JP2009126965A - Styrenic thermoplastic elastomer composition and substrate integrated type temporarily fixed molding - Google Patents
Styrenic thermoplastic elastomer composition and substrate integrated type temporarily fixed molding Download PDFInfo
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- JP2009126965A JP2009126965A JP2007304394A JP2007304394A JP2009126965A JP 2009126965 A JP2009126965 A JP 2009126965A JP 2007304394 A JP2007304394 A JP 2007304394A JP 2007304394 A JP2007304394 A JP 2007304394A JP 2009126965 A JP2009126965 A JP 2009126965A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- 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
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1671—Making multilayered or multicoloured articles with an insert
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- 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
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14754—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles being in movable or releasable engagement with the coating, e.g. bearing assemblies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2221/00—Use of unspecified rubbers as reinforcement
- B29K2221/003—Thermoplastic elastomers
Abstract
Description
本発明は、シール材などの柔軟成形品の支持基材上への仮留めを目的とした射出成形用のスチレン系熱可塑性エラストマー組成物及びそれを用いた基材一体型仮留め成形品に関するものである。さらに詳しくは、本発明は、ポリプロピレン等のポリオレフィン系樹脂の支持基材上に対する成形品の仮留め性が良いこと、すなわち、射出成形時に金型から取り出される際、ポリオレフィン系樹脂製の支持基材からは剥離せず仮留めされた状態で、金型離型性が良い成形品を製造可能で、成形品の量産性に優れるスチレン系熱可塑性エラストマー組成物及びそれを用いた基材一体型仮留め成形品に関するものである。 TECHNICAL FIELD The present invention relates to a styrene-based thermoplastic elastomer composition for injection molding for the purpose of temporarily fixing a flexible molded product such as a sealing material onto a supporting substrate, and a substrate-integrated temporary-fixed molded product using the same. It is. More specifically, the present invention has a good temporary fixability of a molded product on a support substrate of a polyolefin resin such as polypropylene, that is, a support substrate made of a polyolefin resin when taken out from a mold during injection molding. Can be produced in a state of being temporarily fixed without being peeled from the mold, and a styrene-based thermoplastic elastomer composition having excellent mold releasability and excellent mass productivity of the molded product, and a substrate-integrated temporary substrate using the same The present invention relates to a fastening molded product.
電子部品、自動車部品、日用品などの様々な製品に組み込まれるシール材や緩衝材などの成形品の材料として熱可塑性エラストマーが用いられてきている。特にスチレン系熱可塑性エラストマーは、軟化剤の保持性が高いことから低硬度から高硬度まで制御可能であり、そのため、様々な部品に応用されている。このスチレン系熱可塑性エラストマーとしては、スチレン系ブロック共重合体単独で用いられる場合やスチレン系ブロック共重合体とエチレン−プロピレン−非共役ジエン共重合体の混合物、及びスチレン系ブロック共重合体とポリエチレンやポリプロピレンの混合物、また、これらの混合物に更にオイル等の可塑材を混合した混合組成物など、機能性を高めたエラストマー組成物としても用いられている。 Thermoplastic elastomers have been used as materials for molded products such as sealing materials and cushioning materials incorporated in various products such as electronic parts, automobile parts, and daily necessities. In particular, styrenic thermoplastic elastomers can be controlled from low hardness to high hardness because of their high softener retention, and are therefore applied to various parts. The styrenic thermoplastic elastomer includes a styrenic block copolymer used alone, a mixture of a styrenic block copolymer and an ethylene-propylene-nonconjugated diene copolymer, and a styrenic block copolymer and polyethylene. It is also used as an elastomer composition with enhanced functionality, such as a mixture of polypropylene and polypropylene, and a mixture composition obtained by further mixing a plastic material such as oil with these mixtures.
これらの内で柔軟性に富むスチレン系熱可塑性エラストマー組成物を用いて得られた成形品は、シール性などの成形品特性が良好であるが、そのままの成形品単独では、柔軟であるがために、部品として特定の位置に組み込む際、非常に操作性が悪い。 Among these, molded products obtained using a styrenic thermoplastic elastomer composition rich in flexibility have good molded product characteristics such as sealing properties, but the molded product alone is flexible. In addition, when it is assembled as a part at a specific position, the operability is very poor.
従来、柔軟な成形品の組込み作業における操作性を向上させるために、特許文献１や、特許文献２では、柔軟な成形品を剛性を確保できるフィルム（支持基材）に仮留めしておき、成形品を目的の取り付け箇所に固着した後、支持フィルムを成形品から剥がし取る技術を開発し、そのための基材一体型仮留め成形品を提供している。この基材一体型仮留め成形品は、その成形（例えば、射出成形）時に、一時的にフィルム等の支持基材を一緒に挿入し、この支持基材上に成形品を成形すると同時に弱い接着力で仮留めすることで得られる。支持基材として樹脂フィルムなどの所定の剛性を持つものを使用すれば、この基材上に成形された柔軟な成形品を、所望の形状に維持した状態で、部品として所定の位置に位置ズレや変形を生じさせることなく組み付けることができる。 Conventionally, in order to improve the operability in the work of assembling a flexible molded product, in Patent Document 1 and Patent Document 2, the flexible molded product is temporarily attached to a film (support base material) that can ensure rigidity, After fixing the molded product to the target mounting location, we have developed a technology to peel the support film from the molded product, and provide a base-material-integrated temporary-fixed molded product for that purpose. This base material-integrated temporary-fixed molded product temporarily inserts a support base material such as a film together with the base material at the time of molding (for example, injection molding), and at the same time forms a molded product on the support base material, and is weakly bonded. Obtained by temporarily fastening with force. If a support substrate having a predetermined rigidity such as a resin film is used, the flexible molded product formed on the substrate is shifted to a predetermined position as a component while maintaining a desired shape. And can be assembled without causing deformation.
上記従来のフィルム仮留め型の成形品を用いた取り付け方法によれば、オレフィン系熱可塑性エラストマーを成形品材料とした場合で、一時的な仮留めを行う支持基材が成形品材料と同種系のオレフィン系基材を用いる場合では、良好な効果が得られる。 According to the mounting method using the conventional film temporary fixing mold, the supporting base material for temporary temporary fixing is the same type as the molding material in the case where the olefinic thermoplastic elastomer is used as the molding material. In the case of using this olefin-based substrate, a good effect can be obtained.
しかし、先に述べたスチレン系熱可塑性エラストマー組成物などの異種系の材料を成形品材料として用いようとした場合、適正な仮留め性が得ることが難しくなる。そのため、成形品が射出成形時の金型から取り出される際、成形品がポリオレフィン系樹脂製の支持基材から剥離し易くなり、成形品が金型内に残留してしまう場合が生じ得る。 However, when a different type material such as the above-described styrene-based thermoplastic elastomer composition is used as a molded article material, it is difficult to obtain appropriate temporary fixing properties. For this reason, when the molded product is taken out from the mold at the time of injection molding, the molded product is easily peeled off from the support substrate made of polyolefin resin, and the molded product may remain in the mold.
本発明は、上記従来の問題点に鑑みてなされたもので、その課題は、支持基材を構成するポリオレフィン系樹脂と異種材料でありながらも、仮留め一体成形による支持基材への仮留め特性に優れ、成形品とした場合の離型性が良好なスチレン系熱可塑性エラストマー組成物及びそれを用いた基材一体型仮留め成形品を提供することにある。 The present invention has been made in view of the above-described conventional problems, and the problem is that the polyolefin base resin constituting the support base material is a different material, but temporarily fixed to the support base material by temporary fixing integral molding. An object of the present invention is to provide a styrene-based thermoplastic elastomer composition having excellent characteristics and good mold release properties when formed into a molded product, and a substrate-integrated temporary-fixed molded product using the same.
本発明者らは、前記課題を解決するために、鋭意、実験、検討を重ねたところ、以下のような知見を得るに到った。
すなわち、スチレン系ブロック共重合体（Ａ)と、ポリプロピレン（Ｂ）と、ポリウレタン系熱可塑性エラストマー（Ｃ）と、の少なくとも３種の特定材料を含有したスチレン系熱可塑性エラストマー組成物を、フィルム一体型仮留め成形品の成形材料として用いると、オレフィン系樹脂製の支持基材に対する成形品の仮留め特性に優れ、離型性も良好となることが判明した。
In order to solve the above-mentioned problems, the present inventors have made extensive studies, experiments, and studies, and have obtained the following knowledge.
That is, a styrene-based thermoplastic elastomer composition containing at least three specific materials of a styrene-based block copolymer (A), polypropylene (B), and polyurethane-based thermoplastic elastomer (C) is used as a film. It has been found that when used as a molding material for a body temporary fixing molded article, the molded article has excellent temporary fixing characteristics with respect to a support substrate made of an olefin resin, and the mold release property is also improved.
本発明は、上記知見に基づいてなされたものである。すなわち、本発明にかかるスチレン系熱可塑性エラストマー組成物は、成形品をその成形時にオレフィン樹脂系基材上に仮留めして得られる基材一体型仮留め成形品を製造するためのスチレン系熱可塑性エラストマー組成物であって、スチレン系ブロック共重合体(Ａ)、ポリプロピレン(Ｂ)、及びポリウレタン系熱可塑性エラストマー(Ｃ)を含有することを特徴とする。 The present invention has been made based on the above findings. That is, the styrenic thermoplastic elastomer composition according to the present invention comprises a styrenic heat for producing a base material-integrated temporary-fixed molded product obtained by temporarily fixing a molded product on an olefin resin-based substrate at the time of molding. A plastic elastomer composition comprising a styrene block copolymer (A), a polypropylene (B), and a polyurethane thermoplastic elastomer (C).
また、本発明にかかる基材一体型仮留め成形品は、上記本発明のスチレン系熱可塑性エラストマー組成物を用いて得た成形品がオレフィン樹脂系基材上に仮留めされていることを特徴とする。 Moreover, the base material integrated temporary fixing molded product according to the present invention is characterized in that a molded product obtained by using the styrene thermoplastic elastomer composition of the present invention is temporarily fixed on an olefin resin base material. And
本発明にかかるスチレン系熱可塑性エラストマー組成物は、特に、家電や、車載用電子機器等のデバイスが内蔵される筐体（基材と蓋の間）で用いられる各種シール材（防塵、防水、耐透湿）、ダンパー材（緩衝材）などの成形品を取り付け作業時の操作性を向上するために基材に仮留めしてなる基材一体型仮留め成形品の材料組成として、好適である。
また、本発明の基材一体型仮留め成形品によれば、柔軟性、シール性などの成形品特性に優れたスチレン系熱可塑性エラストマー組成物成形品を、基材への仮留め強度を適正に維持するとともに、離型性も良好とすることができ、取り付け対象へ成形品を精度良く固着させることができ、固着後の基材剥離も容易である。
The styrenic thermoplastic elastomer composition according to the present invention includes various sealing materials (dust-proofing, waterproofing, etc.) used in a housing (between a base material and a lid) in which devices such as home appliances and in-vehicle electronic devices are built. Suitable as a material composition of a base-unit-type temporary fixing molded product that is temporarily fixed to a base material in order to improve operability at the time of attaching a molded product such as moisture permeation resistance and a damper material (buffer material). is there.
In addition, according to the substrate-integrated temporary-fixed molded product of the present invention, a styrene-based thermoplastic elastomer composition molded product having excellent molded product characteristics such as flexibility and sealing properties, and appropriate temporary fixing strength to the substrate In addition, the releasability can be improved, the molded product can be fixed to the attachment target with high accuracy, and the substrate can be easily peeled off after fixing.
本発明にかかるスチレン系型熱可塑性エラストマー組成物は、前述のように、成形品をその成形時にオレフィン樹脂系基材上に仮留めして得られる基材一体型仮留め成形品を製造するためのスチレン系熱可塑性エラストマー組成物であって、スチレン系ブロック共重合体(Ａ)、ポリプロピレン(Ｂ)、及びポリウレタン系熱可塑性エラストマー(Ｃ)を含有することを特徴とする。 The styrene-type thermoplastic elastomer composition according to the present invention is, as described above, for producing a base material-integrated temporary-fixed molded product obtained by temporarily fixing a molded product on an olefin resin-based base material at the time of molding. A styrene-based thermoplastic elastomer composition comprising a styrene-based block copolymer (A), a polypropylene (B), and a polyurethane-based thermoplastic elastomer (C).
前記(Ｂ)成分及び（Ｃ）成分の合計含有量としては、前記（Ａ）成分の１００重量部に対して、４〜５０重量部であることが、好ましく、６〜２０重量部であれば、更に好ましい。(Ｂ)成分及び（Ｃ）成分の合計含有量が４重量部未満であると、オレフィン樹脂系基材への仮留め強度を適切な強度に維持することができなくなり、金型から成形品を取り出す時に基材から成形品が剥離しやすくなり、成形品が金型内に付着する場合が出てくる。一方、(Ｂ)成分及び（Ｃ）成分の合計含有量が５０重量部を超えると、成形品自体の柔軟性が不十分になり、基材への仮留め強度も適切な値を超えて大きくなって成形品から基材を剥離することが困難になる。 The total content of the component (B) and the component (C) is preferably 4 to 50 parts by weight, and preferably 6 to 20 parts by weight with respect to 100 parts by weight of the component (A). More preferred. When the total content of the component (B) and the component (C) is less than 4 parts by weight, the temporary fixing strength to the olefin resin base material cannot be maintained at an appropriate strength, and the molded product is removed from the mold. When taking out, the molded product easily peels from the base material, and the molded product may adhere to the mold. On the other hand, when the total content of the component (B) and the component (C) exceeds 50 parts by weight, the flexibility of the molded product itself is insufficient, and the temporary fixing strength to the base material is larger than an appropriate value. It becomes difficult to peel the substrate from the molded product.
前記剥離強度の適切な値とは、金型からの成形品の剥離強度より高く、オレフィン樹脂系基材から成形品を損傷することなく剥離することのできる最大剥離強度以下の値である。この剥離強度は、使用する基材のオレフィン系樹脂の種類や、金型の材質、表面状態などに依存するので、定量化することは、難しい。
なお、上記金型からの剥離強度は、金型の内表面に剥離剤などの表面処理剤を使用しない状態での強度値である。本発明の成形品は、主に精密機器などのシール材として使用される関係から、機器内部を汚染する可能性のある化学成分は使用できないからである。
The appropriate value of the peel strength is a value that is higher than the peel strength of the molded product from the mold and equal to or less than the maximum peel strength at which the molded product can be peeled from the olefin resin base material without damaging it. This peel strength is difficult to quantify because it depends on the type of olefin resin of the substrate used, the material of the mold, the surface condition, and the like.
The peel strength from the mold is a strength value in a state where a surface treatment agent such as a release agent is not used on the inner surface of the mold. This is because the molded product of the present invention cannot use chemical components that can contaminate the inside of the equipment because it is mainly used as a sealing material for precision equipment.
前記（Ｂ）成分：（Ｃ）成分の含有量比は、１：３〜２：１であることが、好ましい。これらの範囲を外れると、基材に対する成形品の仮留め強度が必要な値以下になってしまう。
以下、各成分（Ａ）（Ｂ）（Ｃ）の組成について、順次、詳細に説明する。
The content ratio of the component (B): component (C) is preferably 1: 3 to 2: 1. If it is outside these ranges, the temporary fixing strength of the molded product with respect to the base material will be less than the required value.
Hereinafter, the composition of each component (A) (B) (C) will be described in detail in order.
（スチレン系ブロック共重合体（Ａ））
本発明に用いるスチレン系ブロック共重合体（Ａ）とは、スチレン、αメチルスチレン、３−メチルスチレン、４−プロピルスチレン、４−シクロへキシルスチレン、４−ドテシルスチレンなどのスチレンブロックをベースモノマーとして有するとともに、その他のモノマー成分として、ブタジエン、イソブチレン、イソプレンなどのモノマーを有する共重合体である。
(Styrene block copolymer (A))
The styrenic block copolymer (A) used in the present invention is based on a styrene block such as styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and 4-dodecylstyrene. A copolymer having a monomer and a monomer such as butadiene, isobutylene, or isoprene as the other monomer component.
かかるスチレン系ブロック共重合体（Ａ）として、具体的には、スチレン−イソブチレンブロック共重合体、スチレン−ブタジエンブロック共重合体、スチレン−イソプレンブロック共重合体、スチレン−ブタジェン−イソプレンブロック共重合体、及びそれらの水素添加物等を挙げることができる。これらから選ばれる少なくとも一種をスチレン系ブロック共重合体（Ａ）として使用することができる。 Specific examples of the styrene block copolymer (A) include a styrene-isobutylene block copolymer, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, and a styrene-butadiene-isoprene block copolymer. And hydrogenated products thereof. At least one selected from these can be used as the styrenic block copolymer (A).
（ポリプロピレン（Ｂ））
本発明に用いるポリプロピレン（Ｂ）としては、ホモポリプロピレン、ランダムポリプロピレン、ブロックポリプロピレン等を挙げることができる。これらから選ばれる少なくとも一種をポリプロピレン（Ｂ）として使用することができる。
(Polypropylene (B))
Examples of the polypropylene (B) used in the present invention include homopolypropylene, random polypropylene, and block polypropylene. At least one selected from these can be used as polypropylene (B).
（ポリウレタン系熱可塑性エラストマー（Ｃ））
本発明に用いるポリウレタン系熱可塑性エラストマー（Ｃ）とは、ポリオールとしてエステル基、エーテル基を含有するもの、または、ラクトン系、ポリカーボネート系ポリオールを使用し、これらとイソシアネートとを反応させたポリウレタン系熱可塑性エラストマーである。
前記エーテル基を含有するポリオールとしては、ポリ（オキシテトラメチレン）グリコール、ポリ（オキシプロピレン）グリコール、ポリ（オキシエチレン）グリコールが挙げられる。
前記エステル基を含有するポリオールとしては、アジペート系エステルグリコールが好ましく、ポリジエチレングリコールアジペート、ポリエチレングリコールアジペート、ポリブチレングリコールアジペート、ポリ３−メチルメチルペンタングリコールアジペート、ポリ２−メチルプロパングリコールアジペートなどが挙げられる。また、ラクトン系として、ポリカプロラクトングリコール等も好適である。
前記ポリカーボネート系ポリオールとしては、（ヘキサンジオール１，６−カーボネート）グリコール等が挙げられる。
上記ポリオールの内、特に、ポリエステル系ポリオールを用いたウレタン系熱可塑性エラストマーがスチレン系ブロック共重合体との相溶性が良いので好ましい。
一方、ポリイソシアネートには、トリレンジイソシアネート(ＴＤＩ)、ジフェニルメタンジイソシアネート（ＭＤＩ）、１，６ヘキサメチレンジイソシアネート（ＨＤＩ）等の公知のポリイソシアネートであれば、用いることができる。
(Polyurethane thermoplastic elastomer (C))
The polyurethane-based thermoplastic elastomer (C) used in the present invention is a polyurethane-based heat obtained by reacting an isocyanate group with one containing an ester group or an ether group, or a lactone-based or polycarbonate-based polyol. It is a plastic elastomer.
Examples of the polyol containing an ether group include poly (oxytetramethylene) glycol, poly (oxypropylene) glycol, and poly (oxyethylene) glycol.
The polyol containing an ester group is preferably an adipate ester glycol, and examples thereof include polydiethylene glycol adipate, polyethylene glycol adipate, polybutylene glycol adipate, poly-3-methylmethylpentane glycol adipate, and poly-2-methylpropane glycol adipate. . Further, polycaprolactone glycol or the like is also suitable as the lactone system.
Examples of the polycarbonate polyol include (hexanediol 1,6-carbonate) glycol.
Of the above polyols, urethane-based thermoplastic elastomers using polyester-based polyols are particularly preferred because of their good compatibility with styrene-based block copolymers.
On the other hand, as the polyisocyanate, known polyisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,6 hexamethylene diisocyanate (HDI) can be used.
（その他の成分）
本発明にかかるスチレン系熱可塑性エラストマー組成物には、上記必須成分（Ａ）（Ｂ）（Ｃ）以外に必要に応じて、その他の成分を添加することができる。その他の成分として、例えば、酸化防止剤、発泡剤、架橋剤、架橋助剤、可塑材、帯電防止材、充てん材、粘着付与材、滑材、難燃材を挙げることができる。これらの成分を配合して、射出成形において金型離型性が良くオレフィン樹脂基材への圧着し易い成形品を得ることが出来る。
(Other ingredients)
In addition to the essential components (A), (B), and (C), other components can be added to the styrene-based thermoplastic elastomer composition according to the present invention as necessary. Examples of other components include an antioxidant, a foaming agent, a crosslinking agent, a crosslinking aid, a plasticizer, an antistatic material, a filler, a tackifier, a lubricant, and a flame retardant. By blending these components, it is possible to obtain a molded article having good mold releasability in injection molding and easy to press-bond to an olefin resin substrate.
（スチレン系熱可塑性エラストマー組成物の調製）
前記組成の本発明にかかるスチレン系熱可塑性エラストマー組成物は、上記成分を下記方法により混練することにより、調製される。
すなわち、ドライブレンド、ニーダー、一軸又は二軸混練機、ラボプラストミル、ブラベンダー、バンバリーミキサー、ロール等の公知の混練機を用いて、１８０℃設定で、１０分間〜３０分間、溶融混練する。
(Preparation of styrenic thermoplastic elastomer composition)
The styrenic thermoplastic elastomer composition of the present invention having the above composition is prepared by kneading the above components by the following method.
That is, melt kneading is carried out for 10 minutes to 30 minutes at a setting of 180 ° C. using a known kneader such as dry blend, kneader, uniaxial or biaxial kneader, lab plast mill, Brabender, Banbury mixer, and roll.
（成形品の成形方法）
前記組成の本発明にかかるスチレン系熱可塑性エラストマー組成物を用いた成形品の製造方法としては、通常の射出成形において、オレフィン樹脂製のフィルム等に射出する方法や二色成形方法等の何れの方法によっても、行うことが可能である。
(Molding method of molded products)
As a method for producing a molded article using the styrenic thermoplastic elastomer composition according to the present invention having the above composition, any one of a method of injecting into a film made of an olefin resin or a two-color molding method in normal injection molding It can also be performed by a method.
以下に、本発明の実施例を示す。以下に示す実施例は、本発明を説明するに好適な例示であって、なんら本発明を限定するものではない。なお、以下に示す実施例及び比較例において、特に断らない限り記載の配合量の単位は、重量部である。 Examples of the present invention are shown below. The following examples are preferred examples for explaining the present invention, and do not limit the present invention. In the examples and comparative examples shown below, unless otherwise specified, the unit of the blending amount is part by weight.
（実施例１〜６）
下記（表１）に示すような組成及び組成比に従って、スチレン系熱可塑性エラストマー組成物を調製した。
なお、表中、（Ａ）成分のスチレン−イソブチレン−スチレン共重合体は「ＳＩＢＳ」と略記し、スチレン−ブタジエン−イソプレンブロック共重合体の水素添加物は「ＳＥＥＰＳ」と略記し、スチレン−イソプレンブロック共重合体の水素添加物は「水添ＳＩＳ」と略記し、（Ｂ）成分のブロックポリプロピレンは「ＰＰｂｌｏｃｋ」と略記し、（Ｃ）成分のエステルポリオール系のポリウレタン系熱可塑性エラストマーは「エステル系ＴＰＵ」と略記した。使用した各成分の具体的試料は、以下の通りである。
(Examples 1-6)
Styrenic thermoplastic elastomer compositions were prepared according to the composition and composition ratio as shown below (Table 1).
In the table, the styrene-isobutylene-styrene copolymer of component (A) is abbreviated as “SIBS”, the hydrogenated styrene-butadiene-isoprene block copolymer is abbreviated as “SEEPS”, and styrene-isoprene. The hydrogenated block copolymer is abbreviated as “hydrogenated SIS”, the (B) component block polypropylene is abbreviated as “PP block ”, and the (C) component ester polyol-based polyurethane thermoplastic elastomer is “ Abbreviated as “ester-based TPU”. Specific samples of each component used are as follows.
（ＳＩＢＳ）・・・（株）カネカ製「シブスター０７２Ｔ（商品名）」（ＪＩＳ Ｋ７２１０ ＭＦＲ ６ｇ／１０ｍｉｎ以下 ２３０℃ ２．１６ｋｇ）
（ＰＰblock）・・・（株）プライムポリマー製「Ｊ７０４ＵＧ（商品名）」（ＪＩＳ Ｋ７２１０ ＭＦＲ ５ｇ／１０ｍｉｎ以下 ２３０℃ ２．１６ｋｇ）
（エステルＴＰＵ）・・・（株）クラレ製「クラミロンＳ−８１６５（商品名）」（ＪＩＳ Ｋ７３１１ Ａ硬度 ６５）
（水添ＳＩＳ）・・・スチレン−イソプレンブロック共重合体の水素添加物（ＡＳＴＭ Ｄ１２３８ ＭＦＲ ４ｇ／１０ｍｉｎ以下 ２３０℃ ２．１６ｋｇ）
（ＳＥＥＰＳ）・・・スチレン−ブブタジエン−イソプレンブロック共重合体の水素添加物（ＡＳＴＭ Ｄ１２３８ ＭＦＲ ０．１ｇ／１０ｍｉｎ以下 ２３０℃ ２．１６ｋｇ）
（可塑剤Ａ）・・・出光興産（株）製「ＰＡＯ５０１０（商品名）」（ＪＩＳ Ｋ２２８３ 粘度指数 １３３）
(SIBS): “Sibstar 072T (trade name)” manufactured by Kaneka Corporation (JIS K7210 MFR 6 g / 10 min or less, 230 ° C., 2.16 kg)
(PP block ): “J704UG (trade name)” manufactured by Prime Polymer Co., Ltd. (JIS K7210 MFR 5 g / 10 min or less, 230 ° C., 2.16 kg)
(Ester TPU) ... "Kuramyron S-8165 (trade name)" manufactured by Kuraray Co., Ltd. (JIS K7311 A hardness 65)
(Hydrogenated SIS): Hydrogenated product of styrene-isoprene block copolymer (ASTM D1238 MFR 4 g / 10 min or less, 230 ° C., 2.16 kg)
(SEEPS): Hydrogenated product of styrene-bubutadiene-isoprene block copolymer (ASTM D1238 MFR 0.1 g / 10 min or less, 230 ° C., 2.16 kg)
(Plasticizer A): “PAO5010 (trade name)” manufactured by Idemitsu Kosan Co., Ltd. (JIS K2283, viscosity index 133)
（比較例１〜１０）
下記（表２）、（表３）に示すような成分および組成比に従って、スチレン系熱可塑性エラストマー組成物を調製した。
なお、表中の「ＳＩＢＳ」、「ＰＰｂｌｏｃｋ」、「エステル系ＴＰＵ」は、上記実施例で用いたものと同様の化合物である。また、表中の「ＴＰＥＥ」は、ポリエステル系熱可塑性エラストマーであり、具体的試料として、三菱化学（株）製の「プリマロイＰ１５００Ｎ（商品名）」（ＪＩＳ Ｋ７２１０ ＭＦＲ １１ｇ／１０ｍｉｎ ２３０℃ ２．１６ｋｇ）を使用した。「ＡＣＲ」は、（メタ）アクリル樹脂であり、具体的試料として、（株）クラレ製の「パラペット ＳＡ ＦＷ００１（商品名）」（ＪＩＳ Ｋ７２１０ ＭＦＲ １８ｇ／１０ｍｉｎ ２３０℃ ２．１６ｋｇ）を使用した。「ＥＶＡ」は、エチレン・酢酸ビニル共重合体であり、具体的試料として、三井デュポンポリケミカル社製の「ＥＶＡＦＬＥＸ ＥＶ−２５０（商品名）」（ＪＩＳ Ｋ６７３０ ＭＦＲ １５ｇ／１０ｍｉｎ ２３０℃ ２．１６ｋｇ）を使用した。「ＴＰＶＣ」は、塩化ビニル系エラストマーであり、具体的試料として、アプコ（株）製の「スミフレックスＫ５８ＤＬ１３（商品名）」（ＪＩＳ Ｋ６２５３ Ａ硬度 ４９）を使用した。また、「フッ素系ＴＰＥ（熱可塑性エラストマー）」としては、信越化学（株）製の「ＳＩＦＥＬ９７００（商品名）」（ＪＩＳ Ｋ６２５３ Ａ硬度 ７０）を使用した。
(Comparative Examples 1-10)
Styrenic thermoplastic elastomer compositions were prepared according to the components and composition ratios shown in the following (Table 2) and (Table 3).
In the table, “SIBS”, “PP block ”, and “ester TPU” are the same compounds as those used in the above examples. “TPEE” in the table is a polyester-based thermoplastic elastomer. As a specific sample, “Primalloy P1500N (trade name)” manufactured by Mitsubishi Chemical Corporation (JIS K7210 MFR 11 g / 10 min 230 ° C. 2.16 kg). )It was used. “ACR” is a (meth) acrylic resin, and “Parapet SA FW001 (trade name)” (JIS K7210 MFR 18 g / 10 min 230 ° C. 2.16 kg) manufactured by Kuraray Co., Ltd. was used as a specific sample. “EVA” is an ethylene / vinyl acetate copolymer. As a specific sample, “EVAFLEX EV-250 (trade name)” manufactured by Mitsui DuPont Polychemical Co., Ltd. (JIS K6730 MFR 15 g / 10 min 230 ° C. 2.16 kg) It was used. “TPVC” is a vinyl chloride elastomer, and “Sumiflex K58DL13 (trade name)” (JIS K6253 A hardness 49) manufactured by Apco Corporation was used as a specific sample. Further, “SIFEL 9700 (trade name)” (JIS K6253 A hardness 70) manufactured by Shin-Etsu Chemical Co., Ltd. was used as “fluorine-based TPE (thermoplastic elastomer)”.
上記各実施例及び比較例で得られた組成物の性能を、以下の特性について測定することにより、評価した。評価結果を各表に併記した。 The performance of the compositions obtained in the above Examples and Comparative Examples was evaluated by measuring the following characteristics. The evaluation results are shown in each table.
（成形品のオレフィン樹脂系基材への仮留め性）
オレフィン基材に射出成形を行い、基材との仮留め性を確認した。オレフィン樹脂基材から剥がれず、仮留めされている成形品を○、基材から一部剥がれた成形品を△、殆んど基材に仮留めされていない成形品を×とした。
(Temporary fixability of molded products to olefin resin base materials)
Injection molding was performed on the olefin substrate, and the temporary fixability with the substrate was confirmed. A molded product that was not peeled off from the olefin resin base material and was temporarily fastened was indicated as “◯”, a molded product partially peeled off from the base material was indicated as “Δ”, and a molded product that was hardly temporarily fastened to the base material was indicated as “x”.
（成形品の硬度：（Ａ）硬度）
ＪＩＳ Ｋ６２５３に準拠して、高分子計器（株）製の硬度計（商品名「ショアーＡ硬度計」）を用い、基材一体型仮留め成形品の製造直後の硬度を測定した。
(Hardness of molded product: (A) hardness)
Based on JIS K6253, the hardness immediately after manufacture of a base-material integrated temporary-fixation molded article was measured using the hardness meter (brand name "Shore A hardness meter") by a polymer meter Co., Ltd.
（粘度）
ＪＩＳ Ｋ５４０１に準じて、（株）島津製作所製のフローテスター（商品名「ＣＴ−５００」）を用いて、各組成物の１９０℃〜２１０℃までの粘度（Poise）の平均値を求めて、２００℃平均粘度とした。
(viscosity)
In accordance with JIS K5401, using a flow tester (trade name “CT-500”) manufactured by Shimadzu Corporation, the average value of the viscosity (Poise) from 190 ° C. to 210 ° C. of each composition was determined. The average viscosity was 200 ° C.
上記（表１）〜（表３）に見るように、スチレン系ブロック共重合体(Ａ)、ポリプロピレン(Ｂ)、及びポリウレタン系熱可塑性エラストマー(Ｃ)を同時に含有する組成の本発明のスチレン系熱可塑性エラストマー組成物は、粘度も操作性が良好な範囲にあり、得られる成形品の柔軟性（硬度）もシール材等の用途に適切な範囲にあり、しかも成形品のオレフィン樹脂系基材に対する仮留め性も良好である。これに対して、比較例のスチレン系熱可塑性エラストマー組成物は、（Ａ）成分に対して、（Ｂ）成分か（Ｃ）成分が欠けた構成であるため、仮留め性が不十分であることが分かる。 As seen in the above (Table 1) to (Table 3), the styrenic composition of the present invention having a composition containing the styrenic block copolymer (A), the polypropylene (B), and the polyurethane-based thermoplastic elastomer (C) at the same time. The thermoplastic elastomer composition is in a range where the viscosity and operability are good, the flexibility (hardness) of the resulting molded product is in a range suitable for applications such as sealing materials, and the olefin resin base material of the molded product The temporary fixability to is also good. On the other hand, the styrene-based thermoplastic elastomer composition of the comparative example has a structure in which the component (B) or the component (C) is lacking with respect to the component (A), and thus the temporary fixability is insufficient. I understand that.
（参考例１〜３、実施例９）
参考例として、本発明のスチレン系熱可塑性エラストマー組成物において、（Ｂ）成分と（Ｃ）成分の合計含有量が１重量部（４重量部未満）とした場合（参考例１）、（Ｂ）成分：（Ｃ）成分の含有量比が１９：６とした場合（参考例２）、（Ｂ）成分と（Ｃ）成分の合計含有量が７０重量部（５０重量部超）とした場合（参考例３）、そして、（Ｃ）成分としてエーテルポリオール系のポリウレタン系熱可塑性エラストマー「エーテル系ＴＰＵ」（日本ミラクトン（株）製、商品名「ミラクトンＥ３８０」 ＪＩＳ Ｋ７３１１ Ａ硬度８０）を用いた場合（実施例９）のそれぞれについて、組成物を調製し、前記実施例１〜８と同様にして性能を評価した。その結果を下記（表４）に示す。
(Reference Examples 1 to 3, Example 9)
As a reference example, in the styrenic thermoplastic elastomer composition of the present invention, when the total content of the component (B) and the component (C) is 1 part by weight (less than 4 parts by weight) (Reference Example 1), (B ) Component: When the content ratio of component (C) is 19: 6 (Reference Example 2), when the total content of component (B) and component (C) is 70 parts by weight (over 50 parts by weight) (Reference Example 3) And, as the component (C), an ether polyol-based polyurethane thermoplastic elastomer “ether-based TPU” (manufactured by Nippon Milactone Co., Ltd., trade name “Milactone E380”, JIS K7311 A hardness 80) was used. For each case (Example 9), a composition was prepared and performance was evaluated in the same manner as in Examples 1-8. The results are shown below (Table 4).
本発明にかかるスチレン系熱可塑性エラストマー組成物は、特に、家電や、車載用電子機器等のデバイスが内臓される筐体（基材と蓋の間）で用いられる各種シール材（防塵、防水、耐透湿）、ダンパー材（緩衝材）などの成形品を、取り付け作業時の操作性を向上するために、基材に仮留めしてなる基材一体型仮留め成形品の材料組成として、好適である。特にハードディスク装置や燃料電池のガスケットのような細く柔らかい成形品が求められている用途に好適である。
また、本発明の基材一体型仮留め成形品によれば、柔軟性、シール性などの成形品特性に優れたスチレン系熱可塑性エラストマー組成物成形品を、基材への仮留め強度を適正に維持するとともに、離型性も良好とすることができ、取り付け対象へ成形品を精度良く固着させることができ、固着後の基材剥離も容易である。
したがって、本発明のスチレン系熱可塑性エラストマー組成物及びそれを用いた基材一体型仮留め成形品を用いることにより、ハードディスク装置、車載用電気機器などの工業製品の性能及び信頼性を高めることができる。
The styrenic thermoplastic elastomer composition according to the present invention includes various sealing materials (dust-proof, waterproof, etc.) used in a housing (between the base material and the lid) in which devices such as home appliances and in-vehicle electronic devices are built. In order to improve the operability at the time of attachment work such as moisture permeation resistance) and damper material (buffer material), as a material composition of the base material integrated temporary fixing product formed by temporarily fixing to the base material, Is preferred. It is particularly suitable for applications where thin and soft molded products such as hard disk drives and fuel cell gaskets are required.
In addition, according to the substrate-integrated temporary-fixed molded product of the present invention, a styrene-based thermoplastic elastomer composition molded product having excellent molded product characteristics such as flexibility and sealing properties, and appropriate temporary fixing strength to the substrate In addition, the releasability can be improved, the molded product can be fixed to the attachment target with high accuracy, and the substrate can be easily peeled off after fixing.
Therefore, by using the styrenic thermoplastic elastomer composition of the present invention and a base-material-type temporary fixing product using the same, it is possible to enhance the performance and reliability of industrial products such as hard disk devices and in-vehicle electric devices. it can.
Claims (6)
スチレン系ブロック共重合体(Ａ)、ポリプロピレン(Ｂ)、及びポリウレタン系熱可塑性エラストマー(Ｃ)を含有することを特徴とするスチレン系熱可塑性エラストマー組成物。 A styrene-based thermoplastic elastomer composition for producing a substrate-integrated temporary fixing molded product obtained by temporarily fixing a molded product on an olefin resin-based substrate at the time of molding,
A styrenic thermoplastic elastomer composition comprising a styrenic block copolymer (A), polypropylene (B), and a polyurethane thermoplastic elastomer (C).
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| PCT/JP2008/071467 WO2009069666A1 (en) | 2007-11-26 | 2008-11-26 | Thermoplastic styrene elastomer composition and molded article obtained therefrom provisionally fixed and united to substrate |
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|---|---|---|---|---|
| JP2002147610A (en) * | 2000-11-14 | 2002-05-22 | Mitsubishi Plastics Ind Ltd | Packing with support base and method of manufacturing the same |
| JP2004035746A (en) * | 2002-07-04 | 2004-02-05 | Asahi Rubber Kk | Joint sealing material |
| KR20070027681A (en) * | 2004-07-08 | 2007-03-09 | 니혼 하츠쵸 가부시키가이샤 | Gasket, method of producing the gasket, and gasket installation method |
| JP2007176133A (en) * | 2005-12-28 | 2007-07-12 | Nhk Spring Co Ltd | Polymer-molded part to be temporarily fixed with film, manufacturing process of the molded part and method of mounting and fixing the molded part on main product body |
| JP2008223953A (en) * | 2007-03-14 | 2008-09-25 | Nhk Spring Co Ltd | Film temporarily fastening integrated gasket, and its manufacturing method and its mounting method |
| WO2008126618A1 (en) * | 2007-03-23 | 2008-10-23 | Nhk Spring Co., Ltd. | Irregularly shaped gasket temporarily integral with film and method of producing the same |
-
2007
- 2007-11-26 JP JP2007304394A patent/JP2009126965A/en active Pending
-
2008
- 2008-11-26 WO PCT/JP2008/071467 patent/WO2009069666A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020172559A (en) * | 2019-04-08 | 2020-10-22 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Thermoplastic polyurethane resin composition and molded article |
| JP7349255B2 (en) | 2019-04-08 | 2023-09-22 | コベストロ、ドイチュラント、アクチエンゲゼルシャフト | Thermoplastic polyurethane resin composition and molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009069666A1 (en) | 2009-06-04 |
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