JP5181915B2 - Polyester-based elastic network having excellent quietness and method for producing the same - Google Patents
Polyester-based elastic network having excellent quietness and method for producing the same Download PDFInfo
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Description
本発明は、静粛性に優れたポリエステル系弾性網状構造体に関する。 The present invention relates to a polyester-based elastic network structure excellent in quietness.
現在、寝具用のクッション材としては、発泡ウレタン、非弾性捲縮繊維詰綿、及び非弾性捲縮繊維を接着した樹脂綿や硬綿などが使用されている。 Currently, foamed urethane, inelastic crimped fiber-filled cotton, and resin cotton or hard cotton bonded with inelastic crimped fibers are used as cushion materials for bedding.
しかしながら、発泡−架橋型ウレタンはクッション材としての耐久性は良好だが、透湿透水性に劣り蓄熱性があるため蒸れやすく、かつ、熱可塑性では無いためリサイクルが困難となり焼却される場合、焼却炉の損傷が大きく、かつ、有毒ガス除去に経費が掛かる。このため埋め立てされることが多くなったが、地盤の安定化が困難なため埋め立て場所が限定され経費も高くなっていく問題がある。また、加工性は優れるが製造中に使用される薬品の公害問題などもある。また、熱可塑性ポリエステル接着詰綿では繊維間が固定されていないため、使用時形態が崩れたり、繊維が移動して、かつ、捲縮のへたりで崇高性の低下や弾力性の低下が問題になる。 However, although foam-crosslinked urethane has good durability as a cushioning material, it is easy to steam because it has poor moisture permeability and heat storage, and it is not thermoplastic. The damage of the gas is large, and the toxic gas removal is expensive. As a result, landfills are often used. However, since it is difficult to stabilize the ground, there is a problem that the landfill site is limited and the cost increases. In addition, the processability is excellent, but there is a problem of pollution of chemicals used during production. In addition, since the fibers are not fixed in thermoplastic polyester adhesive-filled cotton, the form of use collapses, the fibers move, and there is a problem of reduced sublimation and elasticity due to crimping. become.
ポリエステル繊維を接着剤で接着した樹脂綿、例えば接着剤にゴム系を用いたもの（例えば、特許文献１〜３参照）、また、架橋性ウレタンを用いたもの（例えば、特許文献４参照）がある。これらのクッション材は耐久性に劣り、且つ、熱可塑性でなく、単一組成でもないためリサイクルも出来ない等の問題、及び加工性の煩雑さや製造中に使用される薬品の公害問題などもある。 Resin cotton in which polyester fibers are bonded with an adhesive, for example, those using a rubber system as an adhesive (for example, see Patent Documents 1 to 3), and those using a crosslinkable urethane (for example, see Patent Document 4) is there. These cushion materials are inferior in durability and have problems such as being unable to be recycled because they are not thermoplastic and not having a single composition, and there are problems such as complexity of workability and pollution of chemicals used during production. .
ポリエステル硬綿を用いているもの（例えば、特許文献５、６参照）があるが、熱接着繊維の繊維成分が脆い非晶性のポリマーを用いるため接着部分が脆く、使用中に接着部分が簡単に破壊されて形態や弾力性が低下するなどの耐久性に劣る問題がある。 Some use polyester hard cotton (see, for example, Patent Documents 5 and 6), but the adhesive part is fragile because the fiber component of the heat-bonding fiber is brittle and the adhesive part is easy to use during use. There is a problem inferior in durability, for example, the shape and elasticity are reduced due to destruction.
また、改良法として、交絡処理する方法（例えば、特許文献７参照）が提案されているが、接着部分の脆さは解決されず弾力性の低下が大きい問題がある。また、加工時の煩雑さもある。更には接着部分が変形しにくくソフトなクッション性を付与しにくい問題もある。このため、接着部分を柔らかい、且つ変形しても回復するポリエステルエラストマーを用いた熱接着繊維を用いたクッション材が提案されている（例えば、特許文献８参照）。この繊維構造物に使われる接着成分のポリエステルエラストマーは融点を低くする為に、ハードセグメントの酸成分にテレフタル酸を５０〜８０モル％含有し、ソフトセグメントとしてのポリアルキレングリコールの含有量が３０〜５０重量％を含有させ、他の酸成分組成としてイソフタル酸等を含有し非晶性が増加させて融点を１８０℃以下にし、且つ低溶融粘度として熱接着部分の形成を良くしてアメーバー状の接着部を形成しているが、芯部にポリエチレンテレフタレートを使った芯鞘型の複合繊維であるため、風合いが硬く、体型にフィットしたものとなりにくいという問題があり、また、複合紡糸繊維を使用することや、再加熱し溶融接着する工程を必要とするためコストが高くなるという問題もある。 Further, as an improved method, a method of entanglement processing (see, for example, Patent Document 7) has been proposed, but there is a problem that the brittleness of the bonded portion is not solved and the elasticity is greatly reduced. Moreover, there is also complexity during processing. Furthermore, there is also a problem that it is difficult to impart a soft cushioning property to the bonded portion that is difficult to deform. For this reason, the cushioning material using the heat-bonding fiber using the polyester elastomer which is soft even if a bonded part is recovered and is deformed has been proposed (see, for example, Patent Document 8). In order to lower the melting point, the polyester elastomer of the adhesive component used in this fiber structure contains 50 to 80 mol% of terephthalic acid in the acid component of the hard segment, and the content of polyalkylene glycol as the soft segment is 30 to 30%. 50% by weight, isophthalic acid or the like as other acid component composition is increased, the amorphous property is increased, the melting point is 180 ° C. or less, and the low melt viscosity improves the formation of the heat-bonded portion, thereby improving the amoeba-like shape. Although an adhesive part is formed, it is a core-sheath type composite fiber using polyethylene terephthalate for the core part, so there is a problem that the texture is hard and it is difficult to fit the body shape, and composite spun fiber is used In addition, there is a problem that the cost increases because a process of reheating and melt bonding is required.
ウレタンの代替品として、ポリオレフィン樹脂と酢酸ビニル樹脂、酢酸ビニル−エチレン共重合体、又はスチレンブタジエンスチレンとの混合物からなるクッション材も検討されている（例えば、特許文献９参照）。しかしこれはウレタンに比べて沈み込みが少なく、２５％圧縮時応力が高い、圧縮と除圧時の応力差が小さいので反発性が高すぎる、他成分と混合されているので耐光性が悪い、繰り返し圧縮時の厚み保持率が悪い、比重が大きく重たくなりやすい等の問題がある。さらにはこのクッション材は異なる素材の組合せであるためリサイクルが困難であるなどの問題もある。 As a substitute for urethane, a cushioning material made of a mixture of a polyolefin resin and a vinyl acetate resin, a vinyl acetate-ethylene copolymer, or styrene butadiene styrene has been studied (for example, see Patent Document 9). However, it has less sinking than urethane, has a high stress at 25% compression, a small difference in stress between compression and decompression, so rebound is too high, and light resistance is poor because it is mixed with other components. There are problems such as poor thickness retention during repeated compression, high specific gravity and high weight. Furthermore, since this cushion material is a combination of different materials, there is a problem that recycling is difficult.
ポリエステル系共重合熱可塑性弾性樹脂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が、圧縮時に繊維同士が衝突したり擦れあう時にギシギシという音が発生するため、寝具に用いた場合、うるさくて寝づらいという問題がある。 A three-dimensional random structure in which a continuous linear body made of polyester copolymer thermoplastic elastic resin is twisted to form a random loop, and the respective loops are brought into contact with each other in a molten state, and most of the contact portion is fused. Although a loop joint structure has been proposed, there is a problem that it is noisy and difficult to sleep when used in bedding because a squeaking sound is generated when fibers collide or rub against each other during compression.
本発明は従来技術の課題を背景になされたもので、耐久性、クッション性の優れ蒸れ難く、特に圧縮時の音を低減したポリエステル系弾性網状構造体及びその製造方法を提供することを目的とする。 The present invention has been made against the background of the problems of the prior art, and has an object to provide a polyester-based elastic network structure that is excellent in durability and cushioning properties and is less likely to be stuffy, and particularly reduced in sound during compression, and a method for producing the same. To do.
本発明者らは上記課題を解決するため、鋭意研究した結果、遂に本発明を完成するに到った。即ち本発明は以下の通りである。
１．曲げ弾性率１５〜７０ＭＰａ、表面硬度３０〜４５Ｄであるポリエステル共重合体からなる繊度が３００デシテックス以上の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のランダムループ表面に、シリコーン系樹脂を含む樹脂が０．４〜４重量％付着しているポリエステル系弾性網状構造体。
２．連続線状体が少なくとも中空率１５％以上の中空繊維からなる上記１に記載のポリエステル系弾性網状構造体。
３．シリコーン系樹脂が、カルボキシル基を有するポリエステル系バインダー及び架橋剤で固着されている上記１または２に記載のポリエステル系弾性網状構造体。
４．シリコーン系樹脂とカルボキシル基を有するポリエステル系バインダー及び架橋剤を、ｐＨ５〜８の水系エマルジョンとして弾性網状構造体に付着させ、４０〜１３０℃で乾燥処理する上記１〜３のいずれかに記載のポリエステル系弾性網状構造体の製造方法。
As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention is as follows.
1. A continuous linear body made of a polyester copolymer having a flexural modulus of 15 to 70 MPa and a surface hardness of 30 to 45 D is twisted to form a random loop, and the loops are brought into contact with each other in a molten state. In addition, a polyester-based elastic network structure in which 0.4 to 4% by weight of a resin containing a silicone-based resin adheres to the random loop surface of a three-dimensional random loop bonded structure obtained by fusing most of the contact portions. .
2. 2. The polyester-based elastic network structure according to 1 above, wherein the continuous linear body is formed of hollow fibers having a hollow ratio of 15% or more.
3. 3. The polyester elastic network structure according to 1 or 2 above, wherein the silicone resin is fixed with a polyester binder having a carboxyl group and a crosslinking agent.
4). The polyester according to any one of 1 to 3 above, wherein a silicone-based resin, a polyester-based binder having a carboxyl group, and a crosslinking agent are attached to an elastic network as a water-based emulsion having a pH of 5 to 8, and dried at 40 to 130 ° C. Of manufacturing an elastic elastic network structure.
本発明によるポリエステル系弾性網状構造体は、圧縮時の音鳴りを軽減しているため、耐久性のあるクッション性と優れた静粛性を有するポリエステル系弾性網状構造体を提供できる。 Since the polyester-based elastic network structure according to the present invention reduces noise during compression, a polyester-based elastic network structure having durable cushioning properties and excellent quietness can be provided.
以下、本発明を詳細に説明する。
本発明でいうポリエステル共重合体と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ー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事例としては、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、琥珀酸、アジピン酸、セバチン酸、ダイマー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、トレ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、エチレンオキシドープロピレンオキシド共重合体等の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３００〜３０００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各１種から構成される三元ブロック共重合体である。熱接着性、耐加水分解性、伸縮性、耐熱性等を考慮すると、ジカルボン酸としてはテレフタル酸、または、及びナフタレン２・６ジカルボン酸、ジオール成分としては１・４ブタンジオール、ポリアルキレンジオールとしてはポリテトラメチレングリコールの三元ブロック共重合体または、ポリエステルジオールとしてポリラクトンの三元ブロック共重合体が特に好ましい。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。また、上記ポリエステルエラストマーは単独または２種類以上混合して使用できる。更には、ポリエステルエラストマーに非エラストマー成分をブレンドされたもの、共重合したもの等も本発明に使用できる。
Hereinafter, the present invention will be described in detail.
The polyester copolymer in the present invention is a polyester ether block copolymer having a thermoplastic polyester as a hard segment and a polyalkylene diol as a soft segment, or a polyester ether block copolymer having an aliphatic polyester as a soft segment. It can be illustrated. More specific examples of polyester ether block copolymers include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene 2,6 dicarboxylic acid, naphthalene 2,7 dicarboxylic acid, diphenyl 4,4 'dicarboxylic acid, -At least one dicarboxylic acid selected from alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, dimer acid, or ester-forming derivatives thereof Aliphatic diols such as 1,4 butanediol, ethylene glycol, tremethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc., and alicyclic diols such as 1,1 cyclohexanedimethanol, 1,4 cyclohexanedimethanol, etc. Or this At least one diol component selected from these ester-forming derivatives and the like, and polyalkylene diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer having an average molecular weight of about 300 to 5,000 Among these, a ternary block copolymer composed of at least one kind. The polyester ester block copolymer is a ternary block copolymer composed of at least one of the dicarboxylic acid, diol, and polyester diol such as polylactone having an average molecular weight of about 300 to 3000. Considering thermal adhesiveness, hydrolysis resistance, stretchability, heat resistance, etc., dicarboxylic acid is terephthalic acid or naphthalene 2,6 dicarboxylic acid, diol component is 1,4 butanediol, polyalkylenediol Is particularly preferably a polytetramethylene glycol ternary block copolymer or a polyester diol polylactone ternary block copolymer. As a special example, a polysiloxane-based soft segment can be used. Moreover, the said polyester elastomer can be used individually or in mixture of 2 or more types. Furthermore, a polyester elastomer blended with a non-elastomeric component or a copolymerized one can be used in the present invention.
本発明のポリエステル系弾性網状構造体は繊度が３００デシテックス以上の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であることが好ましい。 The polyester-based elastic network structure of the present invention twists continuous linear bodies having a fineness of 300 dtex or more to form random loops, and the loops are brought into contact with each other in a molten state, and most of the contact portions are fused. It is preferable that the three-dimensional random loop junction structure is made.
本発明のポリエステル系弾性網状構造体に用いるポリエステル共重合体は、曲げ弾性率が１５〜７０ＭＰａであることが好ましい。曲げ弾性率が７０ＭＰａを超えると、繊維とした時に曲げ硬くなるため圧縮時に繊維同士の衝突及び擦れによるギシギシ音の発生が顕著になるため好ましくない。一方、曲げ弾性率が１５ＭＰａ未満では繊維とした時に柔らかくなりすぎ、クッション体として身体を支えるのに不適当となるため好ましくない。より好ましい曲げ弾性率は２０〜６５ＭＰａである。 The polyester copolymer used for the polyester-based elastic network structure of the present invention preferably has a flexural modulus of 15 to 70 MPa. If the flexural modulus exceeds 70 MPa, it becomes undesirably generated when it is made into a fiber, since the bending sound becomes noticeable due to collision and rubbing between the fibers during compression. On the other hand, if the flexural modulus is less than 15 MPa, the fiber becomes too soft when used as a fiber, which is not preferable for supporting the body as a cushion body. A more preferable bending elastic modulus is 20 to 65 MPa.
本発明のポリエステル系弾性網状構造体に用いるポリエステル共重合体は、表面硬度３０〜４５Ｄであることが好ましい。表面硬度が４５Ｄを超えると、繊維同士の衝突時に発生する音が大きくなるため好ましくない。一方、表面硬度が３０Ｄ未満では繊維表面がベタつくと共に圧縮回復時の剥がれる音が顕著になるため好ましくない。より好ましい表面硬度は３５〜４２Ｄである。 The polyester copolymer used in the polyester-based elastic network structure of the present invention preferably has a surface hardness of 30 to 45D. When the surface hardness exceeds 45D, sound generated at the time of collision between fibers increases, which is not preferable. On the other hand, if the surface hardness is less than 30D, the fiber surface becomes sticky and the peeling sound at the time of compression recovery becomes remarkable, which is not preferable. A more preferable surface hardness is 35 to 42D.
本発明のポリエステル系弾性網状構造体を構成する連続線状体の繊度が３００デシテックス未満では、強度が低くなり反発力が低下するので好ましくない。本発明の連続線状体の好ましい繊度は、優れた反発力の得られる３００デシテックス以上１０００００デシテックス以下であり、１０００００デシテックスを超えると連続線状体の構成本数が少なくなり、圧縮特性が悪くなるので使用部分が限定される場合がある。より好ましい繊度は５００〜５００００デシテックスである。 When the fineness of the continuous linear body constituting the polyester-based elastic network structure of the present invention is less than 300 dtex, the strength is lowered and the repulsive force is lowered, which is not preferable. The preferred fineness of the continuous linear body of the present invention is not less than 300 dtex and not more than 100,000 dtex when excellent repulsive force is obtained, and if it exceeds 100,000 dtex, the number of continuous linear bodies is reduced, and the compression characteristics deteriorate. Use part may be limited. A more preferable fineness is 500 to 50000 dtex.
本発明のポリエステル系弾性網状構造体はランダムループ表面にシリコーン系樹脂を含む樹脂が網状構造体重量に対し０．４〜４重量％付着していることが好ましい。本発明のポリエステル系弾性網状構造体のように表面硬度が比較的低い範囲のポリエステル共重合体からなる網状構造体は、圧縮した時に繊維同士が軽く接着されたような疑似接着の状態になりやすく、圧縮からの回復時において繊維同士が離れる際に「ネチャ」という剥がれ音がしやすい。これはポリエステル共重合体がもつポリマー特性に依存する。この剥がれ音を軽減するためにポリエステル系弾性網状構造体のランダムループ表面にシリコーン系樹脂を含む樹脂が網状構造体重量に対し０．４〜４重量％の範囲で付着されることが好ましい。付着量が０．４重量％未満であると、繊維同士の疑似接着の抑制が出来にくいため好ましくなく、４重量％を越えると、ループ内で樹脂膜が形成され、風合いが硬くなってしまうといった問題が発生しやすいため好ましくない。またループの動きが制限されてしまい、クッション性や風合いが硬くなるという問題が発生しやすく好ましくない。 In the polyester-based elastic network structure of the present invention, it is preferable that a resin containing a silicone-based resin adheres to the random loop surface in an amount of 0.4 to 4% by weight based on the weight of the network structure. A network structure made of a polyester copolymer having a relatively low surface hardness, such as the polyester-based elastic network structure of the present invention, is likely to be in a pseudo-bonded state in which fibers are lightly bonded to each other when compressed. When the fibers are separated from each other during the recovery from the compression, a “necha” peeling sound is likely to occur. This depends on the polymer properties of the polyester copolymer. In order to reduce this peeling sound, it is preferable that a resin containing a silicone resin is adhered to the surface of the random loop of the polyester-based elastic network structure in a range of 0.4 to 4% by weight with respect to the network structure weight. If the adhesion amount is less than 0.4% by weight, it is not preferable because it is difficult to suppress the pseudo-adhesion between the fibers, and if it exceeds 4% by weight, a resin film is formed in the loop and the texture becomes hard. It is not preferable because problems are likely to occur. Further, the movement of the loop is limited, and the problem that the cushioning property and the texture become hard is likely to occur, which is not preferable.
シリコーン系樹脂については特に限定されないが、静粛性からは環状シロキサンが好ましく、耐久性の点からバインダー機能があることや、作業性からアニオン系であることが好ましく、例えば北広ケミカル社製のＴＦ−３５００が一例としてあげられる。シリコーン系樹脂は単独、あるいは必要により２種以上併用することができる。 Although it does not specifically limit about a silicone type resin, Cyclic siloxane is preferable from quietness, It has a binder function from a durable point, and it is preferable that it is anionic from workability, for example, TF-made by Kitahiro Chemical Co., Ltd. 3500 is an example. Silicone resins can be used alone or in combination of two or more if necessary.
本発明のポリエステル系弾性網状構造体を構成する連続線状体の断面形状は特に限定されないが、表面硬度が４２Ｄ以下のポリエステル共重合体を用いる時には、中空断面形状が網状構造体の反発力が向上するので好ましい。好ましい中空率の範囲は１５％以上５０％以下であり、１５％未満であると充分な反発力が得られにくくなるので好ましくなく、また５０％を越えると中空断面が丸ではなく変形した中空断面となり易く、安定したクッション性が得られにくくなるため好ましくない。 The cross-sectional shape of the continuous linear body constituting the polyester-based elastic network structure of the present invention is not particularly limited, but when a polyester copolymer having a surface hardness of 42D or less is used, the hollow cross-sectional shape has a repulsive force of the network structure. Since it improves, it is preferable. The range of the hollow ratio is preferably 15% or more and 50% or less, and if it is less than 15%, it is difficult to obtain a sufficient repulsive force, and if it exceeds 50%, the hollow section is not round but deformed. Since it becomes difficult to obtain a stable cushioning property, it is not preferable.
本発明のポリエステル系弾性網状構造体は、ランダムループ表面に付着しているシリコーン系樹脂がカルボキシル基を有するポリエステル系バインダー、及び架橋剤で固着されていることが好ましい。ポリエステル系バインダー及び架橋剤により、シリコーン系樹脂は網状構造体のランダムループに一層強固に接着されるだけでなく、衝突及び擦れによるギシギシ音が一層軽減される効果があることがわかった。ポリエステル系バインダーは特に限定されないが、セバシン酸やテレフタル酸、５−ナトリウムスルホイソフタル酸等のジカルボン酸とエチレングリコールやネオペンチルグリコール等のグリコールから重縮合されたものが好ましく、さらには酸成分としてトリメリット酸を重縮合させた一部にカルボキシル基を有する飽和ポリエステル樹脂であることが好ましい。またイオン性についてはシリコーン系樹脂と同じアニオン系であることが好ましく、例えば日本ポリマリック有限会社製アクアマックＡ−８６４が一例としてあげられる。ポリエステル系バインダーは単独、あるいは必要により２種以上併用することができる。架橋剤については特に限定されないが、カルボジイミド基を有するものが好ましく、例えば日本ポリマリック有限会社製のカタリストＥ−０３Ａが一例としてあげられる。架橋剤は単独、あるいは必要により２種以上併用することができる。 In the polyester-based elastic network structure of the present invention, the silicone-based resin adhering to the random loop surface is preferably fixed with a polyester-based binder having a carboxyl group and a crosslinking agent. It has been found that the polyester-based binder and the cross-linking agent not only cause the silicone-based resin to be more firmly bonded to the random loop of the network structure but also have an effect of further reducing the squeaking noise caused by collision and rubbing. The polyester binder is not particularly limited, but is preferably a polycondensate of dicarboxylic acid such as sebacic acid, terephthalic acid or 5-sodiumsulfoisophthalic acid and glycol such as ethylene glycol or neopentyl glycol. A saturated polyester resin having a carboxyl group in a part obtained by polycondensation of merit acid is preferable. The ionicity is preferably the same anionic type as that of the silicone resin. For example, Aquamac A-864 manufactured by Nippon Polymeric Co., Ltd. can be mentioned as an example. Polyester binders can be used alone or in combination of two or more if necessary. Although it does not specifically limit about a crosslinking agent, What has a carbodiimide group is preferable, For example, Nippon Polymer Co., Ltd. Catalist E-03A is mention | raise | lifted as an example. The crosslinking agents can be used alone or in combination of two or more if necessary.
本発明のポリエステル系弾性網状構造体の製造方法としては、シリコーン系樹脂とカルボキシル基を有するポリエステル系バインダー及び架橋剤を、ｐＨ５〜８の水系エマルジョンとして弾性網状構造体に付着させ、４０〜１３０℃で乾燥処理することが好ましい。水系エマルジョンのｐＨが５未満であると常温で反応が進みやすくエマルジョンが安定せず、一部凝集が発生してしまうため好ましくない。また、ｐＨが８を越えると高温にしても反応が進みにくく、シリコーン系樹脂やポリエステル系バインダーが固着しにくくなるため好ましくない。有機溶媒にシリコーン系樹脂を溶解させたものを弾性網状構造体に付着させても製造することは可能であるが、人体への影響や系外に放出され環境を汚染することを勘案すると好ましくない。 As a method for producing the polyester-based elastic network structure of the present invention, a silicone-based resin, a polyester-based binder having a carboxyl group and a crosslinking agent are attached to the elastic network structure as a water-based emulsion having a pH of 5 to 8, and the temperature is 40 to 130 ° C. It is preferable to dry-process with. If the pH of the aqueous emulsion is less than 5, the reaction is likely to proceed at room temperature, the emulsion is not stable, and partial agglomeration occurs, which is not preferable. On the other hand, if the pH exceeds 8, the reaction is difficult to proceed even at a high temperature, and the silicone resin and the polyester binder are not easily fixed. Although it is possible to manufacture by dissolving a silicone resin in an organic solvent and attaching it to an elastic network structure, it is not preferable in consideration of the influence on the human body and the release of the system to pollute the environment. .
乾燥温度は４０℃未満であると反応が進みにくく、シリコーン系樹脂やポリエステル系バインダーが固着しにくくなるため好ましくない。また、乾燥温度が１３０℃を越えると、ポリエステル系弾性網状構造体が軟化し、厚みが低下してしまいやすくなるため好ましくない。 When the drying temperature is less than 40 ° C., the reaction is difficult to proceed, and the silicone resin and the polyester binder are not easily fixed, which is not preferable. On the other hand, when the drying temperature exceeds 130 ° C., the polyester-based elastic network structure is softened and the thickness tends to decrease, which is not preferable.
弾性網状構造体は実際の使用に際して多層に重ねても良く、弾性網状構造体層を複合化（一体接着構造）したものとして、エラストマー層／非エラストマー層／エラストマー層のサンドウィッチ構造、エラストマー層／非エラストマー層の２層構造、マトリックスのエラストマー層の内部に部分的に非エラストマー層を配した複合化構造が挙げられる。 The elastic network structure may be stacked in multiple layers in actual use, and the elastic network structure layer is composited (integrated adhesion structure) as an elastomer layer / non-elastomeric layer / elastomeric layer sandwich structure, elastomer layer / non-elastic layer. Examples thereof include a two-layer structure of an elastomer layer and a composite structure in which a non-elastomeric layer is partially disposed inside an elastomer layer of a matrix.
本発明の弾性網状構造体は、要求性能との関係で、ループの大きさの異なるもの、デシテックスの異なるもの、組成の異なるもの、密度の異なるもの等の夫々の網状構造体を適宜選択し、積層あるいは混合してもよい。 The elastic network structure of the present invention is appropriately selected from the respective network structures such as those having different loop sizes, different decitex, different compositions, different densities, etc. in relation to the required performance. You may laminate or mix.
更には、積層構造体表面に必要に応じ、硬綿クッション、好ましくはエラストマー使いの熱接着繊維からなる硬綿クッションを、第二層として配した複合化構造であってもかまわない。 Furthermore, it may be a composite structure in which a hard cotton cushion, preferably a hard cotton cushion made of an elastomeric heat-bonding fiber, is disposed as the second layer on the surface of the laminated structure.
本発明の弾性網状構造体は、シリコーン系樹脂を含む樹脂に、網状構造体重量に対し顔料を０．０１〜１５重量％含有させることが好ましい。樹脂に顔料を添加する目的として、樹脂の付着状態が均一であることを目視確認すること、および着色による意匠性の向上をはかることにある。顔料の代わりに染料を用いた場合は、汗等の水分を含んだ状態で側地と弾性網状構造体が接触し擦れた時、弾性網状構造体の表面に染料が存在すると側地に色移りが起きてしまうため好ましくない。それに対し、顔料であれば汗などの水分に溶けることなどなく、そのような問題が起こらないため好ましい。 The elastic network structure of the present invention preferably contains 0.01 to 15% by weight of a pigment based on the weight of the network structure in a resin containing a silicone resin. The purpose of adding the pigment to the resin is to visually confirm that the adhesion state of the resin is uniform, and to improve the design by coloring. When a dye is used instead of a pigment, when the side base and the elastic network structure are in contact with and rubbed with moisture such as sweat, the color will transfer to the side base if the dye is present on the surface of the elastic network structure. Is not preferable because it will occur. In contrast, pigments are preferred because they do not dissolve in moisture such as sweat and do not cause such problems.
顔料が網状構造体重量に対し０．０１重量％未満であれば、樹脂が付着している状態を見極めにくくなり、品質管理がしにくくなるため好ましくない。また、１５重量％を超えるとコストが高くなってしまうだけでなく、樹脂の接着強度を低下させてしまうため好ましくない。より好ましい顔料の含有量は、０．０３〜１０重量％であり、さらに好ましくは０．０５〜５重量％である。 If the pigment is less than 0.01% by weight based on the weight of the network structure, it is difficult to determine the state where the resin is adhered, and it is difficult to control the quality, which is not preferable. On the other hand, if it exceeds 15% by weight, not only the cost is increased, but also the adhesive strength of the resin is lowered. The content of the pigment is more preferably 0.03 to 10% by weight, still more preferably 0.05 to 5% by weight.
本発明の弾性網状構造体に付着させるシリコーン系樹脂を含む樹脂には、本発明の弾性網状構造体のクッション特性を著しく低下させない範囲で、顔料以外に、抗菌剤、防かび剤、防虫（防ダニ）忌避剤、抗アレルゲン剤（アレルギー沈静化剤）、吸放湿剤、吸湿発熱剤、相変換型温度調節剤（ＭＣＰ）、芳香剤、吸水剤、撥水剤、撥水撥油剤、防汚剤、耐光剤、耐候剤、光触媒系加工剤、柔軟剤、硬化剤、架橋剤、ダル剤などを混合しても良い。その場合は、それらの成分を含めたもの全体を樹脂の付着量と定義する。 In addition to pigments, the resin containing a silicone resin that adheres to the elastic network structure of the present invention does not significantly deteriorate the cushioning properties of the elastic network structure of the present invention. Tick) repellent, anti-allergen (allergy calming agent), moisture-absorbing / releasing agent, moisture-absorbing exothermic agent, phase-converting temperature regulator (MCP), fragrance, water-absorbing agent, water-repellent agent, water- and oil-repellent agent, prevention A soiling agent, a light resistance agent, a weather resistance agent, a photocatalytic processing agent, a softening agent, a curing agent, a crosslinking agent, a dull agent, and the like may be mixed. In that case, the whole thing including those components is defined as the amount of resin adhesion.
また樹脂の付与方法としてスプレー法、浸漬法、シャワー法、などいずれの方法でもかまわない。また、過剰に付着した樹脂を除去するために加圧ローラーによる搾り、振動、振盪、加圧空気の噴きつけ等適宜選択して採用することができる。 Moreover, any method such as a spray method, a dipping method, or a shower method may be used as a resin application method. In addition, in order to remove the excessively adhered resin, it can be appropriately selected and employed, such as squeezing with a pressure roller, vibration, shaking, and blowing of pressurized air.
以下に、実施例を例示し、本発明を具体的に説明するが、本発明はこれらによって限定されるものではない。なお、実施例中における特性値の測定及び評価は下記のようにおこなった。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the measurement and evaluation of the characteristic value in an Example were performed as follows.
（１）繊度
試料を２０ｃｍ×２０ｃｍの大きさに切断し、１０か所から線状体を採集する。１０か所で採集した線状体の４０℃での比重を密度勾配管を用いて測定する。更に、上記１０か所で採集した線状体の断面積を顕微鏡で３０倍に拡大した写真より求め、それより線状体の長さ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（線状体１００００ｍ分の重量）とする（ｎ＝１０の平均値）。
(1) Fineness A sample is cut into a size of 20 cm × 20 cm, and linear bodies are collected from 10 locations. The specific gravity at 40 ° C. of the linear bodies collected at 10 locations is measured using a density gradient tube. Furthermore, the cross-sectional area of the linear body collected at the 10 locations is determined from a photograph magnified 30 times with a microscope, and the volume of the linear body having a length of 10,000 m is determined from the photograph. The value obtained by multiplying the obtained specific gravity and volume is defined as the fineness (weight of linear body 10,000 m) (average value of n = 10).
（２）シリコーン系樹脂を含む樹脂および顔料の付着量
加工前の弾性網状構造体の重量（ｅ）と加工乾燥後の重量（ｆ）を量り、次式にて算出して求めた。
すなわち｛（ｆ−ｅ）／（ｅ）｝×１００より算出する：単位重量％。
(2) Adhesion amount of resin and pigment containing silicone resin The weight (e) of the elastic network structure before processing and the weight (f) after processing and drying were measured and calculated by the following formula.
That is, it is calculated from {(fe) / (e)} × 100: unit weight%.
（３）原料の曲げ弾性率
ＡＳＴＭ Ｄ７９０法に準拠した。
(3) Flexural modulus of raw material It conformed to ASTM D790 method.
（４）表面硬度
ＡＳＴＭ Ｄ２２４９法に準拠した。
(4) Surface hardness It conformed to ASTM D2249 method.
＜実施例１＞
東洋紡績株式会社製の「ペルプレン（登録商標）タイプＰ―４０Ｈ」を用い、抗酸化剤１％を添加混合練込み後ペレット化し、８０℃２４時間真空乾燥して熱可塑性弾性樹脂原料を得た。得られた樹脂の曲げ弾性率と表面硬度を表１に示す。
<Example 1>
Using “Perprene (registered trademark) type P-40H” manufactured by Toyobo Co., Ltd., 1% antioxidant was added, kneaded, pelletized, and vacuum dried at 80 ° C. for 24 hours to obtain a thermoplastic elastic resin raw material. . Table 1 shows the flexural modulus and surface hardness of the obtained resin.
得られた熱可塑性弾性樹脂原料を幅７０ｃｍ、長さ７ｃｍのノズル有効面にＣ型断面をしたノズルより、２４０℃で溶融して、ノズル面２０ｃｍ下に冷却水を配し、幅６０ｃｍのステンレス製エンドレスネットを平行に２．５ｃｍ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、７０℃に加熱した冷却水中へ引込み固化させ、その後、１ｍの長さに切断した。その結果、両面がフラット化された、密度が５０ｋｇ／ｍ３の弾性網状構造体を得た。弾性網状構造体の線状体の繊度は２０００デシテックスであった。弾性網状構造体を圧縮、開放を繰り返すとギシギシという軋み音とネチャという剥がれ音がした。 The obtained thermoplastic elastic resin material was melted at 240 ° C. from a nozzle having a C-shaped cross section on a nozzle effective surface of 70 cm width and 7 cm length, and cooling water was disposed 20 cm below the nozzle surface, and stainless steel having a width of 60 cm. A pair of take-up conveyors are placed in parallel on the surface of the water at 2.5 cm intervals in parallel with the endless net made, and the contact part is fused, while the both sides are sandwiched, at a speed of 1 m / min. Then, it was drawn into cooling water heated to 70 ° C. and solidified, and then cut to a length of 1 m. As a result, an elastic network structure having both surfaces flattened and a density of 50 kg / m 3 was obtained. The fineness of the linear body of the elastic network structure was 2000 dtex. When the elastic net-like structure was repeatedly compressed and released, it was squeaking and squealing.
後加工として、北広ケミカル株式会社製ＴＦ−３５００（シリコーン系バインダー）を２０重量％、日本ポリマリック有限会社製アクアマックＡ−８６４（ポリエステル系バインダー）を３２重量％、日本ポリマック有限会社製カタリストＥ−０３Ａ（架橋剤）を２重量％、青色顔料０．２重量％、イオン交換水４５．８重量％をエマルジョン化し、ｐＨを６．８に調整して混合した混合液を、弾性網状構造体にディップ処方にて付与し、８５℃で１０分間乾燥させた。重量比較から樹脂の弾性網状構造体に対する付着量は１．２重量％であった。得られた弾性網状構造体はヒステリシスロスが少なく、圧縮時のギシギシ音や回復時のネチャという剥がれ音がかなり小さいものであった。 As post-processing, 20% by weight of TF-3500 (silicone binder) manufactured by Kitahiro Chemical Co., Ltd., 32% by weight of Aquamac A-864 (polyester binder) manufactured by Nippon Polymeric Co., Ltd., Catalyst E manufactured by Nippon Polymac Co., Ltd. An elastic network structure was prepared by emulsifying 2% by weight of -03A (crosslinking agent), 0.2% by weight of blue pigment, and 45.8% by weight of ion-exchanged water, adjusting the pH to 6.8 and mixing. Was applied by dip formulation and dried at 85 ° C. for 10 minutes. From the weight comparison, the adhesion amount of the resin to the elastic network structure was 1.2% by weight. The obtained elastic network structure had little hysteresis loss, and a peeling sound such as a squeaking sound during compression and a sticky sound during recovery was considerably small.
＜実施例２＞
繊維断面が中実丸断面になるようにノズルオリフィスを丸型にし、後加工時の乾燥温度を１４０℃にした以外は実施例１に従って、弾性網状構造体を得た。乾燥温度が高かったため、網状弾性体が軟化して、乾燥時に２５ｍｍから２０ｍｍに厚みが減少したものの、静粛性にかなり優れたものであった。
<Example 2>
An elastic network structure was obtained according to Example 1 except that the nozzle orifice was rounded so that the fiber cross-section was a solid round cross-section, and the drying temperature during post-processing was 140 ° C. Since the drying temperature was high, the net-like elastic body was softened and the thickness was reduced from 25 mm to 20 mm during drying, but the silence was considerably excellent.
＜参考例１＞
後加工時のエマルジョンを、日本ポリマリック有限会社製アクアマックＡ−８６４（ポリエステル系バインダー）を３２重量％、日本ポリマック有限会社製カタリストＥ−０３Ａ（架橋剤）を２重量％添加せず、イオン交換水を７７．８重量％にした以外は実施例１に従った。側地でくるんだ時に、被膜が剥がれ、側地に付着したものの、静粛性に優れたものであった。
< Reference Example 1 >
Emulsion at the time of post-processing was added without adding 32% by weight of Aquamac A-864 (polyester binder) manufactured by Nippon Polymeric Co., Ltd. and 2% by weight of Catalyst E-03A (crosslinking agent) manufactured by Nippon Polymac Co. Example 1 was followed except that the exchange water was 77.8% by weight. When wrapped around the side, the film peeled off and adhered to the side, but it was excellent in quietness.
＜実施例３＞
後加工時のエマルジョンのｐＨを９．０に調整した以外は実施例１に従った。アルカリサイドであったため、反応が余り進んでおらず、側地でくるんだ時に、被膜が剥がれ、側地に付着したものの、静粛性に優れたものであった。
<Example 3 >
Example 1 was followed except that the pH of the emulsion during post-processing was adjusted to 9.0. Since it was an alkali side, the reaction did not progress so much, and when it was wrapped in the side, the film was peeled off and adhered to the side, but it was excellent in quietness.
＜実施例４＞
後加工時のエマルジョンのｐＨを４．０に調整した以外は実施例１に従った。エマルジョンの分散性が悪く、凝集が発生し作業性に困難をきたしたが、静粛性に優れたものであった。
<Example 4 >
Example 1 was followed except that the pH of the emulsion during post-processing was adjusted to 4.0. Although the dispersibility of the emulsion was poor and aggregation occurred and the workability was difficult, it was excellent in quietness.
＜比較例１＞
弾性網状構造体の原料として、東洋紡績株式会社製の「ペルプレン（登録商標）タイプＰ−７０Ｂ」を用いた以外は実施例１に従った。得られた樹脂の曲げ弾性率と表面硬度を表１に示す。原料ポリマーが硬いため、圧縮回復時のネチャ音は無かったものの、圧縮時のギシギシ音がうるさいものであった。
<Comparative Example 1>
Example 1 was followed except that “Perprene (registered trademark) type P-70B” manufactured by Toyobo Co., Ltd. was used as a raw material for the elastic network structure. Table 1 shows the flexural modulus and surface hardness of the obtained resin. Since the raw material polymer was hard, there was no sticky sound at the time of compression recovery, but the squeaking sound at the time of compression was noisy.
＜比較例２＞
弾性網状構造体の原料として、東洋紡績株式会社製の「ペルプレン（登録商標）タイプＰ−３０Ｂ」を用いた以外は実施例１に従った。得られた樹脂の曲げ弾性率と表面硬度を表１に示す。原料ポリマーがかなり柔らかいため、乾燥時に網状構造体の厚みが半減してしまうという問題が発生した。音に関しては圧縮時のギシギシ音は無かったものの、圧縮回復時のネチャ音がうるさいものであった。
<Comparative example 2>
Example 1 was followed except that “Perprene (registered trademark) type P-30B” manufactured by Toyobo Co., Ltd. was used as a raw material for the elastic network structure. Table 1 shows the flexural modulus and surface hardness of the obtained resin. Since the raw material polymer is quite soft, there has been a problem that the thickness of the network structure is halved during drying. As for the sound, there was no squeaking noise at the time of compression, but the noise at the time of compression recovery was noisy.
＜比較例３＞
後加工時のエマルジョンの北広ケミカル株式会社製ＴＦ−３５００（シリコーン系バインダー）の代わりに東洋紡績株式会社製「バイロナール（登録商標）ＭＤ−１４８０」（ポリエステル系）を用い、弾性網状構造体に対する樹脂付着量を４．５重量％にした以外は実施例１に従った。シリコーン系樹脂がなかったために、圧縮回復時のネチャ音がうるさいものであった。また、樹脂付着量が多かったため、風合いや作業性が悪いものであった。
<Comparative Example 3>
Resin for elastic network structure by using “Vylonal (registered trademark) MD-1480” (polyester) manufactured by Toyobo Co., Ltd. instead of TF-3500 (silicone-based binder) manufactured by Kitahiro Chemical Co., Ltd. Example 1 was followed except that the amount deposited was 4.5% by weight. Since there was no silicone-based resin, the noise from the compression recovery was noisy. Moreover, since there was much resin adhesion amount, the texture and workability | operativity were bad.
＜比較例４＞
弾性網状構造体に対する樹脂付着量を０．２重量％にした以外は実施例１に従った。シリコーン系樹脂が少なかったために、圧縮回復時のネチャ音がうるさいものであった。
<Comparative example 4>
Example 1 was followed except that the amount of resin adhered to the elastic network structure was 0.2% by weight. Due to the small amount of silicone resin, the sticky sound during compression recovery was noisy.
耐久性、クッション性の優れた蒸れ難く、特に圧縮および回復時の音を低減した弾性網状構造体は寝具等のクッション体に好適に利用できる。
An elastic net-like structure that has excellent durability and cushioning properties and is less likely to be stuffy, and particularly reduced in sound during compression and recovery, can be suitably used for cushions such as bedding.
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| JP5978674B2 (en) * | 2011-09-16 | 2016-08-24 | 東洋紡株式会社 | Elastic network structure with high vibration absorption |
| JP6115015B2 (en) * | 2011-09-16 | 2017-04-19 | 東洋紡株式会社 | Elastic network structure with excellent quietness and hardness |
| JP5966472B2 (en) * | 2011-09-16 | 2016-08-10 | 東洋紡株式会社 | Elastic network structure with high vibration absorption |
| JP5966471B2 (en) * | 2011-09-16 | 2016-08-10 | 東洋紡株式会社 | Elastic network structure with excellent quietness and hardness |
| TWI597232B (en) * | 2012-05-07 | 2017-09-01 | 東洋紡股份有限公司 | Elastic reticular structure with excellent silence and hardness |
| JP2014064767A (en) * | 2012-09-26 | 2014-04-17 | Toyobo Co Ltd | Cushion |
| JP6011204B2 (en) * | 2012-09-26 | 2016-10-19 | 東洋紡株式会社 | bedding |
| JP5569641B1 (en) | 2013-10-28 | 2014-08-13 | 東洋紡株式会社 | Elastic network structure with excellent quietness and lightness |
| JP7370980B2 (en) * | 2017-08-17 | 2023-10-30 | サータ シモンズ ベディング エルエルシー | 3D polymer fiber matrix layer for bedding products |
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| JPH08188945A (en) * | 1995-01-09 | 1996-07-23 | Toray Ind Inc | Formed article of fiber and its production |
| JP2003169729A (en) * | 2001-12-06 | 2003-06-17 | Toyobo Co Ltd | Portable rug |
| JP2004149959A (en) * | 2002-10-30 | 2004-05-27 | Toyobo Co Ltd | Shock absorbing pad for attachment and product using the same |
| JP2004218219A (en) * | 2003-01-10 | 2004-08-05 | Toyobo Co Ltd | Flooring excellent in functionality and mattress |
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