JPH11171967A - New alicyclic epoxyvinyl ether, polymerizable composition and its cured product - Google Patents
New alicyclic epoxyvinyl ether, polymerizable composition and its cured productInfo
- Publication number
- JPH11171967A JPH11171967A JP36329997A JP36329997A JPH11171967A JP H11171967 A JPH11171967 A JP H11171967A JP 36329997 A JP36329997 A JP 36329997A JP 36329997 A JP36329997 A JP 36329997A JP H11171967 A JPH11171967 A JP H11171967A
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- functional group
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- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規な脂環式エポキ
シビニルエーテル、該脂環式エポキシビニルエーテルを
含有する重合性組成物およびその硬化物に関する。The present invention relates to a novel alicyclic epoxy vinyl ether, a polymerizable composition containing the alicyclic epoxy vinyl ether, and a cured product thereof.
【０００２】[0002]
【従来の技術】現在、紫外線硬化型樹脂や電子線硬化型
樹脂などの重合性組成物は主に、インキ、塗料、接着
剤、レジスト、製版材などの多くの分野で用いられてい
る。この重合性組成物の主剤としては、アクリル系モノ
マーや多官能アクリレートが最も一般的である。2. Description of the Related Art At present, polymerizable compositions such as ultraviolet curable resins and electron beam curable resins are mainly used in many fields such as inks, paints, adhesives, resists and plate-making materials. Acrylic monomers and polyfunctional acrylates are most commonly used as the main components of the polymerizable composition.
【０００３】ところが、アクリル系モノマーには皮膚刺
激性や臭気性、酸素による重合抑制作用に付随する諸問
題がある。そこで最近、皮膚低刺激性で低臭気性、かつ
酸素の影響が少ない脂環式エポキシ化合物やビニルエー
テル化合物を用いた、カチオン重合系が注目されるよう
になった。However, acrylic monomers have problems associated with skin irritation, odor, and inhibition of polymerization by oxygen. Therefore, recently, a cationic polymerization system using an alicyclic epoxy compound or a vinyl ether compound having low skin irritation, low odor, and little influence of oxygen has attracted attention.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、低臭気性、
低皮膚刺激性であり、カチオン重合系において硬化速度
が速く、酸素の影響が少ない化合物、重合性組成物を提
供し得るものである。SUMMARY OF THE INVENTION The present invention has a low odor,
It can provide a compound having low skin irritation, a high curing rate in a cationic polymerization system, and little influence of oxygen, and a polymerizable composition.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため、鋭意検討した結果、種々の分野におい
て極めて有用である化合物を見いだし、本発明を完成し
た。すなわち本発明は、（１）式（Ａ）で表される脂環
式エポキシビニルエーテル、Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found compounds that are extremely useful in various fields, and have completed the present invention. That is, the present invention provides (1) an alicyclic epoxy vinyl ether represented by the formula (A):
【０００６】[0006]
【化４】 Embedded image
【０００７】（式（Ａ）中Ｘ1 はその骨格に置換基とし
て式（１）で表される官能基を有する硬化性基、および
その骨格に置換基として式（２）で表される官能基を有
する硬化性基から選ばれる１つ以上を表すが、２個ある
Ｘ1 のうち１個以上は、式（１）で表される官能基を有
する硬化性基である。）(In the formula (A), X 1 is a curable group having a functional group represented by the formula (1) as a substituent on its skeleton, and a functional group represented by the formula (2) as a substituent on its skeleton. Represents one or more selected from curable groups having a group, and at least one of two X 1 is a curable group having a functional group represented by the formula (1).)
【０００８】[0008]
【化５】 Embedded image
【０００９】[0009]
【化６】 Embedded image
【００１０】（式（２）中Ｒ1 は水素原子または炭素数
１〜５のアルキル基を表す。） （２）上記（１）記載の脂環式エポキシビニルエーテル
を含有する重合性組成物、（３）上記（２）記載の重合
性組成物を硬化して得られる硬化物に関する。(In the formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) (2) A polymerizable composition containing the alicyclic epoxy vinyl ether described in the above (1), 3) It relates to a cured product obtained by curing the polymerizable composition according to (2).
【００１１】[0011]
【発明の実施の形態】前記式（Ａ）中Ｘ1 が式（１）で
表される官能基を有する硬化性基および式（２）で表さ
れる官能基を有する硬化性基の場合は、その骨格に式
（１）および式（２）で表される構造を置換基として有
する官能基であれば、同一構造でも互いに異なる構造で
もよく、特に制限はないが、例えば式（１）で表される
官能基を有する硬化性基は、一般式（３）BEST MODE FOR CARRYING OUT THE INVENTION In the above formula (A), when X 1 is a curable group having a functional group represented by the formula (1) and a curable group having a functional group represented by the formula (2), The same structure or different structures may be used as long as the functional group has a structure represented by the formula (1) and the formula (2) as a substituent in its skeleton, and there is no particular limitation. The curable group having a functional group represented by the general formula (3)
【００１２】[0012]
【化７】 Embedded image
【００１３】（式（３）中ａは０〜３の整数を、ｂは０
〜４の整数を、Ｒ2 およびＲ3 は直接結合、カルボニル
基および炭素数１〜４のアルキレン基より選ばれる１つ
以上を、Ｒ4 は炭素数２〜１２のアルキレン基またはハ
ロゲン化アルキレン基を、Ｒ5は炭素数１〜４のアルキ
ル基またはハロゲン化アルキル基をそれぞれ表す。）で
表される構造が好ましく、式（２）で表される官能基を
有する硬化性基は、一般式（４）(In the formula (3), a is an integer of 0 to 3, and b is 0
R 2 and R 3 are one or more selected from a direct bond, a carbonyl group and an alkylene group having 1 to 4 carbon atoms, and R 4 is an alkylene group having 2 to 12 carbon atoms or a halogenated alkylene group. And R 5 represents an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group. ) Is preferable, and the curable group having a functional group represented by the formula (2) is represented by the general formula (4)
【００１４】[0014]
【化８】 Embedded image
【００１５】（式（４）中ａ、ｂ、Ｒ3 、Ｒ4 、および
Ｒ5 は式（３）におけるのと同じ意味を、Ｒ1 は式
（２）におけるのと同じ意味をそれぞれ表す。）で表さ
れる構造が好ましい。(In the formula (4), a, b, R 3 , R 4 and R 5 have the same meaning as in the formula (3), and R 1 has the same meaning as in the formula (2). Is preferred.
【００１６】また、前記において、ａおよびｂとしては
０が好ましく、Ｒ1 としては水素原子が、Ｒ2 としては
カルボニル基が、Ｒ3 としてはメチレン基が、それぞれ
好ましい基として挙げられる。In the above, a and b are preferably 0, R 1 is a hydrogen atom, R 2 is a carbonyl group, and R 3 is a methylene group.
【００１７】前記式（Ａ）で表される脂環式エポキシビ
ニルエーテルの合成自体は、アルコールとハロゲン化合
物との反応や、エステルとアルコールとのエステル交換
反応等、公知の方法に従って合成でき、例えば一般式
（５）The synthesis itself of the alicyclic epoxy vinyl ether represented by the formula (A) can be carried out according to a known method such as a reaction between an alcohol and a halogen compound or a transesterification reaction between an ester and an alcohol. Equation (5)
【００１８】[0018]
【化９】 Embedded image
【００１９】（式（５）中ａ、ｂ、Ｒ3 、Ｒ4 およびＲ
5 は式（３）におけるのと同じ意味を、Ｒ1 は式（１）
におけるのと同じ意味をそれぞれ表す。）で表される化
合物と、式（６）(In the formula (5), a, b, R 3 , R 4 and R
5 has the same meaning as in formula (3), and R 1 has the same meaning as in formula (1)
Has the same meaning as in. And a compound represented by the formula (6)
【００２０】[0020]
【化１０】 Embedded image
【００２１】（式（６）中Ｒ6 は直接結合および炭素数
１〜４のアルキレン基より選ばれる１つ以上を、Ｙ1 は
ハロゲン原子、トシル基、ベンゼンスルホニル基および
メタンスルホニル基から選ばれる１つ以上をそれぞれ表
す。）で表される化合物、或いは式（７）(In the formula (6), R 6 is at least one selected from a direct bond and an alkylene group having 1 to 4 carbon atoms, and Y 1 is selected from a halogen atom, a tosyl group, a benzenesulfonyl group and a methanesulfonyl group. Or at least one of the following :) or a compound represented by the formula (7)
【００２２】[0022]
【化１１】 Embedded image
【００２３】で表される官能基を有するエステル化合物
とを、塩基性化合物の存在下で反応させることによって
得られる。また一般式（８）It is obtained by reacting an ester compound having a functional group represented by the following formula in the presence of a basic compound. Also, the general formula (8)
【００２４】[0024]
【化１２】 Embedded image
【００２５】（式（８）中ａ、ｂ、Ｒ3 、Ｒ4 およびＲ
5 は式（３）におけるのと同じ意味を、Ｒ1 は式（１）
におけるのと同じ意味を、Ｙ2 はハロゲン原子、トシル
基、ベンゼンスルホニル基、およびメタンスルホニル基
から選ばれる１つ以上をそれぞれ表す。）で表される化
合物と、式（９）(In the formula (8), a, b, R 3 , R 4 and R
5 has the same meaning as in formula (3), and R 1 has the same meaning as in formula (1)
And Y 2 represents one or more selected from a halogen atom, a tosyl group, a benzenesulfonyl group, and a methanesulfonyl group. And a compound represented by formula (9)
【００２６】[0026]
【化１３】 Embedded image
【００２７】（式（９）中Ｒ6 は式（６）におけるのと
同じ意味を表す。）で表される化合物とを、塩基性化合
物の存在下で反応させることによっても得られる。(In the formula (9), R 6 has the same meaning as in the formula (6).) A compound represented by the formula (6) is reacted in the presence of a basic compound.
【００２８】また、前記において、Ｙ1 およびＹ2 とし
ては塩素原子が、Ｒ6 としてはメチレン基がそれぞれ好
ましい基として挙げられる。In the above, preferred examples of Y 1 and Y 2 are chlorine atoms and R 6 is a methylene group.
【００２９】前記の方法において用い得る式（５）の化
合物の具体例としては、シクロヘキサンジメチロールモ
ノビニルエーテル、シクロヘキサンジメチロールモノ１
−プロペニルエーテル、２−ヒドロキシエトキシメチル
−２’−ビニロキシエトキシメチルヘキサン、ｐ−ヒド
ロキシフェノキシメチル−ｐ−ビニロキシフェノキシメ
チルヘキサン等が挙げられる。Specific examples of the compound of the formula (5) which can be used in the above method include cyclohexane dimethylol monovinyl ether and cyclohexane dimethylol mono 1
-Propenyl ether, 2-hydroxyethoxymethyl-2'-vinyloxyethoxymethylhexane, p-hydroxyphenoxymethyl-p-vinyloxyphenoxymethylhexane and the like.
【００３０】用いる式（６）の化合物の具体例として
は、１−クロロ−３，４−エポキシシクロヘキサン、１
−クロロメチル−３，４−エポキシシクロヘキサン、１
−ブロモメチル−３，４−エポキシシクロヘキサン、
３，４−エポキシシクロヘキシルメチルトシレート、１
−（２’−クロロエチル）−３，４−エポキシシクロヘ
キサン等が挙げられる。式（６）の化合物の使用量は、
式（５）の化合物１モルに対して通常１モル以上、好ま
しくは、１．２〜３．０モルである。反応温度は通常２
０〜１２０℃、好ましくは４０〜１００℃で、６０℃以
上では加圧下で反応させることができる。反応時間は通
常３０分〜２４時間、好ましくは１〜１０時間である。Specific examples of the compound of the formula (6) include 1-chloro-3,4-epoxycyclohexane,
-Chloromethyl-3,4-epoxycyclohexane, 1
-Bromomethyl-3,4-epoxycyclohexane,
3,4-epoxycyclohexylmethyl tosylate, 1
-(2'-chloroethyl) -3,4-epoxycyclohexane and the like. The amount of the compound of the formula (6) used is
It is usually at least 1 mol, preferably 1.2 to 3.0 mol, per 1 mol of the compound of the formula (5). The reaction temperature is usually 2
The reaction can be carried out at 0 to 120 ° C, preferably 40 to 100 ° C, and at a pressure of 60 ° C or more under pressure. The reaction time is generally 30 minutes to 24 hours, preferably 1 to 10 hours.
【００３１】式（７）で表される官能基を有するエステ
ル化合物については、単官能でも多官能でもよく、特に
制限はないが、例えばメチル−３，４−エポキシシクロ
ヘキサンカルボキシレート、エチル−３，４−エポキシ
シクロヘキサンカルボキシレート、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、エチレングリコールビス（３，
４−エポキシシクロヘキサンカルボキシレート）、トリ
エチレングリコールビス（３，４−エポキシシクロヘキ
サンカルボキシレート）等が挙げられる。式（７）で表
される官能基を有するエステル化合物は、式（５）の化
合物１モルに対して式（７）で表される官能基が通常１
モル当量以上、好ましくは、１．２〜３．０モル当量と
なる量で使用する。反応温度は通常２０〜１２０℃、好
ましくは４０〜１００℃で、反応時間は通常１〜４８時
間、好ましくは５〜２４時間である。The ester compound having a functional group represented by the formula (7) may be monofunctional or polyfunctional, and is not particularly limited. For example, methyl-3,4-epoxycyclohexanecarboxylate, ethyl-3, 4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, ethylene glycol bis (3
4-epoxycyclohexanecarboxylate) and triethylene glycol bis (3,4-epoxycyclohexanecarboxylate). In the ester compound having a functional group represented by the formula (7), the functional group represented by the formula (7) is usually 1 to 1 mol of the compound represented by the formula (5).
It is used in an amount equivalent to or more than a molar equivalent, preferably 1.2 to 3.0 molar equivalent. The reaction temperature is usually 20 to 120 ° C, preferably 40 to 100 ° C, and the reaction time is usually 1 to 48 hours, preferably 5 to 24 hours.
【００３２】用い得る式（８）の化合物の具体例として
は、（４−クロロメチルシクロヘキシル）メチルビニル
エーテル、（４−ブロモメチルシクロヘキシル）メチル
ビニルエーテル、２−クロロエトキシメチル−２’−ビ
ニロキシエトキシメチルヘキサン、ｐ−クロロフェノキ
シメチル−ｐ−ビニロキシフェノキシメチルヘキサン等
が挙げられる。Specific examples of the compound of the formula (8) that can be used include (4-chloromethylcyclohexyl) methyl vinyl ether, (4-bromomethylcyclohexyl) methyl vinyl ether, 2-chloroethoxymethyl-2'-vinyloxyethoxymethyl Hexane, p-chlorophenoxymethyl-p-vinyloxyphenoxymethylhexane and the like can be mentioned.
【００３３】用い得る式（９）の化合物の具体例として
は、３，４−エポキシシクロヘキサノール、３，４−エ
ポキシシクロヘキシルメタノール、２−（３’，４’−
エポキシシクロヘキシル）エタノール、３−（３’，
４’−エポキシシクロヘキシル）プロパノール等が挙げ
られる。式（９）の化合物の使用量は、式（８）の化合
物１モルに対して通常１モル以上、好ましくは、１．２
〜３．０モルである。反応温度は通常２０〜１２０℃、
好ましくは４０〜１００℃で、反応時間は通常３０分〜
２４時間、好ましくは１〜１０時間である。Specific examples of the compound of the formula (9) that can be used include 3,4-epoxycyclohexanol, 3,4-epoxycyclohexylmethanol, and 2- (3 ′, 4′-
Epoxycyclohexyl) ethanol, 3- (3 ′,
4'-epoxycyclohexyl) propanol and the like. The amount of the compound of the formula (9) to be used is generally 1 mol or more, preferably 1.2 mol, per 1 mol of the compound of the formula (8).
~ 3.0 mol. The reaction temperature is usually 20 to 120 ° C,
Preferably at 40 to 100 ° C, the reaction time is usually 30 minutes to
24 hours, preferably 1 to 10 hours.
【００３４】式（５）の化合物と式（６）の化合物との
反応、および、式（８）の化合物と式（９）の化合物と
の反応は、塩基性化合物の存在下で行い、不活性溶媒、
例えばＮ，Ｎ−ジメチルアセトアミド、ジメチルスルホ
キシド、ジメチルホルムアミド、Ｎ−メチルピロリド
ン、Ｎ，Ｎ−ジメチルイミダゾリドンのような非プロト
ン性極性溶媒、トルエン、ヘキサン、ヘプタン等の無極
性溶媒、テトラヒドロフラン、ジグライム、ジオキサ
ン、トリオキサン等、またはこれらの混合溶媒中で行っ
てもよい。これら溶媒の使用量は、式（５）または式
（８）の化合物０．１モルに対して、通常０〜５００ｍ
ｌ、好ましくは５０〜３００ｍｌである。The reaction of the compound of the formula (5) with the compound of the formula (6) and the reaction of the compound of the formula (8) with the compound of the formula (9) are carried out in the presence of a basic compound. Active solvent,
For example, aprotic polar solvents such as N, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, N, N-dimethylimidazolidone, nonpolar solvents such as toluene, hexane, heptane, tetrahydrofuran, diglyme, It may be carried out in dioxane, trioxane or the like, or a mixed solvent thereof. The amount of these solvents to be used is generally 0 to 500 m per 0.1 mol of the compound of the formula (5) or (8).
1, preferably 50 to 300 ml.
【００３５】用い得る塩基性化合物の具体例としては、
水素化ナトリウム、水素化カリウム、水酸化ナトリウ
ム、水酸化カリウムなどのアルカリ金属化合物、金属ナ
トリウム、金属カリウムなどのアルカリ金属、および、
ナトリウムメトキシド、カリウムｔ−ブトキシドなどの
アルカリ金属アルコキシドなどが挙げられ、その使用量
は、式（５）又は式（９）の化合物１．０モルに対して
通常１．０モル以上、好ましくは１．５〜１０モルであ
る。Specific examples of the basic compound that can be used include:
Sodium hydride, potassium hydride, sodium hydroxide, alkali metal compounds such as potassium hydroxide, metal sodium, alkali metal such as metal potassium, and,
Examples thereof include alkali metal alkoxides such as sodium methoxide and potassium t-butoxide. The amount of the alkoxide to be used is usually 1.0 mol or more, preferably 1.0 mol, per 1.0 mol of the compound of the formula (5) or (9). 1.5 to 10 mol.
【００３６】反応終了後、反応混合液を室温まで冷却し
た後、水と、ジエチルエーテルまたはヘキサンなどで抽
出を行い、次いで有機層に無水硫酸ナトリウム、合成ゼ
オライトなどの乾燥剤を加えて乾燥させる。このとき
に、活性炭などの脱色剤を加えてもよい。この後、濾過
し、減圧蒸留等により式（Ａ）で表される本発明の脂環
式エポキシビニルエーテルを得ることができる。After completion of the reaction, the reaction mixture is cooled to room temperature, extracted with water, diethyl ether or hexane, and the like, and the organic layer is dried by adding a drying agent such as anhydrous sodium sulfate and synthetic zeolite. At this time, a decolorizing agent such as activated carbon may be added. Thereafter, the mixture is filtered, and the alicyclic epoxy vinyl ether of the present invention represented by the formula (A) can be obtained by distillation under reduced pressure or the like.
【００３７】式（５）の化合物と式（７）で表される官
能基を有するエステル化合物との反応は、塩基性化合物
の存在下で行い、副生するアルコールを減圧下で除去し
ながら行うのが好ましい。用い得る塩基性化合物の具体
例としては、水酸化ナトリウム、水酸化カリウムなどの
アルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム
などのアルカリ金属炭酸塩、および、ナトリウムメトキ
シド、カリウムｔ−ブトキシドなどのアルカリ金属アル
コキシドなどが挙げられ、その使用量は、式（５）の化
合物１．０モルに対して通常１．０ミリモル以上、好ま
しくは０．０１〜０．１モルである。The reaction between the compound of the formula (5) and the ester compound having a functional group represented by the formula (7) is carried out in the presence of a basic compound, while removing by-product alcohol under reduced pressure. Is preferred. Specific examples of the basic compound that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and sodium methoxide and potassium t-butoxide. Alkali metal alkoxides and the like are used, and the amount of use is usually 1.0 mmol or more, preferably 0.01 to 0.1 mol, per 1.0 mol of the compound of the formula (5).
【００３８】反応終了後、反応混合液を室温まで冷却し
た後、水洗や、減圧蒸留等により式（Ａ）で表される本
発明の脂環式エポキシビニルエーテルを得ることができ
る。After completion of the reaction, the reaction mixture is cooled to room temperature, and then washed with water or distilled under reduced pressure to obtain the alicyclic epoxy vinyl ether of the present invention represented by the formula (A).
【００３９】次に本発明の重合性組成物につき説明す
る。本発明の脂環式エポキシビニルエーテルと重合開始
剤、及びその他必要に応じて種々の重合性化合物、硬化
促進剤、染料、顔料、可塑剤、無機充填剤、溶剤などを
混合して本発明の重合性組成物を得ることができる。重
合開始剤としては、熱重合開始剤、光重合開始剤などの
ラジカル重合やイオン（カチオン）重合を起こしうるも
のであれば特に制限はない。Next, the polymerizable composition of the present invention will be described. The alicyclic epoxy vinyl ether of the present invention is mixed with a polymerization initiator and, if necessary, various polymerizable compounds, curing accelerators, dyes, pigments, plasticizers, inorganic fillers, solvents, etc. Composition can be obtained. The polymerization initiator is not particularly limited as long as it can cause radical polymerization or ionic (cation) polymerization, such as a thermal polymerization initiator or a photopolymerization initiator.
【００４０】用いうる熱重合開始剤の具体例としては、
過酸化ベンゾイル、過酸化アセチル、過酸化ラウロイ
ル、ｔ−ブチルハイドロパーオキサイド、クメンハイド
ロパーオキサイド、アゾビスイソブチロニトリル、アゾ
ビス−２，４−ジメチルバレロニトリル、アゾビスシク
ロヘキサンカルボニトリル等のラジカル開始剤の他、三
フッ化ホウ素、二塩化亜鉛、三塩化アルミニウムなどの
ルイス酸類等の、カチオン重合開始剤等が挙げられる。Specific examples of the thermal polymerization initiator that can be used include:
Radical initiation of benzoyl peroxide, acetyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, etc. In addition to the agents, cationic polymerization initiators such as Lewis acids such as boron trifluoride, zinc dichloride, and aluminum trichloride are included.
【００４１】用いうる光ラジカル重合開始剤の具体例と
しては、２，４−ジエチルチオキサントン、ベンゾフェ
ノン、４−ジメチルアミノイソアミルベンゾエート、４
−ジメチルアミノエチルベンゾエート等が挙げられる。Specific examples of the photoradical polymerization initiator that can be used include 2,4-diethylthioxanthone, benzophenone, 4-dimethylaminoisoamylbenzoate,
-Dimethylaminoethyl benzoate and the like.
【００４２】用いうる光カチオン重合開始剤の具体例と
しては、特公昭５３−３２８３１号、特公昭５２−１４
２７７号、特公昭５２−１４２７８号、特公昭５２−１
４２７９号、特公昭５２−２５６８６号、特公昭６１−
３４７５２号、特開昭５４−５３１８１号、特開昭５４
−９５６８６号、特公昭６１−３６５３０号、特公昭５
９−１９５８１号、特公昭６３−６５６８８号、特開昭
５５−１６４２０４号、特公昭６０−３０６９０号、特
公昭６３−３６３３２号、特公平１−３９４２３号、特
公平２−１０１７１号、特公平５−１５７２１号、特公
平４−６２３１０号、特公昭６２−５７６５３号、特公
平３−１２０８１号、特公平３−１２０８２号、特公平
３−１６３６１号、特公昭６３−１２０９２号、特公昭
６３−１２０９３号、特公昭６３−１２０９５号、特公
昭６３−１２０９４号、特公平２−３７９２４号、特公
平２−３５７６４号、特公平４−１３３７４号、特公平
４−７５９０８号、特公平４−７３４２８号、特公昭５
３−３２８３１号、特開平２−１５０８４８号、特開平
２−２９６５１４号、米国特許第４，０６９，０５５
号、米国特許第４，０６９，０５６号、米国特許第３，
７０３，２９６号等に記載されているスルホニウム塩、
ジアゾニウム塩、アンモニウム塩、ホスホニウム塩、ヨ
ードニウム塩、アルソニウム塩、鉄・アレーン錯体など
が挙げられる。Specific examples of the cationic photopolymerization initiator that can be used include JP-B-53-32831 and JP-B-52-14.
No. 277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-1
No. 4279, JP-B-52-25686, JP-B-61-
34752, JP-A-54-53181, JP-A-54-53181
-95686, JP-B-61-36530, JP-B-5
9-19581, JP-B-63-65688, JP-A-55-164204, JP-B-60-30690, JP-B-63-36332, JP-B1-39423, JP-B2-10171, JP-B2-10171 No. 5-15721, Japanese Patent Publication No. 4-62310, Japanese Patent Publication No. 62-57653, Japanese Patent Publication No. 3-12081, Japanese Patent Publication No. 3-12082, Japanese Patent Publication No. 3-16361, Japanese Patent Publication No. 63-12092, Japanese Patent Publication No. Sho 63 -12093, JP-B-63-12095, JP-B-63-12094, JP-B-2-37924, JP-B-2-35764, JP-B-4-13374, JP-B-4-75908, JP-B-4- 73428 No. 5
3-32831, JP-A-2-150848, JP-A-2-296514, U.S. Pat. No. 4,069,055
No. 4,069,056, U.S. Pat.
703,296 and the like,
Examples thereof include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, arsonium salts, and iron / arene complexes.
【００４３】これらの重合開始剤は式（Ａ）の化合物に
対して、通常０．０１〜５０重量％、好ましくは０．１
〜２０重量％使用され、本発明の硬化物を得る際に式
（Ａ）の化合物と混合してもよいし、本発明の重合性組
成物中に混合してもよい。These polymerization initiators are usually used in an amount of 0.01 to 50% by weight, preferably 0.1% by weight, based on the compound of the formula (A).
-20% by weight, and may be mixed with the compound of the formula (A) when obtaining the cured product of the present invention, or may be mixed in the polymerizable composition of the present invention.
【００４４】本発明の硬化物は、本発明の脂環式エポキ
シビニルエーテルをそのまま、好ましくは本発明の重合
性組成物として、紫外線、電子線、または放射線の照
射、或いは加熱して得ることができる。The cured product of the present invention can be obtained by irradiating the alicyclic epoxy vinyl ether of the present invention as it is, preferably as the polymerizable composition of the present invention, with an ultraviolet ray, an electron beam, or a radiation, or by heating. .
【００４５】[0045]
【実施例】以下に実施例によって本発明を更に詳細に説
明するが、本発明はこれらの実施例に限定されるもので
はない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００４６】実施例１ 温度計、攪拌装置、および分留管のついた１０００ｍｌ
の反応器に、シクロヘキサンジメチロールモノビニルエ
ーテル８５．２ｇ、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１２６．０ｇと、水酸化カリウム１ｇを仕込み、
撹拌しながら反応器内が６０℃になるまで徐々に加熱し
た。その後、反応器内温度を６０℃に保ち、撹拌しなが
ら１５時間反応させた。Example 1 1000 ml with thermometer, stirrer, and fractionating tube
Was charged with 85.2 g of cyclohexane dimethylol monovinyl ether, 126.0 g of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and 1 g of potassium hydroxide,
The reactor was gradually heated to 60 ° C. while stirring. Thereafter, the temperature in the reactor was maintained at 60 ° C., and the reaction was carried out for 15 hours while stirring.
【００４７】次に、反応器内を８０℃まで加熱し、０．
２〜０．２５ｍｍＨｇに減圧して、副生した３，４−エ
ポキシシクロヘキシルメタノールを分留管より除去しな
がら、さらに１２時間反応させた。その後、３，４−エ
ポキシシクロヘキシルメタノールが発生しなくなったの
を確認し、室温まで冷却した後、水２００ｍｌを加え、
ヘキサン３００ｍｌで３回抽出した。次いで、抽出した
有機層を５００ｍｌに濃縮し、無水硫酸ナトリウム５０
ｇを加え、一晩乾燥させた。その後、濾過し、ヘキサン
を減圧除去した後、蒸留して式（１０）で表される本発
明の脂環式エポキシビニルエーテルを得た（収量１００
ｇ、収率６８％）。ＩＲスペクトルより、１６２０ｃｍ
-1にビニルエーテル基特有の吸収と、１７２０ｃｍ-1に
カルボニルの吸収があり、３４００ｃｍ-1付近に水酸基
の吸収がないことを確認した。Next, the inside of the reactor was heated to 80 ° C.
The pressure was reduced to 2 to 0.25 mmHg, and the reaction was further performed for 12 hours while removing by-product 3,4-epoxycyclohexylmethanol from the fractionating tube. Thereafter, it was confirmed that 3,4-epoxycyclohexylmethanol was no longer generated, and after cooling to room temperature, 200 ml of water was added.
Extracted three times with 300 ml of hexane. Next, the extracted organic layer was concentrated to 500 ml, and dried over anhydrous sodium sulfate 50 ml.
g was added and dried overnight. Thereafter, the mixture was filtered, hexane was removed under reduced pressure, and the residue was distilled to obtain the alicyclic epoxy vinyl ether of the present invention represented by the formula (10) (yield: 100).
g, 68% yield). From the IR spectrum, 1620 cm
Absorption specific vinyl ether group to -1, there is absorption of a carbonyl to 1720 cm -1, it was confirmed that no absorption of hydroxyl groups in the vicinity of 3400 cm -1.
【００４８】[0048]
【化１４】 Embedded image
【００４９】[0049]
【発明の効果】本発明のプロペニルエーテルは、低皮膚
刺激性の重合性組成物として、コーティング剤、イン
キ、塗料、接着剤、レジスト、製版材、絶縁材、光学材
料などの種々の分野で極めて有用である。特に光カチオ
ン重合開始剤を含有する本発明の重合性組成物は硬化速
度が速く、酸素による重合阻害がほとんど無いという特
徴を示す。また、低粘度であるため、希釈性、加工性に
も優れる。The propenyl ether of the present invention is extremely polymerizable in various fields such as coating agents, inks, paints, adhesives, resists, plate making materials, insulating materials and optical materials as a polymerizable composition having low skin irritation. Useful. In particular, the polymerizable composition of the present invention containing a cationic photopolymerization initiator is characterized by a high curing rate and little inhibition of polymerization by oxygen. Further, since it has a low viscosity, it has excellent dilutability and workability.
Claims (3)
エーテル。 【化１】 （式（Ａ）中Ｘ1 はその骨格に置換基として式（１）で
表される官能基を有する硬化性基、およびその骨格に置
換基として式（２）で表される官能基を有する硬化性基
から選ばれる１つ以上を表すが、２個あるＸ1 のうち１
個以上は、式（１）で表される官能基を有する硬化性基
である。） 【化２】 【化３】 （式（２）中Ｒ1 は水素原子または炭素数１〜５のアル
キル基を表す。）1. An alicyclic epoxy vinyl ether represented by the formula (A). Embedded image (X 1 in the formula (A) has a curable group having a functional group represented by the formula (1) as a substituent on its skeleton, and a functional group represented by the formula (2) as a substituent on its skeleton. represents one or more selected from curable group, one of the two is X 1
The number is a curable group having a functional group represented by the formula (1). ) Embedded image (In the formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
テルを含有する重合性組成物。2. A polymerizable composition containing the alicyclic epoxy vinyl ether according to claim 1.
られる硬化物。3. A cured product obtained by curing the polymerizable composition according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36329997A JP3778470B2 (en) | 1997-12-16 | 1997-12-16 | Novel alicyclic epoxy vinyl ether, polymerizable composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36329997A JP3778470B2 (en) | 1997-12-16 | 1997-12-16 | Novel alicyclic epoxy vinyl ether, polymerizable composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11171967A true JPH11171967A (en) | 1999-06-29 |
| JP3778470B2 JP3778470B2 (en) | 2006-05-24 |
Family
ID=18478990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36329997A Expired - Fee Related JP3778470B2 (en) | 1997-12-16 | 1997-12-16 | Novel alicyclic epoxy vinyl ether, polymerizable composition and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3778470B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1972622A2 (en) | 2007-03-23 | 2008-09-24 | Daicel Chemical Industries, Ltd. | Vinyl ether compounds and polymerizable compositions |
| JP2008308420A (en) * | 2007-06-13 | 2008-12-25 | Showa Denko Kk | Carboxylic acid ester compound having alicyclic epoxy group and vinyl ether group, and method for producing the ester compound |
| JP2009138116A (en) * | 2007-12-07 | 2009-06-25 | Daicel Chem Ind Ltd | Cation-polymerizable resin composition and cured material thereof |
| JP2009242242A (en) * | 2007-03-26 | 2009-10-22 | Daicel Chem Ind Ltd | Alicyclic epoxy group-containing vinyl ether compound and polymerizable composition |
| US8975349B2 (en) | 2009-06-05 | 2015-03-10 | Daicel Corporation | Cationically polymerizable resin composition and cured object obtained therefrom |
-
1997
- 1997-12-16 JP JP36329997A patent/JP3778470B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1972622A2 (en) | 2007-03-23 | 2008-09-24 | Daicel Chemical Industries, Ltd. | Vinyl ether compounds and polymerizable compositions |
| EP1972622A3 (en) * | 2007-03-23 | 2009-07-01 | Daicel Chemical Industries, Ltd. | Vinyl ether compounds and polymerizable compositions |
| EP2233475A1 (en) | 2007-03-23 | 2010-09-29 | Daicel Chemical Industries, Ltd. | Epoxycyclohexane vinyl ether compounds and their use in polymerizable compositions |
| US7985866B2 (en) | 2007-03-23 | 2011-07-26 | Daicel Chemical Industries, Ltd. | Vinyl ether compounds and polymerizable compositions |
| JP2009242242A (en) * | 2007-03-26 | 2009-10-22 | Daicel Chem Ind Ltd | Alicyclic epoxy group-containing vinyl ether compound and polymerizable composition |
| JP2008308420A (en) * | 2007-06-13 | 2008-12-25 | Showa Denko Kk | Carboxylic acid ester compound having alicyclic epoxy group and vinyl ether group, and method for producing the ester compound |
| JP2009138116A (en) * | 2007-12-07 | 2009-06-25 | Daicel Chem Ind Ltd | Cation-polymerizable resin composition and cured material thereof |
| US8975349B2 (en) | 2009-06-05 | 2015-03-10 | Daicel Corporation | Cationically polymerizable resin composition and cured object obtained therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3778470B2 (en) | 2006-05-24 |
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