JPS62230820A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPS62230820A JPS62230820A JP7502086A JP7502086A JPS62230820A JP S62230820 A JPS62230820 A JP S62230820A JP 7502086 A JP7502086 A JP 7502086A JP 7502086 A JP7502086 A JP 7502086A JP S62230820 A JPS62230820 A JP S62230820A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- parts
- resin composition
- component
- curing 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 17
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 15
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 238000004438 BET method Methods 0.000 abstract description 2
- 229920000571 Nylon 11 Polymers 0.000 abstract description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- -1 sheet Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000007665 sagging Methods 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 150000001354 dialkyl silanes Chemical class 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はエポキシ樹脂組成物に関し、さらに詳しくは接
着剤、塗料等に有利に用いられるエポキシ樹脂組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition that is advantageously used in adhesives, paints, and the like.
エポキシ樹脂は電気絶縁性、耐熱性、防食性、接着性等
の優れた特性を有しており、使用形態も液状、ペースト
状、シート状、粉末状と選択できるため各種分野で使用
されている。また、各種成分の配合が可能であり、使用
目的に応じて硬化物特性を変えることが可能であること
も、幅広く使用されている理由の１つになっている。Epoxy resin has excellent properties such as electrical insulation, heat resistance, corrosion resistance, and adhesiveness, and can be used in liquid, paste, sheet, or powder forms, so it is used in various fields. . In addition, it is possible to mix various components and change the properties of the cured product depending on the purpose of use, which is one of the reasons why it is widely used.
しかしながら、このように優れた特性を有するエポキシ
樹脂も剥離接着性、耐湿性、耐水性等の特性に未だ満足
できない点があり、接着界面の剥＾１１や耐湿性、耐水
性等の要求される用途に対する信頼性に欠ける問題を有
している。However, even with such excellent properties, epoxy resins still have some unsatisfactory properties such as peel adhesion, moisture resistance, and water resistance. It has a problem of lack of reliability for the purpose.
このため、かかるエポキシ樹脂に対してポリアミド樹脂
を混合して上記の特性を改良する試みがなされた（例え
ば、特開昭５９−４６１９号）。For this reason, attempts have been made to improve the above-mentioned properties by mixing polyamide resins with such epoxy resins (for example, JP-A-59-4619).
この種のエボキシーボリアミト樹脂組成物は、剥離接着
性においては充分に実用に耐えるものとなったが、使用
する環境によっては耐湿性及び耐水性に欠ける場合があ
り、その特性の改良が望まれていた。Although this type of epoxy boria mite resin composition has become sufficiently practical in terms of peel adhesion, it may lack moisture resistance and water resistance depending on the environment in which it is used, so it is desirable to improve its properties. It was rare.
そこで、本発明者らは、液状エポキシ樹脂に粉束状ポリ
アミド樹脂と共に疎水性微粉末シリカを混合することに
より上記問題点を解決したエポキシ樹脂組成物が得られ
ることを見出し本発明に至ったものである。Therefore, the present inventors discovered that an epoxy resin composition that solved the above problems could be obtained by mixing a powder bundle polyamide resin and a hydrophobic finely powdered silica with a liquid epoxy resin, which led to the present invention. It is.
即ち、本発明は耐湿性に優れたエポキシ樹脂組成物に関
し、（イ）液状エポキシ樹脂１０（ｌｆｆｉ部、（ロ）
粉末状ポリアミド樹脂５〜５０重量部、（ハ）疎水性微
粉末シリカ０．５〜１０重量部、及び、（ニ）適量の硬
化剤を含有して成ることを特徴とするものである。That is, the present invention relates to an epoxy resin composition with excellent moisture resistance, including (a) liquid epoxy resin 10 (lffi part), (b)
It is characterized by containing 5 to 50 parts by weight of a powdered polyamide resin, (c) 0.5 to 10 parts by weight of hydrophobic finely powdered silica, and (d) an appropriate amount of a curing agent.
本発明において用いられるエポキシ樹脂とは１分子中に
平均２個以上のエポキシ基を有する常温（２５℃）で液
状のエポキシ樹脂を挙げることが ”でき、その具体例
としては、ビスフェノールＡ型エポキシ樹脂が好適であ
り、その他、環状脂肪族エポキシ樹脂、ヒダントイン型
エポキシ樹脂、ノボラック型エポキシ樹脂、グリシジル
エステル型エポキシ樹脂等を例示することができ、本発
明ではこれらを単独、または２種以上混合して使用する
ことができる。上記エポキシ樹脂は通常エポキシ当ｆｆ
１１００〜３０００のものが好適に用いられる。また、
本発明では固形のエポキシ樹脂を液状エポキシ樹脂に溶
解させて液状で用いることもできる。The epoxy resins used in the present invention include epoxy resins that have an average of two or more epoxy groups in one molecule and are liquid at room temperature (25°C). Specific examples include bisphenol A epoxy resins. Other suitable examples include cycloaliphatic epoxy resins, hydantoin type epoxy resins, novolac type epoxy resins, glycidyl ester type epoxy resins, etc. In the present invention, these can be used alone or in combination of two or more types. The above epoxy resins are usually epoxy resins.
1100 to 3000 is preferably used. Also,
In the present invention, a solid epoxy resin can be dissolved in a liquid epoxy resin and used in liquid form.
次に、本発明で用いられる粉末状ポリアミド樹脂は特に
限定はされないが、加熱時におけるエポキシ樹脂との相
溶性が良好な、粒子径２００μｍ以下の粉末を９０重量
％以上含有する粉末状物であることが好ましい。粒子径
が大きすぎるとエポキシ樹脂組成物の塗布時の作業性が
低下する、均一な厚みに塗布することが困難である、接
着力にばらつきが発生する等の欠点を生ずる場合があり
、実用的であるとは言い難い。Next, the powdered polyamide resin used in the present invention is not particularly limited, but it is a powdered material containing 90% by weight or more of powder with a particle size of 200 μm or less, which has good compatibility with the epoxy resin during heating. It is preferable. If the particle size is too large, there may be disadvantages such as reduced workability when applying the epoxy resin composition, difficulty in applying it to a uniform thickness, and variations in adhesive strength. It is difficult to say that it is.
粉末状ポリアミド樹脂の使用量は、液状エポキシ樹脂１
００重量部に対して５〜５０重量部、好ましくは１０〜
３０重量部である。使用量が５重量部未満であると得ら
れる硬化物にｊ／Ｊｌ １７ｊｆｆ接着性、耐薬品性等
の向上がみられず、５０重量部を越えると混合後の性状
が常温でパテ状となり常温での均一混合が困難になる。The amount of powdered polyamide resin used is 1 part of liquid epoxy resin.
5 to 50 parts by weight, preferably 10 to 00 parts by weight
It is 30 parts by weight. If the amount used is less than 5 parts by weight, no improvement in adhesion, chemical resistance, etc. will be observed in the resulting cured product, and if it exceeds 50 parts by weight, the properties after mixing will become putty-like at room temperature. It becomes difficult to mix uniformly.
また、ポリアミド樹脂の特に好適な例としては融点が低
く、エポキシ樹脂との相溶性に特に優れるナイロン１１
、ナイロン１２、及びこれらの共重合ナイロン等が挙げ
られる。In addition, a particularly suitable example of polyamide resin is nylon 11, which has a low melting point and has particularly excellent compatibility with epoxy resin.
, nylon 12, and copolymerized nylons thereof.
本発明で用いられる疎水性微粉末シリカは、通常の微粉
末シリカに比べ吸湿量が小さい。そして本発明ではこの
疎水性微粉末シリカを配合することにより、エポキシ樹
脂組成物の耐湿性を向上させ、ポットライフを改善する
と共に、硬化時の非垂下性に優れ且つ該組成物の硬化物
の耐湿性、耐水性も向上させることができる。The hydrophobic fine powder silica used in the present invention has a smaller amount of moisture absorption than ordinary fine powder silica. In the present invention, by blending this hydrophobic fine powder silica, the moisture resistance of the epoxy resin composition is improved, the pot life is improved, and the cured product of the composition has excellent non-sagging properties during curing. Moisture resistance and water resistance can also be improved.
上記疎水性微粉末シリカとしては、例えば通常の微粉末
シリカの表面のシラノール基がジアルキルシラン等によ
りシロキサン結合に変換されたものを挙げることができ
る。Examples of the above-mentioned hydrophobic fine powder silica include those obtained by converting the silanol groups on the surface of ordinary fine powder silica into siloxane bonds with dialkylsilane or the like.
疎水性微粉末シリカは液状エポキシ樹脂ｌＯＯ重量部に
対し゛ζ０．５〜１０重量部、好ましくは１〜８重量部
の範囲で用いられる。０．５重量部未満の場合は、得ら
れる硬化物の耐湿性、耐水性の向上が顕著でなく、１０
重皿部を越えると液状エポキシ樹脂に均一に分散するの
が困難になる。The hydrophobic fine powder silica is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, per 10 parts by weight of the liquid epoxy resin. If the amount is less than 0.5 parts by weight, the moisture resistance and water resistance of the resulting cured product will not improve significantly, and the
If it exceeds the heavy plate part, it becomes difficult to uniformly disperse it in the liquid epoxy resin.
また、該シリカはＢＥＴ法による表面積３５〜１３０ｍ
２／ｇ、粒子平均径１５〜４０μｍのものが好ましく、
この範囲外では液状エポキシ樹脂への分散性が低下し、
効果の向上度合が不充分になることがある。より好まし
くは、そのｌ３ＥＴ法による表面積１００ｍ”当たりの
吸湿量（２５°Ｃ１相対湿度８０％の空気中における測
定値、以下、単に吸湿量という）が１．５ｍｇ以下のも
のでありこの範囲外では得られる硬化物の耐湿性、耐水
性の向上があまり見られない。In addition, the silica has a surface area of 35 to 130 m by the BET method.
2/g, and preferably has an average particle diameter of 15 to 40 μm,
Outside this range, the dispersibility in liquid epoxy resin decreases,
The degree of improvement in effectiveness may be insufficient. More preferably, the amount of moisture absorbed per 100 m'' of surface area by the 13ET method (measured value in air at 25°C and 80% relative humidity, hereinafter simply referred to as moisture absorption) is 1.5 mg or less, and outside this range There is not much improvement in the moisture resistance and water resistance of the resulting cured product.
本発明において用いられる硬化剤としては、粉末状のも
のを用いるのが好ましく、ジシアンジアミド、イミダゾ
ール化合物、Ｂ Ｆ ：ｌ ’１６体、ヒドラジッド誘
導体等を挙げることができ、本発明組成物の保存性、分
散性の観点から粒子径５μｍ以下の粉末を９０重量％以
上含有する微粉末状ジシアンジアミドが特に好ましい。As the curing agent used in the present invention, it is preferable to use a powdered one, and examples thereof include dicyandiamide, imidazole compounds, B F :l '16 body, hydrazide derivatives, etc. From the viewpoint of dispersibility, finely powdered dicyandiamide containing 90% by weight or more of powder with a particle size of 5 μm or less is particularly preferred.
また、粒子径の粗い硬化剤では均一分散が難しく硬化が
不均一になりやすく、硬化時に未反応で残存した硬化剤
が高温雰囲気下で溶出して耐水性、耐湿性の低下を引き
起こす原因となることがある。硬化剤の使用量は種々の
条件により異なるが通常は液状エポキシ樹脂１００重量
部に対して２〜２０重量部程度である。In addition, if the curing agent has a coarse particle size, it is difficult to disperse it uniformly and curing tends to be uneven, and the curing agent that remains unreacted during curing may elute in a high-temperature atmosphere, causing a decrease in water resistance and moisture resistance. Sometimes. The amount of curing agent used varies depending on various conditions, but is usually about 2 to 20 parts by weight per 100 parts by weight of the liquid epoxy resin.
本発明では粉末状の硬化剤に代えて、あるいはそれと共
に液状の硬化剤を用いることもでき、液状の硬化剤とし
ては例えばアミン系硬化剤、液状酸無水物等を挙げるこ
とができ、より具体的には脂肪族ポリアミン、芳香族ポ
リアミン、無水フタール酸等を挙げることができる。In the present invention, a liquid curing agent can be used instead of or together with a powdered curing agent. Examples of the liquid curing agent include amine-based curing agents, liquid acid anhydrides, etc. Examples include aliphatic polyamines, aromatic polyamines, and phthalic anhydride.
本発明においては、エポキシ樹脂組成物の各成分の混合
方法は特に限定はされず、例えば液状エポキシ樹脂中に
前記割合の粉末状ポリアミド樹脂、疎水性微粉末シリカ
及び適量の硬化剤を加え常温で攪拌混合して調整できる
が、この混合に当たって硬化促進剤、充填剤、添加剤等
の任意成分を同時に添加混合することができる。In the present invention, the method of mixing each component of the epoxy resin composition is not particularly limited. For example, the powdered polyamide resin, hydrophobic fine powder silica, and an appropriate amount of curing agent are added to the liquid epoxy resin in the above proportions, and the mixture is heated at room temperature. The composition can be adjusted by stirring and mixing, and optional components such as a curing accelerator, filler, and additives can be added and mixed at the same time during this mixing.
また、他の方法としては液状エポキシ樹脂を主成分とし
た配合系と硬化剤を主成分とした配合系に分けて使用す
る直前に混合攪拌して用いることもできる。In addition, as another method, it is also possible to divide the composition into a compound system mainly composed of a liquid epoxy resin and a compound system mainly composed of a curing agent, and mix and stir them immediately before use.
前記の任意成分である硬化促進剤としてはテトラアルキ
ルグアニジン、モノアミノピリジン、イミダゾリウムハ
ライド、イミダゾール化合物、無水フタール酸とジエチ
レントリアミンの反応生成物等を挙げることができ、使
用割合は各促進剤の゛種類によって異なるが、通常エポ
キシ樹脂１００重量部に対して０．１〜１０ｆｆｉｆｉ
部の範囲内とすればよい。また、充填剤としては、シリ
カ、クレー、石こう、炭酸カルシウム、石英粉、カリオ
ン、マイカ、アルミナ、水和アルミナ、タルク、ドロマ
イト、ジルコン、チタン化合物、モリブデン化合物、ア
ンチモン化合物等を挙げることができ、本発明ではこれ
ら硬化促進剤及び充填剤は単独あるいは２種以上混合し
て用いられる。また、添加剤としてはシラン系カンプリ
ング剤、顔料、老化防止剤等がある。Examples of the curing accelerator, which is an optional component, include tetraalkylguanidine, monoaminopyridine, imidazolium halide, imidazole compounds, reaction products of phthalic anhydride and diethylenetriamine, etc., and the proportion of each accelerator used depends on the amount of each accelerator. It varies depending on the type, but usually 0.1 to 10 ffifi per 100 parts by weight of epoxy resin.
It may be within the range of the section. In addition, examples of fillers include silica, clay, gypsum, calcium carbonate, quartz powder, carrion, mica, alumina, hydrated alumina, talc, dolomite, zircon, titanium compounds, molybdenum compounds, antimony compounds, etc. In the present invention, these curing accelerators and fillers may be used alone or in combination of two or more. Additionally, additives include silane camping agents, pigments, anti-aging agents, and the like.
本発明のエポキシ樹脂組成物は耐湿性、耐水性の要求さ
れる塗料、接着剤として特に有利に使用でき、この組成
物を塗布後１２０〜２２０℃、４０〜２０分程度の硬化
条件で硬化させることができる。The epoxy resin composition of the present invention can be particularly advantageously used as a paint or adhesive that requires moisture resistance and water resistance, and after application, the composition is cured at 120 to 220°C for about 40 to 20 minutes. be able to.
このとき、エポキシ樹脂組成物とポリアミド樹脂は海鳥
構造を示すのが一般的である。At this time, the epoxy resin composition and polyamide resin generally exhibit a seabird structure.
また、本発明の組成物は剥離接着性に特に優れるので自
動車構造用、航空機構造用、船舶構造用、家庭電気製品
用等の接着剤として用いたときに特に効果的である。Furthermore, the composition of the present invention has particularly excellent peel adhesion properties, so it is particularly effective when used as an adhesive for automobile structures, aircraft structures, ship structures, household electrical appliances, and the like.
以上本発明の詳細な説明するに際し、エポキシ樹脂とし
て液状エポキシ樹脂を取り挙げて説明したが、本発明に
おいては上記液状エポキシ樹脂に代え、場合により固形
のエポキシ樹脂を用いることもできる。In the above detailed description of the present invention, a liquid epoxy resin has been used as the epoxy resin, but in the present invention, a solid epoxy resin may be used instead of the liquid epoxy resin.
以下、本発明を具体的に実施例を挙げて説明する。尚、
実施例中の部は重量部を示す。Hereinafter, the present invention will be specifically explained with reference to Examples. still,
Parts in Examples indicate parts by weight.
実施例１
液状ビスフェノールＡ型エポキシ樹脂（エポキシ当γ１
９０、分子量３８０．１分子中の平均エポキシ基２個）
１００部、粉末状ポリアミド樹脂（粒子径２００μｍ以
下が９０重量％以上）２０部、疎水性微粉末シリカ（Ｂ
ＥＴ法による表面積約１００ｍ”／ｇ、粒子平均怪約１
６．ｃｒｍ、吸湿Ｉ１．５ｍｇ）３部、微粉末状ジシア
ンジアミド５部、効果促進剤として３−（ｐ−クロロフ
ェニル＞ −１−ｔ−ジメチルユレア３部、及び充填剤
として炭酸カルシウム２０部を常温で撹拌混合して本発
明のエポキシ樹脂組成物を得た。Example 1 Liquid bisphenol A type epoxy resin (γ1 per epoxy
90, molecular weight 380. average 2 epoxy groups per molecule)
100 parts, 20 parts of powdered polyamide resin (at least 90% by weight of particles with a particle size of 200 μm or less), hydrophobic fine powder silica (B
Surface area approximately 100m''/g by ET method, particle average density approximately 1
6. crm, 1.5 mg of moisture absorption I), 5 parts of finely powdered dicyandiamide, 3 parts of 3-(p-chlorophenyl>-1-t-dimethylurea) as an effect accelerator, and 20 parts of calcium carbonate as a filler were stirred and mixed at room temperature. An epoxy resin composition of the present invention was obtained.
実施例２
疎水性微粉末シリカを１部とする以外は実施例１と同様
にして本発明のエポキシ樹脂組成物を得た。Example 2 An epoxy resin composition of the present invention was obtained in the same manner as in Example 1 except that 1 part of hydrophobic fine powder silica was used.
実施例３
疎水性微粉末シリカを９部とする以外は実施例１と同様
にして本発明のエポキシ樹脂組成物を得た。Example 3 An epoxy resin composition of the present invention was obtained in the same manner as in Example 1, except that 9 parts of hydrophobic fine powder silica was used.
実施例４
粉末状ポリアミド樹脂を５部、疎水性微粉末シリカを５
部とする以外は実施例１と同様にして本発明のエポキシ
樹脂組成物を得た。Example 4 5 parts of powdered polyamide resin, 5 parts of hydrophobic fine powder silica
An epoxy resin composition of the present invention was obtained in the same manner as in Example 1 except that
実施例５
粉末状ポリアミド樹脂を４０部とする以外は実施例１と
同様にして本発明のエポキシ樹脂組成物を得た。Example 5 An epoxy resin composition of the present invention was obtained in the same manner as in Example 1 except that the powdered polyamide resin was changed to 40 parts.
比較例１
実施例１で用いた疎水性微粉末シリカに代え、親水性微
粉末シリカＣＢＥＴ法による表面積約１３０ｍ”／ｇ、
粒子平均径約１６μｍ、吸湿量３０ｍｇ）２部を用いる
以り［は実施例１と同様にしてエポキシ樹脂組成物を得
た。Comparative Example 1 In place of the hydrophobic fine powder silica used in Example 1, hydrophilic fine powder silica with a surface area of approximately 130 m''/g by CBET method,
An epoxy resin composition was obtained in the same manner as in Example 1 except that 2 parts (particle average diameter: about 16 μm, moisture absorption: 30 mg) were used.
比較例２
比較例１の混合成分のうち粉末状ポリアミド樹脂成分を
除き、その他は比較例１と同様にしてエポキシ樹脂組成
物を得た。Comparative Example 2 An epoxy resin composition was obtained in the same manner as in Comparative Example 1 except for the powdered polyamide resin component among the mixed components of Comparative Example 1.
以上の実施例及び比較例により得られたエポキシ樹脂組
成物について、下記の各種特性を測定した。その結果を
第１表に示す。The following various properties were measured for the epoxy resin compositions obtained in the above Examples and Comparative Examples. The results are shown in Table 1.
〈非垂下性〉
鋼板（１，ＯＸ１５０Ｘ１５０ｍｍ）に上記各側で得ら
れた混合直後及び混合後３０日経過後のエポキシ樹脂組
成物を、それぞれ厚さ１．６ｍｍで２５Ｘ７０．ｍｍの
面積に塗布し、該鋼板を垂直に吊し、１８０℃で３０分
間硬化を行った。その後、硬化物が、塗布した部分の下
端より流れた距離を測定した。<Non-sagging property> The epoxy resin compositions obtained on each side immediately after mixing and 30 days after mixing were placed on a steel plate (1. The coating was applied to an area of 1.2 mm, and the steel plate was hung vertically and cured at 180° C. for 30 minutes. Thereafter, the distance that the cured product flowed from the lower end of the coated area was measured.
〈引張剪断接着力〉
ＪＩＳ Ｋ ６８５０に準じ、上記各側で得られた
混合直後のエポキシ樹脂組成物及び、被着体として鋼板
（ＪｔＳ Ｇ ３１４１．５ｐｃｃ−３Ｄ、１００
ｘ２５ｘ１．６ｍｍ、シングルオーハーラソプ）を用い
て１８０℃で３０分間硬化を行い試験片を作製し、該試
験片に対し、何もしないもの、下記の耐水試験を行った
もの、耐湿試験を行ったものの三者につきそれぞれ２３
℃にて測定した。<Tensile shear adhesive strength> According to JIS K 6850, the epoxy resin composition immediately after mixing obtained on each side and a steel plate (JtS G 3141.5pcc-3D, 100
x 25 x 1.6 mm, Single Oharrasop) was used to cure at 180°C for 30 minutes to prepare test pieces, and the test pieces were subjected to the following water resistance test, moisture resistance test. 23 for each of the three
Measured at ℃.
〈Ｔ剥離接着力〉
ＪＩＳ Ｋ ６８５４に準じ、上記各側で得られた混
合直後のエポキシ樹脂組成物及び、被着体として鋼板（
ＪＩＳ Ｇ ３１４１，５ＰＣＣ−３Ｄ、１００Ｘ
２５Ｘ０．８ｍｒｎ）を用い、塗布厚０．１５ｍｍにて
１８０ ’Ｃで３０分間硬化を行い試験片を作製した。<T peel adhesive strength> According to JIS K 6854, the epoxy resin composition obtained on each side immediately after mixing and a steel plate (
JIS G 3141, 5PCC-3D, 100X
A test piece was prepared by curing at 180'C for 30 minutes with a coating thickness of 0.15 mm.
該試験片に対し、何もしないもの、下記の耐水試験を行
ったもの、耐湿試験を行ったものの三者につきそれぞれ
２３℃にて測定した。Measurements were made at 23° C. for each of the three test pieces: one that did nothing, one that was subjected to the water resistance test described below, and one that was subjected to the moisture resistance test.
く耐水試験〉
上記で得られた試験片をそれぞれ４０部２℃に調整した
恒温水槽に入れ、３０日経過後取り出す。Water Resistance Test> 40 copies of each of the test pieces obtained above were placed in a thermostatic water bath adjusted to 2°C, and taken out after 30 days.
〈耐湿試験〉
上記で得られた試験片をそれぞれ５０℃、相対湿度９０
％に調整した恒温恒温機に入れ、３０日経過後取り出す
。<Humidity test> The test pieces obtained above were tested at 50℃ and relative humidity 90℃.
%, and take it out after 30 days.
以上述べた通り、本発明ではエポキシ樹脂組成物に疎水
性微粉末シリカを混合することにより組成物としての耐
湿性に優れると共に、該３■成物の硬化物の耐湿性、耐
水性も向上させることができる。よって組成物のポット
ライフを向上させると共に、硬化時の非垂下性並びに硬
化物の接着力を向上させることができる。As described above, in the present invention, by mixing hydrophobic finely powdered silica into an epoxy resin composition, the composition has excellent moisture resistance, and the cured product of the three items also improves moisture resistance and water resistance. be able to. Therefore, the pot life of the composition can be improved, and the non-sagging property during curing and the adhesive strength of the cured product can be improved.
Claims (2)
水性微粉末シリカ０．５〜１０重量部、及び、 （ニ）適量の硬化剤 を含有してなるエポキシ樹脂組成物。(1) (a) 100 parts by weight of epoxy resin, (b) 5 to 50 parts by weight of powdered polyamide resin, (c) 0.5 to 10 parts by weight of hydrophobic fine powder silica, and (d) an appropriate amount of curing agent. An epoxy resin composition containing.
求の範囲第１項記載のエポキシ樹脂組成物。(2) The epoxy resin composition according to claim 1, wherein the curing agent is finely powdered dicyandiamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7502086A JPS62230820A (en) | 1986-03-31 | 1986-03-31 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7502086A JPS62230820A (en) | 1986-03-31 | 1986-03-31 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62230820A true JPS62230820A (en) | 1987-10-09 |
Family
ID=13564075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7502086A Pending JPS62230820A (en) | 1986-03-31 | 1986-03-31 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62230820A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02286738A (en) * | 1989-04-28 | 1990-11-26 | Somar Corp | Epoxy resin composition prevented from generating curing strain and method of bonding therewith |
| US5272185A (en) * | 1990-10-26 | 1993-12-21 | The Furukawa Electric Co., Ltd. | Polyphenylenesulfide composition for powder coating |
| JP2013023533A (en) * | 2011-07-19 | 2013-02-04 | Kyocera Chemical Corp | Epoxy resin composition for dip-coating |
| JP2013514439A (en) * | 2009-12-15 | 2013-04-25 | スリーエム イノベイティブ プロパティズ カンパニー | Fluoropolymer film with epoxy adhesive |
| WO2019054392A1 (en) * | 2017-09-15 | 2019-03-21 | 住友精化株式会社 | Epoxy resin composition |
-
1986
- 1986-03-31 JP JP7502086A patent/JPS62230820A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02286738A (en) * | 1989-04-28 | 1990-11-26 | Somar Corp | Epoxy resin composition prevented from generating curing strain and method of bonding therewith |
| US5272185A (en) * | 1990-10-26 | 1993-12-21 | The Furukawa Electric Co., Ltd. | Polyphenylenesulfide composition for powder coating |
| JP2013514439A (en) * | 2009-12-15 | 2013-04-25 | スリーエム イノベイティブ プロパティズ カンパニー | Fluoropolymer film with epoxy adhesive |
| JP2013023533A (en) * | 2011-07-19 | 2013-02-04 | Kyocera Chemical Corp | Epoxy resin composition for dip-coating |
| WO2019054392A1 (en) * | 2017-09-15 | 2019-03-21 | 住友精化株式会社 | Epoxy resin composition |
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