WO2016133119A1 - Corps moulé, stratifié, matériau de préhension pour outils, et outil - Google Patents

Corps moulé, stratifié, matériau de préhension pour outils, et outil Download PDF

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Publication number
WO2016133119A1
WO2016133119A1 PCT/JP2016/054575 JP2016054575W WO2016133119A1 WO 2016133119 A1 WO2016133119 A1 WO 2016133119A1 JP 2016054575 W JP2016054575 W JP 2016054575W WO 2016133119 A1 WO2016133119 A1 WO 2016133119A1
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Prior art keywords
component
weight
thermoplastic elastomer
elastomer composition
content
Prior art date
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PCT/JP2016/054575
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English (en)
Japanese (ja)
Inventor
二朗 佐野
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Ｍｃｐｐイノベーション合同会社
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Application filed by Ｍｃｐｐイノベーション合同会社 filed Critical Ｍｃｐｐイノベーション合同会社
Priority to JP2017500710A priority Critical patent/JP6721566B2/ja
Priority to CN201680009631.7A priority patent/CN107207828A/zh
Publication of WO2016133119A1 publication Critical patent/WO2016133119A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
    • B25G—HANDLES FOR HAND IMPLEMENTS
    • B25G1/00—Handle constructions
    • B25G1/10—Handle constructions characterised by material or shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08K5/01—Hydrocarbons
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • 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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a molded body, a laminate, a grip material for a tool, and a tool, and more specifically, has excellent interlayer fusion strength (hereinafter also referred to as interlayer fusion strength), and has good release properties.
  • Molded body having a member made of a thermoplastic elastomer composition excellent in productivity of a molded body (laminated body), laminated body having a layer made of the thermoplastic elastomer composition, and grip for tool made of the thermoplastic elastomer composition
  • the present invention relates to a material and a tool using the molded body.
  • a polyamide-based resin such as nylon 6 or nylon 12 or a glass resin added thereto is used as a base of a tool such as a power tool.
  • a soft material is used for the grip portion of such a tool because a grip feeling when the tool is gripped by hand is required.
  • Such a soft material used for the grip portion of the tool is required not only to have flexibility, but also to have excellent fusion strength between members with the polyamide-based resin as the base.
  • a polyurethane-based thermoplastic elastomer composition has been mainly used for the grip portion of such a tool (for example, Patent Document 1).
  • a molded body (laminated body) using a polyurethane-based thermoplastic elastomer composition as described in Patent Document 1 is a polyurethane-based thermoplastic elastomer composition and a polyamide-based material. It has been found that while having the advantage of high fusion strength with a substrate such as a resin, the mold releasability during molding is poor and the productivity is poor.
  • the present inventor has a specific thermoplastic elastomer composition excellent in fusion strength with a polyamide-based resin and good mold releasability. It was found that the productivity of the molded body (laminate) was excellent. The present invention has been accomplished based on these findings.
  • the gist of the present invention is as follows [1] to [20].
  • [1] A molded article having a member (1) made of a thermoplastic elastomer composition containing the following components (A) and (B) and a member (2) containing a polyamide-based resin.
  • Component (A) Polypropylene resin containing the following component (A1)
  • Component (A1) Modified polypropylene obtained by modifying a polypropylene resin with an unsaturated carboxylic acid or a derivative thereof
  • thermoplastic elastomer composition the content of the component (A) is 5 to 60% by weight with respect to the total amount of the component (A) and the component (B).
  • the molded body described.
  • the content of the component (A) is 0. 0 with respect to the total amount of the components (A) to (C).
  • the component (A) contains the component (A1) and the following component (A2), and contains 1 to 85% by weight of the component (A1) with respect to the total amount thereof. 4].
  • Component (A2) Polypropylene resin [6] In any one of [1] to [5], the graft ratio of the unsaturated carboxylic acid or derivative thereof of component (A1) is 0.01 to 10% by weight. The molded body described.
  • thermoplastic elastomer composition the content of the component (A) is 5 to 60% by weight with respect to the total amount of the component (A) and the component (B).
  • the laminated body of description [9] The laminate according to [7] or [8], wherein the thermoplastic elastomer composition contains the following component (C).
  • the content of the component (A) is 0.00 with respect to the total amount of the components (A) to (C).
  • the laminate according to [9] which is 5 to 55% by weight, the content of the component (B) is 10 to 60% by weight, and the content of the component (C) is 10 to 60% by weight.
  • the component (A) contains the component (A1) and the following component (A2), and the component (A1) is contained in an amount of 1 to 85% by weight based on the total amount thereof.
  • the graft ratio of the unsaturated carboxylic acid or derivative thereof of component (A1) is 0.01 to 10% by weight, and any one of [7] to [11] Laminated body.
  • a tool grip material comprising a thermoplastic elastomer composition containing the following components (A) and (B).
  • the content of the component (A) is 5 to 60% by weight with respect to the total amount of the component (A) and the component (B).
  • thermoplastic elastomer composition contains the following component (C).
  • component (C) Softener for hydrocarbon rubber
  • the content of the component (A) is 0. 0 with respect to the total amount of the components (A) to (C).
  • the tool grip material according to [15] which is 5 to 55% by weight, the content of the component (B) is 10 to 60% by weight, and the content of the component (C) is 10 to 60% by weight.
  • the component (A) contains the component (A1) and the following component (A2), and the component (A1) is contained in an amount of 1 to 85% by weight based on the total amount thereof.
  • Component (A2) Polypropylene resin
  • the graft ratio of the unsaturated carboxylic acid or derivative thereof of component (A1) is 0.01 to 10% by weight, and any one of [13] to [17] The tool grip material described.
  • a molded body, a laminate, and a tool that have excellent fusion strength between a specific thermoplastic elastomer composition and a polyamide resin, good mold releasability, and excellent productivity.
  • a grip material and a tool using the molded body are provided. Furthermore, since the molded body (laminated body) of the present invention has the above effects, it is particularly suitable as a grip part for a tool.
  • thermoplastic elastomer composition used in the present invention is characterized by containing the following component (A) and component (B).
  • thermoplastic elastomer composition used in the present invention preferably contains the following component (C).
  • thermoplastic elastomer composition used in the present invention has excellent fusion strength with a polyamide resin. This effect is considered to be due to the following reason. That is, in the thermoplastic elastomer composition used in the present invention, it is considered that component (A) constitutes a matrix component and component (B) is dispersed as a rubber component. And the modified polypropylene of the component (A1) in the component (A) gives the fusion property with the polyamide resin, but since the component (A1) constitutes a matrix component, It is thought that it can contribute to fusion property.
  • the component (A) is a polypropylene resin containing “component (A1): a modified polypropylene obtained by modifying a polypropylene resin with an unsaturated carboxylic acid or a derivative thereof” as described above.
  • the component (A) may contain “component (A2): polypropylene resin”.
  • the component (A2) does not include the component (A1).
  • the polypropylene resin used as a raw material of the component (A1) is not particularly limited as long as the propylene monomer unit exceeds 50% by weight, that is, the monomer unit other than propylene is less than 50% by weight.
  • the monomer unit other than propylene is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less.
  • the density of the polypropylene resin used as a raw material for the component (A1) is not particularly limited, but is usually 0.87 g / cm 3 or more, preferably 0.88 g / cm 3 or more, and usually 0.92 g / cm 3. 3 or less, preferably 0.91 g / cm 3 or less.
  • the polypropylene resin used as the component (A2) has a monomer unit other than propylene of less than 5% by weight.
  • the density of the polypropylene resin used as (A2) is not particularly limited, but is usually 0.87 g / cm 3 or more, preferably 0.88 g / cm 3 or more, and usually 0.92 g / cm 3 or less, Preferably it is 0.91 g / cm 3 or less.
  • the raw material of component (A1) and the polypropylene resin in component (A2) are not particularly limited as long as they fall under the above, and examples thereof include propylene homopolymer, propylene / ethylene copolymer, propylene / 1-butene. Copolymers, propylene / ethylene / 1-butene copolymers, propylene / 4-methyl-1-pentene copolymers, copolymers of propylene and other ⁇ -olefins, and copolymers of propylene and other vinyl monomers. A polymer etc. are mentioned.
  • ⁇ -olefins that is, ⁇ -olefins other than propylene are not particularly limited, but usually other than ethylene, preferably 2 to 20 carbon atoms, more preferably 4 to 10 carbon atoms.
  • a hydrocarbon having a heavy bond may be mentioned.
  • other vinyl monomers are not particularly limited, and examples thereof include vinyl acetate, vinyl alcohol, (meth) acrylic acid, (meth) acrylic acid alkyl ester, and styrene derivatives.
  • two or more of the above resins may be used in combination for the polypropylene used for each of the component (A1) and the component (A2).
  • different resins may be used, or they may be the same.
  • each said copolymer any of a block copolymer, a graft copolymer, a random copolymer, etc. may be sufficient.
  • component (A1) and component (A2) a propylene homopolymer, a propylene / ethylene copolymer, or a blend thereof is preferable, and a propylene homopolymer is more preferable.
  • the stereoregularity of the polypropylene resin used for each of the component (A1) and the component (A2), and the propylene chain may be any of isotactic, syndiotactic, atactic or stereoblock.
  • the chain is preferably isotactic, particularly isotactic homopolypropylene.
  • a well-known thing can also be employ
  • the melt flow rate (MFR) of the polypropylene resin used for each of the raw material of component (A1) and component (A2) is not particularly limited, but is ISO 1133 (2011) (230 ° C., load 2.16 kg).
  • the conditions are usually 0.5 g / 10 min or more, preferably 1 g / 10 min or more, more preferably 2 g / 10 min or more, and usually 100 g / 10 min or less, preferably 80 g / 10 min or less, more preferably Is 60 g / 10 min or less, more preferably 40 g / 10 min or less.
  • the MFR of the polypropylene used for each of the raw material of component (A1) and component (A2) is equal to or more than the lower limit value, the cohesive force alone becomes strong and the uniform mixing with other components becomes insufficient. In addition, it is possible to prevent an excessive energy load when producing the thermoplastic elastomer composition used in the present invention. Moreover, it is preferable from the viewpoint of the fluidity
  • the polyolefin resin used for each of the components (A1) and (A2) can be obtained as a commercial product.
  • the polypropylene resin include Novatec (registered trademark) PP series and Wintec (registered trademark) series manufactured by Nippon Polypro Co., Ltd., and appropriate products can be selected and used from these.
  • the polyethylene resin include Novatec (registered trademark) series manufactured by Nippon Polyethylene Co., Ltd. and Creolex (registered trademark) series manufactured by Asahi Kasei Chemicals Co., Ltd. be able to.
  • the component (A1) is a modified polypropylene obtained by modifying the above polypropylene resin with an unsaturated carboxylic acid or a derivative thereof.
  • unsaturated carboxylic acid ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is preferable. Specific examples include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid.
  • Derivatives include, for example, acid anhydrides and carboxylic acid esters, and may be derivatives such as acid halides, amides, and imides. As these derivatives, acid anhydrides are preferred.
  • maleic acid or its anhydride is particularly preferable.
  • these compounds may be used alone or in any combination and ratio.
  • so-called vinylsilanes such as vinyltrimethoxysilane can be used in combination with unsaturated carboxylic acid or a derivative thereof.
  • Any modification may be used for the modification to obtain the component (A1), and it can be obtained by reaction only with heat, but an organic peroxide or the like that generates radicals in the reaction is added as a radical generator. Also good.
  • denaturation method etc. which do not use the solution modification
  • a method can be used in which a polypropylene resin is dissolved in an organic solvent and the like, and a radical generator and an unsaturated carboxylic acid or a derivative thereof are added thereto and graft copolymerized.
  • the organic solvent is not particularly limited, and for example, alkyl group-substituted aromatic hydrocarbons or halogenated hydrocarbons can be used.
  • melt modification method for example, a polypropylene resin, an unsaturated carboxylic acid or a derivative thereof, and a radical generator described later as necessary are mixed in advance and then melt-kneaded in a kneader and reacted, and in the kneader. And a method in which a mixture of a radical generator and an unsaturated carboxylic acid or a derivative thereof is added to the polypropylene resin melted in step 1 and reacted.
  • a Henschel mixer, a ribbon blender, a V-type blender, or the like is usually used for mixing, and a single-screw or twin-screw extruder, a roll, a Banbury mixer, a kneader, or a Brabender mixer can be used for melt-kneading. .
  • the blending ratio of the unsaturated carboxylic acid or the derivative thereof to the polypropylene resin is not particularly limited, but is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more, more preferably 100 parts by weight of the polypropylene resin. It is 0.1 parts by weight or more, and usually 30 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight or less.
  • the radical generator is not particularly limited. Specifically, for example, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne- 3, Lauroyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzo Organic peroxides or organic peresters such as eth, tert-butyl perisobutylate, tert-butyl perpivalate and cumyl perpivalate, and azo such as azobisisobutyronitrile and dimethylazoisobutyrate Compounds and the like can be used.
  • radical generators can be appropriately selected according to the type of raw material polypropylene resin, MFR, type of unsaturated carboxylic acid or derivative thereof, reaction conditions, and the like. The above may be used in any combination and ratio.
  • the blending amount of the radical generator is not particularly limited, but is usually 0.001 to 20 parts by weight, preferably 0.005 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polypropylene resin. Parts, particularly preferably 0.01 to 3 parts by weight.
  • the modified polypropylene corresponding to the above can be used alone, or two or more kinds can be used in any combination and ratio.
  • the MFR [ISO 1133 (2011) (180 ° C., load 2.16 kg)] of the component (A1) is not particularly limited, but is usually 0.1 g / 10 min or more, preferably 1 g / min or more, more preferably 5 g / It is usually not less than 10,000 g / 10 minutes, preferably not more than 5,000 g / 10 minutes, more preferably not more than 3,000 g / 10 minutes, still more preferably not more than 1,000 g / 10 minutes.
  • the graft ratio (modified amount) of the unsaturated carboxylic acid or derivative thereof in component (A1) is not particularly limited, but is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and still more preferably 0.3%. It is 10% by weight or less, more preferably 7.5% by weight or less, and further preferably 5% by weight or less.
  • the amount of modification with the unsaturated carboxylic acid or derivative thereof in the component (A1) is equal to or more than the lower limit, the adhesion performance to the substrate in the thermoplastic elastomer composition used in the present invention is improved. Further, when the amount of modification is not more than the above upper limit value, the thermal stability is improved and the compatibility with other components is improved.
  • the graft ratio means the content of unsaturated carboxylic acid or its derivative component when measured with an infrared spectrometer.
  • absorption specific to a carboxylic acid or a derivative thereof in a sample press-molded into a sheet having a thickness of about 100 ⁇ m, specifically, carbonyl characteristic absorption of 1,900 to 1,600 cm ⁇ 1 (C ⁇ O stretching vibration band) Can be obtained by measuring (the same applies to the following description).
  • the modification denaturation by unsaturated carboxylic acid or its derivative (s) may not remain for 100%, but unsaturated carboxylic acid or its derivative (s) which are not reacting with polypropylene resin may remain in the modified polypropylene.
  • the graft ratio (modification amount) in the present invention means a value measured by the above method.
  • Component (A) may contain component (A2), and the blending ratio of component (A1) and component (A2) is not particularly limited.
  • the content of the component (A1) is preferably 1% by weight or more, more preferably 5% by weight with respect to the total amount of the components (A1) and (A2). % Or more, more preferably 10% by weight or more.
  • an upper limit is not specifically limited, Preferably it is 85 weight% or less, More preferably, it is 65 weight% or less, More preferably, it is 45 weight% or less.
  • the graft ratio (modified amount) by the unsaturated carboxylic acid or its derivative in the component (A) is usually 0.05% by weight or more, preferably 0.5% by weight or more, more preferably 1.5% by weight or more. Moreover, it is 4 weight% or less normally, Preferably it is 3 weight% or less, More preferably, it is 2.5 weight% or less.
  • the adhesive performance to a substrate such as a polyamide resin in the thermoplastic elastomer composition used in the present invention
  • the amount of modification is not more than the above upper limit value, the thermal stability is improved and the compatibility with other materials is improved.
  • the component (A1) or the component (A) may be subjected to treatment for removing unreacted unsaturated carboxylic acid or its derivative.
  • this processing method is not particularly limited, as a specific example, component (A1) or component (A) is placed in a storage tank having a structure in which gas can be blown from the lower part of the device, and the device is heated with a heater or heat transfer oil. There is a method of heating to about 100 ° C., blowing an inert gas such as nitrogen or air from the lower part of the apparatus, and treating for 6 to 24 hours.
  • the component (A) may be preliminarily prepared as a resin composition by melt-kneading the component (A1) and the component (A2), but these are used independently and blended with other components described later. Also good.
  • the component (B) comprises a block copolymer having a polymer block P derived from a vinyl aromatic compound and a polymer block Q derived from at least one of a conjugated diene and isobutylene, and the block copolymer It is at least one block copolymer selected from the group consisting of block copolymers obtained by hydrogenating the coalescence.
  • Component (B) is a block copolymer having at least two blocks P and at least one block Q, and a block copolymer obtained by hydrogenating the block copolymer. It is preferably at least one block copolymer.
  • the monomeric vinyl aromatic compound constituting the block P is not particularly limited, but a styrene derivative such as styrene or ⁇ -methylstyrene is preferable. Of these, styrene is the main component.
  • the block P may contain a monomer other than the vinyl aromatic compound as a raw material.
  • the monomer other than the vinyl aromatic compound examples include ethylene and ⁇ -olefin.
  • the block P contains monomers other than the said vinyl aromatic compound as a raw material, the content becomes like this. Preferably it is less than 50 weight%, More preferably, it is 40 weight% or less. When the content is within this range, heat resistance and compression set tend to be good.
  • Block Q is derived from at least one of conjugated diene and isobutylene.
  • the monomeric conjugated diene that can be used in the block Q is not particularly limited, but is preferably mainly composed of at least one of butadiene and isoprene, more preferably butadiene and isoprene.
  • the block Q may contain a monomer other than the conjugated diene as a raw material.
  • “mainly” in the present invention means 50% by weight or more.
  • Examples of the monomer other than at least one of the conjugated diene and isobutylene include styrene.
  • the content is preferably less than 50% by weight, more preferably 40% by weight or less. When the content is within this range, bleeding out tends to be suppressed.
  • the block copolymer of component (B) may be a hydrogenated block copolymer obtained by hydrogenating a block copolymer having the polymer block P and the polymer block Q. More specifically, it may be a hydrogenated block copolymer obtained by hydrogenating double bonds of the block copolymer block Q.
  • the hydrogenation rate of block Q is not particularly limited, but is preferably 80 to 100% by weight, more preferably 90 to 100% by weight. By hydrogenating the block Q within the above range, the adhesive properties of the resulting thermoplastic elastomer composition tend to be lowered and the elastic properties tend to be increased. The same applies to the case where the block P uses a diene component as a raw material.
  • the hydrogenation rate can be measured by 13 C-NMR.
  • butadiene in the microstructure can take 1,4-addition structure and 1,2-addition structure, but in particular, block Q is hydrogenated.
  • the 1,4-addition structure of butadiene in the microstructure of the block Q is preferably 20 to 100% by weight.
  • the isoprene in the microstructure can take 1,2-addition structure, 1,4-addition structure and 3,4-addition structure.
  • the 1,4-addition structure of isoprene in the microstructure of block Q is 60 to 100% by weight. Is preferred.
  • the block Q is a hydrogenated derivative and the conjugated diene monomer constituting the block Q contains butadiene and isoprene
  • the 1,4-addition structure of butadiene and isoprene in the microstructure of the block Q is Are preferably 20 to 100% by weight and 60 to 100% by weight, respectively.
  • the ratio of the 1,4-addition structure in any case, by setting the ratio of the 1,4-addition structure within the above range, the adhesive property of the resulting thermoplastic elastomer composition tends to decrease and the elastic property tends to increase.
  • the ratio of 1,4-addition structure (hereinafter sometimes referred to as “1,4-microstructure ratio”) can be measured by 13 C-NMR.
  • the component (B) in the present invention is not particularly limited as long as it has a structure having a polymer block P and a polymer block Q, and may be any of linear, branched, radial, etc.
  • the block copolymer represented by the following formula (1) or (2) is more preferably a hydrogenated block copolymer obtained by hydrogenation.
  • the copolymer represented by the following formula (1) or (2) is a hydrogenated block copolymer, the thermal stability is improved.
  • m and n are preferably larger in terms of lowering the order-disorder transition temperature as a rubbery polymer, but smaller in terms of ease of production and cost. Good.
  • component (B) is a hydrogenated block copolymer represented by formula (1) or (2) and block Q is composed of butadiene, 1,4-addition of butadiene in the microstructure of block Q
  • the structure is preferably 20 to 100% by weight.
  • the 1,4-addition structure of isoprene in the microstructure of the block Q is preferably 60 to 100% by weight.
  • the 1,4-addition structure of butadiene and isoprene in the microstructure of the block Q may be 20 to 100% by weight and 60 to 100% by weight, respectively. preferable.
  • the adhesive properties of the resulting thermoplastic elastomer composition tend to decrease and the elastic properties tend to increase.
  • (hydrogenated) block copolymer Since at least one of the block copolymer and the hydrogenated block copolymer (hereinafter sometimes referred to as “(hydrogenated) block copolymer”) is excellent in rubber elasticity, it is represented by the formula (2).
  • the (hydrogenated) block copolymer represented by the formula (1) is more preferable than the (hydrogenated) block copolymer, and represented by the formula (1) in which m is 3 or less (hydrogenated).
  • a block copolymer is more preferred, and a (hydrogenated) block copolymer represented by formula (1) in which m is 2 or less is more preferred, and a formula (1) in which m is 1 (hydrogenated) ) Block copolymers are most preferred.
  • the weight ratio of the block P and the block Q constituting the component (B) is arbitrary, but from the viewpoint of the mechanical strength and thermal fusion strength of the thermoplastic elastomer composition used in the present invention, it is preferable that the block P is larger. On the other hand, it is preferable that the number of blocks P is small in terms of flexibility, profile extrusion moldability, and bleed-out suppression.
  • the weight ratio of the block P in the component (B) is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 30% by weight or more, and preferably 60% by weight or less, more preferably It is 50 wt% or less, more preferably 45 wt% or less.
  • the method for producing the component (B) in the present invention is not particularly limited as long as the above structure and physical properties can be obtained. Specifically, it can be obtained, for example, by performing block polymerization in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798.
  • the hydrogenation (hydrogenation) of the block copolymer is, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 59-133203, and Japan.
  • the reaction can be carried out in an inert solvent in the presence of a hydrogenation catalyst by the method described in JP-A-60-79005.
  • 50% or more of the olefinic double bonds in the polymer block are preferably hydrogenated, more preferably 80% or more are hydrogenated, and in the polymer block It is preferable that 25% or less of the aromatic unsaturated bond is hydrogenated.
  • Examples of such commercially available hydrogenated block copolymers include “KRATON (registered trademark) -G series”, “KRATON (registered trademark) -A series” manufactured by Kraton Polymer, and “Septon (registered)” manufactured by Kuraray. (Trademark) series ", a partial grade of" Hibler (registered trademark) series ",” Tough Tech (registered trademark) series “manufactured by Asahi Kasei Corporation, and the like.
  • non-hydrogenated block copolymers include “KRATON (registered trademark) -D series” manufactured by Kraton Polymer Co., Ltd., some grades of Kuraray “Hibler (registered trademark) series”, and “ And “Tuffprene (registered trademark) series”. Applicable products can be appropriately selected from these and used.
  • the number average molecular weight (Mn) of the component (B) in the present invention is not particularly limited, but is preferably 30,000 or more, more preferably 50,000 or more, further preferably 80,000 or more, and preferably 500. Or less, more preferably 400,000 or less, and still more preferably 300,000 or less. When the number average molecular weight of the component (B) is within the above range, moldability and heat resistance tend to be good.
  • the weight average molecular weight (Mw) of a component (B) is not specifically limited, Preferably it is 50,000 or more, More preferably, it is 80,000 or more, More preferably, it is 100,000 or more, Preferably, it is 550,000 or less. More preferably, it is 500,000 or less, More preferably, it is 400,000 or less. When the weight average molecular weight of the component (B) is within the above range, moldability and heat resistance tend to be good.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of a component (B) are the polystyrene conversion values calculated
  • the component (C) that can be contained in the thermoplastic elastomer used in the present invention is a hydrocarbon rubber softener.
  • Component (C) softens the thermoplastic elastomer composition, improves flexibility, elasticity, processability and fluidity, and contributes to improving the transparency of the laminate and the appearance of the molded body.
  • hydrocarbon rubber softeners examples include mineral oil softeners and synthetic resin softeners.
  • Mineral oil softeners are preferred from the viewpoint of affinity with other components.
  • Mineral oil softeners are generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, with paraffinic oils in which 50% or more of all carbon atoms are paraffinic hydrocarbons, Those in which 30 to 45% of all carbon atoms are naphthenic hydrocarbons are called naphthenic oils, and those in which 35% or more of all carbon atoms are aromatic hydrocarbons are called aromatic oils.
  • paraffinic oil is preferably used in the present invention.
  • the hydrocarbon rubber softening agent may be used alone, or two or more may be used in any combination and ratio.
  • the kinematic viscosity of the hydrocarbon rubber softener at 40 ° C. is not particularly limited, but is preferably 20 centistokes or more, more preferably 50 centistokes or more, and preferably 800 centistokes or less, more preferably 600 centistokes. Below Stokes.
  • the flash point (COC method) of the hydrocarbon rubber softener is preferably 200 ° C. or higher, more preferably 250 ° C. or higher.
  • Component (C) a hydrocarbon rubber softener
  • a hydrocarbon rubber softener can be obtained as a commercial product.
  • the commercially available products include “Nisseki Polybutene (registered trademark) HV series” manufactured by JX Nippon Oil & Energy Corporation, “Diana (registered trademark) process oil PW series” manufactured by Idemitsu Kosan Co., Ltd., etc. Appropriate products can be selected and used from among them.
  • thermoplastic elastomer composition contains the component (A) and the component (B), and preferably contains the component (C).
  • the content of component (A) is preferably at least 5% by weight, more preferably at least 10% by weight, and even more preferably at least 15% by weight, based on the total amount of component (A) and component (B).
  • the upper limit is preferably 60% by weight or less, more preferably 55% by weight or less, and still more preferably 50% by weight or less.
  • the lower limit of the content of component (A) is preferably 0.5% by weight or more, more preferably 2% by weight or more, and still more preferably 5% by weight with respect to the total amount of components (A) to (C).
  • the upper limit is preferably 55% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less, and particularly preferably 30% by weight or less.
  • the content of component (B) is preferably at least 10% by weight, more preferably at least 15% by weight, and even more preferably at least 20% by weight, based on the total amount of components (A) to (C).
  • the upper limit is preferably 60% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less.
  • the content of the component (C) is preferably 10% by weight or more, more preferably 20% by weight or more, and further preferably 30% by weight or more with respect to the total amount of the components (A) to (C).
  • the upper limit is preferably 60% by weight or less, more preferably 57% by weight or less, and still more preferably 55% by weight or less.
  • thermoplastic elastomer composition used in the present invention in addition to the components (A) and (B), other components can be blended as necessary within a range not impairing the effects of the present invention.
  • fillers antioxidants, thermal stabilizers, light stabilizers, ultraviolet absorbers, and neutralizers.
  • thermoplastic resins other than component (A) and component (B) include polyphenylene ether resins; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyoxymethylene Polyoxymethylene resins such as homopolymers and polyoxymethylene copolymers; polymethylmethacrylate resins and polyolefin resins [however, except those corresponding to component (A). ] Etc. are mentioned.
  • elastomer other than the component (A) and the component (B) examples include styrene elastomers such as styrene / butadiene copolymer rubber and styrene / isoprene copolymer rubber [however, those corresponding to the component (B)] except for. ]; Polyester elastomer; polybutadiene and the like.
  • the filler examples include glass fiber, hollow glass sphere, carbon fiber, talc, calcium carbonate, mica, potassium titanate fiber, silica, metal soap, titanium dioxide, and carbon black.
  • a filler When a filler is used, it is usually used in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight as a total of components (A) to (C).
  • antioxidants examples include phenolic antioxidants, phosphite antioxidants, and thioether antioxidants. When an antioxidant is used, it is generally used in an amount of 0.01 to 3 parts by weight with respect to 100 parts by weight as a total of components (A) to (C).
  • thermoplastic elastomer composition is obtained by mixing component (A) and component (B), and other components blended as necessary, using a known method such as a Henschel mixer, V blender or tumbler blender. And then mechanically melt-kneaded by a known method.
  • a general melt-kneader such as a Banbury mixer, various kneaders or a single-screw or twin-screw extruder can be used.
  • thermoplastic elastomer composition used in the present invention has a hardness durometer A measured according to ISO 7619-1 (2010), preferably 90 or less, more preferably 80 or less. Although a minimum is not specifically limited, 30 or more are preferable.
  • the molded body (laminate) of the present invention includes a member (1) [layer (1)] comprising the above-mentioned thermoplastic elastomer composition and a member (2) [layer (2)] containing a polyamide-based resin. It is a body (laminate).
  • member (1) is read as “layer (1)”
  • member (2) is read as “layer (2)”. To do.
  • the member (1) and the member (2) are present in the molded body (laminated body) together with at least one other member, and are formed in advance. It may be a member or a member formed during the production of a molded body. Also, these members may be of any shape, continuous or discontinuous, and need not be in full contact with adjacent members.
  • the molded body only needs to have at least a part of at least two members fixed, and may be formed of a member formed in advance or a member formed simultaneously with the formation of the molded body. It may consist of a member formed simultaneously with formation of a member and a molded object. Each member may have any shape, and may be continuous or discontinuous.
  • the laminate may be a product molded into a product form (molded product) or an intermediate product that is molded into a product.
  • any member other than the member (1) and the member (2) can be provided in the molded body (laminate) of the present invention.
  • the material which comprises these members is not specifically limited, Usually, it is resin.
  • the resin is not particularly limited.
  • the member (2) is not particularly limited as long as it includes a polyamide-based resin.
  • the polyamide-based resin is not particularly limited, and specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11, MXD nylon, Preferred examples include amorphous nylon and terephthalic acid / adipic acid / hexamethylenediamine copolymer. Among these, nylon 6, nylon 66, and nylon 6/66, which are excellent in melting point or rigidity, are more preferable.
  • the flexural modulus of the resin of the member (2) is preferably 20,000 MPa or less, more preferably 10,000 MPa or less, and preferably 1,000 MPa or more, more preferably 1,500 MPa or more.
  • the flexural modulus is a value measured according to ISO 178 (1993).
  • the molded body of the present invention can be produced by, for example, molding and heat-sealing the thermoplastic elastomer composition of the member (1) and the polyamide resin of the member (2).
  • the molding method is not particularly limited, and various molding methods such as normal injection molding, extrusion molding or press molding can be used. In addition, various molding methods such as gas injection molding, injection compression molding, and short shot foam molding can be used as necessary. In the present invention, injection molding is particularly suitable among the molding methods mentioned above. Examples of injection molding include insert injection molding, two-color injection molding, and core back injection molding.
  • the insert injection molding method is a method in which a core material (polyamide-based resin of the member (2)) is injection-molded in advance, and the molded product is inserted into a mold, and then between the molded product and the mold.
  • a surface layer material [thermoplastic elastomer composition of member (1)] is injection-molded in a gap.
  • the two-color injection molding method uses two or more injection molding machines to inject and mold the core material (polyamide resin of the member (2)), and then the mold is rotated or moved. The cavity is exchanged to form a gap between the molded product and the mold, and the surface layer material (thermoplastic elastomer composition of the member (1)) is injection-molded there.
  • the core back injection molding method uses a single injection molding machine and a single mold to inject a core material [polyamide resin of member (2) [layer (2)]]
  • a core material polyamide resin of member (2) [layer (2)]
  • the cavity volume of the mold is enlarged and a surface layer material (thermoplastic elastomer composition of member (1)) is injection molded into the gap between the molded product and the mold.
  • the core material may be molded by using a normal injection molding method or by gas injection molding.
  • the molded body (laminate) of the present invention is excellent in the fusion strength between the thermoplastic elastomer composition and the polyamide-based resin, and has good mold releasability. Therefore, the thermoplastic elastomer composition of the member (1) It is preferable to form a molded body (laminate) with these other resins by two-color injection molding or insert injection molding using the polyamide resin of the member (2). Moreover, the molded object separately shape
  • the member (1) and the member (2) are preferably laminated on the outer side of the member (1). In some cases, a member (layer) other than the members (1) and (2) may be included. Further, the thicknesses of the member (1) and the member (2) are not particularly limited, and the thickness according to each application can be arbitrarily selected.
  • the shape of the molded body (laminate) of the present invention is not particularly limited, and may be any of a sheet shape, a tubular shape, a rod shape, or an irregular shape.
  • a member (1) and a member (2) there is no limitation in particular also in the shape of a member (1) and a member (2), As long as it is a shape which can become a molded object (laminated body), each arbitrary shape can be selected.
  • the fusion strength between the member (1) and the member (2) is preferably 1 N / 25 mm or more, more preferably 10 N / 25 mm or more, and further preferably 30 N / 25 mm or more. It shows that it is excellent in the melt
  • the heat fusion strength is a value measured under the same conditions as the “peeling test” in the examples described later.
  • the tool grip material of the present invention is composed of the above-described thermoplastic elastomer composition.
  • the molding method of the tool grip material is not particularly limited, and various molding methods such as normal injection molding, extrusion molding or press molding can be used.
  • the molded body (laminate) of the present invention is excellent in inter-member (interlayer) fusion strength and also excellent in mold releasability. Further, since the transparency, the appearance of the molded body, and the like are good, the design is also excellent. For this reason, the molded object (laminated body) of this invention is preferable as daily goods which have a base
  • thermoplastic elastomer used in the present invention is particularly preferable as a grip part of a tool. That is, a tool using the molded body of the present invention, more specifically, a grip part and a base, the member (1) is used for the grip part, and the member (2) is used for the base. A tool to be used is provided.
  • the present invention is not limited to the following examples unless it exceeds the gist.
  • the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value.
  • a range defined by a combination of values of the following examples or values of the examples may be used.
  • a1-1 (for comparative example): Maleic anhydride graft-modified ethylene / octene copolymer
  • B-1 “Kraton (registered trademark) G1651HU” (hydrogenated product of styrene / butadiene / styrene block copolymer) [weight average molecular weight (Mw): 250,000, styrene content: 33% by weight]
  • B-2 “Kraton (registered trademark) G1650MU” (hydrogenated product of styrene / butadiene / styrene block copolymer) [weight average molecular weight: 90,000, styrene content: 33% by weight]
  • B-3 “Tuftec (registered trademark) M1943” manufactured by Asahi Kasei Chemicals Co., Ltd. (carboxylic anhydride-modified styrene / butadiene / styrene block copolymer)
  • Component (C)] C-1 "Diana (registered trademark) process oil PW90" (paraffinic oil) manufactured by Idemitsu Kosan Co., Ltd.
  • X-1 for comparative example: "Pandex (registered trademark) T-1180N” (urethane-based thermoplastic elastomer) manufactured by DIC discussion (hardness duro A: 80)
  • thermoplastic elastomer composition The components shown in Tables 1 and 2 were melt-kneaded (cylinder temperature 160 ° C. to 210 ° C.) using a biaxial kneader to produce pellets of a thermoplastic elastomer composition.
  • thermoplastic elastomer composition of the member (1) obtained in each example were subjected to an injection molding machine (“J110AD” manufactured by Nippon Steel Works, mold clamping force 110T), a mold temperature of 40 ° C., and an injection pressure. Injection molding was performed at 147 MPa, a cylinder temperature of 210 ° C., and a cooling time of 30 seconds to obtain a molded body having a size of 100 mm ⁇ 100 mm and a thickness of 2 mm.
  • J110AD manufactured by Nippon Steel Works
  • mold clamping force 110T mold temperature of 40 ° C.
  • injection pressure injection pressure
  • thermoplastic elastomer composition used for the member (1) was measured for Duro A hardness according to ISO 7619-1 (2010).
  • injection molding Using 30% glass-filled nylon 6, using an injection molding machine (“J110AD” manufactured by Nippon Steel Works, mold clamping force 110T), mold temperature 60 ° C., injection pressure 147 MPa, cylinder temperature 260 ° C., cooling time 30 seconds Injection molding was performed to obtain a molded body having a size of 100 mm ⁇ 100 mm and a thickness of 2 mm.
  • Tables 1 and 2 show the compositions and evaluation results of the members (1) of Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-7, and the evaluation results of the obtained molded bodies (laminates). Show.
  • the molded body (laminate) of the present invention has an inter-member (interlayer) fusion strength between the member (1) and the member (2) and It was excellent in mold releasability.
  • Comparative Example 1-6 the component (A) was not used, and instead a maleic anhydride graft-modified ethylene / octene copolymer was used, but the interlayer fusion strength with the polyimide resin was poor. .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : un corps moulé qui présente une excellente résistance de liaison par fusion inter-élément (couche intermédiaire), tout en ayant une bonne aptitude au démoulage et une excellente productivité ; et similaire. La présente invention concerne un corps moulé qui comprend : un élément (1) qui est formé à partir d'une composition d'élastomère thermoplastique contenant le constituant (A) et le constituant (B) décrits ci-dessous ; et un élément (2) qui contient une résine de polyamide. Constituant (A) : une résine de polypropylène contenant le constituant (A1) décrit ci-dessous. Constituant (A1) : un polypropylène modifié obtenu par modification d'une résine de polypropylène avec un acide carboxylique insaturé ou un dérivé de celui-ci. Constituant (B) : au moins un copolymère séquencé choisi dans le groupe constitué de copolymères séquencés, chacun d'eux comprenant un bloc polymère P dérivé d'un composé vinyle aromatique et un bloc polymère Q dérivé d'au moins un élément parmi un diène conjugué et l'isobutylène, et de copolymères séquencés obtenus par hydrogénation des copolymères séquencés décrit ci-dessus.
PCT/JP2016/054575 2015-02-18 2016-02-17 Corps moulé, stratifié, matériau de préhension pour outils, et outil WO2016133119A1 (fr)

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JP2000086840A (ja) * 1998-09-10 2000-03-28 Mitsubishi Chemicals Corp 接着性樹脂組成物及びそれより形成された積層体
JP2002140940A (ja) * 2000-11-01 2002-05-17 Sumitomo Wiring Syst Ltd 絶縁電線
JP2008174596A (ja) * 2007-01-16 2008-07-31 Furukawa Electric Co Ltd:The 難燃性樹脂組成物およびそれを用いた成形物品
JP2009091385A (ja) * 2007-10-03 2009-04-30 Aron Kasei Co Ltd 熱可塑性樹脂配合物、および複合材料、および複合材料の製造方法
JP2009191871A (ja) * 2008-02-12 2009-08-27 Ube Ind Ltd 水素タンクライナー用材料及び水素タンクライナー
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JP2004224944A (ja) * 2003-01-24 2004-08-12 Kuraray Plast Co Ltd 高周波接着性に優れた熱可塑性樹脂組成物
EP1582563A1 (fr) * 2004-03-31 2005-10-05 KRATON Polymers Research B.V. Compositions de copolymère bloc styrène hydrogéné à propriétés de surmoulage à haute température améliorées
ES2453566T3 (es) * 2005-08-26 2014-04-08 Kuraray Co., Ltd. Composición de elastómero termoplástico y artículo moldeado compuesto fabricado a partir de la misma

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JPH06329954A (ja) * 1993-05-27 1994-11-29 Asahi Chem Ind Co Ltd 粉体塗装用ポリプロピレン系樹脂組成物
JP2000086840A (ja) * 1998-09-10 2000-03-28 Mitsubishi Chemicals Corp 接着性樹脂組成物及びそれより形成された積層体
JP2002140940A (ja) * 2000-11-01 2002-05-17 Sumitomo Wiring Syst Ltd 絶縁電線
JP2008174596A (ja) * 2007-01-16 2008-07-31 Furukawa Electric Co Ltd:The 難燃性樹脂組成物およびそれを用いた成形物品
JP2009091385A (ja) * 2007-10-03 2009-04-30 Aron Kasei Co Ltd 熱可塑性樹脂配合物、および複合材料、および複合材料の製造方法
JP2009191871A (ja) * 2008-02-12 2009-08-27 Ube Ind Ltd 水素タンクライナー用材料及び水素タンクライナー
WO2013105392A1 (fr) * 2012-01-11 2013-07-18 株式会社クラレ Composition de polymère thermoplastique et article moulé

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JP6721566B2 (ja) 2020-07-15

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