JP6304292B2 - 耐熱性シートおよびその製造方法 - Google Patents
耐熱性シートおよびその製造方法 Download PDFInfo
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- JP6304292B2 JP6304292B2 JP2016055402A JP2016055402A JP6304292B2 JP 6304292 B2 JP6304292 B2 JP 6304292B2 JP 2016055402 A JP2016055402 A JP 2016055402A JP 2016055402 A JP2016055402 A JP 2016055402A JP 6304292 B2 JP6304292 B2 JP 6304292B2
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- polyolefin
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- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
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- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
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- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
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- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- PJJZFXPJNUVBMR-UHFFFAOYSA-L magnesium benzoate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PJJZFXPJNUVBMR-UHFFFAOYSA-L 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 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
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OKUCEQDKBKYEJY-UHFFFAOYSA-N tert-butyl 3-(methylamino)pyrrolidine-1-carboxylate Chemical compound CNC1CCN(C(=O)OC(C)(C)C)C1 OKUCEQDKBKYEJY-UHFFFAOYSA-N 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Description
さらに詳しくは、本発明(第一の発明)は、耐熱性を有する熱可塑性樹脂の繊維をオレフィン系樹脂に混合して得られる耐熱性樹脂組成物を用いた、耐熱性に優れたシートおよびそれらの製造方法に関する。
ポリオレフィン(a)と、融点が200℃以上、かつガラス転移点がポリオレフィン(a)の融点以下の範囲にある熱可塑性樹脂の繊維(b)と、を必須成分とする樹脂組成物(α)を含む、ポリオレフィン(a)を連続相とし、かつ該熱可塑性樹脂の繊維(b)を分散相とするシート、に関する。
前記シートを多孔質化して得られ、ポリオレフィン(a)を連続相とし、かつ少なくとも該熱可塑性樹脂の繊維(b)を分散相として含む微多孔質のシートに関する。
ポリオレフィン(a)と、融点が200℃以上、かつガラス転移点がポリオレフィン(a)の融点以下の範囲にある熱可塑性樹脂の繊維(b)とを、前記ポリオレフィン(a)の融点以上かつ前記熱可塑性樹脂の繊維(b)の融点以下の温度で混練して、樹脂組成物(α)を得る工程(1)、
前記ポリオレフィン(a)の融点以上の温度かつ前記熱可塑性樹脂の繊維(b)の融点以下に加熱した樹脂組成物(α)をシート化してポリオレフィン(a)を連続相とし、かつ該熱可塑性樹脂の繊維(b)を分散相とするシート材料(β)を得る工程(2)、
を有することを特徴とするシートの製造方法、に関する。
前記ポリオレフィン(a)の融点以上の温度かつ前記熱可塑性樹脂の繊維(b)の融点以下に加熱した樹脂組成物(α)をシート化してポリオレフィン(a)を連続相とし、かつ該熱可塑性樹脂の繊維(b)を分散相とするシート材料(β)を得る工程(2)、を有する。
(1)シートの厚さは特に制限はなく、その用途において求められる厚さの範囲であればよいが、一般的には、5〜200μmの範囲であり、より好ましくは8〜100μmの範囲であり、更に好ましくは10〜40μmの範囲である。
(2)200℃における熱収縮率が3.0%以下である。特に、熱セット前で3.0%以下であるものが好ましく、また熱セット後で2.5%以下であるものがさらに好ましい。一方、熱収縮率は低いほど好ましいため、下限値は特段設定されないが、例えば、0%のものであることが好ましいが、0.01%以上のものであっても良く、さらに0.1%以上のものであっても良い。
(3)機械的強度として、引張強さは20MPa以上である。
(4)シートの膜厚ムラが少なく、熱延伸時の破断を防ぐことができる。
乾燥処理としては、加熱乾燥法又は風乾法等により乾燥する方法を挙げることができる。乾燥温度は、ポリオレフィン(a)の結晶分散温度以下の温度であるのが好ましく、特に結晶分散温度より5℃以上低い温度であるのが好ましい。
(1)ASTM F316−86により定められる平均孔径が0.02〜3〔μm〕の範囲であり、さらに好ましくは0.05〜1〔μm〕の範囲である。
(2)JIS R1634法により定められた空孔率が30〜80〔%〕の範囲である。
(3)JIS P8117法によって定められるガーレー透気度が20〜800秒/100mlの範囲であり、さらに好ましくは50〜500秒/100mlの範囲である。
(4)シャットダウン温度が、130〜150℃の範囲である。
JIS−P8117「紙及び板紙−透気度及び透気抵抗度試験方法(中間領域)−ガーレー法」に準拠し、微多孔質膜のガーレー透気度を測定した。
微多孔質膜を所定の温度に設定した熱風乾燥機中に1分間さらし、ガーレー透気度が10000sec/100ml以上になる温度をシャットダウン温度とした。
得られた微多孔質膜を50mm×50mmに裁断し、JIS−K7133「プラスチック−フィルム及びシート−加熱寸法変化測定方法」に準拠した方法で熱収縮率を測定した(150℃、10分放置後の縦横の収縮率平均)。
溶融型電界紡糸機にポリアリーレンスルフィド樹脂(DIC株式会社製「TR−03G」、融点280℃)を投入し、設定樹脂温度を融点+20℃で電界紡糸し、平均繊維径0.5μmの綿状繊維を作製した。得られた綿状繊維を冷凍粉砕機にて凍結粉砕し、平均繊維径0.5μm、平均繊維長2mm、平均アスペクト比4000のPPS繊維(B1)を得た。
ポリアリーレンスルフィド樹脂の代わりに、シンジオタクチックポリスチレン(出光興産株式会社製「ザレック60ZC」融点270℃、)を用いたこと以外は調製例1と同様にして、平均繊維径0.5μm、平均繊維長2mm、平均アスペクト比4000のSTS繊維(B2)を得た。
ポリアリーレンスルフィド樹脂の代わりに、ポリエチレンテレフタレート(ユニチカ株式会社製「MA−2103」、融点255℃)を用いたこと以外は調製例1と同様にして、平均繊維径0.5μm、平均繊維長2mm、平均アスペクト比4000のPET繊維(B3)を得た。
二軸混練機にポリアリーレンスルフィド樹脂(DIC株式会社製「TR−03G」、融点280℃)を投入し溶融した後、この溶融物を既存の単成分紡糸機を用い融点+20℃の温度で紡糸をした。このとき、吐出量35g/分、チムニーは温度25℃、風速25m/分、紡糸速度1000m/分で引き取り、未延伸糸を得、巻き取ることなく、該未延伸糸を第1ホットローラー温度が90℃、第2ホットローラー温度が150℃のローラー間で3.5倍で延伸した後、カッターロールにて切断することにより、平均繊維径2μm、平均繊維長2mm、平均アスペクト比1000のPPS繊維(B4)を得た。
ポリアリーレンスルフィド樹脂の代わりに、シンジオタクチックポリスチレン(出光興産株式会社製「ザレック60ZC」融点270℃)を用いたこと以外は調整例4と同様にして、平均繊維径2μm、平均繊維長2mm、平均アスペクト比1000のSTS繊維(B5)を得た。
ポリアリーレンスルフィド樹脂の代わりに、ポリエチレンテレフタレート(ユニチカ株式会社製「MA−2103」、融点255℃)を用いたこと以外は調製例4と同様にして、平均繊維径2μm、平均繊維長2mm、平均アスペクト比1000のPET繊維(B6)を得た。
ポリアリーレンスルフィド樹脂の代わりに、ポリプロピレン(株式会社プライムポリマー製「プライムポリプロE111G」、融点160℃)を用いたこと以外は調製例1と同様にして、平均繊維径0.5μm、平均繊維長2mm、平均アスペクト比4000のPP繊維(B7)を得た。
溶液型電界紡糸機に裁断したパラ系アラミド繊維(ケブラー29)のN,N−ジメチルアセトアミド溶液(アラミド濃度20質量%)を投入して電界紡糸し、平均繊維径0.5μmの綿状繊維を作製した。得られた綿状繊維を冷凍粉砕機にて凍結粉砕し、平均繊維径0.5μm、平均繊維長2mm、平均アスペクト比4000のアラミド繊維(B8)を得た。
表1〜3に示す割合で、ポリオレフィン、熱可塑性樹脂の繊維、酸化防止剤をタンブラーで均一に混合し、配合材料とした。
その後、二軸押出機(株式会社日本製鉄所製「TEX−30」)に前記配合材料を投入し、樹脂成分吐出量20kg/hr、スクリュー回転数350rpm、最大トルク60A、設定樹脂温度220℃で、ポリオレフィンを溶融し、熱可塑性樹脂の繊維、酸化防止剤と混練した後、さらに、孔形成剤として流動パラフィンを加え、樹脂組成物を得た。
得られた樹脂組成物をダイ押出成形し、表面を80℃に保ったロール上で冷却し、厚み0.3mmのシート状の試験片を作製した。
このシートをバッチ式二軸延伸機にて、120℃で3×3倍に延伸し、厚み0.03mmの二軸延伸フィルムとした。
得られた二軸延伸フィルムをテンター延伸機で保持しながら125℃で3分間熱固定処理した。
熱固定した二軸延伸フィルムを20cm×20cmのガラス製枠に固定した後、25℃に温調された塩化メチレンで満たされた孔形成剤除去漕中に1時間浸漬し、孔形成剤を除去することにより、膜厚0.03mmの微多孔質のシートを製造した。
・ポリオレフィン
A1 プライムポリマー株式会社製「HI−ZEX 5305EP」、MI=0.8(g/10min)
A2 三井化学株式会社製「HI−ZEX MILLION 340M」、MI=<0.01(g/10min)
A3 プライムポリマー株式会社製「HI−ZEX 7000F」、 MI=0.04(g/10min)
C1 住友化学株式会社製「SUMILIZER GP」
Claims (7)
- ポリオレフィン(a)を連続相とし、かつ少なくとも、融点が200℃以上、かつガラス転移点がポリオレフィン(a)の融点以下の範囲にある熱可塑性樹脂の繊維(b)を分散相とし、ポリオレフィン(a)と、該熱可塑性樹脂の繊維(b)との合計質量(a+b)に対し、ポリオレフィン(a)が50〜95質量%の範囲であり、該熱可塑性樹脂の繊維(b)が5〜50質量%の範囲であること、かつ、JIS P8117法によって定められるガーレー透気度が20〜800秒/100mlの範囲である、微多孔質シート。
- 膜厚が5〜200μmの範囲である、請求項1記載の微多孔質シート。
- ASTM F316−86により定められる平均孔径が0.02〜3〔μm〕の範囲である、請求項1記載の微多孔質シート。
- ポリオレフィン(a)、該熱可塑性樹脂の繊維(b)に加え、さらに酸化防止剤(c)を含有する請求項1〜3のいずれか一項記載の微多孔質シート。
- ポリオレフィン(a)と、該熱可塑性樹脂の繊維(b)との合計質量(a+b)100質量部に対し、酸化防止剤(c)が0.01〜5質量部の範囲である請求項4記載の微多孔質シート。
- 前記微多孔質のシートが電池用単層セパレータである請求項1〜5の何れか一項に記載の微多孔質シート。
- 前記電池が非水電解質二次電池である請求項6記載の微多孔質シート。
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