JP7797239B2 - Shoe sole component and manufacturing method thereof - Google Patents
Shoe sole component and manufacturing method thereofInfo
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- JP7797239B2 JP7797239B2 JP2022026758A JP2022026758A JP7797239B2 JP 7797239 B2 JP7797239 B2 JP 7797239B2 JP 2022026758 A JP2022026758 A JP 2022026758A JP 2022026758 A JP2022026758 A JP 2022026758A JP 7797239 B2 JP7797239 B2 JP 7797239B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、靴底用部材とその製造方法に関する。 The present invention relates to a shoe sole component and a manufacturing method thereof.
従来、ウォーキング、ジョギング、ランニング等に利用される靴底用部材として、低反発発泡体と高反発発泡体を積層したものがある（特許文献１）。
また、ＥＶＡやポリウレタン発泡体、ゴム等を組み合わせて靴底を構成したものも知られている。
Conventionally, shoe sole members used for walking, jogging, running, etc. include those made by laminating low-resilience foam and high-resilience foam (Patent Document 1).
Shoe soles made from a combination of EVA, polyurethane foam, rubber, etc. are also known.
しかしながら、バレーボール、バスケットボール、サッカー、陸上競技の跳躍競技などのように跳躍が重要とされるスポーツ、あるいはジョギングやランニング等に用いられるスポーツ靴には、より軽量で反発弾性が高く、かつ耐荷重性能に優れた靴底用部材が求められている。なお、軽量化を図るために発泡体の発泡倍率を高くすると、反発弾性が低下するようになり、軽量化と反発弾性の両方を向上させることができなかった。これは、無理に発泡倍率を高くすると、セル構造が不均一かつ粗大になったり、セルが集合して鬆が多く発生したりしてその結果反発弾性が低下すると考えられる。 However, for sports where jumping is important, such as volleyball, basketball, soccer, and track and field jumping events, as well as for sports shoes used for jogging and running, there is a demand for lighter sole components that have high resilience and excellent load-bearing capacity. However, if the expansion ratio of the foam is increased to reduce weight, the resilience decreases, and it becomes impossible to improve both weight and resilience. This is thought to be because if the expansion ratio is forced to be high, the cell structure becomes uneven and coarse, or the cells gather together, causing many voids, resulting in a decrease in resilience.
本発明は前記の点に鑑みなされたものであって、跳躍が重要とされるスポーツ、あるいはジョギングやランニング等に用いられるスポーツ用靴に好適な、反発弾性が高い靴底用部材とその製造方法の提供を目的とする。 The present invention has been made in consideration of the above points, and aims to provide a shoe sole member with high resilience suitable for sports in which jumping is important , or for sports shoes used for jogging, running, etc., and a method for manufacturing the same.
第１の発明の態様は、ＪＩＳ Ｋ ６４００－３：２０１１に基づく反発弾性が７０％以上である、片面または両面にスキン層が形成された独立気泡構造の熱可塑性ポリエステルエラストマー発泡体からなる靴底用部材に係る。 The first aspect of the invention relates to a shoe sole component made of a thermoplastic polyester elastomer foam with a closed-cell structure and a skin layer formed on one or both sides, and which has a rebound resilience of 70% or more based on JIS K 6400-3:2011.
第２の発明の態様は、第１の発明の態様において、前記熱可塑性ポリエステルエラストマー発泡体は、溶融粘度調整剤により熱可塑性ポリエステルエラストマーが変性された変性熱可塑性ポリエステルエラストマーの発泡体であることを特徴とする。 A second aspect of the invention is the first aspect of the invention, characterized in that the thermoplastic polyester elastomer foam is a foam of a modified thermoplastic polyester elastomer in which the thermoplastic polyester elastomer has been modified with a melt viscosity modifier.
第３の発明の態様は、第２の発明の態様において、前記溶融粘度調整剤は、熱可塑性ポリエステルエラストマー１００重量部に対して、変性スチレン－アクリル共重合体を０．０５～１．５重量部またはアクリル変性ポリテトラフルオロエチレンを０．０１～１重量部の一方を含み、または変性スチレン－アクリル共重合体とアクリル変性ポリテトラフルオロエチレンの両方を０．０１～１．５重量部含むことを特徴とする。 A third aspect of the invention is the second aspect of the invention, characterized in that the melt viscosity modifier contains either 0.05 to 1.5 parts by weight of a modified styrene-acrylic copolymer or 0.01 to 1 part by weight of an acrylic-modified polytetrafluoroethylene, or 0.01 to 1.5 parts by weight of both a modified styrene-acrylic copolymer and an acrylic-modified polytetrafluoroethylene, per 100 parts by weight of the thermoplastic polyester elastomer.
第４の発明の態様は、第２の発明の態様において、前記溶融粘度調整剤は、エポキシ変性スチレン－アクリル共重合体であり、前記熱可塑性ポリエステルエラストマー１００重量部に対して０．１～１重量部含むことを特徴とする。 A fourth aspect of the invention is the second aspect of the invention, characterized in that the melt viscosity modifier is an epoxy-modified styrene-acrylic copolymer, and is contained in an amount of 0.1 to 1 part by weight per 100 parts by weight of the thermoplastic polyester elastomer.
第５の発明の態様は、第２の発明の態様において、前記溶融粘度調整剤は、アクリル変性ポリテトラフルオロエチレンであり、前記熱可塑性ポリエステルエラストマー１００重量部に対して０．０１～０．８重量部含むことを特徴とする。 A fifth aspect of the invention is the second aspect of the invention, characterized in that the melt viscosity modifier is acrylic-modified polytetrafluoroethylene, and is contained in an amount of 0.01 to 0.8 parts by weight per 100 parts by weight of the thermoplastic polyester elastomer.
第６の発明の態様は、第１から第５の態様の何れか一において、前記靴底用部材がミッドソールにおける足裏の踏みつけ部とかかと部に対応する部位に設けられることを特徴とする。 A sixth aspect of the invention is characterized in that, in any one of the first to fifth aspects, the sole member is provided in the midsole at locations corresponding to the tread and heel areas of the sole of the foot.
第７の発明の態様は、熱可塑性ポリエステルエラストマー発泡体からなる靴底用部材の製造方法において、変性熱可塑性ポリエステルエラストマーを射出成形機内で溶融する溶融工程と、物理発泡剤を超臨界装置により超臨界状態とする超臨界工程と、超臨界状態の前記物理発泡剤を前記射出成形機内に注入し、溶融状態の前記変性熱可塑性ポリエステルエラストマーと混合して、溶融状態の前記変性熱可塑性ポリエステルエラストマーと超臨界状態の前記物理発泡剤との分散溶融混合物にする分散溶融混合工程と、前記分散溶融混合物を、前記射出成形機から可動金型のキャビティに射出する射出工程と、前記可動金型をコアバックして熱可塑性ポリエステルエラストマー発泡体を作成する発泡工程と、を有し、前記熱可塑性ポリエステルエラストマー発泡体は、ＪＩＳ Ｋ ６４００－３：２０１１に基づく反発弾性が７０％以上である、片面または両面にスキン層が形成された独立気泡構造であることを特徴とする。 A seventh aspect of the invention is a method for manufacturing a shoe sole member made of a thermoplastic polyester elastomer foam, comprising the following steps: a melting step in which a modified thermoplastic polyester elastomer is melted in an injection molding machine; a supercritical step in which a physical blowing agent is brought to a supercritical state using a supercritical device; a dispersive melt mixing step in which the supercritical physical blowing agent is injected into the injection molding machine and mixed with the molten modified thermoplastic polyester elastomer to form a dispersed molten mixture of the molten modified thermoplastic polyester elastomer and the supercritical physical blowing agent; an injection step in which the dispersed molten mixture is injected from the injection molding machine into the cavity of a movable mold; and a foaming step in which the movable mold is cored back to produce a thermoplastic polyester elastomer foam; wherein the thermoplastic polyester elastomer foam has a closed-cell structure with a skin layer formed on one or both sides and a rebound resilience of 70% or more based on JIS K 6400-3:2011.
第８の発明の態様は、第７の発明の態様において、前記変性熱可塑性ポリエステルエラストマーは、熱可塑性ポリエステルエラストマーと溶融粘度調整剤とを事前に混合させて作製されたものであることを特徴とする。 An eighth aspect of the invention is the seventh aspect of the invention, characterized in that the modified thermoplastic polyester elastomer is prepared by pre-mixing a thermoplastic polyester elastomer with a melt viscosity modifier.
第９の発明の態様は、第８の発明の態様において、前記溶融粘度調整剤は、熱可塑性ポリエステルエラストマー１００重量部に対して、変性スチレン－アクリル共重合体を０．０５～１．５重量部またはアクリル変性ポリテトラフルオロエチレンを０．０１～１重量部の一方を含み、または変性スチレン－アクリル共重合体とアクリル変性ポリテトラフルオロエチレンの両方を０．０１～１．５重量部含むことを特徴とする。 A ninth aspect of the invention is the eighth aspect of the invention, characterized in that the melt viscosity modifier contains either 0.05 to 1.5 parts by weight of a modified styrene-acrylic copolymer or 0.01 to 1 part by weight of an acrylic-modified polytetrafluoroethylene, or 0.01 to 1.5 parts by weight of both a modified styrene-acrylic copolymer and an acrylic-modified polytetrafluoroethylene, per 100 parts by weight of the thermoplastic polyester elastomer.
第１０の発明の態様は、第８の発明の態様において、前記溶融粘度調整剤は、エポキシ変性スチレン－アクリル共重合体であり、前記熱可塑性ポリエステルエラストマー１００重量部に対して０．１～１重量部含むことを特徴とする。 A tenth aspect of the invention is the eighth aspect of the invention, characterized in that the melt viscosity modifier is an epoxy-modified styrene-acrylic copolymer, and is contained in an amount of 0.1 to 1 part by weight per 100 parts by weight of the thermoplastic polyester elastomer.
第１１の発明の態様は、第８の発明の態様において、前記溶融粘度調整剤は、アクリル変性ポリテトラフルオロエチレンであり、前記熱可塑性ポリエステルエラストマー１００重量部に対して０．０１～０．８重量部含むことを特徴とする。 An eleventh aspect of the invention is the eighth aspect of the invention, characterized in that the melt viscosity modifier is acrylic-modified polytetrafluoroethylene, and is contained in an amount of 0.01 to 0.8 parts by weight per 100 parts by weight of the thermoplastic polyester elastomer.
第１２の発明の態様は、第７から第１１の発明の態様の何れか一において、前記物理発泡剤が、窒素または二酸化炭素であることを特徴とする。 A twelfth aspect of the invention is any one of the seventh to eleventh aspects of the invention, characterized in that the physical foaming agent is nitrogen or carbon dioxide.
本発明によれば、片面または両面にスキン層が形成された独立気泡構造の熱可塑性ポリエステルエラストマー発泡体からなる、軽量で反発弾性が高い靴底用部材が得られる。また、靴底用部材をミッドソールにおける足裏の踏みつけ部とかかと部に対応する部位に設けられるものとすることにより、着地等の際の衝撃をエネルギーに変換にして効率の良い動きを実現できると共に、着地時に足のぶれを抑えて足の安定性を高め、足を保護することができるようになる。 The present invention provides a lightweight, highly resilient shoe sole component made of a closed-cell thermoplastic polyester elastomer foam with a skin layer formed on one or both sides. Furthermore, by providing the shoe sole component in the midsole at the tread and heel areas of the sole, impacts such as those caused by landing can be converted into energy, enabling efficient movement, while also reducing foot wobble when landing, improving foot stability and protecting the foot.
以下、本発明の靴底用部材について説明する。
本発明の靴底用部材は、靴底の一部に設けられるものである。以下に、本発明の靴底用部材の一使用状態について示す。図１に示す靴１０は、ミッドソール２１の一部に本発明の靴底用部材が用いられた例である。符号１１はアッパー、３１はアウトソールであり、前記ミッドソール２１と前記アウトソール３１が靴底を構成する部材である。
The shoe sole member of the present invention will now be described.
The shoe sole member of the present invention is provided as part of a shoe sole. One state in which the shoe sole member of the present invention is used is shown below. Shoe 10 shown in Figure 1 is an example in which the shoe sole member of the present invention is used as part of a midsole 21. Reference numeral 11 denotes an upper, and 31 denotes an outsole, and the midsole 21 and the outsole 31 are components that make up the shoe sole.
図２に示すように、前記ミッドソール２１の上側の面には、図３に示す足の裏における踏みつけ部とかかと部に対応する部位に、本発明の一例の靴底用部材４１、４３が埋設されている。踏み付け部に対応する部位に設けられている靴底用部材４１は、跳躍やランニング等において着地等の際に足の指の付け根付近に加わる衝撃を緩和すると共に、地面を蹴る際の力を反発力で高める作用をする。一方、かかと部に対応する部位に設けられている靴底用部材４３は、跳躍やランニング等において着地等の際にかかと付近に加わる衝撃を緩和する作用をする。 As shown in Figure 2, sole members 41, 43 according to an embodiment of the present invention are embedded in the upper surface of the midsole 21 in areas corresponding to the tread area and heel area of the sole of the foot shown in Figure 3. The sole member 41, which is provided in the area corresponding to the tread area, acts to absorb impacts applied to the area around the base of the toes when landing during jumping, running, etc., and also acts to increase the force of kicking off the ground with repulsion. On the other hand, the sole member 43, which is provided in the area corresponding to the heel, acts to absorb impacts applied to the area around the heel when landing during jumping, running, etc.
前記踏み付け部に対応する部位に設けられている靴底用部材４１は、足の親指の付け根から小指の付け根の範囲に対して作用するように、横長な長方形からなる。一方、かかと部に対応する部位に埋設されている靴底用部材４３は、かかと部の中央に対して作用するように、略円形からなる。前記ミッドソール２１の上面に埋設される靴底用部材４１、４３の厚みは、ミッドソール２１の厚みにもよるが、好ましい範囲として２～２０ｍｍ程度を挙げる。なお、前記靴底用部材４１、４３は、ミッドソール２１の上下を貫通するように埋設されたり、あるいはミッドソール２１の上面または下面に配置されたりしてもよい。 The sole member 41, located in the area corresponding to the footbed, is rectangular and long horizontally, so that it acts on the area from the base of the big toe to the base of the little toe. On the other hand, the sole member 43, embedded in the area corresponding to the heel, is generally circular, so that it acts on the center of the heel. The thickness of the sole members 41, 43 embedded in the upper surface of the midsole 21 depends on the thickness of the midsole 21, but a preferred range is approximately 2 to 20 mm. The sole members 41, 43 may be embedded so that they penetrate the midsole 21 from top to bottom, or may be positioned on the upper or lower surface of the midsole 21.
前記靴底用部材４１、４３は、ＪＩＳ Ｋ ６４００－３：２０１１に基づく反発弾性が７０％以上である、片面または両面にスキン層が形成された独立気泡構造の熱可塑性ポリエステルエラストマー発泡体からなる。前記靴底用部材４１、４３の密度は、例えば、１００～２５０ｋｇ／ｍ３である（密度の測定は、ＪＩＳ Ｋ ７２２２：２００５に基づく）。そのため、前記靴底用部材は、軽量性及び反発弾性に優れ、スポーツ用靴に好適である。 The shoe sole members 41, 43 are made of a closed-cell thermoplastic polyester elastomer foam with a skin layer formed on one or both sides, and have a rebound resilience of 70% or more based on JIS K 6400-3:2011. The shoe sole members 41, 43 have a density of, for example, 100 to 250 kg/ m3 (density measurement is based on JIS K 7222:2005). Therefore, the shoe sole members are lightweight and have excellent rebound resilience, making them suitable for sports shoes.
前記スキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体は、熱可塑性ポリエステルエラストマーを製造原料として、公知の超臨界ガス射出成形法により製造することができる。 The thermoplastic polyester elastomer foam with a closed-cell structure and a skin layer can be produced using a known supercritical gas injection molding method using a thermoplastic polyester elastomer as the manufacturing raw material.
超臨界ガス射出成形法による製造方法では、溶融状態の熱可塑性ポリエステルエラストマーと超臨界状態の物理発泡剤とを分散溶融混合し、金型のキャビティに射出し、次いで金型をコアバックすることにより、目的とする発泡倍率まで発泡させて発泡体を形成する。その後、金型内で発泡体を冷却させ、発泡体を金型から取り出す。発泡体を金型から取り出すことにより、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体が得られる。 In the supercritical gas injection molding manufacturing method, a molten thermoplastic polyester elastomer and a supercritical physical blowing agent are dispersed, melted, and mixed, then injected into a mold cavity. The mold is then cored back to expand the foam to the desired expansion ratio. The foam is then cooled in the mold and removed from the mold. Removal of the foam from the mold yields a closed-cell thermoplastic polyester elastomer foam with a skin layer on the surface.
脱型後、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体に対して、厚みをそのままにして所定の大きさに裁断することにより、スキン層を両面に有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体が得られる。一方、脱型後、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体に対して、その厚みを二分等することにより、スキン層を片面に有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体が得られる。 After demolding, the closed-cell thermoplastic polyester elastomer foam having a skin layer on the surface can be cut to the specified size while maintaining the same thickness, yielding a closed-cell thermoplastic polyester elastomer foam having a skin layer on both sides. On the other hand, after demolding, the closed-cell thermoplastic polyester elastomer foam having a skin layer on the surface can be cut in half to yield a closed-cell thermoplastic polyester elastomer foam having a skin layer on one side.
物理発泡剤としては、窒素や二酸化炭素等を挙げることができる。なお、物理発泡剤に替えて、アゾジカルボンアミド（ＡＤＣＡ）などの化学発泡剤を使用した場合、得られる発泡体のセル構造が粗大となる傾向にあり、物理発泡剤を使用する方が好ましい。 Physical blowing agents include nitrogen and carbon dioxide. However, if a chemical blowing agent such as azodicarbonamide (ADCA) is used instead of a physical blowing agent, the resulting foam tends to have a coarse cell structure, so it is preferable to use a physical blowing agent.
前記スキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体には、溶融粘度調整剤が添加されている。溶融粘度調整剤は、超臨界ガス射出成形法による製造時に、熱可塑性ポリエステルエラストマーの粘度を高めて、良好なセル構造を形成する。前記溶融粘度調整剤としては、変性スチレン－アクリル共重合体、アクリル変性ポリテトラフルオロエチレン、高分子量ポリエステルエラストマー等を挙げることができる。前記溶融粘度調整剤は、単独で使用してもよく、２種類以上を併用してもよい。 A melt viscosity modifier is added to the closed-cell thermoplastic polyester elastomer foam having a skin layer. The melt viscosity modifier increases the viscosity of the thermoplastic polyester elastomer during production by supercritical gas injection molding, forming a good cell structure. Examples of the melt viscosity modifier include modified styrene-acrylic copolymer, acrylic-modified polytetrafluoroethylene, and high-molecular-weight polyester elastomer. The melt viscosity modifier may be used alone or in combination of two or more types.
前記溶融粘度調整剤は、前記変性スチレン－アクリル共重合体または前記アクリル変性ポリテトラフルオロエチレンを使用することがより好ましい。
前記変性スチレン－アクリル共重合体の場合、前記熱可塑性ポリエステルエラストマーのエステル基と変性体（イソシアネート基やエポキシ基等の反応基）が反応し、高分子量化することにより、溶融粘度を高くすることができる（変性スチレン－アクリル共重合体は、鎖延長剤または架橋剤として機能する）。
前記アクリル変性ポリテトラフルオロエチレンの場合、剪断力によりポリテトラフルオロエチレンの繊維の束がほぐれ（フィブリル化）、繊維状のネットワーク構造を形成することにより、溶融粘度を高くすることができる。ポリテトラフルオロエチレンをアクリル変性することにより、前記熱可塑性ポリエステルエラストマーへの分散性が向上し、かつフィブリル化を効率よく発生させることができる（アクリル変性ポリテトラフルオロエチレンは、チクソトロピー剤として機能する）。
It is more preferable to use the modified styrene-acrylic copolymer or the acrylic-modified polytetrafluoroethylene as the melt viscosity modifier.
In the case of the modified styrene-acrylic copolymer, the ester group of the thermoplastic polyester elastomer reacts with the modified product (reactive group such as an isocyanate group or an epoxy group) to increase the molecular weight, thereby increasing the melt viscosity (the modified styrene-acrylic copolymer functions as a chain extender or a crosslinking agent).
In the case of the acrylic-modified polytetrafluoroethylene, the fiber bundles of the polytetrafluoroethylene are loosened (fibrillated) by shear force, forming a fibrous network structure, thereby increasing the melt viscosity. By modifying the polytetrafluoroethylene with an acrylic, the dispersibility in the thermoplastic polyester elastomer is improved and fibrillation can be efficiently induced (the acrylic-modified polytetrafluoroethylene functions as a thixotropic agent).
変性スチレン－アクリル共重合体の変性体（反応基）は、エポキシ基であることが好ましい。エポキシ変性スチレン－アクリル共重合体としては、エポキシ当量が２００～２８００であり、かつ、重量平均分子量（Ｍｗ）が２０００～２５０００であることが好ましく、エポキシ当量が２５０～１８００であり、かつ、重量平均分子量が（Ｍｗ）が４０００～１５０００であることがより好ましい。前記エポキシ変性スチレン－アクリル共重合体のエポキシ当量が２００未満の場合、十分な粘度調整効果が得られず、エポキシ当量が２８００を超えた場合、過度に粘度が上昇し、成形性に悪影響を及ぼすことがある。また、前記エポキシ変性スチレン－アクリル共重合体の重量平均分子量が２０００未満の場合、成形中に揮発したり、成形品の表面にブリードアウトする等、前記発泡体の表面が汚染されるおそれがある。一方、重量平均分子量が２５０００を超える場合、前記熱可塑性ポリエステルエラストマーのエステル基との反応性が低下し、適切に粘度調整が行えなかったり、該熱可塑性ポリエステルエラストマーとの相溶性が悪化するおそれがある。なお、エポキシ当量は、ＪＩＳ Ｋ７２３６：２００１に準拠して測定を行った。 The modified product (reactive group) of the modified styrene-acrylic copolymer is preferably an epoxy group. The epoxy-modified styrene-acrylic copolymer preferably has an epoxy equivalent of 200 to 2800 and a weight-average molecular weight (Mw) of 2000 to 25000, and more preferably an epoxy equivalent of 250 to 1800 and a weight-average molecular weight (Mw) of 4000 to 15000. If the epoxy equivalent of the epoxy-modified styrene-acrylic copolymer is less than 200, sufficient viscosity control effect cannot be achieved. If the epoxy equivalent exceeds 2800, viscosity increases excessively, which may adversely affect moldability. Furthermore, if the weight-average molecular weight of the epoxy-modified styrene-acrylic copolymer is less than 2000, there is a risk of contamination of the foam surface, such as volatilization during molding or bleeding out onto the surface of the molded product. On the other hand, if the weight average molecular weight exceeds 25,000, the reactivity with the ester group of the thermoplastic polyester elastomer decreases, making it difficult to adjust the viscosity appropriately and reducing compatibility with the thermoplastic polyester elastomer. The epoxy equivalent was measured in accordance with JIS K7236:2001.
また、前記エポキシ変性スチレン－アクリル共重合体の添加量は、熱可塑性ポリエステルエラストマーの１００重量部に対して０．０５～１．５重量部が好ましく、０．１～１重量部がより好ましい。０．０５重量部未満では、エポキシ変性スチレン－アクリル共重合体による溶融粘度の調整効果が小さく、一方、１．５重量部を超える場合は熱可塑性ポリエステルエラストマーの粘度が高くなり過ぎ、成形性が悪くなる傾向となる。 The amount of epoxy-modified styrene-acrylic copolymer added is preferably 0.05 to 1.5 parts by weight, and more preferably 0.1 to 1 part by weight, per 100 parts by weight of the thermoplastic polyester elastomer. If the amount is less than 0.05 parts by weight, the effect of the epoxy-modified styrene-acrylic copolymer in adjusting the melt viscosity is small. On the other hand, if the amount exceeds 1.5 parts by weight, the viscosity of the thermoplastic polyester elastomer becomes too high, which tends to deteriorate moldability.
前記アクリル変性ポリテトラフルオロエチレンの添加量は、熱可塑性ポリエステルエラストマーの１００重量部に対して０．０１～１重量部が好ましく、０．０１～０．８重量部がより好ましい。０．０１量部未満では、アクリル変性ポリテトラフルオロエチレンによる溶融粘度の調整効果が小さく、一方、１重量部を超える場合は熱可塑性ポリエステルエラストマーの粘度が高くなり過ぎ、成形性が悪くなる傾向となる。 The amount of acrylic-modified polytetrafluoroethylene added is preferably 0.01 to 1 part by weight, and more preferably 0.01 to 0.8 parts by weight, per 100 parts by weight of thermoplastic polyester elastomer. If the amount is less than 0.01 part, the effect of acrylic-modified polytetrafluoroethylene in adjusting the melt viscosity is small, while if the amount is more than 1 part by weight, the viscosity of the thermoplastic polyester elastomer becomes too high, which tends to result in poor moldability.
前記溶融粘度調整剤を２種類以上併用する場合、種類や添加量は、適宜変更することができる。前記溶融粘度調整剤の総添加量は、熱可塑性ポリエステルエラストマーの１００重量部に対して０．０１～１．５重量部が好ましい。０．０１重量部未満では、溶融粘度の調整効果が小さく、一方、１．５重量部を超える場合は熱可塑性ポリエステルエラストマーの粘度が高くなり過ぎ、成形性が悪くなる傾向となる。 When two or more types of melt viscosity modifiers are used in combination, the type and amount can be changed as appropriate. The total amount of melt viscosity modifiers added is preferably 0.01 to 1.5 parts by weight per 100 parts by weight of thermoplastic polyester elastomer. If it is less than 0.01 part by weight, the effect of adjusting the melt viscosity is small, while if it exceeds 1.5 parts by weight, the viscosity of the thermoplastic polyester elastomer becomes too high, which tends to deteriorate moldability.
前記スキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体は、溶融粘度調整剤以外に、必要に応じて適宜、添加剤を添加することができる。添加剤としては、着色剤、合成樹脂安定剤（酸化防止剤や紫外線吸収剤等）、充填材（フィラー）等が挙げられる。前記発泡体の物性への影響を考慮すると、前記添加剤はペレットや紛体等の固体原料であることが好ましい。 In addition to the melt viscosity modifier, additives can be added to the closed-cell thermoplastic polyester elastomer foam having a skin layer, as needed. Examples of additives include colorants, synthetic resin stabilizers (antioxidants, UV absorbers, etc.), and fillers. Considering the effect on the physical properties of the foam, it is preferable that the additives be in the form of solid raw materials such as pellets or powder.
前記スキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体の発泡倍率は、コアバック前のキャビティ内に充填する樹脂（熱可塑性ポリエステルエラストマー＋溶融粘度調整剤＋超臨界状態の物理発泡剤：以下、単に樹脂と記載する）重量および金型をコアバックさせる量で調整することができる。コアバック後の最終的なキャビティの容量を大きくすることで、発泡倍率を大きくすることができる。前記スキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体の発泡倍率は、４倍～１０倍が好ましく、より好ましくは５倍～９倍である。 The expansion ratio of the thermoplastic polyester elastomer foam with a closed-cell structure and a skin layer can be adjusted by the weight of the resin (thermoplastic polyester elastomer + melt viscosity modifier + supercritical physical blowing agent; hereinafter simply referred to as resin) filled into the cavity before core-backing and the amount of resin used to core-back the mold. The expansion ratio can be increased by increasing the final cavity volume after core-backing. The expansion ratio of the thermoplastic polyester elastomer foam with a closed-cell structure and a skin layer is preferably 4 to 10 times, and more preferably 5 to 9 times.
前記スキン層の存在により、発泡体の引張強度などの機械的強度や摩耗性などの表面強度が向上し、さらに、発泡体に掛かる荷重を面で受けるため、荷重が分散され発泡体のヘタリが防止されたり、高い反発弾性が得られる。前記スキン層は、前記樹脂が金型に充填されてキャビティ内壁に接触して冷却されることで成形される。 The presence of the skin layer improves the foam's mechanical strength, such as tensile strength, and surface strength, such as abrasion resistance. Furthermore, since the load applied to the foam is received over its surface, the load is distributed, preventing the foam from setting and providing high resilience. The skin layer is formed when the resin is filled into a mold and cooled in contact with the inner wall of the cavity.
コアバック前のキャビティ内に充填する樹脂重量は、キャビティ容量と等しいフルショットでも、キャビティ容量よりも少ないショートショットでも、どちらでもよい。ショートショットの場合、キャビティ容積に充填可能な樹脂重量に対して、重量比にして５～２０重量％少ない量の樹脂重量をキャビティに射出する。 The weight of resin filled into the cavity before core-backing can be either a full shot equal to the cavity capacity, or a short shot less than the cavity capacity. In the case of a short shot, the resin injected into the cavity is 5 to 20% less by weight than the resin weight that can fill the cavity volume.
次の熱可塑性ポリエステルエラストマー（略称ＴＰＥＥ）及び溶融粘度調整剤を図４の配合にし、超臨界ガス射出成形法によって物性測定用の実施例１～実施例１６及び比較例１～比較例７の各サンプルを製造した。
・熱可塑性ポリエステルエラストマー１（ＴＰＥＥ－１）：品名；ペルプレンＰ－４０ＢＴＭ、東洋紡社製
・熱可塑性ポリエステルエラストマー２（ＴＰＥＥ－２）：品名；ペルプレンＰ－３０Ｂ、東洋紡社製
・熱可塑性ポリエステルエラストマー３（ＴＰＥＥ－３）：品名；ペルプレンＰ－４０Ｂ、東洋紡社製
・溶融粘度調整剤－１：エポキシ変性スチレン－アクリル共重合体、エポキシ当量＝７１４、重量平均分子量＝９７００
・溶融粘度調整剤－２：エポキシ変性スチレン－アクリル共重合体、エポキシ当量＝２８５、重量平均分子量＝７３００
・溶融粘度調整剤－３：エポキシ変性スチレン－アクリル共重合体、エポキシ当量＝１５００、重量平均分子量＝８５００
・溶融粘度調整剤－４：エポキシ変性スチレン－アクリル共重合体、エポキシ当量＝２８００、重量平均分子量＝２９００
・溶融粘度調整剤－５：品名；メタブレン Ａ－３８００（アクリル変性ポリテトラフルオロエチレン）、三菱レイヨン社製
・物理発泡剤：窒素ガス
The following thermoplastic polyester elastomers (abbreviated as TPEE) and melt viscosity modifiers were blended as shown in FIG. 4, and samples of Examples 1 to 16 and Comparative Examples 1 to 7 for measuring physical properties were produced by supercritical gas injection molding.
Thermoplastic polyester elastomer 1 (TPEE-1): Product name: Pelprene P-40BTM, manufactured by Toyobo Co., Ltd. Thermoplastic polyester elastomer 2 (TPEE-2): Product name: Pelprene P-30B, manufactured by Toyobo Co., Ltd. Thermoplastic polyester elastomer 3 (TPEE-3): Product name: Pelprene P-40B, manufactured by Toyobo Co., Ltd. Melt viscosity adjuster-1: Epoxy-modified styrene-acrylic copolymer, epoxy equivalent = 714, weight average molecular weight = 9700
Melt viscosity modifier-2: epoxy-modified styrene-acrylic copolymer, epoxy equivalent = 285, weight average molecular weight = 7300
Melt viscosity modifier-3: epoxy-modified styrene-acrylic copolymer, epoxy equivalent = 1500, weight average molecular weight = 8500
Melt viscosity modifier-4: epoxy-modified styrene-acrylic copolymer, epoxy equivalent = 2800, weight average molecular weight = 2900
Melt viscosity adjuster-5: Product name: Metablen A-3800 (acrylic modified polytetrafluoroethylene), manufactured by Mitsubishi Rayon Co., Ltd. Physical foaming agent: nitrogen gas
射出成形機は電動射出成形機を用い、また、金型は可動型と固定型間のキャビティが１００×２００ｍｍで初期厚みを０．５ｍｍから５．０ｍｍまで可変できるように構成されたものを用いた。 The injection molding machine used was an electric injection molding machine, and the mold used had a cavity of 100 x 200 mm between the movable and fixed dies, and was configured so that the initial thickness could be adjusted from 0.5 mm to 5.0 mm.
窒素ガスを、超臨界供給装置を用いて超臨界状態とした後、射出成形機のシリンダ内に注入し、シリンダ内で溶融状態とした熱可塑性ポリエステルエラストマーと溶融粘度調整剤を結晶融点１８０℃以上とし、前記窒素ガスを分散溶融混合させた。その後、金型のキャビティに射出し、次いで可動金型をコアバックさせ、冷却させた後に脱型し、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体を得た。 Nitrogen gas was brought to a supercritical state using a supercritical feeder and then injected into the cylinder of an injection molding machine. The thermoplastic polyester elastomer and melt viscosity modifier, which were molten in the cylinder, were brought to a crystalline melting point of 180°C or higher, and the nitrogen gas was dispersed, melted, and mixed. The mixture was then injected into the mold cavity, the movable mold was cored back, and after cooling, the mixture was demolded, yielding a thermoplastic polyester elastomer foam with a closed-cell structure and a skin layer on the surface.
また、熱可塑性ポリエステルエラストマーと溶融粘度調整剤とを事前に混合（反応またはフィブリル化）させた変性熱可塑性ポリエステルエラストマーを作成した後に、上記方法で表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体を得てもよい。変性熱可塑性ポリエステルエラストマーは、熱可塑性ポリエステルエラストマーのエステル基と溶融粘度調整剤－１～４のエポキシ変性スチレン－アクリル共重合体のエポキシ基とが反応し、熱可塑性ポリエステルエラストマーの分子鎖を長くしたり、熱可塑性ポリエステルエラストマー同士を架橋させることにより高分子量化し、また、溶融粘度調整剤－５のアクリル変性ポリテトラフルオロエチレンのポリテトラフルオロエチレンがフィブリル化することにより、溶融時の粘度を高くすることができる。良好なセル構造を得るには、変性熱可塑性ポリエステルエラストマーを用いることが好ましい。 Alternatively, a modified thermoplastic polyester elastomer may be prepared by premixing (reacting or fibrillating) a thermoplastic polyester elastomer with a melt viscosity modifier, followed by the above-described method to obtain a closed-cell thermoplastic polyester elastomer foam having a skin layer on the surface. The modified thermoplastic polyester elastomer undergoes a reaction between the ester groups of the thermoplastic polyester elastomer and the epoxy groups of the epoxy-modified styrene-acrylic copolymers (melt viscosity modifiers 1 to 4), lengthening the molecular chain of the thermoplastic polyester elastomer and crosslinking the thermoplastic polyester elastomers to increase the molecular weight. Furthermore, the fibrillation of the polytetrafluoroethylene in the acrylic-modified polytetrafluoroethylene (melt viscosity modifier 5) increases the viscosity when melted. To obtain a good cell structure, it is preferable to use a modified thermoplastic polyester elastomer.
実施例１は、熱可塑性ポリエステルエラストマーとしてＴＰＥＥ－２を用い、溶融粘度調整剤－１（エポキシ変性スチレン－アクリル共重合体）の添加量を０．５重量部とし、キャビティ空間の初期の厚み（初期厚み）を２ｍｍにし、樹脂をキャビティ容積に対して１００％充填（フルショット）し、その後、コアバック量１７ｍｍで型を開き、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率９．５倍）を、厚み１９ｍｍで製造した。なお、充填する樹脂は比重を１と仮定して重量を容量に換算し、キャビティ容積に対する充填％（充填率）を計算した。 In Example 1, TPEE-2 was used as the thermoplastic polyester elastomer, 0.5 parts by weight of melt viscosity modifier-1 (epoxy-modified styrene-acrylic copolymer) was added, the initial cavity thickness (initial thickness) was 2 mm, and the resin was filled to 100% of the cavity volume (full shot). The mold was then opened with a core-back depth of 17 mm to produce a 19 mm thick, closed-cell thermoplastic polyester elastomer foam (expansion ratio 9.5 times) with a skin layer on the surface. The specific gravity of the resin to be filled was assumed to be 1, and the weight was converted to volume to calculate the filling percentage (filling rate) relative to the cavity volume.
実施例２は、コアバック量を１２ｍｍとした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 2, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7 times) with a thickness of 14 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that the core-back amount was set to 12 mm.
実施例３は、コアバック量を９ｍｍとした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率５．５倍）を、厚み１１ｍｍで製造した。 In Example 3, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 5.5 times) with a thickness of 11 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that the core-back amount was set to 9 mm.
実施例４は、コアバック量を６．８ｍｍとした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率４．４倍）を、厚み８．８ｍｍで製造した。 In Example 4, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 4.4 times) with a thickness of 8.8 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that the core-back amount was set to 6.8 mm.
実施例５は、溶融粘度調整剤－１の添加量を０．０５重量部に変更し、コアバック量を１２ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 5, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7x) with a thickness of 14 mm and a skin layer on the surface was produced in the same manner as Example 1, except that the amount of melt viscosity modifier-1 added was changed to 0.05 parts by weight and the core-back amount was changed to 12 mm.
実施例６は、溶融粘度調整剤－１の添加量を０．１重量部に変更し、コアバック量を１２ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 6, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7 times) with a thickness of 14 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that the amount of melt viscosity modifier-1 added was changed to 0.1 parts by weight and the core-back amount was changed to 12 mm.
実施例７は、溶融粘度調整剤－１の添加量を１重量部に変更し、コアバック量を１２ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 7, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7 times) with a thickness of 14 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that the amount of melt viscosity modifier-1 added was changed to 1 part by weight and the core-back amount was changed to 12 mm.
実施例８は、溶融粘度調整剤－１の添加量を１．５重量部に変更し、コアバック量を１２ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 8, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7x) with a thickness of 14 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that the amount of melt viscosity modifier-1 added was changed to 1.5 parts by weight and the core-back amount was changed to 12 mm.
実施例９は、熱可塑性ポリエステルエラストマーをＴＰＥＥ－３に変更し、コアバック量を１２ｍｍとした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 9, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7x) with a thickness of 14 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that the thermoplastic polyester elastomer was changed to TPEE-3 and the core-back amount was changed to 12 mm.
実施例１０は、溶融粘度調整剤－２（エポキシ変性スチレン－アクリル共重合体）に変更し、添加量を０．５重量部とし、コアバック量を１２ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 10, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7x) with a skin layer on the surface and a thickness of 14 mm was produced in the same manner as in Example 1, except that melt viscosity modifier-2 (epoxy-modified styrene-acrylic copolymer) was used, the amount added was 0.5 parts by weight, and the core-back amount was 12 mm.
実施例１１は、溶融粘度調整剤－３（エポキシ変性スチレン－アクリル共重合体）に変更し、添加量を０．５重量部とし、コアバック量を１２ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 11, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7 times) with a thickness of 14 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that melt viscosity modifier-3 (epoxy-modified styrene-acrylic copolymer) was used in an amount of 0.5 parts by weight and the core-back amount was 12 mm.
実施例１２は、溶融粘度調整剤－４（エポキシ変性スチレン－アクリル共重合体）に変更し、添加量を０．５重量部とし、コアバック量を１２ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率７倍）を、厚み１４ｍｍで製造した。 In Example 12, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 7x) with a skin layer on the surface and a thickness of 14 mm was produced in the same manner as in Example 1, except that melt viscosity modifier-4 (epoxy-modified styrene-acrylic copolymer) was used in an amount of 0.5 parts by weight and the core-back amount was 12 mm.
実施例１３は、溶融粘度調整剤－５（アクリル変性ポリテトラフルオロエチレン）に変更し、添加量を０．０１重量部とし、コアバック量を８ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率５倍）を、厚み１０ｍｍで製造した。 In Example 13, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 5x) with a skin layer on the surface and a thickness of 10 mm was produced in the same manner as in Example 1, except that melt viscosity modifier-5 (acrylic-modified polytetrafluoroethylene) was used in an amount of 0.01 parts by weight and the core-back amount was 8 mm.
実施例１４は、溶融粘度調整剤－５に変更し、添加量を０．８重量部とし、コアバック量を８ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率５倍）を、厚み１０ｍｍで製造した。 In Example 14, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 5x) with a thickness of 10 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that melt viscosity modifier-5 was used, the amount added was 0.8 parts by weight, and the core-back amount was 8 mm.
実施例１５は、溶融粘度調整剤－５に変更し、添加量を１重量部とし、コアバック量を８ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率５倍）を、厚み１０ｍｍで製造した。 In Example 15, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 5x) with a thickness of 10 mm and a skin layer on the surface was produced in the same manner as in Example 1, except that melt viscosity modifier-5 was used in an amount of 1 part by weight and the core-back amount was 8 mm.
実施例１６は、溶融粘度調整剤－１の添加量、０．５重量部と溶融粘度調整剤－５の添加量、０．１重量部とを併用し、コアバック量を８ｍｍにした以外は実施例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率５倍）を、厚み１０ｍｍで製造した。 In Example 16, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 5x) with a skin layer on the surface and a thickness of 10 mm was produced in the same manner as in Example 1, except that 0.5 parts by weight of melt viscosity modifier-1 and 0.1 parts by weight of melt viscosity modifier-5 were added in combination and the core-back amount was set to 8 mm.
比較例として、溶融粘度調整剤を添加していない比較例１～７と、ポリウレタンフォームからなる比較例８と、熱可塑性ポリウレタン発泡ビーズからなる比較例９との各試験体を作成した。各比較例の構成は図５に示す。 For comparative examples, specimens were prepared for Comparative Examples 1 to 7, which did not contain any melt viscosity modifier, Comparative Example 8, which consisted of polyurethane foam, and Comparative Example 9, which consisted of thermoplastic polyurethane foam beads. The configuration of each comparative example is shown in Figure 5.
比較例１は、熱可塑性ポリエステルエラストマーとしてＴＰＥＥ－１を用い、キャビティ空間の初期の厚み（初期厚み）を２ｍｍにし、樹脂をキャビティ容積に対して１００％充填（フルショット）し、コアバック量を０ｍｍとして型を開き、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率１倍）を、厚み２ｍｍで製造した。 In Comparative Example 1, TPEE-1 was used as the thermoplastic polyester elastomer, the initial thickness of the cavity space (initial thickness) was set to 2 mm, the resin was filled to 100% of the cavity volume (full shot), the core-back amount was set to 0 mm, and the mold was opened to produce a thermoplastic polyester elastomer foam (expansion ratio 1x) with a closed-cell structure and a skin layer on the surface, with a thickness of 2 mm.
比較例２は、コアバック量を２ｍｍとした以外は比較例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率２倍）を、厚み４ｍｍで製造した。 In Comparative Example 2, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 2x) with a thickness of 4 mm and a skin layer on the surface was produced in the same manner as Comparative Example 1, except that the core-back amount was set to 2 mm.
比較例３は、コアバック量を４ｍｍとした以外は比較例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率３倍）を、厚み６ｍｍで製造した。 In Comparative Example 3, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 3x) with a thickness of 6 mm and a skin layer on the surface was produced in the same manner as Comparative Example 1, except that the core-back amount was set to 4 mm.
比較例４は、コアバック量を６ｍｍとした以外は比較例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率４倍）を、厚み８ｍｍで製造した。 In Comparative Example 4, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 4x) with a thickness of 8 mm and a skin layer on the surface was produced in the same manner as Comparative Example 1, except that the core-back amount was set to 6 mm.
比較例５は、コアバック量を８ｍｍとした以外は比較例１と同様にして、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率５倍）を、厚み１０ｍｍで製造した。 In Comparative Example 5, a closed-cell thermoplastic polyester elastomer foam (expansion ratio 5x) with a thickness of 10 mm and a skin layer on the surface was produced in the same manner as Comparative Example 1, except that the core-back amount was set to 8 mm.
比較例６は、熱可塑性ポリエステルエラストマーをＴＰＥＥ－２に変更し、キャビティ空間の初期の厚み（初期厚み）を２ｍｍにし、コアバック量を５ｍｍとした以外は比較例１と同様にし、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率３．５倍）を、厚み７ｍｍで製造した。 Comparative Example 6 was the same as Comparative Example 1, except that the thermoplastic polyester elastomer was changed to TPEE-2, the initial thickness of the cavity space (initial thickness) was set to 2 mm, and the core-back amount was set to 5 mm. A thermoplastic polyester elastomer foam (expansion ratio 3.5 times) with a closed-cell structure and a skin layer on the surface was produced to a thickness of 7 mm.
比較例７は、熱可塑性ポリエステルエラストマーをＴＰＥＥ－３に変更し、キャビティ空間の初期の厚み（初期厚み）を２ｍｍにし、コアバック量を４ｍｍとした以外は比較例１と同様にし、表面にスキン層を有する独立気泡構造の熱可塑性ポリエステルエラストマー発泡体（発泡倍率３倍）を、厚み６ｍｍで製造した。 In Comparative Example 7, the thermoplastic polyester elastomer was changed to TPEE-3, the initial thickness of the cavity space (initial thickness) was set to 2 mm, and the core-back amount was set to 4 mm. The same procedures were followed as in Comparative Example 1, and a thermoplastic polyester elastomer foam (expansion ratio 3x) with a closed-cell structure and a skin layer on the surface was produced to a thickness of 6 mm.
比較例８は、密度４５ｋｇ／ｍ３のポリウレタンフォーム（スキン層無し）、品番：ＥＲＧ－Ｈ、イノアックコーポレーション社製を用いた。
比較例９は、密度３００ｋｇ／ｍ３の熱可塑性ポリウレタン発泡ビーズ（スキン層無し）、品番：ＭＣ３８０、ＮＴＷ社製を用いた。
In Comparative Example 8, polyurethane foam (without skin layer) having a density of 45 kg/m 3 , product number: ERG-H, manufactured by Inoac Corporation, was used.
In Comparative Example 9, thermoplastic polyurethane foam beads (without a skin layer) having a density of 300 kg/m 3 , product number: MC380, manufactured by NTW Corporation, were used.
物性測定用の各実施例及び各比較例の各サンプルについて、密度と反発弾性、荷重増加率を測定し、また外観を目視で判断した。結果は図４及び図５に示す。
密度は、実施例１～実施例１６及び比較例１～比較例７の各サンプルから、裁断によって３０φ×各サンプル厚みの密度測定用サンプルを作成し、比較例８及び比較例９については、１０ｍｍのスライス品から裁断によって３０φ×１０ｍｍ厚みの密度測定用サンプルを作成し、ＪＩＳ Ｋ ７２２２：２００５に基づいて測定した。なお、密度測定用サンプルは、比較例８及び比較例９を除き、両面にスキン層を有する。
反発弾性は、密度と同様に、各実施例及び各比較例のサンプルから、裁断によって１００角×各サンプル厚みの反発弾性測定用サンプルを作成し、反発弾性測定用サンプルが１０ｍｍ未満の場合、合計厚みが１０ｍｍ以上と成るように重ね、ＪＩＳ Ｋ ６４００－３：２０１１に基づいて測定した。なお、反発弾性測定用サンプルは、比較例８及び比較例９を除き、両面にスキン層を有する。
The density, impact resilience, and load increase rate of each sample of each Example and Comparative Example for measuring physical properties were measured, and the appearance was visually evaluated. The results are shown in Figures 4 and 5.
Density was measured based on JIS K 7222: 2005. Each of the samples in Examples 1 to 16 and Comparative Examples 1 to 7 was cut to prepare a density measurement sample having a diameter of 30 mm and a thickness of each sample, and for Comparative Examples 8 and 9, a 10 mm slice was cut to prepare a density measurement sample having a diameter of 30 mm and a thickness of 10 mm, and the density was measured based on JIS K 7222: 2005. The density measurement samples had skin layers on both sides, except for Comparative Examples 8 and 9.
As with density, the rebound resilience was measured by cutting samples from each Example and Comparative Example to prepare a 100mm square sample of each sample thickness for measuring rebound resilience, and when the sample for measuring rebound resilience was less than 10mm, the samples were stacked so that the total thickness was 10mm or more, and the measurement was performed in accordance with JIS K 6400-3: 2011. The samples for measuring rebound resilience had skin layers on both sides, except for Comparative Examples 8 and 9.
荷重増加率は、３点曲げ試験により最大荷重値（Ｎ）を測定し、発泡倍率１倍（非発泡）の比較例１の測定値（Ａ）と各実施例及び比較例２～９の測定値（Ｂ）との比から、荷重増加の倍率を下式より求めた。
［荷重増加率（倍）］＝［Ｂ（Ｎ）］／［Ａ（Ｎ）］
３点曲げ試験は、密度と同様に、各実施例及び各比較例のサンプルから、裁断によって１００ｍｍ長さ×１０ｍｍ幅×各サンプル厚みの荷重増加率測定用サンプルを作成し、支点間距離：６０ｍｍ、試験速度：２ｍｍ／分にて測定を行った。なお、測定は、島津社製のＡＵＴＯ ＧＲＡＰＨ ＡＧ-ＩＳを使用し、支持台及び圧子は、ＪＩＳ Ｋ７１７１ ５．３に記載のものを使用した。
荷重増加率が、３倍以上の場合に「○」、２倍以上３倍未満の場合に「△」、２倍未満の場合に「×」とした。
The load increase rate was determined by measuring the maximum load value (N) in a three-point bending test, and calculating the load increase rate from the ratio of the measured value (A) of Comparative Example 1 with an expansion rate of 1 (non-foamed) to the measured value (B) of each Example and Comparative Examples 2 to 9, using the following formula:
[Load increase rate (times)] = [B (N)] / [A (N)]
In the three-point bending test, as with the density test, samples for measuring the load increase rate were cut from each of the examples and comparative examples to prepare samples having a length of 100 mm, a width of 10 mm, and a thickness of each sample, and measurements were performed at a distance between supports of 60 mm and a test speed of 2 mm/min. The measurements were performed using an AUTOGRAPH AG-IS manufactured by Shimadzu Corporation, and the support and indenter were those specified in JIS K7171 5.3.
A load increase rate of 3 times or more was marked "◯", a load increase rate of 2 times or more but less than 3 times was marked "Δ", and a load increase rate of less than 2 times was marked "X".
外観は、セル構造が不均一の場合、表面に鬆や筋が現れるため、外観に鬆や筋が殆ど見られない場合（セル構造が均一な場合）に「〇」、鬆や筋が少し見られる場合（セル構造が僅かに不均一な場合）に「△」、鬆や筋が多く見られる場合（セル構造が著しく不均な場合）に「×」とした。 When the cell structure is uneven, voids and streaks appear on the surface. Therefore, when almost no voids or streaks are visible (when the cell structure is uniform), a "Good" is given; when only a few voids or streaks are visible (when the cell structure is slightly uneven), a "Good" is given; and when many voids or streaks are visible (when the cell structure is significantly uneven), an "Unclear" is given.
実施例１～実施例９（溶融粘度調整剤－１を使用）は、密度が１１０～２４０ｋｇ／ｍ３であり、かつ反発弾性が７０～７７％であり、荷重増加率が３．０～５．２倍であり、軽量で反発弾性が高く、かつ荷重増加率も高いものであった。特に溶融粘度調整剤－１の添加量が０．１～１．０重量部の実施例１～実施例４、実施例６、実施例７及び実施例９は、反発弾性が７１～７７％で、かつ外観の評価が「〇」であり、好ましいものであった。また、溶融粘度調整剤－１の添加量が０．１～１．０重量部で、かつ発泡倍率が５．５倍以上の実施例１～実施例３、実施例６、実施例７及び実施例９は、密度が１１０～１９０ｋｇ／ｍ３であり、かつ反発弾性が７１～７６％であり、高い反発弾性を維持しつつ、より軽量性の高いものであった。さらに溶融粘度調整剤－１の添加量が０．１～１．０重量部で、かつ発泡倍率が７倍以上の実施例１、実施例２、実施例６、実施例７及び実施例９は、密度が１１０～１５０ｋｇ／ｍ３であり、かつ反発弾性が７１～７５％であり、高い反発弾性を維持しつつ、さらに軽量性の高いものであった。 Examples 1 to 9 (using melt viscosity modifier-1) had densities of 110 to 240 kg/ m3 , rebound resilience of 70 to 77%, and load increase rates of 3.0 to 5.2 times, demonstrating lightweight, high rebound resilience, and a high load increase rate. In particular, Examples 1 to 4, 6, 7, and 9, which contained 0.1 to 1.0 parts by weight of melt viscosity modifier-1, had rebound resilience of 71 to 77%, and were evaluated as "good" in appearance, making them preferable. Furthermore, Examples 1 to 3, 6, 7, and 9, which contained 0.1 to 1.0 parts by weight of melt viscosity modifier-1 and had an expansion ratio of 5.5 times or more, had densities of 110 to 190 kg/ m3 , rebound resilience of 71 to 76%, and were lighter in weight while maintaining high rebound resilience. Furthermore, in Examples 1, 2, 6, 7, and 9, in which the amount of melt viscosity modifier-1 added was 0.1 to 1.0 parts by weight and the expansion ratio was 7 times or more, the density was 110 to 150 kg/ m3 and the rebound resilience was 71 to 75%, and they were even lighter in weight while maintaining high rebound resilience.
実施例１０（溶融粘度調整剤－２を使用）は、密度は１５０ｋｇ／ｍ３であり、かつ反発弾性が７６％であり、特に軽量で反発弾性が高く、かつ荷重増加率も３．７倍と高いものであった。 Example 10 (using melt viscosity modifier-2) had a density of 150 kg/ m3 and a rebound resilience of 76%, and was particularly lightweight and had high rebound resilience, with a high load increase rate of 3.7 times.
実施例１１（溶融粘度調整剤－３を使用）は、密度は１５０ｋｇ／ｍ３であり、かつ反発弾性が７４％であり、特に軽量で反発弾性が高く、かつ荷重増加率も３．２倍と高いものであった。 Example 11 (using melt viscosity modifier-3) had a density of 150 kg/ m3 and a rebound resilience of 74%, and was particularly lightweight and had high rebound resilience, with a high load increase rate of 3.2 times.
実施例１２（溶融粘度調整剤－４を使用）は、密度は１５０ｋｇ／ｍ３であり、かつ反発弾性が７１％であり、軽量で反発弾性が高く、かつ荷重増加率も３．１倍と高いものであった。 Example 12 (using melt viscosity modifier-4) had a density of 150 kg/ m3 and a rebound resilience of 71%, and was lightweight, had high rebound resilience, and also had a high load increase rate of 3.1 times.
実施例１３～１５（溶融粘度調整剤－５を使用）は、密度が２００ｋｇ／ｍ３であり、かつ反発弾性が７０～７１％であり、荷重増加率が３．０～３．１倍であり、軽量で反発弾性が高く、かつ荷重増加率も高いものであった。特に溶融粘度調整剤－５の添加量が０．０１～０．８重量部の実施例１３、実施例１４は、外観の評価が「〇」であり、好ましいものであった。 Examples 13 to 15 (using melt viscosity modifier-5) had a density of 200 kg/ m3 , a rebound resilience of 70 to 71%, and a load increase rate of 3.0 to 3.1 times, and were lightweight, had high rebound resilience, and also a high load increase rate. In particular, Examples 13 and 14, which used 0.01 to 0.8 parts by weight of melt viscosity modifier-5, were evaluated as "good" in appearance and were favorable.
実施例１６（溶融粘度調整剤－１と溶融粘度調整剤－５の併用）は、密度が２００ｋｇ／ｍ３であり、かつ反発弾性が７５％であり、荷重増加率が５．１倍であり、軽量で反発弾性が高く、かつ荷重増加率も高いものであった。溶融粘度調整剤－１と溶融粘度調整剤－５を併用しても外観の評価は「〇」であり、好ましいものであった。 Example 16 (a combined use of melt viscosity modifier-1 and melt viscosity modifier-5) had a density of 200 kg/ m3 , a rebound resilience of 75%, and a load increase rate of 5.1 times, and was lightweight, had high rebound resilience, and also a high load increase rate. Even when melt viscosity modifier-1 and melt viscosity modifier-5 were used in combination, the appearance was evaluated as "good", which was preferable.
図４の測定結果に示すように、溶融粘度調整剤として、エポキシ当量が２００～２８００であり、かつ、重量平均分子量（Ｍｗ）が２０００～２５０００であるエポキシ変性スチレン－アクリル共重合体（溶融粘度調整剤－１～４）を使用すれば、軽量で反発弾性が高い熱可塑性ポリエステルエラストマー発泡体が得られ、かつ荷重増加率も３倍以上であり、密度が１１０～２４０ｋｇ／ｍ３の軽量であっても機械特性の低下を抑えることができる。特に、エポキシ当量が２５０～１８００であり、かつ、重量平均分子量（Ｍｗ）が４０００～１５０００であるエポキシ変性スチレン－アクリル共重合体（溶融粘度調整剤－１～３）を使用すれば、より軽量で反発弾性が高い熱可塑性ポリエステルエラストマー発泡体が得られる。 As shown in the measurement results in Figure 4, when an epoxy-modified styrene-acrylic copolymer (melt viscosity modifiers 1 to 4) having an epoxy equivalent of 200 to 2800 and a weight-average molecular weight (Mw) of 2000 to 25000 is used as a melt viscosity modifier, a lightweight thermoplastic polyester elastomer foam with high rebound resilience can be obtained, and the load increase rate is three times or more. Even with a lightweight density of 110 to 240 kg/ m3 , a decrease in mechanical properties can be suppressed. In particular, when an epoxy-modified styrene-acrylic copolymer (melt viscosity modifiers 1 to 3) having an epoxy equivalent of 250 to 1800 and a weight-average molecular weight (Mw) of 4000 to 15000 is used, a thermoplastic polyester elastomer foam with even lighter weight and higher rebound resilience can be obtained.
それに対して、溶融粘度調整剤を含まない比較例１～比較例７、ポリウレタンフォームからなる比較例８、熱可塑性ポリウレタン発泡ビーズからなる比較例９は、軽量性に劣っていたり、反発弾性が低かったり、あるいは両方共劣っていたり、荷重増加率が低かったりした。以下に比較例の測定結果について詳述する。 In contrast, Comparative Examples 1 to 7, which did not contain a melt viscosity modifier, Comparative Example 8, which consisted of polyurethane foam, and Comparative Example 9, which consisted of thermoplastic polyurethane foam beads, were inferior in lightness, had low impact resilience, or both, and had a low rate of load increase. The measurement results for the comparative examples are described in detail below.
比較例１は、発泡倍率が１倍であり、反発弾性については実施例４と同等の７８％であって高いものであったが、密度が１０５０ｋｇ／ｍ３であり、荷重増加率が１．０倍であり、軽量性が極端に劣っており、また、荷重増加率も低かった。
比較例２は、発泡倍率が２倍であり、密度が５３０ｋｇ／ｍ３、反発弾性が６６％であり、荷重増加率が１．９倍であり、軽量性及び反発弾性、荷重増加率の何れも実施例より劣っていた。
比較例３は、発泡倍率が３倍であり、密度が３５０ｋｇ／ｍ３、反発弾性が６２％であり、荷重増加率が２．５倍であり、軽量性及び反発弾性、荷重増加率の何れも実施例より劣っていた。
In Comparative Example 1, the foaming ratio was 1, and the impact resilience was high at 78%, which was the same as that of Example 4. However, the density was 1,050 kg/ m3 , and the load increase rate was 1.0 times, which meant that the lightweight property was extremely poor, and the load increase rate was also low.
In Comparative Example 2, the foaming ratio was 2 times, the density was 530 kg/m 3 , the impact resilience was 66%, and the load increase rate was 1.9 times, and the lightweight property, impact resilience, and load increase rate were all inferior to those of the Examples.
In Comparative Example 3, the foaming ratio was 3 times, the density was 350 kg/m 3 , the impact resilience was 62%, and the load increase rate was 2.5 times, and the lightweight property, impact resilience, and load increase rate were all inferior to those of the Examples.
比較例４は、発泡倍率が４倍であり、実施例４とほぼ同様の発泡倍率であるが、反発弾性が６２％であり、実施例４の反発弾性よりも低い値であった。さらに、比較例４の密度は２６０ｋｇ／ｍ３であり、荷重増加率は、２．７倍であって、実施例４の密度よりも高く、軽量性及び荷重増加率に劣っていた。
比較例５は、発泡倍率が５倍であり、実施例３とほぼ同様の発泡倍率であるが、反発弾性が５５％であり、実施例３の反発弾性よりも低い値であった。さらに、比較例５の密度は２１０ｋｇ／ｍ３であり、荷重増加率は、２．６倍であって、実施例３の密度よりも高く、軽量性及び荷重増加率に劣っていた。
比較例６は、発泡倍率が３．５倍であり、密度が３００ｋｇ／ｍ３、反発弾性が６５％であり、荷重増加率は、２．６倍であり、軽量性及び反発弾性、荷重増加率の何れも実施例より劣っていた。
比較例７は、発泡倍率が３倍であり、密度が３５０ｋｇ／ｍ３、反発弾性が６０％であり、荷重増加率は、２．３倍であり、軽量性及び反発弾性、荷重増加率の何れも実施例より劣っていた。
In Comparative Example 4, the expansion ratio was 4 times, which was almost the same as that of Example 4, but the rebound resilience was 62%, which was a lower value than that of Example 4. Furthermore, the density of Comparative Example 4 was 260 kg/ m3 , and the load increase rate was 2.7 times, which was higher than that of Example 4, and the lightweight property and load increase rate were inferior.
In Comparative Example 5, the expansion ratio was 5 times, which was almost the same as that of Example 3, but the rebound resilience was 55%, which was a lower value than that of Example 3. Furthermore, the density of Comparative Example 5 was 210 kg/ m3 , and the load increase rate was 2.6 times, which was higher than that of Example 3, and the lightweight property and load increase rate were inferior.
Comparative Example 6 had an expansion ratio of 3.5 times, a density of 300 kg/m 3 , a rebound resilience of 65%, and a load increase rate of 2.6 times, and was inferior to the Examples in terms of lightness, rebound resilience, and load increase rate.
Comparative Example 7 had an expansion ratio of 3 times, a density of 350 kg/m 3 , a rebound resilience of 60%, and a load increase rate of 2.3 times, and was inferior to the Examples in terms of lightness, rebound resilience, and load increase rate.
比較例８は、ポリウレタンフォームからなり、密度が４５ｋｇ／ｍ３であり、軽量性に優れているが、反発弾性が５０％であり、かつ荷重増加率は、１．４倍であり、実施例よりも反発弾性及び荷重増加率の低いものであった。
比較例９は、熱可塑性ポリウレタン発泡ビーズからなり、密度が３００ｋｇ／ｍ３、反発弾性が６１％であり、荷重増加率が２．９倍であり、軽量性及び反発弾性、荷重増加率の何れも実施例よりも劣っていた。
Comparative Example 8 was made of polyurethane foam and had a density of 45 kg/ m3 , making it lightweight. However, the rebound resilience was 50% and the load increase rate was 1.4 times, which were lower than those of the Examples.
Comparative Example 9 was made of thermoplastic polyurethane foam beads, had a density of 300 kg/m 3 , a rebound resilience of 61%, and a load increase rate of 2.9 times, and was inferior to the Examples in terms of lightness, rebound resilience, and load increase rate.
このように、各実施例は、軽量で反発弾性が高く、靴底用部材として好適なものである。
なお、本発明の靴底用部材は、ミッドソールの一部に設けるものに限られず、全面または広範囲に設けてもよく、さらに他の靴底構成部材に設けてもよい。
As described above, each of the examples is lightweight and has high resilience, making it suitable for use as a shoe sole member.
The shoe sole member of the present invention is not limited to being provided on a part of the midsole, but may be provided on the entire surface or a wide range, or may be provided on other shoe sole components.
１０ 靴
２１ ミッドソール
４１、４３ 靴底用部材
10 Shoe 21 Midsole 41, 43 Shoe sole member
Claims (1)
熱可塑性ポリエステルエラストマーの粘度を高める溶融粘度調整剤により熱可塑性ポリエステルエラストマーが変性された変性熱可塑性ポリエステルエラストマーを射出成形機内で溶融する溶融工程と、
物理発泡剤を超臨界装置により超臨界状態とする超臨界工程と、
超臨界状態の前記物理発泡剤を前記射出成形機内に注入し、溶融状態の前記変性熱可塑性ポリエステルエラストマーと混合して、溶融状態の前記変性熱可塑性ポリエステルエラストマーと超臨界状態の前記物理発泡剤との分散溶融混合物にする分散溶融混合工程と、
前記分散溶融混合物を、前記射出成形機から可動金型のキャビティに射出する射出工程と、
前記可動金型をコアバックして熱可塑性ポリエステルエラストマー発泡体を作成する発泡工程と、を有し、
前記熱可塑性ポリエステルエラストマー発泡体は、ＪＩＳ Ｋ ６４００－３：２０１１に基づく反発弾性が７１％以上であり、片面または両面にスキン層が形成された独立気泡構造であり、
前記熱可塑性ポリエステルエラストマー発泡体は、３点曲げ試験の最大荷重値が１．４２Ｎ以上である、ことを特徴とする靴底用部材の製造方法。
A method for producing a shoe sole member made of a thermoplastic polyester elastomer foam, comprising:
a melting step of melting a modified thermoplastic polyester elastomer obtained by modifying the thermoplastic polyester elastomer with a melt viscosity modifier that increases the viscosity of the thermoplastic polyester elastomer in an injection molding machine;
a supercritical step of bringing the physical foaming agent into a supercritical state using a supercritical device;
a dispersive melt mixing step of injecting the physical blowing agent in a supercritical state into the injection molding machine and mixing it with the modified thermoplastic polyester elastomer in a molten state to form a dispersed melt mixture of the modified thermoplastic polyester elastomer in a molten state and the physical blowing agent in a supercritical state;
an injection step of injecting the dispersed molten mixture from the injection molding machine into a cavity of a movable mold;
a foaming step of core-backing the movable mold to produce a thermoplastic polyester elastomer foam,
the thermoplastic polyester elastomer foam has a rebound resilience based on JIS K 6400-3:2011 of 71% or more and a closed-cell structure with a skin layer formed on one or both sides;
The method for manufacturing a shoe sole member, wherein the thermoplastic polyester elastomer foam has a maximum load value of 1.42 N or more in a three-point bending test.
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