Classifications

• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • 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
• • 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
• • 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
• • 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
• • 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
• • 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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• 2021
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