JPH03220369A - Treatment of aromatic polyamide fiber - Google Patents
Treatment of aromatic polyamide fiberInfo
- Publication number
- JPH03220369A JPH03220369A JP2010724A JP1072490A JPH03220369A JP H03220369 A JPH03220369 A JP H03220369A JP 2010724 A JP2010724 A JP 2010724A JP 1072490 A JP1072490 A JP 1072490A JP H03220369 A JPH03220369 A JP H03220369A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyamide
- rubber
- treatment
- polyamide fibers
- treated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 79
- 239000004760 aramid Substances 0.000 title claims abstract description 49
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000009832 plasma treatment Methods 0.000 claims abstract description 27
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000126 latex Polymers 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- -1 ethylene urea compound Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 42
- 239000005060 rubber Substances 0.000 abstract description 42
- 230000001976 improved effect Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052786 argon Inorganic materials 0.000 abstract description 3
- XTSFUENKKGFYNX-UHFFFAOYSA-N bis(aziridin-1-yl)methanone Chemical compound C1CN1C(=O)N1CC1 XTSFUENKKGFYNX-UHFFFAOYSA-N 0.000 abstract 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 22
- 230000001070 adhesive effect Effects 0.000 description 22
- 239000007789 gas Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000002657 fibrous material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000006355 external stress Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- 125000005662 2,5-pyridylene group Chemical group [H]C1=NC([*:1])=C([H])C([H])=C1[*:2] 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- WPBZMCGPFHZRHJ-UHFFFAOYSA-N 4-aminobenzohydrazide Chemical compound NNC(=O)C1=CC=C(N)C=C1 WPBZMCGPFHZRHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- QNLWQRKKNCGZNS-UHFFFAOYSA-N benzylbenzene;ethene;urea Chemical compound C=C.C=C.NC(N)=O.C=1C=CC=CC=1CC1=CC=CC=C1 QNLWQRKKNCGZNS-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015115 caffè latte Nutrition 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000000774 hypoallergenic effect Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はゴムとの接着性が改善された芳香族ポリアミド
繊維の処理方法に間するものである。特に本発明は接着
力が高く、しかもゴム複合成型品から芳香族ポリアミド
繊維を剥離した際の芳香族ポリアミド繊維へのゴム付着
率（ＲｕｂｂｅｒＣｏｖｅｒａｇｅ ）が向上し、且つ
柔軟で耐疲労性の優れた芳香族ポリアミド繊維を提供す
る処理方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is directed to a method for treating aromatic polyamide fibers with improved adhesion to rubber. In particular, the present invention has a high adhesive strength, an improved rubber adhesion rate (Rubber Coverage) to the aromatic polyamide fibers when the aromatic polyamide fibers are peeled from the rubber composite molded product, and an aromatic product that is flexible and has excellent fatigue resistance. The present invention relates to a processing method for providing group polyamide fibers.
〈従来技術〉
芳香族ポリアミド繊維は、−ｉに高張力で弾性率が高く
、寸法安定性、耐熱性等にも優れているため、苛酷な条
件下で使用されるタイヤ、伝導ベルト、■ベルト及びホ
ース等のゴム製品補強材料として適している。しかしな
がら、芳香族ポリアミド繊維は、分子構造上、不活性で
あり、また高結晶性であるため、ゴムとの接着性が悪く
、通常、脂肪族ポリアミド繊維とゴムとの接着剤として
用いられているレゾルシン・ホルマリン・ラテックス＜
ＲＦＬ＞をそのまま使用したのでは、ゴムとの強固な接
着を行わせることができないという欠点を有していた。<Prior art> Aromatic polyamide fibers have high tensile strength, high elastic modulus, and excellent dimensional stability and heat resistance, so they can be used in tires, conductive belts, and belts used under harsh conditions. It is also suitable as a reinforcing material for rubber products such as hoses. However, aromatic polyamide fibers are inert due to their molecular structure and are highly crystalline, so they have poor adhesion to rubber and are usually used as an adhesive between aliphatic polyamide fibers and rubber. Resorcinol/Formalin/Latex<
If RFL> was used as is, it had the disadvantage that it could not form strong adhesion to rubber.
そこで、芳香族ポリアミド繊維とゴムとの接着性を改良
しようとして、これまでに数多くの提案が行われてきた
。例えば、芳香族ポリアミド繊維にエポキシ処理と熱処
理及びＲＦＬ、９５理と熱処理を行って、該繊維とゴム
とを接着させる方法（特公昭３９１０５１４号公報）、
芳香族ポリアミド繊維をエポキシ化合物とゴムラテック
スとからなる処理液で処理した後ＲＦＬ処理と熱処理と
を行う方法（特公昭５３−３７４６７号公報）、また芳
香族ポリアミド繊維の表面を減圧下にて低温プラズマ処
理することにより、活性化させ、続いてレゾルシン・ホ
ルマリン初期縮合物とゴムラテックスとの混合物で処理
することによりゴムとの接着性を向上させることが試み
られている。この方法には例えば「芳香族ポリアミド繊
維に低温プラズマ処理を施した後に、レゾルシン−ホル
ムアルデヒド初期縮合物とゴムラテックスとの混合液で
処理することを特徴とするゴム補強用芳香族ポリアミド
繊維の処理方法」 （特開昭６１−１９８８１号公報）
「芳香族ポリアミド繊維の表面を減圧下に低温プラズマ
ガス雰囲気中で処理し、ついでこの処理゛繊維をレゾル
シン−ホルムアルデヒド初期縮合物とゴムラテックスと
からなる接着剤組成物にて接着処理することを特徴とす
る芳香族ポリアミド繊維とゴムとの接着方法」 （特開
昭６０−２５００３６号公報）などがある。Therefore, many proposals have been made in an attempt to improve the adhesiveness between aromatic polyamide fibers and rubber. For example, a method of adhering aromatic polyamide fibers to rubber by subjecting them to epoxy treatment, heat treatment, RFL, 95 and heat treatment (Japanese Patent Publication No. 3910514);
There is a method in which aromatic polyamide fibers are treated with a treatment liquid consisting of an epoxy compound and rubber latex, followed by RFL treatment and heat treatment (Japanese Patent Publication No. 37467/1983), and the surface of aromatic polyamide fibers is treated at low temperature under reduced pressure. Attempts have been made to activate it by plasma treatment, and then to improve its adhesion to rubber by treating it with a mixture of a resorcinol/formalin initial condensate and rubber latex. This method includes, for example, ``a method for treating aromatic polyamide fibers for rubber reinforcement, which comprises subjecting aromatic polyamide fibers to low-temperature plasma treatment and then treating them with a mixed solution of a resorcinol-formaldehyde initial condensate and rubber latex. ” (Japanese Unexamined Patent Publication No. 19881/1988)
``The surface of the aromatic polyamide fiber is treated in a low-temperature plasma gas atmosphere under reduced pressure, and then the treated fiber is adhesively treated with an adhesive composition consisting of a resorcinol-formaldehyde initial condensate and rubber latex.'' ``Method for adhering aromatic polyamide fibers to rubber'' (Japanese Unexamined Patent Publication No. 60-250036).
しかしながら、これらの従来法で処理された芳香族ポリ
アミド繊維は、ゴム複合成型品かち繊維材料を剥離した
際の繊維材料へのゴム付着率が低く、芳香族ポリアミド
繊維材料とゴムとの接着性が不十分であり、十分な接着
力が得られないという問題があるなめ、芳香族ポリアミ
ド繊維をゴム補強用に用いるのに大きな障害となってい
た。However, aromatic polyamide fibers treated with these conventional methods have a low adhesion rate of rubber to the fiber material when the fiber material is peeled off as a rubber composite molded product, and the adhesion between the aromatic polyamide fiber material and rubber is poor. This has been a major hindrance to the use of aromatic polyamide fibers for rubber reinforcement because of the problem that sufficient adhesive strength cannot be obtained.
〈発明の目的〉
本発明は以上の事情を背景として為されたものであり、
本発明の目的は芳香族ポリアミド繊維表面を低温プラズ
マ処理した後、エチレン尿素化合物としゾルシン・ホル
マリン・ゴムラテックスとを含む処理剤で処理すること
によりゴムとの接着性及び疲労性を向上せしめることに
ある。<Object of the invention> The present invention was made against the background of the above circumstances,
The purpose of the present invention is to improve adhesion to rubber and fatigue resistance by subjecting the surface of aromatic polyamide fibers to low-temperature plasma treatment and then treating them with a treatment agent containing an ethylene urea compound and zorcin, formalin, and rubber latex. be.
〈発明の構成〉
すなわち本発明は
（１）芳香族ポリアミド繊維を低温プラズマ処理した後
、レゾルシン・ホルマリン・ゴムラテックス（ＲＦ Ｌ
）に下記一般式（１）で表わされるエチレン尿素化合
物を含む処理剤で処理することを特徴とする芳香族ポリ
アミド繊維の処理方法である。<Structure of the Invention> That is, the present invention provides (1) after subjecting aromatic polyamide fibers to low-temperature plasma treatment, resorcinol formalin rubber latex (RF L
) is a method for treating aromatic polyamide fibers, which is characterized in that the fibers are treated with a treatment agent containing an ethylene urea compound represented by the following general formula (1).
ｇは０，１又は２）
（２）処理剤に含まれるエチレン尿素化合物の量がレゾ
ルシン・ホルマリン・ゴムラテックスに対して、０．５
〜３０重量％である請求項（１）に記載の芳香族ポリア
ミド繊維の処理方法である。(g is 0, 1 or 2) (2) The amount of ethylene urea compound contained in the processing agent is 0.5 relative to resorcinol/formalin/rubber latex.
The method for treating aromatic polyamide fibers according to claim (1), wherein the amount is 30% by weight.
本発明における芳香族ポリアミド繊維とは、芳香族環を
有する繰り返し単位が全体の少なくとも８０％以上を占
める重合体からなる繊維を意味す杭例えば、次の一般式
で表わされる繰り返し単位のうち１種又は２種以上の重
合体又は共重合体からなる繊維を挙げることができる。The aromatic polyamide fiber in the present invention refers to a fiber made of a polymer in which repeating units having an aromatic ring account for at least 80% of the total repeating unit.For example, one type of repeating unit represented by the following general formula: Alternatively, fibers made of two or more types of polymers or copolymers can be mentioned.
（式中Ｒは芳香族または脂肪族の炭化水素残基、ここで
Ｒ１，Ｒ２は同一でも相異なってもよく、水素原子、炭
素数５以下のアルキル基としてはメチル基、エチル基、
１０ピル基、ブチル基、ペンチル基などが挙げられるが
、好ましくは水素原子である。またＡｒとしては、
を例示することができる。なお、−Ｘ−は−〇−−３−
、−Ｎ−から選ばれる基であり、−〇−Ｎ−が好ましく
、更に好ましくは一〇−である。(In the formula, R is an aromatic or aliphatic hydrocarbon residue, R1 and R2 may be the same or different, and the hydrogen atom and the alkyl group having 5 or less carbon atoms include a methyl group, an ethyl group,
Examples include a pyru group, a butyl group, a pentyl group, etc., but a hydrogen atom is preferable. Further, as Ar, the following can be exemplified. In addition, -X- is -〇--3-
, -N-, preferably -0-N-, more preferably 10-.
Ｙ−は−ｏ−、−３−、−３Ｏ２−−ＣＨ２−ＣＨ３
慧
は炭素数５以下のアルキル基を表わす。）−０−Ｓ−、
−−Ｃ−が好ましく、更に好ましくは１
０−である。Ａｒ’は芳香族環を示す。芳香族環として
は例えば１．４−フェニレン基、１，３−フェニレン基
、４．４′−ビフェニレン基、１，５−ナフチレン基、
２．６−ナフチレン基、２，５−ピリジレン基などを挙
げることができるが、好ましくは１．４フエニレン基が
選ばれる。Y- represents -o-, -3-, -3O2--CH2-CH3; and Y- represents an alkyl group having 5 or less carbon atoms. )-0-S-,
--C- is preferred, and 10- is more preferred. Ar' represents an aromatic ring. Examples of aromatic rings include 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 1,5-naphthylene group,
Examples include a 2,6-naphthylene group and a 2,5-pyridylene group, but a 1,4-phenylene group is preferably selected.
芳香族環は、例えばハロゲン基（例えば塩素、臭素、フ
ッ素）、低級アルキル基（メチル基、エチル基、イン１
０ピル基、［ｌ−プロピル基）、低級アルコキシ基（メ
トキシ基、エトキシ基）、シアノ基、アセチル基、ニト
ロ基などを置換基として含んでいてもよい。Aromatic rings include, for example, halogen groups (e.g. chlorine, bromine, fluorine), lower alkyl groups (methyl group, ethyl group, in-1
It may contain a 0-pyl group, [1-propyl group), a lower alkoxy group (methoxy group, ethoxy group), a cyano group, an acetyl group, a nitro group, etc. as a substituent.
これらの重合体あるいは共重合体からなる繊維の代表例
としては、ポリパラアミノベンズアミド、ポリパラフェ
ニレンテレフタラミド、ポリパラアミノベ〉ズヒドラジ
ドテレフタルアミド、ポリテレフタル酸ヒドラジド、ポ
リメタフェニレンイソフタラミド等、もしくはこれらの
共重合体からなる繊維を挙げることができる。Typical examples of fibers made of these polymers or copolymers include polypara-aminobenzamide, polypara-phenylene terephthalamide, poly-para-aminobenzhydrazide terephthalamide, polyterephthalic acid hydrazide, polymetaphenylene isophthalamide, etc. Alternatively, fibers made of these copolymers can be mentioned.
本発明は、芳香族ポリアミド繊維を、ヤーン、コード、
織物（スダレ）等任意の形態にして行うことができる。The present invention uses aromatic polyamide fibers as yarns, cords,
It can be made into any form such as woven fabric (sudare).
例えばヤーンの状態にて低温プラズマ処理した後、コー
ド又は織布となし、次いで暗埋刑で処理してもよいし、
コードの形態で低温プラズマ処理し、次いで織布として
処理剤で処理してもよい。しかし、最も好ましいのは、
処理剤で処理する直前に低温プラズマ処理を施すことで
ある。即ち、低温プラズマ処理により活性化した芳香族
ポリアミド繊維表面をその後の工程で汚すことなく、ま
た活性化の経時変化がわずがな間に処理剤で処理するこ
とにより大きな効果が得られる。For example, the yarn may be treated with low-temperature plasma, then made into a cord or woven fabric, and then buried in the dark.
It may be cold plasma treated in the form of a cord and then treated with a treatment agent as a woven fabric. However, the most preferred is
This involves performing low-temperature plasma treatment immediately before treatment with a treatment agent. That is, a great effect can be obtained by treating the surface of the aromatic polyamide fiber activated by low-temperature plasma treatment with a treatment agent without staining it in subsequent steps and while the activation changes over time.
本発明における低温プラズマ処理とは、各種ガス雰囲気
、Ｘｏ−５〜１０ Ｔｏｒｒの減圧上状態において、オ
ーデイオ波、高周波、マイクロ波のエネルギーにより、
電離状態を生ぜしめ、この中に該芳香族ポリアミド繊維
をさらすことにより、表面を活性化せしめるための処理
を意味する。Low-temperature plasma treatment in the present invention refers to plasma treatment using audio waves, high frequencies, and microwave energy in various gas atmospheres and under reduced pressure of Xo-5 to 10 Torr.
It refers to a treatment for activating the surface by creating an ionized state and exposing the aromatic polyamide fibers therein.
更に詳細に述べれば、低温プラズマ処理用ガスとして非
重合性のアルゴン、ヘリウム、ネオン、窒素、酸素、空
気、アンモニア、−酸化炭素、二酸化炭素、水素、亜硫
酸ガス、−酸化窒素、ホルムアルデヒド、塩化水素など
が例示され、重合性ガスとしては、メタン、エタン、テ
トラフルオロメタンなどが例示される。また気化ガスと
しては、四塩化炭素、水、メチルアミン、アンモニア水
、水蒸気などが例示される。これらのガスは、単独もし
くは２種類以上の混合ガスとして使用することができる
。低温プラズマ処理時のガス圧は、１Ｏ−５Ｔｏｒｒ〜
１０ Ｔｏｒｒの範囲が好ましい。ガス圧を１０ Ｔｏ
ｒｒを越えるとプラズマ処理時の温度上昇が著しく芳香
族ポリアミド繊維表面を変質させ、処理効果が損なわれ
る可能性があるので好ましくない。一方、１Ｏ−５Ｔｏ
ｒｒ未溝のガス圧では安定したプラズマ状態が得られず
、正常な処理を行うことが難しくなる。また、低温プラ
ズマを発生させる電極の構造については特に制限がなく
、棒状、平板状、リング状等種々の形状のものが使用で
きる。More specifically, non-polymerizable argon, helium, neon, nitrogen, oxygen, air, ammonia, carbon oxide, carbon dioxide, hydrogen, sulfur dioxide gas, nitrogen oxide, formaldehyde, hydrogen chloride are used as gases for low-temperature plasma processing. Examples of the polymerizable gas include methane, ethane, and tetrafluoromethane. Examples of the vaporized gas include carbon tetrachloride, water, methylamine, aqueous ammonia, and water vapor. These gases can be used alone or as a mixture of two or more types. The gas pressure during low temperature plasma treatment is 1O-5Torr ~
A range of 10 Torr is preferred. Gas pressure 10 To
If it exceeds rr, the temperature increase during plasma treatment will significantly alter the surface of the aromatic polyamide fiber, which may impair the treatment effect, which is not preferable. On the other hand, 1O-5To
A stable plasma state cannot be obtained at the gas pressure without the rr groove, making it difficult to perform normal processing. Further, there is no particular restriction on the structure of the electrode for generating low-temperature plasma, and various shapes such as rod, flat, ring, etc. can be used.
また処理槽内にｔ極が設置された内部電極型、処理槽外
部に電極が設置された外部電極型、更に容ｌ結合型、誘
導結合型等の種類があるがいずれの方式を用いてもよい
。There are also types such as an internal electrode type in which the t-pole is installed inside the treatment tank, an external electrode type in which the electrode is installed outside the treatment tank, and further types such as the capacitive coupling type and the inductive coupling type. good.
芳香族ポリアミド繊維を低温プラズマ処理することによ
り、ゴムとの接着性が向上する原因は、これまでの検討
結果から次のように考えられる。Based on the results of previous studies, the reason why low-temperature plasma treatment of aromatic polyamide fibers improves the adhesion to rubber is thought to be as follows.
第一は、芳香族ポリアミド繊維を低温プラズマ処理した
ことにより、繊維表面に親水基が生成し水系処理剤であ
るＲＦＬ処理剤に対するぬれ性が向上した結果、該処理
剤を繊維表面に均一に付着させることが可能になったた
めと推定される。これにより、ゴムとの加硫工程で与え
られる熱に対する繊維と処理剤層との間の歪力に対する
抵抗力が向上し、また成形後加えられる外部応力がゴム
層を通し、処理剤と繊維との接着欠陥部に集中すること
なく、均一に応力分散されるためと考えられる。芳香族
ポリアミド繊維表面に親水基が生成したことは、該繊維
に対する、水、フォルムアミド、ヨウ化メチレン等の接
触角から拡張Ｆｏｗｋｅｓの式により算出しな表面張力
の分散成分に対する極性力成分の比が未処理繊維対比増
大していることから推定できる。更にＥＳＣＡによる解
析結果において、未処理繊維対比Ｏｉｓ、’Ｃｉｓ、
Ｎｉｓ／Ｃｉｓの比、特にＯｉｓ／Ｃｉｓの比が増大し
ていることにより明らかである。第二の接着力向上推定
原因はプラズマエツチングの効果であると考えられる。First, by subjecting the aromatic polyamide fiber to low-temperature plasma treatment, hydrophilic groups are generated on the fiber surface, which improves the wettability of the RFL treatment agent, which is a water-based treatment agent, so that the treatment agent is uniformly attached to the fiber surface. It is presumed that this is because it has become possible to This improves the resistance to distortion between the fibers and the treatment agent layer due to the heat applied during the vulcanization process with rubber, and also allows the external stress applied after molding to pass through the rubber layer, allowing the treatment agent and fibers to This is thought to be due to the fact that the stress is evenly distributed without being concentrated on the adhesive defect area. The generation of hydrophilic groups on the surface of aromatic polyamide fibers is calculated from the contact angle of water, formamide, methylene iodide, etc. with the fiber using the extended Fowkes equation.The ratio of the polar force component to the dispersion component of the surface tension This can be estimated from the fact that the amount increases compared to untreated fibers. Furthermore, in the analysis results by ESCA, Ois, 'Cis,
This is evident by the increasing Nis/Cis ratio, especially the Ois/Cis ratio. The second presumed reason for the improvement in adhesive strength is thought to be the effect of plasma etching.
エツチングの効果は、例えば繊維の種類、繊維の電極か
らの距離、ガスの種類、ガス圧力、放電出力、処理時の
繊維張力等の条件により異なるが、プラズマ処理により
繊維表面がスパッタリングされ、繊維軸と垂直方向にシ
ーショアー構造と呼ばれる凹凸が出現する。これにより
、処理剤と繊維との接触面積が増大することにより、ま
たアンカー効果により見かけの接着力が向上すると考え
られる。第三は、プラズマ処理による Ｗｅａｋ ｂａ
ｕｎｄａｒｙ １ａｙｅｒの除去が考えられる、プラズ
マ処理により、繊維表面の結合が弱い層をスバ・ツタリ
ングし、削り取ったり、繊維表面に架橋層を形成し表面
層を強固にすることができると考えられる。これにより
、繊維表面層での接着破壊を防止することができ、接着
力を向上させることができると思われる。以上の３つが
、芳香族ポリアミド繊維をプラズマ処理することにより
ゴムとの接着性を向上させることができる原因と考えら
れるが、プラズマ処理の結果、表面エツチング、表面架
橋が認められない場合でも大きな接着力向上が認められ
ることから、第一の推定原因の効果が大きいと考えられ
る。The effect of etching varies depending on conditions such as the type of fiber, the distance of the fiber from the electrode, the type of gas, the gas pressure, the discharge output, and the fiber tension during treatment. An uneven surface called a seashore structure appears in the vertical direction. It is thought that this increases the contact area between the treatment agent and the fibers and improves the apparent adhesive strength due to the anchor effect. The third is weak ba by plasma treatment.
It is thought that plasma treatment, which is thought to remove the underlayer, can cause the weakly bonded layer on the fiber surface to be scraped and scraped off, or to form a crosslinked layer on the fiber surface to strengthen the surface layer. It is thought that this makes it possible to prevent adhesive failure in the fiber surface layer and improve adhesive strength. The above three factors are thought to be the reasons why plasma treatment of aromatic polyamide fibers improves their adhesion to rubber, but as a result of plasma treatment, even if no surface etching or surface crosslinking is observed, significant adhesion may occur. Since an improvement in strength was observed, it is considered that the first presumed cause had a large effect.
芳香族ポリアミド繊維をプラズマ処理後、ＲＦＬを含む
処理剤で処理することにより、ゴム中での耐疲労性が向
上する推定原因は、プラズマ処理による処理剤の均一付
着と繊維束中への処理剤の浸透性が向上するためである
と推定される。処理剤の均一付着により、外部応力がゴ
ム層、処理剤層を通し、繊維へ均一に伝播されるため、
繊維のある部分へ応力が集中することがなくなるためで
あると考えられる。また、プラズマ処理により繊維束中
へ処理剤が浸透し、単繊維−本一本の表面を被覆するこ
とができる。芳香族ポリアミド繊維は、−船釣にフィブ
リル化しやすく、繊維同志の摩擦でフィブリル化し摩耗
していくため強力が低下していく。しかし、プラズマ処
理により、前述のごとく繊維束内部の単糸表面も処理剤
で被覆され、繊維表面の摩耗が防止でき、ゴム中での耐
疲労性が向上するものと考えられる。The probable cause of the improvement in fatigue resistance in rubber by treating aromatic polyamide fibers with a treatment agent containing RFL after plasma treatment is the uniform adhesion of the treatment agent by the plasma treatment and the treatment agent being applied into the fiber bundle. This is presumed to be due to improved permeability. Due to the uniform adhesion of the treatment agent, external stress is uniformly propagated to the fibers through the rubber layer and treatment agent layer.
This is thought to be because stress is no longer concentrated in a certain part of the fiber. Furthermore, the plasma treatment allows the treatment agent to penetrate into the fiber bundle and coat the surface of each single fiber. Aromatic polyamide fibers tend to fibrillate when fishing on a boat, and as the fibers become fibrillated and wear away due to friction between fibers, their strength decreases. However, by plasma treatment, the surface of the single fibers inside the fiber bundle is also coated with the treatment agent as described above, and it is thought that abrasion of the fiber surface can be prevented and fatigue resistance in the rubber is improved.
しかし、芳香族ポリアミド繊維に前述したプラズマ処理
を施した後、単なるＲＦＬ処理剤だけで処理した場合に
は繊維とゴムとの接着性能は不十分であり、実用に供す
ることができない。そこで、プラズマ処理と接着剤との
種々の組合せを鋭意検討した結果、プラズマ処理を施し
た芳香族ポリアミド繊維をエチレン尿素化合物を含むＲ
ＦＬ処理剤で処理することにより、ゴムとの接着性が飛
躍的に向上することを見出した。この理由は明らかでは
ないが、エチレン尿素化合物は加熱によってエチレンイ
ミン環が開環し、プラズマ処理により生成した芳香族ポ
リアミド繊維表面の一〇Ｈ基、−ＣＯＯＨ基などと反応
するなめであると推定される。本発明の方法で使用され
る処理剤は、レゾルシン・ホルマリン・ゴムラテックス
とエチレン尿素化合物とを含む組成物であるが、ここに
使用するレゾルシン・ホルマリン・ゴムラテックスは通
常ＲＦＬと呼ばれているものであり、レゾルシンとホル
ムアルデヒドとのモル比が１：０．１〜１：８、好まし
くは１：０．５〜１：５、更に好ましくは１：１〜１：
４の範囲で用いられる。However, when aromatic polyamide fibers are subjected to the plasma treatment described above and then treated with a simple RFL treatment agent, the adhesive performance between the fibers and rubber is insufficient and it cannot be put to practical use. Therefore, as a result of intensive studies on various combinations of plasma treatment and adhesives, we found that plasma-treated aromatic polyamide fibers were mixed with R containing an ethylene urea compound.
It has been found that the adhesion to rubber is dramatically improved by treatment with an FL treatment agent. The reason for this is not clear, but it is presumed that the ethyleneimine ring of the ethylene urea compound opens when heated, and reacts with the 10H groups, -COOH groups, etc. on the surface of the aromatic polyamide fibers produced by plasma treatment. be done. The processing agent used in the method of the present invention is a composition containing resorcinol/formalin/rubber latex and an ethylene urea compound, and the resorcinol/formalin/rubber latex used here is usually called RFL. and the molar ratio of resorcinol to formaldehyde is 1:0.1 to 1:8, preferably 1:0.5 to 1:5, more preferably 1:1 to 1:
Used in a range of 4.
ゴムラテックスとしては、例えば天然ゴムラテックス、
スチレン′、ブタジェン′、コポリマーラテックス、ビ
ニフレピリジン、スチレン、ブタジェン′、ターポリマ
ーラテックス、ニトリルゴムラテックス、クロロプレン
ゴムラテックス等があり、これらを単独又は併用して使
用する。これらの中ではビニルピリジン、スチレン、ブ
タジェン、ターポリマーラテックスを単独使用または１
／２量以上使用した場合が優れた性能を示す。レゾルシ
ン・ホルマリンに対するゴムラテックスの配合比率は固
形分重量比で１＝１〜１：１５、好ましくは１：３〜１
：１２の範囲にあるのが好ましい。Examples of rubber latex include natural rubber latex,
There are styrene', butadiene', copolymer latex, vinylepyridine, styrene, butadiene', terpolymer latex, nitrile rubber latex, chloroprene rubber latex, etc., and these can be used alone or in combination. Among these, vinylpyridine, styrene, butadiene, and terpolymer latex are used alone or together.
Excellent performance is shown when an amount of /2 or more is used. The blending ratio of rubber latex to resorcinol/formalin is 1=1 to 1:15, preferably 1:3 to 1 in solid weight ratio.
: Preferably in the range of 12.
ゴムラテックスの比率が少なすぎると処理された芳香族
ポリアミド繊維が硬くなって耐疲労性が恵くなり、逆に
多すぎると満足すべき接着力、ゴムは着率が得られない
。If the ratio of rubber latex is too small, the treated aromatic polyamide fibers will become hard and fatigue resistance will be poor, whereas if it is too large, satisfactory adhesion and rubber adhesion will not be obtained.
本発明で用いるエチレン尿素化合物は次に示す−ｉ式で
表わされるもので、Ｒは芳香族又は脂肪族の炭化水素残
基であり、ρは０ないし２の整数である。The ethylene urea compound used in the present invention is represented by the following formula -i, where R is an aromatic or aliphatic hydrocarbon residue, and ρ is an integer from 0 to 2.
代表的な化合物としては、オクタデシルイソシアネート
、ヘキサメチレンジイソシアネート、イソホロンジイソ
シアネート、トリレンジイソシアネート、メタキシリレ
ンジイソシアネート、ジフェニルメタンジイソシアネー
ト、ナフチレンジイソシアネート、トリフェニルメタン
トリイゾシアネート等の芳香族、脂肪族インシアネート
とエチレンイミンとの反応生成物が挙げられ、特にジフ
ェニルメタンジエチレン尿素等の芳香族エチレン尿素（
ヒ合物が良好な結果を与える。Typical compounds include aromatic and aliphatic incyanates such as octadecyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, metaxylylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, triphenylmethane triisocyanate, and ethylene. Reaction products with imines, especially aromatic ethylene ureas such as diphenylmethane diethylene urea (
Hypoallergenic compounds give good results.
本発明において、処理剤に使用するエチレン尿素化合物
は、加熱によってエチレンイミン環が開環して反応し、
接着性を高めるのであって、加熱によってブロック成分
が遊離し、活性なイソシアネート化合物となるブロック
トイソシアネート化合物とは反応機構が全く異なるもの
である。ががるエチレン尿素化合物を処理剤に添加して
処理すると、接着性、柔軟性共に優れたゴム補強用芳香
族ポリアミド繊維が得られる。In the present invention, the ethylene urea compound used in the treatment agent reacts by opening the ethylene imine ring by heating.
The reaction mechanism is completely different from that of a blocked isocyanate compound, which improves adhesiveness and whose blocking component is liberated by heating to become an active isocyanate compound. When the ethylene urea compound is added to a processing agent and treated, aromatic polyamide fibers for reinforcing rubber with excellent adhesiveness and flexibility can be obtained.
なお、エチレン尿素化合物は、ＲＦＬに対して０．５〜
３０重１％、好ましくは１，０〜２０重１％添加される
。エチレン尿素化合物の添加量が少なすぎると良好な接
着力、ゴム付着率が得られない。In addition, the ethylene urea compound has a value of 0.5 to RFL.
30% by weight, preferably 1.0-20% by weight is added. If the amount of the ethylene urea compound added is too small, good adhesive strength and rubber adhesion rate cannot be obtained.
方添加量が多すぎると処理剤の粘度が著しく上昇して繊
維材料の処理操作が困難となり、そのうえ接着力、ゴム
付着率は飽和に達して、エチレン尿素ｆヒ金物の添加量
を多くしただけの効果が上がらずコストが上昇するだけ
であり、更には処理繊維材料が著しく硬くなり強力も低
下してくるという欠点が生ずる。However, if the amount added is too large, the viscosity of the processing agent will increase significantly, making it difficult to process the fiber material, and in addition, the adhesive strength and rubber adhesion rate will reach saturation. However, the effects of this method are not improved and the cost increases, and furthermore, the treated fiber material becomes extremely hard and its strength decreases.
〈発明の効果〉
本発明の方法により処理した芳香族ポリアミド繊維は従
来の方法に比べ、ゴム顕との接着性及びゴム中での耐疲
労性が向上する。<Effects of the Invention> Compared to conventional methods, the aromatic polyamide fibers treated by the method of the present invention have improved adhesion to a rubber tube and fatigue resistance in rubber.
〈実施例〉
以下、本発明を実施例をあげて具体的に説明する。なお
、実施例においてコード剥離接着力、Ｔ接着力、強力保
持率は次のようにして求めた値である。<Examples> The present invention will be specifically described below with reference to Examples. In the examples, the cord peeling adhesive strength, T adhesive strength, and strong retention rate are values determined as follows.
・コード剥離接着力
処理コードとゴムとの接着力を示すものである。ゴムシ
ート表層近くに５本のコードを埋め、加圧下１５０℃で
３０分間加硫し、次いで５本のコードをゴムシートから
２００ ｍｍ／ｍｉｎの速度で剥離に要した力をｋｇ１
５本で表示したものである。- Cord Peel Adhesive Strength Treatment Indicates the adhesive strength between the cord and rubber. Five cords were buried near the surface layer of the rubber sheet, vulcanized at 150°C for 30 minutes under pressure, and then the force required to peel the five cords from the rubber sheet at a speed of 200 mm/min was calculated as kg1.
It is displayed in 5 pieces.
・Ｔ接着力
処理コードとゴムとの接着力を示すものである。コード
をゴムブロック中に埋め込み、加圧下１５０℃で３０分
間加硫し、次いでコードをゴムブロックから２００ ｍ
ｍ／ｍｉｎの速度で引き抜き、引き抜きに要した力をｋ
ｇ／ａｍで表示したものである。・T adhesive strength indicates the adhesive strength between the cord and rubber. The cord was embedded in a rubber block and vulcanized at 150°C for 30 minutes under pressure, then the cord was removed 200 m from the rubber block.
It is pulled out at a speed of m/min, and the force required for pulling out is k.
It is expressed in g/am.
・強力保持率
耐疲労性を表わす尺度でグツドリッチ式ディスクテスタ
ーにより、コードに回転ディスク盤間で設定伸長６％、
圧縮１８％の繰り返し疲労を３５０万回与えた後、強力
がいくら残存しているかを百分率で表わしたものである
。・Strength retention is a measure of fatigue resistance, using a Gutdrich type disc tester, with an elongation set at 6% between rotating discs on the cord.
This is the amount of strength remaining after 3.5 million repetitions of 18% compression fatigue, expressed as a percentage.
実施例１〜５
全芳香族ポリアミド繊維としては、バラフェニレン′ジ
アミン２５モｌし％、テレフタル酸クロリド５０モル％
、３．４゛−ジアミノ−ジフェニルエーテル２５モル％
からなる重合体を湿式紡糸して得た１５００デニール１
０００フイラメントのマルチフィラメント２本を４０Ｘ
４０Ｔ、、’１０ｃｍで撚糸し３０００デニール／／
２０００フイラメントのコードとした。Examples 1 to 5 Fully aromatic polyamide fibers include 25 mol% paraphenylene diamine and 50 mol% terephthalic acid chloride.
, 3.4′-diamino-diphenyl ether 25 mol%
1500 denier 1 obtained by wet spinning a polymer consisting of
Two multifilaments of 000 filament at 40X
40T, 3000 denier twisted by '10cm//
2000 filament code.
かくして得られたコードを真空装置内に１３．５６ＭＨ
ｚの高周波グロー放電電極とコードの送り出し、捲き取
り装置を具備した低温プラズマ処理装置内で連続的に処
理した。真空装置内を０．０５Ｔｏｒｒまで減圧した後
、Ａｒ（アルゴン） 、 ０２． Ｎ２． ＮＨ３゜Ｃ
Ｆ ４のガスを導入し、圧力を１．Ｑ Ｔｏｒｒとしな
。The code thus obtained was placed in a vacuum device at 13.56MH
It was continuously processed in a low temperature plasma processing apparatus equipped with a Z high frequency glow discharge electrode and a cord feeding and winding device. After reducing the pressure inside the vacuum apparatus to 0.05 Torr, Ar (argon) was applied. N2. NH3°C
Introduce F4 gas and increase the pressure to 1. Q Torr and Shina.
この状態で、１３．５６ Ｍ ＨＺの高周波により、出
力１００Ｗのプラズマ状態をつくった。プラズマ状態が
安定しｆＳ後、プラズマ処理時間が１分間になるように
あらかじめ調整しておいな捲取装置を稼働させ、プラズ
マ処理を施しな。In this state, a plasma state with an output of 100 W was created using a high frequency of 13.56 MHz. After the plasma condition has stabilized and after fS, the winding device, which has been adjusted in advance so that the plasma processing time is 1 minute, is operated and plasma processing is not performed.
以上のごとくプラズマ処理を施したコードをコンピユー
トリーター■処理機（Ｃ，Ａ、リッツラー社製、タイヤ
コード処理機）を用いて、第１表に示す処理剤に浸漬後
、１５０℃で２分間乾燥し、続いて２４０℃で１分間熱
処理しな。該処理芳香族ポリアミド繊維には処理剤の固
形分が６．２重量％付着していた。得られたコードにつ
いてコード剥離接着力、Ｔ接着力、強力保持率を測定し
た。その結果を第２表に示す。The cord treated with plasma as described above was immersed in the treatment agent shown in Table 1 using a computer treater (C, A, manufactured by Ritzler, tire cord treatment machine) at 150°C for 2 minutes. Dry, followed by heat treatment at 240°C for 1 minute. A solid content of 6.2% by weight of the treatment agent was attached to the treated aromatic polyamide fiber. The cord peeling adhesive strength, T adhesive strength, and strength retention rate of the obtained cord were measured. The results are shown in Table 2.
比較例１
プラズマ処理を施さない以外は実施例１と同様の方法に
より得た処理コードについて、コード剥離接着力、Ｔ接
着力、強力保持率を測定した。その結果を第２表に示す
。Comparative Example 1 Cord peel adhesion strength, T adhesion strength, and strong retention rate were measured for a treated cord obtained in the same manner as in Example 1 except that plasma treatment was not performed. The results are shown in Table 2.
実施例６〜８、比較例２〜３
プラズマ処理ガスをＱとし、レゾルシン・ホルマリン・
ゴムラテックスに対するブロックトポリイソシアネート
化合物の量を種々変化させた以外は、実施例１と同様の
方法により得た処理コードについて、コード剥離接着力
、Ｔ接着力、強力保持率を測定した。その結果を第３表
に示す。Examples 6 to 8, Comparative Examples 2 to 3 The plasma processing gas was Q, resorcinol, formalin,
Cord peel adhesion, T-adhesion, and strength retention were measured for treated cords obtained in the same manner as in Example 1, except that the amount of blocked polyisocyanate compound relative to the rubber latex was varied. The results are shown in Table 3.
比較例４
実施例１と同様の全芳香族ポリアミド繊維からなるタイ
ヤコードを第４表に示すエポキシ化合物の第１処理剤に
浸漬した後、１５０℃で２分間乾燥し、ついで２４０℃
で１分間熱処理した。これを更に第５表に示す第２処理
剤に浸漬した後、１５０℃で２分間乾燥し、次いで２４
０℃で１分間熱処理した。このようにして得た全芳香族
ポリアミドコードには、第１処理剤の固形分が２．１重
量％、第２処理剤の固形分が３．２重量％け着していた
。得られた処理コードの評価結果を第３表に示す。Comparative Example 4 A tire cord made of the same wholly aromatic polyamide fiber as in Example 1 was immersed in the first treatment agent of the epoxy compound shown in Table 4, then dried at 150°C for 2 minutes, and then dried at 240°C.
The sample was heat-treated for 1 minute. This was further immersed in the second treatment agent shown in Table 5, dried at 150°C for 2 minutes, and then dried at 24°C.
Heat treatment was performed at 0°C for 1 minute. The thus obtained wholly aromatic polyamide cord had a solid content of 2.1% by weight of the first treatment agent and 3.2% by weight of the second treatment agent. Table 3 shows the evaluation results of the obtained processing codes.
第１表
＊１ レゾルシン・ホルマリン処理縮き杓（ＲＦ樹脂）
酸性触媒で反応させたレゾルシン及びホルマリンの初期
縮合物の４０％アセトン溶液ニツポール■２５１８ＦＳ
（Ｖｐ−５ＢＲ）日本ゼオン社製、ビニルピリジンー
スチレンーブタジエシターボリマーラテックス４０％水
乳化液
＊ ３ ： ッホールｏＬＸ−１１２（ｓＢＲ）日本
ゼオン社製、スチレン−ブタジェン、＊２
コポリマー４０？ろ水乳化液
＊４ ネオコール■５Ｗ−３０
第一工業ＷＪ社製、ジオクチルスルフオサクシネートＮ
ａ塩の３０重量％水溶液
第２表
いずれのプラズマガスで処理したコードもプラズマ処理
しなかったコードに比較し高い接着力、強力保持率を示
す。Table 1 *1 Resorcinol/formalin treated shrink ladle (RF resin) 40% acetone solution of the initial condensate of resorcinol and formalin reacted with an acidic catalyst Nitzpol ■2518FS
(Vp-5BR) Nippon Zeon Co., Ltd., vinyl pyridine-styrene-butadiene ester polymer latex 40% water emulsion *3: HoloLX-112 (sBR) Nippon Zeon Co., Ltd., styrene-butadiene, *2 Copolymer 40? Filtered water emulsion *4 Neocol ■5W-30 Daiichi Kogyo WJ Co., Ltd., dioctyl sulfosuccinate N
30% by weight aqueous solution of a-salt Table 2 The cords treated with any of the plasma gases exhibit higher adhesion and strong retention than cords not treated with plasma.
第３表
第４表
＊つ
ＥＵ ／′ＲＦ Ｌ
レゾルシン・ホルマリン・ゴムラテ・・ｌクスに対する
エチレン尿素化合物の量を重量？≦で示したもの、エチ
レン尿素化合物の添加量が少なすぎたり多すぎたりする
と、接着性、疲労性が低下する。また、プラズマ処理後
、エチレン尿素化合物を適量含むＲＦＬで処理したコー
ドの接着力、疲労性は二浴処理されたコードに比較して
向上してしすることかわかる。Table 3 Table 4 *EU/'RF L Resorcinol/formalin/rubber latte...Is the amount of ethylene urea compound relative to the weight? If the amount of the ethylene urea compound added is too small or too large, the adhesion and fatigue properties will decrease. It can also be seen that after plasma treatment, the adhesive strength and fatigue resistance of the cord treated with RFL containing an appropriate amount of ethylene urea compound are improved compared to the cord treated with two baths.
零４ チバ・ガイギー■製 フェノール・ホルマリン樹脂縮合物のエポキシ化合物 第 つ 表Zero 4 Made by Ciba Geigy Epoxy compound of phenol/formalin resin condensate No. One table
Claims (2)
、レゾルシン・ホルマリン・ゴムラテックス（ＲＦＬ）
に下記一般式（ I ）で表わされるエチレン尿素化合物
を含む処理剤で処理することを特徴とする芳香族ポリア
ミド繊維の処理方法。 ▲数式、化学式、表等があります▼・・・（ I ） （式中Ｒは芳香族または脂肪族の炭化水素残基、ｌは０
，１又は２）(1) After low-temperature plasma treatment of aromatic polyamide fiber, resorcinol-formalin-rubber latex (RFL)
1. A method for treating aromatic polyamide fibers, the method comprising treating aromatic polyamide fibers with a treatment agent containing an ethylene urea compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R is an aromatic or aliphatic hydrocarbon residue, l is 0
, 1 or 2)
ルシン・ホルマリン・ゴムラテックスに対して、０．５
〜３０重量％である請求項（１）に記載の芳香族ポリア
ミド繊維の処理方法。(2) The amount of ethylene urea compound contained in the processing agent is 0.5 relative to resorcinol, formalin, and rubber latex.
The method for treating aromatic polyamide fibers according to claim 1, wherein the amount is 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010724A JPH03220369A (en) | 1990-01-22 | 1990-01-22 | Treatment of aromatic polyamide fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010724A JPH03220369A (en) | 1990-01-22 | 1990-01-22 | Treatment of aromatic polyamide fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03220369A true JPH03220369A (en) | 1991-09-27 |
Family
ID=11758238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010724A Pending JPH03220369A (en) | 1990-01-22 | 1990-01-22 | Treatment of aromatic polyamide fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03220369A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006135347A1 (en) * | 2005-06-17 | 2006-12-21 | Matador Rubber, S.R.O. | Method of treatment of textile reinforcing materials to increase their adhesion to rubber compound |
| JP2015521241A (en) * | 2012-06-01 | 2015-07-27 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | Method for treating textile reinforcement elements with plasma |
| WO2017090270A1 (en) * | 2015-11-24 | 2017-06-01 | 株式会社サンライン | Thread and method for production of same |
-
1990
- 1990-01-22 JP JP2010724A patent/JPH03220369A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006135347A1 (en) * | 2005-06-17 | 2006-12-21 | Matador Rubber, S.R.O. | Method of treatment of textile reinforcing materials to increase their adhesion to rubber compound |
| JP2015521241A (en) * | 2012-06-01 | 2015-07-27 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | Method for treating textile reinforcement elements with plasma |
| WO2017090270A1 (en) * | 2015-11-24 | 2017-06-01 | 株式会社サンライン | Thread and method for production of same |
| JPWO2017090270A1 (en) * | 2015-11-24 | 2018-09-13 | 株式会社サンライン | Yarn and method for producing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2369237C (en) | Rubber composition, a method of making the rubber composition, a power transmission belt made from the rubber composition and a method of making the power transmission belt | |
| EP1129125B1 (en) | Process for producing an adhesive-treated polyester fiber cord | |
| EP0239915A2 (en) | Process for producing a modified fibrous material useful for reinforcing rubber articles | |
| MXPA03006191A (en) | Method for the production of a carbon fibre-based reinforcing element for tyres. | |
| JP2006274528A (en) | Polyester tire cap ply cord and method for producing the same | |
| JPH03220369A (en) | Treatment of aromatic polyamide fiber | |
| JP2006037251A (en) | Treatment liquid for rubber/fiber adhesion and method for producing fiber material for rubber reinforcement | |
| JPH03220368A (en) | Treatment of aromatic polyamide fiber | |
| EP0168131B1 (en) | Method for adhering of aromatic polyamide fibers to rubber | |
| JP4402556B2 (en) | Manufacturing method of carbon fiber cord for rubber reinforcement, and carbon fiber cord for rubber reinforcement | |
| JPH0726415A (en) | Polybenzobisoxazole fiber having improved adhesiveness and its production | |
| JP4198565B2 (en) | Processing method of rubber reinforcing fiber | |
| JP2004100113A (en) | Method of producing carbon fiber cord for rubber reinforcement | |
| JPH06299134A (en) | Adhesive composition for polyester fiber | |
| WO2003076710A1 (en) | Treating agent for rubber-reinforcing glass fiber, rubber-reinforcing cord made with the same, and rubber product | |
| JP4533765B2 (en) | Method for producing rubber reinforcing fiber | |
| JP2005089679A (en) | Treating liquid for rubber/fiber bonding and method for producing fiber material for rubber-reinforcement | |
| JPH0921073A (en) | Aromatic polyamide fiber for reinforcing rubber and its production | |
| JP4213026B2 (en) | Method for producing rubber reinforcing fiber | |
| TWI816956B (en) | Method for manufacturing rubber reinforcing fibers | |
| JPS62282076A (en) | Treatment of rubber reinforcing aromatic polyamide fiber | |
| JPH03227457A (en) | Method for treating aromatic polyamide fiber | |
| JP2001159080A (en) | Adhesive composition for rubber/fiber, synthetic fiber for rubber reinforcement and fiber-reinforced rubber structure | |
| JP2004011090A (en) | Impregnant or binder for textile | |
| JPH01174676A (en) | Production of aromatic polyamide fiber material for reinforcing rubber |