JP4311986B2 - Rubber-to-metal adhesion promoter, method for producing the same, and rubber composition containing the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、ゴムと金属、特にスチールコードとの接着力を高めるための接着促進剤およびこれが配合されたゴム組成物に関する。
【０００２】
【従来の技術】
従来、ラジアルタイヤやベルトコンベア用ベルトなどのゴム製品の補強材としてスチールコードが用いられているが、このスチールコードとゴムとの接着力を向上させるために、ステアリン酸コバルト、ナフテン酸コバルト、コバルト−ボロン錯体等コバルト系有機金属化合物が接着促進剤として使用されている。コバルト系の有機金属化合物は加硫促進効果強いが、しかしその反面コバルトを含有するゴムは保存安定性が低いため、コバルト系以外の有機金属化合物についても検討されており、接着力向上剤として特定の有機金属塩を開示した多数の特許がある。
【０００３】
例えば、有機酸コバルト塩としては、米国特許第１９１９７１８号（特許文献１）には酢酸塩や低分子量脂肪酸塩、特にステアリン酸コバルトが、米国特許第２９１２３５５号（特許文献２）にはオレイン酸コバルト、およびクエン酸コバルトが、英国特許第１１６９３６６号（特許文献３）にはリノレイン酸コバルト、樹脂酸コバルトなどが、米国特許第４０７６６６８号（特許文献４）にはナフテン酸、オクチル酸、トール油酸等のコバルト塩が、特開昭６１−６０７４３号（特許文献５）にはコバルト、カルシウム、マグネシウム、ニッケルおよび亜鉛の主としてプロピオン酸塩が、特開平６−６５１４２号（特許文献６）にはナフタレンあるいはビフェニル構造を有する金属石鹸が特開昭６０−１５４４４号（特許文献７）特開昭６０−１５８２３０号（特許文献８）にはホウ酸コバルト類が、特開昭６０−１９９６４３号（特許文献９）にはチオ硫酸エステルの金属塩が、特開昭５９−２０７９４９号（特許文献１０）や特開平６−３２９８３８号（特許文献１１）には接着力向上剤の金属分のコバルトとニッケルを特定比率にした金属石鹸が、特開平６−３２９８４０号（特許文献１２）には、接着力向上剤の金属分のコバルトと亜鉛を特定比率にした金属石鹸などが開示されている。また、特公平６−４１５２９号（特許文献１３）にはニッケル石鹸に有機モリブデン化合物を配合した接着促進剤も提案されている。さらに、ホウ酸エステルと鉄、コバルト、ニッケル、マンガンの２価カルボン酸塩との反応で得られたホウ酸とカルボン酸の複合金属塩（Ｃｏ−Ｂ系など）も提案されている（特許文献１４（特公昭６３−６３５５１号）。
【０００４】
【特許文献１】
米国特許１９１９７１８号
【特許文献２】
米国特許２９１２３５５号
【特許文献３】
英国特許１１６９３６６号
【特許文献４】
米国特許４０７６６６８号
【特許文献５】
特開昭６１−６０７４３号
【特許文献６】
特開平６−６５１４２号
【特許文献７】
特開昭６０−１５４４４号
【特許文献８】
特開昭６０−１５８２３０号
【特許文献９】
特開昭６０−１９９６４３号
【特許文献１０】
特開昭５９−２０７９４９号
【特許文献１１】
特開平６−３２９８３８号
【特許文献１２】
特開平６−３２９８４０号
【特許文献１３】
特公平６−４１５２９号
【特許文献１４】
特公昭６３−６３５５１号
【０００５】
【発明が解決しようとする課題】
しかしながら、これまでのコバルト系などの接着促進剤は、接着強度においてまだ十分に満足できるものではなかった。
本発明は、こうした状況の下で、従来のコバルト系接着促進剤よりもさらに、金属、特にスチールコードとゴムとの接着力を向上した新規な接着促進剤およびそれを配合したゴム組成物を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者らは、鋭意検討した結果、前記接着促進剤として、モリブデンと２価金属との複合カルボン酸塩とホウ酸エステルとを反応させて得られた、もしくは、モリブデンのカルボン酸塩と２価の金属のホウ酸塩とを反応させて得られた、反応生成物であるモリブデンと２価の金属とホウ素のカルボン酸化合物を含む混合物が有用であることを見出し、本発明に至った。
すなわち、本発明は、
（１）モリブデンのカルボン酸塩と２価金属のカルボン酸塩の混合物にホウ酸エステルを添加し、反応させて得られた反応生成物からなるゴムと金属との接着促進剤、
（２）モリブデンのカルボン酸塩と２価金属のホウ酸塩の混合物を反応させて得られた反応生成物からなるゴムと金属との接着促進剤、
（３）カルボン酸塩が酢酸塩、プロピオン酸塩、ナフテン酸塩、オクタン酸塩、ネオデカン酸塩、ロジン酸塩およびこれらの複合カルボン酸塩からなる群から選ばれることを特徴とする前記（１）または（２）記載のゴムと金属との接着促進剤、
（４）２価の金属が亜鉛またはニッケルであることを特徴とする前記（１）〜（３）のいずれか１つに記載のゴムと金属との接着促進剤、
（５）金属がスチールコードであることを特徴とする前記（１）〜（４）のいずれか１つに記載のゴムと金属との接着促進剤、
（６）モリブデンのカルボン酸塩と２価金属のカルボン酸塩を混合比率２：１〜１：２で混合し、この混合物にホウ酸エステルを、前記モリブデン酸のカルボン酸塩と前記ホウ酸エステルとの反応比率２：１〜１：１、反応温度１５０〜３００℃で反応させることを特徴とするゴムと金属との接着促進剤の製造方法、
（７）モリブデンのカルボン酸塩と２価金属のホウ酸塩を、反応比率２：１〜１：１、反応温度１５０〜３００℃で反応させることを特徴とするゴムと金属との接着促進剤の製造方法、
に関する。
【０００７】
【発明の実施の形態】
本発明に使用するモリブデンのカルボン酸塩は、カルボン酸とモリブデンから形成される石鹸で、該カルボン酸としては、炭素数２〜３０の主鎖を有する天然あるいは合成の飽和もしくは不飽和脂肪酸あるいはこれらの混合物である。
具体的には、プロピオン酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、アラキン酸、ベヘン酸、オレイン酸、リノール酸、リノレイン酸、レシノール酸、１２−ヒドロキシステアリン酸、ダイマー酸、トール油酸、ナフテン酸、ネオデカン酸、樹脂酸、あるいはこれらを主成分とする例えば魚油硬化脂肪酸、牛脂硬化脂肪酸等の天然脂肪酸を例示することができる。
【０００８】
モリブデンのカルボン酸塩を製造する方法としては、これまで報告されている方法を用いることができる。例えば、＋６の原子価のモリブデンからなる群の金属のシュウ酸化合物を４〜５０個の炭素原子を有する炭化水素カルボン酸とを加熱することからなるモリブデン塩類の製造方法（ＵＳＰ３３６２９７２）、モリブデンとカルボン酸の反応において、三酸化モリブデン、シュウ酸、水、ヘキサン酸を加熱する方法（特公昭４２−２１３２６）、モリブデン化合物水溶液を酸性において還元し、これに高沸点の有機酸またはアルコールを混合して加熱反応させ、同時に水および易揮発性化合物を留去することを特徴とするモリブデン有機化合物の製造方法（特公昭５１−４００５９）等を用いることができる。一般にカルボン酸過剰の条件で行った方が反応収率が向上する。
本発明において、モリブデンのカルボン酸塩を得る好ましい方法は、モリブデン酸アンモニウム〔〔（ＮＨ４）６Ｍｏ７Ｏ２４／４Ｈ２Ｏ〕等のモリブデン化合物を過剰量の前記カルボン酸に溶解させて反応させる方法である。
【０００９】
本発明に使用する２価金属のカルボン酸塩を調製するには、２価の金属化合物と前記カルボン酸を直接反応させることが好ましい。この際に、アルコールや芳香族系、パラフィン系の有機溶媒を用いることができる。
が好ましい。
【００１０】
本発明に使用する２価の金属化合物としては、マグネシウム、カルシウム、コバルト、マンガン、鉄、銅、鉛、ジルコニウム、チタン、ストロンチウム、バリウム、亜鉛、カドミウム、ニッケル、レアアース（セリウム、ネオジウム等）等金属の酸化物、水酸化物、炭酸塩、酢酸塩、アルコキシド等を用いることができる。具体的には、酸化亜鉛、酸化マグネシウム、炭酸ニッケル、水酸化亜鉛等を例示することができ、また、これらを２種以上併用してもよい。特に好ましいものは亜鉛またはニッケルの化合物である。
【００１１】
本発明に使用する２価の金属のホウ酸塩としては、前記２価の金属のホウ酸塩を例示することができる。これらは２種併用してもよい。特に好ましいものは亜鉛またはニッケルのホウ酸塩である。
また、本発明に使用するホウ酸エステルとしては、ホウ酸のアルキルあるいはアリールエステルが使用できる。特に好ましいものは、トリブチルボーレートである。
【００１２】
本発明は、前記モリブデンのカルボン酸塩と前記２価の金属のカルボン酸塩との混合物をホウ酸エステルと反応させて得られた反応生成物を、あるいは、前記モリブデンのカルボン酸塩と２価金属のホウ酸塩の混合物を反応させて得られた反応生成物をゴムと金属との接着促進剤とするものである。
前記モリブデンのカルボン酸塩と前記２価の金属のカルボン酸塩との混合比率は、２：１〜１：２が好ましい。また、前記モリブデンのカルボン酸塩と前記ホウ酸エステルとの反応比率は、２：１〜１：１が好ましい。但し、生成物中にホウ素化合物と反応していない前記モリブデンのカルボン酸塩や前記２価の金属のカルボン酸塩が存在しても構わない。反応は、１５０〜３００℃、好ましくは１８０〜２５０℃で３時間〜１５時間行うことが好ましい。
また、前記モリブデンのカルボン酸塩と前記ホウ酸塩との反応比率は、２：１から１：１が好ましい。反応温度は１５０〜３００℃、好ましくは１８０〜２５０℃で３時間〜１５時間行うことが好ましい。
反応溶媒として、高沸点の溶媒、例えばナフテン酸系鉱油やパラフィン系油を使用してもよいが、無溶媒で反応しても問題はない。
【００１３】
本発明の接着促進剤は、タイヤ、ベルトなどに使用される天然ゴム、各種合成ゴム成分１００重量部に対して０．０５〜２０重量部、好ましくは０．１〜１０重量部配合される。この配合により、ゴムと金属、特にスチールコードとの接着力を著しく向上することができる。
【００１４】
【実施例】
以下に本発明を実施例によりさらに詳細に説明する。
実施例
Ｚｎ／Ｂ／Ｍｏ系カルボン酸化合物の合成（本発明品１）
ネオデカン酸５００ｇとモリブデン酸アンモニウム７３ｇを３Ｌフラスコに添加し、２４０℃で１７時間加熱攪拌し、ネオデカン酸モリブデンを得た。
別にネオデカン酸３３．５ｇと酸化亜鉛３１．７ｇ、トルエン２００ｍＬを１Ｌフラスコに入れ、６０℃、３０分間加熱攪拌した。その後１２０℃に昇温した後プロピオン酸５１．５ｇを添加し１時間加熱攪拌し、ネオデカン酸／プロピオン酸亜鉛を得た。この反応混合物に上記操作で合成したネオデカン酸モリブデン６９．６ｇのトルエン溶液を添加し、１９０℃で１時間加熱攪拌後、１９０℃で２時間減圧乾燥した。得られた反応物にトリ−ｎ−ブチルボーレート４５．３ｇを添加し、２２０℃で４時間加熱攪拌した。さらに２２０℃で２時間減圧乾燥し、Ｚｎ／Ｂ／Ｍｏ系カルボン酸化合物の黒色固体を得た。生成物のＭｏ含有率は１１．９％、Ｚｎ含有率は１６．９％、Ｂ含有率は１．０％であった。また、ろ過した結果、固形物残査は０．０２６ｇであった。
【００１５】
Ｎｉ／Ｂ／Ｍｏ系カルボン酸化合物の合成（本発明品２）
ネオデカン酸３３．５ｇ、と炭酸ニッケル（Ｎｉ含有率２９．７％）３１．７ｇ、トルエン２００ｍｌを１Ｌフラスコに入れ、６０℃、３０分間加熱攪拌した。その後、１２０℃に昇温した後プロピオン酸５１．５ｇを添加しさらに１時間加熱攪拌して、ネオデカン酸／プロピオン酸ニッケルを得た。この反応混合物に上記（本発明品１）と同様な方法で合成したネオデカン酸モリブデン６９．６ｇのトルエン溶液を添加し、１９０℃で１時間加熱攪拌後、１９０℃で２時間減圧乾燥した。得られた反応物にトリ−ｎ−ブチルボーレート４５．３ｇを添加し、２２０℃で４時間加熱攪拌した。さらに、２２０℃で２時間減圧乾燥し、Ｎｉ／Ｂ／Ｍｏ系カルボン酸化合物の黒色固体を得た。生成物のＭｏ含有率は１１．５％、Ｎｉ含有率は１４．０％、Ｂ含有率は１．０％であった。反応生成物をろ過した結果、固形物残査は０．０５２ｇであった。
【００１６】
Ｚｎ／Ｍｏ系カルボン酸塩（比較例）の合成（１）
上記Ｚｎ／Ｂ／Ｍｏ系カルボン酸化合物の合成過程で得られたネオデカン酸モリブデンと、ネオデカン酸／プロピオン酸亜鉛の混合物を使用した。
【００１７】
Ｃｏ／Ｂ系カルボン酸化合物（比較例）の合成
特開昭６０−１５８２３０号に記載されている方法に従い、合成した。
【００１８】
上記各接着促進剤を含むゴム組成物を下記表１に示す処方で配合し、調製した。
接着促進剤の添加量は、金属成分の合計が天然ゴム１００重量部に対して０．３重量部になるように以下のように添加した。
ナフテン酸コバルト（Ｃｏ含有率１０．０％）：３重量部
Ｃｏ／Ｂ（コバルト／ホウ素系カルボン酸化合物；Ｃｏ含有率２２．８％）：１．３重量部
Ｚｎ／Ｍｏ（亜鉛／モリブデン系カルボン酸化合物；Ｚｎ含有率１２．５％、Ｍｏ含有率 １１．９％）：２．０重量部
Ｚｎ／Ｂ／Ｍｏ（亜鉛／ホウ素／モリブデン系カルボン酸化合物；Ｚｎ含有率１６．９％、Ｂ含有率１．０％、Ｍｏ含有率１１．９％）：１．０重量部
Ｎｉ／Ｂ／Ｍｏ（ニッケル／ホウ素／モリブデン系カルボン酸化合物；Ｎｉ含有率１４．０％，Ｂ含有率１．０％、Ｍｏ含有率１１．５％）：１．１重量部
【００１９】
（試験方法）
表１に示す量を添加したゴム組成物を、試験用２本ロールにより熟練し、１２ｍｍ厚のゴムシートを作製した。このゴムシートの間に、真鍮（Ｃｕ約７０％、Ｚｎ約３０％）をめっきした１×５×０．２５ｍｍのスチールコードを埋め込み、１４５℃で３０分間加硫し、スチールコードが挟まれたゴム組成物のサンプルを作製した。
得られた各シートサンプル２０個について、ＡＳＴＭ−２２２９に準じる方法で引き抜き試験を行い、ゴムとスチールコードとの接着力を引き抜き力とゴム付着率により測定した。その結果を表２，３に示す。なお、いずれも接着促進剤としてナフテン酸コバルトを使用した場合の平均値を１００としてその相対値として示した。数値が大きいほど結果が良好であること示す。
【００２０】
【表１】
【表２】
【表３】
【発明の効果】
以上説明したように、本発明の接着促進剤によればゴムと金属との接着力を著しく向上することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesion promoter for enhancing the adhesion between rubber and metal, particularly steel cord, and a rubber composition containing the same.
[0002]
[Prior art]
Conventionally, steel cords have been used as reinforcing materials for rubber products such as radial tires and belts for belt conveyors. To improve the adhesion between the steel cord and rubber, cobalt stearate, cobalt naphthenate, cobalt -Cobalt-based organometallic compounds such as boron complexes are used as adhesion promoters. Cobalt-based organometallic compounds have a strong vulcanization-accelerating effect, but on the other hand, rubber containing cobalt has low storage stability, so other organometallic compounds other than cobalt-based compounds are also being investigated and specified as adhesive strength improvers. There are a number of patents that disclose organometallic salts.
[0003]
For example, organic acid cobalt salts include acetates and low molecular weight fatty acid salts, particularly cobalt stearate, in US Pat. No. 1,919,718 (Patent Document 1), and cobalt oleate in US Pat. No. 2,912,355 (Patent Document 2). , And cobalt citrate, British Patent 1169366 (Patent Document 3) includes linolenic acid cobalt, resin acid cobalt, etc., and US Pat. No. 4,076,668 (Patent Document 4) includes naphthenic acid, octylic acid, tall oil acid. And cobalt salts such as cobalt, calcium, magnesium, nickel and zinc are mainly used as propionates, and naphthalene is disclosed as JP-A-6-65142 (patent document 6). Alternatively, a metal soap having a biphenyl structure is disclosed in JP-A-60-15444 (Patent Document 7). No. 158230 (Patent Document 8) includes cobalt borates, JP-A-60-199643 (Patent Document 9) includes a metal salt of a thiosulfate ester, and JP-A-59-207949 (Patent Document 10). Japanese Patent Laid-Open No. 6-329838 (Patent Document 11) discloses a metal soap having a specific ratio of cobalt and nickel of the metal in the adhesive strength improver, and Japanese Patent Laid-Open No. 6-329840 (Patent Document 12). A metal soap having a specific ratio of cobalt and zinc in the metal content of the improver is disclosed. Japanese Patent Publication No. 6-41529 (Patent Document 13) also proposes an adhesion promoter in which an organic molybdenum compound is blended with nickel soap. Further, composite metal salts (such as Co-B series) of boric acid and carboxylic acid obtained by reacting boric acid esters with divalent carboxylates of iron, cobalt, nickel, and manganese have been proposed (Patent Documents). 14 (Japanese Patent Publication No. 63-63551).
[0004]
[Patent Document 1]
US Pat. No. 1,919,718 [Patent Document 2]
US Pat. No. 2,912,355 [Patent Document 3]
British Patent No. 1169366 [Patent Document 4]
US Pat. No. 4,076,668 [Patent Document 5]
Japanese Patent Laid-Open No. 61-60743 [Patent Document 6]
JP-A-6-65142 [Patent Document 7]
JP-A-60-15444 [Patent Document 8]
JP-A-60-158230 [Patent Document 9]
JP-A-60-199643 [Patent Document 10]
JP 59-207949 [Patent Document 11]
JP-A-6-329838 [Patent Document 12]
JP-A-6-329840 [Patent Document 13]
Japanese Patent Publication No. 6-41529 [Patent Document 14]
Japanese Patent Publication No. 63-63551 [0005]
[Problems to be solved by the invention]
However, conventional cobalt-based adhesion promoters have not yet been sufficiently satisfactory in terms of adhesive strength.
Under such circumstances, the present invention provides a novel adhesion promoter having improved adhesion between metals, particularly steel cords and rubber, and a rubber composition containing the same, in addition to conventional cobalt-based adhesion promoters. The purpose is to do.
[0006]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have obtained, as the adhesion promoter, a compound obtained by reacting a composite carboxylate of molybdenum and a divalent metal with a borate ester, or a molybdenum carboxylate and 2 The present inventors have found that a mixture containing molybdenum, which is a reaction product, a divalent metal, and a carboxylic acid compound of boron, obtained by reacting a valent metal borate, is useful.
That is, the present invention
(1) A rubber-metal adhesion promoter comprising a reaction product obtained by adding a borate ester to a mixture of a molybdenum carboxylate and a divalent metal carboxylate,
(2) Adhesion promoter between rubber and metal comprising a reaction product obtained by reacting a mixture of molybdenum carboxylate and divalent metal borate,
(3) The carboxylate is selected from the group consisting of acetate, propionate, naphthenate, octanoate, neodecanoate, rosinate and complex carboxylates thereof (1) ) Or (2) the adhesion promoter between rubber and metal,
(4) The adhesion promoter for rubber and metal according to any one of (1) to (3), wherein the divalent metal is zinc or nickel,
(5) The adhesion promoter between rubber and metal according to any one of (1) to (4), wherein the metal is a steel cord,
(6) A molybdenum carboxylate and a divalent metal carboxylate are mixed at a mixing ratio of 2: 1 to 1: 2, and a boric acid ester is mixed with the mixture of the molybdic acid carboxylate and the boric acid ester. A reaction ratio of 2: 1 to 1: 1 and a reaction temperature of 150 to 300 ° C., and a method for producing an adhesion promoter between rubber and metal,
(7) Rubber and metal adhesion promoter characterized by reacting a carboxylate of molybdenum and a borate of a divalent metal at a reaction ratio of 2: 1 to 1: 1 and a reaction temperature of 150 to 300 ° C. Manufacturing method,
About.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The molybdenum carboxylate used in the present invention is a soap formed from carboxylic acid and molybdenum, and the carboxylic acid may be a natural or synthetic saturated or unsaturated fatty acid having a main chain having 2 to 30 carbon atoms, or these. It is a mixture of
Specifically, propionic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linoleic acid, resinoleic acid, Examples thereof include 12-hydroxystearic acid, dimer acid, tall oil acid, naphthenic acid, neodecanoic acid, resin acid, and natural fatty acids such as fish oil-cured fatty acid and beef tallow-cured fatty acid.
[0008]
As a method for producing molybdenum carboxylate, the methods reported so far can be used. For example, a method for producing molybdenum salts (US Pat. No. 3,362,972) comprising heating a metal oxalic acid compound of the group consisting of +6 valence molybdenum and a hydrocarbon carboxylic acid having 4 to 50 carbon atoms, molybdenum and carbon In the reaction of acid, a method of heating molybdenum trioxide, oxalic acid, water, hexanoic acid (Japanese Examined Patent Publication No. 42-21326), a molybdenum compound aqueous solution is reduced acidic, and a high-boiling organic acid or alcohol is mixed therewith. A method for producing a molybdenum organic compound (Japanese Examined Patent Publication No. 51-40059) or the like, which comprises heating and reacting, and simultaneously distilling off water and a readily volatile compound, can be used. In general, the reaction yield is improved when the reaction is carried out under an excess of carboxylic acid.
In the present invention, a preferred method for obtaining a molybdenum carboxylate is a reaction in which a molybdenum compound such as ammonium molybdate [[(NH 4 ) 6 Mo 7 O 24 / 4H 2 O] is dissolved in an excess amount of the carboxylic acid. It is a method to make it.
[0009]
In order to prepare the divalent metal carboxylate used in the present invention, it is preferable to directly react the divalent metal compound with the carboxylic acid. At this time, alcohol, aromatic or paraffinic organic solvents can be used.
Is preferred.
[0010]
Divalent metal compounds used in the present invention include metals such as magnesium, calcium, cobalt, manganese, iron, copper, lead, zirconium, titanium, strontium, barium, zinc, cadmium, nickel, rare earth (cerium, neodymium, etc.) These oxides, hydroxides, carbonates, acetates, alkoxides and the like can be used. Specifically, zinc oxide, magnesium oxide, nickel carbonate, zinc hydroxide and the like can be exemplified, and two or more of these may be used in combination. Particularly preferred are zinc or nickel compounds.
[0011]
Examples of the divalent metal borate used in the present invention include the divalent metal borate. Two of these may be used in combination. Particularly preferred are zinc or nickel borates.
Further, as the boric acid ester used in the present invention, an alkyl or aryl ester of boric acid can be used. Particularly preferred is tributyl borate.
[0012]
The present invention provides a reaction product obtained by reacting a mixture of the molybdenum carboxylate and the divalent metal carboxylate with a borate ester, or the molybdenum carboxylate and the divalent metal. A reaction product obtained by reacting a mixture of metal borates is used as an adhesion promoter between rubber and metal.
The mixing ratio of the molybdenum carboxylate and the divalent metal carboxylate is preferably 2: 1 to 1: 2. The reaction ratio of the molybdenum carboxylate and the borate ester is preferably 2: 1 to 1: 1. However, the molybdenum carboxylate or the divalent metal carboxylate that has not reacted with the boron compound may be present in the product. The reaction is preferably carried out at 150 to 300 ° C., preferably 180 to 250 ° C. for 3 to 15 hours.
The reaction ratio between the molybdenum carboxylate and the borate is preferably 2: 1 to 1: 1. The reaction temperature is 150 to 300 ° C., preferably 180 to 250 ° C. for 3 to 15 hours.
As the reaction solvent, a solvent having a high boiling point such as naphthenic mineral oil or paraffinic oil may be used.
[0013]
The adhesion promoter of the present invention is blended in an amount of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of natural rubber and various synthetic rubber components used for tires and belts. By this blending, the adhesion between rubber and metal, particularly steel cord, can be significantly improved.
[0014]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
Example Synthesis of Zn / B / Mo carboxylic acid compound (Product 1 of the present invention)
500 g of neodecanoic acid and 73 g of ammonium molybdate were added to a 3 L flask and heated and stirred at 240 ° C. for 17 hours to obtain molybdenum neodecanoate.
Separately, 33.5 g of neodecanoic acid, 31.7 g of zinc oxide, and 200 mL of toluene were placed in a 1 L flask, and heated and stirred at 60 ° C. for 30 minutes. Thereafter, the temperature was raised to 120 ° C., 51.5 g of propionic acid was added, and the mixture was heated and stirred for 1 hour to obtain neodecanoic acid / zinc propionate. To this reaction mixture, a toluene solution of 69.6 g of molybdenum neodecanoate synthesized by the above operation was added, heated and stirred at 190 ° C. for 1 hour, and dried under reduced pressure at 190 ° C. for 2 hours. To the obtained reaction product, 45.3 g of tri-n-butyl borate was added, and the mixture was heated and stirred at 220 ° C. for 4 hours. Furthermore, it dried under reduced pressure at 220 degreeC for 2 hours, and obtained the black solid of the Zn / B / Mo type carboxylic acid compound. The Mo content of the product was 11.9%, the Zn content was 16.9%, and the B content was 1.0%. Moreover, as a result of filtration, the solid substance residue was 0.026g.
[0015]
Synthesis of Ni / B / Mo carboxylic acid compound (Invention product 2)
33.5 g of neodecanoic acid, 31.7 g of nickel carbonate (Ni content 29.7%), and 200 ml of toluene were placed in a 1 L flask, and heated and stirred at 60 ° C. for 30 minutes. Thereafter, the temperature was raised to 120 ° C., 51.5 g of propionic acid was added, and the mixture was further heated and stirred for 1 hour to obtain neodecanoic acid / nickel propionate. To this reaction mixture, a toluene solution of 69.6 g of molybdenum neodecanoate synthesized by the same method as above (Product 1 of the present invention) was added, heated and stirred at 190 ° C. for 1 hour, and then dried under reduced pressure at 190 ° C. for 2 hours. To the obtained reaction product, 45.3 g of tri-n-butyl borate was added, and the mixture was heated and stirred at 220 ° C. for 4 hours. Furthermore, it dried under reduced pressure at 220 degreeC for 2 hours, and obtained the black solid of the Ni / B / Mo type carboxylic acid compound. The Mo content of the product was 11.5%, the Ni content was 14.0%, and the B content was 1.0%. As a result of filtering the reaction product, the solid residue was 0.052 g.
[0016]
Synthesis of Zn / Mo carboxylate (comparative example) (1)
A mixture of molybdenum neodecanoate obtained in the process of synthesizing the Zn / B / Mo carboxylic acid compound and a mixture of neodecanoic acid / zinc propionate was used.
[0017]
Synthesis of Co / B Carboxylic Acid Compound (Comparative Example) Synthesis was performed according to the method described in JP-A-60-158230.
[0018]
A rubber composition containing each of the above adhesion promoters was blended and prepared according to the formulation shown in Table 1 below.
The adhesion promoter was added in the following manner so that the total amount of metal components was 0.3 parts by weight with respect to 100 parts by weight of natural rubber.
Cobalt naphthenate (Co content 10.0%): 3 parts by weight Co / B (cobalt / boron carboxylic acid compound; Co content 22.8%): 1.3 parts by weight Zn / Mo (zinc / molybdenum system) Carboxylic acid compound; Zn content 12.5%, Mo content 11.9%): 2.0 parts by weight Zn / B / Mo (zinc / boron / molybdenum carboxylic acid compound; Zn content 16.9%) B content 1.0%, Mo content 11.9%): 1.0 part by weight Ni / B / Mo (nickel / boron / molybdenum carboxylic acid compound; Ni content 14.0%, B content 1 0.0%, Mo content 11.5%): 1.1 parts by weight
(Test method)
The rubber composition to which the amount shown in Table 1 was added was proficient with two test rolls to produce a rubber sheet having a thickness of 12 mm. A 1 × 5 × 0.25 mm steel cord plated with brass (Cu about 70%, Zn about 30%) was embedded between the rubber sheets, and vulcanized at 145 ° C. for 30 minutes to sandwich the steel cord. A sample of the rubber composition was prepared.
With respect to each of the obtained 20 sheet samples, a pull-out test was performed by a method according to ASTM-2229, and the adhesive force between the rubber and the steel cord was measured by the pull-out force and the rubber adhesion rate. The results are shown in Tables 2 and 3. In all cases, the average value when cobalt naphthenate was used as an adhesion promoter was 100, and the relative value was shown. The larger the value, the better the result.
[0020]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
As described above, according to the adhesion promoter of the present invention, the adhesive force between rubber and metal can be remarkably improved.
Claims (7)
Priority Applications (1)
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| JP2003160213A JP4311986B2 (en) | 2003-06-05 | 2003-06-05 | Rubber-to-metal adhesion promoter, method for producing the same, and rubber composition containing the same |
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| JP2003160213A JP4311986B2 (en) | 2003-06-05 | 2003-06-05 | Rubber-to-metal adhesion promoter, method for producing the same, and rubber composition containing the same |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4417729B2 (en) * | 2004-01-07 | 2010-02-17 | 東洋ゴム工業株式会社 | Rubber-steel cord composite and pneumatic tire |
| US20170253722A1 (en) | 2014-09-12 | 2017-09-07 | Dic Corporation | Rubber-metal adhesion promoter, rubber composition, and tire |
| WO2016039376A1 (en) * | 2014-09-12 | 2016-03-17 | Dic株式会社 | Rubber–metal adhesion promoter, rubber composition, and tire |
| US20230002589A1 (en) * | 2019-09-30 | 2023-01-05 | Bridgestone Corporation | Rubber composition, rubber-metal composite, conveyor belt, hose, crawler, and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4234496A (en) * | 1978-05-26 | 1980-11-18 | Manchem Limited | Complex organo-metallic compounds of boron or phosphorus |
| JPS6015444A (en) * | 1983-07-08 | 1985-01-26 | Bridgestone Corp | Improved rubber composition for tire |
| JPS60158230A (en) * | 1984-01-30 | 1985-08-19 | Dainippon Ink & Chem Inc | Accelerator for bonding rubber to steel cord |
| JP3644599B2 (en) * | 1996-06-26 | 2005-04-27 | 株式会社 ブリヂストン | Adhesion promoter composition and adhesive rubber composition containing the same |
| JPH10298579A (en) * | 1997-04-25 | 1998-11-10 | Toyota Motor Corp | Grease composition |
| JP2002069404A (en) * | 2000-08-28 | 2002-03-08 | Toyo Tire & Rubber Co Ltd | Rubber composition for steel cord adhesion |
| JP4375647B2 (en) * | 2002-07-05 | 2009-12-02 | 東洋ゴム工業株式会社 | Rubber composition containing adhesion promoter for rubber and metal |
| JP4375648B2 (en) * | 2002-07-09 | 2009-12-02 | 東洋ゴム工業株式会社 | Rubber composition containing adhesion promoter for rubber and metal |
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