JP3166257B2 - UV-curable flame-retardant resin composition - Google Patents
UV-curable flame-retardant resin compositionInfo
- Publication number
- JP3166257B2 JP3166257B2 JP36123491A JP36123491A JP3166257B2 JP 3166257 B2 JP3166257 B2 JP 3166257B2 JP 36123491 A JP36123491 A JP 36123491A JP 36123491 A JP36123491 A JP 36123491A JP 3166257 B2 JP3166257 B2 JP 3166257B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- retardant resin
- epoxy
- meth
- ultraviolet
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は紫外線硬化型難燃性樹脂
組成物に関し、特に電子部品や光学部品の接着や被覆等
に有用な紫外線硬化型難燃性樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-curable flame-retardant resin composition, and more particularly to an ultraviolet-curable flame-retardant resin composition useful for bonding or coating electronic parts and optical parts.
【０００２】[0002]
【従来の技術とその課題】従来からビスフェノール型エ
ポキシ樹脂または脂肪族エポキシ樹脂のアクリル酸また
はメタクリル酸付加物はエポキシアクリレートの名で知
られ、紫外線硬化型樹脂または熱硬化性樹脂として電子
部品や光学部品の接着や被覆等の目的に用いられてい
る。これらは被覆等に対する密着性、耐薬品性等に優れ
ているものが多いが、電子部品や光学部品に対する応用
においては、耐熱安定性、低膨張率、屈折率の安定性、
および難燃性等の特性の向上がさらに求められている。
具体的にいえば従来のエポキシアクリレートは、線膨張
率が大きく、また可燃性で自己消火性がない。また、多
官能のエポキシアクリレートも知られているが、これも
硬化後の残留応力が大きく、密着性に対する悪影響やク
ラックの発生が光学的に歪みの原因となるなどの問題が
あった。2. Description of the Related Art Conventionally, an acrylic acid or methacrylic acid adduct of a bisphenol-type epoxy resin or an aliphatic epoxy resin is known as an epoxy acrylate, and is known as an ultraviolet curable resin or a thermosetting resin for electronic parts or optical curable resins. It is used for purposes such as bonding and coating parts. Many of these have excellent adhesion to coatings and the like, chemical resistance, etc., but in applications to electronic components and optical components, heat stability, low expansion coefficient, stability of refractive index,
Further, improvement in characteristics such as flame retardancy is further required.
Specifically, the conventional epoxy acrylate has a large coefficient of linear expansion, is flammable, and has no self-extinguishing property. Polyfunctional epoxy acrylates are also known, but also have a problem such that residual stress after curing is large, and adverse effects on adhesion and generation of cracks cause optical distortion.
【０００３】このように従来のエポキシアクリレートは
電子部品や光学部品に利用する場合に不利な点が多く、
また、性能的にも満足できるものではなかった。As described above, the conventional epoxy acrylate has many disadvantages when used for electronic parts and optical parts.
In addition, performance was not satisfactory.
【０００４】本発明は、難燃性、低膨張率、高屈折率、
可撓性等の物性に優れ、電子部品や光学部品への利用に
適した、紫外線硬化型難燃性樹脂組成物の提供をその目
的とする。The present invention provides a flame retardant, low expansion coefficient, high refractive index,
An object of the present invention is to provide an ultraviolet-curable flame-retardant resin composition having excellent physical properties such as flexibility and suitable for use in electronic components and optical components.
【０００５】[0005]
【発明を解決するための手段】本発明の紫外線硬化型難
燃性樹脂組成物は（Ａ）式The ultraviolet-curable flame-retardant resin composition of the present invention has the formula (A)
【化２】 但しＲはＨ又はメチルを示す、で示されるエポキシ化合
物と（メタ）アクリル酸の１対１反応生成物と、（Ｂ）
（メタ）アクリル酸エステルモノマーと、（Ｃ）ポリブ
タジエンアクリロニトリルエポキシ（メタ）アクリレー
トオリゴマーと、（Ｄ）光開始剤を含有することを特徴
とする。Embedded image However, R represents H or methyl, and a one-to-one reaction product of an epoxy compound represented by (B) and (B)
It is characterized by containing a (meth) acrylate monomer, (C) a polybutadiene acrylonitrile epoxy (meth) acrylate oligomer, and (D) a photoinitiator.
【０００６】本願において（メタ）アクリル酸とはアク
リル酸及び／又はメタクリル酸を意味する。（メタ）ア
クリレートも同様にアクリレート及び／メタクリレート
を意味する。In the present application, (meth) acrylic acid means acrylic acid and / or methacrylic acid. (Meth) acrylate also means acrylate and / or methacrylate.
【０００７】本発明の（Ａ）成分は式Ｉのエポキシ化合
物のエポキシ基（Ｘ）と（メタ）アクリル酸のカルボキ
シル基（Ｙ）との当量比（Ｘ／Ｙ）が１／１になるよう
に混合して反応させることにより容易に得ることができ
る。この合成反応は従来公知の反応に準じて行なうこと
ができる。式Ｉのエポキシ化合物は常温で液状であり、
使用し易いと共に、（メタ）アクリル化することにより
優れた難燃性と高屈折率性能をもたらす。The component (A) of the present invention is such that the equivalent ratio (X / Y) between the epoxy group (X) of the epoxy compound of the formula I and the carboxyl group (Y) of (meth) acrylic acid is 1/1. Can be easily obtained by mixing and reacting. This synthesis reaction can be performed according to a conventionally known reaction. The epoxy compound of Formula I is liquid at room temperature,
It is easy to use and provides excellent flame retardancy and high refractive index performance by being (meth) acrylated.
【０００８】（Ｂ）成分の（メタ）アクリル酸エステル
モノマーはエポキシアクリレート類の架橋剤としての機
能を有するものであり、その種類は特に限定されない
が、通常低級アルキル又はヒドロキシ低級アルキル（メ
タ）アクリレートが好ましく用いられ、特に２−ヒドロ
キシエチルメタクリレート及び２−ヒドロキシプロピル
メタクリレートが好ましく用いられる。The (meth) acrylate monomer of the component (B) has a function as a crosslinking agent for epoxy acrylates, and the type thereof is not particularly limited, but is usually lower alkyl or hydroxy lower alkyl (meth) acrylate. Are preferably used, and particularly, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are preferably used.
【０００９】（Ｃ）成分のポリブタジエンアクリロニト
リルエポキシ（メタ）アクリレートオリゴマーは典型的
には式The polybutadiene acrylonitrile epoxy (meth) acrylate oligomer of component (C) is typically of the formula
【化３】 但しＲはＨ又はメチルを示す、で表わされる。分子量が
３５００〜５０００で、ｎ／ｍが０．１〜０．３のもの
が特に好ましい。（Ｃ）成分は主に可撓性と低膨張率の
性能をもたらす。Embedded image Here, R represents H or methyl. Those having a molecular weight of 3500 to 5000 and n / m of 0.1 to 0.3 are particularly preferred. The component (C) mainly provides flexibility and low expansion coefficient performance.
【００１０】（Ｄ）成分の光開始剤としては従来知られ
た適宜の光開始剤を用いうる。具体例としてはベンジル
ジメチルケタール、２−ヒドロキシ−２−メチル−１−
フェニルプロパン−１−オン等がある。尚必要に応じて
過酸化物等の触媒や重合禁止剤等の上記以外の添加剤を
併用しうる。As the photoinitiator of the component (D), any conventionally known appropriate photoinitiator can be used. Specific examples include benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-
And phenylpropan-1-one. If necessary, a catalyst such as a peroxide or an additive other than the above such as a polymerization inhibitor may be used in combination.
【００１１】（Ａ）〜（Ｄ）成分の使用割合は（Ａ）成
分１００重量部に対し、（Ｂ）成分５〜３０重量部、
（Ｃ）成分５〜３０重量部、（Ｄ）成分０．１〜５重量
部が好ましい。The proportion of the components (A) to (D) used is 5 to 30 parts by weight of the component (B) per 100 parts by weight of the component (A).
Component (C) is preferably 5 to 30 parts by weight, and component (D) 0.1 to 5 parts by weight.
【００１２】本発明の紫外線硬化型難燃性樹脂組成物
は、紫外線照射により硬化するものであり、硬化物は難
燃性で、高屈折率、低線膨張率を有すると共に可撓性を
もち、電子部品や光学部品の接着や被覆において顕著に
優れた効果を示す。The ultraviolet-curable flame-retardant resin composition of the present invention is cured by ultraviolet irradiation, and the cured product is flame-retardant, has a high refractive index and a low linear expansion coefficient, and has flexibility. It has a remarkably excellent effect in bonding and coating electronic parts and optical parts.
【００１３】次に実施例に基づいて本発明を説明する。Next, the present invention will be described based on embodiments.
【００１４】[0014]
【実施例】冷却器、攪拌機および温度調節機つき５００
ｍｌ四ッ口フラスコに臭素化エポキシ化合物（日本化薬
社製Ｏ：ＢＲＯＣ）EXAMPLE 500 with cooler, stirrer and temperature controller
Brominated epoxy compound (O: BROC, manufactured by Nippon Kayaku Co., Ltd.)
【化４】 ６４．４ｇ、メタクリル酸 １７．４ｇ、４−メトキシ
フェノール ４ｍｇ、トルエン ７２ｇ、トリエーテル
アミン ０．２ｇを仕込んだ。つぎに、トルエン環流
下、１１０℃×４時間反応を行なった後、１２０℃で１
５分間減圧でトルエンを除去した。その結果、エポキシ
アクリレートが得られた。このもの酸価は０．７であっ
た。Embedded image 64.4 g, methacrylic acid 17.4 g, 4-methoxyphenol 4 mg, toluene 72 g, and trietheramine 0.2 g were charged. Then, the reaction was carried out at 110 ° C. for 4 hours under a reflux of toluene.
The toluene was removed under reduced pressure for 5 minutes. As a result, an epoxy acrylate was obtained. This had an acid value of 0.7.
【００１５】このエポキシアクリレートにポリブタジエ
ンアクリロニトリルエポキシアクリレートオリゴマー
（分子量約４，０００、ｎ／ｍ＝０．２）と、アクリレ
ートモノマー及び、光開始剤として２−ヒドロキシ−２
−メチル−１−フェニルプロパン−１−オンを配合し、
紫外線硬化型樹脂を得た。A polybutadiene acrylonitrile epoxy acrylate oligomer (molecular weight: about 4,000, n / m = 0.2) is added to the epoxy acrylate, an acrylate monomer, and 2-hydroxy-2 as a photoinitiator.
-Methyl-1-phenylpropan-1-one,
An ultraviolet curable resin was obtained.
【００１６】この紫外線硬化型樹脂を厚み１．４ｍｍで
４ｋｗ高圧水銀灯により１５ｃｍの距離から３０秒間照
射して硬化させた。この硬化物の物性を表１に示す。The ultraviolet-curable resin was cured by irradiating it with a 1.4-mm-thick 4 kW high-pressure mercury lamp from a distance of 15 cm for 30 seconds. Table 1 shows the physical properties of the cured product.
【００１７】[0017]
【表１】 [Table 1]
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０９Ｄ 5/00 Ｃ０９Ｄ 5/00 Ｃ 163/10 163/10 Ｃ０９Ｊ 4/00 Ｃ０９Ｊ 4/00 163/10 163/10 (Ｃ０８Ｆ 290/06 220:30） (56)参考文献 特開 昭61−185542（ＪＰ，Ａ) 特開 昭62−187744（ＪＰ，Ａ) 特開 昭64−81813（ＪＰ，Ａ) 特開 平５−25418（ＪＰ，Ａ) 特開 平２−180913（ＪＰ，Ａ) 特開 平２−47121（ＪＰ，Ａ) 特開 平５−70757（ＪＰ，Ａ) 特開 平１−174519（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 290/00 - 290/14 C08F 299/00 - 299/08 C08F 2/46 - 2/50 C08G 59/00 - 59/72 C08F 20/00 - 20/70 C08F 220/00 - 220/70 C09D 1/00 - 201/10 C09J 1/00 - 201/10 Continued on the front page (51) Int.Cl. 7 Identification code FI C09D 5/00 C09D 5/00 C 163/10 163/10 C09J 4/00 C09J 4/00 163/10 163/10 (C08F 290/06 220 30) (56) References JP-A-61-185542 (JP, A) JP-A-62-187744 (JP, A) JP-A-64-81813 (JP, A) JP-A-5-25418 (JP, A A) JP-A-2-180913 (JP, A) JP-A-2-47121 (JP, A) JP-A-5-70757 (JP, A) JP-A-1-174519 (JP, A) (58) Survey Field (Int.Cl. 7 , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08F 2/46-2/50 C08G 59/00-59/72 C08F 20/00-20 / 70 C08F 220/00-220/70 C09D 1/00-201/10 C09J 1/00-201/10
Claims (2)
物と（メタ）アクリル酸の１対１反応生成物と、（Ｂ）
（メタ）アクリル酸エステルモノマーと、（Ｃ）ポリブ
タジエンアクリロニトリルエポキシ（メタ）アクリレー
トオリゴマーと、（Ｄ）光開始剤を含有することを特徴
とする紫外線硬化型難燃性樹脂組成物。(1) Formula (A) However, R represents H or methyl, and a one-to-one reaction product of an epoxy compound represented by (B) and (B)
An ultraviolet-curable flame-retardant resin composition comprising (meth) acrylic acid ester monomer, (C) polybutadiene acrylonitrile epoxy (meth) acrylate oligomer, and (D) a photoinitiator.
レート又はヒドロキシプロピルメタクリレートである請
求項１記載の紫外線硬化型難燃性樹脂組成物。2. The ultraviolet-curable flame-retardant resin composition according to claim 1, wherein the component (B) is hydroxyethyl methacrylate or hydroxypropyl methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36123491A JP3166257B2 (en) | 1991-12-25 | 1991-12-25 | UV-curable flame-retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36123491A JP3166257B2 (en) | 1991-12-25 | 1991-12-25 | UV-curable flame-retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05170846A JPH05170846A (en) | 1993-07-09 |
| JP3166257B2 true JP3166257B2 (en) | 2001-05-14 |
Family
ID=18472748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36123491A Expired - Fee Related JP3166257B2 (en) | 1991-12-25 | 1991-12-25 | UV-curable flame-retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3166257B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105849161A (en) * | 2014-01-29 | 2016-08-10 | 日本合成化学工业株式会社 | Molded resin object and use thereof |
-
1991
- 1991-12-25 JP JP36123491A patent/JP3166257B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05170846A (en) | 1993-07-09 |
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