【０００１】0001
【産業上の利用分野】本発明は熱可塑性エラストマー不
織布に関する。より詳しくは低モジュラス、高伸縮性、
耐候性に優れ、特に湿布基布などで伸縮性を要求される
用途に好適な熱可塑性エラストマーからなる不織布に関
するものである。FIELD OF THE INVENTION This invention relates to thermoplastic elastomer nonwoven fabrics. More details: low modulus, high elasticity,
The present invention relates to a nonwoven fabric made of a thermoplastic elastomer that has excellent weather resistance and is particularly suitable for applications that require elasticity, such as a poultice base fabric.
【０００２】0002
【従来の技術】従来から伸縮性不織布に対する要望は不
織布業界において盛んでありいろいろなものが出されて
いる。例えば湿布基布として繊維の捲縮を利用した伸縮
性不織布などがあるが伸びや弾性回復性などは不充分で
ある。又ポリマーとしてポリアミド、ポリオレフィン、
ポリエステル系のエラストマーがあるが充分な伸長性は
得られない。なかんずくポリウレタンによる不織布は伸
縮性の点で良好である（特開昭５９−２２３３４７号ほ
か）。しかし湿布基布などに使用するには目が粗く湿布
薬を塗布しにくい、又モジュラスがやや高いためこの用
途に適さないとか耐候性不良、黄変発生などの欠点があ
る。これに対して本発明者らは、特願平２−１０８１７
４号において本発明で使用するブロック共重合体からな
る伸縮性不織布を提案した。この提案によって、伸縮性
及び弾性回復性は十分なものとなり、同時に耐候性も向
上し、黄変など変色の発生も解消された。BACKGROUND OF THE INVENTION There has been a strong demand for stretchable nonwoven fabrics in the nonwoven fabric industry, and various types of fabrics have been proposed. For example, stretchable nonwoven fabrics that utilize fiber crimping are available as poultice base fabrics, but they are insufficient in terms of elongation and elastic recovery. Polyamides, polyolefins,
There are polyester-based elastomers, but they do not have sufficient extensibility. Above all, nonwoven fabrics made of polyurethane have good elasticity (JP-A-59-223347 et al.). However, when used as a poultice base fabric, it has drawbacks such as its rough texture making it difficult to apply poultices, and its slightly high modulus making it unsuitable for this purpose, poor weather resistance, and yellowing. In contrast, the present inventors have proposed patent application No. 2-10817
In No. 4, we proposed a stretchable nonwoven fabric made of a block copolymer for use in the present invention. With this proposal, stretchability and elastic recovery were sufficient, weather resistance was improved, and discoloration such as yellowing was eliminated.
【０００３】しかし、その後の検討の結果、この提案に
よる不織布はロール上に巻き取って長期間放置するとブ
ロック共重合体の粘着性のために、不織布間で膠着を生
じロールを解舒して使用せんとしても解舒不良となると
いう欠点が明らかとなった。However, as a result of subsequent studies, it was found that when the nonwoven fabric according to this proposal is wound on a roll and left for a long period of time, due to the stickiness of the block copolymer, the nonwoven fabrics tend to stick together, making it difficult to unwind the roll and use it. However, it has become clear that the problem is that even if the method is not used, unraveling will be defective.
【０００４】これに対して本発明者らは特願平２−２５
８２７２号において、ブロック共重合体に対してポリオ
レフィンを５〜３０重量％配合することによって、上記
不織布間での膠着解消を提案した。[0004] In response to this, the present inventors filed Japanese Patent Application No. 2-25
In No. 8272, it was proposed to eliminate sticking between the above-mentioned nonwoven fabrics by blending 5 to 30% by weight of polyolefin with respect to the block copolymer.
【０００５】これによって膠着問題はほぼ解決したもの
の、その後の検討でポリオレフィンの配合比率が１５重
量％以下のものはロール状に巻き取った該不織布を毎分
２０ｍ／分以上の速度で解舒した場合には不織布間の僅
かな膠着が原因となって解舒不良を生じることが明らか
になった。[0005] Although this almost solved the sticking problem, subsequent studies revealed that in cases where the blending ratio of polyolefin was 15% by weight or less, the nonwoven fabric wound into a roll was unwound at a speed of 20 m/min or more. It has become clear that in some cases, slight adhesion between nonwoven fabrics causes unwinding failure.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記の提案
の伸縮性、弾性回復性に優れかつ耐候性が良好で黄変な
どの変色のないブロック共重合体からなる伸縮性不織布
の優れた特長を損なうことなく、上記の不織布の膠着を
完全に防止し高速でも安定に解舒できるようにすること
にある。[Problems to be Solved by the Invention] The present invention provides an excellent stretchable nonwoven fabric made of a block copolymer having excellent stretchability and elastic recovery properties, good weather resistance, and no discoloration such as yellowing. The object of the present invention is to completely prevent the above-mentioned nonwoven fabric from sticking without sacrificing its features and to enable stable unwinding even at high speeds.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の問
題点を解決すべく鋭意検討した結果、下記の構成により
解決できることを見いだし、本発明に到達した。[Means for Solving the Problems] The present inventors have made extensive studies to solve the above-mentioned problems, and as a result, have found that the problems can be solved by the following configuration, and have arrived at the present invention.
【０００８】すなわち、本発明は、（１） 芳香族ビ
ニル化合物を主体とする重合体ブロックＡが１０〜５０
重量％と下記［１］式および［２］式（但し、［２］式
は０〜２０モル％の範囲）で表わされる繰返し単位を主
体とする重合体ブロックＢが９０〜５０重量％とよりな
るブロック共重合体９４．５〜８３重量％と結晶性ポリ
オレフィン５〜１５重量％と炭素数１６〜３６の長鎖の
脂肪酸１〜３個がアンモニア又は炭素数５以下のアミン
と結合した脂肪酸アミド、炭素数５以下のアルコールと
結合した脂肪酸エステル及び該脂肪酸のカルシウム塩の
群から選ばれた少なくとも一つの脂肪酸化合物０．５〜
２．０重量％との混合ポリマーの繊維からなる高伸縮性
不織布。であり、That is, the present invention provides (1) a polymer block A mainly composed of an aromatic vinyl compound having 10 to 50
90 to 50% by weight of polymer block B mainly composed of repeating units represented by the following formulas [1] and [2] (however, formula [2] is in the range of 0 to 20 mol%) A fatty acid amide in which 94.5 to 83% by weight of a block copolymer, 5 to 15% by weight of crystalline polyolefin, and 1 to 3 long-chain fatty acids with 16 to 36 carbon atoms are combined with ammonia or an amine with 5 or less carbon atoms. , at least one fatty acid compound selected from the group of fatty acid esters combined with alcohols having 5 or less carbon atoms, and calcium salts of the fatty acids.
Highly elastic nonwoven fabric consisting of fibers of mixed polymer with 2.0% by weight. and
【０００９】（２） 芳香族ビニル化合物を主体とす
る重合体ブロツクＡが１０〜５０重量％と下記［１］式
および［２］式（但し、［２］式は０〜２０モル％の範
囲）で表わされる繰返し単位を主体とする重合体ブロッ
クＢが９０〜５０重量％とよりなるブロック共重合体９
４．５〜８３重量％、結晶性ポリオレフィン５〜１５重
量％及び炭素数１６〜３６の長鎖の脂肪酸１〜３個がア
ンモニア又は炭素数５以下のアミンと結合した脂肪酸ア
ミド、炭素数５以下のアルコールと結合した脂肪酸エス
テル及び該脂肪酸のカルシウム塩の群から選ばれた少な
くとも一つの脂肪酸化合物０．５〜２．０重量％を混合
溶融しメルトブローすることを特徴とする高伸縮性不織
布の製造法。(2) Polymer block A mainly composed of an aromatic vinyl compound is 10 to 50% by weight and the following formulas [1] and [2] (however, formula [2] is in the range of 0 to 20 mol%) ) Block copolymer 9 consisting of 90 to 50% by weight of polymer block B mainly consisting of repeating units represented by
4.5 to 83% by weight, 5 to 15% by weight of crystalline polyolefin, and fatty acid amide in which 1 to 3 long chain fatty acids with 16 to 36 carbon atoms are combined with ammonia or amine with 5 or less carbon atoms, 5 or less carbon atoms Production of a highly elastic nonwoven fabric characterized by mixing and melt-blowing 0.5 to 2.0% by weight of at least one fatty acid compound selected from the group of alcohol-bonded fatty acid esters and calcium salts of the fatty acids. Law.
【００１０】0010
【化３】[Chemical formula 3]
【００１１】（但し、［１］、［２］式においてＲ１〜
Ｒ４の内任意の１〜２個がメチル基であり、残りは水素
原子である。）である。[0011] (However, in formulas [1] and [2], R1 to
Any one or two of R4 are methyl groups, and the rest are hydrogen atoms. ).
【００１２】本発明におけるブロック共重合体は芳香族
ビニル化合物を主体とする重合体ブロックＡと、共役ジ
エン化合物を主体とする重合体ブロックＢ’よりなるブ
ロック共重合体を水素添加し、共役ジエンに基づく脂肪
族二重結合の８０％以上を水素添加することによって得
られる。The block copolymer of the present invention is obtained by hydrogenating a block copolymer consisting of a polymer block A mainly composed of an aromatic vinyl compound and a polymer block B' mainly composed of a conjugated diene compound. It is obtained by hydrogenating 80% or more of the aliphatic double bonds based on.
【００１３】本発明で言うところの芳香族ビニル化合物
としてはスチレンがコスト面も含め最も好ましい。また
、共役ジエンとしては１，３−ブタジエン、イソプレン
、ペンタジエン、ヘキサジエン等があるが本発明の目的
にはイソプレンが適している。[0013] As the aromatic vinyl compound referred to in the present invention, styrene is most preferable in terms of cost as well. Further, conjugated dienes include 1,3-butadiene, isoprene, pentadiene, hexadiene, etc., and isoprene is suitable for the purpose of the present invention.
【００１４】本発明で用いられる水素添加ブロツク共重
合体のスチレン含有量は、１０〜５０重量％の範囲であ
る。スチレンの含有量が１０％以下では成形性、耐熱性
が劣る。スチレンの含有量が５０重量％以上になると伸
縮性、柔軟性が低下し本発明の目的を達し得なくなる。The styrene content of the hydrogenated block copolymer used in the present invention ranges from 10 to 50% by weight. If the styrene content is less than 10%, moldability and heat resistance will be poor. If the styrene content exceeds 50% by weight, the elasticity and flexibility will decrease, making it impossible to achieve the object of the present invention.
【００１５】本発明で用いる水素添加ブロック共重合体
は共役二重結合に基づくイソプレン二重結合の８０％以
上、好ましくは９０％以上を水素添加されていることが
必要である。これ以下では溶融成形時に熱劣化を生じ易
く、また得られた不織布の耐候性も劣り問題である。In the hydrogenated block copolymer used in the present invention, 80% or more, preferably 90% or more of the isoprene double bonds based on conjugated double bonds must be hydrogenated. If it is less than this, thermal deterioration is likely to occur during melt molding, and the resulting nonwoven fabric also has poor weather resistance, which is a problem.
【００１６】次に本発明において重要な点として水素添
加ブロック共重合体（以下ＳＥＰＳと略称する）と結晶
性ポリオレフィンと炭素数１６〜３６の長鎖の脂肪酸１
〜３個がアンモニア又は炭素数５以下のアミンと結合し
た脂肪酸アミド、炭素数５以下のアルコールと結合した
脂肪酸エステル及び該脂肪酸のカルシウム塩の群から選
ばれた少なくとも一つの脂肪酸化合物（以下単に脂肪酸
化合物と略称する）との混合比率をＳＥＰＳ９４．５〜
８３重量％、結晶性ポリオレフィン５〜１５重量％、脂
肪酸化合物０．５〜２．０重量％とすることである。Next, an important point in the present invention is that a hydrogenated block copolymer (hereinafter abbreviated as SEPS), a crystalline polyolefin, and a long chain fatty acid 1 having 16 to 36 carbon atoms
At least one fatty acid compound (hereinafter simply referred to as fatty acid) selected from the group of fatty acid amides in which ~3 atoms are bonded to ammonia or amines having 5 or less carbon atoms, fatty acid esters bonded to alcohols having 5 or less carbon atoms, and calcium salts of the fatty acids. (abbreviated as “compound”) at SEPS94.5~
83% by weight, 5 to 15% by weight of crystalline polyolefin, and 0.5 to 2.0% by weight of fatty acid compound.
【００１７】すなわち、ＳＥＰＳの比率が９４．５重量
％を越えて大きい、つまり結晶性ポリオレフィンと脂肪
酸化合物の比率の和が５．５重量％に満たない（但し脂
肪酸化合物は０．５〜２．０重量％）場合においては、
得られた不織布をロール状に巻き取り放置しておくとＳ
ＥＰＳのもつ粘着性のため、不織布間で強固な膠着を生
じてロールから不織布を解舒することが出来なくなって
しまう。この粘着性はＳＥＰＳが非晶質でありかつまた
ブロック共重合体Ｂ部分のガラス転移点が室温より低い
ことにより生じるもので、正確な理由は分からないが、
結晶性ポリオレフィンがＳＥＰＳと溶融混合時の分散性
が良好で得られた混合繊維中に均一に微分散するものの
、相溶性が余り良くないため繊維表面に露出した状態に
なることにより発現すると考えられる上記膠着への防止
効果が結晶性ポリオレフィンの配合不足で発現しなかっ
たものと考えられる。That is, the ratio of SEPS is greater than 94.5% by weight, that is, the sum of the ratios of crystalline polyolefin and fatty acid compound is less than 5.5% by weight (however, the ratio of fatty acid compound is 0.5 to 2.5% by weight). 0% by weight), in the case of
If the obtained nonwoven fabric is wound into a roll and left to stand, S
Due to the adhesive nature of EPS, strong adhesion occurs between the nonwoven fabrics, making it impossible to unwrap the nonwoven fabrics from the roll. This stickiness is caused by the fact that SEPS is amorphous and the glass transition point of the block copolymer B portion is lower than room temperature. Although the exact reason is unknown,
Although crystalline polyolefin has good dispersibility when melt-mixing with SEPS and is finely dispersed uniformly in the resulting mixed fiber, the compatibility is not very good and it is thought that this occurs when it is exposed on the fiber surface. It is thought that the above-mentioned effect of preventing sticking was not achieved due to insufficient blending of the crystalline polyolefin.
【００１８】また、脂肪酸化合物のもつ滑性効果や離型
効果によって期待される上記膠着への防止効果も上記同
様、配合量不足で十分発現しなかったものと考えられる
。[0018] Furthermore, it is considered that the above-mentioned anti-sticking effect, which is expected due to the lubricating effect and mold release effect of the fatty acid compound, was not sufficiently expressed due to the insufficient amount of the fatty acid compound.
【００１９】それに対してＳＥＰＳの比率が８３重量％
に満たない、すなわち結晶性ポリオレフィンと脂肪酸化
合物の比率の和が１７重量％を越えて大きくなる（但し
脂肪酸化合物の比率は０．５〜２．０重量％）と、前記
不織布間の膠着の発生は全くなくなるものの、得られた
不織布はモジュラスが急激に大きくなり、伸縮性も大き
く減少してしまうというように結晶性ポリオレフィンの
性質の影響が大となって、本発明の不織布の特徴が失わ
れてしまう。[0019] On the other hand, the proportion of SEPS is 83% by weight.
In other words, if the sum of the ratios of crystalline polyolefin and fatty acid compounds exceeds 17% by weight (however, the ratio of fatty acid compounds is 0.5 to 2.0% by weight), adhesion between the nonwoven fabrics will occur. However, the modulus of the obtained nonwoven fabric suddenly increases and the elasticity greatly decreases, so that the properties of the crystalline polyolefin become so significant that the characteristics of the nonwoven fabric of the present invention are lost. I end up.
【００２０】したがって、ＳＥＰＳと、結晶性ポリオレ
フィンと脂肪酸化合物の混合物の混合比率はＳＥＰＳ９
４．５〜８３重量％、結晶性ポリオレフィンと脂肪酸化
合物の混合物５．５〜１７重量％（但し脂肪酸化合物の
比率は０．５〜２．０重量％）でなければならない。Therefore, the mixing ratio of SEPS and the mixture of crystalline polyolefin and fatty acid compound is SEPS9.
4.5 to 83% by weight, and the mixture of crystalline polyolefin and fatty acid compound should be 5.5 to 17% by weight (however, the proportion of fatty acid compound should be 0.5 to 2.0% by weight).
【００２１】次に本発明において重要な点としてＳＥＰ
Ｓ及び結晶性ポリオレフィンに加えて配合する化合物と
して炭素数１６〜３６の長鎖の脂肪酸１〜３個がアンモ
ニア又は炭素数５以下のアミンと結合した脂肪酸アミド
、炭素数５以下のアルコールと結合した脂肪酸エステル
及び該脂肪酸のカルシウム塩の群から選ばれた少なくと
も一つの脂肪酸化合物を用いることにある。Next, an important point in the present invention is SEP
In addition to S and the crystalline polyolefin, compounds to be blended include fatty acid amides in which 1 to 3 long-chain fatty acids with 16 to 36 carbon atoms are combined with ammonia or amines with 5 or less carbon atoms, and alcohols with 5 or less carbon atoms. The present invention consists in using at least one fatty acid compound selected from the group of fatty acid esters and calcium salts of fatty acids.
【００２２】この脂肪酸化合物は一般には合成樹脂用の
滑剤として知られるものである。ここで脂肪酸の炭素数
が１６未満の場合、化合物が低分子量であるためＳＥＰ
Ｓや結晶性ポリオレフィンへの相溶性が良くなり過ぎて
、本発明の目的であるＳＥＰＳ高弾性不織布の膠着防止
効果が発揮されない。それに対して炭素数が３６を越え
て大きくなったり、結合した脂肪酸の数が３を越えて大
きくなると、高分子量化してＳＥＰＳや結晶性ポリオレ
フィンとの相溶性が悪くなってそれらの中への分散が不
良となり、更に、メルトブローン中に激しくブリードア
ウトを生じてノズル汚れ、発煙等のためメルトブローン
の工程調子が著しく低下してしまう。炭素数が１６〜３
６、脂肪酸の数が１〜３の場合には、滑剤はＳＥＰＳに
対して適度の相溶性と分散性を示してメルトブローン中
のブリードアウトも極めて少なく、工程調子を損なうこ
ともない。[0022] This fatty acid compound is generally known as a lubricant for synthetic resins. Here, if the number of carbon atoms in the fatty acid is less than 16, the compound has a low molecular weight, so SEP
The compatibility with S and crystalline polyolefin becomes too good, and the anti-sticking effect of the SEPS highly elastic nonwoven fabric, which is the object of the present invention, is not exhibited. On the other hand, if the number of carbon atoms exceeds 36 or the number of bonded fatty acids exceeds 3, the molecular weight increases and the compatibility with SEPS and crystalline polyolefin deteriorates, making it difficult to disperse into them. In addition, severe bleed-out occurs during melt blowing, resulting in nozzle fouling, smoke generation, etc., and the process performance of melt blowing deteriorates significantly. Carbon number is 16-3
6. When the number of fatty acids is 1 to 3, the lubricant exhibits appropriate compatibility and dispersibility with SEPS, and bleed-out during melt-blowing is extremely small and does not impair process performance.
【００２３】前記のごとく、本発明において脂肪酸化合
物がＳＥＰＳ高伸縮不織布の巻取後の膠着防止を実現す
る正確なメカニズムは分からないが、脂肪酸化合物が本
来から有する滑性効果、離型効果と結晶性ポリオレフィ
ンの前記膠着防止作用とが加成的に発揮されるため、Ｓ
ＥＰＳのゴム状性質に由来するＳＥＰＳ高弾性不織布の
巻取時の膠着防止が実現されるものと推定される。As mentioned above, in the present invention, the exact mechanism by which the fatty acid compound prevents the SEPS highly elastic nonwoven fabric from sticking after being wound up is not known, but the fatty acid compound's inherent lubricating effect, mold release effect, and crystallization effect are unknown. Since the above-mentioned anti-sticking effect of the polyolefin is additively exhibited, S
It is presumed that the SEPS highly elastic nonwoven fabric, which is derived from the rubber-like properties of EPS, can be prevented from sticking during winding.
【００２４】次に本発明で重要な点は、ＳＥＰＳと結晶
性ポリオレフィン全体への脂肪酸化合物の配合量を０．
５〜２．０重量％にしなければならないことである。す
なわち、含有量が０．５重量％に満たない場合には上記
膠着防止効果が著しく小さくなってしまう。それに対し
て配合量が２重量％を越えて多くなると、メルトブロー
ン時にブリードアウトが発生しだして工程調子を低下さ
せ、また、得られた不織布の性能、特に耐光性を悪化さ
せる。従って、脂肪酸化合物の配合量は０．５〜２．０
重量％でなければならず好ましくは０．７〜１．０重量
％である。Next, the important point in the present invention is that the amount of fatty acid compound blended into the SEPS and the crystalline polyolefin as a whole is 0.
The content must be 5 to 2.0% by weight. That is, if the content is less than 0.5% by weight, the above-mentioned anti-sticking effect will be significantly reduced. On the other hand, if the blending amount exceeds 2% by weight, bleed-out will begin to occur during melt-blowing, deteriorating the process performance and also deteriorating the performance of the obtained nonwoven fabric, especially the light resistance. Therefore, the amount of fatty acid compound added is 0.5 to 2.0
It should be 0.7 to 1.0% by weight, preferably 0.7 to 1.0% by weight.
【００２５】本発明を満足する脂肪酸化合物は炭素数１
６〜３６の長鎖の脂肪酸１〜３個がアンモニア又は炭素
数５以下のアミンと結合した脂肪酸アミド、炭素数５以
下のアルコールと結合した脂肪酸エステル及び該脂肪酸
のカルシウム塩の群から選ばれた少なくとも一つの脂肪
酸化合物であり、例えばステアリン酸アミド、ステアリ
ン酸カルシウムなどが挙げられる。特に好ましいものと
してはステアリン酸エチレンビスアミドが挙げられる。これは炭素数３８と比較的長い分子鎖長をもつため極め
て良好な膠着防止効果を示すと同時に熱安定性も高いた
め、メルトブローンの様に比較的高温での溶融状態を経
ることが不可避な製造工程においても安定な工程調子が
維持される。[0025] The fatty acid compound satisfying the present invention has 1 carbon number.
selected from the group of fatty acid amides in which 1 to 3 long-chain fatty acids of 6 to 36 are combined with ammonia or amines having 5 or less carbon atoms, fatty acid esters in which 1 to 3 long-chain fatty acids of 6 to 36 are combined with alcohols having 5 or less carbon atoms, and calcium salts of the fatty acids. At least one fatty acid compound, such as stearamide, calcium stearate, and the like. Particularly preferred is ethylene bisamide stearate. Because it has a relatively long molecular chain length of 38 carbon atoms, it exhibits an extremely good anti-sticking effect and is also highly thermally stable, making it unavoidable to undergo a molten state at a relatively high temperature like melt-blown. Stable process conditions are maintained during the process.
【００２６】本発明においてＳＥＰＳと混合するポリオ
レフィンは、ポリエチレンやポリブチレンなどを使用す
ることも出来るが、膠着防止効果はポリプロピレンが最
も優れており、ポリプロピレンを使用することが好まし
い。ポリプロピレンが優れている理由は正確には分から
ないが、ＳＥＰＳと溶融混合時の分散性が良好で得られ
た混合繊維中に均一に微分散するものの、相溶性があま
りよくないため、繊維表面に露出した状態となりやすい
ためではないかと推定される。[0026] As the polyolefin to be mixed with SEPS in the present invention, polyethylene, polybutylene, etc. can be used, but polypropylene has the best anti-sticking effect, and it is preferable to use polypropylene. The exact reason why polypropylene is superior is not known, but although it has good dispersibility during melt mixing with SEPS and is finely dispersed uniformly in the resulting mixed fiber, its compatibility is not very good, so it does not form on the fiber surface. It is presumed that this is because they tend to be exposed.
【００２７】本発明で用いるＳＥＰＳは炭化水素溶媒中
、有機リチウム化合物あるいは金属ナトリウム等を開始
剤としたアニオン重合により得られる。水素添加反応は
、白金、パラジウム等の貴金属系、有機ニッケル化合物
、有機コバルト化合物あるいはこれらの化合物と他の有
機金属化合物との複合触媒により行うことが出来る。水素添加率は、ヨウ素価測定法により算出することがで
きる。The SEPS used in the present invention can be obtained by anionic polymerization in a hydrocarbon solvent using an organic lithium compound or metallic sodium as an initiator. The hydrogenation reaction can be carried out using a noble metal such as platinum or palladium, an organic nickel compound, an organic cobalt compound, or a composite catalyst of these compounds and other organic metal compounds. The hydrogenation rate can be calculated by the iodine value measurement method.
【００２８】本発明で用いられる熱可塑性エラストマー
は、上述したようなＳＥＰＳを必須成分としてなるもの
であるが、更に必要に応じてパラフィン系オイルなどの
水添物を添加し流動加工性を向上させることもできる。また、ポリマーの耐熱、耐候、難燃などの機能を更に向
上させるため各種添加剤を加えることも可能である。The thermoplastic elastomer used in the present invention has the above-mentioned SEPS as an essential component, but if necessary, a hydrogenated substance such as paraffin oil may be added to improve flowability. You can also do that. Furthermore, various additives can be added to further improve the heat resistance, weather resistance, flame retardance, and other functions of the polymer.
【００２９】本発明において、脂肪酸化合物のＳＥＰＳ
への配合方法は、一般的な組成物の製造に適したと同じ
方法が用いられる。例えば、一旦ヘンシルミキサーやリ
ボンブレンダー等でＳＥＰＳと脂肪酸化合物を混合後、
押出機によって溶融混練する方法、ＳＥＰＳと脂肪酸化
合物を直接２軸混練押出機中で溶融混練する方法、ＳＥ
ＰＳの溶融重合中に脂肪酸化合物を添加する方法等が用
いられる。In the present invention, SEPS of fatty acid compounds
The same method as that suitable for manufacturing a general composition is used for blending into the composition. For example, after mixing SEPS and a fatty acid compound using a Henshil mixer or ribbon blender,
A method of melt-kneading with an extruder, a method of melt-kneading SEPS and a fatty acid compound directly in a twin-screw kneading extruder, SE
A method of adding a fatty acid compound during melt polymerization of PS is used.
【００３０】本発明の高伸縮性不織布は脂肪酸化合物を
配合したＳＥＰＳを原料に用いて通常メルトブローンと
称せられる直接成形法すなわち、熱可塑性樹脂を溶融紡
糸し、これを高速の気体によつて繊維流とした後、シー
ト状に捕集して不織布を製造する方法により製造するこ
とが出来る。すなわち、特開昭４９−１０２５８号公報
、特開昭４９−４８９２１号公報、特開昭５０−１２１
５７０号公報等で種々提案される方法において、押出機
への原料ポリマーの供給をＳＥＰＳと結晶性ポリオレフ
ィンをペレット状で所定の比率になるように計量し混合
した後に行うように変更するだけで製造することが出来
る。The highly elastic nonwoven fabric of the present invention is produced using SEPS blended with a fatty acid compound as a raw material, by a direct molding method usually called melt-blowing, that is, by melt-spinning a thermoplastic resin, and then forming a fiber stream using a high-speed gas. After that, it can be collected in a sheet form to produce a nonwoven fabric. That is, JP-A-49-10258, JP-A-49-48921, and JP-A-50-121.
In the various methods proposed in Publication No. 570, etc., production is possible by simply changing the supply of the raw material polymer to the extruder so that SEPS and crystalline polyolefin are weighed and mixed in a predetermined ratio in the form of pellets. You can.
【００３１】これらメルトブローン法は原料ポリマーを
１ステップで繊維化と不織布化とを行ってしまうため、
膠着性、粘着性をもつポリマーの不織布化に適している
が、本発明の場合も、典型的にそれにあてはまる。[0031] These melt-blowing methods convert the raw material polymer into fibers and non-woven fabrics in one step;
It is suitable for making non-woven fabrics from adhesive and sticky polymers, and this is typically the case in the present invention.
【００３２】本発明に用いる混合ポリマーは耐熱性、流
動性などの加工性に優れ通常の熱可塑性ポリマーである
ポリプロピレンなどと同様な容易さで成形することが可
能であり、溶融粘度、ポリマー吐出量、噴射流体の量を
いろいろ変更することによって任意の不織布を得ること
が可能である。The mixed polymer used in the present invention has excellent processability such as heat resistance and fluidity, and can be molded with ease similar to that of ordinary thermoplastic polymers such as polypropylene. , it is possible to obtain any nonwoven fabric by varying the amount of jetting fluid.
【００３３】[0033]
【実施例】本発明をより具体的に説明するために以下に
本発明の実施例を示すが、本発明の内容はこれらの実施
例に限定されるものではない。本実施例中、不織布物性
はＪＩＳ Ｌ−１０９２によって測定した。[Examples] In order to explain the present invention more specifically, examples of the present invention are shown below, but the content of the present invention is not limited to these examples. In this example, the physical properties of the nonwoven fabric were measured according to JIS L-1092.
【００３４】実施例１〜８、比較例１〜１２撹拌装置付
き耐圧容器中に、シクロヘキサン３，０００重量部、充
分に脱水したスチレン５５重量部及びｎ−ブチルリチウ
ム０．７重量部を加え、６０℃で６０分間重合し、つい
でイソプレン３００重量部を加えて６０分間、次いでス
チレン５５重量部を加えて６０分間重合し、スチレン−
イソプレン−スチレン型ブロック共重合体を合成した。得られたポリマーのスチレン含有量は２７重量％であっ
た。Examples 1 to 8, Comparative Examples 1 to 12 3,000 parts by weight of cyclohexane, 55 parts by weight of sufficiently dehydrated styrene, and 0.7 parts by weight of n-butyllithium were added to a pressure-resistant container equipped with a stirring device. Polymerization was carried out at 60°C for 60 minutes, then 300 parts by weight of isoprene was added and polymerized for 60 minutes, and then 55 parts by weight of styrene was added and polymerized for 60 minutes.
An isoprene-styrene type block copolymer was synthesized. The styrene content of the resulting polymer was 27% by weight.
【００３５】このポリマー溶液のポリマー濃度を１０％
とするようにシクロヘキサンを加え、減圧脱気後水素置
換し、更に０．５重量％／ポリマーのパラジウム触媒を
加え１０ｋｇ／ｃｍ２の水素雰囲気下で水添反応を行な
い、水素添加率９８％の水添ブロック共重合体を得た。このブロック共重合体に対して各種の量のステアリン酸
エチレンビスアミドを配合し、溶融混練後押出してＳＥ
ＰＳペレットを作製した。[0035] The polymer concentration of this polymer solution was reduced to 10%.
Cyclohexane was added as follows, degassed under reduced pressure, replaced with hydrogen, further added with 0.5 wt%/polymer palladium catalyst, and hydrogenated in a hydrogen atmosphere of 10 kg/cm2 to obtain water with a hydrogenation rate of 98%. A block copolymer was obtained. Various amounts of stearic acid ethylene bisamide were blended into this block copolymer, and after melt-kneading, it was extruded and subjected to SE
PS pellets were produced.
【００３６】次に、該ＳＥＰＳのペレットとＭＦＲ（メ
ルトフローレート、２３０℃、荷重２１６０ｇで測定）
が２００のホモポリプロピレンペレットを各々計量し、
所定の比率で混合し、混合ペレットとした。Next, the SEPS pellets and MFR (melt flow rate, measured at 230°C and a load of 2160g)
weigh 200 homopolypropylene pellets each,
They were mixed at a predetermined ratio to form mixed pellets.
【００３７】この混合ペレットを押出機で溶融後、０．
３ｍｍφのオリフィスが１ｍｍピッチに配列し、両側に
加熱気体の噴射用スリットを有するメルトブローン紡糸
装置に送り込み次の条件でメルトブローンを行った。す
なわちメルトブローン装置の温度を２９０℃とし、１ホ
ール当り０．２ｇ／分の割合で所定比率で混合されたポ
リマーを吐出し、２８５℃に加熱した空気をポリマー重
量の４３倍量噴射して繊維化した。これをノズル下方２
０ｃｍの位置に設置された金網ベルトコンベア上で捕集
して目付７０ｇ／ｍ２の不織布とし、後方の巻取機で直
径約５０ｃｍのロール状に巻き取った。After melting this mixed pellet in an extruder, 0.
The material was fed into a melt-blown spinning device having orifices of 3 mm diameter arranged at a pitch of 1 mm and slits for jetting heated gas on both sides, and melt-blown under the following conditions. That is, the temperature of the melt blowing device was set to 290°C, the polymer mixed at a predetermined ratio was discharged at a rate of 0.2 g/min per hole, and air heated to 285°C was injected in an amount 43 times the weight of the polymer to form fibers. did. Plug this into the nozzle lower part 2.
A nonwoven fabric having a basis weight of 70 g/m2 was collected on a wire mesh belt conveyor installed at a position of 0 cm, and wound into a roll with a diameter of about 50 cm using a winder at the rear.
【００３８】表１にＳＥＰＳとポリプロピレン及びステ
アリン酸ビスアミドの混合比率と不織布物性およびロー
ル巻き不織布の解舒性評価結果の比較を示す。Table 1 shows a comparison of the mixing ratio of SEPS, polypropylene, and stearic acid bisamide, the physical properties of the nonwoven fabric, and the results of evaluating the unwinding properties of the rolled nonwoven fabric.
【００３９】ロール巻き不織布の解舒性の評価方法は、
ロール巻き不織布を自由に回転する軸へセットし、２５
ｍ／分の速度で引き取るときの不織布と不織布の剥離の
安定性、すなわち、解舒の安定性として評価した。表１
の評価で「良好」としたものは、全くなんの問題もなく
全量が解舒出来たものである。「不良」としたものは不
織布相互の膠着のため剥離が不安定で解舒が出来なかっ
たものである。[0039] The method for evaluating the unwinding property of the rolled nonwoven fabric is as follows:
Set the rolled nonwoven fabric on the freely rotating shaft, and
The stability of peeling between nonwoven fabrics when taken off at a speed of m/min, that is, the stability of unwinding, was evaluated. Table 1
Items that were evaluated as ``good'' were those that could be unwound in their entirety without any problems. Items marked as "defective" were those in which peeling was unstable and unraveling was not possible due to mutual adhesion of the nonwoven fabrics.
【００４０】[0040]
【表１】[Table 1]
【００４１】この結果から明らかなように本発明に該当
する実施例１〜８では良好に解舒ができると共に、不織
布はいずれも伸度が５００％以上、３０％伸長時応力が
３ｇ／ｃｍ／ｇ／ｍ２以下と高い伸縮性と低モジュラス
とを兼備している。[0041] As is clear from these results, Examples 1 to 8 corresponding to the present invention can be unraveled well, and all nonwoven fabrics have an elongation of 500% or more and a stress at 30% elongation of 3 g/cm/ It has both high elasticity and low modulus of less than g/m2.
【００４２】それに対して、本発明外である比較例１、
２、４、５、７および８では、ロール巻き不織布の解舒
性が不良である。また、本発明外である比較例３、６、
９および１２ではメルトブローン中にノズル汚れが激し
く不織布のサンプリングが不可であった。一方、本発明
外の比較例１０および１１においては、ロール巻き不織
布の解舒性は良好であるが、不織布の伸度は５００％を
下回り、３０％伸長時応力が２ｇ／ｃｍ／ｇ／ｍ２を越
えており本発明の高い伸縮性と低モジュラスは実現され
ていない。On the other hand, Comparative Example 1, which is outside the invention,
In Nos. 2, 4, 5, 7, and 8, the unwinding properties of the rolled nonwoven fabrics were poor. In addition, Comparative Examples 3, 6, which are outside the present invention,
In samples No. 9 and No. 12, the nozzle was heavily contaminated during melt blowing, making it impossible to sample the nonwoven fabric. On the other hand, in Comparative Examples 10 and 11 outside the present invention, the roll-wound nonwoven fabric had good unwinding properties, but the elongation of the nonwoven fabric was less than 500%, and the stress at 30% elongation was 2 g/cm/g/m2. The high elasticity and low modulus of the present invention have not been achieved.
【発明の効果】本発明で得られた不織布は、ロール巻き
からの解舒性が良好であるため、各種製品に加工すると
き取り扱い性に優れており、加硫加工なしで高伸縮、高
弾性でしかも低モジユラスであるため湿布基布などに特
徴が発揮出来る。また、ウレタン弾性繊維などに較べ耐
候性にも優れているため使用時の変退色、黄変が起りに
くいので高温使用以外のあらゆる用途に使用出来る。ま
た低温特性にも優れたものである。[Effects of the invention] The nonwoven fabric obtained by the present invention has good unwinding properties from rolls, so it is easy to handle when processed into various products, and has high elasticity and elasticity without vulcanization. Moreover, because it has a low modulus, it can be used as a base fabric for compresses. In addition, it has superior weather resistance compared to urethane elastic fibers, so it is less likely to discolor, fade, or yellow during use, so it can be used for all purposes other than high-temperature use. It also has excellent low temperature properties.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3372591AJP2821036B2 (en) | 1991-02-01 | 1991-02-01 | High elasticity nonwoven fabric and method for producing the same |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3372591AJP2821036B2 (en) | 1991-02-01 | 1991-02-01 | High elasticity nonwoven fabric and method for producing the same |
| Publication Number | Publication Date |
|---|---|
| JPH04257361Atrue JPH04257361A (en) | 1992-09-11 |
| JP2821036B2 JP2821036B2 (en) | 1998-11-05 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3372591AExpired - Fee RelatedJP2821036B2 (en) | 1991-02-01 | 1991-02-01 | High elasticity nonwoven fabric and method for producing the same |
| Country | Link |
|---|---|
| JP (1) | JP2821036B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003095732A1 (en)* | 2002-05-14 | 2003-11-20 | Kuraray Co., Ltd. | Fiber non-woven fabric |
| JP2004204386A (en)* | 2002-12-25 | 2004-07-22 | Unitica Fibers Ltd | Hot-melt type adhesive fiber with good unwinding performance and method for producing the same |
| US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
| US7531594B2 (en) | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
| US7619026B2 (en) | 2002-08-12 | 2009-11-17 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7622523B2 (en) | 2002-08-12 | 2009-11-24 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003095732A1 (en)* | 2002-05-14 | 2003-11-20 | Kuraray Co., Ltd. | Fiber non-woven fabric |
| US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
| US7531594B2 (en) | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
| US7619026B2 (en) | 2002-08-12 | 2009-11-17 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7622523B2 (en) | 2002-08-12 | 2009-11-24 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7632887B2 (en) | 2002-08-12 | 2009-12-15 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| JP2004204386A (en)* | 2002-12-25 | 2004-07-22 | Unitica Fibers Ltd | Hot-melt type adhesive fiber with good unwinding performance and method for producing the same |
| Publication number | Publication date |
|---|---|
| JP2821036B2 (en) | 1998-11-05 |
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