JPH0570604A - Crosslinking agent and resin composition containing the crosslinking agent and molded product using composition containing the crosslinking agent - Google Patents
Crosslinking agent and resin composition containing the crosslinking agent and molded product using composition containing the crosslinking agentInfo
- Publication number
- JPH0570604A JPH0570604A JP3262761A JP26276191A JPH0570604A JP H0570604 A JPH0570604 A JP H0570604A JP 3262761 A JP3262761 A JP 3262761A JP 26276191 A JP26276191 A JP 26276191A JP H0570604 A JPH0570604 A JP H0570604A
- Authority
- JP
- Japan
- Prior art keywords
- crosslinking agent
- resin composition
- adamantane
- composition containing
- molecule
- 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.)
- Withdrawn
Links
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- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は架橋剤およびこの架橋
剤を含む樹脂組成物ならびにこの架橋剤を含む樹脂組成
物で成形された成形品に関し、さらに詳しくは、架橋反
応が良好な架橋剤と、この架橋剤を含む樹脂組成物、な
らびにこの架橋剤を含む樹脂組成物で成形される機械特
性に優れた成形品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cross-linking agent, a resin composition containing the cross-linking agent, and a molded article molded with the resin composition containing the cross-linking agent. The present invention relates to a resin composition containing this cross-linking agent, and a molded article excellent in mechanical properties molded with the resin composition containing this cross-linking agent.
【０００２】[0002]
【従来の技術】一般に、樹脂組成物で種々の成形品を成
形する場合、水酸基やアミノ基等を有する樹脂を含む樹
脂組成物中に架橋剤を含有させるなどして、機械特性に
優れた成形品を成形することが行われており、この架橋
剤として、通常、ポリイソシアネ−ト化合物が広く用い
られているが、未だ充分に機械特性に優れた成形品は得
られていない。そこで、ポリイソシアネ−ト化合物と架
橋結合する樹脂の構造を改良するなどして、このポリイ
ソシアネ−ト化合物を含む樹脂組成物で成形される成形
品の機械特性を改善することが試みられている。2. Description of the Related Art Generally, when molding various molded articles with a resin composition, a resin composition containing a resin having a hydroxyl group, an amino group or the like contains a cross-linking agent so that molding with excellent mechanical properties is achieved. Molded articles have been formed, and polyisocyanate compounds have been widely used as the crosslinking agent, but molded articles having sufficiently excellent mechanical properties have not yet been obtained. Therefore, it has been attempted to improve the mechanical properties of a molded product molded from a resin composition containing the polyisocyanate compound, for example, by improving the structure of a resin that crosslinks with the polyisocyanate compound.
【０００３】[0003]
【発明が解決しようとする課題】ところが、ポリイソシ
アネ−ト化合物などの架橋剤と架橋結合する樹脂の構造
を改良する方法では、未だ充分に満足できる機械特性を
有する成形品が得られていない場合が少なくない。However, in the method for improving the structure of the resin that crosslinks with a crosslinking agent such as a polyisocyanate compound, a molded article having sufficiently satisfactory mechanical properties may not yet be obtained. Not a few.
【０００４】[0004]
【課題を解決するための手段】この発明は、かかる現状
に鑑み種々検討を行った結果なされたもので、アダマン
タン構造を分子中に有し、かつ架橋に必要な反応性官能
基を有する架橋剤によって良好な架橋結合を形成させ、
この架橋剤を含む樹脂組成物でもって、たとえば、機械
特性に優れたフィルムなどの成形品を形成し、得られる
成形品の機械特性を充分に向上させたものである。SUMMARY OF THE INVENTION The present invention has been made as a result of various studies in view of the present situation, and has a cross-linking agent having an adamantane structure in the molecule and a reactive functional group necessary for cross-linking. To form a good cross-link,
With the resin composition containing this crosslinking agent, for example, a molded product such as a film having excellent mechanical properties is formed, and the mechanical properties of the resulting molded product are sufficiently improved.
【０００５】この発明によれば、架橋剤が、対称形でか
つ歪みにくいアダマンタン構造を分子中に有し、かつ架
橋に必要な反応性官能基を有しているため、この架橋剤
を含む樹脂組成物でもって成形品を成形すると、架橋剤
の分子中に有する構造が対称形でかつ歪みにくいアダマ
ンタン構造により、整った綱目構造の架橋結合が形成さ
れる。According to the present invention, since the cross-linking agent has an adamantane structure which is symmetric and is not easily distorted in the molecule and has a reactive functional group necessary for cross-linking, a resin containing the cross-linking agent is included. When a molded article is molded with the composition, a cross-linking bond having an ordered structure is formed due to the adamantane structure having a symmetrical structure in the molecule of the cross-linking agent and being resistant to distortion.
【０００６】従って、このアダマンタン構造を分子中に
有し、かつ架橋に必要な反応性官能基を有する架橋剤を
含む樹脂組成物からは、機械特性に優れた成形品が得ら
れ、たとえば、このアダマンタン構造を分子中に有し、
かつ架橋に必要な反応性官能基を有する架橋剤を含む樹
脂組成物を基板上に塗布した後、基板を剥離すると、機
械特性に優れた樹脂製フィルムが得られる。Therefore, a resin composition containing a cross-linking agent having the adamantane structure in the molecule and having a reactive functional group necessary for cross-linking gives a molded article excellent in mechanical properties. Having an adamantane structure in the molecule,
Moreover, when a resin composition containing a crosslinking agent having a reactive functional group necessary for crosslinking is applied onto the substrate and then the substrate is peeled off, a resin film having excellent mechanical properties can be obtained.
【０００７】このようにアダマンタン構造を分子中に有
し、かつ架橋に必要な反応性官能基を有する架橋剤は、
アダマンタン構造を分子中に有し、かつ架橋に必要な反
応性官能基を有していれば、いずれの製造法を用いて製
造してもよく、たとえば、工業的に有効な製造法とし
て、２〜４個の水酸基を有するアダマンタンポリオ−ル
に、このアダマンタンポリオ−ルの水酸基と反応する官
能基と、架橋反応する反応性官能基とを併せ持つ化合物
とを反応させて製造される。A cross-linking agent having an adamantane structure in its molecule and a reactive functional group necessary for cross-linking is
As long as it has an adamantane structure in the molecule and has a reactive functional group necessary for crosslinking, it may be produced by any production method. For example, as an industrially effective production method, 2 It is produced by reacting adamantane polyol having 4 to 4 hydroxyl groups with a compound having both a functional group that reacts with the hydroxyl groups of the adamantane polyol and a reactive functional group that undergoes a crosslinking reaction.
【０００８】ここで、アダマンタンポリオ−ルは、アダ
マンタンを三酸化クロム等で酸化してまずアダマンタン
ジオ−ルを得、さらに酸化することにより合成され、た
とえば、アダマンタン−１，３，５−トリオ−ル、アダ
マンタン−１，３，５，７−テトラオ−ルなどが得られ
る。Here, adamantane polyol is synthesized by first oxidizing adamantane with chromium trioxide or the like to obtain adamantane diol, and further oxidizing it. For example, adamantane-1,3,5-triol- , Adamantane-1,3,5,7-tetraol and the like are obtained.
【０００９】また、アダマンタンポリオ−ルの水酸基と
反応する官能基、および架橋反応する反応性官能基とを
併せ持つ化合物としては、たとえば、イソシアネ−ト基
を導入するものとして、トリレンジイソシアネ−ト、ジ
フェニルメタンジイソシアネ−ト、ヘキサメチレンジイ
ソシアネ−トなどが使用され、二重結合を導入するもの
として、イソシアネ−トエチルメタクリレ−トなどが用
いられる。Examples of the compound having both a functional group that reacts with a hydroxyl group of adamantane polyol and a reactive functional group that undergoes a cross-linking reaction include, for example, tolylene diisocyanate for introducing an isocyanate group. , Diphenylmethane diisocyanate, hexamethylene diisocyanate, etc. are used, and isocyanatoethyl methacrylate, etc. is used as a substance for introducing a double bond.
【００１０】なお、アダマンタンポリオ−ルに、このア
ダマンタンポリオ−ルの水酸基と反応する官能基と、架
橋反応する反応性官能基とを併せ持つ化合物とを反応さ
せる際、多段階に反応させてもよく、たとえば、ジイソ
シアネ−トを反応させたアダマンタンポリオ−ルにグリ
シド−ルを反応させてエポキシ基を導入することも可能
である。When a compound having both a functional group that reacts with the hydroxyl group of the adamantane polyol and a reactive functional group that undergoes a cross-linking reaction is reacted with the adamantane polyol, the reaction may be carried out in multiple steps. For example, it is possible to introduce an epoxy group by reacting adamantane polyol reacted with diisocyanate with glycidyl.
【００１１】このようにして得られるアダマンタン構造
を分子中に有し、かつ架橋に必要な反応性官能基を有す
る架橋剤は、１分子当たりの反応性官能基の導入数を２
から４の範囲にするのが好ましく、これらの１分子当た
りの反応性官能基の導入数は、この種の架橋剤を含む樹
脂組成物のポットライフ、およびこの種の架橋剤を含む
樹脂組成物で成形して得られる成形品の機械特性とのか
ねあいから選択すればよい。The cross-linking agent having the adamantane structure thus obtained in the molecule and having the reactive functional group necessary for cross-linking has a reactive functional group introduction number of 2 per molecule.
The number of reactive functional groups to be introduced per molecule is preferably the range from 4 to 4, and the pot life of the resin composition containing the crosslinking agent of this type, and the resin composition containing the crosslinking agent of this type. It may be selected in consideration of the mechanical properties of the molded product obtained by molding with.
【００１２】このようなアダマンタン構造を分子中に有
し、かつ架橋に必要な反応性官能基を有する架橋剤を含
む樹脂組成物は、従来の樹脂組成物で使用する架橋剤に
代えてこのアダマンタン構造を分子中に有し、かつ架橋
に必要な反応性官能基を有する架橋剤を使用して得ら
れ、このアダマンタン構造を分子中に有し、かつ架橋に
必要な反応性官能基を有する架橋剤を含む樹脂組成物か
ら得られる成形品は、従来の樹脂組成物から得られる成
形品と同様にして得られる。The resin composition containing a crosslinking agent having such an adamantane structure in the molecule and having a reactive functional group necessary for crosslinking is prepared by replacing the crosslinking agent used in the conventional resin composition with this adamantane. A crosslinker having a structure in the molecule and a reactive functional group necessary for crosslinking, obtained by using a crosslinking agent, and having this adamantane structure in the molecule and having a reactive functional group necessary for crosslinking The molded product obtained from the resin composition containing the agent is obtained in the same manner as the molded product obtained from the conventional resin composition.
【００１３】なお、この発明で使用するアダマンタン構
造を分子中に有し、かつ架橋に必要な反応性官能基を有
する架橋剤とともに、必要に応じて従来の架橋剤を併用
してもよい。If necessary, a conventional cross-linking agent may be used together with the cross-linking agent having an adamantane structure used in the present invention in the molecule and having a reactive functional group necessary for cross-linking.
【００１４】[0014]
【実施例】次に、この発明の実施例について説明する。
なお、本発明は何らこれらに限定されるものではない。 実施例１ 還流冷却器と滴下漏斗を取り付け窒素置換した三つ口フ
ラスコに、トリレンジイソシアネ−ト５３重量部とクロ
ロホルム６７重量部を仕込み、滴下漏斗に、アダマンタ
ン−１，３，５−トリオ−ル18.4重量部とクロロホルム
４０重量部を仕込んだ。次いで、６０度に昇温後、激し
く撹拌しながらアダマンタン−１，３，５−トリオ−ル
溶液を徐々に滴下した。滴下終了後６０度で３時間保持
し、保持後さらに８０度に昇温して３時間撹拌を続け、
アダマンタン構造を分子中に有し、かつイソシアネ−ト
基を有する架橋剤を得た。EXAMPLES Next, examples of the present invention will be described.
The present invention is not limited to these. Example 1 53 parts by weight of tolylene diisocyanate and 67 parts by weight of chloroform were placed in a three-necked flask equipped with a reflux condenser and a dropping funnel and replaced with nitrogen, and the dropping funnel was charged with adamantane-1,3,5-trio. -18.4 parts by weight and 40 parts by weight of chloroform were charged. Next, after the temperature was raised to 60 ° C., the adamantane-1,3,5-triol solution was gradually added dropwise with vigorous stirring. After the dropping is completed, the temperature is maintained at 60 degrees for 3 hours, the temperature is further raised to 80 degrees, and stirring is continued for 3 hours.
A crosslinking agent having an adamantane structure in the molecule and an isocyanate group was obtained.
【００１５】一方、還流冷却器と滴下漏斗を取り付け窒
素置換した三つ口フラスコに、ジフェニルメタンジイソ
シアネ−ト５０重量部とクロロホルム４５０重量部を仕
込み、滴下漏斗に、分子量１０００のポリブチレンアジ
ペ−ト１００重量部とクロロホルム９００重量部を仕込
んだ。次いで、６０度に昇温後激しく撹拌しながらポリ
ブチレンアジペ−ト溶液を徐々に滴下した。滴下終了後
８０度に昇温して５時間反応を続けた。次に１，４−ブ
タンジオ−ル９重量部とクロロホルム８１重量部を滴下
漏斗に仕込み、これを徐々に滴下し充分に粘度が上がる
まで反応させて、数平均分子量がＧＰＣによるポリスチ
レン換算で２６０００のポリウレタンを得た。On the other hand, 50 parts by weight of diphenylmethane diisocyanate and 450 parts by weight of chloroform were charged into a three-necked flask equipped with a reflux condenser and a dropping funnel and replaced with nitrogen. -100 parts by weight and 900 parts by weight of chloroform were charged. Then, the temperature was raised to 60 ° C., and the polybutylene adipate solution was gradually added dropwise with vigorous stirring. After completion of the dropping, the temperature was raised to 80 ° C. and the reaction was continued for 5 hours. Next, 9 parts by weight of 1,4-butanediol and 81 parts by weight of chloroform were charged into a dropping funnel, which was gradually added dropwise and reacted until the viscosity was sufficiently raised, and the number average molecular weight was 26,000 in terms of polystyrene by GPC. Obtained polyurethane.
【００１６】次いで、上記のようにして得られたアダマ
ンタン構造を分子中に有し、かつイソシアネ−ト基を有
する架橋剤の溶液 2.5重量部と、数平均分子量がＧＰＣ
によるポリスチレン換算で２６０００のポリウレタンの
溶液４０重量部とを混合して樹脂組成物を得、この樹脂
組成物を、テフロン板上に乾燥後の厚さが５０μｍ前後
になるように塗布した。そして、室温で１日乾燥後、３
日間８０度で加熱保存し、テフロン板から剥離して、ポ
リウレタン製架橋フィルムを得た。Next, 2.5 parts by weight of a solution of a crosslinking agent having the adamantane structure obtained in the above-mentioned molecule in the molecule and having an isocyanate group, and a number average molecular weight of GPC
A resin composition was obtained by mixing with 40 parts by weight of a solution of 26000 polyurethane in terms of polystyrene according to the above, and the resin composition was applied onto a Teflon plate so that the thickness after drying was about 50 μm. After drying at room temperature for 1 day, 3
It was stored by heating at 80 ° C for a day and peeled from the Teflon plate to obtain a crosslinked polyurethane film.
【００１７】比較例１ 実施例１における樹脂組成物の組成において、アダマン
タン構造を分子中に有し、かつイソシアネ−ト基を有す
る架橋剤の溶液に代えて、コロネ−トＬ（日本ポリウレ
タン工業社製；三官能性低分子量イソシアネ−ト化合
物）の４０％溶液を 2.5重量部使用した以外は、実施例
１と同様にして樹脂組成物を得、ポリウレタン製架橋フ
ィルムを得た。Comparative Example 1 In the composition of the resin composition in Example 1, instead of a solution of a crosslinking agent having an adamantane structure in the molecule and having an isocyanate group, Coronet L (Nippon Polyurethane Industry Co., Ltd.) was used. A resin composition was obtained in the same manner as in Example 1 except that 2.5 parts by weight of a 40% solution of trifunctional low molecular weight isocyanate compound) was used to obtain a polyurethane crosslinked film.
【００１８】各実施例および比較例で得られたポリウレ
タン製架橋フィルムについて、引っ張り試験を行い、破
壊強度および破壊伸度を測定した。下記表１はその結果
である。The polyurethane cross-linked films obtained in each of the examples and comparative examples were subjected to a tensile test to measure the breaking strength and breaking elongation. Table 1 below shows the results.
【００１９】 [0019]
【００２０】[0020]
【発明の効果】上記表１から明らかなように、この発明
で得られたポリウレタン製架橋フィルム（実施例１）
は、比較例１で得られたポリウレタン製架橋フィルムに
比し、破壊強度および破壊伸度がいずれも大きく、この
ことからこの発明によれば、架橋反応が良好な架橋剤が
得られ、この架橋剤を含む樹脂組成物から、機械特性に
優れた成形品が得られることがわかる。As is apparent from Table 1 above, the polyurethane cross-linked film obtained in the present invention (Example 1)
Is larger in both breaking strength and breaking elongation than the polyurethane cross-linked film obtained in Comparative Example 1. Therefore, according to the present invention, a cross-linking agent having a good cross-linking reaction can be obtained. It can be seen that a molded product having excellent mechanical properties can be obtained from the resin composition containing the agent.
Claims (6)
架橋に必要な反応性官能基を有する架橋剤1. A cross-linking agent having an adamantane structure in the molecule and a reactive functional group necessary for cross-linking.
る請求項１記載の架橋剤2. The crosslinking agent according to claim 1, wherein the reactive functional group is an isocyanate group.
架橋に必要な反応性官能基を有する架橋剤を含んでなる
樹脂組成物3. A resin composition comprising a crosslinking agent having an adamantane structure in the molecule and having a reactive functional group necessary for crosslinking.
アネ−ト基である請求項３記載の樹脂組成物4. The resin composition according to claim 3, wherein the reactive functional group contained in the crosslinking agent is an isocyanate group.
架橋に必要な反応性官能基を有する架橋剤を含んでなる
樹脂組成物で成形した成形品5. A molded product molded from a resin composition containing a crosslinking agent having an adamantane structure in the molecule and having a reactive functional group necessary for crosslinking.
アネ−ト基である請求項５記載の成形品6. The molded article according to claim 5, wherein the reactive functional group contained in the crosslinking agent is an isocyanate group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3262761A JPH0570604A (en) | 1991-09-13 | 1991-09-13 | Crosslinking agent and resin composition containing the crosslinking agent and molded product using composition containing the crosslinking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3262761A JPH0570604A (en) | 1991-09-13 | 1991-09-13 | Crosslinking agent and resin composition containing the crosslinking agent and molded product using composition containing the crosslinking agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0570604A true JPH0570604A (en) | 1993-03-23 |
Family
ID=17380223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3262761A Withdrawn JPH0570604A (en) | 1991-09-13 | 1991-09-13 | Crosslinking agent and resin composition containing the crosslinking agent and molded product using composition containing the crosslinking agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0570604A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399913A (en) * | 2015-12-30 | 2016-03-16 | 中物功能材料研究院有限公司 | Ultraviolet light-cured polyurethane acrylate and preparation method thereof |
| CN105440260A (en) * | 2015-12-30 | 2016-03-30 | 中物功能材料研究院有限公司 | Ultraviolet curing urethane acrylate and preparation method thereof |
| CN105440245A (en) * | 2015-12-30 | 2016-03-30 | 中物功能材料研究院有限公司 | Ultraviolet curing coating and preparation method thereof |
| CN114724775A (en) * | 2022-05-24 | 2022-07-08 | 西北工业大学 | Preparation method of low-temperature polyester polyurethane-based conductive slurry |
-
1991
- 1991-09-13 JP JP3262761A patent/JPH0570604A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399913A (en) * | 2015-12-30 | 2016-03-16 | 中物功能材料研究院有限公司 | Ultraviolet light-cured polyurethane acrylate and preparation method thereof |
| CN105440260A (en) * | 2015-12-30 | 2016-03-30 | 中物功能材料研究院有限公司 | Ultraviolet curing urethane acrylate and preparation method thereof |
| CN105440245A (en) * | 2015-12-30 | 2016-03-30 | 中物功能材料研究院有限公司 | Ultraviolet curing coating and preparation method thereof |
| CN105440245B (en) * | 2015-12-30 | 2018-05-22 | 贾学明 | Ultraviolet-curing paint and preparation method thereof |
| CN105440260B (en) * | 2015-12-30 | 2018-05-29 | 贾学明 | UV-cured polyurethane acrylate and preparation method thereof |
| CN105399913B (en) * | 2015-12-30 | 2018-05-29 | 贾学明 | UV-cured polyurethane acrylate and preparation method thereof |
| CN114724775A (en) * | 2022-05-24 | 2022-07-08 | 西北工业大学 | Preparation method of low-temperature polyester polyurethane-based conductive slurry |
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