such as a decrease in transparency.
- the resin composition of the present invention preferably further contains a processing aid from the viewpoint of processability.
- the processing aid can be appropriately selected from known processing aids. In the present invention, it is particularly preferable to use an acrylic acid processing aid.
- processing aids that can be used in the present invention include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; the above alkyl methacrylates and methyl acrylate, ethyl acrylate, and butyl acrylate.
- a copolymer with a compound etc. can be mentioned. These processing aids may be used alone or in combination of two or more.
- the amount used is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Part.
- the amount of the processing aid used is less than 0.01 parts by mass, the effect of improving the workability may be insufficient.
- the amount exceeds 10 parts by mass the transparency of the resin composition of the present invention decreases. Performance degradation occurs.
- the resin composition of the present invention preferably further contains a ⁇ -diketone compound from the viewpoint of coloring resistance.
- a ⁇ -diketone compound examples include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane.
- Benzoylformylmethane benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, stearoylbenzoylmethane, bis (4-octylbenzoyl) methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis (4-carboxymethylbenzoyl) methane 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, cyclohexane-1,3-dione, 3,6 Dimethyl-2,4-dioxy cyclohexane -1-carboxylate, 2-acetyl cyclohexanone, dimedone, and 2-benzoyl cyclohexane.
- a metal salt of the ⁇ -diketone compound can also be used.
- the metal species that can provide the ⁇ -diketone metal salt include alkali metals such as lithium, sodium, and potassium; magnesium, calcium, strontium, zinc, aluminum, and the like.
- the ⁇ -diketone compound dibenzoylmethane and stearoylbenzoylmethane are preferably used from the viewpoint of coloring resistance and transparency of the resin composition of the present invention.
- the amount of the ⁇ -diketone compound used in the resin composition of the present invention is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts per 100 parts by mass of the vinyl chloride resin. It is preferable that it is a mass part.
- the content of ⁇ -diketone compound is less than 0.01 parts by mass, the effect of improving the coloring resistance may be insufficient.
- the content exceeds 10 parts by mass the thermal stability and transparency of the resin composition of the present invention may be obtained. Degradation of the performance occurs.
- the resin composition of the present invention preferably further contains a phenolic antioxidant from the viewpoint of thermal stability and coloring resistance.
- a phenolic antioxidant 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
- the amount of the phenolic antioxidant used in the resin composition of the present invention is preferably 0.01 to 10 parts by mass, particularly 0.05 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. It is preferably 5 parts by mass.
- the content of the phenolic antioxidant is less than 0.01 parts by mass, the effect of improving the coloration resistance in the resin composition of the present invention may be insufficient.
- the content exceeds 10 parts by mass the transparency is reduced. Etc., performance degradation occurs.
- the resin composition of the present invention preferably further contains one or more sugar alcohols.
- sugar alcohols include mannitol, maltitol, lactitol, sorbitol, erythritol, glycerin, xylitol, inositol, and the like, from the viewpoint of thermal stability, colorability, and transparency of the resin composition of the present invention. It is particularly preferable to use mannitol, maltitol, or lactitol.
- the amount of sugar alcohol used in the composition of the present invention is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the vinyl chloride resin, and the transparency of the resin composition of the present invention From the viewpoint of thermal stability and color resistance, it is preferably used in an amount of 0.005 to 0.5 parts by mass, particularly preferably 0.01 to 0.3 parts by mass.
- the timing when the components (A) to (C), and in some cases, further, a lubricant and other optional additional components are added to the vinyl chloride resin is particularly limited. There is no.
- two or more types selected from the components (A) to (C), lubricants, and other optional components may be pre-packed into a vinyl chloride resin, You may mix
- vinyl chloride resin used in the present invention examples include polyvinyl chloride, post-chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, chloride Vinyl-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary Copolymer, Copolymer of vinyl chloride with alkyl, cycloalkyl or arylmaleimide, Vinyl chloride-styrene-acrylonitrile terpolymer, Vinyl chloride-butadiene copolymer, Vinyl chloride-isoprene copolymer, Chloride Vinyl-chlorinated propylene copolymer
- the resin composition of the present invention may contain metal stabilizers commonly used for vinyl chloride resins, but lead stabilizers, (organic) tin stabilizers, cadmium stabilizers, barium stabilizers. It is not preferable to add an agent from the viewpoint of environmental impact and toxicity.
- metal stabilizers examples include organic acid metal salts other than lead, tin, cadmium, and barium, and composite stabilizers thereof. These organic acid metal salts can be arbitrarily used as long as the effects of the present invention are not impaired. However, when these organic acid metal salts are added, the transparency of the resin composition of the present invention tends to decrease.
- Examples of the organic acid metal salt as the metal stabilizer that can be used in the present invention include metals such as carboxylic acid, organic phosphoric acid, or phenol (Li, Na, K, Ca, Mg, Sr, Zn, Cs). , Al) salts and the like.
- Examples of the carboxylic acid include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid.
- Acid chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linolenic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids; and tallow fatty acid, coconut oil fatty acid , Tung oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid and other naturally occurring acid mixtures; benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylylic acid, salicylic acid, 5-t -Octylsalicylic acid, naphthenic acid, cycl Hexane carboxylic acid and the like.
- organic phosphoric acids examples include mono- or di-octyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, and nonylphenyl phosphonate.
- examples include esters and phosphonic acid stearyl esters.
- phenols examples include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, and dodecylphenol.
- organic acid metal salts may be normal salts, acidic salts, basic salts, or overbased complexes.
- the resin composition of the present invention is preferably used for a hard application without blending a plasticizer because not only the transparency is high but also a molded product having excellent physical properties such as a softening point can be obtained.
- a plasticizer in an amount of 50 parts by mass or less can be added to 100 parts by mass of the vinyl chloride resin and used for semi-rigid applications.
- the plasticizer normally used for vinyl chloride-type resin can be suitably used in the range which does not impair the effect of this invention.
- plasticizer examples include phthalate plasticizers such as dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; dioctyl adipate, diisononyl adipate , Diisodecyl adipate, di (butyl diglycol) adipate and other adipate plasticizers; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (Butoxyethyl) phosphate, octyl di
- Phosphate plasticizer 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 and other polyhydric alcohols, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid Polyester plasticizers using dibasic acids such as acids and using monohydric alcohols or monocarboxylic acids as stoppers as required; tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid plastics Agent, stearic acid plasticizer, citric acid plasticizer , Trimellitic acid-based plasticizer
- the resin composition of the present invention further includes various additives that are usually used as additives for vinyl chloride resins, such as sulfur-based antioxidants, and zinc-modified hydrotals used as component (B).
- sulfur-based antioxidant examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). And ⁇ -alkyl mercaptopropionic esters of polyols.
- hydrotalcite compound other than the zinc-modified hydrotalcite compound used as the component (B) examples include compounds represented by the following formulae. Mg 1-X Al X (OH) 2 (A q- ) X / q ⁇ aH 2 O Where q is 1 or 2, A q ⁇ is a q-valent anion, ie, (CO 3 ) 2 ⁇ or (ClO 4 ) ⁇ , X is 0 ⁇ X ⁇ 0.5, a is Represents 0 or a positive number.
- hydrotalcite other than the zinc-modified hydrotalcite compound used as the component (B), the following may be mentioned.
- Mg 0.692 Al 0.308 (OH) 2 (ClO 4 ) 0.308 ⁇ 0.1H 2 O Mg 0.667 Al 0.333 (OH) 2 (ClO 4 ) 0.333 ⁇ 0.1H 2 O
- epoxy compound examples include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil.
- polyol compound examples include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol stearic acid half ester, bis (dipentaerythritol) adipate, diglycerin. And tris (2-hydroxyethyl) isocyanurate.
- saccharide examples include xylose, sucrose (sucrose), trehalose, fructose, maltose, and lactose.
- 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-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4 2- (2-hydroxyphenyl) benzotriazoles such as tert-octyl-6-benzotriazolyl) phenol, polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole Benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl
- 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, 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, 2,2,6,6-pentamethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis 1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3
- the impact modifier examples include polybutadiene, polyisoprene, polychloroprene, fluorine rubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene graft copolymer.
- Examples of the diene of the ethylene-propylene-diene copolymer rubber include 1,4-hexanediene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene, and the like.
- the filler include calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium aluminate silicate.
- Hydrocalumite, aluminum silicate, magnesium silicate, calcium silicate, silicate metal salts such as zeolite, activated clay, talc, clay, bengara, asbestos, antimony trioxide, silica, glass beads, mica, sericite, Glass flakes, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber, aramid fiber and the like can be mentioned.
- Examples of the flame retardant and flame retardant aid include triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogen flame retardants, silicon flame retardants, phosphate ester flame retardants, and condensed phosphate ester flame retardants.
- Examples include flame retardants, intomesent flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, and organic flame retardant aids.
- triazine ring-containing compound examples include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene
- examples thereof include dimethylamine, tetramethylene dimethylamine, hexamethylene dimethylamine, 1,3-hexylene dimeramine and the like.
- metal hydroxide examples include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.
- phosphate ester flame retardant examples include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl Phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t -Butylphenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (iso
- Examples of the condensed phosphate ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.
- Examples of messengertic flame retardants include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, piperazine pyrophosphate, and the like.
- Examples of the other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof.
- various commercial products such as TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.) and Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.) can be used.
- Examples of the other organic flame retardant aids include pentaerythritol and dipentaerythritol.
- a stabilizing aid usually used for vinyl chloride resins can be added within a range that does not impair the effects of the present invention.
- stabilizing aids include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, zeolite, and perchlorate.
- additives that are usually used in vinyl chloride resins as necessary, for example, crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents , Surface treatment agents, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, antioxidants, light stabilizers, and the like, as long as the effects of the present invention are not impaired. be able to.
- the vinyl chloride resin composition for transparent products of the present invention can be used regardless of the processing method of the vinyl chloride resin, for example, roll processing, extrusion molding, melt casting, pressure molding. It can be suitably used for processing and the like.
- the present invention is not restricted at all by these.
- the 0.6 mm-thick sheets obtained above are bonded together, and pressed at 190 ° C. for 5 minutes to produce 1-mm thick sheets. Using these sheets, the following method is used for ⁇ Transparency test > And ⁇ Color resistance test> were performed. Moreover, about the comparative example which does not use (C) component, the comparative test was done like the above. The results of the examples are shown in Tables 1 to 3, and the results of the comparative examples are shown in Table 1.
- ⁇ Transparency test> The haze value was measured using a haze guard 2 (manufactured by Toyo Seiki Seisakusyo Co., Ltd.) for a sheet of 1 mm thickness that was pressed at 190 ° C. for 5 minutes.
- ⁇ Color resistance test> The yellowness (Y.I.) of a 1 mm thick sheet pressed at 190 ° C. for 5 minutes was measured using a general-purpose color difference meter Color Ace TC-8600A (manufactured by Tokyo Denshoku Co., Ltd.).
- the vinyl chloride resin composition of the present invention is excellent in transparency, heat stability, and coloration resistance, and is particularly suitable for transparent rigid applications and transparent semi-rigid applications, so that glass-like transparency is required.
- it can be applied to industrial boards, decorative boards, trays, films, shrink films, sheets, building materials, water supply and drainage pipes, plates, joints, automotive materials, hoses, IC cases, bottles, etc. Meaningful.
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Abstract
Description
このように、環境に悪影響を与えないだけでなく、耐着色性及び透明性に優れた成型品を得ることのできる、塩化ビニル系樹脂組成物は未だ知られていない。
本発明の第2の目的は、透明性が高いだけでなく、熱安定性、耐着色性及び環境適合性にも優れた、塩化ビニル系樹脂組成物を成形してなる透明成型品を提供することにある。
(A)有機酸亜鉛塩の少なくとも一種、
(B)亜鉛変性ハイドロタルサイト系化合物の少なくとも一種、
(C)亜リン酸エステル化合物の少なくとも一種。
My1Zny2Alx(OH)2(CO3)x/2・mH2O (I)
但し、上式中のMは、マグネシウム又はマグネシウム及びカルシウムを表し、x、y1及びy2は、各々、0<x≦0.5、y1+y2=1-x、y1≧y2、0.3≦y1<1、0<y2<0.5の式で表される条件を満足する数、mは0又は任意の正数を表す。
本発明に用いられる、(A)成分である有機酸亜鉛塩を構成する有機酸としては、カルボン酸、有機リン酸又はフェノール類等が挙げられる。また、上記有機酸亜鉛塩は、酸性塩、塩基性塩又は過塩基性塩の何れであってもよい。
My1Zny2Alx(OH)2(CO3)x/2・mH2O (I)
但し、(I)式中のMは、マグネシウム、又は、マグネシウム及びカルシウムを表すが、本発明の樹脂組成物における透明性の観点から、特にマグネシウムであることが好ましい。x、y1及びy2は、各々、下記の関係式で表される条件を満足する数、mは0又は任意の正数を表す。
0<x≦0.5、 y1+y2=1-x、 y1≧y2、
0.3≦y1<1、及び、0<y2<0.5
Mg0.38Zn0.3Al0.32(OH)2(CO3)0.16・0.2H2O
Mg0.45Zn0.23Al0.32(OH)2(CO3)0.16
Mg0.48Zn0.18Al0.34(OH)2(CO3)0.17
Mg0.48Zn0.2Al0.32(OH)2(CO3)0.16
Mg0.5Zn0.17Al0.33(OH)2(CO3)0.165・0.45H2O
Mg0.5Zn0.18Al0.32(OH)2(CO3)0.16
Mg0.5Zn0.2Al0.3(OH)2(CO3)0.16
Mg0.5Zn0.2Al0.3(OH)2(CO3)0.15・0.52H2O
Mg0.5Zn0.25Al0.25(OH)2(CO3)0.125
Mg0.51Zn0.17Al0.32(OH)2(CO3)0.16
Mg0.52Zn0.16Al0.32(OH)2(CO3)0.16・0.5H2O
Mg0.55Zn0.15Al0.32(OH)2(CO3)0.15
Mg0.6Zn0.14Al0.26(OH)2(CO3)0.13
Mg0.6Zn0.16Al0.24(OH)2(CO3)0.12
Mg0.6Zn0.2Al0.2(OH)2(CO3)0.1
Mg0.4Ca0.1Zn0.18Al0.32(OH)2(CO3)0.16
Mg0.3Ca0.2Zn0.2Al0.3(OH)2(CO3)0.15
Mg0.5Zn0.17Al0.33(OH)2(CO3)0.17・0.5H2O
Mg0.5Zn0.17Al0.33(OH)2(CO3)0.17・0.42H2O
Mg0.6Zn0.16Al0.24(OH)2(CO3)0.12・0.45H2O
Mg0.5Zn0.25Al0.25(OH)2(CO3)0.13・0.39H2O
Mg0.5Zn0.17Al0.33(OH)2(CO3)0.17
Mg0.5Zn0.25Al0.25(OH)2(CO3)0.13
本発明で使用することのできる亜リン酸エステル化合物としては、亜リン酸トリアルキルエステル、亜リン酸ジアルキルエステル、亜リン酸ジアルキルアリルエステル、亜リン酸アルキルアリルエステル、亜リン酸アルキルジアリルエステル、亜リン酸ジアリルエステル、亜リン酸トリアリルエステル等が挙げられる。本発明においては、トリエステルでもジエステルでも使用することができるが、本発明の樹脂組成物の透明性と耐着色性の観点から、トリエステルを使用することが好ましい。また、チオエステルも使用することができる。
これらの有機酸金属塩は、正塩、酸性塩、塩基性塩あるいは過塩基性錯体であってもよい。
Mg1-XAlX(OH)2(Aq-)X/q・aH2O
但し、式中のqは1又は2であり、Aq-はq価のアニオン、即ち(CO3)2-又は(ClO4)-であり、Xは0<X≦0.5、aは0または正数を表す。
Mg0.750Al0.250(OH)2(CO3)0.125・0.5H2O
Mg0.692Al0.308(OH)2(CO3)0.154・0.1H2O
Mg0.683Al0.317(OH)2(CO3)0.159・0.5H2O
Mg0.667Al0.333(OH)2(CO3)0.167・0.1H2O
Mg0.750Al0.250(OH)2(ClO4)0.250・0.5H2O
Mg0.692Al0.308(OH)2(ClO4)0.308・0.1H2O
Mg0.667Al0.333(OH)2(ClO4)0.333・0.1H2O
糖類としては、キシロース、スクロース(シュクロース)、トレハロース、フルクトース、マルトース、ラクトース等が挙げられる。
また、前記その他の有機系難燃助剤としては、例えば、ペンタエリスリトール、ジペンタエリスリトール等が挙げられる。
以下、実施例及び比較例によって本発明を更に詳細に説明するが、本発明はこれらによって何ら制限を受けるものではない。
下記表1~3の配合物をヘンシェルミキサーでブレンドした後、190℃×30rpm(ロールの回転速度)×0.6mm(シート厚)×3分(混練時間)の条件で、ロール混練してシートを作製した。得られたシートを190℃と、200℃のギヤーオーブンに入れ、<熱安定性試験>として黒化時間(分)を測定した。結果は表1~3に示した通りである。
190℃で5分間プレス加工した1mm厚のシートについて、ヘイズガード2(株式会社東洋精機製作所製)を用いてHaze値を測定した。
<耐着色性試験>
190℃で5分間プレス加工した1mm厚のシートについて、汎用型色差計カラーエースTC-8600A(有限会社東京電色製)を用いて黄色度(Y.I.)を測定した。
*1:ZEST1000Z(新第一塩ビ(株)製)
*2:亜鉛変性ハイドロタルサイト:(協和化学工業(株)製)Mg3.0ZnAl2(OH)12(CO3)・3H2O (請求項4の記載方法に変換すると、Mg3/6Zn1/6Al2/6(OH)2(CO3)1/6・0.5H2Oに対応する。)
*3:G-60(フタル酸アルキルエステル系滑剤)(コグニスオレオケミカルズ・ジャパン(株)製)
*4:P-551A(アクリル酸系加工助剤)(三菱レイヨン(株)製)
*5:ステアリルベンゾイルメタン
*6:テトラキス〔メチレン-3-(3’,5’-ジ第三ブチル-4’-ヒドロキシフェニル)プロピオネート〕メタン
*1:ZEST1000Z(新第一塩ビ(株)製)
*2:亜鉛変性ハイドロタルサイト(協和化学工業(株)製)Mg3.0ZnAl2(OH)12(CO3)・3H2O (請求項4の記載方法に変換すると、Mg3/6Zn1/6Al2/6(OH)2(CO3)1/6・0.5H2Oに対応する。)
*3:G-60(フタル酸アルキルエステル系滑剤)(コグニスオレオケミカルズ・ジャパン(株)製)
*4:P-551A(アクリル酸系加工助剤)(三菱レイヨン(株)製)
*5:ステアリルベンゾイルメタン
*6:テトラキス〔メチレン-3-(3’,5’-ジ第三ブチル-4’-ヒドロキシフェニル)プロピオネート〕メタン
*1:ZEST1000Z(新第一塩ビ(株)製)
*2:亜鉛変性ハイドロタルサイト(協和化学工業(株)製)Mg3.0ZnAl2(OH)12(CO3)・3H2O (請求項4の記載方法に変換すると、Mg3/6Zn1/6Al2/6(OH)2(CO3)1/6・0.5H2Oに対応する。)
*3:G-60(フタル酸アルキルエステル系滑剤)(コグニスオレオケミカルズ・ジャパン(株)製)
*4:P-551A(アクリル酸系加工助剤)(三菱レイヨン(株)製)
*5:ステアリルベンゾイルメタン
*6:テトラキス〔メチレン-3-(3’,5’-ジ第三ブチル-4’-ヒドロキシフェニル)プロピオネート〕メタン
Claims (6)
- 塩化ビニル系樹脂100質量部に対して、下記の、(A)成分を0.01~10質量部、(B)成分を0.01~10質量部、及び(C)成分を0.01~3質量部含有してなることを特徴とする、透明製品用塩化ビニル系樹脂組成物;
(A)有機酸亜鉛塩の中から選択された少なくとも一種の塩、
(B)亜鉛変性ハイドロタルサイト系化合物の中から選択された少なくとも一種の化合物、
(C)亜リン酸エステル化合物の中から選択された少なくとも一種の化合物。 - 前記(C)成分が、炭素原子数12~32の亜リン酸エステル化合物である、請求項1に記載された透明製品用塩化ビニル系樹脂組成物。
- 前記(A)成分が、炭素原子数6~18の有機カルボン酸の亜鉛塩である、請求項1又は2に記載された透明製品用塩化ビニル系樹脂組成物。
- 前記(B)成分が、下記一般式(I)で表される亜鉛変性ハイドロタルサイト系化合物である、請求項1~3の何れかに記載された透明製品用塩化ビニル系樹脂組成物;
My1Zny2Alx(OH)2(CO3)x/2・mH2O (I)
但し、式中のMは、マグネシウム、又は、マグネシウム及びカルシウムを表し、x、y1及びy2は、各々、0<x≦0.5、y1+y2=1-x、y1≧y2、0.3≦y1<1、及び0<y2<0.5の式で表される条件を満足する数、mは0または任意の正数を表す。 - 前記組成物が有機スズ系化合物を含有しない、請求項1~4の何れかに記載された透明製品用塩化ビニル系樹脂組成物。
- 請求項1~5の何れかに記載された透明製品用塩化ビニル系樹脂組成物を、成形してなることを特徴とする透明成形品。
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- 2014-02-27 KR KR1020157024341A patent/KR20150127075A/ko not_active Application Discontinuation
- 2014-02-27 CN CN201480013069.6A patent/CN105121542B/zh active Active
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WO2016152484A1 (ja) * | 2015-03-26 | 2016-09-29 | 株式会社Adeka | 塩化ビニル系樹脂組成物 |
CN107250256A (zh) * | 2015-03-26 | 2017-10-13 | 株式会社艾迪科 | 氯乙烯系树脂组合物 |
JPWO2016152484A1 (ja) * | 2015-03-26 | 2018-01-18 | 株式会社Adeka | 塩化ビニル系樹脂組成物 |
WO2018012403A1 (ja) * | 2016-07-14 | 2018-01-18 | 堺化学工業株式会社 | 塩素含有樹脂組成物 |
US10947377B2 (en) | 2016-07-14 | 2021-03-16 | Sakai Chemical Industry Co., Ltd. | Chlorine-containing resin composition |
CN106832410A (zh) * | 2016-12-30 | 2017-06-13 | 北京华腾新材料股份有限公司 | 一种无机含硅阻燃协效剂 |
JP2022115626A (ja) * | 2021-01-28 | 2022-08-09 | 日東化成株式会社 | 臭素化スチレンブタジエンポリマー用安定剤、難燃性樹脂組成物、難燃性樹脂成形体 |
JP7318895B2 (ja) | 2021-01-28 | 2023-08-01 | 日東化成株式会社 | 臭素化スチレンブタジエンポリマー用安定剤、難燃性樹脂組成物、難燃性樹脂成形体 |
CN115354503A (zh) * | 2022-07-14 | 2022-11-18 | 浙江海利得新材料股份有限公司 | 一种制备pvc夹网布的透明糊浆 |
CN115354503B (zh) * | 2022-07-14 | 2024-01-09 | 浙江海利得新材料股份有限公司 | 一种制备pvc夹网布的透明糊浆 |
Also Published As
Publication number | Publication date |
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CN105121542B (zh) | 2018-01-12 |
JPWO2014141608A1 (ja) | 2017-02-16 |
US20160017126A1 (en) | 2016-01-21 |
KR20150127075A (ko) | 2015-11-16 |
JP6514637B2 (ja) | 2019-05-15 |
EP2975086A4 (en) | 2016-10-26 |
EP2975086A1 (en) | 2016-01-20 |
CN105121542A (zh) | 2015-12-02 |
TW201437267A (zh) | 2014-10-01 |
US9382406B2 (en) | 2016-07-05 |
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