JP2007231227A - Vinyl ether copolymer - Google Patents
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Abstract
Description
本発明は、ビニルエーテル共重合体に関し、更に詳しくは、電気電子材料や光学材料樹脂として好適な、側鎖に脂環式骨格と脂肪族骨格を有する新規なビニルエーテル共重合体に関するものである。 The present invention relates to a vinyl ether copolymer, and more particularly to a novel vinyl ether copolymer having an alicyclic skeleton and an aliphatic skeleton in a side chain, which is suitable as an electric electronic material or an optical material resin.
近年、脂環式骨格を有するアクリレート類やエポキシ樹脂の、透明樹脂、接着剤、コーティング材やフォトレジスト用樹脂としての使用が検討されている。 In recent years, the use of acrylates and epoxy resins having an alicyclic skeleton as transparent resins, adhesives, coating materials and photoresist resins has been studied.
しかしながら、アクリレート類やエポキシ樹脂は、皮膚刺激性や臭気といった作業上、環境上の問題があるばかりか、保存安定性に難があり、又、アクリル樹脂はその吸湿性に由来する寸法安定性に問題があるため、これら諸問題の改善手段として、脂環式骨格を有するビニルエーテル系化合物が注目されている。 However, acrylates and epoxy resins not only have environmental problems in terms of skin irritation and odor, but also have difficulty in storage stability, and acrylic resins have dimensional stability due to their hygroscopicity. Since there are problems, vinyl ether compounds having an alicyclic skeleton have attracted attention as means for improving these problems.
上記ビニルエーテル系化合物の重合体としては、例えば特開０１−１０２５０１号公報には、側鎖にノルボルニル基やアダマンチル基のような脂環式骨格を有するポリビニルエーテルと、ポリ（ネオペンペンチルビニルエーテル）とのブレンドポリマー、或いは、側鎖にノルボルニル基やジメタノデカヒドロナフチル基、アダマンチル基などの脂環式骨格を有するビニルエーテルとネオペンチルビニルエーテルとの共重合体が開示されており、又、例えば特開平０１−１０２５０２号公報には、側鎖にノルボルニル基やジメタノデカヒドロナフチル基、アダマンチル基などの脂環式骨格を有するビニルエーテルポリマー、或いは、アダマンチルビニルエーテルとイソブチルビニルエーテルの共重合体など、側鎖に脂環式骨格と脂肪族骨格を有する共重合体が開示されている。又、これらのビニルエーテルポリマー及び共重合体は、そのガラス転移温度（Ｔｇ）が１０５℃乃至２００℃と高く、光透過性にも優れ、且つ吸水性が低いことから、光学用成形体として好適であることが示されている。 Examples of the polymer of the vinyl ether compound include, for example, JP-A-01-102501, polyvinyl ether having an alicyclic skeleton such as norbornyl group or adamantyl group in the side chain, poly (neopentpentyl vinyl ether), Or a copolymer of a vinyl ether having an alicyclic skeleton such as norbornyl group, dimethanodecahydronaphthyl group, adamantyl group or the like in the side chain and neopentyl vinyl ether is disclosed. No. 01-102502 discloses a vinyl ether polymer having an alicyclic skeleton such as a norbornyl group, dimethanodecahydronaphthyl group, and adamantyl group in the side chain, or a copolymer of adamantyl vinyl ether and isobutyl vinyl ether in the side chain. Has an alicyclic skeleton and an aliphatic skeleton Copolymers is disclosed that. In addition, these vinyl ether polymers and copolymers have high glass transition temperatures (Tg) of 105 ° C. to 200 ° C., excellent light transmittance, and low water absorption, so that they are suitable as optical moldings. It is shown that there is.
このように、側鎖にノルボルニル基やジメタノデカヒドロナフチル基のような脂環式骨格を有するビニルエーテルポリマーは、高いガラス転移温度（Ｔｇ）を有するために、透明性を要求される光学材料に用いられている。しかしながら、従来の脂環式骨格を有するビニルエーテルポリマーは、ガラス転移温度（Ｔｇ）が高いため成形の際は高温に保持する必要があり、熱劣化により透明性が損なわれるという問題があった。又、一般的に脂環式骨格を有する重合体は可撓性が低く、複雑な形状の成形品を得ることは困難であった。このため、光学材料分野の短波長への変遷に伴う透明性への要求や、電気電子材料へ求められる高速化に対応するために、よりガラス転移温度が低く、可撓性の改良された脂環式骨格を有するビニルエーテルポリマーが求められている。 Thus, vinyl ether polymers having an alicyclic skeleton such as norbornyl group or dimethanodecahydronaphthyl group in the side chain have a high glass transition temperature (Tg), and thus are optical materials that require transparency. It is used. However, since the conventional vinyl ether polymer having an alicyclic skeleton has a high glass transition temperature (Tg), it has to be maintained at a high temperature during molding, and there is a problem that transparency is impaired due to thermal deterioration. In general, a polymer having an alicyclic skeleton has low flexibility, and it has been difficult to obtain a molded product having a complicated shape. Therefore, in order to respond to the demand for transparency associated with the transition to short wavelengths in the field of optical materials and the high speed required for electric and electronic materials, the glass transition temperature is lower and the flexibility is improved. There is a need for vinyl ether polymers having a cyclic skeleton.
本発明の発明者らの一部は、光学材料や電気電子材料における課題を解決する手段として、側鎖に新規な脂環式骨格を有し、分子量分布の狭いビニルエーテル重合体を提案し、特許出願をしており（特開２００５−１１３０４９号公報参照）、該ビニルエーテル重合体は、耐熱性と低吸湿性及び金属への密着性に優れたものであるが、更に可撓性にも優れた新規なビニルエーテル共重合体を提供するため鋭意検討の結果、特定の脂環式骨格を有するビニルエーテルに、直鎖状のアルキルビニルエーテルを共重合させることにより、ガラス転移温度が低く、可撓性の改善された脂環式骨格を有するビニルエーテル共重合体が得られるのではないかとの知見を得、さらに研究を進めた結果、以下の式（１）で表される、脂肪族骨格と脂環式骨格を共に側鎖に有する共重合体を発明するに至った。
上記本発明のビニルエーテル共重合体は、８−ビニロキシトリシクロ［5.2.1.02,6］デカン
本発明のビニルエーテル共重合体は、側鎖に直鎖状の脂肪族骨格と脂環式骨格を共に有しており、既存の脂環式骨格を有するビニルエーテルポリマーと比較して低いガラス転移温度を有し、可撓性が改良されている。このため、より低い温度で成形が可能となり、これまで困難であった複雑な形状の成形品を得ることも可能であると期待される。 The vinyl ether copolymer of the present invention has both a linear aliphatic skeleton and an alicyclic skeleton in the side chain, and has a lower glass transition temperature compared to a vinyl ether polymer having an existing alicyclic skeleton. And has improved flexibility. For this reason, it becomes possible to mold at a lower temperature, and it is expected that it is possible to obtain a molded product having a complicated shape which has been difficult until now.
本発明のビニルエーテル共重合体は、以下の式（１）で表される、脂肪族骨格と脂環式骨格を共に側鎖に有するものである。
上記式中のｎ及びｍは、それぞれ３０〜６００の整数である。又、ｍ／ｎの比率（％）は、５０／５０〜９５／５が好ましく、６０／４０〜９５／５がより好ましい。ｍの比率が５０％より小さいと、ガラス転移温度が低くなりすぎ、耐熱性や成形性が悪くなる。一方、ｍの比率が９５％を超えると可撓性の改善効果が得られない。 N and m in the above formula are each an integer of 30 to 600. Further, the ratio (%) of m / n is preferably 50/50 to 95/5, and more preferably 60/40 to 95/5. If the ratio of m is less than 50%, the glass transition temperature becomes too low, and the heat resistance and moldability deteriorate. On the other hand, if the ratio of m exceeds 95%, the effect of improving flexibility cannot be obtained.
上記本発明のビニルエーテル共重合体は、８−ビニロキシトリシクロ［5.2.1.02,6］デカン
上記重合は、公知のカチオン重合により行われ、カチオン重合開始剤として一般的に使用される三弗化のホウ素などのルイス酸や硫酸などを用いた方法を挙げることができ、この場合は、仕込みの原料モノマーの比に応じたランダム共重合体を得ることができる。 The polymerization is performed by known cationic polymerization, and a method using Lewis acid such as boron trifluoride or sulfuric acid generally used as a cationic polymerization initiator can be mentioned. A random copolymer corresponding to the ratio of the raw material monomers can be obtained.
又、重合度の制御が容易であり且つ単分散に近い共重合体を得ることが可能なリビングカチオン重合では、分子量分布の狭いランダム共重合体や、重合度を制御したブロック共重合体を得ることができる。 In living cationic polymerization, the degree of polymerization can be easily controlled and a copolymer close to monodispersion can be obtained, and a random copolymer with a narrow molecular weight distribution and a block copolymer with a controlled degree of polymerization are obtained. be able to.
得られたビニルエーテル共重合体は、重合方法の如何に拘わらず本発明の目的を達成することができるものである。 The obtained vinyl ether copolymer can achieve the object of the present invention regardless of the polymerization method.
尚、重合に際して使用する溶媒は、ヘキサンなどの脂肪族溶媒や、トルエン、塩化メチレンなどが用いられるが、特に限定されるものではない。 The solvent used for the polymerization is an aliphatic solvent such as hexane, toluene, methylene chloride or the like, but is not particularly limited.
以下に実施例を示す。 Examples are shown below.
実施例１ ランダム共重合体の合成（１）
窒素置換後、十分に水分を除去したガラス製フラスコ内で、ｎ−ブチルビニルエーテル（以下、ＮＢＶＥと略す。）３０mmolと８−ビニロキシトリシクロ［5.2.1.02,6］デカン（以下、ＴＣＤＶＥと略す。）９０mmolをトルエンに溶解させた。ついで、イソブチルビニルエーテルの酢酸付加物（ＩＢＥＡ）のトルエン溶液と２，４−ジ−tert−ブチルピリジンのトルエン溶液を加え、０℃まで冷却し、四臭化すず（ＳｎＢｒ４)のトルエン溶液を加えて重合を開始した。それぞれの成分の最終濃度は表１に示した。５時間後、反応液を水洗し、トルエンを濃縮した後、メタノールで重合体を析出させた。ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により標準ポリスチレン換算の平均分子量と、示差走査熱量分析装置（ＤＳＣ）でガラス転移温度を測定した。結果を表１に示した。
Example 1 Synthesis of Random Copolymer (1)
In a glass flask from which water had been sufficiently removed after nitrogen substitution, 30 mmol of n-butyl vinyl ether (hereinafter abbreviated as NBVE) and 8-vinyloxytricyclo [5.2.1.0 2,6 ] decane (hereinafter referred to as TCDVE). (Omitted) 90 mmol was dissolved in toluene. Next, a toluene solution of acetic acid adduct (IBEA) of isobutyl vinyl ether and a toluene solution of 2,4-di-tert-butylpyridine were added, cooled to 0 ° C., and a toluene solution of tin tetrabromide (SnBr 4 ) was added. The polymerization was started. The final concentration of each component is shown in Table 1. After 5 hours, the reaction solution was washed with water and concentrated with toluene, and then a polymer was precipitated with methanol. The average molecular weight in terms of standard polystyrene was measured by gel permeation chromatography (GPC), and the glass transition temperature was measured by a differential scanning calorimeter (DSC). The results are shown in Table 1.
実施例２〜４
ＮＢＶＥとＴＣＤＶＥの仕込み比を変えた以外は、実施例１の方法により重合体の合成と分析を行った。これらの結果を表１に示した。
Examples 2-4
The polymer was synthesized and analyzed by the method of Example 1 except that the charging ratio of NBVE and TCDVE was changed. These results are shown in Table 1.
実施例５ ランダム共重合体の合成（２）
窒素置換後、十分に水分を除去したガラス製フラスコ内で、ＮＢＶＥ２０mmolとＴＣＤＶＥ８０mmolをトルエンに溶解させた。系を−３０℃に冷却したところで、三フッ化ホウ素ジエチルエーテル錯体をモノマーに対して５mol％になるように添加し、５時間反応させた。反応液を水洗しトルエン相を濃縮した後メタノールで重合体を析出させた。ＧＰＣによる平均分子量の測定とＤＳＣによるガラス転移温度の測定を行った。結果を表１に示した。
Example 5 Synthesis of Random Copolymer (2)
After nitrogen substitution, 20 mmol of NBVE and 80 mmol of TCDVE were dissolved in toluene in a glass flask from which water had been sufficiently removed. When the system was cooled to −30 ° C., boron trifluoride diethyl ether complex was added so as to be 5 mol% based on the monomer, and reacted for 5 hours. The reaction solution was washed with water and the toluene phase was concentrated, and then a polymer was precipitated with methanol. The average molecular weight was measured by GPC and the glass transition temperature was measured by DSC. The results are shown in Table 1.
実施例６ ブロック共重合体の合成
窒素置換後、十分に水分を除去したガラス製フラスコ内で、ＮＢＶＥ２０mmolとＴＣＤＶＥ６０mmolをトルエンに溶解させた。ついでＩＢＥＡのトルエン溶液と２，４−ジ−tert−ブチルピリジンのトルエン溶液を加え、０℃まで冷却し、四臭化すず(ＳｎＢｒ４)のトルエン溶液を加えて重合を開始した。５時間後、予めトルエンに溶解しておいたＴＣＤＶＥを添加し、更に５時間反応を継続した。反応液を水洗し、トルエンを留去してブロック共重合体を得た。ＧＰＣにより標準ポリスチレン換算の平均分子量と、ＤＳＣによりガラス転移温度を測定した。ブロック共重合体では、それぞれのセグメントに対応するＴｇが観測された。結果を表１に示した。
Example 6 Synthesis of Block Copolymer After substitution with nitrogen, NBVE 20 mmol and TCDVE 60 mmol were dissolved in toluene in a glass flask from which water had been sufficiently removed. Then, a toluene solution of IBEA and a toluene solution of 2,4-di-tert-butylpyridine were added, cooled to 0 ° C., and a toluene solution of tin tetrabromide (SnBr 4 ) was added to initiate polymerization. After 5 hours, TCDVE previously dissolved in toluene was added, and the reaction was continued for another 5 hours. The reaction solution was washed with water, and toluene was distilled off to obtain a block copolymer. The average molecular weight in terms of standard polystyrene was measured by GPC, and the glass transition temperature was measured by DSC. In the block copolymer, Tg corresponding to each segment was observed. The results are shown in Table 1.
比較例 ＴＣＤＶＥホモポリマーの合成
窒素置換後、十分に水分を除去したガラス製フラスコ内で、ＴＣＤＶＥ８０mmolをトルエンに溶解させた。系を−３０℃に冷却したところで、三フッ化ホウ素ジエチルエーテル錯体を添加し、５時間反応させた。反応液を水洗し、トルエン相を濃縮した後、メタノールで重合体を析出させた。ＧＰＣにより標準ポリスチレン換算の平均分子量と、ＤＳＣによりガラス転移温度を測定した。結果を表１に示した。
Comparative Example Synthesis of TCDVE Homopolymer After nitrogen substitution, 80 mmol of TCDVE was dissolved in toluene in a glass flask from which water had been sufficiently removed. When the system was cooled to −30 ° C., boron trifluoride diethyl ether complex was added and reacted for 5 hours. The reaction solution was washed with water and the toluene phase was concentrated, and then a polymer was precipitated with methanol. The average molecular weight in terms of standard polystyrene was measured by GPC, and the glass transition temperature was measured by DSC. The results are shown in Table 1.
Claims (1)
で表されることを特徴とするビニルエーテル共重合体。 Formula (1)
The vinyl ether copolymer characterized by these.
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| JP2006057832A JP2007231227A (en) | 2006-03-03 | 2006-03-03 | Vinyl ether copolymer |
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| JP2006057832A JP2007231227A (en) | 2006-03-03 | 2006-03-03 | Vinyl ether copolymer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008138177A (en) * | 2006-11-10 | 2008-06-19 | Univ Of Fukui | Aba-type triblock copolymer |
| JP2009256554A (en) * | 2008-04-21 | 2009-11-05 | Univ Of Fukui | Curable resin composition and its cured product |
| WO2014157674A1 (en) | 2013-03-29 | 2014-10-02 | 東京応化工業株式会社 | Compound containing structural unit derived from vinyl ether compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015396A (en) * | 2003-06-26 | 2005-01-20 | Maruzen Petrochem Co Ltd | New alicyclic vinyl ether |
| JP2005113049A (en) * | 2003-10-09 | 2005-04-28 | Maruzen Petrochem Co Ltd | New alicyclic vinyl ether polymer |
| JP2005187703A (en) * | 2003-12-26 | 2005-07-14 | Maruzen Petrochem Co Ltd | Cycloalkyl vinyl ether/maleic anhydride copolymer, and hardening agent and hardenable resin composition containing the copolymer |
-
2006
- 2006-03-03 JP JP2006057832A patent/JP2007231227A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015396A (en) * | 2003-06-26 | 2005-01-20 | Maruzen Petrochem Co Ltd | New alicyclic vinyl ether |
| JP2005113049A (en) * | 2003-10-09 | 2005-04-28 | Maruzen Petrochem Co Ltd | New alicyclic vinyl ether polymer |
| JP2005187703A (en) * | 2003-12-26 | 2005-07-14 | Maruzen Petrochem Co Ltd | Cycloalkyl vinyl ether/maleic anhydride copolymer, and hardening agent and hardenable resin composition containing the copolymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008138177A (en) * | 2006-11-10 | 2008-06-19 | Univ Of Fukui | Aba-type triblock copolymer |
| JP2009256554A (en) * | 2008-04-21 | 2009-11-05 | Univ Of Fukui | Curable resin composition and its cured product |
| WO2014157674A1 (en) | 2013-03-29 | 2014-10-02 | 東京応化工業株式会社 | Compound containing structural unit derived from vinyl ether compound |
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