JPH01153783A - Bonding accelerator for steel cord - Google Patents
Bonding accelerator for steel cordInfo
- Publication number
- JPH01153783A JPH01153783A JP62311057A JP31105787A JPH01153783A JP H01153783 A JPH01153783 A JP H01153783A JP 62311057 A JP62311057 A JP 62311057A JP 31105787 A JP31105787 A JP 31105787A JP H01153783 A JPH01153783 A JP H01153783A
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- boron
- rubber
- steel cord
- organic
- 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.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 21
- 239000010959 steel Substances 0.000 title claims description 21
- 229920001971 elastomer Polymers 0.000 claims abstract description 45
- 229910052796 boron Inorganic materials 0.000 claims abstract description 33
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000000344 soap Substances 0.000 claims abstract description 23
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 boron carboxylate Chemical class 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002318 adhesion promoter Substances 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000004327 boric acid Substances 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 12
- HZEIHKAVLOJHDG-UHFFFAOYSA-N boranylidynecobalt Chemical compound [Co]#B HZEIHKAVLOJHDG-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NOXNXVPLDITALF-UHFFFAOYSA-N butoxyboronic acid Chemical compound CCCCOB(O)O NOXNXVPLDITALF-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HOYKPPXKLRXDBR-UHFFFAOYSA-N [O].[Co].[Co] Chemical class [O].[Co].[Co] HOYKPPXKLRXDBR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Reinforced Plastic Materials (AREA)
- Tyre Moulding (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はゴムとスチールとの接着促進剤の改良に関し、
特にゴムとスチールコードとの高温多湿下の長期にわた
る接着力の維持と共にゴムの弾性率の向上が可能な改良
された接着促進剤に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an improvement in adhesion promoters between rubber and steel.
In particular, the present invention relates to an improved adhesion promoter capable of maintaining long-term adhesive strength between rubber and steel cord under high temperature and high humidity conditions, and improving the elastic modulus of rubber.
(従来の技術)
従来、自動車タイヤ、コンベヤベルト等の性能を向上さ
せるために、スチールコードが補強材として使用されて
いる。このようなスチールコードにはその補強効果を高
めるために真鍮メツキ、亜鉛メツキ、青銅メツキなどゴ
ムとの接着力を高める金属メツキが施され、またスチー
ルコードの埋設ゴム組成物にはスチールコードとゴムと
の接着力を向上させる接着促進剤、例えば有機酸のコバ
ルト塩が使用されているが、温熱条件に長期間さらされ
ると接着力が低下するという問題点があった。そこでか
かる問題点を改良する方法として特開昭55−1737
1号公報および特開昭60−158230号公報におい
てゴム補強用スチールコードとゴムとの接着改良、特に
温熱老化後の接着改良のために有機カルボン酸のコバル
ト・ホウ素金属石鹸を接着促進剤として使用することが
提案されている。(Prior Art) Steel cords have conventionally been used as reinforcing materials to improve the performance of automobile tires, conveyor belts, and the like. These steel cords are coated with metal plating, such as brass plating, zinc plating, or bronze plating, to increase their adhesion to the rubber in order to enhance their reinforcing effect, and the embedded rubber composition of the steel cord is made of steel cord and rubber. Adhesion promoters, such as cobalt salts of organic acids, have been used to improve the adhesive strength, but there is a problem in that the adhesive strength decreases when exposed to high temperature conditions for a long period of time. Therefore, as a method to improve this problem,
No. 1 and JP-A-60-158230 disclose the use of organic carboxylic acid cobalt-boron metal soap as an adhesion promoter to improve the adhesion between rubber-reinforcing steel cords and rubber, especially after thermal aging. It is proposed to do so.
(発明が解決しようとする問題点)
しかしながら有機カルボン酸のコバルト・ホウ素金属石
鹸は接着の温熱劣化に対しては著しい改良効果を示すが
、初期接着力、温熱劣化に対する接着力、ゴムの弾性率
などが変動しやすいという欠点があることが判明した。(Problems to be Solved by the Invention) However, cobalt-boron metal soaps of organic carboxylic acids show a remarkable improvement effect on thermal deterioration of adhesives, but they do not improve initial adhesion strength, adhesive strength against thermal deterioration, and elastic modulus of rubber. It has been found that there is a drawback that the values are easily fluctuated.
即ち特開昭60−158230号公報では有機カルボン
酸のコバルト・ホウ素金属石鹸を配合したゴム組成物に
スチールコードを埋め込み145°Cで30分間加硫し
て接着試験を実施しているが、低温長時間加硫であるた
めに工業的生産面からは好ましくない。また特開昭60
−124640号公報に接着促進剤として有機コバルト
・ホウ素錯体を用いることが記載されているが、この場
合もスチールワイヤを埋め込んだゴム組成物を149°
Cで23分加硫して接着評価試料を作成している。That is, in JP-A-60-158230, an adhesion test was conducted by embedding a steel cord in a rubber composition containing an organic carboxylic acid cobalt-boron metal soap and vulcanizing it at 145°C for 30 minutes. Since vulcanization takes a long time, it is not preferable from an industrial production point of view. Also, JP-A-60
-124640 describes the use of an organic cobalt-boron complex as an adhesion promoter;
An adhesion evaluation sample was prepared by vulcanization at C for 23 minutes.
更に特開昭60−238326号公報にもコバルトのカ
ルボン酸塩とアルカリ土類金属の硼酸塩との反応生成物
より成るゴムと金属の接着促進剤が開示されているが、
この場合もまたスチールコードを埋め込んだ接着促進剤
含有ゴム組成物を153°Cで25分加硫して接着評価
試料を作成して接着試験を行なっている。Furthermore, JP-A-60-238326 also discloses a rubber-to-metal adhesion promoter comprising a reaction product of a cobalt carboxylate and an alkaline earth metal borate.
In this case as well, an adhesion evaluation sample was prepared by vulcanizing the adhesion promoter-containing rubber composition in which the steel cord was embedded at 153° C. for 25 minutes, and an adhesion test was conducted.
このように接着性の良否を評価するのであれば、一定温
度で所定時間加硫した試料について判定すればよいが、
工業的に生産されるスチールコード補強ゴム製品では種
々の加硫温度、時間が採用されているため製品性能とし
てはその加硫条件で評価することも必要である。特に生
産性向上のためには高温、短時間加硫が好ましい。従っ
てこのような高温、短時間の加硫条件におけるスチール
コードとゴムとの接着性を改善せしめることのできる接
着促進剤の開発が望まれていた。If the adhesion quality is to be evaluated in this way, it is sufficient to perform the judgment on a sample that has been vulcanized at a constant temperature for a predetermined time.
Since various vulcanization temperatures and times are used for industrially produced steel cord reinforced rubber products, it is also necessary to evaluate product performance based on the vulcanization conditions. In particular, high temperature, short time vulcanization is preferred for improving productivity. Therefore, it has been desired to develop an adhesion promoter that can improve the adhesion between steel cord and rubber under such high-temperature, short-time vulcanization conditions.
(問題点を解決するための手段)
かかる現況下において、本発明者らはスチールコードと
ゴムとの接着性を改善するためには有機カルボン酸のコ
バルト・ホウ素金属石鹸を配合したゴム組成物を高温短
時間で加硫した際にゴムの弾性率の低下、接着性の低下
が見られることに着目し、その改善を試みて本発明を達
成したものである。このようにして、本発明のスチール
コード接着促進剤はスチールコードとゴムとの接着を改
善するために硫黄加硫性ゴム組成物にゴム100重量部
に対してコバルト金属に換算して0.02〜0.5重量
部の範囲の分量で配合され、該接着促進剤が有機カルボ
ン酸と無機コバルト化合物および有機ホウ酸エステルの
反応生成物とする反応混合物から成り、水で抽出される
ホウ素の含有率が0.06重量%以下であることを特徴
とする。(Means for Solving the Problems) Under these current circumstances, the present inventors developed a rubber composition containing a cobalt-boron metal soap, which is an organic carboxylic acid, in order to improve the adhesion between the steel cord and the rubber. The present invention was achieved by focusing on the fact that the elastic modulus and adhesiveness of rubber decrease when vulcanized at high temperature for a short time, and by attempting to improve these problems. In this way, the steel cord adhesion promoter of the present invention is added to a sulfur vulcanizable rubber composition in order to improve the adhesion between steel cord and rubber. The adhesion promoter is a reaction product of an organic carboxylic acid, an inorganic cobalt compound, and an organic boric acid ester, and contains boron, which is extracted with water. The ratio is 0.06% by weight or less.
ここで「水に抽出されるホウ素の含有率」とは、上記反
応混合物を非極性有機溶媒に溶解された後、水を加えて
混合し水層に抽出されたホウ素を定量して反応混合物に
対する重量百分率で示したものである。Here, "the content of boron extracted in water" means that the above reaction mixture is dissolved in a non-polar organic solvent, water is added and mixed, and the amount of boron extracted into the aqueous layer is quantified. It is expressed as a weight percentage.
(作 用)
本発明において有機カルボン酸のコバルト・ホウ素金属
石鹸の水で抽出されるホウ素の量を0.06重量%以下
と限定した理由は0.06重量%を超えると加硫ゴムの
弾性率が低下しすぎて製品性能に悪影響を及ぼすからで
ある。(Function) In the present invention, the amount of boron extracted with water from the organic carboxylic acid cobalt-boron metal soap is limited to 0.06% by weight or less. This is because the rate decreases too much and product performance is adversely affected.
例えば乗用車用ラジアルタイヤのスチールコードベルト
層のゴムの弾性率が小さくなるとベルト層の剛性が低下
しコーナリングパワーが小さくなり操縦の応答性が悪く
なる。また耐久性、乗心地にも悪影響を及ぼす。For example, when the elastic modulus of the rubber in the steel cord belt layer of a radial tire for a passenger car decreases, the rigidity of the belt layer decreases, cornering power decreases, and steering response deteriorates. It also has a negative effect on durability and riding comfort.
高内圧、高荷重で使用する大型ラジアルタイヤ−5=
では特に耐久性を要求されるがスチールコードを埋設す
るゴムの弾性率が低下すると耐久性が悪化し好ましくな
い。Large radial tires used under high internal pressure and high loads are particularly required to have durability, but if the elastic modulus of the rubber in which the steel cord is embedded decreases, the durability deteriorates, which is undesirable.
水で抽出されるホウ素によりゴムの弾性率が低下する度
合が大きくなるのは加硫温度が高温において顕著であり
低温では殆んど差がみられない。The degree to which the elastic modulus of rubber decreases due to boron extracted with water is noticeable at high vulcanization temperatures, and there is almost no difference at low vulcanization temperatures.
この理由は不明であるが、水に抽出されるホウ素化合物
は高温になるほど硫黄と反応しやすくなり、ゴム綱目形
成を減少させているものと推定される。The reason for this is unknown, but it is presumed that boron compounds extracted into water become more likely to react with sulfur as the temperature increases, reducing the formation of rubber grains.
本発明の接着促進剤は、ゴム100重量部に対してコバ
ルト量に換算して0.02〜0.5重量部の範囲の割合
で配合される。The adhesion promoter of the present invention is blended in a proportion ranging from 0.02 to 0.5 parts by weight in terms of cobalt per 100 parts by weight of rubber.
(実施例) 以下本発明を実施例および比較例により説明する。(Example) The present invention will be explained below with reference to Examples and Comparative Examples.
バーサチックR10合成酸(シェル化学■製、商品名)
3モル、プロピオン酸3.1モル混合物に水酸化コバル
ト3モルを添加した後190″Cで反応させ約6モルの
水が生成留去するまで加熱を続けた。生成したコバルト
の有機カルボン酸塩にオルトホウ酸n−ブチル1モルを
添加した後220”Cで反応させ生成したプロピオン酸
ブチルを減圧留去し、留去したプロピオン酸ブチルが約
3モルになるまで加熱を続けてバーサチック酸コバルト
・ホウ素金属石鹸を得た。Versatic R10 synthetic acid (manufactured by Shell Chemical, trade name)
After adding 3 moles of cobalt hydroxide to a mixture of 3 moles of propionic acid and 3.1 moles of propionic acid, the reaction was carried out at 190"C and heating was continued until about 6 moles of water was produced and distilled off. After adding 1 mole of n-butyl orthoborate to the solution, the reaction was carried out at 220"C, and the produced butyl propionate was distilled off under reduced pressure. Heating was continued until the distilled butyl propionate amounted to about 3 moles, and cobalt versatate. A boron metal soap was obtained.
得られたバーサチック酸コバルト・ホウ素金属石鹸Lo
gを0.1mg 単位まで精秤しトルエン300m1
に溶解させた。この溶液に精秤した蒸留水100dを加
え室温で1.5分間撹拌したのち分液ロートに移し30
分間静置後水層を採取した。採取した水層より5戚を精
秤し100m1!のメスフラスコに移したのち蒸留水を
加えて100meとして原子吸光測定用試料を作製した
。原子吸光による定量はホウ素の原子吸光用標準溶液に
より検量線を作成して求めた。The obtained cobalt/boron versatate metal soap Lo
Accurately weigh g to the nearest 0.1 mg and add 300 ml of toluene.
It was dissolved in Add 100 d of precisely weighed distilled water to this solution, stir at room temperature for 1.5 minutes, and then transfer to a separatory funnel for 30 min.
After standing for a minute, the aqueous layer was collected. Precisely weigh 5 relatives from the collected water layer and get 100m1! After transferring the mixture to a volumetric flask, distilled water was added to prepare a sample for atomic absorption measurement. Quantification by atomic absorption was determined by creating a calibration curve using a boron atomic absorption standard solution.
上記のバーサチック酸コバルト・ホウ素金属石鹸に対す
る水に抽出されるホウ素の含有量は0.04重量%であ
った。The content of boron extracted into water for the above cobalt boron versatate metal soap was 0.04% by weight.
上述のバーサチック酸コバルト・ホウ素金属石鹸は合成
例からも判るように、厳密には未反応物、副生成物を含
有した反応混合物であり、これらが水に抽出されるホウ
素の生成原因と推定される。As can be seen from the synthesis example, the above-mentioned versatile cobalt boron metal soap is strictly a reaction mixture containing unreacted substances and by-products, and these are presumed to be the cause of the formation of boron extracted into water. Ru.
上述の合成例と同様にして水酸化コバルトに対しバーサ
チック酸およびオルトホウ酸ブチルを変量して、第1表
に示す水に抽出されるホウ素含有率の異なるものを合成
した。In the same manner as in the above synthesis example, by varying the amount of versatic acid and butyl orthoborate with respect to cobalt hydroxide, compounds having different boron contents extracted in water as shown in Table 1 were synthesized.
プ私m湧礼堅
上述のようにして得られた各バーサチック酸コバルト・
ホウ素金属石鹸を下記組成のゴム組成物に配合し、実施
例1〜5.比較例1〜2のゴム組成物をつくり、物性を
評価し、得た結果を第1表に示す。Each of the cobalt cobalt oxides obtained as described above
Examples 1 to 5 were prepared by blending boron metal soap with a rubber composition having the following composition. Rubber compositions of Comparative Examples 1 and 2 were prepared and their physical properties were evaluated, and the results are shown in Table 1.
蕾 に いたゴム
配合成分 配合(重量部)天然ゴム
100カーボンブラツク(HAF
) 50亜鉛華
8硫黄 5
尚ゴムの100%モジュラスおよびスチールコードとゴ
ムとの接着評価はJIS−に−6301に準拠して実施
した。Rubber compounding ingredients in the buds Compound (parts by weight) Natural rubber
100 carbon black (HAF
) 50 zinc white
8 Sulfur 5 The 100% modulus of the rubber and the adhesion between the steel cord and the rubber were evaluated in accordance with JIS-6301.
接着力指数は各加硫条件での比較例2の剥離抗力を10
0として指数で示しており、指数の大きいほど接着が良
好であることを示す。使用しだすチールコード種はI
X 5 Xo、23である。The adhesion force index is 10 the peel resistance of Comparative Example 2 under each vulcanization condition.
It is shown as an index with 0 as the index, and the larger the index, the better the adhesion. The type of teal code that starts to be used is I.
X 5 Xo, 23.
第1図は第1表の170°C,8分加硫のゴム組成物の
水で抽出されるホウ素の含有量(重量%)と100%モ
ジュラスをプロットした図で、この図から水で抽出され
るホウ素によりゴム弾性率の低下する度合が、高温加硫
で顕著であることがわかる。Figure 1 is a diagram plotting the content (wt%) of boron extracted with water and the 100% modulus of the rubber composition vulcanized at 170°C for 8 minutes in Table 1. It can be seen that the degree to which the rubber elasticity modulus decreases due to boron is remarkable during high-temperature vulcanization.
大隻舅旦並走グ1
実施例1においてバーサチック” 10合成酸のり代り
にナフテン酸とロジン酸を用いた以外は同様にしてナフ
テン酸コバルト・ホウ素金属石鹸およびロジン酸コバル
ト・ホウ素金属石鹸を製造した。A cobalt naphthenate/boron metal soap and a cobalt/rosin acid metal soap were produced in the same manner as in Example 1 except that naphthenic acid and rosin acid were used instead of the Versatic" 10 synthetic acid. did.
次いで実施例1で用いたゴム組成物にバーサチック酸コ
バルト・ホウ素金属石鹸の代りにナフテン酸コバルト・
ホウ素金属石鹸およびロジン酸コバルト・ホウ素金属石
鹸を夫々コバルト元素含有量で0.5重量部添加し、実
施例6および7のゴム組成物をつくった。この等のゴム
組成物につき実施例1と同様に物性を評価し、得た結果
を次の第2表に示す。Next, cobalt naphthenate and cobalt naphthenate were added to the rubber composition used in Example 1 instead of the cobalt versatate and boron metal soap.
Rubber compositions of Examples 6 and 7 were prepared by adding 0.5 parts by weight of boron metal soap and cobalt rosin acid boron metal soap, each having a cobalt element content of 0.5 parts by weight. The physical properties of these rubber compositions were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.
実m亀
実施例5のバーサチック酸コバルト・ホウ素金属石鹸を
用い、評価に用いたゴム組成物として下記の如く、バー
サチック酸コバルト・ホウ素金属石鹸の配合(重量部)
をコバルト元素含有量で0.1 、0.3 、0.5お
よび0.6とした4種のゴム組成物 (No、1〜4)
を作製した。これ等のゴム組成物を夫々155°Cで2
0分加硫し、JIS K6301に準じ100°Cの空
気中において、24時間熱老化させ、そのゴムの引張強
度を測定し、熱老化させる前の強度との比(強力保持率
)を測定した。Using the cobalt and boron versatate metal soap of Example 5, the rubber composition used for evaluation was as follows: The combination of the cobalt and boron versatate (parts by weight)
Four types of rubber compositions with a cobalt element content of 0.1, 0.3, 0.5, and 0.6 (No. 1 to 4)
was created. These rubber compositions were heated at 155°C for 2 hours.
Vulcanized for 0 minutes, heat aged in air at 100°C for 24 hours according to JIS K6301, measured the tensile strength of the rubber, and measured the ratio (strength retention) to the strength before heat aging. .
舌 に いたゴム
配合成分 配合(重量部)天然ゴム
100カーボンブラツク(HAF
) 50亜鉛華
8−13=
この結果第3表に示す如く、バーサチック酸コバルト・
ホウ素金属石鹸の配合量が多くなる程、強力保持率が低
下するが0.5重量部を超えると低下が激しいことが判
った。Rubber compounding ingredients on the tongue Compound (parts by weight) Natural rubber
100 carbon black (HAF
) 50 zinc white
8-13 = As shown in Table 3, the results show that cobalt versatate.
It was found that as the amount of boron metal soap added increases, the strength retention rate decreases, but when it exceeds 0.5 parts by weight, the decrease is severe.
コバルト石鹸のゴム組成物への配合量を増加した場合、
−船釣にゴムの弾性率は増大する。但しバーサチック酸
コバルト・ホウ素金属石鹸の場合、第3表の如く配合量
の増大と供に、ゴム組成物中に含有される水に抽出され
るホウ素の量が増加し、その結果170°Cで加硫した
場合の弾性率が0.6PHRの場合減少することが確認
された。When the amount of cobalt soap added to the rubber composition is increased,
-The elastic modulus of rubber increases during boat fishing. However, in the case of cobalt/boron versatate metal soap, as shown in Table 3, as the blending amount increases, the amount of boron extracted into the water contained in the rubber composition increases, and as a result, the amount of boron extracted into the water contained in the rubber composition increases. It was confirmed that the elastic modulus upon vulcanization was reduced at 0.6 PHR.
(発明の効果)
以上説明してきたように、本発明のスチールコード接着
促進剤は、水で抽出されるホウ素の含有量が0.06重
量%以下である有機カルボン酸コバルト・ホウ素金属石
鹸を主成分とする反応混合物から構成したことにより、
高温でのゴムとスチールコードの接着の維持とともに、
加硫モールド当りのタイヤの生産本数を向上させるのに
必須要件である高温加硫におけるモジュラスの向上即ち
弾性率を向上せしめ、タイヤの操縦性(コーナリングパ
ワー)およびタイヤのベルト部耐久性の低下を防止する
ことができるという効果が得られる。(Effects of the Invention) As explained above, the steel cord adhesion promoter of the present invention mainly contains an organic carboxylic acid cobalt/boron metal soap with a water-extractable boron content of 0.06% by weight or less. By being composed of a reaction mixture as a component,
Along with maintaining the adhesion between rubber and steel cord at high temperatures,
It improves the modulus during high-temperature vulcanization, which is an essential requirement for increasing the number of tires produced per vulcanization mold, or improves the elastic modulus, and reduces the decrease in tire maneuverability (cornering power) and tire belt durability. The effect is that it can be prevented.
第1図は、実施例1〜5、比較例1〜2のゴム組成物を
170°C18分間の高温加硫した場合の水で抽出され
るホウ素の含有率(重量%)とゴムの100%モジュラ
スの関係を示すグラフである。Figure 1 shows the boron content (wt%) extracted with water when the rubber compositions of Examples 1 to 5 and Comparative Examples 1 to 2 were vulcanized at a high temperature of 170°C for 18 minutes and the 100% of the rubber. It is a graph showing the relationship between modulus.
Claims (1)
0.02〜0.5重量部配合するスチールコード接着促
進剤において、該促進剤が有機カルボン酸と無機コバル
ト化合物および有機ホウ酸エステルの反応生成物である
有機カルボン酸コバルト・ホウ素金属石鹸を主成分とす
る反応混合物から成り、水で抽出されるホウ素の含有率
が0.06重量%以下であることを特徴とするスチール
コード接着促進剤。1. In a steel cord adhesion promoter that is blended in an amount of 0.02 to 0.5 parts by weight in terms of cobalt metal per 100 parts by weight of rubber, the promoter is a mixture of an organic carboxylic acid, an inorganic cobalt compound, and an organic borate ester. A steel cord adhesion promoter consisting of a reaction mixture whose main components are organic carboxylic acid cobalt/boron metal soap, which is a reaction product, and characterized in that the content of boron extracted with water is 0.06% by weight or less. agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62311057A JP2823857B2 (en) | 1987-12-10 | 1987-12-10 | Steel cord adhesion promoter and rubber composition containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62311057A JP2823857B2 (en) | 1987-12-10 | 1987-12-10 | Steel cord adhesion promoter and rubber composition containing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01153783A true JPH01153783A (en) | 1989-06-15 |
JP2823857B2 JP2823857B2 (en) | 1998-11-11 |
Family
ID=18012593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62311057A Expired - Lifetime JP2823857B2 (en) | 1987-12-10 | 1987-12-10 | Steel cord adhesion promoter and rubber composition containing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2823857B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7152644B2 (en) | 2001-06-01 | 2006-12-26 | Sumitomo Rubber Industries, Ltd. | Rubber reinforcing steel cord, manufacturing method of rubber reinforcing steel cord and pneumatic tire |
JP2007119619A (en) * | 2005-10-28 | 2007-05-17 | Dainippon Ink & Chem Inc | Hardening promoter for aqueous coating |
JP2007284477A (en) * | 2006-04-12 | 2007-11-01 | Dainippon Ink & Chem Inc | Dryer for oxidative polymerization-curable oily coating and coating comprising the same |
CN100412122C (en) * | 2004-10-27 | 2008-08-20 | 住友橡胶工业株式会社 | Rubber composition for steel cord and steel cord coated thereby |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6015444A (en) * | 1983-07-08 | 1985-01-26 | Bridgestone Corp | Improved rubber composition for tire |
JPS60193701A (en) * | 1984-03-15 | 1985-10-02 | Yokohama Rubber Co Ltd:The | Steel radial tire |
JPS62146936A (en) * | 1985-12-20 | 1987-06-30 | Bridgestone Corp | Rubber composition for bonding steel cord |
-
1987
- 1987-12-10 JP JP62311057A patent/JP2823857B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6015444A (en) * | 1983-07-08 | 1985-01-26 | Bridgestone Corp | Improved rubber composition for tire |
JPS60193701A (en) * | 1984-03-15 | 1985-10-02 | Yokohama Rubber Co Ltd:The | Steel radial tire |
JPS62146936A (en) * | 1985-12-20 | 1987-06-30 | Bridgestone Corp | Rubber composition for bonding steel cord |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7152644B2 (en) | 2001-06-01 | 2006-12-26 | Sumitomo Rubber Industries, Ltd. | Rubber reinforcing steel cord, manufacturing method of rubber reinforcing steel cord and pneumatic tire |
CN100412122C (en) * | 2004-10-27 | 2008-08-20 | 住友橡胶工业株式会社 | Rubber composition for steel cord and steel cord coated thereby |
JP2007119619A (en) * | 2005-10-28 | 2007-05-17 | Dainippon Ink & Chem Inc | Hardening promoter for aqueous coating |
JP2007284477A (en) * | 2006-04-12 | 2007-11-01 | Dainippon Ink & Chem Inc | Dryer for oxidative polymerization-curable oily coating and coating comprising the same |
Also Published As
Publication number | Publication date |
---|---|
JP2823857B2 (en) | 1998-11-11 |
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