WO2021100603A1 - 熱可塑性エラストマー組成物及びその成形体 - Google Patents
熱可塑性エラストマー組成物及びその成形体 Download PDFInfo
- Publication number
- WO2021100603A1 WO2021100603A1 PCT/JP2020/042257 JP2020042257W WO2021100603A1 WO 2021100603 A1 WO2021100603 A1 WO 2021100603A1 JP 2020042257 W JP2020042257 W JP 2020042257W WO 2021100603 A1 WO2021100603 A1 WO 2021100603A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- mass
- elastomer composition
- thermoplastic elastomer
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- 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
- 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
- C08L53/025—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 modified
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Definitions
- the present invention relates to a thermoplastic elastomer composition and a molded product thereof. More specifically, the present invention relates to a thermoplastic elastomer composition having excellent injection moldability, tactile sensation, scratch resistance, and flame retardancy, and a molded product composed of the thermoplastic elastomer composition.
- thermoplastic elastomer softens by heating and has fluidity, and when cooled, it has rubber elasticity.
- Thermoplastic elastomers have the same formability as thermoplastic resins, have unique rubber elasticity, and are recyclable. Therefore, automobile parts, building parts, medical parts, wire coating materials, etc. Widely used for miscellaneous goods.
- Patent Document 1 describes, as a thermoplastic elastomer composition for injection molding, 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.
- Styrene-based elastomers are also actively used in insulated wires, cables, cords, optical fiber core wires, and optical fiber cords used for internal and external wiring of electrical and electronic equipment.
- a non-halogen flame retardant in consideration of the environmental load in order to improve the heat dissipation and flame retardancy of the electric / electronic device which is a heating element.
- a thermoplastic elastomer using magnesium hydroxide as a non-halogen flame retardant is used for a thermoplastic elastomer for electronic / electronic devices such as insulated wires, cables, and cords. Is disclosed.
- Japanese Unexamined Patent Publication No. 2006-83323 Japanese Unexamined Patent Publication No. 2012-107212 Japanese Unexamined Patent Publication No. 2013-072033 Japanese Unexamined Patent Publication No. 2013-072034
- the flame retardancy decreases when the skin of the automobile interior material is thinned, it is necessary to compensate for the decrease in flame retardancy due to the thinning by adding a flame retardant.
- the flame retardants such as magnesium hydroxide disclosed in Patent Documents 2 to 4 are not sufficient to improve the decrease in flame retardancy due to thinning in the above applications. If an attempt is made to improve the flame retardancy by blending a large amount of a flame retardant, the tactile sensation and scratch resistance are lowered, and the moldability and appearance are also impaired.
- An object of the present invention is to provide a thermoplastic elastomer composition capable of exhibiting excellent injection moldability, good tactile sensation, and scratch resistance, and having excellent flame retardancy, and a molded product made of this thermoplastic elastomer composition. There is.
- the present inventor blends a halogen-based flame retardant into a thermoplastic elastomer composition containing a propylene-based polymer, a styrene-based (hydrogenated) block copolymer, and a hydrocarbon-based rubber softener to provide a good tactile sensation.
- the present invention has been completed by finding that it is possible to obtain a molded product that has high flame retardancy while maintaining injection moldability and scratch resistance and is optimal for the skin of an automobile interior material or the like.
- the gist of the present invention lies in the following [1] to [10].
- Thermoplastic elastomer composition Component (A) Propropylene-based polymer Component (B) A block having a polymerization block P mainly composed of at least two aromatic vinyl compound units and a polymer block Q mainly composed of at least one conjugated diene compound unit. Block Polymer and / or its Hydrogen Additive Component (C) Hydrocarbon Rubber Softener Component (D) Halogen Flame Retardant
- thermoplastic elastomer composition according to [1], which further contains silicone.
- Elastomer composition is at least one selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom.
- the content ratio of the component (D) to a total of 100 parts by mass of the component (A), the component (B), the component (C), and the component (D) is 0.9 to 30 parts by mass.
- the thermoplastic elastomer composition according to any one of [1] to [3].
- the component (A) is 1 to 80 parts by mass
- the component (B) is 5 to 80 parts by mass
- the component (C) is 5 to 80 parts.
- thermoplastic elastomer composition according to any one of [1] to [5], wherein the halogen atom content of the halogen-based flame retardant of the component (D) is 70 to 95% by mass.
- thermoplastic elastomer composition obtained by molding the thermoplastic elastomer composition according to any one of [1] to [6].
- thermoplastic elastomer composition obtained by injection-molding the thermoplastic elastomer composition according to any one of [1] to [6].
- thermoplastic elastomer composition according to any one of [1] to [6].
- thermoplastic elastomer composition containing the following components (A) to (D).
- thermoplastic elastomer composition having excellent injection moldability, tactile sensation, scratch resistance, and flame retardancy, and a molded product made of this thermoplastic elastomer composition.
- thermoplastic Elastomer composition of the present invention is characterized by containing the following components (A) to (D) in a predetermined ratio.
- Block Polymer and / or its Hydrogen Additive Component C
- Hydrocarbon Rubber Softener Component D
- thermoplastic elastomer composition of the present invention has the effects of excellent injection moldability, good tactile sensation, scratch resistance, and excellent flame retardancy is presumed as follows.
- a polymerization block P mainly composed of a propylene-based polymer of the component (A), at least two aromatic vinyl compound units of the component (B), and a polymer block Q mainly composed of at least one conjugated diene compound unit.
- the block copolymer and / or its hydrogenated additive having the above and the hydrocarbon-based rubber softening agent of the component (C) provide excellent injection moldability, good tactile sensation, and excellent scratch resistance.
- the halogen-based flame retardant of the component (D) as the flame retardant, it is possible to improve the flame retardancy while maintaining injection moldability, good tactile sensation, and scratch resistance.
- 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 a main component in an amount of 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 in the propylene-based polymer (A) 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 specific examples thereof include a propylene homopolymer, a propylene / ethylene random copolymer, a propylene / ethylene block copolymer, and the like. Can also 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 melt flow rate is at least the above lower limit, the moldability is good and the appearance of the obtained molded product is good.
- the melt flow rate is not more than the above upper limit, the mechanical properties, particularly the tensile fracture strength tend to be good.
- the catalyst used in producing the propylene-based polymer (A) is not particularly limited, but a stereoregular catalyst is preferable.
- a stereoregular catalyst examples 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 two-component catalyst consisting of a transition metal component such as a substance and an alkylaluminum compound or an organometallic component such as a halide, a hydride, or an alkoxide thereof, and nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc. are added to these components. Examples thereof include a three-component catalyst to which an electron donating compound containing the compound 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 organoaluminum 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, or a polymer monomer as a solvent in the presence of the catalyst.
- the bulk polymerization method described above can be mentioned.
- the slurry polymerization 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 propylene-based polymers (A) include polypropylene block copolymers manufactured by SunAllomer Ltd., Novatec® PP manufactured by Japan Polypropylene Corporation, and Waymax (WAYMAX®).
- 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 mixed and used.
- the component (B) used in the present invention includes a polymerization block P mainly composed of at least two aromatic vinyl compound units (hereinafter, may be simply referred to as “block P”) and at least one conjugated diene compound.
- a block copolymer having a polymer block Q mainly composed of a unit hereinafter, may be simply referred to as "block Q" and / or a hydrogenated product thereof (hereinafter, "(hydrogenated) block copolymer”). It may be called.).
- 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 for example, styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-amino.
- Aromatic vinyl compounds such as ethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like can be mentioned.
- styrene, ⁇ -methylstyrene, and p-methylstyrene are preferably used from the viewpoint of availability and productivity.
- Styrene is particularly preferable.
- 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 availability and productivity. Particularly preferred 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 (hydrogenated) block copolymer of component (B) preferably has an aromatic vinyl compound unit of styrene units and a conjugated diene compound unit of butadiene units.
- the block polymer having at least two blocks P and at least one block Q may be linear, branched, radial or the like, and is represented by the following formula (1) or (2). It is preferably a block copolymer to be used.
- P- (QP) m (1) (PQ) n (2) In the formula, P represents block P, Q represents block Q, m represents an integer of 1 to 5, and n represents an integer of 2 to 5.
- P represents block P
- Q represents block Q
- m represents an integer of 1 to 5
- n represents an integer of 2 to 5.
- m and n should be large in terms of lowering the order-disorder transition temperature as a rubber polymer, but should be small in terms of ease of manufacture and cost. ..
- the component (B) is preferably a block copolymer represented by the formula (1), and the block copolymer weight represented by the formula (1) in which m is 3 or less.
- the coalescence is more preferable, the block copolymer represented by the formula (1) in which m is 2 or less is more preferable, and the block copolymer represented by the formula (1) in which m is 1 is most 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 (1), and is a hydrogenated product of the block copolymer represented by the formula (1) having m of 3 or less.
- the block copolymer is a hydrogenated product of the block copolymer represented by the formula (1) in which m is 2 or less, and the block copolymer represented by the formula (1) in which m is 1 is more preferable. Hydrogen additives are most preferred.
- the proportion of block P in the block copolymer of component (B) is preferably high from the viewpoint of mechanical strength of the thermoplastic elastomer composition, and preferably low from the viewpoint of flexibility and difficulty in bleeding out. ..
- the content of block P in the block copolymer of the component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass or more. It is more preferable, and it is particularly preferable that it is 20% by mass or more.
- the content 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, and further preferably 50% by mass or less. It is preferably 40% by mass or less, and particularly preferably 40% by mass or less. The higher the proportion of block P, the better the mechanical strength, and the lower the proportion, the more flexible it tends to be, and the more difficult it is to bleed out.
- 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. .. Specifically, the content of block Q in the block copolymer of the component (B) is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. It is more preferable, and it is particularly preferable that it is 60% by mass or more. On the other hand, the content of block Q in the block copolymer of the component (B) is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.
- It is preferably 80% by mass or less, and particularly preferably 80% by mass or less.
- the weight average molecular weight (Mw) of the (hydrogenated) block copolymer of component (B) is preferably large in terms of heat resistance and mechanical strength, but smaller in terms of molded appearance, fluidity, and moldability. Is preferable.
- 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.
- the weight average molecular weight (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) is preferably a styrene / butadiene / styrene block copolymer and its hydrogen additive, a styrene / isoprene / styrene copolymer and its hydrogen additive, and a styrene / isoprene / butadiene / styrene block copolymer. And its hydrogenated additives.
- component (B) a commercially available product can also be used.
- the commercially available component (C) include “Kraton (registered trademark) G” manufactured by Kraton Polymer, "Septon (registered trademark)” manufactured by Kuraray, and “Tough Tech (registered trademark)” manufactured by Asahi Kasei Corporation. Examples thereof include “SOE (registered trademark)” and “TAIPOL (registered trademark)” manufactured by TSRC.
- the (hydrogenated) block copolymer of the component (B) one type may be used alone, or two or more types may be mixed and used.
- composition of the present invention is effective in improving the flexibility and fluidity of the thermoplastic elastomer composition of the present invention.
- hydrocarbon-based rubber softener a mineral oil-based softener or a synthetic resin-based softener is preferable, and a mineral oil-based softener 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.
- aromatic oils are called aromatic oils.
- the hydrocarbon-based rubber softener used as the component (C) may be any one of the above-mentioned various softeners or a mixture of a plurality of types. Of these, 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 of the hydrocarbon softener at 40 ° C. is preferably low in terms of improving the fluidity of the thermoplastic elastomer composition of the present invention, but is preferably high in terms of the difficulty of fogging and the like. ..
- the kinematic viscosity of the hydrocarbon softener at 40 ° C. is preferably 20 cm Stokes (cSt) or more, more preferably 50 cm Stokes or more, and preferably 800 cm Stokes or less. , 600 cm Stokes or less is more preferable.
- the flash point (COC method) of the hydrocarbon softener for rubber is preferably 200 ° C. or higher, more preferably 250 ° C. or higher.
- the pour point of the hydrocarbon softener for rubber is preferably 20 ° C. or higher and ⁇ 10 ° C. or lower.
- the aniline point of the hydrocarbon softener for rubber is preferably 110 ° C. or higher and 150 ° C. or lower.
- halogen-based flame retardant of the component (D) used in the present invention is effective in improving the flame retardancy while maintaining the tactile sensation and scratch resistance of the thermoplastic elastomer composition of the present invention.
- halogen atom contained in the halogen-based flame retardant of the component (D) a fluorine atom, a chlorine atom, and a bromine atom are preferable, and an excellent flame retardancy imparting / improving effect can be obtained by adding a small amount of the bromine atom. Is more preferable.
- the content of halogen atoms contained in the component (D) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 70% by mass in terms of halogen atom equivalent concentration. That is all.
- the upper limit is preferably 95% by mass or less, and more preferably 90% by mass or less. The higher the halogen atom content, the better the flame retardancy, and the lower the halogen atom content, the lower the mold contamination and environmental load.
- halogen-based flame retardant of the component (D) examples include hexabromocyclododecane, bis (dibromopropyl) tetrabromo-bisphenol A, bis (dibromopropyl) tetrabromo-bisphenol S, tris (dibromopropyl) isocyanurate, and tris (tri).
- it is 1,2-bis (2,3,4,5,6-pentabromophenyl) ethane.
- halogen-based flame retardant of the component (D) one type may be used alone, or two or more types may be mixed and used.
- thermoplastic elastomer composition of the present invention may be used in combination with a flame retardant other than the halogen-based flame retardant, but it is preferably not substantially contained.
- a flame retardant other than the halogen-based flame retardant is preferably not substantially contained.
- substantially free means that the amount is not added in an amount that functions as a flame retardant, and is usually 0.1% by mass or less with respect to the resin component.
- Flame retardants other than halogens are flame retardants that do not contain halogens, such as phosphorus-based flame retardants such as phosphoric acid esters, polyphosphates and red phosphorus, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide. Other examples include silicone-based flame retardants and triazine-based flame retardants.
- the resin component is the total of the component (A) and the component (B) and other resins and elastomers described later which are used as needed.
- the content ratio of the component (D) is 0.01 with respect to a total of 100 parts by mass of the component (A), the component (B), the component (C) and the component (D). ⁇ 30 parts by mass.
- the upper limit thereof is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less.
- the lower limit thereof is preferably 0.5 parts by mass or more, more preferably 0.9 parts by mass or more, and further preferably 1 part by mass or more.
- the content ratio of the component (A), the component (B), the component (C) and the component (D) is such that the component (A) is 1 with respect to 100 parts by mass in total. It is preferable that the component (B) is 5 to 80 parts by mass, the component (C) is 5 to 80 parts by mass, and the component (D) is 0.9 to 30 parts by mass.
- the content ratio is more preferably 5 to 70 parts by mass for the component (A), 10 to 70 parts by mass for the component (B), 10 to 70 parts by mass for the component (C), and 1.0 for the component (D).
- the amount is up to 20 parts by mass, more preferably 5 to 60 parts by mass of the component (A), 10 to 65 parts by mass of the component (B), 10 to 65 parts by mass of the component (C), and 1 part by mass of the component (D). It is .0 to 15 parts by mass, and particularly preferably, the component (A) is 10 to 55 parts by mass, the component (B) is 15 to 55 parts by mass, the component (C) is 15 to 55 parts by mass, and the component (D). Is 1.0 to 12 parts by mass.
- the mass ratio of the component (A) to the component (B) in the thermoplastic elastomer composition of the present invention [mass of the component (A)]: [mass of the component (B)] is 5:95 to 90:10.
- the range is preferably in the range of 10:90 to 80:20, more preferably in the range of 10:90 to 70:30.
- the mass ratio of the component (B) to the component (C) in the thermoplastic elastomer composition of the present invention [mass of the component (B)]: [mass of the component (C)] is 20:80 to 80: It is preferably in the range of 20, more preferably in the range of 25:75 to 75:25, and even more preferably in the range of 25:75 to 65:35.
- thermoplastic elastomer composition of the present invention contains the propylene-based polymer of the component (A) within the above range, the effect of blending the other components can be sufficiently obtained, and then the heat resistance and injection of the component (A) can be obtained. The effect of improving moldability and mechanical properties can be sufficiently obtained.
- thermoplastic elastomer composition of the present invention contains the (hydrocarbonated) block copolymer of the component (B) within the above range, so that the effect of blending other components can be sufficiently obtained, and then the component (B).
- the effects of heat resistance, oil resistance, and bleed resistance of the hydrocarbon softener for the hydrocarbon component (C) can be sufficiently obtained.
- thermoplastic elastomer composition of the present invention contains the hydrocarbon-based rubber softener of the component (C) within the above range, so that the effect of blending other components can be sufficiently obtained, and then the component (C) is used. The effect of improving flexibility and fluidity can be sufficiently obtained.
- thermoplastic elastomer composition of the present invention sufficiently maintains the blending effect of other components and sufficiently improves the flame retardancy. Obtainable.
- thermoplastic elastomer composition of the present invention includes, as 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. ”) May be contained.
- 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.
- the content ratio of the other components is preferably 900 parts by mass or less, more preferably 570 parts by mass or less, and 400 parts by mass when the total of the components (A) to (D) is 100 parts by mass.
- the amount is more preferably 300 parts by mass or less, and particularly preferably 300 parts by mass or less.
- 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 acrylic resin, polycarbonate resin, 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, these Examples thereof include a hydrogenated product, one modified with an acid anhydride or the like to introduce a polar functional group, and one obtained by grafting, random and / or block copolymerizing another monomer.
- the other resins listed above may contain only one type or two or more types.
- 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.
- examples thereof include colorants such as agents, pigments and dyes, antistatic agents, conductive agents, reinforcing agents, fillers, plasticizers, mold release agents, foaming agents and the like.
- silicone is a component that imparts abrasion resistance to the thermoplastic elastomer composition and prevents the stickiness peculiar to the elastomer.
- the type of substituent to which the siloxane main chain is bonded in the molecular structure of silicone is not particularly limited, but dimethylsilicone (dimethylpolysiloxane), methylphenylsilicone, or alkyl-modified silicone is preferably used.
- the kinematic viscosity (25 ° C.) of silicone is usually 1 cm Stokes or more, preferably 5 cm Stokes or more, more preferably 10 cm Stokes or more, and the upper limit is not particularly limited. The higher the kinematic viscosity of silicone, the higher the effect of improving wear resistance and scratch resistance, and the lower the kinematic viscosity, the higher the effect of improving stickiness.
- the content thereof is per 100 parts by mass of the total of the component (A), the component (B), the component (C) and the component (D). It is preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass.
- silicone content is 0.1 parts by mass or more, it is preferable from the viewpoint of improving the abrasion resistance, scratch resistance and stickiness resistance, and when it is 15 parts by mass or less, the mechanical strength and flame retardancy are high. It is preferable from the viewpoint of the above.
- 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 general formula R 1 R 2 NOH (in the formula, R 1 and R 2 each independently represent alkyl) are used.
- R 1 or R 2 is a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, or a heptadecyl group.
- Particularly preferred dialkylhydroxylamines are N, N-dioctadecylhydroxylamine and N, N-dihexadecylhydroxylamine or mixtures thereof.
- 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, and in particular, those having a molecular weight of 500 or more such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane are used. Is preferable. Examples of commercially available products include "Irganox (registered trademark) 1010" manufactured by BASF.
- 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.
- antioxidants may be used alone or in combination of two or more.
- the content of the antioxidant is per 100 parts by mass in total of the component (A), the component (B), the component (C) and the component (D). , Preferably 0.01 to 5 parts by mass.
- the content of the antioxidant is 0.01 parts by mass or more, it is preferable from the viewpoint of improving the heat deterioration property, and when it is 5 parts by mass or less, problems such as bleeding are unlikely to occur, and the composition is mechanical. It is preferable from the viewpoint of strength and the like.
- 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. The hindered amine-based light stabilizer may be used alone or in combination of two or more.
- thermoplastic elastomer composition of the present invention contains a hindered amine-based light stabilizer
- the content thereof is per 100 parts by mass of the total of the component (A), the component (B), the component (C) and the component (D). It is preferably 0.005 to 2 parts by mass, and more preferably 0.01 to 0.5 parts by mass.
- the content of the hindered amine-based light stabilizer is within 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 100 parts by mass in total of the component (A), the component (B), the component (C) and the component (D).
- the amount is preferably 2 parts by mass or less, and more preferably 1 part by mass or less.
- thermoplastic elastomer composition of the present invention is not particularly limited.
- the component (A), the component (B), the component (C) and the component (D) are dried according to a conventional method, and other components added as needed. It can be produced by blending 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. Of these, production by a melt-mixing method using an extruder is preferable from the viewpoint of productivity and good kneading property.
- 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 has a moldability of 2 g / 10 minutes or more in terms of melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a measurement load of 21.2 N by a method conforming to JIS K7210 standards. From the viewpoint of the above, it is preferable, more preferably 5 g / 10 minutes or more, and further preferably 10 g / 10 minutes or more.
- the melt flow rate (MFR) of the thermoplastic elastomer composition of the present invention is preferably 200 g / 10 minutes or less, more preferably 185 g / 10 minutes or less, and 160 g / 10 minutes or less. It is more preferably 10 minutes or less.
- the thermoplastic elastomer composition of the present invention preferably has a tensile elongation of 200% or more, more preferably 300% or more, as measured by a procedure based on the measurement method of JIS K6251.
- the upper limit of tensile elongation is preferably 1500% or less, and more preferably 1200% or less.
- 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 for molding the thermoplastic elastomer composition of the present invention.
- thermoplastic elastomer composition of the present invention examples include an injection molded product, an extruded molded product, and the like.
- 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 product of the present invention is useful as automobile parts, building parts, medical parts, electric wire covering materials, miscellaneous goods, and the like.
- the molded product of the present invention is useful as a skin for automobile interior materials typified by applications such as armrests and console pads because of its good appearance and tactile sensation, scratch resistance and excellent flame retardancy.
- 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 "Septon (registered trademark) 4077” manufactured by Kuraray Co., Ltd.
- X-1 "Kisuma (registered trademark) 5" manufactured by Kyowa Chemical Industry Co., Ltd. Magnesium hydroxide (Mg (OH) 2 )
- X-2 "ADEKA STAB (registered trademark) FP-2200” manufactured by ADEKA CORPORATION Phosphorus-based antioxidant
- E-1 BASF's "Irganox (registered trademark) 1010" Hindered Phenolic Antioxidant F-1: "BY27-001” manufactured by Toray Dow Corning Masterbatch containing dimethyl silicone dimethyl silicone content: 50% by mass
- ⁇ Tactile sensation> The tactile sensation when the injection molded product (350 mm ⁇ 100 mm ⁇ 1.5 mm) prepared from the pellets of the thermoplastic elastomer composition obtained in Examples and Comparative Examples was touched by a human hand or three fingers. It was investigated and evaluated according to the following criteria.
- 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 smooth tactile sensation.
- C Sticky or silky but feels deposits on hands
- ⁇ Scratch resistance Tabor clutch> Tungsten carbide was used for an injection molded product (350 mm ⁇ 100 mm ⁇ 1.5 mm) prepared from pellets of the thermoplastic elastomer composition obtained in Examples and Comparative Examples using a Taber type scratch tester manufactured by Toyo Seiki Seisakusho Co., Ltd. A carbide cutter was attached to a jig with a straight blade, and the state of the test piece when rotated at a speed of 0.5 rpm with a load of 350 g was observed and evaluated according to the following criteria. Most preferably, the scratch resistance of the injection molded product is not cut or penetrated, does not change, or is only surface scraping. A: No change, or part of the surface is scraped B: The entire surface is scraped and part of the surface is cut C: Penetration
- thermoplastic elastomer compositions obtained in Examples and Comparative Examples were measured according to JIS K7210 (1999) under the conditions of a measurement temperature of 230 ° C. and a measurement load of 21.2 N.
- Examples 1 to 5 Comparative Examples 1 to 6
- 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 MFR of the obtained thermoplastic elastomer composition was measured, and the results are shown in Table 1.
- 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.
- Comparative Examples 1 and 2 do not contain a halogen-based flame retardant, have a high combustion rate, and are inferior in flame retardancy.
- Comparative Examples 3 to 5 use magnesium hydroxide as a flame retardant. Of these, Comparative Example 3 in which the amount of magnesium hydroxide compounded was relatively small was faster in combustion speed and inferior in flame retardancy than in Example 2, and the entire surface was scraped or cut by the Tabor scratch test. .. In Comparative Example 4 and Comparative Example 5 in which the amount of magnesium hydroxide was large, the combustion speed was 40 mm / min or less, but a bleeding substance was felt in the hand by tactile evaluation, and the blade made a test piece by the Tabor scratch test. Penetrated. In Comparative Example 6, a phosphorus-based flame retardant was blended instead of the halogen-based flame retardant, but the flame retardant-imparting effect was inferior to that when the halogen-based flame retardant was used.
- the molded product obtained from the thermoplastic elastomer composition of the present invention has excellent flame retardancy, tactile sensation, and scratch resistance, and can be used for automobile parts such as automobile interior parts, building parts, medical parts, electric wire coating materials, miscellaneous goods, and the like. It is preferably used.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
例えば、特許文献2~特許文献4には、非ハロゲン系難燃剤として、水酸化マグネシウムを用いた熱可塑性エラストマーが、絶縁電線・ケーブル・コードなどの電子・電子機器用の熱可塑性エラストマーに使用されることが開示されている。
最近では、これら表皮は、成形加工のし易さと内装工程の簡便さが進んできており、より薄肉化されるようになってきている。
しかし、特許文献2~4に開示されている水酸化マグネシウムなどの難燃剤では、上記用途において、薄肉化に伴う難燃性の低下を改善するには十分ではない。難燃剤の多量配合で難燃性を向上させようとすると、触感や耐傷付き性が低下し、成形性や外観も損なわれる。
成分(A) プロピレン系重合体
成分(B) 少なくとも2個の芳香族ビニル化合物単位を主体とする重合ブロックPと、少なくとも1個の共役ジエン化合物単位を主体とする重合体ブロックQとを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) 炭化水素系ゴム用軟化剤
成分(D) ハロゲン系難燃剤
成分(A) プロピレン系重合体
成分(B) 少なくとも2個の芳香族ビニル化合物単位を主体とする重合ブロックPと、少なくとも1個の共役ジエン化合物単位を主体とする重合体ブロックQとを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) 炭化水素系ゴム用軟化剤
成分(D) ハロゲン系難燃剤
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)~(D)を所定の割合で含むことを特徴とする。
成分(A) プロピレン系重合体
成分(B) 少なくとも2個の芳香族ビニル化合物単位を主体とする重合ブロックPと
、少なくとも1個の共役ジエン化合物単位を主体とする重合体ブロックQとを有するブロ
ック共重合体及び/又はその水素添加物
成分(C) 炭化水素系ゴム用軟化剤
成分(D) ハロゲン系難燃剤
本発明の熱可塑性エラストマー組成物が、射出成形性に優れ、良好な触感、耐傷付き性を有し、かつ難燃性に優れるという効果を奏する理由については、以下の通り推定される。
成分(A)のプロピレン系重合体と、成分(B)の少なくとも2個の芳香族ビニル化合物単位を主体とする重合ブロックPと、少なくとも1個の共役ジエン化合物単位を主体とする重合体ブロックQとを有するブロック共重合体及び/又はその水素添加物と、成分(C)の炭化水素系ゴム用軟化剤により、射出成形性に優れ、良好な触感と耐傷付き性に優れたものとなる。
難燃剤として成分(D)のハロゲン系難燃剤を配合することにより、射出成形性、良好な触感、耐傷付き性を維持しつつ、難燃性を向上させることができる。
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主成分として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。プロピレン系重合体(A)中の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。
これらの触媒の中でも、メタロセン触媒が好ましい。
本発明で用いる成分(B)は、少なくとも2個の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。)と、少なくとも1個の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。)とを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。)である。
P-(Q-P)m (1)
(P-Q)n (2)
(式中PはブロックPを、QはブロックQをそれぞれ表す。mは1~5の整数を表す。nは2~5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。)
(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」測定
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
合して用いてもよい。
本発明で用いる成分(C)の炭化水素系ゴム用軟化剤は、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。
成分(C)として用いる炭化水素系ゴム用軟化剤は、上述の各種軟化剤の何れか1種でも、複数種の混合物でも構わない。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引火点(COC法)は、200℃以上であることが好ましく、250℃以上であることがより好ましい。
炭化水素系ゴム用軟化剤の流動点は20℃以上、-10℃以下が好ましい。
炭化水素系ゴム用軟化剤のアニリン点は110℃以上、150℃以下が好ましい。
本発明で用いる成分(D)のハロゲン系難燃剤は、本発明の熱可塑性エラストマー組成物の触感および耐傷付き性を維持しつつ、難燃性の向上に有効である。
いてもよい。
ここで、樹脂成分とは、成分(A)及び成分(B)と必要に応じて用いられる後述のその他の樹脂やエラストマーの合計である。
本発明の熱可塑性エラストマー組成物において、成分(D)の含有割合は、成分(A)、成分(B)、成分(C)及び成分(D)の合計100質量部に対して、0.01~30質量部である。良好な触感と耐傷付き性の観点からその上限は20質量部以下が好ましく、15質量部以下がより好ましく、12質量部以下が更に好ましい。求められる難燃性を得る観点からその下限は0.5質量部以上が好ましく、0.9質量部以上がより好ましく、1質量部以上が更に好ましい。
本発明の熱可塑性エラストマー組成物には、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。
シリコーンの動粘度(25℃)は通常1センチストークス以上、好ましくは5センチストークス以上、より好ましくは10センチストークス以上であり、上限については特に制限されない。シリコーンの動粘度が高いほど耐摩耗性、耐傷付き性向上の効果が高く、低いほどべたつき改良効果が高い。
ヒンダードアミン系光安定剤は1種を単独で用いても2種以上を混合して用いてもよい。
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い。本発明の熱可塑性エラストマー組成物は、例えば、常法に従って、成分(A)、成分(B)、成分(C)及び成分(D)と、必要に応じて添加される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。
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℃の範囲内であり、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は、JIS K7210の規格に準拠した方法で測定温度230℃、測定荷重21.2Nで測定したメルトフローレート(MFR)が2g/10分以上であることが成形性の観点から好ましく、より好ましくは5g/10分以上であり、更に好ましくは10g/10分以上である。また、成形性の観点から、本発明の熱可塑性エラストマー組成物のメルトフローレート(MFR)は、200g/10分以下であることが好ましく、185g/10分以下であることがより好ましく、160g/10分以下であることが更に好ましい。
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の成形には、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。
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PP(登録商標)BC06C」
プロピレン・エチレン共重合体
ポリ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:クラレ社製「セプトン(登録商標)4077」
スチレン・イソプレン・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:380,000
スチレン単位含有率:30質量%
B-3:旭化成社製「S.O.E.-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: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℃):90センチストークス
D-1:Albemarle Corporation製「SAYTEX(登録商標)8010」
1,2-ビス(2,3,4,5,6-ペンタブロモフェニル)エタン
臭素原子の含有率:82質量%
X-1:協和化学工業株式会社製「キスマ(登録商標)5」
水酸化マグネシウム(Mg(OH)2)
X-2:アデカ株式会社製「アデカスタブ(登録商標)FP-2200」
リン系酸化防止剤
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
F-1:東レ・ダウコーニング社製「BY27-001」
ジメチルシリコーン含有マスターバッチ
ジメチルシリコーン含有率:50質量%
<難燃性:燃焼速度 FMVSS No.302>
FMVSS No.302燃焼試験装置を用い、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×1.5mm)の右端より38mmのバーナー炎を15秒間接炎させて、標線間254mmの燃焼距離における燃焼速度を測定した。試験治具は、ワイヤー有りで測定し、試験回数5回のうちの平均値を算出した。
燃焼速度が遅いほど、難燃性が高い。燃焼速度は、40mm/min以下が好ましく、35mm/min以下がより好ましく、30mm/min以下が更に好ましい。
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×1.5mm)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、または、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×1.5mm)に対して、株式会社東洋精機製作所テーバー式スクラッチテスターを使用して、タングステンカーバイド製カッターを正刃で治具に取り付け、荷重350gで、回転数0.5rpmの速度で回転させたときの試験片の状態を観察し、以下の基準で評価した。
射出成形体の耐傷付き性は、切れや貫通がなく、変化なし、または表面の削れのみであることが最も好ましい。
A:変化なし、または表面の一部に削れ有り
B:表面全体の削れ、かつ表面の一部の切れ有り
C:貫通
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について、JIS K7210(1999)に従って、測定温度230℃、測定荷重21.2Nの条件で測定した。
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×1.5mm)について、JIS K6251の規格に準拠した方法で試験速度:500mm/分にて測定した。
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について、MFRの測定を行い、結果を表-1に示した。
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1.5mm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難燃性、触感、耐傷付き性及び引張伸びの評価を行った。これらの結果を表-1に示した。
表-1から次のことが言える。
実施例1~5は、成分(A)のプロピレン系重合体と、成分(B)の水添ブロック共重合体、及び成分(C)の炭化水素系ゴム用軟化剤と、成分(D)のハロゲン系難燃剤を含むことで、燃焼速度が40mm/min以下であり、かつ触感が優れ、傷付き性評価では、切れがなく耐傷付き性にも優れている。また、MFRの値から成形性にも優れ、引張伸びの値から柔軟性にも優れることが分かる。
比較例3~5は、難燃剤として水酸化マグネシウムを使用している。このうち、水酸化マグネシウムの配合量が比較的少ない比較例3は、実施例2と比較して燃焼速度が速く難燃性に劣り、かつテーバースクラッチテストにより、表面全体に削れや切れが発生した。水酸化マグネシウムの配合量が多い比較例4及び比較例5は、燃焼速度が40mm/min以下であるが、触感評価にて手にブリード物を感じ、またテーバースクラッチテストにより、刃が試験片を貫通した。
比較例6はハロゲン系難燃剤の代わりにリン系難燃剤を配合したものであるが、ハロゲン系難燃剤を用いた場合よりも難燃性付与効果が劣る。
本出願は、2019年11月19日付で出願された日本特許出願2019-208921に基づいており、その全体が引用により援用される。
Claims (10)
- 下記成分(A)~(D)を含み、かつ、成分(D)の含有割合が成分(A)~(D)の合計100質量部に対して0.01~30質量部である、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) 少なくとも2個の芳香族ビニル化合物単位を主体とする重合ブロックPと、少なくとも1個の共役ジエン化合物単位を主体とする重合体ブロックQとを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) 炭化水素系ゴム用軟化剤
成分(D) ハロゲン系難燃剤 - 更に、シリコーンを含有する、請求項1に記載の熱可塑性エラストマー組成物。
- 前記成分(D)のハロゲン系難燃剤のハロゲン原子が、フッ素原子、塩素原子及び臭素原子からなる群より選ばれる1種以上である、請求項1又は2に記載の熱可塑性エラストマー組成物。
- 前記成分(A)、前記成分(B)、前記成分(C)、及び前記成分(D)の合計100質量部に対する前記成分(D)の含有割合が0.9~30質量部である、請求項1~3のいずれか一項に記載の熱可塑性エラストマー組成物。
- 前記成分(A)~(D)の合計100質量部に対し、成分(A)を1~80質量部、成分(B)を5~80質量部、成分(C)を5~80質量部、成分(D)を0.9~30質量部含有する、請求項4に記載の熱可塑性エラストマー組成物。
- 前記成分(D)のハロゲン系難燃剤に含まれるハロゲン原子の含有率が70~95質量%である、請求項1~5のいずれか一項に記載の熱可塑性エラストマー組成物。
- 請求項1~6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成形してなる成形体。
- 請求項1~6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射出成形してなる射出成形体。
- 請求項1~6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自動車部品。
- 下記成分(A)~(D)を含む熱可塑性エラストマー組成物を用いた自動車部品。
成分(A) プロピレン系重合体
成分(B) 少なくとも2個の芳香族ビニル化合物単位を主体とする重合ブロックPと、少なくとも1個の共役ジエン化合物単位を主体とする重合体ブロックQとを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) 炭化水素系ゴム用軟化剤
成分(D) ハロゲン系難燃剤
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20889712.4A EP4063445A4 (en) | 2019-11-19 | 2020-11-12 | THERMOPLASTIC ELASTOMER COMPOSITION AND MOLDING THEREOF |
| CN202080080539.6A CN114729154A (zh) | 2019-11-19 | 2020-11-12 | 热塑性弹性体组合物及其成型体 |
| JP2021558336A JP7567806B2 (ja) | 2019-11-19 | 2020-11-12 | 熱可塑性エラストマー組成物及びその成形体 |
| US17/744,776 US20220275184A1 (en) | 2019-11-19 | 2022-05-16 | Thermoplastic Elastomer Composition and Molded Articles Thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019208921 | 2019-11-19 | ||
| JP2019-208921 | 2019-11-19 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US17/744,776 Continuation US20220275184A1 (en) | 2019-11-19 | 2022-05-16 | Thermoplastic Elastomer Composition and Molded Articles Thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021100603A1 true WO2021100603A1 (ja) | 2021-05-27 |
Family
ID=75981268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2020/042257 Ceased WO2021100603A1 (ja) | 2019-11-19 | 2020-11-12 | 熱可塑性エラストマー組成物及びその成形体 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20220275184A1 (ja) |
| EP (1) | EP4063445A4 (ja) |
| JP (1) | JP7567806B2 (ja) |
| CN (1) | CN114729154A (ja) |
| WO (1) | WO2021100603A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024029197A1 (ja) * | 2022-08-05 | 2024-02-08 | 住友化学株式会社 | ポリプロピレン系樹脂組成物及びこれを含む成形体 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7596737B2 (ja) * | 2020-11-19 | 2024-12-10 | ブリヂストンスポーツ株式会社 | ゴルフボール |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6264852A (ja) * | 1985-09-18 | 1987-03-23 | Hitachi Cable Ltd | 難燃性樹脂組成物 |
| JPS6268845A (ja) * | 1985-09-19 | 1987-03-28 | Hitachi Cable Ltd | 難燃性樹脂組成物 |
| JPS6268846A (ja) * | 1985-09-19 | 1987-03-28 | Hitachi Cable Ltd | 難燃性樹脂組成物 |
| JPS6270439A (ja) * | 1985-09-25 | 1987-03-31 | Hitachi Cable Ltd | 難燃性樹脂組成物 |
| JPH07330986A (ja) * | 1994-06-06 | 1995-12-19 | Toray Ind Inc | 難燃性ポリオレフィンフイルム及びその積層体 |
| JP2000247200A (ja) * | 1999-02-25 | 2000-09-12 | Toyo Tire & Rubber Co Ltd | エアバッグ収納用カバー |
| WO2002000807A1 (en) * | 2000-06-24 | 2002-01-03 | Seong Il Chemical Co., Ltd. | Polyolefin-based hot melt adhesive for deflection yoke |
| JP2018027994A (ja) * | 2016-08-15 | 2018-02-22 | デンカ株式会社 | 熱可塑性樹脂組成物、それを用いたフィラー含有樹脂組成物及び成形体。 |
| JP2018154682A (ja) * | 2017-03-16 | 2018-10-04 | Mcppイノベーション合同会社 | 非発泡成形用熱可塑性エラストマー組成物及びその成形体 |
| JP2019208921A (ja) | 2018-06-05 | 2019-12-12 | 美津濃株式会社 | 跳び縄 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140282A (ja) * | 1997-11-12 | 1999-05-25 | Nippon Zeon Co Ltd | 難燃性重合体組成物および難燃性樹脂成形体 |
| WO2003035705A1 (en) * | 2001-10-23 | 2003-05-01 | Asahi Kasei Kabushiki Kaisha | Hydrogenated copolymer |
| JP2008127482A (ja) * | 2006-11-21 | 2008-06-05 | Asahi Kasei Chemicals Corp | 難燃共重合体組成物及び樹脂シート |
| CN100500799C (zh) * | 2007-01-16 | 2009-06-17 | 北京理工大学 | 一种十溴二苯乙烷母粒的制造方法 |
| US7884150B2 (en) * | 2007-08-17 | 2011-02-08 | Teknor Apex Company | Flame retardant thermoplastic elastomer compositions |
| CN102977490A (zh) * | 2012-12-25 | 2013-03-20 | 胶州市富田化工有限公司 | 一种阻燃聚苯乙烯组合物 |
| CN103265789A (zh) * | 2013-06-07 | 2013-08-28 | 深圳市兴盛迪新材料有限公司 | 高阻燃型丙烯腈-苯乙烯-丁二烯组合物及其制备方法 |
-
2020
- 2020-11-12 CN CN202080080539.6A patent/CN114729154A/zh active Pending
- 2020-11-12 EP EP20889712.4A patent/EP4063445A4/en not_active Withdrawn
- 2020-11-12 WO PCT/JP2020/042257 patent/WO2021100603A1/ja not_active Ceased
- 2020-11-12 JP JP2021558336A patent/JP7567806B2/ja active Active
-
2022
- 2022-05-16 US US17/744,776 patent/US20220275184A1/en not_active Abandoned
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6264852A (ja) * | 1985-09-18 | 1987-03-23 | Hitachi Cable Ltd | 難燃性樹脂組成物 |
| JPS6268845A (ja) * | 1985-09-19 | 1987-03-28 | Hitachi Cable Ltd | 難燃性樹脂組成物 |
| JPS6268846A (ja) * | 1985-09-19 | 1987-03-28 | Hitachi Cable Ltd | 難燃性樹脂組成物 |
| JPS6270439A (ja) * | 1985-09-25 | 1987-03-31 | Hitachi Cable Ltd | 難燃性樹脂組成物 |
| JPH07330986A (ja) * | 1994-06-06 | 1995-12-19 | Toray Ind Inc | 難燃性ポリオレフィンフイルム及びその積層体 |
| JP2000247200A (ja) * | 1999-02-25 | 2000-09-12 | Toyo Tire & Rubber Co Ltd | エアバッグ収納用カバー |
| WO2002000807A1 (en) * | 2000-06-24 | 2002-01-03 | Seong Il Chemical Co., Ltd. | Polyolefin-based hot melt adhesive for deflection yoke |
| JP2018027994A (ja) * | 2016-08-15 | 2018-02-22 | デンカ株式会社 | 熱可塑性樹脂組成物、それを用いたフィラー含有樹脂組成物及び成形体。 |
| JP2018154682A (ja) * | 2017-03-16 | 2018-10-04 | Mcppイノベーション合同会社 | 非発泡成形用熱可塑性エラストマー組成物及びその成形体 |
| JP2019208921A (ja) | 2018-06-05 | 2019-12-12 | 美津濃株式会社 | 跳び縄 |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP4063445A4 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024029197A1 (ja) * | 2022-08-05 | 2024-02-08 | 住友化学株式会社 | ポリプロピレン系樹脂組成物及びこれを含む成形体 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2021100603A1 (ja) | 2021-05-27 |
| CN114729154A (zh) | 2022-07-08 |
| JP7567806B2 (ja) | 2024-10-16 |
| US20220275184A1 (en) | 2022-09-01 |
| EP4063445A4 (en) | 2023-01-04 |
| EP4063445A1 (en) | 2022-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0845498B1 (en) | Process for the preparation of a thermoplastic elastomeric resin composition | |
| CN103797067B (zh) | 交联组合物、交联组合物的制造方法和成型体 | |
| JP7567806B2 (ja) | 熱可塑性エラストマー組成物及びその成形体 | |
| CN118632903A (zh) | 热塑性弹性体组合物及其成型体 | |
| JP4625150B2 (ja) | 難燃性熱可塑性エラストマー樹脂組成物およびその製造方法 | |
| JP2008226850A (ja) | 難燃性熱可塑性エラストマー樹脂組成物およびその製造方法 | |
| JP2009235241A (ja) | 熱可塑性エラストマー組成物、発泡体、及び発泡体の製造方法 | |
| US12466942B2 (en) | Thermoplastic elastomer composition and molded articles thereof | |
| JP3102851B2 (ja) | 熱可塑性エラストマー組成物の製造法 | |
| JP6948003B2 (ja) | 難燃性ポリオレフィン系樹脂組成物 | |
| JP5498207B2 (ja) | 架橋組成物、架橋組成物の製造方法、成形体 | |
| JP6666115B2 (ja) | 樹脂組成物およびそれからなる成形体 | |
| JP2010272531A (ja) | 難燃性熱可塑性エラストマー樹脂組成物およびその製造方法 | |
| JP7571645B2 (ja) | 自動車内装用部材 | |
| JP2021152116A (ja) | 熱可塑性エラストマー組成物 | |
| JP4192007B2 (ja) | 摩擦係数の大きい熱可塑性エラストマー組成物及びそれからなる滑り止め部材 | |
| JP2002338782A (ja) | 自動車ハーネス用グロメット樹脂組成物および自動車ハーネス用グロメット | |
| JP2025119269A (ja) | スチレン系熱可塑性エラストマー組成物およびその成形体 | |
| WO2025164773A1 (ja) | 自動車内装部材用熱可塑性エラストマー組成物およびその成形体 | |
| JP2001064403A (ja) | マスターバッチ及び樹脂組成物 | |
| WO2015060201A1 (ja) | 熱可塑性エラストマー組成物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20889712 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2021558336 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2020889712 Country of ref document: EP Effective date: 20220620 |
|
| WWW | Wipo information: withdrawn in national office |
Ref document number: 2020889712 Country of ref document: EP |
