WO2022210502A1 - 樹脂組成物、樹脂成形体 - Google Patents
樹脂組成物、樹脂成形体 Download PDFInfo
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- WO2022210502A1 WO2022210502A1 PCT/JP2022/014900 JP2022014900W WO2022210502A1 WO 2022210502 A1 WO2022210502 A1 WO 2022210502A1 JP 2022014900 W JP2022014900 W JP 2022014900W WO 2022210502 A1 WO2022210502 A1 WO 2022210502A1
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- mass
- parts
- silane coupling
- coupling agent
- resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 229920005989 resin Polymers 0.000 title claims description 53
- 239000011347 resin Substances 0.000 title claims description 53
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 71
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 58
- 239000004917 carbon fiber Substances 0.000 claims abstract description 58
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims description 29
- 238000000465 moulding Methods 0.000 claims description 25
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 16
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 16
- -1 polybutylene terephthalate Polymers 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 238000011156 evaluation Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 13
- 239000003086 colorant Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011295 pitch Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000006082 mold release agent Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000005243 fluidization Methods 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 description 4
- 235000004416 zinc carbonate Nutrition 0.000 description 4
- 239000011667 zinc carbonate Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 150000007945 N-acyl ureas Chemical class 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ULNRRNBMNIIOJK-UHFFFAOYSA-N isocyanatourea Chemical compound NC(=O)NN=C=O ULNRRNBMNIIOJK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/04—Polysulfides
-
- 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
- H01M50/30—Arrangements for facilitating escape of gases
- H01M50/383—Flame arresting or ignition-preventing means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/122—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
- H01M50/143—Fireproof; Explosion-proof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Definitions
- the present invention relates to a fire-resistant resin composition and a resin molding using the same.
- This application claims priority based on Japanese Patent Application No. 2021-054780 filed in Japan on March 29, 2021, and the contents thereof are incorporated herein.
- an exterior body of a lithium-ion secondary battery (hereinafter sometimes referred to as "battery”) is also often made of a resin material for weight reduction.
- batteries become smaller and have higher energy densities (energy densities of 300 Wh/kg or more), there is a risk that they may heat up to high temperatures depending on how they are used. Therefore, the safety of batteries and battery packs has become more important.
- a lithium-ion secondary battery may experience thermal runaway if it is overcharged or overdischarged, or if an unexpected shock is applied to cause an internal or external short circuit.
- a lithium-ion secondary battery in which thermal runaway occurs generates gas and increases the internal pressure of the battery. If such a situation occurs, there is a possibility that the outer can may burst due to an increase in internal pressure. Therefore, these batteries are provided with an exhaust hole, a safety valve, and the like for venting gas.
- Patent Document 1 discloses a flame-retardant material capable of suppressing fluidization in a high-temperature environment by adding a fibrous substance.
- a resin composition is disclosed.
- Patent Document 2 discloses a polyphenylene sulfide resin composition containing carbon fibers pretreated with a silane coupling agent.
- the present invention has been made in view of such a background, and aims to provide a resin composition that can suppress melting, deformation, and fluidization due to injection of high-temperature gas or flame, and a resin molding using the same. aim.
- the resin composition contains 2 parts by mass or more and 70 parts by mass or less of carbon fiber and 0.3 parts by mass or more and 7 parts by mass or less of a silane coupling agent with respect to 100 parts by mass of the thermoplastic resin. It has been found that the amount of melting deformation when exposed to a flame of 1000 W or more can be suppressed by adopting a configuration that includes the range.
- the present invention proposes the following means. That is, the resin composition of the present invention contains 2 parts by mass or more and 70 parts by mass or less of the carbon fiber and 0.3 parts by mass or more and 7 parts by mass or less of the silane coupling agent with respect to 100 parts by mass of the thermoplastic resin. It is characterized by including in the range.
- the carbon fiber is 2 parts by mass or more and 70 parts by mass or less
- the silane coupling agent is 0.3 parts by mass or more and 7.0 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
- the content ratio of the silane coupling agent to the carbon fibers may be 0.01 or more.
- the carbon fiber is 15 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin, or the content ratio of the silane coupling agent to the carbon fiber (silane coupling agent / carbon fiber) may be 0.1 or more.
- the thermoplastic resin may contain at least one of polyphenylene sulfide, polyamide, polybutylene terephthalate, modified polyphenylene ether, and polycarbonate.
- the silane coupling agent may be at least one of an organosilicon compound and a siloxane compound.
- the organosilicon compound may be at least one of an amine-based silane coupling agent and an epoxy-based silane coupling agent.
- 1 part by mass or more and 50 parts by mass or less of fluororesin may be further included with respect to 100 parts by mass of the thermoplastic resin.
- the resin molding of the present invention is a resin molding using the resin composition according to each of the above items, wherein at least the safety valve is attached to the outer periphery of one or more lithium ion secondary battery cells having a safety valve or an exhaust hole. Alternatively, it is attached so as to cover the exhaust hole.
- FIG. 1 is a perspective view of a lithium ion secondary battery cell to which a resin molded body according to one embodiment of the present invention is attached.
- FIG. 2 is a perspective view showing a lithium ion secondary battery cell to which a resin molded body according to one embodiment of the present invention is attached.
- FIG. 3 is a perspective view of a lithium ion secondary battery cell to which the resin molded body of FIG. 2 is attached.
- 4 is a cross-sectional view taken along the line AA of FIG. 3.
- a resin composition according to one embodiment of the present invention comprises a mixture of a thermoplastic resin, carbon fibers, and a silane coupling agent.
- This resin composition contains 2 parts by mass or more and 70 parts by mass or less of carbon fiber and 0.3 parts by mass or more and 7.0 parts by mass or less of a silane coupling agent with respect to 100 parts by mass of the thermoplastic resin. contains.
- the carbon fiber contained in the resin composition may be 7 parts by mass or more, or the carbon fiber contained in the resin composition may be 23 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
- the silane coupling agent contained in the resin composition may be 0.7 parts by mass or more, and the silane coupling agent contained in the resin composition may be 2.3 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
- this resin composition may further contain a fluorine resin in a range of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. If the amount of carbon fiber is less than 2 parts by mass, sufficient flame retardancy cannot be ensured, and the carbon fiber may be easily melted and deformed by flames. Also, when the silane coupling agent is less than 0.3 parts by mass, sufficient flame retardancy cannot be ensured, and flames may easily melt and deform.
- the content ratio of the silane coupling agent to the carbon fibers contained in the resin composition to 0.01 or more and 80 or less.
- the carbon fiber contained in the resin composition is 15 parts by mass or more and 70 parts by mass or less, or the content ratio of the silane coupling agent to the carbon fiber (silane coupling agent / carbon fiber) is preferably 0.1 or more. That is, the mass ratio of the carbon fiber to 100 parts by mass of the thermoplastic resin is preferably 15 parts by mass or more and 70 parts by mass or less. It is also preferable that the mass ratio of the carbon fiber to 100 mass parts of the thermoplastic resin is 2 mass parts or more and 70 mass parts or less, and the content ratio of the silane coupling agent to the carbon fiber is 0.1 or more.
- thermoplastic resin used in the resin composition examples include polyphenylene sulfide (PPS), polyamide (PA), polybutylene terephthalate (PBT), modified polyphenylene ether (mPPE), polycarbonate (PC), and polypropylene (PP).
- PPS polyphenylene sulfide
- PA polyamide
- PBT polybutylene terephthalate
- mPPE modified polyphenylene ether
- PC polycarbonate
- PP polypropylene
- PPS is particularly preferable as a thermoplastic resin because it has a high melting point (278°C) and glass transition temperature (92-126°C).
- PPS which is a thermoplastic resin suitable for the resin composition, includes oxidative cross-linked PPS that has been heat-treated in the presence of oxygen to increase the melt viscosity, and lithium chloride, an organic acid salt, water, etc., added to the polymerization sequence. Any linear PPS having an increased molecular weight while remaining in a chain form can be used. A mixture of oxidatively crosslinked PPS and linear PPS can also be used.
- both PAN (polyacrylonitrile) carbon fibers using acrylic fibers and pitch-based carbon fibers using pitch can be used.
- a pitch-based carbon fiber may be used as the carbon fiber.
- Pitch-based carbon fibers include isotropic pitch-based carbon fibers and mesophase pitch-based carbon fibers, and either pitch-based carbon fibers can be used.
- Examples of the shape of the carbon fibers used in the resin composition may include a single fiber diameter of 1 to 20 ⁇ m, an average fiber length of 0.01 to 10 mm, and an aspect ratio of about 1.5 to 1,300.
- the silane coupling agent contained in the resin composition is a component that contributes to deformation resistance, and can suppress melt drop of the resin composition during combustion.
- the silane coupling agent contained in the resin composition may be, for example, at least one of an organic silicon compound and a siloxane compound. At least one of an amine-based silane coupling agent and an epoxy-based silane coupling agent may be used as the silane coupling agent (organosilicon compound).
- an amino-terminated amine-based silane coupling agent is more preferable.
- Examples of amine-based silane coupling agents include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(amino Ethyl)-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine and the like can be mentioned.
- epoxy-based silane coupling agents include 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl.
- examples include methyldimethoxysilane and 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane.
- the silane coupling agent contained in the resin composition includes acrylic (for example, 3-acryloxypropyltrimethoxysilane), vinyl, methacrylic, styryl, ureido, isocyanate, isocyanurate, mercapto
- acrylic for example, 3-acryloxypropyltrimethoxysilane
- vinyl methacrylic
- styryl ureido
- isocyanate isocyanurate
- mercapto mercapto
- silane coupling agents such as silanes can also be used.
- silane coupling agent the above-mentioned amine-based silane coupling agent, epoxy-based silane coupling agent, acrylic, vinyl, methacrylic, styryl, ureide, isocyanate, isocyanurate, mercapto, etc.
- a solid silane coupling agent can also be used in addition to the liquid silane coupling agent.
- solid silane coupling agents include X-12-1273ES (manufactured by Shin-Etsu Chemical Co., Ltd.).
- liquid silane coupling agents are superior in that they have functional groups and can be expected to be reactive (in principle, high effects can be expected).
- As a silane coupling agent it is excellent in that it is easy to handle.
- the fluororesin examples include polytetrafluoroethylene (PTFE). It is preferable to use powdered PTFE. For example, PTFE powder having an average particle size of 10 to 30 ⁇ m and a specific surface area determined by the BET method of 0.5 to 5 m 2 /g can be used.
- the fluororesin may be contained in an amount of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
- fluororesins include PTFE, PFA (perfluoroalkoxyalkane), FEP (perfluoroethylene propene copolymer), and the like.
- the resin composition may further contain carbon black as a coloring agent, polyolefin wax, stearyl alcohol, etc. as a release agent, and hydrotalcite, zinc carbonate, etc. as a mold corrosion inhibitor.
- a known production method may be applied to produce the resin composition as described above.
- a thermoplastic resin, carbon fiber, a silane coupling agent, a mold corrosion inhibitor, and a release agent are introduced into a twin-screw extruder, and, for example, the kneading temperature is 270° C. or higher and 300° C. or lower, and the screw rotation speed is is controlled at 100 rpm or more and 300 rpm or less, and the kneading time is 30 minutes or more and 60 minutes or less for granulation, whereby a pellet-shaped resin composition can be formed.
- thermoplastic resin and the silane coupling agent it is preferable to first blend the thermoplastic resin and the silane coupling agent, then add the carbon fiber, and knead after blending.
- the silane coupling agent can be uniformly dispersed in the thermoplastic resin, and the function of suppressing flow and deformation due to flames can be enhanced.
- a thermoplastic resin and a silane coupling agent were dry-blended, and then carbon fiber, a mold corrosion inhibitor, a mold release agent, and a colorant were dry-blended and then dry-blended from the main feeder of a twin-screw extruder. The raw material may be discharged and kneaded.
- Another method is to dry blend a thermoplastic resin and a silane coupling agent, further dry blend a mold corrosion inhibitor, a release agent, and a colorant, and dry blend from the main feeder of a twin screw extruder.
- the carbon fiber may be discharged from a side feeder and kneaded while discharging the raw material.
- a resin molded body can be produced by molding the obtained resin composition by a known molding method such as extrusion molding with an extruder, press molding with a press machine, or injection molding with an injection molding machine.
- the carbon fiber is 2 parts by mass or more and 70 parts by mass or less
- the silane coupling agent is 0.3 parts by mass or more and 7.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
- FIG. 1 is a perspective view of a lithium ion secondary battery cell to which a resin molded body according to one embodiment of the present invention is attached.
- the lithium ion secondary battery cell 1 is, for example, a prismatic battery cell, and is provided with a positive electrode terminal 3 and a negative electrode terminal 4 on one end surface (upper surface in FIG. 1) of an outer can 2 which is a battery container, and between which a positive electrode terminal 3 and a negative electrode terminal 4 are provided. is provided with a safety valve 5.
- the safety valve 5 is When the internal pressure of the lithium ion secondary battery cell 1 rises due to thermal runaway, it operates to eject high-temperature and high-pressure gas to prevent the outer can 2 from bursting.
- FIGS. 2, 3, and FIG. 4 which is a cross-sectional view taken along line AA of FIG. It is attached to the outer periphery of the lithium ion secondary battery cell 1 via (sandwiching) the insulating sheet 7 so as to cover at least the safety valve 5 .
- the resin molding 6 is made of an insulating material or if insulation is not required, the insulating sheet 7 may not be interposed.
- the portion of the insulating sheet 7 that covers the safety valve 5 may or may not be in contact with the safety valve 5 .
- the portion of the resin molding 6 covering the safety valve 5 may or may not be in contact with the safety valve 5 .
- the insulating sheet 7 and the sheet-like resin molded body 6 are both rectangular and substantially the same size, and cover the upper surface of the rectangular parallelepiped lithium ion secondary battery cell 1 including the safety valve 5, It is attached so as to cover the upper part of the rear surface (left and right surfaces in FIG. 4).
- the sizes of the resin molded body 6 and the insulating sheet 7 may not be the same. Both may be joined in advance.
- the lead wires (not shown) connected to the positive electrode terminal 3 and the negative electrode terminal 4 of the lithium ion secondary battery cell 1 are drawn out using the side surfaces not covered by the insulating sheet 7 and the resin molding 6 .
- the lithium-ion secondary battery cell 1 to which the insulating sheet 7 and the sheet-shaped resin molding 6 are attached is housed in an exterior case (not shown). Inside the outer case, the resin molded body 6 that covers the upper front and rear surfaces of the lithium ion secondary battery cell 1 is pressed by the inner wall surface of the outer case, thereby holding the resin molded body 6 .
- the resin molded body 6 of this embodiment is obtained by molding and curing the resin composition of one embodiment described above.
- the thermal conductivity (measurement temperature: 50° C.) measured by the method (SCHF) is less than 1.0 W/m ⁇ K.
- the thermal conductivity is 1.0 W/m ⁇ K or more
- the resin molded body 6 will be damaged by the high-temperature and high-pressure gas ejected from the safety valve and the discharge hole.
- Heat is conducted to the outer case containing the lithium ion secondary battery cell 1 covered with the sheet-shaped resin molded body 6, for example, the member surrounding the resin molded body 6 via the heat, and the outer case is melted and deformed. I have concerns.
- the resin molded body 6 is in the form of a sheet with a uniform thickness, and the thickness of the sheet-shaped resin molded body 6 may be 0.5 mm or more and 10.0 mm or less. It is preferably 7 mm or more and 5 mm or less, more preferably 1.0 mm or more and 2 mm or less. Although it is desirable that the thickness of the resin molded body 6 is uniform, the thickness of the portion of the resin molded body 6 that covers the safety valve 5 falls within the above range, and the thickness of the other portion does not have to fall within the above range. .
- the high-temperature, high-pressure gas ejected from the safety valve 5 forms a through hole in the resin molding 6, and the high-temperature, high-pressure gas is ejected from the through hole, and the insulating sheet 7 and There is a concern that the fire may spread and burn to members outside the lithium ion secondary battery cell 1 covered with the sheet-like resin molding 6 .
- the through-hole serves as an air (oxygen) supply port, and there is a concern that the lithium-ion secondary battery cell 1 itself covered with the insulating sheet 7 and the sheet-like resin molded body 6 may expand fire spread and burnout. .
- the thickness of the sheet-shaped resin molded body 6 exceeds 10.0 mm, high-temperature and high-pressure gas can be blocked, that is, no through holes are formed, but the resin molded body 6 becomes large and the molding process becomes complicated. Become. In addition, it becomes difficult to house the lithium-ion secondary battery cell 1 in an existing exterior case.
- the hardness of the surface of the resin molded body 6 is preferably 50 or more when measured with a type D durometer using a sheet with a thickness of 2 mm of the resin molded body based on JIS K7215. If the hardness of this surface is less than 50, there is concern that the resin molding 6 may be damaged or a through hole may be formed due to the high-temperature/high-pressure gas ejected from the safety valve 5 (in particular, the influence of the pressure (ejection force)). There is The upper limit of the hardness of the surface is 90 as the appropriate upper limit in the above standard, but it may exceed 90 as long as it is within the moldable range.
- a general measuring device can measure up to about 100, and the surface hardness of the resin molding 6 displayed by the measuring device may be 100 or less.
- the resin molded body 6 of the present embodiment is formed using the resin composition described above so as to cover the safety valve 5 of the lithium ion secondary battery cell 1, so that the lithium ion secondary battery is prevented from thermal runaway. Even if this occurs, the high-temperature, high-pressure gas ejected from the safety valve 5 does not form a through-hole in the resin molding 6, and the spread of fire and burnout due to the ejection of the high-temperature, high-pressure gas can be suppressed.
- flame retardant evaluation 1 the type of silane coupling agent, the mixed amount of PTFE, carbon fiber, silane coupling agent, release agent, coloring agent and mold corrosion inhibitor with respect to 100 parts by mass of thermoplastic resin (composition Resin compositions (samples) of Examples 1 to 19 of the present invention and Comparative Examples 1 to 3 with different ratios were prepared. Table 1 shows the composition ratio (parts by mass) of each sample. Each component shown in Table 1 was weighed, dry-blended, and then granulated using a twin-screw extruder to granulate each resin composition of Inventive Examples 1 to 19 and Comparative Examples 1 to 3. . Using this granulated product, injection molding was performed to obtain a sample.
- the raw materials used for producing the resin composition are as follows.
- PPS polyphenylene sulfide
- silane coupling agent (2-1) Amine system: liquid silane coupling agent (2-2) Epoxy system: liquid silane coupling agent (2-3) Acrylic system: liquid silane coupling agent (2-4) Solid system: solid silane Coupling agent (3) carbon fiber: pitch-based carbon fiber, average fiber length 0.36 mm, fiber diameter 13 ⁇ m, aspect ratio 28 (4) Fluorine resin (PTFE): powdery, average particle size 18 ⁇ m, BET specific surface area 2 m 2 /g (5) Colorant: Carbon black (6) Mold release agent: Polyolefin wax (7) Mold corrosion inhibitor: Zinc carbonate (ZnCO 3 )
- the test method for flame retardancy evaluation 1 is to fix a burner with an output of 5580 W vertically downward, prepare a resin composition (sample) of 100 mm ⁇ 120 mm ⁇ 2 mm, and place each sample on the floor at a position 170 mm from the crater of the burner. and placed horizontally. Then, the burner was ignited to apply a flame to each sample. Table 1 shows the results of this flame retardancy evaluation 1.
- the evaluation criterion for flame retardancy evaluation 1 was the time required for the amount of deformation to reach 10 mm (the longer the time, the higher the flame retardancy).
- the carbon fiber is 2 parts by mass or more and 70 parts by mass or less
- the silane coupling agent is 0.3 parts by mass or more and 7 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It has been confirmed that the resin compositions of Examples 1 to 19 of the present invention containing the amount of 10 mm deformation are at least 49 seconds or more, and that good flame retardancy can be ensured.
- thermoplastic resin (Flame retardant evaluation 2) Next, as flame retardancy evaluation 2, the mixture amount (composition ratio) of carbon fiber, silane coupling agent, mold release agent, colorant and mold corrosion inhibitor with respect to 100 parts by mass of thermoplastic resin was constant, and heat was applied. Resin compositions (samples) of Examples 7 and 20 to 24 were prepared by changing only the type of plastic resin. In addition, resin compositions (samples) of Comparative Examples 4 to 7 were prepared using only a thermoplastic resin. Table 2 shows the composition ratio (parts by mass) of each sample. Each component shown in Table 2 was weighed, dry-blended, and then granulated using a twin-screw extruder to granulate each resin composition of Examples 7 and 20 to 24 of the present invention. Using this granule, injection molding was performed to obtain a sample. Further, thermoplastic resins of Comparative Examples 4 to 7 were prepared.
- the raw materials used for producing the resin composition are as follows. (1) PPS: Polyphenylene sulfide (2) PBT: Polybutylene terephthalate (3) PA6: Polyamide 6, a type of polyamide (4) mPPE: modified polyphenylene ether (5) PC: polycarbonate (6) PP: polypropylene (7) Carbon fiber pitch-based carbon fiber, average fiber length 0.36 mm, fiber diameter 13 ⁇ m, aspect ratio 28 (8) PTFE: fluororesin powder, average particle size 18 ⁇ m, BET specific surface area 2 m 2 /g (9) Coloring agent: carbon black (10) Release agent: polyolefin wax (11) Mold corrosion inhibitor: zinc carbonate ( ZnCO3 )
- the test method for flame retardancy evaluation 2 is to fix a burner with an output of 5580 W vertically downward, prepare a resin composition (sample) of 100 mm ⁇ 120 mm ⁇ 2 mm, and place each sample on the floor at a position of 200 mm from the crater of the burner. and placed horizontally. Then, the burner was ignited to apply a flame to each sample. Table 2 shows the results of this flame retardancy evaluation 2.
- the evaluation criteria for flame retardancy evaluation 2 were performed by measuring the amount of deformation of each sample 40 seconds after the start of combustion in the burner. Good: The amount of deformation of the sample is less than 2 mm after 40 seconds from the start of burner combustion. Acceptable: Deformation of the sample is 2 mm or more and less than 20 mm after 40 seconds from the start of burner combustion. Impossible: Deformation of sample is 20 mm or more at 40 seconds after the start of burner combustion, or dripping of molten resin occurs.
- thermoplastic resins are used as thermoplastic resins, and 2 parts by mass or more and 70 parts by mass or less of carbon fiber and a silane coupling agent are added to 100 parts by mass of the thermoplastic resin. It was confirmed that Inventive Examples 7, 20, and 21 containing in the range of 0.3 parts by mass or more and 7 parts by mass or less were most excellent in flame retardancy. Further, mPPE, PC, and PP are used as thermoplastic resins, and 2 parts by mass or more and 70 parts by mass or less of carbon fiber and 0.3 parts by mass or more of a silane coupling agent are used with respect to 100 parts by mass of the thermoplastic resin.
- the respective contents of the mold corrosion inhibitor, the mold release agent, and the colorant in the flame retardant evaluations 1 and 2 described above are examples, and the respective contents of the mold corrosion inhibitor, the mold release agent, and the colorant
- the content can be increased or decreased as desired, and the content is not limited.
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Abstract
Description
本願は、2021年3月29日に、日本に出願された特願2021-054780号に基づき優先権を主張し、それらの内容をここに援用する。
また、特許文献2には、シランカップリング剤で前処理を行った炭素繊維を含むポリフェニレンスルフィド樹脂組成物が開示されている。
即ち、本発明の樹脂組成物は、熱可塑性樹脂100質量部に対して、炭素繊維を2質量部以上かつ70質量部以下、シランカップリング剤を0.3質量部以上かつ7質量部以下の範囲で含むことを特徴とする。
本発明の一実施形態の樹脂組成物は、熱可塑性樹脂と、炭素繊維と、シランカップリング剤とを混合したものから構成されている。この樹脂組成物は、熱可塑性樹脂100質量部に対して、炭素繊維を2質量部以上かつ70質量部以下、シランカップリング剤を0.3質量部以上かつ7.0質量部以下の割合で含有している。
なお、熱可塑性樹脂100質量部に対して、樹脂組成物に含まれる炭素繊維を7質量部以上としてもよく、樹脂組成物に含まれる炭素繊維を23質量部以下としてもよい。
また、熱可塑性樹脂100質量部に対して、樹脂組成物に含まれるシランカップリング剤を0.7質量部以上としてもよく、樹脂組成物に含まれるシランカップリング剤を2.3質量部以下としてもよい。
また、この樹脂組成物は、熱可塑性樹脂100質量部に対して、更にフッ素樹脂を1質量部以上かつ50質量部以下の範囲で含有していてもよい。
なお、炭素繊維が2質量部未満の場合は、難燃性を十分に確保できず、火炎によって容易に溶融変形してしまう場合がある。また、シランカップリング剤が0.3質量部未満の場合も難燃性を十分に確保できず、火炎によって容易に溶融変形してしまう場合がある。
すなわち、熱可塑性樹脂100質量部に対する炭素繊維の質量比率を、15質量部以上かつ70質量部以下とすることが好ましい。
また、熱可塑性樹脂100質量部に対する炭素繊維の質量比率を、2質量部以上かつ70質量部以下とし、かつ炭素繊維に対するシランカップリング剤の含有割合を0.1以上とすることも好ましい。
ピッチ系炭素繊維としては、等方性ピッチ系炭素繊維と、メソフェーズピッチ系炭素繊維があるが、いずれのピッチ系炭素繊維も用いることができる。
樹脂組成物に用いる炭素繊維の形状例としては、単繊維の繊維径が1~20μm、平均繊維長が0.01~10mm、アスペクト比が1.5~1300程度であってもよい。
樹脂組成物に含まれるシランカップリング剤としては、例えば、有機ケイ素化合物およびシロキサン化合物の少なくとも一方であればよい。また、シランカップリング剤(有機ケイ素化合物)としては、アミン系シランカップリング剤およびエポキシ系シランカップリング剤の少なくとも一方であればよい。アミン系シランカップリング剤とエポキシ系シランカップリング剤とを比較した場合、アミノ末端を有するアミン系シランカップリング剤がより好ましい。
固形状シランカップリング剤としては、例えば、X-12-1273ES(信越化学工業株式会社製)等が挙げられる。
液状シランカップリング剤と固形状シランカップリング剤を比較した場合、液状シランカップリング剤としては、官能基があり反応性が望める(原理的に高い効果が期待できる)という点で優れ、固形状シランカップリング剤としては、扱いが簡便という点で優れている。
例えば、二軸押出機に、熱可塑性樹脂、炭素繊維、シランカップリング剤、金型腐食防止剤、離型剤を投入し、例えば、混練加工温度を270℃以上かつ300℃以下、スクリュー回転数を100rpm以上かつ300rpm以下に管理しつつ、混練加工時間を30分以上かつ60分以下として造粒することで、ペレット状の樹脂組成物を形成することができる。
具体的には、熱可塑性樹脂、シランカップリング剤をドライブレンドし、更に炭素繊維、金型腐食防止剤、離型剤、着色剤をドライブレンドし、二軸押出機のメインフィーダーからドライブレンドした原料を吐出し混錬してもよい。また、別の方法としては、熱可塑性樹脂、シランカップリング剤をドライブレンドし、更に金型腐食防止剤、離型剤、着色剤をドライブレンドし、二軸押出機のメインフィーダーからドライブレンドした原料を吐出しながら、サイドフィーダーから炭素繊維を吐出して混錬してもよい。このサイドフィーダーから炭素繊維を供給する方法で製造することで、ドライブレンドする際に炭素繊維の繊維長が短くなることも防止できる。
図1は、本発明の一実施形態に係る樹脂成形体が付設されるリチウムイオン2次電池セルの斜視図である。
このリチウムイオン2次電池セル1は、例えば角型の電池セルであり、電池容器である外装缶2の一端面(図1では上面)に、正極端子3及び負極端子4が設けられると共に、その間に安全弁5が設けられている。
リチウムイオン2次電池セル1が熱暴走して内圧が上昇した場合に作動して、高温・高圧のガスを噴出して外装缶2が破裂するのを防止する。
以下、難燃性評価1として、シランカップリング剤の種類、熱可塑性樹脂100質量部に対するPTFE、炭素繊維、シランカップリング剤、離型剤、着色料および金型腐食防止剤の混合量(組成割合)を変えた本発明例1~19および比較例1~3の樹脂組成物(試料)を作成した。それぞれの試料の組成割合(質量部)を表1に示す。表1に示す各成分を秤取ってドライブレンドし、その後、二軸押出機を用いて造粒することにより、本発明例1~19および比較例1~3の各樹脂組成物を造粒した。この造粒物を用いて射出成型を実施し、試料を得た。
(1)PPS:ポリフェニレンサルファイド
(2)シランカップリング剤:
(2-1)アミン系:液状シランカップリング剤
(2-2)エポキシ系:液状シランカップリング剤
(2-3)アクリル系:液状シランカップリング剤
(2-4)固体系:固形状シランカップリング剤
(3)炭素繊維:ピッチ系炭素繊維、平均繊維長0.36mm、繊維径13μm、アスペクト比28
(4)フッ素樹脂(PTFE):粉末状、平均粒子径18μm、BET比表面積2m2/g
(5)着色剤:カーボンブラック
(6)離型剤:ポリオレフィンワックス
(7)金型腐食防止剤:炭酸亜鉛(ZnCO3)
ドラフトによる局所排気
火力:5580W
気温:18℃
湿度:55%RH
天候:晴れ
試験は試料の一部が溶融して床面に落下した時点で終了とした。
A:113秒以上
B:74秒以上かつ113秒未満
C:63秒以上かつ74秒未満
D:49秒以上かつ63秒未満
E:49秒未満
一方、炭素繊維かシランカップリング剤のいずれか一方を含まない、あるいは両方を含まない比較例1~3の樹脂組成物は、10mm変形量が49秒未満であり、難燃性を確保できず、火炎によって容易に溶融変形してしまうことが確認された。
次に、難燃性評価2として、熱可塑性樹脂100質量部に対する炭素繊維、シランカップリング剤、離型剤、着色料および金型腐食防止剤の混合量(組成割合)を一定にして、熱可塑性樹脂の種類だけを変えた本発明例7、20~24の樹脂組成物(試料)を作成した。また、熱可塑性樹脂だけの比較例4~7の樹脂組成物(試料)を作成した。それぞれの試料の組成割合(質量部)を表2に示す。表2に示す各成分を秤取ってドライブレンドし、その後二軸押出機を用いて造粒することにより、本発明例7、20~24の各樹脂組成物を造粒した。この造粒物を用いて射出成形を実施し、試料を得た。また、比較例4~7の各熱可塑性樹脂を用意した。
(1)PPS:ポリフェニレンサルファイド
(2)PBT:ポリブチレンテレフタレート
(3)PA6:ポリアミドの一種であるポリアミド6
(4)mPPE:変性ポリフェニレンエーテル
(5)PC:ポリカーボネート
(6)PP:ポリプロピレン
(7)炭素繊維ピッチ系炭素繊維、平均繊維長0.36mm、繊維径13μm、アスペクト比28
(8)PTFE:フッ素樹脂粉末状、平均粒子径18μm、BET比表面積2m2/g(9)着色剤:カーボンブラック
(10)離型剤:ポリオレフィンワックス
(11)金型腐食防止剤:炭酸亜鉛(ZnCO3)
ドラフトによる局所排気
火力:5580W
気温:18℃
湿度:55%RH
天候:晴れ
良:バーナー燃焼開始後40秒経過時点での試料の変形量が2mm未満。
可:バーナー燃焼開始後40秒経過時点での試料の変形量が2mm以上かつ20mm未満。
不可:バーナー燃焼開始後40秒経過時点での試料の変形量が20mm以上、または溶融樹脂の滴下発生。
一方、熱可塑性樹脂だけで炭素繊維やシランカップリング剤を含まない比較例4~7は、いずれも40秒経過以前に変形量が20mm以上か溶融樹脂の滴下が発生しており、難燃性樹脂として用いることは困難であることが確認された。
2…外装缶
3…正極端子
4…負極端子
5…安全弁
6…樹脂成形体
7…絶縁シート
Claims (9)
- 熱可塑性樹脂100質量部に対して、炭素繊維を2質量部以上かつ70質量部以下、シランカップリング剤を0.3質量部以上かつ7質量部以下の範囲で含むことを特徴とする樹脂組成物。
- 前記炭素繊維に対する前記シランカップリング剤の含有割合(シランカップリング剤/炭素繊維)が0.01以上であることを特徴とする請求項1に記載の樹脂組成物。
- 前記熱可塑性樹脂100質量部に対して、前記炭素繊維が15質量部以上かつ70質量部以下であることを特徴とする請求項1に記載の樹脂組成物。
- 前記炭素繊維に対する前記シランカップリング剤の含有割合(シランカップリング剤/炭素繊維)が0.1以上であることを特徴とする請求項1または2のいずれかに記載の樹脂組成物。
- 前記熱可塑性樹脂は、ポリフェニレンサルファイド、ポリアミド、ポリブチレンテレフタレート、変性ポリフェニレンエーテル、ポリカーボネートのうち、少なくとも1つを含むことを特徴とする請求項1から4のいずれか一項に記載の樹脂組成物。
- 前記シランカップリング剤は、有機ケイ素化合物、およびシロキサン化合物の少なくとも一方であることを特徴とする請求項1から5のいずれか一項に記載の樹脂組成物。
- 前記有機ケイ素化合物は、アミン系シランカップリング剤、およびエポキシ系シランカップリング剤の少なくとも一方であることを特徴とする請求項6に記載の樹脂組成物。
- 熱可塑性樹脂100質量部に対して、更にフッ素樹脂を1質量部以上かつ50質量部以下の範囲で含むことを特徴とする請求項1から7のいずれか一項に記載の樹脂組成物。
- 請求項1から8のいずれか一項に記載の樹脂組成物を用いた樹脂成形体であって、
安全弁または排気孔を有する1個以上のリチウムイオン2次電池セルの外周に、少なくとも前記安全弁または前記排気孔を覆うように付設されることを特徴とする樹脂成形体。
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US18/284,121 US20240150578A1 (en) | 2021-03-29 | 2022-03-28 | Resin composition and resin molded body |
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2021
- 2021-03-29 JP JP2021054780A patent/JP2022152125A/ja active Pending
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- 2022-03-28 CN CN202280025561.XA patent/CN117321144A/zh active Pending
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- 2022-03-28 US US18/284,121 patent/US20240150578A1/en active Pending
- 2022-03-28 EP EP22780713.8A patent/EP4317291A1/en active Pending
- 2022-03-28 WO PCT/JP2022/014900 patent/WO2022210502A1/ja active Application Filing
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US20240150578A1 (en) | 2024-05-09 |
EP4317291A1 (en) | 2024-02-07 |
JP2022152125A (ja) | 2022-10-12 |
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