JPH05170846A - Ultraviolet-curable flame-retardant resin composition - Google Patents
Ultraviolet-curable flame-retardant resin compositionInfo
- Publication number
- JPH05170846A JPH05170846A JP36123491A JP36123491A JPH05170846A JP H05170846 A JPH05170846 A JP H05170846A JP 36123491 A JP36123491 A JP 36123491A JP 36123491 A JP36123491 A JP 36123491A JP H05170846 A JPH05170846 A JP H05170846A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- epoxy
- ultraviolet
- resin composition
- acrylic acid
- 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
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
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 a UV-curable flame-retardant resin composition, and more particularly to a UV-curable flame-retardant resin composition useful for adhesion and coating of 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 An acrylic acid or methacrylic acid adduct of a bisphenol type epoxy resin or an aliphatic epoxy resin has been known as an epoxy acrylate, and is used as an ultraviolet curable resin or a thermosetting resin for electronic parts and optical components. It is used for the purpose of adhesion and coating of parts. Many of these are excellent in adhesion to coatings, chemical resistance, etc., but in applications to electronic parts and optical parts, heat resistance stability, low expansion coefficient, refractive index stability,
Further improvement of properties such as flame retardancy is required.
Specifically, the conventional epoxy acrylate has a large coefficient of linear expansion, is flammable, and is not self-extinguishing. Polyfunctional epoxy acrylates are also known, but this also has a problem that the residual stress after curing is large, and the adverse effect on the adhesiveness and the 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, conventional epoxy acrylates have many disadvantages when used in electronic parts and optical parts.
Also, the 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 is flame retardant, low expansion coefficient, high refractive index,
It is an object of the present invention to provide an ultraviolet-curable flame-retardant resin composition having excellent physical properties such as flexibility and suitable for use in electronic parts and optical parts.
【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。[Chemical 2] However, R is H or methyl, and a one-to-one reaction product of the epoxy compound and (meth) acrylic acid, and (B)
It is characterized by containing (meth) acrylic acid ester monomer, (C) polybutadiene acrylonitrile epoxy (meth) acrylate oligomer, and (D) 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 formula I and the carboxyl group (Y) of (meth) acrylic acid is 1/1. It can be easily obtained by mixing with and reacting with. This synthetic reaction can be performed according to a conventionally known reaction. The epoxy compound of formula I is liquid at room temperature,
In addition to being easy to use, it is also excellent in 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) acrylic acid ester monomer as the component (B) has a function as a cross-linking agent for epoxy acrylates, and the kind thereof is not particularly limited, but usually lower alkyl or hydroxy lower alkyl (meth) acrylate. Is preferably used, and 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are particularly 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Component (C), the polybutadiene acrylonitrile epoxy (meth) acrylate oligomer, 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。[Chemical 3] However, R represents H or methyl. Particularly preferred are those having a molecular weight of 3500 to 5000 and an n / m of 0.1 to 0.3. 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 photoinitiator can be used. Specific examples include benzyl dimethyl ketal and 2-hydroxy-2-methyl-1-.
Phenylpropan-1-one and the like. If necessary, a catalyst such as a peroxide and 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 proportions of the components (A) to (D) used are 5 to 30 parts by weight of the component (B) with respect to 100 parts by weight of the component (A).
The component (C) is preferably 5 to 30 parts by weight, and the component (D) is 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 irradiation with ultraviolet rays, and the cured product is flame-retardant, has a high refractive index, a low linear expansion coefficient and is flexible. , Shows a remarkably excellent effect in adhesion and coating of 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 explained based on examples.
【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)Examples 500 with cooler, stirrer and temperature controller
Brominated epoxy compound (O: BROC manufactured by Nippon Kayaku Co., Ltd.) in a 4-ml four-necked flask.
【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。[Chemical 4] 64.4 g, methacrylic acid 17.4 g, 4-methoxyphenol 4 mg, toluene 72 g, and tri-amine 0.2 g were charged. Next, the mixture was reacted at 110 ° C for 4 hours under a reflux of toluene, and then at 120 ° C for 1 hour.
Toluene was removed under reduced pressure for 5 minutes. As a result, epoxy acrylate was obtained. The acid value of this product was 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。To this epoxy acrylate, polybutadiene acrylonitrile epoxy acrylate oligomer (molecular weight about 4,000, n / m = 0.2), acrylate monomer and 2-hydroxy-2 as a photoinitiator.
-Methyl-1-phenylpropan-1-one is blended,
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。This UV-curable resin was irradiated with a 4 kW high pressure mercury lamp having a thickness of 1.4 mm from a distance of 15 cm for 30 seconds to cure the resin. The physical properties of this cured product are shown in Table 1.
【0017】[0017]
【表1】 [Table 1]
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. A formula (A): However, R is H or methyl, and a one-to-one reaction product of the epoxy compound and (meth) acrylic acid, and (B)
An ultraviolet-curable flame-retardant resin composition comprising a (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 true JPH05170846A (en) | 1993-07-09 |
JP3166257B2 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) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015115154A1 (en) * | 2014-01-29 | 2015-08-06 | 日本合成化学工業株式会社 | Molded resin object and use thereof |
-
1991
- 1991-12-25 JP JP36123491A patent/JP3166257B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015115154A1 (en) * | 2014-01-29 | 2015-08-06 | 日本合成化学工業株式会社 | Molded resin object and use thereof |
Also Published As
Publication number | Publication date |
---|---|
JP3166257B2 (en) | 2001-05-14 |
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