JPH0256204B2 - - Google Patents
Info
- Publication number
- JPH0256204B2 JPH0256204B2 JP56068729A JP6872981A JPH0256204B2 JP H0256204 B2 JPH0256204 B2 JP H0256204B2 JP 56068729 A JP56068729 A JP 56068729A JP 6872981 A JP6872981 A JP 6872981A JP H0256204 B2 JPH0256204 B2 JP H0256204B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- methylene
- tris
- reinforcing material
- group
- 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 - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 claims description 24
- 239000005060 rubber Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 14
- 239000012779 reinforcing material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 3
- 239000005061 synthetic rubber Substances 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 12
- -1 phosphorus compound Chemical class 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- QDVFEMUCCNYJEY-UHFFFAOYSA-N N-bis(N-cyclohexylsulfanylanilino)phosphoryl-N-cyclohexylsulfanylaniline Chemical compound C1(CCCCC1)SN(P(N(C1=CC=CC=C1)SC1CCCCC1)(N(C1=CC=CC=C1)SC1CCCCC1)=O)C1=CC=CC=C1 QDVFEMUCCNYJEY-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- GGYCZPMPPFOWSU-UHFFFAOYSA-N n-bis(n-propan-2-ylsulfanylanilino)phosphoryl-n-propan-2-ylsulfanylaniline Chemical compound C=1C=CC=CC=1N(SC(C)C)P(=O)(N(SC(C)C)C=1C=CC=CC=1)N(SC(C)C)C1=CC=CC=C1 GGYCZPMPPFOWSU-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 244000286663 Ficus elastica Species 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- YGWAOELBXHNUTG-UHFFFAOYSA-N N-benzylsulfanyl-N-bis(N-benzylsulfanylanilino)phosphorylaniline Chemical compound C(C1=CC=CC=C1)SN(P(N(C1=CC=CC=C1)SCC1=CC=CC=C1)(N(C1=CC=CC=C1)SCC1=CC=CC=C1)=O)C1=CC=CC=C1 YGWAOELBXHNUTG-UHFFFAOYSA-N 0.000 description 1
- UOQDROBBCIIWTF-UHFFFAOYSA-N N-bis(N-butylsulfanylanilino)phosphoryl-N-butylsulfanylaniline Chemical compound C(CCC)SN(P(N(C1=CC=CC=C1)SCCCC)(N(C1=CC=CC=C1)SCCCC)=O)C1=CC=CC=C1 UOQDROBBCIIWTF-UHFFFAOYSA-N 0.000 description 1
- YZTFKYWNUJSELM-UHFFFAOYSA-N N-bis(N-propan-2-ylsulfanylanilino)phosphinothioyl-N-propan-2-ylsulfanylaniline Chemical compound C1(=CC=CC=C1)N(P(N(SC(C)C)C1=CC=CC=C1)(N(SC(C)C)C1=CC=CC=C1)=S)SC(C)C YZTFKYWNUJSELM-UHFFFAOYSA-N 0.000 description 1
- USWBLKWKMYVWES-UHFFFAOYSA-N N-bis[cyclohexyl(propan-2-ylsulfanyl)amino]phosphoryl-N-propan-2-ylsulfanylcyclohexanamine Chemical compound C(C)(C)SN(P(N(C1CCCCC1)SC(C)C)(N(C1CCCCC1)SC(C)C)=O)C1CCCCC1 USWBLKWKMYVWES-UHFFFAOYSA-N 0.000 description 1
- ZDDGXXHKQWDWQA-UHFFFAOYSA-N N-bis[methyl(methylsulfanyl)amino]phosphoryl-N-methylsulfanylmethanamine Chemical compound CSN(P(N(C)SC)(N(C)SC)=O)C ZDDGXXHKQWDWQA-UHFFFAOYSA-N 0.000 description 1
- TUIVIGUOZBXGIA-UHFFFAOYSA-N N-bis[methyl(octadecylsulfanyl)amino]phosphoryl-N-octadecylsulfanylmethanamine Chemical compound C(CCCCCCCCCCCCCCCCC)SN(P(N(C)SCCCCCCCCCCCCCCCCCC)(N(C)SCCCCCCCCCCCCCCCCCC)=O)C TUIVIGUOZBXGIA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229940053194 antiepileptics oxazolidine derivative Drugs 0.000 description 1
- 239000010951 brass Substances 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
- 239000006229 carbon black Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- JLYVRXJEQTZZBE-UHFFFAOYSA-N ctk1c6083 Chemical compound NP(N)(N)=S JLYVRXJEQTZZBE-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 150000002917 oxazolidines Chemical class 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- 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
- C08J2321/00—Characterised by the use of unspecified rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Moulding By Coating Moulds (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴムと補強材と加硫接着する方法に
関するものである。ゴムを補強材により補強する
製品としては、タイヤ、ベルト、ホースなど種々
の製品がある。これらの製品のうち特にタイヤ、
ベルトの製品においては、ゴムと補強材との接着
は非常に重要で、接着性が不充分な場合製品の寿
命が著しく低下してしまう。
そこでゴムと補強材とを接着させるために、旧
来から補強材をあらかじめ接着剤により前処理す
るいわゆる含浸型接着法とゴムへ接着剤を配合す
るいわゆる配合接着法とを２通りの方法が汎用化
している。このうち配合型接着法は含浸型接着法
に比較し、大規模な設備を必要とせず、通常のゴ
ム用配合剤とともに配合させることから、広く業
界で使用されている。
しかしながら、これらいずれの方法もいまだ充
分満足しうるものでなく、接着力をさらに向上さ
せる事は社会的に大きな要求となつている。そこ
で本発明者はゴムと補強材との接着力をらに向上
させるべく鋭意検討した結果、従来のメチレン基
発生体と受容体を配合する配合型接着剤とある特
定のリン系化合物とを併用すると、著しくゴムと
補強材との接着力が向上する事を見出し、本発明
を完成するに至つた。
すなわち、本発明は天然ゴムもしくは合成ゴム
を主成分とする加硫性ゴム混合物と補強材とを加
硫接着する方法において
() 加熱時、メチレンを供与しうる化合物およ
び
() 加熱時、メチレンを受容しうる化合物およ
び
() 一般式(a)で示されるリン系化合物
（ここでR1、R2は夫々アルキル基、アルケニル
基、シクロアルキル基、アリール基をまたＸはＯ
もしくはＳ原子を意味する。）
とを含有して成る加硫性ゴム混合物を使用するこ
とを特徴とするゴムと補強材との加硫接着方法を
提供するものである。
ここで（）の加熱時メチレンを供与しうる化
合物（以下メチレン供与体と略称する）としては
ヘキサメチレンテトラミン、多価メチロール化メ
ラミン誘導体、オキサゾリジン誘導体、多価メチ
ロール化アセチレン尿素などが例示される。
（）の加熱時メチレンを受容しうる化合物
（以下メチレン受容体と略称する）としては、レ
ゾルシン、レゾルシン・ホルムアルデヒド縮合樹
脂、レゾルシン・アルキルフエノール・ホルムア
ルデヒド共縮合樹脂などが例示される。また
（）のリン系化合物のR1又はR2で表わされる基
の例としては、次のものがあげられる：アルキル
基、例えばメチル、エチル、プロピル、イソプロ
ピル、ブチル、イソブチル、tert−ブチル、ヘキ
シル、ｎ−オクチル、tert−オクチル、ｎ−ドデ
シル、tert−ドデシル及びｎ−オクタデシル、ア
ルケニル基、例えばプロペニル、ｎ−ブト−１−
エニル、イソブテニル、ドデセニル及びｎ−オク
タデセニル、シクロアルキル基例えばシクロペン
チル及びシクロヘキシル、アリール基例えばフエ
ニル、ｏ−、ｍ−及びｐ−トリル及びナフチル。
具体的に（）のリン系化合物を例示すれば、
次のものがあげられる。即ちＮ，N′，N″−トリ
ス−イソプロピルチオ−Ｎ，N′，N″−トリフエ
ニル燐酸トリアミド、Ｎ，N′，N″−トリス−ｎ
−ブチルチオ−Ｎ，N′，N″−トリフエニル燐酸
トリアミド、Ｎ，N′，N″−トリス−シクロヘキ
シルチオ−Ｎ，N′，N″−トリフエニル燐酸トリ
アミド、Ｎ，N′，N″−トリス−ベンジルチオ−
Ｎ，N′，N″−トリフエニル燐酸トリアミド、Ｎ，
N′，N″−トリス−ｎ−オクタデシルチオ−Ｎ，
N′，N″−トリメチル燐酸トリアミド、Ｎ，N′，
N″−トリス−メチルチオ−Ｎ，N′，N″−トリメ
チル燐酸トリアミド、Ｎ，N′，N″−トリス−イ
ソプロピルチオ−Ｎ，N′，N″−トリシクロヘキ
シル燐酸トリアミド、Ｎ，N′，N″−トリメチル
−Ｎ，N′，N″−トリメチル−Ｎ，N′，N″−トリ
ス（イソプロピルチオ）ホスホルチオイツクトリ
アミド、Ｎ，N′，N″−トリ−ｎ−ブチル−Ｎ，
N′，N″−トリス（シクロヘキシルチオ）ホスホ
ルチオイツクトリアミド、Ｎ，N′，N″−トリシ
クロヘキシル−Ｎ，N′，N″−トリス（イソプロ
ピルチオ）ホスホルチオイツクトリアミド、Ｎ，
N′，N″−トリメチル−Ｎ，N′，N″−トリス（フ
エニルチオ）ホスホルチオイツクトリアミド、
Ｎ，N′，N″−トリフエニル−Ｎ，N′，N″−トリ
ス（イソプロピルチオ）ホスホルチオイツクトリ
アミドなどである。
本発明に使用される（）のメチレン供与体は
通常ゴム100重量部に対し、１〜10重量部（以下
PHRと略）、好ましくは２〜5PHR、（）のメ
チレン受容体は、通常１〜10PHR、好ましくは
２〜5PHR、また（）のリン系化合物は、通常
0.05〜5PHR好ましくは0.1〜3PHR添加され、そ
の他は従来の配合型接着法における緒条件がその
まま適用しうる。
また適用されるゴムとしては天然ゴムをはじめ
合成ゴム、たとえばスチレン・ブタジエン共重合
ゴム、ポリイソプレンゴム、ポリブタジエンゴム
アクリロニトリル・ブタジエン共重合ゴム、ポリ
クロロプレンゴムなどが包含される。補強材とし
ては、木綿、ナイロン、ポリエステル、レーヨ
ン、ケブラーなどの有機補強材をはじめ真ちゆう
メツキしたスチールコード、亜鉛メツキしたスチ
ールコード、ガラスコードなどの無機補強材が含
有される。
また本発明においてゴム配合物中にはカーボン
ブラツクなどの各種の配合剤を含有させるが、更
に接着性を助長するために含水シリカを添加配合
してもよい。
次に本発明を実施例をもつて詳述するが、本発
明は実施例記載の方法のみに限定されるものでは
ない。
実施例 １
天然ゴム100重量部（以下部とあるのは重量部
である。）をバンバリーミキサー内に投入して１
分間予備混合した後HAFブラツク45部、軟化剤
３部、ステアリン酸２部、イオウ2.5部、亜鉛華
５部を添加し、２分間混練した。その後、第１表
に示すメチレン供与体、メチレン受容体及びリン
系混合物を各２部および加硫促進剤（ソクシノー
ルCZ：住友化学商標）を添加し、更に1.5分間混
練し、ダンプした。なお混練時のバンバリーミキ
サーのケーシング温度は120〜125℃であつた。
その後、接着試験に供するためかくして得られ
たゴム組成物を10インチロールを用いて適当な厚
さにシーテイングし、インデイア・ラバー・ワー
ルド誌114巻３月号第213〜219頁（1946年）で示
されるいわゆる「Ｈテスト」により未処理ナイロ
ンコード（1260d／２）とゴムとの接着性を調べ
た。なお、接着試験用試料の加硫条件は、145℃
で30分とし、接着力は試料９ケの平均値で示し
た。
なお使用したリン系化合物の内容は以下に示
す。
(A) Ｎ，N′，N″−トリス−イソプロピルチオ−
Ｎ，N′，N″−トリフエニル燐酸トリアミド
(B) Ｎ，N′，N″−トリス−シクロヘキシルチオ
−Ｎ，N′，N″−トリフエニル燐酸トリアミド
(C) Ｎ，N′，N″−トリス−ベンヂルチオ−Ｎ，
N′，N″−トリシクロヘキシル燐酸トリアミド
(D) Ｎ，N′，N″−トリシクロヘキシル−Ｎ，
N′，N″−トリス（イソプロピルチオ）ホスホ
ルチオイツクトリアミド
The present invention relates to a method of vulcanizing and adhering rubber and reinforcing material. There are various products such as tires, belts, and hoses that have rubber reinforced with reinforcing materials. Among these products, especially tires,
In belt products, the adhesion between the rubber and the reinforcing material is very important, and if the adhesion is insufficient, the life of the product will be significantly shortened. Therefore, in order to bond rubber and reinforcing material, two methods have been widely used: the so-called impregnating adhesive method, in which the reinforcing material is pretreated with an adhesive, and the so-called blended adhesive method, in which an adhesive is blended with the rubber. ing. Among these, the compound adhesive method is widely used in the industry because it does not require large-scale equipment compared to the impregnation adhesive method, and it is compounded with ordinary rubber compounding agents. However, none of these methods is yet fully satisfactory, and there is a great social need to further improve the adhesive strength. Therefore, as a result of intensive studies to further improve the adhesive strength between the rubber and the reinforcing material, the inventor of the present invention has developed a combination adhesive that combines a conventional methylene group generator and receptor with a specific phosphorus compound. As a result, it was discovered that the adhesive force between the rubber and the reinforcing material was significantly improved, and the present invention was completed. That is, the present invention provides a method for vulcanizing and adhering a reinforcing material to a vulcanizable rubber mixture containing natural rubber or synthetic rubber as a main component, which includes () a compound capable of donating methylene when heated; Acceptable compounds and () phosphorus compounds represented by general formula (a) (Here, R 1 and R 2 are an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group, respectively, and X is an O
Or it means an S atom. ) A vulcanizable adhesion method for bonding rubber and a reinforcing material is provided, which is characterized by using a vulcanizable rubber mixture containing the following. Here, examples of compounds capable of donating methylene upon heating (hereinafter referred to as methylene donor) include hexamethylenetetramine, polyvalent methylolated melamine derivatives, oxazolidine derivatives, and polyvalent methylolated acetylene urea. Examples of the compound that can accept methylene upon heating (hereinafter referred to as methylene acceptor) include resorcin, resorcin/formaldehyde condensation resin, and resorcin/alkylphenol/formaldehyde cocondensation resin. Examples of the group represented by R 1 or R 2 of the phosphorus compound in () include the following: Alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl , n-octyl, tert-octyl, n-dodecyl, tert-dodecyl and n-octadecyl, alkenyl groups such as propenyl, n-but-1-
enyl, isobutenyl, dodecenyl and n-octadecenyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, aryl groups such as phenyl, o-, m- and p-tolyl and naphthyl. Specifically, the phosphorus compounds in () are as follows:
The following can be mentioned. Namely, N,N',N''-tris-isopropylthio-N,N',N''-triphenylphosphoric triamide, N,N',N''-tris-n
-Butylthio-N,N',N''-triphenylphosphoric triamide, N,N',N''-tris-cyclohexylthio-N,N',N''-triphenylphosphoric triamide, N,N',N''-tris- benzylthio
N,N′,N″-triphenylphosphoric triamide, N,
N′,N″-tris-n-octadecylthio-N,
N′,N″-trimethylphosphoric acid triamide, N,N′,
N″-tris-methylthio-N,N′,N″-trimethylphosphoric triamide, N,N′,N″-tris-isopropylthio-N,N′,N″-tricyclohexylphosphoric triamide, N,N′, N″-trimethyl-N,N′,N″-trimethyl-N,N′,N″-tris(isopropylthio)phosphorothioictriamide, N,N′,N″-tri-n-butyl-N,
N',N''-tris(cyclohexylthio)phosphorthioycttriamide, N,N',N''-tricyclohexyl-N,N',N''-tris(isopropylthio)phosphorthioycttriamide, N,
N′,N″-trimethyl-N,N′,N″-tris(phenylthio)phosphorthioltriamide,
N,N',N''-triphenyl-N,N',N''-tris(isopropylthio)phosphorthioictriamide and the like. The methylene donor () used in the present invention is usually 1 to 10 parts by weight (hereinafter referred to as
(abbreviated as PHR), preferably 2 to 5 PHR, the methylene receptor in () is usually 1 to 10 PHR, preferably 2 to 5 PHR, and the phosphorus compound in () is usually
0.05 to 5 PHR, preferably 0.1 to 3 PHR, is added, and other conditions can be applied as they are in conventional compound adhesive methods. Rubbers that can be used include natural rubber as well as synthetic rubbers such as styrene-butadiene copolymer rubber, polyisoprene rubber, polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, and polychloroprene rubber. Examples of reinforcing materials include organic reinforcing materials such as cotton, nylon, polyester, rayon, and Kevlar, as well as inorganic reinforcing materials such as brass-plated steel cord, galvanized steel cord, and glass cord. Further, in the present invention, various compounding agents such as carbon black are contained in the rubber compound, but hydrated silica may be added and compounded to further promote adhesion. Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to the methods described in the examples. Example 1 100 parts by weight of natural rubber (hereinafter parts are by weight) was put into a Banbury mixer and 1
After premixing for 1 minute, 45 parts of HAF black, 3 parts of softener, 2 parts of stearic acid, 2.5 parts of sulfur, and 5 parts of zinc white were added and kneaded for 2 minutes. Thereafter, 2 parts each of the methylene donor, methylene acceptor, and phosphorus mixture shown in Table 1 and a vulcanization accelerator (Soccinol CZ: Sumitomo Chemical trademark) were added, and the mixture was kneaded for an additional 1.5 minutes and dumped. The casing temperature of the Banbury mixer during kneading was 120 to 125°C. Thereafter, the rubber composition thus obtained was sheeted to an appropriate thickness using a 10-inch roll for adhesion testing, and was published in India Rubber World, Vol. 114, March issue, pp. 213-219 (1946). The adhesion between untreated nylon cord (1260d/2) and rubber was investigated using the so-called "H test" shown below. The vulcanization conditions for the adhesive test sample were 145°C.
The adhesive strength was expressed as the average value of 9 samples. The contents of the phosphorus compounds used are shown below. (A) N,N′,N″-tris-isopropylthio-
N,N',N''-triphenylphosphoric triamide (B) N,N',N''-tris-cyclohexylthio-N,N',N''-triphenylphosphoric triamide (C) N,N',N''-tris -benzylthio-N,
N',N''-tricyclohexyl phosphoric acid triamide (D) N,N',N''-tricyclohexyl-N,
N′,N″-tris(isopropylthio)phosphorthioctriamide
【表】【table】
【表】
実施例 ２
実施例１と同様にして得た下記組成からなるゴ
ム組成物を用い、ASTM−Ｄ−2229法に準拠し、
７×４×0.007″真ちゆうメツキスチールコードと
ゴムとの接着性について調べた。
結果を第２表に示す。
なお加硫時間は、150℃で１時間とし、接着力
は試料12ケの試験値の平均値とした。
ゴム組成物
部
天然ゴム 50.0
SBR＃1500 50.0
ステアリン酸 1.5
HAFブラツク 50.0
亜鉛華 5.0
イオウ 3.0
ソクシノールNBS*1 1.0
メチレン供与体 2.0
メチレン受容体 2.0
リン系化合物 2.0
＊１ 加硫促進剤（住友化学商標）[Table] Example 2 Using a rubber composition having the following composition obtained in the same manner as in Example 1, according to ASTM-D-2229 method,
The adhesion between the 7 x 4 x 0.007'' brass plated steel cord and rubber was investigated. The results are shown in Table 2. The vulcanization time was 1 hour at 150°C, and the adhesive strength of the 12 samples was The average value of the test values was used. Rubber composition part Natural rubber 50.0 SBR#1500 50.0 Stearic acid 1.5 HAF black 50.0 Zinc white 5.0 Sulfur 3.0 Soccinol NBS *1 1.0 Methylene donor 2.0 Methylene acceptor 2.0 Phosphorus compound 2.0 *1 Addition Sulfur accelerator (Sumitomo Chemical trademark)
Claims (1)
硫性ゴム混合物と補強材とを加硫接着する方法に
おいて () 加熱時、メチレンを供与しうる化合物およ
び () 加熱時、メチレンを受容しうる化合物およ
び () 一般式(a)で示されるリン系化合物 （ここで、R1、R2は夫々アルキル基、アルケニ
ル基、シクロアルキル基、アリール基を、またＸ
はＯもしくはＳ原子を意味する。） とを含有して成る加硫性ゴム混合物を使用するこ
とを特徴とするゴムと補強材との加硫接着法。[Scope of Claims] 1. A method for vulcanizing and adhering a reinforcing material to a vulcanizable rubber mixture containing natural rubber or synthetic rubber as a main component, comprising: () a compound capable of donating methylene upon heating; and () upon heating; Compounds that can accept methylene and () phosphorus compounds represented by general formula (a) (Here, R 1 and R 2 each represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and
means an O or S atom. ) A vulcanization bonding method for bonding rubber and a reinforcing material, characterized by using a vulcanizable rubber mixture containing the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56068729A JPS57182416A (en) | 1981-05-06 | 1981-05-06 | Vulcanizing adhesion of rubber to reinforcement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56068729A JPS57182416A (en) | 1981-05-06 | 1981-05-06 | Vulcanizing adhesion of rubber to reinforcement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57182416A JPS57182416A (en) | 1982-11-10 |
| JPH0256204B2 true JPH0256204B2 (en) | 1990-11-29 |
Family
ID=13382165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56068729A Granted JPS57182416A (en) | 1981-05-06 | 1981-05-06 | Vulcanizing adhesion of rubber to reinforcement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57182416A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005067189A (en) * | 2003-08-05 | 2005-03-17 | Bridgestone Corp | Vulcanized bond of rubber and resin member, and method for producing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3797171B2 (en) * | 2001-09-25 | 2006-07-12 | 東海ゴム工業株式会社 | Small mount for stepping motor and small mount for small motor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993468A (en) * | 1972-07-24 | 1974-09-05 | ||
| JPS5391990A (en) * | 1977-01-24 | 1978-08-12 | Sumitomo Chem Co Ltd | Adhesion between rubber and reinforcing material during vulcanization |
-
1981
- 1981-05-06 JP JP56068729A patent/JPS57182416A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993468A (en) * | 1972-07-24 | 1974-09-05 | ||
| JPS5391990A (en) * | 1977-01-24 | 1978-08-12 | Sumitomo Chem Co Ltd | Adhesion between rubber and reinforcing material during vulcanization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005067189A (en) * | 2003-08-05 | 2005-03-17 | Bridgestone Corp | Vulcanized bond of rubber and resin member, and method for producing the same |
| JP4603819B2 (en) * | 2003-08-05 | 2010-12-22 | 株式会社ブリヂストン | Vulcanized adhesive body of rubber and resin member and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57182416A (en) | 1982-11-10 |
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