JP2013023533A - Epoxy resin composition for dip-coating - Google Patents
Epoxy resin composition for dip-coating Download PDFInfo
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本発明は、ディップコート用エポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin composition for dip coating.
揺変性（チクソトロピー性）を有するエポキシ樹脂組成物は、コンデンサー、抵抗器、ハイブリッドＩＣ等の小型電子部品のディップコート用樹脂として広く用いられている。このような揺変性エポキシ樹脂組成物においては、硬化剤添加後のエポキシ樹脂組成物の揺変性の経時低下の小さいこと、硬化物の耐湿性の良好なこと等が要求される。硬化剤混合後のエポキシ樹脂組成物の揺変性の経時低化が大きいと、早い時間で「タレ」を生じて均一な厚さの塗膜を得ることができない。また、耐湿性が低いと、塗膜の電気特性が低下し、電子部品を安全に保護することができなくなる。 Epoxy resin compositions having thixotropic properties (thixotropic properties) are widely used as dip coating resins for small electronic components such as capacitors, resistors, and hybrid ICs. In such thixotropic epoxy resin composition, it is required that the thixotropic modification of the epoxy resin composition after the addition of the curing agent is small, the moisture resistance of the cured product is good. If the time-lapse deterioration of the thixotropic property of the epoxy resin composition after mixing the curing agent is large, “sag” occurs in an early time, and a coating film having a uniform thickness cannot be obtained. In addition, when the moisture resistance is low, the electrical properties of the coating film are deteriorated and the electronic components cannot be safely protected.
ところで、揺変性を有するエポキシ樹脂組成物は、エポキシ樹脂にコロイド状のシリカやベントナイト等の充填剤を添加することによって得ることができるが、このような充填剤のみの添加では十分な揺変性を付与することはできない。 By the way, an epoxy resin composition having thixotropy can be obtained by adding a filler such as colloidal silica or bentonite to the epoxy resin. It cannot be granted.
特許文献１には、コロイド状シリカとともに、ホルムアミドやジメチルホルムアミド等のアミド化合物と、メチルカルビトール、ジエチレングリコール、エチレングリコール等のヒドロキシル基含有化合物とを添加することにより、揺変性を高めたエポキシ樹脂組成物が開示されている。しかし、この組成物では、揺変性は改善されるものの、ヒドロキシル基含有化合物の多量の添加により、硬化物の耐湿性が低下するという問題があった。 Patent Document 1 discloses an epoxy resin composition having improved thixotropic properties by adding an amide compound such as formamide and dimethylformamide and a hydroxyl group-containing compound such as methyl carbitol, diethylene glycol, and ethylene glycol together with colloidal silica. Things are disclosed. However, in this composition, although thixotropy is improved, there is a problem that the moisture resistance of the cured product decreases due to the addition of a large amount of the hydroxyl group-containing compound.
一方、特許文献２には、揺変性及び耐湿性を改善するために、エポキシ樹脂を含む第１液と硬化剤を含む第２液からなる２液型エポキシ樹脂組成物において、第１液と第２液との混合物の２５℃での初期及び６時間保存後の構造粘性比を特定の範囲にしたものが開示されている。しかし、この組成物では、親水性のシリカが使用されているため、水分を吸収しやすく、組成物の可使時間（ポットライフ）が短いという問題があった。 On the other hand, in Patent Document 2, in order to improve thixotropy and moisture resistance, a two-component epoxy resin composition comprising a first liquid containing an epoxy resin and a second liquid containing a curing agent is used. A structure in which the ratio of the structural viscosity of the mixture with the two liquids at the initial stage at 25 ° C. and after storage for 6 hours is in a specific range is disclosed. However, in this composition, since hydrophilic silica is used, there is a problem that it is easy to absorb moisture, and the pot life of the composition is short.
本発明は、上記従来技術の課題を解決するためになされたもので、揺変性に優れるとともに、その経時低下が小さく、また硬化物の耐湿性が良好で、さらに可使時間も長いディップコート用エポキシ樹脂組成物を提供することを目的としている。 The present invention has been made to solve the above-mentioned problems of the prior art, and is excellent in thixotropic properties, has a small deterioration over time, has good moisture resistance of a cured product, and has a long pot life. An object is to provide an epoxy resin composition.
上記目的を達成するため、本発明の一態様に係るディップコート用エポキシ樹脂組成物は、（Ａ）液状のビスフェノールグリシジルエーテル型エポキシ樹脂と、（Ｂ）ブチルグリシジルエーテルと、（Ｃ）親水性シリカ及び疎水性シリカとを含む第１液と、（Ｄ）液状の芳香族アミン系硬化剤と、（Ｅ）トリエタノールアミンとを含む第２液とからなることを特徴としている。 In order to achieve the above object, an epoxy resin composition for dip coating according to one embodiment of the present invention comprises (A) a liquid bisphenol glycidyl ether type epoxy resin, (B) butyl glycidyl ether, and (C) hydrophilic silica. And a first liquid containing hydrophobic silica, (D) a liquid aromatic amine curing agent, and (E) a second liquid containing triethanolamine.
本発明によれば、揺変性に優れるとともに、その経時低下が小さく、また硬化物の耐湿性が良好で、さらに可使時間も長いディップコート用エポキシ樹脂組成物を得ることができる。 According to the present invention, it is possible to obtain an epoxy resin composition for dip coating which is excellent in thixotropic property, has a small deterioration with time, has good moisture resistance of the cured product, and has a long pot life.
以下、本発明の実施の形態を説明する。 Embodiments of the present invention will be described below.
本発明のディップコート用エポキシ樹脂組成物は、（Ａ）液状のビスフェノールグリシジルエーテル型エポキシ樹脂と、（Ｂ）ブチルグリシジルエーテルと、（Ｃ）親水性シリカ及び疎水性シリカとを含む第１液と、（Ｄ）液状の芳香族アミン系硬化剤と、（Ｅ）トリエタノールアミンとを含む第２液から構成される。 The epoxy resin composition for dip coating of the present invention comprises (A) a liquid bisphenol glycidyl ether type epoxy resin, (B) butyl glycidyl ether, and (C) a first liquid containing hydrophilic silica and hydrophobic silica. (D) It is comprised from the 2nd liquid containing a liquid aromatic amine type hardening | curing agent and (E) triethanolamine.
まず、第１液に使用される各成分について説明する。第１液に用いられる（Ａ）成分のビスフェノールグリシジルエーテル型エポキシ樹脂は、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、水添ビスフェノールＡ等のビスフェノール類とエピクロルヒドリンを反応させることによって得られるエポキシ樹脂であり、常温で液状のものであれば特に制限されることなく使用される。（Ａ）成分のエポキシ樹脂は、１種を単独で使用してもよく、２種以上を混合して使用してもよい。 First, each component used for the first liquid will be described. The (A) component bisphenol glycidyl ether type epoxy resin used in the first liquid is an epoxy resin obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol AD, hydrogenated bisphenol A and epichlorohydrin, If it is liquid at normal temperature, it will be used without any particular limitation. (A) The epoxy resin of a component may be used individually by 1 type, and 2 or more types may be mixed and used for it.
第１液に用いられる（Ｂ）成分のブチルグリシジルエーテルは、本発明の組成物の粘度を低下させるための反応性希釈剤として添加される成分であり、その配合量は、上記（Ａ）成分のエポキシ樹脂１００質量部に対し、５〜２０質量部の範囲が好ましい。配合量が５質量部未満では、本発明の組成物を適正な粘度に調節することができず、また、配合量が２０質量部を超えると、硬化物の特性が不良となる。 The butyl glycidyl ether of the component (B) used in the first liquid is a component added as a reactive diluent for reducing the viscosity of the composition of the present invention, and the blending amount thereof is the above component (A). The range of 5-20 mass parts is preferable with respect to 100 mass parts of epoxy resin. If the blending amount is less than 5 parts by mass, the composition of the present invention cannot be adjusted to an appropriate viscosity, and if the blending amount exceeds 20 parts by mass, the properties of the cured product become poor.
なお、本発明の組成物には、ブチルグリシジルエーテル以外の反応性希釈剤も、本発明の効果を阻害しない範囲で配合してもよい。そのような反応性希釈剤としては、例えば、フェニルグリシジルエーテル、アルキルフェノールグリシジルエーテル、アリルグリシジルエーテル、ブタンジオールジグリシジルエーテル、ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル等が挙げられる。希釈効率の点からは、ブチルグリシジルエーテルの単独使用が好ましい In addition, you may mix | blend reactive diluents other than butyl glycidyl ether with the composition of this invention in the range which does not inhibit the effect of this invention. Examples of such reactive diluents include phenyl glycidyl ether, alkylphenol glycidyl ether, allyl glycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like. From the viewpoint of dilution efficiency, it is preferable to use butyl glycidyl ether alone.
第１液に用いられる（Ｃ）成分は揺変性付与剤として添加される成分である。本発明においては、親水性シリカと疎水性シリカが使用される。親水性シリカとしては、四塩化ケイ素の火炎加水分解法により得られるフュームドシリカで、表面に親水性のシラノール基（Ｓｉ−ＯＨ）を有し、一次粒子径が５〜２０ｎｍで、比表面積が４０〜４００ｍ２／ｇのものが好ましい。このような親水性フュームドシリカの市販品としては、例えば、アエロジル＃３００、＃２００（以上、いずれも日本アエロジル（株）製 商品名）等が挙げられる。また、疎水性シリカとしては、上記のような親水性フュームドシリカを、シラン、シロキサン等で化学的に処理することによって疎水化したフュームドシリカで、一次粒子径が７〜２５ｎｍで、比表面積（ＢＥＴ）が５０〜５００ｍ２／ｇのものが好ましい。このような疎水性フュームドシリカの市販品としては、例えば、ＲＹ２００Ｓ（日本アエロジル（株）製 商品名）等が挙げられる。なお、上記親水性シリカおよび疎水性シリカの一次粒子径は、例えば、動的光散乱法により測定することができる。 The component (C) used in the first liquid is a component added as a thixotropic agent. In the present invention, hydrophilic silica and hydrophobic silica are used. As the hydrophilic silica, fumed silica obtained by a flame hydrolysis method of silicon tetrachloride, having a hydrophilic silanol group (Si-OH) on the surface, a primary particle diameter of 5 to 20 nm, and a specific surface area. The thing of 40-400 m < 2 > / g is preferable. Examples of such commercially available products of hydrophilic fumed silica include Aerosil # 300 and # 200 (both are trade names manufactured by Nippon Aerosil Co., Ltd.). The hydrophobic silica is fumed silica that has been hydrophobized by chemically treating the hydrophilic fumed silica as described above with silane, siloxane, etc., and has a primary particle size of 7 to 25 nm and a specific surface area. (BET) is preferably 50 to 500 m 2 / g. Examples of such commercially available products of hydrophobic fumed silica include RY200S (trade name, manufactured by Nippon Aerosil Co., Ltd.). The primary particle diameter of the hydrophilic silica and hydrophobic silica can be measured by, for example, a dynamic light scattering method.
これらの親水性シリカ及び疎水性シリカの配合量は、合計量で、上記（Ａ）成分のエポキシ樹脂１００質量部に対し２．０〜５．０質量部の範囲が好ましく、３．０〜４．０質量部の範囲がより好ましい。配合量が２．０質量部未満では、揺変性が不十分となり、５．０質量部を超えると、粘度、揺変性が過度に高くなって、均一な膜厚でコーティングすることが困難になる。また、このような量で配合される親水性シリカ及び疎水性シリカの配合比は、疎水性シリカの割合がシリカ全体の１０〜５０質量％となる範囲が好ましく、２０〜３０質量％となる範囲がより好ましい。疎水性シリカの割合が１０質量％未満では、組成物の可使時間（ポットライフ）を十分に長くすることができないばかりか、第１液と第２液混合後の粘度が上昇し、塗装仕上がりが不良となるおそれがある。また、５０質量％を超えると、揺変性が低下して親水性シリカ及び疎水性シリカがともに沈降しやすくなる。 The blending amount of these hydrophilic silica and hydrophobic silica is a total amount, and is preferably in the range of 2.0 to 5.0 parts by mass with respect to 100 parts by mass of the epoxy resin as the component (A), and 3.0 to 4 A range of 0.0 part by mass is more preferable. If the blending amount is less than 2.0 parts by mass, thixotropy becomes insufficient, and if it exceeds 5.0 parts by mass, the viscosity and thixotropy become excessively high and it becomes difficult to coat with a uniform film thickness. . Further, the blending ratio of the hydrophilic silica and the hydrophobic silica blended in such an amount is preferably a range in which the proportion of the hydrophobic silica is 10 to 50% by mass of the entire silica, and a range in which the ratio is 20 to 30% by mass. Is more preferable. If the proportion of the hydrophobic silica is less than 10% by mass, the pot life of the composition cannot be made sufficiently long, and the viscosity after mixing the first and second liquids increases, resulting in a finished coating. May become defective. Moreover, when it exceeds 50 mass%, thixotropy falls and both hydrophilic silica and hydrophobic silica will precipitate easily.
次に、第２液に使用される各成分について説明する。第２液に用いられる（Ｄ）成分の芳香族アミン系硬化剤は、常温で液状のものであれば、特に制限されることなく使用される。その具体例としては、メタフェニレンジアミンとジアミノジフェニルメタンの共融混合物、そのような共融混合物とエポキシ化合物との付加物（例えば、アンカミンＺ（エアプロダクツ（株）製 商品名）等）、ジアミノジエチルジフェニルメタン（例えば、カヤハード（日本化薬（株）製 商品名）等）、ジアミノジフェニルメタンのクルード（例えば、ＭＤＡ−１５０（三井東圧化学（株）製 商品名）等）、ジエチルトルエンジアミン、アニリンとホリマリンの縮合物（例えば、ラッカマイドＷＨ−６１９（大日本インキ化学工業（株）製 商品名）等）等が挙げられる。これらの芳香族系アミン硬化剤は、１種を単独で使用してもよく、２種以上を混合して使用してもよい。（Ｄ）成分の芳香族アミン系硬化剤としては、反応性や、硬化物の耐熱性、耐湿性等の点から、なかでもメタフェニレンジアミンとジアミノジフェニルメタンの共融混合物、そのような共融混合物とエポキシ化合物との付加物が好ましい。 Next, each component used for the second liquid will be described. The aromatic amine curing agent (D) used in the second liquid is not particularly limited as long as it is liquid at room temperature. Specific examples thereof include a eutectic mixture of metaphenylenediamine and diaminodiphenylmethane, an adduct of such an eutectic mixture and an epoxy compound (for example, Ancamine Z (trade name, manufactured by Air Products), etc.), diaminodiethyl Diphenylmethane (for example, Kayahard (trade name, manufactured by Nippon Kayaku Co., Ltd.), etc., Crude of diaminodiphenylmethane (for example, MDA-150 (trade name, manufactured by Mitsui Toatsu Chemicals), etc.), diethyltoluenediamine, aniline Examples include condensates of holymarin (for example, racamide WH-619 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.)). These aromatic amine curing agents may be used alone or in a combination of two or more. As the aromatic amine curing agent of component (D), eutectic mixture of metaphenylenediamine and diaminodiphenylmethane, especially such eutectic mixture from the viewpoint of reactivity, heat resistance and moisture resistance of the cured product, etc. Adducts of benzene and epoxy compounds are preferred.
この（Ｄ）成分の芳香族アミン系硬化剤の配合量は、（Ａ）成分のエポキシ樹脂１００質量部に対し、１〜４０質量部の範囲が好ましく、１５〜３５質量部の範囲がより好ましい。配合量が１質量部未満では、ガラス転移温度が下がって耐熱性が低下するおそれがある。また、配合量が４０質量部を超えると、耐湿性が低下するおそれがある。 The blending amount of the aromatic amine curing agent as the component (D) is preferably in the range of 1 to 40 parts by mass, more preferably in the range of 15 to 35 parts by mass with respect to 100 parts by mass of the epoxy resin of the component (A). . If the blending amount is less than 1 part by mass, the glass transition temperature may decrease and the heat resistance may decrease. Moreover, when a compounding quantity exceeds 40 mass parts, there exists a possibility that moisture resistance may fall.
なお、エポキシ樹脂の他の硬化剤、例えば、酸無水物系、イミダゾール系、ジシアンジアミド系、脂肪族アミン系等の硬化剤の使用は、組成物の揺変性を低下させ、また硬化物の耐湿性も低下させることから、硬化剤成分は芳香族アミン系硬化剤のみの使用が好ましい。 The use of other curing agents for epoxy resins, such as acid anhydrides, imidazoles, dicyandiamides, aliphatic amines, etc. reduces the thixotropic properties of the composition, and the moisture resistance of the cured product. Therefore, it is preferable to use only an aromatic amine curing agent as the curing agent component.
第２液に用いられる（Ｅ）成分のトリエタノールアミンは、親水性シリカ及び疎水性シリカによりもたらされる揺変性を増強するために配合される成分であり、その配合量は、（Ａ）成分のエポキシ樹脂１００質量部に対し、０．１〜２．０質量部の範囲が好ましく、１．０〜１．５質量部の範囲がより好ましい。配合量が０．１質量部未満では、揺変性増強効果が小さく、また、配合量が２．０質量部を超えると、エポキシ樹脂と芳香族アミン系硬化剤との硬化反応を促進させ、組成物の可使時間を短縮させるおそれがある。 The (E) component triethanolamine used in the second liquid is a component blended to enhance thixotropy caused by the hydrophilic silica and the hydrophobic silica. The range of 0.1-2.0 mass parts is preferable with respect to 100 mass parts of epoxy resin, and the range of 1.0-1.5 mass parts is more preferable. If the blending amount is less than 0.1 parts by mass, the thixotropic enhancing effect is small, and if the blending amount exceeds 2.0 parts by mass, the curing reaction between the epoxy resin and the aromatic amine curing agent is promoted, and the composition There is a risk of shortening the pot life.
なお、トリエタノールアミンの低級カルボン酸塩（アセテートや、プロピオネート等）や無機酸塩も揺変性を増強させる作用を有するが、これらの使用は、硬化物の吸水率を上げ、電気絶縁性を低下させるおそれがあることから、揺変性増強剤としてはトリエタノールアミンの単独使用が好ましい。 In addition, triethanolamine lower carboxylate (acetate, propionate, etc.) and inorganic acid salt have the effect of enhancing thixotropy, but their use increases the water absorption rate of the cured product and lowers the electrical insulation. Therefore, it is preferable to use triethanolamine alone as the thixotropic agent.
本発明のディップコート用エポキシ樹脂組成物には、以上説明した成分の他に、本発明の効果を阻害しない範囲で、必要に応じて、上記親水性シリカ及び疎水性シリカ以外の充填剤、難燃剤、着色剤、その他の添加剤を配合することができる。例えば、充填剤としては、結晶シリカ、溶融シリカ、炭酸カルシウム、タルク、マイカ、アルミナ、水酸化アルミニウム、ホワイトカーボン、ジルコニア、チタンホワイト、ベンガラ、炭化ケイ素、窒化ホウ素、窒化アルミ、窒化ケイ素、マグネシア、マグネシウムシリケート等の粉末が挙げられる。難燃剤としては、粉末状有機ハロゲン化合物、赤リン、リン酸エステル、三酸化アンチモン等が挙げられる。着色剤としては、カーボンブラック、コバルトブルー等の各種顔料・染料が挙げられる。なお、これらの成分は、第１液及び第２液のいずれか一方に配合してもよく、あるいはその両方に配合してもよい。充填剤の沈殿防止の点からは、第１液に配合することが好ましい。 In the epoxy resin composition for dip coating of the present invention, in addition to the components described above, a filler other than the above-described hydrophilic silica and hydrophobic silica, if necessary, within a range not impairing the effects of the present invention, A flame retardant, a coloring agent, and other additives can be blended. For example, as filler, crystalline silica, fused silica, calcium carbonate, talc, mica, alumina, aluminum hydroxide, white carbon, zirconia, titanium white, bengara, silicon carbide, boron nitride, aluminum nitride, silicon nitride, magnesia, Examples thereof include powders such as magnesium silicate. Examples of the flame retardant include powdery organic halogen compounds, red phosphorus, phosphate esters, antimony trioxide and the like. Examples of the colorant include various pigments and dyes such as carbon black and cobalt blue. In addition, you may mix | blend these components with any one of a 1st liquid and a 2nd liquid, or may mix | blend with both. From the viewpoint of preventing the precipitation of the filler, it is preferable to blend in the first liquid.
本発明のディップコート用エポキシ樹脂組成物は、前述したように、（Ａ）液状のビスフェノールグリシジルエーテル型エポキシ樹脂と、（Ｂ）ブチルグリシジルエーテルと、（Ｃ）親水性シリカ及び疎水性シリカとを含む第１液と、（Ｄ）液状の芳香族アミン系硬化剤と、（Ｅ）トリエタノールアミンとを含む第２液から構成され、使用時に両液を所定割合で混合して使用される。 As described above, the epoxy resin composition for dip coating of the present invention comprises (A) liquid bisphenol glycidyl ether type epoxy resin, (B) butyl glycidyl ether, (C) hydrophilic silica and hydrophobic silica. It comprises a second liquid containing a first liquid containing, (D) a liquid aromatic amine-based curing agent, and (E) triethanolamine, and both liquids are mixed at a predetermined ratio during use.
第１液の調製は、（Ａ）成分の液状のビスフェノールグリシジルエーテル型エポキシ樹脂に（Ｃ）成分の親水性シリカ及び疎水性シリカを添加し、攪拌混合した後、（Ｂ）成分のブチルグリシジルエーテルを添加して、さらに短時間、例えば、３０分間程度攪拌混合することにより行われる。前述した任意成分の充填剤、難燃剤、着色剤等を添加する場合には、例えば、３本ロール等で混合分散させればよい。（Ａ）成分のエポキシ樹脂と（Ｃ）成分の親水性シリカ及び疎水性シリカとの撹拌混合は、第１液の粘度がほぼ平衡状態の粘度（平衡粘度）に到達している平衡粘度組成物が得られるように行うことが好ましい。このためには、エポキシ樹脂に親水性シリカ及び疎水性シリカを添加し、通常、２時間以上、好ましくは３〜５時間攪拌する。第１液を得るための攪拌混合装置としては、例えば、プラネタリーミキサー等を用いることができる。 The first liquid was prepared by adding (C) component hydrophilic silica and hydrophobic silica to (A) component liquid bisphenol glycidyl ether type epoxy resin, stirring and mixing, and then (B) component butyl glycidyl ether. And stirring and mixing for a further short time, for example, about 30 minutes. When adding the above-mentioned optional fillers, flame retardants, colorants and the like, for example, they may be mixed and dispersed by a three-roll roll or the like. In the case of stirring and mixing the epoxy resin of component (A) and the hydrophilic silica and hydrophobic silica of component (C), the viscosity of the first liquid reaches an almost equilibrium viscosity (equilibrium viscosity). It is preferable to carry out such that For this purpose, hydrophilic silica and hydrophobic silica are added to the epoxy resin, and the mixture is usually stirred for 2 hours or more, preferably 3 to 5 hours. As a stirring and mixing device for obtaining the first liquid, for example, a planetary mixer or the like can be used.
次に、本発明を実施例によりさらに詳細に説明する。なお、本発明はこれらの実施例に何ら限定されるものではない。また、以下の記載において、「部」は「質量部」を示すものとする。 Next, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to these Examples at all. In the following description, “part” means “part by mass”.
（実施例１）
ビスフェノールグリシジルエーテル型エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂（三菱化学（株）製 商品名 ｊＥＲ８２８；エポキシ当量１８８）１００部に、反応性希釈剤としてブチルグリシジルエーテル（阪本薬品工業（株）製 商品名 ＢＧＥ−Ｒ）２０．５部、親水性フュームドシリカ（日本アエロジル（株）製 商品名 アエロジル＃３００；一次粒子径７μｍ、比表面積３００ｍ２／ｇ；親水性シリカ（１）と表記）４．５部、及び疎水性フュームドシリカ（日本アエロジル（株）製 商品名 ＲＹ２００Ｓ；一次粒子径１５μｍ、比表面積８０ｍ２／ｇ）０．５部を添加し、その添加後３時間攪拌混合して平衡粘度到達度１００％の第１液を調製した。この第１液の調製には、（株）井上製作所製のダブルプラネタリーミキサー（型式 ＰＬＭ−５）を用い、自転速度８４ｒｐｍ、公転速度２６ｒｍｐで撹拌した。また、芳香族アミン系硬化剤（エアプロダクツ（株）製 商品名 アンカミンＺ）２５部に、トリエタノールアミン６部を常法により添加し混合して第２液を調製した。この後、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
Example 1
100 parts of bisphenol A type epoxy resin (trade name jER828; epoxy equivalent 188) manufactured by Mitsubishi Chemical Corporation as bisphenol glycidyl ether type epoxy resin, and butyl glycidyl ether (trade name manufactured by Sakamoto Pharmaceutical Co., Ltd.) -R) 20.5 parts, hydrophilic fumed silica (Nippon Aerosil Co., Ltd., trade name Aerosil # 300; primary particle size 7 μm, specific surface area 300 m 2 / g; expressed as hydrophilic silica (1)) 4.5 And 0.5 part of hydrophobic fumed silica (trade name RY200S manufactured by Nippon Aerosil Co., Ltd .; primary particle size 15 μm, specific surface area 80 m 2 / g), and after mixing, the mixture is stirred and mixed for 3 hours to obtain an equilibrium viscosity. A first solution having a reach of 100% was prepared. For the preparation of the first liquid, a double planetary mixer (model PLM-5) manufactured by Inoue Seisakusho Co., Ltd. was used and stirred at a rotation speed of 84 rpm and a revolution speed of 26 rpm. Moreover, 6 parts of triethanolamine was added to 25 parts of an aromatic amine-based curing agent (trade name Ancamine Z, manufactured by Air Products Co., Ltd.) by a conventional method to prepare a second liquid. Then, these 1st liquids and 2nd liquids were mixed and the epoxy resin composition was obtained.
（実施例２）
第１液における親水性フュームドシリカ（アエロジル＃３００）の配合量を５部に増量した以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
(Example 2)
A first liquid and a second liquid were prepared in the same manner as in Example 1 except that the amount of the hydrophilic fumed silica (Aerosil # 300) in the first liquid was increased to 5 parts, and these first liquids were further prepared. And the 2nd liquid was mixed and the epoxy resin composition was obtained.
（実施例３）
第１液における疎水性フュームドシリカ（ＲＹ２００Ｓ）の配合量を１部に増量した以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
(Example 3)
A first liquid and a second liquid are prepared in the same manner as in Example 1 except that the amount of the hydrophobic fumed silica (RY200S) in the first liquid is increased to 1 part. Further, the first liquid and the second liquid are prepared. Two liquids were mixed to obtain an epoxy resin composition.
（実施例４）
第２液におけるトリエタノールアミンの配合量を８．５部に増量した以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
Example 4
A first liquid and a second liquid are prepared in the same manner as in Example 1 except that the amount of triethanolamine in the second liquid is increased to 8.5 parts. Further, these first liquid and second liquid are added. An epoxy resin composition was obtained by mixing.
（実施例５）
第１液において、親水性フュームドシリカ（アエロジル＃３００）に代えて、親水性フュームドシリカ（日本アエロジル（株）製 商品名 アエロジル＃２００；一次粒子径１２μｍ、比表面積２００ｍ２／ｇ；親水性シリカ（２）と表記）を用いた以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
(Example 5)
In the first liquid, instead of hydrophilic fumed silica (Aerosil # 300), hydrophilic fumed silica (trade name Aerosil # 200 manufactured by Nippon Aerosil Co., Ltd .; primary particle size 12 μm, specific surface area 200 m 2 / g; hydrophilic The first liquid and the second liquid were prepared in the same manner as in Example 1 except that the functional silica (indicated as (2)) was used, and the first liquid and the second liquid were further mixed to obtain an epoxy resin composition. Got.
（比較例１）
第１液において、疎水性フュームドシリカ（ＲＹ２００Ｓ）を非配合とした以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
(Comparative Example 1)
In the first liquid, except that the hydrophobic fumed silica (RY200S) was not blended, the first liquid and the second liquid were prepared in the same manner as in Example 1, and these first liquid and second liquid were further added. An epoxy resin composition was obtained by mixing.
（比較例２）
第１液における反応性希釈剤として、ブチルグリシジルエーテル（ＢＧＥ−Ｒ）に代えて、トリメチロールプロパン・ポリグリシジルエーテル（阪本薬品工業（株）製 商品名 ＳＲ−ＴＭＰ）を用いた以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
(Comparative Example 2)
Example except that trimethylolpropane polyglycidyl ether (trade name SR-TMP manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used as the reactive diluent in the first liquid instead of butyl glycidyl ether (BGE-R). The 1st liquid and the 2nd liquid were prepared like No. 1, and also these 1st liquid and the 2nd liquid were mixed and the epoxy resin composition was obtained.
（比較例３）
第１液において、ブチルグリシジルエーテル（ＢＧＥ−Ｒ）を非配合とし、かつ親水性フュームドシリカ（アエロジル＃３００）の配合量を３．５部とするとともに、第２液における芳香族アミン系硬化剤（アンカミンＺ）及びトリエタノールアミンの配合量をそれぞれ２０．５部及び５部とした以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
(Comparative Example 3)
In the first liquid, butyl glycidyl ether (BGE-R) is not blended, and the blending amount of hydrophilic fumed silica (Aerosil # 300) is 3.5 parts, and the aromatic amine-based curing in the second liquid The first liquid and the second liquid were prepared in the same manner as in Example 1 except that the blending amounts of the agent (ancamine Z) and triethanolamine were 20.5 parts and 5 parts, respectively. And the 2nd liquid was mixed and the epoxy resin composition was obtained.
（比較例４）
第１液において、親水性フュームドシリカ（アエロジル＃３００）を非配合とした以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
(Comparative Example 4)
The first liquid and the second liquid were prepared in the same manner as in Example 1 except that the hydrophilic fumed silica (Aerosil # 300) was not blended in the first liquid, and these first and second liquids were further prepared. The liquid was mixed to obtain an epoxy resin composition.
（比較例５）
第２液において、芳香族アミン系硬化剤（アンカミンＺ）に代えて脂肪族アミン系硬化剤（ハンツマン（株）製 商品名 ジェファーミンＤ４００）を用いた以外は実施例１と同様にして第１液及び第２液を調製し、さらに、これらの第１液及び第２液を混合してエポキシ樹脂組成物を得た。
(Comparative Example 5)
In the second liquid, the same procedure as in Example 1 was performed except that an aliphatic amine-based curing agent (trade name Jeffamine D400 manufactured by Huntsman Co., Ltd.) was used instead of the aromatic amine-based curing agent (Ancamine Z). A liquid and a second liquid were prepared, and the first liquid and the second liquid were mixed to obtain an epoxy resin composition.
上記各実施例及び各比較例で得られたエポキシ樹脂組成物について、下記に示す方法で各種特性を評価した。結果を組成とともに表１に示す。 About the epoxy resin composition obtained by each said Example and each comparative example, various characteristics were evaluated by the method shown below. The results are shown in Table 1 together with the composition.
［粘度Ｉ］
回転粘度計（芝浦システム（株）製 ビスメトロンＶＧＨ型粘度計）を用いて、第１液及び第２液の混合１分後の粘度を２５℃で測定した。
［ゲルタイム］
ＪＩＳ Ｃ ２１０５に準拠し、エポキシ樹脂組成物が１２０℃の熱板上でゲル化するまでの時間（秒）を測定した。
［チクソトロピー指数（ＴＩ）］
回転粘度計（芝浦システム（株）製 ビスメトロンＶＧＨ型粘度計）を用いて、第１液及び第２液の混合直後、２．５時間後、５．０時間後、７．５時間後、及び１０．０時間後の、２５℃における２０回転の粘度（η２０）と４回転での粘度（η４）を測定し、次式により求めた。
ＴＩ＝η４／η２０
［粘度II］
回転粘度計（芝浦システム（株）製 ビスメトロンＶＧＨ型粘度計）を用いて、第１液及び第２液の混合直後、２．５時間後、５．０時間後、７．５時間後、及び１０．０時間後の粘度を２５℃で測定した。
[Viscosity I]
Using a rotational viscometer (Bismometron VGH viscometer manufactured by Shibaura System Co., Ltd.), the viscosity after 1 minute of mixing the first and second liquids was measured at 25 ° C.
[Geltime]
In accordance with JIS C 2105, the time (seconds) until the epoxy resin composition gelled on a hot plate at 120 ° C. was measured.
[Thixotropic index (TI)]
Using a rotational viscometer (Bismometron VGH viscometer manufactured by Shibaura System Co., Ltd.), immediately after mixing of the first liquid and the second liquid, 2.5 hours, 5.0 hours, 7.5 hours, and After 10.0 hours, the viscosity (η 20 ) at 20 revolutions at 25 ° C. and the viscosity (η 4 ) at 4 revolutions were measured and determined by the following equation.
TI = η 4 / η 20
[Viscosity II]
Using a rotational viscometer (Bismometron VGH viscometer manufactured by Shibaura System Co., Ltd.), immediately after mixing of the first liquid and the second liquid, 2.5 hours, 5.0 hours, 7.5 hours, and The viscosity after 10.0 hours was measured at 25 ° C.
［塗装性Ｉ］
細線を接合させたアルミニウム製の直径３ｍｍの真球をエポキシ樹脂組成物中に３秒間浸漬させた後、これを引上げ、真球を細線でつり下げた状態で１１０℃にて４時間加熱して、表面のエポキシ樹脂組成物を硬化させた。この間、エポキシ樹脂組成物のたれ落ちがなかった場合を「○（合格）」とし、たれ落ちがあった場合を「×（不合格）」とした。
［塗装性II］
上記のアルミニウム製真球上に形成した硬化被膜の表面状態を目視で観察し、下記の基準で評価した。
○：全体が均一
△：一部不均一な部分あり
×：ほぼ全体が不均一
［煮沸吸収率］
エポキシ樹脂組成物を１００℃、６時間の条件で加熱し硬化させて得られた硬化物を１００℃の沸騰水中に１時間浸漬し、次式より求めた。
煮沸吸水率（％）
＝{（煮沸後の硬化物重量−煮沸前の硬化物重量）／煮沸後の硬化物重量｝×１００
［体積抵抗率］
エポキシ樹脂組成物を１００℃、６時間の条件で加熱成形してＪＩＳ Ｋ ６９１１に規定する寸法のテストピースを作製し、このテストピースを１２０℃、２気圧（約０．２ＭＰａ）、９５％ＲＨの条件で５０時間加湿した後、表面に付着している水分をよく拭き取り２５℃にて体積抵抗率を測定した。測定値が１×１０１１Ω・ｃｍ以上であった場合を「○」とし、それ未満であった場合を「×」とした。
[Paintability I]
An aluminum sphere with a diameter of 3 mm joined with fine wires was immersed in the epoxy resin composition for 3 seconds, then pulled up and heated at 110 ° C. for 4 hours with the true sphere suspended by the fine wires. The epoxy resin composition on the surface was cured. During this time, the case where there was no dripping of the epoxy resin composition was designated as “◯ (passed)”, and the case where there was dripping was designated as “x (failed)”.
[Paintability II]
The surface state of the cured film formed on the aluminum sphere was visually observed and evaluated according to the following criteria.
○: Entirely uniform △: Partially non-uniform portion ×: Almost entirely non-uniform [boiling absorption rate]
A cured product obtained by heating and curing the epoxy resin composition at 100 ° C. for 6 hours was immersed in boiling water at 100 ° C. for 1 hour, and determined from the following formula.
Boiling water absorption (%)
= {(Weight of cured product after boiling−weight of cured product before boiling) / weight of cured product after boiling} × 100
[Volume resistivity]
The epoxy resin composition was thermoformed at 100 ° C. for 6 hours to produce a test piece having the dimensions specified in JIS K 6911. The test piece was 120 ° C., 2 atm (about 0.2 MPa), 95% RH. After humidifying for 50 hours under the above conditions, the moisture adhering to the surface was thoroughly wiped off and the volume resistivity was measured at 25 ° C. The case where the measured value was 1 × 10 11 Ω · cm or more was “◯”, and the case where the measured value was less than that was “×”.
表１及び表２から明らかなように、本発明の実施例のエポキシ樹脂組成物は、揺変性に優れるとともに、揺変性及び粘度の経時変化が小さく、初期はもとより長時間経過後も優れた塗装性を有しており、さらに、硬化物の耐湿性も良好であることが確認された。 As is apparent from Tables 1 and 2, the epoxy resin compositions of the examples of the present invention are excellent in thixotropic properties, have small thixotropic properties and small changes in viscosity over time, and have excellent coating after a long time from the beginning. Furthermore, it was confirmed that the moisture resistance of the cured product was also good.
Claims (5)
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| CN111592848A (en) * | 2020-06-04 | 2020-08-28 | 杭州每步材料科技有限公司 | High-thixotropy underwater epoxy grouting material and preparation method thereof |
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| JP2019056030A (en) * | 2017-09-20 | 2019-04-11 | シンフォニアテクノロジー株式会社 | varnish |
| CN111592848A (en) * | 2020-06-04 | 2020-08-28 | 杭州每步材料科技有限公司 | High-thixotropy underwater epoxy grouting material and preparation method thereof |
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