JP2022127710A - Laminate, method for manufacturing the same, and adhesive for bonding chlorosulfonated polyolefin - Google Patents
Laminate, method for manufacturing the same, and adhesive for bonding chlorosulfonated polyolefin Download PDFInfo
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- chloroprene rubber
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 50
- 239000000853 adhesive Substances 0.000 title claims description 19
- 230000001070 adhesive effect Effects 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 title description 16
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 58
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 31
- 238000004073 vulcanization Methods 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 229920002681 hypalon Polymers 0.000 claims description 25
- 238000013329 compounding Methods 0.000 claims description 17
- 239000012744 reinforcing agent Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012763 reinforcing filler Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000005060 rubber Substances 0.000 description 15
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- -1 hydrotalcite compound Chemical class 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000002210 silicon-based material Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000370 acceptor Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000010060 peroxide vulcanization Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010059 sulfur vulcanization Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920004411 Skyprene® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Laminated Bodies (AREA)
Abstract
Description
本発明はクロロスルホン化ポリオレフィン加硫物層を有する積層体およびその製造方法に関する。 The present invention relates to a laminate having a chlorosulfonated polyolefin vulcanizate layer and a method for producing the same.
クロロスルホン化ポリオレフィンとしては、クロロスルホン化ポリエチレン（ＣＳＭ）やアルキル化クロロスルホン化ポリエチレン（ＡＣＳＭ）が市販されている。クロロスルホン化ポリオレフィンは、加工性、機械的強度や耐摩耗性などの力学的物性、および、耐熱性、対候性、耐油性、耐薬品性などの耐久性が優れるゴムである。 As chlorosulfonated polyolefins, chlorosulfonated polyethylene (CSM) and alkylated chlorosulfonated polyethylene (ACSM) are commercially available. Chlorosulfonated polyolefin is a rubber excellent in mechanical properties such as workability, mechanical strength and wear resistance, and durability such as heat resistance, weather resistance, oil resistance and chemical resistance.
一般的に合成ゴム素材の特性は、その原料ゴムの種類だけでなく、カーボン等に代表される補強剤や、コストダウンのための充填剤、加工性を改善するオイルや加工助剤、加硫と呼ばれる架橋反応をおこなう薬剤など、いわゆる配合剤の種類にも大きく影響される。
補強剤としては一般的にカーボンが用いられるが、クロロスルホン化ポリオレフィンは一般的に着色性や明色安定性に優れるため、黒以外で用いられることも多い。しかし、補強材としてカーボンを用いた場合は黒い加硫ゴムとなるため、その他の色の加硫ゴムを得るためにはカーボンでは無く無機質の白色の補強剤が用いられることも多い。クロロスルホン化ポリオレフィンの加硫の方法として、大きく分類して、チウラム系化合物を用いた硫黄系加、マレイミド系化合物を用いたマレイミド加硫、過酸化物を用いた過酸化物加硫などが挙げられる。硫黄系加硫では、破断伸びや強度などの力学物性がより優れ、過酸化物加硫では耐熱性や耐黄変性などがより優れるというように加硫系によって特徴があるため、目的によって使い分けられるのが一般的である。そのため、例えば表と裏で異なる色相や特徴が要求される場合などは、要求にあわせて補強剤の種類や加硫系など、各種配合剤を選定し、それらを積層体とすることで要求物性を満たすことができる。一般的に、同じゴム同士、例えばクロロプレンゴム同士であれば、配合が異なっても未加硫物同士を同時に加硫して接着するいわゆる加硫接着が可能である。しかし、クロロスルホン化ポリオレフィンは接着性に乏しく、同じ加硫系を用いた場合でも加硫接着が困難であった。
In general, the characteristics of synthetic rubber materials are not limited to the type of raw material rubber, but also reinforcing agents such as carbon, fillers for cost reduction, oils and processing aids to improve processability, vulcanization It is also greatly affected by the type of so-called compounding agents such as agents that perform a cross-linking reaction called
Carbon is generally used as a reinforcing agent, but chlorosulfonated polyolefin is generally excellent in colorability and bright color stability, so it is often used in colors other than black. However, when carbon is used as a reinforcing material, the vulcanized rubber becomes black. Therefore, in order to obtain vulcanized rubber of other colors, an inorganic white reinforcing material is often used instead of carbon. Vulcanization methods for chlorosulfonated polyolefins can be broadly classified into sulfur vulcanization using thiuram compounds, maleimide vulcanization using maleimide compounds, and peroxide vulcanization using peroxides. be done. Sulfur-based vulcanization has superior mechanical properties such as elongation at break and strength, while peroxide vulcanization has superior heat resistance and yellowing resistance. is common. Therefore, for example, when different hues and characteristics are required for the front and back, various compounding agents such as the type of reinforcing agent and vulcanization system are selected according to the request, and these are combined into a laminate with the required physical properties. can satisfy In general, if rubbers of the same type, such as chloroprene rubbers, are mixed with different compounds, unvulcanized materials can be vulcanized at the same time and adhered to each other by so-called vulcanization adhesion. However, chlorosulfonated polyolefin has poor adhesiveness, and vulcanization adhesion was difficult even when the same vulcanization system was used.
これまでに、ハイドロタルサイト化合物およびケイ素含有化合物を配合したクロロスルホン化ポリオレフィン組成物とニトリルゴム組成物とクロロプレンゴム組成物とを加硫接着させる技術が報告されている（例えば、特許文献１参照）。 So far, a technique has been reported for vulcanization bonding of a chlorosulfonated polyolefin composition containing a hydrotalcite compound and a silicon-containing compound, a nitrile rubber composition, and a chloroprene rubber composition (see, for example, Patent Document 1). ).
しかしながら、この方法では、クロロスルホン化ポリオレフィンの配合にハイドロタルサイト化合物やケイ素化合物が必須であり、配合が限定されて任意の配合ができないため、必ずしも要求される色や物性などの要求を満たすことができないという問題があった。 However, in this method, a hydrotalcite compound and a silicon compound are essential for compounding the chlorosulfonated polyolefin. There was a problem that it was not possible to
本発明は、上記の課題に鑑みてなされたものであり、その目的は複数のクロロスルホン化ポリオレフィン加硫物層界面が強固に積層された積層体およびその製造方法を提供するものである。 The present invention has been made in view of the above problems, and its object is to provide a laminate in which a plurality of chlorosulfonated polyolefin vulcanizate layer interfaces are strongly laminated, and a method for producing the same.
本発明者らは、上記課題を解決する為に鋭意検討した結果、ケイ素含有化合物を含むクロロプレンゴムを介することでクロロスルホン化ポリエチレン加硫物層を強固に接着可能であることを見出し、本発明を完成するに至った。 The present inventors have made intensive studies to solve the above problems, and found that a chlorosulfonated polyethylene vulcanizate layer can be strongly adhered through a chloroprene rubber containing a silicon-containing compound. was completed.
すなわち本発明の各態様は、以下の［１］～［６］である。
［１］ 複数のクロロスルホン化ポリオレフィン加硫物層を有する積層体であって、クロロスルホン化ポリオレフィン加硫物層とクロロスルホン化ポリオレフィン加硫物層の間に、クロロプレンゴム１００重量部に対しケイ素化合物を２０～１００重量部含むクロロプレンゴム加硫物層を有する積層体。
［２］ クロロスルホン化ポリオレフィン加硫物層が配合剤として無機の補強剤または充填剤、並びに加硫剤および／または加硫促進剤を含み、その配合剤の種類および／または量が積層される層ごとに異なることを特徴とする、［１］に記載の積層体。
［３］ ケイ素化合物を含むクロロプレンゴム未加硫物成形体を、クロロスルホン化ポリエチレン未加硫物成形体の間に配置した後、加硫することを特徴とする［１］又は［２］に記載の積層体の製造方法。
［４］ ケイ素化合物を含むクロロプレンゴム未加硫物を溶剤に溶解し、その溶解液をクロロスルホン化ポリエチレン未加硫物成形体に塗布し、ついで別のクロロスルホン化ポリエチレン未加硫物成形体を重ね合わせ積層体を形成した後、加硫することを特徴とする［１］又は［２］に記載の積層体の製造方法。
［５］ ケイ素化合物、クロロプレンゴム及び加硫剤、又はケイ素化合物、クロロプレンゴム及び加硫促進剤を含むクロロスルホン化ポリオレフィン接合用接着剤。
［６］ さらに溶剤を含む［５］に記載のクロロスルホン化ポリオレフィン接合用接着剤。
That is, each aspect of the present invention is the following [1] to [6].
[1] A laminate having a plurality of chlorosulfonated polyolefin vulcanizate layers, wherein silicon A laminate having a chloroprene rubber vulcanizate layer containing 20 to 100 parts by weight of a compound.
[2] The chlorosulfonated polyolefin vulcanizate layer contains an inorganic reinforcing agent or filler, and a vulcanizing agent and/or a vulcanization accelerator as compounding agents, and the type and/or amount of the compounding agents are laminated. The laminate according to [1], which is different for each layer.
[3] The method according to [1] or [2], characterized in that a chloroprene rubber unvulcanized molded article containing a silicon compound is placed between chlorosulfonated polyethylene unvulcanized molded articles and then vulcanized. A method for manufacturing the described laminate.
[4] A chloroprene rubber unvulcanized material containing a silicon compound is dissolved in a solvent, the solution is applied to a chlorosulfonated polyethylene unvulcanized molded article, and then another chlorosulfonated polyethylene unvulcanized molded article is applied. is laminated to form a laminate, and then vulcanized.
[5] A chlorosulfonated polyolefin bonding adhesive comprising a silicon compound, a chloroprene rubber and a vulcanizing agent, or a silicon compound, a chloroprene rubber and a vulcanization accelerator.
[6] The chlorosulfonated polyolefin bonding adhesive according to [5], which further contains a solvent.
本発明によれば、界面が強固に接合された任意の配合のクロロスルホン化ポリオレフィン加硫物積層体を提供することが可能となる。 According to the present invention, it is possible to provide a chlorosulfonated polyolefin vulcanizate laminate of any composition with strongly bonded interfaces.
以下本発明を更に詳細に説明する。 The present invention will be described in more detail below.
本発明の一態様である積層体は、複数のクロロスルホン化ポリオレフィン加硫物層を有するものであり、隣接するそれぞれのクロロスルホン化ポリオレフィン加硫物層の間にケイ素化合物を含むクロロプレンゴム加硫物層を有する。 One aspect of the present invention is a laminate having a plurality of chlorosulfonated polyolefin vulcanizate layers, and a chloroprene rubber vulcanizate containing a silicon compound between adjacent chlorosulfonated polyolefin vulcanizate layers. have a material layer.
クロロスルホン化ポリオレフィンとは、各種ポリオレフィンを塩素化およびクロロスルホン化したものをいう。原料となるポリオレフィンとしては、ポリエチレン、ポリプロピレンなどの単独重合体や、エチレンとプロピレン、エチレンとブテン、エチレンと酢酸ビニルの共重合体（ＥＶＡ）などが挙げられるが、ポリエチレンを原料としたクロロスルホン化ポリエチレンが代表的である。クロロスルホン化ポリエチレンとしては、東ソー（株）製 ＴＯＳＯ－ＣＳＭ（登録商標）やｅｘｔｏｓ（登録商標）などが挙げられる。 Chlorosulfonated polyolefin refers to various polyolefins chlorinated and chlorosulfonated. Polyolefins used as raw materials include homopolymers such as polyethylene and polypropylene, and copolymers (EVA) of ethylene and propylene, ethylene and butene, and ethylene and vinyl acetate. Polyethylene is typical. Examples of chlorosulfonated polyethylene include TOSO-CSM (registered trademark) and extos (registered trademark) manufactured by Tosoh Corporation.
本発明の一態様である積層体を構成するクロロスルホン化ポリオレフィン加硫物層には、加硫をするための配合剤として、無機の補強剤または充填剤、および加硫剤および／または加硫促進剤を含む。例えば、上層は耐油性に優れ、中間層は柔軟性に優れ、下層は耐水性に優れるなど、積層された各層が異なる特性を示すことができるようその配合剤の種類および／または量が積層される層ごとに異なることが好ましい。 The chlorosulfonated polyolefin vulcanizate layer constituting the laminate that is one aspect of the present invention contains an inorganic reinforcing agent or filler, and a vulcanizing agent and/or vulcanizing agent as compounding agents for vulcanization. Contains accelerators. For example, the upper layer has excellent oil resistance, the middle layer has excellent flexibility, and the lower layer has excellent water resistance. preferably different for each layer.
無機の補強剤としては、カーボンブラックやシリカ、ホワイトカーボンなどが挙げられる。無機の充填剤としては、炭酸カルシウムやクレー、シリカなどが挙げられる。加硫剤としては、多官能性モノマーが使用され、例えばトリアリルイソシアヌレート、エチレングリコールジメタクリレート、ジビニルベンゼン、Ｎ，Ｎ’－ｍ－フェニレンビスマレイミド等が挙げられる。加硫促進剤としては、チオウレア化合物やチウラム化合物、マレイミド化合物、過酸化物などが挙げられる。また、この他に、一般的にクロロスルホン化ポリオレフィンに用いられる配合剤を用いることができる。 Examples of inorganic reinforcing agents include carbon black, silica, and white carbon. Inorganic fillers include calcium carbonate, clay, silica and the like. As the vulcanizing agent, polyfunctional monomers are used, such as triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, N,N'-m-phenylenebismaleimide, and the like. Vulcanization accelerators include thiourea compounds, thiuram compounds, maleimide compounds, peroxides and the like. In addition, compounding agents generally used for chlorosulfonated polyolefins can be used.
一般的にクロロスルホン化ポリオレフィンの加硫に用いられる加硫系としては、例えばチウラム系化合物を用いた硫黄系加硫、マレイミド系化合物を用いたマレイミド加硫、過酸化物を用いた過酸化物加硫などが挙げられ、硫黄系加硫では、破断伸びや強度などの力学物性がより優れ、過酸化物加硫では耐熱性や耐黄変性などがより優れるというように、加硫系によって特徴がある。また、加硫の際に発生する塩素化合物を補足するために受酸剤が用いられる。一般的にロロスルホン化ポリオレフィンに用いられる受酸剤としては、酸化マグネシウム、酸化カルシウムなどの金属酸化物や、ハイドロタルサイトなどが挙げられる。本発明で用いる受酸剤は特に限定するものでは無いが、受酸が不十分であると加硫の進行を妨げる為、十分な受酸剤量を添加する事が好ましい。一般的に、酸化マグネシウムであればクロロスルホン化ポリオレフィン１００重量部に対し２重量部以上、ハイドロタルサイトであれば８重量部以上が用いられる。 Vulcanization systems generally used for vulcanization of chlorosulfonated polyolefins include, for example, sulfur vulcanization using thiuram compounds, maleimide vulcanization using maleimide compounds, and peroxide vulcanization using peroxides. Vulcanization etc., and characteristics depending on the vulcanization system, such as superior mechanical properties such as elongation at break and strength with sulfur vulcanization, and superior heat resistance and yellowing resistance with peroxide vulcanization. There is Also, an acid acceptor is used to supplement chlorine compounds generated during vulcanization. Examples of acid acceptors generally used for rolosulfonated polyolefins include metal oxides such as magnesium oxide and calcium oxide, hydrotalcite, and the like. Although the acid acceptor used in the present invention is not particularly limited, it is preferable to add a sufficient amount of the acid acceptor because insufficient acid acceptance hinders the progress of vulcanization. In general, magnesium oxide is used in an amount of 2 parts by weight or more per 100 parts by weight of chlorosulfonated polyolefin, and hydrotalcite is used in an amount of 8 parts by weight or more.
本発明の一態様である積層体は、ケイ素化合物を含むクロロプレンゴム加硫物層を有する。クロロプレンゴムは、２－クロロ－１，３ブタジエンの単量体、または、２－クロロ－１，３ブタジエンの単量体と、２－クロロ－１，３ブタジエンの単量体と共重合可能な他の単量体を１種類以上共重合したものをいい、各社から市販されている。例えば、東ソー（株）製のスカイプレンなどが挙げられる。クロロプレンゴムには、硫黄を共重合した硫黄変性クロロプレンゴムと非硫黄変性クロロプレンゴムが存在するが、本発明ではどちらのクロロプレンゴムでも用いることが可能である。クロロプレンゴム加硫物は、クロロプレンゴムを加硫したものである。クロロプレンゴム加硫物層はクロロプレンゴム１００重量部に対しケイ素化合物を２０～１００重量部、好ましくは３０～８０重量部添加したものを加硫したものである。ケイ素化合物を２０重量部以上１００重量部以下とすることで、クロロスルホン化ポリオレフィン加硫物層と優れた接着強度を得ることができる。 A laminate that is one aspect of the present invention has a chloroprene rubber vulcanizate layer containing a silicon compound. The chloroprene rubber is copolymerizable with a monomer of 2-chloro-1,3 butadiene or a monomer of 2-chloro-1,3 butadiene and a monomer of 2-chloro-1,3 butadiene. It refers to a copolymer obtained by copolymerizing one or more other monomers, and is commercially available from each company. For example, Skyplane manufactured by Tosoh Corporation can be used. Chloroprene rubber includes sulfur-modified chloroprene rubber copolymerized with sulfur and non-sulfur-modified chloroprene rubber, and either chloroprene rubber can be used in the present invention. A chloroprene rubber vulcanizate is obtained by vulcanizing chloroprene rubber. The chloroprene rubber vulcanizate layer is obtained by vulcanizing 20 to 100 parts by weight, preferably 30 to 80 parts by weight of a silicon compound added to 100 parts by weight of chloroprene rubber. By setting the silicon compound to 20 parts by weight or more and 100 parts by weight or less, excellent adhesive strength with the chlorosulfonated polyolefin vulcanizate layer can be obtained.
ケイ素化合物としては、補強剤としてシリカが一般的に用いられ、また、ケイ酸アルミニウムなどのケイ酸化合物、および各種クレーなどが用いられる。また、クロロプレンゴム未加硫物は、加硫を行うため、加硫促進剤、金属酸化物などの配合剤を含む事が好ましい。配合剤はクロロプレンゴムの加硫に一般的に用いられるものであれば特に限定するものでは無いが、エチレンチオウレアなどのチオウレア化合物、テトラメチルチウラムジスルフィドなどのチウラム系化合物などを用いることで一般的にクロロプレンゴムは優れた加硫特性，加硫物性を有することが知られている。金属酸化物としては、酸化マグネシウムおよび酸化亜鉛がクロロプレンゴム１００重量部に対し、それぞれ２～１０重量部使用されるのが一般的である。 As the silicon compound, silica is generally used as a reinforcing agent, and silicic acid compounds such as aluminum silicate and various clays are also used. Moreover, since the unvulcanized chloroprene rubber is vulcanized, it preferably contains compounding agents such as vulcanization accelerators and metal oxides. The compounding agent is not particularly limited as long as it is generally used for vulcanization of chloroprene rubber, but thiourea compounds such as ethylene thiourea, thiuram compounds such as tetramethylthiuram disulfide, etc. can be generally used. Chloroprene rubber is known to have excellent vulcanization characteristics and physical properties. As metal oxides, magnesium oxide and zinc oxide are generally used in an amount of 2 to 10 parts by weight each per 100 parts by weight of chloroprene rubber.
本発明の一態様である積層体の製造方法は、ケイ素化合物を含むクロロプレンゴム未加硫物成形体を、クロロスルホン化ポリエチレン未加硫物成形体の間に配置した後、加硫する、または、ケイ素化合物を含むクロロプレンゴム未加硫物を溶剤に溶解し、その溶解液をクロロスルホン化ポリエチレン未加硫物成形体に塗布し、ついで別のクロロスルホン化ポリエチレン未加硫物成形体を重ね合わせ積層体を形成した後、加硫することで積層体とすることができる。例えば、クロロスルホン化ポリオレフィン未加硫物をシート状に成型し、その上面に、ケイ素化合物を含むクロロプレンゴム未加硫物を重ねてから別のクロロスルホン化ポリオレフィン未加硫物を重ね合わせた状態とし、加熱等により加硫し接合する方法や、ケイ素化合物を含むクロロプレンゴム未加硫物を有機溶剤等に溶解し、それを箱型に成型したクロロスルホン化ポリオレフィン未加硫物の１面に塗布、乾燥後、別のクロロスルホン化ポリオレフィン未加硫物をその面に重ね合わせた状態にて加熱し、接合する方法などが挙げられる。 A method for producing a laminate, which is one aspect of the present invention, includes disposing a chloroprene rubber unvulcanized molded article containing a silicon compound between chlorosulfonated polyethylene unvulcanized molded articles and vulcanizing the molded article, or , A chloroprene rubber unvulcanized product containing a silicon compound is dissolved in a solvent, the solution is applied to a chlorosulfonated polyethylene unvulcanized molded product, and another chlorosulfonated polyethylene unvulcanized molded product is layered. A laminate can be obtained by vulcanizing after forming a laminated laminate. For example, a state in which a chlorosulfonated polyolefin unvulcanized material is molded into a sheet, a chloroprene rubber unvulcanized material containing a silicon compound is layered on the upper surface, and another chlorosulfonated polyolefin unvulcanized material is layered thereon. Then, a method of vulcanizing and bonding by heating, etc., or dissolving a chloroprene rubber unvulcanized material containing a silicon compound in an organic solvent or the like and molding it into a box shape on one side of a chlorosulfonated polyolefin unvulcanized material After application and drying, another chlorosulfonated polyolefin unvulcanized material is superimposed on the surface and then heated to bond.
クロロスルホン化ポリオレフィン未加硫物およびクロロプレンゴム未加硫物を成型する方法は特に限定するものではないが、例えば、それぞれの未加硫物を押出機により重ねて押出成形する多層成形や、それぞれの混合物をオープンロールまたはカレンダーロール等で圧延し、シート状に成型後、金型に重ねて入れて任意の形状に成型する方法などが挙げられる。本発明ではクロロスルホン化ポリオレフィン未加硫成形体の形状、大きさ、厚みについては特に限定するものではなく、任意の形状のもの同士を積層体とすることが可能である。 The method for molding the chlorosulfonated polyolefin unvulcanized material and the chloroprene rubber unvulcanized material is not particularly limited, but examples include multilayer molding in which the respective unvulcanized materials are stacked and extruded using an extruder, and A mixture of the above is rolled with an open roll, calendar roll, or the like, formed into a sheet, and then placed in a mold to be formed into an arbitrary shape. In the present invention, the shape, size, and thickness of the unvulcanized chlorosulfonated polyolefin molded article are not particularly limited, and it is possible to laminate articles of any shape together.
ケイ素化合物を含むクロロプレンゴム未加硫物の形状は特に限定するものでは無いが、積層体の物性への影響を少なくしたい場合は２ｍｍ以下の薄いシート状とするのが好ましく、更には、０．５ｍｍ以下の薄膜とするのが好ましい。０．５ｍｍ以下の薄膜とする方法としては、ケイ素化合物を含むクロロプレンゴム未加硫物を有機溶剤等に溶解し、それを塗布する方法などが挙げられる。 The shape of the unvulcanized chloroprene rubber containing a silicon compound is not particularly limited, but if it is desired to reduce the effect on the physical properties of the laminate, it is preferably in the form of a thin sheet of 2 mm or less. A thin film of 5 mm or less is preferable. A method of forming a thin film of 0.5 mm or less includes a method of dissolving a chloroprene rubber unvulcanized product containing a silicon compound in an organic solvent or the like and applying the solution.
ケイ素化合物を含むクロロプレンゴム未加硫物を有機溶剤等に溶解する方法は特に限定するものでは無く、ケイ素化合物を含むクロロプレンゴム未加硫物を容器に入れ、そこに有機溶剤を加え、混合する事で作製する事ができる。有機溶剤の量は特に限定するものでは無いが、ケイ素化合物を含むクロロプレンゴム未加硫物の濃度が３～１０％程度となるよう調整するのが好ましい。３％以上とすることで薄膜をクロロスルホン化ポリオレフィン未加硫物の上に効率よく形成することが可能となり、１０％以下とすることで溶解性および塗布性に優れた接着剤を得ることができる。有機溶剤の種類は特に限定するものでは無く、単独または混合により未加硫のクロロプレンゴムを溶解可能なものであれば用いることができる。例えば、ベンゼン、トルエン、キシレン、クロロホルム、メチルエチルケトン、酢酸プロピル、酢酸ブチル、や、ヘキサン－シクロヘキサン－酢酸エチル－アセトンの混合液などが挙げられる。 The method of dissolving the unvulcanized chloroprene rubber containing a silicon compound in an organic solvent is not particularly limited. It can be made by hand. Although the amount of the organic solvent is not particularly limited, it is preferable to adjust the concentration of the unvulcanized chloroprene rubber containing the silicon compound to about 3 to 10%. By making it 3% or more, it becomes possible to efficiently form a thin film on the unvulcanized chlorosulfonated polyolefin, and by making it 10% or less, it is possible to obtain an adhesive with excellent solubility and coating properties. can. The type of organic solvent is not particularly limited, and any organic solvent can be used as long as it can dissolve the unvulcanized chloroprene rubber either singly or in combination. Examples include benzene, toluene, xylene, chloroform, methyl ethyl ketone, propyl acetate, butyl acetate, and mixtures of hexane-cyclohexane-ethyl acetate-acetone.
クロロスルホン化ポリオレフィン未加硫物は、クロロスルホン化ポリオレフィンと各種の配合剤とを混合・混錬することにより得られる。クロロスルホン化ポリオレフィンと各種の配合剤を混合・混錬する手法については特に限定するものではなく、通常知られているゴムの混錬と同様の方法にておこなうことができる。例えば、受酸剤、補強剤、充填剤、可塑剤、老化防止剤等をロール、ニーダーバンバリー等の混練機またはオープンロールによってクロロスルホン化ポリオレフィンと混合することができる。 The unvulcanized chlorosulfonated polyolefin is obtained by mixing and kneading the chlorosulfonated polyolefin and various compounding agents. The method of mixing and kneading the chlorosulfonated polyolefin and various compounding agents is not particularly limited, and the same method as commonly known kneading of rubber can be used. For example, acid acceptors, reinforcing agents, fillers, plasticizers, anti-aging agents and the like can be mixed with the chlorosulfonated polyolefin by rolls, a kneader such as a kneader Banbury, or an open roll.
ケイ素化合物を含むクロロプレンゴム未加硫物は、クロロプレンゴムにケイ素含有化合物およびその他各種の配合剤を混合・混錬することにより得られる。クロロプレンゴムに各種の配合剤を混合・混錬する手法については特に限定するものではなく、通常知られているゴムの混錬と同様の方法にておこなうことができる。例えば、受酸剤、補強剤、充填剤、可塑剤、老化防止剤、加硫剤、加硫促進剤、過酸化物、金属酸化物等をロール、ニーダーバンバリー等の混練機またはオープンロールによってクロロプレンゴムと混合することができる。 A chloroprene rubber unvulcanized product containing a silicon compound is obtained by mixing and kneading a chloroprene rubber with a silicon-containing compound and various other compounding agents. The method of mixing and kneading the various compounding agents with the chloroprene rubber is not particularly limited, and can be carried out in the same manner as commonly known kneading of rubber. For example, acid acceptors, reinforcing agents, fillers, plasticizers, anti-aging agents, vulcanizing agents, vulcanization accelerators, peroxides, metal oxides, etc. are added to chloroprene by kneading machines such as kneader Banbury or open rolls. Can be mixed with rubber.
加硫方法については、特に限定するものではなく、通常のゴムの加硫方法にて実施することが可能であり、例えば、得られた未加硫物成形体を、熱プレスや加硫釜内部にて加熱したり、紫外線や電磁波などによりエネルギーを与えることで行うことができる。一般的には加熱加硫が行われる。加硫温度については、１２０～２００℃にて実施可能であるが、加硫速度や加硫時のゴムの熱分解抑制の観点から、１４０～１８０℃が好ましい。また、加硫時間は加硫温度が低いほど、また、加硫するものの形状が大きく内部まで熱が伝わりにくい場合ほど長くなるが、一般的２時間以内で、小さいものであれば１６０℃にて２０分程度で可能である。 The vulcanization method is not particularly limited, and it is possible to perform vulcanization by a normal rubber vulcanization method. It can be carried out by heating with , or by applying energy by ultraviolet rays, electromagnetic waves, or the like. Heat vulcanization is generally performed. The vulcanization temperature can be 120 to 200° C., but is preferably 140 to 180° C. from the viewpoint of vulcanization speed and suppression of thermal decomposition of rubber during vulcanization. In addition, the lower the vulcanization temperature, the longer the vulcanization time, and the larger the shape of the object to be vulcanized and the less heat is transmitted to the inside, but generally within 2 hours. It is possible in about 20 minutes.
本発明の一態様であるクロロスルホン化ポリオレフィン接合用接着剤は、ケイ素化合物、クロロプレンゴム及び加硫剤、又はケイ素化合物、クロロプレンゴム及び加硫促進剤を含むものである。また、さらに溶剤を含んでいてもよい。 A chlorosulfonated polyolefin bonding adhesive that is one aspect of the present invention comprises a silicon compound, a chloroprene rubber and a vulcanizing agent, or a silicon compound, a chloroprene rubber and a vulcanization accelerator. In addition, it may further contain a solvent.
本発明を以下の実施例により具体的に説明する。但し、本発明はこれらに限定されるものではない。 The present invention is specifically described by the following examples. However, the present invention is not limited to these.
本実施例における積層体の作製およびその接着強度の測定は以下のように実施した。
＜未加硫物作製＞
クロロスルホン化ポリエチレンまたはクロロプレンゴムと、表１に示す所定の割合の配合剤とを３Ｌ加圧型ニーダーにて混錬後、８インチオープンロールにて間隙１．４ｍｍでシート状に成型した。
Preparation of the laminate and measurement of the adhesive strength in this example were carried out as follows.
<Production of unvulcanized product>
After kneading chlorosulfonated polyethylene or chloroprene rubber and compounding agents at a predetermined ratio shown in Table 1 with a 3 L pressure kneader, the mixture was molded into a sheet with an 8-inch open roll with a gap of 1.4 mm.
＜接着剤の作製＞
表１の配合で作製したクロロプレン未加硫物１０ｇと９０ｇのトルエンを約３００ｍｌ容量の蓋つきガラス瓶に入れ、蓋をして密栓した後ボールミル架台上で室温にて１６時間回転混合させ溶解し、クロロプレン未加硫物を含む溶液とした。
＜積層体の作製１＞
シート状に成型したクロロスルホン化ポリエチレン未加硫物をハサミで裁断し、２０ｃｍ×２０ｃｍのシートを２枚作製した。また、同様にクロロプレンゴム未加硫物をハサミで裁断し、２０ｃｍ×２０ｃｍのシートを作製し、クロロスルホン化ポリエチレン未加硫物の上にクロロプレンゴム未加硫物を重ね、その上にクロロスルホン化ポリエチレン未加硫物を重ねた後、厚４ｍｍの金型に入れ、加熱圧縮成型機を用いて１６０℃にて２０分間１５０ｋｇ／ｍ２にて圧縮成形し、積層体を得た。なお、シートを重ねる際、一部に２ｍｍ幅ＰＥＴフィルムを挟むことで接着しないようにして、接着強度測定の際の掴みしろとした。
＜積層体の作製２＞
シート状に成型したクロロスルホン化ポリエチレン未加硫物をハサミで裁断し、２０ｃｍ×２０ｃｍのシートを２枚作製した。作製したシートそれぞれの片面にクロロプレン未加硫物接着剤を塗布し、２３℃にて３０分風乾した後、シートの接着剤塗布面を重ねて２０ｃｍ×２０ｃｍ、厚み５ｍｍの金型に入れ、加熱圧縮成型機を用いて１６０℃にて２０分間１５０ｋｇ／ｍ２にて圧縮成形し、積層体を得た。なお、シートを重ねる際、一部にＰＥＴフィルムを挟むことで接着しないようにして、接着強度測定の際の掴みしろとした。
＜接着強度の測定＞
積層体を２５℃にて１日養生した後、２５ｍｍ幅に打抜き、剥離試験機にて、１８０度剥離を行い、２３℃における剥離強度の測定と剥離状態を観察した。剥離試験機に装着する際にはＰＥＴフィルムを剥がし、治具の掴みしろとし、剥離速度は２００ｍｍ／ｍｉｎとした。
<Preparation of adhesive>
10 g of the unvulcanized chloroprene prepared according to the formulation shown in Table 1 and 90 g of toluene were placed in a glass bottle with a lid of about 300 ml, tightly sealed with a lid, and then dissolved by rotating and mixing on a ball mill stand at room temperature for 16 hours, A solution containing a chloroprene unvulcanized product was prepared.
<Production of laminate 1>
The sheet-shaped chlorosulfonated polyethylene unvulcanized product was cut with scissors to prepare two sheets of 20 cm×20 cm. Similarly, the unvulcanized chloroprene rubber was cut with scissors to prepare a sheet of 20 cm x 20 cm. After stacking unvulcanized poly(ethylene) products, they were placed in a 4 mm thick mold and compression molded at 160° C. for 20 minutes at 150 kg/m 2 using a hot compression molding machine to obtain a laminate. When the sheets were stacked, a PET film having a width of 2 mm was partially sandwiched to prevent the sheets from sticking to each other, which was used as a grasping margin for measuring the adhesive strength.
<Production of laminate 2>
The sheet-shaped chlorosulfonated polyethylene unvulcanized product was cut with scissors to prepare two sheets of 20 cm×20 cm. A chloroprene unvulcanized adhesive is applied to one side of each of the prepared sheets, air-dried at 23° C. for 30 minutes, and then placed in a mold of 20 cm × 20 cm and 5 mm in thickness, with the adhesive-coated surfaces of the sheets overlapped, and heated. A laminate was obtained by compression molding at 160° C. for 20 minutes at 150 kg/m 2 using a compression molding machine. In addition, when the sheets were stacked, a PET film was partially sandwiched to prevent the sheets from adhering to each other, which was used as a grasping margin when measuring the adhesive strength.
<Measurement of adhesive strength>
After the laminate was aged at 25°C for one day, it was punched out to a width of 25 mm and peeled 180° with a peel tester, and the peel strength was measured at 23°C and the state of peeling was observed. When attaching to the peel tester, the PET film was peeled off and used as a gripping margin for the jig, and the peeling speed was set at 200 mm/min.
剥離状態は、クロロプレンゴムとクロロスルホン化ポリエチレンの界面が明白な界面剥離、界面が判別できないゴム破壊、およびそれらの混在のどれに該当するかを目視で確認した。 The state of detachment was visually confirmed as to whether the detachment was clear at the interface between the chloroprene rubber and the chlorosulfonated polyethylene, the rubber was destroyed with the interface not being discernible, or the mixture thereof.
実施例１
クロロプレンゴムとして、東ソー（株）製のクロロプレンゴムであるスカイプレンＴＳＲ－５１を、クロロスルホン化ポリエチレンとして、東ソー（株）製のＴＯＳＯ－ＣＳＭ ＴＳ－５３０を用いた。表１のＣＲ配合において、ケイ素含有化合物としてシリカ（東ソー・シリカ（株）製ＶＮ３）３０重量部を配合し、上記＜積層体の作製１＞に従い、ケイ素化合物含有クロロプレン未加硫物シートを作製し、配合１のクロロスルホン化ポリエチレン未加硫物シートと重ね、さらにその上に配合２のクロロスルホン化ポリエチレン未加硫物シートを重ねた後、加熱圧縮成型機を用いて積層体を作製した。積層体の各層の間の剥離強度は大きく、剥離状態はゴム破壊であった。
Example 1
Skyprene TSR-51, which is a chloroprene rubber manufactured by Tosoh Corporation, was used as the chloroprene rubber, and TOSO-CSM TS-530 manufactured by Tosoh Corporation was used as the chlorosulfonated polyethylene. In the CR formulation of Table 1, 30 parts by weight of silica (VN3 manufactured by Tosoh Silica Co., Ltd.) was blended as a silicon-containing compound, and a silicon compound-containing chloroprene unvulcanized sheet was produced according to the above <Preparation of laminate 1>. Then, the chlorosulfonated polyethylene unvulcanized sheet of formulation 1 was layered, and the chlorosulfonated polyethylene unvulcanized sheet of formulation 2 was further layered thereon, and then a laminate was produced using a hot compression molding machine. . The peel strength between each layer of the laminate was high, and the peel state was rubber fracture.
実施例２
表１のＣＲ配合において、ケイ素含有化合物としてデキシクレーを４０重量部配合した以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。強度は大きく、剥離状態はゴム破壊であった。
Example 2
A laminate was prepared in the same manner as in Example 1, except that 40 parts by weight of dexiclee was added as the silicon-containing compound in the CR composition of Table 1, and the peel strength and peeling state were confirmed. The strength was high, and the state of peeling was rubber failure.
実施例３
表１のＣＲ配合において、ケイ素含有化合物としてデキシクレーを８０重量部配合した以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。強度は大きく、剥離状態はゴム破壊であった。
Example 3
A laminate was produced in the same manner as in Example 1, except that 80 parts by weight of dexiclee was added as the silicon-containing compound in the CR formulation of Table 1, and the peel strength and peeling state were confirmed. The strength was high, and the state of peeling was rubber failure.
実施例４
用いるクロロスルホン化ポリエチレン未加硫物を配合１と３に変更した以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。強度は大きく、剥離状態はゴム破壊であった。
Example 4
A laminate was produced in the same manner as in Example 1 except that the chlorosulfonated polyethylene unvulcanized material used was changed to formulations 1 and 3, and the peel strength and peel state were confirmed. The strength was high, and the state of peeling was rubber failure.
実施例５
用いるクロロスルホン化ポリエチレン未加硫物を配合１と４に変更した以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。強度は大きく、剥離状態はゴム破壊であった。
Example 5
A laminate was produced in the same manner as in Example 1, except that the chlorosulfonated polyethylene unvulcanized product used was changed to compounds 1 and 4, and the peel strength and peel state were confirmed. The strength was high, and the state of peeling was rubber failure.
実施例６
上記＜積層体の作製２＞に従い、クロロプレン未加硫物をトルエンに溶解して接着剤として塗布した以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。強度は大きく、剥離状態はゴム破壊であった。
Example 6
A laminate was produced in the same manner as in Example 1 except that the chloroprene unvulcanized product was dissolved in toluene and applied as an adhesive according to the above <Preparation of laminate 2>, and the peel strength and peeling state were confirmed. The strength was high, and the state of peeling was rubber failure.
実施例７
上記＜積層体の作製２＞に従い、クロロプレン未加硫物をトルエンに溶解して接着剤として塗布した以外は実施例３と同様に積層体を作製し、剥離強度と剥離状態を確認した。強度は大きく、剥離状態はゴム破壊であった。
Example 7
A laminate was produced in the same manner as in Example 3, except that the unvulcanized chloroprene was dissolved in toluene and applied as an adhesive according to the above <Preparation of laminate 2>, and the peel strength and peeling state were confirmed. The strength was high, and the state of peeling was rubber failure.
比較例１
クロロプレンゴムに配合するシリカの量を１０重量部とした以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。結果を表３に示す。強度は小さく、剥離状態は界面破壊であった。
Comparative example 1
A laminate was produced in the same manner as in Example 1, except that the amount of silica compounded in the chloroprene rubber was changed to 10 parts by weight, and the peel strength and peel state were confirmed. Table 3 shows the results. The strength was small, and the state of peeling was interfacial failure.
比較例２
クロロプレンゴムに配合するケイ素含有化合物をデキシクレー１５重量部とした以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。結果を表３に示す。強度は小さく、剥離状態は界面破壊であった。
Comparative example 2
A laminate was produced in the same manner as in Example 1 except that 15 parts by weight of dexiclee was used as the silicon-containing compound to be blended with the chloroprene rubber, and the peel strength and the peel state were confirmed. Table 3 shows the results. The strength was small, and the state of peeling was interfacial failure.
比較例３
クロロプレンゴムに配合するケイ素含有化合物をデキシクレー１２０重量部とした以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。結果を表３に示す。強度は小さく、剥離状態は界面破壊であった。
Comparative example 3
A laminate was produced in the same manner as in Example 1 except that 120 parts by weight of dexiclee was used as the silicon-containing compound to be blended with the chloroprene rubber, and the peel strength and the peel state were confirmed. Table 3 shows the results. The strength was small, and the state of peeling was interfacial failure.
比較例４
クロロプレンゴムに配合するシリカの量を１０重量部とし、用いるクロロスルホン化ポリエチレン未加硫物配合を１と３に変更した以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。結果を表３に示す。強度は小さく、剥離状態は界面破壊であった。
Comparative example 4
A laminate was prepared in the same manner as in Example 1, except that the amount of silica compounded in the chloroprene rubber was changed to 10 parts by weight and the compounding of the chlorosulfonated polyethylene unvulcanized product used was changed to 1 and 3, and the peel strength and peel state were measured. It was confirmed. Table 3 shows the results. The strength was small, and the state of peeling was interfacial failure.
比較例５
クロロプレンゴムに配合するシリカの量を１０重量部とし、用いるクロロスルホン化ポリエチレン未加硫物配合を１と４に変更した以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。結果を表３に示す。強度は小さく、剥離状態は界面破壊であった。
Comparative example 5
A laminate was prepared in the same manner as in Example 1, except that the amount of silica blended in the chloroprene rubber was 10 parts by weight, and the blend of the chlorosulfonated polyethylene unvulcanized product used was changed to 1 and 4, and the peel strength and peel state were measured. It was confirmed. Table 3 shows the results. The strength was small, and the state of peeling was interfacial failure.
比較例６
クロロプレンゴムにケイ素化合物を配合しなかった以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。結果を表３に示す。強度は小さく、剥離状態は界面破壊であった。
Comparative example 6
A laminate was produced in the same manner as in Example 1, except that the chloroprene rubber was not mixed with a silicon compound, and the peel strength and peel state were checked. Table 3 shows the results. The strength was small, and the state of peeling was interfacial failure.
比較例７
クロロプレンゴムにケイ素化合物を配合せず、用いるクロロスルホン化ポリエチレン未加硫物配合を１と３に変更した以外は実施例１と同様に積層体を作製し、剥離強度と剥離状態を確認した。結果を表３に示す。強度は小さく、剥離状態は界面破壊であった。
Comparative example 7
A laminate was produced in the same manner as in Example 1, except that the chloroprene rubber was not compounded with a silicon compound and the chlorosulfonated polyethylene unvulcanized compound was changed to 1 and 3, and the peel strength and peel state were confirmed. Table 3 shows the results. The strength was small, and the state of peeling was interfacial failure.
比較例８
ケイ素化合物を含まないクロロプレン未加硫物をトルエンに溶解して接着剤として接合する面に塗布・乾燥した以外は実施例３と同様に積層体を作製し、剥離強度と剥離状態を確認した。結果を表３に示す。強度は小さく、剥離状態は界面破壊であった。
Comparative example 8
A laminate was prepared in the same manner as in Example 3 except that a chloroprene unvulcanized product containing no silicon compound was dissolved in toluene and applied as an adhesive to the surfaces to be joined and dried, and the peel strength and peel state were confirmed. Table 3 shows the results. The strength was small, and the state of peeling was interfacial failure.
本発明のクロロスルホン化ポリオレフィンが強固に接着した積層体、およびその接着用組成物は、クロロスルホン化ポリオレフィンの優れた性能を有する２層ホースや被覆材作成などに利用することができる。 The laminates to which the chlorosulfonated polyolefins of the present invention are strongly adhered and the adhesive compositions therefor can be used to produce two-layer hoses and covering materials that have excellent performance of chlorosulfonated polyolefins.
Claims (6)
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