JP4584503B2 - Weave fabric - Google Patents
Weave fabric Download PDFInfo
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- JP4584503B2 JP4584503B2 JP2001237050A JP2001237050A JP4584503B2 JP 4584503 B2 JP4584503 B2 JP 4584503B2 JP 2001237050 A JP2001237050 A JP 2001237050A JP 2001237050 A JP2001237050 A JP 2001237050A JP 4584503 B2 JP4584503 B2 JP 4584503B2
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- warp
- dtex
- polyketone
- fiber
- fibers
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- 239000004744 fabric Substances 0.000 title claims description 72
- 239000000835 fiber Substances 0.000 claims description 144
- 229920001470 polyketone Polymers 0.000 claims description 110
- 238000010438 heat treatment Methods 0.000 claims description 26
- 229920001971 elastomer Polymers 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000002759 woven fabric Substances 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 6
- 239000004816 latex Substances 0.000 claims description 5
- 229920000126 latex Polymers 0.000 claims description 5
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 17
- 238000009941 weaving Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000012779 reinforcing material Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002657 fibrous material Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002964 rayon Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008602 contraction Effects 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
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- 229920000728 polyester Polymers 0.000 description 3
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
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- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
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- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OXPCWUWUWIWSGI-MSUUIHNZSA-N Lauryl oleate Chemical compound CCCCCCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC OXPCWUWUWIWSGI-MSUUIHNZSA-N 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
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- 238000000418 atomic force spectrum Methods 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- Tires In General (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ポリケトン繊維を経糸として用いたすだれ織物に関する。さらに詳しくは、ポリケトン繊維を用いた経糸と、緯糸とのすべりが小さいために目ずれがなく均質で、加熱時の収縮が小さいために平坦性に優れたすだれ織物に関する。本発明のすだれ織物は、接着剤を付与した後にゴム補強材料等に使用され、タイヤやベルト、ホース等のゴム補強用繊維材料等に極めて有用である。
【０００２】
【従来の技術】
タイヤやベルト、ホース等のゴム製品においては、製品の強度を担うための材料として主に、スチール等の金属繊維材料、レーヨンやナイロン６６繊維、ポリエチレンテレフタレート繊維等の有機繊維材料が用いられてきた。
しかしながら、スチール等の金属繊維材料は力学性能には優れるものの、比重が大きいため重くなってしまう問題がある。一方、従来の汎用有機繊維材料についても、レーヨンは力学強度が低く、水や高湿度下で物性が低下する問題、ナイロン６６繊維は弾性率が小さく、加重下での寸法安定性が低く、加熱下での熱収縮も大きいなどの問題、ポリエチレンテレフタレート繊維は加熱下での熱収縮が大きい問題、があった。
【０００３】
これら従来の有機繊維材料に代わりうる材料として、一酸化炭素とエチレン、プロペンのようなオレフィンをパラジウムやニッケルを触媒として重合させることにより、一酸化炭素とオレフィンが実質完全に交互共重合した脂肪族ポリケトンが得られることが見いだされ（工業材料、１２月号、第５ページ、１９９７年）、ポリケトンを繊維化する研究が行われている。
ポリケトン繊維は、従来のポリオレフィン繊維に比べて融点が高く、また高強度および高弾性率を有することが知られており、この優れた物性を活かして産業資材用途、特にタイヤやベルト、ホース等のゴム補強材料として展開が期待されている。
【０００４】
繊維材料をゴム補強材として使用する場合、通常は、繊維を撚糸後、接着剤を付与してコード状とし、あるいは、すだれ織物状としてゴム材料中に埋設する。
これまでポリケトン繊維についてはいくつかの技術が開示されているが（例えば、特開平１−１２４６１７号公報、特開平２−１１２４１３号公報、特表平４−５０５３４４号公報、特開平４−２２８６１３号公報、特表平７−５０８３１７号公報、特表平８−５０７３２８号公報、米国特許第５９５５０１９号明細書、国際公開９９／１８１４３号パンフレット、国際公開第００／０９６１１号パンフレット等）、これらの先行技術においては、高強度および高弾性率を有するポリケトン繊維に関する技術の記載があるのみで、ポリケトン繊維をすだれ織物に用いることに関して一切記載されていない。
特開平１−１２４６１７号公報、特開平９−３２４３７７号公報、特開平９−３２９１９８号公報、特開平１１−３３４３１３号公報、特開平１１−３３６９５７号公報、特開２０００−１４２０２４号公報、特開２０００−１４２０２５号公報に、特開２０００−１９０７０５号公報、特開２０００−２６４０１２号公報等には、ポリケトンコードやポリケトンコードを経糸に用いたすだれ織物に関する技術が開示されている。
【０００５】
しかしながら、本発明者等の研究によると、これらの先行技術に開示されているコードおよびすだれ織物は、下記の（イ）〜（ハ）の問題を有していることが判明した。しかし、先行技術には、これらの問題に関する記載やこれらの問題を解決する手段、さらには高性能で高品位のすだれ織物を製造する技術に関しては全く記載されていない。
（イ）ポリケトン繊維およびポリケトン繊維からなるコードは、摩擦係数が小さく、すだれ織物の経糸として用いると、緯糸との間に滑りが生じて経糸の打ち込み間隔が不均一になる、いわゆる「目ずれ」が起こりやすい。
（ロ）高強度および高弾性率を有するポリケトン繊維およびポリケトン繊維からなるコードは熱収縮応力が高く、すだれ織物に製織後の熱収縮によってすだれ織物が歪んで平坦性が損なわれる。
（ハ）高強度および高弾性率を有するポリケトン繊維およびポリケトン繊維からなるコードは、撚糸時や製織時に毛羽やフィブリルができやすく、すだれ織物上や織機上に毛玉や粉が発生し品位や工程通過性が低下する。
【０００６】
【本発明が解決しようとする課題】
本発明は、このような問題を解決し、
（１）経糸と緯糸とのすべりによって経糸間隔が不均一になる目ずれが起こらない、均質なすだれ織物を提供すること、
（２）すだれ織物製織時や製織後の熱収縮によってひずみを起こさず、寸法安定性および平坦性に優れたすだれ織物を提供すること、
（３）撚糸時や製織時に毛羽やフィブリル状物の発生がなく、すだれ織物上や織機上にも毛玉や粉のない高品位のすだれ織物を工程通過性よく提供すること、である。
【０００７】
【課題を解決するための手段】
本発明者らは、上記の目的を達成するために鋭意研究を行い、本発明を完成するに至った。
すなわち、本発明は、経糸と緯糸とから構成されたすだれ織物において、経糸を構成する繊維の５０質量％以上がポリケトン繊維であって、経糸と緯糸との繊維−繊維間静止摩擦係数（μｓ）が０．２以上であることを特徴とするすだれ織物である。
【０００８】
本発明のすだれ織物は、構成する繊維の５０質量％以上がポリケトン繊維である経糸と、緯糸とから構成されている。本発明のすだれ織物の経糸の形態は、コードまたはストランドである。コードとは、一方向に撚糸した糸を数本引き揃え、逆方向に撚糸した糸である。ストランドとは、長繊維の束を無撚あるいは１００Ｔ／ｍ以下の軽い撚りをかけた糸である。
本発明において、ポリケトン繊維は、繰り返し単位の９５〜１００質量％、好ましくは９７質量％以上、より好ましくは１００質量％が化学式（１）で示す、１−オキソトリメチレンから構成されたポリケトンからなる繊維である。
【０００９】
【化１】
繰り返し単位中の１−オキソトリメチレンの割合が高いほど分子鎖の規則性が向上し、高結晶性で高配向度の繊維が得られる。したがって、この繊維を用いることによって高強度、高弾性率および高耐熱性を有する経糸が得られる。
本発明のすだれ織物は、強度、寸法安定性、耐熱性、およびゴムとの接着性に優れるものであるが、そのためには経糸を構成する繊維の５０質量％以上がポリケトン繊維であることが必要である。
【００１１】
本発明のすだれ織物に用いられる経糸の種類として、例えば、（イ）ポリケトン繊維のみからなるコード、（ロ）ポリケトン繊維のみからなるストランド、（ハ）ポリケトン繊維とポリケトン繊維以外の繊維とを混撚または交撚したコード、（ニ）ポリケトン繊維とポリケトン繊維以外の繊維とを混繊したストランド、（ホ）ポリケトン繊維以外の繊維からなるコード、（ヘ）ポリケトン繊維以外の繊維からなるストランド、等が挙げられる。以後、上記（イ）を「ポリケトンコード」、（ロ）を「ポリケトンストランド」、（イ）、（ハ）を「ポリケトン繊維からなるコード」、（ロ）、（ニ）を「ポリケトン繊維からなるストランド」という。
【００１２】
（ハ）および（ニ）の場合には、１本のコードまたはストランド中にポリケトン繊維が５０質量％以上含まれていることが好ましい。
経糸は、（イ）〜（ニ）から選ばれた少なくとも一種、または（イ）〜（ニ）から選ばれた少なくとも一種と（ホ）および（ヘ）から選ばれた少なくとも一種とから構成されていてもよい。
いずれにしても、ポリケトン繊維は、すだれ織物における全経糸中に５０質量％以上、好ましくは７５質量％以上、より好ましくは９０質量％以上、最も好ましくは１００質量％用いられる。経糸中のポリケトン繊維の割合が５０質量％未満の場合、すだれ織物の強度、寸法安定性、耐熱性、およびゴムとの接着性のいずれかの性能が不十分となる。
【００１３】
ポリケトン繊維以外の繊維としては、その割合が５０質量％未満であれば特に制限はなく、用途および目的に応じて、ポリアミド繊維、ポリエステル繊維、レーヨン繊維、アラミド繊維等、公知の繊維が用いられる。ポリケトン繊維以外の繊維が５０質量％を越えると、例えば、ポリエステル繊維やポリアミド繊維よりなる経糸の場合には強度や寸法安定性が損なわれ、レーヨン繊維よりなる経糸の場合には強度が大きく損なわれ、アラミド繊維よりなる経糸の場合にはゴムとの接着性が大きく損なわれる。
【００１４】
本発明のすだれ織物は、経糸の５０質量％以上、より好ましくは８０質量％以上、更に好ましくは１００質量％がポリケトンコードであることが好ましい。経糸中にポリケトンコードの割合が少ない場合、すだれ織物の強度、寸法安定性、耐熱性、およびゴムとの接着性、成型品の耐疲労性の全てにおいて優れたすだれ織物を得ることが難しくなる。
本発明のすだれ織物は、経糸と緯糸との繊維−繊維間静止摩擦係数（以下、μｓ、と略することがある）が０．２以上、好ましくは０．２５以上、より好ましくは０．３以上である。前述したように、ポリケトン繊維を用いた経糸は、他の繊維を用いた経糸に比べて、緯糸との摩擦に対して特に滑りやすい。したがって、ポリケトン繊維を用いた経糸のμｓを０．２以上に設定することは本発明において極めて重要である。μｓが０．２未満では、製織時の経糸にかかる張力の変動によって、あるいは、巻き取り後反物として保管時に経糸と緯糸とが滑り、経糸の間隔が不均等となってすだれ織物の品位が低下するばかりか、経糸密度が変動し、均質な製品を得ることができなくなる。一方、μｓの値には、上限はないが、高すぎるとゴム補強材として用いた場合、成形時に緯糸切断後の緯糸除去がスムースにいかなくなるため、３以下であることが好ましい。
【００１５】
すだれ織物を構成する経糸と緯糸との繊維−繊維間静止摩擦係数（μｓ）は、経糸を構成する繊維の単糸繊度、総繊度、油剤の種類や油剤付与率、さらにコードの場合には撚糸数、撚り形態等の組み合わせによって変化するため、所望のμｓが得られるように、これらの条件を調節する。ポリケトン繊維以外の繊維からなる経糸は、緯糸とのμｓが、通常、０．２以上であるので、ポリケトン繊維を含む経糸について、μｓを０．２以上にする必要がある。もちろん、ポリケトン繊維以外の繊維からなる経糸のμｓも０．２未満の場合には、同様にμｓを０．２以上にする必要がある。
【００１６】
以下、ポリケトン繊維を含む経糸を例に挙げて説明する。ポリケトン繊維以外の繊維からなる経糸についてもこれに準じればよい。
単糸繊度の設定
経糸に用いるポリケトン繊維の単糸繊度は、目ずれ防止の観点からは小さいほどμｓが大きくなり好ましい。しかし、単糸繊度が小さすぎると断糸が起こりやすくなり、延伸性、撚糸性、製織性等の工程通過性の低下や、毛羽による品位の低下が起こるため、好ましくは０．１〜１０ｄｔｅｘ、より好ましくは０．５〜５ｄｔｅｘ、最も好ましくは０．８〜２ｄｔｅｘである。単糸の断面形状は特に制限はないが、丸断面が好ましい。
【００１７】
油剤の選定
経糸の表面には油剤が付着していることが好ましい。延伸性や撚糸性の観点からは、平滑性や潤滑性を高める油剤が付着していることが好ましいが、油剤の平滑性が高すぎると経糸と緯糸とのすべりが生じる。したがって、ポリケトン繊維−ポリケトン繊維間の動摩擦係数（以下、μｄ、と略することがある）が、好ましくは０．０１〜０．７、より好ましくは０．０５〜０．６、最も好ましくは０．１〜０．５であり、経糸と緯糸とのμｓが０．２以上となるように油剤組成を決定することが好ましい。
【００１８】
本発明のすだれ織物の経糸に用いるポリケトン繊維に使用可能な油剤成分については特に限定はなく、例えば、特願２０００−１９９９５号に記載の油剤を使用することができる。平滑性および耐摩耗性を付与するために、エステル化合物、鉱物油、またはポリエーテル化合物を含有する油剤が好ましい。油剤には、その成分の乳化剤、制電剤、熱安定剤等を含有することが好ましい。
油剤の付着量が、０．１質量％未満であると摩擦抵抗の低減効果が不十分であり、１０質量％を越えるとロールやガイドの汚れ等の問題が生じるため、ポリケトン繊維に対して０．１〜１０質量％が好ましく、より好ましくは０．３〜５質量％、最も好ましくは０．５〜２質量％である。
【００１９】
経糸の繊度、撚糸数
ポリケトン繊維からなるコードおよびポリケトン繊維からなるストランドの総繊度は３００〜３００００ｄｔｅｘであることが好ましく、より好ましくは５００〜７０００ｄｔｅｘである。３００ｄｔｅｘ未満では、強撚コードとした際にμｓが小さくなる。また、３００００ｄｔｅｘを越えるとすだれ織物反の取り扱い性が低下する。
なお、本発明のすだれ織物に用いるポリケトン繊維からなるコード、ポリケトン繊維からなるストランド以外の経糸についても、総繊度は３００〜３００００ｄｔｅｘであることが好ましく、５００〜７０００ｄｔｅｘであることがより好ましい。
【００２０】
経糸にポリケトン繊維からなるコードを用いる場合、その撚糸数は特に制限はなく、用途に応じて選定され、下記式で表される上撚りの撚り係数Ｋが１０００〜３００００の範囲のものが好適である。
Ｋ＝Ｙ×Ｄ0.5
ここで、Ｙは、コード１ｍあたりの撚り数（Ｔ／ｍ）、Ｄは、コードの総表示繊度（ｄｔｅｘ）である。総表示繊度とは、撚糸に用いた全繊維の繊度の和であり、例えば、１６７０ｄｔｅｘのポリケトン繊維を３本撚り合わせた場合、撚糸物の総表示繊度は５０１０ｄｔｅｘ（１６７０／３）となる。
また、ストランドとして用いる場合は撚糸数は０〜１００Ｔ／ｍが好ましく、摩擦係数および糸の集束性の観点から５〜１０Ｔ／ｍがより好ましい。
【００２１】
本発明のすだれ織物は、主に、ゴム補強材料用途に用いられる、すだれ織物の製造中に、接着剤付与やゴム加硫等の加熱処理工程を通過する。しかしながら、高度に延伸されたポリケトン繊維からなるコードおよびストランドは非常に強い熱収縮力を示し、すだれの変形や成型品の歪みが起こりやすい。このため、ポリケトン繊維からなるコードおよびポリケトン繊維からなるストランドは熱収縮応力が小さいことが好ましく、最大熱収縮応力が０．０１〜０．６ｃＮ／ｄｔｅｘであることが好ましく、より好ましくは０．０５〜０．５ｃＮ／ｄｔｅｘ、最も好ましくは０．１〜０．４ｃＮ／ｄｔｅｘである。最大熱収縮応力が０．６ｃＮ／ｄｔｅｘを越えると、すだれ織物の収縮力が強くなり緯糸の変形や織り密度にムラが生じたり、成型品が変形する場合がある。一方、最大熱収縮応力が０．０１ｃＮ／ｄｔｅｘ未満の場合、熱セット性が低下し織物や成型品にたるみが生じることがある。
【００２２】
緯糸の種類および繊度
本発明のすだれ織物に用いる緯糸の種類および繊度については、μｓが本発明の範囲に入るものであれば特に制限はなく、用途および目的に応じて選定することができる。コストおよび取り扱い性の観点からポリエステル繊維、ポリアミド繊維およびセルロース繊維が好ましく、ポリケトン繊維との摩擦特性や加工時の裁断性の観点から綿繊維、ポリノジック繊維、ビスコースレーヨン繊維、銅アンモニアレーヨン繊維等のセルロース繊維が特に好ましく用いられる。
【００２３】
すだれの形態保持能力や加工時の裁断性、および経糸との摩擦特性の観点から緯糸の繊度を適当な範囲内とすることが望ましく、長繊維の場合５０〜５００ｄｔｅｘ、短繊維の場合１０s〜４０sが好ましい。
本発明のすだれ織物の経糸にポリケトン繊維を５０質量％以上含むコードは、その特性として、高強度および高寸法安定性であることが望まれ、引っ張り強度が７ｃＮ／ｄｔｅｘ以上が好ましく、より好ましくは１０ｃＮ／ｄｔｅｘ以上、最も好ましくは１２ｃＮ／ｄｔｅｘ以上である。また、２．０ｃＮ／ｄｔｅｘ荷重時の伸度が５％以下であることが好ましく、より好ましくは４％以下、最も好ましくは３％以下である。引っ張り強度が７ｃＮ／ｄｔｅｘ未満の場合、補強材として十分な強度を発揮させるためには、コードの総本数を増やす必要がある。２．０ｃＮ／ｄｔｅｘ荷重時の伸度が５％を越える場合、荷重がかかった際のコードの伸びが大きくなり、材料が寸法変化しやすくなる。
【００２４】
上述の高性能の経糸を得るためには、経糸に用いるポリケトン繊維が高強度、高弾性率および高寸法安定性であることが必要であり、ポリケトン繊維の引っ張り強度は１０ｃＮ／ｄｔｅｘ以上、弾性率は２５０ｃＮ／ｄｔｅｘ以上であることが好ましく、より好ましくは引っ張り強度は５ｃＮ／ｄｔｅｘ以上、弾性率は３５０ｃＮ／ｄｔｅｘ以上のポリケトン繊維を経糸に用いる。ポリケトン繊維の熱特性は、１５０℃×３０分の乾熱処理による収縮率が０〜２％、最大熱収縮応力が０．０１〜０．６ｃＮ／ｄｔｅｘであることが好ましく、より好ましくは乾熱収縮率が０〜１％、最大熱収縮応力が０．１〜０．４ｃＮ／ｄｔｅｘである。
【００２５】
経糸が毛羽や断糸等のない高品位のものであるためには、経糸に用いるポリケトン繊維が延伸性および撚糸性に優れたものであることが重要であり、具体的にはポリケトン繊維−ポリケトン繊維間の動摩擦係数（μｄ）が０．０１〜０．７であることが好ましく、より好ましくは０．０５〜０．３である。
本発明のすだれ織物の構成は特に制限はなく、経糸密度、緯糸密度、すだれの幅および長さ等、任意に選定することができる。経糸密度はハイエンズ、ミドルエンズ、ロウエンズのいずれであってもよいが、すだれ織物の均質性および取り扱い性の点から、経糸密度は５〜８０本／５ｃｍ、緯糸密度は１〜１０本／５ｃｍであることが好ましい。
【００２６】
本発明のすだれ織物は、樹脂、接着剤等、繊維以外の成分等を含んでいてもよく、その成分や量については特に限定されない。樹脂としては、エポキシ樹脂やフェノール樹脂等の熱硬化性樹脂、ポリエステル樹脂、ポリアミド樹脂等の熱可塑性樹脂等、公知のものを使用できる。ゴム補強材として用いる場合には、ゴムとすだれ織物との接着性を強化するために、織物に接着剤を付着させたものを用いる。接着剤の種類は特に限定されず、公知の接着剤をそのまま、あるいは組成比を適宜選定して用いることができる。中でも、ＲＦＬ（レゾルシン−ホルマリン−ラテックス）液を主成分とする接着剤を用いるのが一般的であり、この場合、ＲＦＬ液単独で用いてもよく、必要に応じてエポキシ化合物やイソシアネート化合物、フェノール化合物等、その他の薬液と混合して用いてもよい。すだれ織物への接着剤の付着量は特に制限はなく、用途および目的に応じて所望の量を付与すればよいが、力学的性質や工程通過性、ゴムとの接着性の観点からすだれ織物に対して０．１〜２０質量％付与するのが好ましく、より好ましくは１〜１０質量％、最も好ましくは２〜８質量％である。
【００２７】
次に、本発明のすだれ織物の製造法について説明する。
経糸に用いるポリケトン繊維は、公知の湿式紡糸法（ポリケトンを溶剤に溶解した後に凝固浴中で繊維状とし、脱溶剤、乾燥を経て熱延伸を行う方法）で製造することができる。高強度、高弾性率および高寸法安定性を有するポリケトン繊維を生産性よく工業的に製造するには、金属塩を溶剤とする湿式紡糸法が好適に用いられる。
【００２８】
溶解に用いるポリケトンは、繰り返し単位の１−オキソトリメチレンの割合が９５〜１００質量％、極限粘度が２〜２０であることが好ましい。このポリケトンをハロゲン化亜鉛、ハロゲン化アルカリ金属、ハロゲン化アルカリ土類金属等を含有する溶液（例えば、塩化亜鉛／塩化カルシウム水溶液）に溶解する。溶解した溶液を、紡糸口金より水等の液体中に吐出して糸条とした後、塩酸等の酸水溶液により金属塩を洗浄除去する。次いで、乾燥した後に、２００〜２８０℃にて５倍以上の熱延伸を行う。高強度のポリケトン繊維を製造する場合には、総延伸倍率を好ましくは１０倍以上、より好ましくは１２倍以上とし、２段以上の多段延伸を行うことが好ましい。
この際に、延伸前および／または延伸後に油剤を付与して延伸時および撚糸時のμｄを低減すると共に、延伸後および／または撚糸後に再度油剤を付与して経糸のμｓを０．２以上とすることが重要である。さらに、すだれ織物の熱収縮を抑制する目的で、多段延伸終了後に１００〜２８０℃で０．００１〜１ｃＮ／ｄｔｅｘの低張力熱処理を行い、ポリケトン繊維の熱収縮応力を下げることが好ましい。
【００２９】
このようにして得られたポリケトン繊維を撚糸してコードに加工し、あるいは、引き揃えてストランドとして用いる。コードに加工する場合、撚糸の種類、方法、合撚本数については特に制限はなく、片撚り糸、もろ撚り糸、ピッコもろ撚り糸、強撚糸など任意の方法が採用され、合撚する本数も１本撚り、２本撚り等、特に制限はなく、３本以上の合撚であってもよい。撚糸数も用途、使用環境等に応じて任意に選定すればよく、一般的には、上撚りの撚り係数Ｋが１０００〜３００００の範囲で撚糸される。この際、撚糸張力を、下撚り／上撚り共に０．０１〜０．２ｃＮ／ｄｔｅｘとすることが好ましい。
【００３０】
このようにして得られたポリケトン繊維を少なくとも一部に含むコードおよび／またはストランドを５〜８０本／５ｃｍに配列し、製織機にて緯糸を１〜１０本／５ｃｍの割合で打ち込むことによって、本発明のすだれ織物が得られる。
得られたすだれ織物に、濃度１０〜３０質量％のＲＦＬ液を付着させ、少なくとも１００℃の熱をかけて固着させる工程（いわゆるＤｉｐ処理）を通すことによりＲＦＬ処理織物が得られる。
ＲＦＬ液の好ましい組成としては、レゾルシン０．１〜１０質量％、ホルマリン０．１〜１０質量％、ラテックス１〜２８質量％であり、より好ましい組成としてはレゾルシン０．５〜３質量％、ホルマリン０．５〜３質量％、ラテックス１０〜２５質量％である。すだれ織物に付与したＲＦＬ液の乾燥温度は、好ましくは１４０〜２００℃で、少なくとも１０秒、好ましくは２０〜１２０秒間乾燥熱処理する。
【００３１】
乾燥後のすだれ織物を、ヒートセットゾーンおよびノルマライジングゾーンにて熱処理する。この際、熱処理条件（熱処理温度および熱処理時の張力、熱処理時間）を特定範囲内とすることが重要である。熱処理温度は、好ましくは１５０〜２５０℃、より好ましくは１８０〜２３０℃である。熱処理張力は、好ましくは（最大熱収縮応力±０．２）ｃＮ／ｄｔｅｘ、より好ましくは最大熱収縮応力である。熱処理時間は好ましくは１０〜３００秒、より好ましくは３０〜１２０秒の範囲である。
ノルマライジングゾーンの熱処理温度および熱処理時間は、上述のヒートセット温度および熱処理時間の範囲内であることが好ましい。ノルマライジングゾーンの熱処理時の張力はヒートセットゾーンの熱処理時の張力の１０〜８０％程度とすることが好ましい。
【００３２】
【発明の実施の形態】
本発明を、実施例により具体的に説明するが、それらは本発明の範囲を限定するものではない。
本発明に用いられる各測定値の測定方法は次の通りである。
（１）極限粘度［η］
極限粘度［η］は次の定義式に基づいて求められる値である。
【００３３】
（２）繊度、引っ張り強度、弾性率および２．０ｃＮ／ｄｔｅｘ荷重時の伸度
繊度は、試料を２５℃、５５％湿度下で４８時間静置後、試料１００ｍの質量Ｗ1（ｇ）を計量し、Ｗ1×１００を繊度（ｄｔｅｘ）とする。この試料を、試料長２５０ｍｍ、クロスヘッド速度３００ｍｍ／分の条件で、引っ張り強度、弾性率、２．０ｃＮ／ｄｔｅｘ荷重時の伸度を測定する。
【００３４】
（３）樹脂付着率
コード５ｍを１０５℃で５時間加熱した後に絶乾質量Ｗ2（ｇ）を計量する。次いで、コードを１ｍｍ長に細断して、２００ｍｌのヘキサフルオロイソプロパノールにて攪拌下、６０℃、２時間溶解する。溶解後ろ過し、得られた残さを１０５℃で５時間加熱処理した後に質量Ｗ3（ｇ）を精秤し、下式から樹脂付着率を求める。
樹脂付着率 ＝ （Ｗ3×１０）／（Ｗ2）×１００ （％）
【００３５】
（４）乾熱収縮率
オーブン中で１５０℃、３０分の乾熱処理を行い、熱処理前後の繊維長を、１／３０（ｃＮ／ｄｔｅｘ）の荷重をかけて計測して下式により求める。
乾熱収縮率＝（Ｌb−Ｌa）／（Ｌb）×１００ （％）
式中、Ｌbは熱処理前の繊維長、Ｌaは熱処理後の繊維長である。
【００３６】
（５）最大熱収縮応力、最大熱収縮温度
ＣＯＲＤ−ＴＥＳＴＥＲ（商標）（Ｇｏｏｄｒｉｃｈ Ｔｙｐｅ）（東洋精機製作所（株）社製）を用いて、下記の条件で一定変位下における繊維およびコードの熱収縮力特性を測定する。
ＴｅｍｐｅｒａｔｕｒｅＰｒｏｇｒａｍ ： ＥＸＰモード
ΘM ： ２５０℃
Ｔ1 ： ３分
初荷重 ： １／８０（ｇ／ｄｔｅｘ）
初期試料長 ： ２５０ｍｍ
計測された温度−収縮力カーブから最大の収縮力Ｆmax（ｃＮ）および最大の収縮力を示す温度Ｔmax（℃）を読みとり、Ｔmaxを最大熱収縮温度とする。Ｆmaxを試料の繊度（ｄｔｅｘ）で除して最大熱収縮応力σMAX（ｃＮ／ｄｔｅｘ）を求める。
【００３７】
（６）経糸と緯糸間の静止摩擦係数（μｓ）
図１に示す装置を用いて測定を行う。長さ約６９０ｍの緯糸１を円筒２の周りに、綾角１５°で約０．２ｃＮ／ｄｔｅｘの張力を掛けて巻き付ける。更に、長さ３０．５ｃｍの経糸３をこの円筒に掛ける。この時、経糸３は円筒２の上にあり、円筒の巻き付け方向と平行にする。円筒２に掛けた経糸３の片方の端に、荷重が０．１ｃＮ／ｄｔｅｘ（対経糸）の重り４を結び、他方の端にはストレインゲージ５を連結させる。次に、円筒２を１ｍｍ／分の周速で回転させ、張力をストレインゲージ５で測定する。こうして測定した張力からμｓを下記の式より求める。
μｓ＝（１／π）×ｌｎ（Ｔ2／Ｔ1）
式中、Ｔ1は繊維に掛けた重りの重さ、Ｔ2はストレインゲージにて測定した張力、ｌｎは自然対数、πは円周率を示す。
【００３８】
（７）ポリケトン繊維−ポリケトン繊維間の動摩擦係数（μｄ）
図２に示す装置を用いて測定を行う。長さ約６９０ｍのポリケトン繊維（Ａ）６を円筒２の周りに、綾角１５°で約０．２ｃＮ／ｄｔｅｘの張力を掛けて巻き付け、更に円筒２に巻き付けた繊維と同じ長さ３０．５ｃｍのポリケトン繊維（Ｂ）７をこの円筒に掛ける。この時、ポリケトン繊維（Ｂ）７は円筒の上にあり、円筒の巻き付け方向と平行にする。円筒２に掛けたポリケトン繊維（Ｂ）７の片方の端に荷重が０．１ｃＮ／ｄｔｅｘ（対ポリケトン繊維（Ｂ））の重り４を結び、他方の端にはストレインゲージ５を連結させる。次に、円筒を１８ｍ／分の周速で回転させ、張力をストレインゲージ５で測定する。こうして測定した張力からμｄを下記の式より求める。
μｄ＝（１／π）×ｌｎ（Ｔ2／Ｔ1）
式中、Ｔ1は繊維に掛けた重りの重さ、Ｔ2は測定した時の張力、ｌｎは自然対数、πは円周率を示す。
【００３９】
【実施例１】
常法により調製したエチレンと一酸化炭素が完全交互共重合した極限粘度６．０のポリケトンを、塩化カルシウム４０質量％／塩化亜鉛２２質量％を含有する水溶液に溶解して、ポリケトン濃度６．５質量％のドープを得た。得られたドープを８０℃に加温し、紡口径０．１５ｍｍφ、Ｌ／Ｄ＝１、ホール数２５０の紡口より１０ｍｍのエアーギャップを通した後に、２質量％の塩化カルシウム、１．１質量％の塩化亜鉛および０．１質量％の塩酸を含有する−２℃の水からなる凝固浴中に、吐出量２２．５ｃｃ／分の速度で押し出して糸条とし、引き取り速度５ｍ／分で曳き取った。
【００４０】
引き続き、糸条を塩酸水溶液、水で順次洗浄した後に、ＩＲＧＡＮＯＸ（登録商標）（Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ社製）１０９８、ＩＲＧＡＮＯＸ（登録商標）（Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ社製）１０７６をそれぞれ０．０５質量％ずつ（対ポリケトン）配合した後に、２２５℃にて定長乾燥した。さらに、２２５℃で７倍の延伸を行った後に、このポリケトン繊維６本を合糸し濃度１質量％の油剤エマルジョンを付与した後に、２４０℃で１．５倍、２５０℃で１．３倍、２５７℃で１．２倍の、トータル１６．４倍の４段延伸を行った。このポリケトン繊維に濃度７．５質量％の油剤エマルジョンを付与し、２２０℃で１５秒間（張力＝０．１ｃＮ／ｄｔｅｘ）の熱処理を行った。
【００４１】
油剤は以下の組成のものを用いた。
オレイン酸ラウリルエステル／ビスオキシエチルビスフェノールＡ／ポリエーテル（プロピレンオキシド／エチレンオキシド＝３５／６５：分子量２００００）／ポリエチレンオキシド１０モル付加オレイルエーテル／ポリエチレンオキシド１０モル付加ひまし油エーテル／ステアリルスルホン酸ナトリウム／ジオクチルリン酸ナトリウム＝３０／３０／１０／５／２３／１／１（質量％比）。
【００４２】
延伸性は良好で、延伸時に毛羽や断糸等の不具合はなかった。
得られたポリケトン繊維の繊度は１５１０ｄｔｅｘ、引っ張り強度は１７．０ｃＮ／ｄｔｅｘ、弾性率は３５５ｃＮ／ｄｔｅｘであり、優れた物性を有していた。また乾熱収縮率は０．４％、最大熱収縮応力は０．２５ｃＮ／ｄｔｅｘであり、優れた熱収縮特性を具備していた。この繊維のμｄは０．２２であった。
このポリケトン繊維をＺ方向に下撚り後、これを２本引きそろえＳ方向に上撚りして撚り合わせ、ポリケトンコードとした。撚糸条件は、下撚り：撚糸数は３９０Ｔ／ｍ、撚糸張力は０．８Ｎ（０．０５ｃＮ／ｄｔｅｘ）、上撚り：撚糸数は３９０Ｔ／ｍ、撚糸張力は１．８Ｎ（０．０５ｃＮ／ｄｔｅｘ）であった（上撚りの撚り係数は２１４３２）。撚糸性は良好で、撚糸時に毛羽や断糸等の工程上の不具合は見られなかった。
【００４３】
得られたポリケトンコードの繊度は３６２０ｄｔｅｘで、引っ張り強度は１２．７ｃＮ／ｄｔｅｘ、２．０ｃＮ／ｄｔｅｘ荷重時の伸度は３．１％であり、優れた力学特性を有していた。また、最大熱収縮温度は２１８℃、最大熱収縮応力は０．２０ｃＮ／ｄｔｅｘ、乾熱収縮率は０．５％であり、安定な熱収縮特性を有するものであった。
このポリケトンコードを経糸として、緯糸に２０sの綿紡績糸を用い、経糸密度が４０本／５ｃｍ、緯糸密度が４本／５ｃｍ、幅１４００ｍｍのすだれ織物を製織した。製織時に毛羽やフィブリル状物の発生はなく、織機にも糸くずや毛玉の付着は観察されず製織性は良好であった。経糸と緯糸とのμｓは０．３２であった。得られたすだれ織物は平坦で目ずれがなく、品位の優れたものであった。
【００４４】
【実施例２】
実施例１で得られたすだれ織物を、下記の液組成のＲＦＬ液に浸漬した後に、１６０℃、８０秒の乾燥処理、２２０℃で４５秒の定長ヒートセット処理、さらに２２０℃で４５秒のノルマライジング処理を行った。
（ＲＦＬ液組成）
レゾルシン ２２．０部
ホルマリン（３０質量％） ３０．０部
水酸化ナトリウム（１０質量％） １４．０部
水 ５７０．０部
ビニルピリジンラテックス（４１質量％） ３６４．０部
このようにして得られたすだれ織物のＲＦＬ樹脂付着率は５．５質量％であった。すだれ織物は平坦で、熱収縮による歪み等は全く観察されず、経糸コード密度も均等で目ずれがなく、高品位のものであった。
【００４５】
【比較例１】
実施例１において、１段延伸後の合糸本数を３本とし、延伸終了後に付与する仕上げ剤のエマルジョン濃度を３０質量％とし、延伸終了後の熱セットを行わない以外は同様にして紡糸、乾燥、延伸を行い、繊度が７９１ｄｔｅｘのポリケトン繊維を製造した。得られたポリケトン繊維の引っ張り強度は１６．１ｃＮ／ｄｔｅｘ、弾性率は３１４ｃＮ／ｄｔｅｘであり、乾熱収縮率は１．９％、最大熱収縮応力は０．７２ｃＮ／ｄｔｅｘ、μｄは０．０７であった。
【００４６】
このポリケトン繊維を実施例１と同様にして撚糸を行い（下撚り／上撚り共に３９０Ｔ／ｍ：上撚りの撚り係数＝１５５１２）、ポリケトンコードを得た。このポリケトン繊維からなるコードの繊度は１８０１ｄｔｅｘ、引っ張り強度は１３．１ｃＮ／ｄｔｅｘ、２．０ｃＮ／ｄｔｅｘ荷重時の伸度は３．０％、最大熱収縮温度は０．６６ｃＮ／ｄｔｅｘ、乾熱収縮率は１．９％であった。
このポリケトン繊維からなるコードを経糸に、１０sの綿紡績糸を緯糸として用い、経糸密度７５本／５ｃｍ、緯糸密度５本／５ｃｍ、幅５００ｍｍのすだれ織物を製織した。経糸と緯糸とのμｓは０．０８であった。得られたすだれ織物には長さ１ｍあたり２〜１０カ所の目ずれがあり、実施例１のすだれ織物と比べて品位の劣るものであった。
【００４７】
【比較例２】
比較例１で得られたすだれ織物を、実施例２と同様の処方でＲＦＬ液処理を行った。得られたすだれＲＦＬ処理織物は、目ずれだけでなく、長さ１ｍあたり１〜２カ所に熱収縮による歪みがあり、平坦性が不良で品位の劣るものであった。
このすだれ織物のＲＦＬ樹脂付着率は６．２質量％であった。
【００４８】
【発明の効果】
本発明のすだれ織物は、強度、寸法安定性、耐熱性に優れたポリケトン繊維からなる経糸と、緯糸とからなり力学的、熱的性質に優れたものである。さらには本発明のすだれ織物は、経糸と緯糸とのすべりによる目ずれがなく、熱収縮によってひずみを起こさず寸法安定性、平坦性に優れ、毛羽やフィブリル状物、毛玉、粉のない高品位のすだれ織物であり、撚糸や製織、ＲＦＬ処理等の工程通過性にも優れるものである。
本発明のすだれ織物は、接着剤を付与した後にゴム補強材料として好適に用いられ、具体的には、タイヤやベルト、ホース等のゴム補強用繊維材料として極めて有用である。
【図面の簡単な説明】
【図１】経糸と緯糸間の静止摩擦係数（μｓ）の測定装置の概略図。
【図２】ポリケトン繊維−ポリケトン繊維間の動摩擦係数（μｄ）の測定装置の概略図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a braided fabric using polyketone fibers as warp yarns. More specifically, the present invention relates to a braided woven fabric that is uniform with no misalignment due to small slip between a warp and a weft using polyketone fibers, and excellent in flatness due to small shrinkage during heating. The weave fabric of the present invention is used as a rubber reinforcing material or the like after applying an adhesive, and is extremely useful for a rubber reinforcing fiber material such as a tire, belt or hose.
[0002]
[Prior art]
In rubber products such as tires, belts and hoses, metal fiber materials such as steel, organic fiber materials such as rayon, nylon 66 fibers, and polyethylene terephthalate fibers have been mainly used as materials for bearing the strength of the products. .
However, although metal fiber materials such as steel are excellent in mechanical performance, there is a problem that they become heavy due to their large specific gravity. On the other hand, with regard to conventional general-purpose organic fiber materials, rayon has a low mechanical strength, and the physical properties deteriorate under water and high humidity. Nylon 66 fiber has a low elastic modulus, low dimensional stability under load, and heating. There was a problem such as a large thermal shrinkage underneath, and a polyethylene terephthalate fiber had a large thermal shrinkage under heating.
[0003]
As a material that can replace these conventional organic fiber materials, carbon monoxide and olefins such as ethylene and propene are polymerized using palladium or nickel as a catalyst, so that carbon monoxide and olefin are almost completely alternately copolymerized aliphatic. It has been found that polyketones can be obtained (Industrial Materials, December issue,
Polyketone fibers are known to have a higher melting point than conventional polyolefin fibers, and to have high strength and high elastic modulus. Utilizing these excellent physical properties, they can be used for industrial materials, especially tires, belts, hoses, etc. Development as a rubber reinforcing material is expected.
[0004]
When the fiber material is used as a rubber reinforcing material, usually, the fiber is twisted and then an adhesive is applied to form a cord, or a braided fabric is embedded in the rubber material.
Until now, several techniques have been disclosed for polyketone fibers (for example, JP-A-1-124617, JP-A-2-112413, JP-A-4-505344, JP-A-4-228613). No. 7-508317, JP-A-8-507328, US Pat. No. 5,955,019, WO 99/18143, WO 00/09611, etc.) In the technology, there is only a description of the technology relating to polyketone fibers having high strength and high elastic modulus, and there is no description regarding the use of the polyketone fibers in an interwoven fabric.
JP-A-1-124617, JP-A-9-324377, JP-A-9-329198, JP-A-11-334313, JP-A-11-336957, JP2000-142024, JP Japanese Laid-Open Patent Publication No. 2000-142025, Japanese Laid-Open Patent Publication No. 2000-190705, Japanese Laid-Open Patent Publication No. 2000-264012, and the like disclose polyketone cords and techniques related to a weave fabric using polyketone cords as warps.
[0005]
However, according to the studies by the present inventors, it has been found that the cords and the weave fabrics disclosed in these prior arts have the following problems (a) to (c). However, the prior art does not describe at all about the description of these problems, the means for solving these problems, and the technique for producing high-performance and high-quality interwoven fabrics.
(A) The cord made of polyketone fiber and polyketone fiber has a small coefficient of friction, and when used as a warp of a weave fabric, slippage occurs between the wefts and the warp driving interval becomes non-uniform, so-called “misalignment” Is likely to occur.
(B) Polyketone fibers having high strength and high elastic modulus and cords made of polyketone fibers have high heat shrinkage stress, and the interwoven fabric is distorted by thermal contraction after weaving and the flatness is impaired.
(C) Polyketone fiber and polyketone fiber cords with high strength and high modulus are easy to fluff and fibril during twisting and weaving, and fluff and powder are generated on the weaving fabric and loom. Passability decreases.
[0006]
[Problems to be solved by the present invention]
The present invention solves such a problem,
(1) To provide a uniform interwoven fabric in which the slippage between the warp and the weft does not cause misalignment in which the warp interval is not uniform.
(2) To provide a weave fabric excellent in dimensional stability and flatness without causing distortion due to heat shrinkage during weaving fabric weaving or after weaving,
(3) To provide a high-quality interwoven fabric free from fluff and powder on the interpenetrating fabric and the loom with good processability, without generation of fluff and fibrillar materials during twisting and weaving.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have intensively studied to achieve the above object, and have completed the present invention.
That is, according to the present invention, in the interwoven fabric composed of warp and weft, 50% by mass or more of the fibers constituting the warp is polyketone fiber, and the fiber-fiber static coefficient of friction between the warp and the weft (μs). Is an interwoven fabric characterized in that the woven fabric is 0.2 or more.
[0008]
The weave fabric of the present invention is composed of warp yarns and weft yarns in which 50% by mass or more of the constituent fibers are polyketone fibers. The warp form of the weave fabric of the present invention is a cord or a strand. A cord is a yarn in which several yarns twisted in one direction are aligned and twisted in the opposite direction. A strand is a yarn in which a bundle of long fibers is untwisted or lightly twisted at 100 T / m or less.
In the present invention, the polyketone fiber is composed of a polyketone composed of 1-oxotrimethylene in which 95 to 100% by mass, preferably 97% by mass or more, more preferably 100% by mass of the repeating unit is represented by the chemical formula (1). Fiber.
[0009]
[Chemical 1]
As the proportion of 1-oxotrimethylene in the repeating unit is higher, the regularity of the molecular chain is improved, and a fiber with high crystallinity and high degree of orientation can be obtained. Therefore, by using this fiber, a warp having high strength, high elastic modulus and high heat resistance can be obtained.
The weave fabric of the present invention is excellent in strength, dimensional stability, heat resistance, and adhesiveness to rubber. To that end, it is necessary that 50% by mass or more of the fibers constituting the warp are polyketone fibers. It is.
[0011]
The types of warp used in the weave fabric of the present invention include, for example, (a) a cord made of only polyketone fiber, (b) a strand made only of polyketone fiber, and (c) a mixed twist of polyketone fiber and fibers other than polyketone fiber. Stranded cords, (d) strands mixed with polyketone fibers and fibers other than polyketone fibers, (e) cords made of fibers other than polyketone fibers, (f) strands made of fibers other than polyketone fibers, etc. It is done. Thereafter, (b) above is “polyketone cord”, (b) is “polyketone strand”, (b), (c) is “cord made of polyketone fiber”, (b), (d) is “polyketone fiber” It is called “strand”.
[0012]
In the case of (c) and (d), it is preferable that 50% by mass or more of polyketone fiber is contained in one cord or strand.
The warp is composed of at least one selected from (i) to (d), or at least one selected from (b) to (d) and at least one selected from (e) and (f). May be.
In any case, the polyketone fiber is used in an amount of 50% by mass or more, preferably 75% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass in the total warp in the interwoven fabric. When the ratio of the polyketone fiber in the warp is less than 50% by mass, the performance of any one of the strength, dimensional stability, heat resistance, and adhesiveness to rubber of the weave fabric is insufficient.
[0013]
The fiber other than the polyketone fiber is not particularly limited as long as the ratio is less than 50% by mass, and known fibers such as polyamide fiber, polyester fiber, rayon fiber, and aramid fiber are used depending on the application and purpose. When the amount of fibers other than polyketone fibers exceeds 50% by mass, for example, in the case of warp made of polyester fiber or polyamide fiber, the strength and dimensional stability are impaired, and in the case of warp made of rayon fiber, the strength is greatly impaired. In the case of warp made of aramid fibers, the adhesiveness with rubber is greatly impaired.
[0014]
In the weave fabric of the present invention, it is preferable that 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass of the warp is polyketone cord. When the ratio of the polyketone cord is small in the warp, it is difficult to obtain a braid fabric excellent in all of the strength, dimensional stability, heat resistance, adhesion to rubber, and fatigue resistance of the molded product.
The interwoven fabric of the present invention has a fiber-to-fiber static friction coefficient (hereinafter sometimes referred to as μs) of warp and weft of 0.2 or more, preferably 0.25 or more, more preferably 0.3. That's it. As described above, warps using polyketone fibers are particularly slippery against friction with wefts compared to warps using other fibers. Accordingly, it is extremely important in the present invention to set the μs of warp yarns using polyketone fibers to 0.2 or more. If μs is less than 0.2, the warp and wefts slip during storage due to fluctuations in the tension applied to the warp during weaving, or when stored as a fabric after winding, resulting in uneven spacing of the warp and lowering the quality of the weave fabric. In addition, the warp density fluctuates and a homogeneous product cannot be obtained. On the other hand, although there is no upper limit to the value of μs, when it is too high, when used as a rubber reinforcing material, weft removal after cutting of the weft does not go smoothly at the time of molding, so it is preferably 3 or less.
[0015]
The fiber-to-fiber static friction coefficient (μs) of the warp and weft yarns constituting the weave fabric is the single yarn fineness, total fineness, type of oil agent and oil agent application rate, and twisted yarn in the case of cords. These conditions are adjusted so that a desired μs can be obtained because it varies depending on the combination of the number, the twist form, and the like. A warp made of fibers other than polyketone fibers usually has a μs with a weft of 0.2 or more. Therefore, for a warp containing polyketone fibers, μs needs to be 0.2 or more. Of course, when the μs of a warp made of fibers other than polyketone fibers is also less than 0.2, it is necessary to set μs to 0.2 or more similarly.
[0016]
Hereinafter, a warp containing polyketone fiber will be described as an example. The same applies to warps made of fibers other than polyketone fibers.
Single yarn fineness setting
From the viewpoint of preventing misalignment, the single yarn fineness of the polyketone fiber used for warp is preferably as μs increases as it decreases. However, if the single yarn fineness is too small, yarn breakage is likely to occur, and process passability such as drawability, twisting property, weaving property and the like are deteriorated, and the quality is lowered by fluff. More preferably, it is 0.5-5 dtex, Most preferably, it is 0.8-2 dtex. The cross-sectional shape of the single yarn is not particularly limited, but a round cross section is preferable.
[0017]
Selection of oil
It is preferable that the oil agent adheres to the surface of the warp. From the viewpoint of stretchability and twistability, it is preferable that an oil agent that improves smoothness and lubricity is attached, but if the oil agent is too smooth, warp and weft slip occur. Accordingly, the coefficient of dynamic friction between the polyketone fiber and the polyketone fiber (hereinafter sometimes abbreviated as μd) is preferably 0.01 to 0.7, more preferably 0.05 to 0.6, and most preferably 0. The oil composition is preferably determined so that the μs between the warp and the weft is 0.2 or more.
[0018]
There is no particular limitation on the oil component that can be used for the polyketone fiber used for the warp of the weave fabric of the present invention. For example, the oil agent described in Japanese Patent Application No. 2000-19995 can be used. In order to impart smoothness and wear resistance, an oil containing an ester compound, a mineral oil, or a polyether compound is preferred. The oil agent preferably contains an emulsifier, an antistatic agent, a heat stabilizer and the like as its components.
If the adhesion amount of the oil agent is less than 0.1% by mass, the effect of reducing the frictional resistance is insufficient, and if it exceeds 10% by mass, problems such as contamination of the rolls and guides occur. 0.1 to 10% by mass is preferable, more preferably 0.3 to 5% by mass, and most preferably 0.5 to 2% by mass.
[0019]
Fineness of warp, number of twisted yarns
The total fineness of the cord made of polyketone fiber and the strand made of polyketone fiber is preferably 300 to 30000 dtex, more preferably 500 to 7000 dtex. If it is less than 300 dtex, μs becomes small when a strong twisted cord is used. On the other hand, if it exceeds 30000 dtex, the handleability of the weave fabric will deteriorate.
The total fineness is preferably 300 to 30000 dtex and more preferably 500 to 7000 dtex for the warp yarns other than the cords made of polyketone fibers and the strands made of polyketone fibers used for the weave fabric of the present invention.
[0020]
When a cord made of polyketone fiber is used for the warp, the number of twisted yarns is not particularly limited, and is selected according to the use, and the twist factor K of the upper twist represented by the following formula is preferably in the range of 1000 to 30000. is there.
K = Y × D0.5
Here, Y is the number of twists per 1 m of cord (T / m), and D is the total display fineness (dtex) of the cord. The total displayed fineness is the sum of the fineness of all fibers used in the twisted yarn. For example, when three 1670 dtex polyketone fibers are twisted together, the total displayed fineness of the twisted yarn is 5010 dtex (1670/3).
Further, when used as a strand, the number of twisted yarns is preferably 0 to 100 T / m, and more preferably 5 to 10 T / m from the viewpoint of the coefficient of friction and yarn convergence.
[0021]
The bamboo woven fabric of the present invention passes through a heat treatment step such as application of an adhesive or rubber vulcanization during the production of the bamboo woven fabric mainly used for rubber reinforcement materials. However, cords and strands made of highly-stretched polyketone fibers exhibit a very strong heat-shrinking force and are prone to deformation of the blind and distortion of the molded product. Therefore, the cord made of polyketone fiber and the strand made of polyketone fiber preferably have a small heat shrinkage stress, and the maximum heat shrinkage stress is preferably 0.01 to 0.6 cN / dtex, more preferably 0.05. ˜0.5 cN / dtex, most preferably 0.1 to 0.4 cN / dtex. If the maximum heat shrinkage stress exceeds 0.6 cN / dtex, the shrinkage force of the weave fabric becomes strong, and the deformation of the weft and the weave density may be uneven, or the molded product may be deformed. On the other hand, when the maximum heat shrinkage stress is less than 0.01 cN / dtex, the heat setting property may be lowered, and sagging may occur in the woven fabric or molded product.
[0022]
Weft type and fineness
The type and fineness of the weft used in the weave fabric of the present invention are not particularly limited as long as μs falls within the scope of the present invention, and can be selected according to the application and purpose. Polyester fiber, polyamide fiber and cellulose fiber are preferable from the viewpoint of cost and handleability, and cotton fiber, polynosic fiber, viscose rayon fiber, copper ammonia rayon fiber, etc. from the viewpoint of friction characteristics with polyketone fiber and cutting property at the time of processing. Cellulose fibers are particularly preferably used.
[0023]
It is desirable that the fineness of the weft yarn is within an appropriate range from the viewpoint of the shape retention capability of the blind, the cutting property at the time of processing, and the friction characteristics with the warp, and 50 to 500 dtex for long fibers, 10 for short fibers.s~ 40sIs preferred.
The cord containing 50% by mass or more of polyketone fibers in the warp of the weave fabric of the present invention is desired to have high strength and high dimensional stability as its characteristics, and preferably has a tensile strength of 7 cN / dtex or more. 10 cN / dtex or more, most preferably 12 cN / dtex or more. Further, the elongation at a load of 2.0 cN / dtex is preferably 5% or less, more preferably 4% or less, and most preferably 3% or less. When the tensile strength is less than 7 cN / dtex, it is necessary to increase the total number of cords in order to exhibit sufficient strength as a reinforcing material. When the elongation at a load of 2.0 cN / dtex exceeds 5%, the elongation of the cord when a load is applied becomes large, and the material easily changes in dimensions.
[0024]
In order to obtain the above-mentioned high-performance warp, it is necessary that the polyketone fiber used for the warp has high strength, high elastic modulus and high dimensional stability. The tensile strength of the polyketone fiber is 10 cN / dtex or more, and the elastic modulus Is preferably 250 cN / dtex or more, and more preferably, polyketone fiber having a tensile strength of 5 cN / dtex or more and an elastic modulus of 350 cN / dtex or more is used for the warp. The thermal properties of the polyketone fiber are preferably such that the shrinkage ratio after dry heat treatment at 150 ° C. for 30 minutes is 0 to 2% and the maximum heat shrinkage stress is 0.01 to 0.6 cN / dtex, more preferably dry heat shrinkage. The rate is 0 to 1%, and the maximum heat shrinkage stress is 0.1 to 0.4 cN / dtex.
[0025]
In order for the warp to be of high quality with no fluff or breakage, it is important that the polyketone fiber used for the warp is excellent in stretchability and twistability. Specifically, polyketone fiber-polyketone The dynamic friction coefficient (μd) between the fibers is preferably 0.01 to 0.7, and more preferably 0.05 to 0.3.
There is no restriction | limiting in particular in the structure of the weave fabric of this invention, A warp density, a weft density, the width and length of a weave, etc. can be selected arbitrarily. The warp density may be any of high end, middle end, and low end, but from the standpoint of homogeneity and handleability of the weave fabric, the warp density is 5 to 80 / 5cm and the weft density is 1 to 10 / 5cm. It is preferable.
[0026]
The weave fabric of the present invention may contain components other than fibers, such as resin and adhesive, and the components and amounts thereof are not particularly limited. As the resin, known resins such as thermosetting resins such as epoxy resins and phenol resins, and thermoplastic resins such as polyester resins and polyamide resins can be used. When used as a rubber reinforcing material, in order to reinforce the adhesion between the rubber and the braided fabric, a material obtained by attaching an adhesive to the fabric is used. The type of the adhesive is not particularly limited, and a known adhesive can be used as it is or by appropriately selecting the composition ratio. In particular, an adhesive mainly composed of an RFL (resorcin-formalin-latex) liquid is generally used. In this case, the RFL liquid may be used alone, and an epoxy compound, an isocyanate compound, or phenol may be used as necessary. You may mix and use other chemicals, such as a compound. There are no particular restrictions on the amount of adhesive that can be applied to the weave fabric, and a desired amount may be given depending on the application and purpose. However, from the viewpoint of mechanical properties, processability, and adhesion to rubber, It is preferable to give 0.1-20 mass% with respect to it, More preferably, it is 1-10 mass%, Most preferably, it is 2-8 mass%.
[0027]
Next, the manufacturing method of the weave fabric of this invention is demonstrated.
The polyketone fiber used for the warp can be produced by a known wet spinning method (a method in which the polyketone is dissolved in a solvent and then made into a fiber form in a coagulation bath, followed by solvent removal and drying, followed by hot drawing). In order to industrially produce polyketone fibers having high strength, high elastic modulus and high dimensional stability with high productivity, a wet spinning method using a metal salt as a solvent is preferably used.
[0028]
The polyketone used for dissolution preferably has a repeating unit of 1-oxotrimethylene of 95 to 100% by mass and an intrinsic viscosity of 2 to 20. This polyketone is dissolved in a solution (for example, zinc chloride / calcium chloride aqueous solution) containing zinc halide, alkali metal halide, alkaline earth metal halide or the like. The dissolved solution is discharged from a spinneret into a liquid such as water to form a thread, and then the metal salt is washed away with an acid aqueous solution such as hydrochloric acid. Next, after drying, the film is stretched by 5 times or more at 200 to 280 ° C. When producing a high-strength polyketone fiber, it is preferable that the total draw ratio is preferably 10 times or more, more preferably 12 times or more, and multistage drawing of two or more stages is performed.
At this time, an oil agent is applied before drawing and / or after drawing to reduce μd at the time of drawing and twisting, and an oil agent is applied again after drawing and / or after twisting so that the μs of the warp is 0.2 or more. It is important to. Further, for the purpose of suppressing the thermal shrinkage of the braided fabric, it is preferable to lower the heat shrinkage stress of the polyketone fiber by performing a low-tensile heat treatment of 0.001 to 1 cN / dtex at 100 to 280 ° C. after the completion of the multistage stretching.
[0029]
The polyketone fiber thus obtained is twisted and processed into a cord, or is drawn and used as a strand. When processing into cords, there are no particular restrictions on the type, method, and number of twisted yarns, and any method such as single twisted yarn, cocoon twisted yarn, picco cocoon twisted yarn, or strong twisted yarn is adopted, and the number of twisted yarns is also twisted by one There are no particular restrictions such as two twists, and three or more twists may be used. The number of twisted yarns may be arbitrarily selected according to the application, use environment, etc. Generally, the twisting coefficient K of the upper twist is twisted in the range of 1000 to 30000. At this time, it is preferable that the twisting yarn tension is 0.01 to 0.2 cN / dtex for both the lower twist and the upper twist.
[0030]
By arranging cords and / or strands containing at least a part of the polyketone fibers obtained in this way in 5 to 80 pieces / 5 cm, and driving the wefts in a ratio of 1 to 10 pieces / 5 cm with a weaving machine, The weave fabric of the present invention is obtained.
An RFL-treated fabric is obtained by attaching an RFL liquid having a concentration of 10 to 30% by mass to the obtained braided fabric and passing through a step of fixing by applying heat of at least 100 ° C. (so-called Dip treatment).
The preferred composition of the RFL solution is resorcin 0.1 to 10% by weight, formalin 0.1 to 10% by weight, latex 1 to 28% by weight, and the more preferred composition is resorcin 0.5 to 3% by weight, formalin. They are 0.5-3 mass% and latex 10-25 mass%. The drying temperature of the RFL solution applied to the brazing fabric is preferably 140 to 200 ° C. and is subjected to a drying heat treatment for at least 10 seconds, preferably 20 to 120 seconds.
[0031]
The dried weave fabric is heat-treated in a heat setting zone and a normalizing zone. At this time, it is important that the heat treatment conditions (heat treatment temperature, tension during heat treatment, heat treatment time) are within a specific range. The heat treatment temperature is preferably 150 to 250 ° C, more preferably 180 to 230 ° C. The heat treatment tension is preferably (maximum heat shrinkage stress ± 0.2) cN / dtex, more preferably maximum heat shrinkage stress. The heat treatment time is preferably in the range of 10 to 300 seconds, more preferably 30 to 120 seconds.
It is preferable that the heat treatment temperature and heat treatment time of the normalizing zone are within the ranges of the heat set temperature and heat treatment time described above. The tension during heat treatment in the normalizing zone is preferably about 10 to 80% of the tension during heat treatment in the heat set zone.
[0032]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be specifically described by way of examples, but they are not intended to limit the scope of the present invention.
The measuring method of each measured value used in the present invention is as follows.
(1) Intrinsic viscosity [η]
The intrinsic viscosity [η] is a value obtained based on the following definition formula.
[0033]
(2) Fineness, tensile strength, elastic modulus, and elongation at 2.0 cN / dtex load
The fineness was determined by leaving the sample at 25 ° C. and 55% humidity for 48 hours,1Weigh (g) and1X100 is defined as a fineness (dtex). The sample is measured for tensile strength, elastic modulus, and elongation at 2.0 cN / dtex load under the conditions of a sample length of 250 mm and a crosshead speed of 300 mm / min.
[0034]
(3) Resin adhesion rate
Absolutely dry mass W after heating 5m of code 5m at 105 ° C2Weigh (g). Next, the cord is chopped into 1 mm lengths and dissolved in 200 ml of hexafluoroisopropanol under stirring at 60 ° C. for 2 hours. After dissolution, the mixture was filtered, and the resulting residue was heat-treated at 105 ° C. for 5 hours.Three(G) is precisely weighed, and the resin adhesion rate is obtained from the following equation.
Resin adhesion rate = (WThree× 10) / (W2) X 100 (%)
[0035]
(4) Dry heat shrinkage
A dry heat treatment is performed at 150 ° C. for 30 minutes in an oven, and the fiber length before and after the heat treatment is measured by applying a load of 1/30 (cN / dtex) and obtained by the following equation.
Dry heat shrinkage = (Lb-La) / (Lb) X 100 (%)
Where LbIs the fiber length before heat treatment, LaIs the fiber length after heat treatment.
[0036]
(5) Maximum heat shrinkage stress, maximum heat shrink temperature
Using a CORD-TESTER (trademark) (Goodrich Type) (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the thermal contraction force characteristics of fibers and cords under a constant displacement are measured under the following conditions.
TemperatureProgram: EXP mode
ΘM : 250 ° C
T1 : 3 minutes
Initial load: 1/80 (g / dtex)
Initial sample length: 250 mm
Maximum contraction force F from measured temperature-contraction force curvemax(CN) and the temperature T showing the maximum contraction forcemaxRead (℃) and TmaxIs the maximum heat shrinkage temperature. FmaxIs divided by the fineness (dtex) of the sample to obtain the maximum heat shrinkage stress σMAX(CN / dtex) is obtained.
[0037]
(6) Coefficient of static friction between warp and weft (μs)
Measurement is performed using the apparatus shown in FIG. A weft 1 having a length of about 690 m is wound around a
μs = (1 / π) × ln (T2/ T1)
Where T1Is the weight of the weight on the fiber, T2Is a tension measured with a strain gauge, ln is a natural logarithm, and π is a circumference.
[0038]
(7) Coefficient of dynamic friction between polyketone fiber and polyketone fiber (μd)
Measurement is performed using the apparatus shown in FIG. A polyketone fiber (A) 6 having a length of about 690 m is wound around the
μd = (1 / π) × ln (T2/ T1)
Where T1Is the weight of the weight on the fiber, T2Is the measured tension, ln is the natural logarithm, and π is the circumference.
[0039]
[Example 1]
A polyketone having an intrinsic viscosity of 6.0, which is prepared by a conventional method and is completely copolymerized with ethylene and carbon monoxide, is dissolved in an aqueous solution containing 40% by mass of calcium chloride / 22% by mass of zinc chloride to obtain a polyketone concentration of 6.5. A mass% dope was obtained. The obtained dope was heated to 80 ° C., passed through a 10 mm air gap from a nozzle with a nozzle diameter of 0.15 mmφ, L / D = 1, and the number of holes of 250, then 2% by mass of calcium chloride, 1.1 In a coagulation bath consisting of -2 ° C water containing 0.1% by mass of zinc chloride and 0.1% by mass of hydrochloric acid, the yarn is extruded at a rate of 22.5 cc / min and discharged at a rate of 5 m / min. I picked it up.
[0040]
Subsequently, after the yarn was sequentially washed with an aqueous hydrochloric acid solution and water, 0.05% by mass of IRGANOX (registered trademark) (manufactured by Ciba Specialty Chemicals) 1098 and IRGANOX (registered trademark) (manufactured by Ciba Specialty Chemicals) 1076 respectively. After blending (with polyketone), it was dried at 225 ° C. for a fixed length. Further, after stretching 7 times at 225 ° C., 6 polyketone fibers were combined to give an oil emulsion having a concentration of 1% by mass, then 1.5 times at 240 ° C. and 1.3 times at 250 ° C. Four-stage stretching of 1.2 times at 257 ° C. and a total of 16.4 times was performed. An oil agent emulsion having a concentration of 7.5% by mass was applied to the polyketone fiber, and heat treatment was performed at 220 ° C. for 15 seconds (tension = 0.1 cN / dtex).
[0041]
The oil having the following composition was used.
Oleic acid lauryl ester / bisoxyethyl bisphenol A / polyether (propylene oxide / ethylene oxide = 35/65: molecular weight 20000) / polyethylene oxide 10 mol addition oleyl ether / polyethylene oxide 10 mol addition castor oil ether / sodium stearylsulfonate / dioctyllin Sodium acid = 30/30/10/5/23/1/1 (mass% ratio).
[0042]
The drawability was good, and there were no defects such as fuzz and yarn breakage during drawing.
The obtained polyketone fiber had excellent properties, with a fineness of 1510 dtex, a tensile strength of 17.0 cN / dtex, and an elastic modulus of 355 cN / dtex. Further, the dry heat shrinkage rate was 0.4%, the maximum heat shrinkage stress was 0.25 cN / dtex, and the heat shrinkage characteristics were excellent. The μd of this fiber was 0.22.
After this polyketone fiber was twisted in the Z direction, two of the polyketone fibers were lined up and twisted together in the S direction to form a polyketone cord. The twisting conditions are: lower twist: twist number 390 T / m, twist tension 0.8 N (0.05 cN / dtex), upper twist: twist number 390 T / m, twist tension 1.8 N (0.05 cN / dtex) (The twist coefficient of the upper twist is 21432). The twisting property was good, and there were no problems in the process such as fluff and yarn breakage during twisting.
[0043]
The resulting polyketone cord had a fineness of 3620 dtex, a tensile strength of 12.7 cN / dtex, and an elongation at a load of 2.0 cN / dtex of 3.1%, and had excellent mechanical properties. The maximum heat shrinkage temperature was 218 ° C., the maximum heat shrinkage stress was 0.20 cN / dtex, and the dry heat shrinkage rate was 0.5%, which had stable heat shrinkage characteristics.
Using this polyketone cord as a warp, weft 20sUsing a cotton spun yarn, a weave fabric with a warp density of 40 / 5cm, a weft density of 4 / 5cm, and a width of 1400mm was woven. There was no generation of fluff or fibrils during weaving, and no lint or fluff was observed on the loom, and weaving was good. The μs between the warp and the weft was 0.32. The obtained weave fabric was flat, free from misalignment, and excellent in quality.
[0044]
[Example 2]
The soaking fabric obtained in Example 1 was immersed in an RFL solution having the following liquid composition, followed by a drying treatment at 160 ° C. for 80 seconds, a constant-length heat setting treatment at 220 ° C. for 45 seconds, and further at 220 ° C. for 45 seconds. The normalizing process was performed.
(RFL solution composition)
Resorcin 22.0 parts
Formalin (30% by mass) 30.0 parts
Sodium hydroxide (10% by mass) 14.0 parts
570.0 parts of water
Vinylpyridine latex (41% by mass) 364.0 parts
The RFL resin adhesion rate of the interwoven fabric thus obtained was 5.5% by mass. The interwoven fabric was flat, no distortion due to heat shrinkage was observed, the warp cord density was uniform, no misalignment, and high quality.
[0045]
[Comparative Example 1]
In Example 1, the number of combined yarns after one-stage stretching was set to 3, the emulsion concentration of the finishing agent to be applied after the end of stretching was set to 30% by mass, and spinning was similarly performed except that heat setting after the end of stretching was not performed. Drying and stretching were performed to produce polyketone fibers having a fineness of 791 dtex. The resulting polyketone fiber has a tensile strength of 16.1 cN / dtex, an elastic modulus of 314 cN / dtex, a dry heat shrinkage of 1.9%, a maximum heat shrinkage stress of 0.72 cN / dtex, and μd of 0.07. Met.
[0046]
This polyketone fiber was twisted in the same manner as in Example 1 (both twisted / upper twisted: 390 T / m: twisted coefficient of the upper twist = 15512) to obtain a polyketone cord. The cord made of this polyketone fiber has a fineness of 1801 dtex, a tensile strength of 13.1 cN / dtex, an elongation at 2.0 cN / dtex of 3.0%, a maximum heat shrinkage temperature of 0.66 cN / dtex, and dry heat shrinkage The rate was 1.9%.
Using this polyketone fiber cord as a warp, 10sWas used as a weft to weave a weave fabric having a warp density of 75 / 5cm, a weft density of 5 / 5cm, and a width of 500mm. The μs between the warp and the weft was 0.08. The obtained weave fabric had 2 to 10 misalignments per 1 m in length, which was inferior in quality to the weave fabric of Example 1.
[0047]
[Comparative Example 2]
The comb fabric obtained in Comparative Example 1 was treated with the RFL solution in the same formulation as in Example 2. The obtained tinned RFL-treated fabric was not only misaligned, but also had distortion due to heat shrinkage at 1 to 2 locations per 1 m length, had poor flatness and poor quality.
This tinted fabric had an RFL resin adhesion rate of 6.2% by mass.
[0048]
【The invention's effect】
The weave fabric of the present invention is composed of warp yarns made of polyketone fibers excellent in strength, dimensional stability and heat resistance, and weft yarns, and is excellent in mechanical and thermal properties. Furthermore, the weave fabric of the present invention has no misalignment due to slippage between the warp and the weft, does not cause distortion due to heat shrinkage, is excellent in dimensional stability and flatness, and is free from fluff, fibrillar material, fluff, and powder. It is a high quality interwoven fabric, and has excellent processability such as twisted yarn, weaving, and RFL treatment.
The weave fabric of the present invention is suitably used as a rubber reinforcing material after applying an adhesive. Specifically, it is extremely useful as a rubber reinforcing fiber material for tires, belts, hoses and the like.
[Brief description of the drawings]
FIG. 1 is a schematic view of an apparatus for measuring a coefficient of static friction (μs) between a warp and a weft.
FIG. 2 is a schematic view of an apparatus for measuring a dynamic friction coefficient (μd) between a polyketone fiber and a polyketone fiber.
Claims (9)
Ｋ＝Ｙ×Ｄ0.5
（式中、Ｙは、コード１ｍあたりの撚り数（Ｔ／ｍ）、Ｄは、コードの総表示繊度（ｄｔｅｘ））The warp is a cord containing 50% by mass or more of polyketone fiber, the twist coefficient K of the upper twist shown by the following formula is twisted at 1000 to 30000, the tensile strength is 7 cN / dtex or more, and 2.0 cN / The weave fabric according to claim 1 or 2, wherein the elongation at dtex load is 5% or less.
K = Y × D 0.5
(In the formula, Y is the number of twists per 1 m of cord (T / m), and D is the total display fineness of the cord (dtex)).
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| JP2001237050A JP4584503B2 (en) | 2001-08-03 | 2001-08-03 | Weave fabric |
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| JP2001237050A JP4584503B2 (en) | 2001-08-03 | 2001-08-03 | Weave fabric |
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| JP4584503B2 true JP4584503B2 (en) | 2010-11-24 |
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| JP2001237050A Expired - Lifetime JP4584503B2 (en) | 2001-08-03 | 2001-08-03 | Weave fabric |
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