WO2005103146A1 - Composition de résine et procédé de fabrication de celle-ci - Google Patents
Composition de résine et procédé de fabrication de celle-ci Download PDFInfo
- Publication number
- WO2005103146A1 WO2005103146A1 PCT/JP2005/007169 JP2005007169W WO2005103146A1 WO 2005103146 A1 WO2005103146 A1 WO 2005103146A1 JP 2005007169 W JP2005007169 W JP 2005007169W WO 2005103146 A1 WO2005103146 A1 WO 2005103146A1
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- WO
- WIPO (PCT)
- Prior art keywords
- component
- resin composition
- isobutylene
- polymer
- mainly composed
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims description 30
- 230000008569 process Effects 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 106
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 47
- 230000035699 permeability Effects 0.000 claims abstract description 35
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 229920001083 polybutene Polymers 0.000 claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 claims abstract description 12
- 229920000573 polyethylene Polymers 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 11
- 239000007924 injection Substances 0.000 abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 32
- 229920001971 elastomer Polymers 0.000 description 13
- 239000005060 rubber Substances 0.000 description 11
- -1 styrene-ethylene-butylene-styrene Chemical class 0.000 description 11
- 238000000465 moulding Methods 0.000 description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 229920001400 block copolymer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 229920001384 propylene homopolymer Polymers 0.000 description 6
- 229920005549 butyl rubber Polymers 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000013016 damping Methods 0.000 description 4
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 229930006722 beta-pinene Natural products 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- NMUWSGQKPAEPBA-UHFFFAOYSA-N 1,2-dibutylbenzene Chemical compound CCCCC1=CC=CC=C1CCCC NMUWSGQKPAEPBA-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ROXBGVUYVWABMT-UHFFFAOYSA-N OOSOO Chemical compound OOSOO ROXBGVUYVWABMT-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NRJXUPLBIUZXLW-UHFFFAOYSA-N ethene;prop-1-ene;styrene Chemical compound C=C.CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 NRJXUPLBIUZXLW-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UQUAAQFOUDTPQJ-UHFFFAOYSA-N trihydroxy phosphite Chemical compound P(OO)(OO)OO UQUAAQFOUDTPQJ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
Definitions
- the present invention relates to a resin composition and a method for producing the same. More specifically, the present invention includes a styrene-based polymer block, an isobutylene-based polymer block, a styrene-based polymer block, and an isobutylene-based triblock copolymer, which is also strong, and has high flexibility, air permeation resistance, and permeation resistance.
- a resin composition that has excellent wettability and good injection moldability, and is suitable for forming, for example, an insulator for a recording medium driving device, a gasket for an HDD, a shock absorber for an HDD, a tube for transporting a medical infusion, and the like. It is about.
- a material obtained by blending a bridging agent, a reinforcing agent, or the like with rubbers such as natural rubber or synthetic rubber and crosslinking under high temperature and high pressure has been widely used.
- rubbers such as natural rubber or synthetic rubber and crosslinking under high temperature and high pressure
- crosslinked rubber does not show thermoplasticity
- recycling molding like thermoplastic resin is generally impossible.
- thermoplastic elastomers that can easily produce molded articles by using general-purpose melt molding techniques such as hot press molding, injection molding, and extrusion molding, like ordinary thermoplastic resins. Is being developed.
- thermoplastic elastomer an olefin type, a urethane type, an ester type, a styrene type, a butyl chloride type and the like have been developed and are commercially available. Since these are easy to recycle, they have recently been used in a wide range of fields such as automobile parts, home electric parts, wire covering materials, medical parts, sundries, footwear and the like.
- styrene-based thermoplastic elastomers are rich in flexibility and excellent in rubber elasticity at room temperature.
- Styrene-based thermoplastic elastomers include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-ethylene-butylene-styrene block copolymers.
- SBS styrene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- hydrogenated styrene-ethylene-butylene-styrene block copolymers hydrogenated styrene-ethylene-butylene-styrene block copolymers.
- SEBS styrene ethylene propylene styrene block copo
- isobutylene is one of the most flexible, excellent rubber elasticity at room temperature, and excellent thermal stability, weather resistance, vibration damping, gas noria, and sealing.
- An isobutylene-based block copolymer containing a polymer block mainly composed of a polymer block mainly composed of an aromatic vinyl-based compound is known.
- this isobutylene-based block copolymer was not always satisfactory in terms of compression set.
- thermoplastic elastomer a technique of compounding a rubber and an organic polymer to improve the performance of a thermoplastic elastomer has been known for a long time.
- polyolefins such as polypropylene and polyolefins such as EPDM and IIR are known.
- EPDM and IIR polyolefins
- SEBS styrene-based elastomer
- a crystalline olefin resin and an olefin-based resin are used.
- a technology for crosslinking a system rubber with an organic peroxide for example, see Patent Document 1
- an organic peroxide for example, see Patent Document 1
- a special structure of isobutylene rubber for example, see Patent Document 2
- the present inventors have developed a low-hardness thermoplastic resin having high gas-tightness that can be used for various applications (see Patent Document 3). Oil components are added, and depending on the application, the gas confidentiality of the material may decrease.
- thermoplastic elastomer that has a well-balanced level of flexibility, air permeability, moisture permeability, compression set, injection moldability, etc. at a high level. This was the actual situation.
- Patent Document 1 Japanese Patent Publication No. 53-21021
- Patent Document 2 Japanese Patent Application Laid-Open No. 9-137007
- Patent Document 3 International Publication Number WO03 / 027183
- the present invention provides a resin composition which is rich in flexibility, excellent in air permeation resistance and moisture permeation resistance, has good injection moldability, and is capable of injection molding. It is intended to do so.
- the present inventors have conducted intensive studies to develop a resin composition having the above-mentioned excellent functions, and as a result, a specific isobutylene-based triblock copolymer, an ethylene-based polymer and a Z or A resin composition containing a propylene polymer and liquid polybutene, and having specific values for air permeability, moisture permeability, hardness and melt flow rate [MFR], is suitable for the purpose. I found it.
- a resin composition having specific values of air permeability, moisture permeability, hardness and melt flow rate [MFR] can be suitable for the purpose.
- the above resin composition can be produced by melt-kneading the above-mentioned components under specific conditions.
- the present invention has been completed based on strong knowledge.
- the hard component refers to a component having a softening temperature or a melting point higher than room temperature
- the soft component refers to a component that is liquid or rubbery at room temperature.
- one polymer molecule contains a hard component and a soft component! /
- the hard component is called a node segment and the soft component is called a soft segment. .
- the present invention provides: (A-l) (b)-(a)-(b) isobutylene type having (a) a polymer block mainly composed of isobutylene units and (b) a polymer block mainly composed of styrene units.
- A-2) (b) having a weight average molecular weight of 50,000 to 80,000 having (a) a polymer block mainly composed of isobutylene units and (b) a polymer block mainly composed of styrene units.
- (B-2) (c) a polymer block mainly composed of isobutylene units, and (d) a polymer block mainly composed of styrene units.
- a weight-average molecular weight of 90,000 to 130,000 (d)-(c)-(d) -type isobutylene-based triblock copolymer is blended at a mass ratio of 20:80 to 60:40, (1) to (3), and
- A-3) (a) having a soft segment having a polymer blocking power mainly composed of isobutylene units and (b) a hard segment having a polymer blocking power mainly composed of styrene units, and (b)-(a) -(b) Ratio of total node components including at least one isobutylene-based triblock copolymer and including all hard segments and all soft components including the soft segments Total node components Z (all hard components + (All soft components) characterized by having a mass ratio in the range of 0.25 to 0.40, having the properties of the above (1) to (3), and having the properties of the above (4 ') Fat set Products (hereinafter sometimes referred to as "third invention"),
- the resin composition of the first invention comprises (A-1) (a) a polymer block mainly composed of isobutylene units, and (b) a polymer block mainly composed of styrene units.
- a composition comprising (b)-(a)-(b) type isobutylene-based triblock copolymer, (B-1) ethylene-based polymer and Z or propylene-based polymer, and (C) liquid polybutene It is.
- a polymer block mainly composed of isobutylene units refers to a polymer block containing isobutylene units in an amount of 50% by mass or more, preferably 70% by mass or more. More preferably, it refers to a polymer block occupying 90% by mass or more.
- the monomer that forms a unit other than the isobutylene unit in the polymer block mainly composed of an isobutylene unit is not particularly limited as long as it is a monomer that can be cationically polymerized.
- aromatics genes such as isoprene, butadiene, and dibutylbenzene, aryl ethers, and monomers such as ⁇ -pinene. These may be used alone or in combination of two or more.
- the monomer that forms a unit other than the styrene unit in the polymer block mainly composed of styrene units is not particularly limited as long as it is a monomer that can be cationically polymerized.
- Monomers such as aromatic butyls such as olestyrene, ⁇ -methynolestyrene, tert-butyl styrene, monochlorostyrene, dichlorostyrene, methoxystyrene and indene, aliphatic olefins, gens, aryl ethers and ⁇ -pinene Can be illustrated. These may be used alone or in combination of two or more.
- the (A-1) component isobutylene-based triblock copolymer used at the time of compounding is (b)-(a) one (b) type, and (a) a polymer block mainly composed of isobutylene units and (b) ) Styrene
- the content ratio of the polymer block mainly composed of units from the viewpoint of the physical properties of the obtained resin composition, (a) the polymer block mainly composed of isobutylene units has a content of 60 to 60%.
- the content of (b) the polymer block mainly composed of styrene units is 40 to 15% by mass, and the content of the (a) polymer block is 65 to 80% by mass and the content of the (b) polymer block is 85% by mass. It is particularly preferred that the content of the block is 35 to 20% by mass.
- the weight average molecular weight of the isobutylene-based triblock copolymer of the component (A-1) used at the time of compounding is not particularly limited, but the mechanical properties and moldability of the obtained resin composition are not limited. 50,000-200,000 force S preferred, especially 60,000-150,000 force S preferred.
- the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC method).
- the method for producing the isobutylene-based triblock copolymer there is no particular limitation on the method for producing the isobutylene-based triblock copolymer.
- a conventionally known method can be used.
- a monofunctional component such as ⁇ -chloro-isopropylbenzene
- a bifunctional component such as 1,4-bis ( ⁇ -chloro mouth isopropyl) benzene (also referred to as ⁇ dicum milk mouth ride) or a 1,3,5 tris ( ⁇ -chloro mouth isopropyl)
- Trifunctional components such as benzene are used as initiators and chain transfer agents, and Lewis acids such as BC1 and TiCl are used as catalysts.
- a polymer mainly composed of isobutylene units having a controlled molecular weight is formed by using a bifer method (for example, a method disclosed in US Pat. Subsequently, by adding and copolymerizing a monomer mainly composed of styrene, a desired isobutylene-based triblock copolymer can be obtained.
- an ethylene polymer and a Z or propylene polymer are used as the component (B-1).
- ethylene-based polymer examples include high-, medium-, and low-density polyethylene, linear low-density polyethylene, ultrahigh-molecular-weight polyethylene, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. can do.
- examples of the propylene-based polymer include a propylene homopolymer, a propylene-ethylene block copolymer, a random copolymer, and a propylene-ethylene-gen compound copolymer.
- crystalline polypropylene resins are preferred. Crystalline polypropylene resins include, for example, crystalline isotactic polymers.
- Tick propylene homopolymer homopolymer part with low ethylene unit content, ethylene propylene random copolymer, propylene homopolymer power and copolymer part with relatively high ethylene-propylene random copolymer power with relatively high ethylene unit content
- a homopolymer or copolymer component in the propylene block copolymer and a crystalline propylene ethylene ⁇ -polymer obtained by copolymerizing an a-olefin such as butene 1. And olefin copolymers.
- one or more of the above-mentioned ethylene polymers may be used, or one or more of a propylene polymer may be used. These may be used in combination with one or more propylene-based polymers.
- the liquid polybutene used as the component (C) is preferably a liquid polybutene having a number average molecular weight of about 200 to 3,000 mainly containing isobutylene units.
- Such liquid polybutenes include, for example, butadiene from a C fraction produced by naphtha decomposition.
- a liquid butyl rubber obtained by copolymerizing a small amount of isoprene with butyl rubber can be used. These may be used alone or in combination of two or more. By containing these liquid polybutenes, the resin composition has improved flexibility without deteriorating the steam barrier property.
- the resin composition of the first invention has the following properties.
- air permeability was measured using a sheet sample with a thickness of 0. 5mm QilS K7126;
- a method (differential pressure method), 40 ° C] is 200 cm 3 Z (m 2 '24 hr 'atm) or less, and has excellent gas nori properties.
- the air permeability is preferably 180 cm 3 Z (m 2 ⁇ 24 hr ⁇ atm) or less, and more preferably 160 cm V (m 2 ⁇ 24 hr ⁇ atm) or less.
- the lower limit of the air permeability is not particularly limited, but is usually about 50 cm 3 Z (m 2 ⁇ 24 hr ⁇ atm).
- Moisture permeability (JIS Z0208; 40 ° C, 90% RH) is less than 2. OgZ (m 2 '24hr), and it is excellent in noria against water vapor.
- the transparent humidity preferably 1. 8g / (m 2 '24hr ) or less, preferably to be al 1. 7g / (m 2' 24hr ) or less, particularly preferably 1. 5g / (m 2 '24hr ) or less It is.
- the lower limit of the moisture permeability is not particularly limited, but is usually about 0.5 gZ (m 2 '24 hr).
- Menoleto flow rate [MFR] JIS K7210; 190.C, 52.185N (5.325 Kgf)
- MFR Menoleto flow rate
- the preferred MFR is between 10 and 80 gZlO, more preferably between 10 and 60 gZlO.
- Tensile strength and elongation are preferably 5 MPa or more and 400% or more, respectively, preferably 6 MPa or more and 500% or more. Is more preferable.
- the content ratio of the component (A-1), the component (B-1) and the component (C) in the resin composition of the first invention is as follows because the resin composition has the above-mentioned properties.
- the component (B-1) is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of the component A-1).
- the component (C) is preferably 1 to 40 parts by mass, more preferably 5 to 40 parts by mass. In particular, it is preferable that the component (B-1) is 10 to 30 parts by mass and the component (C) is 15 to 35 parts by mass.
- the resin composition of the second invention comprises (A-2) (a) a polymer block mainly composed of isobutylene units, and (b) a polymer block mainly composed of styrene units.
- the isobutylene-based triblock copolymers (A-2) and (B-2) The polymer blocks mainly composed of isobutylene units shown in (a) and (c) are the same as the polymer block mainly composed of (a) isobutylene units in the first invention.
- the (b) and (d) polymer blocks mainly composed of styrene units are the same as the (b) polymer blocks mainly composed of styrene units in the first invention.
- the isobutylene-based triblock copolymer of the component (A-2) and the isobutylene-based triblock copolymer of the component (B-2) are of the (b)-(a)-(b) type and (d)-(c)-(d) type, (a) the content ratio of a polymer block mainly composed of isobutylene units and (b) a polymer block mainly composed of styrene units, and (c) isobutylene units.
- the content ratio of the polymer block mainly composed of isobutylene units and the polymer block mainly composed of styrene units is the same as that of the isobutylene triblock of the component (A-2).
- the coalesced and the isobutylene-based triblock copolymer of the component (B-2) may be the same or different.
- the weight average molecular weight of the isobutylene-based triblock copolymer of the component (A-2) is selected from the range of 50,000 to 80,000, and the component (B-2)
- the weight average molecular weight of the isobutylene triblock copolymer is selected from the range of 90,000 to 130,000.
- the number average molecular weight of the component (A-2) is less than 50,000, the obtained resin composition has too high a fluidity to cause burrs at the time of injection molding, and is stable in extrusion molding. A molded product cannot be obtained.
- the number average molecular weight of the component (B-2) exceeds 130,000, moldability deteriorates and injection molding becomes difficult.
- the weight average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography method (GPC method).
- GPC method gel permeation chromatography method
- the method for producing the isobutylene-based triblock copolymer is the same as the method for producing the (A1) component isobutylene-based triblock copolymer of the first invention.
- the resin composition of the second invention has the same properties as (1) air permeability, (2) moisture permeability, and (3) hardness as the resin composition of the first invention. In addition, it has the following properties.
- MFR Melt flow rate
- JIS K7210; 270.C, 98.0665N (10Kgf) is less than 5 OOOgZlO.
- a preferred MFR is 3000 gZlO or less, more preferably 2000 gZlO or less, particularly preferably lOOOOgZlO or less.
- the (5 ') tensile strength and elongation (JIS K6251; dumbbell-shaped No. 3, 23 ° C) be 5 MPa or more and 300% or more, respectively, 6 MPa or more and 500% or less. More preferably, it is above.
- the resin composition of the third invention comprises (A-3) (a) a soft segment having a polymer block strength mainly composed of isobutylene units, and (b) a polymer block mainly composed of styrene units. (B)-(a)-(b) -type isobutylene-based triblock copolymer having at least one kind having a hard component and a hard component. ) A composition containing an olefin polymer having 2 to 6 carbon atoms.
- the ratio of the total node component to the total soft component in the composition is 0.25 to 0.2% by mass ratio of the total hard component Z (the total hard component + the total soft component). Selected within the range of 0.40.
- this ratio is in the above range, it becomes possible to obtain a resin composition that satisfies predetermined physical properties described later.
- the mass ratio is large, the flexibility is insufficient, and when it is small, the air permeability and the moisture permeability tend to be large.
- the preferable mass ratio of all hard components Z (all hard components + all soft components) is in the range of 0.28 to 0.37.
- the polymer block mainly composed of (a) isobutylene unit is mainly composed of the (a) isobutylene unit in the first invention. Same as for the polymer block.
- the (b) polymer block mainly composed of styrene units is the same as the (b) polymer block mainly composed of styrene units in the first invention.
- the isobutylene-based triblock copolymer of the component (A-3) used at the time of compounding is of the (b)-(a)-(b) type, and (a) a polymer block mainly composed of isobutylene units.
- the content ratio of the polymer block mainly composed of (b) styrene units is the same as the content ratio of (a) and (b) in the first invention.
- the isobutylene-based triblock of the component (A-3) is When only one polymer is used, it is difficult to obtain a resin composition having predetermined physical properties described below.
- the component (A-3) the force of using two or more isobutylene-based triblock copolymers having different molecular weights in combination, or as the component (A-3), an isobutylene-based triblock copolymer
- one or more copolymers are used, and as the component (B-3), a olefin-based polymer having 2 to 6 carbon atoms, which is a hard component and Z or a soft component, is preferably used.
- (a-1) an isobutylene-based triblock copolymer having a weight average molecular weight in the range of 50,000 to 80,000, and (a-2) a weight average molecular weight
- An isobutylene-based triblock copolymer in the range of 90,000 to 130,000 is blended at a weight ratio of 20:80 to 60:40, and the hard segment Z (node segment + soft segment) mass
- a resin composition having specified physical properties can be obtained by using a resin having a specific gravity in the range of 0.25 to 0.40, preferably 0.28 to 0.37.
- the average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC) in the same manner as described above.
- a resin composition having predetermined properties can be obtained, and the object of the present invention can be achieved.
- a preferred blending ratio is in the range of 25:75 to 45:55 by mass.
- the hard component when a hard component and a olefin polymer having 2 to 6 carbon atoms as a soft component are used as the component (B-3), the hard component may be, for example, an ethylene polymer.
- the hard component may be, for example, an ethylene polymer.
- Examples of the ethylene polymer include high-, medium-, and low-density polyethylene, linear low-density polyethylene, ultra-high-molecular-weight polyethylene, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. And the like.
- examples of the propylene-based polymer include a propylene homopolymer, a propylene-ethylene block copolymer, a random copolymer, and a propylene-ethylene-gen compound copolymer.
- crystalline polypropylene resin is preferred.
- examples of the crystalline polypropylene resin include an isotactic propylene homopolymer having crystallinity, an ethylene propylene random copolymer having a small ethylene unit content, and the like.
- a propylene block copolymer comprising a homo part having an unified, propylene homopolymer power and a copolymer part having an ethylene-propylene random copolymer having a relatively large ethylene unit content, and further comprising the propylene block copolymer.
- a crystalline propylene ethylene ⁇ -olefin copolymer comprising a copolymer of a-olefin such as butene 1 and the like.
- liquid polybutene is preferably used as the soft component.
- the liquid polybutene one having a number average molecular weight of 200 to 3,000 mainly containing isobutylene units is preferable, and one having a number average molecular weight of about 1,000 to 3,000 is more preferable.
- the C fraction power generated by naphtha decomposition The remaining fraction obtained by extracting butadiene is
- Isobutylene obtained by copolymerizing some butene-11 obtained as it is as raw material Or a low-polymer of high-purity isobutylene or a liquid butyl rubber obtained by copolymerizing isobutylene with a small amount of isoprene. These may be used alone or in combination of two or more.
- the ratio of the total hard component to the total soft component in the composition is determined by the ratio of the total hard component Z (the total hard component + the total soft component) to the mass.
- Dani so as to be in the range of 0.25 to 0.40, preferably 0.28 to 0.37, a resin composition having predetermined physical properties can be obtained. .
- the resin composition of the third invention has the same properties as the resin composition of the first invention with respect to (1) air permeability, (2) moisture permeability, and (3) hardness, It has the same properties as 4 ′) MFR and (5 ′) tensile strength and elongation as the resin composition of the second invention.
- the compression set measured at 70 ° C for 22 hours based on JIS K6262 is preferably 95% or less, more preferably 90% or less, and Excellent permanent distortion properties. That is, it has good resilience in heat molding.
- the resin composition of the present invention includes the component (A-1), the component (A-2), the component (A-3),
- thermoplastic elastomers and other components may be used as long as the object of the present invention is not impaired.
- the resin composition of the present invention can be efficiently produced according to the method of the present invention described below.
- the above-mentioned components and various optional components used as required are put into a melt-kneading apparatus, and melt-kneaded at a temperature of 140 to 230 ° C.
- a resin composition having the above-mentioned properties can be produced.
- the temperature during melt-kneading is within the above range, decomposition (block cutting) of the isobutylene-based triblock copolymer of the components (A-1), (A-2), and (A3) is suppressed.
- a resin composition having predetermined MFR and other physical properties can be obtained.
- the temperature is between 180 and 230 ° C, more preferably the temperature is between 200 and 220 ° C.
- melt kneading apparatus examples include a closed kneading apparatus such as Labo Plastomill, Brabender, Banbury mixer 1, kneader, and roll, or a batch kneading apparatus, a single screw extruder, and a twin screw extruder. And the like can be used.
- a closed kneading apparatus such as Labo Plastomill, Brabender, Banbury mixer 1, kneader, and roll
- a batch kneading apparatus a single screw extruder, and a twin screw extruder. And the like can be used.
- the resin composition of the present invention thus obtained can be molded using a molding method and a molding apparatus generally used for a thermoplastic resin composition, and examples thereof include extrusion molding, injection molding, and the like. Melt molding can be performed by press molding, blow molding, or the like.
- the resin composition of the present invention has a high level of balance of flexibility, air permeability resistance, moisture permeability resistance, injection moldability, etc., and is molded into a sheet, molded article, adhesive, foam, etc.
- Civil engineering sheets sheets such as waterproof sheets, sealing materials such as packing materials, sealing materials, gaskets, plugs, damping materials for construction, damping materials for automobiles, vehicles and home appliances such as CD dampers, vibration damping materials, and It can be used for insulators for recording media drives, gaskets for HDDs, shock absorbers for HDDs, and tubes for transporting medical fluids.
- the JIS- ⁇ hardness was measured according to JIS K6253 (after 15 seconds).
- dumbbell shape No. 3 was measured at 23 ° C. (4) Air permeability
- a sheet having a thickness of 0.5 mm was measured at 40 ° C and 90% RH.
- JIS K6262 it was measured at 70 ° C. for 22 hours.
- Polymer A Styrene isobutylene styrene triblock copolymer, weight average molecular weight of about 65,000, a styrene polymer block content of 30 mass 0/0
- Polymer B Polypropylene [Novatech BC05B manufactured by Nippon Polychem Co., Ltd.]
- Polymer C liquid polybutene [Nisseki Chemical Co., Ltd., trademark “HV300”, number average molecular weight 1400] [0036] [Table 1]
- Polymer D Styrene isobutylene styrene triblock copolymer, weight average molecular weight about 100,000, styrene polymer block content 30% by mass
- the resin composition of the present invention has a high level of balance of flexibility, air permeability resistance, moisture permeability resistance, compression set characteristics, injection moldability, extrusion moldability, and the like. It can be used for insulators, HDD gaskets, HDD shock absorbers, medical infusion transport tubes, and the like.
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Abstract
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JP2004127214A JP2005307049A (ja) | 2004-04-22 | 2004-04-22 | 樹脂組成物及びその製造方法 |
JP2004127213A JP2005307048A (ja) | 2004-04-22 | 2004-04-22 | 樹脂組成物及びその製造方法 |
JP2004127275A JP2005307054A (ja) | 2004-04-22 | 2004-04-22 | 樹脂組成物及びその製造方法 |
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