WO2021153183A1 - 熱可塑性エラストマー組成物及びそれよりなる成形体 - Google Patents
熱可塑性エラストマー組成物及びそれよりなる成形体 Download PDFInfo
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- WO2021153183A1 WO2021153183A1 PCT/JP2021/000338 JP2021000338W WO2021153183A1 WO 2021153183 A1 WO2021153183 A1 WO 2021153183A1 JP 2021000338 W JP2021000338 W JP 2021000338W WO 2021153183 A1 WO2021153183 A1 WO 2021153183A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
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- 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
- C08L53/02—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 of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Definitions
- the present invention relates to a thermoplastic elastomer composition and a molded product made of the thermoplastic elastomer composition.
- thermoplastic elastomer is softened by heating and has fluidity, and when cooled, it has rubber elasticity.
- the thermoplastic elastomer has the same formability as the thermoplastic resin, has unique rubber elasticity, and is recyclable. For this reason, thermoplastic elastomers are widely used in automobile parts such as the skin of automobile interior materials, building parts, medical parts, electric wire covering materials, and miscellaneous goods.
- Patent Document 1 describes, as an injection molding thermoplastic elastomer composition, at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound.
- a so-called styrene-based elastomer containing a block copolymer composed of the above, a hydrogenated block copolymer obtained by hydrogenating the block copolymer, and a propylene-based block copolymer is disclosed.
- Patent Document 1 describes that this styrene-based elastomer can be used as an automobile interior material.
- thermoplastic elastomer composition a silicone oil having a viscosity (JIS Z8803, 25 ° C.) of 100,000 centistokes (cSt) or more is used for a styrene-based or olefin-based rubber to increase the mechanical strength. It is described that low temperature impact resistance and surface scratch resistance can be improved while maintaining the temperature.
- thermoplastic resin depends on the transparency of the resin, and the higher the transparency, the better the decorativeness.
- An object of the present invention is to provide a thermoplastic elastomer composition capable of obtaining a molded product having excellent tactile sensation and transparency, and a molded product made of the same.
- the present inventor has at least two polymerization blocks P mainly composed of a propylene-based polymer and an aromatic vinyl compound unit, and at least one polymer block Q mainly composed of a conjugated diene compound unit. It has been found that by blending a specific organopolysiloxane into a thermoplastic elastomer composition containing a copolymer and / or a hydrogenated product thereof, a molded product having excellent tactile sensation and transparency can be provided.
- the gist of the present invention is the following [1] to [5].
- thermoplastic elastomer composition containing the following components (A) to (C).
- Component (A) Propylene-based polymer
- Component (B) Having at least two polymerization blocks P mainly composed of aromatic vinyl compound units, and at least one polymer block Q mainly composed of conjugated diene compound units.
- Block copolymer and / or its hydrogenated component (C) aryl group-containing organopolysiloxane
- thermoplastic elastomer composition according to [1], wherein the component (C) is an organopolysiloxane containing an aralkyl group.
- R 1 in the formula (1) represents a hydrocarbon group having 1 to 18 carbon atoms.
- R 2 represents an aralkyl group having 7 to 12 carbon atoms.
- thermoplastic elastomer composition A molded product using the thermoplastic elastomer composition according to any one of [1] to [4].
- the gist of the present invention is also the following ⁇ 1> to ⁇ 7>.
- thermoplastic elastomer composition containing the following components (A) to (C).
- Component (A) Propylene-based polymer
- Component (B) Having at least two polymerization blocks P mainly composed of aromatic vinyl compound units, and at least one polymer block Q mainly composed of conjugated diene compound units.
- Component (C) Aralkyl group-containing organopolysiloxane having a repeating unit represented by the following formula (1) in the molecule.
- R 1 in the formula (1) represents a hydrocarbon group having 1 to 18 carbon atoms.
- R 2 represents an aralkyl group having 7 to 12 carbon atoms.
- the component (C) is an elastomer group-containing organopolysiloxane having a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (2) in the molecule, ⁇ 1.
- the thermoplastic elastomer composition is an elastomer group-containing organopolysiloxane having a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (2) in the molecule, ⁇ 1.
- the thermoplastic elastomer composition is an elastomer group-containing organopolysiloxane having a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (2) in the molecule, ⁇ 1.
- the thermoplastic elastomer composition is an elastomer group-containing organopolysiloxane having a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (2) in the molecule, ⁇ 1.
- the thermoplastic elastomer composition
- R 3 and R 4 in the formula (2) independently represent an organic group having 1 to 18 carbon atoms.
- thermoplastic elastomer composition according to ⁇ 1> or ⁇ 2>, wherein R 1 is a methyl group.
- thermoplastic elastomer composition according to ⁇ 3> wherein R 3 and R 4 are independently alkyl groups having 1 to 3 carbon atoms.
- thermoplastic elastomer composition according to ⁇ 4> wherein R 3 and R 4 are methyl groups.
- thermoplastic elastomer composition according to any one of ⁇ 1> to ⁇ 5>, wherein the aromatic vinyl compound unit of the component (B) is a styrene unit and the conjugated diene compound unit is a butadiene unit. ..
- thermoplastic elastomer composition according to any one of ⁇ 1> to ⁇ 6>.
- thermoplastic elastomer composition capable of obtaining a molded product having excellent tactile sensation and transparency, and a molded product made of the same.
- thermoplastic Elastomer composition The thermoplastic elastomer composition of the present invention is characterized by containing the following components (A) to (C), and may further contain the following components (D).
- D Hydrocarbon-based rubber softener
- thermoplastic elastomer composition of the present invention has the effect of being able to obtain a molded product having excellent tactile sensation and transparency.
- thermoplastic elastomer composition of the present invention exerts such an effect are not clear, but it is presumed as follows.
- thermoplastic elastomer composition containing a propylene-based polymer of component (A) and a (hydrogenated) block copolymer of component (B) has a structure of a component (from a microscopic point of view). It forms a so-called sea-island structure in which a plurality of islands of component (B) exist in the sea of A). The presence of the component (C) in the sea-island structure of the component (A) and the component (B) tends to make the component (B) more easily dispersed in the sea of the component (A). .. As a result, the amount of the dispersion of the component (B) whose dispersion diameter is smaller than the wavelength of visible light increases, and it is presumed that the transparency of the elastomer composition of the present invention is improved.
- the aryl group contained in the component (C) interacts with the aromatic group of the aromatic vinyl compound unit contained in the component (B), so that the component (C) is unevenly distributed around the component (B). It will be easier. Therefore, the component (C) tends to be present in large quantities at the interface between the component (A) and the component (B). As a result, it is presumed that the scattering of light at the interface between the component (A) and the component (B) is suppressed and the transparency is improved.
- the propylene-based polymer of the component (A) used in the present invention (hereinafter, may be referred to as “propylene-based polymer (A)”) is contained in the monomer unit constituting the propylene-based polymer (A). Any propylene unit may be contained as long as it contains 50% by mass or more. From the viewpoint of heat resistance, rigidity, crystallinity, chemical resistance, etc., the content of the propylene unit in the propylene-based polymer (A) is preferably 60% by mass or more, more preferably 75% by mass or more, and further. It is preferably 90% by mass or more. The upper limit of the content of the propylene unit is not particularly limited, and may be 100% by mass.
- the content of the propylene unit in the component (A) and each constituent unit of the other copolymerization components described below can be determined by infrared spectroscopy.
- the type of the propylene-based polymer (A) is not particularly limited, and specifically, a propylene homopolymer or a propylene / ethylene copolymer (for example, a propylene / ethylene random copolymer or a propylene / ethylene block copolymer) can be used. Can be mentioned. Any of these propylene-based polymers (A) can be used.
- the melt flow rate (JIS K7210, 230 ° C., 21.2 N load) of the propylene-based polymer (A) is not particularly specified, but is usually 0.05 to 200 g / 10 minutes and 0.05 to 100 g / g. It is preferably 10 minutes, more preferably 0.1 to 80 g / 10 minutes.
- the catalyst used in producing the propylene-based polymer (A) is not particularly limited, but for example, a polymerization method using a stereoregular catalyst is preferable.
- the stereoregular catalyst include, but are not limited to, a Ziegler catalyst and a metallocene catalyst. Among these catalysts, a metallocene catalyst is preferable.
- the transition metal catalyst is not limited to the following, but for example, a titanium halide compound such as titanium trichloride, titanium tetrachloride, or trichloroethoxytitanium, or contact between the titanium halide compound and a magnesium compound typified by magnesium halide.
- a titanium halide compound such as titanium trichloride, titanium tetrachloride, or trichloroethoxytitanium
- a magnesium compound typified by magnesium halide.
- Two-component catalysts of transition metal components such as substances and organometallic components such as alkylaluminum compounds or their halides, hydrides, and alkoxides; further, those components include nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc.
- a three-component catalyst to which an electron-donating compound containing is added;
- the metallocene catalyst is not limited to the following, but for example, a transition metal compound of Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton and a stable ion by reacting with the metallocene compound. It is a catalyst composed of a co-catalyst that can be activated into a state and, if necessary, an organic aluminum compound, and any known catalyst can be used.
- the metallocene compound is preferably a crosslinked metallocene compound capable of stereoregular polymerization of propylene, and more preferably a crosslinked metallocene compound capable of isoregular polymerization of propylene.
- Examples of the method for producing the propylene-based polymer (A) include a slurry method using an inert solvent, a solution method, a vapor phase method using substantially no solvent, and a polymerized monomer as a solvent in the presence of the catalyst. Bulk polymerization method may be mentioned.
- the slurry method it can be carried out in an inert hydrocarbon or liquid monomer such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene and xylene.
- the polymerization temperature is usually ⁇ 80 to 150 ° C., preferably 40 to 120 ° C.
- the polymerization pressure is preferably 1 to 60 atm.
- the molecular weight of the obtained propylene-based polymer (A) can be adjusted with hydrogen or another known molecular weight adjusting agent.
- the polymerization is carried out by a continuous reaction or a batch reaction, and the conditions may be the conditions usually used.
- the polymerization reaction may be carried out in one stage or in multiple stages.
- propylene-based polymer (A) a commercially available product can be used.
- examples of commercially available products include polypropylene block copolymers manufactured by SunAllomer Ltd., Novatec (registered trademark) PP manufactured by Japan Polypropylene Corporation, and Waymax (WAYMAX (registered trademark)).
- propylene-based polymer (A) Only one type of propylene-based polymer (A) may be used, or two or more types having different copolymerization compositions and physical properties may be used in combination.
- the component (B) used in the present invention is mainly composed of at least two polymerization blocks P (hereinafter, may be simply referred to as “block P”) mainly composed of an aromatic vinyl compound unit and a conjugated diene compound unit. It is a (hydrogenated) block copolymer having at least one of the polymer block Q (hereinafter, may be simply referred to as “block Q”).
- mainly means that the target monomer unit is contained in the target polymer block in an amount of 50 mol% or more.
- the aromatic vinyl compound constituting the block P is not particularly limited, and is, for example, styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-amino. Examples thereof include ethyl styrene and N, N-diethyl-p-aminoethyl styrene. Among these, styrene, ⁇ -methylstyrene, and p-methylstyrene are preferably used from the viewpoint of availability and productivity. More preferably, it is styrene.
- the block P may be composed of one type of aromatic vinyl compound unit, or may be composed of two or more types of aromatic vinyl compound units.
- the block P may contain a monomer unit other than the vinyl aromatic compound unit.
- the conjugated diene compound constituting block Q is a diolefin having a pair of conjugated double bonds.
- the conjugated diene compound is not limited to the following, and is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene. , 2-Methyl-1,3-pentadiene and 1,3-hexadiene.
- 1,3-butadiene and isoprene are preferably used from the viewpoint of productivity. More preferably, it is 1,3-butadiene.
- Block Q may be composed of one kind of conjugated diene compound unit, or may be composed of two or more kinds of conjugated diene compound units.
- the block Q may contain a monomer unit other than the conjugated diene compound unit.
- the block polymer having at least two blocks P and at least one block Q may be linear, branched, radial or the like.
- a block copolymer represented by the following formula (I) or (II) is preferable.
- P represents block P.
- Q represents block Q.
- m represents an integer from 1 to 5.
- n represents an integer from 1 to 5.
- the component (B) is preferably a block copolymer represented by the formula (I), and the block copolymer weight represented by the formula (I) in which m is 3 or less.
- the coalescence is more preferable, the block copolymer represented by the formula (I) in which m is 2 or less is further preferable, and the block copolymer represented by the formula (I) in which m is 1 is particularly preferable.
- the component (B) may be a hydrogenated product of a block copolymer having a block P and a block Q.
- it is preferably a hydrogenated product of the block copolymer represented by the formula (I), and the hydrogenated product of the block copolymer represented by the formula (I) having m of 3 or less.
- the block copolymer is a hydrogenated product of the block copolymer represented by the formula (I) in which m is 2 or less, and the block copolymer represented by the formula (I) in which m is 1 is more preferable.
- Hydrogen additives are particularly preferred.
- the content ratio of the block P in the block copolymer of the component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more. It is particularly preferably 20% by mass or more.
- the content ratio of the block P in the block copolymer of the component (B) is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less. It is particularly preferably 40% by mass or less.
- the proportion of block Q in the block copolymer of component (B) is preferably large from the viewpoint of flexibility and bleed-out difficulty of the thermoplastic elastomer composition, and preferably small from the viewpoint of mechanical strength. ..
- the content ratio of the block Q in the block copolymer of the component (B) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more. It is particularly preferably 60% by mass or more.
- the content ratio of the block Q in the block copolymer of the component (B) is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. It is particularly preferably 80% by mass or less.
- the weight average molecular weight (Mw) of the (hydrogenated) block copolymer of component (B) is preferably 10,000 or more, more preferably 30,000 or more, and 800,000 or less. Is more preferable, 650,000 or less is more preferable, and 500,000 or less is further preferable. In the above range, the Mw of the (hydrogenated) block copolymer of the component (B) is preferably large in terms of heat resistance and mechanical strength, and preferably small in terms of molded appearance, fluidity, and moldability. .. By setting the Mw of the (hydrogenated) block copolymer of the component (B) in the above range, it is possible to obtain a thermoplastic elastomer composition having excellent heat resistance, mechanical strength, molded appearance, fluidity and moldability. can.
- Mw is a polystyrene-equivalent weight average molecular weight measured under the following conditions by gel permeation chromatography (hereinafter, may be abbreviated as “GPC”).
- GPC gel permeation chromatography
- the component (B) preferably includes a styrene / butadiene / styrene block copolymer and its hydrogenated product, and a styrene / isoprene / butadiene / styrene block copolymer and its hydrogenated product.
- ком ⁇ онент (B) a commercially available product can also be used.
- Specific examples of commercially available products include “Kraton (registered trademark) G” manufactured by Kraton Polymer Co., Ltd., “Septon (registered trademark)” manufactured by Kuraray Co., Ltd., “Tough Tech (registered trademark)” manufactured by Asahi Kasei Corporation, and “SO.
- Examples include “E (registered trademark)” and “TAIPOL (registered trademark)” manufactured by TSRC.
- component (B) As the (hydrogenated) block copolymer of component (B), only one type may be used, or two or more types may be used in combination.
- the aryl group of the aryl group-containing organopolysiloxane of the component (C) used in the present invention is an aryl group in a broad sense including a heteroaryl group, and is, for example, a phenyl group, a naphthyl group, a tolyl group, a xsilyl group, a pyridyl group, and a pyrimidinyl. Examples include a group and a thienyl group.
- the aryl group-containing organopolysiloxane may be any as long as it has an aryl group, and the aryl group may be contained in the aryl group-containing organopolysiloxane via a linking group such as an alkylene group.
- the group containing such an aryl group include an araquil group. That is, the aryl group-containing organopolysiloxane may be an aralkyl group-containing organopolysiloxane.
- the tactile sensation can be improved while maintaining the transparency of the thermoplastic elastomer composition of the present invention.
- an aryl group-containing organopolysiloxane having a repeating unit represented by the following formula (1A) in the molecule is more preferable.
- R 11 and R 12 are hydrocarbon groups having 1 to 20 carbon atoms which may independently have a hydrogen atom or a substituent. However , at least one of R 11 and R 12 may be an aryl group or a group containing an aryl group, and both R 11 and R 12 may be a group containing an aryl group or an aryl group.
- Preferred groups of R 11 include R 1 and R 2 in the formula (1) described later.
- preferred groups of R 12 include R 1 and R 2 in the formula (1) described later.
- the aryl group-containing organopolysiloxane is preferably an aralkyl group-containing organopolysiloxane because it is more excellent in maintaining transparency and improving the tactile sensation, and the aralkyl group-containing organopolysiloxane is contained in the molecule.
- An aralkyl group-containing organopolysiloxane having a repeating unit represented by the following formula (1) is more preferable.
- R 1 in the formula (1) represents a hydrocarbon group having 1 to 18 carbon atoms.
- R 2 represents an aralkyl group having 7 to 12 carbon atoms.
- R 1 is a hydrocarbon group having 1 to 18 carbon atoms, and an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group is used. Can be mentioned.
- R 1 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
- R 2 is an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a phenylalkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group and a 2-phenylpropyl group. From the viewpoint of maintaining transparency and improving tactile sensation, R 2 is preferably a 2-phenylpropyl group.
- the aralkyl group-containing organopolysiloxane of the component (C) is an aralkyl group-containing organopolysiloxane having a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (2) in the molecule. It is preferable to have.
- R 3 and R 4 in the formula (2) independently represent an organic group having 1 to 18 carbon atoms.
- examples of the organic group having 1 to 18 carbon atoms of R 3 and R 4 include an alkyl group, an aryl group, an alkenyl group, an alkoxy group and an epoxy group. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a phenyl group, a methoxy group and an ethoxy group. From the viewpoint of industrial availability, R 3 and R 4 are more preferably independent alkyl groups, more preferably alkyl groups having 1 to 3 carbon atoms, and particularly preferably methyl groups. ..
- the aryl group content of the aryl group-containing organopolysiloxane of the component (C) is preferably 1 to 60 mol%, more preferably 5 to 55 mol%, based on the total organic groups bonded to the silicon atom. It is preferably 5 to 50 mol%, more preferably 5 to 50 mol%. When the content of the aryl group is in the above range, it becomes easy to obtain a thermoplastic elastomer composition having excellent transparency.
- the content of the aralkyl group in the aralkyl group-containing organopolysiloxane of the component (C) is preferably 1 to 60 mol% and 5 to 55 mol% of all the organic groups bonded to the silicon atom. More preferably, it is more preferably 5 to 50 mol%.
- the content of the aralkyl group is in the above range, it becomes easy to obtain a thermoplastic elastomer composition having excellent transparency.
- the kinematic viscosity (25 ° C.) of the aryl group-containing organopolysiloxane of the component (C) used in the present invention is preferably 1 cSt or more, more preferably 5 cSt or more, still more preferably 10 cSt or more.
- the upper limit of the kinematic viscosity (25 ° C.) of the aryl group-containing organopolysiloxane is not particularly limited, but is preferably 1.5 million cSt or less, more preferably 1 million cSt or less, and further preferably 500,000 cSt or less. The higher the kinematic viscosity in the above range, the higher the effect of improving wear resistance.
- the lower the kinematic viscosity in the above range the better the transparency tends to be, and the stickiness improving effect is high, resulting in a good feel.
- desired wear resistance, transparency and stickiness improving effect can be obtained.
- component (C) a commercially available product can also be used.
- Specific examples of commercially available products include “KF-410” and “X22-1877” manufactured by Shin-Etsu Chemical Co., Ltd., “Wacker (registered trademark) TN” manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and “XIAMETER” manufactured by Dow Toray Co., Ltd. (Registered trademark) OFX-0203, 0230 “and” DOWNSIL (registered trademark) SH 510, 550, 710 ".
- aryl group-containing organopolysiloxane of the component (C) only one type may be used, or two or more types may be used in combination.
- thermoplastic elastomer composition of the present invention may contain a hydrocarbon softener for rubber as a component (D).
- a hydrocarbon softener for rubber is effective in improving the flexibility and fluidity of the thermoplastic elastomer composition of the present invention.
- hydrocarbon-based rubber softening agent a mineral oil-based softening agent or a synthetic resin-based softening agent is preferable, and a mineral oil-based softening agent is more preferable, because it has a high affinity for the component (B).
- Mineral oil-based softeners are generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons, and paraffinic hydrocarbons, and 50% or more of all carbon atoms are carbon atoms derived from paraffinic hydrocarbons.
- Paraffin oils those in which 30 to 45% of all carbon atoms are carbon atoms derived from naphthenic hydrocarbons are naphthenic oils, and those in which 35% or more of all carbon atoms are carbon atoms derived from aromatic hydrocarbons They are called aromatic oils.
- any one of the above-mentioned various softeners may be used alone, or two or more thereof may be used in combination.
- paraffin oil is preferable because it has a good hue.
- Examples of the synthetic resin softener include polybutene and low molecular weight polybutadiene.
- the kinematic viscosity at 40 ° C. measured by a method according to JIS K2283, which is a softening agent for hydrocarbon rubbers, is preferably 20 cSt or more, and more preferably 50 cSt or more.
- the kinematic viscosity is preferably 800 cSt or less, and more preferably 600 cSt or less.
- the kinematic viscosity of the hydrocarbon softener for rubber is preferably low in terms of improving the fluidity of the thermoplastic elastomer composition of the present invention, and higher in terms of the difficulty of fogging and the like. preferable.
- the content ratios of the component (A) and the component (B) are 1 to 99% by mass of the component (A) and 1 to 99% by mass of the component (B) with respect to a total of 100% by mass of these. It is preferably 99 to 1% by mass. More preferably, the component (A) is 5 to 95% by mass, the component (B) is 95 to 5% by mass, and more preferably, the component (A) is 10 to 90% by mass and the component (B) is 90 to 90 to 90% by mass. It is 10% by mass, and particularly preferably, the component (A) is 25 to 80% by mass and the component (B) is 75 to 20% by mass.
- the content of the component (C) is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total of the component (A) and the component (B). It is 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, particularly preferably 0.1 to 12 parts by mass, and even more preferably 0.5 to 12 parts by mass.
- the content of the component (D) is preferably 0 to 100 parts by mass, more preferably 0 to 100 parts by mass, per 100 parts by mass of the component (B). It is 90 parts by mass, more preferably 0 to 85 parts by mass, and particularly preferably 0 to 80 parts by mass.
- thermoplastic elastomer composition of the present invention contains the propylene-based polymer of the component (A) in the above range, so that the effect of blending the other components can be sufficiently obtained, and then the heat resistance and the machine of the component (A) are obtained. The effect of improving the target characteristics can be sufficiently obtained.
- thermoplastic elastomer composition of the present invention contains the (hydrogenated) block copolymer of the component (B) in the above range, so that the compounding effect of the other components can be sufficiently obtained, and then the component (B) is used. Sufficient heat resistance and oil resistance can be obtained.
- thermoplastic elastomer composition of the present invention sufficiently obtains the blending effect of other components and maintains transparency while maintaining transparency.
- the effect of improving the tactile sensation can be sufficiently obtained.
- thermoplastic elastomer composition of the present invention contains the hydrocarbon-based rubber softening agent of the component (D) in the above range, so that the compounding effect of the other components can be sufficiently obtained, and then the flexibility of the component (D) is obtained. The effect of improving the property and fluidity can be sufficiently obtained.
- thermoplastic elastomer composition of the present invention is, if necessary, other components other than the components (A) to (D) (in the present specification, simply "other components"", as long as the object of the present invention is not impaired. It may be referred to as).
- other components include resins and elastomers other than the components (A) and (B) (these may be collectively referred to as “other resins” in the present specification) and various additives.
- thermoplastic elastomer composition of the present invention examples include polyolefin resins (excluding those corresponding to the component (A)), polyester resins, polyamide resins, and styrene resins (however, the components).
- Resins such as (excluding those corresponding to (B)), acrylic resin, polycarbonate resin, polyphenylene ether, polyvinyl chloride resin; ethylene / propylene / copolymer rubber (EPM), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), ethylene / butene copolymer rubber (EBM), ethylene / propylene / butene copolymer rubber and other olefin-based elastomers; polyamide-polyamide copolymers and other polyamide-based elastomers; polyvinyl chloride-based elastomers and polybutadiene-based elastomers; Examples thereof include those hydrogenated products, those modified with acid anhydrides and the like to introduce polar functional groups; and those obtained by grafting, random and / or block copolymerizing other monomers.
- one type may be used alone, or two or more types may be used in combination.
- Additives that can be contained in the thermoplastic elastomer composition of the present invention include antioxidants, crystal nucleating agents, molding processing aids such as lubricants, ultraviolet absorbers, light stabilizers such as hindered amine compounds, and hydrolysis resistance improvement.
- Agents, pigments, colorants such as dyes, antistatic agents, conductive agents, reinforcing agents, fillers, plasticizers (excluding those corresponding to the above component (D)), mold release agents, foaming agents, etc. Can be mentioned.
- polysiloxane is a component that imparts abrasion resistance to the thermoplastic elastomer composition and prevents stickiness peculiar to the elastomer.
- the type of substituent bonded to the siloxane main chain in the molecular structure of polysiloxane is not particularly limited, but dimethylpolysiloxane (dimethylsilicone) is preferably used among them.
- the kinematic viscosity (25 ° C.) of the polysiloxane is preferably 1 cSt or more, more preferably 5 cSt or more, still more preferably 10 cSt or more, and the upper limit is not particularly limited.
- the kinematic viscosity is the kinematic viscosity at 25 ° C. measured using an Ubberode viscometer according to ASTM D445-46T (or JIS Z8803).
- the content thereof is preferably 0.1 to 15 parts by mass per 100 parts by mass of the total of the component (A) and the component (B). Yes, more preferably 0.1 to 10 parts by mass.
- this content is 0.1 part by mass or more, it is preferable from the viewpoint of improving the wear resistance and stickiness resistance, and when it is 15 parts by mass or less, it is preferable from the viewpoint of mechanical strength, mold contamination and the like.
- thermoplastic elastomer composition of the present invention as an antioxidant (heat stabilizer), a hydroxylamine-based antioxidant, a dithiocarbamate-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant, A phosphorus-based antioxidant or the like can be blended.
- an antioxidant heat stabilizer
- N, N-dialkylhydroxylamine is preferable, and compounds represented by the formula R a R b NOH (in the formula, Ra and R b each independently represent alkyl) can be mentioned. Be done.
- preferred Ra or R b is a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, or a heptadecyl group.
- Particularly preferred dialkylhydroxylamines are N, N-dioctadecylhydroxylamine, N, N-dihexadecylhydroxylamine, or mixtures thereof. Examples of the commercially available product include "Irganox (registered trademark) 1010" manufactured by BASF.
- dithiocarbamate-based antioxidant a metal salt of dialkyldithiocarbamic acid is preferable, nickel dialkyldithiocarbamate is preferable, and nickel dibutyldithiocarbamate is particularly preferable because it has a large effect of improving heat aging resistance.
- hindered phenolic antioxidants can be used, such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, which has a molecular weight of 500 or more. preferable.
- Sulfur-based antioxidants are compounds containing sulfur such as thioether-based, dithioate-based, mercaptobenzimidazole-based, thiocarbanilide-based, and thiodipropion ester-based compounds. However, it does not include those corresponding to the above-mentioned dithiocarbamate-based antioxidants. Among these, thiodipropion ester compounds are particularly preferable.
- phosphorus-based antioxidant examples include phosphorus-containing compounds such as phosphoric acid, phosphite, hypophosphoric acid derivative, phenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite.
- One type of antioxidant may be used alone, or two or more types may be used in combination.
- the content of the antioxidant is preferably 0.01 to 5 parts by mass per 100 parts by mass of the total of the component (A) and the component (B). Is.
- this content is 0.01 part by mass or more, it is preferable from the viewpoint of improving the heat resistance deterioration effect, and when it is 5 parts by mass or less, problems such as bleeding are unlikely to occur, and from the viewpoint of mechanical strength of the composition. Etc. are preferable.
- the hindered amine-based light stabilizer is a compound containing a hindered piperidine structure, and known ones can be used.
- Examples of commercially available hindered amine-based light stabilizers include the "Chinubin (registered trademark)" series manufactured by BASF.
- One type of hindered amine light stabilizer may be used alone, or two or more types may be used in combination.
- thermoplastic elastomer composition of the present invention contains a hindered amine-based light stabilizer
- the content thereof is preferably 0.005 to 2 parts by mass per 100 parts by mass of the total of the component (A) and the component (B). Yes, more preferably 0.01 to 0.5 parts by mass.
- this content is in the above range, the weather resistance is sufficient, and bleeding to the surface of the molded product is unlikely to occur, which is preferable.
- the total content of the additives such as the above-mentioned antioxidant in the thermoplastic elastomer composition of the present invention is preferably 2 parts by mass or less per 100 parts by mass of the total of the component (A) and the component (B). More preferably, it is by mass or less.
- thermoplastic elastomer composition The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited, and for example, the component (A), the component (B) and the component (C) are added as needed according to a conventional method. It can be produced by dry-blending the component (D) and other components and then melt-kneading.
- the mixing device used at that time is not particularly limited, and examples thereof include a kneading device such as a Banbury mixer, a lab plast mill, a single-screw extruder, and a twin-screw extruder.
- the melting temperature at the time of kneading can be appropriately set, but is usually in the range of 130 to 300 ° C, preferably in the range of 150 to 250 ° C.
- thermoplastic elastomer composition of the present invention is not particularly limited, but it is particularly useful as a molding material for automobile parts, building parts, medical parts, electric wire covering materials, miscellaneous goods, and the like.
- thermoplastic elastomer composition of the present invention By molding the thermoplastic elastomer composition of the present invention, it can be used as various molded products.
- various molding methods such as an ordinary injection molding method and an extrusion molding method can be used.
- Specific examples of the molded product of the present invention formed by molding the thermoplastic elastomer composition of the present invention include an injection molded product and an extrusion molded product.
- the molding conditions for injection molding the thermoplastic elastomer composition of the present invention are as follows.
- the molding temperature is usually 160 to 250 ° C, preferably 170 to 220 ° C.
- the injection pressure is usually 5 to 100 MPa, preferably 10 to 80 MPa.
- the mold temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C.
- thermoplastic elastomer composition of the present invention can also be used as a composite molded article by heat-sealing to an olefin-based hard resin such as a propylene resin.
- the molded body of the present invention is useful as automobile parts, building parts, medical parts, electric wire covering materials, miscellaneous goods, etc., but is typified by applications such as armrests and console pads because of its highly transparent appearance and tactile sensation. It is useful as a skin for automobile interior materials.
- thermoplastic elastomer composition the raw materials used for preparing the thermoplastic elastomer composition and the method for evaluating the obtained thermoplastic elastomer composition are as follows.
- B-1 TSRC "TAIPOL (registered trademark) 6159” Hydrogenated styrene-butadiene-styrene block copolymer Weight average molecular weight: 400,000 Styrene unit content: 30% by mass
- B-2 "SOE-SS (registered trademark) S1605" manufactured by Asahi Kasei Corporation Hydrogenated styrene-butadiene-styrene block copolymer Weight average molecular weight: 200,000 Styrene unit content: 60% by mass
- X-1 "BY27-001” manufactured by Toray Dow Corning Dimethylpolysiloxane Masterbatch Dimethylpolysiloxane content: 50% by mass
- X-2 "KF96-1000cs” manufactured by Shin-Etsu Chemical Co., Ltd.
- Thermoplastic Elastomer Composition ⁇ Tactile sensation>
- the injection molded product 350 mm ⁇ 100 mm ⁇ 2 mm
- the tactile sensation of the injection-molded article is preferably one in which no bleeding material is generated on the surface and does not adhere to the hand, and more preferably a free-flowing tactile sensation.
- Examples 1 to 4 Comparative Examples 1 to 8
- the raw materials were mixed according to the formulations shown in Table 1, and the obtained mixture was melt-kneaded (cylinder temperature 180 ° C. to 200 ° C.) by a twin-screw kneader to produce pellets of a thermoplastic elastomer composition.
- the obtained thermoplastic elastomer composition was subjected to a mold clamping force of 180 tons by an electric injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C., 350 mm in length ⁇ 100 mm in width.
- Comparative Examples 1, 3 and 6 do not contain polysiloxane and are inferior in tactile sensation.
- Comparative Example 2 contained dimethylpolysiloxane and had an excellent tactile sensation, but its transparency was deteriorated as compared with Comparative Example 1.
- Example 1 contains a propylene-based polymer of the component (A), a hydrogenated block copolymer of the component (B), and an aryl group-containing organopolysiloxane of the component (C), so that the tactile sensation is excellent. Compared with Comparative Example 2 containing dimethylpolysiloxane, it is also excellent in transparency. The transparency of Example 1 is almost the same as that of Comparative Example 1 containing no polysiloxane.
- Comparative Examples 4, 5 and 8 contained dimethylpolysiloxane and had an excellent tactile sensation, but the transparency was deteriorated as compared with Comparative Example 3.
- Example 2 contains the propylene-based polymer of the component (A), the hydrogenated block copolymer of the component (B), and the aryl group-containing organopolysiloxane of the component (C), so that the tactile sensation is excellent. It is also excellent in transparency as compared with Comparative Examples 4 and 5 containing dimethylpolysiloxane. The transparency of Example 2 is almost the same as that of Comparative Example 3 containing no polysiloxane.
- Comparative Example 7 contained dimethylpolysiloxane and had an excellent tactile sensation, but its transparency was deteriorated as compared with Comparative Example 6.
- Example 3 contains the propylene-based polymer of the component (A), the hydrogenated block copolymer of the component (B), and the aryl group-containing organopolysiloxane of the component (C), so that the tactile sensation is excellent. Compared with Comparative Example 7 containing dimethylpolysiloxane, it is also excellent in transparency. The transparency of Example 3 is improved rather than that of Comparative Example 6 which does not contain polysiloxane.
- Example 4 contains the propylene-based polymer of the component (A), the hydrogenated block copolymer of the component (B), and the aryl group-containing organopolysiloxane of the component (C), so that the tactile sensation is excellent. Compared with Comparative Examples 4, 5 and 8 containing only dimethylpolysiloxane, the transparency is also excellent.
- thermoplastic elastomer composition of the present invention Since the molded product obtained from the thermoplastic elastomer composition of the present invention is excellent in transparency and tactile sensation, it is suitably used for automobile parts such as automobile interior materials, building parts, medical parts, electric wire coating materials, miscellaneous goods and the like. ..
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Abstract
Description
成分(A) プロピレン系重合体
成分(B) 芳香族ビニル化合物単位を主体とする重合ブロックPを少なくとも2個有し、かつ、共役ジエン化合物単位を主体とする重合体ブロックQを少なくとも1個有するブロック共重合体及び/又はその水素添加物
成分(C) アリール基含有オルガノポリシロキサン
成分(A) プロピレン系重合体
成分(B) 芳香族ビニル化合物単位を主体とする重合ブロックPを少なくとも2個有し、かつ、共役ジエン化合物単位を主体とする重合体ブロックQを少なくとも1個有するブロック共重合体及び/又はその水素添加物
成分(C) 分子中に下記式(1)で表される繰り返し単位を有するアラルキル基含有オルガノポリシロキサン
本発明は以下の説明に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。
本明細書において、「~」を用いてその前後に数値又は物性値を挟んで表現する場合、その前後の値を含むものとして用いることとする。
本発明の熱可塑性エラストマー組成物は、下記成分(A)~(C)を含むことを特徴とするものであり、更に下記成分(D)を含んでいてもよい。
成分(A) プロピレン系重合体
成分(B) 芳香族ビニル化合物単位を主体とする重合ブロックPを少なくとも2個有し、かつ、共役ジエン化合物単位を主体とする重合体ブロックQを少なくとも1個有するブロック共重合体及び/又はその水素添加物(以下「(水添)ブロック共重合体」と称す場合がある。)
成分(C) アリール基含有オルガノポリシロキサン
成分(D) 炭化水素系ゴム用軟化剤
本発明の熱可塑性エラストマー組成物は、触感と透明性に優れた成形体を得ることができるという効果を奏する。
このような成分(A)と成分(B)の海島構造に、更に成分(C)が存在することにより、成分(B)が成分(A)の海の中に微分散しやすくなる傾向がある。これにより、分散径が可視光の光波長よりも小さい成分(B)の分散体が増加するため、本発明のエラストマー組成物の透明性が向上すると推測される。
本発明で用いる成分(A)のプロピレン系重合体(以下「プロピレン系重合体(A)」と称す場合がある。)としては、プロピレン系重合体(A)を構成する単量体単位中にプロピレン単位を50質量%以上含有するものであればよい。耐熱性、剛性、結晶性、耐薬品性等の観点から、プロピレン系重合体(A)中のプロピレン単位の含有率は、好ましくは60質量%以上であり、より好ましくは75質量%以上、更に好ましくは90質量%以上である。プロピレン単位の含有率の上限については特に限定されず、100質量%であってもよい。
本発明で用いる成分(B)は、芳香族ビニル化合物単位を主体とする重合ブロックP(以下、単に「ブロックP」と称す場合がある。)の少なくとも2個と、共役ジエン化合物単位を主体とする重合体ブロックQ(以下、単に「ブロックQ」と称す場合がある。)の少なくとも1個とを有する(水添)ブロック共重合体である。
P-(Q-P)m (I)
(P-Q)n (II)
式中PはブロックPを表す。QはブロックQを表す。mは1~5の整数を表す。nは1~5の整数を表す。
ブロックP、ブロックQがそれぞれ複数存在する場合に、それらの化合物単位はそれぞれ同一でも異なっていてもよい。
成分(B)のブロック共重合体中のブロックPの含有割合は、70質量%以下であることが好ましく、60質量%以下であることがより好ましく、50質量%以下であることが更に好ましく、40質量%以下であることが特に好ましい。
上記範囲でブロックPの割合が高くなるほど、機械的強度に優れ、低くなるほど、柔軟性に優れ、ブリードアウトしにくい傾向にある。上記範囲とすることでブリードアウトを抑制しながら機械的強度と柔軟性を両立しやすくなる。
成分(B)のブロック共重合体中のブロックQの含有割合は、30質量%以上であることが好ましく、40質量%以上であることがより好ましく、50質量%以上であることが更に好ましく、60質量%以上であることが特に好ましい。
成分(B)のブロック共重合体中のブロックQの含有割合は、95質量%以下であることが好ましく、90質量%以下であることがより好ましく、85質量%以下であることが更に好ましく、80質量%以下であることが特に好ましい。
上記範囲でブロックQの割合が高くなるほど、柔軟性に優れ、ブリードアウトしにくい傾向にあり、低くなるほど、機械的強度に優れる傾向にある。上記範囲とすることでブリードアウトを抑制しながら機械的強度と柔軟性を両立しやすくなる。
成分(B)の(水添)ブロック共重合体のMwは、上記範囲において、耐熱性、機械的強度の点では大きい方が好ましく、成形外観及び流動性、成形性の点では小さい方が好ましい。成分(B)の(水添)ブロック共重合体のMwを上記範囲とすることで、耐熱性、機械的強度、成形外観、流動性及び成形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。
(測定条件)
機器:日本ミリポア社製「150C ALC/GPC」
カラム:昭和電工社製「AD80M/S」3本
検出器:FOXBORO社製赤外分光光度計「MIRANIA」
波長:3.42μm
溶媒:o-ジクロロベンゼン
温度:140℃
流速:1cm3/分
注入量:200マイクロリットル
濃度:2mg/cm3
酸化防止剤として2,6-ジ-t-ブチル-p-フェノール0.2質量%添加
本発明で用いる成分(C)のアリール基含有オルガノポリシロキサンのアリール基は、ヘテロアリール基を含む広義のアリール基であり、例えば、フェニル基、ナフチル基、トリル基、キシリル基、ピリジル基、ピリミジニル基、チエニル基が挙げられる。また、アリール基含有オルガノポリシロキサンは、アリール基を有するものであればよく、該アリール基は、アルキレン基等の連結基を介してアリール基含有オルガノポリシロキサンに含まれていてもよい。このようなアリール基を含む基としては、アラキル基が挙げられる。即ち、アリール基含有オルガノポリシロキサンはアラルキル基含有オルガノポリシロキサンであってもよい。
R11の好ましい基としては、後掲の式(1)におけるR1とR2が挙げられる。同様にR12の好ましい基としては、後掲の式(1)におけるR1とR2が挙げられる。
本発明の熱可塑性エラストマー組成物は、成分(D)として炭化水素系ゴム用軟化剤を含んでいてもよい。炭化水素系ゴム用軟化剤を含むことは、本発明の熱可塑性エラストマー組成物の柔軟性、流動性の向上に有効である。
これらのうち、色相が良好であることから、パラフィン系オイルが好ましい。
炭化水素系ゴム用軟化剤の動粘度は上記範囲のうちで、本発明の熱可塑性エラストマー組成物の流動性の向上という点では低い方が好ましく、フォギング等の起こり難さの点では高い方が好ましい。動粘度を上記範囲とすることで、本発明の熱可塑性エラストマー組成物の流動性の向上を図った上でフォギング等の発生を抑制できる。
本発明の熱可塑性エラストマー組成物において、成分(A)及び成分(B)の含有割合は、これらの合計100質量%に対して、成分(A)が1~99質量%、成分(B)が99~1質量%であることが好ましい。より好ましくは、成分(A)が5~95質量%、成分(B)が95~5質量%であり、更に好ましくは、成分(A)が10~90質量%、成分(B)が90~10質量%であり、特に好ましくは、成分(A)が25~80質量%、成分(B)が75~20質量%である。
本発明の熱可塑性エラストマー組成物は、本発明の目的を損なわない範囲で、必要に応じて、成分(A)~(D)以外の他の成分(本明細書において、単に「その他の成分」と称することがある。)を含有していてもよい。その他の成分としては、成分(A)、(B)以外の樹脂やエラストマー(本明細書においてはこれらをまとめて単に「その他の樹脂」と称することがある。)や各種添加剤が挙げられる。
ヒンダードアミン系光安定剤の市販品としてはBASF社製「チヌビン(登録商標)」シリーズが挙げられる。
ヒンダードアミン系光安定剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の熱可塑性エラストマー組成物の製造方法は、特に限定されるものではなく、例えば、常法に従って、成分(A)、成分(B)及び成分(C)と、必要に応じて添加される成分(D)やその他の成分とをドライブレンドした後、溶融混練することにより製造することができる。
その際に用いられる混合装置としては、特に限定されないが、例えば、バンバリーミキサー、ラボプラストミル、単軸押出機、二軸押出機等の混練装置が挙げられる。このうち、押出機を用いた溶融混合法により製造することが、生産性、良混練性の点から好ましい。
混練時の溶融温度は、適宜設定することができるが、通常130~300℃の範囲であり、150~250℃の範囲であることが好ましい。
本発明の熱可塑性エラストマー組成物の用途には特に制限はないが、特に、自動車部品、建築部品、医療用部品、電線被覆材、雑貨等の成形材料として有用である。
本発明の熱可塑性エラストマー組成物を成形することにより、種々の成形体として用いることができる。本発明の熱可塑性エラストマー組成物には、通常の射出成形法、押出成形法等の各種成形方法を用いることができる。
本発明の熱可塑性エラストマー組成物を成形してなる本発明の成形体の具体例としては、射出成形体、押出成形体が挙げられる。
成形温度は、通常160~250℃であり、好ましくは170~220℃である。
射出圧力は、通常5~100MPaであり、好ましくは10~80MPaである。
金型温度は通常10~80℃であり、好ましくは20~60℃である。
以下の実施例における各種の製造条件や評価結果の値は、本発明の実施態様における上限又は下限の好ましい値としての意味をもつものであり、好ましい範囲は前記した上限又は下限の値と、下記実施例の値又は実施例同士の値との組み合わせで規定される範囲であってもよい。
<成分(A)>
A-1:日本ポリプロ社製「ノバテック(登録商標)PP BC06C」
プロピレン・エチレンブロック共重合体
プロピレン単位含有率:91質量%
MFR(JIS K7210、230℃、21.2N荷重):60g/10分
B-1:TSRC社製「TAIPOL(登録商標)6159」
スチレン・ブタジエン・スチレンブロック共重合体の水素添加物
重量平均分子量:400,000
スチレン単位含有率:30質量%
B-2:旭化成社製「SOE-SS(登録商標)S1605」
スチレン・ブタジエン・スチレンブロック共重合体の水素添加物
重量平均分子量:200,000
スチレン単位含有率:60質量%
C-1:信越化学工業社製「KF-410」
前記式(1)で表される繰り返し単位と前記式(2)で表される繰り返し単位とを有するアラルキル基含有オルガノポリシロキサン
式(1)中のR1:メチル基
式(1)中のR2:2-フェニルプロピル基
式(2)中のR3,R4:メチル基
アラルキル基含有率:39モル%
動粘度(25℃):900cSt
D-1:出光興産社製「ダイアナ プロセスオイルPW90」
パラフィン系オイル
動粘度(40℃):90cSt
X-1:東レ・ダウコーニング社製「BY27-001」
ジメチルポリシロキサンマスターバッチ
ジメチルポリシロキサン含有率:50質量%
X-2:信越化学工業社製「KF96-1000cs」
ジメチルポリシロキサン
動粘度(25℃):1000cSt
E-1:BASF社製「イルガノックス(登録商標)1010」
ヒンダードフェノール系酸化防止剤
<触感>
実施例及び比較例で得られた熱可塑性エラストマー組成物のペレットから作成した射出成形体(350mm×100mm×2mm)について、人の手指3本で撫でるように触った際の触感を調べ、下記基準で評価した。
射出成形体の触感は、ブリード物が表面に発生しておらず、手に付着しないものが好ましく、より好ましくはさらさらした触感である。
A:さらさらしており、手に付着物を感じない
B:少しさらさらしており、手に付着物を感じない
C:べたべたしている、又は、さらさらしているが手に付着物を感じる
実施例及び比較例で得られた熱可塑性エラストマー組成物のペレットから作成した射出成形体(350mm×100mm×2mm)について、日本電色工業株式会社製のNDH-2000型HAZE計を使用して、厚さ方向の全光線透過率(単位:%)を測定した。
表-1に示す配合で原料を混合し、得られた混合物を二軸混練機により溶融混練(シリンダー温度180℃~200℃)し、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を、型締力180tで、電動の射出成形機(住友重機械工業株式会社製)で、シリンダー温度200℃、金型温度40℃にて、縦350mm×横100mm×厚さ2mmのシート状の金型中に射出速度40mm/秒で射出充填した。充填完了後30秒間冷却してから射出成形体を取り出した。得られた射出成形体について触感及び透明性の評価を行い、結果を表-1に示した。
表-1から次のことが言える。
比較例2は、ジメチルポリシロキサンを含んでおり、触感は優れるが、比較例1と比較して透明性が悪化した。
本出願は、2020年1月30日付で出願された日本特許出願2020-013855と、2020年10月13日付で出願された日本特許出願2020-172653に基づいており、その全体が引用により援用される。
Claims (5)
- 下記成分(A)~(C)を含む熱可塑性エラストマー組成物。
成分(A) プロピレン系重合体
成分(B) 芳香族ビニル化合物単位を主体とする重合ブロックPを少なくとも2個有し、かつ、共役ジエン化合物単位を主体とする重合体ブロックQを少なくとも1個有するブロック共重合体及び/又はその水素添加物
成分(C) アリール基含有オルガノポリシロキサン - 前記成分(C)がアラルキル基含有オルガノポリシロキサンである、請求項1に記載の熱可塑性エラストマー組成物。
- 前記R1がメチル基である、請求項3に記載の熱可塑性エラストマー組成物。
- 請求項1~4のいずれか一項に記載の熱可塑性エラストマー組成物を用いた成形体。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202180011814.3A CN115038750B (zh) | 2020-01-30 | 2021-01-07 | 热塑性弹性体组合物以及由其制成的成形体 |
| JP2021574581A JP7605137B2 (ja) | 2020-01-30 | 2021-01-07 | 熱可塑性エラストマー組成物及びそれよりなる成形体 |
| EP21747972.4A EP4098694B1 (en) | 2020-01-30 | 2021-01-07 | Thermoplastic elastomer composition and molded body formed therefrom |
| US17/872,052 US12466942B2 (en) | 2020-01-30 | 2022-07-25 | Thermoplastic elastomer composition and molded articles thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020013855 | 2020-01-30 | ||
| JP2020-013855 | 2020-01-30 | ||
| JP2020-172653 | 2020-10-13 | ||
| JP2020172653 | 2020-10-13 |
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| US17/872,052 Continuation US12466942B2 (en) | 2020-01-30 | 2022-07-25 | Thermoplastic elastomer composition and molded articles thereof |
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| EP (1) | EP4098694B1 (ja) |
| JP (1) | JP7605137B2 (ja) |
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| WO (1) | WO2021153183A1 (ja) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2022150620A (ja) * | 2021-03-26 | 2022-10-07 | Mcppイノベーション合同会社 | 自動車内装用部材 |
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| JP7571645B2 (ja) | 2021-03-26 | 2024-10-23 | Mcppイノベーション合同会社 | 自動車内装用部材 |
Also Published As
| Publication number | Publication date |
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| CN115038750A (zh) | 2022-09-09 |
| US12466942B2 (en) | 2025-11-11 |
| EP4098694A4 (en) | 2023-06-21 |
| JPWO2021153183A1 (ja) | 2021-08-05 |
| US20220372265A1 (en) | 2022-11-24 |
| JP7605137B2 (ja) | 2024-12-24 |
| EP4098694B1 (en) | 2025-04-09 |
| EP4098694A1 (en) | 2022-12-07 |
| CN115038750B (zh) | 2024-07-23 |
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