JP2002256057A - Curable composition - Google Patents
Curable compositionInfo
- Publication number
- JP2002256057A JP2002256057A JP2001056660A JP2001056660A JP2002256057A JP 2002256057 A JP2002256057 A JP 2002256057A JP 2001056660 A JP2001056660 A JP 2001056660A JP 2001056660 A JP2001056660 A JP 2001056660A JP 2002256057 A JP2002256057 A JP 2002256057A
- Authority
- JP
- Japan
- Prior art keywords
- curable composition
- formula
- hydrocarbon group
- epoxy resin
- represented
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱硬化または活性
エネルギー線硬化により、吸水率が低く、耐熱性および
耐候性に優れた硬化物を与える硬化性組成物に関する。
該硬化性組成物は粘度が低いため作業性に優れ、封止
材、接着剤、成形材料および注型材料等の材料として有
用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition which gives a cured product having low water absorption and excellent heat resistance and weather resistance by heat curing or active energy ray curing.
The curable composition has excellent workability due to its low viscosity, and is useful as a material such as a sealing material, an adhesive, a molding material, and a casting material.
【０００２】[0002]
【従来の技術】エポキシ化合物を熱硬化あるいは活性エ
ネルギー線硬化させるカチオン硬化技術は公知であり、
各種エポキシ化合物、各種硬化剤およびカチオン硬化開
始剤の材料が広く市販されている。エポキシ化合物とし
ては、ビスフェノールＡのジグリシジルエーテル、ビス
フェノールＦのジグリシジルエーテル、フェノールノボ
ラック型エポキシ樹脂などの芳香族エポキシ樹脂、シク
ロオレフィンの過酢酸酸化により得られる３，４−エポ
キシシクロヘキシルメチル−３’，４’−エポキシシク
ロヘキサンカルボキシレート等の環状脂肪族エポキシ樹
脂あるいは水添ビスフェノールＡ等のアルコール類をエ
ポキシ化して得られるアルコール型エポキシ樹脂などが
知られている。一方、電気分野の用途では、近年、電気
機器の小型化により電気回路の多層化、高密化が進み、
それに伴い使用されるエポキシ樹脂に対しては、低誘電
率化、耐アーク性、耐トラッキング性が要求されてい
る。これらの電気特性向上のためには、芳香族エポキシ
樹脂よりも、芳香環を持たない環状脂肪族エポキシ樹脂
あるいはアルコール型エポキシ樹脂が有利であることが
知られている。しかしながら、水添ビスフェノールＡ等
のアルコールをエポキシ化させたアルコール型エポキシ
樹脂は、その製造上、製品中に多量の塩素が残存しやす
く、その結果、電気絶縁性の低下、誘電率、誘電正接値
の上昇等電気特性の著しい劣化を招く。さらに、耐熱性
も上記芳香族エポキシ樹脂と比べてかなり低下する。こ
のような塩素の残存や耐熱性の改善のため、環状脂肪族
エポキシ樹脂が使用されている。しかしながら、一般に
広く使用されている環状脂肪族エポキシ樹脂である３，
４−エポキシシクロヘキシルメチル−３’，４’−エポ
キシシクロヘキサンカルボキシレートはその分子中に存
在するエステル基の寄与により、吸水率が比較的に高い
ことが知られている。2. Description of the Related Art Cationic curing techniques for curing epoxy compounds with heat or active energy rays are known.
Materials of various epoxy compounds, various curing agents and cationic curing initiators are widely commercially available. Examples of the epoxy compound include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, aromatic epoxy resins such as phenol novolak type epoxy resin, and 3,4-epoxycyclohexylmethyl-3 ′ obtained by peracetic acid oxidation of cycloolefin. And cycloaliphatic epoxy resins such as 4,4'-epoxycyclohexanecarboxylate and alcohol-type epoxy resins obtained by epoxidizing alcohols such as hydrogenated bisphenol A. On the other hand, in applications in the electric field, in recent years, the miniaturization of electric devices has led to the increase in the number and density of electric circuits,
Accordingly, the epoxy resin used is required to have a low dielectric constant, arc resistance, and tracking resistance. It is known that a cycloaliphatic epoxy resin having no aromatic ring or an alcoholic epoxy resin is more advantageous than an aromatic epoxy resin for improving these electrical properties. However, in the production of alcohol type epoxy resins obtained by epoxidizing alcohol such as hydrogenated bisphenol A, a large amount of chlorine tends to remain in the product, resulting in a decrease in electric insulation, a dielectric constant, and a dielectric loss tangent value. The electrical characteristics are remarkably degraded, for example, the rise of the temperature. Further, the heat resistance is considerably reduced as compared with the aromatic epoxy resin. Cycloaliphatic epoxy resins are used to improve the residual chlorine and heat resistance. However, the generally used cycloaliphatic epoxy resin 3,3
It is known that 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate has a relatively high water absorption due to the contribution of an ester group present in the molecule.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記の問題
を解決し、封止材、接着剤、成形材料、注型材料等の材
料として有用な、熱硬化または活性エネルギー線硬化に
より、吸水率が低く、耐熱性に優れた硬化物を与える低
粘度で作業性に優れた硬化性組成物を提供することを目
的とするものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and is useful as a material for a sealing material, an adhesive, a molding material, a casting material, or the like. It is an object of the present invention to provide a curable composition having a low viscosity and excellent workability, which gives a cured product having a low heat resistance.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意研究を重ねた結果、これらの目的を達
成できる硬化性組成物を見出し本発明を完成するに至っ
た。すなわち、本発明は、下記式（１）で表される１分
子中に２個のオキセタニル基を有する脂肪族オキセタン
化合物（ａ）、環状脂肪族エポキシ樹脂（ｂ）およびカ
チオン重合開始剤（ｃ）からなる硬化性組成物である。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found a curable composition which can achieve these objects and completed the present invention. That is, the present invention provides an aliphatic oxetane compound (a) having two oxetanyl groups in one molecule represented by the following formula (1), a cycloaliphatic epoxy resin (b), and a cationic polymerization initiator (c) And a curable composition comprising:
【０００５】[0005]
【化４】 Embedded image
【０００６】（式中、Ｒ1およびＲ2は水素原子、アルキ
ル基または置換炭化水素基を示し、Ｒ 3は下記式（２）
で表される有機基を示す。）(Where R1And RTwoIs a hydrogen atom,
Or a substituted hydrocarbon group; ThreeIs the following formula (2)
Represents an organic group represented by )
【０００７】[0007]
【化５】 Embedded image
【０００８】（式中、ｎは０〜５の整数を示し、Ｒ4は
炭素数２〜１２の直鎖状あるいは分枝状脂肪族炭化水素
基を示す。）(Wherein, n represents an integer of 0 to 5, and R 4 represents a linear or branched aliphatic hydrocarbon group having 2 to 12 carbon atoms.)
【０００９】[0009]
【発明の実施の形態】以下、本発明について詳細に説明
する。（ａ）成分の前記式（１）で表されるオキセタニ
ル基を有する化合物は、１分子中に２個のオキセタニル
基を有する脂肪族オキセタン化合物である。前記式
（１）においてＲ３は前記式（２）で表される有機基を
示し、式（２）においてｎは０〜５の整数であり、ｎが
６以上の場合は本発明の特徴である低粘度の組成物が得
られない。式（１）で表される化合物の中でも、高い耐
熱性および低い吸水率の硬化物が得られるという理由か
ら、下記式（３）で表される脂肪族オキセタン化合物が
好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The compound having an oxetanyl group represented by the formula (1) as the component (a) is an aliphatic oxetane compound having two oxetanyl groups in one molecule. In the formula (1), R3 represents an organic group represented by the formula (2), and in the formula (2), n is an integer of 0 to 5, and when n is 6 or more, it is a feature of the present invention. A low-viscosity composition cannot be obtained. Among the compounds represented by the formula (1), an aliphatic oxetane compound represented by the following formula (3) is preferable because a cured product having high heat resistance and a low water absorption is obtained.
【００１０】[0010]
【化６】 Embedded image
【００１１】（式中、Ｒ1およびＲ2は水素原子、アルキ
ル基または置換炭化水素基を示す。）(Wherein R 1 and R 2 represent a hydrogen atom, an alkyl group or a substituted hydrocarbon group)
【００１２】さらに好ましくは、下記式（４）で表され
る｛ビス（３−エチル−３−オキセタニルメチル）エー
テル｝であり、市販品である東亞合成（株）製ＯＸＴ−
２２１（商品名）が使用できる。More preferably, it is a bis (3-ethyl-3-oxetanylmethyl) ether represented by the following formula (4), which is a commercially available product OXT- manufactured by Toagosei Co., Ltd.
221 (trade name) can be used.
【００１３】[0013]
【化７】 Embedded image
【００１４】本発明における（ｂ） 成分は、一般的に
シクロオレフィンをエポキシ化して得られる環状脂肪族
エポキシ樹脂であり、その具体例として、油化シェルエ
ポキシ社製エピコート１７１（商品名）、旭チバ社製ア
ラルダイトＣＹ１７８（商品名）、チッソ（株）製チッ
ソノックス２０６およびチッソノックス２０５（いずれ
も商品名）、ダイセル化学工業（株）製セロキサイド２
０２１、エポリードＧＴ３０１、エポリードＧＴ３０
２、エポリードＧＴ４０１およびエポリードＧＴ４０３
（いずれも商品名）などが例示される。The component (b) in the present invention is a cycloaliphatic epoxy resin generally obtained by epoxidizing a cycloolefin, and specific examples thereof include Epicoat 171 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd .; Araldite CY178 (trade name) manufactured by Ciba, Chisso Nox 206 and Chisso Knox 205 (trade name) manufactured by Chisso Corporation, Celloxide 2 manufactured by Daicel Chemical Industries, Ltd.
021, EPOLID GT301, EPOLID GT30
2. Eporide GT401 and Eporide GT403
(Both are trade names).
【００１５】前記環状脂肪族エポキシ樹脂は、分子量が
１２０〜１，０００であることが好ましい。分子量が１
２０未満であると環状脂肪族エポキシ化合物の揮発性が
高く、作業環境や塗工時の加工特性を著しく悪化させ
る。分子量が１，０００を越えると組成物の粘度が高く
なるため、所定形状に注型、成形あるいは均一に塗工す
ることが困難となる。特に好ましい化合物としては、
３，４−エポキシシクロヘキシルメチル−３’，４’−
エポキシシクロヘキサンカルボキシレートが挙げられ
る。The cycloaliphatic epoxy resin preferably has a molecular weight of 120 to 1,000. Molecular weight 1
When it is less than 20, the volatility of the cycloaliphatic epoxy compound is high, and the working environment and processing characteristics during coating are significantly deteriorated. When the molecular weight exceeds 1,000, the viscosity of the composition becomes high, so that it becomes difficult to cast, mold or uniformly apply the composition into a predetermined shape. Particularly preferred compounds include
3,4-epoxycyclohexylmethyl-3 ', 4'-
Epoxy cyclohexane carboxylate.
【００１６】本発明の硬化性組成物は、脂肪族オキセタ
ン化合物（ａ）１０〜８０重量部に対して、環状脂肪族
エポキシ樹脂（ｂ）９０〜２０重量部の割合で用いるこ
とが好ましい。（ｂ）環状脂肪族エポキシ樹脂が２０重
量部未満であると硬化物の耐熱性が減少し、また、９０
重量部を越えると硬化物の吸水率が高くなるため好まし
くない。The curable composition of the present invention is preferably used in a proportion of 90 to 20 parts by weight of the cyclic aliphatic epoxy resin (b) to 10 to 80 parts by weight of the aliphatic oxetane compound (a). (B) When the amount of the cycloaliphatic epoxy resin is less than 20 parts by weight, the heat resistance of the cured product decreases, and
Exceeding part by weight is not preferred because the water absorption of the cured product increases.
【００１７】カチオン重合開始剤（ｃ）は、光あるいは
熱の適応により活性化され酸成分を生成し、組成物中の
開環重合性基のカチオン開環重合を誘発するように作用
する潜在性を有するものである。光潜在性を有するカチ
オン重合開始剤としては、光を照射されて活性化され開
環重合性基の開環を誘発する任意の光カチオン重合開始
剤が用いることができ、オニウム塩類および有機金属錯
体類などを例示することができる。前記オニウム塩類と
してはジアゾニウム塩、スルホニウム塩およびヨードニ
ウム塩等が挙げられる。また、有機金属錯体類として
は、例えば、鉄−アレン錯体、チタノセン錯体およびア
リールシラノール−アルミニウム錯体などが挙げられ
る。市販品である、オプトマーＳＰ−１５０｛商品名、
旭電化工業（株）製｝、オプトマーＳＰ−１７０｛商品
名、旭電化工業（株）製｝、ＵＶＥ−１０１４（商品
名、ゼネラルエレクトロニクス社製）およびＣＤ−１０
１２（商品名、サートマー社製）などを利用することも
できる。The cationic polymerization initiator (c) is activated by the application of light or heat to generate an acid component, and has the potential to act to induce cationic ring-opening polymerization of the ring-opening polymerizable group in the composition. It has. As the cationic polymerization initiator having photolatent, any cationic photopolymerization initiator that is activated by irradiation with light and induces ring opening of a ring-opening polymerizable group can be used, and includes onium salts and organometallic complexes. And the like. Examples of the onium salts include diazonium salts, sulfonium salts, and iodonium salts. Further, examples of the organometallic complexes include an iron-allene complex, a titanocene complex, and an arylsilanol-aluminum complex. Commercial product, Optomer SP-150 ｛trade name,
Asahi Denka Kogyo Co., Ltd., Optomer SP-170, trade name, Asahi Denka Kogyo Co., Ltd., UVE-1014 (trade name, manufactured by General Electronics) and CD-10
12 (trade name, manufactured by Sartomer Co.) can also be used.
【００１８】熱潜在性を有するカチオン重合開始剤とし
ては、加熱により活性化され開環重合性基の開環を誘発
する任意の熱カチオン重合開始剤が用いられ、第四級ア
ンモニウム塩、ホスホニウム塩およびスルホニウム塩等
の各種オニウム塩類、有機金属錯体類などが例示され
る。上記オニウム塩類としては、例えば、アデカオプト
ンＣＰ−６６およびアデカオプトンＣＰ−７７｛いずれ
も商品名、旭電化工業（株）社製｝、サンエイドＳＩ−
６０Ｌ、サンエイドＳＩ−８０ＬおよびサンエイドＳＩ
−１００Ｌ｛いずれも商品名、三新化学工業（株）
製｝、およびＣＩシリーズ｛日本曹達（株）製｝などの
市販の化合物を用いることができる。また、有機金属錯
体類としては、例えば、アルコキシシラン−アルミニウ
ム錯体などが挙げられる。また、カチオン重合開始剤の
配合割合は、前記（ａ）成分および（ｂ）成分の合計量
１００重量部に対し、０．０１〜５重量部の範囲とする
ことが好ましい。カチオン重合開始剤の配合割合が０．
０１重量部未満の場合には、光あるいは熱の作用により
活性化しても、開環重合性基の開環反応を十分に進行さ
せることができないことがあり、重合後の耐熱性および
吸水率が不十分となる場合が有る。また、５重量部を超
えて配合したとしても、重合を進行する作用はそれ以上
高まらず、逆に耐熱性および吸水率が低下することがあ
る。As the cationic polymerization initiator having a thermal potential, any thermal cationic polymerization initiator which is activated by heating to induce ring opening of a ring-opening polymerizable group is used, and quaternary ammonium salts and phosphonium salts And various onium salts such as sulfonium salts, and organometallic complexes. Examples of the onium salts include Adeka Opton CP-66 and Adeka Opton CP-77 (both are trade names, manufactured by Asahi Denka Kogyo KK), and Sun Aid SI-
60L, Sun-Aid SI-80L and Sun-Aid SI
-100L ｛All are trade names, Sanshin Chemical Industry Co., Ltd.
And commercially available compounds such as CI series (manufactured by Nippon Soda Co., Ltd.). Examples of the organometallic complexes include, for example, an alkoxysilane-aluminum complex. The proportion of the cationic polymerization initiator is preferably in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total of the components (a) and (b). When the compounding ratio of the cationic polymerization initiator is 0.
If the amount is less than 01 parts by weight, even if activated by the action of light or heat, the ring-opening reaction of the ring-opening polymerizable group may not be able to proceed sufficiently, and the heat resistance and water absorption after polymerization may be poor. It may be insufficient. Further, even if it is added in an amount exceeding 5 parts by weight, the effect of promoting the polymerization does not further increase, and conversely, heat resistance and water absorption may decrease.
【００１９】本発明の硬化性組成物には、必要に応じて
以下の各成分を添加配合することができる。 （１）粉末状の補強剤および充填剤であり、例えば、酸
化アルミニウム、酸化マグネシウムなどの金属酸化物、
炭酸カルシウム、炭酸マグネシウムなどの金属炭酸塩、
ケイソウ土粉、塩基性ケイ酸マグネシウム、焼成クレ
イ、微粉末シリカ、溶融シリカ、結晶シリカなどのケイ
素化合物、水酸化アルミニウムなどの金属水酸化物、そ
の他、カオリン、マイカ、石英粉末、グラファイト、二
硫化モリブデン等、さらに繊維質の補強剤や充填剤、た
とえばガラス繊維、セラミック繊維、カーボンファイバ
ー、アルミナ繊維、炭化ケイ素繊維、ボロン繊維、ポリ
エステル繊維及びポリアミド繊維等である。これらは組
成物１００重量部に対して、１０〜９００重量部配合さ
れることが好ましい。 （２）着色剤、顔料および難燃剤であり、例えば、二酸
化チタン、鉄黒、モリブデン赤、紺青、群青、カドミウ
ム黄、カドミウム赤、三酸化アンチモン、赤燐、ブロム
化合物及びトリフェニルホスフェイト等である。これら
は本発明の組成物１００重量部に対して、０．１〜２０
重量部配合されることが好ましい。 （３）さらに、最終的な接着層、成形品などにおける樹
脂の性質を改善する目的で種々の硬化性モノマー、オリ
ゴマーおよび合成樹脂を配合することができる。例え
ば、モノエポキシ等のエポキシ樹脂用希釈剤、フェノー
ル樹脂、アルキド樹脂、メラミン樹脂、フッ素樹脂、塩
化ビニル樹脂、アクリル樹脂、シリコーン樹脂、ポリエ
ステル樹脂等の１種または２種以上の組み合わせを挙げ
ることができる。これら樹脂類の配合割合は、本発明の
樹脂組成物の本来の性質を損なわない範囲の量である組
成物１００重量部に対して５０重量部以下が好ましい。The following components can be added to the curable composition of the present invention, if necessary. (1) powdered reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide;
Metal carbonates such as calcium carbonate and magnesium carbonate,
Diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powder silica, fused silica, silicon compounds such as crystalline silica, metal hydroxides such as aluminum hydroxide, other, kaolin, mica, quartz powder, graphite, disulfide Molybdenum and the like, and fibrous reinforcing agents and fillers such as glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber, and polyamide fiber. These are preferably blended in an amount of 10 to 900 parts by weight based on 100 parts by weight of the composition. (2) Colorants, pigments, and flame retardants, such as titanium dioxide, iron black, molybdenum red, dark blue, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromide compounds, and triphenyl phosphate. is there. These are 0.1 to 20 parts by weight based on 100 parts by weight of the composition of the present invention.
It is preferred to be blended by weight. (3) Further, various curable monomers, oligomers and synthetic resins can be blended for the purpose of improving the properties of the resin in the final adhesive layer, molded article and the like. For example, a diluent for epoxy resins such as monoepoxy, a phenol resin, an alkyd resin, a melamine resin, a fluororesin, a vinyl chloride resin, an acrylic resin, a silicone resin, a polyester resin, and the like, or a combination of two or more of them. it can. The mixing ratio of these resins is preferably 50 parts by weight or less with respect to 100 parts by weight of the composition, which is an amount that does not impair the original properties of the resin composition of the present invention.
【００２０】本発明の組成物および任意成分の配合手段
としては、加熱溶融混合、ロール、ニーダーによる溶融
混練、適当な有機溶剤を用いての湿式混合および乾式混
合等が挙げられる。Examples of means for blending the composition of the present invention and optional components include heat-melt mixing, melt-kneading using a roll or a kneader, wet mixing using an appropriate organic solvent, and dry mixing.
【００２１】本発明の硬化性組成物は、熱カチオン重合
開始剤を用いた場合は熱により、また、活性エネルギー
線カチオン重合開始剤を用いた場合は活性エネルギー線
で硬化される。熱カチオン重合の場合は、通常、その熱
カチオン重合開始剤がカチオン種やルイス酸の発生を開
始する温度以上で行われ、通常５０〜２００℃にて実施
される。光照射により重合を行う場合に用いることので
きる光源としては特に限定されるものではないが、波長
４００ｎｍ以下に発光分布を有する、例えば、低圧水銀
灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカル
ランプ、ブラックライトランプ、マイクロウェーブ励起
水銀灯およびメタルハライドランプなどを用いることが
できる。組成物への光照射強度は、目的とする製品毎に
制御されるものであって特に限定されるものではない
が、光潜在性開始剤の活性化に有効な光波長領域（光重
合開始剤によって異なるが、通常３００〜４２０ｎｍの
光が用いられる。）の光照射強度が０．１〜１００ｍＷ
／ｃｍ2 であることが好ましい。組成物への光照射強度
が０．１ｍＷ／ｃｍ2 未満であると、反応時間が長くな
り過ぎ、１００ｍＷ／ｃｍ2 を超えると、ランプから輻
射される熱および組成物の重合時の発熱により、得られ
る粘着剤層の凝集力の低下や黄変あるいは支持体の劣化
が生じる恐れがある。組成物への光照射時間は、目的と
する製品毎に制御されるものであって特に限定されるも
のではないが、前記光波長領域での光照射強度と光照射
時間の積として表される積算光量が１０〜５，０００ｍ
ｊ／ｃｍ2となるように設定されることが好ましい。上
記粘着剤組成物への積算光量が１０ｍｊ／ｃｍ2 未満で
あると、光潜在性開始剤よりの活性種の発生が十分でな
く、得られる粘着剤層の粘着特性の低下が生じるおそれ
があり、５，０００ｍｊ／ｃｍ2 を超えると、照射時間
が非常に長時間となり、生産性向上のためには不利なも
のとなる。また、活性エネルギー線照射後０．１〜数分
後には、ほとんどの組成物はカチオン重合により指触乾
燥するが、カチオン重合反応を促進するために加熱を併
用することも場合によっては好ましい。熱により重合を
行う場合は一般的に知られた方法により熱を適応するこ
とができ、その条件などは特に限定されるものではな
い。The curable composition of the present invention is cured by heat when a thermal cationic polymerization initiator is used, and by an active energy ray when an active energy ray cationic polymerization initiator is used. In the case of thermal cationic polymerization, the thermal cationic polymerization is usually carried out at a temperature not lower than the temperature at which the generation of cationic species or Lewis acid starts, and is usually carried out at 50 to 200 ° C. The light source that can be used when performing polymerization by light irradiation is not particularly limited, but has a light emission distribution at a wavelength of 400 nm or less, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a chemical. Lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like can be used. The light irradiation intensity on the composition is controlled for each target product and is not particularly limited. However, the light wavelength region (photopolymerization initiator) effective for activating the photolatent initiator is used. Light of 300 to 420 nm is usually used.)
/ Cm 2 . When the light irradiation intensity on the composition is less than 0.1 mW / cm 2 , the reaction time becomes too long, and when it exceeds 100 mW / cm 2 , the heat radiated from the lamp and the heat generated during the polymerization of the composition cause There is a possibility that the cohesive strength of the obtained pressure-sensitive adhesive layer is reduced, yellowing is caused, or the support is deteriorated. The light irradiation time on the composition is controlled for each target product and is not particularly limited, but is expressed as a product of light irradiation intensity and light irradiation time in the light wavelength region. Integrated light amount is 10-5,000m
It is preferably set to be j / cm 2 . When the integrated light amount to the pressure-sensitive adhesive composition is less than 10 mj / cm 2 , the generation of active species from the photolatent initiator is not sufficient, and the pressure-sensitive adhesive property of the obtained pressure-sensitive adhesive layer may be deteriorated. 5,000 mj / cm 2 , the irradiation time becomes extremely long, which is disadvantageous for improving the productivity. In addition, almost 0.1 to several minutes after the irradiation with the active energy ray, most compositions dry to the touch by cation polymerization. However, it is sometimes preferable to use heating in combination to promote the cation polymerization reaction. When performing polymerization by heat, heat can be applied by a generally known method, and the conditions and the like are not particularly limited.
【００２２】[0022]
【実施例】以下に、実施例および比較例を挙げて本発明
をさらに詳しく説明する。なお、各例中の部は重量部を
意味する。 実施例１ ＯＸＴ−２２１（商品名、東亞合成（株）製：ビス（３
−エチル−３−オキセタニルメチル）エーテル）２５
部、ＵＶＲ−６１１０（商品名、ユニオンカーバイド
製：３，４−エポキシシクロヘキシルメチル−３’，
４’−エポキシシクロヘキサンカルボキシレート）７５
部、および熱潜在性カチオン開始剤として、ＣＰ−６６
｛商品名、旭電化（株）製｝０．５部を均一になるよ
う、室温で充分攪拌混合した後、減圧脱泡して、硬化性
組成物を得た。次いで、上記組成物を型内に流し込み、
８０℃で１時間、１００℃で１時間、さらに１８０℃で
２時間オーブン中硬化させることにより試験片を得た。The present invention will be described below in more detail with reference to Examples and Comparative Examples. In addition, the part in each example means a weight part. Example 1 OXT-221 (trade name, manufactured by Toagosei Co., Ltd .: bis (3
-Ethyl-3-oxetanylmethyl) ether) 25
Part, UVR-6110 (trade name, manufactured by Union Carbide: 3,4-epoxycyclohexylmethyl-3 ′,
4'-epoxycyclohexanecarboxylate) 75
Parts, and CP-66 as a heat-latent cationic initiator
<< Trade name, manufactured by Asahi Denka Co., Ltd. >> 0.5 parts was sufficiently stirred and mixed at room temperature to be uniform, and then defoamed under reduced pressure to obtain a curable composition. Next, the composition is poured into a mold,
A test piece was obtained by curing in an oven at 80 ° C. for 1 hour, at 100 ° C. for 1 hour, and further at 180 ° C. for 2 hours.
【００２３】比較例１〜３ 表１に示したように、比較例１ではＵＶＲ−６１１０、
比較例２ではエピコートＥ−８２８（商品名、油化シェ
ルエポキシ製）およびＣＰ−６６を１部に増量、また、
比較例３ではＯＸＴ−２２１を１００部、それぞれ用い
る以外は、実施例１と同様の操作を行い試験片を得た。Comparative Examples 1-3 As shown in Table 1, in Comparative Example 1, UVR-6110,
In Comparative Example 2, Epicoat E-828 (trade name, manufactured by Yuka Shell Epoxy) and CP-66 were increased to 1 part, and
In Comparative Example 3, a test piece was obtained by performing the same operation as in Example 1 except that 100 parts of OXT-221 was used.
【００２４】[0024]
【表１】 [Table 1]
【００２５】上記実施例１および比較例１〜３に示した
組成物の粘度、粘弾性特性および煮沸吸水率を下記の方
法により測定した。粘度および粘弾性測定の貯蔵弾性率
の２００℃および２５０℃における測定値ならびに煮沸
吸水率の測定結果を下記表２に、また、粘弾性スペクト
ルを図１に示す。 粘度測定：配合後の組成物の粘度を２５℃においてＥ型
粘度計にて測定した。 粘弾性測定：ＪＩＳ Ｋ７１９８に従い、厚さ1ｍｍの
硬化物をセイコーインスツルメント社製のＤＭＳ−６１
００型動的粘弾性測定装置を用いて１０Ｈｚの周波数に
おいて引っ張り振動モードにて測定した。 煮沸吸水率：ＪＩＳ Ｋ６９１１に示されている試験方
法により測定した。The viscosities, viscoelastic properties and boiling water absorption of the compositions shown in Example 1 and Comparative Examples 1 to 3 were measured by the following methods. Table 2 below shows the measured values of the storage elastic modulus at 200 ° C. and 250 ° C. of the viscosity and the viscoelasticity measurement, and the measurement results of the boiling water absorption, and FIG. 1 shows the viscoelastic spectrum. Viscosity measurement: The viscosity of the composition after blending was measured at 25 ° C. with an E-type viscometer. Viscoelasticity measurement: In accordance with JIS K7198, a cured product having a thickness of 1 mm was subjected to DMS-61 manufactured by Seiko Instruments Inc.
The measurement was performed in a tensile vibration mode at a frequency of 10 Hz using a 00 type dynamic viscoelasticity measuring apparatus. Boiling water absorption: Measured by a test method shown in JIS K6911.
【００２６】[0026]
【表２】 [Table 2]
【００２７】表２に示したように、実施例１の組成物の
粘度は汎用に用いられている比較例２の組成物と比較し
て非常に低いものであった。表２および図１から明らか
なように、実施例１および比較例１の組成物より得られ
た硬化物は、２００℃および２５０℃においても貯蔵弾
性率は高い値を維持していたが、比較例２および３の組
成物からの硬化物はこの温度において貯蔵弾性率が大き
く低下していた。また、煮沸吸水率の測定において、実
施例１および比較例３は非常に低い吸水率を示してい
た。As shown in Table 2, the viscosity of the composition of Example 1 was much lower than that of the composition of Comparative Example 2 which is used for general purposes. As is clear from Table 2 and FIG. 1, the cured products obtained from the compositions of Example 1 and Comparative Example 1 maintained a high storage modulus even at 200 ° C. and 250 ° C. The cured products from the compositions of Examples 2 and 3 had a large decrease in storage modulus at this temperature. In the measurement of the boiling water absorption, Example 1 and Comparative Example 3 showed extremely low water absorption.
【００２８】[0028]
【発明の効果】本発明の硬化性組成物は低粘度であるた
めに作業性が高く、また、組成物から得られる硬化物
は、吸水率が低く、耐熱性および耐候性に非常に優れて
いるため、広範な用途に応用展開が可能である。特に、
封止材、接着剤、成形材料、注型材料等の材料として、
電気・電子分野等の用途において有利に使用できる。According to the present invention, the curable composition of the present invention has low workability due to its low viscosity, and the cured product obtained from the composition has a low water absorption and is very excellent in heat resistance and weather resistance. Therefore, it can be applied to a wide range of applications. In particular,
As materials for sealing materials, adhesives, molding materials, casting materials, etc.
It can be used advantageously in applications such as the electric and electronic fields.
【図１】実施例１および比較例１〜３の組成物の粘弾性
スペクトルを示す。FIG. 1 shows viscoelastic spectra of the compositions of Example 1 and Comparative Examples 1 to 3.
Claims (3)
オキセタニル基を有する脂肪族オキセタン化合物
（ａ）、環状脂肪族エポキシ樹脂（ｂ）およびカチオン
重合開始剤（ｃ）からなる硬化性組成物。 【化１】 （式中、Ｒ1およびＲ2は水素原子、アルキル基または置
換炭化水素基を示し、Ｒ3は下記式（２）で表される有
機基を示す。） 【化２】 （式中、ｎは０〜５の整数を示し、Ｒ4は炭素数２〜１
２の直鎖状あるいは分枝状脂肪族炭化水素基を示す。）1. An aliphatic oxetane compound (a) having two oxetanyl groups in one molecule represented by the following formula (1), a cycloaliphatic epoxy resin (b) and a cationic polymerization initiator (c): Curable composition. Embedded image (In the formula, R 1 and R 2 represent a hydrogen atom, an alkyl group or a substituted hydrocarbon group, and R 3 represents an organic group represented by the following formula (2).) (In the formula, n represents an integer of 0 to 5, and R 4 has 2 to 1 carbon atoms.
2 represents a linear or branched aliphatic hydrocarbon group. )
（３）で表されるオキセタン化合物である請求項１記載
の硬化性組成物。 【化３】 （式中、Ｒ1およびＲ2は水素原子、アルキル基または置
換炭化水素基を示す。）2. The curable composition according to claim 1, wherein the aliphatic oxetane compound is an oxetane compound represented by the following formula (3). Embedded image (In the formula, R 1 and R 2 represent a hydrogen atom, an alkyl group or a substituted hydrocarbon group.)
ポキシシクロヘキシルメチル−３’，４’−エポキシシ
クロヘキサンカルボキシレートである、請求項１あるい
は請求項２記載の硬化性組成物。3. The curable composition according to claim 1, wherein the cycloaliphatic epoxy resin is 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.
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| JP2001056660A JP3876630B2 (en) | 2001-03-01 | 2001-03-01 | Curable composition |
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|---|---|---|---|
| JP2001056660A JP3876630B2 (en) | 2001-03-01 | 2001-03-01 | Curable composition |
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| JP3876630B2 JP3876630B2 (en) | 2007-02-07 |
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| WO2004033532A1 (en) * | 2002-10-11 | 2004-04-22 | Toagosei Co., Ltd. | Cationically polymerizable composition containing metal oxide particles |
| EP1518899A3 (en) * | 2003-09-18 | 2005-08-03 | Fuji Photo Film Co., Ltd. | Photocurable adhesive and bonding process employing same |
| JP2006191150A (en) * | 2006-03-28 | 2006-07-20 | Sumitomo Bakelite Co Ltd | Insulating sheet, insulating sheet with metal foil, and multilayer printed wiring board |
| WO2007037434A1 (en) * | 2005-09-29 | 2007-04-05 | Cmet Inc. | Resin composition for optical three-dimensional molded object |
| JP2007284655A (en) * | 2006-03-20 | 2007-11-01 | Fujifilm Corp | Curable composition, and ink composition and inkjet-recording method by using the same |
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| JP2011176371A (en) * | 2011-06-03 | 2011-09-08 | Sumitomo Bakelite Co Ltd | Insulation sheet for build-up, insulation sheet with metal foil, and multilayer printed wiring board |
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| JP5916220B2 (en) | 2012-07-19 | 2016-05-11 | 日本化薬株式会社 | Energy ray curable resin composition and cured product thereof |
| JP6284217B2 (en) | 2013-03-29 | 2018-02-28 | 日本化薬株式会社 | Energy ray curable resin composition and cured product thereof |
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| JPWO2004033532A1 (en) * | 2002-10-11 | 2006-02-09 | 東亞合成株式会社 | Cationic polymerization composition containing metal oxide fine particles |
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