JP4335498B2 - Adhesive composition for vulcanization adhesion - Google Patents
Adhesive composition for vulcanization adhesion Download PDFInfo
- Publication number
- JP4335498B2 JP4335498B2 JP2002209473A JP2002209473A JP4335498B2 JP 4335498 B2 JP4335498 B2 JP 4335498B2 JP 2002209473 A JP2002209473 A JP 2002209473A JP 2002209473 A JP2002209473 A JP 2002209473A JP 4335498 B2 JP4335498 B2 JP 4335498B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- silane coupling
- water
- vulcanization
- coupling agent
- 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.)
- Expired - Fee Related
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- 239000000853 adhesive Substances 0.000 title claims description 26
- 230000001070 adhesive effect Effects 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 title claims description 14
- 238000004073 vulcanization Methods 0.000 title claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- -1 alkylene glycol monoalkyl ether Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920003987 resole Polymers 0.000 claims description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 239000003021 water soluble solvent Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920001973 fluoroelastomer Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 229920001967 Metal rubber Polymers 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、加硫接着用接着剤組成物に関する。更に詳しくは、金属とフッ素ゴムとの接着に優れ、水ベースであることを特徴とする加硫接着用接着剤組成物に関する。
【０００２】
【従来技術の内容】
従来、金属とフッ素ゴムとの加硫接着用接着剤としては、樹脂、硬化剤、シランカップリング剤、ゴム等をシンナー、アルコール、メチルエチルケトン等有機溶剤を用いて溶解させた溶剤型接着剤が用いられる。これは、接着剤の原料が溶剤にのみ溶解することに起因する。しかしながら、近年、これらの溶剤の揮散による環境汚染が深刻な問題としてクローズアップされるようになり、環境にやさしい水性塗料や無溶剤型接着剤の開発の必要性が高まってきている。
具体的な対策として、接着成分を水溶性のシランカップリング剤のみとしたり、水溶性樹脂やエマルジョン型樹脂等の開発がなされているが、水溶性のシランカップリング剤のみでは耐水接着性に劣り、水溶性樹脂やエマルジョン型樹脂には界面活性剤等、接着を阻害する成分が少なからず含まれる事もあり、接着性能が現行より劣るのが現状である。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、レゾール型フェノール樹脂とシランカップリング剤を接着成分とし、不揮発性で水との相溶性が良く、ＢＴＸを排除した溶剤と水を溶媒として使用した水系の加硫接着剤組成物を得ることであり、更には、従来の接着性能を維持し、かつ環境面、作業場での衛生安全面上悪影響を与えないものを提供することにある。
【０００４】
【課題を解決するための手段】
本発明の目的は、接着成分としてレゾール型フェノール樹脂、シランカップリング剤、溶剤としてエチレングリコールモノアルキルエーテル、水からなる加硫接着用接着剤組成物によって達成される。
【０００５】
本発明である加硫接着剤組成物の接着成分として用いられるレゾール型フェノール樹脂は、以下の化１のような一般式で表され、これは、アルカリ金属等塩基性触媒下、フェノール類とホルムアルデヒドを反応させることにより得られる。ここで、フェノール類の例としては、ｍ−及びｐ−クレゾール、これらの混合物、フェノール、ビスフェノールA等が挙げられ、フェノール性水酸基に対して０−或いはｐ−位に２個または３個の置換可能な核水素原子を有する物であれば使用可能である。レゾール系フェノール樹脂としては、全１００重量部に対し１−１０重量部使用する。
【０００６】
【課題を解決するための手段】
同様に、本接着成分として使用されるアミノ系シランカップリング剤としては、以下の化２のような一般式で表される。式中のＲはアミノ基、Ｎ−β（アミノエチル）γ−アミノ基等のアミノ基を表わすことができ、Ｒ′はアルコキシ基を表わすことができ、ｍは０−１を表わす。アミノ系シランカップリング剤の代表的具体例としては、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン等を挙げることができる。アミノ系シランカップリング剤としては、全１００重量部に対し１−１０重量部使用する。
【０００７】
【化２】
本発明である加硫接着剤組成物の溶剤として使用されるエチレングリコールモノアルキルエーテルは以下の化３ような一般式で表される。
【０００９】
【化３】
ここで、Rはアルキル基を示す。エチレングリコールモノアルキルエーテルの具体例としては、エチレングリコールモノブチルエーテル、エチレングリコールモノイソプロピルエーテル等が挙げられる。
エチレングリコールモノアルキルエーテルとしては、全１００重量部に対し５−９９重量部、好ましくは１０−５０重量部使用する。エチレングリコールモノアルキルエーテルの割合がこの範囲以下になると樹脂が溶解し難く、また、水との混合性も悪くなる。エチレングリコールモノアルキルエーテルの割合が多いほど溶液としての安定性は優れる。
【００１１】
【実施例】
本発明の実施例について以下に述べる。
【表１】
上記の処理済み金属板上に、フッ素ゴムの未加硫配合物を１９０℃、４ｍｉｎでプレス加硫を行った。
以上の実施例及び比較例で得られた加硫接着物について、社内規格に基づき、初期、熱水(９５℃)浸漬試験後のゴム剥離試験を行った。結果を表２に示す。
【００１２】
【表２】
【発明の効果】
上記、各実施例、比較例より明らかなように、本発明で得られた加硫接着用接着剤組成物を用いることで、環境面、作業場での衛生安全面に負荷を与えることなく、従来通りの接着性能を維持できるようになった。[0001]
[Industrial application fields]
The present invention relates to an adhesive composition for vulcanization adhesion. More specifically, the present invention relates to an adhesive composition for vulcanization adhesion, which is excellent in adhesion between metal and fluororubber and is water-based.
[0002]
[Contents of prior art]
Conventionally, as adhesives for vulcanization adhesion between metal and fluoro rubber, solvent type adhesives in which resin, curing agent, silane coupling agent, rubber, etc. are dissolved using organic solvents such as thinner, alcohol, methyl ethyl ketone, etc. have been used. It is done. This is due to the fact that the raw material of the adhesive dissolves only in the solvent. However, in recent years, environmental pollution due to the volatilization of these solvents has become a serious problem, and the need for the development of environmentally friendly water-based paints and solventless adhesives has increased.
As specific countermeasures, water-soluble silane coupling agents are used as the only adhesive component, and water-soluble resins and emulsion type resins have been developed. However, water-soluble silane coupling agents alone are inferior in water-resistant adhesion. In addition, the water-soluble resin and the emulsion type resin sometimes contain not only a component such as a surfactant, but also the adhesive performance is inferior to the present.
[0003]
[Problems to be solved by the invention]
An object of the present invention is an aqueous vulcanized adhesive composition using a resol type phenolic resin and a silane coupling agent as an adhesive component, non-volatile and having good compatibility with water, and using a solvent excluding BTX and water as a solvent. It is another object of the present invention to provide a product that maintains the conventional adhesive performance and does not adversely affect the environment and the health and safety of the workplace.
[0004]
[Means for Solving the Problems]
The object of the present invention is achieved by an adhesive composition for vulcanization adhesion comprising a resol type phenol resin as a bonding component, a silane coupling agent, an ethylene glycol monoalkyl ether as a solvent, and water.
[0005]
The resol type phenol resin used as an adhesive component of the vulcanized adhesive composition of the present invention is represented by the general formula as shown in the following chemical formula 1, which is based on phenols and formaldehyde under a basic catalyst such as an alkali metal. It is obtained by reacting. Here, examples of phenols include m- and p-cresol, mixtures thereof, phenol, bisphenol A, etc., and 2 or 3 substitutions at the 0- or p-position with respect to the phenolic hydroxyl group. Any material having a possible nuclear hydrogen atom can be used. As a resol type phenol resin, 1-10 weight part is used with respect to 100 weight part in total.
[0006]
[Means for Solving the Problems]
Similarly, the amino silane coupling agent used as the adhesive component is represented by the general formula as shown in the following chemical formula 2. In the formula, R can represent an amino group such as an amino group or N-β (aminoethyl) γ-amino group, R ′ can represent an alkoxy group, and m represents 0-1. Typical examples of the amino silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (amino And ethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, and the like. As an amino-type silane coupling agent, 1-10 weight part is used with respect to 100 weight part in total .
[0007]
[Chemical formula 2]
The ethylene glycol monoalkyl ether used as a solvent for the vulcanized adhesive composition of the present invention is represented by the following general formula.
[0009]
[Chemical 3]
Here, R represents an alkyl group. Specific examples of ethylene glycol monoalkyl ether include ethylene glycol monobutyl ether and ethylene glycol monoisopropyl ether.
The ethylene glycol monoalkyl ether is used in an amount of 5-99 parts by weight, preferably 10-50 parts by weight, based on 100 parts by weight. If the proportion of ethylene glycol monoalkyl ether is below this range, the resin is difficult to dissolve and the miscibility with water also deteriorates. The greater the proportion of ethylene glycol monoalkyl ether, the better the stability as a solution.
[0011]
【Example】
Examples of the present invention will be described below.
[Table 1]
On the treated metal plate, the unvulcanized compound of fluororubber was subjected to press vulcanization at 190 ° C. for 4 minutes.
The vulcanized adhesives obtained in the above Examples and Comparative Examples were initially subjected to a rubber peeling test after a hot water (95 ° C.) immersion test based on in-house standards. The results are shown in Table 2.
[0012]
[Table 2]
【The invention's effect】
As is clear from each of the above examples and comparative examples, by using the adhesive composition for vulcanization adhesion obtained in the present invention, it is not necessary to give a load to the environment and the sanitary safety aspect in the workplace. The street adhesive performance can be maintained.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002209473A JP4335498B2 (en) | 2002-07-18 | 2002-07-18 | Adhesive composition for vulcanization adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002209473A JP4335498B2 (en) | 2002-07-18 | 2002-07-18 | Adhesive composition for vulcanization adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004051735A JP2004051735A (en) | 2004-02-19 |
| JP4335498B2 true JP4335498B2 (en) | 2009-09-30 |
Family
ID=31933308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002209473A Expired - Fee Related JP4335498B2 (en) | 2002-07-18 | 2002-07-18 | Adhesive composition for vulcanization adhesion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4335498B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4626315B2 (en) * | 2005-01-25 | 2011-02-09 | Ｎｏｋ株式会社 | Vulcanized adhesive composition |
| JP4957052B2 (en) * | 2006-04-04 | 2012-06-20 | Ｎｏｋ株式会社 | Vulcanized adhesive composition |
| JP2024052040A (en) * | 2022-09-30 | 2024-04-11 | 内山工業株式会社 | Vulcanizable adhesive composition |
-
2002
- 2002-07-18 JP JP2002209473A patent/JP4335498B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004051735A (en) | 2004-02-19 |
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