JP5978674B2 - Elastic network structure with high vibration absorption - Google Patents
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Description
本発明は、連続線状体の三次元ランダムループ接合構造体からなる弾性網状構造体に関する。 The present invention relates to an elastic network structure composed of a continuous linear three-dimensional random loop joint structure.
ポリエステル系熱可塑性エラストマーからなる連続線状体を曲がりくねらせランダムループを形成し、夫々のループを互いに溶融状態で接触せしめて、接触部の大部分を融着させてなる三次元ランダムループ接合構造体が提案されている（特許文献１）。しかしながら、ポリエステル系熱可塑性エラストマーの振動吸収性は通常低く、従って、該樹脂単独で構成されている三次元ランダムループ接合構造体においても振動吸収性が低いという問題があった。 A three-dimensional random loop joining structure in which continuous linear bodies made of polyester thermoplastic elastomer are twisted to form random loops, and the respective loops are brought into contact with each other in a molten state, and most of the contact portions are fused. A body has been proposed (Patent Document 1). However, the vibration-absorbing property of the polyester-based thermoplastic elastomer is usually low. Therefore, there is a problem that the vibration-absorbing property is low even in the three-dimensional random loop joint structure constituted by the resin alone.
本発明は、振動吸収性が高く、クッション性に優れた弾性網状構造体を提供することを目的とする。 An object of the present invention is to provide an elastic network structure having high vibration absorption and excellent cushioning properties.
本発明者らが鋭意検討した結果、三次元ランダムループ接合構造体を構成する連続線状体を特定の熱可塑性エラストマーで構成することで、振動吸収性が高く、クッション性に優れた網状構造体を見出し、本発明に至った。 As a result of intensive studies by the present inventors, a network structure having high vibration absorption and excellent cushioning properties is obtained by configuring a continuous linear body constituting a three-dimensional random loop joint structure with a specific thermoplastic elastomer. And found the present invention.
すなわち、本発明は、以下の構成からなる。
（項１）
１００〜１０００００デシテックスの連続線状体を曲がりくねらせランダムル−プを形成し、夫々のル−プを互いに溶融状態で接触せしめて、接触部の大部分を融着させてなる三次元ランダムル−プ接合構造体からなる網状構造体であって、該連続線状体がポリエステル系熱可塑性エラストマー（ａ）１０〜９０質量部、及びポリスチレン系熱可塑性エラストマー（ｂ）９０〜１０質量部を含む樹脂組成物で構成されていることを特徴とする網状構造体。
（項２）
ポリエステル系熱可塑性エラストマーがポリエステルエーテルブロック共重合体又はポリエステルエステルブロック共重合体である、項１に記載の網状構造体。
（項３）
ポリエステル系熱可塑性エラストマーがポリエステルエーテルブロック共重合体である、項２に記載の網状構造体。
（項４）
ポリスチレン系熱可塑性エラストマーが、スチレン−ブタジエンランダム共重合体、スチレン−イソプレンランダム共重合体、及びこれらの水素添加共重合体からなる群より選ばれた少なくとも１種である、項１〜３のいずれかに記載の網状構造体。
（項５）
ポリスチレン系熱可塑性エラストマーがスチレン‐ブタジエンランダム共重合体又は水素添加スチレン‐ブタジエンランダム共重合体である、項４に記載の網状構造体。
（項６）
連続線状体が中空断面である項１〜５のいずれかに記載の網状構造体。
（項７）
連続線状体が異形断面である項１〜５のいずれかに記載の網状構造体。
That is, this invention consists of the following structures.
(Claim 1)
A three-dimensional random loop formed by twisting a continuous linear body of 100 to 100,000 decitex to form a random loop, bringing the respective loops into contact with each other in a molten state, and fusing most of the contact portions. A network structure comprising a bonded structure, wherein the continuous linear body includes 10 to 90 parts by mass of the polyester-based thermoplastic elastomer (a) and 90 to 10 parts by mass of the polystyrene-based thermoplastic elastomer (b). A network structure comprising a resin composition.
(Section 2)
Item 2. The network structure according to Item 1, wherein the polyester-based thermoplastic elastomer is a polyester ether block copolymer or a polyester ester block copolymer.
(Section 3)
Item 3. The network structure according to Item 2, wherein the polyester-based thermoplastic elastomer is a polyester ether block copolymer.
(Section 4)
Any of paragraphs 1 to 3, wherein the polystyrene-based thermoplastic elastomer is at least one selected from the group consisting of a styrene-butadiene random copolymer, a styrene-isoprene random copolymer, and a hydrogenated copolymer thereof. A network structure according to any one of the above.
(Section 5)
Item 5. The network structure according to Item 4, wherein the polystyrene-based thermoplastic elastomer is a styrene-butadiene random copolymer or a hydrogenated styrene-butadiene random copolymer.
(Claim 6)
Item 6. The network structure according to any one of Items 1 to 5, wherein the continuous linear body has a hollow cross section.
(Claim 7)
Item 6. The network structure according to any one of Items 1 to 5, wherein the continuous linear body has an irregular cross section.
従前のポリエステル系熱可塑性エラストマー単独で構成されている網状構造体は振動吸収性が低いものであったが、本発明の網状構造体は、振動吸収性を大幅に向上させた点で優れた効果を有する。 The network structure composed of the conventional polyester-based thermoplastic elastomer alone has low vibration absorption, but the network structure of the present invention is excellent in that the vibration absorption is greatly improved. Have
本発明の網状構造体は、繊度が１００〜１０００００デシテックスの連続した線条（本明細書では、「連続線状体」ということがある。）を曲がりくねらせ、該線条同士を接触させ、接触部を融着して３次元網状構造を形成している。このことで、非常に大きい応力で、大変形を与えても、融着一体化した三次元ランダムループからなる網状構造全体が変形して応力を吸収し、応力が解除されると熱可塑性エラストマーのゴム弾性が発現して、構造体は元の形態に回復することができる。なお、本発明の網状構造体を形成する線状の繊度は１００〜１０００００デシテックスであることが好ましい。１００デシテックス以下では抗圧縮強力が低くなり反発力が低下するので好ましくない。１０００００デシテックス以上では線状体の個々の抗圧縮性は大きいが、構成本数が少なくなるため力の分散が悪くなる。そのため、１００kg／cm2 以上の著しく大きい圧縮力を受けた場合に、応力集中によるへたり（圧縮永久歪み）が発生し、使用部分が制限される場合がある。より好ましくは３００〜５００００デシテックスであり、更に好ましくは５００〜３００００デシテックスである。なお、本発明において、単一繊度の線条からなる連続線状体だけでなく、繊度の異なる線条を使用し、見掛け密度との組合せで最適な構成とすることもできる。 The network structure of the present invention comprises a continuous filament having a fineness of 100 to 100,000 dtex (in this specification, sometimes referred to as “continuous filament”), and the filaments are brought into contact with each other, The contact portion is fused to form a three-dimensional network structure. As a result, even when a large deformation is caused by a very large stress, the entire network structure composed of the fused three-dimensional random loop is deformed to absorb the stress, and when the stress is released, the thermoplastic elastomer Rubber elasticity develops and the structure can recover to its original form. In addition, it is preferable that the linear fineness which forms the network structure of this invention is 100-100000 decitex. Less than 100 dtex is not preferable because the anti-compression strength is lowered and the repulsive force is lowered. Above 100,000 decitex, the individual bodies have a large anti-compressibility, but the number of components decreases, so that the dispersion of force is worsened. Therefore, when a remarkably large compressive force of 100 kg / cm @ 2 or more is applied, a sag due to stress concentration (compression set) may occur, and the use portion may be limited. More preferably, it is 300-50000 decitex, More preferably, it is 500-30000 decitex. In the present invention, not only a continuous linear body composed of single fine filaments but also filaments having different finenesses can be used to obtain an optimum configuration in combination with the apparent density.
本発明の網状構造体を形成する連続線条体は、ポリエステル系熱可塑性エラストマー（ａ）１０〜９０質量部、ポリスチレン系熱可塑性エラストマー（ｂ）９０〜１０質量部を含む樹脂組成物で構成されていることが好ましい。（ａ）９０〜１００質量部、（ｂ）１０〜０質量部となると振動吸収性を高く保つことができなくなる、また、（ａ）０〜１０質量部、（ｂ）９０〜１００質量部となると弾発が小さくなり過ぎて適度なクッション性を保つことができなくなる。より好ましくは（ａ）１５〜８５質量部、（ｂ）８５〜１５質量部を含む樹脂組成物であり、更に好ましくは（ａ）２０〜８０質量部、（ｂ）８０〜２０質量部を含む樹脂組成物である。 The continuous filament forming the network structure of the present invention is composed of a resin composition containing 10 to 90 parts by mass of a polyester-based thermoplastic elastomer (a) and 90 to 10 parts by mass of a polystyrene-based thermoplastic elastomer (b). It is preferable. When (a) 90 to 100 parts by mass, (b) 10 to 0 parts by mass, vibration absorbability cannot be kept high, (a) 0 to 10 parts by mass, (b) 90 to 100 parts by mass If this happens, the projectile will be too small to maintain an appropriate cushioning property. More preferably, it is a resin composition containing (a) 15 to 85 parts by mass and (b) 85 to 15 parts by mass, and more preferably (a) 20 to 80 parts by mass and (b) 80 to 20 parts by mass. It is a resin composition.
ポリエステル系熱可塑性エラストマーとしては、熱可塑性ポリエステルをハードセグメントとし、ポリアルキレンジオールをソフトセグメントとするポリエステルエーテルブロック共重合体、または脂肪族ポリエステルをソフトセグメントとするポリエステルエステルブロック共重合体が例示できる。ポリエステルエーテルブロック共重合体のより具体的な構成としては、テレフタル酸、イソフタル酸、ナフタレン−２，６−ジカルボン酸、ナフタレン−２，７−ジカルボン酸、ジフェニル−４，４’−ジカルボン酸等の芳香族ジカルボン酸、１・４シクロヘキサンジカルボン酸等の脂環族ジカルボン酸、コハク酸、アジピン酸、セバチン酸ダイマ−酸等の脂肪族ジカルボン酸または、これらのエステル形成性誘導体などから選ばれたジカルボン酸の少なくとも１種と、１・４ブタンジオール、エチレングリコール、トリメチレングリコール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール等の脂肪族ジオール、１・１シクロヘキサンジメタノール、１・４シクロヘキサンジメタノール等の脂環族ジオール、またはこれらのエステル形成性誘導体などから選ばれたジオール成分の少なくとも１種、および平均分子量が約３００〜５０００のポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、またはエチレンオキシド−プロピレンオキシド共重合体などから選ばれたポリアルキレンジオールのうち少なくとも１種から構成される三元ブロック共重合体である。ポリエステルエステルブロック共重合体としては、上記ジカルボン酸とジオール及び平均分子量が約３００〜５０００のポリラクトン等のポリエステルジオールのうち少なくとも１種から構成される三元ブロック共重合体が例示される。熱接着性、耐加水分解性、伸縮性、耐熱性等を考慮すると、好ましくは、（１）ジカルボン酸としてテレフタル酸または／およびイソフタル酸、ジオ−ル成分として１・４ブタンジオール、ポリアルキレンジオールとしてポリテトラメチレングリコールからなる３元ブロック共重合体、および（２）ジカルボン酸としてテレフタル酸または／およびナフタレン−２・６−ジカルボン酸、ジオ−ル成分として１・４ブタンジオール、ポリエステルジオールとしてポリラクトンからなる３元ブロック共重合体である。特に好ましくは、（１）ジカルボン酸としてテレフタル酸または／およびイソフタル酸、ジオ−ル成分として１・４ブタンジオール、ポリアルキレンジオールとしてポリテトラメチレングリコールからなる３元ブロック共重合体である。特殊な例では、ポリシロキサン系のソフトセグメントを導入したものも使うことができる。 Examples of the polyester-based thermoplastic elastomer include a polyester ether block copolymer having a thermoplastic polyester as a hard segment and a polyalkylene diol as a soft segment, or a polyester ester block copolymer having an aliphatic polyester as a soft segment. More specific configurations of the polyester ether block copolymer include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, and the like. Dicarboxylic acids selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids such as 1,4 cyclohexane dicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid dimer acid, or ester-forming derivatives thereof. At least one kind of acid and aliphatic diols such as 1,4 butanediol, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, 1,1 cyclohexanedimethanol, 1,4 cyclohexanedimethanol Alicyclic dio such as Or at least one diol component selected from these ester-forming derivatives and the like, and polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or ethylene oxide-propylene oxide copolymer having an average molecular weight of about 300 to 5000 It is a ternary block copolymer composed of at least one selected polyalkylenediol. Examples of the polyester ester block copolymer include a ternary block copolymer composed of at least one of the dicarboxylic acid, a diol, and a polyester diol such as a polylactone having an average molecular weight of about 300 to 5000. In consideration of thermal adhesiveness, hydrolysis resistance, stretchability, heat resistance, etc., (1) terephthalic acid or / and isophthalic acid as dicarboxylic acid, 1.4 butanediol, polyalkylenediol as diol component Terephthalic acid or / and naphthalene-2 · 6-dicarboxylic acid as a dicarboxylic acid, 1.4 butanediol as a diol component, and polylactone as a polyester diol A ternary block copolymer consisting of Particularly preferred is (1) a ternary block copolymer comprising terephthalic acid or / and isophthalic acid as the dicarboxylic acid, 1.4 butanediol as the diol component, and polytetramethylene glycol as the polyalkylenediol. As a special example, a polysiloxane-based soft segment can be used.
ポリスチレン系熱可塑性エラストマーとしては、動的粘弾性測定装置を用いて測定した２３℃でのＴａｎδが０．１０以上のものを用いることが好ましい。Ｔａｎδ（タンジェント・デルタ）とは、動的粘弾性測定装置を用いて測定した損失弾性率Ｅ”と貯蔵弾性率Ｅ’との比Ｅ”／Ｅ’であり、数値が高い程、振動減衰性が高くなり、網状構造体の振動吸収性が高くなる。２３℃でのＴａｎδが０．１０未満では、充分な振動減衰性が発現せず、網状構造体の振動吸収性が不十分となる。より好ましくは０．２０以上、更に好ましくは０．３０以上である。また、特に好ましくは、動的粘弾性測定装置を用いて測定したＴａｎδが、０℃〜２３℃の範囲全てにおいて０．１０以上を満たしていることである。これにより、広範の温度域で充分な振動減衰性が発現し、網状構造体の振動吸収性を高く保つことができる。Ｔａｎδが０．１０以上を満たすポリスチレン系熱可塑性エラストマーの好ましい例として、スチレン−ブタジエンランダム共重合体やスチレン−イソプレンランダム共重合体、あるいはそれらを水素添加したものを挙げることができる。 As the polystyrene-based thermoplastic elastomer, those having a Tan δ at 23 ° C. of 0.10 or more measured using a dynamic viscoelasticity measuring device are preferably used. Tanδ (tangent delta) is a ratio E ″ / E ′ of loss elastic modulus E ″ and storage elastic modulus E ′ measured using a dynamic viscoelasticity measuring device. And the vibration absorption of the network structure is increased. When Tan δ at 23 ° C. is less than 0.10, sufficient vibration damping is not exhibited, and the vibration absorption of the network structure is insufficient. More preferably, it is 0.20 or more, More preferably, it is 0.30 or more. Moreover, it is particularly preferable that Tan δ measured using a dynamic viscoelasticity measuring device satisfies 0.10 or more in the entire range of 0 ° C to 23 ° C. As a result, sufficient vibration damping is developed in a wide temperature range, and the vibration absorption of the network structure can be kept high. Preferable examples of the polystyrene-based thermoplastic elastomer satisfying Tan δ of 0.10 or more include styrene-butadiene random copolymers, styrene-isoprene random copolymers, and those obtained by hydrogenation thereof.
本発明の網状構造体を形成する連続線状体は、動的粘弾性測定装置を用いて測定した２３℃でのＴａｎδが０．１０以上であることが好ましい。２３℃でのＴａｎδが０．１０未満では、網状構造体の振動吸収性が不十分となる。より好ましくは０．１２以上、更に好ましくは０．１５以上である。また、特に好ましくは、動的粘弾性測定装置を用いて測定したＴａｎδが、０℃〜２３℃の範囲全てにおいて０．１０以上を満たしていることである。これにより、広範の温度域で振動吸収性を高く保つことができる。一方、上限は特に規定されないが、好ましくは１．０以下、より好ましくは０．８以下、特に好ましくは０．５以下である。１．０以上であると、クッション性の観点から好ましくない。 The continuous linear body forming the network structure of the present invention preferably has a Tan δ at 23 ° C. of 0.10 or more measured using a dynamic viscoelasticity measuring apparatus. If Tan δ at 23 ° C. is less than 0.10, the vibration absorption of the network structure is insufficient. More preferably, it is 0.12 or more, More preferably, it is 0.15 or more. Moreover, it is particularly preferable that Tan δ measured using a dynamic viscoelasticity measuring device satisfies 0.10 or more in the entire range of 0 ° C to 23 ° C. As a result, high vibration absorption can be maintained in a wide temperature range. On the other hand, the upper limit is not particularly defined, but is preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.5 or less. If it is 1.0 or more, it is not preferable from the viewpoint of cushioning properties.
本発明の網状構造体の２５％圧縮時硬さは、１ｋｇ／Φ２００ｍｍ以上であることが好ましい。２５％圧縮時硬さとは、網状構造体をΦ２００ｍｍ径の円形状の圧縮板にて７５％まで圧縮して得た応力−歪み曲線の２５％圧縮時の応力である。２５％圧縮時硬さが１ｋｇ／Φ２００ｍｍより小さいと、クッション性が損なわれてしまう。より好ましくは、５ｋｇ／Φ２００ｍｍ以上、特に好ましくは１０ｋｇ／Φ２００ｍｍ以上である。上限は特に規定されないが、好ましくは５０ｋｇ／Φ２００ｍｍ以下、より好ましくは４５ｋｇ／Φ２００ｍｍ以下、特に好ましくは４０ｋｇ／Φ２００ｍｍ以下である。５０ｋｇ／Φ２００ｍｍ以上であると硬くなりすぎ、クッション性の観点から好ましくない。 The 25% compression hardness of the network structure of the present invention is preferably 1 kg / Φ200 mm or more. The hardness at 25% compression is the stress at the time of 25% compression of the stress-strain curve obtained by compressing the network structure to 75% with a circular compression plate having a diameter of 200 mm. If the hardness at 25% compression is less than 1 kg / Φ200 mm, the cushioning properties are impaired. More preferably, it is 5 kg / Φ200 mm or more, and particularly preferably 10 kg / Φ200 mm or more. The upper limit is not particularly defined, but is preferably 50 kg / Φ200 mm or less, more preferably 45 kg / Φ200 mm or less, and particularly preferably 40 kg / Φ200 mm or less. If it is 50 kg / Φ200 mm or more, it becomes too hard, which is not preferable from the viewpoint of cushioning properties.
本発明の網状構造体を構成する連続線条体の樹脂部分には、目的に応じて種々の添加剤を配合することができる。添加剤としては、フタル酸エステル系、トリメリット酸エステル系、脂肪酸系、エポキシ系、アジピン酸エステル系、ポリエステル系の可塑剤、公知のヒンダードフェノール系、硫黄系、燐系、アミン系の酸化防止剤、ヒンダードアミン系、トリアゾール系、ベンゾフェノン系、ベンゾエート系、ニッケル系、サリチル系などの光安定剤、帯電防止剤、過酸化物などの分子調整剤、エポキシ系化合物、イソシアネート系化合物、カルボジイミド系化合物などの反応基を有する化合物、金属不活性剤、有機及び無機系の核剤、中和剤、制酸剤、防菌剤、蛍光増白剤、充填剤、難燃剤、難燃助剤、有機及び無機系の顔料などを添加することができる。 Various additives can be blended in the resin portion of the continuous filaments constituting the network structure of the present invention depending on the purpose. Additives include phthalate ester, trimellitic acid ester, fatty acid, epoxy, adipic acid ester, polyester plasticizer, known hindered phenol, sulfur, phosphorus and amine oxidation Inhibitors, hindered amines, triazoles, benzophenones, benzoates, nickels, salicyls and other light stabilizers, antistatics, peroxides and other molecular modifiers, epoxy compounds, isocyanate compounds, carbodiimide compounds Compounds having reactive groups such as, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent whitening agents, fillers, flame retardants, flame retardant aids, organic In addition, inorganic pigments and the like can be added.
本発明の網状構造体を構成する連続線条体の樹脂部分は、示差走査型熱量計にて測定した融解曲線において、融点以下に吸熱ピークを有するのが好ましい。融点以下に吸熱ピークを有するものは、耐熱耐へたり性が吸熱ピ−クを有しないものより著しく向上する。例えば、本発明の好ましいポリエステル系熱可塑性エラストマーとして、ハードセグメントの酸成分に剛直性のあるテレフタル酸やナフタレン２・６ジカルボン酸などを９０モル％以上、より好ましくは９５モル％以上、特に好ましくは１００モル％含有するものとグリコ−ル成分をエステル交換後、必要な重合度まで重合し、次いで、ポリアルキレンジオールとして、好ましくは平均分子量が５００以上５０００以下、より好ましくは１０００以上３０００以下のポリテトラメチレングリコールを１０重量％以上７０重量％以下、より好ましくは２０重量％以上６０重量％以下で共重合させた場合、ハードセグメントの酸成分に剛直性のあるテレフタル酸やナフタレン２・６ジカルボン酸の含有量が多いとハ−ドセグメントの結晶性が向上し、塑性変形しにくく、かつ、耐熱抗へたり性が向上する。加えて、溶融熱接着後更に融点より少なくとも１０℃以上低い温度でアニ−リング処理すると、より耐熱抗へたり性が向上する。圧縮歪みを付与してからアニ−リングすると更に耐熱抗へたり性が向上する。このような処理をした網状構造体の線条は、示差走査型熱量計（ＤＳＣ）で測定した融解曲線に室温以上融点以下の温度で吸熱ピークをより明確に発現する。なおアニ−リングしない場合は融解曲線に室温以上融点以下に吸熱ピ−クを発現しない。このことから類推するに、アニ−リングにより、ハ−ドセグメントが再配列され、疑似結晶化様の架橋点が形成され、耐熱抗へたり性が向上しているのではないかとも考えられる。（以下、このアニーリング処理を「疑似結晶化処理」ということがある。） The resin portion of the continuous filaments constituting the network structure of the present invention preferably has an endothermic peak below the melting point in the melting curve measured with a differential scanning calorimeter. Those having an endothermic peak below the melting point have significantly improved heat sag resistance than those having no endothermic peak. For example, as a preferable polyester-based thermoplastic elastomer of the present invention, terephthalic acid or naphthalene 2,6-dicarboxylic acid having a rigid hard segment acid component is 90 mol% or more, more preferably 95 mol% or more, particularly preferably. After the transesterification of the glycol component and the component containing 100 mol%, the polymer is polymerized to the required degree of polymerization, and then the polyalkylene diol is preferably a polyalkylene diol having an average molecular weight of 500 or more and 5000 or less, more preferably 1000 or more and 3000 or less. When tetramethylene glycol is copolymerized in an amount of 10 wt% to 70 wt%, more preferably 20 wt% to 60 wt%, terephthalic acid or naphthalene 2.6 dicarboxylic acid having a rigid hard segment acid component When there is much content of hard, crystallinity of hard segment improves , Hardly plastically deformed, and to improve the sexual sag resistant anti. In addition, if the annealing treatment is further performed at a temperature lower than the melting point by at least 10 ° C. after the fusion bonding, the heat resistance and sag resistance is further improved. Heat annealing resistance is further improved by annealing after applying compressive strain. The filaments of the network structure subjected to such treatment more clearly express an endothermic peak at a temperature not lower than the melting point and not higher than the melting point in the melting curve measured by a differential scanning calorimeter (DSC). When annealing is not performed, the endothermic peak does not appear in the melting curve above the room temperature and below the melting point. By analogy with this, it is considered that the hard segments are rearranged by annealing and pseudo-crystallization-like cross-linking points are formed, and the heat resistance and sag resistance are improved. (Hereinafter, this annealing process may be referred to as “pseudo crystallization process”.)
断面形状は特には限定されないが、中空断面や異形断面にすることで、抗圧縮性や嵩だか性を付与でき、低繊度化したい場合には特に好ましい。抗圧縮性は用いる素材のモジュラスにより調整して、柔らかい素材では中空率や異形度を高くし初期圧縮応力の勾配を調整できるし、ややモジュラスの高い素材では中空率や異形度を低くして座り心地が良好な抗圧縮性を付与する。中空断面や異形断面の他の効果として中空率や異形度を高くすることで、同一の抗圧縮性を付与した場合、より軽量化が可能となる。 The cross-sectional shape is not particularly limited, but it is particularly preferable when the hollow cross-section or the irregular cross-section can be imparted with an anti-compression property and bulkiness and it is desired to reduce the fineness. The compressibility can be adjusted according to the modulus of the material used, and the softness of the material can increase the hollowness and the degree of deformation to adjust the gradient of the initial compressive stress. Gives comfort and good compressibility. As another effect of the hollow cross section and the modified cross section, by increasing the hollow ratio and the deformity, when the same anti-compression property is given, the weight can be further reduced.
本発明の網状構造体の具体的な態様は、平均の見掛け密度の好ましい範囲が、クッション材としての機能が発現できる０．００５ｇ／ｃｍ３以上０．２０ｇ／ｃｍ３ 以下である。０．００５ｇ／ｃｍ３未満では反発力が失われるのでクッション材には不適当であり、０．２０ｇ／ｃｍ３ を越えると反発力が高すぎて座り心地が悪くなり好ましくない。本発明のより好ましい見掛け密度は０．０１ｇ／ｃｍ３〜０．１０ｇ／ｃｍ３ であり、更に好ましい範囲は０．０３ｇ／ｃｍ３〜０．０６ｇ／ｃｍ３ である。本発明の網状構造体は、繊度の異なる線条からなる複数層を積層し、各層の見掛け密度を変えることにより好ましい特性を付与することができる。例えば、繊度の細い表面層と繊度の太い基本層からなる場合は、表面層の密度はやや高くして構成本数を多くし、線条の一本が受ける応力を少なくして応力の分散を良くし、且つ臀部を支えるクッション性も向上させることで座り心地を向上させることができる。基本層は繊度を太くして少し硬くし、振動吸収と体型保持を受け持つ層としてより緻密な層とするため、やや繊度の細い線条で、且つ高密度とすることができる。これにより座席フレーム面から受ける振動や反発応力を基本層に均一に伝達し、全体が変形してエンルギー変換できるようにし、座り心地を良くすると共にクッションの耐久性も向上させることもできる。さらに、座席のサイドの厚みと張りを付与させるために部分的に繊度をやや細くして高密度化することもできる。このように各層はその目的に応じ好ましい密度と繊度を任意に選択できる。なお、網状構造体の各層の厚みは、特に限定されないが、クッション体としての機能が発現されやすい３mm以上とするのが好ましく５mm以上とするのが特に好ましい。 Specific embodiments of the network structure of the present invention, the preferred range of the average apparent density is not more than 0.005 g / cm 3 or more 0.20 g / cm 3 which functions as a cushion material can be expressed. If it is less than 0.005 g / cm 3 , the repulsive force is lost, so it is unsuitable for a cushioning material. If it exceeds 0.20 g / cm 3 , the repulsive force is too high and the seating comfort is deteriorated. More preferred apparent density of the present invention is 0.01g / cm 3 ~0.10g / cm 3 , more preferable range is 0.03g / cm 3 ~0.06g / cm 3 . The network structure of the present invention can be provided with preferable characteristics by laminating a plurality of layers composed of filaments having different finenesses and changing the apparent density of each layer. For example, if the surface layer is composed of a fine surface layer and a thick basic layer, the density of the surface layer is slightly increased to increase the number of components, and the stress applied to one of the filaments is decreased to improve the stress distribution. In addition, it is possible to improve the sitting comfort by improving the cushioning property that supports the buttocks. Since the basic layer is thicker and slightly harder, and is a denser layer that is responsible for vibration absorption and body shape retention, the basic layer can have a slightly finer filament and a higher density. As a result, vibrations and repulsive stresses received from the seat frame surface are uniformly transmitted to the basic layer so that the whole can be deformed and converted into energy, thereby improving the sitting comfort and improving the durability of the cushion. Furthermore, in order to give the seat side thickness and tension, the fineness can be partially reduced to increase the density. Thus, each layer can arbitrarily select a preferable density and fineness according to the purpose. The thickness of each layer of the network structure is not particularly limited, but is preferably 3 mm or more, and more preferably 5 mm or more, because the function as a cushion body is easily exhibited.
網状構造体の構造体外表面は、曲がりくねらせた線条が途中で３０°以上、好ましくは４５°以上曲げられ実質的に面がフラット化されており、接触部の大部分が融着している表層部を有することが好ましい。このことで、網状構造体面の該線条の接触点が大幅に増加して接着点を形成するため、座った時の臀部の局部的な外力も臀部に異物感を与えずに構造面で受け止められ、面構造が全体で変形して内部の構造体全体も変形して応力を吸収し、応力が解除されると弾性樹脂のゴム弾性が発現して、構造体は元の形態に回復することができる。実質的にフラット化されてない場合、臀部に異物感を与え、表面に局部的な外力が掛かかり、表面の線条及び接着点部分までに選択的に応力集中が発生する場合があり、応力集中による疲労が発生して耐へたり性が低下する場合がある。構造体外表面がフラット化された場合、ワディング層を使用しないで、又は非常に薄いワディング層を積層し、側地で表面を覆い自動車用、鉄道用等の座席や椅子又はベッド用、ソファー用、布団用等のクッションマットにすることができる。構造体外表面フラット化されていない場合は、網状構造体の表面に比較的厚め（好ましくは１０mm以上）のワディング層を積層して側地で表面を覆って座席やクッションマットを形成する必要がある。必要に応じてワディング層との接着または側地との接着は表面がフラットな場合は容易であるが、フラット化されていない場合は凸凹なため接着が不完全になる。 The outer surface of the structure of the net-like structure has a curved surface that is bent 30 ° or more, preferably 45 ° or more in the middle, and is substantially flattened, and most of the contact portion is fused. It is preferable to have a surface layer part. As a result, the contact points of the filaments on the surface of the network structure are greatly increased to form adhesion points, so that the local external force of the buttocks when sitting is received on the structure surface without giving a sense of foreign matter to the buttocks. The surface structure is deformed as a whole, the entire internal structure is also deformed to absorb the stress, and when the stress is released, the elastic elasticity of the elastic resin appears and the structure is restored to its original form. Can do. If it is not substantially flattened, it gives a feeling of foreign matter to the buttocks, local external force is applied to the surface, and stress concentration may occur selectively up to the surface stripes and adhesion points. There is a case where fatigue due to concentration occurs and the sag resistance decreases. When the outer surface of the structure is flattened, do not use a wading layer or laminate a very thin wading layer and cover the surface with the side ground, for seats or chairs or beds for automobiles, railways, etc., for sofas, It can be used as a cushion mat for futons. If the outer surface of the structure is not flattened, a relatively thick (preferably 10 mm or more) wadding layer needs to be laminated on the surface of the network structure, and the seat and cushion mat must be formed by covering the surface with the side ground. . If necessary, adhesion to the wadding layer or adhesion to the side is easy when the surface is flat, but when the surface is not flattened, the adhesion is incomplete and uneven.
次に本発明の三次元ランダムループ接合構造からなる網状構造体の製造方法について以下に述べるが、以下の方法は一例であって、これに限定するものではない。
まず、一般的な溶融押出機を用いて熱可塑性エラストマーを融点より１０〜８０℃高い温度に加熱して溶融状態とし、複数のオリフィスを持つノズルより下向きに吐出させ、自然降下させループを形成させる。このときノズル面と樹脂を固化させる冷却媒体上に設置した引取りコンベアとの距離、樹脂の溶融粘度、オリフィスの孔径と吐出量などによりループ径と線状体の繊度がきまる。冷却媒体上に設置した間隔が調整可能な一対の引取りコンベアで溶融状態の吐出線状体を挟み込み停留させることでループが発生し、オリフィスの孔間隔を発生ループが接触できる孔間隔にしておくことで発生したループを互いに接触させ、接触することでループがランダムな三次元形態を形成しつつ接触部は融着する。次いでランダムな三次元形態を形成しつつ接触部が融着した連続線状体を連続して冷却媒体中に引込み固化させ網状構造体を形成する。
Next, although the manufacturing method of the network structure which consists of a three-dimensional random loop junction structure of this invention is described below, the following method is an example and is not limited to this.
First, using a general melt extruder, the thermoplastic elastomer is heated to a temperature 10 to 80 ° C. higher than the melting point to be in a molten state, discharged downward from a nozzle having a plurality of orifices, and naturally lowered to form a loop. . At this time, the loop diameter and the fineness of the linear body are determined by the distance between the nozzle surface and the take-up conveyor installed on the cooling medium for solidifying the resin, the melt viscosity of the resin, the orifice diameter and the discharge amount, and the like. A pair of take-up conveyors that can be adjusted on the cooling medium can be adjusted so that a molten discharge linear body is sandwiched and stopped to generate a loop, and the hole interval of the orifice is set to a hole interval at which the generated loop can contact. The generated loops are brought into contact with each other, and the contact portions are fused while the loops form a random three-dimensional form. Next, the continuous linear body in which the contact portion is fused while continuously forming a random three-dimensional form is continuously drawn into the cooling medium and solidified to form a network structure.
オリフィスの形状は特に限定されないが、異形断面（例えば三角形、Ｙ型、星型等の断面二次モ−メントが高くなる形状）や中空断面（例えば三角中空、丸型中空、突起つきの中空等となるよう形状）とすることで溶融状態の吐出線条が形成する３次元構造が流動緩和し難くし、逆に接触点での流動時間を長く保持して接着点を強固にできるので特に好ましい。特開平１−２０７５号公報に記載の接着のための加熱をする場合、３次元構造が緩和し易くなり平面的構造化し、３次元立体構造化が困難となるので好ましくない。構造体の特性向上効果としては、見掛けの嵩を高くでき軽量化になり、また抗圧縮性が向上し、弾発性も改良できて、へたり難くなる。中空断面では中空率が８０％を越えると断面が潰れ易くなるので、中空断面を採用する場合の中空率は、好ましくは軽量化の効果が発現できる１０％以上７０％以下、より好ましくは２０％以上６０％以下である。 The shape of the orifice is not particularly limited, but may be an irregular cross-section (for example, a triangle, Y-type, star-shaped, etc. with a high secondary cross-section moment) or a hollow cross-section (for example, a triangular hollow, a round hollow, a hollow with protrusions, etc.) It is particularly preferable that the three-dimensional structure formed by the melted discharge filaments is difficult to flow relax, and conversely the flow time at the contact point can be kept long to strengthen the adhesion point. In the case of heating for adhesion described in JP-A-1-2075, the three-dimensional structure is easy to relax, and a planar structure is formed, making it difficult to form a three-dimensional structure. As an effect of improving the characteristics of the structure, the apparent bulk can be increased, the weight can be reduced, the anti-compression property can be improved, the elasticity can be improved, and the structure cannot be easily set. Since the cross section tends to be crushed when the hollow ratio exceeds 80% in the hollow cross section, the hollow ratio in the case of employing the hollow cross section is preferably 10% or more and 70% or less, more preferably 20%, at which the effect of weight reduction can be exhibited. It is 60% or less.
オリフィスの孔間ピッチは、線状が形成するル−プが充分接触できるピッチとする必要がある。緻密な構造にするには孔間ピッチを短くし、粗密な構造にするには孔間ピッチを長くする。本発明の孔間ピッチは好ましくは３mm〜２０mm、より好ましくは５mm〜１０mmである。本発明では所望に応じ異密度化や異繊度化もできる。列間のピッチ又は孔間のピッチも変えた構成、及び列間と孔間の両方のピッチも変える方法などで異密度層を形成できる。また、オリフィスの断面積を変えて吐出時の圧力損失差を付与すると、溶融した熱可塑性エラストマーが同一ノズルから一定の圧力で押し出される吐出量が圧力損失の大きいオリフィスほど少なくなる原理を用いて、異繊度化できる。 The pitch between the holes of the orifices needs to be a pitch that can sufficiently contact the loop formed by the linear shape. The pitch between holes is shortened to obtain a dense structure, and the pitch between holes is increased to obtain a dense structure. The pitch between holes of the present invention is preferably 3 mm to 20 mm, more preferably 5 mm to 10 mm. In the present invention, different density and different fineness can be achieved as desired. The different density layer can be formed by a configuration in which the pitch between rows or the pitch between holes is changed, and a method in which both the pitch between rows and between holes are also changed. In addition, when changing the cross-sectional area of the orifice to give a pressure loss difference at the time of discharge, using the principle that the amount of discharge by which the molten thermoplastic elastomer is pushed out from the same nozzle at a constant pressure becomes smaller as the orifice has a larger pressure loss, Different fineness can be achieved.
次いで、引取りネットで溶融状態の三次元立体構造体両外表面を挟み込み、両面の溶融状態の曲がりくねった吐出線条を３０°以上折り曲げて変形させ、表面をフラット化すると同時に、曲げられていない吐出線条との接触点を接着して構造を形成する。その後、連続して冷却媒体（通常は室温の水を用いるのが冷却速度を早くでき、コスト面でも安くなるので好ましい。）で急冷して本発明の三次元ランダムループ接合構造体からなる網状構造体を得る。次いで水切り乾燥するが、冷却媒体中に界面活性剤等を添加すると、水切りや乾燥がしにくくなったり、熱可塑性エラストマーが膨潤したりすることもあり好ましくない。本発明の好ましい方法としては、一旦冷却後、疑似結晶化処理を行う。疑似結晶化処理温度は、少なくとも融点（Ｔｍ）より１０℃以上低く、Ｔａｎδのα分散立ち上がり温度（Ｔαｃｒ）以上で行う。この処理で、融点以下に吸熱ピ−クを持ち、疑似結晶化処理しないもの（吸熱ピ−クを有しないもの）より耐熱耐へたり性が著しく向上する。本発明の好ましい疑似結晶化処理温度は（Ｔαｃｒ＋１０℃）から（Ｔｍ−２０℃）である。単なる熱処理により疑似結晶化させると耐熱耐へたり性が向上する。更には一旦冷却後、１０％以上の圧縮変形を付与してアニ−リングすることで耐熱耐へたり性が著しく向上するのでより好ましい。また、一旦冷却後、乾燥工程を経する場合、乾燥温度をアニ−リング温度とすることで同時に疑似結晶化処理を行うができる。また、別途疑似結晶化処理を行うができる。 Next, both outer surfaces of the melted three-dimensional structure are sandwiched by a take-off net, and the twisted discharge filaments on both surfaces are bent and deformed by 30 ° or more, and the surface is flattened and not bent at the same time. A structure is formed by adhering contact points with the discharge filaments. After that, the network structure comprising the three-dimensional random loop joint structure of the present invention is continuously cooled rapidly with a cooling medium (usually room temperature water is preferable because the cooling rate can be increased and the cost is reduced). Get the body. Next, draining and drying are performed. However, adding a surfactant or the like to the cooling medium is not preferable because draining or drying becomes difficult and the thermoplastic elastomer may swell. As a preferred method of the present invention, a pseudo crystallization treatment is performed after cooling. The pseudo-crystallization temperature is at least 10 ° C. lower than the melting point (Tm) and is equal to or higher than the Tan dispersion α dispersion rising temperature (Tαcr). With this treatment, the heat sag resistance is remarkably improved as compared with those having an endothermic peak below the melting point and not subjected to pseudo-crystallization treatment (no endothermic peak). The preferred pseudocrystallization temperature of the present invention is from (Tαcr + 10 ° C.) to (Tm−20 ° C.). When pseudo-crystallization is performed by simple heat treatment, heat sag resistance is improved. Furthermore, after cooling, it is more preferable to apply 10% or more of compressive deformation and perform annealing so that the heat sag resistance is remarkably improved. Moreover, when it passes through a drying process once after cooling, a pseudo crystallization process can be performed simultaneously by making drying temperature into annealing temperature. In addition, a pseudo crystallization process can be performed separately.
次いで所望の長さまたは形状に切断してクッション材に用いる。本発明の網状構造体をクッション材に用いる場合、その使用目的、使用部位により使用する樹脂、繊度、ル−プ径、嵩密度を選択する必要がある。例えば、表層のワディングに用いる場合は、ソフトなタッチと適度の沈み込みと張りのある膨らみを付与するために、低密度で細い繊度、細かいル−プ径にするのが好ましく、中層のクッション体としては、共振振動数を低くし、適度の硬さと圧縮時のヒステリシスを直線的に変化させて体型保持性を良くし、耐久性を保持させるために、中密度で太い繊度、やや大きいル−プ径が好ましい。勿論、用途との関係で要求性能に合うべく他の素材、例えば短繊維集合体からなる硬綿クッション材、不織布等と組合せて用いることも可能である。また、樹脂製造過程以外でも性能を低下させない範囲で製造過程から成形体に加工し、製品化する任意の段階で難燃化、防虫抗菌化、耐熱化、撥水撥油化、着色、芳香等の機能付与を薬剤添加等の処理加工ができる。 Next, it is cut into a desired length or shape and used as a cushioning material. When the network structure of the present invention is used for a cushioning material, it is necessary to select a resin, a fineness, a loop diameter, and a bulk density to be used depending on the purpose of use and the use site. For example, when used for surface wading, it is preferable to have a low density, fine fineness, and a fine loop diameter in order to give a soft touch, moderate subsidence, and a tight bulge. In order to lower the resonant frequency, linearly change the appropriate hardness and hysteresis at the time of compression, improve the body shape retention, and maintain durability, medium density, thick fineness, slightly larger The diameter is preferable. Of course, it can be used in combination with other materials such as a hard cotton cushion material made of short fiber aggregates, non-woven fabric, etc. to meet the required performance in relation to the application. In addition, it can be processed into a molded product from the manufacturing process as long as the performance is not deteriorated even outside the resin manufacturing process, and flame retardant, antibacterial, heat resistance, water and oil repellency, coloring, fragrance, etc. It is possible to perform processing such as adding a drug to impart the function.
以下に実施例で本発明を詳述する。
なお、実施例中の評価は以下の方法で行った。
The present invention is described in detail below with reference to examples.
In addition, evaluation in an Example was performed with the following method.
＜樹脂特性＞
・ 融点（Ｔｍ）
島津製作所ＴＡ５０、ＤＳＣ５０型示差熱分析計を使用し、１０ｇの試料を昇温速度２０℃／分で２０℃から２５０℃まで測定した吸発熱曲線から吸熱ピーク（融解ピーク）温度を求めた。
・ 曲げ弾性率
射出成形機によって長さ１２５ｍｍ×幅１２ｍｍ×厚み６ｍｍの試験片を作成し、ＡＳＴＭ Ｄ７９０規格により測定した。
・ 原料樹脂のＴａｎδ
測定に用いたサンプルは、設定温度２３０℃のヒートプレスによって厚さ３００ｕｍのシートサンプルに成形し、長さ２３ｍｍ×幅５ｍｍに切り出して作成した。動的粘弾性測定装置（ＵＢＭ社製Ｒｈｅｏｇｅｌ−Ｅ−４０００）を用い、サンプルの長辺の両端各４ｍｍ部分を引張治具で固定し、１１Ｈｚ、昇温速度２℃／分で測定した２３℃のＴａｎδ（損失弾性率Ｅ”と貯蔵弾性率Ｅ’との比Ｅ”／Ｅ’）値を用いた。
<Resin characteristics>
・ Melting point (Tm)
Using a Shimadzu TA50, DSC50 differential thermal analyzer, an endothermic peak (melting peak) temperature was determined from an endothermic curve obtained by measuring a 10 g sample from 20 ° C. to 250 ° C. at a rate of temperature increase of 20 ° C./min.
-Flexural modulus Test pieces having a length of 125 mm, a width of 12 mm and a thickness of 6 mm were prepared by an injection molding machine, and measured according to the ASTM D790 standard.
・ Tanδ of raw material resin
The sample used for the measurement was formed into a sheet sample having a thickness of 300 μm by a heat press at a set temperature of 230 ° C. and cut into a length of 23 mm and a width of 5 mm. Using a dynamic viscoelasticity measuring device (Rhegel-E-4000 manufactured by UBM), the 4 mm portions at both ends of the long side of the sample were each fixed with a tensile jig, and measured at 11 Hz and a heating rate of 2 ° C./min. Tanδ (ratio E ″ / E ′ of loss elastic modulus E ″ and storage elastic modulus E ′) was used.
＜網状構造体特性＞
（１）連続線条体のＴａｎδ
測定に用いたサンプルは、網状構造体を設定温度２３０℃のヒートプレスによって厚さ３００ｕｍのシートサンプルに成形し、長さ２３ｍｍ×幅５ｍｍに切り出して作成した。動的粘弾性測定装置（ＵＢＭ社製Ｒｈｅｏｇｅｌ−Ｅ−４０００）を用い、サンプルの長辺の両端各４ｍｍ部分を引張治具で固定し、１１Ｈｚ、昇温速度２℃／分で測定した２３℃のＴａｎδ（損失弾性率Ｅ”と貯蔵弾性率Ｅ’との比Ｅ”／Ｅ’）値を用いた。
（２）２５％圧縮硬さ
試料を３０cm×３０cmの大きさに切断し、オリエンテック社製テンシロンにてφ２００mm圧縮板にて７５％まで圧縮して得た応力−歪み曲線の２５％圧縮時の応力で示す。（ｎ＝３の平均値）
（３）見掛け密度
試料を１５cm×１５cmの大きさに切断し、４か所の高さを測定し、体積を求め、試料の重さを体積で徐した値（ｇ／ｃｍ３）で示す。（ｎ＝４の平均値）
（４）線条の繊度
網状構造体を２０ｃｍ×２０ｃｍの大きさに切断し、１０か所から長さ１ｃｍの線条体を採取する。１０か所で採取した線条体の４０℃での比重を密度勾配管を用いて測定する。更に、上記１０か所で採取した線条体の断面積を顕微鏡で拡大した写真より求め、それより、線条体の長さ１００００ｍ分の体積を求める。得られた比重と体積を乗じた値を繊度（線条体１００００ｍ分のグラム重量：デシテックスｄｔｅｘ）とする。（ｎ＝１０の平均値）。
（５）中空率
網状構造体から線条を採取し、液体窒素で冷却した後に割断し、その断面を電子顕微鏡で倍率５０倍にて観察し、得られた画像をＣＡＤシステムにて解析して樹脂部分の断面積（Ａ）と中空部分の断面積（Ｂ）を測定し、｛Ｂ／（Ａ＋Ｂ）｝×１００の式により中空率を算出した。
<Network structure characteristics>
(1) Tanδ of continuous striatum
The sample used for the measurement was formed by forming a network structure into a sheet sample having a thickness of 300 μm by a heat press at a set temperature of 230 ° C., and cutting it into a length of 23 mm × a width of 5 mm. Using a dynamic viscoelasticity measuring device (Rhegel-E-4000 manufactured by UBM), the 4 mm portions at both ends of the long side of the sample were each fixed with a tensile jig, and measured at 11 Hz and a heating rate of 2 ° C./min. Tanδ (ratio E ″ / E ′ of loss elastic modulus E ″ and storage elastic modulus E ′) was used.
(2) 25% compression hardness The sample was cut into a size of 30 cm × 30 cm, and the stress-strain curve obtained by compressing to 75% with a φ200 mm compression plate using Tensilon manufactured by Orientec Corp. Indicated by stress. (Average value of n = 3)
(3) Apparent density A sample is cut into a size of 15 cm × 15 cm, the heights at four locations are measured, the volume is determined, and the weight of the sample is expressed as a value (g / cm 3 ) that is gradually reduced. (Average value of n = 4)
(4) Fineness of filaments The network structure is cut into a size of 20 cm × 20 cm, and a filament having a length of 1 cm is collected from 10 locations. The specific gravity at 40 ° C. of the striatum collected at 10 locations is measured using a density gradient tube. Further, the cross-sectional area of the striatum sampled at the 10 locations is determined from a photograph enlarged with a microscope, and the volume of the striatum length of 10,000 m is determined therefrom. The value obtained by multiplying the obtained specific gravity and volume is defined as the fineness (gram weight of striatum 10000 m: decitex dtex). (Average value of n = 10).
(5) Hollow ratio A strip is taken from a network structure, and after cooling with liquid nitrogen, it is cleaved, its cross section is observed with an electron microscope at a magnification of 50 times, and the obtained image is analyzed with a CAD system. The cross-sectional area (A) of the resin part and the cross-sectional area (B) of the hollow part were measured, and the hollow ratio was calculated by the formula {B / (A + B)} × 100.
＜合成例１＞
ジメチルテレフタレート（ＤＭＴ）と１，４−ブタンジオール（１，４−ＢＤ）とポリテトラメチレングリコール（ＰＴＭＧ：平均分子量１０００）を少量の触媒と仕込み、常法によりエステル交換後、昇温減圧しつつ重縮合せしめ、ＤＭＴ／１，４−ＢＤ／ＰＴＭＧ＝１００／９３／７ｍｏｌ％のポリエステルエーテルブロック共重合エラストマーを生成させ、次いで抗酸化剤１％を添加混合練込み後ペレット化し、５０℃４８時間真空乾燥してポリエステル系熱可塑性エラストマー原料（Ａ−１）を得た。その特性を表１に示す。
<Synthesis Example 1>
Dimethyl terephthalate (DMT), 1,4-butanediol (1,4-BD) and polytetramethylene glycol (PTMG: average molecular weight 1000) are charged with a small amount of catalyst, and after transesterification by a conventional method, while raising the temperature and reducing the pressure Polycondensation was carried out to produce a polyester ether block copolymer elastomer of DMT / 1,4-BD / PTMG = 100/93/7 mol%, then 1% of an antioxidant was added, kneaded, pelletized, and 50 ° C. for 48 hours. Vacuum drying was performed to obtain a polyester-based thermoplastic elastomer raw material (A-1). The characteristics are shown in Table 1.
＜合成例２＞
ジメチルテレフタレート（ＤＭＴ）と１，４−ブタンジオール（１，４−ＢＤ）とポリテトラメチレングリコール（ＰＴＭＧ：平均分子量１０００）を少量の触媒と仕込み、常法によりエステル交換後、昇温減圧しつつ重縮合せしめ、ＤＭＴ／１，４−ＢＤ／ＰＴＭＧ＝１００／８４／１６ｍｏｌ％のポリエステルエーテルブロック共重合エラストマーを生成させ、次いで抗酸化剤１％を添加混合練込み後ペレット化し、５０℃４８時間真空乾燥してポリエステル系熱可塑性エラストマー原料（Ａ−２）を得た。その特性を表１に示す。
<Synthesis Example 2>
Dimethyl terephthalate (DMT), 1,4-butanediol (1,4-BD) and polytetramethylene glycol (PTMG: average molecular weight 1000) are charged with a small amount of catalyst, and after transesterification by a conventional method, while raising the temperature and reducing the pressure Polycondensation was carried out to produce a polyester ether block copolymer elastomer of DMT / 1,4-BD / PTMG = 100/84/16 mol%, then 1% antioxidant was added and kneaded, pelletized, and 50 ° C. for 48 hours. The polyester-based thermoplastic elastomer raw material (A-2) was obtained by vacuum drying. The characteristics are shown in Table 1.
＜実施例１＞
１０ｋｇの合成例1で得られたポリエステル系熱可塑性エラストマー（Ａ−１）および９０ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．０７ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．０７ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径１．０ｍｍの丸型中実形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．０ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで７０℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Example 1>
10 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1 and 90 kg of a hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals), 0.07 kg of hindered phenolic antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.07 kg of phosphorus antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed in a tumbler for 5 minutes, and then screwed. The mixture was melt-kneaded with a twin screw extruder having a diameter of 57 mm at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in a strand shape, and cooled to obtain pellets of a resin composition. From the nozzle in which a round solid shape orifice having a hole diameter of 1.0 mm is arranged at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction on the nozzle effective surface of the obtained resin composition having a width of 65 cm and a length of 5 cm, Melting at a temperature of 240 ° C., discharging a single hole at a discharge rate of 2.0 g / min, arranging cooling water under 30 cm of the nozzle surface, and a pair of pulling stainless steel endless nets with a width of 70 cm in parallel at intervals of 5 cm. Taking up the take-out conveyor so that it comes out partly on the surface of the water, pulling it into the cooling water at a speed of 1 m / min while sandwiching both sides while fusing the contact part, then solidify it, then hot air dryer at 70 ° C After the crystallization treatment for 15 minutes, the crystallization treatment was performed, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜実施例２＞
１０ｋｇの合成例1で得られたポリエステル系熱可塑性エラストマー（Ａ−１）および９０ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．０７ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．０７ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで７０℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Example 2>
10 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1 and 90 kg of a hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals), 0.07 kg of hindered phenolic antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.07 kg of phosphorus antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed in a tumbler for 5 minutes, and then screwed. The mixture was melt-kneaded with a twin screw extruder having a diameter of 57 mm at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in a strand shape, and cooled to obtain pellets of a resin composition. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is fused, and the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 70 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜実施例３＞
２０ｋｇの合成例1で得られたポリエステル系熱可塑性エラストマー（Ａ−１）および８０ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．５ｋｇのトリメリット酸エステル系可塑剤（ＤＩＣ社製「モノサイザーＷ７０５」）、１０ｋｇのポリエステル系可塑剤（ＤＩＣ社製「ポリサイザーＡ５５」）、０．１０ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．１０ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで７０℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Example 3>
20 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1 and 80 kg of a hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals), 0.5 kg trimellitic acid ester plasticizer (“Monicizer W705” manufactured by DIC), 10 kg polyester plasticizer (“Policizer A55” manufactured by DIC), 0.10 kg hindered phenol antioxidant ( ADEKA “ADK STAB AO330”) and 0.10 kg of phosphoric antioxidant (ADEKA “ADK STAB PEP36”) were mixed in a tumbler for 5 minutes, and then the cylinder temperature was 220 ° C. with a twin screw extruder having a screw diameter of 57 mm. , Melt kneading at 130 rpm, and extruding into a water bath in strands After cooling, to obtain pellets of the resin composition. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is fused, and the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 70 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜実施例４＞
３０ｋｇの合成例1で得られたポリエステル系熱可塑性エラストマー（Ａ−１）および７０ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．５ｋｇのトリメリット酸エステル系可塑剤（ＤＩＣ社製「モノサイザーＷ７０５」）、１０ｋｇのポリエステル系可塑剤（ＤＩＣ社製「ポリサイザーＡ５５」）、０．１５ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．１５ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで７５℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Example 4>
30 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1 and 70 kg of a hydrogenated styrene-butadiene random copolymer (SBR) ("SOE S1611" manufactured by Asahi Kasei Chemicals), 0.5 kg trimellitic acid ester plasticizer (DIC monosizer W705), 10 kg polyester plasticizer (DIC polysizer A55), 0.15 kg hindered phenol antioxidant ( ADEKA “ADK STAB AO330”) and 0.15 kg of phosphoric antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed in a tumbler for 5 minutes, and the cylinder temperature was 220 ° C. with a twin screw extruder having a screw diameter of 57 mm. , Melt kneading at 130 rpm, and extruding into a water bath in strands After cooling, to obtain pellets of the resin composition. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is fused, and the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 75 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜実施例５＞
７０ｋｇの合成例２で得られたポリエステル系熱可塑性エラストマー（Ａ−２）および３０ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．５ｋｇのトリメリット酸エステル系可塑剤（ＤＩＣ社製「モノサイザーＷ７０５」）、１０ｋｇのポリエステル系可塑剤（ＤＩＣ社製「ポリサイザーＡ５５」）、０．２５ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．２５ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで１００℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Example 5>
70 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2 and 30 kg of a hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals), 0.5 kg trimellitic acid ester plasticizer (DIC monosizer W705), 10 kg polyester plasticizer (DIC polysizer A55), 0.25 kg hindered phenol antioxidant ( ADEKA “ADK STAB AO330”) and 0.25 kg of phosphorus antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed in a tumbler for 5 minutes, and then the cylinder temperature was 220 ° C. with a twin screw extruder having a screw diameter of φ57 mm. , Melt-kneaded at a screw speed of 130 rpm and extruded into a strand in a water bath After cooling Te to obtain a pellet of the resin composition. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is melted, the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 100 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜実施例６＞
８０ｋｇの合成例２で得られたポリエステル系熱可塑性エラストマー（Ａ−２）および２０ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．５ｋｇのトリメリット酸エステル系可塑剤（ＤＩＣ社製「モノサイザーＷ７０５」）、１０ｋｇのポリエステル系可塑剤（ＤＩＣ社製「ポリサイザーＡ５５」）、０．２５ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．２５ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで１００℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Example 6>
80 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2 and 20 kg of a hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals), 0.5 kg trimellitic acid ester plasticizer (DIC monosizer W705), 10 kg polyester plasticizer (DIC polysizer A55), 0.25 kg hindered phenol antioxidant ( ADEKA “ADK STAB AO330”) and 0.25 kg of phosphorus antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed in a tumbler for 5 minutes, and then the cylinder temperature was 220 ° C. with a twin screw extruder having a screw diameter of φ57 mm. , Melt-kneaded at a screw speed of 130 rpm and extruded into a strand in a water bath After cooling Te to obtain a pellet of the resin composition. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is melted, the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 100 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜実施例７＞
９０ｋｇの合成例２で得られたポリエステル系熱可塑性エラストマー（Ａ−２）および１０ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．５ｋｇのトリメリット酸エステル系可塑剤（ＤＩＣ社製「モノサイザーＷ７０５」）、１０ｋｇのポリエステル系可塑剤（ＤＩＣ社製「ポリサイザーＡ５５」）、０．２５ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．２５ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで１００℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Example 7>
90 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2 and 10 kg of a hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals), 0.5 kg trimellitic acid ester plasticizer (DIC monosizer W705), 10 kg polyester plasticizer (DIC polysizer A55), 0.25 kg hindered phenol antioxidant ( ADEKA “ADK STAB AO330”) and 0.25 kg of phosphorus antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed in a tumbler for 5 minutes, and then the cylinder temperature was 220 ° C. with a twin screw extruder having a screw diameter of φ57 mm. , Melt-kneaded at a screw speed of 130 rpm and extruded into a strand in a water bath After cooling Te to obtain a pellet of the resin composition. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is melted, the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 100 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜比較例１＞
１００ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで７０℃の熱風乾燥機中で１５分疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Comparative Example 1>
100 kg of hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals Corporation) is a round hollow shape with a hole diameter of 3.0 mm on the effective surface of a nozzle having a width of 65 cm and a length of 5 cm. From a nozzle in which orifices are arranged at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, the nozzle is melted at a temperature of 240 ° C. and discharged at a single hole discharge rate of 2.5 g / min. Cooling water is distributed, a stainless steel endless net with a width of 70 cm is arranged in parallel at intervals of 5 cm so that a pair of take-out conveyors are partly exposed on the surface of the water, and the both sides are fused while the contact portions are fused. While being sandwiched, it was drawn into solidified cooling water at a rate of 1 m / min and then subjected to pseudo crystallization treatment in a hot air dryer at 70 ° C. for 15 minutes, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜比較例２＞
５ｋｇの合成例1で得られたポリエステル系熱可塑性エラストマー（Ａ−１）および２０ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．０５ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．０５ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで７０℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Comparative example 2>
5 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1 and 20 kg of a hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals), After mixing 0.05 kg of hindered phenolic antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.05 kg of phosphoric antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) for 5 minutes with a tumbler, screw The mixture was melt-kneaded with a twin screw extruder having a diameter of 57 mm at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in a strand shape, and cooled to obtain pellets of a resin composition. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is fused, and the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 70 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜比較例３＞
９５ｋｇの合成例２で得られたポリエステル系熱可塑性エラストマー（Ａ−２）および５ｋｇの水添スチレン−ブタジエンランダム共重合体（ＳＢＲ）（旭化成ケミカルズ社製「Ｓ．Ｏ．Ｅ．Ｓ１６１１」）、０．５ｋｇのトリメリット酸エステル系可塑剤（ＤＩＣ社製「モノサイザーＷ７０５」）、１０ｋｇのポリエステル系可塑剤（ＤＩＣ社製「ポリサイザーＡ５５」）、０．２５ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．２５ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２２０℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで１００℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Comparative Example 3>
95 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2 and 5 kg of a hydrogenated styrene-butadiene random copolymer (SBR) (“SOE S1611” manufactured by Asahi Kasei Chemicals), 0.5 kg trimellitic acid ester plasticizer (DIC monosizer W705), 10 kg polyester plasticizer (DIC polysizer A55), 0.25 kg hindered phenol antioxidant ( ADEKA “ADK STAB AO330”) and 0.25 kg of phosphoric antioxidant (ADEKA “ADK STAB PEP36”) were mixed in a tumbler for 5 minutes, and the cylinder temperature was 220 ° C. with a twin screw extruder having a screw diameter of 57 mm. , Melt kneading at 130 rpm, and extruding into a water bath in strands After cooling, to obtain pellets of the resin composition. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is melted, the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 100 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜比較例４＞
１００ｋｇの合成例２で得られたポリエステル系熱可塑性エラストマー（Ａ−２）および０．２５ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．２５ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２００℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２４０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで１００℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Comparative example 4>
100 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2 and 0.25 kg of a hindered phenol-based antioxidant (“ADEKA STAB AO330” manufactured by ADEKA), 0.25 kg of a phosphorus-based antioxidant ("ADEKA STAB PEP36" manufactured by ADEKA) was mixed for 5 minutes with a tumbler, melted and kneaded with a twin screw extruder with a screw diameter of 57 mm at a cylinder temperature of 200 ° C and a screw rotation speed of 130 rpm, and extruded into a water bath in a strand shape. After cooling, pellets of the resin composition were obtained. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 240 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is melted, the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 100 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
＜比較例５＞
１００ｋｇの合成例１で得られたポリエステル系熱可塑性エラストマー（Ａ−１）および０．２５ｋｇのヒンダードフェノール系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＡＯ３３０」）、０．２５ｋｇの燐系酸化防止剤（ＡＤＥＫＡ社製「アデカスタブＰＥＰ３６」）をタンブラーにて５分間混合した後、スクリュー径φ５７ｍｍの二軸押出機でシリンダー温度２００℃、スクリュー回転数１３０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅６５ｃｍ、長さ５ｃｍのノズル有効面に孔径３．０ｍｍの丸型中空形状オリフィスを幅方向５．２ｍｍ、長さ方向６．０ｍｍの間隔で配列したノズルより、２５０℃の温度で溶融して、単孔吐出量を２．５ｇ／分で吐出させ、ノズル面３０ｃｍ下に冷却水を配し、幅７０ｃｍのステンレス製エンドレスネットを平行に５ｃｍ間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分１ｍの速度で冷却水中へ引込み固化させ、次いで１００℃の熱風乾燥機中で１５分疑似結晶化処理した後、疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表２に示す。
<Comparative Example 5>
100 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1 and 0.25 kg of a hindered phenol antioxidant (“ADEKA STAB AO330” manufactured by ADEKA), 0.25 kg of a phosphorus-based antioxidant ("ADEKA STAB PEP36" manufactured by ADEKA) was mixed for 5 minutes with a tumbler, melted and kneaded with a twin screw extruder with a screw diameter of 57 mm at a cylinder temperature of 200 ° C and a screw rotation speed of 130 rpm, and extruded into a water bath in a strand shape. After cooling, pellets of the resin composition were obtained. From the nozzle in which a round hollow orifice having a hole diameter of 3.0 mm is arranged on a nozzle effective surface having a width of 65 cm and a length of 5 cm on the effective surface of the obtained resin composition at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, 250 Melting at a temperature of ° C, discharging a single hole at a rate of 2.5 g / min, arranging cooling water under 30 cm of the nozzle surface, and taking a pair of stainless endless nets with a width of 70 cm at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is melted, the both sides are sandwiched and drawn into the cooling water at a speed of 1 m / min, and then solidified in a 100 ° C hot air dryer. After 15 minutes of pseudo crystallization treatment, pseudo crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
本発明は、高い振動吸収性を示す網状構造体に関するものであり、その特性を生かして車両用座席や寝具などに使用可能である。 The present invention relates to a net-like structure having high vibration absorption, and can be used for a vehicle seat, bedding, and the like by utilizing the characteristics.
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| JP6492710B2 (en) * | 2015-02-04 | 2019-04-03 | 東洋紡株式会社 | Network structure with excellent low resilience |
| CN109477268B (en) | 2016-07-13 | 2021-12-28 | 东洋纺株式会社 | Net-shaped structure |
| JP7002010B2 (en) | 2018-05-31 | 2022-02-04 | パナソニックＩｐマネジメント株式会社 | Speaker system and noise control device |
| KR102092457B1 (en) * | 2018-06-15 | 2020-05-22 | (주)휴이노베이션 | Cyclohexanedimethanol Pitch-based Plasticizer and Resin Composition Comprising the Same |
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| JP2003012905A (en) * | 2001-07-03 | 2003-01-15 | Asahi Kasei Corp | Cushioning body |
| JP4341325B2 (en) * | 2002-08-08 | 2009-10-07 | チッソ株式会社 | Elastic nonwoven fabric and fiber product using the same |
| JP2004149959A (en) * | 2002-10-30 | 2004-05-27 | Toyobo Co Ltd | Shock absorbing pad for attachment and product using the same |
| JP4193686B2 (en) * | 2003-12-15 | 2008-12-10 | チッソ株式会社 | Elastic nonwoven fabric and textiles using the same |
| JP2006200119A (en) * | 2004-12-21 | 2006-08-03 | Toyobo Co Ltd | Lightweight elastic net-like structure having excellent chemical resistance |
| JP5181915B2 (en) * | 2008-08-13 | 2013-04-10 | 東洋紡株式会社 | Polyester-based elastic network having excellent quietness and method for producing the same |
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