WO2023276883A1 - エアバッグ収納カバー及びその製造方法、熱可塑性エラストマー組成物、成形体、並びに複合成形体 - Google Patents
エアバッグ収納カバー及びその製造方法、熱可塑性エラストマー組成物、成形体、並びに複合成形体 Download PDFInfo
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- WO2023276883A1 WO2023276883A1 PCT/JP2022/025321 JP2022025321W WO2023276883A1 WO 2023276883 A1 WO2023276883 A1 WO 2023276883A1 JP 2022025321 W JP2022025321 W JP 2022025321W WO 2023276883 A1 WO2023276883 A1 WO 2023276883A1
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- Prior art keywords
- mass
- styrene
- thermoplastic elastomer
- elastomer composition
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Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L23/14—Copolymers of propene
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1676—Making multilayered or multicoloured articles using a soft material and a rigid material, e.g. making articles with a sealing part
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions
- the present invention relates to an airbag storage cover excellent in low-temperature impact resistance, high-temperature strength and light transmittance, a method for producing the same, and a thermoplastic elastomer composition capable of providing such an airbag storage cover.
- the present invention also relates to molded articles and composite molded articles using this thermoplastic elastomer composition.
- An automotive airbag system is a system that protects the driver and passengers in the event of a collision, and consists of a device that senses the impact of a collision and an airbag device.
- Airbag devices are installed in the steering wheel, the instrument panel in front of the front passenger seat, the driver's seat and front passenger seat, the front and side pillars, and the like.
- thermoplastic elastomer composition as a material with improved low-temperature impact resistance and high-temperature strength.
- thermoplastic elastomer composition for airbags is known to use a propylene-based resin as the hard segment and an olefin-based rubber such as ethylene-propylene elastomer (EPDM, EPR, etc.) or a styrene-based elastomer as the soft segment.
- an olefin-based rubber such as ethylene-propylene elastomer (EPDM, EPR, etc.) or a styrene-based elastomer
- thermoplastic elastomer composition used for an airbag which contains a propylene-based resin, a styrene/butadiene/styrene block copolymer (SBS), and an ethylene/ ⁇ -olefin copolymer. ing.
- Patent Documents 2 and 3 there are known techniques for increasing the transparency of thermoplastic elastomer compositions containing propylene-based resins and styrene-based elastomers.
- Patent Document 4 a propylene-based resin, a styrene-based elastomer, and ethylene/ ⁇ - A product containing an olefin copolymer has been proposed.
- Patent Document 5 discloses that a fine powder can be easily produced at room temperature, and furthermore, it has excellent scratch resistance, heat resistance, and molded appearance.
- a thermoplastic elastomer composition for powder molding has been proposed which can give a molded article having excellent properties such as.
- thermoplastic elastomer composition for an airbag storage cover in Patent Document 6, a propylene-based polymer, an olefin-based elastomer, a styrene-based elastomer, and an acrylic resin are blended to provide low-temperature impact resistance, molding appearance, and injection molding. There has been proposed a thermoplastic elastomer composition for an airbag storage cover having excellent properties.
- This type of airbag storage cover consists of a surface layer made of a film that serves as an interface for a touch panel display, and an airbag storage cover layer provided so as to be in contact with the surface layer.
- Embedded switch In such a configuration, the airbag storage cover needs to be made of a material that transmits light so that the user can easily see the lighting of the switch. Therefore, the thermoplastic elastomer composition used for the airbag storage cover layer is required to have light transmittance to the extent that the user can visually recognize the lighting of the switch, in addition to the low-temperature impact resistance and high-temperature strength that are conventionally required. is becoming
- thermoplastic elastomer composition used in the airbag described in Patent Document 1 has good low-temperature impact resistance and high-temperature strength, but has poor light transmittance. not intended.
- a thermoplastic elastomer using a propylene-based resin as a hard segment and an olefin-based rubber such as an ethylene-propylene elastomer (EPDM, EPR, etc.) as a soft segment mainly has optical transparency.
- EPDM, EPR, etc. ethylene-propylene elastomer
- thermoplastic elastomer composition described in Patent Document 2 has good transparency, it does not satisfy the low-temperature impact resistance and high-temperature strength required for airbag applications.
- thermoplastic elastomer compositions of Patent Documents 3 and 4 have good transparency and high-temperature strength, but do not satisfy low-temperature impact resistance.
- thermoplastic elastomer compositions of Patent Documents 5 and 6 no consideration is given to low-temperature impact resistance, high-temperature strength, transparency, or light transmittance.
- the present invention has been made in view of the problems of the prior art as described above.
- An object of the present invention is to provide an airbag storage cover that is excellent in low-temperature impact resistance, high-temperature strength, and light transmittance, and that is suitable for combination with a touch panel film, a thermoplastic elastomer composition, and the thermoplastic elastomer composition.
- An object of the present invention is to provide a molded article and a composite molded article.
- thermoplastic elastomer composition containing a propylene-based random copolymer and a specific styrene-based elastomer is excellent in low-temperature impact resistance, high-temperature strength, and optical transparency, and is suitable for combination with a touch panel film.
- the inventors have found that it is possible to provide an airbag storage cover and a molded article suitable for both, and have completed the present invention.
- the gist of the present invention resides in the following [1] to [20].
- thermoplastic elastomer composition containing a propylene-based random copolymer and a styrene-based elastomer having a glass transition temperature in the range of -65°C to -45°C, wherein the thermoplastic elastomer composition 100
- An airbag storage cover made of a thermoplastic elastomer composition in which the total content of the propylene-based random copolymer and the styrene-based elastomer is more than 40% by mass and not more than 100% by mass.
- thermoplastic elastomer composition has a melt flow rate of 1.0 g/10 min or more and 50 g/10 min or less at a temperature of 230°C and a measurement load of 21.18 N according to JIS K7210 (1999).
- the airbag storage cover according to any one of [3].
- thermoplastic elastomer composition further contains 10 parts by mass or more and 100 parts by mass or less of an ethylene/ ⁇ -olefin copolymer with respect to 100 parts by mass of the propylene-based random copolymer, [1] to [ 5]
- the airbag storage cover according to any one of the above items.
- the styrene elastomer comprises a hydrogenated styrene/conjugated diene block copolymer (b1) having a styrene unit content of 10% by mass or more and 15% by mass or less, and a styrene unit content of 25% by mass or more and 35% by mass.
- thermoplastic elastomer composition was injection-molded under the conditions of a resin temperature of 200°C and a mold temperature of 40°C, and a sheet-like test piece having a thickness of 2 mm was measured according to JIS K7136-1, and the total light transmittance was 65. % or more, the airbag storage cover according to any one of [1] to [8].
- thermoplastic elastomer composition was injection-molded under the conditions of a resin temperature of 200°C and a mold temperature of 40°C, and a sheet-shaped test piece having a thickness of 2 mm was measured according to JIS K7136-1, and the haze was 70% or less.
- the airbag storage cover according to any one of [1] to [9].
- thermoplastic elastomer composition having a melt flow rate of 1.0 g/10 min or more and 50 g/10 min or less at 230° C. and a measured load of 21.18 N.
- thermoplastic elastomer composition was injection-molded under the conditions of a resin temperature of 200°C and a mold temperature of 40°C. % or more, the thermoplastic elastomer composition according to [12].
- thermoplastic elastomer composition was injection molded under conditions of a resin temperature of 200°C and a mold temperature of 40°C.
- the thermoplastic elastomer composition according to [12] or [13].
- a thermoplastic elastomer composition
- thermoplastic elastomer composition according to any one of [12] to [15], wherein the linear styrene elastomer has a styrene unit content of 20% by mass or more and 25% by mass or less.
- the linear styrene elastomer is a hydrogenated styrene/conjugated diene block copolymer (b1) having a styrene unit content of 10% by mass or more and 15% by mass or less, and a styrene unit content of 25% by mass. % or more and 35% by mass or less of a hydrogenated styrene/conjugated diene block copolymer (b2), and the thermoplastic elastomer composition according to [16].
- thermoplastic elastomer composition made of the thermoplastic elastomer composition according to any one of [12] to [17].
- a composite molded article having a first layer containing the thermoplastic elastomer composition according to any one of [12] to [17] and a second layer consisting of a resin film.
- a first layer made of a thermoplastic elastomer composition containing a propylene-based random copolymer and a styrene-based elastomer having a glass transition temperature in the range of -65°C or higher and -45°C or lower;
- a composite molded body having a second layer consisting of:
- the present invention also includes the following ⁇ 1> to ⁇ 11>.
- thermoplastic elastomer composition for an airbag containing the following component (A) and component (B).
- thermoplastic elastomer composition for airbags was injection-molded under the conditions of a resin temperature of 200°C and a mold temperature of 40°C. % or less, the thermoplastic elastomer composition for airbags according to ⁇ 1>.
- thermoplastic elastomer composition for an airbag is 70% by mass or more and 100% by mass or less.
- thermoplastic for airbags according to any one of ⁇ 1> to ⁇ 3>, wherein the content of component (B) relative to 100 parts by mass of component (A) is 20 parts by mass or more and 200 parts by mass or less.
- Elastomer composition is 20 parts by mass or more and 200 parts by mass or less.
- thermoplastic for airbags according to any one of ⁇ 1> to ⁇ 4>, further comprising 10 parts by mass or more and 100 parts by mass or less of the following component (C) with respect to 100 parts by mass of the component (A) Elastomer composition.
- component (C) Ethylene/ ⁇ -olefin copolymer
- thermoplastic elastomer composition for airbags according to any one of ⁇ 1> to ⁇ 5>, wherein the component (B) has a styrene unit content of 20% by mass or more and 25% by mass or less.
- the component (B) is a hydrogenated styrene/conjugated diene block copolymer (b1) having a styrene unit content of 10% by mass or more and 15% by mass or less, and a styrene unit content of 25% by mass or more.
- thermoplastic elastomer composition for airbags according to any one of ⁇ 1> to ⁇ 7>.
- thermoplastic elastomer composition for airbags according to any one of ⁇ 1> to ⁇ 7> and a second layer consisting of a resin film.
- thermoplastic elastomer composition for airbags according to any one of ⁇ 1> to ⁇ 7>.
- thermoplastic elastomer composition for airbags containing a propylene polymer and a styrene elastomer having a glass transition temperature of -65°C or higher and -45°C or lower, wherein the thermoplastic elastomer composition for airbags
- thermoplastic elastomer composition for airbags having a haze of 70% or less measured according to JIS K7136-1 on a 2 mm-thick sheet-like specimen obtained by injection molding under the conditions of a resin temperature of 200°C and a mold temperature of 40°C. .
- thermoplastic elastomer composition of the present invention is excellent in low-temperature impact resistance, high-temperature strength and optical transparency, and is also suitable for combination with touch panel films. Therefore, according to the thermoplastic elastomer composition of the present invention, it is possible to obtain molded articles and composite molded articles that are excellent in low-temperature impact resistance, high-temperature strength, and light transmittance, and that are suitable for combination with films for touch panels, and airbag storage. A cover is provided.
- the airbag storage cover of the present invention includes a driver airbag storage cover, a front passenger airbag storage cover, a pedestrian airbag storage cover, a knee airbag storage cover, a side airbag storage cover, and a curtain airbag storage cover. It can be suitably used for any of bag storage covers and the like.
- the airbag storage cover of the present invention is suitable as an airbag storage cover incorporating a touch panel display due to its excellent transparency and suitability for combination with a touch panel film.
- thermoplastic elastomer composition First, the thermoplastic elastomer composition according to the present invention will be described.
- thermoplastic elastomer composition constituting the airbag storage cover of the present invention is a thermoplastic containing a propylene-based random copolymer and a styrene-based elastomer having a glass transition temperature in the range of ⁇ 65° C. or more and ⁇ 45° C. or less.
- An elastomer composition, wherein the total content of the propylene-based random copolymer and the styrene-based elastomer in 100% by mass of the thermoplastic elastomer composition is more than 40% by mass and not more than 100% by mass.
- composition hereinafter, this thermoplastic elastomer composition may be referred to as "thermoplastic elastomer composition I").
- thermoplastic elastomer composition of the present invention comprises a propylene-based random copolymer, a styrene unit content of 20% by mass or more and 35% by mass or less, and a glass in the range of -65°C or more and -45°C or less.
- thermoplastic elastomer composition containing a linear styrene-based elastomer having a transition temperature, wherein the propylene-based random copolymer and the linear styrene-based elastomer in 100% by mass of the thermoplastic elastomer composition
- the content is more than 40% by mass and 100% by mass or less
- the content of the linear styrene elastomer is 45 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass of the propylene random copolymer
- JIS K7210 (1999) a thermoplastic elastomer composition having a melt flow rate of 1.0 g/10 min or more and 50 g/10 min or less at a temperature of 230° C.
- thermoplastic elastomer composition II The product may be referred to as "thermoplastic elastomer composition II").
- the thermoplastic elastomer composition II is a preferred embodiment in which the styrenic elastomer of the thermoplastic elastomer composition I is used in a specific proportion.
- the thermoplastic elastomer composition I and the thermoplastic elastomer composition II are referred to as “thermoplastic elastomer compositions of the present invention”.
- thermoplastic elastomer composition of the present invention is excellent in low-temperature impact resistance, high-temperature strength and light transmittance, and is suitable for combination with a touch panel film. Although the details of why the thermoplastic elastomer composition of the present invention exhibits such effects are not clear, the following is presumed as the reason why such effects are exhibited.
- Propylene-based polymers include propylene homopolymers and propylene-based copolymers, and propylene-based copolymers include propylene-based random copolymers and propylene-based block copolymers.
- the ethylene propylene copolymer that contributes to light scattering is not included, and the propylene random copolymer has a lower crystallinity, so the thermoplastic elastomer composition is particularly excellent in light transmission. I will provide a.
- the refractive index of a styrene-based elastomer is also correlated with the styrene unit content, and that the higher the styrene unit content, the higher the refractive index. Therefore, by setting the styrene unit content of the styrene-based elastomer to a specific range, the refractive index of the propylene-based random copolymer and the refractive index of the styrene-based elastomer can be brought close to each other, and the light transmittance can be improved.
- a hydrogenated product of a styrene/conjugated diene block copolymer can be specifically used as the styrene-based elastomer.
- the styrene unit content is the content of styrene units derived from raw material styrene and introduced into the hydrogenated product of the styrene/conjugated diene block copolymer.
- styrene elastomer a styrene elastomer having a glass transition temperature in the range of -65°C or higher and -45°C or lower, more preferably a specific styrene unit content, and still more preferably a linear styrene elastomer.
- the styrene-based elastomer has two or more glass transition temperatures, at least one glass transition temperature should be in the range of -65°C or higher and -45°C or lower.
- the propylene-based random copolymer used in the thermoplastic elastomer composition of the present invention contains propylene units and other monomers such as ethylene units, ⁇ -olefin units other than propylene, and monomer units other than ethylene and ⁇ -olefins. It is a random copolymer with polymer units.
- the propylene unit content of the propylene-based random copolymer is usually 50% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 94% by mass or more, and the upper limit is It is preferably 99% by mass or less.
- the content of propylene units in the propylene-based random copolymer is at least the above lower limit, heat resistance and rigidity tend to be improved. If the content of propylene units in the propylene-based random copolymer is equal to or less than the above upper limit, the crystallinity is low, so that the obtained thermoplastic elastomer composition has improved light transmittance.
- the content of propylene units in the propylene-based random copolymer can be determined by infrared spectroscopy.
- Examples of ⁇ -olefin units other than propylene contained in the propylene-based random copolymer include ⁇ -olefins having 4 to 20 carbon atoms.
- Examples of ⁇ -olefins having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4- methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene and the like.
- ⁇ -olefins having 4 to 10 carbon atoms, and more preferred are ethylene, 1-butene, 1-hexene and 1-octene.
- the propylene-based random copolymer may contain only one of these ⁇ -olefin units and ethylene units, or may contain two or more thereof.
- propylene-based random copolymers include propylene/ethylene random copolymers, propylene/1-butene random copolymers, propylene/1-hexene random copolymers, propylene/1-octene random copolymers, propylene/ethylene/1-butene random copolymer, propylene/ethylene/1-hexene random copolymer, and propylene/ethylene/1-octene random copolymer.
- a random copolymer of propylene and at least one monomer selected from ethylene and ⁇ -olefins having 4 to 10 carbon atoms is preferred.
- the melt flow rate (MFR) of the propylene-based random copolymer is not limited, but is usually 0.1 g/min or more, preferably 10 g/10 min or more, more preferably 20 g/min or more, from the viewpoint of appearance of the molded article. It is 10 minutes or more, more preferably 25 g/10 minutes or more, and usually 200 g/10 minutes or less, and from the viewpoint of tensile strength, preferably 150 g/10 minutes or less, more preferably 100 g/10 minutes or less.
- the melt flow rate of a propylene-based random copolymer is measured according to JIS K7210 (1999) under conditions of a measurement temperature of 230°C and a measurement load of 21.18N.
- a known polymerization method using a known olefin polymerization catalyst is used.
- a multi-stage polymerization method using a Ziegler-Natta catalyst can be mentioned.
- a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like can be used, and two or more of these methods may be combined.
- the propylene-based random copolymer used in the thermoplastic elastomer composition of the present invention can also be a commercially available product.
- the propylene-based random copolymer can be procured from the manufacturers listed below, and can be selected as appropriate.
- thermoplastic elastomer composition of the present invention may contain only one type of propylene-based random copolymer, or may contain two or more types having different monomer compositions and physical properties. .
- the styrene elastomer used in the thermoplastic elastomer composition of the present invention has a glass transition temperature in the range of -65°C to -45°C. If it is a styrene-based elastomer having a glass transition temperature in the range of -65°C or higher and -45°C or lower, it is thermoplastic with excellent light transmittance, low-temperature impact resistance, and high-temperature strength in combination with a propylene-based random copolymer. It can be an elastomeric composition.
- the glass transition temperature of the styrene-based elastomer is preferably in the range of -65°C or higher and -50°C or lower.
- the glass transition temperature of a styrene-based elastomer is measured by the DSC method.
- the glass transition temperature of each styrene elastomer may be within or outside the glass transition temperature range described above. At least one glass transition temperature should be in the range of -45°C or lower, preferably in the range of -65°C or higher and -50°C or lower.
- the styrene-based elastomer used in the present invention preferably has a styrene unit content of 20% by mass or more and 35% by mass or less from the viewpoint of low-temperature impact resistance, high-temperature strength, and light transmittance.
- the styrene unit content of the styrene-based elastomer is more preferably 21% by mass or more from the viewpoint of strength and heat resistance, and more preferably 30% by mass or less from the viewpoint of flexibility and impact resistance, and even more preferably. is 28% by mass or less, particularly preferably 25% by mass or less.
- the styrene unit content of the styrene-based elastomer can be calculated by performing proton NMR measurement with a nuclear magnetic resonance apparatus and quantifying the characteristic groups of styrene.
- the styrene unit content when using two or more types of styrene elastomers can also be calculated by proportional calculation from the styrene unit content of each styrene elastomer and the blending mass ratio of each styrene elastomer.
- the styrene unit content of each styrene elastomer may be within or outside the preferred range of the styrene unit content described above. is within the preferred range of the styrene unit content mentioned above.
- a hydrogenated styrene/conjugated diene block copolymer (b1) having a styrene unit content of 10% by mass or more and 15% by mass or less, and a styrene unit content of 25% by mass or more and 35% by mass or less.
- the following hydrogenated styrene/conjugated diene block copolymer (b2) is used in combination so that the styrene unit content is 20% by mass or more and 35% by mass or less, particularly 20% by mass or more and 25% by mass or less. This makes it easier to achieve both high-temperature strength, low-temperature impact resistance, and light transmittance.
- the hydrogenated styrene/conjugated diene block copolymer (b1) and the hydrogenated styrene/conjugated diene block copolymer (b2) are hydrogenated styrene/conjugated diene/styrene block copolymers, respectively. is preferred.
- a suitable conjugated diene in the hydrogenated product of the styrene/conjugated diene block copolymer as the styrene elastomer is butadiene, isoprene or a mixture thereof.
- hydrogenated styrene/conjugated diene block copolymers include hydrogenated styrene/butadiene block copolymers (hereinafter sometimes simply abbreviated as “SEBS”).
- a polymer having a double bond in the molecular structure such as styrene-butadiene-styrene block copolymer (SBS) is used as a styrene-based elastomer by using a hydrogenated product of a styrene-conjugated diene block copolymer.
- SBS styrene-butadiene-styrene block copolymer
- a hydrogenated product of a styrene-conjugated diene block copolymer In a thermoplastic elastomer composition having high visible light and ultraviolet transmittance as compared with , good light resistance can be maintained.
- the propylene-based random copolymer described above has a styrene unit content of 20% by mass or more and 35% by mass or less, particularly 20% by mass or more and 25% by mass or less, and a temperature range of ⁇ 65° C.
- thermoplastic elastomer composition excellent in low-temperature impact resistance, high-temperature strength, and light transmittance can be obtained by using in combination a hydrogenated styrene/conjugated diene block copolymer having a glass transition temperature of .
- the styrene-based elastomer used in the present invention is preferably a linear styrene-based elastomer.
- a straight-chain styrene-based elastomer can be easily dispersed in a propylene-based random copolymer and can further improve light transmittance.
- the linear styrene elastomer is, for example, a hydrogenated product of a styrene/conjugated diene block copolymer in which the conjugated diene portion is butadiene, isoprene, or a mixture thereof.
- a styrene/ethylene/butylene/styrene copolymer, which is a hydrogenated product of a butadiene block copolymer, can be mentioned.
- the hydrogenated product of the styrene/conjugated diene block copolymer as the styrene elastomer preferably has a 1,2-microstructure of 60 mol% or less, more preferably 45 mol% or less, as analyzed by the NMR method. Those having a 1,2-microstructure of 60 mol % or less are preferable from the viewpoint of moldability and flexibility. From the viewpoint of weather resistance, the hydrogenation rate of the hydrogenated styrene/conjugated diene block copolymer as the styrene elastomer is preferably 90 mol % or more, more preferably 95 mol % or more.
- the weight average molecular weight (Mw) of the styrene-based elastomer is preferably 40,000 or more, more preferably 45,000 or more, still more preferably 48,000 or more, from the viewpoint of releasability. From the viewpoint of transparency, the weight average molecular weight (Mw) of the styrene-based elastomer is preferably 120,000 or less, more preferably 110,000 or less, and even more preferably 105,000 or less.
- the lower limit of the mass average molecular weight (Mw) of the styrene-based elastomer is preferably 125,000 or more, more preferably 130,000 or more, still more preferably 135,000 or more, and 140,000 or more. is particularly preferred.
- the upper limit of the mass average molecular weight (Mw) is preferably 350,000 or less, more preferably 325,000 or less, even more preferably 300,000 or less, from the viewpoint of fluidity.
- the weight average molecular weight of the styrene elastomer can be obtained by measuring a mixture of each component of the styrene elastomer by the GPC method described below.
- the weight average molecular weight of each styrene elastomer may be within or outside the preferred range of the weight average molecular weight of the styrene elastomer. It may be within the preferred range of molecular weight.
- the mass average molecular weight (Mw) of the styrene elastomer is measured by a gel permeation chromatography method (GPC method), and can be measured, for example, under the following conditions.
- Equipment "HLC-8220 GPC (R)” manufactured by Tosoh Corporation
- Detector Differential refractive index detector (RI/built-in)
- Solvent chloroform Temperature: 40°C Flow rate: 0.25 mL/min
- Injection volume 0.1% by mass x 20 ⁇ L
- Calibration sample Monodisperse polystyrene
- Calibration method Polystyrene conversion
- Calibration curve approximation formula Cubic formula (hyperbola): Exclusion limit setting time 12 minutes
- a styrene-based elastomer can be produced by, for example, synthesizing a styrene/conjugated diene block copolymer in an inert solvent using a lithium catalyst according to the method described in Japanese Patent Publication No. 40-23798. , JP-B-42-8704, JP-B-43-6636, JP-A-59-133203, JP-A-60-79005, by the method described in the hydrogenation catalyst in an inert solvent. A method of hydrogenating in the presence can be mentioned.
- Styrene-based elastomers are also available as commercial products.
- examples of styrene-based elastomers include "Kraton (registered trademark) G” manufactured by Kraton Polymer Co., Ltd., "Septon (registered trademark)” manufactured by Kuraray Co., Ltd., and "Tuftec (registered trademark)” manufactured by Asahi Kasei Corporation.
- thermoplastic elastomer composition of the present invention may contain only one type of styrene elastomer, or may contain two or more types having different monomer compositions and physical properties.
- thermoplastic elastomer composition of the present invention may further contain an ethylene/ ⁇ -olefin copolymer.
- the ethylene/ ⁇ -olefin copolymer has ⁇ -olefin units such as propylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, Examples include those having 1-octene as a structural unit.
- the ⁇ -olefin is preferably an ⁇ -olefin having 4 to 8 carbon atoms and having a carbon-carbon double bond at the terminal carbon atom, such as propylene, 1-butene, 1-hexene and 1-octene.
- the ethylene/ ⁇ -olefin copolymer may be obtained by copolymerizing only one kind of ⁇ -olefin with ethylene, or by copolymerizing two or more kinds of ⁇ -olefins with ethylene.
- the content of ethylene units in the ethylene/ ⁇ -olefin copolymer is preferably large in order to prevent fusion due to blocking of the ethylene/ ⁇ -olefin copolymer. From the viewpoint of low-temperature impact resistance, the smaller the number, the better.
- the lower limit of the ethylene unit content of the ethylene/ ⁇ -olefin copolymer is usually 50% by mass or more, preferably 55% by mass, with respect to the total 100% by mass of the ethylene units and ⁇ -olefin units. % by mass or more, more preferably 60% by mass or more, and even more preferably 65% by mass or more.
- the upper limit is usually 99% by mass or less, preferably 80% by mass or less.
- the ethylene unit content, the ⁇ -olefin unit content, and the later-described non-conjugated diene unit content in the ethylene/ ⁇ -olefin copolymer can be determined by infrared spectroscopy.
- the ethylene/ ⁇ -olefin copolymer may have other monomer units such as monomer units based on a non-conjugated diene (non-conjugated diene units).
- the nonconjugated dienes include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene.
- Chain non-conjugated dienes cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6- cyclic non-conjugated dienes such as chloromethyl-5-isopropenyl-2-norbornene; Preferred are 5-ethylidene-2-norbornene and dicyclopentadiene.
- the content thereof is usually 10% by mass with respect to 100% by mass of the entire ethylene/ ⁇ -olefin copolymer. Below, it is preferably 5% by mass or less.
- the melt flow rate (MFR) of the ethylene/ ⁇ -olefin copolymer is not limited, but is usually 10 g/10 min or less, preferably 8.0 g/10 min or less, more preferably 5 from the viewpoint of strength. 0 g/10 minutes or less, more preferably 3.0 g/10 minutes or less.
- the melt flow rate of the ethylene/ ⁇ -olefin copolymer is usually 0.01 g/10 min or more, preferably 0.05 g/10 min or more, more preferably 0.05 g/10 min or more, from the viewpoint of fluidity. 10 g/10 minutes or more.
- the melt flow rate of the ethylene/ ⁇ -olefin copolymer is measured according to ASTM D1238 under conditions of a measurement temperature of 190°C and a measurement load of 21.18N.
- the density of the ethylene/ ⁇ -olefin copolymer is preferably 0.88 g/cm 3 or less from the viewpoint of low-temperature impact resistance. On the other hand, from the viewpoint of transparency, that is, refractive index, it is preferably 0.86 g/cm 3 or more.
- the density of the ethylene/ ⁇ -olefin copolymer can be measured by the ISO 1183-A method (measurement temperature: 23°C).
- the ethylene/ ⁇ -olefin copolymer is also available as a commercial product.
- Commercially available products corresponding to ethylene/ ⁇ -olefin copolymers include, for example, Engage (registered trademark) and INFUSE (registered trademark) manufactured by Dow Chemical Company.
- thermoplastic elastomer composition of the present invention may contain only one type of ethylene/ ⁇ -olefin copolymer, or may contain two or more types having different monomer compositions and physical properties. good.
- the thermoplastic elastomer composition of the present invention may contain a crystal nucleating agent.
- a crystal nucleating agent a diacetal crystal nucleating agent is preferable. By mixing a diacetal-based crystal nucleating agent, crystallization of the propylene-based random copolymer is promoted, and it is expected that light transmittance is improved.
- Known diacetal crystal nucleating agents can be used, such as Gelol (registered trademark) D, Gelol (registered trademark) MD and Gelol (registered trademark) DXR available from Shin Nippon Rika Co., Ltd., and Mirad 3988 available from Milliken (USA). , MIRAD NX8000, MIRAD NX8000J, MIRAD NX8000K, MIRAD NX8000ECO, and SIPAXNA-2 of GCHTECHNOLORY (China). These may use only 1 type and may use 2 or more types.
- the total content of the propylene-based random copolymer and the styrene-based elastomer in the thermoplastic elastomer composition of the present invention is 100% of the thermoplastic elastomer composition from the viewpoint of the effects of excellent low-temperature impact resistance, high-temperature strength, and light transmittance. It is usually more than 40% by mass, preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, and 80% by mass or more. is particularly preferred, and 85% by mass or more is particularly preferred. Its upper limit is 100% by mass.
- the content ratio of the styrene elastomer to 100 parts by mass of the propylene random copolymer is usually 20 parts by mass or more, preferably 45 parts by mass or more and 250 parts by mass or less.
- the lower limit of the content of the styrene-based elastomer with respect to 100 parts by mass of the propylene-based random copolymer is more preferably 60 parts by mass or more, more preferably 70 parts by mass or more, from the viewpoint of low-temperature impact resistance and light transmission. It is preferably 80 parts by mass or more, and particularly preferably 80 parts by mass or more.
- the upper limit of the content of the styrene-based elastomer with respect to 100 parts by mass of the propylene-based random copolymer is more preferably 200 parts by mass or less, further preferably 150 parts by mass or less, and 140 parts by mass. is particularly preferably 130 parts by mass or less, and particularly preferably 130 parts by mass or less.
- thermoplastic elastomer composition of the present invention contains an ethylene/ ⁇ -olefin copolymer
- 10 parts by mass or more of the ethylene/ ⁇ -olefin copolymer is added to 100 parts by mass of the propylene-based random copolymer. It is preferable to include 100 parts by mass or less.
- the lower limit of the content of the ethylene/ ⁇ -olefin copolymer with respect to 100 parts by mass of the propylene-based random copolymer is more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, from the viewpoint of low-temperature impact resistance. More preferably, it is particularly preferably 40 parts by mass or more.
- the upper limit of the content of the ethylene/ ⁇ -olefin copolymer with respect to 100 parts by mass of the propylene-based random copolymer is more preferably 70 parts by mass or less, more preferably 60 parts by mass or less, from the viewpoint of high-temperature strength. , 55 parts by mass or less.
- the content of the crystal nucleating agent in the thermoplastic elastomer composition of the present invention may be propylene-based random copolymer, styrene 0.05 per 100 parts by mass of the total of the system elastomer and the ethylene/ ⁇ -olefin copolymer (the total of the propylene-based random copolymer and the styrene-based elastomer when the ethylene/ ⁇ -olefin copolymer is not contained) It is preferably used in an amount of not less than 5.0 parts by mass, more preferably not less than 0.05 parts by mass and not more than 1.0 parts by mass.
- thermoplastic elastomer composition of the present invention contains, in addition to the propylene-based random copolymer, styrene-based elastomer, ethylene/ ⁇ -olefin copolymer, and crystal nucleating agent, the following components within a range that does not significantly impair the effects of the present invention:
- the following additives, inorganic fillers, organic fillers, propylene random copolymers, styrene elastomers, and resins other than ethylene / ⁇ -olefin copolymers hereinafter referred to as "other resins"
- other optional components can be added.
- Additives include colorants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, lubricants, anti-fogging agents, anti-blocking agents, slip agents, flame retardants, dispersants, and antistatic agents. , electrical conductivity imparting agents, metal deactivators, molecular weight modifiers, antibacterial agents, fluorescent whitening agents and the like. These additives are usually 0.01 parts by mass of each additive with respect to a total of 100 parts by mass of the propylene-based random copolymer, the styrene-based elastomer, and the ethylene/ ⁇ -olefin copolymer used as necessary. It can be blended and used in the range of 2 parts by mass or less.
- thermoplastic elastomer composition of the present invention examples include low-density polyethylene, polyester elastomers, urethane elastomers, polyester resins, polyamide resins, polyurethane resins, styrene resins, polycarbonate resins, polyvinyl chloride resins, and resins other than the above. (excluding those corresponding to styrene-based elastomers and ethylene/ ⁇ -olefin copolymers).
- the other resins listed above may contain only one type or two or more types.
- thermoplastic elastomer composition of the present invention is prepared by extruding the propylene-based random copolymer and styrene-based elastomer, and optionally the ethylene/ ⁇ -olefin copolymer and other components into a conventional extruder or Banbury extruder. It can be produced by kneading according to a conventional method using a mixer, roll, Brabender plastograph, kneader Brabender, or the like. Among these manufacturing methods, it is preferable to use an extruder, particularly a twin-screw extruder.
- thermoplastic elastomer composition of the present invention When the thermoplastic elastomer composition of the present invention is produced by kneading with an extruder or the like, it is usually melt-kneaded while being heated to 155°C or higher and 240°C or lower, preferably 180°C or higher and 220°C or lower. At this time, a known cross-linking agent or cross-linking auxiliary agent may be blended and then subjected to dynamic heat treatment to allow partial cross-linking.
- thermoplastic elastomer of the present invention contains the propylene-based random copolymer and the styrene-based elastomer, optionally an ethylene/ ⁇ -olefin copolymer, and a crystal nucleating agent to improve high-temperature strength and low-temperature impact resistance. and excellent in light transmittance.
- thermoplastic elastomer composition of the present invention is preferably used for airbag storage covers.
- the "airbag storage cover” means a container in general for storing an airbag.
- the opening when the airbag deploys, or the entire container integrated with this opening in a container in which an airbag is housed, the opening when the airbag deploys, or the entire container integrated with this opening.
- the thermoplastic elastomer composition of the present invention preferably has the following physical properties.
- Izod impact strength In the present invention, Izod impact strength at ⁇ 35° C., ⁇ 40° C. and ⁇ 45° C. according to ISO180 is used as an index of low-temperature impact resistance.
- the molded article of the thermoplastic elastomer composition of the present invention preferably has an Izod impact strength of 50 kJ/m 2 or more, more preferably 70 kJ/m 2 or more.
- the upper limit of the Izod impact strength of the thermoplastic elastomer composition of the present invention is not particularly limited, it is usually 150 kJ/m 2 or less.
- the melt flow rate (MFR) at a temperature of 230° C. and a measurement load of 21.18 N according to JIS K7210 (1999) is used as an index of injection moldability of the thermoplastic elastomer composition.
- the thermoplastic elastomer composition of the present invention preferably has a melt flow rate of 1.0 g/10 min or more and 50 g/10 min or less in order to have excellent injection moldability.
- the MFR of the thermoplastic elastomer composition for airbags is 1.0 g/10 minutes or more, the fluidity tends to be good, and when it is 50 g/10 minutes or less, burrs and the like during molding can be easily suppressed. preferred.
- the MFR of the thermoplastic elastomer composition for airbags is more preferably 2.0 g/10 minutes or more, still more preferably 2.5 g/10 minutes or more.
- the MFR of the thermoplastic elastomer composition is more preferably 40 g/10 minutes or less, still more preferably 20 g/10 minutes or less, particularly preferably 17 g/10 minutes or less, and particularly preferably 17 g/10 minutes or less. is 15 g/10 minutes or less.
- the thermoplastic elastomer composition of the present invention preferably has a tensile elongation at break at 23° C. of 300% or more, more preferably 350% or more, according to JIS K6251. If the tensile elongation at break at 23°C is equal to or higher than the above lower limit, the expandability of the airbag storage cover made of the thermoplastic elastomer composition of the present invention tends to be good due to good elongation of the material.
- the upper limit of the tensile elongation at break of the thermoplastic elastomer composition of the present invention is not particularly limited, it is usually 1500% or less.
- the tensile strength at break measured when measuring the tensile elongation at break is preferably 10 MPa or more, more preferably 12 MPa or more. If the tensile breaking strength at 23°C is equal to or higher than the above lower limit, the expandability of the airbag storage cover made of the thermoplastic elastomer composition of the present invention tends to be good due to the high material strength.
- the upper limit of the tensile breaking strength of the thermoplastic elastomer composition of the present invention is not particularly limited, it is usually 25 MPa.
- the thermoplastic elastomer composition of the present invention preferably has a tensile breaking strength of 4.5 MPa or more at 85° C. according to JIS K6251, more preferably 5.0 MPa or more. It is more preferably 5.5 MPa or more. If the tensile breaking strength at 85°C is equal to or higher than the above lower limit, the airbag storage cover made of the thermoplastic elastomer composition of the present invention tends to have good expandability due to high material strength.
- the upper limit of the tensile breaking strength of the thermoplastic elastomer composition of the present invention is not particularly limited, it is usually 8 MPa or less.
- thermoplastic elastomer composition of the present invention preferably has a flexural modulus of 600 MPa or less, more preferably 200 MPa or more and 550 MPa or less, as measured according to JIS K7203. If the flexural modulus of the thermoplastic elastomer composition is equal to or less than the upper limit, the low-temperature impact resistance tends to be good, and if it is equal to or more than the lower limit, the rigidity tends to be excellent.
- the thermoplastic elastomer composition of the present invention is prepared by injection molding the thermoplastic elastomer composition under the conditions of a resin temperature of 200°C and a mold temperature of 40°C.
- the total light transmittance measured based on K7136-1 is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more, particularly 75% or more. preferable. With such a numerical range, when used as an airbag housing cover, the light transmission is good and the lighting of the switch becomes easy to see.
- thermoplastic elastomer composition of the present invention is prepared by injection molding the thermoplastic elastomer composition at a resin temperature of 200°C and a mold temperature of 40°C.
- the haze measured based on -1 is preferably 70% or less, more preferably 60% or less, even more preferably 50% or less, and particularly preferably 40% or less. From the viewpoint of visibility of the switch, it is essential that the above-mentioned total light transmittance is good. , making it easier to see the lighting of the switch more clearly.
- the haze preferably exceeds 70%, more preferably 75% or more, and even more preferably 80% or more.
- the total light transmittance is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more, and particularly preferably 75% or more.
- thermoplastic elastomer composition of the present invention in general, an ordinary injection molding method, or, if necessary, using various molding methods such as gas injection molding, injection compression molding, short shot foam molding, etc. It can be a molded body such as an airbag storage cover.
- thermoplastic elastomer composition of the present invention is injection-molded into a molded article such as an airbag storage cover. Molding conditions for injection molding are as follows.
- the molding temperature for injection molding the thermoplastic elastomer composition is usually 150°C or higher and 300°C or lower, preferably 180°C or higher and 280°C or lower.
- the injection pressure is usually 5 MPa or more and 100 MPa or less, preferably 10 MPa or more and 80 MPa or less.
- the mold temperature is usually 0°C or higher and 80°C or lower, preferably 20°C or higher and 60°C or lower.
- thermoplastic elastomer composition containing a propylene-based random copolymer and a styrene-based elastomer having a glass transition temperature in the range of ⁇ 65° C. or more and ⁇ 45° C. or less; and a second layer made of a resin film.
- the composite molded article of the present invention having a layer of and is suitable as an airbag storage cover. That is, the thermoplastic elastomer composition of the present invention can be integrated with a resin film to form a composite molded article, and a first layer containing the thermoplastic elastomer composition of the present invention and a second layer consisting of a resin film can be formed.
- the composite molding of the present invention having a layer is suitable as an airbag storage cover.
- resin films include polypropylene films, polyethylene films, polyolefin thermoplastic elastomer films, and polyester films.
- the composite molded article of the present invention can be molded by an insert molding method.
- a resin film is incorporated in a mold before molding, and then the mold is filled with the thermoplastic elastomer composition of the present invention to produce a first film made of the thermoplastic elastomer composition of the present invention.
- a composite molded article of the present invention having a layer and a second layer composed of a resin film can be obtained.
- the thermoplastic elastomer composition of the present invention is excellent in high-temperature strength, low-temperature impact resistance and light transmittance, and is suitably used as a molding material for airbag storage covers.
- airbag storage covers for example, when a high-speed moving object such as a car is in a collision accident, the airbag system of the airbag system operates by sensing the impact or deformation and protects the occupant by inflating and deploying. It is suitable as a bag storage cover.
- the airbag storage cover of the present invention is suitable as an airbag storage cover arranged at a visible position such as a touch panel display.
- thermoplastic elastomer compositions for airbags of ⁇ 1> to ⁇ 11>> In the thermoplastic elastomer composition for airbags ⁇ 1> to ⁇ 11> described above, as an example of the propylene-based polymer of component (A), the propylene-based random copolymer contained in the thermoplastic elastomer composition of the present invention described above is used. polymers. Propylene-based polymers other than propylene-based random copolymers include, in addition to propylene homopolymers and propylene units, ethylene units, ⁇ -olefin units other than propylene, and monomer units other than ethylene and ⁇ -olefins.
- a propylene-based block copolymer containing preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 6% by mass or less is mentioned.
- Preferred examples of the ⁇ -olefin unit contained in the propylene-based block polymer are the same as those of the ⁇ -olefin unit of the propylene-based random copolymer.
- propylene-based polymers other than propylene-based random copolymers include propylene homopolymers, propylene/ethylene block copolymers, propylene/1-butene block copolymers, propylene/1-hexene block copolymers, propylene/ 1-octene block copolymer, propylene/ethylene/1-butene block copolymer, propylene/ethylene/1-hexene block copolymer, propylene/ethylene/1-octene block copolymer, propylene alone in the first step
- a propylene-based block copolymer obtained by polymerizing a polymer and then polymerizing a propylene/ethylene copolymer in the second step can be exemplified.
- a propylene homopolymer Preferably, a propylene homopolymer, a block copolymer of propylene and at least one monomer selected from ethylene and an ⁇ -olefin having 4 to 10 carbon atoms, and a propylene homopolymer polymerized in the first step.
- a propylene-based block copolymer obtained by polymerizing a propylene/ethylene copolymer in the second step.
- the physical properties and others of the propylene-based polymer of component (A) are the same as those of the propylene-based random copolymer described above.
- thermoplastic elastomer composition for airbags ⁇ 1> to ⁇ 11> and other detailed descriptions, refer to the styrene elastomer and other descriptions in the thermoplastic elastomer composition of the present invention. applies.
- [Styrene-based elastomer] (b-1): Kraton (registered trademark) G1652 manufactured by Kraton Polymer Co., Ltd. Hydrogenated styrene-butadiene block copolymer (styrene-ethylene-butylene-styrene copolymer (SEBS)) Mass average molecular weight (Mw): 70,000 Styrene unit content: 30% by mass Glass transition temperature: -55°C (b-2): Kraton (registered trademark) G1657 manufactured by Kraton Polymer Co., Ltd.
- Hydrogenated styrene-butadiene block copolymer (styrene-ethylene-butylene-styrene copolymer (SEBS)) Mass average molecular weight (Mw): 180,000 Styrene unit content: 31% by mass Glass transition temperature: -55°C (b-4): Kraton (registered trademark) G1651 manufactured by Kraton Polymer Co., Ltd. Hydrogenated styrene-butadiene block copolymer (styrene-ethylene-butylene-styrene copolymer (SEBS)) Weight average molecular weight (Mw): 260,000 Styrene unit content: 33% by mass Glass transition temperature: -55°C
- Ethylene/ ⁇ -olefin copolymer (C-1): Dow Chemical Company Engage (registered trademark) 8100 Ethylene-octene copolymer MFR (ASTM D1238): 1 g/10 minutes (measurement conditions 190°C, load 21.18 N (2.16 kgf)) Density (ISO 1183-A method): 0.87 g/cm 3 (measurement temperature: 23°C) (C-2): Dow Chemical Company Engage (registered trademark) 8150 Ethylene-octene copolymer MFR (ASTM D1238): 0.5 g/10 minutes (measurement conditions 190°C, load 21.18 N (2.16 kgf)) Density (ISO 1183-A method): 0.87 g/cm 3 (measurement temperature: 23°C)
- [Crystal nucleating agent] (D-1) Gelol (registered trademark) MD manufactured by Shin Nippon Rika Co., Ltd. 1,3:2,4-bis-O-(4-methylbenzylidene)-D-sorbitol Melting point: 255-267°C
- pellets of the thermoplastic elastomer composition obtained in each example were used, and an in-line screw type injection molding machine (manufactured by Toshiba Machine Co., Ltd., "IS130") was used with an injection pressure of 50 MPa and a cylinder At a set temperature of 190° C. (resin temperature of 200° C.) and a mold temperature of 40° C., a test sheet was injection-molded for each test.
- an in-line screw type injection molding machine manufactured by Toshiba Machine Co., Ltd., "IS130”
- High temperature tensile breaking strength (85 ° C.): Tensile breaking test (JIS-3 dumbbell, tensile speed 500 mm / min) (unit: %) Based on JIS K6251 (JIS-3 dumbbell), a test piece for tensile test (sheet of thickness 2 mm ⁇ width 120 mm ⁇ length 80 mm) was punched out. The tensile breaking strength of this punched test piece was measured in an atmosphere of 85° C. according to JIS K6251. The larger the value of the tensile breaking strength, the better the evaluation. In Table 1 below, the value of the tensile breaking strength at 85°C indicated with ">" indicates that the measured strength reached the upper limit of the equipment and did not break. The numbers refer to the stress at which the upper limit of the instrument is reached, and in this evaluation this stress can be equated with the breaking stress.
- Total light transmittance The total light transmittance of an injection-molded sheet having a thickness of 2 mm, a width of 120 mm, and a length of 80 mm was measured according to JIS K7136-1. It was evaluated that the larger the total light transmittance value, the better the light transmittance.
- Example 1 As shown in Table-1, antioxidant ( BASF Japan Co., Ltd. trade name Irgastab (registered trademark) FS301FF) 0.15 parts by mass, light stabilizer (HALS (SONGWON SABOSTAB (registered trademark) UV119) 0.2 parts by mass, UV absorber (BASF Japan Co., Ltd. Tinuvin (registered trademark) 326) 0.1 parts by mass and 0.2 parts by mass of silicone oil (KF96-100CS manufactured by Shin-Etsu Chemical Co., Ltd.) were blended for 1 minute in a Henschel mixer.
- antioxidant BASF Japan Co., Ltd. trade name Irgastab (registered trademark) FS301FF) 0.15 parts by mass
- HALS SONGWON SABOSTAB (registered trademark) UV119
- UV absorber BASF Japan Co., Ltd. Tinuvin (registered trademark) 326) 0.1 parts by mass and 0.2 parts by mass of silicone oil (KF96-100CS manufactured by Shin-Etsu Chemical Co., Ltd
- thermoplastic elastomer composition produced pellets of a thermoplastic elastomer composition.
- the pellets of the obtained thermoplastic elastomer composition were evaluated for the above 1) to 7). These evaluation results are shown in Table-1.
- a composite molded article was prepared by insert molding using the obtained thermoplastic elastomer composition pellets and a polypropylene film. Specifically, Novatec (registered trademark) PP MG03E manufactured by Japan Polypropylene Co., Ltd. was pressed to a thickness of 0.5 mm, cut into 100 mm squares, set in a mold of 100 mm ⁇ 100 mm ⁇ 3 mm, and injected the pellets. Molded. By this method, a composite molded article in which the first layer made of the thermoplastic elastomer composition and the second layer made of the polypropylene film were fused and integrated could be obtained.
- Novatec registered trademark
- PP MG03E manufactured by Japan Polypropylene Co., Ltd. was pressed to a thickness of 0.5 mm, cut into 100 mm squares, set in a mold of 100 mm ⁇ 100 mm ⁇ 3 mm, and injected the pellets. Molded.
- thermoplastic elastomer composition Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the formulations shown in Tables 1 and 2 were used. In the same manner as in Example 1, 100 parts by mass in total of the propylene-based random copolymer, the styrene-based elastomer or other styrene-based elastomer, and the optionally used ethylene/ ⁇ -olefin copolymer were oxidized.
- Inhibitor (trade name Irgastab (registered trademark) FS301FF manufactured by BASF Japan) 0.15 parts by weight, light stabilizer (HALS (SABOSTAB (registered trademark) UV119 manufactured by SONGWON) 0.2 parts by weight, ultraviolet absorber (BASF Japan 0.1 parts by mass of Tinuvin (registered trademark) 326 manufactured by Co., Ltd. and 0.2 parts by mass of silicone oil (KF96-100CS manufactured by Shin-Etsu Chemical Co., Ltd.) were blended respectively. omitted.
- the pellets of the obtained thermoplastic elastomer composition were evaluated for the above 1) to 7). These evaluation results are shown in Tables 1 and 2.
- Comparative Example 1 is an example in which (b'-1), which is a hydrogenated styrene/butadiene block copolymer having a glass transition temperature exceeding ⁇ 45° C., was blended, but the result was that the low-temperature impact resistance was significantly inferior. became.
- Comparative Example 2 is an example in which the compound corresponding to Example 2 of Patent Document 6 was blended, but the result was inferior in high-temperature strength.
- Comparative Example 3 is an example in which the total content of the propylene-based random copolymer and the styrene-based elastomer was blended to 37.5% by mass, but resulted in poor high-temperature strength.
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Abstract
Description
成分(A):プロピレン系重合体
成分(B):スチレン単位含有率が20質量%以上35質量%以下であり、かつ、ガラス転移温度が-65℃以上-45℃以下である、スチレン・共役ジエンブロック共重合体の水素添加物
成分(C):エチレン・α-オレフィン共重合体
まず、本発明に係る熱可塑性エラストマー組成物について説明する。
また、本発明の熱可塑性エラストマー組成物は、プロピレン系ランダム共重合体と、スチレン単位含有率が20質量%以上35質量%以下であり、かつ、-65℃以上-45℃以下の範囲にガラス転移温度を有する直鎖状スチレン系エラストマーとを含有する熱可塑性エラストマー組成物であって、熱可塑性エラストマー組成物100質量%における前記プロピレン系ランダム共重合体と前記直鎖状スチレン系エラストマーの合計の含有率が40質量%を超え100質量%以下であり、前記プロピレン系ランダム共重合体100質量部に対する前記直鎖状スチレン系エラストマーの含有量が45質量部以上250質量部以下であり、JIS K7210(1999年)に準拠した温度230℃、測定荷重21.18Nでのメルトフローレートが1.0g/10分以上50g/10分以下である、熱可塑性エラストマー組成物(以下、この熱可塑性エラストマー組成物を「熱可塑性エラストマー組成物II」と称す場合がある。)である。
上記の通り、熱可塑性エラストマー組成物IIは、熱可塑性エラストマー組成物Iにおけるスチレン系エラストマーのうちの限定されたスチレン系エラストマーを特定の割合で用いた好適態様である。
以下において、熱可塑性エラストマー組成物Iと熱可塑性エラストマー組成物IIを「本発明の熱可塑性エラストマー組成物」と称す。
本発明の熱可塑性エラストマー組成物は、低温耐衝撃性、高温強度および光透過性に優れると共に、タッチパネル用フィルムとの複合化にも適するという効果を奏する。
本発明の熱可塑性エラストマー組成物がこのような効果を奏する理由の詳細は定かではないが、このような効果が発現する理由については、次のようなことが推測される。
ここで、スチレン単位含有率とは、原料スチレンに由来してスチレン・共役ジエンブロック共重合体の水素添加物に導入されるスチレン単位の含有率である。
ここで、スチレン系エラストマーがガラス転移温度を2以上有する場合、少なくとも1つのガラス転移温度が-65℃以上-45℃以下の範囲にあればよい。
本発明の熱可塑性エラストマー組成物に用いるプロピレン系ランダム共重合体は、プロピレン単位と、エチレン単位、プロピレン以外のα-オレフィン単位、エチレンおよびα-オレフィン以外の単量体単位等の他の単量体単位とのランダム共重合体である。
プロピレン系ランダム共重合体中のプロピレン単位の含有率は、赤外分光法により求めることができる。
プロピレン系ランダム共重合体には、これらのα-オレフィン単位およびエチレン単位の1種のみが含まれていてもよく、2種以上が含まれていてもよい。
本発明の熱可塑性エラストマー組成物に用いるスチレン系エラストマーは、-65℃以上-45℃以下の範囲にガラス転移温度を有する。-65℃以上-45℃以下の範囲にガラス転移温度を有するスチレン系エラストマーであれば、プロピレン系ランダム共重合体との組み合わせで、光透過性、低温耐衝撃性、高温強度に優れた熱可塑性エラストマー組成物とすることができる。
スチレン系エラストマーのガラス転移温度は、-65℃以上-50℃以下の範囲に存在することが、低温耐衝撃性の観点から好ましい。
スチレン系エラストマーのガラス転移温度はDSC法によって測定される。
スチレン系エラストマーのスチレン単位含有率は、強度と耐熱性の観点から、より好ましくは21質量%以上であり、柔軟性と耐衝撃性の観点から、より好ましくは30質量%以下であり、更に好ましくは28質量%以下であり、特に好ましくは25質量%以下である。
スチレン系エラストマーのスチレン単位含有率は、核磁気共鳴装置によって、プロトンNMR測定を行い、スチレンの特性基の定量を行うことによって算出できる。
また、前述のプロピレン系ランダム共重合体に、スチレン単位含有率が20質量%以上35質量%以下、特に20質量%以上25質量%以下であり、かつ、-65℃以上-45℃以下の範囲にガラス転移温度を有するスチレン・共役ジエンブロック共重合体の水素添加物を組み合わせて用いることで、低温耐衝撃性、高温強度および光透過性に優れた熱可塑性エラストマー組成物を得ることができる。
ここで、直鎖状スチレン系エラストマーとは、例えば、スチレン・共役ジエンブロック共重合体の共役ジエン部分がブタジエン、イソプレン又はこれらの混合物であるものの水素添加物であり、具体的には、スチレン・ブタジエンブロック共重合体の水素添加物であるスチレン・エチレン・ブチレン・スチレン共重合体が挙げられる。
また、スチレン系エラストマーの質量平均分子量(Mw)は透明性の観点から、120,000以下が好ましく、より好ましくは110000以下、更に好ましくは105000以下である。
機器:東ソー株式会社製「HLC-8220 GPC(R)」
カラム:東ソー株式会社製「TSKgel Super HM-M(6.0mm I.D×15cm×2+G)」
検出器:示差屈折率検出器(RI/内蔵)
溶媒:クロロホルム
温度:40℃
流速:0.25mL/分
注入量:0.1質量%×20μL
較正試料:単分散ポリスチレン
較正法:ポリスチレン換算
較正曲線近似式:3次式(双曲線):排除限界設定時間 12分
本発明の熱可塑性エラストマー組成物は、低温耐衝撃性の観点から、更に、エチレン・α-オレフィン共重合体を含有していてもよい。
エチレン・α-オレフィン共重合体のメルトフローレートは、ASTM D1238に従い、測定温度190℃、測定荷重21.18Nの条件で測定される。
エチレン・α-オレフィン共重合体の密度はISO 1183-A法(測定温度:23℃)により測定することができる。
本発明の熱可塑性エラストマー組成物は、結晶核剤を含有していてもよい。結晶核剤としては、ジアセタール系結晶核剤が好ましい。ジアセタール系結晶核剤を混合することにより、前記プロピレン系ランダム共重合体の結晶化が促進され、光透過性が改善されることが期待される。
これらは1種のみを用いてもよく、2種以上を用いてもよい。
本発明の熱可塑性エラストマー組成物におけるプロピレン系ランダム共重合体とスチレン系エラストマーの合計の含有率は、低温耐衝撃性、高温強度および光透過性に優れる効果の観点から、熱可塑性エラストマー組成物100質量%に対し、通常40質量%を超え、50質量%以上であることが好ましく、70質量%以上であることがより好ましく、75質量%以上であることが更に好ましく、80質量%以上であることが特に好ましく、85質量%以上であることがとりわけ好ましい。その上限は100質量%である。
本発明の熱可塑性エラストマー組成物には、上記のプロピレン系ランダム共重合体、スチレン系エラストマー、エチレン・α-オレフィン共重合体、結晶核剤以外に本発明の効果を著しく損なわない範囲内で、各種目的に応じて以下の添加剤、無機フィラー、有機フィラーや、プロピレン系ランダム共重合体、スチレン系エラストマー、およびエチレン・α-オレフィン共重合体以外の樹脂(以下、「その他の樹脂」と称する。)等の任意成分を配合することができる。
本発明の熱可塑性エラストマー組成物は、上記プロピレン系ランダム共重合体、およびスチレン系エラストマーと、必要に応じて用いられる、エチレン・α-オレフィン共重合体、その他の成分を通常の押出機やバンバリーミキサー、ロール、ブラベンダープラストグラフ、ニーダーブラベンダー等を用いて常法に従って混練して製造することができる。これらの製造方法の中でも、押出機、特に二軸押出機を用いることが好ましい。
本発明の熱可塑性エラストマーは、前記プロピレン系ランダム共重合体とスチレン系エラストマー、必要に応じてエチレン・α-オレフィン共重合体、更には結晶核剤を含むことにより、高温強度、低温耐衝撃性および光透過性に優れるものである。
このような用途において、本発明の熱可塑性エラストマー組成物は、以下のような物性を有することが好ましい。
本発明において、ISO180による-35℃、-40℃および-45℃におけるアイゾット衝撃強度を低温耐衝撃性の指標とする。本発明の熱可塑性エラストマー組成物の成形体のアイゾット衝撃強度は、50kJ/m2以上であることが好ましく、70kJ/m2以上であることがより好ましい。本発明の熱可塑性エラストマー組成物のアイゾット衝撃強度の上限は特に制限されないが、通常150kJ/m2以下である。
本発明において、JIS K7210(1999年)に準拠した温度230℃、測定荷重21.18Nでのメルトフローレート(MFR)を熱可塑性エラストマー組成物の射出成形性の指標とする。本発明の熱可塑性エラストマー組成物は、射出成形性に優れたものとするため、このメルトフローレートが1.0g/10分以上50g/10分以下であることが好ましい。エアバッグ用熱可塑性エラストマー組成物のMFRが1.0g/10分以上であると流動性が良好となる傾向にあり、また、50g/10分以下であると成形時のバリ等を抑えやすいために好ましい。流動性の観点からは、エアバッグ用熱可塑性エラストマー組成物のMFRはより好ましくは2.0g/10分以上であり、更に好ましくは2.5g/10分以上である。一方、射出成形時にバリ等を抑える観点からは、熱可塑性エラストマー組成物のMFRはより好ましくは40g/10分以下、更に好ましくは20g/10分以下、特に好ましくは17g/10分以下、とりわけ好ましくは15g/10分以下である。
本発明の熱可塑性エラストマー組成物は、材料強度の観点から、JIS K6251に準拠した23℃での引張破壊伸びが300%以上であることが好ましく、350%以上であることがより好ましい。23℃での引張破壊伸びが、上記下限以上であれば、材料伸びがよいために本発明の熱可塑性エラストマー組成物よりなるエアバッグ収納カバーの展開性が良好となる傾向がある。本発明の熱可塑性エラストマー組成物の引張破断伸びの上限は特に制限されないが、通常1500%以下である。
同様の観点から、この引張破壊伸びの測定時に測定される引張破壊強度は10MPa以上であることが好ましく、12MPa以上であることがより好ましい。23℃での引張破壊強度が上記下限以上であれば、材料強度が高いために本発明の熱可塑性エラストマー組成物よりなるエアバッグ収納カバーの展開性が良好となる傾向がある。本発明の熱可塑性エラストマー組成物の引張破壊強度の上限は特に限定されないが、通常25MPaである。
本発明の熱可塑性エラストマー組成物は、材料強度の観点から、JIS K6251に準拠した85℃での引張破壊強度が4.5MPa以上であることが好ましく、5.0MPa以上であることがより好ましく、5.5MPa以上であることがさらに好ましい。85℃での引張破壊強度が、上記下限以上であれば、材料強度が高いために本発明の熱可塑性エラストマー組成物よりなるエアバッグ収納カバーの展開性が良好となる傾向がある。本発明の熱可塑性エラストマー組成物の引張破壊強度の上限は特に制限されないが、通常8MPa以下である。
本発明の熱可塑性エラストマー組成物は、JIS K7203に準拠して測定した曲げ弾性率が600MPa以下、特に200MPa以上550MPa以下であることが好ましい。熱可塑性エラストマー組成物の曲げ弾性率が上記上限以下であれば、低温耐衝撃性が良好となる傾向にあり、上記下限以上であれば、剛性に優れる傾向がある。
本発明の熱可塑性エラストマー組成物は、光透過性の観点から、前記熱可塑性エラストマー組成物を、樹脂温度200℃、金型温度40℃の条件で射出成形した厚み2mmのシート状試験片をJIS K7136-1に基づいて測定した全光線透過率が60%以上であることが好ましく、65%以上であることがより好ましく、70%以上であることが更に好ましく、75%以上であることが特に好ましい。このような数値範囲とすることで、エアバッグ収納カバーとして用いた場合に、光透過性が良好でありスイッチの点灯を視認しやすくなる。
本発明の熱可塑性エラストマー組成物は、透明性の観点から、前記熱可塑性エラストマー組成物を、樹脂温度200℃、金型温度40℃の条件で射出成形した厚み2mmのシート状試験片をJIS K7136-1に基づいて測定したヘーズが70%以下であることが好ましく、60%以下であることがより好ましく、50%以下であることが更に好ましく、40%以下であることが特に好ましい。スイッチの視認性の観点から前述の全光線透過率が良好であることが必須であるが、透明性の評価指標であるヘーズが上記数値範囲を満たすことで、エアバッグ収納カバーとして用いた場合に、スイッチの点灯をよりクリアに視認しやすくなる。
本発明の熱可塑性エラストマー組成物を用いて、一般に、通常の射出成形法、又は、必要に応じて、ガスインジェクション成形法、射出圧縮成形法、ショートショット発泡成形法等の各種成形法を用いてエアバッグ収納カバー等の成形体とすることができる。特に、本発明の熱可塑性エラストマー組成物を射出成形することによりエアバッグ収納カバー等の成形体とすることが好ましい。射出成形を行う際の成形条件は以下の通りである。
プロピレン系ランダム共重合体と、-65℃以上-45℃以下の範囲にガラス転移温度を有するスチレン系エラストマーとを含有する熱可塑性エラストマー組成物からなる第一の層と、樹脂フィルムからなる第二の層とを有する本発明の複合成形体は、エアバッグ収納カバーとして好適である。
即ち、本発明の熱可塑性エラストマー組成物は樹脂フィルムと一体となって複合成形体とすることもでき、本発明の熱可塑性エラストマー組成物を含む第一の層と、樹脂フィルムからなる第二の層とを有する本発明の複合成形体がエアバッグ収納カバーとして好適である。
本発明の熱可塑性エラストマー組成物は高温強度、低温耐衝撃性および光透過性に優れ、エアバッグ収納カバーの成形材料として好適に用いられる。特に、このエアバッグ収納カバーの中でも、例えば、自動車等の高速移動体が衝突事故等の際に、その衝撃や変形を感知することにより作動し、膨張展開によって乗員を保護するエアバッグシステムのエアバッグ収納カバーとして好適である。
とりわけ、その優れた光透過性により、本発明のエアバッグ収納カバーは、タッチパネル式ディスプレイ等視認可能な位置に配置されるエアバッグ収納カバーとして好適である。
前述の<1>~<11>のエアバッグ用熱可塑性エラストマー組成物において、成分(A)のプロピレン系重合体の一例として、前述の本発明の熱可塑性エラストマー組成物に含まれるプロピレン系ランダム共重合体が挙げられる。プロピレン系ランダム共重合体以外のプロピレン系重合体としては、プロピレンの単独重合体、プロピレン単位に加え、エチレン単位、プロピレン以外のα-オレフィン単位、エチレンおよびα-オレフィン以外の単量体単位等を好ましくは15質量%以下、より好ましくは10質量%以下、更に好ましくは6質量%以下含有するプロピレン系ブロック共重合体が挙げられる。プロピレン系ブロック重合体に含まれるα-オレフィン単位、その好適例は、前述のプロピレン系ランダム共重合体のα-オレフィン単位におけると同様である。
プロピレン系ランダム共重合体以外のプロピレン系重合体としては、プロピレン単独重合体、プロピレン・エチレンブロック共重合体、プロピレン・1-ブテンブロック共重合体、プロピレン・1-ヘキセンブロック共重合体、プロピレン・1-オクテンブロック共重合体、プロピレン・エチレン・1-ブテンブロック共重合体、プロピレン・エチレン・1-ヘキセンブロック共重合体、プロピレン・エチレン・1-オクテンブロック共重合体、第1工程でプロピレン単独重合体を重合し、続いて第2工程でプロピレン・エチレン共重合体を重合して得られるプロピレン系ブロック共重合体等を例示することができる。好ましくは、プロピレン単独重合体、エチレンおよび炭素数4以上10以下のα-オレフィンから選ばれる少なくとも1種の単量体とプロピレンとのブロック共重合体、第1工程でプロピレン単独重合体を重合し、続いて第2工程でプロピレン・エチレン共重合体を重合して得られるプロピレン系ブロック共重合体である。
成分(A)のプロピレン系重合体の物性、その他については、前述のプロピレン系ランダム共重合体におけると同様である。
<1>~<11>のエアバッグ用熱可塑性エラストマー組成物における成分(B)のスチレン系エラストマー及びその他の詳細な説明については、本発明の熱可塑性エラストマー組成物におけるスチレン系エラストマー及びその他の説明が適用される。
[プロピレン系ランダム共重合体]
(A-1):日本ポリプロ社製 ノバテック(登録商標)PP MG03E
プロピレン・エチレンランダム共重合体
MFR(JIS K7210(1999年)):30g/10分(測定条件:230℃、荷重21.18N(2.16kgf))
プロピレン単位含有率:96質量%
(b-1):クレイトンポリマー社製 Kraton(登録商標)G1652
スチレン・ブタジエンブロック共重合体の水素添加物(スチレン・エチレン・ブチレン・スチレン共重合体(SEBS))
質量平均分子量(Mw):70,000
スチレン単位含有率:30質量%
ガラス転移温度:-55℃
(b-2):クレイトンポリマー社製 Kraton(登録商標)G1657
スチレン・ブタジエンブロック共重合体の水素添加物(スチレン・エチレン・ブチレン・スチレン共重合体(SEBS))
質量平均分子量(Mw):110,000
スチレン単位含有率:13質量%
ガラス転移温度:-55℃
(b-3):クレイトンポリマー社製 Kraton(登録商標)G1654
スチレン・ブタジエンブロック共重合体の水素添加物(スチレン・エチレン・ブチレン・スチレン共重合体(SEBS))
質量平均分子量(Mw):180,000
スチレン単位含有率:31質量%
ガラス転移温度:-55℃
(b-4):クレイトンポリマー社製 Kraton(登録商標)G1651
スチレン・ブタジエンブロック共重合体の水素添加物(スチレン・エチレン・ブチレン・スチレン共重合体(SEBS))
質量平均分子量(Mw):260,000
スチレン単位含有率:33質量%
ガラス転移温度:-55℃
(b’-1):クレイトンポリマー社製 Kraton(登録商標)G1643
スチレン・ブタジエンブロック共重合体の水素添加物(スチレン・エチレン・ブチレン・スチレン共重合体(SEBS))
質量平均分子量(Mw):60,000
スチレン単位含有率:20質量%
ガラス転移温度:-35℃
(C-1):ダウケミカル社製 Engage(登録商標)8100
エチレン・オクテン共重合体
MFR(ASTM D1238):1g/10分(測定条件190℃、荷重21.18N(2.16kgf))
密度(ISO 1183-A法):0.87g/cm3(測定温度:23℃)
(C-2):ダウケミカル社製 Engage(登録商標)8150
エチレン・オクテン共重合体
MFR(ASTM D1238):0.5g/10分(測定条件190℃、荷重21.18N(2.16kgf))
密度(ISO 1183-A法):0.87g/cm3(測定温度:23℃)
(D-1):新日本理化社製 ゲルオール(登録商標)MD
1,3:2,4-ビス-O-(4-メチルベンジリデン)-D-ソルビトール
融点:255-267℃
(E-1):三菱ケミカル社製 アクリペット(登録商標)VH
PMMA(ポリメチルメタクリレート)
MFR(JIS K7210(1999年)):2.0g/10分(測定温度230℃、測定荷重37.3N)
荷重たわみ温度(ISO 75-2):100℃(測定荷重1.8MPa)
1)射出成形性:メルトフローレート(MFR)
JIS K7210(1999年)に従って、温度230℃、荷重21.18Nの条件で測定した。
上記射出成形により、ノッチの付いた厚さ10mm×幅4mm×長さ80mmのアイゾット衝撃強度測定用試験片に成形し、ISO180(2010年)に従って、温度-35℃、-40℃、-45℃で測定した。また、アイゾット衝撃試験で非破壊のものを「P」、破壊寸前で皮一枚残っているものを「H」、破壊されたものを「C」とした。アイゾット衝撃強度の値が大きいものほど、また、非破壊「P」のものほど低温耐衝撃性に優れるものと評価した。
JIS K7203に従って、スパン間64mm、曲げ速度1mm/分の条件下で測定した。
JIS K6251に準拠(JIS-3号ダンベル)して引張試験用の試験片(厚さ2mm×幅120mm×長さ80mmのシート)を打ち抜いた。この打ち抜き試験片について、JIS K6251に従って、引張破壊伸びと引張破壊強度を23℃の雰囲気下にて測定した。引張破壊伸びおよび引張破壊強度の値が大きいほど優れるものと評価した。
JIS K6251に準拠(JIS-3号ダンベル)して引張試験用の試験片(厚さ2mm×幅120mm×長さ80mmのシート)を打ち抜いた。この打ち抜き試験片について、JIS K6251に従って、引張破壊強度を85℃の雰囲気下にて測定した。引張破壊強度の値が大きいほど優れるものと評価した。
後掲の表-1において、85℃の引張破壊強度の数値に「>」を付けて示したものは、その測定強度において機器の上限に達したため破断しなかったことを示す。数字は、機器の上限に達したときの応力を意味し、本評価では、この応力は破断応力と同様とみなすことができる。
厚さ2mm×幅120mm×長さ80mmの射出成形シートについて、JIS K7136-1に従ってヘーズを測定した。ヘーズの値が小さいものほど透明性に優れるものと評価した。
厚さ2mm×幅120mm×長さ80mmの射出成形シートについて、JIS K7136-1に従って全光線透過率を測定した。全光線透過率の値が大きいものほど光透過性に優れるものと評価した。
[実施例1]
表-1に示すように、(A-1)100質量部、(b-1)100質量部、(A-1)と(b-1)の合計100質量部に対して、酸化防止剤(BASFジャパン社製 商品名イルガスタブ(登録商標)FS301FF)0.15質量部、光安定剤(HALS(SONGWON社製 SABOSTAB(登録商標)UV119)0.2質量部、紫外線吸収剤(BASFジャパン社製 チヌビン(登録商標)326)0.1質量部、シリコーンオイル(信越化学工業社製 KF96-100CS)0.2質量部をヘンシェルミキサーにて1分間ブレンドした。同方向二軸押出機(東芝機械社製「TEM-26SS」、L/D=48.5、シリンダブロック数:12)へ25kg/hの速度で前記ブレンド物を投入し、160℃以上210℃以下の範囲で昇温させ溶融混練を行い、熱可塑性エラストマー組成物のペレットを製造した。
得られた熱可塑性エラストマー組成物のペレットについて、前記1)~7)の評価を行った。それらの評価結果を表-1に示す。
具体的には、日本ポリプロ社製 ノバテック(登録商標)PP MG03Eを厚み0.5mmにプレスしたフィルムを100mm四方にカットし、これを100mm×100mm×3mmの金型にセットし、上記ペレットを射出成形した。
この手法で熱可塑性エラストマー組成物からなる第一の層とポリプロピレンフィルムからなる第二の層とが融着一体化した複合成形体を得ることができた。
表-1,2に示す配合にした以外は実施例1と同様にして熱可塑性エラストマー組成物のペレットを得た。実施例1と同様に、プロピレン系ランダム共重合体と、スチレン系エラストマー又は他のスチレン系エラストマーと、必要に応じて用いられるエチレン・α-オレフィン共重合体との合計100質量部に対し、酸化防止剤(BASFジャパン社製 商品名イルガスタブ(登録商標)FS301FF)0.15質量部、光安定剤(HALS(SONGWON社製 SABOSTAB(登録商標)UV119)0.2質量部、紫外線吸収剤(BASFジャパン社製 チヌビン(登録商標)326)0.1質量部、シリコーンオイル(信越化学工業社製 KF96-100CS)0.2質量部をそれぞれ配合した。これらの配合量については表-1,2において記載を省略した。
得られた熱可塑性エラストマー組成物のペレットについて、前記1)~7)の評価を行った。それらの評価結果を表-1,2に示す。
実施例1~8は、高温強度、低温耐衝撃性および光透過性のいずれも良好であった。
比較例1は、ガラス転移温度が-45℃を超えるスチレン・ブタジエンブロック共重合体の水素添加物である(b’-1)を配合した例であるが、低温耐衝撃性に著しく劣る結果となった。
比較例2は、特許文献6の実施例2相当を配合した例であるが、高温強度に劣る結果となった。
比較例3は、プロピレン系ランダム共重合体とスチレン系エラストマーの合計の含有率を37.5質量%となるように配合した例であるが、高温強度に劣る結果となった。
本出願は、2021年6月30日付で出願された日本特許出願2021-108344と、2021年12月21日付で出願された日本特許出願2021-207288に基づいており、その全体が引用により援用される。
Claims (20)
- プロピレン系ランダム共重合体と、-65℃以上-45℃以下の範囲にガラス転移温度を有するスチレン系エラストマーとを含有する熱可塑性エラストマー組成物であって、該熱可塑性エラストマー組成物100質量%における、前記プロピレン系ランダム共重合体と前記スチレン系エラストマーの合計の含有率が40質量%を超え100質量%以下である熱可塑性エラストマー組成物よりなるエアバッグ収納カバー。
- 視認可能な位置に配される、請求項1に記載のエアバッグ収納カバー。
- 前記スチレン系エラストマーが直鎖状である、請求項1又は2に記載のエアバッグ収納カバー。
- 前記熱可塑性エラストマー組成物のJIS K7210(1999年)に準拠した温度230℃、測定荷重21.18Nでのメルトフローレートが1.0g/10分以上50g/10分以下である、請求項3に記載のエアバッグ収納カバー。
- 前記熱可塑性エラストマー組成物における前記プロピレン系ランダム共重合体100質量部に対する前記スチレン系エラストマーの含有量が45質量部以上250質量部以下である、請求項4に記載のエアバッグ収納カバー。
- 前記熱可塑性エラストマー組成物が、前記プロピレン系ランダム共重合体100質量部に対して、更にエチレン・α-オレフィン共重合体を10質量部以上100質量部以下含む、請求項1又は2に記載のエアバッグ収納カバー。
- 前記スチレン系エラストマーのスチレン単位含有率が20質量%以上25質量%以下である、請求項1又は2に記載のエアバッグ収納カバー。
- 前記スチレン系エラストマーが、スチレン単位含有率が10質量%以上15質量%以下のスチレン・共役ジエンブロック共重合体の水素添加物(b1)と、スチレン単位含有率が25質量%以上35質量%以下のスチレン・共役ジエンブロック共重合体の水素添加物(b2)とからなる、請求項7に記載のエアバッグ収納カバー。
- 前記熱可塑性エラストマー組成物を、樹脂温度200℃、金型温度40℃の条件で射出成形した厚み2mmのシート状試験片をJIS K7136-1に基づいて測定した全光線透過率が65%以上である、請求項1又は2に記載のエアバッグ収納カバー。
- 前記熱可塑性エラストマー組成物を、樹脂温度200℃、金型温度40℃の条件で射出成形した厚み2mmのシート状試験片をJIS K7136-1に基づいて測定したヘーズが70%以下である、請求項1又は2に記載のエアバッグ収納カバー。
- 請求項1又は2に記載のエアバッグ収納カバーの製造方法であって、前記熱可塑性エラストマー組成物を射出成形する工程を有する、エアバッグ収納カバーの製造方法。
- プロピレン系ランダム共重合体と、スチレン単位含有率が20質量%以上35質量%以下であり、かつ、-65℃以上-45℃以下の範囲にガラス転移温度を有する直鎖状スチレン系エラストマーとを含有する熱可塑性エラストマー組成物であって、該熱可塑性エラストマー組成物100質量%における前記プロピレン系ランダム共重合体と前記直鎖状スチレン系エラストマーの合計の含有率が40質量%を超え100質量%以下であり、前記プロピレン系ランダム共重合体100質量部に対する前記直鎖状スチレン系エラストマーの含有量が45質量部以上250質量部以下であり、JIS K7210(1999年)に準拠した温度230℃、測定荷重21.18Nでのメルトフローレートが1.0g/10分以上50g/10分以下である、熱可塑性エラストマー組成物。
- 前記熱可塑性エラストマー組成物を、樹脂温度200℃、金型温度40℃の条件で射出成形した厚み2mmのシート状試験片をJIS K7136-1に基づいて測定した全光線透過率が65%以上である、請求項12に記載の熱可塑性エラストマー組成物。
- 前記熱可塑性エラストマー組成物を、樹脂温度200℃、金型温度40℃の条件で射出成形した厚み2mmのシート状試験片をJIS K7136-1に基づいて測定したヘーズが70%以下である、請求項12又は13に記載の熱可塑性エラストマー組成物。
- 前記プロピレン系ランダム共重合体100質量部に対して、更にエチレン・α-オレフィン共重合体を10質量部以上100質量部以下含む、請求項12又は13に記載の熱可塑性エラストマー組成物。
- 前記直鎖状スチレン系エラストマーのスチレン単位含有率が20質量%以上25質量%以下である、請求項12又は13に記載の熱可塑性エラストマー組成物。
- 前記直鎖状スチレン系エラストマーが、スチレン単位含有率が10質量%以上15質量%以下のスチレン・共役ジエンブロック共重合体の水素添加物(b1)と、スチレン単位含有率が25質量%以上35質量%以下のスチレン・共役ジエンブロック共重合体の水素添加物(b2)とからなる、請求項16に記載の熱可塑性エラストマー組成物。
- 請求項12又は13に記載の熱可塑性エラストマー組成物よりなる成形体。
- 請求項12又は13に記載の熱可塑性エラストマー組成物を含む第一の層と、樹脂フィルムからなる第二の層とを有する複合成形体。
- プロピレン系ランダム共重合体と、-65℃以上-45℃以下の範囲にガラス転移温度を有するスチレン系エラストマーとを含有する熱可塑性エラストマー組成物からなる第一の層と、樹脂フィルムからなる第二の層とを有する複合成形体。
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JP (1) | JPWO2023276883A1 (ja) |
KR (1) | KR20240028359A (ja) |
WO (1) | WO2023276883A1 (ja) |
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WO2024135737A1 (ja) * | 2022-12-21 | 2024-06-27 | Mcppイノベーション合同会社 | エアバッグ収納カバー及びエアバッグ収納カバー用熱可塑性エラストマー組成物 |
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JP2019127530A (ja) * | 2018-01-24 | 2019-08-01 | Mcppイノベーション合同会社 | エアバッグ収納カバー用熱可塑性エラストマー組成物及びエアバッグ収納カバー |
JP2020158615A (ja) * | 2019-03-26 | 2020-10-01 | Mcppイノベーション合同会社 | 熱可塑性エラストマー組成物、成形体及びエアバッグ収納カバー |
JP2021108344A (ja) | 2019-12-27 | 2021-07-29 | 日亜化学工業株式会社 | 半導体素子の製造方法 |
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2022
- 2022-06-24 WO PCT/JP2022/025321 patent/WO2023276883A1/ja active Application Filing
- 2022-06-24 EP EP22833030.4A patent/EP4365036A4/en active Pending
- 2022-06-24 JP JP2023531901A patent/JPWO2023276883A1/ja active Pending
- 2022-06-24 KR KR1020237045072A patent/KR20240028359A/ko unknown
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2023
- 2023-12-22 US US18/395,443 patent/US20240123938A1/en active Pending
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JPS436636B1 (ja) | 1963-04-25 | 1968-03-12 | ||
JPS428704B1 (ja) | 1963-12-26 | 1967-04-20 | ||
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JP2014077128A (ja) * | 2012-09-19 | 2014-05-01 | Mitsubishi Chemicals Corp | エアバッグ収納カバー |
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JP2019127530A (ja) * | 2018-01-24 | 2019-08-01 | Mcppイノベーション合同会社 | エアバッグ収納カバー用熱可塑性エラストマー組成物及びエアバッグ収納カバー |
JP2020158615A (ja) * | 2019-03-26 | 2020-10-01 | Mcppイノベーション合同会社 | 熱可塑性エラストマー組成物、成形体及びエアバッグ収納カバー |
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JPWO2023276883A1 (ja) | 2023-01-05 |
EP4365036A4 (en) | 2024-10-09 |
KR20240028359A (ko) | 2024-03-05 |
US20240123938A1 (en) | 2024-04-18 |
EP4365036A1 (en) | 2024-05-08 |
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