JP2014101483A - Rubber-metal complex, tire obtained by using the same, and method of determining vulcanizing time - Google Patents
Rubber-metal complex, tire obtained by using the same, and method of determining vulcanizing time Download PDFInfo
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- 239000002184 metal Substances 0.000 claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 81
- 229920001971 elastomer Polymers 0.000 claims abstract description 78
- 239000005060 rubber Substances 0.000 claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 13
- 238000004073 vulcanization Methods 0.000 claims description 44
- 239000002905 metal composite material Substances 0.000 claims description 35
- 229910001369 Brass Inorganic materials 0.000 claims description 8
- 239000010951 brass Substances 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 241000872198 Serjania polyphylla Species 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- -1 organic acid cobalt salt Chemical class 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YJEUJARPQSLENW-UHFFFAOYSA-M B([O-])([O-])[O-].C(CCCCCC(C)(C)C)(=O)[O-].[Co+4] Chemical compound B([O-])([O-])[O-].C(CCCCCC(C)(C)C)(=O)[O-].[Co+4] YJEUJARPQSLENW-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- JQALNNOQTGZTJZ-UHFFFAOYSA-N [[4,6-bis[bis(methoxymethyl)amino]-1,3,5-triazin-2-yl]-(methoxymethyl)amino]methanol Chemical compound COCN(CO)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 JQALNNOQTGZTJZ-UHFFFAOYSA-N 0.000 description 1
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 1
- WEZJBAOYGIDDLB-UHFFFAOYSA-N cobalt(3+);borate Chemical compound [Co+3].[O-]B([O-])[O-] WEZJBAOYGIDDLB-UHFFFAOYSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 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 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Ropes Or Cables (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム−金属複合体、これを用いたタイヤおよび加硫時間決定方法に関するものであり、詳しくは、ゴムおよび金属間が強固に接着されているゴム−金属複合体、これを用いたタイヤ並びにゴムおよび金属間の強固な接着状態を得るための加硫時間を決定する方法に関するものである。 The present invention relates to a rubber-metal composite, a tire using the same, and a vulcanization time determination method, and more specifically, a rubber-metal composite in which a rubber and a metal are firmly bonded to each other. The present invention relates to a method for determining a vulcanization time for obtaining a strong adhesion state between a tire and rubber and metal.
自動車用タイヤには強い衝撃や大きな荷重がかかるため、補強材として金属コードが用いられている。このような金属コードを被覆するゴムは、タイヤの信頼性および耐久性の観点から、金属コードと強固に接着させる必要がある。
従来、スチールコードとゴムとの接着性を改良するためには、ゴム中に有機酸コバルト塩を配合することが一般的である（例えば特許文献１等参照）。
しかしながら従来技術を単に適用しただけでは、現在高いレベルで求められているタイヤの信頼性および耐久性を満たす程度まで、ゴムおよび金属間を強固に接着させることが困難である。
一方、金属コードを被覆するゴムの加硫時間により、両者間の接着強度が変化することは知られているが、その加硫時間をコントロールして、ゴムおよび金属間の強固な接着状態を得ようとする試みは現在のところ成功していない。
A metal cord is used as a reinforcing material because a strong impact or a large load is applied to an automobile tire. The rubber covering the metal cord needs to be firmly bonded to the metal cord from the viewpoint of tire reliability and durability.
Conventionally, in order to improve the adhesion between the steel cord and the rubber, it is common to blend an organic acid cobalt salt in the rubber (see, for example, Patent Document 1).
However, simply applying the prior art makes it difficult to firmly bond rubber and metal to the extent that the tire reliability and durability currently required at a high level are satisfied.
On the other hand, it is known that the adhesive strength between the two changes depending on the vulcanization time of the rubber covering the metal cord, but the vulcanization time is controlled to obtain a strong adhesion state between the rubber and the metal. Attempts to do so have not been successful so far.
したがって本発明の目的は、ゴムおよび金属間が強固に接着されているゴム−金属複合体、これを用いたタイヤ並びにゴムおよび金属間の強固な接着状態を得るための加硫時間を決定する方法を提供することにある。 Accordingly, an object of the present invention is to provide a rubber-metal composite in which rubber and metal are firmly bonded, a tire using the same, and a method for determining a vulcanization time for obtaining a strong bonded state between rubber and metal. Is to provide.
本発明者らは鋭意研究を重ねた結果、ゴム−金属複合体のゴム−金属界面における金属表面をＸ線光電子分光法（ＸＰＳ）により測定したとき、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔに対して、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａが特定の比率である場合に、ゴムおよび金属間の強固な接着状態が得られることを見出し、本発明を完成することができた。
すなわち本発明は以下のとおりである。
１． ジエン系ゴムを含むゴム組成物と金属とからなり、前記ゴム組成物と前記金属とが前記ゴム組成物の加硫により接着してなるゴム−金属複合体であって、
前記ゴム組成物と前記金属との界面における前記金属表面をＸ線光電子分光法により測定したとき、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔと、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａとの関係が、下記式（１）を満たすことを特徴とするゴム−金属複合体。
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．３５ （１）
２．前記結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔと、前記連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａとの関係が、下記式（２）を満たすことを特徴とする前記１に記載のゴム−金属複合体。
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．４２ （２）
３．前記金属が、真鍮、亜鉛または銅であることを特徴とする前記１または２に記載のゴム−金属複合体。
４．前記金属が、真鍮をめっきしたスチールワイヤであることを特徴とする前記３に記載のゴム−金属複合体。
５．前記ゴム組成物が、前記ジエン系ゴム１００質量部に対し、カーボンブラックを３０〜８０質量部の割合で含むことを特徴とする前記１〜３のいずれかに記載のゴム−金属複合体。
６．前記１〜５のいずれかに記載のゴム−金属複合体を使用してなるタイヤ。
７．ジエン系ゴムを含むゴム組成物と金属とからなるとともに前記ゴム組成物と前記金属とが前記ゴム組成物の加硫により接着してなるゴム−金属複合体における、前記ゴム組成物の加硫時間を決定する方法であって、
前記ゴム組成物と前記金属との界面における前記金属表面をＸ線光電子分光法により測定したとき、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体と、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａとの関係が、下記式（１）を満たす加硫時間を、前記ゴム組成物の加硫時間と定めることを特徴とする加硫時間決定方法。
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．３５ （１）
８．前記結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔと、前記連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａとの関係が、下記式（２）を満たすことを特徴とする前記７に記載の加硫時間決定方法。
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．４２ （２）
As a result of intensive studies, the present inventors have determined that the entire S2p peak area having a binding energy of 160 to 166 eV when the metal surface at the rubber-metal interface of the rubber-metal composite is measured by X-ray photoelectron spectroscopy (XPS). The present invention was completed by finding that a strong adhesion state between rubber and metal can be obtained when the peak area A of the binding energy 163 to 164 eV, which is the central peak of chain sulfur, is a specific ratio with respect to T. We were able to.
That is, the present invention is as follows.
1. A rubber-metal composite comprising a rubber composition containing a diene rubber and a metal, wherein the rubber composition and the metal are bonded by vulcanization of the rubber composition,
When the metal surface at the interface between the rubber composition and the metal is measured by X-ray photoelectron spectroscopy, the entire peak area T of S2p having a binding energy of 160 to 166 eV and a binding energy of 163 to 163 are the central peak of chain sulfur. A rubber-metal composite, wherein the relationship with the peak area A of 164 eV satisfies the following formula (1).
The area A / the whole peak area T ≧ 0.35 (1)
2. The relationship between the total peak area T of S2p having the binding energy of 160 to 166 eV and the peak area A of the binding energy of 163 to 164 eV, which is the central peak of the chain sulfur, satisfies the following formula (2): 2. The rubber-metal composite according to 1.
The area A / the entire peak area T ≧ 0.42 (2)
3. 3. The rubber-metal composite as described in 1 or 2 above, wherein the metal is brass, zinc or copper.
4). 4. The rubber-metal composite as described in 3 above, wherein the metal is a steel wire plated with brass.
5. 4. The rubber-metal composite as described in any one of 1 to 3 above, wherein the rubber composition contains 30 to 80 parts by mass of carbon black with respect to 100 parts by mass of the diene rubber.
6). A tire comprising the rubber-metal composite according to any one of 1 to 5 above.
7). Vulcanization time of the rubber composition in a rubber-metal composite comprising a rubber composition containing a diene rubber and a metal, and the rubber composition and the metal bonded together by vulcanization of the rubber composition A method of determining
When the metal surface at the interface between the rubber composition and the metal is measured by X-ray photoelectron spectroscopy, the entire peak area of S2p with a binding energy of 160 to 166 eV and a binding energy of 163 to 164 eV, which is the central peak of chain sulfur. A vulcanization time determination method characterized in that a vulcanization time satisfying the following formula (1) with respect to the peak area A of the rubber composition is determined as a vulcanization time of the rubber composition.
The area A / the whole peak area T ≧ 0.35 (1)
8). The relationship between the total peak area T of S2p having the binding energy of 160 to 166 eV and the peak area A of the binding energy of 163 to 164 eV, which is the central peak of the chain sulfur, satisfies the following formula (2): 8. The vulcanization time determination method according to 7.
The area A / the entire peak area T ≧ 0.42 (2)
本発明のゴム−金属複合体は、ゴム−金属界面における金属表面をＸ線光電子分光法（ＸＰＳ）により測定したとき、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔに対して、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａが特定の比率であるので、ゴムおよび金属間の強固な接着状態が得られる。
該ゴム−金属複合体を使用したタイヤは、ゴム−金属複合体におけるゴムおよび金属間の強固な接着状態が得られているので、信頼性および耐久性を高いレベルで満足することができる。
また本発明の加硫時間決定方法によれば、ゴムおよび金属間の強固な接着状態が得られる最適な加硫時間を決定することができるので、加硫時間をコントロールするという簡単な手段によって、ゴムおよび金属間が強固に接着したゴム−金属複合体を得ることができる。
The rubber-metal composite of the present invention has a chain sulfur content with respect to the entire peak area T of S2p having a binding energy of 160 to 166 eV when the metal surface at the rubber-metal interface is measured by X-ray photoelectron spectroscopy (XPS). Since the peak area A of the binding energy 163 to 164 eV which is the central peak is a specific ratio, a strong adhesion state between the rubber and the metal can be obtained.
In the tire using the rubber-metal composite, a strong adhesion state between the rubber and the metal in the rubber-metal composite is obtained, so that reliability and durability can be satisfied at a high level.
Further, according to the vulcanization time determination method of the present invention, it is possible to determine the optimal vulcanization time for obtaining a strong adhesion state between the rubber and the metal, and therefore, by a simple means of controlling the vulcanization time, A rubber-metal composite in which rubber and metal are firmly bonded can be obtained.
以下、本発明をさらに詳細に説明する。
まず、本発明で使用されるゴム組成物について説明する。
Hereinafter, the present invention will be described in more detail.
First, the rubber composition used in the present invention will be described.
（ジエン系ゴム）
本発明で使用されるジエン系ゴムは、ゴム組成物に配合することができる任意のゴムを用いることができ、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、その分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル、アルコキシシリル、カルボキシル、ヒドロキシル基等で末端変性されていても、エポキシ化されていてもよい。
(Diene rubber)
As the diene rubber used in the present invention, any rubber that can be blended in the rubber composition can be used. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene -Butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), etc. are mentioned. These may be used alone or in combination of two or more. The molecular weight and microstructure are not particularly limited, and may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or may be epoxidized.
本発明におけるゴム組成物は、ジエン系ゴム１００質量部に対し、カーボンブラックを３０〜８０質量部配合するのが好ましく、５０〜７０質量部配合するのがさらに好ましい。カーボンブラックをこの範囲で使用することにより、ゴムおよび接着の補強という点で効果がある。また、カーボンブラックの窒素吸着比表面積（Ｎ２ＳＡ）は例えば７０〜１１０ｍ２／ｇの範囲が好ましい。なお、窒素吸着比表面積（Ｎ２ＳＡ）はＪＩＳ Ｋ６２１７−２に準拠して求めた値である。 The rubber composition in the present invention preferably contains 30 to 80 parts by mass, more preferably 50 to 70 parts by mass of carbon black with respect to 100 parts by mass of the diene rubber. Use of carbon black in this range is effective in terms of reinforcing rubber and adhesion. The nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably in the range of 70 to 110 m 2 / g, for example. The nitrogen adsorption specific surface area (N 2 SA) is a value determined in accordance with JIS K6217-2.
また本発明では、ゴムおよび金属間の強固な接着状態を得るため、有機酸コバルト塩を配合するのが好ましい。有機酸コバルト塩としては、例えばナフテン酸コバルト、ネオデカン酸コバルト、ステアリン酸コバルト、ロジン酸コバルト、バーサチック酸コバルト、トール油酸コバルト、ホウ酸ネオデカン酸コバルト、アセチルアセトナートコバルト等を例示することができる。また、ホウ素を含む有機酸コバルト塩、例えばオルトホウ酸コバルト等も使用できる。有機酸コバルト塩は、ジエン系ゴム１００質量部に対し、例えば０．１〜１０質量部の範囲で使用できる。 Moreover, in this invention, in order to obtain the strong adhesion state between rubber | gum and a metal, it is preferable to mix | blend organic acid cobalt salt. Examples of the organic acid cobalt salt include cobalt naphthenate, cobalt neodecanoate, cobalt stearate, cobalt rosinate, cobalt versatate, cobalt tall oil, cobalt borate neodecanoate, cobalt acetylacetonate and the like. . Also, organic acid cobalt salts containing boron, such as cobalt orthoborate, can be used. The organic acid cobalt salt can be used in the range of, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
また本発明では、ゴムの硬度を上げるために、ノボラック型フェノール系樹脂および硬化剤を配合することもできる。本発明で使用するノボラック型フェノール系樹脂は、本発明の効果およびゴム中への分散性という観点から、ノボラック型フェノール系樹脂が、ノボラック型フェノール樹脂、ノボラック型クレゾール樹脂、ノボラック型レゾルシン樹脂のいずれかあるいはそれらの混合物であることが好ましい。また、オイル変性フェノール樹脂としてカシュー変性フェノール樹脂も好ましく使用できる。硬化剤としては、ノボラック型フェノール系樹脂を硬化可能なものであればよく、とくに制限されないが、例えばヘキサメチレンテトラミン、ＨＭＭＭ（ヘキサメトキシメチロールメラミンの部分縮合物）、ＰＭＭＭ（ヘキサメチロールメラミンペンタメチルエーテルの部分縮合物）、ヘキサエトキシメチルメラミン、パラ−ホルムアルデヒドのポリマー、メラミンのＮ−メチロール誘導体等が挙げられる。
ジエン系ゴム１００質量部に対し、ノボラック型フェノール系樹脂は例えば０．１〜２０質量部、硬化剤は例えば０．１〜２０質量部の範囲で使用できる。
Moreover, in this invention, in order to raise the hardness of rubber | gum, a novolak type phenol resin and a hardening | curing agent can also be mix | blended. From the viewpoint of the effects of the present invention and the dispersibility in rubber, the novolak type phenolic resin used in the present invention is any of novolak type phenolic resin, novolac type cresol resin, novolac type resorcin resin. Or a mixture thereof. A cashew-modified phenol resin can also be preferably used as the oil-modified phenol resin. The curing agent is not particularly limited as long as it can cure the novolac type phenolic resin. For example, hexamethylenetetramine, HMMM (partial condensate of hexamethoxymethylolmelamine), PMMM (hexamethylolmelamine pentamethyl ether). A partial condensate), hexaethoxymethylmelamine, a polymer of para-formaldehyde, an N-methylol derivative of melamine, and the like.
The novolak type phenol resin can be used in the range of 0.1 to 20 parts by mass, and the curing agent can be used in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber.
また本発明におけるゴム組成物は、各種充填剤、例えばシリカ、クレー、タルク、炭酸カルシウム等の無機充填剤を配合することができる。また、加硫又は架橋剤、加硫又は架橋促進剤、各種充填剤、各種オイル、老化防止剤、可塑剤等のゴム組成物に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。なお、加硫剤としては硫黄を使用し、その使用量はジエン系ゴム１００質量部に対し、３〜１０質量部が好ましい。 The rubber composition in the present invention may contain various fillers such as silica, clay, talc, calcium carbonate and the like. In addition, various additives generally blended in rubber compositions such as vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various fillers, various oils, anti-aging agents, and plasticizers can be blended. Such an additive can be kneaded by a general method to form a composition, which can be used for vulcanization or crosslinking. The blending amounts of these additives can be set to conventional general blending amounts as long as the object of the present invention is not violated. In addition, sulfur is used as the vulcanizing agent, and the amount used is preferably 3 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
本発明に使用される金属としては、例えば真鍮、亜鉛、銅等が挙げられる。本発明のゴム−金属複合体をタイヤ用途に使用する場合、該金属が真鍮をめっきしたスチールワイヤであるときに、ゴムおよび金属間の強固な接着状態を得ることができ、とくに好ましい。また本発明のゴム−金属複合体をタイヤ用途に使用する場合、本発明のゴム−金属複合体は、例えばアンダートレッドに埋設されるベルト、カーカス、ビード等に有利に使用できる。
本発明のゴム−金属複合体を調製する方法は、例えば前記の各種成分をバンバリーミキサーやロールミキサーなどの汎用の混合機を用いて混合しゴム組成物を調製し、これに金属コードを埋設させ、常法にしたがって加硫すればよい。なお加硫時間の決定方法は下記で説明する。
Examples of the metal used in the present invention include brass, zinc, copper and the like. When the rubber-metal composite of the present invention is used for a tire application, when the metal is a steel wire plated with brass, a strong adhesion state between the rubber and the metal can be obtained, which is particularly preferable. When the rubber-metal composite of the present invention is used for tires, the rubber-metal composite of the present invention can be advantageously used for, for example, a belt, a carcass, a bead or the like embedded in an under tread.
The method for preparing the rubber-metal composite of the present invention includes, for example, mixing the above-mentioned various components using a general-purpose mixer such as a Banbury mixer or a roll mixer to prepare a rubber composition, and embedding a metal cord in the rubber composition. Vulcanization may be performed according to a conventional method. The method for determining the vulcanization time will be described below.
本発明のゴム−金属複合体は、前記ゴム組成物と前記金属との界面における前記金属表面をＸ線光電子分光法により測定したとき、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔと、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａとの関係が、下記式（１）を満たすことを特徴とする。
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．３５ （１）
When the metal surface at the interface between the rubber composition and the metal is measured by X-ray photoelectron spectroscopy, the rubber-metal composite of the present invention has an entire peak area T of S2p having a binding energy of 160 to 166 eV, The relationship with the peak area A of the binding energy 163 to 164 eV which is the central peak of sulfur satisfies the following formula (1).
The area A / the whole peak area T ≧ 0.35 (1)
本発明者は検討を重ねた結果、金属表面に存在する連鎖硫黄が、ある一定値以上となる場合、ゴムおよび金属間の強固な接着状態が得られるという新たな知見を見出した。ここで連鎖硫黄とは、−Ｓｎ−（ｎは２〜８である）で表されるポリスルフィドである。原料硫黄は一般的に８個の硫黄原子が連なって環状構造を形成している。ゴム組成物の加硫により原料硫黄のＳ−Ｓ結合が切断され、前記のような金属表面に存在する連鎖硫黄が出現する。この連鎖硫黄が金属表面にどの程度存在するのか、をＸ線光電子分光法（ＸＰＳ）により測定する。
本発明において、Ｘ線光電子分光法（ＸＰＳ）は、周知のＸ線光電子分光装置を用い、例えば励起Ｘ線１６５〜１５００ｅＶ、好ましくは２００〜１２５０ｅＶとし、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔと、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａを求める。ピーク面積全体Ｔとピーク面積Ａとの関係が上記式（１）を満たす場合、ゴムおよび金属間の強固な接着状態が得られる。なお、ピーク面積全体Ｔおよびピーク面積Ａは、公知の演算装置により容易に算出可能である。
As a result of repeated studies, the present inventor has found a new finding that when the chain sulfur existing on the metal surface exceeds a certain value, a strong adhesion state between the rubber and the metal can be obtained. Here, the chain sulfur is a polysulfide represented by -Sn- (n is 2 to 8). The raw material sulfur generally forms a cyclic structure in which eight sulfur atoms are linked. By vulcanization of the rubber composition, the S—S bond of the raw material sulfur is cut, and chain sulfur existing on the metal surface as described above appears. The extent to which this chain sulfur is present on the metal surface is measured by X-ray photoelectron spectroscopy (XPS).
In the present invention, X-ray photoelectron spectroscopy (XPS) is performed using a well-known X-ray photoelectron spectrometer, for example, excitation X-rays of 165 to 1500 eV, preferably 200 to 1250 eV, and the entire peak area of S2p having a binding energy of 160 to 166 eV. T and the peak area A of the binding energy 163 to 164 eV, which is the central peak of chain sulfur, are determined. When the relationship between the entire peak area T and the peak area A satisfies the above formula (1), a strong adhesion state between the rubber and the metal is obtained. The total peak area T and the peak area A can be easily calculated by a known arithmetic device.
次に、図１を参照しながら、ゴム組成物と金属との界面における金属表面をＸ線光電子分光法（ＸＰＳ）により測定する具体的な方法について説明する。
図１に示すように、まず、ゴム組成物から調製した試験シート１２、１４、金属板２２を用意する。試験シート１２、１４の金属板２２側にろ紙３２、３４を設置し、金属板２２を、ろ紙３２、３４介して試験シート１２、１４でサンドイッチする。得られた積層体を所定の加硫温度で加硫し、Ｘ線光電子分光分析の直前に、金属板２２から試験シート１２、１４とろ紙３２、３４とを分離する。ろ紙３２、３４の存在により、金属板２２から試験シート１２、１４は容易に分離可能となる。
続いて、金属板２２の表面に対し、上記のような条件でＸ線光電子分光分析を行い、上記のピーク面積全体Ｔとピーク面積Ａとの関係を求める。
また、加硫時間を種々変更すること以外は、同一条件でＸ線光電子分光分析を行い、上記のピーク面積全体Ｔとピーク面積Ａとの関係を求める。
このような方法により得られるＸ線光電子分光法（ＸＰＳ）では、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのＸ線光電子分光スペクトルを明確に得ることができ、加硫時間の変化により、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピークの増減が把握できる。
続いて、ピーク面積全体Ｔとピーク面積Ａとの関係が上記式（１）を満たす加硫時間を、ゴムおよび金属間の強固な接着状態が得られる最適加硫時間と判断する。面積Ａ／前記ピーク面積全体Ｔが０．４２以上である場合、とくに強固な接着状態を得ることができる。
Next, a specific method for measuring the metal surface at the interface between the rubber composition and the metal by X-ray photoelectron spectroscopy (XPS) will be described with reference to FIG.
As shown in FIG. 1, first,
Subsequently, the surface of the
Further, except that various vulcanization times are changed, X-ray photoelectron spectroscopic analysis is performed under the same conditions, and the relationship between the entire peak area T and the peak area A is obtained.
In the X-ray photoelectron spectroscopy (XPS) obtained by such a method, an X-ray photoelectron spectrum of S2p having a binding energy of 160 to 166 eV can be clearly obtained. The increase or decrease of the peak of the binding energy 163 to 164 eV can be grasped.
Subsequently, the vulcanization time in which the relationship between the entire peak area T and the peak area A satisfies the above formula (1) is determined as the optimum vulcanization time for obtaining a strong adhesion state between the rubber and the metal. When the area A / the whole peak area T is 0.42 or more, a particularly strong adhesion state can be obtained.
上記で得られた最適加硫時間は、次のように適用する。
上記のＸ線光電子分光分析に用いたものと同じゴム組成物を、ゴム−金属複合体におけるゴム組成物として用いる。逆に言えば、ゴム−金属複合体に使用すべきゴム組成物を、上記のＸ線光電子分光分析に使用する。
上記のＸ線光電子分光分析により得られた最適加硫時間を、ゴム−金属複合体の調製時の加硫時間として採用する。
これにより、金属表面に連鎖硫黄が多く存在することになり、ゴムおよび金属間の強固な接着状態を得ることができる。
なお上記ではゴム組成物から調製した試験シート、金属板およびろ紙を用いた試験方法を例示したが、これとは別に、加硫時間を種々変更して実際のゴム−金属複合体を調製し、そこから金属のみを分離して、その表面をＸ線光電子分光分析し、上記のピーク面積全体Ｔとピーク面積Ａとの関係を求め、最適加硫時間を決定してもよい。
The optimum vulcanization time obtained above is applied as follows.
The same rubber composition as that used for the X-ray photoelectron spectroscopy is used as the rubber composition in the rubber-metal composite. In other words, the rubber composition to be used for the rubber-metal composite is used for the X-ray photoelectron spectroscopic analysis.
The optimum vulcanization time obtained by the above X-ray photoelectron spectroscopic analysis is adopted as the vulcanization time when preparing the rubber-metal composite.
Thereby, a lot of chain sulfur exists on the metal surface, and a strong adhesion state between the rubber and the metal can be obtained.
In addition, although the test method using the test sheet, the metal plate, and the filter paper prepared from the rubber composition was exemplified above, separately, an actual rubber-metal composite was prepared by variously changing the vulcanization time, Only the metal may be separated therefrom, the surface thereof may be subjected to X-ray photoelectron spectroscopy analysis, the relationship between the above peak area T and the peak area A may be obtained, and the optimum vulcanization time may be determined.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.
実施例１〜５および比較例１〜７
（ゴム組成物の調製）
表１に示す配合（質量部）において、加硫系（加硫促進剤、硫黄）を除く成分を１．７リットルの密閉式バンバリーミキサーで５分間混練した後、ミキサー外に放出させて室温冷却した。続いて、該組成物を同バンバリーミキサーに再度入れ、加硫系を加えて混練し、ゴム組成物を得た。
Examples 1-5 and Comparative Examples 1-7
(Preparation of rubber composition)
In the composition (parts by mass) shown in Table 1, the components excluding the vulcanization system (vulcanization accelerator, sulfur) were kneaded for 5 minutes with a 1.7 liter closed Banbury mixer, then discharged outside the mixer and cooled to room temperature. did. Subsequently, the composition was put into the Banbury mixer again, and a vulcanization system was added and kneaded to obtain a rubber composition.
（Ｘ線光電子分光分析）
図１に示すように、まず、ゴム組成物を用いて厚さ２ｍｍのシートを調製し、試験シート１２、１４とした。これとは別に金属板２２を用意した。金属板２２は、厚さ１．５ｍｍのＣｕ／Ｚｎ比＝６５／３５の真鍮板（（株）ニラコ製）である。試験シート１２、１４の金属板２２側にろ紙（Ｎｏ．１）３２、３４を設置し、金属板２２を、ろ紙３２、３４介して試験シート１２、１４でサンドイッチした。得られた積層体を１７０℃で種々の加硫時間で加硫し、Ｘ線光電子分光分析の直前に、金属板２２から試験シート１２、１４とろ紙３２、３４とを分離した。続いて、金属板２２の表面に対し、１０６０ｅＶの励起Ｘ線を照射し、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔと、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａを求め、両者の比を算出した。なお、Ｘ線光電子分光分析装置は、高エネルギー加速器研究機構のＢＬ−１３を使用し、積層体の作成方法は穂高武，石川泰弘，森邦夫：日本ゴム協会誌，77，79（2004）を参考にした。
(X-ray photoelectron spectroscopy)
As shown in FIG. 1, first, a sheet having a thickness of 2 mm was prepared using the rubber composition, and used as
（ゴム−金属複合体におけるゴムおよび金属間の接着状態の評価）
ＡＳＴＭ Ｄ１８７１に準拠し、上記のゴム組成物およびブラスメッキワイヤーを用いて接着引抜力を測定した。加硫時間は、上記のＸ線光電子分光分析で採用した種々の加硫時間と同じにした。
結果を表１に併せて示す。
(Evaluation of adhesion between rubber and metal in rubber-metal composite)
In accordance with ASTM D1871, the adhesion pulling force was measured using the above rubber composition and brass plating wire. The vulcanization time was the same as the various vulcanization times employed in the above X-ray photoelectron spectroscopy analysis.
The results are also shown in Table 1.
＊１：ＮＲ（ＲＳＳ＃３）
＊２：カーボンブラック（東海カーボン（株）製シーストＫＨ、Ｎ２ＳＡ＝９３ｍ２／ｇ）
＊３：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊４：老化防止剤（フレキシス社製サントフレックス６ＰＰＤ）
＊５：ステアリン酸コバルト（ＤＩＣ社製）
＊６：硫黄（アクゾノーベル（株）製クリステックスＨＳ ＯＴ ２０）
＊７：加硫促進剤（大内新興化学工業（株）製ノクセラーＤＺ）
* 1: NR (RSS # 3)
* 2: Carbon black (Toast Carbon Co., Ltd. Seast KH, N 2 SA = 93 m 2 / g)
* 3: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 4: Anti-aging agent (Santflex 6PPD manufactured by Flexis)
* 5: Cobalt stearate (manufactured by DIC)
* 6: Sulfur (Akzo Nobel Kristex HS OT 20)
* 7: Vulcanizing accelerator (Ouchi Shinsei Chemical Co., Ltd. Noxeller DZ)
上記の表１から明らかなように、実施例１〜５で調製されたゴム−金属複合体は、ゴム−金属界面における金属表面をＸ線光電子分光法（ＸＰＳ）により測定したとき、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔに対して、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａが特定の比率を満たす最適加硫時間を採用しているので、これを満たさない各比較例に対し、接着引抜力が高く、ゴムおよび金属間の強固な接着状態が得られていることが分かる。 As is clear from Table 1 above, the rubber-metal composites prepared in Examples 1 to 5 have a binding energy of 160 when the metal surface at the rubber-metal interface was measured by X-ray photoelectron spectroscopy (XPS). Since the peak area A of the binding energy 163 to 164 eV, which is the central peak of the chain sulfur, is employed for the entire peak area T of S2p of ˜166 eV, the optimum vulcanization time satisfying a specific ratio is adopted, so this is not satisfied It can be seen that, for each comparative example, the adhesion pulling force is high, and a strong adhesion state between the rubber and the metal is obtained.
Claims (8)
前記ゴム組成物と前記金属との界面における前記金属表面をＸ線光電子分光法により測定したとき、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体Ｔと、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａとの関係が、下記式（１）を満たすことを特徴とするゴム−金属複合体。
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．３５ （１） A rubber-metal composite comprising a rubber composition containing a diene rubber and a metal, wherein the rubber composition and the metal are bonded by vulcanization of the rubber composition,
When the metal surface at the interface between the rubber composition and the metal is measured by X-ray photoelectron spectroscopy, the entire peak area T of S2p having a binding energy of 160 to 166 eV and a binding energy of 163 to 163 are the central peak of chain sulfur. A rubber-metal composite, wherein the relationship with the peak area A of 164 eV satisfies the following formula (1).
The area A / the whole peak area T ≧ 0.35 (1)
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．４２ （２） The relationship between the entire peak area T of S2p having the binding energy of 160 to 166 eV and the peak area A of the binding energy of 163 to 164 eV, which is the central peak of the chain sulfur, satisfies the following formula (2): Item 2. A rubber-metal composite according to Item 1.
The area A / the entire peak area T ≧ 0.42 (2)
前記ゴム組成物と前記金属との界面における前記金属表面をＸ線光電子分光法により測定したとき、結合エネルギー１６０〜１６６ｅＶのＳ２ｐのピーク面積全体と、連鎖硫黄の中心ピークである結合エネルギー１６３〜１６４ｅＶのピーク面積Ａとの関係が、下記式（１）を満たす加硫時間を、前記ゴム組成物の加硫時間と定めることを特徴とする加硫時間決定方法。
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．３５ （１） Vulcanization time of the rubber composition in a rubber-metal composite comprising a rubber composition containing a diene rubber and a metal, and the rubber composition and the metal bonded together by vulcanization of the rubber composition A method of determining
When the metal surface at the interface between the rubber composition and the metal is measured by X-ray photoelectron spectroscopy, the entire peak area of S2p with a binding energy of 160 to 166 eV and a binding energy of 163 to 164 eV, which is the central peak of chain sulfur. A vulcanization time determination method characterized in that a vulcanization time satisfying the following formula (1) with respect to the peak area A of the rubber composition is determined as a vulcanization time of the rubber composition.
The area A / the whole peak area T ≧ 0.35 (1)
前記面積Ａ／前記ピーク面積全体Ｔ ≧ ０．４２ （２） The relationship between the entire peak area T of S2p having the binding energy of 160 to 166 eV and the peak area A of the binding energy of 163 to 164 eV, which is the central peak of the chain sulfur, satisfies the following formula (2): Item 8. The vulcanization time determination method according to Item 7.
The area A / the entire peak area T ≧ 0.42 (2)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04293940A (en) * | 1991-03-25 | 1992-10-19 | Yokohama Rubber Co Ltd:The | Rubber composition for covering steel cord and rubber article prepared by using the same |
| JPH0565370A (en) * | 1991-09-10 | 1993-03-19 | Bridgestone Corp | Tire |
| JPH05185136A (en) * | 1990-12-27 | 1993-07-27 | Kunio Mori | Surface treatment of steel wire |
| JP2011241391A (en) * | 2010-04-23 | 2011-12-01 | Yokohama Rubber Co Ltd:The | Rubber-metal composite and pneumatic tire using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05185136A (en) * | 1990-12-27 | 1993-07-27 | Kunio Mori | Surface treatment of steel wire |
| JPH04293940A (en) * | 1991-03-25 | 1992-10-19 | Yokohama Rubber Co Ltd:The | Rubber composition for covering steel cord and rubber article prepared by using the same |
| JPH0565370A (en) * | 1991-09-10 | 1993-03-19 | Bridgestone Corp | Tire |
| JP2011241391A (en) * | 2010-04-23 | 2011-12-01 | Yokohama Rubber Co Ltd:The | Rubber-metal composite and pneumatic tire using the same |
Non-Patent Citations (1)
| Title |
|---|
| 清水 克典, 鹿久保 隆志, 網野 直也, 小澤 健一: "X線高分解能光電子分光を用いた黄銅/ゴム接着界面観察", 日本ゴム協会誌, vol. 第８８巻第８号, JPN6016033835, August 2015 (2015-08-01), JP, pages 291 - 296, ISSN: 0003533379 * |
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