WO2008018521A1 - Composition de résine de chlorure de vinyle transparente et de retardement des flammes et produit moulé - Google Patents

Composition de résine de chlorure de vinyle transparente et de retardement des flammes et produit moulé Download PDF

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Publication number
WO2008018521A1
WO2008018521A1 PCT/JP2007/065560 JP2007065560W WO2008018521A1 WO 2008018521 A1 WO2008018521 A1 WO 2008018521A1 JP 2007065560 W JP2007065560 W JP 2007065560W WO 2008018521 A1 WO2008018521 A1 WO 2008018521A1
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resin
chlorinated
resin composition
temperature decomposition
mass
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PCT/JP2007/065560
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English (en)
Japanese (ja)
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Shoji Ito
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Mitsubishi Plastics, Inc.
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Priority to JP2008528864A priority Critical patent/JPWO2008018521A1/ja
Publication of WO2008018521A1 publication Critical patent/WO2008018521A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/286—Chlorinated polyethylene
    • 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
    • C08L27/08—Homopolymers or copolymers of vinylidene chloride
    • 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
    • C08L27/22—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 modified by chemical after-treatment
    • C08L27/24—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 modified by chemical after-treatment halogenated

Definitions

  • the present invention relates to a chlorinated bur resin composition capable of forming a transparent and flame-retardant molded article, and a molded article obtained by molding the composition.
  • Chlorinated chlorinated resins contain chlorine in the molecule and are not only excellent in flame retardancy, but also have a wide range of additives, so mechanical properties, heat resistance, moldability The weather resistance can be adjusted over a wide range and has been used for various purposes.
  • molded products of rigid chlorinated resin-based resin compositions are interior and exterior materials for transportation equipment such as aircraft, ships and vehicles; interior and exterior materials for buildings; daily necessaries such as furniture and office equipment; housing for home appliances and electronic devices. Materials: Used as parts of semiconductor devices.
  • Patent Document 1 for the purpose of a transparent chlorinated resin based on FM standards, a zinc compound is converted into an amount of metallic zinc per 100 parts by weight of chlorinated resin.
  • a transparent flame-retardant chlorinated chlorinated resin molded article containing 5 parts by weight and 0.5 to 7 parts by weight of a tin stabilizer and molded into a desired shape is disclosed.
  • Patent Document 2 discloses that a transparent chlorinated bulle-based resin molded body having flame retardancy is laminated with a low chlorinated bulle layer and a high chlorinated bulle layer. There is disclosed a transparent flame retardant chlorinated resin-based resin molded body having an average chlorination degree of 60% or more and formed into a desired shape.
  • resins having different compositions are laminated, there is a problem that a difference in refractive index is generated at the resin interface, and it is difficult to obtain high transparency, and the process becomes complicated and productivity does not increase. In order to increase productivity, if a single layer is used, it will be difficult to ensure sufficient transparency as well as insufficient flame retardancy.
  • Patent Document 3 discloses that in a chlorinated resin-based resin composition containing an organotin stabilizer, an organozinc compound as a high-temperature decomposition accelerator in an amount of 0.01 to 0.01 mass!
  • an organozinc compound as a high-temperature decomposition accelerator in an amount of 0.01 to 0.01 mass!
  • a chlorinated bur resin composition and a molded product obtained from the same are disclosed. Transparency and flame retardancy can be secured, but in addition to further improvement in transparency and flame retardancy, improvement in processability is expected.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-192520
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2005-15620
  • Patent Document 3 Japanese Patent Publication No. 2004-300299
  • the present invention relates to a chlorinated bur resin resin composition having excellent transparency and flame retardancy, thermal stability and lubricity necessary to ensure high productivity, and a molded article obtained therefrom.
  • the purpose is to provide.
  • the present inventor has 1 to 50 parts by mass of a chlorine-containing resin having a high-temperature decomposition accelerating function and an organic compound having a high-temperature decomposition inhibiting function for 100 parts by mass of a chlorinated resin. ; ⁇ 7 parts by mass, thermal stabilizer with low-temperature decomposition inhibitory function (including thermal stabilization aid)
  • a chlorine-containing resin having a high-temperature decomposition promoting function According to the chlorinated resin resin composition of the present invention, a chlorine-containing resin having a high-temperature decomposition promoting function.
  • the inherently chlorinated buyl chloride resin has V, ! /, Transparency can be maintained at the same level, and high! /, Thermal stability and lubricity necessary to ensure productivity are excellent.
  • the molded article of the present invention obtained by extrusion molding, calender press molding or extrusion continuous press molding of such a salted bull resin composition is excellent in transparency and flame retardancy, and has high productivity. It has the thermal stability which can be molded.
  • the present bull chloride resin composition As an example of the embodiment of the present invention, and the present bull chloride resin composition.
  • the molded body (hereinafter referred to as “main molded body”) will be described.
  • main molded body the molded body
  • the present chlorinated bur resin composition contains a high temperature decomposition accelerator, a low temperature decomposition inhibitor and a high temperature decomposition inhibitor in addition to the chlorinated resin as a base resin.
  • System resin composition contains a high temperature decomposition accelerator, a low temperature decomposition inhibitor and a high temperature decomposition inhibitor in addition to the chlorinated resin as a base resin.
  • the high temperature decomposition accelerator is a substance having a function of promoting the decomposition of the chlorinated resin in the high temperature region
  • the high temperature decomposition inhibitor is an agent that inhibits the decomposition of the chlorinated resin in the high temperature region.
  • a low-temperature decomposition inhibitor is a substance that has a function of suppressing the decomposition of a chlorinated resin in a low temperature region.
  • the dehydrochlorination behavior starts from the processing temperature range up to 220 ° C, and the dehydrochlorination behavior is prominent around 220 ° C to 370 ° C. This is the temperature range that occurs. Above this temperature range, for example, 450 ° C or higher, the main chain of the chlorinated resin may be broken, or carbon of the chlorinated resin may be burned or carbonized. Therefore, in the present invention, the decomposition in the low temperature region refers to the decomposition behavior in the temperature range up to 220 ° C., which is the forming temperature range, and the decomposition in the high temperature region means that the main chain is broken. Decomposition behavior in the temperature range above 450 ° C where carbon combustion occurs.
  • the high-temperature decomposition promoting function in the present invention means that the chlorinated resin is 450 ° C or higher. Therefore, it can be said that this function promotes decomposition by breaking the main chain of the chlorinated resin and carbonization by combustion of carbon in the chlorinated resin.
  • the high-temperature decomposition inhibiting function in the present invention can be said to be a function of inhibiting the decomposition and carbonization of the chlorinated bur resin at 450 ° C. or higher.
  • the low-temperature decomposition inhibiting function in the present invention is a function that inhibits the start of dehydrochlorination behavior from a chlorinated bur resin at less than 220 ° C.
  • bur compounds that can be copolymerized with the chlorinated bulu component are not particularly limited.
  • fatty acid butyl esters such as butyl acetate and butyl propionate
  • alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate
  • alkyl acrylate esters such as methyl acrylate, ethyl acrylate and butyl acrylate ⁇ -olefins such as ethylene, propylene, styrene, etc .
  • Anolequino vinenoreatenore such as vinylenolemethinoreatenore, vinylenobutinoleatenore, etc .
  • Unsaturation such as allylic acid, methacrylic acid, maleic anhydride, etc.
  • Carboxylic acid or its acid anhydride can be mentioned, and these can be used alone or in combination of two or
  • the copolymerization amount of the other bulu compound does not exceed 30% by mass, the inherent flame retardancy and high transparency of the chlorinated bur resin will not be impaired.
  • the bull compound is preferably contained in a range not exceeding 30% by mass.
  • the amount of copolymerization is preferably 20% by mass, more preferably 10% by mass, from the viewpoints of transparency and flame retardancy.
  • the average degree of polymerization of the chlorinated resin is preferably 300 to 2,000, more preferably 500 to 1,500. If the average degree of polymerization is too small, the molded product may not have sufficient strength. If it is too large, it is difficult to sufficiently knead the molded product during molding. May decrease.
  • chlorinated resin those polymerized by various methods such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and the like, which do not particularly limit the polymerization method, can be used.
  • the high-temperature decomposition accelerator is effective in reducing the amount of smoke generated in the high-temperature region by promoting the cleavage and carbonization of the main chain of the chlorinated bur resin during combustion of the molded body (for example, 450 ° C or higher). It is a plus.
  • a chlorine-containing resin capable of generating hydrogen chloride which has an action of promoting the cleavage of the main chain of the chlorinated resin, is preferred.
  • chlorine-containing resin having a function of promoting high-temperature decomposition chlorinated polyethylene resin, post-chlorinated butyl chloride resin, vinylidene chloride resin, etc. are particularly preferred and can be cited as examples.
  • the above chlorinated polyethylene is a resin obtained by chlorinating polyethylene having a mass average molecular weight of 50,000 to 350,000, having a chlorine content of 28 to 43% by mass, and the heat of crystal melting by the DSC method.
  • Examples thereof include chlorinated polyethylene that is 25 cal / g or less.
  • it is a resin obtained by chlorinating polyethylene with a mass average molecular weight of 50,000 to 150,000, which has a chlorine content of 28 to 35% by mass and a crystal melting heat by DSC method of 10 to 25 cal / g.
  • a chlorinated polyethylene is preferred.
  • the post-chlorinated butyl chloride resin is preferably one having an average degree of polymerization of 500 to 1400 of the chlorinated butyl resin before chlorination. If the average degree of polymerization is less than 500, impact resistance may be reduced, and if it exceeds 1400, melt flowability may be reduced and molding may be difficult.
  • the amount is 58 to 70% by weight, preferably 60 to 70% by weight. If the average chlorine content is too low, the heat resistance will be reduced and deformation will occur, and if it is too high, especially if it exceeds 70 mass%, the fluidity will be greatly reduced and molding will be difficult.
  • Examples of vinylidene chloride resins include homopolymers and copolymers of vinylidene chloride. That power S. It is preferable to use a copolymer having a difference between the thermal decomposition temperature and the melting point, that is, a copolymer.
  • copolymer of vinylidene chloride a copolymer obtained by copolymerizing vinylidene chloride and a known radical polymerizable monomer alone or in combination of two or more thereof can be used.
  • radical polymerizable monomer examples include unsaturated fatty acids such as butyl chloride, acrylonitrile, acrylic acid or methacrylic acid and esters thereof, buresters such as butyl acetate, vinyl ketones, olefins such as ethylene and propylene, n Mention may be made of monomers containing special functional groups such as methylatanolenoamide and cyclohexylmaleimide.
  • composition of the copolymer of vinylidene chloride and the above monomer is not particularly limited, but in order to satisfy flame retardancy, the content of vinylidene chloride is 65 to 99% by mass, preferably 80 to 97% by mass. It ’s better to choose!
  • the molecular weight of the vinylidene chloride copolymer is not particularly limited, but the mass average molecular weight is 30000 to 150,000, preferably 50 000 to 120,000, in terms of additive properties and physical properties of the molded article. Masle.
  • Examples of the polymerization method of the polymer of vinylidene chloride include suspension polymerization, emulsion polymerization, bulk polymerization, gas phase polymerization, and the like. From the viewpoint of obtaining a good powder at low cost, suspension polymerization is particularly preferable.
  • the high-temperature decomposition accelerator is added in a small amount! /, And carbonization is not promoted during combustion! /. On the other hand, flame retardancy is not improved. Deterioration of warm water whitening will occur. Therefore, the content of the high-temperature decomposition accelerator is 5 to 30 parts by mass, especially 10 to 20 parts by mass, even though! To 50 parts by mass is preferable with respect to 100 parts by mass of the chlorinated resin. I like it!
  • the low-temperature decomposition inhibitor it is preferable to select and use one having good transparency from those conventionally known as heat stabilizers for bull chloride and heat stabilizers.
  • heat stabilizers for bull chloride and heat stabilizers.
  • Stabilizers lead-based stabilizers, metals such as potassium, magnesium, norium, zinc, cadmium, lead and 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, Metal stalagmite stabilizers derived from fatty acids such as oleic acid, ricinoleic acid, behenic acid, Ba-Zn, Ca-Zn, Ba-Ca-Sn, Ca-Mg-Sn, Ca- Zn-Sn-based, Pb Ba-based, Pb Ba-Ca-based and other complex metal stalagmite stabilizers, metal groups such as sodium and zinc, and 2-ethylhexanoic acid, isodecanoic acid, trialkylacetic acid, etc.
  • metal stalagmite stabilizers derived from fatty acids such as oleic acid, ricinoleic acid, behenic acid, Ba-Zn, Ca-Zn, Ba-
  • Branched fatty acid, olein Usually, two or more kinds selected from aromatic acids such as unsaturated fatty acids such as ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, coalic acid, benzoic acid, salicylic acid and substituted derivatives thereof.
  • aromatic acids such as unsaturated fatty acids such as ricinoleic acid and linoleic acid
  • alicyclic acids such as naphthenic acid, coalic acid, benzoic acid, salicylic acid and substituted derivatives thereof.
  • Metal salt stabilizers derived from organic acids, these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, etc., and phosphorous esters, epoxy compounds, coloring inhibitors, transparency improvements
  • Metal stabilizers such as metal salt liquid stabilizers that contain stabilizers such as additives, light stabilizers, antioxidants, plate-out inhibitors, lubricants, epoxy resins, epoxidized vegetable oils, epoxidized fatty acid alkyl esters, Epoxy compounds such as epoxidized aromatic alkyl ester, phosphorus is substituted with alkyl group, aryl group, cycloacryl group, alkoxyl group, etc., and propylene group
  • Organic stabilizers such as dihydric alcohols such as recall, hydroquinone, bisphenol A, etc., light stabilizers of hindered amines or nickel complexes, trimethylolpropane, pentaerythritol, sonolevitol, and
  • organotin stabilizers organotin stabilizers, metal stone stabilizers, zeolites, hydrated talcite, aluminum and magnesium hydroxides are preferred. From the viewpoints of excellent anti-dissolution function and transparency, tin-based stabilizers and metal stalagmite-based stabilizers are particularly suitable.
  • Zeolite, hydrated talcite, aluminum hydroxide and magnesium hydroxide are used as heat stabilization aids.
  • tin stabilizers examples include malate tin stabilizers, laurate tin stabilizers, mercapto tin stabilizers, etc. Among them, mercapto tin stabilizers that are advantageous in terms of transparency are particularly preferable. .
  • alkaline earth metal salts such as magnesium salts and sodium salts, and zinc salts.
  • calcium salts, magnesium salts, norlium salts, and zinc salts are particularly preferable. These can be used alone or in combination of two or more.
  • fatty acid of metal sarcophagus examples include saturated purine acid, undecanoic acid, 2-ethylhexoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, araquinic acid, And unsaturated fatty acids such as petroceric acid, oleic acid, linoleic acid, linoleic acid and arachidonic acid, and aromatic fatty acids such as benzoic acid and t-pitreubenzoic acid.
  • zeolite examples include synthetic zeolite such as zeolite A, zeolite X and zeolite Y, partially or completely acid-treated products thereof, or aluminum ions of those treated with metal ions (for example, calcium, magnesium and zinc ions). Mention may be made of silicates. Among these, sodium ion-exchanged A-type zeolite, which has good thermal stability, is particularly preferable.
  • Examples of the hyde talcite include those represented by the following formulas (1) to (4).
  • a is a positive talcite expressed by 0. 01 ⁇ a / (x + y) ⁇ l.
  • n is an integer greater than 1
  • a positive number, Y is selected from the group consisting of phosphorous oxyacid, thiooxyacid, nitrogen oxyacid, boron oxyacid, carbonic acid, halogen hydroacid, halogen oxyacid, perhalogen oxyacid, and carboxylic acid.
  • M is a divalent metal ion such as Mg, Ca, Zn, Y is CO 2 —, S
  • Omicron 2 such divalent Anion, and what a is represented by the 0 or a positive is a number
  • Formula (4) Mg Al (OH) (A 2 —) P (A—)-aZ-bH 0 (where A 2 — is a divalent carbon such as CO 2 xy 2x + 3y ⁇ zq 2 3
  • A— is a halogen oxyacid ion
  • Z is a polyhydric alcohol or its partial ester
  • p and q are numbers satisfying l ⁇ q / (2p + q) ⁇ l / 10
  • a and b are 0.01 01 ⁇ a / (x + y) ⁇ 1.0 03 ⁇ 4t O ⁇ b / (x + y) ⁇ 1.0), and examples thereof include composite hydroxides described in Japanese Patent Publication No. 3-36839.
  • Examples of the aluminum hydroxide and magnesium hydroxide include aluminum hydroxide and magnesium hydroxide. Further, hydroxides obtained by subjecting these hydroxide powders to surface treatment may be used. As this surface treatment agent, it is preferable to use a material containing a fatty acid or a molybdenum compound in terms of dispersibility and flame retardancy.
  • the above-mentioned inorganic low-temperature decomposition inhibitor has a lower limit value of the average particle diameter of 0.01 am or more, preferably (or 0.05 to 111 or more, an upper limit straight (or less than 0.6 tom, preferably (It is less than 0.3 ⁇ m. If the average particle size is 0.01 am or more, it is easy to handle without aggregation with the heat stabilizer itself. On the other hand, if it is less than 0.6 m, Transparency is good because it is smaller than the wavelength of visible light.
  • an organic tin mercapto-based stabilizer having a refractive index close to that of a vinyl chloride resin, hydrated talcite, magnesium hydroxide Um compounds are particularly preferred.
  • the blending amount of the low-temperature decomposition inhibitor is 1 mass part or more, preferably 2 mass parts or more, more preferably 3 mass parts or more when the chlorinated resin is 100 mass parts.
  • the upper limit is 10 parts by mass or less, preferably 8 parts by mass or less, and more preferably 6 parts by mass or less. If the blending amount of the low-temperature decomposition inhibitor is 1 part by mass or more, the low-temperature decomposition is not promoted and the moldability is good, and if it is 10 parts by mass or less, the flame retardancy is good.
  • the present chlorinated resin composition it is important to add an organic compound having a high-temperature decomposition inhibiting function as a high-temperature decomposition inhibitor in addition to the above-described ingredients.
  • the high-temperature decomposition inhibitor has a function of imparting physical properties, molding processability, and the like, so that it is a lubricant, processing aid, impact modifier, plasticizer, antistatic agent, ultraviolet absorber, and antioxidant.
  • a preferred example is an agent, and it is preferable to use one or more selected from these in combination.
  • Examples of the lubricant include pure hydrocarbons such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, and low molecular weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxy fatty acids; Fatty acid amides such as fatty acid amides and bis fatty acid amides; Esters such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polydaricol esters of fatty acids, fatty alcohol esters of fatty acids (ester waxes); Examples thereof include metal sarcophagus, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, fatty acid and polyhydric alcohol partial ester, fatty acid and polydaricol, polyglycerol partial ester, and the like. Of these, lower alcohol esters of fatty acids having excellent high-temperature decomposition inhibiting function, polyhydric alcohol esters of fatty acids such as glycerides, and
  • One of these can be used alone, or two or more can be used in combination.
  • Examples of the processing aid include methyl metatalylate, ethyl metatalylate, and butyl. Homopolymers or copolymers of alkyl metatalates such as metatalates; Copolymers of the above alkyl metatalates and alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, etc .; And a copolymer of styrene, ⁇ -methylstyrene, butyltoluene and other aromatic bur compounds; a copolymer of the above alkyl methacrylate and a burcyan compound such as acrylonitrile and methacrylonitrile.
  • alkyl metatalates such as metatalates
  • Copolymers of the above alkyl metatalates and alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, etc .
  • a copolymer of methyl metatalylate, butyl atylate and ethyl metatalylate having an excellent function of inhibiting high-temperature decomposition is particularly preferable.
  • One of these can be used alone, or two or more can be used in combination.
  • the above impact modifier include polybutadiene, polyisoprene, polychloroprene, fluorine rubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene styrene copolymer, methyl methacrylate-butadiene styrene Graft copolymer, acrylonitrile-styrene-butadiene copolymer rubber, acrylonitrile-styrene butadiene-based graft copolymer, styrene butadiene styrene block copolymer rubber, styrene isoprene styrene copolymer rubber, styrene ethylene-butylene styrene copo
  • acrylonitrile-styrene-butadiene copolymer rubber acrylonitrile-styrene-butadiene graft copolymer, etc., which have a low high-temperature decomposition inhibiting function, are particularly preferred.
  • These impact modifiers can be used alone or in combination of two or more.
  • EPDM ethylene propylene copolymer rubber
  • examples of the ethylene propylene copolymer rubber include 1,4 xanthene, dicyclopentagen, methylene norbornene, ethylidene norbornene, propenyl norbornene, and the like. These impact modifiers can be used alone or in combination of two or more.
  • plasticizer examples include dimethyl phthalate, jetyl phthalate, dibutyl phthalate, dihexino phthalate, dinonole manoleo octino phthalate, 2-etheno hexeno phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate.
  • Disononyl phthalate didecyl phthalate, diisodecyl phthalate, diunedecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl otachinole Phthalic acid esters such as phthalate, octinolevenoino phthalate, nonolemanolehexenolenenoremaneno dedecenorephthalate, normaloctyl normal decyl phthalate -Type plasticizers; tricresinorephosphate, tri-2-ethylenohexenorephosphate, triphenenorephosphate, 2-ethinorexenoresinenophosphate, credinoresinenophosphate, etc.
  • One of these can be used alone, or two or more can be used in combination.
  • a cationic surfactant As the above-mentioned antistatic agent, a cationic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.
  • anionic surfactants include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, aliphatic amines, amide sulfates, dibasic fatty acid ester sulfonates, fatty acid amide sulfonates, alkylamides.
  • examples include reel sulfonates, formalin-condensed naphthalene sulfonates, and mixtures thereof.
  • cationic surfactant examples include aliphatic ammine salts, quaternary ammonium salts, alkyl pyridinium salts, and mixtures thereof.
  • Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol esters, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, and mixtures thereof. Can do.
  • a mixture of a nonionic surfactant and a cation surfactant or a cationic surfactant may be used.
  • amphoteric surfactants include imidazoline type, higher alkylamino type (betaine type), sulfate ester, phosphate ester type, and sulfonic acid type.
  • nonionic surfactants having a low high-temperature decomposition inhibiting function are preferred, and among them, sorbitan alkyl esters are more preferred.
  • Examples of the ultraviolet absorber include hindered phenols, salicylic acid esters, benzophenones, and benzotriazoles. Among them, the high-temperature decomposition inhibiting function is low! / A benzotriazole-based UV absorber is particularly preferred! /.
  • Examples of the antioxidant include phenolic antioxidants such as 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), tris (mixed mono and genoylphenyl) phosphite, etc. And thioether-based antioxidants such as distearyl thiodipropionate. Of these, phenolic antioxidants such as 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), which have a low high-temperature decomposition inhibiting function, are particularly preferred!
  • the lower limit for 100 parts by mass is 0.1 parts by mass or more, preferably 0.8 parts by mass or more, more preferably 1.6 parts by mass or more, and the upper limit is 7 parts by mass or less, preferably 5 parts by mass. Hereinafter, it is more preferably 4 parts by mass or less.
  • the present chlorinated resin composition can be obtained by mixing a predetermined amount of chlorinated resin, a high temperature decomposition accelerator, a low temperature decomposition inhibitor and a high temperature decomposition inhibitor using a blender, a Henschel mixer or the like. At this time, other compounding agents such as a heat resistance improver and a pigment may be blended in an appropriate amount.
  • This chlorinated resin-based resin composition can be processed into a main product by molding it into a shape of a film, sheet, plate, pipe, odd-shaped product, etc. by extrusion molding, calendar molding, press molding method or continuous press molding. it can.
  • the calendar press molding method is a molding method under mild conditions, and therefore, an organotin stabilizer with a wide range of selection of a stabilizer having a low-temperature decomposition inhibiting function. Satisfactory metal calcite stabilizer, zeolite, hydrated talcite, aluminum and magnesium hydroxides alone or in combination of two or more.
  • a thin plate can be preferably molded at the calendar molding stage.
  • a plurality of plates are laminated at a press molding stage to obtain a desired thickness. Therefore, the calendar press molding method changes the thickness of the molded body without requiring a major change in the molding machine when changing the thickness of the molded body. Can be.
  • a plurality of plates obtained in the calendar molding stage are laminated in the press molding stage to obtain a plate having a desired thickness, but a plurality of plates obtained in the calendar molding stage are used.
  • the body has a certain degree of thickness fluctuation due to molding conditions, etc., and this thickness fluctuation is combined with thickness fluctuation caused by conditions at the press molding stage, resulting in poor thickness accuracy. Yes.
  • the extrusion molding method is a molding method under severe conditions of high temperature and high pressure compared with the calendar press molding method, and therefore, the selection range of a stabilizer having a low temperature decomposition inhibiting function is narrow. It is necessary to use tin stabilizers, metal stone stabilizers, zeolite, hydrated talcite, aluminum-based and magnesium-based hydroxides in combination.
  • a suitable combination includes a combination of an organic tin stabilizer and one or more of zeolite, hydrated talcite, and magnesium hydroxide.
  • the continuous extrusion press molding method has no problem of wrinkling and delamination (solvent resistance), and the extruded plate is pressed subsequent to extrusion, so the wavy phenomenon is
  • This is a particularly preferable molding method in that a plate having a desired thickness can be obtained with high thickness accuracy.
  • Examples of the low-temperature decomposition inhibitor suitably used in the extrusion continuous press molding method include organotin stabilizers, anodic talcite, magnesium hydroxide, and the like.
  • the flame retardancy of a flame retardant chlorinated resin molding can be evaluated using a cone calorimeter in accordance with ASTME1354.
  • the flame retardant properties evaluated by the combustion test using a corn calorimeter include the maximum calorific value due to combustion per unit area and unit time (maximum calorific value, also referred to as PHRR; unit: kW / m 2 ), Average value of calorific value by combustion per unit area and unit time (average heat rate, also described as AHRR; unit: kW / m 2 ), total heat value by combustion (also described as total heat value, THR; unit: Mj / m 2 ), average value of mass reduction rate due to combustion per unit area and unit time (also referred to as mass reduction rate, AMLR; unit: g / sec 'm 2 ), reduction due to combustion per unit area and unit time Maximum value of light volume (maximum dimming volume, also described as PSEA; unit: m 2 / g), average value of light volume due to
  • a value evaluated by a combustion test using a corn calorimeter is used as an indicator of flame retardancy.
  • the FM standard is a standard obtained by submitting test specimens to the industry mutual insurance organization and evaluating the industry mutual insurance organization, so it takes time to obtain the evaluation results and is inefficient.
  • the combustion test using the corn calorimeter is efficient because it can be performed by the inventors.
  • FPI has a strong correlation with indices related to calorific values such as PHRR, AHRR, and THR measured by a corn calorimeter.
  • SDI has a strong correlation with indicators related to dimming volume such as PSEA and ASEA.
  • CDI has a strong correlation with mass loss indicators such as AMLR.
  • the approximate value of the FM standard can be obtained efficiently.
  • FPI is required to be 6 or less and SDI is required to be 0.4 or less!
  • PHRR is 130kW / m 2 or less
  • AHRR is 65 kW / m 2 or less
  • AMLR is 13g / sec 'm 2 or less
  • PSEA is 1500m 2 / It is preferable that the ASEA is 800 g 2 / kg or less.
  • the upper limit of the average heat release rate (AHRR) measured according to AS TME1354 of the molded product when molded into a thickness of 5 am using this chlorinated resin resin is 65 kW / m 2 or less, preferably 50 kW / m 2 or less, more preferably 30 kW / m 2 or less.
  • the upper limit of the average specific attenuation area (ASEA) measured according to ASTM E1354 of the molded product is 800 m 2 / kg or less It is preferably 600 m 2 / kg or less, more preferably 500 m 2 / kg or less.
  • the FM standard can be satisfied.
  • the average heating rate (AHRR) and average specific attenuation surface of the molded body measured according to AST ME1354 are measured.
  • the product (ASEA) it is preferable to add chlorine-containing resin having a high temperature decomposition promoting function and to reduce the number of organic compounds having a high temperature decomposition inhibiting function.
  • the molded article has a total light transmittance of 55 to 100%, preferably 65 to 100%, more preferably 70 to 100%, and a haze value of 0 to 20%, preferably 0. It is desirable that the molded body is 10%, more preferably 0 to 5%, particularly when the thickness is 5 mm.
  • a chlorine-containing resin having a high-temperature decomposition promoting function and a heat stabilizer having a low-temperature decomposition suppressing function are added as little as possible. It is preferable to adjust.
  • the molded product has not only excellent flame retardancy but also excellent transparency. Therefore, especially by using rigid chlorinated resin moldings, interior and exterior materials for transportation equipment such as aircraft, ships and vehicles; interior and exterior materials for buildings; daily goods such as furniture and office equipment; housings for home appliances and electronic devices
  • Material Can be used suitably as a component of a semiconductor device
  • the inventor has identified a specific organic compound together with a specific high-temperature decomposition accelerator and a low-temperature decomposition inhibitor, particularly an organic compound having an excellent function as a lubricant or a processing aid.
  • a specific high-temperature decomposition accelerator and a low-temperature decomposition inhibitor particularly an organic compound having an excellent function as a lubricant or a processing aid.
  • Such an organic compound functions as a high-temperature decomposition inhibitor in a system in which the specific high-temperature decomposition accelerator and the low-temperature decomposition inhibitor coexist.
  • the decomposition of the base material resin (Buhl chloride resin) at high temperatures is well controlled. Furthermore, the flame retardant resin is further improved in flame retardancy.
  • the other characteristic of the above organic compound is that it functions as a lubricant or processing aid because it does not require the use of ordinary lubricants or processing aids that are generally used in chlorinated resin. Therefore, the high and / or transparency inherent to the chlorinated resin that is impaired by the blending of these auxiliaries can be maintained at the same level.
  • Chlorine-containing resin high temperature decomposition accelerator in the table
  • high temperature decomposition inhibitory organic compound table
  • a thermal stabilizer having a low-temperature decomposition-promoting function (“low-temperature decomposition inhibitor” in the table) are blended in the proportions shown in Tables 1 and 2, and A system resin composition was obtained.
  • the obtained chlorinated resin composition was formed by the molding methods shown in Table 1 and Table 2, and the properties of the molded body were evaluated by methods according to the respective molding methods (details below). reference).
  • a chlorine-containing resin having a high-temperature decomposition accelerating function high-temperature decomposition accelerator in the table
  • an organic compound having a high-temperature decomposition-inhibiting function high temperature in the table
  • Decomposition stabilizer organic compound having a high-temperature decomposition-inhibiting function
  • thermal stabilizer having a low-temperature decomposition promoting function
  • low-temperature decomposition inhibitor in the table were blended in the proportions shown in Table 3 to obtain a comparative bull chloride resin composition.
  • the obtained chlorinated resin-based resin composition was molded by each molding method shown in Table 3, and the characteristics of the molded body were evaluated by a method according to each molding method (see below for details). .
  • the numerical value of the blending ratio is the parts by mass of each compound with respect to 100 parts by mass of the chlorinated resin.
  • chlorinated resin a chlorinated resin having a polymerization degree of 800 (trade name “TH-800” manufactured by Taiyo PVC Co., Ltd.) was used.
  • Chlorinated polyethylene resin Trade name "404B” manufactured by Showa Denko
  • Vinylidene chloride resin Product name "Saranl68” manufactured by Dow Chemical
  • Zinc compound Zinc laurate (trade name "ZS-3” manufactured by Kosho)
  • Lubricant Cognis brand name "Kuchikiol G60"
  • Plasticizer Product name "DINA”, manufactured by G +
  • Antistatic agent Trade name “Electro Stripper TS-5” manufactured by Kao Corporation
  • UV absorber Trade name “Chinubin P” manufactured by Ciba Specialty
  • Antioxidant Product name "Ilganox 1076” manufactured by Ciba Specialty
  • Organotin-based stabilizer Product name "N-2000E” manufactured by Nitto Kasei Co., Ltd.
  • Metal stone stabilizer Product name "NMZ43” manufactured by Shinagawa Chemical
  • Hydeguchi Talsite Kyowa Chemical Co., Ltd. product name "Al force Mizer 1"
  • Aluminum-based hydroxide Kawai Lime Industry Co., Ltd. product name "ALH”
  • Magnesium hydroxide Trade name “Madasarat F” manufactured by Kyowa Chemical Co., Ltd.
  • compositions of Examples and Comparative Examples were kneaded with a 180 ° C calender roll, sheeted to a thickness of 1 mm, and the obtained 6 sheets were stacked to form a 200 ° C hot plate (10 cm x 10 cm, thickness 5 mm). Then, AHRR (kW / m 2 ) and ASEA (m 2 / kg) were measured according to ASTME1354 using a cone calorimeter manufactured by Atlas Co., Ltd. for 15 minutes.
  • compositions of Examples and Comparative Examples were kneaded with a 180 ° C. calender roll, sheeted to a thickness of 0.5 mm, and 6 sheets of the obtained sheets were stacked, and then pressed with a 200 ° C. hot plate to a thickness of 2 mm for 10 minutes.
  • the change in yellowness ( ⁇ YI) between the molded body that was less molded and the molded body that was pressed for 20 minutes was measured with a color difference meter.
  • the total light transmittance (%) and haze value (%) were measured for the transparency of the calender press molded body obtained by molding in the same manner as in the above flame retardancy evaluation.
  • Molding processability at the time of molding as in the following (2) to (4) was evaluated according to the following criteria. ⁇ : Local decomposition does not occur, the resin temperature and the resin pressure can be controlled, color unevenness and streaks do not occur, and a good molded product can be obtained.
  • a molded body cannot be obtained because local decomposition occurs and it is difficult to control with resin temperature and pressure.
  • compositions of Examples and Comparative Examples were extruded into a 5 mm thick plate, and AHRR (kW / m 2 ) and ASEA (m 2 / kg) were measured for this molded body in the same manner as the calendar press molded body. did.
  • compositions of Examples and Comparative Examples were extruded into a 4 mm thick plate at 200 ° C. with a twin-screw extruder, and the yellowing change ( ⁇ YI) of the obtained molded body was measured with a color difference meter.
  • Molding processability at the time of molding as in the following (2) to (4) was evaluated according to the following criteria. ⁇ : Local decomposition does not occur, the resin temperature and resin pressure can be controlled, and it adheres to the continuous press plate Since it can be peeled off, a good molded product can be obtained. In addition, streaks and color irregularities cannot be detected by visual inspection.
  • Partial decomposition occurs, but a molded product that can be adjusted by the resin temperature and the resin pressure and that has no practical problem within the range of condition adjustment of the continuous press plate can be obtained. Although there are streaks and uneven color, there is no practical problem.
  • compositions of Examples and Comparative Examples were extruded into a 10 mm thick plate with a twin-screw extruder, and this was continuously press molded into a 5 mm thickness with a 200 ° C hot plate.
  • AHRR kW / m 2
  • ASEA m 2 / kg
  • compositions of Examples and Comparative Examples were extruded into a 4 mm thick plate with a twin-screw extruder, and this was press molded with a hot plate at 200 ° C to a thickness of 2 mm for 10 minutes and a molded body for 20 minutes.
  • the change in yellowness ( ⁇ YI) with the molded body was measured with a color difference meter.
  • the present invention has sufficient flame retardancy, thermal stability during molding, and other various properties, and when formed into a molded body, it has sufficient flame retardancy, high transparency, good appearance, and high softness. It is possible to obtain a chlorinated resin resin composition having various crystallization temperatures and other excellent properties.
  • molded articles obtained from various molding methods of this composition are excellent in flame retardancy and transparency, have a high softening temperature with a small amount of smoke generation, and have a good appearance.
  • Molded articles made of the resin composition of the present invention using a nyl-based resin are used for aircraft, ships, vehicles and other transport equipment inside and outside equipment; building interior and exterior materials; furniture, office equipment and other daily necessities; household appliances, electronic equipment, etc. Housing material; suitable as a component of a semiconductor device.
  • a molded body by the extrusion continuous press molding method is excellent in solvent resistance that does not return during thermal processing and has a high thickness accuracy, and thus is suitably used as a base material for various molded bodies as described above. be able to.

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Abstract

L'invention concerne une composition de résine de chlorure de vinyle transparente qui présente une stabilité thermique et une onctuosité nécessaires pour assurer une productivité élevée, en plus d'une excellente transparence et d'une capacité de retardement des flammes. L'invention concerne également un corps moulé obtenu à partir de cette composition de résine de chlorure de vinyle. L'invention concerne en particulier une composition de résine de chlorure de vinyle caractérisée en ce qu'elle contient, pour 100 parts en masse de résine de chlorure vinyle, de 1 à 50 parts en masse d'une résine contenant du chlore ayant une fonction d'accélération de décomposition à haute température, de 0,1 à 7 parts en masse d'un composé organique ayant une fonction d'inhibition de décomposition à haute température, et de 1 à 10 parts en masse d'un stabilisant thermique (comprenant un assistant de stabilisant thermique) ayant une fonction de suppression de décomposition à basse température. L'invention concerne également en particulier un corps moulé obtenu à partir de cette composition de résine de chlorure de vinyle.
PCT/JP2007/065560 2006-08-08 2007-08-08 Composition de résine de chlorure de vinyle transparente et de retardement des flammes et produit moulé WO2008018521A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010093122A (ja) * 2008-10-09 2010-04-22 Dainippon Printing Co Ltd 太陽電池モジュール用充填材シートおよびそれを用いた太陽電池モジュール
WO2019065742A1 (fr) * 2017-09-27 2019-04-04 積水化学工業株式会社 Composition de résine destinée à un moulage
WO2019065748A1 (fr) * 2017-09-27 2019-04-04 積水化学工業株式会社 Composition de résine pour le moulage par injection
CN110294903A (zh) * 2019-02-20 2019-10-01 广东光塑科技股份有限公司 一种高透明无味耐高温pvc改性材料及其制备方法
JP2020186806A (ja) * 2019-05-17 2020-11-19 積水化学工業株式会社 耐熱透明継手
CN115785588A (zh) * 2022-07-21 2023-03-14 深圳市好亚通防护用品有限公司 一种永久静电耗散pvc鞋底材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10251916A (ja) * 1997-03-11 1998-09-22 Kanegafuchi Chem Ind Co Ltd 繊維用塩化ビニル系樹脂組成物及び該樹脂組成物を用いてなる塩化ビニル系繊維
JP2000186180A (ja) * 1998-12-22 2000-07-04 Mitsubishi Chem Mkv Co 塩化ビニル系樹脂組成物
JP2003514942A (ja) * 1999-11-19 2003-04-22 ジョージア・ガルフ・コーポレイション 難煙および難燃性プレナム組成物
WO2006035867A1 (fr) * 2004-09-29 2006-04-06 Kaneka Corporation Fibre polychlorure de vinyle de faible coloration initiale

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10251916A (ja) * 1997-03-11 1998-09-22 Kanegafuchi Chem Ind Co Ltd 繊維用塩化ビニル系樹脂組成物及び該樹脂組成物を用いてなる塩化ビニル系繊維
JP2000186180A (ja) * 1998-12-22 2000-07-04 Mitsubishi Chem Mkv Co 塩化ビニル系樹脂組成物
JP2003514942A (ja) * 1999-11-19 2003-04-22 ジョージア・ガルフ・コーポレイション 難煙および難燃性プレナム組成物
WO2006035867A1 (fr) * 2004-09-29 2006-04-06 Kaneka Corporation Fibre polychlorure de vinyle de faible coloration initiale

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010093122A (ja) * 2008-10-09 2010-04-22 Dainippon Printing Co Ltd 太陽電池モジュール用充填材シートおよびそれを用いた太陽電池モジュール
WO2019065742A1 (fr) * 2017-09-27 2019-04-04 積水化学工業株式会社 Composition de résine destinée à un moulage
WO2019065748A1 (fr) * 2017-09-27 2019-04-04 積水化学工業株式会社 Composition de résine pour le moulage par injection
JPWO2019065742A1 (ja) * 2017-09-27 2019-11-14 積水化学工業株式会社 成形用樹脂組成物
JPWO2019065748A1 (ja) * 2017-09-27 2019-11-14 積水化学工業株式会社 射出成形用樹脂組成物
CN110520473A (zh) * 2017-09-27 2019-11-29 积水化学工业株式会社 注塑成形用树脂组合物
CN110621737A (zh) * 2017-09-27 2019-12-27 积水化学工业株式会社 成形用树脂组合物
US11692091B2 (en) 2017-09-27 2023-07-04 Sekisui Chemical Co., Ltd. Resin composition for injection molding
US11866574B2 (en) 2017-09-27 2024-01-09 Sekisui Chemical Co., Ltd. Resin composition for molding
CN110294903A (zh) * 2019-02-20 2019-10-01 广东光塑科技股份有限公司 一种高透明无味耐高温pvc改性材料及其制备方法
JP2020186806A (ja) * 2019-05-17 2020-11-19 積水化学工業株式会社 耐熱透明継手
CN115785588A (zh) * 2022-07-21 2023-03-14 深圳市好亚通防护用品有限公司 一种永久静电耗散pvc鞋底材料及其制备方法

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