WO2022138522A1 - 熱可塑性エラストマー組成物および成形体 - Google Patents
熱可塑性エラストマー組成物および成形体 Download PDFInfo
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- WO2022138522A1 WO2022138522A1 PCT/JP2021/046904 JP2021046904W WO2022138522A1 WO 2022138522 A1 WO2022138522 A1 WO 2022138522A1 JP 2021046904 W JP2021046904 W JP 2021046904W WO 2022138522 A1 WO2022138522 A1 WO 2022138522A1
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- thermoplastic elastomer
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- styrene
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- C08L23/08—Copolymers of ethene
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Definitions
- the present invention relates to a thermoplastic elastomer composition, and more particularly to a thermoplastic elastomer composition suitable for insert injection molding.
- the present invention also relates to a molded product using a thermoplastic elastomer composition.
- thermoplastic elastomer composition is an extremely useful material in industry because it melts at the processing temperature during its molding process and can be molded by a well-known resin molding method.
- thermoplastic elastomer composition capable of insert injection molding and a housing made of different materials for various packing applications used in a high temperature environment.
- thermoplastic resin composition containing an amorphous propylene-1-butene copolymer, a crystalline polypropylene resin, and an acid-modified polyolefin wax for applications such as films, sheets, bottles, and sealing materials.
- thermoplasticity containing a propylene-based polymer, a polylactic acid-based resin, an ethylene-based polymer containing an epoxy group, elastomers, and an acid-modified polyolefin wax for applications such as automobile interior / exterior parts.
- Compositions have been proposed.
- Patent Document 3 an excess plasticizer or / and a softening agent is added to a main polymer containing a styrene-isoprene-styrene copolymer (SEPS) or a styrene-butadiene-styrene copolymer (SEBS) as a main component.
- SEPS styrene-isoprene-styrene copolymer
- SEBS styrene-butadiene-styrene copolymer
- thermoplastic resin composition described in Patent Document 1 has a poor compression set at 100 ° C. of 75 to 84%, and cannot withstand use as a packing or a sealing material.
- the thermoplastic composition described in Patent Document 2 has poor compression set and cannot withstand use as a packing or a sealing material.
- the styrene copolymer as the main polymer has no heat-sealing property with different materials, and a large amount of plasticizer such as isoparaffin oil is added. There was a problem that there was no heat-sealing adhesiveness with different materials.
- the present inventors have considered reducing the amount of the plasticizer added in order to improve the heat-sealing adhesiveness, but the fluidity is lowered and it is not suitable for insert injection molding. In addition, the hardness tends to increase, which makes it unsuitable for applications such as packings, sealing materials, weather strips, and interior skin materials.
- an object of the present invention is to provide a thermoplastic elastomer composition having excellent resistance to compression set in a high temperature environment, fluidity during melt molding, and heat-sealing adhesiveness with different materials.
- a thermoplastic elastomer composition containing a resin component and an additive.
- the resin component contains a styrene-based block copolymer containing a covalently bonded crosslinked portion and a polyolefin having a weight average molecular weight of 80,000 or more and 500,000 or less, and the content of the styrene-based block copolymer is the above.
- the content of the polyolefin is 40% by mass or more and 95% by mass or less with respect to the entire resin component, and the content of the polyolefin is 5% by mass or more and 60% by mass or less with respect to the entire resin component.
- the additive is an acid-modified compound having a functional group derived from a carboxylic acid having a weight average molecular weight of 1,000 or more and less than 80,000 and / or a derivative thereof, and / or a polyester compound, and the styrene-based block co-weight.
- thermoplastic elastomer compositions comprising a conjugate and a cross-linking agent capable of cross-linking at least one of the polyolefins.
- the content of the acid-modified compound is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin component.
- the content of the polyester compound is preferably 1 part by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the resin component.
- the polyolefin contains at least one kind of polypropylene and maleic anhydride-modified polypropylene, and the weight average molecular weight of the polypropylene and maleic anhydride-modified polypropylene is 100,000 or more and 200,000. ..
- the polyolefin comprises at least one of an ethylene-butene copolymer and a maleic anhydride-modified ethylene-butene copolymer, the ethylene-butene copolymer and a maleic anhydride-modified ethylene-butene.
- the weight average molecular weight of the copolymer is preferably 80,000 or more and 160,000 or less.
- the weight average molecular weight of the acid-modified compound is preferably 10,000 or more and 77,000 or less.
- the acid-modified compound is a maleic anhydride-modified compound.
- the maleic anhydride-modified compound is at least one selected from the group consisting of maleic anhydride-modified polyolefin, maleic anhydride-modified polybutadiene, and isobutylene-maleic anhydride copolymer. preferable.
- the styrene block copolymer is a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-isoprene-butadiene-styrene block copolymer, styrene-.
- the cross-linking agent is at least one selected from the group consisting of a peroxide-based cross-linking agent and a fatty acid metal salt-based cross-linking agent.
- the additive further contains a plasticizer, and the content of the plasticizer is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin component.
- the plasticizer is a process oil.
- thermoplastic elastomer composition is used for insert injection molding.
- thermoplastic elastomer composition In another aspect of the present invention, a molded product using the above-mentioned thermoplastic elastomer composition is provided.
- the molded product is a packing, a sealing material, a weather strip, or an interior skin material.
- thermoplastic elastomer composition having excellent resistance to compression set in a high temperature environment, fluidity during melt molding, and heat-sealing adhesiveness with different materials. Further, according to the present invention, it is possible to provide a molded product using such a thermoplastic elastomer composition.
- thermoplastic Elastomer composition of the present invention contains a specific resin component and an additive.
- the thermoplastic elastomer composition is suitable for packings, sealing materials, weather strips, and interior skin materials because it has excellent resistance to compression set in a high temperature environment and heat-sealing adhesiveness with different materials. Further, since the thermoplastic elastomer composition has excellent fluidity during melt molding, it can be suitably used for insert injection molding.
- each component will be described in detail.
- the thermoplastic elastomer composition contains at least a styrene-based block copolymer containing a covalently bonded crosslinked portion and a polyolefin as a resin component.
- the resin component of the thermoplastic elastomer composition contains a styrene copolymer containing a covalent bond cross-linked portion, so that it is excellent in compression set in a high temperature environment, but it cannot sufficiently obtain fluidity during melt molding.
- the styrene-based block copolymer phase becomes the domain and the polyolefin phase becomes the matrix, and the fluidity at the time of melt molding is maintained while ensuring good compression set. Obtainable.
- the "styrene-based block copolymer” may be a copolymer having a styrene block structure at any site.
- the "covalent bond cross-linking portion” may be a site that cross-links the molecules of the styrene-based block copolymer by a covalent bond, and its form is not particularly limited.
- cross-linking portion that crosslinks the molecules of the styrene-based block copolymer
- carbon cross-linking, oxygen cross-linking, and sulfur can be formed from the viewpoint of being able to form a stronger cross-link and being excellent in the ease of cross-linking.
- It is preferably composed of at least one crosslink selected from the group consisting of crosslinks, and more preferably composed of carbon crosslinks.
- styrene-based block copolymer containing the covalently bonded crosslinked polymer examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-isoprene-butadiene-styrene block.
- SBS styrene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- SIS styrene-isoprene-butadiene-styrene block
- SIBS Polymer
- SEBS styrene-ethylene-butylene-styrene block copolymer
- SEPS styrene-ethylene-propylene-styrene block copolymer
- SEBS SEEPS
- SEEPS SEEPS
- two or more in combination it is preferable to use two or more in combination.
- two or more types so that one has a low cross-linking density after cross-linking (for example, SEBS) and the other has a high cross-linking density after cross-linking (for example, SBS).
- SEBS low cross-linking density after cross-linking
- SBS high cross-linking density after cross-linking
- SBS and SEBS in combination.
- the mass ratio (SBS: SEBS) thereof is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is better to use SEBS. Further, when SBS and SEBS are used in combination, it is preferable to combine SEBS and radial SBS from the viewpoint of resistance to compression set in a high temperature environment and further improvement in fluidity during melt molding.
- the "radial shape" of SBS referred to here means a structure in which molecular chains are radially connected, and the "linear shape” means that the molecular structure is a linear structure. It was
- the styrene content of the styrene-based block copolymer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass. When the styrene content is within the above range, the balance between thermoplasticity and rubber elasticity is good.
- the styrene content in the styrene-based block copolymer can be measured by a method based on the IR method described in JIS K6239 (issued in 2007).
- the weight average molecular weight (Mw) of the styrene-based block copolymer is preferably 30,000 or more and 1,000,000 or less, and preferably 100,000 or more and 800,000 or less, from the viewpoint of mechanical strength and the like. Is more preferable, and more preferably 200,000 or more and 700,000 or less.
- the number average molecular weight (Mn) is preferably 10,000 or more and 600,000 or less, more preferably 50,000 or more and 550,000 or less, and 100,000 or more and 500,000 or less. Is even more preferable.
- the dispersity (Mw / Mn) of the molecular weight distribution is preferably 5 or less, and more preferably 1 to 3.
- the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersion degree (Mw / Mn) of the molecular weight distribution can be obtained by a so-called gel permeation chromatography (GPC) method.
- a commercially available product may be used as the styrene-based block copolymer containing the covalent bond cross-linking portion.
- the polyolefin is not particularly limited, and conventionally known polyolefins can be used.
- Examples of the polyolefin include ethylene, propylene, butene-1, penten-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1,3-methylpentene-1, 4-methylpentene-1,3.
- the above-mentioned polyolefin may be acid-denatured by a conventionally known method.
- the acid-modified polyolefin is not particularly limited as long as it is an acid-modified polyolefin resin.
- Examples of the acid used for the modification include a carboxylic acid and / or a derivative thereof, and an unsaturated carboxylic acid and / or a derivative thereof is particularly preferable.
- the unsaturated carboxylic acid and / or its derivative includes an unsaturated compound having one or more carboxy groups, an ester of an unsaturated carboxylic acid compound having a carboxy group and an alcohol, and an unsaturated carboxylic acid compound having a carboxy group and an amine.
- An unsaturated compound having one or more amide and acid anhydride groups for example, an unsaturated dicarboxylic acid anhydride.
- the unsaturated group include a vinyl group, a vinylene group, an unsaturated cyclic hydrocarbon group and the like.
- unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, succinic acid, glutaric acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, nadic acid, and endosis-bicyclo [ 2,2,1] Hept-5-ene-2,3-dicarboxylic acid and the like can be mentioned.
- these derivatives may have forms such as acid halides, amides, imides, and esters, and for example, maleic chloride, malenylimide, maleic anhydride, citraconic anhydride, monomethyl maleate, and dimethyl maleate. And so on.
- unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid or acid anhydrides thereof are particularly preferable.
- the weight average molecular weight (Mw) of the polyolefin is 80,000 or more and 500,000 or less, preferably 85,000 or more, more preferably 90,000 or more, still more preferable, from the viewpoint of mechanical strength and the like. Is 100,000 or more, preferably 400,000 or less, more preferably 350,000 or less, and further preferably 300,000 or less.
- the Mw of the polyolefin is preferably 85,000 or more and 500,000 or less, more preferably 90,000 or more and 400,000 or less, and further preferably 100,000 or more and 350,000 or less.
- the Mw is preferably 100,000 or more and 200,000 or less.
- the Mw is preferably 80,000 or more and 160,000 or less.
- Mw weight average molecular weight
- GPC gel permeation chromatography
- the content of the styrene-based block copolymer is 40% by mass or more and 95% by mass or less, and the lower limit is preferably 50% by mass or more, more preferably 55% by mass or less, based on the total resin component. It is more preferably 60% by mass or more, and the upper limit value is preferably 90% by mass or less, and more preferably 85% by mass or less.
- the content of the polyolefin is 5% by mass or more and 60% by mass or less, preferably 10% by mass or more, more preferably 15% by mass or less, and an upper limit value with respect to the entire resin component. Is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.
- thermoplastic elastomer composition can be obtained.
- the thermoplastic elastomer composition preferably contains, as an additive, an acid-modified compound having a functional group derived from a carboxylic acid and / or a derivative thereof.
- the functional group of the acid-modified compound include a carboxy group, a carbonyl group, an acid anhydride group, an ester group, an amide group and the like. More specifically, functional groups derived from unsaturated carboxylic acids and / or derivatives thereof, which will be described later, can be mentioned.
- the acid-modified compound may contain one or more of these functional groups.
- the acid-modified compound may contain other functional groups such as a hydroxyl group and an ether group as long as the performance of the thermoplastic elastomer composition is not impaired.
- Examples of the acid-modified compound include compounds obtained by acid-modifying a conventionally known polymer with a carboxylic acid and / or a derivative thereof.
- the polymer the above-mentioned polyolefin, polybutadiene, or the like can be used.
- the acid-modified compound also includes a copolymer of an ⁇ -olefin and an unsaturated carboxylic acid and / or a derivative thereof.
- the above-mentioned unsaturated carboxylic acid and / or its derivative is an unsaturated compound having one or more carboxy groups, an ester of an unsaturated carboxylic acid compound having a carboxy group and an alcohol, an unsaturated carboxylic acid compound having a carboxy group and an amine.
- An unsaturated compound having one or more acid anhydride groups (for example, an unsaturated dicarboxylic acid anhydride). Examples of the unsaturated group include a vinyl group, a vinylene group, an unsaturated cyclic hydrocarbon group and the like.
- unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, succinic acid, glutaric acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, nadic acid, and endosis-bicyclo [ 2,2,1] Hept-5-ene-2,3-dicarboxylic acid and the like can be mentioned. Further, these derivatives may have forms such as acid halides, amides, imides, and esters, and for example, maleic chloride, malenylimide, maleic anhydride, citraconic anhydride, monomethyl maleate, and dimethyl maleate. And so on. Among these, unsaturated dicarboxylic acid or its acid anhydride is preferable, and maleic acid or its acid anhydride is particularly preferable.
- the acid-modified compound is preferably a maleic anhydride-modified compound, and examples thereof include maleic anhydride-modified polyolefin, maleic anhydride-modified polybutadiene, and isobutylene-maleic anhydride copolymer. These maleic anhydride-modified compounds may be used alone or in combination of two or more.
- the amount of modification of the acid-modified polyolefin resin by unsaturated carboxylic acid is not particularly limited, but is preferably 0.1% by mass or more and 10% by mass or less, and 0.5% by mass or more and 8.0% by mass, based on the polyolefin resin before modification. %% by mass or less is more preferable, and 1.0% by mass or more and 6.0% by mass or less is further preferable.
- the amount of modification by the unsaturated carboxylic acid in the acid-modified polyolefin resin is within the above range, the heat-sealing adhesiveness with different materials can be improved.
- a commercially available product may be used as the acid-modified compound.
- Commercially available products of maleic anhydride-modified polyolefin wax include, for example, the trade names "Toyo Tuck PMA-L", “Toyo Tuck PMA-F6", “Toyo Tuck PMA-LE” manufactured by Toyobo Co., Ltd., and those manufactured by Mitsubishi Chemical Corporation. Diacarna 30M and the like can be mentioned.
- Examples of commercially available products of maleic anhydride-modified liquid polybutadiene include trade names "Ricon 130MA8" and “Ricon 131MA17” manufactured by Clay Valley, and "Lithene ultra AL-15MA” manufactured by DKSH Japan.
- Examples of commercially available products of the isobutylene-maleic anhydride copolymer include the trade name "isovan 04" manufactured by Kuraray.
- the weight average molecular weight (Mw) of the acid-modified compound is 1,000 or more and less than 80,000, preferably 77,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less. Also, it is preferably 10,000 or more, more preferably 30,000 or more, and further preferably 45,000 or more. In particular, the Mw of the acid-modified compound is preferably 10,000 or more and 77,000 or less, more preferably 30,000 or more and 70,000 or less, and further preferably 45,000 or more and 60,000 or less. Such a weight average molecular weight (Mw) can be determined by a so-called gel permeation chromatography (GPC) method.
- GPC gel permeation chromatography
- the content of the acid-modified compound is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 45 parts by mass or less, and further preferably 10 parts by mass with respect to 100 parts by mass of the resin component. It is 40 parts by mass or less.
- the content of the acid-modified compound is within the above range, the heat-sealing adhesiveness with different materials can be improved.
- the thermoplastic elastomer composition preferably contains a polyester compound as an additive.
- the polyester compound may be crystalline or amorphous.
- Examples of the polyester compound include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN), as well as an acid component or a diol component. Examples thereof include modified polyester modified from the above. These polyester compounds may be used alone or in combination of two or more.
- the weight average molecular weight (Mw) of the polyester compound is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, and preferably 200,000 or less. , More preferably 100,000 or less, still more preferably 60,000 or less.
- the Mw of the polyester compound is preferably 1,000 or more and 200,000 or less, more preferably 2,000 or more and 100,000 or less, and further preferably 3,000 or more and 60,000 or less.
- Such a weight average molecular weight (Mw) is determined by using HLC-8220GPC manufactured by Tosoh Corporation, TSKgel SuperMultipore HZ-M manufactured by Tosoh Corporation, and solvent THF at a temperature of 40 ° C. for organic solvent-based size exclusion chromatography manufactured by Tosoh Corporation as a standard sample. It is a value obtained by using a standard polystyrene kit PSDQuick MP-M.
- polyester compound a commercially available product may be used.
- examples of commercially available products include trade names "Byron Resin 200”, “Byron Resin 220”, “Byron Resin GM-380”, and “Byron Resin GA-6400” manufactured by Toyobo Co., Ltd.
- the content of the polyester compound is preferably 10 parts by mass or more and 70 parts by mass or less, more preferably 20 parts by mass or more and 60 parts by mass or less, and further preferably 30 parts by mass or more with respect to 100 parts by mass of the resin component. It is 50 parts by mass or less.
- the content of the polyester compound is within the above range, the heat-sealing adhesiveness with different materials can be improved.
- the thermoplastic elastomer composition contains, as an essential additive, a styrene-based block copolymer and a cross-linking agent capable of cross-linking at least one of the polyolefins.
- the cross-linking agent is not particularly limited as long as it can form a cross-link on at least one of a styrene-based block copolymer and a polyolefin, but is not particularly limited, but is a peroxide-based cross-linking agent, a fatty acid metal salt-based cross-linking agent, and sulfur.
- Cross-linking agent phenol resin-based cross-linking agent, amino resin-based cross-linking agent, quinone-based cross-linking agent, halogen-based cross-linking agent, azo-based cross-linking agent, aldehyde-based cross-linking agent, epoxy-based cross-linking agent, bipolar compound-based cross-linking agent, optical-based A cross-linking agent or the like can be preferably used.
- a peroxide-based cross-linking agent, a fatty acid metal salt-based cross-linking agent, and a sulfur-based cross-linking agent are more preferable, and a peroxide-based cross-linking agent and a fatty acid metal salt-based cross-linking agent are particularly preferable.
- Such a peroxide-based cross-linking agent is not particularly limited, and is, for example, a covalent bond consisting of so-called carbon (oxygen) cross-linking by reacting with a cross-linking double bond in the main chain of a styrene-based block copolymer.
- a cross-linking agent made of a known peroxide capable of forming a cross-linking portion can be appropriately used.
- an organic peroxide is particularly preferable.
- organic peroxides examples include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-di (t-butyl peroxide).
- Butylperoxy) Valerate 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexin-3 and other peroxyesters; diacetyl Examples thereof include diacyl peroxides such as peroxyuroyl peroxide, dibenzoyl peroxide, p-chlorobenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,3-bis (t-butylperoxyisopropyl) benzene can be preferably used.
- such an organic peroxide preferably has a half-life temperature of 50 to 250 ° C. (more preferably 100 to 230 ° C.) for 1 minute.
- Examples of the organic peroxide satisfying such conditions include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-di (t-butyl).
- 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5 are used from the viewpoint of having a higher half-life temperature.
- -Di (t-butylperoxy) hexine-3, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene are more preferred, and 2,5-dimethyl-2,5-di (t-).
- Butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3 are particularly preferred.
- a peroxide-based cross-linking agent one type may be used alone, or two or more types may be used in combination.
- cross-linking aids include divinyl compounds such as divinylbenzene; oxime compounds such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime; N-methyl-N-4-dinitrosoaniline.
- Nitroso compounds such as nitrosobenzene; Malereimide compounds such as trimethylolpropane-N, N'-m-phenylenedi maleimide; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate and the like.
- Polyfunctional Methacrylate Monomer Polyfunctional Vinyl Monomer such as Vinyl Butyrate and Vinyl Stearate; Other Examples thereof include sulfur, diphenylguanidine, triallyl cyanurate, zinc dimethacrylate, zinc diacrylate and the like.
- the above-mentioned fatty acid metal salt-based cross-linking agent is a fatty acid metal salt formed of a metal and a fatty acid.
- a fatty acid metal salt is preferably at least one selected from the group consisting of a divalent fatty acid metal salt and a trivalent fatty acid metal salt.
- the divalent or trivalent metal is at least one selected from, for example, aluminum, chromium, iron, gallium, indium, calcium, zinc, magnesium, beryllium, barium, and strontium. Is preferable.
- trivalent metals are more preferable from the viewpoint of obtaining a thermoplastic elastomer composition having higher crosslink density and higher resistance to compression set.
- the fatty acid is preferably a fatty acid having 5 to 80 carbon atoms (more preferably 10 to 70, still more preferably 15 to 60).
- fatty acids for example, stearic acid, oleic acid, palmitic acid, linoleic acid, linolenic acid, arachidonic acid, icosapentaenoic acid, docosahexaenoic acid, montanic acid, and lauric acid are more preferred, stearic acid, oleic acid, and so on. Stearic acid is particularly preferred.
- divalent fatty acid metal salt suitable as such a fatty acid metal salt examples include zinc distearate, calcium distearate, magnesium distearate, barium distearate and the like.
- trivalent fatty acid metal salt more suitable as such a fatty acid metal salt for example, aluminum tristearate, distearate (hydroxy) aluminum, monostearic acid (dihydroxy) aluminum, methylaluminum stearate, and stearate. Ethylaluminum acid can be mentioned, and among these, aluminum tristearate, (hydroxy) aluminum disstearate, (dihydroxy) aluminum monostearate is preferable, and aluminum tristearate and (hydroxy) distearate are more preferable. ..
- the sulfur-based cross-linking agent is not particularly limited, and a known sulfur-based cross-linking agent capable of reacting with the cross-linking double bond to form a covalent bond cross-linking portion composed of so-called sulfur cross-linking is appropriately used. can.
- sulfur-based cross-linking agents include sulfur-based sulfurizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, inert sulfur, oil-treated sulfur, dimorphophosphorindisulfide, and alkylphenol disulfide.
- Zinc flower Zinc flower, magnesium oxide, litharge, p-quinone dioxime, p-dibenzoyl quinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosulfur, methylene dianiline and the like.
- powdered sulfur, sedimentation sulfur, highly dispersible sulfur, surface-treated sulfur, inert sulfur, and oil-treated sulfur are preferable, among which powder sulfur and oil-treated sulfur are more preferable, and oil-treated sulfur is more preferable. More preferred.
- such a sulfur-based cross-linking agent may be used individually by 1 type, or may be used in combination of 2 or more type.
- a sulfur-based cross-linking agent When a sulfur-based cross-linking agent is used as such a cross-linking agent, it is preferable to use a cross-linking aid (vulcanization accelerator and / or vulcanization accelerator) when obtaining the reaction product.
- vulcanization accelerators include thiazole-based (MBT, MBTS, ZnMBT, etc.), sulfenamide-based (CBS, DCBS, BBS, etc.), guanidine-based (DPG, DOTG, OTBG, etc.), and thiuram-based (Thiram).
- TMTD TMTD
- TMTM TMTM
- TBzTD TTD
- TOTN tetrakis (2-ethylhexyl) thiuram disulfide, etc.
- ZTC dithiocarbamate-based
- NaBDC thiourea-based
- ETU thiourea-based
- ZnBX xanthogenate-based
- the vulcanization accelerator is preferable.
- a vulture-promoting aid for example, zinc oxide (for example, 3 kinds of zinc oxide); fatty acids such as stearate, acetyl acid, propionic acid, butanoic acid, acrylic acid, maleic acid; zinc acetylate, Zinc fatty acid such as zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, zinc maleate and the like are preferable.
- zinc oxide for example, 3 kinds of zinc oxide
- fatty acids such as stearate, acetyl acid, propionic acid, butanoic acid, acrylic acid, maleic acid
- zinc acetylate Zinc fatty acid such as zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, zinc maleate and the like are preferable.
- reaction product of such a styrene-based block copolymer having a crosslinkable double bond in the main chain and a crosslinking agent SBS, SEBS, etc.
- a reaction product of at least one selected from the group consisting of SIS and SEEPS and a peroxide-based cross-linking agent is more preferable, and at least one selected from the group consisting of SBS, SEBS and SEEPS and a peroxide-based cross-linking.
- a reaction product with the agent is more preferable.
- the method for preparing a reaction product of such a styrene-based block copolymer having a crosslinkable double bond in the main chain and a crosslinking agent is not particularly limited, and for example, the main chain has a crosslinkable double bond.
- a mixture containing a styrene-based block copolymer, the cross-linking agent and, if necessary, a cross-linking aid is prepared under temperature conditions (preferably 60 to 250 ° C.) such that the cross-linking double bond reacts with the cross-linking agent.
- a method of preparing by mixing (for example, mixing with a pressurized kneader) may be adopted.
- the temperature conditions in such a reaction may be appropriately set to a temperature at which the crosslinking reaction proceeds, depending on the type of the crosslinking agent and the like.
- the content of the cross-linking agent is preferably 0.1 part by mass or more and 10 parts by mass or less, and more preferably 0.5 part by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the styrene block copolymer. More preferably, it is 1 part by mass or more and 5 parts by mass or less.
- the content of the cross-linking agent is within the above range, the heat-sealing adhesiveness with different materials can be improved.
- the thermoplastic elastomer composition comprises a plasticizer as an optional additive.
- a plasticizer it is preferable to use a process oil from the viewpoint that the fluidity at the time of melt molding can be further improved.
- the "process oil” is not particularly limited, and known process oils can be appropriately used.
- paraffin oil paraffin oil
- naphthen oil naphthen oil
- aroma oil as an oil, can be used.
- Oil and the like.
- a process oil a commercially available one may be appropriately used.
- paraffin oil is suitable from the viewpoint that higher compatibility with elastomers can be obtained and yellowing due to thermal deterioration can be suppressed at a higher level.
- the paraffin oil suitable as such a process oil is not particularly limited, and known paraffin oils (for example, those described in paragraphs [0153] to [0157] of JP-A-2017-57323) are used. Can be used as appropriate.
- a correlation ring analysis (nd-M ring analysis) based on ATM D3238-85 was performed on the oil, and the percentage of the paraffin carbon number to the total carbon number (paraffin).
- the paraffin oil preferably has a kinematic viscosity of 5 mm 2 / s to 1000 mm 2 / s at 40 ° C., measured in accordance with JIS K 2283 (issued in 2000), and is preferably 10 to 900 mm 2 . It is more preferably / s, and even more preferably 15 to 800 mm 2 / s.
- the fluidity of the thermoplastic elastomer composition of the present invention can be further improved.
- the paraffin oil preferably has an aniline point of 0 ° C. to 150 ° C., more preferably 10 to 145 ° C., as measured by a U-shaped tube method based on JIS K2256 (issued in 2013). It is more preferably 15 to 145 ° C.
- the aniline point By setting the aniline point within the above range, higher compatibility between the elastomer components can be obtained.
- the method for measuring the kinematic viscosity and the aniline point the methods described in paragraphs [0153] to [0157] of JP-A-2017-57323 can be adopted. Further, the method for preparing such a process oil is not particularly limited, and a known method can be appropriately adopted. Further, as such a process oil, a commercially available product may be used.
- the content of the plasticizer is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 80 parts by mass or less, and further preferably 20 parts by mass or more with respect to 100 parts by mass of the resin component. It is 60 parts by mass or less.
- the content of the plasticizer is within the above range, the fluidity at the time of melt molding can be improved.
- the thermoplastic elastomer composition may contain any other additive in addition to the above-mentioned additives.
- Other additives include a reinforcing agent (a kind of filler: for example, silica, carbon black, etc.), a filler having an amino group introduced therein, an amino group-containing compound other than the amino group-introduced filler, and a metal element.
- the molded product of the present invention is obtained by using the above-mentioned thermoplastic elastomer composition.
- examples of the molded product include those obtained by performing insert injection molding of the above-mentioned thermoplastic elastomer composition together with a housing which is a different material. Since the thermoplastic elastomer composition of the present invention is excellent in resistance to compression set in a high temperature environment, fluidity during melt molding, and heat fusion adhesion with different materials, the obtained molded product is a packing. Suitable as a sealing material, weather strip, and interior skin material. Further, the obtained molded body can be suitably used for, for example, an in-vehicle electrical device.
- thermoplastic elastomer composition ⁇ Manufacturing of thermoplastic elastomer composition> [Example 1] The blended raw material in which the following resin components and additives were mixed was melt-kneaded at 180 to 240 ° C. using a twin-screw extruder or the like, and the strands were discharged. The obtained strands were pelletized to produce a thermoplastic elastomer composition.
- Resin component 20 parts by mass of maleic anhydride-modified polypropylene (PP) (acid modification amount: 1.8% by mass, molecular weight (Mw): 153,000, manufactured by RIKEN Vitamin Co., Ltd., trade name: Rrotede MG670P) 20 parts by mass-styrene-ethylene-butylene- Styrene block copolymer (SEBS) (molecular weight (Mw): 300,000, manufactured by LCY, trade name: GP7533) 40 parts by mass ⁇ Styrene-butadiene-styrene block copolymer (SBS) (Molecular weight (Mw): 80,000, manufactured by LCY, trade name: GP3527) 40 parts by mass (additive) ⁇ Paraffin oil (made by ENEOS, trade name: YU8J) 30 parts by mass ⁇ Maleic anhydride-modified polyolefin wax 1 (acid modification amount: 1.5% by mass, molecular weight (Mw)
- Example 2 The heat was changed in the same manner as in Example 1 except that the resin component was changed as follows, the amount of paraffin oil added was changed to 40 parts by mass, and the amount of anhydrous maleic acid-modified polyolefin wax 1 was changed to 10 parts by mass. A thermoplastic elastomer composition was produced.
- thermoplastic elastomer composition was produced in the same manner as in Example 2 except that the amount of the organic peroxide cross-linking agent added was changed to 3.2 parts by mass and the amount of the cross-linking aid added was changed to 16 parts by mass.
- Example 4 Instead of maleic anhydride-modified polyolefin wax 1, 10 parts by mass of maleic anhydride-modified polyolefin wax 2 (acid modification amount: 1.5% by mass, manufactured by Toyo Spinning Co., Ltd., trade name: Toyotac PMA-F6) was added. , A thermoplastic elastomer composition was produced in the same manner as in Example 2.
- Example 5 instead of the maleic anhydride-modified polyolefin wax 1, the anhydrous maleic acid-modified polyolefin wax 3 (acid modification amount: 2.0% by mass, molecular weight (Mw): about 60,000, manufactured by Toyo Boseki Co., Ltd., trade name: Toyotack PMA- A thermoplastic elastomer composition was produced in the same manner as in Example 2 except that 10 parts by mass of LE) was added.
- Example 6 The amount of paraffin oil added was changed to 60 parts by mass, and instead of the anhydrous maleic acid-modified polyolefin wax 1, the anhydrous maleic acid-modified liquid polybutadiene (molecular weight (Mw): about 2700, manufactured by Clay Valley, trade name: Ricon 130MA8).
- Mw molecular weight
- Ricon 130MA8 A thermoplastic elastomer composition was produced in the same manner as in Example 1 except that 10 parts by mass was added.
- thermoplastic elastomer composition was produced in the same manner as in Example 1 except that the amount of paraffin oil added was changed to 60 parts by mass and the amount of maleic anhydride-modified polyolefin wax 1 was changed to 10 parts by mass.
- Example 8 The amount of maleic anhydride-modified PP added was changed to 15 parts by mass, the amount of SEBS added was changed to 42.5 parts by mass, the amount of SBS added was changed to 42.5 parts by mass, and the amount of paraffin oil added was changed. Same as in Example 1 except that the amount was changed to 60 parts by mass, the amount of the organic peroxide cross-linking agent added was changed to 1.7 parts by mass, and the amount of the cross-linking aid added was changed to 8.5 parts by mass. To produce a thermoplastic elastomer composition.
- Example 9 The amount of maleic anhydride-modified PP added was changed to 10 parts by mass, and the ethylene-butene copolymer (EBM) (molecular weight (Mw): 87,000, manufactured by Mitsui Kagaku Co., Ltd., trade name: Toughmer DF7350) was added by 10 parts by mass.
- EBM ethylene-butene copolymer
- Toughmer DF7350 thermoplastic elastomer composition was produced in the same manner as in Example 7 except that it was added.
- Example 10 Heat was applied in the same manner as in Example 8 except that 10 parts by mass of maleic anhydride-modified liquid polybutadiene was added and 10 parts by mass of an isobutylene-maleic anhydride copolymer (manufactured by Kuraray, trade name: Isoban 18) was added. A thermoplastic elastomer composition was produced.
- Example 11 The amount of maleic anhydride-modified PP added was changed to 20 parts by mass, EBM was added by 20 parts by mass, the amount of SEBS added was changed to 30 parts by mass, the amount of SBS added was changed to 30 parts by mass, and paraffin oil.
- the amount of maleic anhydride-modified polyolefin wax 1 was changed to 5 parts by mass, the amount of maleic anhydride-modified liquid polybutadiene was changed to 5 parts by mass, and isobutylene-maleine anhydride was added. Except for changing the amount of acid copolymer added to 5 parts by mass, the amount of organic peroxide cross-linking agent added to 1.2 parts by mass, and the amount of cross-linking aid added to 6 parts by mass.
- a thermoplastic elastomer composition was produced in the same manner as in Example 10.
- Example 12 The amount of maleic anhydride-modified PP added was changed to 10 parts by mass, the amount of SEBS added was changed to 45 parts by mass, the amount of SBS added was changed to 45 parts by mass, and the amount of paraffin oil added was changed to 50 parts by mass. Except that the amount of the organic peroxide cross-linking agent was changed to 1.8 parts by mass and the amount of the cross-linking aid was changed to 9 parts by mass without adding the isobutylene-maleic anhydride copolymer. , A thermoplastic elastomer composition was produced in the same manner as in Example 10.
- thermoplastic elastomer composition was produced in the same manner as in Example 7 except that 20 parts by mass of EBM was added instead of the maleic anhydride-modified PP.
- Example 14 Heat was applied in the same manner as in Example 7 except that polypropylene (PP) (molecular weight (Mw): 190,000, manufactured by SunAllomer Ltd., trade name: PM870A) was added in an amount of 20 parts by mass instead of the maleic anhydride-modified PP. A thermoplastic elastomer composition was produced.
- PP polypropylene
- Mw molecular weight
- thermoplastic elastomer composition was produced in the same manner as in Example 14 except that the addition amount of the maleic anhydride-modified polyolefin wax 1 was changed to 30 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 7 except that the maleic anhydride-modified polyolefin wax 1 was not added.
- thermoplastic elastomer composition was produced in the same manner as in Example 1 except that the maleic anhydride-modified polyolefin wax 1 was not added.
- thermoplastic elastomer composition was produced in the same manner as in Example 10 except that no organic peroxide cross-linking agent was added and no cross-linking aid was added.
- thermoplastic elastomer composition was produced in the same manner as in Example 2 except that the maleic anhydride-modified polyolefin wax 1 was not added.
- thermoplastic elastomer composition was produced in the same manner as in Comparative Example 4 except that the amount of paraffin oil added was changed to 50 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 2 except that no organic peroxide cross-linking agent was added and no cross-linking aid was added.
- Example 7 Melting in the same manner as in Example 7 except that the amount of maleic anhydride-modified PP added was changed to 6 parts by mass, the amount of SEBS added was changed to 47 parts by mass, and the amount of SBS added was changed to 47 parts by mass. Although it was kneaded, the composition was not cohesive and could not be pelletized.
- Example 8 The composition was melt-kneaded in the same manner as in Example 7 except that the amount of SEBS added was changed to 50 parts by mass and the amount of SBS added was changed to 50 parts by mass without adding maleic anhydride-modified PP. It was not cohesive and could not be pelletized.
- Example 16 The amount of EBM added was changed to 5 parts by mass, PP (manufactured by Sun Aroma Co., Ltd., trade name: PM870A) was added by 15 parts by mass, and the amount of maleic anhydride-modified polyolefin wax 1 added was changed to 30 parts by mass, and the polyester compound was added.
- Thermoplastic elastomer composition in the same manner as in Example 13 except that 1 (crystalline PET, molecular weight (Mw): 42,000, manufactured by Toyo Boseki Co., Ltd., trade name: Byron resin GM-380) was added in an amount of 10 parts by mass. Manufactured.
- thermoplastic elastomer composition was produced in the same manner as in Example 16 except that the addition amount of the polyester compound 1 was changed to 30 parts by mass.
- Example 18 Same as Example 16 except that 10 parts by mass of polyester compound 2 (elastomer PET, molecular weight (Mw): 41,000, manufactured by Toyobo Co., Ltd., trade name: Byron resin 200) was added instead of polyester compound 1. To produce a thermoplastic elastomer composition.
- polyester compound 2 elastomer PET, molecular weight (Mw): 41,000, manufactured by Toyobo Co., Ltd., trade name: Byron resin 200
- thermoplastic elastomer composition was produced in the same manner as in Example 18 except that the addition amount of the polyester compound 2 was changed to 30 parts by mass.
- Example 20 Same as Example 16 except that 10 parts by mass of polyester compound 3 (elastomer PET, molecular weight (Mw): 5,500, manufactured by Toyobo Co., Ltd., trade name: Byron resin 220) was added instead of polyester compound 1. To produce a thermoplastic elastomer composition.
- polyester compound 3 elastomer PET, molecular weight (Mw): 5,500, manufactured by Toyobo Co., Ltd., trade name: Byron resin 220
- thermoplastic elastomer composition was produced in the same manner as in Example 20 except that the addition amount of the polyester compound 3 was changed to 30 parts by mass.
- Example 22 Example 16 except that 10 parts by mass of polyester compound 4 (crystalline PET, molecular weight (Mw): 25,000, manufactured by Toyobo Co., Ltd., trade name: Byron resin GA-6400) was added instead of the polyester compound 1. Similarly, a thermoplastic elastomer composition was produced.
- polyester compound 4 crystalline PET, molecular weight (Mw): 25,000, manufactured by Toyobo Co., Ltd., trade name: Byron resin GA-6400
- thermoplastic elastomer composition was produced in the same manner as in Example 22 except that the addition amount of the polyester compound 4 was changed to 30 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 19 except that the amount of paraffin oil added was changed to 50 parts by mass and maleic anhydride-modified polyolefin wax 1 was not added.
- Example 25 5 parts by mass of maleic anhydride-modified EBM was added instead of EBM, and the amount of paraffin oil added was changed to 40 parts by mass.
- Fatty acid metal salt-based cross-linking agent aluminum tristearate, manufactured by Nichiyu Co., Ltd., trade name: AL
- a thermoplastic elastomer composition was produced in the same manner as in Example 24 except that 2.4 parts by mass of ⁇ 900) was added.
- thermoplastic elastomer composition was produced in the same manner as in Example 25 except that the amount of paraffin oil added was changed to 60 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 26 except that the addition amount of the polyester compound 2 was changed to 45 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 25 except that the amount of the polyester compound 2 added was changed to 45 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 25, except that the amount of maleic anhydride-modified EBM added was changed to 10 parts by mass and the amount of PP added was changed to 10 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 29, except that the amount of paraffin oil added was changed to 60 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 30 except that the amount of the polyester compound 2 added was changed to 45 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 29, except that the amount of the polyester compound 2 added was changed to 45 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 32, except that the amount of the fatty acid metal salt-based cross-linking agent added was changed to 4.8 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 32, except that the amount of maleic anhydride-modified EBM added was changed to 15 parts by mass and the amount of PP added was changed to 5 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 1 except that the resin components and additives were changed as follows.
- Polyester compound 2 45 parts by mass ⁇
- Fatty acid metal salt-based cross-linking agent 2.4 parts by mass ⁇
- Organic peroxide cross-linking agent 1.8 parts by mass ⁇
- Cross-linking aid manufactured by Mitsubishi Chemical Co., Ltd., trade name: TAIC WH-60
- antioxidant manufactured by ADEKA, trade name: AO-50
- Example 36 The amount of maleic anhydride-modified PP added was changed to 3.75 parts by mass, the amount of maleic anhydride-modified EBM added was changed to 1.25 parts by mass, and the amount of SEBS added was changed to 47.5 parts by mass. Examples except that the addition amount of SBS was changed to 47.5 parts by mass, the addition amount of the cross-linking aid was changed to 9.5 parts by mass, and the addition amount of the antioxidant was changed to 0.59 parts by mass. A thermoplastic elastomer composition was produced in the same manner as in 35.
- thermoplastic elastomer composition was produced in the same manner as in Example 35, except that the amount of the antioxidant added was changed to 0.63 parts by mass.
- Example 37 The amount of maleic anhydride-modified PP added was changed to 15 parts by mass, the amount of maleic anhydride-modified EBM added was changed to 5 parts by mass, the amount of SEBS added was changed to 40 parts by mass, and the amount of SBS added was 40 parts. Change to parts by mass, change the amount of paraffin oil added to 70 parts by mass, change the amount of polyester compound 2 added to 40 parts by mass, change the amount of cross-linking aid added to 8 parts by mass, and change the antioxidant.
- a thermoplastic elastomer composition was produced in the same manner as in Example 35, except that the amount of the above was changed to 0.5 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 37, except that the amount of paraffin oil added was changed to 60 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 38, except that 0.5 part by mass of an antioxidant 2 (manufactured by ADEKA, trade name: PEP-36) was added.
- an antioxidant 2 manufactured by ADEKA, trade name: PEP-36
- thermoplastic elastomer composition was prepared in the same manner as in Example 39, except that 8 parts by mass of the cross-linking aid 2 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DCP) was added instead of the cross-linking aid (TAIC). Manufactured.
- the cross-linking aid 2 manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DCP
- Example 41 The amount of maleic anhydride-modified PP added was changed to 11.25 parts by mass, the amount of maleic anhydride-modified EBM added was changed to 3.75 parts by mass, and the amount of SEBS added was changed to 42.5 parts by mass. The amount of SBS added was changed to 42.5 parts by mass, the amount of cross-linking aid 2 added was changed to 8.5 parts by mass, the amount of antioxidant added was changed to 0.53 parts by mass, and the antioxidant was added. A thermoplastic elastomer composition was produced in the same manner as in Example 40, except that the addition amount of 2 was changed to 0.53 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 37, except that the amount of the polyester compound 2 added was changed to 40 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 42, except that 9 parts by mass of the cross-linking aid 2 was added instead of the cross-linking aid (TAIC) and 0.56 parts by mass of the antioxidant 2 was added. did.
- thermoplastic elastomer composition was produced in the same manner as in Example 38, except that a fatty acid metal salt-based cross-linking agent was not added.
- thermoplastic elastomer composition was produced in the same manner as in Example 38, except that the amount of the polyester compound 2 added was changed to 45 parts by mass.
- thermoplastic elastomer composition was the same as in Example 45, except that the addition amount of the polyester compound 2 was changed to 40 parts by mass and 5 parts by mass of a compatibilizer (manufactured by Osaka Gas Chemical Co., Ltd., trade name: Maricon) was added. Manufactured a thing.
- thermoplastic elastomer composition was produced in the same manner as in Example 45, except that the amount of maleic anhydride-modified PP added was changed to 10 parts by mass and the amount of maleic anhydride-modified EBM added was changed to 10 parts by mass. ..
- thermoplastic elastomer composition was produced in the same manner as in Example 47, except that the amount of paraffin oil added was changed to 50 parts by mass.
- thermoplastic elastomer composition was produced in the same manner as in Example 46, except that 0.5 parts by mass of a cyclic trifunctional alcohol (manufactured by Nissei Corporation, trade name: Tanac P) was added instead of the compatibilizer. did.
- a cyclic trifunctional alcohol manufactured by Nissei Corporation, trade name: Tanac P
- Example 50 The amount of maleic anhydride-modified PP added was changed to 11.25 parts by mass, the amount of maleic anhydride-modified EBM added was changed to 3.75 parts by mass, and the amount of SEBS added was changed to 42.5 parts by mass.
- the amount of SBS added was changed to 42.5 parts by mass, the amount of organic peroxide cross-linking agent added was changed to 1.7 parts by mass, the amount of cross-linking aid added was changed to 8.5 parts by mass, and oxidation was performed.
- a thermoplastic elastomer composition was produced in the same manner as in Example 45, except that the amount of the inhibitor added was changed to 0.53 parts by mass.
- Example 51 11.25 parts by mass of PP was added instead of maleic anhydride-modified PP, 3.75 parts by mass of EBM was added instead of maleic anhydride-modified EBM, and the amount of polyester compound 2 added was changed to 40 parts by mass.
- a thermoplastic elastomer composition was produced in the same manner as in Example 45, except that a fatty acid metal salt-based cross-linking agent was not added.
- thermoplastic elastomer compositions produced in Examples 1 to 51 and Comparative Examples 1 to 6 and 9 were evaluated for the following items. The evaluation results are shown in Tables 1-6.
- the thermoplastic elastomer compositions of Comparative Examples 7 and 8 could not be measured for the following physical properties, and were therefore not evaluated as “ ⁇ ”.
- thermoplastic elastomer composition obtained in each Example and Comparative Example a sheet for use in evaluating the characteristics of the composition was prepared as follows. First, using a pressure press with a water-cooled cooling function, heat to 200 ° C., then put 43 g of the thermoplastic elastomer composition in a mold measuring 15 cm in length, 15 cm in width, and 2 mm in thickness, and before pressurization. After heating (preheating) at 200 ° C.
- thermoplastic elastomer composition after pressing was taken out from the mold to obtain a sheet for measurement having a thickness of 2 mm.
- JIS-A hardness (JIS-A hardness) Using the sheets for each measurement obtained as described above, the A hardness was measured by a hardness tester (manufactured by Teclock Co., Ltd., trade name: Durometer GX02A) in accordance with JIS K6253-3.
- the compression set was obtained as follows. First, the sheet for measurement was heated at 125 ° C. for 30 minutes to remove residual molding strain. After that, the above measurement sheets were punched out into a disk shape having a diameter of 29 mm, and seven sheets were superposed to prepare a sample so that the height (thickness) was 12.5 ⁇ 0.5 mm. Using the sample obtained in this way, the compression set (unit:%) after being compressed by 25% with a special jig and left at 125 ° C for 22 hours is measured according to JIS K6262 (issued in 2013). did.
- vulcanized rubber compression set constant strain tester SCM-1008L manufactured by Dumbbell Co., Ltd. was used.
- the compression set is less than 70%, it can be said that the resistance to the compression set in a high temperature environment is good.
- thermoplastic elastomer composition (Liquidity) Melt flow rate (MFR, unit: g / 10 minutes) according to Method B described in JIS K6922-2 (issued in 2010) using each thermoplastic elastomer composition obtained in each Example and Comparative Example. ) was measured. That is, using each of the above thermoplastic elastomer compositions, using the trade name "Melt Indexer G-01" manufactured by Toyo Seiki Seisakusho as a melt flow rate measuring device, 3 g of the thermoplastic elastomer composition was placed in the furnace body of the device. After the addition, the temperature was kept at 230 ° C.
- the mass (g) that flows out per unit time is measured from the opening of the orifice member (opening with a diameter of 1 mm) (the temperature is kept at 230 ° C. for 5 minutes in the furnace body, and then the load is started before the outflow.
- the measurement of the mass of the thermoplastic elastomer composition to be carried out is started), and the measurement is performed by converting to the mass (g) of the thermoplastic elastomer composition flowing out in 10 minutes. If the MFR is 2 (g / 10min) or more, it can be said that the fluidity is good.
- thermoplastic elastomer composition obtained in each Example and Comparative Example and a polybutylene terephthalate (PBT) resin piece
- a bond strength measurement test piece according to JIS K 6850 shear bond strength test
- JIS K 6850 shear bond strength test
- the adhesive strength (MPa) between the molded product made of the thermoplastic elastomer composition and the PBT resin plate was measured by a tensile tester. When the adhesive strength is 0.15 MPa or more, it can be said that the heat-sealing adhesiveness is good.
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Abstract
Description
樹脂成分と添加剤を含む熱可塑性エラストマー組成物であって、
前記樹脂成分が、共有結合架橋部を含むスチレン系ブロック共重合体と、重量平均分子量が80,000以上500,000以下のポリオレフィンとを含み、前記スチレン系ブロック共重合体の含有量が、前記樹脂成分全体に対して、40質量%以上95質量%以下であり、前記ポリオレフィンの含有量が、前記樹脂成分全体に対して、5質量%以上60質量%以下であり、
前記添加剤が、重量平均分子量が1,000以上80,000未満のカルボン酸および/またはその誘導体に由来する官能基を有する酸変性化合物、および/または、ポリエステル化合物と、前記スチレン系ブロック共重合体および前記ポリオレフィンの少なくとも1種を架橋し得る架橋剤とを含むことを特徴とする、熱可塑性エラストマー組成物が提供される。
本発明の熱可塑性エラストマー組成物は、特定の樹脂成分と添加剤を含むものである。当該熱可塑性エラストマー組成物は、高温環境下の圧縮永久歪に対する耐性および異種素材との熱融着接着性に優れるため、パッキン、シール材、ウェザーストリップ、および内装表皮材用として好適である。また、当該熱可塑性エラストマー組成物は、溶融成形時の流動性に優れるため、インサート射出成形に好適に用いることができる。以下、各成分について詳細に説明する。
熱可塑性エラストマー組成物は、樹脂成分として、少なくとも、共有結合架橋部を含むスチレン系ブロック共重合体と、ポリオレフィンとを含む。通常、熱可塑性エラストマー組成物樹脂成分は、共有結合架橋部を含むスチレン共重合体を含むことで、高温環境下の圧縮永久歪に優れる一方、溶融成形時の流動性が十分に得られない。しかし、本発明においては、ポリオレフィンを配合することで、スチレン系ブロック共重合体相がドメインとなり、ポリオレフィン相がマトリクスとなって、良好な圧縮永久歪を確保したまま、溶融成形時の流動性を得ることができる。
本発明において「スチレン系ブロック共重合体」とは、いずれかの部位にスチレンブロック構造を有するコポリマーであればよい。また、「共有結合架橋部」とは、共有結合によりスチレン系ブロック共重合体の分子同士を架橋する部位であればよく、その形態は特に制限されるものではない。スチレン系ブロック共重合体の分子同士を架橋する共有結合架橋部としては、より強固な架橋の形成が可能であるとともに、架橋形成の簡便さに優れるといった観点から、炭素架橋、酸素架橋、および硫黄架橋からなる群から選択される少なくとも1種の架橋からなることが好ましく、炭素架橋からなることがより好ましい。
ポリオレフィンとしては、特に限定されず、従来公知のポリオレフィンを用いることができる。ポリオレフィンとしては、例えば、エチレン、プロピレン、ブテン-1、ペンテン-1、2-メチルブテン-1、3-メチルブテン-1、ヘキセン-1、3-メチルペンテン-1、4-メチルペンテン-1、3,3-ジメチルブテン-1、ヘプテン-1、メチルヘキセン-1、ジメチルペンテン-1、トリメチルブテン-1、エチルペンテン-1、オクテン-1、メチルペンテン-1、ジメチルヘキセン-1、トリメチルペンテン-1、エチルヘキセン-1、メチルエチルペンテン-1、ジエチルブテン-1、プトピルペンテン-1、デセン-1、メチルノネン-1、ジメチルオクテン-1、トリメチルヘプテン-1、エチルオクテン-1、メチルエチルヘプテン-1、ジエチルヘキセン-1、ドデセン-1およびヘキサドデセン-1等のα-オレフィンの単独重合体、あるいは、これらα-オレフィンの任意の二種以上を原料モノマーとする共重合体を挙げることができる。これらの中でも、プロピレンの単独重合体(ポリプロピレン)およびエチレン-ブテン共重合体が好ましい。これらのポリオレフィンは、1種単独で使用してもよく、2種以上を組み合わせて使用してもよい。
また、ポリオレフィンの含有量は、樹脂成分全体に対して、5質量%以上60質量%以下であり、下限値は好ましくは10質量%以上であり、より好ましくは15質量%以下であり、上限値は好ましくは50質量%以下であり、より好ましくは45質量%以下であり、さらに好ましくは40質量%以下である。
スチレン系ブロック共重合体とポリオレフィンの含有量が上記範囲内であれば、高温環境下の圧縮永久歪に対する耐性、溶融成形時の流動性、および異種素材との熱融着接着性のバランスに優れた熱可塑性エラストマー組成物を得ることができる。
(酸変性化合物)
熱可塑性エラストマー組成物は、添加剤として、カルボン酸および/またはその誘導体に由来する官能基を有する酸変性化合物を含むことが好ましい。酸変性化合物の官能基としては、例えば、カルボキシ基、カルボニル基、酸無水物基、エステル基、およびアミド基等が挙げられる。より詳細には、後述する不飽和カルボン酸および/またはその誘導体に由来する官能基が挙げられる。酸変性化合物は、これらのうち1つまたは複数の官能基を含んでよい。また、酸変性化合物は、熱可塑性エラストマー組成物の性能を損ねない範囲で他の官能基、例えば、ヒドロキシル基、エーテル基等を含んでもよい。熱可塑性エラストマー組成物にカルボン酸および/またはその誘導体に由来する官能基を有する酸変性化合物を配合することで、インサート射出成形した際に、酸変性化合物の官能基により異種素材との熱融着接着性を向上させることができる。
熱可塑性エラストマー組成物は、添加剤として、ポリエステル化合物を含むことが好ましい。ポリエステル化合物は、結晶性および非晶性のいずれでもよい。ポリエステル化合物としては、例えば、ポリエチレンテレフタレート(PET)、ポリトリメチレンテレフタレート(PTT)、ポリブチレンテレフタレート(PBT)、ポリエチレンナフタレート(PEN)、およびポリブチレンナフタレート(PBN)、ならびに酸成分もしくはジオール成分を変性した変性ポリエステル等が挙げられる。これらのポリエステル化合物は1種単独で使用してもよく、2種以上を組み合わせて使用してもよい。
熱可塑性エラストマー組成物は、必須の添加剤として、スチレン系ブロック共重合体およびポリオレフィンの少なくとも1種を架橋し得る架橋剤を含む。架橋剤としては、スチレン系ブロック共重合体およびポリオレフィンの少なくとも1種に架橋を形成することが可能なものであれば特に制限されないが、過酸化物系架橋剤、脂肪酸金属塩系架橋剤、硫黄系架橋剤、フェノール樹脂系架橋剤、アミノ樹脂系架橋剤、キノン系架橋剤、ハロゲン系架橋剤、アゾ系架橋剤、アルデヒド系架橋剤、エポキシ系架橋剤、双極性化合物系架橋剤、光系架橋剤等を好適に使用することができる。これらの中でも、過酸化物系架橋剤、脂肪酸金属塩系架橋剤、硫黄系架橋剤がより好ましく、過酸化物系架橋剤および脂肪酸金属塩系架橋剤が特に好ましい。
熱可塑性エラストマー組成物は、任意の添加剤として、可塑剤を含む。可塑剤としては、溶融成形時の流動性をより向上させることが可能となるといった観点から、プロセスオイルを用いることが好ましい。このような「プロセスオイル」としては、特に制限されず、公知のプロセスオイルを適宜使用することができ、例えば、パラフィンオイル(パラフィン系オイル)、ナフテンオイル(ナフテン系オイル)、アロマオイル(アロマ系オイル)等が挙げられる。このようなプロセスオイルとしては、市販のものを適宜使用してもよい。
熱可塑性エラストマー組成物は、上述の添加剤以外に、任意の他の添加剤を含んでもよい。他の添加剤としては、補強剤(充填剤の一種:例えばシリカ、カーボンブラック等)、アミノ基を導入してなる充填剤、該アミノ基導入充填剤以外のアミノ基含有化合物、金属元素を含む化合物、老化防止剤、酸化防止剤、顔料(染料)、前記プロセスオイル以外の可塑剤、揺変性付与剤、紫外線吸収剤、難燃剤、溶剤、界面活性剤(レベリング剤を含む)、消臭剤(重曹等)、分散剤、脱水剤、防錆剤、接着付与剤、帯電防止剤、クレイ以外のフィラー、滑剤、スリップ剤、光安定剤、導電性付与剤、防菌剤、中和剤、軟化剤、充填材、着色剤、熱伝導性充填材、相溶化剤などの各種の添加剤を含有することができる。
本発明の成形体は、上記の熱可塑性エラストマー組成物を用いて得られるものである。具体的には、成形体としては、上記の熱可塑性エラストマー組成物を、異種素材である筐体とともにインサート射出成形を行って得られたものが挙げられる。本発明の熱可塑性エラストマー組成物は、高温環境下の圧縮永久歪に対する耐性、溶融成形時の流動性、および異種素材との熱融着接着性に優れるため、得られた成形体は、パッキン、シール材、ウェザーストリップ、内装表皮材として好適である。また、得られた成形体は、例えば、車載電装デバイス等に好適に使用できる。
[実施例1]
以下の樹脂成分と添加剤を混合したブレンド原料を二軸押出機等により180~240℃で溶融混練し、ストランドを吐出した。得られたストランドをペレタイズして、熱可塑性エラストマー組成物を製造した。
(樹脂成分)
・無水マレイン酸変性ポリプロピレン(PP)(酸変性量:1.8質量%、分子量(Mw):153,000、理研ビタミン社製、商品名:リケエイドMG670P) 20質量部
・スチレン-エチレン-ブチレン-スチレンブロック共重合体(SEBS)(分子量(Mw):300,000、LCY社製、商品名:GP7533)
40質量部
・スチレン-ブタジエン-スチレンブロック共重合体(SBS)(分子量(Mw):80,000、LCY社製、商品名:GP3527) 40質量部
(添加剤)
・パラフィンオイル(ENEOS社製、商品名:YU8J) 30質量部
・無水マレイン酸変性ポリオレフィンワックス1(酸変性量:1.5質量%、分子量(Mw):約75000、東洋紡社製、商品名:トーヨータックPMA-L) 30質量部
・有機過酸化物架橋剤(日油社製、商品名:パーヘキシン25B-40)
1.6質量部
・架橋助剤(三菱ケミカル社製、商品名:TAIC WH-60)8質量部
・酸化防止剤(ADEKA社製、商品名:AO-50) 0.5質量部
樹脂成分を以下の通りに変更し、さらにパラフィンオイルの添加量を40質量部、無水マレイン酸変性ポリオレフィンワックス1の添加量を10質量部に変更した以外は、実施例1と同様にして、熱可塑性エラストマー組成物を製造した。
(樹脂成分)
・無水マレイン酸変性ポリプロピレン(PP)(理研ビタミン社製、商品名:リケエイドMG670P) 10質量部
・無水マレイン酸変性エチレン-ブテン共重合体(EBM)(酸変性量:2.2質量%、分子量(Mw):156,000、三井化学社製、商品名:タフマーMH5040) 10質量部
・スチレン-エチレン-ブチレン-スチレンブロック共重合体(SEBS)(LCY社製、商品名:GP7533) 40質量部
・スチレン-ブタジエン-スチレンブロック共重合体(SBS)(LCY社製、商品名:GP3527) 40質量部
有機過酸化物架橋剤の添加量を3.2質量部、架橋助剤の添加量を16質量部に変更した以外は、実施例2と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性ポリオレフィンワックス1の代わりに、無水マレイン酸変性ポリオレフィンワックス2(酸変性量:1.5質量%、東洋紡社製、商品名:トーヨータックPMA-F6)を10質量部添加した以外は、実施例2と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性ポリオレフィンワックス1の代わりに、無水マレイン酸変性ポリオレフィンワックス3(酸変性量:2.0質量%、分子量(Mw):約60,000、東洋紡社製、商品名:トーヨータックPMA-LE)を10質量部添加した以外は、実施例2と同様にして、熱可塑性エラストマー組成物を製造した。
パラフィンオイルの添加量を60質量部に変更し、無水マレイン酸変性ポリオレフィンワックス1の代わりに、無水マレイン酸変性液状ポリブタジエン(分子量(Mw):約2700、クレイバレー社製、商品名:Ricon 130MA8)を10質量部添加した以外は、実施例1と同様にして、熱可塑性エラストマー組成物を製造した。
パラフィンオイルの添加量を60質量部に変更し、無水マレイン酸変性ポリオレフィンワックス1の添加量を10質量部に変更した以外は、実施例1と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を15質量部に変更し、SEBSの添加量を42.5質量部に変更し、SBSの添加量を42.5質量部に変更し、パラフィンオイルの添加量を60質量部に変更し、有機過酸化物架橋剤の添加量を1.7質量部に変更し、架橋助剤の添加量を8.5質量部に変更した以外は、実施例1と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を10質量部に変更し、エチレン-ブテン共重合体(EBM)(分子量(Mw):87,000、三井化学社製、商品名:タフマーDF7350)を10質量部添加した以外は、実施例7と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性液状ポリブタジエンを10質量部添加し、イソブチレン-無水マレイン酸共重合体(クラレ社製、商品名:イソバン18)を10質量部添加した以外は、実施例8と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を20質量部に変更し、EBMを20質量部添加し、SEBSの添加量を30質量部に変更し、SBSの添加量を30質量部に変更し、パラフィンオイルの添加量を40質量部に変更し、無水マレイン酸変性ポリオレフィンワックス1の添加量を5質量部に変更し、無水マレイン酸変性液状ポリブタジエンの添加量を5質量部に変更し、イソブチレン-無水マレイン酸共重合体の添加量を5質量部に変更し、有機過酸化物架橋剤の添加量を1.2質量部に変更し、架橋助剤の添加量を6質量部に変更した以外は、実施例10と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を10質量部に変更し、SEBSの添加量を45質量部に変更し、SBSの添加量を45質量部に変更し、パラフィンオイルの添加量を50質量部に変更し、イソブチレン-無水マレイン酸共重合体を添加せず、有機過酸化物架橋剤の添加量を1.8質量部に変更し、架橋助剤の添加量を9質量部に変更した以外は、実施例10と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの代わりに、EBMを20質量部添加した以外は、実施例7と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの代わりに、ポリプロピレン(PP)(分子量(Mw):190,000、サンアロマー社製、商品名:PM870A)を20質量部添加した以外は、実施例7と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性ポリオレフィンワックス1の添加量を30質量部に変更した以外は、実施例14と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性ポリオレフィンワックス1を添加しなかった以外は、実施例7と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性ポリオレフィンワックス1を添加しなかった以外は、実施例1と同様にして、熱可塑性エラストマー組成物を製造した。
有機過酸化物架橋剤を添加せず、架橋助剤を添加しなかった以外は、実施例10と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性ポリオレフィンワックス1を添加しなかった以外は、実施例2と同様にして、熱可塑性エラストマー組成物を製造した。
パラフィンオイルの添加量を50質量部に変更した以外は、比較例4と同様にして、熱可塑性エラストマー組成物を製造した。
有機過酸化物架橋剤を添加せず、架橋助剤を添加しなかった以外は、実施例2と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を6質量部に変更し、SEBSの添加量を47質量部に変更し、SBSの添加量を47質量部に変更した以外は、実施例7と同様にして溶融混練したが、組成物にまとまりが無く、ペレット化できなかった。
無水マレイン酸変性PPを添加せず、SEBSの添加量を50質量部に変更し、SBSの添加量を50質量部に変更した以外は、実施例7と同様にして溶融混練したが、組成物にまとまりが無く、ペレット化できなかった。
EBMの添加量を5質量部に変更し、PP(サンアロマー社製、商品名:PM870A)を15質量部添加し、無水マレイン酸変性ポリオレフィンワックス1の添加量を30質量部に変更し、ポリエステル化合物1(結晶性PET、分子量(Mw):42,000、東洋紡社製、商品名:バイロン樹脂GM-380)を10質量部添加した以外は、実施例13と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物1の添加量を30質量部に変更した以外は、実施例16と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物1の代わりに、ポリエステル化合物2(非晶性PET、分子量(Mw):41,000、東洋紡社製、商品名:バイロン樹脂200)を10質量部添加した以外は、実施例16と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物2の添加量を30質量部に変更した以外は、実施例18と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物1の代わりに、ポリエステル化合物3(非晶性PET、分子量(Mw):5,500、東洋紡社製、商品名:バイロン樹脂220)を10質量部添加した以外は、実施例16と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物3の添加量を30質量部に変更した以外は、実施例20と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物1の代わりに、ポリエステル化合物4(結晶性PET、分子量(Mw):25,000、東洋紡社製、商品名:バイロン樹脂GA-6400)を10質量部添加した以外は、実施例16と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物4の添加量を30質量部に変更した以外は、実施例22と同様にして、熱可塑性エラストマー組成物を製造した。
パラフィンオイルの添加量を50質量部に変更し、無水マレイン酸変性ポリオレフィンワックス1を添加しなかった以外は、実施例19と同様にして、熱可塑性エラストマー組成物を製造した。
EBMの代わりに無水マレイン酸変性EBMを5質量部添加し、パラフィンオイルの添加量を40質量部に変更し、脂肪酸金属塩系架橋剤(トリステアリン酸アルミニウム、日油社製、商品名:AL-900)を2.4質量部添加した以外は、実施例24と同様にして、熱可塑性エラストマー組成物を製造した。
パラフィンオイルの添加量を60質量部に変更した以外は、実施例25と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物2の添加量を45質量部に変更した以外は、実施例26と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物2の添加量を45質量部に変更した以外は、実施例25と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性EBMの添加量を10質量部に変更し、PPの添加量を10質量部に変更した以外は、実施例25と同様にして、熱可塑性エラストマー組成物を製造した。
パラフィンオイルの添加量を60質量部に変更した以外は、実施例29と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物2の添加量を45質量部に変更した以外は、実施例30と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物2の添加量を45質量部に変更した以外は、実施例29と同様にして、熱可塑性エラストマー組成物を製造した。
脂肪酸金属塩系架橋剤の添加量を4.8質量部に変更した以外は、実施例32と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性EBMの添加量を15質量部に変更し、PPの添加量を5質量部に変更した以外は、実施例32と同様にして、熱可塑性エラストマー組成物を製造した。
樹脂成分および添加剤を以下の通りに変更した以外は、実施例1と同様にして、熱可塑性エラストマー組成物を製造した。
(樹脂成分)
・無水マレイン酸変性PP 7.5質量部
・無水マレイン酸変性EBM 2.5質量部
・SEBS 45質量部
・SBS 45質量部
(添加剤)
・パラフィンオイル 60質量部
・ポリエステル化合物2 45質量部
・脂肪酸金属塩系架橋剤 2.4質量部
・有機過酸化物架橋剤 1.8質量部
・架橋助剤(三菱ケミカル社製、商品名:TAIC WH-60)9質量部
・酸化防止剤(ADEKA社製、商品名:AO-50) 0.5質量部
無水マレイン酸変性PPの添加量を3.75質量部に変更し、無水マレイン酸変性EBMの添加量を1.25質量部に変更し、SEBSの添加量を47.5質量部に変更し、SBSの添加量を47.5質量部に変更し、架橋助剤の添加量を9.5質量部に変更し、酸化防止剤の添加量を0.59質量部に変更した以外は、実施例35と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPおよび無水マレイン酸変性EBMを添加せず、SEBSの添加量を50質量部に変更し、SBSの添加量を50質量部に変更し、架橋助剤の添加量を10質量部に変更し、酸化防止剤の添加量を0.63質量部に変更した以外は、実施例35と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を15質量部に変更し、無水マレイン酸変性EBMの添加量を5質量部に変更し、SEBSの添加量を40質量部に変更し、SBSの添加量を40質量部に変更し、パラフィンオイルの添加量を70質量部に変更し、ポリエステル化合物2の添加量を40質量部に変更し、架橋助剤の添加量を8質量部に変更し、酸化防止剤の添加量を0.5質量部に変更した以外は、実施例35と同様にして、熱可塑性エラストマー組成物を製造した。
パラフィンオイルの添加量を60質量部に変更した以外は、実施例37と同様にして、熱可塑性エラストマー組成物を製造した。
酸化防止剤2(ADEKA社製、商品名:PEP-36)を0.5質量部添加した以外は、実施例38と同様にして、熱可塑性エラストマー組成物を製造した。
架橋助剤(TAIC)の代わりに架橋助剤2(新中村化学社製、商品名:A-DCP)を8質量部添加した以外は、実施例39と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を11.25質量部に変更し、無水マレイン酸変性EBMの添加量を3.75質量部に変更し、SEBSの添加量を42.5質量部に変更し、SBSの添加量を42.5質量部に変更し、架橋助剤2の添加量を8.5質量部に変更し、酸化防止剤の添加量を0.53質量部に変更し、酸化防止剤2の添加量を0.53質量部に変更した以外は、実施例40と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物2の添加量を40質量部に変更した以外は、実施例37と同様にして、熱可塑性エラストマー組成物を製造した。
架橋助剤(TAIC)の代わりに架橋助剤2を9質量部添加し、酸化防止剤2を0.56質量部添加した以外は、実施例42と同様にして、熱可塑性エラストマー組成物を製造した。
脂肪酸金属塩系架橋剤を添加しなかった以外は、実施例38と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物2の添加量を45質量部に変更した以外は、実施例38と同様にして、熱可塑性エラストマー組成物を製造した。
ポリエステル化合物2の添加量を40質量部に変更し、相溶化剤(大阪ガスケミカル社製、商品名:マリコン)を5質量部添加した以外は、実施例45と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を10質量部に変更し、無水マレイン酸変性EBMの添加量を10質量部に変更した以外は、実施例45と同様にして、熱可塑性エラストマー組成物を製造した。
パラフィンオイルの添加量を50質量部に変更した以外は、実施例47と同様にして、熱可塑性エラストマー組成物を製造した。
相溶化剤の代わりに環状の三官能アルコール(日星産業社製、商品名:タナックP)を0.5質量部添加した以外は、実施例46と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの添加量を11.25質量部に変更し、無水マレイン酸変性EBMの添加量を3.75質量部に変更し、SEBSの添加量を42.5質量部に変更し、SBSの添加量を42.5質量部に変更し、有機過酸化物架橋剤の添加量を1.7質量部に変更し、架橋助剤の添加量を8.5質量部に変更し、酸化防止剤の添加量を0.53質量部に変更した以外は、実施例45と同様にして、熱可塑性エラストマー組成物を製造した。
無水マレイン酸変性PPの代わりにPPを11.25質量部添加し、無水マレイン酸変性EBMの代わりにEBMを3.75質量部添加し、ポリエステル化合物2の添加量を40質量部に変更し、脂肪酸金属塩系架橋剤を添加しなかった以外は、実施例45と同様にして、熱可塑性エラストマー組成物を製造した。
実施例1~51および比較例1~6、9で製造した熱可塑性エラストマー組成物の物性を下記の項目について評価した。評価結果を表1~6に示した。なお、比較例7および8の熱可塑性エラストマー組成物は下記の物性測定が実施できなかったため、未評価「-」とした。
各実施例および比較例で得られた各熱可塑性エラストマー組成物を用いて、以下のようにして、組成物の特性の評価に使用するためのシートを調製した。まず、水冷冷却機能付の加圧プレス機を用い、200℃に加熱した後、縦15cm、横15cm、厚み2mmの大きさの金型に熱可塑性エラストマー組成物43gを入れて、加圧前に200℃で5分間加熱(予熱)し、次いで、温度:200℃、使用圧力:20Mpa、加圧時間:5分の条件で加圧(熱プレス)した後、使用圧力:20MPa、加圧時間:2分の条件で水冷冷却プレスを更に行い、前記金型からプレス後の熱可塑性エラストマー組成物を取り出して、厚み2mmの測定用のシートを得た。
上述のようにして得られた各測定用のシートを用いて、JIS K 6253-3に準拠して、硬度計(テクロック社製、商品名:デュロメータGX02A)により、A硬度を測定した。
上述のようにして得られた各測定用のシートを用いて、以下のようにして、圧縮永久歪(C-Set)を求めた。まず、上記測定用のシートを125℃で30分間加熱し、残留している成形歪を取り除いた。その後上記測定用のシートを直径29mmの円盤状に打ち抜いて7枚重ね合わせ、高さ(厚み)が12.5±0.5mmになるようにしてサンプルを調製した。このようにして得られたサンプルを用い、専用治具で25%圧縮し、125℃で22時間放置した後の圧縮永久歪(単位:%)をJIS K6262(2013年発行)に準拠して測定した。なお、圧縮装置としてはダンベル社製の商品名「加硫ゴム圧縮永久歪試験器 SCM-1008L」を用いた。圧縮永久歪が70%未満であれば、高温環境下の圧縮永久歪に対する耐性が良好であると言える。
各実施例および比較例で得られた各熱可塑性エラストマー組成物を用いて、JIS K6922-2(2010年発行)に記載のB法に準拠してメルトフローレート(MFR、単位:g/10分)を測定した。すなわち、上記の各熱可塑性エラストマー組成物を用い、メルトフローレート測定装置として東洋精機製作所製の商品名「Melt Indexer G-01」を用いて、該装置の炉体内に熱可塑性エラストマー組成物を3g添加した後、温度を230℃にして5分間保持した後、230℃に維持しつつ、10kgに荷重する条件で、前記炉体の下部に接続されている直径1mm、長さ8mmの筒状のオリフィス部材の開口部(直径1mmの開口部)から、単位時間あたりに流出する質量(g)を測定(前記炉体内において温度を230℃にして5分間保持した後、荷重を開始してから流出する熱可塑性エラストマー組成物の質量の測定を開始する)し、10分間に流出する熱可塑性エラストマー組成物の質量(g)に換算することにより求めた。MFRが2(g/10min)以上であれば、流動性が良好であると言える。
各実施例および比較例で得られた各熱可塑性エラストマー組成物と、ポリブチルテレフタレート(PBT)樹脂片とを用いて、JIS K 6850(せん断接着強さ試験)に準じた接着強度測定試験片をインサート射出成形にて製造した。得られた接着強度測定試験片を用いて、引張試験機によって、熱可塑性エラストマー組成物からなる成形体とPBT樹脂板との接着強度(MPa)を測定した。接着強度が0.15MPa以上であれば、熱融着接着性が良好であると言える。
Claims (15)
- 樹脂成分と添加剤を含む熱可塑性エラストマー組成物であって、
前記樹脂成分が、共有結合架橋部を含むスチレン系ブロック共重合体と、重量平均分子量が80,000以上500,000以下のポリオレフィンとを含み、前記スチレン系ブロック共重合体の含有量が、前記樹脂成分全体に対して、40質量%以上95質量%以下であり、前記ポリオレフィンの含有量が、前記樹脂成分全体に対して、5質量%以上60質量%以下であり、
前記添加剤が、重量平均分子量が1,000以上80,000未満のカルボン酸および/またはその誘導体に由来する官能基を有する酸変性化合物、および/または、ポリエステル化合物と、前記スチレン系ブロック共重合体および前記ポリオレフィンの少なくとも1種を架橋し得る架橋剤とを含むことを特徴とする、熱可塑性エラストマー組成物。 - 前記酸変性化合物の含有量が、前記樹脂成分100質量部に対して、1質量部以上50質量部以下である、請求項1に記載の熱可塑性エラストマー組成物。
- 前記ポリエステル化合物の含有量が、前記樹脂成分100質量部に対して、10質量部以上70質量部以下である、請求項1または2に記載の熱可塑性エラストマー組成物。
- 前記ポリオレフィンが、ポリプロピレンおよび無水マレイン酸変性ポリプロピレンの少なくとも1種を含み、
前記ポリプロピレンおよび無水マレイン酸変性ポリプロピレンの重量平均分子量が100,000以上200,000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。 - 前記ポリオレフィンが、エチレン-ブテン共重合体および無水マレイン酸変性エチレン-ブテン共重合体の少なくとも1種を含み、
前記エチレン-ブテン共重合体および無水マレイン酸変性エチレン-ブテン共重合体の重量平均分子量が80,000以上160,000以下である、請求項1~4のいずれか一項に記載の熱可塑性エラストマー組成物。 - 前記酸変性化合物の重量平均分子量が10,000以上77,000以下である、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。
- 前記酸変性化合物が、無水マレイン酸変性化合物である、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。
- 前記無水マレイン酸変性化合物が、無水マレイン酸変性ポリオレフィン、無水マレイン酸変性ポリブタジエン、およびイソブチレン-無水マレイン酸共重合体からなる群から選択される少なくとも1種である、請求項7に記載の熱可塑性エラストマー組成物。
- 前記スチレン系ブロック共重合体が、スチレン-ブタジエン-スチレンブロック共重合体、スチレン-イソプレン-スチレンブロック共重合体、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、スチレン-エチレン-ブチレン-スチレンブロック共重合体、スチレン‐エチレン‐プロピレン-スチレンブロック共重合体、およびスチレン‐エチレン‐エチレン‐プロピレン-スチレンブロック共重合体からなる群から選択される少なくとも1種である、請求項1~8のいずれか一項に記載の熱可塑性エラストマー組成物。
- 前記架橋剤が、過酸化物系架橋剤および脂肪酸金属塩系架橋剤からなる群から選択される少なくとも1種である、請求項1~9のいずれか一項に記載の熱可塑性エラストマー組成物。
- 前記添加剤が、可塑剤をさらに含み、
前記可塑剤の含有量が、前記樹脂成分100質量部に対して、5質量部以上100質量部以下である、請求項1~10のいずれか一項に記載の熱可塑性エラストマー組成物。 - 前記可塑剤が、プロセスオイルである、請求項11に記載の熱可塑性エラストマー組成物。
- インサート射出成形に用いられる、請求項1~12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1~13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てなる、成形体。
- パッキン、シール材、ウェザーストリップ、または内装表皮材である、請求項14に記載の成形体。
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KR1020237024668A KR20230123507A (ko) | 2020-12-25 | 2021-12-20 | 열가소성 엘라스토머 조성물 및 성형체 |
US18/259,187 US20240052157A1 (en) | 2020-12-25 | 2021-12-20 | Thermoplastic elastomer composition and molded article |
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JP2021150599A JP2022103044A (ja) | 2020-12-25 | 2021-09-15 | 熱可塑性エラストマー組成物および成形体 |
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KR100273511B1 (ko) | 1998-03-13 | 2001-03-02 | 장용균 | 폴리에스테르필름의제조방법 |
CN107118495A (zh) * | 2017-06-20 | 2017-09-01 | 泉州盈创新材料技术开发有限公司 | 一种高熔体强度高粘结性热塑性弹性体及其制备方法 |
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2021
- 2021-12-20 WO PCT/JP2021/046904 patent/WO2022138522A1/ja active Application Filing
- 2021-12-20 US US18/259,187 patent/US20240052157A1/en active Pending
- 2021-12-20 KR KR1020237024668A patent/KR20230123507A/ko unknown
- 2021-12-20 EP EP21910667.1A patent/EP4269489A1/en active Pending
- 2021-12-20 TW TW110147701A patent/TWI811903B/zh active
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JPH10273511A (ja) | 1997-03-31 | 1998-10-13 | Kinugawa Rubber Ind Co Ltd | 軟質エラストマー組成物及びその製造方法 |
WO2008023758A1 (en) * | 2006-08-23 | 2008-02-28 | Jsr Corporation | Thermoplastic resin composition and molded article obtained from the same |
WO2008146739A1 (ja) * | 2007-05-25 | 2008-12-04 | Kuraray Co., Ltd. | 熱可塑性重合体組成物 |
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JP2010174196A (ja) | 2009-01-30 | 2010-08-12 | Umg Abs Ltd | 熱可塑性樹脂組成物および成形品 |
JP2010254799A (ja) | 2009-04-24 | 2010-11-11 | Sumitomo Chemical Co Ltd | 熱可塑性樹脂組成物及びその成形体 |
JP2013028761A (ja) * | 2011-07-29 | 2013-02-07 | Aron Kasei Co Ltd | 熱可塑性エラストマー組成物 |
JP2017057323A (ja) | 2015-09-17 | 2017-03-23 | Jxエネルギー株式会社 | 熱可塑性エラストマー組成物及びその製造方法 |
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US20240052157A1 (en) | 2024-02-15 |
TW202235521A (zh) | 2022-09-16 |
KR20230123507A (ko) | 2023-08-23 |
TWI811903B (zh) | 2023-08-11 |
EP4269489A1 (en) | 2023-11-01 |
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