JP4632861B2 - Epoxy resin composition - Google Patents
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- JP4632861B2 JP4632861B2 JP2005146164A JP2005146164A JP4632861B2 JP 4632861 B2 JP4632861 B2 JP 4632861B2 JP 2005146164 A JP2005146164 A JP 2005146164A JP 2005146164 A JP2005146164 A JP 2005146164A JP 4632861 B2 JP4632861 B2 JP 4632861B2
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Description
本発明は、保存安定性、加熱時の硬化反応性に優れ、かつ含浸性に優れたエポキシ樹脂組成物の製造方法に関する。 The present invention relates to a method for producing an epoxy resin composition having excellent storage stability, curing reactivity upon heating, and excellent impregnation properties.
一般に、含浸用樹脂組成物として、液状エポキシ樹脂に液状酸無水物硬化剤を配合した含浸用樹脂組成物が広く用いられている。このエポキシ樹脂と酸無水物硬化剤からなる組成物は、そのままでは加熱時の硬化反応性が遅いため、通常、硬化性を改善するためにアミン類、イミダゾール類に代表される硬化促進剤を併用する。 In general, as an impregnating resin composition, an impregnating resin composition in which a liquid acid anhydride curing agent is blended with a liquid epoxy resin is widely used. The composition comprising this epoxy resin and acid anhydride curing agent is slow in curing reactivity when heated as it is, and usually used together with a curing accelerator represented by amines and imidazoles to improve curability. To do.
しかしながら、硬化促進剤を添加すると、硬化反応性は改善されるものの、保存安定性が劣り、作業温度においてもエポキシ樹脂と酸無水物硬化剤との重合が起きるため、徐々に増粘し、やがて使用不可能になる。つまり保存安定性が限定され、また管理限界粘度を超えた場合には廃棄処分が必要となり作業管理上ならびに経済的、環境的な面からも問題が多い。 However, when a curing accelerator is added, the curing reactivity is improved, but the storage stability is inferior, and the polymerization of the epoxy resin and the acid anhydride curing agent occurs even at the working temperature. Unusable. In other words, storage stability is limited, and when the control limit viscosity is exceeded, disposal is necessary, and there are many problems in terms of work management as well as economical and environmental aspects.
一方、近年、各種のエポキシ樹脂に対するマイクロカプセルを応用した熱潜在型硬化促進剤が提案され実用に供されているが、エポキシ樹脂組成物などに不溶の粉体であり、エポキシ樹脂組成物に分散して用いられるため、含浸などの作業においては微細な隙間に含浸されず含浸不良や硬化不良を起こし易い。 On the other hand, in recent years, thermal latent curing accelerators using microcapsules for various epoxy resins have been proposed and put into practical use, but they are insoluble in epoxy resin compositions and dispersed in epoxy resin compositions. Therefore, in work such as impregnation, the fine gaps are not impregnated, and impregnation and curing are liable to occur.
さらに、熱潜在型硬化促進剤として各種の金属アセチルアセトネート化合物が提案されている。しかしいずれも融点が高く、エポキシ樹脂や酸無水物に溶解しにくく、溶解させるためには80℃以上の高温で長時間を要する。そのため溶解時に高温に曝されることによる保存安定性の低下や、調合作業に手間がかかり問題であった。
また、これらの熱潜在型硬化促進剤は、樹脂の保管時に、促進剤の析出や沈降が起こりやすく、樹脂の管理上も問題があった。
Furthermore, various metal acetylacetonate compounds have been proposed as thermal latent curing accelerators. However, all of them have a high melting point and are difficult to dissolve in an epoxy resin or an acid anhydride, and it takes a long time at a high temperature of 80 ° C. or higher to dissolve. For this reason, it has been a problem that the storage stability is lowered by being exposed to a high temperature at the time of dissolution, and the preparation work is troublesome.
In addition, these thermal latent curing accelerators are prone to precipitation and settling of the accelerator during storage of the resin, and there is a problem in the management of the resin.
本発明の目的は、上述の問題点を克服し、保存安定性、含浸性、硬化特性などに優れたエポキシ樹脂組成物の製造方法を提供するものである。 The object of the present invention is to overcome the above-mentioned problems and to provide a method for producing an epoxy resin composition having excellent storage stability, impregnation properties, curing characteristics, and the like.
本発明の目的を達成するために、金属アセチルアセトネートを、エポキシ樹脂と不活性な溶剤と共に、ボールミルまたはホモミキサーで微粉末スラリーとし、そのスラリーをエポキシ樹脂に混合し、用いた溶剤を除去後加熱することによって、エポキシ樹脂中に硬化促進剤を安定して溶解し、そのエポキシ樹脂と酸無水物硬化剤を混合することによって、保存安定性、硬化性、含浸性などに優れたエポキシ樹脂組成物の製造方法を提供するものである。 To achieve the object of the present invention, metal acetylacetonate is made into a fine powder slurry with a ball mill or a homomixer together with an epoxy resin and an inert solvent, the slurry is mixed with the epoxy resin, and the solvent used is removed. Epoxy resin composition with excellent storage stability, curability, impregnation, etc. by dissolving the curing accelerator stably in the epoxy resin by heating and mixing the epoxy resin and acid anhydride curing agent The manufacturing method of a thing is provided.
以下、本発明について詳細な説明を行う。本発明に用いられる金属アセチルアセトネートを構成する金属として、アルミニウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、ジルコニウムなどが挙げられるが、特に好ましくはコバルト(II)アセチルアセトネート、コバルト(III)アセチルアセトネート、マンガン(III)アセチルアセトネートである。 The present invention will be described in detail below. Examples of the metal constituting the metal acetylacetonate used in the present invention include aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, and the like, and particularly preferably cobalt (II) acetylacetonate and cobalt. (III) acetylacetonate, manganese (III) acetylacetonate.
この金属アセチルアセトネートを微粉末にするためのエポキシ樹脂と混和し不活性な溶剤としては、アセトン、メチルエチルケトン、ベンゼン、トルエン、ヘキサン、シクロヘキサン、クロロホルム等があげられ、これらは後に減圧下に除去することを考慮して、できるだけ沸点の低い溶剤が好ましい。 Examples of the inert solvent mixed with the epoxy resin for making the metal acetylacetonate into a fine powder include acetone, methyl ethyl ketone, benzene, toluene, hexane, cyclohexane, chloroform and the like, which are later removed under reduced pressure. In view of this, a solvent having a boiling point as low as possible is preferable.
またエポキシ樹脂は、1分子内に2個以上のエポキシ基を含むエポキシ樹脂であれば特に限定されるものではなく、市販の汎用性のエポキシ樹脂が問題なく使用できる。例えば、ビスフェノールA型、ビスフェノールF型、ビスフェノールAD型、ビスフェノールS型等ビスフェノール化合物のジグリシジルエーテル化合物、多価フェノールノのポリグリシジルエーテル化合物、フェノールノボラック、クレゾールノボラック、トリヒドロキシフェニルメタン、トリヒドロキシフェニルプロパン、テトラヒドロキシフェニルエタン、ポリビニルフェノール等のグリシジルエーテル化合物、芳香族アミン化合物から誘導されるグリシジルアミン型化合物、グリシジルエステル型化合物、ポリアルキレンエーテル類のグリシジルエーテル化合物、脂環式エポキシ化合物、トリグリジルイソシアヌレート等の含複素環エポキシ化合物、ヒダントイン型エポキシ化合物、これらのハロゲン置換体エポキシ化合物等が単独あるいは2種以上の混合物として用いる。特に、本発明の主旨である液状を実現するためには常温で比較的低粘度の液状エポキシ樹脂を主成分として用いる事が望ましい。 The epoxy resin is not particularly limited as long as it is an epoxy resin containing two or more epoxy groups in one molecule, and a commercially available general-purpose epoxy resin can be used without any problem. For example, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type and the like bisphenol compound diglycidyl ether compound, polyphenolic polyglycidyl ether compound, phenol novolac, cresol novolac, trihydroxyphenylmethane, trihydroxyphenyl Glycidyl ether compounds such as propane, tetrahydroxyphenylethane, polyvinylphenol, glycidylamine type compounds derived from aromatic amine compounds, glycidyl ester type compounds, glycidyl ether compounds of polyalkylene ethers, alicyclic epoxy compounds, triglycidyl Heterocyclic epoxy compounds such as isocyanurates, hydantoin type epoxy compounds, and halogen-substituted epoxy compounds alone Rui used as a mixture of two or more. In particular, in order to realize the liquid state that is the gist of the present invention, it is desirable to use a liquid epoxy resin having a relatively low viscosity at room temperature as a main component.
さらに、本発明に用いられる液状の酸無水物とはメチルテトラヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、メチルエンドメチレンテトラヒドロフタル酸無水物などが単独、あるいは混合して用いられる。 Furthermore, as the liquid acid anhydride used in the present invention, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride and the like are used alone or in combination.
以下に、これらの化合物を用いてエポキシ樹脂組成物を得る方法を述べる。はじめに溶剤に金属アセチルアセトネートを10〜30重量%になるように混合し、その混合液をボールミルあるいはホモミキサーにて所定の時間混合粉砕し、金属アセチルアセトネートの微粉末含有スラリーとし、このスラリーをエポキシ樹脂中に混合溶解した後、速やかに減圧下において、溶剤を除去し若干加熱する事によってエポキシ樹脂に金属アセチルアセトネートを溶解させることが可能になる。金属アセチルアセトネートを溶解する際には、80℃以下に加温して溶解させることも可能である。またエポキシ樹脂と混合して減圧下に溶剤を除去する過程でも、必要最小限の加温(望ましくは60℃以下)をすることも可能である。 Below, the method of obtaining an epoxy resin composition using these compounds is described. First, metal acetylacetonate is mixed with the solvent so as to be 10 to 30% by weight, and the mixed solution is mixed and pulverized for a predetermined time with a ball mill or a homomixer to form a metal acetylacetonate fine powder-containing slurry. It is possible to dissolve the metal acetylacetonate in the epoxy resin by quickly removing the solvent and heating slightly under reduced pressure after mixing and dissolving in the epoxy resin. When the metal acetylacetonate is dissolved, it can be dissolved by heating to 80 ° C. or lower. Further, even in the process of mixing with an epoxy resin and removing the solvent under reduced pressure, it is possible to perform the minimum necessary heating (desirably 60 ° C. or less).
この時の、エポキシ樹脂中の金属アセチルアセトネートの溶解量は0.3〜3重量%になるように調整するのが望ましい。溶解量が0.3重量%以下では、硬化促進剤としての効果が十分でなく、得られる組成物の加熱時の硬化反応性に劣る。 At this time, it is desirable to adjust the dissolution amount of the metal acetylacetonate in the epoxy resin to be 0.3 to 3% by weight. When the dissolution amount is 0.3% by weight or less, the effect as a curing accelerator is not sufficient, and the curing reactivity upon heating of the resulting composition is inferior.
溶解量が3重量%を超えると、エポキシ樹脂中に溶解しきれず、析出を起こしたり、また硬化物の特性が劣ることになり好ましくない。 If the dissolution amount exceeds 3% by weight, it cannot be dissolved in the epoxy resin, causing precipitation, and the properties of the cured product are inferior.
このようにして得られた、金属アセチルアセトネート溶解エポキシ樹脂を、硬化剤である酸無水物に所定量を加え、目的とするエポキシ樹脂組成物を得ることができる。 A predetermined amount of the metal acetylacetonate-dissolved epoxy resin thus obtained can be added to an acid anhydride as a curing agent to obtain a target epoxy resin composition.
以下、本発明による実施形態を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
金属アセチルアセトネートとしてコバルト(II)アセチルアセトネート1gと不活性溶剤としてアセトン5mlをホモミキサーで混合し、速やかにエポキシ樹脂としてビスフェノールF型エポキシ樹脂であるエピコート806(油化シェル社製)100gに混合攪拌し、減圧下にアセトンを除去して50℃に加温したところ容易に溶解し、透明な硬化促進剤溶解エポキシ樹脂を得た。
この硬化促進剤溶解エポキシ樹脂に酸無水物としてメチルテトラヒドロフタル酸無水物HN2200(日立化成社製)を80g混合し、赤紫色透明のエポキシ樹脂組成物を得た。
1 g of cobalt (II) acetylacetonate as metal acetylacetonate and 5 ml of acetone as inert solvent are mixed with a homomixer, and quickly added to 100 g of Epicoat 806 (manufactured by Yuka Shell) as a bisphenol F type epoxy resin as an epoxy resin. After mixing and stirring, acetone was removed under reduced pressure and the mixture was heated to 50 ° C. and dissolved easily to obtain a transparent curing accelerator-dissolved epoxy resin.
80 g of methyltetrahydrophthalic anhydride HN2200 (manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride was mixed with this curing accelerator-dissolved epoxy resin to obtain a red-purple transparent epoxy resin composition.
実施例1において金属アセチルアセトネートをコバルト(III)アセチルアセトネート、不活性溶剤としてクロロホルムを用いた以外は、同様の手法で緑色透明のエポキシ樹脂組成物を得た。 A green transparent epoxy resin composition was obtained in the same manner as in Example 1 except that cobalt (III) acetylacetonate was used as the metal acetylacetonate and chloroform was used as the inert solvent.
実施例1において金属アセチルアセトネートをマンガン(III)アセチルアセトネート、不活性溶剤としてヘキサンとした以外は、同様の手法で茶褐色透明のエポキシ樹脂組成物を得た。 A brownish brown transparent epoxy resin composition was obtained in the same manner as in Example 1 except that the metal acetylacetonate was manganese (III) acetylacetonate and hexane was used as the inert solvent.
比較例1においてエポキシ樹脂は実施例1と同じビスフェノールF型エポキシ樹脂であるエピコート806を100g、酸無水物硬化剤としてメチルテトラヒドロフタル酸無水物 HN2200(日立化成社製)80g、硬化促進剤としてベンジルジメチルアミン0.5gを添加して淡黄色透明のエポキシ樹脂組成物を得た。 In Comparative Example 1, the epoxy resin is 100 g of Epicoat 806, which is the same bisphenol F type epoxy resin as in Example 1, 80 g of methyltetrahydrophthalic anhydride HN2200 (manufactured by Hitachi Chemical Co., Ltd.) as the acid anhydride curing agent, and benzyl as the curing accelerator. 0.5 g of dimethylamine was added to obtain a light yellow transparent epoxy resin composition.
比較例2においてエポキシ樹脂、酸無水物硬化剤は、比較例1と同様で、硬化促進剤としてマイクロカプセル型の熱潜在性硬化促進剤HX3741(旭化成社製)4g(比較例2)を混合し、エポキシ樹脂組成物を得た。 In Comparative Example 2, the epoxy resin and the acid anhydride curing agent are the same as in Comparative Example 1, and 4 g (Comparative Example 2) of microcapsule type thermal latent curing accelerator HX3741 (manufactured by Asahi Kasei Co., Ltd.) is mixed as a curing accelerator. An epoxy resin composition was obtained.
比較例3においてメチルテトラヒドロフタル酸無水物HN2200(日立化成社製)80gに硬化促進剤としてコバルト(II)アセチルアセトネート1gを100℃、2hrかけて酸無水物に溶解し、比較例1のエポキシ樹脂100gを混合し、赤紫色半透明のエポキシ樹脂組成物を得た。 In Comparative Example 3, 1 g of cobalt (II) acetylacetonate as a curing accelerator was dissolved in 80 g of methyltetrahydrophthalic anhydride HN2200 (manufactured by Hitachi Chemical Co., Ltd.) at 100 ° C. for 2 hours. 100 g of resin was mixed to obtain a reddish purple translucent epoxy resin composition.
以上の実施例1〜3 比較例1〜3で得られたエポキシ樹脂組成物について以下の特性を評価した。
(加熱時の硬化性)150℃でのゲル化時間を測定した。
(保存安定性)エポキシ樹脂組成物を40℃に保管した場合の組成物の粘度が初期の2倍になるまでの日数を測定して評価した。
(保管後の状態)保存安定性評価後の、エポキシ樹脂組成物の硬化促進剤の析出や沈降状態を観察した。
(含浸性)減圧濾過用フィルターホルダーに、厚さ0.18mmのガラスクロスを3枚重ね、50℃で減圧濾過を行ない、濾過されたエポキシ樹脂組成物の150℃でのゲル化時間を測定した。
Examples 1 to 3 The following properties were evaluated for the epoxy resin compositions obtained in Comparative Examples 1 to 3.
(Curing property during heating) The gelation time at 150 ° C. was measured.
(Storage stability) The number of days until the viscosity of the composition when the epoxy resin composition was stored at 40 ° C. doubled the initial value was measured and evaluated.
(State after storage) Precipitation and sedimentation state of the curing accelerator of the epoxy resin composition after storage stability evaluation was observed.
(Impregnation) Three glass cloths having a thickness of 0.18 mm were stacked on a filter holder for vacuum filtration, and vacuum filtration was performed at 50 ° C., and the gelation time at 150 ° C. of the filtered epoxy resin composition was measured.
以上の評価結果を表-1に示す。
以上、実施例および比較例で示したとおり、比較例1では保存安定性が劣り、比較例2では含浸性が劣り、保管後に硬化促進剤の沈降が生じ、比較例3では保存安定性が劣るとともに保管後に硬化促進剤の沈降が生じるが、実施例の製造方法のような本発明によるエポキシ樹脂組成物は、保存安定性、加熱時の硬化性に優れ、かつ含浸性が優れているため、実用上大いに有用である。
As described above, as shown in Examples and Comparative Examples, Comparative Example 1 has poor storage stability, Comparative Example 2 has poor impregnation properties, precipitation of the curing accelerator occurs after storage, and Comparative Example 3 has poor storage stability. In addition, precipitation of the curing accelerator occurs after storage, but the epoxy resin composition according to the present invention such as the production method of the example is excellent in storage stability, curability at the time of heating, and excellent in impregnation property. It is very useful in practice.
以上述べたことから、本発明のエポキシ樹脂組成物は、電機機器の絶縁コイル等を製造する分野において、特に含浸用途において幅広く利用可能である。 As described above, the epoxy resin composition of the present invention can be widely used in the field of producing insulating coils and the like of electrical equipment, particularly in impregnation applications.
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JPH01158026A (en) * | 1987-12-16 | 1989-06-21 | Toyo Electric Mfg Co Ltd | Production of curing accelerator for epoxy resin |
JPH01292056A (en) * | 1988-05-18 | 1989-11-24 | Toyo Electric Mfg Co Ltd | Production of epoxy resin composition |
JPH0525255A (en) * | 1991-07-17 | 1993-02-02 | Toyo Electric Mfg Co Ltd | Production of cure accelerator for epoxy resin |
JPH06192396A (en) * | 1992-12-25 | 1994-07-12 | Nissan Chem Ind Ltd | One pack type epoxy resin composition |
JPH08306572A (en) * | 1995-04-27 | 1996-11-22 | Hitachi Ltd | Manufacture of insulated coil |
JPH10298267A (en) * | 1997-04-22 | 1998-11-10 | Hitachi Ltd | Curing composition for epoxy |
JP2000026578A (en) * | 1998-07-14 | 2000-01-25 | Hitachi Ltd | Epoxy resin composition |
JP2005154638A (en) * | 2003-11-27 | 2005-06-16 | Toyo Electric Mfg Co Ltd | Epoxy resin composition |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH01158026A (en) * | 1987-12-16 | 1989-06-21 | Toyo Electric Mfg Co Ltd | Production of curing accelerator for epoxy resin |
JPH01292056A (en) * | 1988-05-18 | 1989-11-24 | Toyo Electric Mfg Co Ltd | Production of epoxy resin composition |
JPH0525255A (en) * | 1991-07-17 | 1993-02-02 | Toyo Electric Mfg Co Ltd | Production of cure accelerator for epoxy resin |
JPH06192396A (en) * | 1992-12-25 | 1994-07-12 | Nissan Chem Ind Ltd | One pack type epoxy resin composition |
JPH08306572A (en) * | 1995-04-27 | 1996-11-22 | Hitachi Ltd | Manufacture of insulated coil |
JPH10298267A (en) * | 1997-04-22 | 1998-11-10 | Hitachi Ltd | Curing composition for epoxy |
JP2000026578A (en) * | 1998-07-14 | 2000-01-25 | Hitachi Ltd | Epoxy resin composition |
JP2005154638A (en) * | 2003-11-27 | 2005-06-16 | Toyo Electric Mfg Co Ltd | Epoxy resin composition |
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