WO2011096596A2 - ポリオレフィン系樹脂用添加剤のための分散剤、ポリオレフィン系樹脂組成物及び成形体 - Google Patents
ポリオレフィン系樹脂用添加剤のための分散剤、ポリオレフィン系樹脂組成物及び成形体 Download PDFInfo
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- WO2011096596A2 WO2011096596A2 PCT/JP2011/060181 JP2011060181W WO2011096596A2 WO 2011096596 A2 WO2011096596 A2 WO 2011096596A2 JP 2011060181 W JP2011060181 W JP 2011060181W WO 2011096596 A2 WO2011096596 A2 WO 2011096596A2
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- WIPO (PCT)
- Prior art keywords
- additive
- dispersant
- polyolefin
- olefin resin
- alkyl methacrylate
- Prior art date
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical class CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 description 1
- 239000001601 sodium adipate Substances 0.000 description 1
- 235000011049 sodium adipate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- IEFYQJPRHOKDLM-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-5-methyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C IEFYQJPRHOKDLM-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/34—Higher-molecular-weight carboxylic acid esters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
-
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a dispersant for an additive for polyolefin resin, a polyolefin resin composition containing the dispersant, an additive for polyolefin resin, and a polyolefin resin, and a molding obtained by molding the polyolefin resin composition.
- a dispersant for an additive for polyolefin resin a polyolefin resin composition containing the dispersant, an additive for polyolefin resin, and a polyolefin resin
- a molding obtained by molding the polyolefin resin composition about the body.
- olefin-based resins such as polyethylene, polypropylene, and polybutene are one of the general-purpose resins that are most widely used in the fields of automobiles, home appliances and the like because they have excellent basic physical properties such as light weight and high rigidity. is there. Then, against the background of diversification and high functionality of needs for olefinic resins, olefinic resins are used in a form in which various additives are added.
- Patent Document 1 proposes a method of blending a phosphate-based flame retardant with a polypropylene resin.
- Patent Document 2 proposes a method of blending a thermoplastic ester resin with a phosphate ester flame retardant and an alkyl methacrylate polymer mainly composed of a methyl methacrylate unit.
- the flame retardancy may not be sufficiently exhibited.
- Olefinic resins have a slow crystallization rate after thermoforming, so it is known to add a crystal nucleating agent for the purpose of improving the molding cycle during processing and improving the rigidity and transparency of the molded product.
- a crystal nucleating agent for example, low molecular organic compounds such as phosphate ester metal salts, carboxylic acid ester salts and sorbitol, and inorganic compounds such as talc are generally used.
- a crystal nucleating agent is usually a powder, the dispersibility particularly when blended with an olefin resin is insufficient, and the crystallinity may not be sufficiently high.
- the average particle size of the crystal nucleating agent be 10 ⁇ m or less (Patent Document 3).
- the crystal nucleating agent is a fine powder, secondary agglomeration occurs, so that the effect of improving dispersibility is not sufficient.
- an olefin-based resin contains an organic or inorganic foaming agent for the purpose of reducing the weight of the molded body, reducing the material cost, and improving the sound deadening characteristics and texture of the molded body.
- a general organic or inorganic foaming agent is usually a powder, dispersibility particularly when blended with an olefin resin is insufficient, and the above object may not be sufficiently achieved. That is, if the foaming agent is not uniformly dispersed in the olefin-based resin, foaming agent aggregates are generated, and the foaming agent aggregates cause large bubbles or pinholes in the foam, and the appearance of the foam becomes poor, and the mechanical properties of the foam easily deteriorate.
- Patent Document 4 uses an alkyl methacrylate polymer having an alkyl group having 2 to 6 carbon atoms as an olefin resin to improve the dispersibility of the filler as an additive. There is a proposed method.
- an object of the present invention is to provide an additive for an olefin resin that can further enhance the additive effect of the additive in the resulting molded article by increasing the dispersibility of various additives in the olefin resin. It is to provide a versatile dispersant.
- the present invention relates to an additive for polyolefins, comprising an alkyl methacrylate polymer having an alkyl methacrylate (a1) unit having an alkyl group having 2 or more carbon atoms as a main component and having a mass average molecular weight of 15,000 to 145,000. It is the dispersing agent (A) of (B).
- this invention is a polyolefin resin composition containing the dispersing agent (A) of the additive for polyolefins (B), the additive for polyolefins (B), and the polyolefin resin (C).
- this invention is a molded object obtained by shape
- the present invention provides a master batch after the dispersant (A) for the polyolefin additive (B), the total amount of the polyolefin additive (B) and a part of the polyolefin resin (C) are used. It is a manufacturing method of the said polyolefin resin composition which mix
- the dispersant for additives for olefinic resins of the present invention exhibits an effect of improving dispersibility in olefinic resins over a wide range of additives, and the additive effect of various additives in the resulting molded product improves.
- the dispersant (A) of the additive for olefin resin (B) of the present invention includes an alkyl methacrylate polymer mainly composed of an alkyl methacrylate (a1) unit having an alkyl group having 2 or more carbon atoms.
- the alkyl methacrylate polymer of the present invention is mainly composed of an alkyl methacrylate (a1) unit having an alkyl group having 2 or more carbon atoms.
- the alkyl methacrylate unit of the present invention is an alkyl methacrylate (a1) unit having an alkyl group having 2 or more carbon atoms.
- the carbon number of the alkyl group of the alkyl methacrylate unit is 2 or more, the dispersibility of the olefin resin additive (B) in the olefin resin (C) is excellent.
- n-butyl methacrylate is preferably an alkyl methacrylate unit having an alkyl group having 2 to 6 carbon atoms, and an alkyl methacrylate unit having an alkyl group having 4 carbon atoms. More preferred are units, i-butyl methacrylate units, sec-butyl methacrylate units, and t-butyl methacrylate units, and even more preferred are i-butyl methacrylate units.
- the alkyl methacrylate polymer of the present invention contains an alkyl methacrylate (a1) unit having an alkyl group having 2 or more carbon atoms as a main component. That is, the content of the alkyl methacrylate (a1) unit having an alkyl group having 2 or more carbon atoms in the alkyl methacrylate polymer is 50% by mass or more in 100% by mass of all the monomer units of the alkyl methacrylate polymer. It is preferable that it is 70 mass% or more, and it is more preferable that it is 85 mass% or more.
- the content of the alkyl methacrylate (a1) unit having an alkyl group having 2 or more carbon atoms is 50% by mass or more, the dispersibility of the additive for olefin resin (B) in the olefin resin (C) is improved. Excellent.
- the alkyl methacrylate polymer containing 50% by mass or more of an alkyl methacrylate (a1) unit having an alkyl group having 2 or more carbon atoms according to the present invention has 50 masses of an alkyl methacrylate (a1) having an alkyl group having 2 or more carbon atoms. It is obtained by polymerizing the monomer component (a) containing at least%.
- alkyl methacrylate (a1) having an alkyl group having 2 or more carbon atoms examples include ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t- Examples thereof include butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate and stearyl methacrylate.
- These alkyl methacrylate (a1) may be used individually by 1 type, and may use 2 or more types together.
- alkyl methacrylates (a1) having an alkyl group having 2 or more carbon atoms alkyl methacrylates having an alkyl group having 2 to 6 carbon atoms are preferable, and alkyl methacrylates having an alkyl group having 4 carbon atoms are more preferable. I-butyl methacrylate is more preferred.
- the carbon number is 2 or more, the dispersibility of the olefin resin additive (B) in the olefin resin (C) is excellent. Moreover, it is excellent in the powder handleability of the dispersing agent (A) as carbon number is 6 or less.
- the monomer component (a) may contain another monomer (a2) that can be copolymerized in addition to the alkyl methacrylate (a1) having an alkyl group having 2 or more carbon atoms, if necessary.
- these other monomers (a2) include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, and chlorostyrene; (meth) acrylic acid; n-butyl acrylate; methyl (meth) acrylate; Vinyl cyanide monomers such as (meth) acrylonitrile; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; olefins such as ethylene, propylene and butylene Is mentioned.
- These other monomers (a2) may be used individually by 1 type, and may use 2 or more types together.
- “(meth) acrylate” means “acrylate” or “methacrylate”.
- the composition ratio of the monomer component (a) is an alkyl having 2 or more carbon atoms in a total of 100% by mass of the alkyl methacrylate (a1) having an alkyl group having 2 or more carbon atoms and another monomer (a2).
- the alkyl (meth) acrylate (a1) having a group is 50% by mass or more
- the other monomer (a2) is 50% by mass or less
- the other monomer (a2) is preferably 30% by mass or less, and the alkyl (meth) acrylate (a1) having an alkyl group having 2 or more carbon atoms is 85% by mass or more, The other monomer (a2) is more preferably 15% by mass or less.
- the alkyl methacrylate (a1) having an alkyl group having 2 or more carbon atoms is 50% by mass or more, that is, the other monomer (a2) is 50% by mass or less.
- the dispersibility of the olefin resin additive (B) is improved.
- Examples of the polymerization method of the alkyl methacrylate polymer include known polymerization methods such as emulsion polymerization, soap-free emulsion polymerization, fine suspension polymerization, suspension polymerization, bulk polymerization, and solution polymerization.
- emulsion polymerization, soap-free emulsion polymerization, and suspension polymerization are preferable from the viewpoint of blending the dispersant (A) and the olefin resin additive (B), and emulsion polymerization is preferable. It is more preferable.
- the particle structure when the alkyl methacrylate polymer is polymerized by using a polymerization method capable of obtaining a particle structure such as emulsion polymerization or soap-free emulsion polymerization may be a single layer structure or a multilayer structure.
- the particle structure is a multilayer structure particle, it is preferable that the particle structure is a three-layer structure or less from the viewpoint of economy.
- a known emulsifier can be used as an emulsifier when the alkyl methacrylate polymer is obtained by emulsion polymerization.
- reactive emulsifiers for example, an anionic emulsifier, a nonionic emulsifier, a polymer emulsifier, an unsaturated double bond capable of radical polymerization in the molecule.
- reactive emulsifiers reactive emulsifiers.
- anionic emulsifier examples include “New Coal 560 SF”, “New Coal 562 SF”, “New Coal 707 SF”, “New Coal 707 SN”, “New Coal 714 SF”, “New Coal 723 SF”, “New Coal 740 SF”, “New Call 2308SF”, “New Call 2320SN”, “New Call 1305SN”, “New Call 271A”, “New Call 271NH”, “New Call 210”, “New Call 220”, “New Call RA331”, “New Call "Cole RA332” (trade name, manufactured by Nippon Emulsifier Co., Ltd.); “Latemul B-118E”, “Lebenol WZ”, "Neoperex G15” (trade name, manufactured by Kao Corporation); "Hitenol N08” (product) Name, Daiichi Kogyo Seiyaku Co., Ltd.) That.
- nonionic emulsifier examples include “Nonipol 200” and “New Pole PE-68” (trade names, manufactured by Sanyo Chemical Industries, Ltd.).
- polymer emulsifier examples include polyvinyl alcohol, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl (meth) acrylate, and polyvinylpyrrolidone.
- reactive emulsifiers examples include “Antox MS-60” and “Antox MS-2N” (trade names, manufactured by Nippon Emulsifier Co., Ltd.); “Eleminol JS-2” (trade names, manufactured by Sanyo Chemical Industries, Ltd.) "Latemuru S-120", “Latemuru S-180", “Latemuru S-180A”, “Latemuru PD-104" (manufactured by Kao Corporation); “Adekaria Soap SR-10", “Adekaria Soap” “SE-10” (trade name, manufactured by ADEKA Corporation); “Aqualon KH-05”, “Aqualon KH-10”, “Aqualon HS-10” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Reactive anionic emulsifiers: “Adekalia Soap NE-10”, “Adekalia Soap ER-10”, “Adekalia Soap NE-20”, “Ade
- radical polymerization initiator for obtaining the alkyl methacrylate polymer
- examples of the radical polymerization initiator include persulfate compounds such as potassium persulfate, sodium persulfate, and ammonium persulfate; azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile Oil-soluble azo compounds such as 2,2′-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ , 2,2′-azobis ⁇ 2- Methyl-N- [2- (1-hydroxyethyl)] propionamide ⁇ , 2,2′-azobis ⁇ 2-methyl
- radical polymerization initiators may be used alone or in combination of two or more.
- reducing agents such as sodium bisulfite, ferrous sulfate, ascorbate, can also be used in combination with the said radical polymerization initiator.
- the pulverization method of the alkyl methacrylate polymer is not particularly limited, and can be appropriately selected depending on the polymerization method.
- the powdering method of the alkyl methacrylate polymer when the alkyl methacrylate polymer is obtained by emulsion polymerization includes, for example, a coagulation method, a spray drying method, a centrifugal separation method, and a freeze drying method.
- a coagulation method and a spray drying method are preferable from the viewpoint of homogeneity of the resulting alkyl methacrylate polymer powder.
- the alkyl methacrylate polymer latex When pulverizing alkyl methacrylate polymer latex using the coagulation method, the alkyl methacrylate polymer latex is brought into contact with the coagulant at 30 to 90 ° C, coagulated with stirring to form a slurry, and dehydrated and dried. By doing so, the alkyl methacrylate polymer can be powdered.
- the coagulant used in the coagulation method include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as formic acid and acetic acid; inorganic salts such as aluminum sulfate, magnesium sulfate and calcium sulfate; organics such as calcium acetate Examples include salts.
- the alkyl methacrylate polymer latex When the alkyl methacrylate polymer latex is pulverized using the spray drying method, the alkyl methacrylate polymer latex is spray-dried with a spray dryer under conditions of an inlet temperature of 120 to 220 ° C. and an outlet temperature of 40 to 90 ° C.
- the alkyl methacrylate polymer can be powdered.
- the outlet temperature is preferably from 40 to 80 ° C., more preferably from 40 to 70 ° C., from the viewpoint of the ability to disintegrate the alkyl methacrylate polymer powder into primary particles.
- alkyl methacrylate polymer of the present invention the same polymer may be used alone, or two or more polymers having different compositions, molecular weights, particle sizes, etc. may be used in combination.
- the mass average molecular weight of the alkyl methacrylate polymer of the present invention is from 15,000 to 145,000, preferably from 20,000 to 130,000, more preferably from 25,000 to 100,000.
- the resulting dispersant (A) has excellent powder handling properties.
- the mass average molecular weight of the alkyl methacrylate polymer is measured by gel permeation chromatography (GPC).
- the tetrahydrofuran-soluble content of the alkyl methacrylate polymer was used as a sample and subjected to molecular weight measurement using GPC.
- the measurement conditions of GPC were as follows, and the mass average molecular weight was determined from a calibration curve using standard polystyrene.
- Eluent THF
- Eluent flow rate 0.35 ml / min Measurement temperature: 40 ° C Sample injection volume 10 ⁇ l (sample concentration 0.1%)
- the method for adjusting the mass average molecular weight of the alkyl methacrylate polymer is not particularly limited, and examples thereof include a method for adjusting the amount of polymerization initiator and a method for adjusting the amount of chain transfer agent.
- chain transfer agents examples include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, n-butyl mercaptan; carbon tetrachloride, ethylene bromide And halogen compounds such as ⁇ -methylstyrene dimer.
- chain transfer agents may be used individually by 1 type, and may use 2 or more types together.
- the amount of chain transfer agent used can be appropriately adjusted according to the weight average molecular weight of the alkyl methacrylate polymer, the type of chain transfer agent used, the composition ratio of the monomers, and the like.
- the dispersant (A) of the present invention may contain an anti-blocking agent such as Aerosil (registered trademark), if necessary, in addition to the alkyl methacrylate polymer.
- an anti-blocking agent such as Aerosil (registered trademark)
- the olefin resin composition of the present invention contains the dispersant (A) of the present invention, an additive for olefin resin (B), and an olefin resin (C).
- the dispersant (A) of the present invention contains the alkyl methacrylate polymer of the present invention.
- the dispersant (A) of the present invention plays a role of enhancing the dispersibility of the olefin resin additive (B) when blending the olefin resin additive (B) into the olefin resin (B).
- the olefin resin additive (B) of the present invention may be a known olefin resin additive.
- the olefin resin additive (B) include flame retardants, crystal nucleating agents, foaming agents, pigments, fillers, stabilizers, lubricants, flame retardant aids, and the like.
- flame retardants include brominated flame retardants, phosphate flame retardants, phosphate ester flame retardants, metal hydroxide flame retardants, nitrogen flame retardants, silicone flame retardants, and hindered amine flame retardants.
- brominated flame retardants include “FR-1025M”, “FR-1524”, “FR-2124”, “F-2016”, “F-2300”, “F-2310”, “F-2300H”.
- phosphate flame retardant examples include “ADK STAB FP-2100J”, “ADK STAB FP-2200”, “ADK STAB FP-2200S” (trade name, ADEKA Corporation); “Fire Cut P770” (trade name, Suzuhiro Chemical Co., Ltd.).
- Examples of the phosphate ester flame retardant include “TPP”, “TCP”, “TXP”, “CDP”, “CR-733S”, “CR-741”, “PX-200”, “TMCPP”, “ “CR-900”, “CR-509”, “CR-530", “CR-504L” (trade name, Daihachi Chemical Industry Co., Ltd.); “ADK STAB PFR”, “ADK STAB FP-500”, “ADK STAB FP" -600 “(trade name, ADEKA Corporation).
- Examples of the metal hydroxide flame retardant include a flame retardant containing magnesium hydroxide as a main component, a flame retardant containing aluminum hydroxide as a main component, and a mixture thereof.
- Examples of the nitrogen flame retardant include a flame retardant mainly composed of melamine cyanurate.
- Examples of the silicone flame retardant include a silicone oil flame retardant having a linear molecular structure and a silicone resin flame retardant having a crosslinked structure.
- Examples of the hindered amine flame retardant include a hindered amine compound having a NOR structure, and specifically, “Frame Stub NOR 116FF” (trade name, Ciba Japan Co., Ltd.). These flame retardants may be used alone or in combination of two or more.
- phosphate-based flame retardants and phosphate ester-based flame retardants are preferable, and phosphate-based flame retardants are more preferable because of excellent dispersibility of the flame retardant in the olefin resin (C). preferable.
- the composition ratio of the olefin resin (C) and the flame retardant can be appropriately set according to the type of flame retardant and the required level of flame retardant.
- the content of the resin-based resin (C) is preferably 30 to 97% by mass, the content of the flame retardant is preferably 3 to 70% by mass, and the content of the olefin-based resin (C) is 50 to 95% by mass.
- the content of is more preferably 5 to 50% by mass.
- the crystal nucleating agent is not particularly limited as long as it is an inorganic compound such as talc, and is generally used as a crystal nucleating agent for olefin resins.
- the following sorbitol compounds and organic phosphate esters are used.
- Metal salts can be preferably used.
- sorbitol compounds include 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-bis (4-methylbenzylidene) sorbitol, 1,3,2,4-bis (4-ethyl).
- organic phosphate metal salt examples include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis (4, 6-di-t-butylphenyl) phosphate, lithium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2′-ethylidene-bis (4,6- Di-t-butylphenyl) phosphate, calcium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-methylene-bis (4 , 6-di-t-butylphenyl) phosphate], aluminum-tris [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate] 2,2'-methylenebis (4,6-di-t-butylphenyl)
- crystal nucleating agents examples include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids. Specifically, aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, thiophenecarboxylic acid Examples thereof include sodium and sodium pyrolecarboxylate. These can be used alone or in combination of two or more.
- the composition ratio of the olefin resin (C) and the crystal nucleating agent is such that the total content of the olefin resin (C) and the crystal nucleating agent is 100% by mass, and the content of the olefin resin (C) is 95 to 99.99% by mass,
- the content of the crystal nucleating agent is preferably 0.01 to 5% by mass, the content of the olefin resin (C) is 97 to 99.95% by mass, and the content of the crystal nucleating agent is 0.05 to 3%. More preferably, it is mass%.
- the content of the crystal nucleating agent is 0.01% by mass or more, the mechanical properties of the obtained molded body are improved. Moreover, if the content rate of a crystal nucleating agent is 5 mass% or less, the external appearance defect derived from the undispersed material of a crystal nucleating agent can be suppressed.
- the foaming agent is not particularly limited as long as it is generally used as a foaming agent for olefin resins, and may be a reactive type, a thermal decomposition type, an inorganic type, or an organic type. As long as the effects of the present invention are not impaired, these may be used alone or in combination of two or more.
- Examples of the reactive type include inorganic chemical foaming agents such as a mixture of sodium hydrogen carbonate (sodium bicarbonate) and an acid such as citric acid; and organic chemical foaming agents such as isocyanate compounds.
- inorganic chemical foaming agents such as sodium hydrogen carbonate, ammonium hydrogen carbonate, ammonium carbonate, zinc carbonate, sodium nitrate, sodium citrate; azo compounds, nitroso compounds, sulfonyl hydrazide compounds, sulfonyl semicarbazide compounds, triazole compounds, Examples thereof include organic chemical foaming agents such as tetrazole compounds.
- the organic chemical foaming agent examples include azodicarbonamide (abbreviation ADCA), barium azodicarboxylate (abbreviation Ba-AC), N, N′-dinitrosopentamethylenetetramine (abbreviation DPT), azobisisobutyrate.
- Examples include rhonitrile (abbreviation AIBN), p, p'-oxybisbenzenesulfonyl hydrazide (abbreviation OBSH), p-toluenesulfonyl hydrazide (abbreviation TSH), 5-phenyltetrazole (abbreviation 5-PT), diazoaminobenzene, and the like.
- the foaming agent may be a reactive type or a thermal decomposition type as described above, but is preferably a thermal decomposition type.
- the composition ratio between the olefin resin (C) and the foaming agent was 75 to 99.9% by mass of the olefin resin (C) and 0% of the foaming agent in a total of 100% by mass of the olefin resin (C) and the foaming agent.
- the content is preferably 1 to 25% by mass, more preferably 90 to 99.5% by mass of the olefin resin (C), and more preferably 0.5 to 10% by mass of the foaming agent.
- the foaming agent is 0.1% by mass or more, a foamed molded product having a sufficient expansion ratio can be obtained in the molded product obtained. Moreover, the appearance defect derived from the undispersed foaming agent can be suppressed as a foaming agent is 25 mass% or less.
- the pigment is not particularly limited as long as it is generally used as a pigment of an olefin resin.
- organic pigments such as azo, phthalocyanine, quinacridone, dioxazine, perylene, and isoindolinone
- inorganic pigments such as titanium oxide, petals, red lead, carbon black, iron black, ultramarine, and cobalt blue. These organic pigments and inorganic pigments may be used alone or in combination of two or more.
- the composition ratio of the olefin resin (C) and the pigment can be appropriately set according to the intended use of the molded article to be obtained, but the olefin resin (C) is a total of 100% by mass of the olefin resin (C) and the pigment. 95 to 99.99% by mass, pigment is preferably 0.01 to 5% by mass, olefin resin (C) is 98 to 99.95% by mass, and pigment is 0.05 to 2% by mass. Is more preferable.
- the pigment content is 0.01% by mass or more, a coloring effect is obtained in the obtained molded body. Moreover, the appearance defect originating in the undispersed pigment can be suppressed as a pigment is 5 mass% or less.
- filler examples include calcium carbonate, talc, glass fiber, carbon fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black, magnesium hydroxide, and aluminum hydroxide. . These fillers may be used individually by 1 type, and may use 2 or more types together.
- Stabilizers include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5- Phenolic antioxidants such as methyl-4-hydroxyphenyl) propionate]; Phosphorous antioxidants such as tris (monononylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite; Sulfur-based antioxidants such as lauryl thiodipropionate; hindered amines such as “Tinuvin-770” (trade name, manufactured by Ciba Japan), “Adekastab LA-57” (trade name, manufactured by ADEKA) Light stabilizer, “Tinubin 1577FF” (trade name, manufactured by Ciba Japan Co., Ltd.), “Adeka Stub LA-32” (product) Include ultraviolet absorbers such as (L
- lubricant examples include sodium, calcium or magnesium salts of lauric acid, palmitic acid, oleic acid or stearic acid. These lubricants may be used individually by 1 type, and may use 2 or more types together.
- flame retardant aid examples include metal oxides such as zinc oxide; and hydroxyl group-containing compounds such as pentaerythritol. These flame retardant aids may be used alone or in combination of two or more.
- a well-known olefin resin can be used for the olefin resin (C) of the present invention.
- the olefin resin (C) include polypropylene (PP), high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), poly-1-butene, polyisobutylene, and ethylene.
- -Random copolymer or block copolymer of propylene random copolymer or block copolymer of ethylene-propylene-1-butene, ethylene-propylene-diene terpolymer, ethylene or propylene and cyclopentadiene Random copolymer in which vinyl monomer such as vinyl acetate, methacrylic acid ester, acrylic acid ester, and aromatic vinyl monomer is added to 50% by mass or less with respect to copolymer or ethylene or propylene.
- Block copolymers or graft polymers are olefinic resins (C) may be used alone or in combination of two or more.
- the content of the dispersant (A) in the olefin resin composition of the present invention can be appropriately set according to the type of the olefin resin additive (B), but the olefin resin (C) and olefin resin addition
- the total amount of the agent (B) is preferably from 0.01 to 35 parts by mass, more preferably from 0.1 to 25 parts by mass, and from 0.2 to 10 parts by mass. More preferred is 0.3 to 5 parts by mass.
- the dispersibility of the olefin resin additive (B) in the olefin resin (C) is excellent. Further, when the content of the dispersant (A) is 35 parts by mass or less, the dispersibility of the olefin resin additive (B) can be improved without changing the basic characteristics of the olefin resin.
- the olefin resin composition of the present invention contains a polytetrafluoroethylene-containing resin (D) in addition to the dispersant (A), the additive for olefin resin (B) and the olefin resin (C) of the present invention. But you can.
- the polytetrafluoroethylene-containing resin (D) in the olefin-based resin composition of the present invention, dripping at the time of combustion of the obtained molded product can be prevented.
- a phosphate-based flame retardant that imparts flame retardancy by forming a foamed carbonized layer is used as the olefin-based additive (B)
- polytetrafluoroethylene contributes to foamed layer formation.
- the olefin resin composition preferably contains a polytetrafluoroethylene-containing resin (D).
- Polytetrafluoroethylene refers to a homopolymer of tetrafluoroethylene or a copolymer of a monomer mixture mainly composed of tetrafluoroethylene.
- monomers other than tetrafluoroethylene in the monomer mixture include hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether. These monomers may be used individually by 1 type, and may use 2 or more types together.
- the mass average molecular weight of polytetrafluoroethylene is preferably 1 million to 50 million, and more preferably 3 million to 30 million.
- the mass average molecular weight of polytetrafluoroethylene is 1,000,000 or more, the molded article obtained is excellent in flame retardancy. Moreover, it is excellent in the dispersibility of the flame retardant in an olefin resin composition as the mass average molecular weight of polytetrafluoroethylene is 50 million or less.
- unmodified polytetrafluoroethylene may be used as it is without modifying polytetrafluoroethylene, or modified polytetrafluoroethylene obtained by modifying polytetrafluoroethylene is used. May be.
- Examples of the unmodified polytetrafluoroethylene include “Teflon (registered trademark) T5”, “Teflon (registered trademark) T6”, “Teflon (registered trademark) 6C”, “Teflon (registered trademark) 6C-J”, “ “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 7A”, “Teflon (registered trademark) 7J”, “Teflon (registered trademark) 30”, “Teflon (registered trademark) 30B”, “Teflon (registered trademark)” 30J “,” Teflon (registered trademark) 30N “,” Teflon (registered trademark) 100 “,” Teflon (registered trademark) 110 “,” Teflon (registered trademark) 120 “,” Teflon (registered trademark) 327 “,” Teflon “ (Registered trademark) 850 "(trade name,
- modified polytetrafluoroethylene examples include “methabrene A-3000”, “methabrene A-3800”, “methabrene A-3750”, “methabrene A-3700” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.); “449” (trade name, manufactured by Chemtura Corporation); “AD-001", “CX-500” (trade name, manufactured by Shandong Todake Co., Ltd.); “SN-3300”, “SN-3300B2", “SN -3300B3 "(trade name, manufactured by Shine Polymer Co., Ltd.).
- One of these polytetrafluoroethylene-containing resins (D) may be used alone, or two or more thereof may be used in combination regardless of the presence or absence of modification.
- the content of the polytetrafluoroethylene-containing resin (D) is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the olefin resin (C) and the flame retardant, and 0.05 to 3 The amount is more preferably part by mass, and further preferably 0.1 to 2 parts by mass.
- the content of the polytetrafluoroethylene-containing resin (D) is 0.01 parts by mass or more, the obtained molded article is excellent in flame retardancy.
- the content of the polytetrafluoroethylene-containing resin (D) is 5 parts by mass or less, an excessive load is not applied when the olefin resin composition is melt-kneaded, and the extrusion can be easily performed.
- melt kneading such as extrusion kneading and roll kneading can be used.
- the melt kneading method is not particularly limited, and the dispersant (A) of the present invention, the additive for olefin resin (B), the olefin resin (C), and if necessary, a polytetrafluoroethylene-containing resin.
- (D) may be melt-kneaded at the same time, and a masterbatch was produced by melt-kneading the dispersant (A) and the olefin-based resin additive (B) in total and a part of the olefin-based resin (C). Thereafter, the remainder of the master batch and the olefin resin (C), and if necessary, the polytetrafluoroethylene-containing resin (D) may be melt-kneaded.
- the melt-kneading temperature can be appropriately set according to the type of the olefin resin resin (C).
- the melt kneading temperature is preferably 160 to 280 ° C, more preferably 180 to 240 ° C.
- the molded article of the present invention is obtained by molding the olefin resin composition of the present invention.
- a known molding method can be used, and examples thereof include extrusion molding, injection molding, calendar molding, blow molding, thermoforming, foam molding, and melt spinning.
- the molded article of the present invention is suitable for a sheet material such as an optical sheet, a film material such as a food film, an automobile member, a household appliance member, a medical member, and a building member.
- the flexural modulus of the molded body was measured according to JIS K-7171.
- the test piece (length 80mm, thickness 10m, width 4mm) obtained by injection molding was used as a molded object.
- Dispersibility of foaming agent (number of undispersed foaming agent) Extrusion molding was performed under the temperature conditions described below where the foaming agent was not decomposed, and the number of undispersed foaming agents present in the obtained strand (diameter 2 mm) was evaluated. As an evaluation procedure, the strand was observed using a stereomicroscope, the number of undispersed foaming agents exceeding 100 ⁇ m per 10 cm of the strand length was counted, observation was performed at any 10 locations, and the undispersed per 10 cm of the strand length was observed. The average value of the number of objects was determined, and the dispersibility was evaluated according to the following criteria. ⁇ : The number of undispersed foaming agents is 5/10 cm or less. ⁇ : The number of undispersed foaming agents exceeds 5/10 cm.
- An undispersed pigment exceeding 200 ⁇ m for a blue pigment and a white pigment and 500 ⁇ m for a black pigment is recognized as a spot by visual observation and affects the appearance of the molded body.
- the internal temperature was raised to 73 ° C., and a mixture of 0.2 part cumene hydroperoxide, 1.5 parts n-octyl mercaptan, 98 parts i-butyl methacrylate and 2 parts n-butyl acrylate was added over 1 hour.
- the solution was added dropwise and further maintained at the same temperature for 1 hour to obtain an alkyl methacrylate polymer latex.
- the obtained alkyl methacrylate polymer latex was cooled to 25 ° C., dropped into 500 parts of 70 ° C. hot water containing 5 parts of calcium acetate, and then heated to 90 ° C. for coagulation. The resulting coagulated product was separated and washed, and then dried at 60 ° C.
- the obtained alkyl methacrylate polymer had a mass average molecular weight of 20,000.
- the obtained alkyl methacrylate polymer powder was used as a dispersant (A1).
- i-BMA i-butyl methacrylate
- n-BMA n-butyl methacrylate
- n-BA n-butyl acrylate
- MMA methyl methacrylate
- olefin resin (C) polypropylene resin “NOVATEC FY-4” (trade name, manufactured by Nippon Polypro Co., Ltd., melt flow rate 5 g / 10 min), and as flame retardant (B1), phosphate-based resin is difficult.
- a flame retardant “ADEKA STAB FP-2200” (trade name, manufactured by ADEKA Corporation) was used.
- the obtained olefin-based resin composition was injection-molded at a molding temperature of 200 ° C. using a 100-ton injection molding machine (model name “SE-100DU”, manufactured by Sumitomo Heavy Industries, Ltd.). / 16 inch test bar). This was used as a test piece for an ignition resistance test.
- the resulting olefinic resin composition was injection-molded at a molding temperature of 200 ° C. using a 100-ton injection molding machine (model name “SE-100DU”, manufactured by Sumitomo Heavy Industries, Ltd.). (100 ⁇ 100 ⁇ 3 mm square plate) was obtained. This was used as a test piece for evaluating the total calorific value. Further, the obtained molded body (1/16 inch test bar) was pressurized using a hydraulic molding machine (manufactured by Shoji Iron Works Co., Ltd.) under conditions of a molding temperature of 190 ° C. and a molding pressure of 10 MPa for 5 minutes. Pressing was performed for 5 minutes and cooling for 5 minutes to obtain a molded body (film) having a thickness of 50 ⁇ m. This was made into the flame retardant dispersibility evaluation test film. Table 3 shows the results of evaluation of dispersibility, results of evaluation of ignition resistance, and results of evaluation of total combustion heat generation.
- Example 6 Comparative Examples 5 and 6
- An olefin resin composition was obtained.
- a molded body (1/16 inch test bar) was obtained from the obtained olefin resin composition in the same manner as in Example 1. This was used as a flame retardant (UL94) test specimen.
- Example 2 a molded body (film) was obtained from the obtained molded body (1/16 inch test bar) in the same manner as in Example 1. This was made into the flame retardant dispersibility evaluation test film. Table 4 shows the results of evaluation of dispersibility and evaluation of flame retardancy (UL94).
- Example 7, Comparative Examples 7 and 8 A masterbatch (M1-3) comprising the dispersant (A), the flame retardant (B), and the olefin resin (C) and the olefin resin (C) were blended in the ratios shown in Table 5 and mixed by hand blending. .
- the olefin resin (C) polypropylene resin “NOVATEC FY-4” (trade name, manufactured by Nippon Polypro Co., Ltd., melt flow rate 5 g / 10 min) was used. After that, using a 100t injection molding machine (model name “SE-100DU”, manufactured by Sumitomo Heavy Industries, Ltd.), injection molding was performed at a molding temperature of 200 ° C., and a molded body (1/16 inch test bar).
- the molded products obtained in Examples 1 to 5 containing the dispersant containing the alkyl methacrylate polymer of the present invention have excellent dispersibility and flame retardancy of the flame retardant. outstanding. Further, the molded body obtained in Example 6 in which the polytetrafluoroethylene-containing resin (D) was further blended was excellent in dispersibility of the flame retardant and flame retardancy. Furthermore, the molded body obtained in Example 7 using the master batch was also excellent in the dispersibility of the flame retardant and the flame retardancy.
- the molded body obtained in Comparative Example 1 in which a dispersant containing an alkyl methacrylate polymer having a methyl methacrylate unit whose main component is a methyl methacrylate unit having an alkyl group outside the scope of the present invention is blended is a flame retardant. Inferior in dispersibility and flame retardancy.
- blended polytetrafluoroethylene containing resin (D) was inferior to the dispersibility of a flame retardant, and was inferior to flame retardance.
- the molded body obtained in Comparative Example 7 using the master batch was similarly inferior in dispersibility of the flame retardant and inferior in flame retardancy.
- the molded body obtained in Comparative Examples 2 and 3 containing a dispersant containing an alkyl methacrylate polymer having a mass average molecular weight of 170,000 and 800,000, which is outside the scope of the present invention, has a flame retardant dispersibility. Inferior, inferior in flame retardancy.
- the molded bodies obtained in Comparative Examples 4, 6, and 8 in which the dispersant containing the alkyl methacrylate polymer was not blended were inferior in dispersibility of the flame retardant and inferior in flame retardancy.
- Example 8 As olefin resin (C), polypropylene resin “NOVATEC-PP FY-4” (trade name, manufactured by Nippon Polypro Co., Ltd., melt flow rate: 5 g / 10 min), 99.5 parts, as crystal nucleating agent (B) Sorbitol-based crystal nucleating agent 1,3,2,4-dibenzylidenesorbitol, 1,3,2,4-bis (4-methylbenzylidene) -D-sorbitol “Gelol MD” (trade name, Shin Nippon Rika Co., Ltd.) 0.5 parts by weight) and 0.5 part of the dispersant (A2) were blended and mixed by hand blending.
- C polypropylene resin “NOVATEC-PP FY-4” (trade name, manufactured by Nippon Polypro Co., Ltd., melt flow rate: 5 g / 10 min), 99.5 parts, as crystal nucleating agent (B) Sorbitol-based crystal nucleating agent 1,3,2,4-dibenzylidenesorbi
- pellets of the olefin resin composition were obtained.
- the obtained pellets were injection molded using an injection molding machine (model name “SE-100DU”, manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a molding temperature of 200 ° C. and a mold temperature of 60 ° C. A molded body was obtained.
- Example 9 and 10 Comparative Examples 9 to 11, Reference Example 1
- a molded body was obtained in the same manner as in Example 8, except that the composition was changed to the composition shown in Table 6.
- Table 6 shows the dispersibility (number of undispersed crystal nucleating agents) and flexural modulus of the molded products obtained in Examples 8 to 10, Comparative Examples 9 to 11, and Reference Example 1.
- Table 6 shows the following compounds.
- PP Polypropylene (trade name “NOVATEC FY-4”, manufactured by Nippon Polypro Co., Ltd.)
- Gelall MD Sorbitol-based crystal nucleating agent (trade name “Gelall MD”, manufactured by Shin Nippon Rika Co., Ltd.)
- crystal nucleating agent (B) phosphate ester metal salt-based crystal nucleating agent sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate “ADK STAB NA-11” (trade name, ( The product was obtained in the same manner as in Example 8, except that the composition was changed to ADEKA Co., Ltd. and the composition was changed to the composition shown in Table 7.
- Table 7 shows the dispersibility (number of undispersed crystal nucleating agents) and flexural modulus of the molded products obtained in Examples 11 to 13, Comparative Examples 12 to 14, and Reference Example 1.
- PP Polypropylene (trade name “NOVATEC FY-4”, manufactured by Nippon Polypro Co., Ltd.)
- NA-11 Phosphate metal salt-based crystal nucleating agent “ADK STAB NA-11” (trade name, manufactured by ADEKA Corporation)
- the molded bodies obtained in Comparative Examples 9 and 12 in which a dispersant containing an alkyl methacrylate polymer having a methyl methacrylate unit whose main component is a methyl methacrylate unit having an alkyl group outside the scope of the present invention, The dispersibility of the crystal nucleating agent and the flexural modulus of the molded product were inferior.
- the molded bodies obtained in Comparative Examples 10 and 13 containing a dispersant containing an alkyl methacrylate polymer having a mass average molecular weight of 170,000 which is outside the scope of the present invention are dispersibility of the crystal nucleating agent of the molded body.
- the flexural modulus was inferior.
- Reference Example 1 not containing a crystal nucleating agent the flexural modulus was inferior.
- Example 14 99 parts of polypropylene resin “NOVATEC-PP FY-4” (trade name, manufactured by Nippon Polypro Co., Ltd., melt flow rate: 5 g / 10 min) as olefin resin (C), azodicarbonamide as foaming agent (B) 1 part of “Vinole Hall AC # 3” (trade name, manufactured by Eiwa Chemical Industry Co., Ltd.) and 1 part of dispersant (A2) were blended and mixed by hand blending.
- Examples 15 and 16, Comparative Examples 15 to 17, Reference Example 2 Except having changed the composition into the composition shown in Table 8, strands and pellets of the olefin resin composition were obtained in the same manner as in Example 14. Thereafter, a cylindrical foamed molded article (diameter 5 mm) was obtained from the obtained pellets in the same manner as in Example 14.
- Table 8 shows the evaluation results of the dispersibility (the number of undispersed foaming agents) and foam moldability of the olefin resin compositions obtained in Examples 14 to 16, Comparative Examples 15 to 17, and Reference Example 2.
- PP Polypropylene (trade name “Novatec PP FY-4”, manufactured by Nippon Polypro Co., Ltd.)
- ADCA Azodicarbonamide (trade name “Binihol AC # 3”, manufactured by Eiwa Kasei Kogyo Co., Ltd.)
- Example 17 to 19, Comparative Examples 18 to 20, Reference Example 3 Polyethylene resin “NOVATEC-PE UR350” (trade name, manufactured by Nippon Polyethylene Co., Ltd., melt flow rate: 5 g / 10 min) as the olefin resin (C), sodium bicarbonate “Selbon SC-” as the blowing agent (B) K ”(trade name, manufactured by Eiwa Kasei Kogyo Co., Ltd.), the cylinder temperature was changed to 140 ° C., and the olefin resin composition was prepared in the same manner as in Example 14 except that the blending composition was changed to the composition shown in Table 9. Strands and pellets were obtained. Thereafter, a cylindrical foamed molded article (diameter 5 mm) was obtained in the same manner as in Example 14 except that the obtained pellet was changed to a cylinder temperature of 180 ° C.
- NOVATEC-PE UR350 trade name, manufactured by Nippon Polyethylene Co., Ltd., melt flow rate: 5 g / 10 min
- Table 9 shows the evaluation results of the dispersibility (number of undispersed foaming agents) and foam moldability of the olefin resin compositions obtained in Examples 17 to 19, Comparative Examples 18 to 20, and Reference Example 3.
- PE Polyethylene (trade name “NOVATEC-PE UR350”, manufactured by Nippon Polyethylene Co., Ltd.)
- Baking soda Sodium bicarbonate (trade name “Selfon SC-K”, manufactured by Eiwa Kasei Kogyo Co., Ltd.)
- the olefin resin compositions obtained in Examples 14 to 19 in which the dispersant containing the alkyl methacrylate polymer of the present invention was blended were effective in dispersing the foaming agent in the strand. Excellent and excellent foam moldability.
- Comparative Examples 17 and 20 not containing the dispersant of the present invention the obtained olefin resin compositions were inferior in dispersibility of the foaming agent in the strands and inferior in foam moldability.
- the olefin-based resin composition obtained in Comparative Examples 15 and 18 containing a dispersant containing an alkyl methacrylate-based polymer whose main component is a methyl methacrylate unit having a carbon number of 1 alkyl group outside the scope of the present invention is The dispersibility of the foaming agent in the strand was poor, and the foam moldability was poor. Furthermore, the olefin resin compositions obtained in Comparative Examples 16 and 19 containing a dispersant containing an alkyl methacrylate polymer having a mass average molecular weight of 170,000 which is outside the scope of the present invention are the foaming agent in the strand. It was inferior in dispersibility and inferior in foam moldability.
- Example 20 99.5 parts of polypropylene resin “NOVATEC-PP FY-4” (trade name, manufactured by Nippon Polypro Co., Ltd., melt flow rate: 5 g / 10 min) as olefin resin (C), blue pigment as pigment (B) 0.5 part of “Ultramarine 1900” (trade name, manufactured by Daiichi Kasei Kogyo Co., Ltd.) and 0.5 part of dispersant (A2) were blended and mixed by hand blending.
- Example 21 and 22 Comparative Examples 21 to 23
- a sheet molded body was obtained in the same manner as in Example 20 except that the blending composition was changed to the composition shown in Table 10.
- Table 10 shows the evaluation results of the molded appearance (number of undispersed pigments) of the sheet molded bodies obtained in Examples 20 to 22 and Comparative Examples 21 to 23.
- PP Polypropylene (trade name “Novatec PP FY-4”, manufactured by Nippon Polypro Co., Ltd.)
- Ultramarine Blue pigment (trade name “Ultramarine 1900”, manufactured by Daiichi Kasei Kogyo Co., Ltd.)
- Example 23 Comparative Examples 24 and 25
- a sheet molded body was obtained in the same manner as in Example 20, except that the blending composition was changed to the composition described in Table 11.
- the pigment (B) a white pigment (titanium oxide) “R-830” (trade name, manufactured by Ishihara Sangyo Co., Ltd.) was used.
- Table 11 shows the evaluation results of the molding appearance (number of undispersed pigments) of the sheet molded bodies obtained in Example 23 and Comparative Examples 24 and 25.
- PP Polypropylene (trade name “Novatec PP FY-4”, manufactured by Nippon Polypro Co., Ltd.)
- Titanium oxide White pigment (trade name, “R-830”, manufactured by Ishihara Sangyo Co., Ltd.)
- Example 24 A sheet molded body was obtained in the same manner as in Example 20, except that the blending composition was changed to the composition described in Table 12.
- the pigment (B) a black pigment (carbon black) “CB960” (trade name, manufactured by Mitsubishi Chemical Corporation) was used.
- Table 12 shows the evaluation results of the molded appearance (number of undispersed pigments) of the sheet molded bodies obtained in Example 24 and Comparative Examples 26 and 27.
- the sheet molded bodies obtained in Examples 20 to 24 containing the dispersant containing the alkyl methacrylate polymer of the present invention have excellent pigment dispersibility and good molded appearance.
- Met the obtained sheet molded article was inferior in the dispersibility of the pigment and inferior in the molded appearance.
- the sheet molded body obtained in Comparative Example 22 containing a dispersant containing an alkyl methacrylate polymer having a mass average molecular weight of 170,000 which is outside the scope of the present invention is inferior in pigment dispersibility and has a molded appearance. inferior.
- the dispersant (A) of the present invention exerts an effect of improving the dispersibility of the olefin additive in the obtained molded product with respect to a wide range of olefin additives. It was confirmed that the addition effect was remarkably improved.
- the molded product obtained using the dispersant (A) of the present invention is excellent in the effect of adding an additive for olefins, a sheet material such as an optical sheet, a film material such as a food film, a member for automobiles, a member for home appliances, It is suitable for medical members and building members.
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Abstract
Description
しかしながら、オレフィン系樹脂に対する難燃剤の分散性が十分でないことから、その難燃性が十分に発揮できない場合がある。
結晶核剤としては、例えば、リン酸エステル金属塩系、カルボン酸エステル塩系及びソルビトール系等の低分子有機化合物やタルク等の無機化合物が一般的に使用されている。
しかしながら、このような結晶核剤は、通常、粉末であるため、特にオレフィン系樹脂に配合する際の分散性が不十分で、結晶化度が十分に高くならない場合がある。そこで、結晶核剤の分散性向上を目的として、結晶核剤の平均粒径を10μm以下にすることが提案されている(特許文献3)。しかしながら、結晶核剤を微粉末とすれば、二次凝集が生じるため、分散性の向上効果は十分ではなかった。
一般的な有機系または無機系発泡剤は、通常、粉末であるため、特にオレフィン系樹脂に配合する際の分散性が不十分となり、上記目的が十分に達成できない場合がある。すなわち、オレフィン系樹脂に、均一に発泡剤を分散させないと、発泡剤の凝集物が発生し、その発泡剤凝集物により、発泡体中に大気泡あるいはピンホール等が発生し、発泡体の外観が不良となり、また発泡体の機械的特性が低下しやすくなる。
また、本発明は、前記オレフィン系樹脂組成物を成形して得られる成形体である。
更に、本発明は、ポリオレフィン用添加剤(B)の分散剤(A)、ポリオレフィン用添加剤(B)の全量及びポリオレフィン系樹脂(C)の一部とでマスターバッチを製造した後、前記マスターバッチ及びポリオレフィン系樹脂(C)の残部を配合する前記ポリオレフィン系樹脂組成物の製造方法である。
すなわち、アルキルメタクリレート系重合体中の炭素数が2以上のアルキル基を有するアルキルメタクリレート(a1)単位の含有率は、アルキルメタクリレート系重合体の全単量体単位100質量%中、50質量%以上であり、70質量%以上であることが好ましく、85質量%以上であることがより好ましい。
炭素数が2以上のアルキル基を有するアルキルメタクリレート(a1)単位の含有率が50質量%以上であると、オレフィン系樹脂(C)中でのオレフィン系樹脂用添加剤(B)の分散性に優れる。
炭素数が2以上であると、オレフィン系樹脂(C)中でのオレフィン系樹脂用添加剤(B)の分散性に優れる。また、炭素数が6以下であると、得られる分散剤(A)の粉体取扱性に優れる。
尚、本明細書において、「(メタ)アクリレート」は、「アクリレート」又は「メタクリレート」を示す。
炭素数が2以上のアルキル基を有するアルキルメタクリレート(a1)が50質量%以上であると、すなわち他の単量体(a2)が50質量%以下であると、オレフィン系樹脂(C)中でのオレフィン系樹脂用添加剤(B)の分散性が向上する。
ノニオン性乳化剤としては、例えば、「ノニポール200」、「ニューポールPE-68」(商品名、三洋化成工業(株)製)が挙げられる。
高分子乳化剤としては、例えば、ポリビニルアルコール、ポリヒドロキシエチル(メタ)アクリレート、ポリヒドロキシプロピル(メタ)アクリレート、ポリビニルピロリドンが挙げられる。
反応性乳化剤としては、例えば、「Antox MS-60」、「Antox MS-2N」(商品名、日本乳化剤(株)製);「エレミノールJS-2」(商品名、三洋化成工業(株)製);「ラテムルS-120」、「ラテムルS-180」、「ラテムルS-180A」、「ラテムルPD-104」(花王(株)製);「アデカリアソープSR-10」、「アデカリアソープSE-10」(商品名、(株)ADEKA製);「アクアロンKH-05」、「アクアロンKH-10」、「アクアロンHS-10」(商品名、第一工業製薬(株)製)等の反応性アニオン乳化剤;「アデカリアソープNE-10」、「アデカリアソープER-10」、「アデカリアソープNE-20」、「アデカリアソープER-20」、「アデカリアソープNE-30」、「アデカリアソープER-30」、「アデカリアソープNE-40」、「アデカリアソープER-40」(商品名、(株)ADEKA製);「アクアロンRN-10」、「アクアロンRN-20」、「アクアロンRN-30」、「アクアロンRN-50」(商品名、第一工業製薬(株)製)等の反応性ノニオン性乳化剤が挙げられる。
これらの乳化剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
ラジカル重合開始剤としては、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩系化合物;アゾビスイソブチロニトリル、2,2’-アゾビス(2-メチルブチロニトリル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2-フェニルアゾ-4-メトキシ-2,4-ジメチルバレロニトリル等の油溶性アゾ系化合物;2,2’-アゾビス{2-メチル-N-[1,1-ビス(ヒドロキシメチル)-2-ヒドロキシエチル]プロピオンアミド}、2,2’-アゾビス{2-メチル-N-[2-(1-ヒドロキシエチル)]プロピオンアミド}、2,2’-アゾビス{2-メチル-N-[2-(1-ヒドロキシブチル)]プロピオンアミド}、2,2’-アゾビス[2-(5-メチル-2-イミダゾリン-2-イル)プロパン]及びその塩類、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]及びその塩類、2,2’-アゾビス[2-(3,4,5,6-テトラヒドロピリミジン-2-イル)プロパン]及びその塩類、2,2’-アゾビス{2-[1-(2-ヒドロキシエチル)-2-イミダゾリン-2-イル]プロパン}及びその塩類、2,2’-アゾビス(2-メチルプロピオンアミジン)及びその塩類、2,2’-アゾビス(2-メチルプロピオンアミジン)及びその塩類、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]及びその塩類等の水溶性アゾ系化合物;過酸化ベンゾイル、クメンヒドロパーオキシド、t-ブチルヒドロパーオキシド、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシイソブチレート等の有機過酸化物が挙げられる。
これらのラジカル重合開始剤は、1種を単独で用いてもよく、2種以上を併用してもよい。また、乳化重合法にて重合を行う場合には、重亜硫酸ナトリウム、硫酸第一鉄、アスコルビン酸塩等の還元剤を、上記ラジカル重合開始剤と組合せて用いることもできる。
アルキルメタクリレート系重合体の質量平均分子量が1万5000以上であると、得られる分散剤(A)の粉体取扱性に優れる。また、アルキルメタクリレート系重合体の質量平均分子量が14万5000以下であると、オレフィン系樹脂(C)中でのオレフィン系樹脂用添加剤(B)の分散性に優れる。
尚、アルキルメタクリレート系重合体の質量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定される。
アルキルメタクリレート系重合体のテトラヒドロフラン可溶分を試料として、GPCを用いて分子量の測定に供した。
GPCの測定条件は下記の通りで、標準ポリスチレンによる検量線から質量平均分子量を求めた。
装置:東ソー(株)製「HLC8220」
カラム:東ソー(株)製「TSKgel SuperMultiporeHZ-H」(内径4.6mm×長さ15cm×2本、排除限界4×107(推定))
溶離液:THF
溶離液流量:0.35ml/分
測定温度:40℃
試料注入量 10μl(試料濃度0.1%)
これらの連鎖移動剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
臭素系難燃剤としては、例えば、「FR-1025M」、「FR-1524」、「FR-2124」、「F-2016」、「F-2300」、「F-2310」、「F-2300H」(商品名、ICL-IPジャパン(株)製);「フレームカット 120G」、「フレームカット 121K」、「フレームカット 122K」(商品名、東ソー(株)製);「SAYTEX RB-100」、「SAYTEX BT-93」、「SAYTEX BT-93W」、「SAYTEX 8010」、「SAYTEX HP-7010P」(商品名、アルベマール日本(株))が挙げられる。
リン酸塩系難燃剤としては、例えば、「アデカスタブ FP-2100J」、「アデカスタブ FP-2200」、「アデカスタブ FP-2200S」(商品名、(株)ADEKA);「ファイアカットP770」(商品名、鈴裕化学(株))が挙げられる。
リン酸エステル系難燃剤としては、例えば、「TPP」、「TCP」、「TXP」、「CDP」、「CR-733S」、「CR-741」、「PX-200」、「TMCPP」、「CR-900」、「CR-509」、「CR-530」、「CR-504L」(商品名、大八化学工業(株));「アデカスタブ PFR」、「アデカスタブ FP-500」、「アデカスタブ FP-600」(商品名、(株)ADEKA)が挙げられる。
金属水酸化物系難燃剤としては、例えば、水酸化マグネシウムを主成分とした難燃剤、水酸化アルミニウムを主成分とした難燃剤、これらの混合物が挙げられる。
チッソ系難燃剤としては、例えば、メラミンシアヌレートを主成分とした難燃剤が挙げられる。
シリコーン系難燃剤としては、例えば、直鎖状の分子構造を有するシリコーンオイル系難燃剤、架橋構造を有するシリコーン樹脂系難燃剤が挙げられる。
ヒンダードアミン系難燃剤としては、例えば、NOR構造を有するヒンダードアミン化合物が挙げられ、具体的には、「フレームスタブ NOR 116FF」(商品名、チバ・ジャパン(株))が挙げられる。
これらの難燃剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
これらの難燃剤の中でも、オレフィン系樹脂(C)中での難燃剤の分散性に優れることから、リン酸塩系難燃剤、リン酸エステル系難燃剤が好ましく、リン酸塩系難燃剤がより好ましい。
熱分解型では、炭酸水素ナトリウム、炭酸水素アンモニウム、炭酸アンモニウム、炭酸亜鉛、硝酸ナトリウム、クエン酸ナトリウム等の無機系化学発泡剤;アゾ化合物、ニトロソ化合物、スルホニルヒドラジド化合物、スルホニルセミカルバジド化合物、トリアゾール化合物、テトラゾール化合物等の有機系化学発泡剤が挙げられる。
有機系化学発泡剤の具体例としては、アゾジカルボンアミド(略称ADCA)、バリウムアゾジカルボキシレート(略称Ba-AC)、N,N’-ジニトロソペンタメチレンテトラミン(略称DPT)、アゾビスイソブチロニトリル(略称AIBN)、p,p’-オキシビスベンゼンスルホニルヒドラジド(略称OBSH)、p-トルエンスルホニルヒドラジド(略称TSH)、5-フェニルテトラゾール(略称5-PT)、ジアゾアミノベンゼン等が挙げられる。
発泡剤としては、前記のように反応型であっても熱分解型であってもよいが、好ましくは熱分解型である。
これらの充填剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
これらの安定化剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
これらの滑剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
これらの難燃助剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
本発明のオレフィン系樹脂組成物にポリテトラフルオロエチレン含有樹脂(D)を含むことで、得られる成形体の燃焼時の滴下を防止することができる。特に、オレフィン系添加剤(B)として、発泡炭化層を形成させて難燃性を付与するリン酸塩系難燃剤を用いる場合、ポリテトラフルオロエチレンが発泡層形成に寄与するので、本発明のオレフィン系樹脂組成物にポリテトラフルオロエチレン含有樹脂(D)を含むことが好ましい。
単量体混合物中のテトラフルオロエチレン以外の単量体としては、例えば、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、フルオロアルキルエチレン、パーフルオロアルキルビニルエーテルが挙げられる。
これらの単量体は、1種を単独で用いてもよく、2種以上を併用してもよい。
ポリテトラフルオロエチレンの質量平均分子量が100万以上であると、得られる成形体の難燃性に優れる。また、ポリテトラフルオロエチレンの質量平均分子量が5000万以下であると、オレフィン系樹脂組成物中での難燃剤の分散性に優れる。
未変性ポリテトラフルオロエチレンとしては、例えば、「テフロン(登録商標) T5」、「テフロン(登録商標) T6」、「テフロン(登録商標) 6C」、「テフロン(登録商標) 6C-J」、「テフロン(登録商標) 6J」、「テフロン(登録商標) 7A」、「テフロン(登録商標) 7J」、「テフロン(登録商標) 30」、「テフロン(登録商標) 30B」、「テフロン(登録商標) 30J」、「テフロン(登録商標) 30N」、「テフロン(登録商標) 100」、「テフロン(登録商標) 110」、「テフロン(登録商標) 120」、「テフロン(登録商標) 327」、「テフロン(登録商標) 850」、(商品名、デュポン(株)製);「フルオン G201」、「フルオン G307」、「フルオン CD1」、「フルオン CD141」、「フルオン CD123」、「フルオン CD076」、「フルオン CD090」、「フルオン AD911L」、「フルオン AD983L」、「フルオン G163」、「フルオン G192」、「フルオン G307」(商品名、旭硝子(株)製);「ポリフロンMPA FA-500C」(商品名、ダイキン(株)製)が挙げられる。
変性ポリテトラフルオロエチレンとしては、「メタブレンA-3000」、「メタブレンA-3800」、「メタブレンA-3750」、「メタブレンA-3700」(商品名、三菱レイヨン(株)製);「ブレンデックス449」(商品名、ケムチュラ(株)製);「AD-001」、「CX-500」(商品名、山東東岳(株)製);「SN-3300」、「SN-3300B2」、「SN-3300B3」(商品名、シャインポリマー(株)製)が挙げられる。
これらのポリテトラフルオロエチレン含有樹脂(D)は、1種を単独で用いてもよく、変性の有無に関わらず2種以上を併用してもよい。
ポリテトラフルオロエチレン含有樹脂(D)の含有量が0.01質量部以上であると、得られる成形体の難燃性に優れる。ポリテトラフルオロエチレン含有樹脂(D)の含有量が5質量部以下であると、オレフィン系樹脂組成物を溶融混練する際に過剰な負荷がかからず、容易に押出成形が可能となる。
溶融混練方法は、特に限定されるものではなく、本発明の分散剤(A)、オレフィン系樹脂用添加剤(B)、オレフィン系樹脂(C)、必要に応じて、ポリテトラフルオロエチレン含有樹脂(D)を同時に溶融混練してもよく、分散剤(A)及びオレフィン系樹脂用添加剤(B)の全量とオレフィン系樹脂(C)の一部とで溶融混練してマスターバッチを製造した後、前記マスターバッチ及びオレフィン系樹脂(C)の残部、必要に応じて、ポリテトラフルオロエチレン含有樹脂(D)を溶融混練してもよい。
成形方法は、公知の成形方法を用いることができ、例えば、押出成形、射出成形、カレンダー成形、ブロー成形、熱成形、発泡成形、溶融紡糸が挙げられる。
アルキルメタクリレート系重合体のテトラヒドロフラン可溶分を試料として、ゲルパーミエーションクロマトグラフィー(GPC)を用いて分子量の測定に供した。
GPCの測定条件は下記の通りで、標準ポリスチレンによる検量線から質量平均分子量を求めた。
装置:東ソー(株)製「HLC8220」
カラム:東ソー(株)製「TSKgel SuperMultiporeHZ-H」 (内径4.6mm×長さ15cm×2本、排除限界4×107(推定))
溶離液:THF
溶離液流量:0.35ml/分
測定温度:40℃
試料注入量 10μl(試料濃度0.1%)
得られた成形体(フィルム)中に存在する難燃剤の未分散物の数を評価した。評価手順としては、成形体を実体顕微鏡を用いて観察し、1視野(6mm×8mm)あたりの100μmを越える難燃剤の未分散物の数をカウントし、10視野について観察を実施し、1視野あたりの未分散物数の平均値を求め、以下の基準で分散性を判断した。
○:難燃剤の未分散物数が15個/視野以下
×:難燃剤の未分散物数が15個/視野を超える
得られた成形体(1/16インチの試験棒)を用い、試験環境23±2℃、炎の大きさ20mm、接炎時間10秒、測定回数5回の条件で、燃焼試験を実施し、以下の基準で燃焼性を判断した。
○:接炎により、5回とも試験棒に引火しない。
×:接炎により、1回以上試験棒に引火し、燃焼する。
得られた成形体(100×100×3mmの試験片)について、コーンカロリーメーター(株式会社東洋精機製作所製 C3型)を用い、輻射熱50KW/m2の条件で着火より500秒経過時間までの総燃焼発熱量を求めた。総燃焼発熱量は少ないほど火勢が弱く難燃性が高いと判断される。
得られた成形体(1/16インチの試験棒)を用い、UL94の規格に準拠して難燃性を判断した。試験の概要は以下のとおりである。
垂直に保持した試料の下端に10秒間ガスバーナーの炎を接炎させる。燃焼が30秒以内に止まったならば、さらに10秒間接炎させる。上記試験を1試料において5回実施し、以下の基準により判定する。
「V-0」:以下の項目を全て満たすこと
1.いずれの接炎の後も、10秒以上燃焼を続ける試料がない
2.5個の試料に対する10回の接炎に対する総燃焼時間が50秒を超えない
3.固定用クランプの位置まで燃焼する試料がない
4.試料の下方に置かれた脱脂綿を発火させる燃焼する粒子を落下させる試料がない
5.2回目の接炎の後、30秒以上赤熱を続ける試料がない
「V-1」:以下の項目を全て満たすこと
1.いずれの接炎の後も、30秒以上燃焼を続ける試料がない
2.5個の試料に対する10回の接炎に対する総燃焼時間が250秒を超えない
3.固定用クランプの位置まで燃焼する試料がない
4.試料の下方に置かれた脱脂綿を発火させる燃焼する粒子を落下させる試料がない
5.2回目の接炎の後、60秒以上赤熱を続ける試料がない
「V-2」:以下の項目を全て満たすこと
1.いずれの接炎の後も、30秒以上燃焼を続ける試料がない
2.5個の試料に対する10回の接炎に対する総燃焼時間が250秒を超えない
3.固定用クランプの位置まで燃焼する試料がない
4.試料の下方に置かれた脱脂綿を発火させる燃焼する粒子の落下が許容される
5.2回目の接炎の後、60秒以上赤熱を続ける試料がない
「不適合(Failure)」:上記判定基準に満たないもの
成形体(横×縦×厚み=50mm×100mm×2mm)中に存在する結晶核剤の未分散物の数を評価した。評価手順としては、成形体を実体顕微鏡を用いて観察し、1視野(2mm×3mm)あたりの50μmを越える結晶核剤の未分散物の数をカウントし、10視野について観察を実施し、1視野あたりの未分散物数の平均値を求め、以下の基準で分散性を評価した。
○:結晶核剤の未分散物数が1個/視野以下
×:結晶核剤の未分散物数が1個/視野を超える
成形体の曲げ弾性率を、JIS K-7171に準じて測定した。尚、成形体として、射出成形により得られた試験片(長さ80mm、厚さ10m、幅4mm)を用いた。
発泡剤が分解しない後述する温度条件において押出成形を行い、得られたストランド(直径2mm)中に存在する発泡剤の未分散物の数を評価した。評価手順としては、ストランドを実体顕微鏡を用いて観察し、ストランド長10cmあたりの100μmを越える発泡剤の未分散物の数をカウントし、任意の10箇所について観察を実施し、ストランド長10cmあたりの未分散物数の平均値を求め、以下の基準で分散性を評価した。
○:発泡剤の未分散物数が5個/10cm以下
×:発泡剤の未分散物数が5個/10cmを超える
発泡成形体中に存在する粗大気泡数の数を評価した。評価手順としては、発泡成形体の断面を実体顕微鏡を用いて観察し、断面(直径φ5 mm)あたりの0.4mmを越える粗大気泡の数をカウントし、任意の10箇所について観察を実施し、1断面積あたりの粗大気泡数の平均値を求め、以下の基準で分散性を評価した。0.4mmを越える粗大気泡は成形体の外観に影響を与える。
○:粗大気泡の数が1個/断面以下
×:粗大気泡の数が1個/断面を超える
シート成形体(幅×厚み=80mm×0.3mm)中に存在する顔料の未分散物の数を評価した。評価手順としては、シート成形体を実体顕微鏡を用いて観察し、100cm2あたりの、青色顔料及び白色顔料では200μmを越える、黒色顔料では500μmを越える顔料の未分散物の数をカウントし、1000cm2(100cm2を10箇所)について観察を実施し、100cm2あたりの未分散物数の平均値を求め、以下の基準で分散性を評価した。青色顔料及び白色顔料では200μm、黒色顔料では500μmを越える顔料未分散物は、目視においてブツとして認識され、成形体の外観に影響を与える。
○:顔料の未分散物数が5個/100cm2以下
×:顔料の未分散物数が5個/100cm2を超える
温度計、窒素導入管、冷却管及び攪拌装置を備えたセパラブルフラスコ(容量5リットル)に、イオン交換水225部(2250グラム)、ドデシルベンゼンスルホン酸ナトリウム2.5部、硫酸第一鉄0.0002部、エチレンジアミン四酢酸二ナトリウム0.0006部、アスコルビン酸0.48部を仕込み、セパラブルフラスコ内を窒素置換した。次いで、内温を73℃まで昇温させ、クメンヒドロパーオキシド0.2部、n-オクチルメルカプタン1.5部、i-ブチルメタクリレート98部、n-ブチルアクリレート2部の混合物を1時間かけて滴下し、更に同温で1時間保持して、アルキルメタクリレート系重合体ラテックスを得た。
得られたアルキルメタクリレート系重合体ラテックスを25℃まで冷却後、酢酸カルシウム5部を含む70℃の温水500部中に滴下した後、90℃まで昇温させて凝析させた。得られた凝析物を分離洗浄後、60℃で12時間乾燥させて、アルキルメタクリレート系重合体粉体を得た。得られたアルキルメタクリレート系重合体の質量平均分子量は、2万であった。
得られたアルキルメタクリレート系重合体粉体を分散剤(A1)とした。
単量体成分の組成、連鎖移動剤量を表1に記載のように変更したこと以外は、製造例1と同様にして、アルキルメタクリレート系重合体粉体を得た。
得られたアルキルメタクリレート系重合体粉体を、分散剤(A2)~(A8)とした。
分散剤(A2)10部、リン酸塩系難燃剤(B2)「アデカスタブ FP-2100J」(商品名、(株)ADEKA製)70部をハンドブレンドで混合し、当該混合物をフィーダー1(機種名「CE-T-1型」((株)クボタ製)を用いて4.8kg/hrの速度で押出機に供給した。また、ポリプロピレン樹脂「ノバテックPP FY-4」(日本ポリプロ(株)製、メルトフローレート5g/10分)をフィーダー2(機種名「ALS-254」(産業機電(株))を用いて1.2kg/hrの速度で押出機に供給した。押出機はφ26mm同方向二軸押出機(機種名「TEM-26SS」(東芝機械(株)製)、L/D=64.6)を用い、スクリュー回転数200rpm、シリンダー温度180℃の条件で溶融混練をし、マスターバッチ(M1)を得た。得られたマスターバッチ(M1)の組成比は、難燃剤(B2)/PP樹脂/分散剤(A2)=70/20/10(wt%)であった。
分散剤の種類及び量、オレフィン系樹脂の量を表2に記載のように変更したこと以外は、製造例9と同様にして、マスターバッチ(M2)、(M3)を得た。なお、フィーダー1及び2の合計の供給速度は6.0kg/hrとして、フィーダー1及び2の供給速度を調整して組成比を変更した。
分散剤(A)、難燃剤(B)及びオレフィン系樹脂(C)を表3に記載の比率で配合し、ハンドブレンドで混合した。その後、φ30mm同方向二軸押出機(機種名「BT-30」、(株)プラスチック工学研究所製、L/D=30)を用い、スクリュー回転数200rpm、シリンダー温度200℃の条件で溶融混練をし、オレフィン系樹脂組成物を得た。
尚、オレフィン系樹脂(C)として、ポリプロピレン樹脂「ノバテック FY-4」(商品名、日本ポリプロ(株)製、メルトフローレート5g/10分)、難燃剤(B1)として、リン酸塩系難燃剤「アデカスタブ FP-2200」(商品名、(株)ADEKA製)を用いた。
得られたオレフィン系樹脂組成物を100t射出成形機(機種名「SE-100DU」、住友重機械工業(株)製)を用い、成形温度200℃の条件で射出成形を行い、成形体(1/16インチの試験棒)を得た。これを耐着火性試験用試験片とした。
また、得られたオレフィン系樹脂組成物を100t射出成形機(機種名「SE-100DU」、住友重機械工業(株)製)を用い、成形温度200℃の条件で射出成形を行い、成形体(100×100×3mmの角板)を得た。これを総燃焼発熱量評価用試験片とした。
また、得られた成形体(1/16インチの試験棒)を油圧成形機(庄司鉄工所(株)製)を用い、成形温度190℃、成形圧力10MPaの条件で、予熱5分、加圧5分、冷却5分の手順でプレスし、厚さ50μmの成形体(フィルム)を得た。これを難燃剤分散性評価用試験フィルムとした。
分散性評価結果、耐着火性評価結果、総燃焼発熱量評価結果を表3に示した。
分散剤(A)、難燃剤(B)、オレフィン系樹脂(C)及びポリテトラフルオロエチレン含有樹脂(D)の配合組成を表4の組成に変更した以外は、実施例1と同様の方法でオレフィン系樹脂組成物を得た。
ポリテトラフルオロエチレン含有樹脂(D)として、変性ポリテトラフルオロエチレン「メタブレンA-3800」(商品名、三菱レイヨン(株)製)を用いた。
得られたオレフィン系樹脂組成物を、実施例1と同様な方法で成形体(1/16インチの試験棒)を得た。これを難燃性(UL94)試験用試験片とした。
また、得られた成形体(1/16インチの試験棒)を、実施例1と同様な方法で成形体(フィルム)を得た。これを難燃剤分散性評価用試験フィルムとした。
分散性評価結果、難燃性(UL94)評価結果を表4に示した。
分散剤(A)と難燃剤(B)及びオレフィン系樹脂(C)からなるマスターバッチ(M1~3)とオレフィン系樹脂(C)を表5の記載の比率で配合し、ハンドブレンドで混合した。尚、オレフィン系樹脂(C)として、ポリプロピレン樹脂「ノバテック FY-4」(商品名、日本ポリプロ(株)製、メルトフローレート5g/10分)を用いた。
その後、100t射出成形機(機種名「SE-100DU」、住友重機械工業(株)製)を用い、成形温度200℃の条件で射出成形を行い、成形体(1/16インチの試験棒)を得た。これを難燃性(UL94)試験用試験片とした。
また、得られた成形体(1/16インチの試験棒)を、実施例1と同様な方法で成形体(フィルム)を得た。これを難燃剤分散性評価用試験フィルムとした。
分散性評価結果、難燃性(UL94)評価結果を表5に示した。
一方、本発明の範囲外となるアルキル基の炭素数が1のメチルメタクリレート単位を主成分とするアルキルメタクリレート系重合体を含む分散剤を配合した比較例1で得られた成形体は、難燃剤の分散性、難燃性に劣った。また、ポリテトラフルオロエチレン含有樹脂(D)を配合した比較例5で得られた成形体は、難燃剤の分散性に劣り、難燃性に劣った。更にマスターバッチを用いた比較例7で得られた成形体も同様に、難燃剤の分散性に劣り、難燃性に劣った。
また、本発明の範囲外となる質量平均分子量が17万及び80万のアルキルメタクリレート系重合体を含む分散剤を配合した比較例2,3で得られた成形体は、難燃剤の分散性に劣り、難燃性に劣った。アルキルメタクリレート系重合体を含む分散剤を配合しなかった比較例4、6、8で得られた成形体も同様に、難燃剤の分散性に劣り、難燃性に劣った。
オレフィン系樹脂(C)としてポリプロピレン系樹脂「ノバテック-PP FY-4」(商品名、日本ポリプロ(株)製、メルトフローレート:5g/10分)99.5部、結晶核剤(B)としてソルビトール系結晶核剤1・3,2・4-ジベンジリデンソルビトール、1・3,2・4-ビス(4-メチルベンジリデン)-D-ソルビトール「ゲルオールMD」(商品名、新日本理化(株)製)0.5部、分散剤(A2)0.5部を配合し、ハンドブレンドで混合した。その後、φ30mm同方向二軸押出機(機種名「BT-30」、(株)プラスチック工学研究所製、L/D=30)にて、スクリュー回転数200rpm、シリンダー温度200℃の条件で押出成形し、オレフィン系樹脂組成物のペレットを得た。
その後、得られたペレットを、射出成形機(機種名「SE-100DU」、住友重機工業(株)製)を用いて、成形温度200℃、金型温度60℃の条件で射出成形を行い、成形体を得た。
配合組成を表6記載の組成に変更した以外は、実施例8と同様の方法で成形体を得た。
PP:ポリプロピレン(商品名「ノバテックFY-4」、日本ポリプロ(株)製)
ゲルオールMD:ソルビトール系結晶核剤(商品名「ゲルオールMD」、新日本理化(株)製)
結晶核剤(B)としてリン酸エステル金属塩系結晶核剤ナトリウム-2,2’-メチレン-ビス(4,6-ジ-t-ブチルフェニル)ホスフェート「アデカスタブNA-11」(商品名、(株)ADEKA製)に変更し、配合組成を表7記載の組成に変更した以外は、実施例8と同様の方法で成形体を得た。
PP:ポリプロピレン(商品名「ノバテックFY-4」、日本ポリプロ(株)製)
NA-11:リン酸エステル金属塩系結晶核剤「アデカスタブNA-11」(商品名、(株)ADEKA製)
オレフィン系樹脂(C)としてポリプロピレン系樹脂「ノバテック-PP FY-4」(商品名、日本ポリプロ(株)製、メルトフローレート:5g/10分)99部、発泡剤(B)としてアゾジカルボンアミド「ビニホールAC#3」(商品名、永和化成工業(株)製)1部、分散剤(A2)1部を配合し、ハンドブレンドで混合した。その後、φ25mm単軸押出機(機種名「TP-25」、サーモプラスチクス工業(株)製、L/D=20)にて、スクリュー回転数30rpm、シリンダー温度180℃の条件で押出成形し、オレフィン系樹脂組成物のストランド及びペレットを得た。
その後、得られたペレットを、丸型ダイスを取り付けたφ25mm単軸押出機(機種名「TP-25」、サーモプラスチクス工業(株)製、L/D=20)にて、スクリュー回転数30rpm、シリンダー温度220℃の条件で押出発泡成形し、円柱状発泡成形体(直径5mm)を得た。
配合組成を表8記載の組成に変更した以外は、実施例14と同様の方法でオレフィン系樹脂組成物のストランド及びペレットを得た。
その後、得られたペレットを実施例14と同様の方法により、円柱状発泡成形体(直径5mm)を得た。
PP:ポリプロピレン(商品名「ノバテックーPP FY-4」、日本ポリプロ(株)製)
ADCA:アゾジカルボンアミド(商品名「ビニホールAC#3」、永和化成工業(株)製)
オレフィン系樹脂(C)としてポリエチレン系樹脂「ノバテック-PE UR350」(商品名、日本ポリエチレン(株)製、メルトフローレート:5g/10分)、発泡剤(B)として炭酸水素ナトリウム「セルボンSC-K」(商品名、永和化成工業(株)製)、シリンダー温度140℃に変更し、配合組成を表9記載の組成に変更した以外は、実施例14と同様の方法でオレフィン系樹脂組成物のストランド及びペレットを得た。
その後、得られたペレットを、シリンダー温度180℃に変更した以外は、実施例14と同様の方法により、円柱状発泡成形体(直径5mm)を得た。
PE:ポリエチレン(商品名「ノバテック-PE UR350」、日本ポリエチレン(株)製)
重曹:炭酸水素ナトリウム(商品名「セルボンSC-K」、(永和化成工業(株)製)
オレフィン系樹脂(C)としてポリプロピレン系樹脂「ノバテック-PP FY-4」(商品名、日本ポリプロ(株)製、メルトフローレート:5g/10分)99.5部、顔料(B)として青色顔料「群青1900」(商品名、第一化成工業(株)製)0.5部、分散剤(A2)0.5部を配合し、ハンドブレンドで混合した。その後、Tダイ金型を取り付けたφ25mm単軸押出機(機種名「TP-25」、サーモプラスチクス工業(株)製、L/D=20)にて、スクリュー回転数30rpm、シリンダー温度190℃の条件で押出成形し、シート成形体を得た。
配合組成を表10記載の組成に変更した以外は、実施例20と同様の方法でシート成形体を得た。
配合組成を表11記載の組成に変更した以外は、実施例20と同様の方法でシート成形体を得た。
尚、顔料(B)として、白色顔料(酸化チタン)「R-830」(商品名、石原産業(株)製)を用いた。
配合組成を表12記載の組成に変更した以外は、実施例20と同様の方法でシート成形体を得た。
尚、顔料(B)として、黒色顔料(カーボンブラック)「CB960」(商品名、三菱化学(株)製)を用いた。
PP:ポリプロピレン(商品名「ノバテックーPP FY-4」、日本ポリプロ(株)製)
カーボンブラック:黒色顔料(商品名、「CB960」、三菱化学(株)製)
Claims (9)
- 炭素数が2以上のアルキル基を有するアルキルメタクリレート(a1)単位を主成分とし、質量平均分子量が1万5000~14万5000であるアルキルメタクリレート系重合体を含む、ポリオレフィン用添加剤(B)の分散剤(A)。
- 前記(a1)単位が、アルキル基の炭素数が4のアルキルメタクリレート単位である、請求項1記載のポリオレフィン用添加剤(B)の分散剤(A)。
- 前記(a1)単位が、i-ブチルメタクリレート単位である、請求項1記載のポリオレフィン用添加剤(B)の分散剤(A)。
- ポリオレフィン用添加剤(B)が難燃剤、結晶核剤、発泡剤及び顔料から選ばれる少なくとも1種である請求項1~3のいずれか1項に記載のポリオレフィン用添加剤(B)の分散剤(A)。
- 請求項1~3のいずれか1項に記載のポリオレフィン用添加剤(B)の分散剤(A)、ポリオレフィン用添加剤(B)及びポリオレフィン系樹脂(C)を含むポリオレフィン系樹脂組成物。
- ポリオレフィン用添加剤(B)が難燃剤、結晶核剤、発泡剤及び顔料から選ばれる少なくとも1種である請求項5記載のポリオレフィン系樹脂組成物。
- 請求項5記載のポリオレフィン系樹脂組成物を成形して得られる成形体。
- ポリオレフィン用添加剤(B)の分散剤(A)の全量、ポリオレフィン用添加剤(B)の全量及びポリオレフィン系樹脂(C)の一部とでマスターバッチを製造した後、前記マスターバッチ及び前記ポリオレフィン系樹脂(C)の残部を配合する請求項5記載のポリオレフィン系樹脂組成物の製造方法。
- ポリオレフィン用添加剤(B)が難燃剤、結晶核剤、発泡剤及び顔料から選ばれる少なくとも1種である請求項8記載のポリオレフィン系樹脂組成物の製造方法。
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JP2020104410A (ja) * | 2018-12-27 | 2020-07-09 | 新日本理化株式会社 | 発泡樹脂成形品の製造方法および該方法で使用される結晶核剤マスターバッチおよびその製造方法ならびに発泡樹脂成形品 |
WO2021241682A1 (ja) | 2020-05-28 | 2021-12-02 | 三菱ケミカル株式会社 | 樹脂組成物及び成形体 |
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KR101855267B1 (ko) * | 2016-09-19 | 2018-05-04 | 롯데케미칼 주식회사 | 폴리올레핀계 난연성 발포체 제조용 수지 조성물 및 이로부터 형성된 난연성 발포체 |
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WO2011096596A3 (ja) | 2011-10-20 |
TW201138940A (en) | 2011-11-16 |
JPWO2011096596A1 (ja) | 2013-06-13 |
CN102933650A (zh) | 2013-02-13 |
EP2565230A2 (en) | 2013-03-06 |
EP2565230B1 (en) | 2015-09-09 |
JP5794146B2 (ja) | 2015-10-14 |
KR101484829B1 (ko) | 2015-01-20 |
EP2565230A4 (en) | 2013-11-06 |
KR20120138818A (ko) | 2012-12-26 |
US20130085196A1 (en) | 2013-04-04 |
TWI561296B (en) | 2016-12-11 |
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