JPS62174223A - One-component epoxy resin composition - Google Patents
One-component epoxy resin compositionInfo
- Publication number
- JPS62174223A JPS62174223A JP1620286A JP1620286A JPS62174223A JP S62174223 A JPS62174223 A JP S62174223A JP 1620286 A JP1620286 A JP 1620286A JP 1620286 A JP1620286 A JP 1620286A JP S62174223 A JPS62174223 A JP S62174223A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- compound
- component
- resin composition
- phenolic
- 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 47
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000199 molecular distillation Methods 0.000 claims abstract description 8
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- 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 abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000000047 product Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 12
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229940079877 pyrogallol Drugs 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- SRUQARLMFOLRDN-UHFFFAOYSA-N 1-(2,4,5-Trihydroxyphenyl)-1-butanone Chemical compound CCCC(=O)C1=CC(O)=C(O)C=C1O SRUQARLMFOLRDN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 102100039386 Ketimine reductase mu-crystallin Human genes 0.000 description 3
- 101000772180 Lithobates catesbeianus Transthyretin Proteins 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔技術分野〕 この発明は、電気、電子用途の接着剤、塗料。[Detailed description of the invention] 〔Technical field〕 This invention applies to adhesives and paints for electrical and electronic applications.
シール剤、ＩＣ封止材等として用いられる一液性エポキ
シ樹脂組成物に関する。The present invention relates to a one-component epoxy resin composition used as a sealant, IC sealant, etc.
一液性エポキシ樹脂組成物のなかには、ジヒドラジド系
化合物を硬化剤としてエポキシ樹脂に分散させたものが
ある。この樹脂組成物から得られる硬化物は、高い耐熱
性、電気絶縁性、密着性および保存安定性を有したもの
となる。したがって、ジヒドラジド系化合物は、−液性
硬化剤として優れているといえる。Some one-component epoxy resin compositions include those in which a dihydrazide compound is dispersed in an epoxy resin as a curing agent. A cured product obtained from this resin composition has high heat resistance, electrical insulation, adhesion, and storage stability. Therefore, it can be said that dihydrazide compounds are excellent as -liquid curing agents.
しかしながら、ジヒドラジド系化合物を用いた場合、つ
ぎのような問題が生じていた。すなわち、■ 樹脂組成
物の硬化温度が高＜（１４０〜１９０℃）、硬化速度も
遅い。硬化速度を速くするため触媒を加えることが考え
られるが、硬化促進作用の高い触媒がない。■ 得られ
る硬化物は、内部ＮＨが残存するため、他の硬化剤を用
いた場合の硬化物に比べて吸湿率が大きい。■ エポキ
シ樹脂の種類によっては、ジヒドラジド系化合物は、エ
ポキシ樹脂の結晶化の種となることがあるので、使いに
（い。However, when dihydrazide compounds are used, the following problems have occurred. That is, (1) the curing temperature of the resin composition is high (140 to 190°C) and the curing speed is slow. It is possible to add a catalyst to increase the curing speed, but there is no catalyst that has a high curing accelerating effect. (2) The resulting cured product has a higher moisture absorption rate than cured products obtained using other curing agents because internal NH remains. ■ Depending on the type of epoxy resin, dihydrazide compounds may become seeds for crystallization of the epoxy resin, so be careful when using them.
この発明は、このような事情に鑑みてなされたものであ
って、硬化物の耐熱性、電気絶縁性、密着性、保存安定
性および吸湿率に優れるとともに、硬化速度も速く、結
晶化しにくく、そのうえ、低粘度でＣ１含有率の低い一
液性エポキシ樹脂組成物を提供することを目的としてい
る。This invention was made in view of the above circumstances, and provides a cured product that has excellent heat resistance, electrical insulation, adhesion, storage stability, and moisture absorption rate, has a fast curing speed, is resistant to crystallization, Moreover, it is an object of the present invention to provide a one-component epoxy resin composition with low viscosity and low C1 content.
発明者は、前記のような目的を達成するため研究を重ね
た。その結果、まず、硬化剤として、ジヒドラジド系化
合物とフェノール性ＯＨを有する化合物（以下、ｒＯＨ
化合物」と記す）とを併用するようにすれば、前記■お
よび■の問題が解決されて、耐熱性等のすぐれた硬化物
が得られるというジヒドラジド系化合物の特徴を損なう
ことなく、硬化物の吸湿率が優れたものとなり、樹脂組
成物の硬化速度が速くなるということを見出したー液性
エポキシ樹脂組成物の硬化剤としてＯＨ化合物が用いら
れている例は、これまでほとんどなかった。これは、Ｏ
Ｈ化合物の反応性が非常に悪く、エポキシ樹脂中に分散
させるのが困難であるといったような理由による。しか
し、ジヒドラジド系化合物とＯ）（化合物とを併用する
と、前記のような効果が得られるのである。The inventor conducted repeated research in order to achieve the above objectives. As a result, first, as a curing agent, a dihydrazide compound and a compound having phenolic OH (rOH
By using dihydrazide-based compounds in combination, the above-mentioned problems (1) and (2) can be solved, and the cured products can be improved without impairing the characteristics of dihydrazide compounds, which are the ability to obtain cured products with excellent heat resistance. It has been found that the moisture absorption rate is excellent and the curing speed of the resin composition is increased.There have been few examples of using an OH compound as a curing agent for liquid epoxy resin compositions. This is O
This is because the reactivity of the H compound is very poor and it is difficult to disperse it in an epoxy resin. However, when a dihydrazide compound and O)(compound are used together), the above-mentioned effects can be obtained.
他方、液状エポキシ樹脂としては、種々の性能全体から
みて、８２８タイプと呼ばれるものが優れているので、
これが最も汎用されている。この８２８タイプのエポキ
シ樹脂は、ビスフェノールＡとエピクロルヒドリンとの
反応から作られるエポキシ当量１８０〜１９０の樹脂で
あって、平均構造は、つぎの式（ａ）であられされる。On the other hand, as a liquid epoxy resin, the one called 828 type is superior in terms of overall performance, so
This is the most commonly used. This 828 type epoxy resin is a resin having an epoxy equivalent of 180 to 190 made from the reaction of bisphenol A and epichlorohydrin, and has an average structure expressed by the following formula (a).
・ ・ ・（ａ）
式（ａｌ中、０．１〜０．２とあるように、このエポキ
シ樹脂は、つぎの式（ｂ）、 （Ｃ）であられされる２
種の化合物を中心構造とする混合物である。・ ・ ・(a) Formula (as shown in 0.1 to 0.2 in al, this epoxy resin is expressed by the following formulas (b) and (C) 2
It is a mixture whose central structure is a species compound.
・ ・ ・（ｂｌ
（ビスフェノールＡジグリシジルエーテル）そして、（
ｂｌ式の化合物を１０〜２０％、（ｃ）式の化合物を８
０〜９０％含んでいる。中）式および（Ｃ）式の化合物
は、単独ではそれぞれ室温で固体であるが、混融してお
れば、室温では、結晶化がおこらない。・ ・ ・(bl (bisphenol A diglycidyl ether) and (
10-20% of the compound of formula bl, 8% of the compound of formula (c)
Contains 0-90%. The compounds of formula (middle) and formula (C) are each solid at room temperature when used alone, but if they are mixed together, crystallization does not occur at room temperature.
８２８タイプのエポキシ樹脂を分子蒸溜して、ビスフェ
ノールＡジグリシジルエーテルの含有量が９５重量％以
上の分子蒸溜品とすると、室温で結晶化が起こりやすく
なり、液状組成物として使うには困難である。When 828 type epoxy resin is subjected to molecular distillation to produce a molecular distilled product containing 95% by weight or more of bisphenol A diglycidyl ether, crystallization tends to occur at room temperature, making it difficult to use as a liquid composition. .
しかし、この分子蒸溜品は、っぎのような特徴をもって
いる。すなわち、■ ８２８タイプのエポキシ樹脂と液
状での粘度を比べた場合、平均分子量が低くなっている
ため、約半分となっている。■ （ｂ）式および（Ｃ）
式の化合物と異なる構造の不純物が除かれて精製されて
いる。そして、不純物は主としてＣＩを含む化合物であ
るから、ＣＩ含有量が大幅に低くなっている。したがっ
て、ＩＣ封止等に適用できれば、ＩＣ等の信顛性を向上
させうるということが期待できる。■ 主成分が、８２
８タイプのエポキシ樹脂とほとんど変わらないことから
、これと同様の優れた硬化物性能が期待できる。しかし
、ジヒドラジド系化合物を硬化剤として、前記分子蒸溜
品（結晶性エポキシ樹脂）に加えて、エポキシ樹脂組成
物とした場合、ジヒドラジド系化合物が結晶化の種とな
りやすく、使いにくいものとなる。However, this molecularly distilled product has unique characteristics. That is, when comparing the viscosity of the 828 type epoxy resin in liquid form, it is approximately half that of the 828 type epoxy resin due to its lower average molecular weight. ■ Formula (b) and (C)
It has been purified by removing impurities with a structure different from that of the compound of formula. Since the impurities are mainly compounds containing CI, the CI content is significantly low. Therefore, if it can be applied to IC sealing etc., it can be expected that the reliability of IC etc. can be improved. ■ The main component is 82
Since it is almost the same as Type 8 epoxy resin, we can expect the same excellent performance of the cured product. However, when a dihydrazide compound is used as a curing agent and added to the molecular distillation product (crystalline epoxy resin) to form an epoxy resin composition, the dihydrazide compound tends to become a seed for crystallization, making it difficult to use.
ところが、発明者らは、ジヒドラジド系化合物とＯＨ化
合物とを硬化剤として併用することとして、ＯＨ化合物
を前記分子蒸溜品に加えてなる液状組成物にジヒドラジ
ド系化合物を加えることとすれば、結晶化する恐れが少
なくなりこの発明の目的を達成することができるという
ことを見出した。この結果、ここに、この発明を完成し
た。However, the inventors found that if a dihydrazide compound and an OH compound are used together as a curing agent, and the dihydrazide compound is added to a liquid composition obtained by adding the OH compound to the molecular distillation product, crystallization will occur. It has been found that the object of the present invention can be achieved with less fear of As a result, this invention has now been completed.
したがって、この発明は、分子蒸溜により得られるビス
フェノールＡジグリシジルエーテルの含有量が９５重量
％以上のエポキシ樹脂に、フェノール性ＯＨを持つ化合
物が加えられた液状組成物にジヒドラジド系化合物が加
えられている一液性エポキシ樹脂組成物をその要旨とし
ている。Therefore, the present invention provides a liquid composition in which a compound having phenolic OH is added to an epoxy resin containing 95% by weight or more of bisphenol A diglycidyl ether obtained by molecular distillation, and a dihydrazide compound added thereto. The gist is a one-component epoxy resin composition.
以下に、この発明の詳細な説明する。The present invention will be explained in detail below.
前記のように、この発明では、エポキシ樹脂として、分
子蒸溜により得られるビスフェノールＡジグリシジルエ
ーテルの含有量が９５重量％以上のものを用いる。この
ものは、たとえば、ビスフェノールＡとエピクロルヒド
リンとを反応させてエポキシ当量１８０〜１９０のエポ
キシ樹脂をつ（す、このエポキシ樹脂を分子蒸溜すれば
得ることができる。As described above, in the present invention, an epoxy resin containing 95% by weight or more of bisphenol A diglycidyl ether obtained by molecular distillation is used. This product can be obtained, for example, by reacting bisphenol A and epichlorohydrin to obtain an epoxy resin having an epoxy equivalent of 180 to 190, and then molecularly distilling this epoxy resin.
硬化剤として用いられるＯＨ化合物としては、フェノー
ルノボラック樹脂、ハイドロキノン（ヒドロキノン）、
レゾルシン、カテコール、ビスフェノールＡ、ビスフェ
ノールＢ、ビスフェノールＦｌビスフェノールＳ、ピロ
ガロール、フロログルシン、ポリパラビニルフェノール
等があげられる。また、ビフェニル、ベンゾフェノン、
ジフェニルアミン等のベンゼン環（置換するベンゼン環
）にＯＨ基が結合している化合物等、たとえば、２・２
′・４・４′−テトラヒドロキシベンゾフェノン（ＴＨ
ＢＰ）等もあげられる。ＯＨ化合物は、フェノール性Ｏ
Ｈを複数個有するのが好ましいが、硬化速度の促進およ
び前記分子蒸溜品のエポキシ樹脂の結晶化阻止を特に期
待する場合であって、あまり使用量が多くないときは、
フェノール性ＯＨを１個しか有しないものであっても得
られる硬化物の物性に大きな影響はない。ＯＨ化合物が
２種類以上併用されるようであってもよい。OH compounds used as curing agents include phenol novolac resin, hydroquinone (hydroquinone),
Examples include resorcinol, catechol, bisphenol A, bisphenol B, bisphenol Fl bisphenol S, pyrogallol, phloroglucin, and polyparavinylphenol. Also, biphenyl, benzophenone,
Compounds in which an OH group is bonded to a benzene ring (substituted benzene ring) such as diphenylamine, for example, 2.2
',4,4'-tetrahydroxybenzophenone (TH
BP) etc. can also be mentioned. OH compounds are phenolic O
It is preferable to have a plurality of H, but when acceleration of the curing rate and prevention of crystallization of the molecularly distilled epoxy resin are particularly expected, and when the amount used is not very large,
Even if it has only one phenolic OH, it does not have a big effect on the physical properties of the cured product obtained. Two or more types of OH compounds may be used in combination.
硬化剤として用いられるジヒドラジド系化合物としては
、ＮＨｚ ＮＨＲ−ＮＨＮＨｚ （Ｒは有機基）の構
造を持つものなら特に限定はされないが、たとえば、ア
ジピン酸ジヒドラジド、イソフタル酸ジヒドラジド、ド
デカンニ酸ジヒドラジド等の二塩基酸ジヒドラジドやつ
ぎの（ｄ）式であられされるトリアジン系ジヒドラジド
等があげられ、２種以上が併用されるようであってもよ
い。The dihydrazide compound used as a curing agent is not particularly limited as long as it has a structure of NHz NHR-NHNHz (R is an organic group); Examples include acid dihydrazide and triazine dihydrazide represented by the following formula (d), and two or more types may be used in combination.
（Ｒ＋ 、ＲｚはＨまたはアルキル基）この発明にかか
る一液性エポキシ樹脂組成物は、前記分子蒸溜品のエポ
キシ樹脂にＯＨ化合物を加えて溶解させた液状組成物に
ジヒドラジド系化合物を加えて固体分散させる等すると
得ることができる。(R+, Rz is H or an alkyl group) The one-component epoxy resin composition according to the present invention is obtained by adding a dihydrazide compound to a liquid composition obtained by adding an OH compound to the molecularly distilled epoxy resin and dissolving it. It can be obtained by dispersing it.
硬化剤のほか、希釈剤、充填材、カップリング剤、レベ
リング剤、離型剤、消泡剤、顔料等の添加剤が、使用目
的に応じ必要に応じて用いられる。また、硬化速度をい
っそう上げるため、イミダゾール類等を触媒として少量
添加するようにしてもよい。このことにより、この発明
の効果は損なわれない。In addition to the curing agent, additives such as a diluent, a filler, a coupling agent, a leveling agent, a mold release agent, an antifoaming agent, and a pigment are used as necessary depending on the purpose of use. Further, in order to further increase the curing speed, a small amount of imidazole or the like may be added as a catalyst. This does not impair the effects of the invention.
ジヒドラジド系化合物は、エポキシ基１モルに対してｏ
、ｏｉモル（０，０４当量）以上０．２５モル（１，０
当り以下用いるのが好ましく、０．０５モル（０，２当
量）以上０．２５モル以下用いるのがより好ましい。０
．０１モル未満では効果が小さくなる傾向にあり、０．
２５モルを越えると得られる硬化物の吸水率が太き（な
る傾向にあるからである。しかし、特に低吸湿であるこ
とが要求されない場合は、０．２５モルを越えて用いる
ようであってもよい。ＯＨ化合物は、エポキシ基１モル
に対するフェノール性ＯＨ基の割合が０．０５モル（当
量）以上０．６モル（当ｆｆ１）以下となるようにして
用いるのが好ましく、０．０５モル以上０．５モル以下
となるようにして用いるのがより好ましい。０．０５モ
ル未満では効果が小さくなる傾向にあり、０゜６モルを
越えると得られる硬化物の物性が好ましくなくなる傾向
にあるからである。ジヒドラジド系化合物とＯＨ化合物
の合計使用量は、特に制限をうけないが、エポキシ基に
対する当量で０．５〜０、８当量とするのが、エポキシ
基の反応量からいって好ましい。The dihydrazide compound is o per mole of epoxy group.
, oi mole (0,04 equivalent) or more 0.25 mole (1,0
It is preferable to use less than 0.05 mol (0.2 equivalent) and more preferably 0.25 mol or less. 0
．． If the amount is less than 0.01 mol, the effect tends to be small;
This is because when the amount exceeds 25 mol, the water absorption rate of the cured product obtained tends to be high. However, if particularly low moisture absorption is not required, it is likely that more than 0.25 mol is used. The OH compound is preferably used in such a manner that the ratio of phenolic OH group to 1 mole of epoxy group is 0.05 mole (equivalent) or more and 0.6 mole (equivalent) or less, and 0.05 mole. It is more preferable to use it in an amount of 0.5 mol or less.If it is less than 0.05 mol, the effect tends to be small, and if it exceeds 0.6 mol, the physical properties of the cured product obtained tend to become unfavorable. The total amount of the dihydrazide compound and OH compound to be used is not particularly limited, but it is preferably 0.5 to 0.8 equivalents relative to the epoxy group, considering the amount of reaction of the epoxy group. .
この発明にかかる一液性エポキシ樹脂組成物は、前記の
ように構成されているので、硬化物の耐熱性、電気絶縁
性、密着性、保存安定性および吸湿率に優れるとともに
硬化速度も速く、結晶化しに＜＜、そのうえ、低粘度で
ＣＩ含有率も低くなるのである。Since the one-component epoxy resin composition according to the present invention is configured as described above, the cured product has excellent heat resistance, electrical insulation, adhesion, storage stability, and moisture absorption rate, and has a fast curing speed. In addition, it has a low viscosity and a low CI content.
つぎに、実施例および比較例について説明する（実施例
１）
分子蒸溜したエポキシ樹脂（ビスフェノールＡジグリシ
ジルエーテルの含有量が９５重量％以上）として東部化
成■製のエポキシ樹脂ＹＤ８１２５、エポキシ当量１７
３）、ジヒドラジド系化合物として、つぎの式（Ｉｌｌ
）であられされるトリアジン系ジヒドラジド（日本ヒド
ラジン工業■製、以下ｒ２．４ＨＴＪと記す）、ＯＨ化
合物としてピロガロール（牛丼化学薬品■製）を用いる
こととした。分子蒸溜したエポキシ樹脂、２．４ＨＴお
よびピロガロールは、以下の実施例および比較例で用い
る場合においても同じものを用いた。Next, Examples and Comparative Examples will be described (Example 1) Epoxy resin YD8125 manufactured by Tobu Kasei ■, epoxy equivalent: 17 as a molecularly distilled epoxy resin (content of bisphenol A diglycidyl ether of 95% by weight or more).
3), as a dihydrazide compound, the following formula (Ill
) and pyrogallol (manufactured by Gyudon Chemicals Ltd.) as the OH compound. The same molecularly distilled epoxy resin, 2.4HT, and pyrogallol were used in the following Examples and Comparative Examples.
エポキシ樹脂１７３ｇ （エポキシ基１モル）に対して
、ピロガロール８．４ ｇ （０，０６６７モル。8.4 g (0,0667 mol) of pyrogallol per 173 g (1 mol epoxy group) of epoxy resin.
０．２当量）を加え、１５０℃で５分間加熱して溶解さ
せた。つぎに、冷却し、室温にもどすと均一透明液体と
なった混合物が得られた。この混合物に、２．４ＨＴ２
５．５ｇ （０，１５モル、０，６当量）を加え、真空
らいかい機により分散させて一液性エポキシ樹脂組成物
を得た。0.2 equivalent) was added and heated at 150° C. for 5 minutes to dissolve. Next, the mixture was cooled and returned to room temperature to obtain a mixture that became a homogeneous transparent liquid. Add 2.4HT2 to this mixture.
5.5 g (0.15 mol, 0.6 equivalent) was added and dispersed using a vacuum sieve to obtain a one-component epoxy resin composition.
（比較例１）
ピロガロールを用いず、２，４ＨＴを３４ｇ（０，２モ
ル、０．８当量）用いるようにしたほかは、実施例１と
同様の方法で一液性エポキシ樹脂組成物をつくった。(Comparative Example 1) A one-component epoxy resin composition was prepared in the same manner as in Example 1, except that 34 g (0.2 mol, 0.8 equivalent) of 2,4HT was used instead of pyrogallol. Ta.
（比較例２）
分子蒸溜したエポキシ樹脂の代わりに分子蒸溜しない通
常の８２８タイプのエポキシ樹脂（東部化成■製のＹＤ
１２８）を用いるようにしたほかは、実施例１と同様の
方法で一液性エポキシ樹脂組成物をつくった。(Comparative Example 2) Instead of molecularly distilled epoxy resin, normal 828 type epoxy resin (manufactured by Tobu Kasei) was used instead of molecularly distilled epoxy resin.
A one-component epoxy resin composition was prepared in the same manner as in Example 1, except that 128) was used.
（実施例２〜８）
第１表に示す配合により、実施例１と同様の方法で一液
性エポキシ樹脂組成物をつくった。(Examples 2 to 8) One-component epoxy resin compositions were prepared in the same manner as in Example 1 using the formulations shown in Table 1.
第１表中、ＴＨＢＰは、２・２′・４・４′−テトラヒ
ドロキシベンゾフェノンをあられす。In Table 1, THBP stands for 2,2',4,4'-tetrahydroxybenzophenone.
実施例１〜８および比較例１，２につき、ポットライフ
（４０″Ｃ）、１６０℃でのゲルタイム、５℃で１力月
保存後の状態、硬化物からの抽出水の電気伝導度および
３０℃での粘度を測定した。For Examples 1 to 8 and Comparative Examples 1 and 2, pot life (40″C), gel time at 160°C, state after storage for 1 month at 5°C, electrical conductivity of water extracted from the cured product, and 30°C The viscosity at °C was measured.
結果を第１表に示す。ただし１．ゲルタイムは熱板法に
より測定した。電気伝導度は、つぎのようにして測定し
た。硬化物（硬化条件は１５０℃、４時間）５ｇを粉砕
して２０メツシユアンダーとしたのち、５０ｇの原潜水
を加えて１００℃で２０時間還流を行った。このあと、
硬化物をろ過によりろ別し、ろ液の電気伝４度を測定し
た。粘度はＥ型粘度計により測定した。The results are shown in Table 1. However, 1. Gel time was measured by hot plate method. Electric conductivity was measured as follows. After pulverizing 5 g of the cured product (curing conditions were 150° C. for 4 hours) to obtain 20 mesh under, 50 g of original water was added and refluxed at 100° C. for 20 hours. after this,
The cured product was separated by filtration, and the electrical conductivity of the filtrate was measured. The viscosity was measured using an E-type viscometer.
第１表より、実施例１〜８は、いずれも、ポットライフ
が長くて保存安定性が優れ、ゲルタイムが短くて硬化速
度が速く、結晶化しにくく、抽出水の電気伝導度が低く
て０１等の不純物が少なく（低イオン）、そのうえ粘度
も低いことがわかる。これに対し、比較例１は、硬化速
度が遅（、結晶化しやすいことがわかる。比較例２は、
不純物が多く粘度が高いことがわかる。From Table 1, Examples 1 to 8 all have a long pot life and excellent storage stability, a short gel time and fast curing speed, are difficult to crystallize, and have a low electrical conductivity of the extracted water, such as 01. It can be seen that there are few impurities (low ions) and also low viscosity. On the other hand, Comparative Example 1 has a slow curing speed (it is easy to crystallize). Comparative Example 2 has
It can be seen that there are many impurities and the viscosity is high.
（実施例９）
分子蒸溜したエポキシ樹脂（ＹＤ８１２５）１７３ｇに
対して、フェノールノボラック１９ｇ（０、１当ｆｆ１
）、２・２′・４・４′−テトラヒドロキシベンゾフェ
ノン（ＴＨＢＰ、牛丼化学薬品■製）１８．６ ｇ （
０，０７５モル、０．３当量）を力■えて、１６０℃で
１０分間処理して透明均一溶液を得た。これに、２．４
ＨＴ１７．Ｏｇ （０，１モル、０．４当ｆｉｔ）を加
えて、真空らいかい機によって３０分間らいかいして、
均一分散させた。得られた配合物を３７ｇとり、溶融シ
リカ（電気化学工業■製）６０ｇ、 シランカップリ
ング斉りＡ−１８７（日本ユニカー（魯菊製）０．６ｇ
、 カーボンブランク０．４ｇおよびフェニルグリシジ
ルエーテル２ｇと混合し、真空ニーダ中で３０分間混練
して、液状のＩＣ封止用材料（−液性エポキシ樹脂組成
物）を得た。(Example 9) To 173 g of molecularly distilled epoxy resin (YD8125), 19 g of phenol novolak (0.1 per ff1
), 2,2',4,4'-tetrahydroxybenzophenone (THBP, manufactured by Gyudon Chemical Co., Ltd.) 18.6 g (
0.075 mol, 0.3 equivalent) was treated at 160° C. for 10 minutes to obtain a transparent homogeneous solution. In addition to this, 2.4
HT17. Add Og (0.1 mol, 0.4 equivalent fit) and boil for 30 minutes in a vacuum sieve machine.
Uniformly dispersed. Take 37 g of the obtained mixture, add 60 g of fused silica (manufactured by Denki Kagaku Kogyo ■), and 0.6 g of silane coupling A-187 (manufactured by Nippon Unicar (manufactured by Rogiku)).
The mixture was mixed with 0.4 g of carbon blank and 2 g of phenyl glycidyl ether, and kneaded for 30 minutes in a vacuum kneader to obtain a liquid IC sealing material (liquid epoxy resin composition).
（比較例３）
分子蒸溜したエポキシ樹脂（ＹＯ２１２５）に代えて、
分子蒸溜しない通常の８２８タイプの工ポキシ樹脂（Ｙ
Ｄ１２８）を用いるようにしたほかは、実施例９と同じ
ようにして、液状のＩＣ封止用材料をつくった。(Comparative Example 3) Instead of molecularly distilled epoxy resin (YO2125),
Normal 828 type engineered poxy resin (Y
A liquid IC sealing material was produced in the same manner as in Example 9, except that D128) was used.
（比較例４）
フェノールノボラックおよびＴＨＢＰを用いずに、２，
４ＨＴを３４．０ｇ（０，８当量）を用いるようにした
ほかは実施例９と同じようにして、液状のＩＣ封止用材
料をつくった。(Comparative Example 4) 2, without using phenol novolac and THBP.
A liquid IC sealing material was prepared in the same manner as in Example 9, except that 34.0 g (0.8 equivalent) of 4HT was used.
実施例９および比較例３．４につき、１６０℃でのゲル
タイム、５℃で１週間保存後の状態、および硬化物から
の抽出水の電気伝導度を測定した。また、これらを用い
て封止を行ったＣＭＯ３実素子のＰＣＴ寿命を測定した
。結果を第２表に示す。ただし、ゲルタイムは熱板法に
より測定し、抽出水伝導度は前述したのと同じ方法によ
り測定した。また、ＰＣＴ寿命は、封止したＣＭＯ５素
子（硬化条件は１５０℃、４時間）をＰＣＴ２ａｔｍで
処理しくｎ＝１０）、半数が不良となった時間を示すこ
ととした。For Example 9 and Comparative Example 3.4, the gel time at 160°C, the state after one week of storage at 5°C, and the electrical conductivity of water extracted from the cured product were measured. Furthermore, the PCT life of a CMO3 actual device sealed using these materials was measured. The results are shown in Table 2. However, the gel time was measured by the hot plate method, and the extracted water conductivity was measured by the same method as described above. In addition, PCT life is determined to indicate the time at which half of the sealed CMO5 elements (curing conditions: 150° C., 4 hours) became defective when treated with PCT2atm (n=10).
第２表より、実施例９は、ゲルタイムが短くて硬化速度
が速く、結晶化しに＜＜、抽出水伝導度が低いのでＣＩ
等の不純物が少なく （低イオン）、封止を行った０Ｍ
Ｏ３素子の耐湿信頼性が高いことがわかる。これに対し
、比較例３は、不純物が多く、封止を行った０ＭＯ３素
子の耐湿信頼性が低いことがわかる。また、比較例４は
、硬化時間が長く、結晶化しやすく、不純物が多く、そ
のうえ、封止をおこなった０ＭＯ３素子の耐湿信頼性も
低いことがわかる。From Table 2, Example 9 has a short gel time, a fast curing speed, less crystallization, and a lower extracted water conductivity, so the CI
0M with low impurities such as (low ions) and sealed
It can be seen that the moisture resistance reliability of the O3 element is high. On the other hand, it can be seen that Comparative Example 3 contains many impurities and the moisture resistance reliability of the sealed OMO3 element is low. Furthermore, it can be seen that Comparative Example 4 takes a long time to cure, is easily crystallized, contains many impurities, and also has low moisture resistance reliability of the sealed OMO3 element.
この発明にがかる一液性エポキシ樹脂組成物は、分子蒸
溜により得られるビスフェノールＡジグリシジルエーテ
ルの含有量が９５重世％以上のエポキシ樹脂に、フェノ
ール性ＯＨを持つ化合物が加えられた液状組成物にジヒ
ドラジド系化合物が加えられているので、硬化物の耐熱
性、電気絶縁性、密着性、保存安定性および吸湿率に優
れるとともに硬化速度も速く、結晶化しにくく、そのう
え、低粘度で、ＣＩ含有率も低い。The one-component epoxy resin composition according to the present invention is a liquid composition in which a compound having phenolic OH is added to an epoxy resin containing 95% or more of bisphenol A diglycidyl ether obtained by molecular distillation. Because a dihydrazide compound is added to the cured product, the cured product has excellent heat resistance, electrical insulation, adhesion, storage stability, and moisture absorption rate, has a fast curing speed, is resistant to crystallization, and has a low viscosity and contains CI. The rate is also low.
Claims (2)
シジルエーテルの含有量が９５重量％以上のエポキシ樹
脂に、フェノール性ＯＨを持つ化合物が加えられた液状
組成物にジヒドラジド系化合物が加えられている一液性
エポキシ樹脂組成物。(1) A liquid composition in which a dihydrazide compound is added to a liquid composition in which a compound having phenolic OH is added to an epoxy resin containing 95% by weight or more of bisphenol A diglycidyl ether obtained by molecular distillation. epoxy resin composition.
が０．０５モル以上０．５モル以下となるようにしてフ
ェノール性ＯＨを持つ化合物を含むとともに、ジヒドラ
ジド系化合物を０．０５モル以上０．２５モル以下含む
特許請求の範囲第１項記載の一液性エポキシ樹脂組成物
。(2) Contains a compound with phenolic OH such that the phenolic OH group is 0.05 mol or more and 0.5 mol or less per 1 mol of epoxy group, and contains 0.05 mol or more of a dihydrazide compound. The one-component epoxy resin composition according to claim 1, which contains 0.25 mol or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1620286A JPS62174223A (en) | 1986-01-27 | 1986-01-27 | One-component epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1620286A JPS62174223A (en) | 1986-01-27 | 1986-01-27 | One-component epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62174223A true JPS62174223A (en) | 1987-07-31 |
Family
ID=11909922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1620286A Pending JPS62174223A (en) | 1986-01-27 | 1986-01-27 | One-component epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62174223A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0324115A (en) * | 1989-06-22 | 1991-02-01 | Nippon Kayaku Co Ltd | Epoxy resin composition |
| US5547758A (en) * | 1992-04-20 | 1996-08-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Insulating material |
-
1986
- 1986-01-27 JP JP1620286A patent/JPS62174223A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0324115A (en) * | 1989-06-22 | 1991-02-01 | Nippon Kayaku Co Ltd | Epoxy resin composition |
| US5547758A (en) * | 1992-04-20 | 1996-08-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Insulating material |
| US5576362A (en) * | 1992-04-20 | 1996-11-19 | Denki Kagaku Kogyo Kabushiki Kaisha | Insulating material and a circuit substrate in use thereof |
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