JPH08283199A - Fullerene derivative, resin composition and its cured material - Google Patents
Fullerene derivative, resin composition and its cured materialInfo
- Publication number
- JPH08283199A JPH08283199A JP11106595A JP11106595A JPH08283199A JP H08283199 A JPH08283199 A JP H08283199A JP 11106595 A JP11106595 A JP 11106595A JP 11106595 A JP11106595 A JP 11106595A JP H08283199 A JPH08283199 A JP H08283199A
- Authority
- JP
- Japan
- Prior art keywords
- fullerene
- fullerene derivative
- formula
- compound
- resin composition
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光機能材料に有用なフ
ラーレン誘導体、該誘導体を必須重合成分とする高分子
化合物、それらを含む樹脂組成物、及びそれを硬化して
なる硬化物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fullerene derivative useful for an optical functional material, a polymer compound containing the derivative as an essential polymerization component, a resin composition containing the same, and a cured product obtained by curing the same.
【０００２】[0002]
【従来の技術】フラーレンは、新たな非線形材料、光ス
イッチ等の光機能材料として注目されている。しかしな
がらフラーレンは、微粉末でありそのままの状態で光機
能材料に用いる事は困難であった。そこで例えば、ＣＶ
Ｄ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉ
ｏｎ）法によるフィルム化が試みられている。BACKGROUND OF THE INVENTION Fullerenes are attracting attention as new nonlinear materials and optical functional materials such as optical switches. However, fullerenes are fine powders, and it was difficult to use fullerenes as they are in optical functional materials. So, for example, CV
D (Chemical Vapor Depositi
on) method has been attempted.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、ＣＶＤ
法によるフィルムの調製は煩雑な操作手順を要し、歩留
まりが悪いという欠点を有している。また、ＣＶＤ法に
より調製したフィルムは脆く、実用面で困難がある。[Problems to be Solved by the Invention] However, CVD
Preparation of a film by the method requires complicated operation procedures and has a drawback that the yield is low. In addition, the film prepared by the CVD method is brittle and practically difficult.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
解決を目的に鋭意検討した結果、フラーレンに（メタ）
アクリロイル基を導入することにより、容易に充分な膜
強度を有するフィルム（光機能材料）が出来る事を見出
し本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies aimed at solving the above problems, the present inventors have found that (fullerene) is (meta)
It was found that a film (optical functional material) having a sufficient film strength can be easily prepared by introducing an acryloyl group, and the present invention has been completed.
【０００５】すなわち本発明は、（１）式（１）That is, the present invention is based on the equation (1)
【０００６】[0006]
【化３】 Embedded image
【０００７】（式中Ｒ1 は、直接結合か炭素数１〜６の
アルキレン結合を表し、Ｒ2 は、水素原子、あるいはメ
チル基を表し、Ｘは−Ｓ−，−ＮＨ−，−ＮＲ−，−Ｏ
−のいずれかを表し、Ｙは−Ｏ−、−ＮＲ−、−ＮＨ−
のいずれかを表す。ｎは１〜３０の整数を表し、(Wherein R 1 represents a direct bond or an alkylene bond having 1 to 6 carbon atoms, R 2 represents a hydrogen atom or a methyl group, and X represents —S—, —NH—, —NR—. , -O
Represents any one of-, Y is -O-, -NR-, -NH-.
Represents either n represents an integer of 1 to 30,
【０００８】[0008]
【化４】 [Chemical 4]
【０００９】は、フラーレン分子に存在する二重結合の
うち、１〜ｎ個の結合が単結合になった基を表す。）で
表されるフラーレン誘導体、（２）上記（１）記載のフ
ラーレン誘導体を必須重合成分とする高分子化合物、
（３）上記（１）記載のフラーレン誘導体、及び／また
は上記（２）記載の高分子化合物を含む樹脂組成物、
（４）上記（３）記載の樹脂組成物を硬化してなる硬化
物に関する。Represents a group in which 1 to n of the double bonds present in the fullerene molecule are single bonds. ), A fullerene derivative represented by (2), (2) a polymer compound containing the fullerene derivative according to (1) above as an essential polymerization component,
(3) A resin composition containing the fullerene derivative described in (1) above and / or the polymer compound described in (2) above.
(4) A cured product obtained by curing the resin composition according to (3).
【００１０】本発明のフラーレン誘導体の合成法を以下
に詳細に示す。The synthetic method of the fullerene derivative of the present invention will be described in detail below.
【００１１】本発明において使用するフラーレンとは、
一般式Ｃｘで表される化合物である。ｘは特に限定され
ないが６０、７０、７６、７８、８２、８４、９０、９
６等が例示される。The fullerenes used in the present invention are
It is a compound represented by the general formula Cx. x is not particularly limited, but is 60, 70, 76, 78, 82, 84, 90, 9
6 etc. are illustrated.
【００１２】本発明の、フラーレン誘導体は、同一分子
内に（メタ）アクリロイル基を有する官能基及びこれと
は別に活性水素を有する官能基を有する化合物をフラー
レンに求核付加反応させることにより得られる。The fullerene derivative of the present invention is obtained by nucleophilic addition reaction of fullerene with a compound having a functional group having a (meth) acryloyl group in the same molecule and a compound having a functional group having an active hydrogen in addition to the functional group. .
【００１３】活性水素を持つ官能基の具体例として水酸
基、メルカプト基、１級アミノ基、２級アミノ基等が挙
げられる。（メタ）アクリロイル基を有する官能基と活
性水素を有する官能基を有する化合物の用いうる具体例
としては、ヒドロキシメチル（メタ）アクリレート、ヒ
ドロキシエチル（メタ）アクリレート、ヒドロキシプロ
ピル（メタ）アクリレート、ヒドロキシエチルアクリル
アミド、アクリルアミド、アミノメチル（メタ）アクリ
レート、アミノエチル（メタ）アクリレート、アミノプ
ロピル（メタ）アクリレート、Ｎ−メチルアミノエチル
（メタ）アクリレート、、Ｎ−エチルアミノメチル（メ
タ）アクリレート、Ｎ−メチルアミノエチル（メタ）ア
クリレート、Ｎ−エチルアミノエチル（メタ）アクリレ
ート、Ｎ−メチルアミノプロピル（メタ）アクリレー
ト、Ｎ−エチルアミノプロピル（メタ）アクリレート等
が挙げられる。また、これらを２種以上併用する事も可
能である。以下これらの（メタ）アクリロイル基を有す
る官能基と活性水素を有する官能基を有する化合物を化
合物（Ａ）という。Specific examples of the functional group having active hydrogen include a hydroxyl group, a mercapto group, a primary amino group and a secondary amino group. Specific examples of the compound having a functional group having a (meth) acryloyl group and a functional group having an active hydrogen include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyethyl. Acrylamide, acrylamide, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N-ethylaminomethyl (meth) acrylate, N-methylamino Examples thereof include ethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, and N-ethylaminopropyl (meth) acrylate. It is also possible to use two or more of these in combination. Hereinafter, the compound having a functional group having these (meth) acryloyl groups and a functional group having active hydrogen is referred to as a compound (A).
【００１４】これら化合物（Ａ）のフラーレンへの導入
は、フラーレンへの求核付加反応により行う。具体的に
は、活性水素を有する基が１級、あるいは２級アミノ基
である場合には例えば次のようにして行う。フラーレン
をトルエン、あるいはベンゼンに溶解させ溶液とする。
この時の溶液のフラーレンの濃度は、０．１〜３ｗｔ％
であり、好ましくは０．５〜２ｗｔ％である。この溶液
に、化合物（Ａ）をそのまま、あるいはテトラヒドロフ
ラン（ＴＨＦ）、メチルイソブチルケトン（ＭＩＢ
Ｋ）、あるいはエーテル等の活性水素を持たない極性溶
媒に溶解させたものを加え、１０〜１１０℃で１時間〜
４８時間撹拌する事により本発明のフラーレン誘導体が
得られる。この時の化合物（Ａ）の使用量はフラーレン
１モルに対し活性水素当量で１〜８０当量であり、好ま
しくは３〜６０当量である。The introduction of these compounds (A) into fullerenes is carried out by a nucleophilic addition reaction to the fullerenes. Specifically, when the group having active hydrogen is a primary or secondary amino group, it is carried out as follows, for example. Dissolve fullerene in toluene or benzene to prepare a solution.
The concentration of fullerene in the solution at this time is 0.1 to 3 wt%
And preferably 0.5 to 2 wt%. In this solution, the compound (A) as it is, or tetrahydrofuran (THF), methyl isobutyl ketone (MIB
K) or one dissolved in a polar solvent having no active hydrogen such as ether, and added at 10 to 110 ° C. for 1 hour to
The fullerene derivative of the present invention can be obtained by stirring for 48 hours. At this time, the amount of the compound (A) used is 1 to 80 equivalents, preferably 3 to 60 equivalents in terms of active hydrogen equivalent to 1 mol of fullerene.
【００１５】また、活性水素を有する官能基が水酸基、
あるいはメルカプト基である場合には、例えば次のよう
にして行う。あらかじめ脱水したＴＨＦ、ＭＩＢＫ、あ
るいはエーテル等の溶媒に金属ナトリウム、あるいは水
素化ナトリウムを加える。そこへ化合物（Ａ）を室温、
あるいは氷冷しながら滴下を行い０〜５０℃で３０分〜
５時間撹拌を行い化合物（Ａ）のナトリウム塩溶液を得
る。このナトリウム塩溶液ををあらかじめ脱水したトル
エン、あるいはベンゼンにフラーレンを溶解した溶液に
室温、あるいは氷冷しながら滴下し、滴下終了後１０〜
６０℃で１〜２４時間撹拌する事により本発明のフラー
レン誘導体が得られる。この時のフラーレン溶液の濃度
は、０．１〜３ｗｔ％であり、好ましくは０．５〜２ｗ
ｔ％である。また、化合物（Ａ）の使用量は、フラーレ
ン１モルに対し活性水素当量で１〜６０当量であり、好
ましくは１〜３０当量である。Further, the functional group having active hydrogen is a hydroxyl group,
Alternatively, when it is a mercapto group, it is carried out as follows, for example. Metallic sodium or sodium hydride is added to a previously dehydrated solvent such as THF, MIBK, or ether. Compound (A) at room temperature,
Or add dropwise while cooling with ice, and at 0-50 ° C for 30 minutes-
Stir for 5 hours to obtain a sodium salt solution of compound (A). This sodium salt solution is added dropwise to previously dehydrated toluene or a solution of fullerene in benzene at room temperature or while cooling with ice.
The fullerene derivative of the present invention can be obtained by stirring at 60 ° C for 1 to 24 hours. The concentration of the fullerene solution at this time is 0.1 to 3 wt%, preferably 0.5 to 2 w
t%. The amount of the compound (A) used is 1 to 60 equivalents, preferably 1 to 30 equivalents, in terms of active hydrogen equivalent to 1 mol of fullerene.
【００１６】本発明のフラーレン誘導体を、光重合開始
剤と混合して紫外線、可視光線を照射したり、あるいは
ラジカル重合開始剤と混合して必要により加熱すること
により、容易に本発明の高分子化合物を得る事が出来
る。The fullerene derivative of the present invention can be easily mixed with a photopolymerization initiator to irradiate it with ultraviolet rays or visible light, or can be mixed with a radical polymerization initiator and heated as necessary to easily obtain the polymer of the present invention. You can get the compound.
【００１７】上記に於いて用いうる光重合開始剤の具体
例としては、１−ヒドロキシシクロヘキシルフェニルケ
トン、ジベンゾイル、ベンゾイルメチルエーテル、ｐ−
クロロベンゾフェノン、ｐ−メトキシベンゾフェノン、
ベンゾイルパーオキサイド、ジ−ｔ−ブチルパーオキサ
イド等が挙げられる。これら光重合開始剤は、単独ある
いは、２種以上組み合わせて用いる事が出来る。これら
光重合開始剤の使用量は、前記フラーレン誘導体１００
重量部に対して通常０．０５〜１０重量部、好ましくは
０．１〜６重量部である。Specific examples of the photopolymerization initiator usable in the above include 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoyl methyl ether, p-
Chlorobenzophenone, p-methoxybenzophenone,
Examples thereof include benzoyl peroxide and di-t-butyl peroxide. These photopolymerization initiators can be used alone or in combination of two or more kinds. The amount of these photopolymerization initiators to be used is the fullerene derivative 100
The amount is usually 0.05 to 10 parts by weight, preferably 0.1 to 6 parts by weight with respect to parts by weight.
【００１８】また、上記に於いてラジカル重合開始剤と
しては、過酸化物系化合物、アミン系化合物が挙げられ
る。用いうる過酸化物系化合物の具体例としては、ベン
ゾイルパーオキサイド、ｐ−クロロベンゾイルパーオキ
サイド、２，４−ジクロロベンゾイルパーオキサイド、
ｔ−ブチルヒドロパーオキサイド、ジ−ｔ−ブチルパー
オキサイド、ジクミルパーオキサイド、ｔ−ブチルパー
オキシアセテート、ｔ−ブチルパーオキシベンゾエート
等が挙げられる。In the above, examples of the radical polymerization initiator include peroxide compounds and amine compounds. Specific examples of the peroxide compound that can be used include benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide,
Examples thereof include t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate.
【００１９】用いうるアミン系の化合物の具体例として
は、Ｎ，Ｎ−ジエタノール−ｐ−トルイジン、ジメチル
−ｐ−トルイジン、ｐ−トルイジン、メチルアミン、ｔ
−ブチルアミン、メチルエチルアミン、ジフェニルアミ
ン、４，４′−ジニトロジフェニルアミン、ｏ−ニトロ
アミン、ｐ−ブロモアニリン、２，４，６−トリブロモ
アニリン等が挙げられる。これら過酸化物系、及びアミ
ン系化合物の使用量は、前記フラーレン誘導体１００重
量部に対して、通常０．０１〜５重量部、好ましくは
０．０５〜３重量部である。Specific examples of amine compounds that can be used include N, N-diethanol-p-toluidine, dimethyl-p-toluidine, p-toluidine, methylamine and t.
-Butylamine, methylethylamine, diphenylamine, 4,4'-dinitrodiphenylamine, o-nitroamine, p-bromoaniline, 2,4,6-tribromoaniline and the like. The amount of these peroxide-based and amine-based compounds used is usually 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the fullerene derivative.
【００２０】本発明の樹脂組成物は、本発明のフラーレ
ン誘導体、及び／または本発明の高分子化合物を含有す
る。本発明の高分子化合物を例えばアセトン、ＴＨＦ、
エーテル等の揮発性溶剤に溶解、及び／または分散した
本発明の樹脂組成物は、そのまま硝子等の基板にキャス
トした後、乾燥して任意の厚さの光機能フィルムを得る
事が出来る。この場合、溶剤の使用量は通常フラーレン
誘導体と高分子化合物の合計重量１００重量部に対し１
〜２００重量部である。The resin composition of the present invention contains the fullerene derivative of the present invention and / or the polymer compound of the present invention. The polymer compound of the present invention is, for example, acetone, THF,
The resin composition of the present invention dissolved and / or dispersed in a volatile solvent such as ether can be cast as it is on a substrate such as glass and then dried to obtain an optical functional film having an arbitrary thickness. In this case, the amount of the solvent used is usually 1 per 100 parts by weight of the total weight of the fullerene derivative and the polymer compound.
~ 200 parts by weight.
【００２１】また、本発明のフラーレン誘導体と前記光
重合開始剤、または前記ラジカル開始剤を前記と同量混
合して本発明の樹脂組成物とする事もできる。この場
合、本発明の樹脂組成物をガラス、石英等の基板にキャ
ストした後、光照射、あるいは加熱する事により容易に
光機能フィルムとする事が出来る。The fullerene derivative of the present invention and the photopolymerization initiator or the radical initiator may be mixed in the same amount as described above to obtain the resin composition of the present invention. In this case, the resin composition of the present invention can be cast into a substrate such as glass or quartz and then irradiated with light or heated to easily form an optical functional film.
【００２２】本発明の樹脂組成物は、必要により重合開
始剤（光重合開始剤またはラジカル重合開始剤）ととも
に反応性二重結合を有する化合物を含有していても良
い。反応性二重結合としては、加熱操作、紫外線や電子
線等の照射により硬化反応する基であれば特に制限な
く、（メタ）アクリロイル基、ビニル基、アリル基等が
例示され、これらの反応基を有する化合物として（メ
タ）アクリル酸、（メタ）アクリル酸メチル、（メタ）
アクリルアミド、スチレン、アリルアミン、アリルアル
コール等が用いうる具体例として挙げられる。これら化
合物の使用量は、本発明のフラーレン誘導体中に存在す
る反応性二重結合１モルに対し反応性二重結合基当量で
０．１〜３００当量であり、好ましくは５〜１００当量
である。The resin composition of the present invention may optionally contain a compound having a reactive double bond together with a polymerization initiator (photopolymerization initiator or radical polymerization initiator). The reactive double bond is not particularly limited as long as it is a group that undergoes a curing reaction by heating operation, irradiation with ultraviolet rays or electron beams, and examples thereof include (meth) acryloyl group, vinyl group and allyl group. (Meth) acrylic acid, methyl (meth) acrylate, (meth)
Specific examples that can be used include acrylamide, styrene, allylamine, and allyl alcohol. The amount of these compounds used is 0.1 to 300 equivalents, preferably 5 to 100 equivalents, in terms of the reactive double bond group equivalent relative to 1 mol of the reactive double bond present in the fullerene derivative of the present invention. .
【００２３】上記において光重合開始剤の使用量は、フ
ラーレン誘導体とこれとは別の上記反応性二重結合を有
する化合物の合計重量１００重量部に対して通常０．０
５〜１０重量部である。また、ラジカル重合開始剤の使
用量は、フラーレン誘導体と反応性二重結合を有する化
合物の合計重量１００重量部に対して通常０．０１〜５
重量部である。In the above, the amount of the photopolymerization initiator used is usually 0.0 based on 100 parts by weight of the total weight of the fullerene derivative and another compound having the above reactive double bond.
It is 5 to 10 parts by weight. The amount of the radical polymerization initiator used is usually 0.01 to 5 with respect to 100 parts by weight of the total weight of the fullerene derivative and the compound having a reactive double bond.
Parts by weight.
【００２４】さらに、本発明の樹脂組成物は、必要に応
じて帯電防止剤、紫外線吸収剤、重合禁止剤、染色剤、
増感剤、レベリング剤などの各種添加物を含有していて
も良い。これらの添加物の含有量は、本発明のフラーレ
ン誘導体と本発明の高分子化合物の合計重量１００重量
部に対して、通常０．０１〜１０重量部、好ましくは
０．０５〜５重量部である。本発明の樹脂組成物は上記
した各成分を所定の割合で均一に混合することにより得
られる。Further, the resin composition of the present invention contains an antistatic agent, an ultraviolet absorber, a polymerization inhibitor, a dyeing agent, if necessary.
It may contain various additives such as a sensitizer and a leveling agent. The content of these additives is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the fullerene derivative of the present invention and the polymer compound of the present invention. is there. The resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components in a predetermined ratio.
【００２５】以下に実施例を挙げて更に本発明を具体的
に説明する。The present invention will be described in more detail with reference to the following examples.
【００２６】実施例１ 撹拌装置、滴下ロート、及び冷却管を取り付けた２００
ｍｌの三口フラスコに炭素数６０のフラーレン１００ｍ
ｇ、トルエン１００ｍｌを入れ室温で撹拌しトルエン溶
液とした。そこに、アミノプロピルメタアクリレートの
１０重量％ＴＨＦ溶液１２ｍｌを滴下ロートから徐々に
滴下した。滴下終了後、２５℃で２４時間撹拌し、反応
させた。反応液を分液ロートに移し、トルエンを１００
ｍｌ加え、油層を水で数回洗浄を行った。得られたトル
エン溶液を無水硫酸マグネシウムで脱水を行った後、溶
媒を減圧蒸留で除去した。得られた固形物を再びトルエ
ンに溶解させ、分取クロマトグラフィーにより未反応物
と分離精製を行った後、溶媒を減圧蒸留で除去し茶色の
粉体（本発明のフラーレン誘導体、以下化合物（Ａ−
１）という）１４２ｍｇを得た。Example 1 200 equipped with a stirrer, dropping funnel, and cooling tube
100m fullerene with 60 carbons in a three-necked flask.
g and 100 ml of toluene were added and stirred at room temperature to obtain a toluene solution. Then, 12 ml of a 10 wt% THF solution of aminopropyl methacrylate was gradually added dropwise from a dropping funnel. After the dropping was completed, the mixture was reacted by stirring at 25 ° C. for 24 hours. Transfer the reaction mixture to a separatory funnel and add 100 toluene.
ml was added, and the oil layer was washed with water several times. The obtained toluene solution was dehydrated with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained solid matter was dissolved again in toluene, and after separation and purification from the unreacted matter by preparative chromatography, the solvent was removed by distillation under reduced pressure to remove the brown powder (fullerene derivative of the present invention, hereinafter referred to as compound (A −
1)) 142 mg was obtained.
【００２７】得られた粉体の赤外線吸収スペクトル分析
を行った結果、５７６ｃｍ-1と５２７ｃｍ-1にフラーレ
ンＣ６０に由来する吸収、１１００ｃｍ-1にＣ−Ｎに由
来する吸収、１６４０ｃｍ-1にＣ＝Ｃに由来する吸収、
１６８０ｃｍ-1にＣ＝Ｏに由来する吸収、３０６０ｃｍ
-1にＣ−Ｈに由来する吸収、３２００ｃｍ-1にＮ−Ｈに
由来する吸収がみられた。The obtained powder infrared absorption spectrum analysis of the result of the absorption derived from fullerene C60 to 576cm -1 and 527cm -1, absorption derived from 1100 cm -1 to C-N, C to 1640 cm -1 = Absorption derived from C,
Absorption derived from C = O at 1680 cm -1 , 3060 cm
The absorption derived from C—H was observed at −1, and the absorption derived from N—H was observed at 3200 cm −1 .
【００２８】また、1 Ｈ−ＮＭＲ（４００ＭＨｚ，ジメ
チルスルホキシド（ＤＭＳＯ））による分析の結果、δ
＝２．２５（ｓ，３Ｈ，ＣＨ3 ），３．４３（ｔ，２
Ｈ，ＮＨＣＨ2 ），４．２２（ｔ，２Ｈ，ＯＣＨ2 ），
５．６９（ｓ，１Ｈ，ＣＨ2 ＝），６．１３（ｓ，１
Ｈ，ＣＨ2 ＝），６．２９（ｓ，１Ｈ，Ｃ６０ Ｃ−
Ｈ）であった。Further, as a result of analysis by 1 H-NMR (400 MHz, dimethyl sulfoxide (DMSO)), δ
= 2.25 (s, 3H, CH 3 ), 3.43 (t, 2)
H, NHCH 2 ), 4.22 (t, 2H, OCH 2 ),
5.69 (s, 1H, CH 2 =), 6.13 (s, 1
H, CH 2 =), 6.29 (s, 1H, C60 C-
H).
【００２９】また、13Ｃ−ＮＭＲ（１００ＭＨｚ，ＤＭ
ＳＯ）による分析の結果、δ＝２８．８７（ＣＨ3 ），
４８．２５（ＮＨＣＨ2 ），６９．６７（ＯＣＨ2 ），
６５．４２〜６８．６６（Ｃ６０ Ｃ−Ｈ），６８．８
７〜６９．３５（Ｃ６０ Ｃ−ＮＨ），１２５．２４
（ＣＨ2 ＝），１３９．４５（Ｃ＝），１４０．３３〜
１４４．８９９（Ｃ６０ Ｃ），１６４．５５（Ｃ＝
Ｏ）であった。その結果、化合物（Ａ−１）は、以下の
式（２）で表される構造であった。Further, 13 C-NMR (100 MHz, DM
SO) analysis showed δ = 28.87 (CH 3 ),
48.25 (NHCH 2 ), 69.67 (OCH 2 ),
65.42 to 68.66 (C60 C-H), 68.8
7-69.35 (C60 C-NH), 125.24
(CH 2 =), 139.45 (C =), 140.33-
144.899 (C60 C), 164.55 (C =
O). As a result, the compound (A-1) had a structure represented by the following formula (2).
【００３０】[0030]
【化５】 Embedded image
【００３１】（式中ｎは１以上の整数を表し、(In the formula, n represents an integer of 1 or more,
【００３２】[0032]
【化６】 [Chemical 6]
【００３３】は、フラーレンＣ６０の分子中に存在する
二重結合のうちｎ個の結合が単結合になった基を表
す。）Represents a group in which n of double bonds existing in the molecule of fullerene C60 are single bonds. )
【００３４】実施例２ 撹拌装置、滴下ロート、窒素導入管、及び冷却管を取り
付けた２００ｍｌの四口フラスコを窒素置換した後、炭
素数６０のフラーレン１００ｍｇ、脱水トルエン１００
ｍｌを投入し、室温で撹拌し溶解させた。そこに、あら
かじめＮａＨでナトリウムメトキシドとしたヒドロキシ
エチルメタクリレートの１０重量％ＴＨＦ溶液１０ｍｌ
を滴下ロートから徐々に滴下した。滴下終了後、２５℃
で１２時間撹拌し、反応させた。反応液を分液ロートに
移し、トルエンを１００ｍｌ加え、油層を水で数回洗浄
を行った。得られたトルエン溶液を無水硫酸マグネシウ
ムで脱水を行った後、溶媒を減圧蒸留で除去した。得ら
れた固形物を再びトルエンに溶解させ、分取クロマトグ
ラフィーにより未反応物と精製分離を行った後、溶媒を
減圧蒸留し黒色の粉体（本発明のフラーレン誘導体、以
下化合物（Ａ−２）という）１９６ｍｇを得た。Example 2 A 200 ml four-necked flask equipped with a stirrer, a dropping funnel, a nitrogen introducing tube, and a cooling tube was replaced with nitrogen, and then 100 mg of fullerene having 60 carbon atoms and 100 parts of dehydrated toluene.
ml was added, and the mixture was stirred at room temperature and dissolved. 10 ml of a 10 wt% THF solution of hydroxyethyl methacrylate, which was previously made into sodium methoxide with NaH, was added thereto.
Was gradually dropped from the dropping funnel. 25 ℃ after dropping
The mixture was stirred for 12 hours and reacted. The reaction solution was transferred to a separating funnel, 100 ml of toluene was added, and the oil layer was washed with water several times. The obtained toluene solution was dehydrated with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained solid matter is dissolved again in toluene, and purified and separated from the unreacted matter by preparative chromatography, and then the solvent is distilled under reduced pressure to obtain a black powder (fullerene derivative of the present invention, hereinafter referred to as compound (A-2 )) Was obtained.
【００３５】得られた粉体の赤外線吸収スペクトル分析
を行った結果、５７６ｃｍ-1と５２７ｃｍ-1にフラーレ
ンＣ６０に由来する吸収、１０９６ｃｍ-1、１３００ｃ
ｍ-1にＣ−Ｏ−Ｃに由来する吸収、１６５０ｃｍ-1にＣ
＝Ｃに由来する吸収、１６８０ｃｍ-1にＣ＝Ｏに由来す
る吸収、２９５０ｃｍ-1にＣ−Ｈに由来する吸収がみら
れた。The obtained powder infrared absorption spectrum analysis of the result of the absorption derived from fullerene C60 to 576cm -1 and 527cm -1, 1096cm -1, 1300c
m −1 absorption derived from C—O—C, C at 1650 cm −1
= Absorption derived and C, absorption derived from 1680 cm -1 to C = O, absorption derived from the C-H to 2950 cm -1 was observed.
【００３６】また、1 Ｈ−ＮＭＲ（４００ＭＨｚ，ＤＭ
ＳＯ）による分析の結果、δ＝２．３５（ｓ，３Ｈ，Ｃ
Ｈ3 ），３．６８（ｔ，２Ｈ，ＣＨ2 ），４．３２
（ｔ，２Ｈ，ＣＨ2 ），５．６３（ｓ，１Ｈ，ＣＨ
2 ＝），６．０３（ｓ，１Ｈ，ＣＨ2＝），６．７８
（ｓ，１Ｈ，Ｃ６０ Ｃ−Ｈ）であった。Further, 1 H-NMR (400 MHz, DM
As a result of analysis by SO, δ = 2.35 (s, 3H, C
H 3), 3.68 (t, 2H, CH 2), 4.32
(T, 2H, CH 2 ), 5.63 (s, 1H, CH
2 =), 6.03 (s, 1H, CH 2 =), 6.78
(S, 1H, C60 C-H).
【００３７】また、13Ｃ−ＮＭＲ（１００ＭＨｚ，ＤＭ
ＳＯ）による分析の結果、δ＝２８．９６（ＣＨ3 ），
５９．１２〜６２．２５（Ｃ６０ Ｃ−Ｈ），６３．４
８（ＯＣＨ2 ），６８．６７（ＯＣＨ2 ），７８．８７
〜７９．３２（Ｃ６０ Ｃ−Ｏ），１２５．３４（ＣＨ
2 ＝），１３８．４１（Ｃ＝），１４１．２１〜１４
５．４５（Ｃ６０ Ｃ），１６７．１２（Ｃ＝Ｏ）であ
った。その結果、化合物（Ａ−２）は、以下の式（３）
で表される構造であった。Further, 13 C-NMR (100 MHz, DM
SO) analysis showed that δ = 28.96 (CH 3 ),
59.12-62.25 (C60 C-H), 63.4.
8 (OCH 2 ), 68.67 (OCH 2 ), 78.87
~ 79.32 (C60 C-O), 125.34 (CH
2 =), 138.41 (C =), 141.21-14
The values were 5.45 (C60 C) and 167.12 (C = O). As a result, the compound (A-2) has the following formula (3):
It was a structure represented by.
【００３８】[0038]
【化７】 [Chemical 7]
【００３９】（式中ｎ及び(Where n and
【００４０】[0040]
【化８】 Embedded image
【００４１】は式（２）におけるのと同じ意味を表
す。）Represents the same meaning as in formula (2). )
【００４２】実施例３ 実施例１で得られた化合物（Ａ−１）を用いて、以下の
組成を有する本発明の樹脂組成物（Ｂ−１）を調製し
た。 化合物（Ａ−１） １２０ｍｇ メタクリル酸メチル ２００ｍｇ ベンゾフェノン １５ｍｇ ｐ−Ｎ，Ｎージメチルアミノアセトフェノン ５ｍｇ トルエン １０ｍｌ この樹脂組成物（Ｂ−１）を、バーコーターを用いて硝
子板上に塗布し、乾燥後、高圧水銀灯を用いて紫外線を
１１０ｍＪ／ｃｍ2 照射する事により硬化皮膜（Ｃ−
１）を得た。Example 3 Using the compound (A-1) obtained in Example 1, a resin composition (B-1) of the present invention having the following composition was prepared. Compound (A-1) 120 mg Methyl methacrylate 200 mg Benzophenone 15 mg p-N, N-Dimethylaminoacetophenone 5 mg Toluene 10 ml This resin composition (B-1) was applied on a glass plate using a bar coater and dried. , cured film by irradiating 110 mJ / cm 2 of ultraviolet rays by a high-pressure mercury lamp (C-
1) was obtained.
【００４３】実施例４ 実施例２で得られた化合物（Ａ−２）を用いて、以下の
組成を有する本発明の樹脂組成物（Ｂ−２）を調製し
た。 化合物（Ａ−２） １２０ｍｇ メタクリル酸メチル １５０ｍｇ ベンゾフェノン １３ｍｇ ｐ−Ｎ，Ｎージメチルアミノアセトフェノン ６ｍｇ トルエン １０ｍｌ この樹脂組成物（Ｂ−２）を、バーコーターを用いて硝
子板上に塗布し、乾燥後、高圧水銀灯を用いて紫外線を
９０ｍＪ／ｃｍ2 照射する事により硬化皮膜（Ｃ−２）
を得た。Example 4 Using the compound (A-2) obtained in Example 2, a resin composition (B-2) of the present invention having the following composition was prepared. Compound (A-2) 120 mg Methyl methacrylate 150 mg Benzophenone 13 mg p-N, N-Dimethylaminoacetophenone 6 mg Toluene 10 ml This resin composition (B-2) was applied on a glass plate using a bar coater and dried. , Cured film (C-2) by irradiating with UV light of 90 mJ / cm 2 using a high pressure mercury lamp
I got
【００４４】分光光度計（Ｕ−３２１０形自記分光光度
計（日立社製））を用いて得られた硬化皮膜の吸収スペ
クトルを測定した。その結果、硬化皮膜（Ｃ−１）では
３２７ｎｍ、２５６ｎｍ、２２０ｎｍに、硬化皮膜（Ｃ
−２）では、３２８ｎｍ、２５６ｎｍ、２１５ｎｍに吸
収が見られた。The absorption spectrum of the obtained cured film was measured using a spectrophotometer (U-3210 type self-recording spectrophotometer (manufactured by Hitachi)). As a result, the cured film (C-1) has a thickness of 327 nm, 256 nm, and 220 nm.
In -2), absorption was observed at 328 nm, 256 nm, and 215 nm.
【００４５】また、得られた硬化皮膜の鉛筆硬度をＪＩ
Ｓ Ｋ−５４０１に準じて測定した。その結果、硬化皮
膜（Ｃ−１）では１Ｈ、硬化皮膜（Ｃ−２）では１Ｈで
あった。Further, the pencil hardness of the obtained cured film was measured by JI
It was measured according to SK-5401. As a result, the cured coating (C-1) was 1H, and the cured coating (C-2) was 1H.
【００４６】[0046]
【発明の効果】本発明のフラーレン誘導体は、容易に薄
膜化でき、光触媒、３次非線形光学材料として極めて有
用である。The fullerene derivative of the present invention can be easily made into a thin film and is extremely useful as a photocatalyst and a third-order nonlinear optical material.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 323/30 7419−4Ｈ Ｃ０７Ｃ 323/30 Ｃ０８Ｆ 20/10 ＭＬＹ Ｃ０８Ｆ 20/10 ＭＬＹ Ｃ０９Ｄ 4/02 ＰＤＳ Ｃ０９Ｄ 4/02 ＰＤＳ 133/04 ＰＦＹ 133/04 ＰＦＹ Ｇ０２Ｆ 1/35 ５０４ Ｇ０２Ｆ 1/35 ５０４ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C07C 323/30 7419-4H C07C 323/30 C08F 20/10 MLY C08F 20/10 MLY C09D 4/02 PDS C09D 4/02 PDS 133/04 PFY 133/04 PFY G02F 1/35 504 G02F 1/35 504
Claims (4)
合を表し、Ｒ2 は、水素原子、あるいはメチル基を表
し、Ｘは−Ｓ−，−ＮＨ−，−ＮＲ−，−Ｏ−のいずれ
かを表し、Ｙは−Ｏ−、−ＮＲ−、−ＮＨ−のいずれか
を表す。ｎは１〜３０の整数を表し、 【化２】 は、フラーレン分子に存在する二重結合のうち、１〜ｎ
個の結合が単結合になった基を表す。）で表されるフラ
ーレン誘導体。1. A formula (1): (In the formula, R 1 represents a direct bond or an alkylene bond having 1 to 6 carbon atoms, R 2 represents a hydrogen atom or a methyl group, and X represents —S—, —NH—, —NR—, —O. Represents any one of-, Y represents any one of -O-, -NR-, and -NH-, n represents an integer of 1 to 30, and Is 1 to n of double bonds existing in the fullerene molecule.
It represents a group in which individual bonds are single bonds. ) The fullerene derivative represented by.
合成分とする高分子化合物。2. A polymer compound containing the fullerene derivative according to claim 1 as an essential polymerization component.
または請求項２記載の高分子化合物を含む樹脂組成物。3. A fullerene derivative according to claim 1, and / or
Alternatively, a resin composition containing the polymer compound according to claim 2.
硬化物。4. A cured product obtained by curing the resin composition according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11106595A JP3615263B2 (en) | 1995-04-13 | 1995-04-13 | Fullerene derivative, resin composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11106595A JP3615263B2 (en) | 1995-04-13 | 1995-04-13 | Fullerene derivative, resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08283199A true JPH08283199A (en) | 1996-10-29 |
| JP3615263B2 JP3615263B2 (en) | 2005-02-02 |
Family
ID=14551512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11106595A Expired - Fee Related JP3615263B2 (en) | 1995-04-13 | 1995-04-13 | Fullerene derivative, resin composition and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3615263B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998089A (en) * | 1996-09-13 | 1999-12-07 | The Institute Of Physical And Chemical Research | Photosensitive resin composition comprising fullerene |
| JP2002063917A (en) * | 2000-08-18 | 2002-02-28 | Sony Corp | Electrochemical device and its usage |
| US6528231B1 (en) | 1999-01-25 | 2003-03-04 | Riken | Photosensitive resin composition, printed wiring board, substrate for disposing semiconductor chips, semiconductor device and processes for producing a printed wiring board, a substrate for disposing semiconductor chips and a semiconductor device |
| JP2005120232A (en) * | 2003-10-16 | 2005-05-12 | Mitsubishi Chem Mkv Co | Ultraviolet absorbable coating composition and ultraviolet absorbable film |
| JP2008284685A (en) * | 2002-11-19 | 2008-11-27 | Samsung Electronics Co Ltd | Pattern formation method using surface-modified carbon nanotube |
| JP2010235651A (en) * | 2009-03-30 | 2010-10-21 | National Institute For Materials Science | Water-repellent supramolecular organization and method for manufacturing the same |
| US8383317B2 (en) | 2003-02-26 | 2013-02-26 | Samsung Electronics Co., Ltd. | Method of making carbon nanotube patterned film or carbon nanotube composite using carbon nanotubes surface-modified with polymerizable moieties |
| DE10120463B4 (en) * | 2001-04-26 | 2017-03-09 | Robert Bosch Gmbh | Method for producing a plastic component with a microstructured, back-injected foil layer, in particular a cover plate in front of a display of a car radio |
-
1995
- 1995-04-13 JP JP11106595A patent/JP3615263B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998089A (en) * | 1996-09-13 | 1999-12-07 | The Institute Of Physical And Chemical Research | Photosensitive resin composition comprising fullerene |
| US6528231B1 (en) | 1999-01-25 | 2003-03-04 | Riken | Photosensitive resin composition, printed wiring board, substrate for disposing semiconductor chips, semiconductor device and processes for producing a printed wiring board, a substrate for disposing semiconductor chips and a semiconductor device |
| US6709804B2 (en) | 1999-01-25 | 2004-03-23 | Riken | Printed wiring board and semiconductor device and processes to prepare the same |
| JP2002063917A (en) * | 2000-08-18 | 2002-02-28 | Sony Corp | Electrochemical device and its usage |
| DE10120463B4 (en) * | 2001-04-26 | 2017-03-09 | Robert Bosch Gmbh | Method for producing a plastic component with a microstructured, back-injected foil layer, in particular a cover plate in front of a display of a car radio |
| JP2008284685A (en) * | 2002-11-19 | 2008-11-27 | Samsung Electronics Co Ltd | Pattern formation method using surface-modified carbon nanotube |
| US8383317B2 (en) | 2003-02-26 | 2013-02-26 | Samsung Electronics Co., Ltd. | Method of making carbon nanotube patterned film or carbon nanotube composite using carbon nanotubes surface-modified with polymerizable moieties |
| JP2005120232A (en) * | 2003-10-16 | 2005-05-12 | Mitsubishi Chem Mkv Co | Ultraviolet absorbable coating composition and ultraviolet absorbable film |
| JP2010235651A (en) * | 2009-03-30 | 2010-10-21 | National Institute For Materials Science | Water-repellent supramolecular organization and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3615263B2 (en) | 2005-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5187825B2 (en) | Hyperbranched polymer and method for producing the same | |
| JP3173368B2 (en) | Polymer compound and chemically amplified positive resist material | |
| TWI267700B (en) | Photocurable compositions and flexographic printing plates comprising the same | |
| TWI286556B (en) | Crosslinkable resin compositions | |
| JP2007146149A (en) | Fluorescent polymer fine particle, method for producing fluorescent polymer fine particle, fluorescence-detecting kit and method for detecting the fluorescence | |
| Liang et al. | Novel polymerizable HMPP-type photoinitiator with carbamate: Synthesis and photoinitiating behaviors | |
| JP4421614B2 (en) | Star polymer, acid-decomposable resin composition, resist composition and di (meth) acrylate compound | |
| JP3615263B2 (en) | Fullerene derivative, resin composition and cured product thereof | |
| CN105384852A (en) | Benzophenone-based polymerizable photoinitiator and preparation method thereof | |
| CN110167993B (en) | Emulsion particles, emulsion comprising same and preparation method of emulsion | |
| JPH01319504A (en) | Composition, coating support and production of said support copolimer is photoinitiator | |
| Blencowe et al. | A carbene insertion approach to functionalised poly (ethylene oxide)-based gels | |
| JP4463649B2 (en) | Photoradical polymerization initiator, photosensitive resin composition, and article | |
| Sandholzer et al. | ROMP based photoinitiator‐coinitiator systems with improved migration stability | |
| JP2007146098A (en) | Imide monomer and its production method, and active energy ray-curable composition | |
| JP2001206917A (en) | Polymer compound and chemical amplification positive type resist material | |
| JP2003277723A (en) | Polymerizable gelatinizer and gel prepared using it | |
| Barım | Synthesis and thermal degradation kinetics of poly (benzyl methacrylate)/graphite composites | |
| US9822204B2 (en) | Vinyl ether functional oligomers and methods for making and using same | |
| JPH09235321A (en) | New ester and its use | |
| JP2002003559A (en) | Crosslinking resin composition | |
| JP6551624B2 (en) | Calixarene compound, curable composition and cured product | |
| JPH0336066B2 (en) | ||
| JPH0129372B2 (en) | ||
| JPS62232410A (en) | Actinic radiation-curable resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040825 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040928 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20041029 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20041029 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071112 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20101112 |
|
| LAPS | Cancellation because of no payment of annual fees |