JPS646949B2 - - Google Patents
Info
- Publication number
- JPS646949B2 JPS646949B2 JP56206373A JP20637381A JPS646949B2 JP S646949 B2 JPS646949 B2 JP S646949B2 JP 56206373 A JP56206373 A JP 56206373A JP 20637381 A JP20637381 A JP 20637381A JP S646949 B2 JPS646949 B2 JP S646949B2
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- treatment
- water
- aromatic polyamide
- urethane rubber
- 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.)
- Expired
Links
- 238000011282 treatment Methods 0.000 claims description 69
- 239000000835 fiber Substances 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 29
- 229920006311 Urethane elastomer Polymers 0.000 claims description 26
- 239000004760 aramid Substances 0.000 claims description 26
- 229920003235 aromatic polyamide Polymers 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000004846 water-soluble epoxy resin Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 229920001971 elastomer Polymers 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- -1 isocyanate compounds Chemical class 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- IVVWBIJMWBNKFV-UHFFFAOYSA-N 3,3'-Dichloro-4,4'-diaminodiphenyl ether Chemical compound C1=C(Cl)C(N)=CC=C1OC1=CC=C(N)C(Cl)=C1 IVVWBIJMWBNKFV-UHFFFAOYSA-N 0.000 description 1
- UCNCZASVJWGNBZ-UHFFFAOYSA-N 3-(2-ethyl-5-methyl-1h-imidazol-4-yl)propanenitrile Chemical compound CCC1=NC(CCC#N)=C(C)N1 UCNCZASVJWGNBZ-UHFFFAOYSA-N 0.000 description 1
- IHBSKUPQOWXMOX-UHFFFAOYSA-N 3-(2-methyl-1h-imidazol-5-yl)propanenitrile Chemical compound CC1=NC(CCC#N)=CN1 IHBSKUPQOWXMOX-UHFFFAOYSA-N 0.000 description 1
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical group CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Moulding By Coating Moulds (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Description
本発明は芳香族ポリアミド繊維とウレタンゴム
との接着方法に関する。
伝動ベルト、コンベヤベルト或いはタイヤ等の
ゴム製品は苛酷な条件下での使用に耐えるため
に、従来より補強材として繊維がゴムに接着され
ている。芳香族ポリアミド繊維は抗張力、高弾性
率、耐熱性、寸法安定性等にすぐれているため、
上記のようなゴム補強材として好適であるが、高
結晶性の分子構造を有するところから、一般にゴ
ムとの接着性に劣る。例えば、脂肪族ポリアミド
繊維とゴムとの接着には通常、レゾルシンとホル
マリンの初期縮合物とゴムラテツクスとからなる
所謂RFL液が用いられているが、このような
RFL液によつては芳香族ポリアミド繊維をゴム
に接着させることは困難である。このために、
RFL液処理に先立つて、イソシアネート化合物
やエポキシ化合物等を含有する処理液で繊維を処
理する方法も提案されているが、一方において繊
維とゴムとの接着がゴムの種類及びその配合によ
つて著しく影響を受けることは既によく知られて
いるところであり、特にウレタンゴムの場合、従
来より他のゴムに適用される方法によつては芳香
族ポリアミド繊維と強固に接着させることが困難
であるほか、接着処理の安定性に欠ける。
例えば、天然ゴムと芳香族ポリアミド繊維との
接着には界面活性剤と水溶液エポキシ樹脂を含有
する水溶液からなる第１処理液で処理後、レゾル
シン−ホルマリン初期縮合物とビニルピリジンラ
テツクスからなるRFL液の第２処理液で処理す
る方法が知られているが、この方法をウレタンゴ
ムに適用した場合、芳香族ポリアミド繊維との接
着力は著しく小さい。また、第１処理液としてイ
ソシアネート化合物の有機溶液を用いる方法も知
られているが、ウレタンゴムに適用すると、接着
処理の安定性に欠ける。有機溶液を用いるために
環境汚染を招来するおそれもある。
本発明は上記に鑑みてなされたものであつて、
接着処理の安定性にすぐれると共に、強固な接着
力を発現させることができる芳香族ポリアミド繊
維とウレタンゴムとの接着方法を提供することを
目的とする。
本発明による芳香族ポリアミド繊維とウレタン
ゴムとの接着方法は、芳香族ポリアミド繊維を水
溶性エポキシ樹脂と水溶性硬化剤を含有する水溶
液よりなる第１処理液に浸漬し、熱処理した後、
レゾルシンとホルマリンの初期縮合物と水性ウレ
タン樹脂を主成分とする第２処理液に浸漬し、熱
処理し、次いで未架橋ウレタンゴム配合物に密着
させて加硫することを特徴とする。
本発明において第１の処理液に用いる水溶性エ
ポキシ樹脂としてポリグリセリンポリグリシジル
エーテル、グリセリンジグリシジルエーテル、
１，４−ブタンジオールジグリシジルエーテル、
XB−2793（チバ・ガイギー社製ジメチルヒダン
トイン骨格を有するジエポキシ化合物）等を例示
することができるが、好ましくはポリグリセリン
ポリグリシジルエーテルが用いられる。
ポリグリセリンポリグリシジルエーテルは好ま
しくは次の一般式
で表わされ、ここにＸは−OH又は
The present invention relates to a method for bonding aromatic polyamide fibers and urethane rubber. BACKGROUND OF THE INVENTION In order for rubber products such as power transmission belts, conveyor belts, and tires to withstand use under severe conditions, fibers have traditionally been bonded to rubber as reinforcing materials. Aromatic polyamide fibers have excellent tensile strength, high modulus, heat resistance, dimensional stability, etc.
Although it is suitable as a rubber reinforcing material as described above, it generally has poor adhesion to rubber because it has a highly crystalline molecular structure. For example, a so-called RFL liquid consisting of an initial condensate of resorcin and formalin and rubber latex is usually used to bond aliphatic polyamide fibers and rubber.
It is difficult to adhere aromatic polyamide fibers to rubber depending on the RFL liquid. For this,
A method has also been proposed in which fibers are treated with a treatment solution containing isocyanate compounds, epoxy compounds, etc. prior to RFL solution treatment, but on the other hand, the adhesion between fibers and rubber is significantly affected by the type of rubber and its formulation. It is already well known that urethane rubber is affected by this, and in the case of urethane rubber in particular, it is difficult to firmly bond it to aromatic polyamide fibers using methods conventionally applied to other rubbers. Adhesion process lacks stability. For example, to bond natural rubber and aromatic polyamide fibers, after treatment with a first treatment solution consisting of an aqueous solution containing a surfactant and an aqueous epoxy resin, an RFL solution consisting of a resorcinol-formalin initial condensate and vinylpyridine latex is used. A method of treating urethane rubber with a second treatment liquid is known, but when this method is applied to urethane rubber, the adhesive strength with aromatic polyamide fibers is extremely small. A method using an organic solution of an isocyanate compound as the first treatment liquid is also known, but when applied to urethane rubber, the stability of the adhesive treatment is lacking. Since an organic solution is used, there is also a risk of environmental pollution. The present invention has been made in view of the above, and includes:
It is an object of the present invention to provide a method for adhering aromatic polyamide fibers and urethane rubber, which has excellent stability in adhesion treatment and can develop strong adhesive force. The method of adhering aromatic polyamide fibers and urethane rubber according to the present invention includes immersing aromatic polyamide fibers in a first treatment liquid consisting of an aqueous solution containing a water-soluble epoxy resin and a water-soluble curing agent, heat-treating the fibers, and then heat-treating the aromatic polyamide fibers.
It is characterized by being immersed in a second treatment liquid whose main components are an initial condensate of resorcinol and formalin and an aqueous urethane resin, heat-treated, and then brought into close contact with an uncrosslinked urethane rubber compound and vulcanized. In the present invention, the water-soluble epoxy resin used in the first treatment liquid includes polyglycerin polyglycidyl ether, glycerin diglycidyl ether,
1,4-butanediol diglycidyl ether,
Examples include XB-2793 (diepoxy compound having a dimethylhydantoin skeleton manufactured by Ciba Geigy), but polyglycerin polyglycidyl ether is preferably used. The polyglycerin polyglycidyl ether preferably has the following general formula: where X is -OH or
【式】を示す。本発明においては
ｎが１〜５であるポリグリセリンポリグリシジル
エーテルが好ましく用いられる。
また、水溶性硬化剤としては中温硬化型の水溶
性アミンが好ましく用いられるが、特に２−エチ
ル−４−メチルイミダゾールや２−エチル−４−
メチル−５−シアノエチルイミダゾール等の水溶
性イミダゾール系硬化剤が好ましく用いられる。
第１処理液は水溶性エポキシ樹脂を１〜10重量
％、好ましくは２〜８重量％、水溶性硬化剤0.05
〜1.5重量％、好ましくは0.1〜0.5重量％及び水残
部からなるとき、特に良好な接着力を発現する。
本発明の方法においては、芳香族ポリアミド繊
維を上記のような第１の処理液に浸漬し、180〜
270℃、好ましくは200〜250℃の温度に加熱する。
加熱時間は普通30秒乃至３分程度である。第１処
理液に浸漬後の繊維の加熱処理は、繊維をロール
で導きつつ、加熱炉内で行なうが、加熱炉内での
繊維に加える張力の大きさもウレタンゴムとの接
着力に大きい影響を及ぼし、0.8〜1.5ｇ／デニー
ル(d)の範囲が好ましい。
次に、本発明で用いる第２の処理液はレゾルシ
ン−ホルマリン初期縮合物と水性ウレタン樹脂と
を主成分とする水性分散液であつて、固形分とし
て、好ましくはレゾルシン−ホルマリン初期縮合
物1.8〜4.2重量％、ウレタン樹脂15〜25重量％及
びカーボンブラツク0.5〜7.5重量％を含有する。
水性ウレタン樹脂には強制乳化型ウレタン樹脂水
デイスパージヨン、水溶性ウレタン樹脂、自己乳
化型ウレタン樹脂等を含むが、特に強制乳化型ウ
レタン樹脂水デイスパージヨンが好ましく用いら
れる。第２の処理液がこのようにウレタン樹脂と
カーボンブラツクを含有するため、芳香族ポリア
ミド繊維とウレタンゴムとを特に強固に接着させ
る。
芳香族ポリアミド繊維を第２の処理液に浸漬後
の加熱温度は110〜180℃、好ましくは120〜150℃
であり、加熱時間は通常、30秒乃至３分の範囲で
ある。前記したと同様に加熱の際に繊維には0.05
〜0.2ｇ／ｄの張力を加えるのが好ましい。
このようにして芳香族ポリアミド繊維を第２の
処理液に浸漬し、加熱処理後、未架橋ウレタンゴ
ム配合物に密着させ、ウレタンゴムを架橋させれ
ば芳香族ポリアミド繊維とウレタンゴムとを強固
に接着させることができる。ウレタンゴムの架橋
条件は特に制限されず、架橋剤も適宜に用いられ
る。
以上のように本発明の方法においては、水溶性
エポキシ樹脂と水溶性硬化剤を含有する第１の処
理液水溶液で芳香族ポリアミド繊維を処理し、次
にレゾルシン−ホルマリン初期縮合物と水性ウレ
タン樹脂を含有する第２処理液で処理するという
２段処理により、従来は困難であつた芳香族ポリ
アミド繊維とウレタンゴムとを強固に接着するこ
とができ、更に、本発明の方法によれば第１及び
第２の処理液に浸漬、熱処理した繊維が長期にわ
たつて放置してもウレタンゴムとのすぐれた接着
性を保持しており、この接着処理の安定性と相俟
つて、一貫して水性処理であることから、操作
性、経済性にすぐれ、環境汚染のおそれもない。
尚、本発明において用いる芳香族ポリアミド繊
維は例えばポリ−ｐ−フエニレンフタルアミド、
ポリベンズアミド等よりなる繊維であり、繊維に
はコード、織布等の形態をも含む。
以下に本発明の実施例を説明する。尚、部及び
％はそれぞれ重量部及び重量％である。
実施例
処理１
芳香族ポリアミド繊維からなる1500d／２×３
コード（デユポン社Kevlar）を次の組成の第１
処理液に浸漬後、1.0ｇ／ｄの張力を加えつつ、
240℃の温度で１分間熱処理した。
ポリグリセリンポリグリシジルエーテル（デナコ
ールEX521、ナガセ化成） 4.5部
２−エチル−４−メチル−５−シアノエチルイミ
ダゾール 0.5
脱イオン水 95.0
次に、上記繊維を次の組成のRFL液よりなる
第２処理液に浸漬後、0.1ｇ／ｄの張力を加えつ
つ、150℃の温度で１分間熱処理した。
レゾルシン−ホルマリン初期縮合物（アドハ−
Ｎ、固形分50％、保土谷化学工業(株)） 7.2部
強制乳化型ウレタン樹脂水デイスパージヨン（デ
スモコールKA8066、固形分40％、住友バイエル
ウレタン(株)） 50.0
カーボンブラツク水分散液（固形分20％） 7.5
28％アンモニア 1.2
37％ホルマリン 1.4
脱イオン水 32.7
このように接着処理したコードを３日間放置
後、次の組成を有する未架橋ウレタンゴム配合物
シートに密着させた後、100℃で２時間、次に45
℃で48時間加熱して架橋加硫し、接着物を得た。
未架橋ウレタンゴム（APR882、デユポン社）
100.0部
ジオクチルフタレート 15.0
３，3′−ジクロロ−４，4′−ジアミノジフエニル
エーテル 16.5
比較のために、下記の第１処理液及び第２処理
液を用い、上記と同じ芳香族ポリアミド繊維コー
ドをウレタンゴムに接着する処理２〜６を行なつ
た。
処理２
第１処理液
XB−2793（チバ・ガイギー社） 2.23部
５％ジオクチルナトリウムスルホスクシネート
（界面活性剤、固形分75％） 0.56
脱イオン水 97.21
第２処理液
レゾルシン−ホルマリン初期縮合物（前出） 6.1
ビニルピリジンラテツクス（固形分41％） 45.0
カーボンブラツク水分散液（前出） 13.9
28％アンモニア 1.1
37％ホルマリン 2.0
脱イオン水 31.9
第１処理液浸漬後の熱処理は繊維コードに１
ｇ／ｄの張力を加えながら、243℃の温度で１分
行ない、第２処理液浸漬後の熱処理は0.3ｇ／ｄ
の張力の下に232℃で１分行なつた。
処理３
ポリメチレンポリフエニルイソシアネートを５
％濃度にトリクレンに溶解して第１処理液とし、
繊維コードをこの第１処理液に浸漬後、処理１と
同じ熱処理を行なつた。次に、第２処理液を用い
る処理を処理１と全く同様に行なつた。
処理４
処理１と同じ第１処理液による処理を行なつた
後、第２処理液としてフエノール樹脂（ケムロツ
ク218、固形分20％、Lord社）50部をメタノール
50部に溶解したものを用い、第２処理液に繊維コ
ードを浸漬後、0.1ｇ／ｄの張力を加えつつ、80
℃の温度で１分間熱処理した。
処理５
処理１において第１処理液浸漬後の熱処理を
0.3ｇ／ｄの張力の下に行なつた以外は処理１と
全く同じ。
処理６
処理１において第２処理液浸漬後の熱処理を
1.0[Formula] is shown. In the present invention, polyglycerin polyglycidyl ethers in which n is 1 to 5 are preferably used. As the water-soluble curing agent, medium-temperature curing water-soluble amines are preferably used, especially 2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole.
A water-soluble imidazole curing agent such as methyl-5-cyanoethyl imidazole is preferably used.
The first treatment liquid contains 1 to 10% by weight of a water-soluble epoxy resin, preferably 2 to 8% by weight, and 0.05% of a water-soluble curing agent.
Particularly good adhesion is exhibited when it consists of ~1.5% by weight, preferably 0.1-0.5% by weight and the remainder of water. In the method of the present invention, aromatic polyamide fibers are immersed in the first treatment liquid as described above, and
Heat to a temperature of 270°C, preferably 200-250°C.
Heating time is usually about 30 seconds to 3 minutes. The heating treatment of the fibers after immersion in the first treatment liquid is carried out in a heating furnace while guiding the fibers with rolls, but the amount of tension applied to the fibers in the heating furnace also has a large effect on the adhesive strength with the urethane rubber. The range of 0.8 to 1.5 g/denier (d) is preferred. Next, the second treatment liquid used in the present invention is an aqueous dispersion containing as main components an initial condensate of resorcinol-formalin and an aqueous urethane resin, and preferably has a solid content of 1.8 to 1.8 to an initial condensate of resorcinol-formalin. 4.2% by weight, 15-25% by weight of urethane resin and 0.5-7.5% by weight of carbon black.
Water-based urethane resins include forced emulsification type urethane resin water dispersions, water-soluble urethane resins, self-emulsifying urethane resins, etc., and forced emulsification type urethane resin water dispersions are particularly preferably used. Since the second treatment liquid contains the urethane resin and carbon black in this way, the aromatic polyamide fiber and the urethane rubber are bonded particularly firmly. The heating temperature after immersing the aromatic polyamide fiber in the second treatment liquid is 110 to 180°C, preferably 120 to 150°C.
The heating time is usually in the range of 30 seconds to 3 minutes. 0.05 to the fiber during heating as described above.
Preferably, a tension of ~0.2 g/d is applied. In this way, the aromatic polyamide fiber is immersed in the second treatment liquid, and after heat treatment, it is brought into close contact with the uncrosslinked urethane rubber compound, and by crosslinking the urethane rubber, the aromatic polyamide fiber and the urethane rubber are strengthened. Can be glued. The conditions for crosslinking the urethane rubber are not particularly limited, and a crosslinking agent may be used as appropriate. As described above, in the method of the present invention, aromatic polyamide fibers are treated with a first treatment solution aqueous solution containing a water-soluble epoxy resin and a water-soluble curing agent, and then a resorcinol-formalin initial condensate and an aqueous urethane resin are treated. By the two-stage treatment of treating with a second treatment liquid containing The fibers immersed and heat-treated in the second treatment liquid maintain excellent adhesion to urethane rubber even after being left for a long period of time. Since it is a treatment, it is easy to operate and economical, and there is no risk of environmental pollution. The aromatic polyamide fibers used in the present invention include, for example, poly-p-phenylene phthalamide,
It is a fiber made of polybenzamide, etc., and includes forms such as cords and woven fabrics. Examples of the present invention will be described below. Note that parts and % are parts by weight and % by weight, respectively. Example treatment 1 1500d/2×3 made of aromatic polyamide fiber
Cord (DuPont Kevlar) with the following composition:
After immersing in the treatment solution, while applying a tension of 1.0 g/d,
Heat treatment was performed at a temperature of 240°C for 1 minute. Polyglycerin polyglycidyl ether (Denacol EX521, Nagase Kasei) 4.5 parts 2-ethyl-4-methyl-5-cyanoethylimidazole 0.5 Deionized water 95.0 Next, the above fibers were treated with a second treatment solution consisting of an RFL solution with the following composition. After dipping, heat treatment was performed at a temperature of 150° C. for 1 minute while applying a tension of 0.1 g/d. Resorcinol-formalin initial condensate (Aadhaar)
N, solid content 50%, Hodogaya Chemical Industry Co., Ltd.) 7.2 parts Forced emulsification type urethane resin water dispersion (Desmocol KA8066, solid content 40%, Sumitomo Bayer Urethane Co., Ltd.) 50.0 Carbon Black water dispersion ( Solid content: 20%) 7.5 28% ammonia 1.2 37% formalin 1.4 Deionized water 32.7 After the cord thus adhesively treated was left for 3 days, it was brought into close contact with an uncrosslinked urethane rubber compound sheet having the following composition, and then 100% 2 hours at 45°C, then 45°C.
The adhesive was cross-linked and vulcanized by heating at ℃ for 48 hours to obtain an adhesive. Uncrosslinked urethane rubber (APR882, DuPont)
100.0 parts Dioctyl phthalate 15.0 3,3'-dichloro-4,4'-diaminodiphenyl ether 16.5 For comparison, the same aromatic polyamide fiber cord as above was prepared using the following first treatment liquid and second treatment liquid. Processes 2 to 6 for adhering to urethane rubber were performed. Treatment 2 First treatment liquid XB-2793 (Ciba Geigy) 2.23 parts 5% dioctyl sodium sulfosuccinate (surfactant, solid content 75%) 0.56 Deionized water 97.21 Second treatment liquid Resorcinol-formalin initial condensate (Previously mentioned) 6.1 Vinylpyridine latex (solid content 41%) 45.0 Carbon black aqueous dispersion (previously) 13.9 28% Ammonia 1.1 37% Formalin 2.0 Deionized water 31.9 Heat treatment after immersion in the first treatment solution is applied to the fiber cord. 1
The heat treatment was carried out at 243℃ for 1 minute while applying a tension of 0.3 g/d after being immersed in the second treatment solution.
The test was carried out at 232°C for 1 minute under a tension of . Treatment 3 Polymethylene polyphenyl isocyanate 5
% concentration in trichlene to prepare a first treatment solution,
After immersing the fiber cord in this first treatment liquid, the same heat treatment as in treatment 1 was performed. Next, treatment using the second treatment liquid was carried out in exactly the same manner as treatment 1. Treatment 4 After treatment with the same first treatment solution as in Treatment 1, 50 parts of phenol resin (Chemrock 218, 20% solids, Lord) was added to methanol as the second treatment solution.
After immersing the fiber cord in the second treatment liquid, it was heated to 80 parts while applying a tension of 0.1 g/d.
Heat treatment was carried out at a temperature of 0.degree. C. for 1 minute. Treatment 5 Heat treatment after immersion in the first treatment solution in Treatment 1
Exactly the same as treatment 1 except that it was carried out under a tension of 0.3 g/d. Treatment 6 Heat treatment after immersion in the second treatment solution in Treatment 1
1.0
【表】
(注) 数値は５回の実験値の平均値である。
ｇ／ｄの張力の下に行なつた以外は処理１と全く
同じ。
以上の処理１〜６により得た芳香族ポリアミド
繊維コードとウレタンゴムとの接着力を表に示
す。明らかに従来知られているエポキシ樹脂水溶
液とRFL液を用いる２段処理（処理２）によつ
ては、芳香族ポリアミド繊維コードはウレタンゴ
ムに強固に接着しない。また、処理３及び４は接
着力に関しては良好な結果を与えたが、接着処理
安定性に欠ける。本発明の方法によれば、接着処
理をして10日後にウレタンゴムと接着しても、接
着力は接着処理して３日後に接着したときと実質
的に同じである。更に、処理５により第１の処理
液浸漬後の熱処理時に繊維を加える張力が0.8
ｇ／ｇより小さいとき、コード破断強さが小さ
く、処理６により第２の処理液浸漬後の熱処理時
の張力が0.2ｇ／ｄより大きいとき、接着力の小
さいことが明らかであろう。[Table] (Note) The values are the average values of 5 experimental values.
Exactly the same as treatment 1 except that it was carried out under a tension of g/d. The adhesive strength between the aromatic polyamide fiber cord and urethane rubber obtained by the above treatments 1 to 6 is shown in the table. Apparently, the aromatic polyamide fiber cord does not adhere firmly to the urethane rubber by the conventionally known two-stage treatment (treatment 2) using an aqueous epoxy resin solution and an RFL liquid. Furthermore, although treatments 3 and 4 gave good results in terms of adhesive strength, they lacked adhesive processing stability. According to the method of the present invention, even if it is bonded to urethane rubber 10 days after the adhesive treatment, the adhesive strength is substantially the same as when it is bonded 3 days after the adhesive treatment. Furthermore, due to treatment 5, the tension applied to the fiber during heat treatment after immersion in the first treatment liquid was 0.8.
It is clear that when the cord breaking strength is smaller than g/g, the cord breaking strength is small, and when the tension during the heat treatment after immersion in the second treatment liquid in treatment 6 is larger than 0.2 g/d, the adhesive strength is small.
Claims (1)
と水溶性硬化剤を含有する水溶液よりなる第１処
理液に浸漬し、熱処理した後、レゾルシンとホル
マリンの初期縮合物と水性ウレタン樹脂を主成分
とする第２処理液に浸漬し、熱処理し、次いで未
架橋ウレタンゴム配合物に密着させて加硫するこ
とを特徴とする芳香族ポリアミド繊維とウレタン
ゴムとの接着方法。 ２ 水溶性エポキシ樹脂がポリグリセリンポリグ
リシジルエーテルであり、水溶性硬化剤がイミダ
ゾール系硬化剤であり、水性ウレタン樹脂が強制
乳化型ウレタン樹脂水デイスパージヨンであるこ
とを特徴とする特許請求の範囲第１項記載の芳香
族ポリアミド繊維とウレタンゴムとの接着方法。 ３ 芳香族ポリアミド繊維を第１の処理液に浸漬
後、繊維に0.8〜2.0ｇ／ｄの範囲の張力を加えな
がら180〜270℃の温度に加熱し、第２の処理液に
浸漬後、繊維に0.01〜0.5ｇ／ｄの範囲の張力を
加えながら120〜150℃の温度に加熱することを特
徴とする特許請求の範囲第１項又は第２項記載の
芳香族ポリアミド繊維とウレタンゴムとの接着方
法。[Scope of Claims] 1 Aromatic polyamide fibers are immersed in a first treatment solution consisting of an aqueous solution containing a water-soluble epoxy resin and a water-soluble curing agent, and then heat-treated, and then an initial condensate of resorcinol and formalin and a water-based urethane resin are added. A method for adhering aromatic polyamide fibers and urethane rubber, the method comprising immersing the fibers in a second treatment liquid containing as a main component, heat-treating the fibers, and then vulcanizing the fibers by bringing them into close contact with an uncrosslinked urethane rubber compound. 2 Claims characterized in that the water-soluble epoxy resin is polyglycerin polyglycidyl ether, the water-soluble curing agent is an imidazole-based curing agent, and the water-based urethane resin is a forced emulsification type urethane resin water dispersion. A method for bonding aromatic polyamide fiber and urethane rubber according to item 1. 3 After immersing the aromatic polyamide fibers in the first treatment liquid, the fibers are heated to a temperature of 180 to 270°C while applying a tension in the range of 0.8 to 2.0 g/d, and after being immersed in the second treatment liquid, the fibers are heated to a temperature of 180 to 270 ° C. The aromatic polyamide fiber and urethane rubber according to claim 1 or 2 are heated to a temperature of 120 to 150°C while applying a tension in the range of 0.01 to 0.5 g/d. Adhesion method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56206373A JPS58107322A (en) | 1981-12-21 | 1981-12-21 | Bonding method for aromatic polyamide fiber to urethane rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56206373A JPS58107322A (en) | 1981-12-21 | 1981-12-21 | Bonding method for aromatic polyamide fiber to urethane rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58107322A JPS58107322A (en) | 1983-06-27 |
| JPS646949B2 true JPS646949B2 (en) | 1989-02-07 |
Family
ID=16522246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56206373A Granted JPS58107322A (en) | 1981-12-21 | 1981-12-21 | Bonding method for aromatic polyamide fiber to urethane rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58107322A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62149978A (en) * | 1985-12-24 | 1987-07-03 | 東邦レーヨン株式会社 | Special treated carbon fiber cord for reinforcing rubber |
| US4803101A (en) * | 1987-06-29 | 1989-02-07 | E. I Du Pont De Nemours And Company | Microcrack resistant composites |
-
1981
- 1981-12-21 JP JP56206373A patent/JPS58107322A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58107322A (en) | 1983-06-27 |
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