JP5676337B2 - Polyparaphenylene terephthalamide fiber composite and production method thereof - Google Patents
Polyparaphenylene terephthalamide fiber composite and production method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims description 167
- 239000002131 composite material Substances 0.000 title claims description 88
- -1 Polyparaphenylene terephthalamide Polymers 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 69
- 239000004593 Epoxy Substances 0.000 claims description 66
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920000126 latex Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000004816 latex Substances 0.000 claims description 7
- 239000000600 sorbitol Substances 0.000 claims description 7
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 6
- 229920000223 polyglycerol Polymers 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004848 polyfunctional curative Substances 0.000 claims description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001755 resorcinol Drugs 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 48
- 238000010438 heat treatment Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 13
- 239000005060 rubber Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000009987 spinning Methods 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003014 reinforcing effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 3
- GFRHRWJBYWRSJE-UHFFFAOYSA-N bis(16-methylheptadecyl) hexanedioate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCCCCCC(C)C GFRHRWJBYWRSJE-UHFFFAOYSA-N 0.000 description 3
- QZULIRBSQUIUTA-CLFAGFIQSA-N bis[(z)-octadec-9-enyl] hexanedioate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC\C=C/CCCCCCCC QZULIRBSQUIUTA-CLFAGFIQSA-N 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 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 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 description 1
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Description
本発明はゴム材料や樹脂材料の補強用に好適で、高ヤング率で、寸法安定性が良好で、耐熱性に優れたポリパラフェニレンテレフタルアミド繊維複合体およびその製造方法、ならびにその用途に関するものである。 The present invention relates to a polyparaphenylene terephthalamide fiber composite which is suitable for reinforcing rubber materials and resin materials, has a high Young's modulus, good dimensional stability, and excellent heat resistance, a method for producing the same, and uses thereof It is.
ポリパラフェニレンテレフタルアミド（以下、ＰＰＴＡと記す）繊維は、紡糸時にポリマー溶解の溶媒として濃硫酸を用い液晶状態とした後、口金によるせん断を与えて結晶化度の高い糸に形成される。溶媒である濃硫酸は、紡糸直後に水洗およびアルカリにより中和処理され、２００℃以上で乾燥・熱処理された後、フィラメントとして巻き取られて製造されることが知られている（特許文献１）。 Polyparaphenylene terephthalamide (hereinafter referred to as PPTA) fiber is formed into a highly crystallized yarn by applying concentrated sulfuric acid as a solvent for polymer dissolution at the time of spinning to a liquid crystal state, and then applying shear by a die. It is known that concentrated sulfuric acid, which is a solvent, is neutralized by washing and alkali immediately after spinning, dried and heat-treated at 200 ° C. or higher, and then wound up as a filament (Patent Document 1). .
ＰＰＴＡ繊維は、高強度、高弾性率、高耐熱性、非導電性、錆びないなどの高い機能性と、有機繊維特有のしなやかさと軽量性を併せ持った合成繊維である。これらの特長から、自動車や自動二輪、および自転車用のタイヤ、自動車用歯付きベルト、コンベヤ等の補強材料として用いられている。また、光ファイバーケーブルの補強やロープにも利用されている。さらに、防弾チョッキや、刃物に対して切れにくい性質を利用した作業用手袋や、作業服などの防護衣料、燃え難さを利用した消防服への応用も行われている。 PPTA fiber is a synthetic fiber that has both high functionality such as high strength, high elastic modulus, high heat resistance, non-conductivity, and no rust, and the flexibility and lightness peculiar to organic fibers. Because of these features, they are used as reinforcing materials for automobiles, motorcycles, bicycle tires, automobile toothed belts, conveyors, and the like. It is also used for reinforcing optical cables and ropes. In addition, it is also applied to bulletproof vests, working gloves that are difficult to cut against blades, protective clothing such as work clothes, and fire-fighting clothes that are difficult to burn.
これらの利用分野において、ＰＰＴＡ繊維を補強用繊維としてゴムと接着させる場合はレゾルシン・ホルマリン・ラテックス（以下、ＲＦＬと記す）処理を行う必要があるが、ＲＦＬはＰＰＴＡ繊維への付着性が良くない。そこで通常はＰＰＴＡ繊維にエポキシ化合物等で処理を行った後に、ＲＦＬ処理を行うという方法がとられている（特許文献２、特許文献３等）。 In these fields of application, when PPTA fibers are bonded to rubber as reinforcing fibers, it is necessary to carry out a resorcin / formalin / latex (hereinafter referred to as RFL) treatment, but RFL has poor adhesion to PPTA fibers. . Therefore, usually, a method of performing RFL treatment after treating PPTA fiber with an epoxy compound or the like is employed (Patent Document 2, Patent Document 3, etc.).
また、ＰＰＴＡ繊維にあらかじめエポキシ化合物の接着剤被覆をしておく方法（特許文献４）や、エポキシ化合物を繊維表面だけではなく繊維に浸透させる方法（特許文献５、特許文献６）が知られており、これらのＰＰＴＡ繊維にＲＦＬ処理を行うことも可能である。 Also known are a method in which PPTA fibers are coated with an epoxy compound adhesive in advance (Patent Document 4) and a method in which the epoxy compound penetrates not only the fiber surface but also the fibers (Patent Documents 5 and 6). It is also possible to perform RFL treatment on these PPTA fibers.
しかしながら、特許文献２や特許文献３等に記載されたＲＦＬを付着させる方法は、２浴以上の処理工程が必要であり生産の際に効率的ではない。特許文献４に記載されているのは、紡糸の際にエポキシ化合物の接着剤を被覆する方法であるが、中和、洗浄の工程の後にエポキシ化合物と硬化剤の水溶液を繊維に添加した後、熱ドラムで硬化させるため、熱ドラムへの付着物が多量に発生して頻繁にドラムを清掃する必要があり生産の際に効率が悪い。特許文献５および６に記載された方法は、エポキシ化合物を繊維表面だけではなく繊維に浸透させて接着強度の向上を試みているが、エポキシ化合物の水溶液で処理を行うだけで追油を行わないため繊維表面の擦過により、ＰＰＴＡ繊維の弱点であるフィブリル化が容易に生じてしまい、毛羽が発生するという問題点がある。 However, the method of attaching RFL described in Patent Document 2, Patent Document 3, and the like requires a treatment process of two or more baths and is not efficient in production. Patent Document 4 describes a method of coating an epoxy compound adhesive during spinning, but after adding an aqueous solution of an epoxy compound and a curing agent to the fiber after the steps of neutralization and washing, Since it is cured by a thermal drum, a large amount of deposits are generated on the thermal drum, and it is necessary to frequently clean the drum, which is inefficient during production. In the methods described in Patent Documents 5 and 6, an attempt is made to improve the adhesive strength by allowing the epoxy compound to penetrate not only the fiber surface but also the fiber. For this reason, there is a problem in that fibrillation, which is a weak point of PPTA fiber, easily occurs due to abrasion of the fiber surface, and fluff is generated.
本発明の目的は、上記従来技術の欠点を解消し、ＰＰＴＡ繊維本来の高耐熱性および高ヤング率を保持しながら、接着強度が高く、ゴム材料、樹脂材料の補強用として有用な繊維複合体および製造法、さらにはゴム補強用として優れた耐熱性を持つ高強力コードを提供することにある。 An object of the present invention is to solve the above-mentioned disadvantages of the prior art, and maintain a high heat resistance and a high Young's modulus inherent in PPTA fibers, while having high adhesive strength and useful for reinforcing rubber materials and resin materials. Another object of the present invention is to provide a high-strength cord having excellent heat resistance as a manufacturing method and further for reinforcing rubber.
本発明は上記課題を解決するため、次の手段をとるものである。 In order to solve the above problems, the present invention takes the following means.
（１）硬化性エポキシ化合物を含む油剤（硬化性エポキシ化合物のみからなる油剤を除く）を繊維骨格内に浸透させたポリパラフェニレンテレフタルアミド繊維複合体であって、１００〜１６０℃で乾燥することにより調整された水分量が１５〜２００重量％であり、かつ硬化性エポキシ化合物を含む油剤中の硬化性エポキシ化合物の繊維への含浸量が、上記繊維の水分量を０重量％に換算したときの繊維重量に対して０．１重量％以上２．０重量％以下であることを特徴とするポリパラフェニレンテレフタルアミド繊維複合体。
(1) A polyparaphenylene terephthalamide fiber composite in which an oil containing a curable epoxy compound (excluding an oil containing only a curable epoxy compound) is infiltrated into the fiber skeleton, and is dried at 100 to 160 ° C. When the amount of water adjusted by 15 to 200% by weight and the amount of impregnation into the fiber of the curable epoxy compound in the oil containing the curable epoxy compound is converted to 0% by weight of the fiber A polyparaphenylene terephthalamide fiber composite characterized by being 0.1 wt% or more and 2.0 wt% or less with respect to the fiber weight of the fiber.
（２）硬化性エポキシ化合物を含む油剤（硬化性エポキシ化合物のみからなる油剤を除く）および、硬化剤を含む油剤を繊維骨格内に浸透させたポリパラフェニレンテレフタルアミド繊維複合体であって、１００〜１６０℃で乾燥することにより調整された水分量が１５〜２００重量％であり、 かつ上記繊維の水分量を０重量％に換算したときの繊維重量に対して硬化性エポキシ化合物を含む油剤中の硬化性エポキシ化合物の繊維への含浸量が、０．１重量％以上２．０重量％以下、硬化剤を含む油剤中の硬化剤の繊維への含浸量が、０．０２重量％以上１．０重量％以下であることを特徴とするポリパラフェニレンテレフタルアミド繊維複合体。
(2) A polyparaphenylene terephthalamide fiber composite in which an oil agent containing a curable epoxy compound (excluding an oil agent composed only of a curable epoxy compound) and an oil agent containing a curing agent are permeated into the fiber skeleton, In an oil containing a moisture content adjusted by drying at ˜160 ° C. of 15 to 200 wt%, and containing a curable epoxy compound with respect to the fiber weight when the moisture content of the fiber is converted to 0 wt% The amount of the curable epoxy compound impregnated into the fiber is 0.1 wt% or more and 2.0 wt% or less, and the amount of the impregnation into the fiber of the curing agent in the oil containing the curing agent is 0.02 wt% or more 1 A polyparaphenylene terephthalamide fiber composite characterized by being less than 0.0% by weight.
（３）油剤に含まれる硬化性エポキシ化合物がグリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテルから選ばれる１種類または、２種類以上の混合物である上記（１）または（２）記載のポリパラフェニレンテレフタルアミド繊維複合体。 (3) The above (1), wherein the curable epoxy compound contained in the oil is one kind or a mixture of two or more kinds selected from glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether. Or the polyparaphenylene terephthalamide fiber composite as described in (2).
（４）油剤に含まれる硬化剤が三級アミンである上記（２）記載のポリパラフェニレンテレフタルアミド繊維複合体。 (4) The polyparaphenylene terephthalamide fiber composite according to (2) above, wherein the curing agent contained in the oil is a tertiary amine.
（５）上記（１）または（２）記載の繊維複合体を緊張下で熱処理することにより、水分率を１５重量％未満としたことを特徴とする熱処理後のポリパラフェニレンテレフタルアミド繊維複合体。 (5) A polyparaphenylene terephthalamide fiber composite after heat treatment, wherein the fiber composite according to (1) or (2) is heat-treated under tension to make the moisture content less than 15% by weight. .
（６）上記（５）記載のポリパラフェニレンテレフタルアミド繊維複合体を用いたことを特徴とするコード。 (6) A cord using the polyparaphenylene terephthalamide fiber composite as described in (5) above.
（７）上記（５）記載のポリパラフェニレンテレフタルアミド繊維複合体を０．１〜５ｍｍにカットしたフロック状の短繊維複合体。 (7) A flock-like short fiber composite obtained by cutting the polyparaphenylene terephthalamide fiber composite according to the above (5) into 0.1 to 5 mm.
（８）上記（５）記載のポリパラフェニレンテレフタルアミド繊維複合体にレゾルシン・ホルマリン・ラテックス（ＲＦＬ）による浸漬処理を施した後、０．１〜５ｍｍにカットしたフロック状の短繊維複合体。 (8) A flock-like short fiber composite cut into 0.1 to 5 mm after the polyparaphenylene terephthalamide fiber composite described in (5) above is subjected to an immersion treatment with resorcin / formalin latex (RFL).
（９）ポリパラフェニレンテレフタルアミド硫酸溶液を紡出・中和し、１００〜１６０℃で５〜２０秒間乾燥することにより水分率１５〜２００重量％を保つようにしたポリパラフェニレンテレフタルアミド繊維に、硬化性エポキシ化合物を含む油剤（硬化性エポキシ化合物のみからなる油剤を除く）を付与して繊維骨格内に浸透させた後、続いて巻き取り工程でボビンに巻き取ることを特徴とするポリパラフェニレンテレフタルアミド繊維複合体の製造方法。
(9) A polyparaphenylene terephthalamide sulfuric acid solution is spun and neutralized and dried at 100 to 160 ° C. for 5 to 20 seconds to maintain a moisture content of 15 to 200% by weight. The polyparaffin is characterized in that an oil containing a curable epoxy compound (excluding an oil containing only a curable epoxy compound) is applied and infiltrated into the fiber skeleton, and then wound on a bobbin in a winding process. A method for producing a phenylene terephthalamide fiber composite.
（１０）ポリパラフェニレンテレフタルアミド硫酸溶液を紡出・中和し、１００〜１６０℃で５〜２０秒間乾燥することにより水分率１５〜２００重量％を保つようにしたポリパラフェニレンテレフタルアミド繊維に、硬化性エポキシ化合物を含む油剤（硬化性エポキシ化合物のみからなる油剤を除く）および、硬化剤を含む油剤を付与して繊維骨格内に浸透させた後、続いて巻き取り工程でボビンに巻き取ることを特徴とするポリパラフェニレンテレフタルアミド繊維複合体の製造方法。
(10) A polyparaphenylene terephthalamide fiber prepared by spinning and neutralizing a polyparaphenylene terephthalamide sulfuric acid solution and drying at 100 to 160 ° C. for 5 to 20 seconds to maintain a moisture content of 15 to 200% by weight. , An oil containing a curable epoxy compound (excluding an oil containing only a curable epoxy compound) and an oil containing a curing agent are applied and infiltrated into the fiber skeleton, and then wound on a bobbin in a winding process. A process for producing a polyparaphenylene terephthalamide fiber composite characterized by the above.
（１１）油剤に含まれる硬化性エポキシ化合物がグリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテルから選ばれる１種類または、２種類以上の混合物である上記（９）または（１０）記載のポリパラフェニレンテレフタルアミド繊維複合体の製造方法。
(11) The above (9), wherein the curable epoxy compound contained in the oil is one kind or a mixture of two or more kinds selected from glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether. Or the manufacturing method of the polyparaphenylene terephthalamide fiber composite as described in (10).
（１２）油剤に含まれる硬化剤が三級アミンである上記（１０）記載のポリパラフェニレンテレフタルアミド繊維複合体の製造方法。 (12) The method for producing a polyparaphenylene terephthalamide fiber composite according to (10), wherein the curing agent contained in the oil is a tertiary amine.
（１３）上記（９）〜（１２）いずれか記載の製造方法によって得られたポリパラフェニレンテレフタルアミド繊維複合体をボビンから巻き出して緊張下で熱処理することにより、水分率を１５重量％未満としたことを特徴とするポリパラフェニレンテレフタルアミド繊維複合体の製造方法。 (13) The polyparaphenylene terephthalamide fiber composite obtained by the production method according to any one of (9) to (12) above is unwound from a bobbin and heat-treated under tension, so that the moisture content is less than 15% by weight. A process for producing a polyparaphenylene terephthalamide fiber composite, characterized in that
本発明では、従来の問題点であった、ＲＦＬを付着させる方法で２浴以上の処理工程が必要であり生産が効率的ではなかった点；紡糸の際にエポキシ化合物の接着剤をあらかじめ被覆しておく方法で、エポキシ化合物と硬化剤の水溶液を繊維に添加した後、熱ドラムで硬化させるため熱ドラムへの付着物が多量に発生して頻繁にドラムを清掃する必要があり生産が効率的でなかった点；エポキシ化合物を繊維表面だけではなく繊維に浸透させる方法で、繊維に油剤を含有しなかったため繊維表面の擦過により毛羽が発生するという点；等を改善できる。 In the present invention, the method of attaching RFL, which has been a conventional problem, requires a treatment step of two or more baths and is not efficient in production; an epoxy compound adhesive is coated in advance during spinning. In this method, after adding an aqueous solution of an epoxy compound and a curing agent to the fiber and curing it with a thermal drum, a large amount of deposits are generated on the thermal drum and the drum needs to be cleaned frequently. It is possible to improve the point that fuzz is generated by rubbing the fiber surface because the fiber does not contain an oil agent by the method of allowing the epoxy compound to penetrate not only the fiber surface but also the fiber.
それにより、ＰＰＴＡ繊維本来の高ヤング率を保持しながら、接着強度が高く、ゴム材料、樹脂材料の補強用として有用な繊維複合体を提供できる。特に本発明のＰＰＴＡ繊維複合体は優れた耐熱性を持つので、ＲＦＬ処理時に被る高温による強力低下が少ないので高強力なゴム補強用コードを提供することができる。 Thereby, while maintaining the high Young's modulus inherent in PPTA fibers, it is possible to provide a fiber composite having high adhesive strength and useful for reinforcing rubber materials and resin materials. In particular, since the PPTA fiber composite of the present invention has excellent heat resistance, it is possible to provide a high-strength rubber-reinforcing cord because there is little decrease in strength due to high temperatures experienced during RFL treatment.
本発明におけるポリパラフェニレンテレフタルアミド（ＰＰＴＡ）とは、テレフタル酸とパラフェニレンジアミンを重縮合して得られる重合体であるが、少量のジカルボン酸およびジアミンを共重合したものも使用でき、重合体または共重合体の分子量は通常２０，０００〜２５，０００が好ましい。 The polyparaphenylene terephthalamide (PPTA) in the present invention is a polymer obtained by polycondensation of terephthalic acid and paraphenylene diamine, but a polymer obtained by copolymerizing a small amount of dicarboxylic acid and diamine can also be used. Or, the molecular weight of the copolymer is usually preferably 20,000 to 25,000.
ＰＰＴＡ繊維は、ＰＰＴＡを濃硫酸に溶解し、その粘調な溶液を紡糸口金から押し出し、空気中または水中に紡出することによりフィラメント状にした後、水酸化ナトリウム水溶液で中和し、最終的には１２０〜５００℃の乾燥・熱処理をして得られる。 PPTA fibers are made by dissolving PPTA in concentrated sulfuric acid, extruding the viscous solution from a spinneret, spinning into air or water, neutralizing with an aqueous sodium hydroxide solution, and finally Is obtained by drying and heat treatment at 120 to 500 ° C.
本発明のＰＰＴＡ繊維の製造方法の代表例としては、ＰＰＴＡを濃硫酸に溶解して、１８〜２０重量％の粘調な溶液とし、これを紡糸口金から吐出して、わずかの間空気中に紡出後、水中へ紡糸する。この時、口金吐出時のせん断速度を２５，０００〜５０，０００ｓｅｃ−１にするのが好ましい。その後、紡糸浴中で凝固した繊維を水酸化ナトリウム水溶液で中和処理した後、１００〜１６０℃で、好ましくは５〜２０秒間乾燥する。このようにして、本発明の硬化性エポキシ化合物含浸前のＰＰＴＡ繊維の状態となる。続けて、この含浸処理前のＰＰＴＡ繊維に硬化性エポキシ化合物を含む油剤または、硬化性エポキシ化合物を含む油剤および硬化剤を含む油剤を含浸し、続いて巻き取り工程でボビンに巻き取り、本発明のＰＰＴＡ繊維複合体を得る。さらに、ボビンから巻き出して緊張下で熱処理して水分率を１５重量％未満とすることで、本発明のＰＰＴＡ繊維複合体を得る。 As a typical example of the production method of the PPTA fiber of the present invention, PPTA is dissolved in concentrated sulfuric acid to obtain a viscous solution of 18 to 20% by weight, and this is discharged from the spinneret to be in the air for a short time. After spinning, spin into water. At this time, it is preferable to set the shear rate during discharge of the die to 25,000 to 50,000 sec −1 . Thereafter, the fiber solidified in the spinning bath is neutralized with an aqueous sodium hydroxide solution, and then dried at 100 to 160 ° C., preferably for 5 to 20 seconds. Thus, it will be in the state of the PPTA fiber before impregnation of the curable epoxy compound of this invention. Subsequently, the PPTA fiber before the impregnation treatment is impregnated with an oil containing a curable epoxy compound or an oil containing a curable epoxy compound and an oil containing a curing agent, and then wound on a bobbin in a winding process. Of PPTA fiber composite. Furthermore, the PPTA fiber composite of the present invention is obtained by unwinding from the bobbin and heat-treating under tension to make the moisture content less than 15% by weight.
本発明のＰＰＴＡ繊維複合体は、温度１００〜１６０℃で熱処理条件などを変更しながら、ＰＰＴＡ繊維の結晶サイズが５０オングストローム未満の状態を保ち、かつ、水分率が１５〜２００重量％、好ましくは２０〜５０重量％の状態を保つようなＰＰＴＡ繊維とし、そこに硬化性エポキシ化合物を含む油剤あるいは、硬化性エポキシ化合物を含む油剤と硬化剤を含む油剤を浸透させることによって得られる。 The PPTA fiber composite of the present invention maintains the PPTA fiber crystal size of less than 50 angstroms while changing the heat treatment conditions at a temperature of 100 to 160 ° C., and the moisture content is 15 to 200% by weight, preferably PPTA fibers that maintain a state of 20 to 50% by weight are obtained and impregnated with an oil containing a curable epoxy compound or an oil containing a curable epoxy compound and an oil containing a curing agent.
ＰＰＴＡ繊維の結晶サイズが５０オングストローム以上では、硬化性エポキシ化合物および油剤を繊維骨格内に浸透させるのが困難となる。また、水分率が１５重量％未満では硬化性エポキシ化合物を含む油剤あるいは、硬化性エポキシ化合物を含む油剤と硬化剤を含む油剤を繊維骨格内に浸透させるのが困難となり、水分率が２００重量％を超えると繊維を巻き取る工程が困難になりコストアップの要因となる。 When the crystal size of the PPTA fiber is 50 angstroms or more, it is difficult to penetrate the curable epoxy compound and the oil into the fiber skeleton. If the moisture content is less than 15% by weight, it becomes difficult to permeate the fiber skeleton with an oil containing a curable epoxy compound, or an oil containing a curable epoxy compound and an oil containing a curing agent, and the moisture content is 200% by weight. If it exceeds 1, the process of winding the fiber becomes difficult, which increases the cost.
硬化性エポキシ化合物および硬化剤は、ＰＰＴＡ繊維の水分量を０％に換算した繊維重量に対して、硬化性エポキシ化合物を含む油剤に含まれる硬化性エポキシ化合物を０．１〜２．０重量％、好ましくは０．２〜１．０重量％含浸・浸透させ、硬化剤を含む油剤中の硬化剤を０．０２〜１．０重量％、好ましくは０．０４〜０．５重量％含浸・浸透させるのがよい。 The curable epoxy compound and the curing agent are 0.1 to 2.0% by weight of the curable epoxy compound contained in the oil containing the curable epoxy compound with respect to the fiber weight in which the moisture content of the PPTA fiber is converted to 0%. , Preferably 0.2 to 1.0 wt% impregnated and infiltrated, 0.02 to 1.0 wt%, preferably 0.04 to 0.5 wt% impregnated hardener in an oil containing a hardener It should be infiltrated.
用いられる硬化性エポキシ化合物は、グリセロール、ソルビトール、ポリグリセロールなどの多価アルコールのグリシジルエーテルから選ばれる１種以上または、２種以上の混合物であることが好ましい。例えば、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテルなどが挙げられる。 The curable epoxy compound used is preferably one or more selected from glycidyl ethers of polyhydric alcohols such as glycerol, sorbitol, and polyglycerol, or a mixture of two or more. Examples thereof include glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, and the like.
用いられる硬化剤は、アミンであることが好ましく、特に三級アミンが好ましい。例えば、ジメチルオクチルアミン、ジメチルデシルアミン、ジメチルラウリルアミンや、脂肪族一級アミンにエチレンオキサイドを付加した長鎖アルキルポリオキシエチレン型三級アミンなどが挙げられる。 The curing agent used is preferably an amine, particularly a tertiary amine. Examples thereof include dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, and long-chain alkylpolyoxyethylene type tertiary amine obtained by adding ethylene oxide to an aliphatic primary amine.
用いられる油剤は、ＰＰＴＡ繊維に用いられる一般的な油剤、例えば、炭素数１８以下の低分子量脂肪酸エステル、ポリエーテル、鉱物油などが挙げられる。 Examples of the oil used include general oils used for PPTA fibers, such as low molecular weight fatty acid esters having 18 or less carbon atoms, polyethers, and mineral oils.
硬化性エポキシ化合物は、上記油剤中に約２０〜６０重量％、好ましくは３０〜５０重量％の量で用いられる。また、硬化剤は、上記油剤中に約３〜２０重量％、好ましくは５〜１０重量％の量で用いられる。 The curable epoxy compound is used in the oil agent in an amount of about 20 to 60% by weight, preferably 30 to 50% by weight. The curing agent is used in the oil agent in an amount of about 3 to 20% by weight, preferably 5 to 10% by weight.
硬化性エポキシ化合物を含む油剤、ならびに硬化剤を含む油剤をＰＰＴＡ繊維に付与する方法は、特に限定されず、従来公知の任意の方法が採用されてよく、例えば、浸漬給油法、スプレー給油法、ローラー給油法、計量ポンプを用いたガイド給油法等の方法でＰＰＴＡ繊維に付与される。 The method for imparting the oil agent containing the curable epoxy compound and the oil agent containing the curing agent to the PPTA fiber is not particularly limited, and any conventionally known method may be employed. For example, an immersion oil supply method, a spray oil supply method, It is applied to the PPTA fiber by a method such as a roller oiling method or a guide oiling method using a metering pump.
硬化性エポキシ化合物を含む油剤または、硬化性エポキシ化合物を含む油剤および硬化剤を含む油剤をＰＰＴＡ繊維骨格内に浸透させＰＰＴＡ繊維複合体となした後、続いてこのＰＰＴＡ繊維複合体を巻き取り工程でボビンに巻き取る。 An oil agent containing a curable epoxy compound or an oil agent containing a curable epoxy compound and an oil agent containing a curing agent are permeated into the PPTA fiber skeleton to form a PPTA fiber composite, and then the PPTA fiber composite is wound up. Take it up on the bobbin.
巻き取ったＰＰＴＡ繊維複合体をボビンから巻き出して緊張下で熱処理することにより、水分率を１５重量％未満、より好ましくは１０重量％未満とする。熱処理の条件は特に限定されない。例えば８０〜３００℃、好ましくは１００〜２５０℃で熱処理をした場合、水分率は１５重量％未満にすることができる。この熱処理によりＰＰＴＡ繊維複合体のハンドリング性が良好になる。 The wound PPTA fiber composite is unwound from a bobbin and heat-treated under tension, so that the moisture content is less than 15% by weight, more preferably less than 10% by weight. The conditions for the heat treatment are not particularly limited. For example, when heat treatment is performed at 80 to 300 ° C., preferably 100 to 250 ° C., the moisture content can be less than 15% by weight. This heat treatment improves the handleability of the PPTA fiber composite.
本発明のＰＰＴＡ繊維複合体は各種用途に有用であり、特にゴム材料、樹脂材料の補強用として有用である。ゴム補強用に使用する場合は、本発明のＰＰＴＡ繊維複合体にＲＦＬによる浸漬処理を施す。浸漬処理を施す方法は特に限定されるものではないが、通常、ゴムラテックス１００重量部に対してレゾルシン−ホルムアルデヒド初期縮合物を２〜２０重量部含有させた混合物を、通常固形分濃度で５〜２５重量％程度含有するＲＦＬ処理液に、ＰＰＴＡ繊維複合体を浸漬するなどしてＰＰＴＡ繊維複合体に混合物を付着させた後、１００〜２６０℃で熱処理する方法が採用される。 The PPTA fiber composite of the present invention is useful for various applications, and particularly useful for reinforcing rubber materials and resin materials. When used for rubber reinforcement, the PPTA fiber composite of the present invention is subjected to an immersion treatment by RFL. Although the method for performing the dipping treatment is not particularly limited, usually, a mixture containing 2 to 20 parts by weight of the resorcin-formaldehyde initial condensate with respect to 100 parts by weight of the rubber latex is usually 5 to 5 in solids concentration. A method of heat treating at 100 to 260 ° C. after adhering the mixture to the PPTA fiber composite by immersing the PPTA fiber composite in an RFL treatment solution containing about 25% by weight is employed.
ゴムラテックスとしては、ビニルピリジン−スチレン−ブタジエン共重合体ゴムラテックス、スチレン−ブタジエン系ゴムラテックス、アクリロニトリル−ブタジエン系ゴムラテックス、クロロプレン系ゴムラテックス、クロロスルホン化ポリエチレンゴムラテックス、アクリレート系ゴムラテックスおよび天然ゴムラテックスなどが挙げられ、レゾルシン−ホルムアルデヒド初期縮合物としては、レゾルシン−ホルムアルデヒドを酸触媒またはアルカリ触媒下で縮合させて得られたノボラック型縮合物などが挙げられる。処理液には、ブロックドポリイソシアネート化合物、エチレンイミン化合物、ポリイソシアネートとエチレンイミンとの反応物などから選ばれた１種以上の化合物が混合されていてもよい。 Examples of rubber latex include vinylpyridine-styrene-butadiene copolymer rubber latex, styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, chloroprene rubber latex, chlorosulfonated polyethylene rubber latex, acrylate rubber latex and natural rubber. Examples of the resorcin-formaldehyde initial condensate include novolak condensates obtained by condensing resorcin-formaldehyde in the presence of an acid catalyst or an alkali catalyst. In the treatment liquid, one or more compounds selected from a blocked polyisocyanate compound, an ethyleneimine compound, a reaction product of polyisocyanate and ethyleneimine, and the like may be mixed.
本発明のＰＰＴＡ繊維複合体は、硬化性エポキシ化合物が繊維表面および内部に浸透しているのでＲＦＬ処理液の付着性が良い上に、ＲＦＬ高温処理を行ったときコードの強力低下が生じにくいという利点を持つ。硬化性エポキシ化合物とともに硬化剤が浸透しているＰＰＴＡ繊維複合体は、硬化剤の触媒効果により硬化性エポキシ化合物が反応しやすくなるという利点を持つ。 In the PPTA fiber composite of the present invention, the adhesive property of the RFL treatment liquid is good because the curable epoxy compound penetrates the fiber surface and inside, and the strength of the cord is hardly lowered when the RFL high temperature treatment is performed. With advantages. A PPTA fiber composite in which a curing agent is infiltrated with a curable epoxy compound has an advantage that the curable epoxy compound easily reacts due to the catalytic effect of the curing agent.
また、本発明のＰＰＴＡ繊維複合体にＲＦＬによる浸漬処理を施して０．１〜５ｍｍにカットしたフロック状の短繊維複合体は、ゴムベルトに使用される補強材としても有用である。 Further, the floc-like short fiber composite obtained by subjecting the PPTA fiber composite of the present invention to an immersion treatment by RFL and cutting to 0.1 to 5 mm is also useful as a reinforcing material used for a rubber belt.
本発明のＰＰＴＡ繊維複合体にＲＦＬ処理を施さずに０．１〜５ｍｍにカットしたフロック状の短繊維複合体は、歯車に使用される紙、織物、編物、不織布にも有用である。 The floc-like short fiber composite cut into 0.1 to 5 mm without subjecting the PPTA fiber composite of the present invention to RFL treatment is also useful for paper, woven fabric, knitted fabric and nonwoven fabric used for gears.
そのほか、本発明のＰＰＴＡ繊維複合体は、その優れた性質を利用して、紙、織物、編み物、不織布などの布帛、さらにプリント配線板用シート状物などに有用である。 In addition, the PPTA fiber composite of the present invention is useful for fabrics such as paper, woven fabric, knitted fabric and non-woven fabric, and sheet-like materials for printed wiring boards by utilizing its excellent properties.
以下、実施例を示すが、実施例中の各測定値は次の方法にしたがった。 Hereinafter, although an Example is shown, each measured value in an Example followed the following method.
（１）水分量
試料約５ｇの重量を測定し、３００℃×２０分の熱処理を行い、２５℃６５％ＲＨで５分間放置した後、再度重量を測定する。ここで使う水分率は、［乾燥前重量−乾燥後重量］／［乾燥後重量］で得られるドライベース水分率である。
(1) Water content About 5 g of the sample is weighed, heat-treated at 300 ° C. for 20 minutes, left at 25 ° C. and 65% RH for 5 minutes, and then weighed again. The moisture content used here is the dry base moisture content obtained by [weight before drying−weight after drying] / [weight after drying].
（２）繊維の引張強力
テンシロンを使用してＪＩＳ Ｌ １０１３に準じて測定した。
(2) Tensile strength of fiber It was measured according to JIS L 1013 using Tensilon.
（３）コードの引張強力
テンシロンを使用してＪＩＳ Ｌ １０１７に準じて測定した。
(3) Tensile strength of cord The tensile strength was measured according to JIS L 1017 using Tensilon.
（４）接着強力（Ｔ−引抜力）
ＪＩＳ Ｌ １０１７の接着力−Ａ法に準じて下記条件で処理コ−ドを未加硫ゴムに埋め込み、加圧下で１５０℃、３０分プレス加硫を行ない、放冷後、コードをゴムブロックから３０ｃｍ／ｍｉｎの速度で引き抜き、その引き抜き荷重をＮ／ｃｍで表示した。接着評価におけるゴムコンパウンドとしては、天然ゴムを主成分とするカーカス配合の未加硫ゴムを使用した。
(4) Adhesive strength (T-drawing force)
Adhesive strength of JIS L 1017-Treated cord is embedded in unvulcanized rubber under the following conditions according to the A method, press vulcanized under pressure at 150 ° C for 30 minutes, allowed to cool, and then the cord is removed from the rubber block. Drawing was performed at a speed of 30 cm / min, and the drawing load was displayed in N / cm. As a rubber compound in the adhesion evaluation, an unvulcanized rubber containing carcass containing natural rubber as a main component was used.
［実施例１］
通常の方法で得られたＰＰＴＡ（分子量約２０，０００）１ｋｇを４ｋｇの濃硫酸に溶解し、直径０．１ｍｍのホールを１０００個有する口金からせん断速度３０，０００ｓｅｃ−１となるよう吐出し、４℃の水中に紡糸した後、１０重量％の水酸化ナトリウム水溶液で、１０℃×１５秒の条件で中和処理し、その後、１１０℃×１５秒間の低温乾燥をして、水分率３５重量％の処理前のＰＰＴＡ繊維（水分率０重量％換算のとき繊度１６７０ｄｔｅｘ）になるように調製した。
[Example 1]
1 kg of PPTA (molecular weight of about 20,000) obtained by a usual method is dissolved in 4 kg of concentrated sulfuric acid, and discharged from a die having 1000 holes with a diameter of 0.1 mm so that the shear rate is 30,000 sec −1 . After spinning in 4 ° C water, neutralize with 10% by weight sodium hydroxide aqueous solution at 10 ° C for 15 seconds, and then dry at 110 ° C for 15 seconds at a low moisture content of 35%. % Of PPTA fiber before treatment (fineness 1670 dtex when converted to 0% by weight).
このＰＰＴＡ繊維に、硬化性エポキシ化合物としてトリグリセロールトリグリシジルエーテルを５０重量％含有する油剤（ジイソステアリルアジペート／ジオレイルアジペート／硬化ヒマシ油エチレンオキサイド／鉱物油の混合物）を、水分率０重量％換算としたときの繊維に１．０重量％含浸し、硬化性エポキシ化合物を含有する油剤をＰＰＴＡ繊維に浸透させた後、巻き取り工程でボビンに巻き取り、水分率３５重量％のＰＰＴＡ繊維複合体を製造した。 An oil agent (a mixture of diisostearyl adipate / dioleyl adipate / cured castor oil ethylene oxide / mineral oil) containing 50% by weight of triglycerol triglycidyl ether as a curable epoxy compound is added to this PPTA fiber, and the water content is 0% by weight. After impregnating 1.0% by weight of the converted fiber and impregnating the PPTA fiber with an oil containing a curable epoxy compound, it is wound on a bobbin in a winding process and a PPTA fiber composite having a moisture content of 35% by weight. The body was manufactured.
この後、このＰＰＴＡ繊維複合体をボビンから巻き出し、コンピュートリータ処理機（リッツラー社製）を用いて、３．９Ｎの張力での緊張下１３０℃２０秒間熱処理をして巻き取り、水分率が６．９重量％のＰＰＴＡ繊維複合体を得た。 Thereafter, the PPTA fiber composite is unwound from the bobbin and wound up by heat treatment at 130 ° C. for 20 seconds under a tension of 3.9 N using a compute treater (manufactured by Ritzler). A 6.9 wt% PPTA fiber composite was obtained.
得られたＰＰＴＡ繊維複合体のマルチフィラメント２本を用いて、下撚１５．７回／１０ｃｍ，上撚１５．７回／１０ｃｍの撚数で撚糸してコードとした。 Using two obtained multifilaments of PPTA fiber composite, a cord was formed by twisting with a twist number of 15.7 times / 10 cm for the lower twist and 15.7 times / 10 cm for the upper twist.
別途、水酸化ナトリウムの存在下でビニルピリジン−スチレン−ブタジエンラテックス１００重量部に対し、レゾルシン１モルに対しホルムアルデヒドを０．３０モル反応させて得られた初期縮合物を１７重量部混合し、２４時間熟成させた（Ａ）液を準備した。調製した（Ａ）液に、ジフェニルメタン−ビス４，４´−Ｎ，Ｎ´−ジエチレンイミン１５重量部の水分散液にトリヒドロキシエチルイソシアヌレート１２重量部を水で溶解したものを混合することにより、固形分濃度２０％のＲＦＬ処理液を得た。 Separately, 17 parts by weight of an initial condensate obtained by reacting 0.30 mol of formaldehyde with 1 mol of resorcin is mixed with 100 parts by weight of vinylpyridine-styrene-butadiene latex in the presence of sodium hydroxide, A liquid (A) which was aged for time was prepared. By mixing the prepared liquid (A) with 12 parts by weight of trihydroxyethyl isocyanurate dissolved in water in an aqueous dispersion of 15 parts by weight of diphenylmethane-bis 4,4′-N, N′-diethyleneimine An RFL treatment solution having a solid content concentration of 20% was obtained.
続いて上記のＰＰＴＡ繊維複合体で作製したコードを、コンピュートリータ処理機（リッツラー社製）を用いて、前記ＲＦＬ処理液に浸漬（固形分付着量８重量％）し、１４０℃で１５０秒乾燥し、続いて２４５℃で６０秒間熱処理することにより、ＲＦＬディップコードを作製した。 Subsequently, the cord made of the PPTA fiber composite was immersed in the RFL treatment solution (solid content 8 wt%) using a computer treater (Ritzler) and dried at 140 ° C. for 150 seconds. Subsequently, an RFL dip cord was produced by heat treatment at 245 ° C. for 60 seconds.
［実施例２］
通常の方法で得られたＰＰＴＡ（分子量約２０，０００）１ｋｇを４ｋｇの濃硫酸に溶解し、直径０．１ｍｍのホールを１０００個有する口金からせん断速度３０，０００ｓｅｃ−１となるよう吐出し、４℃の水中に紡糸した後、１０重量％の水酸化ナトリウム水溶液で、１０℃×１５秒の条件で中和処理し、その後、１１０℃×１５秒間熱処理して、水分率３５重量％の処理前のＰＰＴＡ繊維（水分率０重量％換算のとき繊度１６７０ｄｔｅｘ）になるように調製した。
[Example 2]
1 kg of PPTA (molecular weight of about 20,000) obtained by a usual method is dissolved in 4 kg of concentrated sulfuric acid, and discharged from a die having 1000 holes with a diameter of 0.1 mm so that the shear rate is 30,000 sec −1 . After spinning in water at 4 ° C., neutralize with 10% by weight aqueous sodium hydroxide solution at 10 ° C. for 15 seconds, and then heat-treat at 110 ° C. for 15 seconds to give a moisture content of 35% by weight. It was prepared so as to be the previous PPTA fiber (fineness 1670 dtex when converted to 0% by weight moisture content).
このＰＰＴＡ繊維に、硬化剤としてジメチルデシルアミンを１０重量％含有する油剤（ジイソステアリルアジペート／ジオレイルアジペート／硬化ヒマシ油エチレンオキサイド／鉱物油の混合物）を、水分率０重量％換算としたときの繊維に０．６重量％含浸し、続いて硬化性エポキシ化合物としてソルビトールポリグリシジルエーテルを５０重量％含有する油剤（ジイソステアリルアジペート／ジオレイルアジペート／硬化ヒマシ油エチレンオキサイド／鉱物油の混合物）を、水分率０重量％換算としたときの繊維に１．０重量％含浸して、硬化性エポキシ化合物、硬化剤および油剤をＰＰＴＡ繊維に浸透させた後、巻き取り工程でボビンに巻き取り、水分率３５重量％のＰＰＴＡ繊維複合体を製造した。
この後、この繊維複合体をボビンから巻き出し、コンピュートリータ処理機（リッツラー社製）を用いて、３．９Ｎの張力での緊張下１１０℃４０秒間熱処理をして巻き取り、水分率が６．８重量％の繊維複合体を得た。
得られたＰＰＴＡ繊維複合体を用いて、以下、実施例１と同様にしてＲＦＬディップコードを作製した。
When an oil agent (diisostearyl adipate / dioleyl adipate / hardened castor oil ethylene oxide / mineral oil mixture) containing 10% by weight of dimethyldecylamine as a hardener is converted to a water content of 0% by weight in this PPTA fiber An oil containing 0.6% by weight of a fiber and subsequently containing 50% by weight of sorbitol polyglycidyl ether as a curable epoxy compound (a mixture of diisostearyl adipate / dioleyl adipate / hardened castor oil ethylene oxide / mineral oil) Is impregnated into 1.0% by weight of the fiber when the moisture content is converted to 0% by weight, and the PPTA fiber is infiltrated with the curable epoxy compound, the curing agent and the oil agent, and then wound on the bobbin in the winding process, A PPTA fiber composite having a moisture content of 35% by weight was produced.
Thereafter, the fiber composite is unwound from a bobbin, and is wound by heat treatment at 110 ° C. for 40 seconds under a tension of 3.9 N using a compute treater (manufactured by Ritzler). 8% by weight of fiber composite was obtained.
Using the obtained PPTA fiber composite, an RFL dip cord was produced in the same manner as in Example 1 below.
［比較例１］
実施例１において、硬化性エポキシ化合物を含有する油剤のかわりに、硬化性エポキシ化合物（グリセロールトリグリシジルエーテル）を水溶媒に分散溶解させ、ＰＰＴＡ繊維が水分率０重量％換算としたときに硬化性エポキシ化合物を０．５重量％となるように浸透させた後、巻き取り工程でボビンに巻き取り、水分率３５重量％のＰＰＴＡ繊維複合体を製造した。この後、この繊維複合体をボビンから巻き出し、コンピュートリータ処理機（リッツラー社製）を用いて、３．９Ｎの張力での緊張下１３０℃２０秒間熱処理をして巻き取り、水分率が７．０重量％の繊維複合体を得た。
得られたＰＰＴＡ繊維複合体を用いて、以下、実施例１と同様にしてＲＦＬディップコードを作製した。
[Comparative Example 1]
In Example 1, instead of the oil agent containing the curable epoxy compound, the curable epoxy compound (glycerol triglycidyl ether) was dispersed and dissolved in an aqueous solvent, and the curable property was obtained when the PPTA fiber was converted to a moisture content of 0% by weight. After impregnating the epoxy compound so as to be 0.5% by weight, it was wound around a bobbin in a winding step to produce a PPTA fiber composite having a moisture content of 35% by weight. Thereafter, the fiber composite is unwound from a bobbin, and is wound by heat treatment at 130 ° C. for 20 seconds under a tension of 3.9 N using a compute treater (manufactured by Ritzler). A 0.0% by weight fiber composite was obtained.
Using the obtained PPTA fiber composite, an RFL dip cord was produced in the same manner as in Example 1 below.
［比較例２］
実施例１において、低温乾燥を行わずに圧搾ローラーにＰＰＴＡ繊維を通し、水分率３５０重量％の処理前のＰＰＴＡ繊維を調製した以外は、実施例１と同様の方法でＰＰＴＡ繊維複合体を製造した。得られた繊維複合体の水分率は３５０重量％であった。この後、この繊維複合体をボビンから巻き出し、コンピュートリータ処理機（リッツラー社製）を用いて、３．９Ｎの張力での緊張下１６０℃２０秒間熱処理をして巻き取り、水分率が１２．０重量％の繊維複合体を得た。
得られたＰＰＴＡ繊維複合体を用いて、以下、実施例１と同様にしてＲＦＬディップコードを作製した。
[Comparative Example 2]
In Example 1, a PPTA fiber composite was produced in the same manner as in Example 1 except that PPTA fibers were passed through a squeezing roller without performing low-temperature drying, and PPTA fibers before treatment with a moisture content of 350% by weight were prepared. did. The moisture content of the obtained fiber composite was 350% by weight. Thereafter, the fiber composite is unwound from a bobbin, and is wound by heat treatment at 160 ° C. for 20 seconds under a tension of 3.9 N using a compute treater (manufactured by Ritzler). A 0.0% by weight fiber composite was obtained.
Using the obtained PPTA fiber composite, an RFL dip cord was produced in the same manner as in Example 1 below.
［比較例３］
実施例２において、中和後、２００℃で１５秒間熱処理を行った他は、実施例２と同様の方法でＰＰＴＡ繊維複合体を製造した。得られた繊維複合体の水分率は１０．２重量％であった。
得られたＰＰＴＡ繊維複合体を用いて、以下、実施例１と同様にしてＲＦＬディップコードを作製した。
[Comparative Example 3]
In Example 2, a PPTA fiber composite was produced in the same manner as in Example 2 except that after neutralization, heat treatment was performed at 200 ° C. for 15 seconds. The moisture content of the obtained fiber composite was 10.2% by weight.
Using the obtained PPTA fiber composite, an RFL dip cord was produced in the same manner as in Example 1 below.
実施例および比較例で得たＰＰＴＡ繊維複合体および、それらを用いて作製したＲＦＬディップコードの特性を表１に示す。 Table 1 shows the properties of the PPTA fiber composites obtained in Examples and Comparative Examples and the RFL dip cords produced using them.
表１の結果から、本実施例で得たＰＰＴＡ繊維複合体は、緊張熱処理後の引張強力が高い上に、毛羽の量も少なく、しかも、水分量を適切な範囲に調製していないＰＰＴＡ繊維複合体（比較例２、３）に比べて、ＲＦＬディップコードの張力低下が生じにくく、接着強力が高いことがわかる。 From the results in Table 1, the PPTA fiber composite obtained in this example has a high tensile strength after tension heat treatment, a small amount of fluff, and a PPTA fiber that has not been prepared with an appropriate amount of water. Compared to the composite (Comparative Examples 2 and 3), it can be seen that the tension of the RFL dip cord is less likely to decrease and the adhesive strength is high.
これに対し、油剤を用いずに硬化性エポキシ化合物を含浸して得たＰＰＴＡ繊維複合体（比較例１）は、緊張熱処理後の引張強力が低く繊維が毛羽立っており、しかも、ＲＦＬディップ処理後にコードの張力低下が生じた。繊維水分率が高い状態で硬化性エポキシ化合物を含浸して得たＰＰＴＡ繊維複合体（比較例２）は、緊張熱処理後の引張強力が低く、しかも、ＲＦＬディップ処理後にコードの張力低下が生じた。繊維水分率が低い状態で硬化性エポキシ化合物を含浸して得たＰＰＴＡ繊維複合体（比較例３）は、緊張熱処理後の引張強力の低下は小さいが、ＲＦＬディップ処理後にコードの張力低下が生じた。 In contrast, the PPTA fiber composite obtained by impregnating a curable epoxy compound without using an oil agent (Comparative Example 1) has low tensile strength after tension heat treatment and fibers are fluffy, and after RFL dip treatment. The cord tension decreased. The PPTA fiber composite (Comparative Example 2) obtained by impregnating a curable epoxy compound with a high fiber moisture content has low tensile strength after tension heat treatment, and further, the cord tension decreased after RFL dipping treatment. . PPTA fiber composite obtained by impregnating a curable epoxy compound with a low fiber moisture content (Comparative Example 3) has a small decrease in tensile strength after tension heat treatment, but a decrease in cord tension after RFL dipping treatment. It was.
本発明のポリパラフェニレンテレフタルアミド繊維複合体は、ゴム、プラスチック、紙等の分野に有用である。 The polyparaphenylene terephthalamide fiber composite of the present invention is useful in the fields of rubber, plastic, paper and the like.
Claims (13)
１００〜１６０℃で乾燥することにより調整された水分量が１５〜２００重量％であり、
かつ硬化性エポキシ化合物を含む油剤中の硬化性エポキシ化合物の繊維への含浸量が、上記繊維の水分量を０重量％に換算したときの繊維重量に対して０．１重量％以上２．０重量％以下である
ことを特徴とするポリパラフェニレンテレフタルアミド繊維複合体。
A polyparaphenylene terephthalamide fiber composite in which an oil containing a curable epoxy compound (excluding an oil containing only a curable epoxy compound) is infiltrated into the fiber skeleton,
The water content adjusted by drying at 100 to 160 ° C. is 15 to 200% by weight,
And the impregnation amount to the fiber of the curable epoxy compound in the oil containing the curable epoxy compound is 0.1% by weight or more and 2.0% with respect to the fiber weight when the moisture content of the fiber is converted to 0% by weight. A polyparaphenylene terephthalamide fiber composite characterized by being less than or equal to% by weight.
１００〜１６０℃で乾燥することにより調整された水分量が１５〜２００重量％であり、
かつ上記繊維の水分量を０重量％に換算したときの繊維重量に対して硬化性エポキシ化合物を含む油剤中の硬化性エポキシ化合物の繊維への含浸量が、０．１重量％以上２．０重量％以下、硬化剤を含む油剤中の硬化剤の繊維への含浸量が、０．０２重量％以上１．０重量％以下である
ことを特徴とするポリパラフェニレンテレフタルアミド繊維複合体。
A polyparaphenylene terephthalamide fiber composite in which an oil agent containing a curable epoxy compound (excluding an oil agent composed only of a curable epoxy compound) and an oil agent containing a curing agent are infiltrated into the fiber skeleton,
The water content adjusted by drying at 100 to 160 ° C. is 15 to 200% by weight,
And the impregnation amount to the fiber of the curable epoxy compound in the oil containing the curable epoxy compound with respect to the fiber weight when the water content of the fiber is converted to 0% by weight is 0.1% by weight or more and 2.0%. A polyparaphenylene terephthalamide fiber composite, wherein the amount of impregnation of the hardener in the oil containing the hardener is 0.02 wt% or more and 1.0 wt% or less.
A polyparaphenylene terephthalamide sulfuric acid solution is spun and neutralized and dried at 100 to 160 ° C. for 5 to 20 seconds to maintain a moisture content of 15 to 200% by weight. Polyparaphenylene terephthalamide, which is characterized by applying an oil containing an epoxy compound (excluding an oil containing only a curable epoxy compound) and infiltrating the fiber skeleton, and then winding it on a bobbin in a winding process A method for producing a fiber composite.
A polyparaphenylene terephthalamide sulfuric acid solution is spun and neutralized and dried at 100 to 160 ° C. for 5 to 20 seconds to maintain a moisture content of 15 to 200% by weight. An oil agent containing an epoxy compound (excluding an oil agent composed only of a curable epoxy compound) and an oil agent containing a curing agent are applied and infiltrated into the fiber skeleton, and then wound around a bobbin in a winding process. A method for producing a polyparaphenylene terephthalamide fiber composite.
The curable epoxy compound contained in the oil is one kind or a mixture of two or more kinds selected from glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether. A method for producing a polyparaphenylene terephthalamide fiber composite.
A polyparaphenylene terephthalamide fiber composite obtained by the production method according to any one of claims 9 to 12 is unwound from a bobbin and heat-treated under tension, so that the moisture content is less than 15% by weight. A method for producing a polyparaphenylene terephthalamide fiber composite.
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| JP6172992B2 (en) * | 2013-03-28 | 2017-08-02 | 東レ・デュポン株式会社 | Method for producing reinforcing short fibers |
| JP6296588B2 (en) * | 2013-03-28 | 2018-03-20 | 東レ・デュポン株式会社 | Process for producing polyparaphenylene terephthalamide fiber composite pulp |
| JP6381109B2 (en) * | 2014-03-25 | 2018-08-29 | 東レ・デュポン株式会社 | Aromatic polyamide short fiber for rubber reinforcement |
| JP6385226B2 (en) * | 2014-09-26 | 2018-09-05 | 東レ・デュポン株式会社 | Aromatic polyamide fiber for reinforcing rubber, twisted cord of aromatic polyamide fiber, and fiber reinforced rubber composite material |
| JP2016176168A (en) * | 2015-03-20 | 2016-10-06 | 東レ・デュポン株式会社 | Cord for rubber reinforcement |
| JP6643777B2 (en) * | 2015-10-27 | 2020-02-12 | 東レ・デュポン株式会社 | Aramid fiber cord for rubber reinforcement |
| JP6782544B2 (en) * | 2016-02-19 | 2020-11-11 | 東レ・デュポン株式会社 | Polyparaphenylene terephthalamide fiber composite and polycarbonate resin composite material |
| JP6890370B2 (en) * | 2017-01-13 | 2021-06-18 | 東レ・デュポン株式会社 | Aramid short fiber bundle for rubber reinforcement |
| JP6997499B2 (en) * | 2017-03-31 | 2022-02-10 | 東レ・デュポン株式会社 | Fiber sheet for building reinforcement |
| JP6442034B2 (en) * | 2017-12-20 | 2018-12-19 | 東レ・デュポン株式会社 | Polyparaphenylene terephthalamide fiber composite pulp |
| JP7160541B2 (en) * | 2018-02-27 | 2022-10-25 | 帝人株式会社 | Aromatic polyamide short fiber bundle for rubber reinforcement and rubber composition |
| JP7250583B2 (en) * | 2019-03-27 | 2023-04-03 | 東レ・デュポン株式会社 | Aramid staple fiber bundle for rubber reinforcement and method for producing the same |
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| JPH02216280A (en) * | 1988-10-26 | 1990-08-29 | Teijin Ltd | Wholly aromatic polyamide fiber |
| JP3793341B2 (en) * | 1997-12-19 | 2006-07-05 | 東レ・デュポン株式会社 | Process for producing polyparaphenylene terephthalamide fiber composite |
| JP2001146686A (en) * | 1999-11-12 | 2001-05-29 | Toray Ind Inc | Fiber for reinforcing rubber, the production thereof and hose therefrom |
| JP4162685B2 (en) * | 2006-03-13 | 2008-10-08 | 東レ・デュポン株式会社 | Polyparaphenylene terephthalamide fiber composite and use thereof |
| JP2007297722A (en) * | 2006-04-27 | 2007-11-15 | Du Pont Toray Co Ltd | Poly-para-phenylene terephthalamide fiber and method for producing the same fiber and its use |
| JP5222228B2 (en) * | 2009-05-28 | 2013-06-26 | 帝人株式会社 | Totally aromatic polyamide fiber |
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