WO2008018521A1 - Transparent flame-retardant vinyl chloride resin composition and molded body - Google Patents
Transparent flame-retardant vinyl chloride resin composition and molded body Download PDFInfo
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- 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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- 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
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- 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 halogen-containing compounds
- C08L23/286—Chlorinated polyethene
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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
- C08L27/08—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
Description
明 細 書 Specification
塩化ビュル系樹脂組成物及び成形体 BULLIUM CHLORIDE RESIN COMPOSITION AND MOLDED BODY
技術分野 Technical field
[0001] 本発明は、透明で難燃性を備えた成形体を成形することができる塩化ビュル系樹 脂組成物及びこの組成物を成形して得られる成形体に関する。 [0001] 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.
背景技術 Background art
[0002] 塩化ビュル系樹脂は、分子中に塩素を含有しており、難燃性に優れるのみならず、 各種の添加剤を広い含有量で添加できるため、機械的特性、耐熱性、成形性、耐候 性などを広範囲にわたって調整することができ、様々な用途に用いられてきた。例え ば硬質塩化ビュル系樹脂組成物の成形品は、航空機、船舶、車両等の輸送機内外 装材;建築物内外装材;家具、事務用具等の日用品;家電機器、電子機器等のハウ ジング材;半導体装置の部品等として使用されてきた。 [0002] 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. For example, 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.
[0003] しかし、塩化ビュル系樹脂は、火災等により耐熱温度以上の高温に晒されると、分 子内の塩素に起因して、多量に発煙すると共に、塩素ガスや塩化水素ガス等の有毒 ガスを発生する。このため、添加剤の種類及び配合量を検討することにより、有毒ガ スの発生を抑制することが試みられてきた。 However, when chlorinated resin is exposed to a temperature higher than the heat-resistant temperature due to a fire or the like, a large amount of smoke is generated due to chlorine in the molecule, and a toxic gas such as chlorine gas or hydrogen chloride gas is generated. Is generated. For this reason, attempts have been made to suppress the generation of toxic gases by examining the types and amounts of additives.
[0004] 例えば特許文献 1には、 FM規格を満足する透明塩化ビュル系樹脂を目的として、 塩化ビュル系樹脂 100重量部に対して、亜鉛化合物を金属亜鉛量に換算して 0. 00 5〜5重量部、錫安定剤を 0. 5〜7重量部含有し、所望の形状に成形してなる透明 難燃性塩化ビュル系樹脂成形体が開示されている。 [0004] For example, in 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.
しかし、この開示技術では、十分な難燃性を確保できず、加工条件によっては粉末 の亜鉛化合物由来の分散不良焼け等の外観不良の可能性を有し、また滑性や熱安 定性に劣り成形加工性が悪!/、ためその改良が望まれて!/、た。 However, with this disclosed technology, sufficient flame retardancy cannot be ensured, and depending on the processing conditions, there is a possibility of poor appearance such as poorly dispersed burn derived from the zinc compound of the powder, and inferior lubricity and thermal stability. Molding processability is bad! Therefore, the improvement is desired! /.
[0005] また、特許文献 2には、難燃性を有する透明塩化ビュル系樹脂成形体を目的として 、塩素化度が低い塩化ビュル層と塩素化度が高い塩化ビュル層を積層し、成形体内 の平均塩素化度が 60%以上で、所望の形状に成形してなる透明難燃性塩化ビュル 系樹脂成形体が開示されている。 しかし、この開示技術では、組成の異なる樹脂を積層するため、その樹脂界面で屈 折率差が生じ、高い透明性を得ることが難しい上、工程が煩雑となり生産性が上がら ない問題がある。生産性を上げるために、単層にすると、難燃性が不十分となるばか りでなぐ十分な透明性の確保も困難となる。 [0005] Further, 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. However, in this disclosed technology, since 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.
[0006] さらに特許文献 3には、有機錫安定剤を含む塩化ビュル系樹脂組成物において、 塩化ビュル系樹脂 100質量部に対して、高温分解促進剤として有機亜鉛化合物 0. 01〜;!質量部、低温分解抑制剤として金属水酸化物 0. 001〜;!質量部を有すること を特徴とする塩化ビュル系樹脂組成物及びそれから得られた成形品が開示されてい この開示内容では、優れた透明性と難燃性を確保することができるが、さらなる透明 性と難燃性の向上に加えて加工性の向上が期待される。 [0006] Further, 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! In particular, 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.
[0007] 以上のように、従来の塩化ビュル樹脂成形体は、高い透明性と難燃性と共に、高い 生産性を同時に満足することが困難であった。 [0007] As described above, it has been difficult for the conventional chlorinated resin molded body of resin to satisfy high productivity as well as high transparency and flame retardancy.
[0008] 特許文献 1:特開 2001— 192520号公報 [0008] Patent Document 1: Japanese Patent Laid-Open No. 2001-192520
特許文献 2:特開 2005— 15620号公報 Patent Document 2: Japanese Unexamined Patent Publication No. 2005-15620
特許文献 3:特開 2004— 300299号公幸 Patent Document 3: Japanese Patent Publication No. 2004-300299
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0009] 本発明は、優れた透明性、難燃性とともに、高い生産性を確保するのに必要な熱 安定性および滑性を備えた塩化ビュル系樹脂組成物、並びに、これから得られる成 形体を提供することを目的とする。 [0009] 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.
課題を解決するための手段 Means for solving the problem
[0010] かかる目的のため、本発明者は、塩化ビュル系樹脂 100質量部に対し、高温分解 促進機能を有する塩素含有樹脂 1〜50質量部、高温分解阻害機能を有する有機化 合物 0.;!〜 7質量部、低温分解抑制機能を有する熱安定剤 (熱安定化助剤を含む)[0010] For this purpose, 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)
1〜; 10質量部を含むことを特徴とする塩化ビュル系樹脂組成物及びその成形体を 提案する。 1 to; Proposed a chlorinated bur resin composition and a molded body thereof containing 10 parts by mass.
[0011] 本発明の塩化ビュル系樹脂組成物によれば、高温分解促進機能を有する塩素含 有樹脂の分解促進機能と、高温分解阻害機能を有する有機化合物の分解阻害機能 との相乗効果により、難燃性に優れるば力、りでなぐ塩化ビュル系樹脂が本来有して V、る高!/、透明性をそのままのレベルで維持することができると共に、高!/、生産性を確 保するのに必要な熱安定性、滑性においても優れたものとなる。そして、このような塩 化ビュル系樹脂組成物を押出成形、カレンダープレス成形、あるいは押出連続プレ ス成形して得られる本発明の成形体は、透明性、難燃性に優れると共に、高い生産 性をもって成形することができる熱安定性を有するものとなる。 [0011] According to the chlorinated resin resin composition of the present invention, a chlorine-containing resin having a high-temperature decomposition promoting function. By virtue of the synergistic effect of the decomposition promoting function of the resin-containing resin and the decomposition inhibiting function of the organic compound having the high-temperature decomposition inhibiting function, it is excellent in flame retardancy, and 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.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0012] 以下、本発明の実施形態の一例としての塩化ビュル系樹脂組成物(以下「本塩化 ビュル系樹脂組成物」という)、並びに、本塩化ビュル系樹脂組成物を成形して得ら れる成形体(以下「本成形体」という)について説明する。但し、本発明の範囲が以下 に説明する実施形態に限定されるものではない。 [0012] Hereinafter, it is obtained by molding the bull chloride resin composition (hereinafter referred to as "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. However, the scope of the present invention is not limited to the embodiments described below.
[0013] 本塩化ビュル系樹脂組成物は、母材樹脂としての塩化ビュル系樹脂のほかに、高 温分解促進剤、低温分解抑制剤および高温分解阻害剤を含有することを特徴とする 塩化ビュル系樹脂組成物である。 [0013] 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.
[0014] ここで、高温分解促進剤とは、高温領域における塩化ビュル系樹脂の分解を促進 する機能を有する物質であり、高温分解阻害剤とは、高温領域における塩化ビュル 系樹脂の分解を阻害する機能を有する物質であり、低温分解抑制剤とは、低温領域 における塩化ビュル系樹脂の分解を抑制する機能を有する物質である。 [0014] Here, the high temperature decomposition accelerator is a substance having a function of promoting the decomposition of the chlorinated resin in the high temperature region, and 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.
なお、塩化ビュル系樹脂の分解挙動に関して言えば、加工温度領域である 220°C までは脱塩酸挙動が開始する温度領域であり、 220°Cから 370°C付近が脱塩酸挙 動が盛んに生じる温度領域である。それ以上の温度領域、例えば 450°C以上では、 塩化ビュル系樹脂の主鎖の切断により分解されたり、塩化ビュル系樹脂の炭素の燃 焼や炭化が起きたりする。よって、本発明において、低温領域における分解とは、成 形加工温度領域である 220°Cまでの温度領域における分解挙動のことを!/、い、高温 領域における分解とは、主鎖の切断やカーボン燃焼が生じる 450°C以上の温度領域 における分解挙動のことをいう。 In terms of the decomposition behavior of chlorinated resin, 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.
また、本発明における高温分解促進機能とは、塩化ビュル系樹脂が、 450°C以上 において、塩化ビュル系樹脂の主鎖の切断により分解されることや、塩化ビュル系樹 脂内の炭素の燃焼によって炭化されることを、促進する機能であると言える。また、本 発明における高温分解阻害機能とは、前記した 450°C以上での、塩化ビュル系樹脂 の分解や炭化を阻害する機能であると言える。さらに、本発明における低温分解抑 制機能とは、 220°C未満において塩化ビュル系樹脂からの脱塩酸挙動が開始する のを抑制する機能であると言える。 In addition, 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. In addition, 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. Furthermore, it can be said that 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.
[0015] (塩化ビュル系樹脂) [0015] (Buluric chloride resin)
本塩化ビュル系樹脂組成物において、母材樹脂として用いることができる塩化ビニ ル系樹脂としては、塩化ビュルの単独重合体、塩化ビュルと他のビュル化合物の共 重合体を挙げることができ、これらは単独或いはこれら 2種の混合樹脂として使用す ること力 Sでさる。 Examples of the vinyl chloride resin that can be used as a base resin in the present chlorinated resin composition include homopolymers of chlorinated chloride and copolymers of chlorinated chloride and other bulle compounds. Can be used alone or as a mixture of these two.
[0016] 上記の共重合体において、塩化ビュル成分と共重合し得る他のビュル化合物とし ては、特に限定するものではない。例えば酢酸ビュル、プロピオン酸ビュル等の脂肪 酸ビュルエステル;メタクリル酸メチル、メタクリル酸ェチル、メタクリル酸ブチル等のメ タクリル酸アルキルエステル;アクリル酸メチル、アクリル酸ェチル、アクリル酸ブチル 等のアクリル酸アルキルエステノレ;エチレン、プロピレン、スチレン等の α —ォレフィン ;ビニノレメチノレエーテノレ、ビニノレブチノレエーテノレ等のァノレキノレビニノレエーテノレ;アタリ ル酸、メタクリル酸、無水マレイン酸等の不飽和カルボン酸、あるいはその酸無水物 等を挙げることができ、これらは 1種又は 2種以上を組み合わせて用いることができる [0016] In the above-mentioned copolymer, other bur compounds that can be copolymerized with the chlorinated bulu component are not particularly limited. For example, 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 Α-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 more.
〇 Yes
[0017] 前記の共重合体において、他のビュル化合物の共重合量が 30質量%を超えなけ れば、塩化ビュル系樹脂本来の難燃性や高い透明性を損なうことがないため、当該 他のビュル化合物は 30質量%を超えない範囲で含有するのが好ましい。また、前記 の共重合量は、透明性、難燃性の観点より、好ましくは 20質量%、さらに好ましは 10 質量%である。 [0017] In the above-mentioned copolymer, if 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.
[0018] 塩化ビュル系樹脂の平均重合度は 300〜2, 000であるのが好ましぐより好ましく は 500〜; 1 , 500である。平均重合度が小さ過ぎると、成形体が充分な強度とならな いおそれがあり、大き過ぎれば、成形加工時に充分に混練させることが難しぐ加工 性が低下するおそれがある。 [0018] 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.
[0019] 塩化ビュル系樹脂は、その重合方法を特に制限するものではなぐ乳化重合法、 懸濁重合法、塊状重合法等の種々の方法を用いて重合されたものを使用することが できる。 [0019] As the 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.
[0020] (高温分解促進剤) [0020] (High-temperature decomposition accelerator)
高温分解促進剤は、高温領域にお!/、て (例えば 450°C以上)成形体の燃焼時に、 塩化ビュル系樹脂の主鎖の切断および炭化を促進し、発煙量を低減する役割を果 たすものである。 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.
[0021] 高温分解促進剤としては、塩化ビュル系樹脂の主鎖の切断挙動を促進する作用の ある、塩化水素を発生させることができる塩素含有樹脂が好ましレ、。 [0021] As the high-temperature decomposition accelerator, 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.
高温分解促進機能を有する塩素含有樹脂としては、塩素化ポリエチレン樹脂、後 塩素化塩化ビュル樹脂、塩化ビニリデン樹脂などを特に好ましレ、ものとして挙げるこ と力 Sできる。 As the 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.
[0022] 上記の塩素化ポリエチレンとしては、質量平均分子量 50, 000—350, 000のポリ エチレンを塩素化して得られる樹脂であって、塩素含量 28〜43質量%、 DSC法に よる結晶融解熱 25cal/g以下である塩素化ポリエチレン等を例示することができる。 中でも、透明性の観点から、質量平均分子量 50, 000—150, 000のポリエチレンを 塩素化して得られる樹脂であって、塩素含量 28〜35質量%、 DSC法による結晶融 解熱 10〜25cal/gである塩素化ポリエチレンが好ましい。 [0022] 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. Among them, from the viewpoint of transparency, 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.
[0023] 後塩素化塩化ビュル樹脂としては、塩素化前の塩化ビュル樹脂の平均重合度とし て 500〜; 1400のものが好ましい。平均重合度が 500未満では耐衝撃性が低下する 可能性があり、 1400を超えると溶融流動性が低下して成形が困難となる可能性があ また、後塩素化塩化ビュル樹脂の平均塩素含有量は 58〜70質量%、好ましくは 6 0〜70質量%である。平均塩素含有量が少なすぎると耐熱性が低下して変形が発生 しゃすくなり、多すぎると、特に 70質量%を超えると、流動性が大きく低下して成形が 困難となる。 [0023] 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.
[0024] 塩化ビユリデン樹脂としては、塩化ビユリデンの単独重合体及び共重合体を挙げる こと力 Sできる。熱分解温度と融点との間に差のあるもの、すなわち共重合体を用いる のが好ましい。 [0024] 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.
塩化ビニリデンの共重合体としては、塩化ビニリデンと、公知のラジカル重合性モノ マーを単独あるいは 2種以上とを共重合させたものを用いることができる。 As the 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.
このラジカル重合性モノマーとしては、塩化ビュル、アクリロニトリル、アクリル酸又は メタアクリル酸等の不飽和脂肪酸及びこれらのエステル類、酢酸ビュル等のビュルェ ステル類、ビニルケトン類、エチレンやプロピレン等のォレフィン類、 n メチルアタリ ノレアミド、シクロへキシルマレイミド等の特種官能基を含有するモノマー等を挙げるこ と力 Sできる。 Examples of the radical polymerizable monomer 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.
塩化ビニリデンと前記モノマーとの共重合体の組成は、特に限定されないが、難燃 性を満足させるには、塩化ビニリデンの含有量が 65〜99質量%、好ましくは 80〜97 質量%であるものを選定するのが好まし!/、。 The 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!
また、塩化ビニリデンの共重合体の分子量は、特に限定されるものではないが、加 ェ性、成形体の物性等の点で質量平均分子量が 30000〜 150000、好ましくは 50 000〜; 120000カ好ましレヽ。 Further, 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.
塩化ビユリデンの重合体の重合方法としては、懸濁重合、乳化重合、塊状重合、気 相重合等を挙げることができ、良好な粉状体を安価に得る観点から、特に懸濁重合 が好ましい。 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.
[0025] 高温分解促進剤は、添加量が少な!/、と、燃焼時に炭化が促進されな!/、ので難燃性 が向上しない一方、添加量が多過ぎると、透明性の低下ゃ耐温水白化性の悪化など が生じるようになる。よって、高温分解促進剤の含有量は、塩化ビュル系樹脂 100質 量部に対し、;!〜 50質量部が好ましぐ中でも 5〜30質量部、その中でも特に 10〜2 0質量部であるのが好まし!/、。 [0025] 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!
[0026] (低温分解抑制剤) [0026] (Low-temperature decomposition inhibitor)
低温分解抑制剤としては、従来から塩化ビュル用の熱安定剤や熱安定化助剤とし て知られているものの中から、透明性が良好なものを選択して使用するのが好ましい 。例えば、ブチル錫マレート、ォクチル錫マレート、ジー nアルキル錫メルカプチド、ジ n アルキル錫ジラウレート、ジブチル錫ジマレート、ジブチル錫ラウリルメルカプ チド、ジォクチル錫 S, S '—ビス (イソォクチルーメルカプトアセテート)、ジブチル 錫ビス イソォクチルチオグリコレート、ジー(n ォクチル)錫マレート重合体、ジブ チル錫メルカプトプロピオナート等の錫系安定剤、鉛系安定剤、カリウム、マグネシゥ ム、ノ リウム、亜鉛、カドミウム、鉛等の金属と、 2—ェチルへキサン酸、ラウリル酸、ミリ スチン酸、パルミチン酸、ステアリン酸、ヒドロキシステアリン酸、ォレイン酸、リシノー ル酸、ベヘン酸等の脂肪酸から誘導される金属石鹼系安定剤、 Ba— Zn系、 Ca-Z n系、 Ba— Ca— Sn系、 Ca— Mg— Sn系、 Ca— Zn— Sn系、 Pb Ba系、 Pb Ba— Ca系等の複合金属石鹼系安定剤、ノ リウム、亜鉛等の金属基と、 2—ェチルへキサ ン酸、イソデカン酸、トリアルキル酢酸等の分岐脂肪酸、ォレイン酸、リシノール酸、リ ノール酸等の不飽和脂肪酸、ナフテン酸等の脂環族酸、石炭酸、安息香酸、サリチ ル酸及びそれらの置換誘導体等の芳香族酸の中から選ばれる通常 2種以上の有機 酸とから誘導される金属塩系安定剤、これら安定剤を石油系炭化水素、アルコール、 グリセリン誘導体等の有機溶剤に溶解し、さらに亜リン酸エステル、エポキシ化合物、 発色防止剤、透明性改良剤、光安定剤、酸化防止剤、プレートアウト防止剤、滑剤 等の安定化助剤を配合した金属塩液状安定剤等の金属系安定剤、エポキシ樹脂、 エポキシ化植物油、エポキシ化脂肪酸アルキルエステル、エポキシ化芳香族アルキ ルエステル等のエポキシ化合物、リンがアルキル基、ァリール基、シクロアクリル基、 アルコキシル基等で置換され、かつプロピレングリコール等の二価アルコール、ヒドロ キノン、ビスフエノール A等の芳香族化合物を有する有機亜リン酸エステル、ヒンダ一 ドアミン又はニッケル錯塩の光安定剤、トリメチロールプロパン、ペンタエリスリトール、 ソノレビトーノレ、マンニトール等の多価アルコール、 /3—ァミノクロトン酸エステル、 2— フエニルインドール、ジフエ二ルチオ尿素、ジシアンジアミド等の含窒素化合物、ジァ ルキルチオジブロピオン酸エステル等の含硫黄化合物、ァセト酢酸ェチル、デヒドロ 酢酸、 /3—ジケトン等のケト化合物、有機ケィ素化合物、ホウ酸エステル等の非金属 系安定剤などを好ましい例として挙げることができる。これらの中から選択したものを それぞれ単独で用いてもよ!/、し、 2種以上を組み合わせて用いてもよ!/、。 As 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. For example, butyltin malate, octyltin malate, di-n-alkyltin mercaptide, di-n-alkyltin dilaurate, dibutyltin dimalate, dibutyltin lauryl mercap Tin, dioctyltin S, S '-bis (isooctyl-mercaptoacetate), dibutyltin bisisooctylthioglycolate, di (noctyl) tin malate polymer, dibutyltin mercaptopropionate, etc. 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. 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. 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 mannitol Nitrogen-containing compounds such as dihydric alcohol, / 3-aminocrotonic acid ester, 2-phenylindole, diphenylthiourea and dicyandiamide, sulfur-containing compounds such as dialkylthiodibropionate, acetyl acetate, dehydroacetic acid, / Preferred examples include keto compounds such as 3-diketones, organic cage compounds, and nonmetallic stabilizers such as boric acid esters. You can use one of these selected alone! /, Or use two or more in combination! /.
以上の中でも、有機錫系安定剤、金属石鹼系安定剤、ゼォライト、ハイド口タルサイ ト類、アルミニウム系、マグネシウム系水酸化物が好ましぐその中でも特に、低温分 解抑制機能及び透明性がともに優れる観点から、錫系安定剤、金属石鹼系安定剤 が特に好適である。 Of these, 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.
なお、ゼォライト、ハイド口タルサイト類、アルミニウム系水酸化物、マグネシウム系水 酸化物は熱安定化助剤として用いられてレ、る。 Zeolite, hydrated talcite, aluminum hydroxide and magnesium hydroxide are used as heat stabilization aids.
[0027] 錫系安定剤としては、マレート系錫安定剤、ラウレート系錫安定剤、メルカプト系錫 系安定剤などを挙げることができ、中でも、透明性に有利なメルカプト系錫安定剤が 特に好ましい。 [0027] Examples of tin stabilizers 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. .
[0028] 金属石鹼系安定剤としては、炭素数 10〜22、特に 14〜; 18の飽和〜不飽和脂肪 酸の金属石鹼、例えばナトリウム塩、カリウム塩等のアルカリ金属塩;カルシウム塩、 マグネシウム塩、ノ リウム塩等のアルカリ土類金属塩、亜鉛塩等を挙げることができ、 これらの中でも、カルシウム塩、マグネシウム塩、ノ リウム塩、亜鉛塩が特に好適であ る。これらは単独でも 2種以上の組合せでも使用できる。 [0028] As the metal stalagmite stabilizer, a metal sarcophagus of a saturated to unsaturated fatty acid having 10 to 22 carbon atoms, particularly 14 to 18; an alkali metal salt such as a sodium salt or a potassium salt; a calcium salt; Examples thereof include alkaline earth metal salts such as magnesium salts and sodium salts, and zinc salts. Among these, calcium salts, magnesium salts, norlium salts, and zinc salts are particularly preferable. These can be used alone or in combination of two or more.
金属石鹼の脂肪酸としては、例えば力プリン酸、ゥンデカン酸、 2ェチルへキソイン 酸、ラウリン酸、ミリスチン酸、パルミチン酸、マーガリン酸、ステアリン酸、ァラキン酸 等の飽和脂肪酸、リンデル酸、ッズ酸、ペトロセリン酸、ォレイン酸、リノール酸、リノレ ン酸、ァラキドン酸等の不飽和脂肪酸、安息香酸、 t プチルー安息香酸等の芳香 族脂肪酸を挙げることができる。 Examples of the fatty acid of metal sarcophagus 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.
中でも、透明性の観点から言えば、同じ炭素数であれば脂肪酸亜鉛より芳香族脂 肪酸亜鉛が好ましぐまた、炭素数は短いほうが塩化ビュル系樹脂に対して相容性 がよぐ高い透明性を得やすいので好ましい。よって、 tーブチルー安息香酸や 2ェチ ルへキソイン酸のカルシウム、亜鉛塩などが特に好適である。 Among them, from the viewpoint of transparency, if the number of carbon atoms is the same, zinc aromatic fatty acid is preferred to fatty acid zinc, and the shorter the number of carbons, the better the compatibility with the chlorinated resin. It is preferable because transparency can be easily obtained. Therefore, t-butyl-benzoic acid and calcium and zinc salts of 2-ethylhexoic acid are particularly suitable.
[0029] ゼォライトとしては、例えばゼォライト A、ゼォライト X、ゼォライト Y等の合成ゼォライ ト、その部分ないしは完全酸処理物、あるいはそれらの金属イオン(例えばカルシゥ ム、マグネシウム、亜鉛イオン)交換処理物のアルミノ珪酸塩を挙げることができる。こ れらの中でも、熱安定性付与が良好なナトリウムイオン交換 A型ゼオライトが特に好 適である。 [0029] Examples of zeolite 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.
[0030] ハイド口タルサイト類としては、次の式(1)〜(4)で表されるものを挙げることができる [0030] Examples of the hyde talcite include those represented by the following formulas (1) to (4).
〇 すなわち、式(1): Mg Al (OH) CO - aH 0 (式中、 x, yは l/4≤x/y≤8を x y 2x+3y-2 3 2 Yes That is, formula (1): Mg Al (OH) CO-aH 0 (where x, y is l / 4≤x / y≤8 xy 2x + 3y-2 3 2
満足する正数、 aは 0. 01≤a/ (x + y)≤l . 0を満足する正数である)で表されるハ イド口タルサイトや、 A positive number satisfying, a is a positive talcite expressed by 0. 01≤a / (x + y) ≤l.
式(2) : Mg Al (OH) ' (Υ— ) . aH Ο (式中、 χ, yは l/4≤x/y≤8を満足す y 2x+3y- 2 n 2 Formula (2): Mg Al (OH) '(Υ—). AH Ο (where χ, y satisfies l / 4≤x / y≤8 y 2x + 3y- 2 n 2
る正数、 nは 1以上の整数、 bは〇<b≤2、 b'n = 2を満足する正数、 aは 0. 01≤a/ (x + y)≤l . 0を満足する正数、 Yはリンのォキシ酸、ィォゥのォキシ酸、窒素のォキ シ酸、ホウ素のォキシ酸、炭酸、ハロゲン水素酸、ハロゲン酸素酸、過ハロゲン酸素 酸、カルボン酸からなる群より選ばれる少なくとも 1種の整数モル単位の酸ァニオンを 組合せることができる単独な!/、しは複合のァニオンを表す)で表されるものや、 式(3): M Al (OH) (Y) - aH 0 (式中、 x, y, zは l/4≤x/y≤8及び z/x Positive number, n is an integer greater than 1, b is 〇 <b≤2, positive number satisfying b'n = 2, a satisfies 0.01≤a / (x + y) ≤l .0 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. Can be combined with at least one integer mole unit of acid anion! / Represents a complex anion) or formula (3): M Al (OH) (Y)- aH 0 (where x, y, z are l / 4≤x / y≤8 and z / x
x y 2x+3y- 2z z 2 x y 2x + 3y- 2z z 2
+ y〉l/20を満足する正数、 Mは Mg, Ca, Zn等二価の金属イオン、 Yは CO 2— , S + y> l / 20 positive number, M is a divalent metal ion such as Mg, Ca, Zn, Y is CO 2 —, S
3 Three
Ο 2等の二価のァニオン、 aは 0又は正の数である)で表されるものや、 Omicron 2 such divalent Anion, and what a is represented by the 0 or a positive is a number),
4 Four
式(4): Mg Al (OH) (A2— )P(A— ) - aZ-bH 0 (式中、 A2—は CO 2等の 2価ァニ x y 2x+3y~z q 2 3 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
オン、 A—はハロゲン酸素酸イオン、 Zは多価アルコール又はその部分エステル、 X, y 及び zは z = 2p + q、 8≥ (x/y)≥1/4及び z/ (x + y)〉1/20を満足する正数で あって、 p及び qは l≥q/ (2p + q)≥l/10を満足する数であり、 a及び bは 0. 01≤ a/ (x + y)≤1. 0¾t O≤b/ (x + y)≤1. 0)の化学組成を有し、特公平 3— 3683 9号公報記載の複合水酸化物などを挙げることができる。 ON, A— is a halogen oxyacid ion, Z is a polyhydric alcohol or its partial ester, X, y and z are z = 2p + q, 8≥ (x / y) ≥1 / 4 and z / (x + y )〉 Is a positive number satisfying 1/20, p and q are numbers satisfying l≥q / (2p + q) ≥l / 10, and a and b are 0.01 01≤ a / (x + y) ≤1.0 0¾t O≤b / (x + y) ≤1.0), and examples thereof include composite hydroxides described in Japanese Patent Publication No. 3-36839.
[0031] アルミニウム系水酸化物およびマグネシウム系水酸化物としては、水酸化アルミ二 ゥム、水酸化マグネシウム等を挙げることができる。また、これら水酸化物粉末に表面 処理を施した水酸化物でもよい。この表面処理剤としては、脂肪酸やモリブデン化合 物を含むものを用いることが分散性、難燃性の面で好ましレ、。 [0031] 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.
[0032] 上記無機系の低温分解抑制剤は、平均粒径の下限値が 0. 01 a m以上、好ましく (ま 0. 05〃111以上、上限ィ直 (ま、 0. 6〃m未満、好ましく (ま 0. 3〃m未満である。平均 粒径が 0. 01 a m以上であれば熱安定剤自体で凝集してしまうことがなく取り扱い易 い。他方、 0. 6 m未満であれば、可視光の波長より小さいため透明性が良い。 [0032] 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.
[0033] 以上の点から、低温分解抑制剤としては、透明性を勘案すると、屈折率が塩化ビニ ル系樹脂に近い有機錫メルカプト系安定剤、ハイド口タルサイト類、水酸化マグネシ ゥム系化合物が特に好ましレ、。 [0033] In view of the above, as a low-temperature decomposition inhibitor, considering transparency, 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.
[0034] 低温分解抑制剤は、添加しないと動的熱安定性が低すぎて成形加工ができず、添 加量が多すぎると、透明性、物性低下を生じ、満足できる成形体が得られない。よつ て、低温分解抑制剤の配合量は、塩化ビュル系樹脂を 100質量部とした場合に、下 限値は、 1質量部以上、好ましくは 2質量部以上、さらに好ましくは 3質量部以上であ り、上限値は、 10質量部以下、好ましくは 8質量部以下、さらに好ましくは 6質量部以 下である。低温分解抑制剤の配合量が、 1質量部以上であれば低温分解が促進され ず成形性が良ぐまた 10質量部以下であれば、難燃性が良好である。 [0034] If the low-temperature decomposition inhibitor is not added, the dynamic thermal stability is too low to be molded, and if the addition amount is too large, transparency and physical properties are lowered, and a satisfactory molded product is obtained. Absent. Therefore, 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.
[0035] (高温分解阻害剤) [0035] (High-temperature decomposition inhibitor)
本塩化ビュル系樹脂組成物においては、上記の配合成分以外に、高温分解阻害 剤として、高温分解阻害機能を有する有機化合物を配合することが重要である。 In 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.
[0036] この高温分解阻害剤としては、物性、成形加工性などの付与機能を併せて有する 点から、滑剤、加工助剤、衝撃改良剤、可塑剤、帯電防止剤、紫外線吸収剤、酸化 防止剤などを好ましい例として挙げることができ、これらから選ばれる 1種又は 2種以 上を組合せて使用するのが好ましレ、。 [0036] 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.
[0037] 上記の滑剤としては、例えば流動パラフィン、天然パラフィン、マイクロワックス、合 成パラフィン、低分子量ポリエチレン等の純炭化水素系;ハロゲン化炭化水素系;高 級脂肪酸、ォキシ脂肪酸等の脂肪酸系;脂肪酸アミド、ビス脂肪酸アミド等の脂肪酸 アミド系;脂肪酸の低級アルコールエステル、グリセリド等の脂肪酸の多価アルコール エステル、脂肪酸のポリダリコールエステル、脂肪酸の脂肪族アルコールエステル( エステルワックス)等のエステル系;金属石鹼、脂肪アルコール、多価アルコール、ポ リグリコール、ポリグリセロール、脂肪酸と多価アルコールの部分エステル、脂肪酸と ポリダリコール、ポリグリセロールの部分エステル等を挙げることができる。中でも、高 温分解阻害機能に優れた脂肪酸の低級アルコールエステル、グリセリド等の脂肪酸 の多価アルコールエステル及びその部分エステルが特に好ましい。 [0037] 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 partial esters thereof are particularly preferable.
これらは、これらから選ばれる 1種を単独で用いることもできるし、また、 2種以上を 組合せて併用することもできる。 One of these can be used alone, or two or more can be used in combination.
[0038] 上記の加工助剤としては、例えばメチルメタタリレート、ェチルメタタリレート、ブチル メタタリレート等のアルキルメタタリレートの単独重合体又は共重合体;上記アルキル メタタリレートと、メチルアタリレート、ェチルアタリレート、ブチルアタリレート等のアル キルアタリレートとの共重合体;上記アルキルメタタリレートと、スチレン、 α—メチルス チレン、ビュルトルエン等の芳香族ビュル化合物との共重合体;上記アルキルメタタリ レートと、アクリロニトリル、メタタリロニトリル等のビュルシアン化合物等との共重合体 等を挙げること力 Sできる。中でも、高温分解阻害機能に優れたメチルメタアタリレートと ブチルアタリレート及びェチルメタアタリレートとの共重合体が特に好ましい。これらは 、これらから選ばれる 1種を単独で用いることもできるし、また、 2種以上を組合せて併 用することあでさる。 [0038] 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, α-methylstyrene, butyltoluene and other aromatic bur compounds; a copolymer of the above alkyl methacrylate and a burcyan compound such as acrylonitrile and methacrylonitrile. Force S Of these, 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.
このようなアクリル系加工助剤を適当量添加することにより、難燃性の向上効果を得 ること力 Sでき、成形時に成形機駆動部の負荷が高くなり、成形が困難となることがない 上記の衝撃改良剤としては、ポリブタジエン、ポリイソプレン、ポリクロ口プレン、フッ 素ゴム、スチレン一ブタジエン系共重合体ゴム、メタクリル酸メチル一ブタジエン一ス チレン系共重合体、メタクリル酸メチルーブタジエン スチレン系グラフト共重合体、 アクリロニトリル一スチレン一ブタジエン系共重合体ゴム、アクリロニトリル一スチレン ブタジエン系グラフト共重合体、スチレン ブタジエン スチレンブロック共重合体 ゴム、スチレン イソプレン スチレン共重合体ゴム、スチレン エチレンーブチレン スチレン共重合体ゴム、エチレン プロピレン共重合体ゴム、エチレン プロピレ ン一ジェン共重合体ゴム(EPDM)、シリコーン含有アクリル系ゴム、シリコーン/ァク リル複合ゴム系グラフト共重合体、シリコーン系ゴム等を挙げることができる。中でも、 高温分解阻害機能が低いアクリロニトリル—スチレン—ブタジエン系共重合体ゴム、 アクリロニトリル一スチレン一ブタジエン系グラフト共重合体などが特に好ましい。これ らの衝撃改良剤は、これらから選ばれる 1種を単独で用いることもできるし、また、 2種 以上を組合せて併用することもできる。 By adding an appropriate amount of such an acrylic processing aid, it is possible to obtain an effect of improving flame retardancy, and the load on the molding machine drive part during molding will not increase and molding will not be difficult. Examples of 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 copolymer Combined rubber, ethylene propylene Coalescing rubber, ethylene propylene down one diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone / § click Lil composite rubber graft copolymer, and silicone-based rubber. Of these, 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.
なお、上記のエチレン プロピレン ジェン共重合体ゴム(EPDM)のジェンとして は、 1 , 4 キサンジェン、ジシクロペンタジェン、メチレンノルボルネン、ェチリデン ノルボルネン、プロぺニルノルボルネン等を挙げることができる。 これらの衝撃改良剤は 1種又は 2種以上を組み合わせて用いることができる。 Examples of the ethylene propylene copolymer rubber (EPDM) 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.
上記の可塑剤としては、例えばジメチルフタレート、ジェチルフタレート、ジブチルフ タレート、ジへキシノレフタレート、ジノノレマノレオクチノレフタレート、 2—ェチノレへキシノレ フタレート、ジイソォクチルフタレート、ジカプリルフタレート、ジノニルフタレート、ジィ ソノニルフタレート、ジデシルフタレート、ジイソデシルフタレート、ジゥンデシルフタレ ート、ジラウリルフタレート、ジトリデシルフタレート、ジベンジルフタレート、ジシクロへ キシルフタレート、ブチルベンジルフタレート、ォクチルデシルフタレート、ブチルオタ チノレフタレート、ォクチノレべンジノレフタレート、ノノレマノレへキシノレノノレマノレデシノレフタ レート、ノルマルォクチルノルマルデシルフタレート等のフタル酸エステル系可塑剤; トリクレジノレホスフェート、トリ一 2—ェチノレへキシノレホスフェート、トリフエニノレホスフエ ート、 2—ェチノレへキシノレジフエニノレホスフェート、クレジノレジフエニノレホスフェート等 のリン酸エステル系可塑剤;ジー2—ェチルへキシルアジペート、ジイソデシルアジぺ ート、ノノレマノレ才クチノレ一ノノレマノレデシノレアジペート、ノノレマノレへプチノレ一ノノレマノレノ ニルアジペート、ジイソォクチルアジペート、ジイソノルマルォクチルアジペート、ジノ ルマルォクチルアジペート、ジデシルアジペート等のアジピン酸エステル系可塑剤; ジブチノレセバケート、ジー 2—ェチノレへキシノレセバケート、ジイソォクチノレセバケート 、ブチルベンジルセバケート等のセバチン酸エステル系可塑剤;ジー 2—ェチルへキ シルァゼレート、ジへキシルァゼレート、ジイソォクチルァゼレート等のァゼライン酸ェ ステル系可塑剤;タエン酸トリエチル、ァセチルクェン酸トリエチル、クェン酸トリブチ ノレ、ァセチルクェン酸トリブチル、ァセチルクェン酸トリー 2—ェチルへキシル等のク ェン酸エステル系可塑剤;メチルフタリルェチルダリコレート、ェチルフタリルェチルダ リコレート、ブチルフタリルブチルダリコレート等のグリコール酸エステル系可塑剤;トリ ブチルトリメリテート、トリーノルマルへキシルトリメリテート、トリー 2—ェチルへキシルト リメリテート、トリ一ノルマルォクチルトリメリテート、トリ一イソクチルトリメリテート、トリ一 イソデシルトリメリテート等のトリメリット酸エステル系可塑剤;ジ— 2—ェチルへキシル イソフタレート、ジー 2—ェチルへキシルテレフタレート等のフタル酸異性体エステル 系可塑剤;メチルァセチルリシノレート、ブチルァセチルリシノレート等のリシリノール 酸エステル系可塑剤;ポリプロピレンアジペート、ポリプロピレンセバケート及びこれら の変型ポリエステル等のポリエステル系可塑剤;エポキシ化大豆油、エポキシブチル ステアレート、エポキシ(2—ェチルへキシル)ステアレート、エポキシ化あまに油、 2— ェチルへキシルエポキシトーレート等のエポキシ系可塑剤などを挙げることができる。 中でも、高温分解阻害機能が低いリン酸エステル系可塑剤が特に好ましい。 Examples of the plasticizer 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. Agents: G-2-ethylhexyl adipate, diisodecyl adipate, noremanole-old cutinore nonorenoredecenorea dipate, noremanole heptinoreno noremanoleno nil adipate, diisooctyl adipate, diisonormaloctyl adipate, dinool Adipic acid ester plasticizers such as octyl adipate and didecyl adipate; dibutinorecebacate, di-2-ethinorehexinorebacate, diisooctinorecebacate, sebacic acid esters such as butylbenzyl sebacate Plasticizers; Gaseline acid ester plasticizers such as di-2-ethylhexylazelate, dihexylazelate, diisooctylazelate; triethyl taenoate, triethyl acetyl citrate, tributyl catenate, tributyl acetyl citrate, acetyl citrate Crynate plasticizers such as tree 2-ethylhexyl; Glycolic acid ester plasticizers such as methylphthalyl ethyl dallicolate, ethyl phthalyl cetyl lycolate, butyl phthalyl butyl dalicolate; Tri butyl trimelli Trimellitic acid ester plastics such as tate, tri-norhexyl trimellitate, tri-2-ethylhexyl trimellitate, tri-normal octyl trimellitate, tri-isooctyl trimellitate, tri-isodecyl trimellitate Agent; — Phthalic acid isomer ester plasticizers such as 2-ethylhexyl isophthalate and di-2-ethylhexyl terephthalate; Ricillinol acid plasticizers such as methyl acetyl ricinoleate and butyl acetyl ricinoleate; Polypropylene adipate Polypropylene sebacate and these Polyester plasticizers such as modified polyesters of epoxy; Epoxy plastics such as epoxidized soybean oil, epoxybutyl stearate, epoxy (2-ethylhexyl) stearate, epoxidized linseed oil, 2-ethylhexylepoxytorate An agent etc. can be mentioned. Among these, a phosphate ester plasticizer having a low high-temperature decomposition inhibiting function is particularly preferable.
これらは、これらから選ばれる 1種を単独で用いることもできるし、また、 2種以上を 組合せて併用することもできる。 One of these can be used alone, or two or more can be used in combination.
[0041] 上記の帯電防止剤としては、ァユオン性界面活性剤、カチオン性界面活性剤、非 イオン性界面活性剤、両性界面活性剤を用いることができる。 [0041] As the above-mentioned antistatic agent, a cationic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.
ァニオン性界面活性剤としては、脂肪酸塩類、高級アルコール硫酸エステル塩類、 液体脂肪油硫酸エステル塩類、脂肪族ァミン、アミドの硫酸塩類、二塩基性脂肪酸 エステルのスルホン塩類、脂肪酸アミドスルホン酸塩類、アルキルァリールスルホン 酸塩類、ホルマリン縮合のナフタレンスルホン酸塩類及びこれらの混合物等を挙げる こと力 Sでさる。 Examples of the 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.
カチオン性界面活性剤としては、脂肪族ァミン塩類、第四級アンモニゥム塩類、ァ ルキルピリジゥム塩及びこれらの混合物等を挙げることができる。 Examples of the cationic surfactant include aliphatic ammine salts, quaternary ammonium salts, alkyl pyridinium salts, and mixtures thereof.
非イオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル類、ポリオキ シエチレンアルキルフエノールエステル類、ポリオキシエチレンアルキルエステル類、 ソルビタンアルキルエステル類、ポリオキシエチレンソルビタンアルキルエステル類及 びこれらの混合物等を挙げることができる。 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.
非イオン性界面活性剤と、ァユオン性界面活性剤あるいはカチオン性界面活性剤 との混合物でもよい。 A mixture of a nonionic surfactant and a cation surfactant or a cationic surfactant may be used.
両性界面活性剤としては、イミダゾリン型、高級アルキルアミノ型 (ベタイン型)、硫 酸エステル、リン酸エステル型、スルホン酸型等を挙げることができる。 Examples of amphoteric surfactants include imidazoline type, higher alkylamino type (betaine type), sulfate ester, phosphate ester type, and sulfonic acid type.
中でも、高温分解阻害機能が低い非イオン性界面活性剤が好ましぐ特にその中 でもソルビタンアルキルエステル類がより好ましい。 Of these, nonionic surfactants having a low high-temperature decomposition inhibiting function are preferred, and among them, sorbitan alkyl esters are more preferred.
[0042] 上記の紫外線吸収剤としては、ヒンダードフエノール、サリチル酸エステル、ベンゾ フエノン、ベンゾトリアゾール等を挙げることができる。中でも、高温分解阻害機能が 低!/、ベンゾトリアゾール系の紫外線吸収剤が特に好まし!/、。 [0043] 上記の酸化防止剤としては、 4, 4'ーブチリデンビスー(6— tーブチルー 3—メチル フエノール)等のフエノール系酸化防止剤、トリス(ミックスドモノ及びジーノユルフェ二 ル)ホスファイト等のホスファイト系酸化防止剤、ジステアリルチオジプロピオネート等 のチォエーテル系酸化防止剤等を挙げることができる。中でも、高温分解阻害機能 が低い 4, 4'ーブチリデンビスー(6— t—ブチルー 3—メチルフエノール)等のフエノ ール系酸化防止剤が特に好まし!/、。 [0042] 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! /. [0043] 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!
[0044] 高温分解阻害剤は、多過ぎると難燃性がかえって悪化し、少な過ぎると難燃性の向 上効果を得ることができないため、高温分解阻害剤の含有量は、塩化ビュル系樹脂 100質量部に対して下限が 0. 1質量部以上、好ましくは 0. 8質量部以上、さらに好 ましくは 1. 6質量部以上、上限値は、 7質量部以下、好ましくは 5質量部以下、さらに 好ましくは、 4質量部以下である。 [0044] If the amount of the high-temperature decomposition inhibitor is too large, the flame retardancy will be deteriorated. If the amount is too small, the effect of improving the flame retardancy cannot be obtained. 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.
[0045] (本塩化ビュル系樹脂組成物の製造方法) [0045] (Method for producing the present chlorinated resin resin composition)
本塩化ビュル系樹脂組成物は、所定量の塩化ビュル系樹脂、高温分解促進剤、 低温分解抑制剤及び高温分解阻害剤を、プレンダーゃヘンシェルミキサー等を用い て混合することで得ること力できる。このとき、耐熱向上剤や顔料等、他の配合剤を適 当な量で配合してもよい。 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.
[0046] (本成形体の製造) [0046] (Manufacture of the molded body)
本塩化ビュル系樹脂組成物を押出成形、カレンダー成形、プレス成形法あるいは 連続プレス成形により、フィルム、シート、板材、パイプ、異型品などの形状に成形す ることにより、本成体に加工することができる。 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.
[0047] なお、上記の成形方法のうち、カレンダープレス成形法は、穏やかな条件での成形 法であるため、低温分解抑制機能をもつ安定剤の選択の幅が広ぐ有機錫系安定剤 、金属石鹼系安定剤、ゼォライト、ハイド口タルサイト類、アルミニウム系、マグネシゥ ム系水酸化物の単独でも 2種以上でも満足できる。 [0047] Of the above molding methods, 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.
また、カレンダープレス成形法は、カレンダー成形段階では、薄い板体が好ましく 成形できる。そして、所望厚みの板体とするためには、プレス成形段階で、複数枚の 板を積層し所望の厚みを得る。したがって、カレンダープレス成形法は、成形体の厚 みを変更する場合に成形機の大きな変更を必要としなぐ成形体の厚みの変更を行 なうことができる。 In the calendar press molding method, a thin plate can be preferably molded at the calendar molding stage. In order to obtain a plate having a desired thickness, 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.
[0048] さらに、カレンダープレス成形法は、カレンダー成形段階で得られる複数枚の板体 を、プレス成形段階で積層して所望厚みの板体とするが、カレンダー成形段階で得 られる複数枚の板体は、成形時の条件等により或る程度の厚みの振れを持っており 、この厚みの振れに、プレス成形段階での条件等により生じる厚みの振れが相乗さ れ、厚み精度においても劣っている。 [0048] Further, in the calendar press molding method, 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.
[0049] 一方、押出成形法は、カレンダープレス成形法に比べれば、高温'高圧と言う過酷 な条件での成形法であるため、低温分解抑制機能をもつ安定剤の選択の幅が狭く、 有機錫系安定剤、金属石鹼系安定剤、ゼォライト、ハイド口タルサイト類、アルミユウ ム系、マグネシウム系水酸化物の併用が必要となる。好適な組み合わせとしては、有 機錫系安定剤と、ゼォライト、ハイド口タルサイト類、マグネシウム系水酸化物の 1種以 上との組み合わせなどが挙げられる。 [0049] On the other hand, 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.
押出成形法においては、いわゆる艷戻り現象が生じてしまうという問題はなぐまた 一度の押出で所望の厚みの板体を得ることができるため、層間剥離 (耐溶剤性)の問 題もない。 In the extrusion molding method, there is no problem that a so-called rebound phenomenon occurs, and a plate having a desired thickness can be obtained by one extrusion, so there is no problem of delamination (solvent resistance).
押出成形法は、押出条件の微妙な変動や、押出された板体を引き出す際の微妙な 条件変動等を調節することによって、板体に波打ち現象が生じたり、厚みが均一にな らない等の問題を防ぐことが可能である。 In the extrusion molding method, by adjusting subtle fluctuations in extrusion conditions, subtle fluctuations in conditions when drawing out the extruded plate, etc., the wavy phenomenon occurs in the plate and the thickness does not become uniform. It is possible to prevent problems.
[0050] また、押出連続プレス成形法は、艷戻りの問題や層間剥離 (耐溶剤性)の問題がな いばかりか、押出された板体を、押出しに引き続いてプレスするため、波打ち現象は 生じないし、所望の厚みの板体を、高い厚み精度で得ることができる点で特に好まし い成形方法である。 [0050] In addition, 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.
なお、押出連続プレス成形法に好適に使用される低温分解抑制剤としては、有機 錫系安定剤、ノ、イド口タルサイト類、マグネシウム系水酸化物などを挙げることができ 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.
[0051] (本成形体) [0051] (Formed body)
難燃性塩化ビュル系樹脂成形体の難燃性は、一般的に、 ASTME1354に準じ、 コーンカロリメータを用いて評価することができる。 コーンカロリメータを用いた燃焼試験により評価される難燃特性としては、単位面積 及び単位時間当たりの燃焼による発熱量の最大値 (最大発熱量、 PHRRとも記載す る;単位: kW/m2)、単位面積及び単位時間当たりの燃焼による発熱量の平均値( 平均発熱速度、 AHRRとも記載する;単位: kW/m2)、燃焼による総発熱量 (総発熱 量、 THRとも記載する;単位: Mj/m2)、単位面積及び単位時間当たりの燃焼による 質量減少率の平均値(質量減少率、 AMLRとも記載する;単位: g/sec 'm2)、単位 面積及び単位時間当たりの燃焼による減光体積の最大値 (最大減光体積、 PSEAと も記載する;単位: m2/g)、単位面積及び単位時間当たりの燃焼による減光体積の 平均値(平均比減光面積、 ASEAとも記載する;単位: m2/kg)等を挙げることがで きる。 In general, 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 combustion per unit area and unit time (average specific dimming area, also described as ASEA) (Unit: m 2 / kg).
[0052] 従来、難燃性の指標の一つとしては、産業相互保険組織 (FactoryMutual Syste m)が定める評価基準が有効に利用されてきた。この評価基準は、 ClassNumber 4 910として挙げられているクリーンルーム材料の難燃性テスト(FMRC、 CleanRoom Materials Flammability TestProtocol)に基づいて測定され、難燃性を示す延 焼指数 FPI、発煙性を示す発煙指数 SDI、腐食性ガス発生を示す腐食指数 CDI等 が指標 (FM規格とも記載する)とされる。 [0052] Conventionally, as one of the flame retardant indicators, evaluation criteria established by the Industrial Mutual Insurance Organization (Factory Mutual System) have been used effectively. This evaluation standard was measured based on the Clean Room Materials Flammability Test Protocol (FMRC) listed as ClassNumber 4 910, and the flame spread index FPI indicating smoke resistance, and the smoke index indicating smoke generation SDI, corrosion index CDI indicating corrosive gas generation, etc. are used as indicators (also described as FM standards).
本発明においては、 FM規格に代えて、コーンカロリメータを用いた燃焼試験により 評価される値を難燃性の指標とした。 FM規格は、産業相互保険組織に試験片を提 出し、産業相互保険組織が評価して得られる規格であるため、評価結果が得られる までに時間を要し、非効率的であるのに対し、コーンカロリメータを用いた燃焼試験 は、発明者らによって行うことができるため、効率的である。 In the present invention, instead of the FM standard, 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.
特に、 FPIは、コーンカロリメータによって測定される PHRR、 AHRR及び THR等 の発熱量に関する指標と強い相関を有する。また、 SDIは、 PSEA及び ASEA等の 減光体積に関する指標と強い相関を有する。さらに、 CDIは、 AMLR等の質量減少 に関する指標と強い相関を有する。 In particular, FPI has a strong correlation with indices related to calorific values such as PHRR, AHRR, and THR measured by a corn calorimeter. In addition, SDI has a strong correlation with indicators related to dimming volume such as PSEA and ASEA. Moreover, CDI has a strong correlation with mass loss indicators such as AMLR.
従って、コーンカロリメータを用いて難燃性を評価することにより、 FM規格の凡その 値を、効率的に得ることができる。 Therefore, by evaluating the flame retardancy using a corn calorimeter, the approximate value of the FM standard can be obtained efficiently.
[0053] FM規格にぉレ、ては、 FPIが 6以下、 SDIが 0. 4以下と要求されて!/、る力 本発明 においては、この規格と同等以上として、 PHRRが 130kW/m2以下、 AHRRが 65 kW/m2以下、 THR力 OOMj/m2以下、 AMLRが 13g/sec 'm2以下、 PSEAが 1500m2/g以下、 ASEAが 800m2/kg以下であるのが好ましい。 [0053] According to FM standards, FPI is required to be 6 or less and SDI is required to be 0.4 or less! In this case, PHRR is 130kW / m 2 or less, AHRR is 65 kW / m 2 or less, THR force OOMj / 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.
[0054] 本塩化ビュル系樹脂組成物を使用して、厚さ 5 a mに成形した場合に成形体の AS TME1354に準じて測定される平均発熱速度(AHRR)の上限ィ直は、 65kW/m2以 下、好ましくは 50kW/m2以下、さらに好ましくは 30kW/m2以下である。また本発 明の樹脂組成物を使用して、厚さ 5 mに成形した場合に成形体の ASTME1354 に準じて測定される平均比減光面積 (ASEA)の上限値は、 800m2/kg以下、好ま しくは 600m2/kg以下、さらに好ましくは 500m2/kg以下である。 [0054] 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. In addition, when the resin composition of the present invention is used to mold to a thickness of 5 m, 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.
平均発熱速度(AHRR) 65kW/m2以下で、平均比減光面積 (ASEA)の上限値 力 S800m2/kg以下であれば、上記 FM規格を満足することが可能である。 If the average heat generation rate (AHRR) is 65 kW / m 2 or less and the upper limit of the average specific attenuation area (ASEA) is S800 m 2 / kg or less, the FM standard can be satisfied.
[0055] なお、本塩化ビュル系樹脂組成物を使用して、厚さ 5 mに成形した場合に、 AST ME1354に準じて測定される成形体の平均発熱速度 (AHRR)及び平均比減光面 積 (ASEA)を一定の範囲に調節するには、高温分解促進機能を有する塩素含有樹 脂を入れ、高温分解阻害機能を有する有機化合物を入れる部数を少なくするのが好 ましい。 [0055] In addition, when the bull chloride-based resin composition is used and molded to a thickness of 5 m, the average heating rate (AHRR) and average specific attenuation surface of the molded body measured according to AST ME1354 are measured. In order to adjust the product (ASEA) to a certain range, 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.
[0056] 本成形体は、全光線透過率が 55〜; 100%、好ましくは 65〜; 100%、さらに好ましく は 70〜; 100%であって、ヘイズ値が 0〜20%、好ましくは 0〜; 10%、さらに好ましくは 0〜5%である成形体であることが望ましぐ特に厚さ 5mmのときにこのような特性を 有することが望ましい。 [0056] 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.
本成形体において、全光線透過率およびヘイズを好ましい範囲に調節をする為に は、高温分解促進機能を有する塩素含有樹脂および低温分解抑制機能を有する熱 安定剤を可能な限り少なく添加することにより調節するのが好ましい。 In this molded product, in order to adjust the total light transmittance and the haze to a preferable range, 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.
[0057] 本成形体は、難燃性に優れるばかりでなぐ透明性にも優れる特徴を有するもので ある。従って、特に硬質塩化ビュル樹脂成形体とすることにより、航空機、船舶、車両 等の輸送機内外装材;建築物内外装材;家具、事務用具等の日用物品;家電機器、 電子機器等のハウジング材;半導体装置の部品等として好適に使用することができる [0057] 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
〇 [0058] (用語の解説) Yes [0058] (Glossary of terms)
本発明において、「Χ〜Υ」(X, Υは任意の数字)と記載した場合、特にことわらない 限り「X以上 Υ以下」の意図と共に、「Xより大きく Υよりも小さいことが好ましい」旨の意 図も包含する。 In the present invention, when “Χ to Υ” (X, Υ is an arbitrary number) is described, it is preferably “larger than X and smaller than と 共 に” with the intention of “X or more and Υ or less” unless otherwise specified. The intention to this effect is also included.
[0059] 本発明者は、特定の高温分解促進剤と低温分解抑制剤と共に、特定の有機化合 物であって、特に滑剤や加工助剤などとしても優れた機能を有する有機化合物を、 特定の割合となるように塩化ビュル系樹脂に配合したところ、次の知見を得、かかる 知見に基づき本発明を想到したものである。 [0059] 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. When blended with a chlorinated resin such that the ratio is as follows, the following knowledge was obtained and the present invention was conceived based on this knowledge.
(1)このような有機化合物は、上記特定の高温分解促進剤と低温分解抑制剤と共存 する系において、高温分解阻害剤として機能する。 (1) 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.
(2)この高温分解阻害剤としての機能(分解阻害機能) 、上記高温分解促進剤の 分解促進機能と相俟って、母材樹脂 (塩化ビュル系樹脂)の高温での分解を良好に コントロールし、塩化ビュル系樹脂に一層優れた難燃性を付与する。 (2) Combined with the function as a high-temperature decomposition inhibitor (decomposition-inhibiting function) and the above-described high-temperature decomposition accelerator, 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.
(3)上記有機化合物のもう一方の特性である滑剤や加工助剤などとしての機能が、 一般に塩化ビュル系樹脂に使用されている通常の滑剤や加工助剤などの使用を不 要とするため、これら助剤の配合で損なわれる塩化ビュル系樹脂が本来有している 高!/、透明性を、そのままのレベルで維持することができる。 (3) 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.
実施例 Example
[0060] 以下、実施例及び比較例によりさらに詳しく説明するが、本発明は下記実施例に何 ら制限を受けるものではない。 [0060] Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
[0061] 〔実施例;!〜 16〕 [0061] [Examples !!-16]
重合度 800の塩化ビュル樹脂 (塩化ビュルのホモポリマー)に対して、高温分解促 進機能を有する塩素含有樹脂 (表中の「高温分解促進剤」 )、高温分解阻害機能を 有する有機化合物 (表中の「高温分解阻害剤」 )、低温分解促成機能を有する熱安 定剤 (表中の「低温分解抑制剤」)を、表 1および表 2に示す割合で配合し、本発明の 塩化ビュル系樹脂組成物を得た。 Chlorine-containing resin (high temperature decomposition accelerator in the table) and high temperature decomposition inhibitory organic compound (table) ) And 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.
また、得られた塩化ビュル系樹脂組成物を、表 1及び表 2に示した各成形方法で成 形し、それぞれの成形方法に応じた方法で成形体の特性を評価した (詳しくは下記 参照)。 In addition, 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).
[0062] 〔比較例;!〜 11〕 [0062] [Comparative Example ;! to 11]
実施例で使用したものと同じ塩化ビュル樹脂に対して、高温分解促進機能を有す る塩素含有樹脂 (表中の高温分解促進剤)、高温分解阻害機能を有する有機化合 物 (表中の高温分解阻害剤)、低温分解促成機能を有する熱安定剤 (表中の低温分 解抑制剤)を、表 3に示す割合で配合し、比較の塩化ビュル系樹脂組成物を得た。 また、得られた塩化ビュル系樹脂組成物を、表 3に示した各成形方法で成形し、そ れぞれの成形方法に応じた方法で成形体の特性を評価した (詳しくは下記参照)。 For the same chlorinated resin used in the examples, a chlorine-containing resin having a high-temperature decomposition accelerating function (high-temperature decomposition accelerator in the table) and an organic compound having a high-temperature decomposition-inhibiting function (high temperature in the table) Decomposition stabilizer) and a 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. In addition, 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). .
[0063] なお、表 1 3において、配合割合の数値は、塩化ビュル樹脂 100質量部に対する 各配合物の質量部である。 [0063] In Tables 13 and 13, 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.
塩化ビュル樹脂には、重合度 800の塩化ビュル樹脂(大洋 PVC社製商品名 "TH — 800")を使用した。 As the chlorinated resin, a chlorinated resin having a polymerization degree of 800 (trade name “TH-800” manufactured by Taiyo PVC Co., Ltd.) was used.
[0064] 高温分解促進機能を有する塩素含有樹脂として、次の樹脂を使用した (表 1 3参 昭) [0064] The following resins were used as chlorine-containing resins having a high-temperature decomposition accelerating function (see Table 13).
塩素化ポリエチレン樹脂:昭和電工社製商品名 "404B" Chlorinated polyethylene resin: Trade name "404B" manufactured by Showa Denko
後塩素化塩化ビュル樹脂:カネ力製商品名 "H527" Post chlorinated chlorinated resin: Trade name "H527" by Kanechi
塩化ビニリデン樹脂:ダウケミカル製商品名 "Saranl68" Vinylidene chloride resin: Product name "Saranl68" manufactured by Dow Chemical
亜鉛化合物:ラウリン酸亜鉛 (耕正社製商品名 "ZS - 3") Zinc compound: Zinc laurate (trade name "ZS-3" manufactured by Kosho)
[0065] 高温分解阻害機能を有する有機化合物として、次の化合物を使用した (表 1 3参 昭) [0065] The following compounds were used as organic compounds having a high-temperature decomposition inhibiting function (see Table 13).
滑剤:コグニス社製商品名 "口キシオール G60" Lubricant: Cognis brand name "Kuchikiol G60"
加工助剤:ローム &ハース社製商品名 "K— 120N" Processing aid: Rohm & Haas product name "K- 120N"
衝撃改良剤:ローム &ハース社製商品名" BTA712" Impact modifier: Rohm & Haas product name "BTA712"
可塑剤:ジエイプラス社製商品名 "DINA" Plasticizer: Product name "DINA", manufactured by G +
帯電防止剤:花王社製商品名 "エレクトロストリッパー TS - 5" 紫外線吸収剤:チバスぺシャリティ社製商品名 "チヌビン P" Antistatic agent: Trade name “Electro Stripper TS-5” manufactured by Kao Corporation UV absorber: Trade name “Chinubin P” manufactured by Ciba Specialty
酸化防止剤:チバスぺシャリティ社製商品名"ィルガノックス 1076" Antioxidant: Product name "Ilganox 1076" manufactured by Ciba Specialty
[0066] 高温分解阻害機能を有する有機化合物として、次の化合物を使用した (表 1 3参 昭) [0066] The following compounds were used as organic compounds having a function of inhibiting high-temperature decomposition (see Table 13). Akira)
有機錫系安定剤:日東化成社製商品名 "N— 2000E" Organotin-based stabilizer: Product name "N-2000E" manufactured by Nitto Kasei Co., Ltd.
金属石鹼系安定剤:品川化工社製商品名" NMZ43" Metal stone stabilizer: Product name "NMZ43" manufactured by Shinagawa Chemical
ゼォライト:東ソ一社製商品名" GSL— 1000" Zeolite: Tosohichi product name "GSL—1000"
ハイド口タルサイト:協和化学社製商品名 "アル力マイザ 1" アルミニウム系水酸化物:河合石灰工業社製商品名 "ALH" Hydeguchi Talsite: Kyowa Chemical Co., Ltd. product name "Al force Mizer 1" Aluminum-based hydroxide: Kawai Lime Industry Co., Ltd. product name "ALH"
マグネシウム系水酸化物:協和化学社製商品名 "マダサラット F" Magnesium hydroxide: Trade name "Madasarat F" manufactured by Kyowa Chemical Co., Ltd.
[0067] 〔カレンダープレス成形及び得られた成形体の評価方法〕 [Calendar press molding and evaluation method of the obtained molded body]
下記の評価方法で評価した結果を表 1 3に併せて示した。 The results of evaluation using the following evaluation methods are also shown in Table 13.
[0068] (1)成形加工性: [0068] (1) Formability:
下記(2) (4)のように成形した際の成形加工性を次の基準で評価した。 〇:ロールに粘着、局所的な分解が発生せず、またプレスでプレス板から剥離が 可能で表面平滑で、色むら、スジのない成形体が得られる。 The following criteria evaluated the moldability at the time of shaping | molding like following (2) (4). ◯: No sticking or local decomposition occurs on the roll, and it can be peeled off from the press plate with a press, and a molded product with smooth surface, no color unevenness and streaks can be obtained.
△ :ロールに粘着、局所的な分解が一部発生するが、またプレスでプレス板から 剥離が可能で表面平滑で、一部色むらスジがあるが実用上問題のない成形体が得 られる。 Δ: Some sticking and local decomposition occur on the roll, but it can be peeled off from the press plate with a press, and the molded product can be obtained with a smooth surface and some uneven color streaks but no practical problems.
X:ロールに粘着、局所的な分解が発生し、カレンダーシートが得られない。 X: The roll is sticky and local decomposition occurs, and a calendar sheet cannot be obtained.
[0069] (2)難燃性: [0069] (2) Flame retardancy:
実施例及び比較例の組成物を、 180°Cのカレンダーロールで混練し、 1mm厚にシ ティングし、得られたシート 6枚を重ね、 200°Cの熱板(10cmX 10cm、厚さ 5mm) で 15分間プレス成形し、このカレンダープレス成形体について、アトラス社製コーン カロリメータを用い、 ASTME1354に準じ、 AHRR(kW/m2)と ASEA(m2/kg)を 測定した。 The 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.
[0070] (3)熱安定性: [0070] (3) Thermal stability:
実施例及び比較例の組成物を、 180°Cのカレンダーロールで混練し、 0. 5mm厚 にシーティングし、得られたシート 6枚を重ね、 200°Cの熱板で 2mm厚に 10分間プ レス成形した成形体と 20分間プレス成形した成形体との黄味変化( Δ YI)を色差計 で測定した。 [0071] (4)透明性: The 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 (ΔYI) 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. [0071] (4) Transparency:
上記の難燃性評価と同様に成形して得られたカレンダープレス成形体における透 明性を、 JISK 7105に準じ、全光線透過率(%)とヘイズ値(%)とを測定した。 In accordance with JISK 7105, 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.
[0072] 〔押出成形及び得られた成形体の評価方法〕 [Extrusion molding and evaluation method of the obtained molded body]
下記の評価方法で評価した結果を表 1〜 3に併せて示した。 The results evaluated by the following evaluation methods are also shown in Tables 1 to 3.
[0073] (1)成形加工性: [0073] (1) Formability:
下記(2)〜(4)のように成形した際の成形加工性を次の基準で評価した。 〇:局所的な分解が発生せず、樹脂温、樹脂圧が制御でき、色むら、スジが発生 せず 良好な成形体が得られる。 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.
△:局所的な分解、色むら、スジがー部発生するが、樹脂温、樹脂圧で調整可能 で実用上問題ない成形体が得られる。 Δ: Local decomposition, uneven color, and streaks occur, but a molded article that can be adjusted by the resin temperature and the resin pressure and has no practical problem is obtained.
X:局所的な分解が発生し、樹脂温、樹脂圧で制御困難であるため成形体が得ら れなレ、。 X: A molded body cannot be obtained because local decomposition occurs and it is difficult to control with resin temperature and pressure.
[0074] (2)難燃性: [0074] (2) Flame retardancy:
実施例及び比較例の組成物を 5mm厚の板状に押出成形し、この成形体について 、前記カレンダープレス成形体と同様に AHRR(kW/m2)と ASEA(m2/kg)を測 定した。 The 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.
[0075] (3)熱安定性: [0075] (3) Thermal stability:
実施例及び比較例の組成物を、二軸押出機で 4mm厚の板状に 200°Cで押出成 形し、得られた成形体の黄味変化( Δ YI)を色差計で測定した。 The 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 (ΔYI) of the obtained molded body was measured with a color difference meter.
[0076] (4)透明性: [0076] (4) Transparency:
二軸押出機で lmm厚の板状に押出成形し、得られた成形体における透明性を、 前記カレンダープレス成形体と同様に評価した。 It was extruded into a lmm-thick plate using a twin screw extruder, and the transparency of the resulting molded product was evaluated in the same manner as the calendar press molded product.
[0077] 〔連続プレス成形及び得られた成形体の評価方法〕 [Continuous press molding and evaluation method of the obtained molded body]
下記の評価方法で評価した結果を表 1〜 3に併せて示した。 The results evaluated by the following evaluation methods are also shown in Tables 1 to 3.
[0078] (1)成形加工性: [0078] (1) Formability:
下記(2)〜(4)のように成形した際の成形加工性を次の基準で評価した。 〇:局所的な分解が発生せず、樹脂温、樹脂圧が制御でき、連続プレス板に粘着 させず剥離が可能であるため良好な成形体が得られる。またスジ、色むらが目視によ り発見できない。 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.
△:局所的な分解が一部発生するが、樹脂温、樹脂圧で調整可能で連続プレス 板の条件調整の範囲で実用上問題ない成形体が得られる。またスジ、色むらがある ものの実用上問題ない。 Δ: 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.
X:局所的な分解が発生し、樹脂温、樹脂圧で制御困難であるとともに連続プレ ス板で粘着し成形体が得られな!/、。 X: Local decomposition occurs, it is difficult to control with the resin temperature and pressure, and the molded product cannot be obtained by sticking with the continuous press plate!
[0079] (2)難燃性: [0079] (2) Flame retardancy:
実施例及び比較例の組成物を、二軸押出機で 10mm厚の板状に押出成形し、こ れを 200°Cの熱板で 5mm厚に連続プレス成形し、この押出プレス成形体について、 前記カレンダープレス成形体と同様に AHRR (kW/m2)と ASEA (m2/kg)を測定 した。 The 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 ) and ASEA (m 2 / kg) were measured in the same manner as the calender press compact.
[0080] (3)熱安定性: [0080] (3) Thermal stability:
実施例及び比較例の組成物を、二軸押出機で 4mm厚の板状に押出成形し、これ を 200°Cの熱板で 2mm厚に 10分間プレス成形した成形体と 20分間プレス成形した 成形体との黄味変化( Δ YI)を色差計で測定した。 The 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 (ΔYI) with the molded body was measured with a color difference meter.
[0081] (4)透明性: [0081] (4) Transparency:
上記の難燃性評価と同様に成形して得られた押出プレス成形体における透明性を 、前記カレンダープレス成形体と同様に評価した。 Transparency in an extrusion press-molded product obtained by molding in the same manner as in the above flame retardant evaluation was evaluated in the same manner as the calendar press-formed product.
[0082] [表 1] [0082] [Table 1]
〔〕0083 [] 0083
本発明は、十分な難燃性、成形加工時における熱安定性、その他の各種特性を有 すると共に、成形体とした場合に、十分な難燃性、高い透明性、良好な外観、高い軟 化温度、その他の優れた各種特性を有する、塩化ビュル系樹脂組成物を得ることが できる。 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.
また、この組成物を各種の成形法で得られる成形体は、難燃性及び透明性に優れ 、発煙量も少なぐ高い軟化温度を有し、外観も良好となるため、特に硬質の塩化ビ ニル系樹脂を使用した本発明の樹脂組成物による成形体は、航空機、船舶、車両等 の輸送機内外機材;建築物内外装材;家具、事務用具等の日用品;家電機器、電子 機器等のハウジング材;半導体装置の部品等として好適である。 In addition, 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.
特に、押出連続プレス成形法による成形体は、熱加工時の艷戻りがなぐ耐溶剤性 に優れ、かつ高い厚み精度を有するため、上記のような種々の成形体の原体として 良好に使用することができる。 In particular, 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.
Claims
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| JP2008528864A JPWO2008018521A1 (en) | 2006-08-08 | 2007-08-08 | Vinyl chloride resin composition and molded body |
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| JP2006-215762 | 2006-08-08 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010093122A (en) * | 2008-10-09 | 2010-04-22 | Dainippon Printing Co Ltd | Filler sheet for solar cell module, and solar cell module using the same |
| WO2019065742A1 (en) * | 2017-09-27 | 2019-04-04 | 積水化学工業株式会社 | Resin composition for molding |
| WO2019065748A1 (en) * | 2017-09-27 | 2019-04-04 | 積水化学工業株式会社 | Resin composition for injection molding |
| CN110294903A (en) * | 2019-02-20 | 2019-10-01 | 广东光塑科技股份有限公司 | High-transparency odorless high-temperature-resistant PVC modified material and preparation method thereof |
| JP2020186806A (en) * | 2019-05-17 | 2020-11-19 | 積水化学工業株式会社 | Heat-resistant transparent joint |
| CN115785588A (en) * | 2022-07-21 | 2023-03-14 | 深圳市好亚通防护用品有限公司 | Permanent static dissipative PVC (polyvinyl chloride) sole material and preparation method thereof |
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| JPH10251916A (en) * | 1997-03-11 | 1998-09-22 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based resin composition for fiber and vinyl chloride-based fiber using the same |
| JP2000186180A (en) * | 1998-12-22 | 2000-07-04 | Mitsubishi Chem Mkv Co | Vinyl chloride resin composition |
| JP2003514942A (en) * | 1999-11-19 | 2003-04-22 | ジョージア・ガルフ・コーポレイション | Smoke retardant and flame retardant plenum compositions |
| WO2006035867A1 (en) * | 2004-09-29 | 2006-04-06 | Kaneka Corporation | Polyvinyl chloride fiber reduced in initial coloration |
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- 2007-08-08 WO PCT/JP2007/065560 patent/WO2008018521A1/en not_active Ceased
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| JPH10251916A (en) * | 1997-03-11 | 1998-09-22 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based resin composition for fiber and vinyl chloride-based fiber using the same |
| JP2000186180A (en) * | 1998-12-22 | 2000-07-04 | Mitsubishi Chem Mkv Co | Vinyl chloride resin composition |
| JP2003514942A (en) * | 1999-11-19 | 2003-04-22 | ジョージア・ガルフ・コーポレイション | Smoke retardant and flame retardant plenum compositions |
| WO2006035867A1 (en) * | 2004-09-29 | 2006-04-06 | Kaneka Corporation | Polyvinyl chloride fiber reduced in initial coloration |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010093122A (en) * | 2008-10-09 | 2010-04-22 | Dainippon Printing Co Ltd | Filler sheet for solar cell module, and solar cell module using the same |
| WO2019065742A1 (en) * | 2017-09-27 | 2019-04-04 | 積水化学工業株式会社 | Resin composition for molding |
| WO2019065748A1 (en) * | 2017-09-27 | 2019-04-04 | 積水化学工業株式会社 | Resin composition for injection molding |
| JPWO2019065748A1 (en) * | 2017-09-27 | 2019-11-14 | 積水化学工業株式会社 | Resin composition for injection molding |
| JPWO2019065742A1 (en) * | 2017-09-27 | 2019-11-14 | 積水化学工業株式会社 | Molding resin composition |
| CN110520473A (en) * | 2017-09-27 | 2019-11-29 | 积水化学工业株式会社 | Injection molded resin combination |
| CN110621737A (en) * | 2017-09-27 | 2019-12-27 | 积水化学工业株式会社 | Resin composition for molding |
| 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 (en) * | 2019-02-20 | 2019-10-01 | 广东光塑科技股份有限公司 | High-transparency odorless high-temperature-resistant PVC modified material and preparation method thereof |
| JP2020186806A (en) * | 2019-05-17 | 2020-11-19 | 積水化学工業株式会社 | Heat-resistant transparent joint |
| CN115785588A (en) * | 2022-07-21 | 2023-03-14 | 深圳市好亚通防护用品有限公司 | Permanent static dissipative PVC (polyvinyl chloride) sole material and preparation method thereof |
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| Publication number | Publication date |
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| JPWO2008018521A1 (en) | 2010-01-07 |
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