JP3594105B2 - Vulcanized adhesive composition - Google Patents
Vulcanized adhesive composition Download PDFInfo
- Publication number
- JP3594105B2 JP3594105B2 JP29565196A JP29565196A JP3594105B2 JP 3594105 B2 JP3594105 B2 JP 3594105B2 JP 29565196 A JP29565196 A JP 29565196A JP 29565196 A JP29565196 A JP 29565196A JP 3594105 B2 JP3594105 B2 JP 3594105B2
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- JP
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- Prior art keywords
- cresol
- mixture
- phenol resin
- adhesive composition
- novolak
- 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
Links
- 239000000203 mixture Substances 0.000 title claims description 33
- 239000000853 adhesive Substances 0.000 title claims description 19
- 230000001070 adhesive effect Effects 0.000 title claims description 19
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 26
- 239000005011 phenolic resin Substances 0.000 claims description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- 229920000800 acrylic rubber Polymers 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- 229920001967 Metal rubber Polymers 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 7
- 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 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 239000011134 resol-type phenolic resin Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- PHVAHRJIUQBTHJ-UHFFFAOYSA-N 3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1 PHVAHRJIUQBTHJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VPSXHKGJZJCWLV-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylpiperidin-4-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCN(CC1)CC VPSXHKGJZJCWLV-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 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
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- -1 p-substituted phenol Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、加硫接着剤組成物に関する。更に詳しくは、金属とアクリルゴムとの加硫接着に有効に用いられる加硫接着剤組成物に関する。
【０００２】
【従来の技術】
金属とアクリルゴムとの加硫接着に、フェノールやｐ−置換フェノールから導かれたノボラック型フェノール樹脂を主成分とし、これにヘキサメチレンテトラミンを硬化剤として添加した加硫接着剤組成物などが用いられている。しかしながら、このような加硫接着剤組成物には、次のような欠点がみられる。
（１）ヘキサメチレンテトラミンのガスが発生し、焼付炉内を汚染する
（２）硬化皮膜が着色する
（３）有効期限が短い
（４）他の接着剤塗布金具に付着すると、接着不良の原因となる
【０００３】
【発明が解決しようとする課題】
本発明の目的は、金属とアクリルゴムとの加硫接着に用いられる、ノボラック型フェノール樹脂を接着性成分とする加硫接着剤組成物であって、ヘキサメチレンテトラミンを硬化剤として使用し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】
かかる本発明の目的は、m-クレゾールとp-クレゾールとの混合物から得られたノボラック型フェノール樹脂を接着性成分とし、これに変性されていないレゾール型フェノール樹脂を硬化剤として添加し、金属への焼付が約１００〜２００℃の範囲で行なわれる加硫接着剤組成物によって達成される。
【０００５】
【発明の実施の形態】
本発明に係る加硫接着剤組成物の接着性成分は、ｍ−クレゾールとｐ−クレゾールとの混合物から得られたノボラック型フェノール樹脂よりなる。ノボラック型フェノール樹脂は、フェノール類とホルムアルデヒドとを酸性触媒（塩酸、しゅう酸等）の存在下で反応させることによって得られるが、その際フェノール類としてｍ−クレゾールとｐ−クレゾールとの混合物が用いられる。ここで用いられるｍ−クレゾールとｐ−クレゾールとの混合物は、コールタールより得られるクレゾール３異性体混合物からｏ−クレゾールを初留として除いた残渣のｍ−およびｐ−混合物としてとらえられる。
【０００６】
また、このようなノボラック型フェノール樹脂の硬化剤として用いられるレゾール型フェノール樹脂としては、フェノール類とホルムアルデヒドとを塩基性触媒（アルカリ金属、マグネシウムの水酸化物等）の存在下で反応させることによって得られる変性されていないものが使用されるが、その際のフェノール類としては、例えばフェノール、ｍ−クレゾールとｐ−クレゾールとの混合物、ｐ−第３ブチルフェノール、ｐ−フェニルフェノール、ビスフェノールＡ等のフェノール性水酸基に対してｏ−および／または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ものであれば任意のものを用いることができる。
【０００７】
ノボラック型フェノール樹脂とそれの硬化剤としてのレゾール型フェノール樹脂とは、前者の１００重量部に対して、後者が約１０〜２００重量部、好ましくは約４０〜７０重量部の割合で用いられる。レゾール型フェノール樹脂の割合がこれ以下では、ノボラック型フェノール樹脂の硬化が十分に行われず、一方これ以上の割合で用いられると、ゴムとの相溶性が悪くなる。これらのフェノール樹脂類は、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール等のアルコール類が一般に用いられる有機溶媒中に、約５〜２０重量％の固型分濃度で溶解させた有機溶媒溶液として調製されて用いられる。
【０００８】
このような有機溶媒溶液よりなる加硫接着剤組成物を用いての加硫接着は、軟鋼、ステンレススチール、アルミニウム、アルミニウムダイキャスト等の金属上にこれを塗布し、室温下で風乾させた後、約１００〜２００℃で約５〜１０分間程度の乾燥を行い、そこに未加硫のアクリルゴム配合物を接合させ、約１８０〜２００℃で加圧加硫させることによって行われる。
【０００９】
未加硫のアクリルゴム配合物としては、例えば次のようなものが用いられる。
【発明の効果】
本発明に係る加硫接着剤組成物は、約１００〜２００℃の広範囲の焼付温度での接着が可能であり、しかもその際の焼付は約３〜５分間程度の短時間で十分である。また、硬化剤として変性されていないレゾール型フェノール樹脂が用いられ、ヘキサメチレンテトラミンが用いられていないため、ヘキサメチレンテトラミンを用いたときみられるそれの飛散による焼付炉の汚染や接着不良等が防止される。
【００１１】
【実施例】
次に、実施例について本発明を説明する。
【００１２】
参考例１
（ｍ−クレゾール−ｐ−クレゾール混合物から得られたノボラック型フェノール樹脂）
ｍ，ｐ−クレゾール混合物を反応釜中で９５℃に加熱し、そこにしゅう酸を加えた後、攪拌しながら混合物がおだやかに沸騰するような添加速度でホルムアルデヒド溶液を加えた。このときの混合比は、ｍ，ｐ−クレゾール混合物１モルに対してしゅう酸が０．０２モル、ホルムアルデヒドが０．８５モルである。全部のホルムアルデヒド溶液を加え終った後、９５℃に約９０分間保った。その後、常圧蒸留で脱水し、更に真空中で１６０℃迄加熱し、未反応物を除去して目的物を得た。
【００１３】
参考例２
（フェノールから得られたノボラック型フェノール樹脂）
参考例１において、ｍ，ｐ−クレゾール混合物の代わりに、フェノールが用いられた。
【００１４】
参考例３
（ｍ−クレゾール−ｐ−クレゾール混合物から得られたレゾール型フェノール樹脂）
反応釜中にｍ，ｐ−クレゾール混合物、ホルムアルデヒド水溶液および水酸化バリウム・８水和物を加え、７０℃で２時間攪拌しながら加熱した。このときの混合比は、ｍ，ｐ−クレゾール混合物１モルに対してホルムアルデヒドが１．５モル、水酸化バリウム・８水和物が０．０２モルである。その後、ｐＨを６〜７にするのに十分な量の１０％硫酸を加えた。アスピレーターで減圧にし（約３０〜５０ｍｍＨｇ）、蒸留できるようにセットしたコンデンサを通して脱水し、目的物を得た。
【００１５】
参考例４
（ビスフェノールＡから得られたレゾール型フェノール樹脂）
参考例３において、ｍ，ｐ−クレゾール混合物の代わりに、ビスフェノールＡが用いられた。
【００１６】
参考例５
（フェノールから得られたレゾール型フェノール樹脂）
参考例３において、ｍ，ｐ−クレゾール混合物の代わりに、フェノールが用いられた。
【００１７】
実施例１
参考例１のノボラック型フェノール樹脂 ７重量部
参考例３のレゾール型フェノール樹脂 ３ 〃
メチルエチルケトン ９０ 〃
【００１８】
実施例２
参考例１のノボラック型フェノール樹脂 ５重量部
参考例４のレゾール型フェノール樹脂 ５ 〃
メチルエチルケトン ９０ 〃
【００１９】
比較例１
参考例１のノボラック型フェノール樹脂 １０重量部
ヘキサメチレンテトラミン １ 〃
メタノール ８９ 〃
【００２０】
比較例２
参考例２のノボラック型フェノール樹脂 １０重量部
ヘキサメチレンテトラミン １ 〃
メタノール ８９ 〃
【００２１】
比較例３
参考例２のノボラック型フェノール樹脂 ５重量部
参考例５のレゾール型フェノール樹脂 ５ 〃
メチルエチルケトン ９０ 〃
【００２２】
以上の各成分からなる実施例１〜２および比較例１〜３の加硫接着剤組成物を、リン酸亜鉛処理した軟鋼板上に塗布し、室温条件下に１０分間放置して風乾させた後、１２０℃、１５０℃、１８０℃または２００℃の各焼付温度で５分間の焼付処理が行われた。
【００２３】
これらの加硫接着剤焼付軟鋼板に、前記配合例Ｉ〜ＩＩの未加硫アクリルゴムコンパウンドを接合させ、２００℃、４分間の加圧加硫が行われた。得られた接着物について、９０°剥離試験による接着強度およびゴム残り面積率の測定が行われた。
【００２４】
得られた結果は、次の表に示される。
【００２６】
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a vulcanized adhesive composition. More specifically, the present invention relates to a vulcanized adhesive composition which is effectively used for vulcanizing adhesion between a metal and an acrylic rubber.
[0002]
[Prior art]
For vulcanization adhesion between metal and acrylic rubber, a vulcanization adhesive composition containing a novolak-type phenol resin derived from phenol or p-substituted phenol as a main component and adding hexamethylenetetramine as a curing agent thereto is used. Have been. However, such vulcanized adhesive compositions have the following disadvantages.
(1) Hexamethylenetetramine gas is generated and contaminates the inside of the baking furnace. (2) The cured film is colored. (3) The expiration date is short. (4) If it adheres to other adhesive coating hardware, it may cause poor adhesion. [0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a vulcanized adhesive composition containing a novolak-type phenol resin as an adhesive component, which is used for vulcanization bonding between a metal and an acrylic rubber, and does not use hexamethylenetetramine as a curing agent. To provide.
[0004]
[Means for Solving the Problems]
An object of the present invention is to provide a novolak-type phenol resin obtained from a mixture of m-cresol and p-cresol as an adhesive component, and to add a non-modified resol-type phenol resin as a curing agent to the metal. Is achieved by a vulcanized adhesive composition in which baking is carried out at a temperature in the range of about 100 to 200 ° C.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
The adhesive component of the vulcanized adhesive composition according to the present invention comprises a novolak-type phenol resin obtained from a mixture of m-cresol and p-cresol. The novolak-type phenol resin is obtained by reacting phenols with formaldehyde in the presence of an acidic catalyst (hydrochloric acid, oxalic acid, etc.). In this case, a mixture of m-cresol and p-cresol is used as the phenol. Can be The mixture of m-cresol and p-cresol used herein is regarded as an m- and p-mixture of a residue obtained by removing o-cresol as a first distillation from a cresol 3 isomer mixture obtained from coal tar.
[0006]
As the resol type phenol resin used as a curing agent of such a novolak phenolic resin by reacting a phenol and formaldehyde in the presence of a basic catalyst (alkali metal hydroxides such as magnesium) The obtained unmodified product is used . Examples of the phenols at this time include phenol, a mixture of m-cresol and p-cresol, p-tert-butylphenol, p-phenylphenol, bisphenol A and the like. Any one can be used as long as it has two or three substitutable nuclear hydrogen atoms at the o- and / or p-positions with respect to the phenolic hydroxyl group.
[0007]
The novolak-type phenol resin and the resol-type phenol resin as a curing agent thereof are used in an amount of about 10 to 200 parts by weight, preferably about 40 to 70 parts by weight, based on 100 parts by weight of the former. When the proportion of the resol-type phenolic resin is less than this, the novolak-type phenolic resin is not sufficiently cured, while when used at a higher proportion, the compatibility with the rubber deteriorates. These phenolic resins are prepared as an organic solvent solution in which ketones such as acetone and methyl ethyl ketone and alcohols such as methanol and ethanol are dissolved in a generally used organic solvent at a solid content of about 5 to 20% by weight. It is prepared and used.
[0008]
Vulcanization bonding using a vulcanizing adhesive composition comprising such an organic solvent solution is applied on a metal such as mild steel, stainless steel, aluminum, or aluminum die cast, and air-dried at room temperature. and drying of about 5 to 10 minutes at about 100 to 200 ° C., there is bonded the unvulcanized acrylic rubber compounds, is carried out by press vulcanization at about 180 to 200 ° C..
[0009]
As the unvulcanized acrylic rubber compound, for example, the following are used.
【The invention's effect】
The vulcanized adhesive composition according to the present invention is capable of bonding at a wide range of baking temperatures of about 100 to 200 ° C., and in that case, baking in a short time of about 3 to 5 minutes is sufficient. Furthermore, resol-type phenolic resin which is not modified is used, since no hexamethylenetetramine is used, contamination or adhesion failure, etc. of the baking furnace by Tokizane is that of scattered with hexamethylenetetramine prevention as a curing agent Is done.
[0011]
【Example】
Next, the present invention will be described with reference to examples.
[0012]
Reference Example 1
(Novolak-type phenol resin obtained from m-cresol-p-cresol mixture)
The m, p-cresol mixture was heated to 95 ° C in a reaction kettle, oxalic acid was added thereto, and then the formaldehyde solution was added with stirring at a rate such that the mixture boiled gently. The mixing ratio at this time is 0.02 mol of oxalic acid and 0.85 mol of formaldehyde with respect to 1 mol of the m, p-cresol mixture. After all the formaldehyde solution was added, the mixture was kept at 95 ° C. for about 90 minutes. Thereafter, the product was dehydrated by atmospheric distillation, and further heated to 160 ° C. in a vacuum to remove unreacted substances to obtain an intended product.
[0013]
Reference Example 2
(Novolak type phenol resin obtained from phenol)
In Reference Example 1, phenol was used instead of the m, p-cresol mixture.
[0014]
Reference Example 3
(Resol type phenol resin obtained from m-cresol-p-cresol mixture)
An m, p-cresol mixture, an aqueous formaldehyde solution and barium hydroxide octahydrate were added into a reaction vessel, and the mixture was heated at 70 ° C. with stirring for 2 hours. The mixing ratio at this time is 1.5 mol of formaldehyde and 0.02 mol of barium hydroxide octahydrate per 1 mol of the m, p-cresol mixture. Thereafter, sufficient 10% sulfuric acid was added to bring the pH to 6-7. The pressure was reduced with an aspirator (approximately 30 to 50 mmHg), and the solution was dehydrated through a condenser set so that distillation could be performed, to obtain an intended product.
[0015]
Reference example 4
(Resole type phenol resin obtained from bisphenol A)
In Reference Example 3, bisphenol A was used instead of the m, p-cresol mixture.
[0016]
Reference example 5
(Resol type phenol resin obtained from phenol)
In Reference Example 3, phenol was used instead of the m, p-cresol mixture.
[0017]
Example 1
Novolak type phenolic resin of Reference Example 7 7 parts by weight Resol type phenolic resin of Reference Example 3
Methyl ethyl ketone 90〃
[0018]
Example 2
Novolak type phenolic resin of Reference Example 1 5 parts by weight Resol type phenolic resin of Reference Example 4 5%
Methyl ethyl ketone 90〃
[0019]
Comparative Example 1
Novolak type phenol resin of Reference Example 1 10 parts by weight hexamethylenetetramine 1%
89% methanol
[0020]
Comparative Example 2
Novolak type phenol resin of Reference Example 10 10 parts by weight hexamethylenetetramine 1%
89% methanol
[0021]
Comparative Example 3
Novolak type phenolic resin of Reference Example 2 5 parts by weight Resol type phenolic resin of Reference Example 5
Methyl ethyl ketone 90〃
[0022]
The vulcanized adhesive compositions of Examples 1 and 2 and Comparative Examples 1 to 3 composed of the above components were applied on a mild steel plate treated with zinc phosphate, and allowed to stand at room temperature for 10 minutes and air-dried. Thereafter, a baking treatment was performed at 120 ° C., 150 ° C., 180 ° C., or 200 ° C. for 5 minutes.
[0023]
The unvulcanized acrylic rubber compounds of Formulation Examples I and II were joined to these vulcanized adhesive-baked mild steel sheets, and pressure-cured at 200 ° C. for 4 minutes. With respect to the obtained adhesive, the adhesive strength and the remaining rubber area ratio were measured by a 90 ° peel test.
[0024]
The results obtained are shown in the following table .
[0026]
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29565196A JP3594105B2 (en) | 1996-10-17 | 1996-10-17 | Vulcanized adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29565196A JP3594105B2 (en) | 1996-10-17 | 1996-10-17 | Vulcanized adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10121020A JPH10121020A (en) | 1998-05-12 |
| JP3594105B2 true JP3594105B2 (en) | 2004-11-24 |
Family
ID=17823412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29565196A Expired - Fee Related JP3594105B2 (en) | 1996-10-17 | 1996-10-17 | Vulcanized adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3594105B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4571263B2 (en) * | 2000-02-25 | 2010-10-27 | 株式会社ブリヂストン | Adhesive rubber composition |
| EP1593726B1 (en) * | 2003-02-12 | 2013-08-21 | Nok Corporation | Water-based vulcanizable adhesive composition |
| JP4929807B2 (en) | 2006-04-13 | 2012-05-09 | Ｎｏｋ株式会社 | Vulcanized adhesive composition |
| JP4876683B2 (en) | 2006-04-13 | 2012-02-15 | Ｎｏｋ株式会社 | Acrylic rubber-metal composite |
| JP4935902B2 (en) | 2007-06-06 | 2012-05-23 | Ｎｏｋ株式会社 | Acrylic rubber-metal composite |
| JP5943166B2 (en) | 2014-05-08 | 2016-06-29 | Nok株式会社 | Ethylene acrylic rubber composition, ethylene acrylic rubber, rubber metal composite and bonded piston seal |
-
1996
- 1996-10-17 JP JP29565196A patent/JP3594105B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10121020A (en) | 1998-05-12 |
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