JPH10330463A - Ultraviolet-curing type resin composition - Google Patents
Ultraviolet-curing type resin compositionInfo
- Publication number
- JPH10330463A JPH10330463A JP14182397A JP14182397A JPH10330463A JP H10330463 A JPH10330463 A JP H10330463A JP 14182397 A JP14182397 A JP 14182397A JP 14182397 A JP14182397 A JP 14182397A JP H10330463 A JPH10330463 A JP H10330463A
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet
- resin
- resin composition
- irradiation
- phenol
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気、電子部品の
封入材料や接着剤として有用な、耐熱性および耐湿性に
優れた紫外線硬化型樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable resin composition having excellent heat resistance and moisture resistance, which is useful as an encapsulating material or adhesive for electric and electronic parts.
【０００２】[0002]
【従来の技術】紫外線照射によって発生するカチオン種
を活性種とする、カチオン硬化型の紫外線硬化型樹脂と
しては、エポキシ樹脂が多く使用されている。エポキシ
樹脂としては、一般に脂環式エポキシ樹脂が用いられる
ことが多いが、分子内に芳香環を有していないため、紫
外線照射によって硬化して得られる硬化物はガラス転移
点（Ｔｇ）が低くなり、耐熱性が低いと言う問題があ
る。また、エポキシ樹脂は分子内の極性が高いため、吸
湿性が大きく耐湿性が低いと言う問題もある。2. Description of the Related Art Epoxy resins are widely used as a cation-curable ultraviolet-curable resin in which a cationic species generated by ultraviolet irradiation is an active species. In general, an alicyclic epoxy resin is often used as the epoxy resin. However, since the epoxy resin does not have an aromatic ring in the molecule, a cured product obtained by curing by ultraviolet irradiation has a low glass transition point (Tg). Therefore, there is a problem that heat resistance is low. Further, the epoxy resin has a high polarity in the molecule, and thus has a problem that it has a high hygroscopicity and low moisture resistance.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来の紫外
線硬化型樹脂のこのような問題点に鑑みてなされたもの
で、紫外線照射によってＴｇの高い硬化物が得られ、電
子部品の封入材料や接着剤に用いられる、耐熱性、耐湿
性の優れた紫外線硬化型樹脂組成物を提供することを目
的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the conventional ultraviolet-curable resin, and a cured product having a high Tg can be obtained by irradiation with ultraviolet light. It is an object of the present invention to provide an ultraviolet-curable resin composition having excellent heat resistance and moisture resistance, which is used for adhesives and adhesives.
【０００４】[0004]
【課題を解決するための手段】即ち本発明は、フェノー
ル類および／またはフェノール樹脂（Ａ）、分子内に２
個以上の炭素−炭素不飽和結合を有する化合物（Ｂ）、
および、紫外線の照射により酸を発生するカチオン硬化
開始剤（Ｃ）を必須とする紫外線硬化型樹脂組成物であ
る。That is, the present invention relates to a phenol and / or phenol resin (A) having two or less phenols per molecule.
A compound (B) having at least two carbon-carbon unsaturated bonds,
Further, it is an ultraviolet-curable resin composition essentially including a cationic curing initiator (C) that generates an acid upon irradiation with ultraviolet light.
【０００５】[0005]
【発明の実施の形態】本発明による（Ａ），（Ｂ），
（Ｃ）３つの成分を必須とする紫外線硬化型樹脂組成物
は、紫外線照射で生成した酸（カチオン種）によって反
応開始される、フェノール類やフェノール樹脂と炭素−
炭素不飽和結合との、フリーデルクラフツ型の重合、硬
化反応によって、Ｔｇの高い硬化物を与えるものであ
る。フェノール樹脂硬化物の高い耐熱性、耐湿性を、紫
外線硬化型樹脂で実現するところにその特徴がある。DESCRIPTION OF THE PREFERRED EMBODIMENTS (A), (B),
(C) A UV-curable resin composition containing three components as essential components is composed of a phenol or a phenol resin and a carbon-containing resin, which are initiated by an acid (cationic species) generated by irradiation with ultraviolet light.
By a Friedel-Crafts type polymerization and curing reaction with a carbon unsaturated bond, a cured product having a high Tg is provided. The feature is that the high heat resistance and moisture resistance of the cured phenolic resin are realized by an ultraviolet curable resin.
【０００６】本発明において用いるフェノール類および
／またはフェノール樹脂は、電子供与性置換基を有する
ものであることがより好ましい。電子供与性置換基は、
フリーデルクラフツ型の重合、硬化反応において、芳香
環をより強く活性化し、炭素−炭素不飽和結合を有する
化合物との反応性が高くなり、Ｔｇのより高い硬化物が
得られる。The phenols and / or phenol resins used in the present invention more preferably have an electron donating substituent. The electron donating substituent is
In the Friedel-Crafts type polymerization and curing reaction, the aromatic ring is more strongly activated, the reactivity with the compound having a carbon-carbon unsaturated bond is increased, and a cured product having a higher Tg is obtained.
【０００７】本発明において用いられるフェノール類と
は、プラスチック大辞典（1994年，(株)工業調査会発
行）６０１頁に記載されているように、水酸基がベンゼ
ン環、ナフタリン環など、芳香族環に直接結合している
化合物の総称をいう。その例としては、フェノール、ク
レゾール、カテコール、ヒドロキノン、２−ヒドロキシ
ベンジルアルコール、ニトロフェノール、ビフェノー
ル、ビスフェノールＡ、ビスフェノールＦ、トリフェノ
ールメタン化合物、ナフトールなどが例示できる。ま
た、フェノール樹脂の例としては、フェノールノボラッ
ク樹脂、クレゾールノボラック樹脂、ジシクロペンタジ
エン変性フェノール樹脂、テルペン変性フェノール樹
脂、ナフトール類とカルボニル基含有化合物との共縮合
樹脂などが例示できる。これらのフェノール類およびフ
ェノール樹脂は、１種類を単独で用いても良く、あるい
は２種以上を混合して用いても何ら差し支えはない。The phenols used in the present invention are, as described in the Plastics Dictionary (1994, published by the Industrial Research Institute, Inc., p. 601), a hydroxyl group having an aromatic ring such as a benzene ring or a naphthalene ring. A general term for compounds directly bonded to. Examples thereof include phenol, cresol, catechol, hydroquinone, 2-hydroxybenzyl alcohol, nitrophenol, biphenol, bisphenol A, bisphenol F, triphenolmethane compounds, naphthol, and the like. Examples of the phenol resin include a phenol novolak resin, a cresol novolak resin, a dicyclopentadiene-modified phenol resin, a terpene-modified phenol resin, and a co-condensation resin of a naphthol and a carbonyl group-containing compound. These phenols and phenol resins may be used singly or as a mixture of two or more.
【０００８】また、分子内に２個以上の炭素−炭素不飽
和結合を有する化合物としては、分子内に２個以上の２
重結合や３重結合を有するものであれば、特に限定はさ
れないが、具体的に例示すれば、１,６-ヘプタジエン、
１,７-オクタジイン、３-アリル-１,６-ヘプタジエン、
３-アリル-１,７-オクタジイン、１,４-ジビニルシクロ
ヘキサン、１，４-シクロヘキサンジメタノールジビニ
ルエーテル、４,４-ジメチル-ヘプタ-１-エン-６-イ
ン、ジビニルベンゼン、１,６-ジビニルナフタレン、ビ
ニルエーテル樹脂、ビニルチオエーテル樹脂、ブタジエ
ンとスチレンの共重合物などが挙げられる。これらの分
子内に２個以上の炭素−炭素不飽和結合を有する化合物
は、１種類、あるいは２種以上を混合して使用しても何
ら差し支えはない。[0008] Compounds having two or more carbon-carbon unsaturated bonds in the molecule include two or more carbon-carbon unsaturated bonds in the molecule.
There is no particular limitation as long as it has a heavy bond or a triple bond, but specific examples include 1,6-heptadiene,
1,7-octadiyne, 3-allyl-1,6-heptadiene,
3-allyl-1,7-octadiyne, 1,4-divinylcyclohexane, 1,4-cyclohexanedimethanol divinyl ether, 4,4-dimethyl-hept-1-en-6-yne, divinylbenzene, 1,6- Examples thereof include divinylnaphthalene, vinyl ether resin, vinyl thioether resin, and a copolymer of butadiene and styrene. These compounds having two or more carbon-carbon unsaturated bonds in the molecule may be used alone or in combination of two or more.
【０００９】さらに、紫外線の照射により酸を発生する
カチオン硬化開始剤としては、トリアリールスルホニウ
ム塩が広く使用されている。その他にも、ヨードニウム
塩、ジアゾニウム塩系などは当業者に公知であるが、紫
外線の照射で酸を発生させるものであれば、特にこれら
に限定されない。Further, triarylsulfonium salts are widely used as a cationic curing initiator which generates an acid upon irradiation with ultraviolet rays. In addition, iodonium salts, diazonium salts, and the like are known to those skilled in the art, but are not particularly limited as long as they generate an acid upon irradiation with ultraviolet rays.
【００１０】本発明による紫外線硬化型樹脂組成物に
は、（Ａ），（Ｂ），（Ｃ）３つの必須成分の他に、消
泡剤、カップリング剤、希釈剤、チキソ性付与剤、充填
剤などの各種添加剤を、必要に応じて添加することは何
ら差し支えない。[0010] In addition to the three essential components (A), (B) and (C), the ultraviolet-curable resin composition according to the present invention comprises an antifoaming agent, a coupling agent, a diluent, a thixotropic agent, Various additives such as fillers may be added as needed.
【００１１】[0011]
【実施例】以下、実施例により本発明を具体的に示す
が、これによって本発明が限定されるものではない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by these examples.
【００１２】（実施例１〜６および比較例１、２）実施
例および比較例における各成分の配合は表１に示した通
りとし、各成分をディスパーザーを用いて加熱、熔融、
混合し、粘稠な液状の樹脂組成物を得た。得られた樹脂
組成物を紫外線によって硬化させ、Ｔｇの測定および耐
湿性の評価を行なった。(Examples 1 to 6 and Comparative Examples 1 and 2) The components in the Examples and Comparative Examples were mixed as shown in Table 1, and each component was heated, melted using a disperser.
The mixture was mixed to obtain a viscous liquid resin composition. The obtained resin composition was cured by ultraviolet rays, and Tg was measured and moisture resistance was evaluated.
【００１３】[0013]
【表１】 [Table 1]
【００１４】（Ｔｇの測定）４０×４０×１ｍｍの２枚
のガラス板の間に、４０×４０×１ｍｍのシリコーン樹
脂シートの中央部に２０×２０ｍｍの窓を刳り貫いて作
成した枠板を挟み、枠板の窓部に樹脂組成物を流し込ん
で密封した後、高圧水銀ランプにより、照度１２０mW／
cm2で１２０秒間紫外線を照射して硬化させ、硬化物を
得た。硬化物のＴｇは動的粘弾性測定装置を用いて測定
し、ｔａｎδのピークが最高となる温度とした。結果は
表１にまとめて示した通りである。(Measurement of Tg) Between two glass plates of 40 × 40 × 1 mm, a frame plate created by hollowing out a window of 20 × 20 mm in the center of a silicone resin sheet of 40 × 40 × 1 mm was sandwiched. After pouring the resin composition into the window of the frame plate and sealing it, an illuminance of 120 mW /
The resin was cured by irradiating it with ultraviolet rays at cm 2 for 120 seconds to obtain a cured product. The Tg of the cured product was measured using a dynamic viscoelasticity measuring device, and was determined as the temperature at which the peak of tan δ was the highest. The results are as shown in Table 1.
【００１５】（耐湿性評価）Ｔｇの測定に用いた試験片
と同様にして調整した硬化物を、１２５℃で１２０時間
プレッシャークッカー処理し、１２０時間後の硬化物の
べとつきを指触法で評価した。べとつきのない場合は合
格とし、べとつきのある場合は不合格とした。結果は表
１にまとめた通りである。(Evaluation of Moisture Resistance) A cured product prepared in the same manner as the test piece used for measuring Tg was subjected to a pressure cooker treatment at 125 ° C. for 120 hours, and the tackiness of the cured product after 120 hours was evaluated by a finger touch method. . If there was no stickiness, it was judged as pass, and if there was stickiness, it was judged as failed. The results are as summarized in Table 1.
【００１６】表１の結果から明らかなように、実施例１
〜６はいずれもＴｇが１００℃以上を示し、耐湿性も合
格しており、エポキシ樹脂を用いた比較例に比べて耐熱
性に優れ、耐湿性も良好であることが分かる。As is clear from the results shown in Table 1, Example 1
All of the samples No. to No. 6 have a Tg of 100 ° C. or higher, and also passed the moisture resistance. It can be seen that they have excellent heat resistance and good moisture resistance as compared with the comparative example using the epoxy resin.
【００１７】[0017]
【発明の効果】以上に述べた通り、本発明による紫外線
硬化型樹脂組成物は、従来の光カチオン硬化系では成し
遂げることが出来なかった、耐熱性および耐湿性の向上
を達成しており、電気、電子部品の封入材料や接着剤に
用いられる、耐熱性、耐湿性の優れた樹脂組成物を提供
するものである。As described above, the ultraviolet-curable resin composition according to the present invention achieves an improvement in heat resistance and moisture resistance, which cannot be achieved by a conventional photo-cationic curing system. Another object of the present invention is to provide a resin composition having excellent heat resistance and moisture resistance, which is used as an encapsulating material or an adhesive for electronic components.
Claims (2)
樹脂（Ａ）、分子内に２個以上の炭素−炭素不飽和結合
を有する化合物（Ｂ）、および、紫外線の照射により酸
を発生するカチオン硬化開始剤（Ｃ）を必須とする紫外
線硬化型樹脂組成物。1. A phenol and / or a phenol resin (A), a compound having two or more carbon-carbon unsaturated bonds in a molecule (B), and a cationic curing initiator which generates an acid upon irradiation with ultraviolet rays An ultraviolet-curable resin composition comprising (C) as an essential component.
樹脂が、電子供与性置換基を有するものであることを特
徴とする、請求項１記載の紫外線硬化型樹脂組成物。2. The ultraviolet-curable resin composition according to claim 1, wherein the phenol and / or the phenol resin has an electron-donating substituent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14182397A JP3265466B2 (en) | 1997-05-30 | 1997-05-30 | UV curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14182397A JP3265466B2 (en) | 1997-05-30 | 1997-05-30 | UV curable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10330463A true JPH10330463A (en) | 1998-12-15 |
| JP3265466B2 JP3265466B2 (en) | 2002-03-11 |
Family
ID=15300966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14182397A Expired - Fee Related JP3265466B2 (en) | 1997-05-30 | 1997-05-30 | UV curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3265466B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7935739B2 (en) | 2005-02-17 | 2011-05-03 | Asahi Kasei Chemicals Corporation | Cationic curable composition and cured product thereof |
-
1997
- 1997-05-30 JP JP14182397A patent/JP3265466B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7935739B2 (en) | 2005-02-17 | 2011-05-03 | Asahi Kasei Chemicals Corporation | Cationic curable composition and cured product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3265466B2 (en) | 2002-03-11 |
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