JPH0859896A - Adhesive rubber composition and composite material - Google Patents
Adhesive rubber composition and composite materialInfo
- Publication number
- JPH0859896A JPH0859896A JP6198186A JP19818694A JPH0859896A JP H0859896 A JPH0859896 A JP H0859896A JP 6198186 A JP6198186 A JP 6198186A JP 19818694 A JP19818694 A JP 19818694A JP H0859896 A JPH0859896 A JP H0859896A
- Authority
- JP
- Japan
- Prior art keywords
- rubber composition
- weight
- zinc
- parts
- adhesive rubber
- 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.)
- Withdrawn
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 61
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 33
- 239000000853 adhesive Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 organic acid cobalt salt Chemical class 0.000 claims description 12
- 239000000463 material Substances 0.000 abstract description 32
- 150000001868 cobalt Chemical class 0.000 abstract description 4
- 150000007524 organic acids Chemical class 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 10
- 229910001335 Galvanized steel Inorganic materials 0.000 description 9
- 239000008397 galvanized steel Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000002905 metal composite material Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920004413 Skyprene® B-10 Polymers 0.000 description 2
- 238000007586 pull-out test Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- 229920004395 Baypren® 110 Polymers 0.000 description 1
- 229920004410 Butaclor® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- HKPHPIREJKHECO-UHFFFAOYSA-N butachlor Chemical compound CCCCOCN(C(=O)CCl)C1=C(CC)C=CC=C1CC HKPHPIREJKHECO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、難燃性や耐熱性に優れ
たポリクロロプレン系のゴム組成物であって、亜鉛との
接着性に優れ、コンベヤベルト等の複合材に好適に利用
可能な接着性ゴム組成物、およびこの接着性ゴム組成物
を用いた複合材に関する。TECHNICAL FIELD The present invention is a polychloroprene-based rubber composition having excellent flame retardancy and heat resistance, which has excellent adhesiveness to zinc and can be suitably used for composite materials such as conveyor belts. Adhesive rubber composition and composite material using this adhesive rubber composition.
【０００２】[0002]
【従来の技術】各種のコンベヤベルトやホース、タイヤ
等は、基本的にゴムあるいは樹脂材料で形成されるが、
高い機械的強度が要求される用途では、スチールコード
やスチールベルト、あるいは金属補強板等の金属補強材
で補強されたゴム／金属複合材とされている。このよう
な複合材に利用される金属材料としては、安価でかつ耐
食性に優れているという理由で、スチールコード等に亜
鉛メッキや真鍮メッキを施した、亜鉛メッキ材や真鍮メ
ッキ材が使用されている。2. Description of the Related Art Various conveyor belts, hoses, tires, etc. are basically made of rubber or resin material.
For applications requiring high mechanical strength, it is a rubber / metal composite material reinforced with a metal reinforcing material such as a steel cord, a steel belt, or a metal reinforcing plate. As a metal material used for such a composite material, a zinc-plated material or a brass-plated material obtained by galvanizing or brass-plating a steel cord or the like is used because it is inexpensive and has excellent corrosion resistance. There is.
【０００３】ところで、難燃性や耐熱性に優れた材料と
して、ポリクロロプレン（クロロプレンゴム＝ＣＲ）が
知られており、これらの特性が要求される各種の用途に
利用されている。前述のゴム／金属複合材においても、
難燃性等を要求される用途にはポリクロロプレンを使用
することが望まれる。ところが、ポリクロロプレンは金
属との接着性、特に亜鉛との接着性が低く、ポリクロロ
プレンと亜鉛メッキ材とを組み合わせた複合材は実現さ
れていない。By the way, polychloroprene (chloroprene rubber = CR) is known as a material having excellent flame retardancy and heat resistance, and is used in various applications where these characteristics are required. Even in the above-mentioned rubber / metal composite material,
It is desirable to use polychloroprene for applications requiring flame retardancy and the like. However, polychloroprene has low adhesiveness to metals, particularly to zinc, and a composite material in which polychloroprene and a galvanized material are combined has not been realized.
【０００４】そのため、亜鉛メッキ材が用いられる複合
材において、特に難燃性が要求される用途に使用される
ものは、天然ゴム等のゴム（樹脂）材料に難燃剤を配合
することによって、難燃性が付与されている。しかしな
がら、このような複合材の難燃性は十分ということはで
きず、ポリクロロプレンと亜鉛メッキ材とを組み合わせ
た複合材、すなわち亜鉛との接着性に優れたポリクロロ
プレン系ゴム材料の出現が望まれている。[0004] Therefore, among the composite materials using galvanized materials, those used particularly for applications requiring flame retardancy are difficult to mix by adding a flame retardant to a rubber (resin) material such as natural rubber. Flammability is imparted. However, the flame retardancy of such a composite material cannot be said to be sufficient, and a composite material in which a polychloroprene and a galvanized material are combined, that is, a polychloroprene rubber material excellent in adhesiveness with zinc is desired to appear. It is rare.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、前記
従来技術の問題点を解決することにあり、亜鉛メッキ材
や金属亜鉛等の表面が亜鉛の材料との接着性に優れたポ
リクロロプレン系の接着性ゴム組成物、および、この接
着性ゴム組成物と亜鉛メッキ材等とを組み合わせた、ゴ
ムと表面が亜鉛の材料との接着性が高く、機械的強度や
耐熱性・難燃性に優れた複合材を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and polychloroprene excellent in adhesiveness to a zinc-plated material, metallic zinc or the like whose surface is zinc. -Based adhesive rubber composition, and a combination of this adhesive rubber composition and a galvanized material, which has high adhesiveness between rubber and a material with a zinc surface, and has high mechanical strength, heat resistance, and flame retardancy. To provide an excellent composite material.
【０００６】[0006]
【課題を解決するための手段】前記目的を達成するため
に、本発明の接着性ゴム組成物は、非硫黄変性ポリクロ
ロプレン１００重量部に対し、有機酸コバルト塩をコバ
ルト量に換算して０．２〜０．７重量部、酸化亜鉛を３
〜８重量部、硫黄を１〜５重量部、２−メルカプトイミ
ダゾリンを０．５〜１重量部、それぞれ配合したことを
特徴とする接着性ゴム組成物を提供する。In order to achieve the above object, the adhesive rubber composition of the present invention has an organic acid cobalt salt of 0 parts in terms of cobalt content based on 100 parts by weight of non-sulfur modified polychloroprene. 2 to 0.7 parts by weight, zinc oxide 3
-8 parts by weight, 1-5 parts by weight of sulfur, and 0.5-1 part by weight of 2-mercaptoimidazoline, respectively, are provided to provide an adhesive rubber composition.
【０００７】また、本発明の複合材は、前記接着性ゴム
組成物と、表面が亜鉛である部材とを接触し、前記接着
性ゴム組成物を加硫してなることを特徴とする複合材を
提供する。The composite material of the present invention is characterized in that the adhesive rubber composition is brought into contact with a member having a surface of zinc, and the adhesive rubber composition is vulcanized. I will provide a.
【０００８】以下、本発明の接着性ゴム組成物、およ
び、これを用いた複合材について詳細に説明する。The adhesive rubber composition of the present invention and the composite material using the same will be described below in detail.
【０００９】本発明の接着性ゴム組成物は、難燃性や耐
熱性に優れたクロロプレン系のゴム組成物であり、主鎖
に硫黄を有さない非硫黄変性ポリクロロプレン、いわゆ
るＷタイプのポリクロロプレンを基材として用いる。The adhesive rubber composition of the present invention is a chloroprene type rubber composition excellent in flame retardancy and heat resistance, and is a non-sulfur modified polychloroprene having no sulfur in the main chain, so-called W type poly Chloroprene is used as the substrate.
【００１０】本発明に利用可能な非硫黄変性ポリクロロ
プレンには特に限定はなく、公知の各種の非硫黄変性ポ
リクロロプレンや、市販品の非硫黄変性ポリクロロプレ
ンが好適に利用される。具体的には、ネオプレンＷ、同
ＷＭ−１、同ＷＨＶ、同ＷＨＶ−１４０、同ＷＨＶ−２
００、同ＷＢ、同ＷＸ−Ｊ、同ＷＲＴ、同ＷＸ−Ｋ（以
上、昭和電工・デュポン社製）、デンカクロロプレンＭ
−３０、同Ｍ−４０、同Ｍ−１００、同Ｍ−１２０、同
Ｍ−１３０Ｌ、同Ｍ−１３０Ｈ、同Ｓ−４０Ｖ、同ＤＣ
Ｒ−３９、同ＤＣＲ−３６、同ＤＣＲ−３０、同ＤＣＲ
−３１、同ＤＣＲ−３５、同ＤＣＲ−５０（以上、電気
化学工業社製）、ＢＡＹＰＲＥＮ１１０、同１１０ＶＳ
Ｃ、同１１２、同１１５、同１１６、同１２４、同１２
６、同１３０、同２１０、同２１１、同２１４、同２１
５、同２１６、同２２６、同２３０、同２３５（以上、
Ｂａｙｅｒ社製）、ＢｕｔａｃｌｏｒＭＣ−１０、同Ｍ
Ｃ−２０、同ＭＣ−３０、同ＭＣ−３１、同ＭＥ−２
０、同ＭＨ−３０、同ＭＨ−３１、ＭＣ−１２２、同Ｍ
Ｃ−３２２、同ＭＣ−３２３（以上、Ｄｉｓｔｕｇｉｌ
社製）、ＳｋｙｐｒｅｎｅＢ−１０、同Ｂ−３０、同Ｂ
−３１、同Ｂ−５、同Ｙ−３０、同Ｙ−３０Ｈ、同Ｙ−
３１、同Ｙ−２０Ｅ（以上、東ソー社製）等が好適に例
示される。中でも特に、ネオプレンＷＲＴ、デンカクロ
ロプレンＳ−４０Ｖ、ＢＡＹＰＲＥＮＥ１１０、Ｂｕｔ
ａｃｌｏｒＭＣ−１０、ＳｋｙｐｒｅｎｅＢ−１０等は
好適に使用される。The non-sulfur-modified polychloroprene usable in the present invention is not particularly limited, and various known non-sulfur-modified polychloroprenes and commercially available non-sulfur-modified polychloroprenes are preferably used. Specifically, neoprene W, same WM-1, same WHV, same WHV-140, same WHV-2.
00, the same WB, the same WX-J, the same WRT, the same WX-K (above, Showa Denko / Dupont), Denka Chloroprene M
-30, same M-40, same M-100, same M-120, same M-130L, same M-130H, same S-40V, same DC
R-39, DCR-36, DCR-30, DCR
-31, DCR-35, DCR-50 (above, manufactured by Denki Kagaku Kogyo KK), BAYPREN110, 110VS
C, 112, 115, 116, 124, 12
6, the same 130, the same 210, the same 211, the same 214, the same 21
5, 216, 226, 230, 235 (above,
(Manufactured by Bayer), Butaclor MC-10, and M
C-20, MC-30, MC-31, ME-2
0, MH-30, MH-31, MC-122, M
C-322, MC-323 (above, Distigil
Company), Skyprene B-10, Same B-30, Same B
-31, B-5, Y-30, Y-30H, Y-
31 and Y-20E (above, manufactured by Tosoh Corporation) are preferably exemplified. Among them, Neoprene WRT, Denkachloroprene S-40V, BAYPRENE110, But
Acolor MC-10, Skyprene B-10 and the like are preferably used.
【００１１】本発明の接着性ゴム組成物は、このような
非硫黄変性ポリクロロプレン１００重量部に、有機酸コ
バルト塩をコバルト量に換算して０．２〜０．７重量
部、酸化亜鉛を３〜８重量部、硫黄を１〜５重量部、２
−メルカプトイミダゾリンを０．５〜１重量部を配合し
てなるものである。本発明においては、これらの各成分
を所定量配合することにより、亜鉛メッキスチールコー
ドや亜鉛メッキ鋼板等の亜鉛メッキ材や金属亜鉛材料等
の表面が亜鉛の材料（以下、便宜的に表面亜鉛材とす
る）との良好な接着性を得ることができ、従来のポリク
ロロプレン配合では不可能であった、ポリクロロプレン
と表面亜鉛材とによるゴム／金属複合材を可能としたも
のである。The adhesive rubber composition of the present invention comprises, in 100 parts by weight of such a non-sulfur-modified polychloroprene, 0.2 to 0.7 parts by weight of a cobalt salt of an organic acid, and zinc oxide. 3 to 8 parts by weight, 1 to 5 parts by weight of sulfur, 2
-Mercaptoimidazoline is added in an amount of 0.5 to 1 part by weight. In the present invention, by mixing these components in predetermined amounts, a zinc-plated material such as a galvanized steel cord or a galvanized steel sheet, or a material having a zinc surface such as a metallic zinc material (hereinafter, a surface zinc material for convenience sake). It is possible to obtain a rubber / metal composite material of polychloroprene and a surface zinc material, which was not possible with the conventional compounding of polychloroprene.
【００１２】有機酸コバルト塩の配合量は、非硫黄変性
ポリクロロプレン１００重量部に対して、コバルト量換
算で０．２〜０．７重量部である。有機酸コバルト塩の
配合量が０．２重量部未満では、表面亜鉛材との良好な
接着性を得ることができない。また、有機酸コバルト塩
の配合量が多すぎると、加硫物の引っ張り強度や伸び等
の物性が悪くなってしまうが、０．７重量部以下であれ
ば、高い物性を要求される用途以外であれば、実用上問
題はない。例えば、本発明の接着性ゴム組成物をコンベ
アベルト等の機械的強度を要求される用途に利用するた
めには、良好な物性を得るために、有機酸コバルト塩の
配合量をコバルト量換算で０．２〜０．５重量部とする
のが好ましい。The compounding amount of the organic acid cobalt salt is 0.2 to 0.7 parts by weight in terms of cobalt amount based on 100 parts by weight of the non-sulfur modified polychloroprene. If the amount of the organic acid cobalt salt is less than 0.2 parts by weight, good adhesion with the surface zinc material cannot be obtained. Further, if the amount of the organic acid cobalt salt is too large, physical properties such as tensile strength and elongation of the vulcanized product will be deteriorated, but if it is 0.7 parts by weight or less, it is not used for applications requiring high physical properties. If so, there is no problem in practical use. For example, in order to use the adhesive rubber composition of the present invention in applications where mechanical strength such as a conveyor belt is required, in order to obtain good physical properties, the compounding amount of the organic acid cobalt salt is calculated in terms of cobalt amount. It is preferably 0.2 to 0.5 parts by weight.
【００１３】本発明に配合される有機酸コバルト塩とし
ては、特に限定はなく、公知の各種のものが利用可能で
あるが、具体的には、ナフテン酸コバルト、ステアリン
酸コバルト、オクチル酸コバルト、オレイン酸コバルト
等が好適に例示される。また、ＧＭＡ−Ｌ１０（大崎工
業社製）、マノボンドＣ−１６、同Ｃ−２２．５（以
上、ＭＡＮＣＨＥＭ ＬＩＭＩＴＥＤ社製）等の市販品
も好適に利用可能である。The organic acid cobalt salt to be blended in the present invention is not particularly limited and various known ones can be used. Specifically, cobalt naphthenate, cobalt stearate, cobalt octylate, Preferable examples include cobalt oleate. Further, commercially available products such as GMA-L10 (manufactured by Osaki Industry Co., Ltd.), Manobond C-16, and C-22.5 (manufactured by MANCHEM LIMITED) are also suitably usable.
【００１４】本発明の接着性ゴム組成物は、主たる加硫
剤として酸化亜鉛を配合する。酸化亜鉛の配合量は、非
硫黄変性ポリクロロプレン１００重量部に対して３〜８
重量部である。酸化亜鉛の配合量をこの範囲とすること
により、スコーチタイム等の未加硫物性と接着性とを良
好なものとすることができる。好ましくは、酸化亜鉛の
配合量を４〜６重量部とすることにより、スコーチタイ
ムはもちろん、温水下や湿熱下等で劣化させた際の耐水
接着性（耐熱性、耐老化性）等の点でより好適な結果を
得ることができる。The adhesive rubber composition of the present invention contains zinc oxide as a main vulcanizing agent. The compounding amount of zinc oxide is 3 to 8 with respect to 100 parts by weight of non-sulfur modified polychloroprene.
Parts by weight. By setting the compounding amount of zinc oxide within this range, it is possible to improve the unvulcanized physical properties such as scorch time and the adhesiveness. Preferably, the amount of zinc oxide is set to 4 to 6 parts by weight so that not only the scorch time but also the water-resistant adhesion (heat resistance, aging resistance) when deteriorated under hot water or moist heat, etc. Can obtain more suitable results.
【００１５】通常の非硫黄変性ポリクロロプレンは、加
硫剤としては酸化亜鉛が主に利用されている。また、非
硫黄変性ポリクロロプレンの加硫促進剤としては、２−
メルカプトイミダゾリン、ジオルソトリルグアジン・ジ
カテコールボレート等の各種の物が知られている。本発
明の接着性ゴム組成物においては、前述のように、加硫
剤として酸化亜鉛を使用し、加硫促進剤として２−メル
カプトイミダゾリンを選択して通常は添加しない硫黄と
組み合わせて配合し、さらに前述の有機酸コバルト塩を
含有することによって、表面亜鉛材との良好な接着性を
有する非硫黄変性クロロプレン系のゴム組成物を実現し
たものである。In the usual non-sulfur modified polychloroprene, zinc oxide is mainly used as a vulcanizing agent. Further, as a vulcanization accelerator for non-sulfur-modified polychloroprene, 2-
Various substances such as mercaptoimidazoline and diorsotolyl guadin dicatecholborate are known. In the adhesive rubber composition of the present invention, as described above, zinc oxide is used as a vulcanizing agent, 2-mercaptoimidazoline is selected as a vulcanization accelerator, and is blended in combination with sulfur which is not usually added, Further, by containing the above-mentioned cobalt salt of an organic acid, a non-sulfur-modified chloroprene rubber composition having good adhesion to a surface zinc material is realized.
【００１６】硫黄の配合量は、非硫黄変性ポリクロロプ
レン１００重量部に対して１〜５重量部である。硫黄の
配合量が１重量部未満では、表面亜鉛材との十分な接着
性を得ることができず、逆に、５重量部を超えて配合さ
れると、スコーチタイムが短く、実用上好ましくない。
好ましくは、硫黄の配合量を１〜３重量部とすることに
より、スコーチタイム、ブルーム、過加硫時の平坦加硫
性等の点でより好適な結果を得る。The content of sulfur is 1 to 5 parts by weight based on 100 parts by weight of non-sulfur modified polychloroprene. If the content of sulfur is less than 1 part by weight, sufficient adhesion with the surface zinc material cannot be obtained, and if it exceeds 5 parts by weight, the scorch time is short and it is not preferable in practice. .
Preferably, by setting the amount of sulfur to be 1 to 3 parts by weight, more preferable results are obtained in terms of scorch time, bloom, flat vulcanizability during overvulcanization, and the like.
【００１７】一方、２−メルカプトイミダゾリンの配合
量は、非硫黄変性ポリクロロプレン１００重量部に対し
て０．５〜１重量部である。２−メルカプトイミダゾリ
ンの配合量が０．５重量部未満では、引っ張り強度や破
断伸び等の加硫物性が実用上十分ではなく、逆に１重量
部を超えて配合されると、表面亜鉛材との接着性を十分
に得ることができない。好ましくは、２−メルカプトイ
ミダゾリンの配合量を０．５〜０．８重量部とすること
により、温水下や湿熱下等で劣化させた際の耐水接着性
がより向上する等の点でより好適な結果を得る。On the other hand, the compounding amount of 2-mercaptoimidazoline is 0.5 to 1 part by weight with respect to 100 parts by weight of non-sulfur-modified polychloroprene. If the blending amount of 2-mercaptoimidazoline is less than 0.5 part by weight, the vulcanized physical properties such as tensile strength and elongation at break are not practically sufficient, and conversely if it is blended in excess of 1 part by weight, it becomes a surface zinc material. It is not possible to obtain sufficient adhesiveness. Preferably, the blending amount of 2-mercaptoimidazoline is set to 0.5 to 0.8 parts by weight, which is more preferable in that the water-resistant adhesive property when deteriorated under hot water or wet heat is further improved. Get good results.
【００１８】本発明の接着性ゴム組成物の調製方法には
特に限定はなく、通常のゴム組成物と同様でよいが、例
えば、バンバリミキサー等の混練機に、非硫黄変性ポリ
クロロプレンおよび有機酸コバルト塩を投入して十分に
混練し、次いで、残りの各種の配合剤を投入する方法が
好適に例示される。なお、本発明の接着性ゴム組成物に
おいては、上記必須成分以外にも、必要に応じて、カー
ボンブラック、可塑材、充填剤、滑剤等、通常のゴム
（樹脂）組成物に添加される各種の添加剤を加えてもよ
いのはもちろんである。The method for preparing the adhesive rubber composition of the present invention is not particularly limited and may be the same as a usual rubber composition. For example, a non-sulfur-modified polychloroprene and an organic acid may be added to a kneading machine such as a Banbury mixer. A preferable example is a method of adding a cobalt salt, sufficiently kneading, and then adding the remaining various compounding agents. In the adhesive rubber composition of the present invention, in addition to the above essential components, various kinds of carbon black, plasticizers, fillers, lubricants, and the like, which are added to ordinary rubber (resin) compositions, are added as necessary. Needless to say, the additive may be added.
【００１９】前述のように、本発明の接着性ゴム組成物
は、従来のクロロプレン系ゴム組成物では不可能であっ
た、亜鉛との良好な接着性を有する。本発明の複合材
は、この本発明の接着性ゴム組成物と、表面亜鉛材とを
接触し、この状態で接着性ゴム組成物を加硫してなる複
合材である。As described above, the adhesive rubber composition of the present invention has good adhesiveness to zinc, which is impossible with the conventional chloroprene rubber composition. The composite material of the present invention is a composite material obtained by contacting the adhesive rubber composition of the present invention with a surface zinc material and vulcanizing the adhesive rubber composition in this state.
【００２０】利用可能な表面亜鉛材には特に限定はな
く、亜鉛メッキスチールコード、亜鉛メッキスチールベ
ルト、亜鉛メッキ鋼板等の亜鉛メッキ材や、金属亜鉛製
の部材等、表面が亜鉛である各種の部材、より正確に
は、本発明の接着性ゴム組成物との接触面（その少なく
とも一部）が亜鉛である物であれば、すべての物が利用
可能である。There are no particular restrictions on the surface zinc material that can be used, and various types of zinc surfaces such as galvanized steel cords, galvanized steel belts, galvanized steel sheets and other galvanized materials, and members made of metallic zinc can be used. Any member can be used, more precisely, as long as the contact surface (at least a part of it) with the adhesive rubber composition of the present invention is zinc.
【００２１】本発明の複合材の製造方法は、公知の各種
のゴム／金属複合材と同様でよく、前述の本発明の接着
性ゴム組成物を所定形状に成形し、補強材等の表面亜鉛
材と組合わせ、必要に応じて両者を加圧密着しながら、
加熱・加硫すればよい。例えば、コンベアベルトであれ
ば、本発明の接着性ゴム組成物を板状に成形し、成形し
た２枚の板状ゴム組成物で亜鉛メッキスチールコードを
挟持し、プレスしつつ加熱・加硫して製造することがで
きる。なお、接着性ゴム組成物の成形方法には特に限定
はなく、射出成形、モールド成形等、公知のゴム組成物
の成形方法がすべて利用可能である。The method for producing the composite material of the present invention may be the same as various known rubber / metal composite materials, and the above-mentioned adhesive rubber composition of the present invention is molded into a predetermined shape and surface zinc such as a reinforcing material is formed. Combining with materials, pressurizing and adhering both as necessary,
It may be heated and vulcanized. For example, in the case of a conveyor belt, the adhesive rubber composition of the present invention is formed into a plate shape, a galvanized steel cord is sandwiched between the two formed plate-shaped rubber compositions, and heating / vulcanization is performed while pressing. Can be manufactured. The method for molding the adhesive rubber composition is not particularly limited, and all known methods for molding a rubber composition such as injection molding and molding can be used.
【００２２】このような本発明の複合材は、公知のゴム
／金属複合材のすべてに利用可能である。具体的には、
前述のコンベアベルトを初めとして、マリンホースや耐
圧ホース等の各種のホース、各種の自動車部品等に好適
に利用可能である。中でも、亜鉛メッキスチールコード
が通常に使用されるコンベアベルトには、特に好適に利
用される。The composite material of the present invention as described above can be used for all known rubber / metal composite materials. In particular,
It can be suitably used for various hoses such as marine hoses and pressure hoses, various automobile parts, and the like, including the above-mentioned conveyor belt. Among them, the galvanized steel cord is particularly preferably used for a conveyor belt which is usually used.
【００２３】以上、本発明の接着性ゴム組成物、および
この接着性ゴム組成物を用いた複合材について詳細に説
明したが、本発明は上記の例に限定されず、本発明の要
旨を逸脱しない範囲において、各種の改良および変更を
行ってもよいのはもちろんである。Although the adhesive rubber composition of the present invention and the composite material using the adhesive rubber composition have been described above in detail, the present invention is not limited to the above examples and deviates from the gist of the present invention. It goes without saying that various improvements and changes may be made without departing from the scope.
【００２４】[0024]
【実施例】以下、本発明の具体的実施例を挙げ、本発明
をより詳細に説明する。EXAMPLES The present invention will be described in more detail with reference to specific examples of the present invention.
【００２５】下記表１に示される各種のゴム組成物を調
製し（単位＝重量部）、得られた各ゴム組成物につい
て、下記の各種の特性を調べた。なお、ゴム組成物の調
製は、まず、バンバリミキサーにポリクロロプレンを投
入して混練し、次いで有機酸コバルト塩を投入して混練
し、その後、残りの成分を投入、混練することによって
行った。なお、バンバリミキサーからの放出温度は約１
１０℃であった。また、各ゴム組成物には、表１に示さ
れる成分以外に、ポリクロロプレン１００重量部に対し
て、酸化マグネシウム４重量部、水酸化アルミニウム３
０重量部、ＦＥＦカーボン４０重量部、ペトロラタム５
重量部、およびナフテンオイル５重量部を、それぞれ添
加した。表１において、非硫黄変性ポリクロロプレンは
ネオプレンＷＲＴ（昭和電工・デュポン社製）、硫黄変
性ポリクロロプレンはネオプレンＧＲＴ（昭和電工・デ
ュポン社製）、有機酸コバルト塩はＧＭＡ−Ｌ１０（大
崎工業社製）である。さらに、有機酸コバルト塩は、コ
バルト量に換算した含有量である。また、比較例１１に
おいては、２−メルカプトイミダゾリンの代わりに２−
メルカプトベンゾチアゾールを添加した。Various rubber compositions shown in Table 1 below were prepared (unit = parts by weight), and the obtained rubber compositions were examined for the following various characteristics. The rubber composition was prepared by first adding polychloroprene to a Banbury mixer and kneading, then adding an organic acid cobalt salt and kneading, and then adding and kneading the remaining components. The discharge temperature from the Banbury mixer is about 1
It was 10 ° C. In addition to the components shown in Table 1, each rubber composition contained 4 parts by weight of magnesium oxide and 3 parts of aluminum hydroxide based on 100 parts by weight of polychloroprene.
0 parts by weight, 40 parts by weight of FEF carbon, 5 petrolatum
Parts by weight and 5 parts by weight of naphthenic oil were added respectively. In Table 1, non-sulfur-modified polychloroprene is neoprene WRT (Showa Denko / Dupont), sulfur-modified polychloroprene is neoprene GRT (Showa Denko / Dupont), and organic acid cobalt salt is GMA-L10 (Osaki Kogyo). ). Furthermore, the organic acid cobalt salt is the content converted into the amount of cobalt. In Comparative Example 11, 2-mercaptoimidazoline was used instead of 2-mercaptoimidazoline.
Mercaptobenzothiazole was added.
【００２６】試験方法は、下記のとおりである。 ［未加硫物性］ＪＩＳ Ｋ ６３００に準じて、ムーニ
ースコーチタイムを測定した。 ［加硫物性］各ゴム組成物を１５０℃で３０分間加圧加
硫し、ＪＩＳ Ｋ ６３０１に準じて引張強さＴB 、伸
びＥB およびスプリング固さＨS を、それぞれ測定し
た。The test method is as follows. [Unvulcanized physical properties] Mooney scorch time was measured according to JIS K6300. [Vulcanization Properties] Each rubber composition was pressure-vulcanized at 150 ° C. for 30 minutes, and the tensile strength T B , the elongation E B, and the spring hardness H S were measured according to JIS K6301.
【００２７】［初期接着性］デシケータ中に保管して防
塵防湿処置を施してある直径４．１mmの亜鉛メッキスチ
ールコードに、厚さ１５mmの板状に成形した上記各ゴム
組成物を密着し、１５０℃で３０分間加圧加硫を行っ
た。 得られたゴム／亜鉛メッキスチールコード複合体の引き
抜き試験を行い、ゴム被覆率を測定した。[Initial Adhesion] Each of the above rubber compositions formed into a plate shape having a thickness of 15 mm was adhered to a zinc-plated steel cord having a diameter of 4.1 mm which was stored in a desiccator and subjected to a dustproof and moistureproof treatment, Pressure vulcanization was performed at 150 ° C. for 30 minutes. The rubber / galvanized steel cord composite thus obtained was subjected to a pull-out test to measure the rubber coverage.
【００２８】［耐水接着性］上記初期接着性の試験と同
様にして得られたゴム／亜鉛メッキスチールコード複合
体の必要部分を密ロウでシールし、温度５０℃、相対湿
度９５％の恒温恒湿層内で２１日間放置した。その後、
同様の引き抜き試験を行い、ゴム被覆率を測定した。[Water-Resistant Adhesiveness] A necessary portion of the rubber / zinc plated steel cord composite obtained in the same manner as the above initial adhesiveness test is sealed with a dense wax, and the temperature is kept at 50 ° C. and the relative humidity is 95%. It was left for 21 days in the wet layer. afterwards,
The same pull-out test was performed to measure the rubber coverage.
【００２９】なお、上記引き抜き試験において、ゴム被
覆率とは、引き抜き後のスチールコード表面に残存する
ゴムの被覆面積をスチールコード表面積に対する割り合
いで示したものであり、従って、高いもの程接着性が高
い。In the above-mentioned pulling test, the rubber coverage is a ratio of the coating area of the rubber remaining on the surface of the steel cord after the pulling to the steel cord surface area. Is high.
【００３０】以上の各試験の結果を、下記表１に示す。The results of each of the above tests are shown in Table 1 below.
【００３１】[0031]
【表１】 [Table 1]
【００３２】上記表１に示されるように、硫黄および／
または有機酸コバルト塩の含有量が本発明の範囲より少
ない比較例１〜３および比較例１０は、十分な接着性を
得ることができない。硫黄の含有量が本発明の範囲より
多い比較例４は、伸び、引っ張り強さ共に低い。有機酸
コバルト塩の含有量が本発明の範囲より多い比較例５は
伸びが低い。２−メルカプトイミダゾリンの含有量が本
発明の範囲より多い比較例６は酸化亜鉛の量が本発明の
範囲より少ない比較例８は、接着性が低い。硫黄変性ポ
リクロロプレンを使用した比較例７は、スコーチタイム
が短く、また接着性も低い。酸化亜鉛の量が本発明の範
囲より多い比較例９は、スコーチタイムが短い。さら
に、２−メルカプトイミダゾリンの代わりに２−メルカ
プトベンゾチアゾールを使用した比較例１１は、接着性
が低い。これに対して、本発明の実施例１〜３は、亜鉛
めっきスチールコードとの接着性が高く、しかも、スコ
ーチタイムや伸び等の未加硫および加硫物性にも優れた
ものである。以上の結果より、本発明の効果は明らかで
ある。As shown in Table 1 above, sulfur and / or
Alternatively, in Comparative Examples 1 to 3 and Comparative Example 10 in which the content of the organic acid cobalt salt is less than the range of the present invention, sufficient adhesiveness cannot be obtained. Comparative Example 4 having a sulfur content higher than the range of the present invention has low elongation and tensile strength. The elongation is low in Comparative Example 5 in which the content of the organic acid cobalt salt is more than the range of the present invention. Comparative Example 6 in which the content of 2-mercaptoimidazoline is more than the range of the present invention, Comparative Example 8 in which the amount of zinc oxide is less than the range of the present invention has low adhesiveness. Comparative Example 7 using the sulfur-modified polychloroprene has a short scorch time and low adhesiveness. Comparative Example 9 in which the amount of zinc oxide exceeds the range of the present invention has a short scorch time. Furthermore, the comparative example 11 which used 2-mercapto benzothiazole instead of 2-mercapto imidazoline has low adhesiveness. On the other hand, Examples 1 to 3 of the present invention have high adhesiveness to the galvanized steel cord, and are also excellent in unvulcanized and vulcanized physical properties such as scorch time and elongation. From the above results, the effect of the present invention is clear.
【００３３】[0033]
【発明の効果】以上、詳細に説明したように、本発明の
接着性ゴム組成物は、ポリクロロプレン系の組成物であ
るにもかかわらず亜鉛めっき材等の表面亜鉛材との接着
性が高く、難燃性や耐熱性を要求される各種のゴム／金
属複合材等に好適に利用可能である。また、本発明の複
合材は、上記接着性ゴム組成物を利用したものであっ
て、ゴムと表面亜鉛材との接着性が高い、高強度かつ耐
熱性および難燃性に優れた複合材である。As described above in detail, the adhesive rubber composition of the present invention has a high adhesiveness with the surface zinc material such as the galvanized material even though it is a polychloroprene-based composition. It can be suitably used for various rubber / metal composite materials and the like that require flame retardancy and heat resistance. Further, the composite material of the present invention is a composite material using the above-mentioned adhesive rubber composition, which has high adhesiveness between the rubber and the surface zinc material, high strength and excellent heat resistance and flame retardancy. is there.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 111/00 ＪＤＰ ＪＤＴ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C09J 111/00 JDP JDT
Claims (2)
に対し、有機酸コバルト塩をコバルト量に換算して０．
２〜０．７重量部、酸化亜鉛を３〜８重量部、硫黄を１
〜５重量部、２−メルカプトイミダゾリンを０．５〜１
重量部、それぞれ配合したことを特徴とする接着性ゴム
組成物。1. An organic acid cobalt salt in terms of cobalt content of 100 parts by weight based on 100 parts by weight of non-sulfur-modified polychloroprene.
2 to 0.7 parts by weight, zinc oxide 3 to 8 parts by weight, sulfur 1
~ 5 parts by weight, 0.5-1 of 2-mercaptoimidazoline
An adhesive rubber composition characterized by being mixed in each part by weight.
面が亜鉛である部材とを接触し、前記接着性ゴム組成物
を加硫してなることを特徴とする複合材。2. A composite material obtained by contacting the adhesive rubber composition according to claim 1 with a member having a zinc surface and vulcanizing the adhesive rubber composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6198186A JPH0859896A (en) | 1994-08-23 | 1994-08-23 | Adhesive rubber composition and composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6198186A JPH0859896A (en) | 1994-08-23 | 1994-08-23 | Adhesive rubber composition and composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0859896A true JPH0859896A (en) | 1996-03-05 |
Family
ID=16386912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6198186A Withdrawn JPH0859896A (en) | 1994-08-23 | 1994-08-23 | Adhesive rubber composition and composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0859896A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014092191A1 (en) * | 2012-12-14 | 2014-06-19 | 横浜ゴム株式会社 | Rubber composition and conveyor belt |
| WO2022071217A1 (en) * | 2020-09-30 | 2022-04-07 | 株式会社大阪ソーダ | Carboxyl group-containing acrylic rubber composition and multilayer body |
-
1994
- 1994-08-23 JP JP6198186A patent/JPH0859896A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014092191A1 (en) * | 2012-12-14 | 2014-06-19 | 横浜ゴム株式会社 | Rubber composition and conveyor belt |
| JP2014118459A (en) * | 2012-12-14 | 2014-06-30 | Yokohama Rubber Co Ltd:The | Rubber composition and conveyer belt |
| CN104837911A (en) * | 2012-12-14 | 2015-08-12 | 横滨橡胶株式会社 | Rubber composition and conveyor belt |
| WO2022071217A1 (en) * | 2020-09-30 | 2022-04-07 | 株式会社大阪ソーダ | Carboxyl group-containing acrylic rubber composition and multilayer body |
| JPWO2022071217A1 (en) * | 2020-09-30 | 2022-04-07 | ||
| EP4223511A4 (en) * | 2020-09-30 | 2024-10-30 | Osaka Soda Co., Ltd. | ACRYLIC RUBBER COMPOSITION CONTAINING CARBOXYL GROUP AND MULTILAYER BODIES |
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Legal Events
| Date | Code | Title | Description |
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| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20011106 |