JP2008144014A - Rubber cement composition - Google Patents

Rubber cement composition Download PDF

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JP2008144014A
JP2008144014A JP2006331790A JP2006331790A JP2008144014A JP 2008144014 A JP2008144014 A JP 2008144014A JP 2006331790 A JP2006331790 A JP 2006331790A JP 2006331790 A JP2006331790 A JP 2006331790A JP 2008144014 A JP2008144014 A JP 2008144014A
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Kazuyuki Umeda
和幸 梅田
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Yokohama Rubber Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber cement composition which can simultaneously satisfy adhesiveness before vulcanization and adhesiveness after vulcanization for SBR-based tire treads having high NR compounding ratios. <P>SOLUTION: This rubber cement composition comprises (i) 100 pts.wt. of a rubber component comprising 95 to 60 pts.wt. of SBR and 5 to 40 pts.wt. of BR containing 1,4-trans components in an amount of ≥20 wt.%, (ii) 20 to 70 pts.wt. of carbon black, and (iii) 2 to 40 pts.wt. of an adhesive resin, wherein all solid contents of (i) to (iii) are uniformly dispersed in an organic solvent in a concentration of 2 to 20 wt.%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明はゴムセメント組成物に関し、更に詳細には、従来のSBR系スプライスセメントの組成に特定のBR成分を配合することで、SBR−NR配合系タイヤトレッドにおける所要の加硫前の粘着性と加硫後の接着性とを同時に満足させるゴムセメント組成物に関する。   The present invention relates to a rubber cement composition, and more specifically, by adding a specific BR component to the composition of a conventional SBR-based splice cement, the required pre-vulcanization tackiness in an SBR-NR-containing tire tread The present invention relates to a rubber cement composition that simultaneously satisfies adhesiveness after vulcanization.

従来、汎用タイヤトレッドにはSBR(スチレン−ブタジエンゴム)が使用されているため、SBR系のスプライスセメントとは相性が良い。しかしながら、NR(天然ゴム)の配合比の高いSBR系タイヤトレッドに対して当該SBR系のスプライスセメントを使用すると、未加硫時での粘着力が弱く、製造工程中における加硫前の保管時に、その接合スプライス部に口開き現象が生じるという問題があった。一方、当該セメントそのものをNR系スプライスセメントにした場合には、未加硫時での粘着力は確保されるものの、SBRとそのNRとの間に相溶性が起こらず、加硫後の接着力が劣るという問題があった。よって、NR配合比の高いSBR系タイヤトレッドに対して有効なスプライスセメントの開発が、強く望まれている。   Conventionally, since SBR (styrene-butadiene rubber) has been used for general-purpose tire treads, it is compatible with SBR-based splice cement. However, if the SBR splice cement is used for an SBR tire tread with a high blending ratio of NR (natural rubber), the adhesive strength when unvulcanized is weak, and during storage before vulcanization during the production process There is a problem that a mouth opening phenomenon occurs in the joint splice portion. On the other hand, when the cement itself is an NR-type splice cement, the adhesive strength when unvulcanized is ensured, but no compatibility occurs between SBR and its NR, and the adhesive strength after vulcanization. There was a problem that was inferior. Therefore, the development of an effective splice cement for the SBR tire tread having a high NR compounding ratio is strongly desired.

先行技術として、タイヤ用に使用されるセメントとして液状BR(液状ブタジエンゴム)等の液状エラストマーを配合した無溶剤セメントに係る技術が、以下の特許文献1に開示されているが、当該無溶剤セメントは液状ゴムであるためゴムとしてのバルクな強度が得にくく、加硫接着力の点で不安が残る。また、以下の特許文献2及び3には、タイヤ用スプライスセメントとして、IR(イソプレンゴム)−SBRのブレンドを主成分とするものが開示されているが、その接着性には優れているものの、相溶性が十分でなく、満足する加硫接着力が得にくいものであった。   As a prior art, a technique related to a solventless cement in which a liquid elastomer such as liquid BR (liquid butadiene rubber) is blended as a cement used for tires is disclosed in Patent Document 1 below. Since it is a liquid rubber, it is difficult to obtain bulk strength as a rubber, and anxiety remains in terms of vulcanization adhesion. In addition, in the following Patent Documents 2 and 3, as a splice cement for tires, one having a blend of IR (isoprene rubber) -SBR as a main component is disclosed, but its adhesiveness is excellent, The compatibility was not sufficient, and satisfactory vulcanization adhesion was difficult to obtain.

特開2000−191840号公報JP 2000-191840 A 特開2006−241346号公報JP 2006-241346 A 特開2006−265391号公報JP 2006-265391 A

よって、本発明では、SBR及びNRと相溶する特定のBR成分をSBR系スプライスセメントに配合することで、NR配合比の高いSBR系タイヤトレッドに対して、加硫前の粘着性と加硫後の接着性を同時に満足させるゴムセメント組成物を提供することを目的とする。   Therefore, in the present invention, by blending a specific BR component that is compatible with SBR and NR into the SBR splice cement, the SBR tire tread having a high NR compounding ratio can be used for adhesion and vulcanization before vulcanization. An object of the present invention is to provide a rubber cement composition that satisfies the later adhesiveness at the same time.

本発明によれば、(i)SBR95〜60重量部と1,4−トランス成分を20重量%以上有するBR5〜40重量部とからなるゴム成分100重量部に対して、(ii)カーボンブラック20〜70重量部及び(iii)粘着樹脂2〜40重量部を含有し、前記(i)〜(iii)の全固形物を2〜20重量%の濃度で有機溶媒中に均一分散してなるゴムセメント組成物が提供される。   According to the present invention, (ii) carbon black 20 with respect to 100 parts by weight of rubber component consisting of 95 to 60 parts by weight of SBR and 5 to 40 parts by weight of BR having 20% by weight or more of 1,4-trans component. -70 parts by weight and (iii) 2 to 40 parts by weight of an adhesive resin, and a rubber obtained by uniformly dispersing the total solids of (i) to (iii) in an organic solvent at a concentration of 2 to 20% by weight A cement composition is provided.

本発明者は、上記NRの配合比の高いSBR−NR系タイヤトレッドに対して有効なスプライスセメントを鋭意探索していたところ、この度、SBR/NR双方と相溶し、かつ樹脂特性をもつ特殊なBRとしての1,4−トランス成分を20重量%以上有するBRを、特定量で従来のSBR系スプライスセメントに配合すると、加硫前の粘着性と加硫後の接着性とに良好な両立性が図られ、優れたゴムセメント組成物が得られることを見出したものである。   The present inventor has been diligently searching for an effective splice cement for the SBR-NR tire tread having a high blending ratio of NR, and this time, a special compound having compatibility with both SBR / NR and resin characteristics. When blending a specific amount of BR having a 1,4-trans component of 20% by weight or more as a brilliant BR with a conventional SBR-based splice cement, both adhesiveness before vulcanization and adhesiveness after vulcanization can be achieved. It has been found that the rubber cement composition can be obtained with excellent properties.

よって、本発明では、具体的には、(i)SBR95〜60重量部と1,4−トランス成分を20重量%以上有するBR5〜40重量部とからなるゴム成分100重量部に対して、(ii)カーボンブラック20〜70重量部及び(iii)粘着樹脂2〜40重量部を含有し、前記(i)〜(iii)の全固形物を2〜20重量%の濃度で有機溶媒中に均一分散してなるゴムセメント組成物が提供される。   Therefore, in the present invention, specifically, (i) 100 parts by weight of a rubber component composed of 95 to 60 parts by weight of SBR and 5 to 40 parts by weight of BR having 20% by weight or more of 1,4-trans component, ii) containing 20 to 70 parts by weight of carbon black and (iii) 2 to 40 parts by weight of adhesive resin, and uniformly adding the total solids of (i) to (iii) in an organic solvent at a concentration of 2 to 20% by weight. Dispersed rubber cement compositions are provided.

本発明のゴムセメント組成物に配合されるSBR成分としては、好ましくは、20〜40重量%の結合スチレン含有量を有し、かつ7〜25重量%のビニル量(1,2−結合量)を有するSBRが用いられる。当該SBRの配合量としては、95〜60重量部の量で使用される。当該SBRの配合量が95重量部を超えると、NRを含むタイヤトレッドに対して未加硫時での粘着性が不十分となるので好ましくなく、逆に60重量部未満であると、SBRを含むタイヤトレッドに対して接着力が不十分となるので好ましくない。   The SBR component blended in the rubber cement composition of the present invention preferably has a bound styrene content of 20 to 40% by weight and a vinyl content of 7 to 25% by weight (1,2-bond amount). SBR with The amount of SBR used is 95 to 60 parts by weight. When the blending amount of the SBR exceeds 95 parts by weight, the tackiness at the time of unvulcanized with respect to the tire tread containing NR is not preferable, and conversely, when the blending amount is less than 60 parts by weight, This is not preferable because the adhesive force is insufficient with respect to the tire tread.

本発明のゴムセメント組成物に配合されるBR成分としては、そのミクロ構造中に1,4−トランス構造単位を20重量%以上含むBRが有効に用いられる。当該BRとして、その分子内部に適度なトランス構造を有すると、樹脂化による粘着性と対象のタイヤトレッド部材中に含まれるSBR及びNRとの相溶性による加硫接着性とを併せ有することが可能となる。当該トランス構造が20重量部以下のBRでは、樹脂化が十分でないので特にNRとの接着性が不十分となり、好ましくない。また、当該1,4−トランス成分を20重量部以上有するBRの配合量は、5〜40重量部、より好ましくは20〜35重量部の量で使用される。当該1,4−トランス成分を20重量%以上有するBRの配合量が、5重量部未満では所期の粘着、接着力を得ることができず、逆に40重量部を超えると、ゴムセメント組成物の粘度が上がり、ハンドリング性が損われるので好ましくない。   As the BR component to be blended in the rubber cement composition of the present invention, BR containing 20% by weight or more of 1,4-trans structural unit in its microstructure is effectively used. When the BR has an appropriate trans structure inside the molecule, it can have both adhesiveness due to resinification and vulcanization adhesiveness due to compatibility with SBR and NR contained in the target tire tread member. It becomes. When the transformer structure is 20 parts by weight or less, since resinization is not sufficient, adhesion with NR is particularly insufficient, which is not preferable. Moreover, the compounding quantity of BR which has the said 1, 4- trans component 20 weight part or more is 5-40 weight part, More preferably, it is used in the quantity of 20-35 weight part. When the blending amount of BR having 20% by weight or more of the 1,4-trans component is less than 5 parts by weight, the desired tackiness and adhesive strength cannot be obtained. This is not preferable because the viscosity of the product increases and the handling property is impaired.

本発明のゴムセメント組成物に配合されるカーボンブラックとしては、その等級がHAFと同等あるいはHAFより細かいものを使用することが、加硫接着時の強度を上げるなどの理由で好ましい。当該カーボンブラックの配合量としては、20〜70重量部の量で使用される。この配合量が20重量部未満では、加硫接着時の強度が不十分になるので好ましくなく、逆に70重量部を超えると、ゴムセメント組成物の粘度が上がり、ハンドリング性が損われるので好ましくない。   As the carbon black to be blended in the rubber cement composition of the present invention, it is preferable to use a carbon black whose grade is equal to or finer than HAF for the purpose of increasing the strength during vulcanization adhesion. The carbon black is used in an amount of 20 to 70 parts by weight. If the blending amount is less than 20 parts by weight, the strength at the time of vulcanization adhesion becomes insufficient, which is not preferable. On the other hand, if it exceeds 70 parts by weight, the viscosity of the rubber cement composition increases and handling properties are impaired. Absent.

本発明のゴムセメント組成物に配合される粘着樹脂としては、例えば、フェノール系樹脂、テルペン系樹脂、変性テルペン系樹脂、水添テルペン系樹脂、ロジン系樹脂又はクマロン−インデン樹脂などが挙げられる。これらの粘着樹脂は、一種以上の混合粘着樹脂として用いられてもよい。当該粘着性樹脂の配合量としては、2〜40重量部の量で用いられる。この配合量が2重量部未満では、ゴムセメント組成物の加硫前の粘着力が十分でなく、逆に、40重量部を超ええると、ゴムセメント組成物の粘度が上がり、ハンドリング性が損われるので好ましくない。   Examples of the adhesive resin blended in the rubber cement composition of the present invention include phenolic resins, terpene resins, modified terpene resins, hydrogenated terpene resins, rosin resins, and coumarone-indene resins. These adhesive resins may be used as one or more mixed adhesive resins. The amount of the adhesive resin used is 2 to 40 parts by weight. If the blending amount is less than 2 parts by weight, the adhesive strength before vulcanization of the rubber cement composition is not sufficient, and conversely if it exceeds 40 parts by weight, the viscosity of the rubber cement composition increases and handling properties are impaired. This is not preferable.

以上の各成分(i)〜(iii)は、その全固形物が2〜20重量%の濃度となるように有機溶媒中に均一分散されて、本発明のゴムセメント組成物となる。かかる有機溶媒として使われるものには、例えば、ゴム成分を溶解させるヘキサン、ヘプタン、石油エーテル、シクロヘキサン、又はトルエンが挙げられる。この固形物濃度が2重量%未満では、タイヤトレッドのゴム成分とゴムセメント組成物中のゴム分子の相互浸透性の低下により接着不良となり、また20重量%を超えるとゴムセメント組成物の粘度が上がり、ハンドリング性が損われるので好ましくない。   Each of the above components (i) to (iii) is uniformly dispersed in an organic solvent so that the total solids thereof have a concentration of 2 to 20% by weight, and the rubber cement composition of the present invention is obtained. Examples of such an organic solvent include hexane, heptane, petroleum ether, cyclohexane, or toluene that dissolves the rubber component. If the solids concentration is less than 2% by weight, the adhesion between the rubber component of the tire tread and the rubber molecules in the rubber cement composition will be poor, and if it exceeds 20% by weight, the viscosity of the rubber cement composition will be low. This is not preferable because the handling property is deteriorated.

このゴムセメント組成物には、その他の配合剤として、例えば、老化防止剤、亜鉛華等の加硫助剤、硫黄加硫剤、加硫促進剤が適宜配合され、それらの配合量も通常の範囲内で配合することができる。   In this rubber cement composition, as other compounding agents, for example, aging inhibitors, vulcanization aids such as zinc white, sulfur vulcanizing agents, vulcanization accelerators are appropriately blended, and the blending amounts thereof are also usual. It can mix | blend within the range.

以下に示す実施例及び比較例を参照して、本発明を更に詳しく説明するが、本発明の技術的範囲がその実施例に限定されないことはいうまでもない。   The present invention will be described in more detail with reference to the following examples and comparative examples, but it goes without saying that the technical scope of the present invention is not limited to these examples.

実施例1〜比較例1〜4
1)粘着性試験: 以下の表2で示すタイヤトレッド用ゴム配合A及びBを混練して得られたゴム組成物を、所定の金型を用いて裏打ち材の布と共に幅10mm、ゲージ2mm厚で押出してゴム帯状片とし、これを長さ150mmに切断してゴム試験片を作製した。このゴム試験片上に、以下の表1に示す配合から得た各例のゴムセメント組成物を塗付し、1時間放置して完全に有機溶剤を揮発させて、試験体とした。試験は、PICMAタックメーターを用いて、各試験体について、圧着荷重:4.9N 、圧着時間:0秒、剥離速度:120mm/分、温度:20℃、湿度:65%の条件下に、タック値を測定した。数値が大きい程、粘着性が良好であることを示す。
Examples 1 to Comparative Examples 1 to 4
1) Tackiness test: A rubber composition obtained by kneading rubber treads A and B for tire tread shown in Table 2 below, together with a cloth for a backing material using a predetermined mold, a width of 10 mm, a gauge of 2 mm thickness Were extruded into rubber strips, which were cut to a length of 150 mm to prepare rubber test pieces. On each rubber test piece, the rubber cement composition of each example obtained from the composition shown in Table 1 below was applied, and left for 1 hour to completely evaporate the organic solvent, thereby obtaining a test specimen. The test was carried out using a PICMA tack meter for each test piece under the conditions of pressure bonding load: 4.9 N, pressure bonding time: 0 seconds, peeling speed: 120 mm / min, temperature: 20 ° C., humidity: 65%. The value was measured. It shows that adhesiveness is so favorable that a numerical value is large.

2)接着性試験: 以下の表2で示すタイヤトレッド用ゴム配合A及びBを混練して得られたゴム組成物からなる所定の195/60R15タイヤのトレッドのスプライス部分に、以下の表1に示す配合から得た各例のゴムセメント組成物を塗付後、加硫して、試験タイヤとした。この試験タイヤの前記スプライス部を当該トレッドが剥がれる方向にグラインダーで逆バフを行い、深さ2mmの剥離亀裂が発生した場合を×、2mm未満の剥離亀裂が発生した場合を△、全く亀裂が発生しなかった場合を○として評価した。亀裂の発生しない方が、接着力は良好である。   2) Adhesion test: In the tread splice portion of a predetermined 195 / 60R15 tire made of a rubber composition obtained by kneading the rubber blends A and B for tire tread shown in Table 2 below, The rubber cement composition of each example obtained from the formulation shown was applied and then vulcanized to obtain a test tire. When the splice part of this test tire is reverse-buffed with a grinder in the direction in which the tread is peeled off, a peeling crack with a depth of 2 mm occurs. The case where it did not do was evaluated as (circle). The adhesive force is better when cracks do not occur.

粘着試験及び接着試験の結果を、以下の表1に示す。

Figure 2008144014
The results of the adhesion test and the adhesion test are shown in Table 1 below.
Figure 2008144014

上記試験体および試験タイヤの作製に用いたタイヤトレッド用ゴム配合を、以下の表2に示す。

Figure 2008144014
The rubber composition for the tire tread used for the production of the test specimen and the test tire is shown in Table 2 below.
Figure 2008144014

表1の結果によれば、比較例1では、従来のSBR系スプライスセメントゴム組成物を使用すると、SBR系タイヤトレッドとの粘着性に問題はないが、NR系タイヤトレッドとの粘着性が極度に劣り、加硫接着性でも劣っていることが分る。比較例2では、同セメントゴム組成物にNRを配合すると、粘着性の問題は無くなるが、SBR系タイヤトレッドとの加硫接着性が劣っていることが分る。また、比較例3では、従来のSBR系スプライスセメントゴム組成物に一般的なBRを配合した場合には、これがSBR/NR両者の中間的なSP値(溶解度パラメーター)を有することで、中庸的な加硫接着性を得ることができるが、高シスBR分子は樹脂化しないので、NR系タイヤトレッドとの粘着性が改善されないことが分る。更に、比較例4では、比較例3の配合BRに代えてビニル含有量が高いBRを従来のSBR系スプライスセメントゴム組成物に加えていることで、当該BRによる樹脂化が期待できるものの、その樹脂化の度合いが不十分であって、NR系タイヤトレッドとの粘着性が改善されていないことが分る。これに対して、実施例1のように、分子内部に樹脂化するトランス構造を含有する特定のBRを従来のSBR系スプライスセメントゴム組成物に配合した場合には、NR系タイヤトレッドに対して、そのSBR/NRとの相溶性に基づく加硫接着性と、樹脂化による粘着性の向上が見られ、優れた粘着性と加硫接着性の両立が図られていることが分る。   According to the results of Table 1, in Comparative Example 1, when the conventional SBR splice cement rubber composition is used, there is no problem with the adhesiveness with the SBR tire tread, but the adhesiveness with the NR tire tread is extremely high. It is found that the vulcanization adhesion is also poor. In Comparative Example 2, when NR is added to the cement rubber composition, the problem of tackiness is eliminated, but it can be seen that the vulcanization adhesion with the SBR tire tread is poor. Further, in Comparative Example 3, when general BR is blended with the conventional SBR-based splice cement rubber composition, this has an intermediate SP value (solubility parameter) between both SBR / NR, which is moderate. It can be seen that, although high vulcanized adhesiveness can be obtained, the high cis BR molecule is not converted into a resin, so that the tackiness with the NR tire tread is not improved. Further, in Comparative Example 4, although BR having a high vinyl content is added to the conventional SBR-based splice cement rubber composition instead of the blended BR of Comparative Example 3, resinization with the BR can be expected. It can be seen that the degree of resinification is insufficient and the adhesiveness with the NR tire tread is not improved. On the other hand, as in Example 1, when a specific BR containing a trans structure that is resinized inside the molecule is blended with a conventional SBR-based splice cement rubber composition, the NR-based tire tread Thus, it can be seen that the vulcanized adhesiveness based on the compatibility with the SBR / NR and the adhesiveness improved by the resinization are improved, and both excellent adhesiveness and vulcanized adhesiveness are achieved.

よって、本発明のゴムセメント組成物を用いてタイヤトレッドのスプライス部を接合したタイヤトレッドとなせば、極めて優れたタイヤトレッド部材が得られることは、明らかである。   Therefore, it is clear that an extremely excellent tire tread member can be obtained by using the rubber cement composition of the present invention to obtain a tire tread in which the splice portions of the tire tread are joined.

Claims (4)

(i)SBR95〜60重量部と1,4−トランス成分を20重量%以上有するBR5〜40重量部とからなるゴム成分100重量部に対して、(ii)カーボンブラック20〜70重量部及び(iii)粘着樹脂2〜40重量部を含有し、前記(i)〜(iii)の全固形物を2〜20重量%の濃度で有機溶媒中に均一分散してなるゴムセメント組成物。   (I) with respect to 100 parts by weight of a rubber component composed of 95 to 60 parts by weight of SBR and 5 to 40 parts by weight of BR having 20% by weight or more of a 1,4-trans component, and (ii) 20 to 70 parts by weight of carbon black and ( iii) A rubber cement composition containing 2 to 40 parts by weight of an adhesive resin and uniformly dispersing the total solids (i) to (iii) in an organic solvent at a concentration of 2 to 20% by weight. 前記粘着樹脂が、フェノール樹脂、テルペン系樹脂、変性テルペン系樹脂、水添テルペン系樹脂、ロジン系樹脂及びクマロン−インデン樹脂からなる群より選ばれる少なくとも一種である、請求項1項に記載のゴムセメント組成物。   The rubber according to claim 1, wherein the adhesive resin is at least one selected from the group consisting of a phenol resin, a terpene resin, a modified terpene resin, a hydrogenated terpene resin, a rosin resin, and a coumarone-indene resin. Cement composition. 前記有機溶媒が、ヘキサン、ヘプタン、石油エーテル、シクロヘキサン及びトルエンからなる群より選ばれる少なくとも一種である、請求項1又は2に記載のゴムセメント組成物。   The rubber cement composition according to claim 1 or 2, wherein the organic solvent is at least one selected from the group consisting of hexane, heptane, petroleum ether, cyclohexane and toluene. 請求項1〜3のいずれか1項に記載のゴムセメント組成物を用いて接合したタイヤトレッド。   A tire tread joined using the rubber cement composition according to claim 1.
JP2006331790A 2006-12-08 2006-12-08 Rubber cement composition Pending JP2008144014A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012522088A (en) * 2009-03-31 2012-09-20 ソシエテ ド テクノロジー ミシュラン Use of aryldinitrile oxide in adhesive compositions
CN109777320A (en) * 2019-01-23 2019-05-21 保定华月胶带有限公司 A kind of less salt height bonding zinc coat adhesive glue and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012522088A (en) * 2009-03-31 2012-09-20 ソシエテ ド テクノロジー ミシュラン Use of aryldinitrile oxide in adhesive compositions
CN109777320A (en) * 2019-01-23 2019-05-21 保定华月胶带有限公司 A kind of less salt height bonding zinc coat adhesive glue and preparation method thereof

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