JPH05156127A - Thixotropic epoxy resin composition - Google Patents
Thixotropic epoxy resin compositionInfo
- Publication number
- JPH05156127A JPH05156127A JP4148495A JP14849592A JPH05156127A JP H05156127 A JPH05156127 A JP H05156127A JP 4148495 A JP4148495 A JP 4148495A JP 14849592 A JP14849592 A JP 14849592A JP H05156127 A JPH05156127 A JP H05156127A
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- epoxy resin
- thixotropic
- less
- mixture
- 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.)
- Granted
Links
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、揺変性エポキシ樹脂組
成物に関するものである。FIELD OF THE INVENTION The present invention relates to a thixotropic epoxy resin composition.
【０００２】[0002]
【従来技術及びその問題点】揺変性（チクソトロピック
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化の小さいことと、硬
化物の耐湿性の良好なことが要求される。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、
コーティング膜厚が一定せず、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、塗膜の
耐湿性が悪いと、塗膜の電気特性が悪化し、電子部品を
安全に保護することができなくなる。揺変性を有するエ
ポキシ樹脂組成物は、エポキシ樹脂に対して、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
加によっては、得られる組成物は満足する揺変性を有し
ない。BACKGROUND OF THE INVENTION Epoxy resin compositions having thixotropic properties are widely used as dip coating resins for small electronic parts such as capacitors, resistors and hybrid ICs. In such a thixotropic epoxy resin composition, it is required that the thixotropy of the epoxy resin composition after the addition of the curing agent is less reduced with time and that the cured product has good moisture resistance. When the thixotropic deterioration of the epoxy resin composition after mixing with the curing agent is large,
The coating film thickness is not constant and sagging occurs in a short time, so that a coating film having a uniform thickness cannot be obtained. In addition, when the moisture resistance of the coating film is poor, the electrical characteristics of the coating film deteriorate, and it becomes impossible to safely protect the electronic component. The thixotropic epoxy resin composition can be obtained by adding a filler such as colloidal silica or bentonite to the epoxy resin, but it can be obtained by adding only such a filler. The composition does not have satisfactory thixotropy.
【０００３】特開平１−１８８５５２号公報には、前記
エポキシ樹脂組成物の揺変性を改良するために、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とも
に、メチルカルビトールや、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を添加
したものが開示されている。しかし、この組成物では、
揺変性の改善は得られるものの、その硬化物の耐湿性の
点では不満足で、特に、そのヒドロキシル基含有化合物
の多量の添加により、硬化物の耐湿性が損われるという
問題を含む。In order to improve thixotropy of the epoxy resin composition, JP-A-1-188552 discloses an amide compound such as formamide or dimethylformamide, as well as a hydroxyl group such as methyl carbitol, diethylene glycol or ethylene glycol. It is disclosed that a compound containing the compound is added. However, with this composition,
Although thixotropy can be improved, it is unsatisfactory in terms of moisture resistance of the cured product, and in particular, the addition of a large amount of the hydroxyl group-containing compound impairs the moisture resistance of the cured product.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、揺変性にす
ぐれるとともに、耐湿性のすぐれた硬化物を与えるエポ
キシ樹脂組成物を提供することをその課題とする。An object of the present invention is to provide an epoxy resin composition which is excellent in thixotropy and gives a cured product having excellent moisture resistance.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。The present inventors have completed the present invention as a result of intensive studies to solve the above problems.
【０００６】即ち、本発明によれば、全塩素含有率が１
６００ｐｐｍ以下で可ケン化塩素含有率が１００ｐｐｍ
以下の常温で液状のビスフェノールグリシジルエーテル
型エポキシ樹脂中に揺変性付与剤としてコロイダルシリ
カを均一に添加混合してなる第１液と、常温で液状の芳
香族アミン系硬化剤からなる第２液とから構成され、該
第１液と第２液との混合物の２５℃での初期構造粘性比
が２〜６の範囲にあり、かつ該混合物の６時間保存後に
おける２５℃での構造粘性比の低下率が２５％以下であ
ることを特徴とする揺変性エポキシ樹脂組成物が提供さ
れる。That is, according to the present invention, the total chlorine content is 1
Saponifiable chlorine content below 600ppm is 100ppm
A first liquid obtained by uniformly adding and mixing colloidal silica as a thixotropic agent to a bisphenol glycidyl ether type epoxy resin which is liquid at room temperature, and a second liquid which is an aromatic amine-based curing agent which is liquid at room temperature. The initial structural viscosity ratio of the mixture of the first liquid and the second liquid at 25 ° C is in the range of 2 to 6, and the structural viscosity ratio of the mixture at 25 ° C after storage for 6 hours is Provided is a thixotropic epoxy resin composition characterized by a reduction rate of 25% or less.
【０００７】本発明においては、エポキシ樹脂として、
全塩素含有率が１６００ｐｐｍ以下、可ケン化塩素含有
率が１００ｐｐｍ以下で、かつ常温で液状のビスフェノ
ールジグリシジルエーテル型エポキシ樹脂を用いる。こ
のものは、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などのビスフェ
ノール類とエピクロルヒドリンを反応させて得られる常
温で液状のエポキシ樹脂で、精製などにより全塩素含有
率を１６００ｐｐｍ以下、可ケン化塩素含有率を１００
ｐｐｍ以下に調整したものである。全塩素含有率が１６
００ｐｐｍを超えたり、可ケン化塩素含有率が１００ｐ
ｐｍを超えると、組成物の揺変性の経時低下が大きく、
硬化物の耐湿性も劣るようになる。In the present invention, as the epoxy resin,
A bisphenol diglycidyl ether type epoxy resin having a total chlorine content of 1600 ppm or less, a saponifiable chlorine content of 100 ppm or less and being liquid at room temperature is used. This is an epoxy resin that is liquid at room temperature and is obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol AD, and hydrogenated bisphenol A with epichlorohydrin. Chlorinated content of 100
It is adjusted to be ppm or less. Total chlorine content is 16
Exceeding 00ppm, or content of saponifiable chlorine is 100p
When it exceeds pm, the thixotropy of the composition is largely decreased with time,
The moisture resistance of the cured product also becomes poor.
【０００８】本発明で用いる硬化剤としては、常温で液
状の芳香族アミンであり、他の硬化剤たとえば酸無水物
系、イミダゾール系、ジシアンジアミド系などのもので
は、組成物の揺変性が劣り、また硬化物の耐湿性も劣
る。常温で液状の芳香族アミンとしては、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と
エポキシ化合物との付加物（アンカミンＺ：アンカ−ケ
ミカル社製）、ジアミノジエチルジフェニルメタン（カ
ヤハード：日本化薬社製）、ジアミノジフェニルメタン
のクルード（ＭＤＡ−１５０：三井東圧化学社製）、ジ
エチルトルエンジアミン（エチル社製）、アニリンとホ
リマリンの縮合物（ラッカマイドＷＨ−６１９：大日本
インキ化学社製）などがある。硬化剤の添加量は、エポ
キシ樹脂１００重量部に対し、１〜４０重量部、好まし
くは１５〜３５重量部の割合である。The curing agent used in the present invention is an aromatic amine which is liquid at room temperature, and other curing agents such as acid anhydride type, imidazole type and dicyandiamide type have poor thixotropic properties, Moreover, the moisture resistance of the cured product is also poor. As the aromatic amine that is liquid at room temperature, an adduct of eutectic mixture of metaphenylenediamine and diaminodiphenylmethane and an epoxy compound (Ancamine Z: manufactured by Anka Chemical Co., Ltd.), diaminodiethyldiphenylmethane (Kayahard: manufactured by Nippon Kayaku Co., Ltd.) , Crude of diaminodiphenylmethane (MDA-150: manufactured by Mitsui Toatsu Kagaku Co., Ltd.), diethyltoluenediamine (manufactured by Ethyl Co.), condensate of aniline and forimarin (laccamide WH-619: manufactured by Dainippon Ink and Chemicals, Inc.) and the like. The amount of the curing agent added is 1 to 40 parts by weight, preferably 15 to 35 parts by weight, based on 100 parts by weight of the epoxy resin.
【０００９】本発明では、揺変性付与剤としてコロイダ
ルシリカを用いる。このものは、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と呼ばれる一
次粒子径が７〜４０ｎｍで、比表面積が５０〜３８０ｍ
2／ｇのシリカで、その表面には、親水性のシラノール
基（Ｓｉ−ＯＨ）と疎水性のシロキサン（Ｓｉ−Ｏ−Ｓ
ｉ）が存在している。市販されているものには、アエロ
ジル（日本アエロジル社製）がある。コロイダルシリカ
の添加量は、特に限定されるものではないが、エポキシ
樹脂１００重量部に対して、好ましくは２．０〜５．０
重量部である。２．０重量部未満では、充分な揺変性が
得られず、５．０重量部より多いと粘度、揺変性が著し
く高くなり、均一な膜厚でコーティングできない。In the present invention, colloidal silica is used as the thixotropic agent. This product has a primary particle size of 7 to 40 nm called fumed silica obtained by a flame hydrolysis method of silicon tetrachloride and a specific surface area of 50 to 380 m.
2 / g of silica, the surface of which has a hydrophilic silanol group (Si-OH) and a hydrophobic siloxane (Si-O-S).
i) is present. There is Aerosil (manufactured by Nippon Aerosil Co., Ltd.) in the market. The amount of colloidal silica added is not particularly limited, but is preferably 2.0 to 5.0 with respect to 100 parts by weight of the epoxy resin.
Parts by weight. If it is less than 2.0 parts by weight, sufficient thixotropy cannot be obtained, and if it is more than 5.0 parts by weight, viscosity and thixotropy are remarkably increased, and coating with a uniform film thickness cannot be performed.
【００１０】本発明においては、コロイダルシリカによ
りもたらされる揺変性を増強する目的で、揺変性増強
剤、例えばトリエタノールアミンや、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）や無機酸塩を添加することができる。その添加量
は、特に限従されるものではないが、エポキシ樹脂１０
０重量部に対して、好ましくは０．１〜２．０重量部で
ある。０．１重量部より少ないと格別の揺変性増強効果
が得られず、２．０重量部より多い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
可使時間を著しく短縮させる。In the present invention, for the purpose of enhancing thixotropy caused by colloidal silica, thixotropy enhancing agents such as triethanolamine, lower carboxylic acid salts of triethanolamine (acetate, propionate, etc.) and inorganic acids. Salt can be added. The addition amount is not particularly limited, but the epoxy resin 10
It is preferably 0.1 to 2.0 parts by weight with respect to 0 parts by weight. If the amount is less than 0.1 part by weight, no particular thixotropy-enhancing effect can be obtained, and if the amount is more than 2.0 parts by weight, the curing reaction between the epoxy resin and the aromatic amine curing agent is promoted, and the pot life of the composition is increased. Significantly shorten.
【００１１】電子部品をディップコートする場合の塗膜
厚さは、通常、０．２〜０．４ｍｍの厚さである場合が
多い。しかし、０．２ｍｍより薄膜にコートする場合
や、原料樹脂液の粘度が高いために所定の膜厚を得にく
い場合には、本発明組成物の粘性低下の目的のために反
応性希釈剤を添加するのがよい。反応性希釈剤として
は、分子内にエポキシ基を１ケ以上有するエポキシ化合
物で２５℃の粘度が２００ｃｐｓ以下のものが用いられ
る。たとえば、ブチルグリシジルエーテル、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な
どがある。反応性希釈剤の添加量は、エポキシ樹脂と反
応性希釈剤の混合物中３０ｗｔ％以下、好ましくは１〜
３０ｗｔ％、さらに好ましくは５〜２０ｗｔ％である。
３０ｗｔ％より多いと硬化物特性が悪くなる。In the case of dip-coating electronic parts, the coating film thickness is usually 0.2 to 0.4 mm in many cases. However, when a thin film having a thickness of less than 0.2 mm is coated or when it is difficult to obtain a predetermined film thickness due to the high viscosity of the raw material resin liquid, a reactive diluent is used for the purpose of decreasing the viscosity of the composition of the present invention. Good to add. As the reactive diluent, an epoxy compound having one or more epoxy groups in the molecule and having a viscosity at 25 ° C. of 200 cps or less is used. For example, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, allyl glycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like. The amount of the reactive diluent added is 30 wt% or less in the mixture of the epoxy resin and the reactive diluent, preferably 1 to
It is 30 wt%, more preferably 5 to 20 wt%.
If it exceeds 30 wt%, the properties of the cured product will deteriorate.
【００１２】本発明の組成物においては、上記成分の他
に必要に応じて、コロイダルシリカ以外の粉末充填剤、
難燃剤、着色剤などを添加することができる。粉末充填
剤として、結晶性シリカ、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、
ホワイトカーボンなどが用いられる。難燃剤としては、
粉末状有機ハロゲン化合物、赤リン、三酸化アンチモン
などが用いられる。着色剤としては、各種の顔料・染料
が用いられる。In the composition of the present invention, in addition to the above components, if necessary, a powder filler other than colloidal silica,
Flame retardants, colorants and the like can be added. As a powder filler, crystalline silica, fused silica, calcium carbonate, talc, mica, alumina, aluminum hydroxide,
White carbon or the like is used. As a flame retardant,
Powdered organic halogen compounds, red phosphorus, antimony trioxide, etc. are used. As the colorant, various pigments and dyes are used.
【００１３】本発明の組成物は、コロイダルシリカ及び
必要に応じての反応性希釈剤をあらかじめ添加混合した
エポキシ樹脂からなる第１液と、必要に応じて揺変性増
強剤をあらかじめ添加混合した芳香族アミン系硬化剤か
らなる第２液とから構成され、使用時に両液を所定割合
で混合して使用される。粉末充填剤、難燃剤、着色剤等
の補助成分は前記第１液又は第２液あるいは両液に添加
混合することができるが、好ましくは第１液に添加す
る。The composition of the present invention comprises a first liquid consisting of an epoxy resin to which colloidal silica and, if necessary, a reactive diluent have been added and mixed, and an aroma to which a thixotropic enhancer has been added and mixed, if necessary. It is composed of a second liquid consisting of a group amine curing agent, and both liquids are mixed at a predetermined ratio at the time of use. Auxiliary components such as powder filler, flame retardant, colorant and the like can be added to and mixed with the first liquid, the second liquid, or both liquids, but are preferably added to the first liquid.
【００１４】本発明の第１液と第２液からなる組成物の
第１の特徴は、両液の混合直後（初期）における混合物
の２５℃での構造粘性比（回転粘度計で２０回転での粘
度に対する４回転での粘度の比）が、２．０〜６．０の
範囲であり、好ましくは、２．５〜４．５の範囲であ
る。２．０より小さいとコーティング後「タレ」が生
じ、６．０を超えると揺変性が強すぎて均一にコーティ
ングが出来なくなる。この初期構造粘性比は、コロイダ
ルシリカの添加量や、揺変性増強剤の添加量等により調
節することができる。The first characteristic of the composition comprising the first liquid and the second liquid of the present invention is that the structural viscosity ratio of the mixture at 25 ° C. immediately after the mixing of the two liquids (the initial stage) (at 20 rotations with a rotary viscometer) The ratio of the viscosity at 4 rotations to the viscosity of 4) is in the range of 2.0 to 6.0, preferably 2.5 to 4.5. If it is less than 2.0, "dripping" occurs after coating, and if it exceeds 6.0, thixotropy is so strong that uniform coating cannot be performed. This initial structural viscosity ratio can be adjusted by the amount of colloidal silica added, the amount of thixotropic enhancer added, and the like.
【００１５】本発明の組成物の第２の特徴は、両液の混
合物の６時間保存後の構造粘性比の低下率が２５％以下
である。この構造粘性比の低下率が２５％を超えるよう
になると、膜厚の均一な塗膜を得ることが困難になる。
好ましい構造粘性比の低下率は２２％以下である。本発
明の組成物の場合、前記構造粘性比の低下率は、通常、
１０〜２２％の範囲内である。構造粘性比の低化率が前
記のような制限された範囲内にある組成物は、エポキシ
樹脂として前記した特定のものを用いるとともに、第１
液として、そ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を用いることにより得る
ことができる。換言すれば、第１液の調製に際し、第１
液と第２液との混合物の構造粘性比の低下率が２５％以
下になるように、前記した特定のエポキシ樹脂とコロイ
ダルシリカを均一に撹拌混合すればよい。第１液と第２
液からなるエポキシ樹脂組成物において、第１液と第２
液との混合物の構造粘性比低下率が前記のような制限さ
れた範囲にあるものは、本発明者らが初めて見出したも
のである。The second feature of the composition of the present invention is that the reduction rate of the structural viscosity ratio of the mixture of both solutions after storage for 6 hours is 25% or less. If the reduction rate of the structural viscosity ratio exceeds 25%, it becomes difficult to obtain a coating film having a uniform film thickness.
A preferable decrease rate of the structural viscosity ratio is 22% or less. In the case of the composition of the present invention, the reduction rate of the structural viscosity ratio is usually
It is within the range of 10 to 22%. The composition having a structural viscosity ratio lowering ratio within the limited range as described above uses the above-mentioned specific epoxy resin and
As a liquid, its viscosity is almost in equilibrium (equilibrium viscosity)
Can be obtained by using an equilibrium viscosity composition that has reached In other words, when preparing the first liquid,
The above-mentioned specific epoxy resin and colloidal silica may be uniformly stirred and mixed so that the decrease rate of the structural viscosity ratio of the mixture of the liquid and the second liquid is 25% or less. First liquid and second
In an epoxy resin composition comprising a liquid, a first liquid and a second liquid
It is the first time that the present inventors have found that the structural viscosity ratio lowering ratio of the mixture with the liquid is in the above-mentioned limited range.
【００１６】本発明の第１液の調製は、前記特定エポキ
シ樹脂にコロイダルシリカを添加し、撹拌混合すること
によって行われる。反応性希釈剤を添加する場合には、
エポキシ樹脂とコロイダルシリカとの撹拌混合が終った
後、反応性希釈剤を添加し、さらに短時間（約３０分間
程度）撹拌混合すればよい。本発明においては、エポキ
シ樹脂とコロイダルシリカの撹拌混合は、前記したよう
に、平衡粘度組成物が得られるように行う。このために
は、エポキシ樹脂にコロイダルシリカを添加し、長時
間、通常、２時間以上、好ましくは３〜５時間とする。
従来の方法では、エポキシ樹脂に対してコロイダルシリ
カを添加し、添加開始後混合撹拌する時間は、通常、３
０分程度であり、長くても約１時間程度である。このよ
うな撹拌混合時間では、本発明の組成物を得ることはで
きない。前記第１液を得るための撹拌装置としては、例
えば、ダブルプラネタリーミキサーを用いることができ
る。この撹拌装置の回転速度は、自転速度が７０〜９５
ｒ．ｐ．ｍ、公転速度が２２〜３３ｒ．ｐ．ｍ．であ
る。撹拌温度は、２０〜４０℃、好ましくは２５〜３５
℃である。The first liquid of the present invention is prepared by adding colloidal silica to the specific epoxy resin and stirring and mixing. When adding a reactive diluent,
After the stirring and mixing of the epoxy resin and the colloidal silica are completed, the reactive diluent may be added, and the stirring and mixing may be further performed for a short time (about 30 minutes). In the present invention, the stirring and mixing of the epoxy resin and the colloidal silica are carried out so as to obtain an equilibrium viscosity composition as described above. For this purpose, colloidal silica is added to the epoxy resin and the time is set to a long time, usually 2 hours or more, preferably 3 to 5 hours.
In the conventional method, the colloidal silica is added to the epoxy resin, and the time for mixing and stirring after the start of addition is usually 3
It is about 0 minutes, and about 1 hour at the longest. The composition of the present invention cannot be obtained with such stirring and mixing time. As the stirring device for obtaining the first liquid, for example, a double planetary mixer can be used. The rotation speed of this stirring device is 70-95.
r. p. m, the revolution speed is 22 to 33 r. p. m. Is. The stirring temperature is 20 to 40 ° C, preferably 25 to 35
℃.
【００１７】なお、本明細書において第１液に関して言
う、平衡粘度組成物とは、下記式で示される平衡粘度到
達度が９７％以上のものと定義される。 Ｒ：平衡粘度到達度 Ａ：平衡粘度 Ｂ：撹拌混合終了時の粘度In the present specification, the equilibrium viscosity composition referred to as the first liquid is defined as one having an equilibrium viscosity attainment degree of 97% or more, which is represented by the following formula. R: Achievement of equilibrium viscosity A: Equilibrium viscosity B: Viscosity at the end of stirring and mixing
【００１８】[0018]
【発明の効果】本発明の組成物は、前記した如き特定の
第１液と第２液からなるものであり、使用に際し、両液
を混合して使用される。そして、本発明の組成物では、
第１液と第２液との混合物は、初期構造粘性比が２〜６
という特定範囲に規定され、かつ混合物の６時間保存後
の構造粘性比の低下率が２５％以下に規定されているこ
とから、初期塗装性にすぐれるとともに、長時間経過後
においてもすぐれた塗装性を有している。また、本発明
の組成物では、全塩素含有率及び可ケン化塩素含有率が
規定されたビスフェノールグリシジルエーテル型エポキ
シ樹脂を用いるとともに、芳香族アミン系硬化剤を用い
たことから、前記のように、第１液と第２液の混合物の
構造粘性比の低下が少ない上に、耐湿性の良好な硬化物
を与える。The composition of the present invention comprises the above-mentioned specific first liquid and second liquid, and both liquids are mixed before use. And in the composition of the present invention,
The mixture of the first liquid and the second liquid has an initial structural viscosity ratio of 2 to 6
It is specified in the following specific range, and the decrease rate of the structural viscosity ratio after the mixture is stored for 6 hours is specified to be 25% or less, so that it has excellent initial paintability and excellent coating even after a long time has passed. Have sex. Further, in the composition of the present invention, the total chlorine content and the content of saponifiable chlorine are defined as bisphenol glycidyl ether type epoxy resin, and since the aromatic amine curing agent is used, as described above. , Which gives a cured product having good moisture resistance as well as a small decrease in the structural viscosity ratio of the mixture of the first liquid and the second liquid.
【００１９】[0019]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。なお、以下において示す部は重量部を示す。ま
た、表１に示した性能評価項目は、以下のようにして測
定されたものである。EXAMPLES Next, the present invention will be described in more detail by way of examples. In addition, the part shown below shows a weight part. The performance evaluation items shown in Table 1 are measured as follows.
【００２０】〔測定法〕 （１） 構造粘性比（チクソトロピック指数） 回転粘度計（芝浦システム社製：ビスメトロンＶＧＨ型
粘度計）を用いて、２５℃における２０回転の粘度と４
回転での粘度を測定し、次式により求めた。 （２）構造粘性比の低下率 硬化剤混合直後の構造粘性比の初期値と一定時間経過後
の構造粘性比を測定し、次式により求める。 （３）塗装性 細線を接合させたアルミニウム製の直径３ｍｍの真球を
組成物中に３秒間浸漬させた後、これを引上げ、真球を
その細線につり下げた状態で１１０℃にて４時間加熱し
て、表面に硬化樹脂被膜の形成された球体を作る。次の
この球体の垂直方向の直径Ｙ（ｍｍ）と、水平方向の直
径Ｘ（ｍｍ）を測定し、両者の比Ｙ／Ｘを測定して変形
率とする。この変形率が０．９以上、１．１未満の場合
には合格とし、０．９未満及び１．１以上の場合には不
合格とする。 （４）加湿後の体積固有抵抗値 ＪＩＳ Ｋ−６９１１に規定する寸法のテストピースを
１２０℃、２気圧、９５％ＲＨの条件で５０時間加湿
し、表面に付着している水分をよく拭き取り、２５℃に
て体積固有抵抗を測定し、その測定値が、５×１０12Ω
・ｃｍ以上を○、それ未満を×とした。[Measurement Method] (1) Structural Viscosity Ratio (Thixotropic Index) Using a rotational viscometer (manufactured by Shibaura System Co .: Vismetron VGH type viscometer), a viscosity of 20 rotations at 25 ° C. and 4
The viscosity at rotation was measured and determined by the following formula. (2) Decrease rate of structural viscosity ratio The initial value of the structural viscosity ratio immediately after the mixing of the curing agent and the structural viscosity ratio after a lapse of a fixed time are measured and calculated by the following formula. (3) Paintability A 3 mm diameter true sphere to which a fine wire is joined is immersed in the composition for 3 seconds, and then pulled up, and the true sphere is hung on the fine wire at 110 ° C for 4 seconds. It is heated for a period of time to form spheres having a cured resin coating formed on the surface. Next, the diameter Y (mm) in the vertical direction and the diameter X (mm) in the horizontal direction of this sphere are measured, and the ratio Y / X of the two is measured to obtain the deformation rate. If the deformation rate is 0.9 or more and less than 1.1, it is judged as acceptable, and if it is less than 0.9 or 1.1 or more, it is judged as unacceptable. (4) Volume specific resistance value after humidification A test piece having dimensions specified in JIS K-6911 is humidified for 50 hours under the conditions of 120 ° C, 2 atmospheric pressure and 95% RH, and the water adhering to the surface is wiped off well, The volume resistivity is measured at 25 ° C and the measured value is 5 × 10 12 Ω.
-Cm or more was marked with ◯ and less than it was marked with x.
【００２１】実施例１ 表１に示す成分組成を与える第１液と第２液を作り、両
者を混合した。この場合、第１液はエポキシ樹脂にコロ
イダルシリカを添加し、その添加後、３時間撹拌混合し
たものであり、その平衡粘度到達度１００％である。第
２液は、液状の変性芳香族ポリアミン（エピキュアＺ、
アンカ−ケミカル社製）にブチルグリシジルエーテルと
トリエタノールアミン（Ｎ（Ｃ2Ｈ5ＯＨ）3）を常法に
より添加混合したものである。なお、第１液の撹拌装置
としては、ダブルプラネタリーミキサー（（株）井上製
作所製、型式ＰＬＭ−５）を用いた。また、その撹拌速
度は、自転速度：８４ｒｐｍ、公転速度：２６ｒｍｐで
あった。前記の第１液と第２液との混合物についての特
性を調べ、その結果を表１に示す。Example 1 A first liquid and a second liquid having the composition shown in Table 1 were prepared and mixed together. In this case, the first liquid was obtained by adding colloidal silica to an epoxy resin, stirring the mixture for 3 hours after the addition, and achieving the equilibrium viscosity of 100%. The second liquid is a liquid modified aromatic polyamine (Epicure Z,
It is a mixture of butyl glycidyl ether and triethanolamine (N (C 2 H 5 OH) 3 ) added to Anker Chemical Co., Ltd. by a conventional method. A double planetary mixer (manufactured by Inoue Seisakusho, Model PLM-5) was used as a stirring device for the first liquid. The stirring speed was as follows: rotation speed: 84 rpm and revolution speed: 26 rpm. The characteristics of the mixture of the first liquid and the second liquid were examined, and the results are shown in Table 1.
【００２２】なお、表１に示した配合成分の具体的内容
は以下の通りである。 （１）エピコート８２８ ビスフェノールＡ系ジグリシジルエーテル、油化シェル
エポキシ（株）製、可ケン化塩素含有率：３６０ｐｐ
ｍ、全塩素含有率：１７３０ｐｐｍ （２）エピコート８２８ＥＬ エピコート８２８の高純度品、油化シェルエポキシ
（株）製、可ケン化塩素含有率：８０ｐｐｍ、全塩素含
有率：１４３０ｐｐｍ （３）エピコート８２８ＵＳ エピコート８２８の高純度品、油化シェルエポキシ
（株）製、可ケン化塩素含有率：２４ｐｐｍ、全塩素含
有率：１１３０ｐｐｍ （４）エピコートＹＬ−９８０ ビスフェノールＡ系ジグリシジルエーテルの超高純度
品、油化シェルエポキシ（株）製、可ケン化塩素含有
率：３ｐｐｍ、全塩素含有率：８０ｐｐｍ （５）反応性希釈剤 ブチルグリシジルエーテル （６）アエロジル＃３００ コロイダルシリカ（親水性超微粒子シリカ、日本アエロ
ジル（株）製 （７）エピキュアＺ 硬化剤（液状の変性芳香族ポリアミン、アンカーケミカ
ル社製） （８）トリエタノールアミン〔Ｎ（Ｃ2Ｈ5ＯＨ）3〕 揺変性増強剤The specific contents of the compounding ingredients shown in Table 1 are as follows. (1) Epicoat 828 bisphenol A diglycidyl ether, manufactured by Yuka Shell Epoxy Co., Ltd., Saponifiable chlorine content: 360 pp
m, total chlorine content: 1730 ppm (2) Epicoat 828EL High-purity product of Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd. Saponifiable chlorine content: 80 ppm, total chlorine content: 1430 ppm (3) Epicoat 828US Epicoat 828 high-purity product, manufactured by Yuka Shell Epoxy Co., Ltd., Saponifiable chlorine content: 24 ppm, total chlorine content: 1130 ppm (4) Epicoat YL-980 Bisphenol A-based diglycidyl ether ultra-high purity product, oil Chromium Shell Epoxy Co., Ltd., Saponifiable chlorine content: 3 ppm, total chlorine content: 80 ppm (5) Reactive diluent butyl glycidyl ether (6) Aerosil # 300 Colloidal silica (hydrophilic ultrafine silica, Nippon Aerosil) (7) Epicure Z curing agent (liquid modified aromatic polyamine Anchor Chemical Corp.) (8) Triethanolamine [N (C 2 H 5 OH) 3 ] thixotropic enhancer
【００２３】[0023]
【表１】 [Table 1]
【００２４】実施例２ 実施例１で示した撹拌装置を用いて、エピコート８２８
ＵＳ９０部にエアロジル＃３００を３部添加し、種々の
撹拌混合時間で撹拌混合した後、ブチルグリシジルエー
テル１０部を添加し、３０分間さらに撹拌混合して、表
２に示した性状の第１液を得た。次に、この第１液を、
エピキュアＺ２０部とトリエタノールアミン０．５部か
らなる第２液と混合し、得られた組成物の初期構造粘性
比、構造粘性比の低下率及び塗装性を測定した。その結
果を表２に示す。なお、表２に示したＡ液は、エポキシ
樹脂とコロイダルシリカの撹拌混合物であり、Ｂ液は、
この混合物にさらにブチルグリシジルエーテルを添加混
合したものである。Example 2 Using the stirring apparatus shown in Example 1, Epicoat 828
After adding 3 parts of Aerosil # 300 to 90 parts of US and stirring and mixing for various stirring and mixing times, 10 parts of butyl glycidyl ether was added and further stirred and mixed for 30 minutes to prepare a first liquid having the properties shown in Table 2. Got Next, this first liquid
The second composition consisting of 20 parts of Epicure Z and 0.5 part of triethanolamine was mixed, and the initial structural viscosity ratio, the reduction rate of the structural viscosity ratio and the coating property of the obtained composition were measured. The results are shown in Table 2. The liquid A shown in Table 2 is a stirred mixture of an epoxy resin and colloidal silica, and the liquid B is
Butyl glycidyl ether was further added and mixed to this mixture.
【００２５】[0025]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 163/00 ＰＪＰ 8830−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C09D 163/00 PJP 8830-4J
Claims (4)
ケン化塩素含有率が１００ｐｐｍ以下の常温で液状のビ
スフェノールグリシジルエーテル型エポキシ樹脂中に揺
変性付与剤としてコロイダルシリカを均一に添加混合し
てなる第１液と、常温で液状の芳香族アミン系硬化剤か
らなる第２液とから構成され、該第１液と第２液との混
合物の２５℃での初期構造粘性比が２〜６の範囲にあ
り、かつ該混合物の６時間保存後における２５℃での構
造粘性比の低下率が２５％以下であることを特徴とする
揺変性エポキシ樹脂組成物。1. A colloidal silica as a thixotropic agent is uniformly added and mixed into a bisphenol glycidyl ether type epoxy resin which is liquid at room temperature and has a total chlorine content of 1600 ppm or less and a saponifiable chlorine content of 100 ppm or less. It is composed of a first liquid and a second liquid composed of an aromatic amine-based curing agent which is liquid at room temperature, and a mixture of the first liquid and the second liquid has an initial structural viscosity ratio at 25 ° C. of 2 to 6. A thixotropic epoxy resin composition which is in the range and has a decrease rate of the structural viscosity ratio at 25 ° C. of 25% or less after the mixture is stored for 6 hours.
求項１の組成物。2. The composition of claim 1 wherein said first liquid contains a reactive diluent.
求項１又は２組成物。3. The composition according to claim 1, wherein the second liquid contains a thixotropic enhancer.
又はそのカルボン酸塩である請求項３の組成物。4. The composition according to claim 3, wherein the thixotropic enhancer is triethanolamine or a carboxylate thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4148495A JP2575998B2 (en) | 1991-05-15 | 1992-05-15 | Thixotropic epoxy resin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13979291 | 1991-05-15 | ||
| JP3-139792 | 1991-05-15 | ||
| JP4148495A JP2575998B2 (en) | 1991-05-15 | 1992-05-15 | Thixotropic epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05156127A true JPH05156127A (en) | 1993-06-22 |
| JP2575998B2 JP2575998B2 (en) | 1997-01-29 |
Family
ID=26472497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4148495A Expired - Lifetime JP2575998B2 (en) | 1991-05-15 | 1992-05-15 | Thixotropic epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2575998B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09310027A (en) * | 1996-05-24 | 1997-12-02 | Nippon Aerojiru Kk | Thickener for polyethereal polymer |
| JPH1143643A (en) * | 1997-04-11 | 1999-02-16 | Shimizu Corp | Low out-gas paint |
| JP2008179835A (en) * | 1995-05-16 | 2008-08-07 | 3M Co | Curable resin sol and its composition |
| JP2013023533A (en) * | 2011-07-19 | 2013-02-04 | Kyocera Chemical Corp | Epoxy resin composition for dip-coating |
| JP2013095889A (en) * | 2011-11-04 | 2013-05-20 | Kyocera Chemical Corp | Epoxy resin composition for dip coating |
| JP2019085460A (en) * | 2017-11-02 | 2019-06-06 | 日本ペイント株式会社 | Substrate-adjusting coating composition and method for forming multilayer coated film |
| CN115029045A (en) * | 2022-05-06 | 2022-09-09 | 中国船舶重工集团公司第七二五研究所 | Preparation method of surface defect finishing material of marine environment composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5418720A (en) * | 1977-07-12 | 1979-02-13 | Nippon Gakki Seizo Kk | Electronic musical instrument |
| JPS6291934A (en) * | 1985-10-18 | 1987-04-27 | Toyo Ink Mfg Co Ltd | Solder resist composition |
| JPS62290717A (en) * | 1986-06-09 | 1987-12-17 | Asahi Chem Ind Co Ltd | Epoxy resin liquid composition for electronic component |
| JPS63128018A (en) * | 1986-11-19 | 1988-05-31 | Sunstar Giken Kk | Epoxy resin composition |
| JPH01188552A (en) * | 1988-01-22 | 1989-07-27 | Ube Ind Ltd | Epoxy resin composition for imparting thixotropic property |
-
1992
- 1992-05-15 JP JP4148495A patent/JP2575998B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5418720A (en) * | 1977-07-12 | 1979-02-13 | Nippon Gakki Seizo Kk | Electronic musical instrument |
| JPS6291934A (en) * | 1985-10-18 | 1987-04-27 | Toyo Ink Mfg Co Ltd | Solder resist composition |
| JPS62290717A (en) * | 1986-06-09 | 1987-12-17 | Asahi Chem Ind Co Ltd | Epoxy resin liquid composition for electronic component |
| JPS63128018A (en) * | 1986-11-19 | 1988-05-31 | Sunstar Giken Kk | Epoxy resin composition |
| JPH01188552A (en) * | 1988-01-22 | 1989-07-27 | Ube Ind Ltd | Epoxy resin composition for imparting thixotropic property |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008179835A (en) * | 1995-05-16 | 2008-08-07 | 3M Co | Curable resin sol and its composition |
| JP2012144736A (en) * | 1995-05-16 | 2012-08-02 | 3M Co | Curable resin sol and its composition |
| JPH09310027A (en) * | 1996-05-24 | 1997-12-02 | Nippon Aerojiru Kk | Thickener for polyethereal polymer |
| JPH1143643A (en) * | 1997-04-11 | 1999-02-16 | Shimizu Corp | Low out-gas paint |
| JP2013023533A (en) * | 2011-07-19 | 2013-02-04 | Kyocera Chemical Corp | Epoxy resin composition for dip-coating |
| JP2013095889A (en) * | 2011-11-04 | 2013-05-20 | Kyocera Chemical Corp | Epoxy resin composition for dip coating |
| JP2019085460A (en) * | 2017-11-02 | 2019-06-06 | 日本ペイント株式会社 | Substrate-adjusting coating composition and method for forming multilayer coated film |
| CN115029045A (en) * | 2022-05-06 | 2022-09-09 | 中国船舶重工集团公司第七二五研究所 | Preparation method of surface defect finishing material of marine environment composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2575998B2 (en) | 1997-01-29 |
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