JP6723803B2 - Vinyl aromatic hydrocarbon polymer, polymer composition and molded article - Google Patents
Vinyl aromatic hydrocarbon polymer, polymer composition and molded article Download PDFInfo
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- JP6723803B2 JP6723803B2 JP2016080619A JP2016080619A JP6723803B2 JP 6723803 B2 JP6723803 B2 JP 6723803B2 JP 2016080619 A JP2016080619 A JP 2016080619A JP 2016080619 A JP2016080619 A JP 2016080619A JP 6723803 B2 JP6723803 B2 JP 6723803B2
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- polymer
- molecular weight
- anionic
- anionic polymer
- polymerization initiator
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- 229920000642 polymer Polymers 0.000 title claims description 127
- -1 Vinyl aromatic hydrocarbon Chemical class 0.000 title claims description 64
- 229920002554 vinyl polymer Polymers 0.000 title claims description 47
- 239000000203 mixture Substances 0.000 title claims description 21
- 229920006318 anionic polymer Polymers 0.000 claims description 66
- 239000003505 polymerization initiator Substances 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 44
- 230000001588 bifunctional effect Effects 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 31
- 238000005227 gel permeation chromatography Methods 0.000 claims description 25
- 239000007822 coupling agent Substances 0.000 claims description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 150000002900 organolithium compounds Chemical class 0.000 claims description 7
- 150000001993 dienes Chemical class 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 21
- 230000008878 coupling Effects 0.000 description 19
- 238000010168 coupling process Methods 0.000 description 19
- 238000005859 coupling reaction Methods 0.000 description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 18
- 238000009826 distribution Methods 0.000 description 16
- 235000013305 food Nutrition 0.000 description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
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- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
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- HTJFSXYVAKSPNF-UHFFFAOYSA-N 2-[2-(oxiran-2-yl)ethyl]oxirane Chemical compound C1OC1CCC1CO1 HTJFSXYVAKSPNF-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Description
本発明はビニル芳香族炭化水素系重合体、重合体組成物及び成形体に関する。 The present invention relates to a vinyl aromatic hydrocarbon polymer, a polymer composition and a molded product.
一般的にビニル芳香族炭化水素系重合体は、ラジカル重合法、及びアニオン重合法によって製造されている。 Generally, a vinyl aromatic hydrocarbon polymer is produced by a radical polymerization method and an anionic polymerization method.
ラジカル重合法によるビニル芳香族炭化水素重合体の製造では、製造時に副生物としてビニル芳香族炭化水素のオリゴマーが生成されることや、ビニル芳香族炭化水素が単量体のまま残存し易いことがよく知られている。例えば、非特許文献１によれば１００℃以上のスチレンの熱重合ではスチレン二量体、スチレン三量体等のオリゴマーの副生を伴い、その量は約１質量％程度になるとされている。また具体的なオリゴマー成分は主として１−フェニル−４−（１’−フェニルエチル）テトラリン、１，２−ジフェニルシクロブタンからなり、その他に２，４−ジフェニル−１−ブテンと２，４，６−トリフェニル−１−ヘキセンが存在するとされている。 In the production of a vinyl aromatic hydrocarbon polymer by a radical polymerization method, an oligomer of a vinyl aromatic hydrocarbon is produced as a by-product during production, and the vinyl aromatic hydrocarbon tends to remain as a monomer. well known. For example, according to Non-Patent Document 1, thermal polymerization of styrene at 100° C. or higher is accompanied by by-production of oligomers such as styrene dimer and styrene trimer, and the amount thereof is about 1 mass %. Further, the specific oligomer component is mainly composed of 1-phenyl-4-(1'-phenylethyl)tetralin and 1,2-diphenylcyclobutane, and in addition, 2,4-diphenyl-1-butene and 2,4,6- Triphenyl-1-hexene is said to be present.
この様に、現在広く実施されているラジカル重合法によるビニル芳香族炭化水素系重合体は、その製造方法に起因してビニル芳香族炭化水素単量体及びビニル芳香族炭化水素オリゴマー等から成る低分子量体を多く含む。更に、ラジカル重合法によるビニル芳香族炭化水素系重合体は、一般に安定性に劣り、成形加工時の機械的履歴又は熱的履歴によって、重合体中のビニル芳香族炭化水素単量体及びビニル芳香族炭化水素オリゴマー等の低分子量体が増大しやすい。成形加工時に新たに生成する低分子量体も、重合時に生成する低分子量体と同様の問題を来す。例えば電気製品材料、雑貨材料、食品包装材料や食品容器材料に用いた場合、重合体中に含まれる低分子量体が原因となって種々の問題を来すため低減が望まれている。 As described above, the vinyl aromatic hydrocarbon-based polymer by the radical polymerization method which is widely used at present has a low content of a vinyl aromatic hydrocarbon monomer and a vinyl aromatic hydrocarbon oligomer due to its production method. Contains a large amount of molecular weight substances. Furthermore, vinyl aromatic hydrocarbon-based polymers produced by radical polymerization generally have poor stability, and the vinyl aromatic hydrocarbon monomer and vinyl aromatic hydrocarbon in the polymer may be affected by mechanical or thermal history during molding. Low molecular weight substances such as group hydrocarbon oligomers are likely to increase. The low molecular weight substance newly formed during the molding process has the same problem as the low molecular weight substance generated during the polymerization. For example, when it is used as an electric appliance material, a miscellaneous material, a food packaging material or a food container material, various problems arise due to the low molecular weight polymer contained in the polymer, and therefore reduction is desired.
一方、ビニル芳香族炭化水素重合体は、有機リチウムを用いたアニオン重合法によって製造されることも広く知られている。特許文献１には、アニオン重合法によるポリスチレンの製造において、二量体含有量が１ｐｐｍ、三量体含有量が１７０ｐｐｍであることが記載されており、ラジカル重合法によるビニル芳香族炭化水素重合体の製造よりも副生物である低分子量体の生成が少ないことが知られている。 On the other hand, it is also widely known that the vinyl aromatic hydrocarbon polymer is produced by an anionic polymerization method using organic lithium. Patent Document 1 describes that in the production of polystyrene by the anionic polymerization method, the dimer content is 1 ppm and the trimer content is 170 ppm, and a vinyl aromatic hydrocarbon polymer by the radical polymerization method. It is known that the production of low molecular weight by-products is less than that of the production of
しかし、アニオン重合法で得られるビニル芳香族炭化水素系重合体は狭い分子量分布を示し、成形、加工性が劣り、通常は好ましいものではない。 However, the vinyl aromatic hydrocarbon-based polymer obtained by the anionic polymerization method shows a narrow molecular weight distribution and is inferior in moldability and processability, and is usually not preferable.
また、大気中の水分や、単量中や溶媒中に含まれる水分の影響により重合開始剤が失活するためアニオン重合法により数平均分子量が５０万以上の高分子量重合体を安定的に製造することは困難だと考えられていた。 Further, since the polymerization initiator is deactivated due to the influence of moisture in the atmosphere or moisture contained in the solvent or in the solvent, a high-molecular weight polymer having a number average molecular weight of 500,000 or more is stably produced by the anionic polymerization method. Was thought to be difficult to do.
アニオン重合法で得られるビニル芳香族炭化水素系重合体の分子量分布拡大の一つの方策として、アルコール等の添加により、反応性末端を部分失活する技術や、重合開始剤の分割フィード、例えば二段分割フィードの技術が挙げられ、両者とも、結果的に分子量の高い重合体と分子量の低い重合体のブレンド組成として、分子量分布を拡大できる。しかし、この様な方法でもいくつかの問題がある。例えば、得られる重合体は低分子量体を多量に含む組成の重合体となり、この様な重合体は力学特性や耐熱性に劣る等の問題がある。また、製造工程が複雑化して生産性が低下する等の問題も有する。 As one measure for expanding the molecular weight distribution of a vinyl aromatic hydrocarbon polymer obtained by an anionic polymerization method, there is a technique of partially deactivating the reactive terminal by adding an alcohol or the like, or a divided feed of a polymerization initiator, for example, A technique of stage-divided feed can be mentioned, and as a result, the molecular weight distribution can be expanded as a blend composition of a polymer having a high molecular weight and a polymer having a low molecular weight. However, even this method has some problems. For example, the obtained polymer is a polymer having a composition containing a large amount of low molecular weight substances, and such a polymer has problems such as poor mechanical properties and heat resistance. There is also a problem that the manufacturing process is complicated and the productivity is lowered.
分子量分布を拡大する他の方策として、重合終了後にカップリング剤を添加して、分子量分布の拡大を図る方法が公知である。即ち、予めやや分子量の低い重合体を重合し、それをカップリングして分子量を部分的にジャンプさせ、分子量分布を拡大する方法である。例えば、特許文献２には、二つのリビング末端を有するリビングポリマーの混合物を、少なくとも３つの反応性官能基を有するカップリング剤でカップリングすることにより、高分子量体の重合体を製造する方法が記載されている。 As another measure for expanding the molecular weight distribution, a method is known in which a coupling agent is added after the completion of polymerization to expand the molecular weight distribution. That is, it is a method of preliminarily polymerizing a polymer having a slightly low molecular weight and coupling it to partially jump the molecular weight to expand the molecular weight distribution. For example, Patent Document 2 discloses a method for producing a polymer having a high molecular weight by coupling a mixture of living polymers having two living ends with a coupling agent having at least three reactive functional groups. Have been described.
成形加工性を改善するために、高分子量体の分子量分布の拡大を達成するためには、３官能性以上の多官能性カップリング剤の使用が必要と考えられてきたが、この様な方法で分子量分布が拡大した場合、重合体は特異的な流動性を示して、シート押出し性や発泡特性において通常好ましくなく、成形、加工性に問題があった。 It has been considered necessary to use a trifunctional or higher-functional polyfunctional coupling agent in order to improve the molding processability and achieve the broadening of the molecular weight distribution of the high molecular weight compound. When the molecular weight distribution is widened, the polymer shows a specific fluidity, which is usually unfavorable in sheet extrudability and foaming property, and there is a problem in molding and processability.
本発明は、上記問題と実状に鑑み、低分子量体が低減され、拡大された分子量分布を有するビニル芳香族炭化水素系重合体、重合体組成物及び成形体を提供することを目的とする。 The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide a vinyl aromatic hydrocarbon-based polymer, a polymer composition, and a molded product having a reduced low molecular weight product and an expanded molecular weight distribution.
本発明者は、様々な重合法を検討した結果、二官能性重合開始剤を用いてアニオン重合体を作製し、さらに二官能性カップリング剤を用いてアニオン重合体をカップリングさせることにより、ビニル芳香族炭化水素系重合体中の低分子量体が低減され、拡大された分子量分布を有するビニル芳香族炭化水素系重合体となることを見出し、本発明を完成するに至った。 The present inventor, as a result of examining various polymerization methods, to produce an anionic polymer using a bifunctional polymerization initiator, by further coupling the anionic polymer using a bifunctional coupling agent, The inventors have found that the low molecular weight polymer in the vinyl aromatic hydrocarbon-based polymer is reduced, resulting in a vinyl aromatic hydrocarbon-based polymer having an expanded molecular weight distribution, and completed the present invention.
上記課題を解決する本発明は、以下より構成される。
（１）二官能性重合開始剤を主成分とする重合開始剤によりビニル芳香族炭化水素を含有する単量体がアニオン重合したアニオン重合体Ａ１と、二官能性カップリング剤により前記アニオン重合体Ａ１がカップリングしたアニオン重合体Ａ２とを含有するビニル芳香族炭化水素系重合体であって、
ゲル・パーミネーション・クロマトグラフィー法により測定され、ポリスチレン換算で求められる数平均分子量曲線において、アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対し、
前記アニオン重合体Ａ２に由来する面積比率が４０％以上であり、
数平均分子量が５０万以上の重合体の面積比率が１５％以上である、重合体。
（２）前記二官能性重合開始剤の含有量が前記重合開始剤の総和に対し、６０〜１００ｍｏｌ％である、（１）に記載の重合体。
（３）前記二官能性重合開始剤が、有機リチウム化合物とジビニル芳香族化合物との反応物である、（１）または（２）に記載の重合体。
（４）前記二官能性カップリング剤が、ジエポキシ化合物である（１）〜（３）の何れか一つに記載の重合体。
（５）前記単量体がさらに共役ジエンを含む、（１）〜（４）の何れか一つに記載の重合体。
（６）前記二官能性カップリング剤の添加量が、前記アニオン重合体Ａ１に対し７０〜１５０ｍｏｌ％である、（１）〜（５）の何れか一つに記載の重合体。
（７）ゲル・パーミネーション・クロマトグラフィー法により測定され、ポリスチレン換算で求められる数平均分子量曲線において、アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対し、前記アニオン重合体Ａ２に由来する面積が５０％以上である、（１）〜（６）の何れか一つに記載の重合体。
（８）（１）〜（７）の何れか一つに記載の重合体を含む重合体組成物。
（９）（８）に記載の重合体組成物を用いた成形体。
The present invention for solving the above-mentioned problems is configured as follows.
(1) Anionic polymer A1 in which a monomer containing a vinyl aromatic hydrocarbon is anionically polymerized by a polymerization initiator containing a bifunctional polymerization initiator as a main component, and the anionic polymer A1 is polymerized by a bifunctional coupling agent. A vinyl aromatic hydrocarbon-based polymer containing A1 and a coupled anionic polymer A2,
In the number average molecular weight curve measured by gel permeation chromatography and determined in terms of polystyrene, with respect to the total area of the anionic polymer A1 and the anionic polymer A2,
The area ratio derived from the anionic polymer A2 is 40% or more,
A polymer in which the area ratio of a polymer having a number average molecular weight of 500,000 or more is 15% or more.
(2) The polymer according to (1), wherein the content of the bifunctional polymerization initiator is 60 to 100 mol% based on the total amount of the polymerization initiators.
(3) The polymer as described in (1) or (2), wherein the bifunctional polymerization initiator is a reaction product of an organic lithium compound and a divinyl aromatic compound.
(4) The polymer as described in any one of (1) to (3), wherein the bifunctional coupling agent is a diepoxy compound.
(5) The polymer as described in any one of (1) to (4), wherein the monomer further contains a conjugated diene.
(6) The polymer according to any one of (1) to (5), wherein the amount of the bifunctional coupling agent added is 70 to 150 mol% with respect to the anionic polymer A1.
(7) Derived from the anionic polymer A2 with respect to the total area of the anionic polymer A1 and the anionic polymer A2 in the number average molecular weight curve measured by gel permeation chromatography and determined in terms of polystyrene. The polymer according to any one of (1) to (6), which has an area of 50% or more.
(8) A polymer composition containing the polymer according to any one of (1) to (7).
(9) A molded product using the polymer composition according to (8).
本発明によれば、低分子量体が低減され、拡大された分子量分布を有するビニル芳香族炭化水素系重合体、重合体組成物及び成形体を提供することができる。 According to the present invention, it is possible to provide a vinyl aromatic hydrocarbon-based polymer, a polymer composition, and a molded product in which low molecular weight substances are reduced and which has an expanded molecular weight distribution.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
［第一実施形態］
本発明に係る第一実施形態のビニル芳香族炭化水素系重合体は、二官能性重合開始剤を主成分とする重合開始剤によりビニル芳香族炭化水素を含有する単量体がアニオン重合したアニオン重合体Ａ１と、二官能性カップリング剤により前記アニオン重合体Ａ１がカップリングしたアニオン重合体Ａ２とを含有し、ゲル・パーミネーション・クロマトグラフィー法により測定され、ポリスチレン換算で求められる数平均分子量曲線において、アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対し、前記アニオン重合体Ａ２に由来する面積が４０％以上であり、数平均分子量が５０万以上の重合体の面積が１５％以上であるビニル芳香族炭化水素系重合体である。
[First embodiment]
The vinyl aromatic hydrocarbon-based polymer of the first embodiment according to the present invention is an anion in which a monomer containing a vinyl aromatic hydrocarbon is anionically polymerized by a polymerization initiator having a bifunctional polymerization initiator as a main component. The polymer A1 and the anionic polymer A2 in which the anionic polymer A1 is coupled with a bifunctional coupling agent are contained, and the number average molecular weight determined by gel permeation chromatography and determined in terms of polystyrene In the curve, the area derived from the anionic polymer A2 is 40% or more and the area of the polymer having a number average molecular weight of 500,000 or more is 15% with respect to the total area of the anionic polymer A1 and the anionic polymer A2. The above is a vinyl aromatic hydrocarbon polymer.
＜ビニル芳香族炭化水素系重合体＞
ビニル芳香族炭化水素系重合体は、二官能性重合開始剤を主成分とする重合開始剤によりビニル芳香族炭化水素を含有する単量体がアニオン重合したアニオン重合体Ａ１と、二官能性カップリング剤により前記アニオン重合体Ａ１がカップリングしたアニオン重合体Ａ２とを含有する。
<Vinyl aromatic hydrocarbon polymer>
The vinyl aromatic hydrocarbon-based polymer includes an anionic polymer A1 in which a monomer containing a vinyl aromatic hydrocarbon is anionically polymerized by a polymerization initiator containing a bifunctional polymerization initiator as a main component, and a bifunctional cup. It contains an anionic polymer A2 in which the anionic polymer A1 is coupled by a ring agent.
＜アニオン重合体Ａ１＞
アニオン重合体Ａ１は、ビニル芳香族炭化水素を含有する単量体が、二官能性アニオン重合開始剤を主成分とするアニオン重合開始剤によりアニオン重合した重合体である。
<Anionic polymer A1>
The anionic polymer A1 is a polymer in which a monomer containing a vinyl aromatic hydrocarbon is anionically polymerized with an anionic polymerization initiator containing a bifunctional anionic polymerization initiator as a main component.
本発明のアニオン重合体Ａ１の数平均分子量は７万〜２３万であり、８万〜２０万がより好ましい。数平均分子量を７万以上とすることで、アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対する５０万以上の面積比率が１５％より少なくなることを抑制して、成形性等の改善効果を維持することができる。一方、数平均分子量を２３万以下とすることで、数平均分子量が５０万以上の面積比率が多く低分子量成分が少ない場合に生じる場合がある押出時のメルトフラクチャーの発生を抑制して、外観を良好に保つことができる。 The number average molecular weight of the anionic polymer A1 of the present invention is 70,000 to 230,000, and more preferably 80,000 to 200,000. By setting the number average molecular weight to 70,000 or more, the area ratio of 500,000 or more to the total area of the anionic polymer A1 and the anionic polymer A2 is suppressed from being less than 15%, and the effect of improving the moldability and the like is suppressed. Can be maintained. On the other hand, by setting the number average molecular weight to 230,000 or less, it is possible to suppress the occurrence of melt fracture at the time of extrusion that may occur when the number ratio of the number average molecular weight is 500,000 or more and the low molecular weight component is small, so that the appearance Can be kept good.
（単量体）
本発明において用いられる単量体は、ビニル芳香族炭化水素を含有する。単独で用いてもよく、アニオン重合可能な他の単量体を添加して共重合させてもよい。
(Monomer)
The monomer used in the present invention contains a vinyl aromatic hydrocarbon. They may be used alone or may be copolymerized by adding another anionically polymerizable monomer.
ビニル芳香族炭化水素としては、スチレン、ｏ−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、２，４−ジメチルスチレン、２，５−ジメチルスチレン、３，４−ジメチルスチレン、α−メチルスチレン、ビニルナフタレン、ビニルアントラセン等が含まれるが、特に一般的なものとしてはスチレンが挙げられる。 Examples of vinyl aromatic hydrocarbons are styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene and α-. Methylstyrene, vinylnaphthalene, vinylanthracene and the like are included, but styrene is particularly common.
アニオン重合可能な他の単量体としては、共役ジエンが挙げられる。共役ジエンには１，３−ブタジエン、２−メチル−１，３−ブタジエン（イソプレン）、２，３−ジメチル−１，３ブタジエン、１，３−ペンタジエン、１，３−ヘキサジエン等が含まれるが、特に一般的なものとしては１，３−ブタジエン、イソプレンが挙げられる。 Examples of other anionically polymerizable monomers include conjugated dienes. Conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3 butadiene, 1,3-pentadiene and 1,3-hexadiene. 1,3-Butadiene and isoprene are particularly common.
（アニオン重合開始剤）
本発明において用いられるアニオン重合開始剤は、二官能性アニオン重合開始剤を主成分とする。ここで、単官能性とは一つの重合部位を有することを意味し、二官能性とは二つの重合部位を有することを意味する。つまり、二官能性アニオン重合開始剤とは二つの重合部位を有する開始剤を意味する。本発明では、アニオン重合開始剤として二官能性アニオン重合開始剤を単独で用いてもよく、単官能性アニオン重合開始剤と併用してもよい。しかしながら、単官能性アニオン重合開始剤は重合部位を一つしか有さないため、単官能性アニオン重合体により重合した重合体の片末端では、カップリングが起こらない。したがって、二官能性アニオン重合開始剤と単官能性アニオン重合開始剤とを併用する場合、二官能性アニオン重合開始剤の含有量が少ないと、単官能性アニオン重合開始剤により重合した重合体の割合が増加することで、直鎖状にポリマーが３本以上カップリングする重合体の割合が減少し、結果としてアニオン重合体Ａ２の割合が減少する。本発明において、二官能性アニオン重合開始剤は重合開始剤の総和に対し、６０ｍｏｌ％以上含まれることが好ましく、７０ｍｏｌ％以上含まれることがより好ましい。上限値は特に限定されず、１００ｍｏｌ％以下、９８ｍｏｌ％以下又は９５ｍｏｌ％以下とすることができる。
(Anionic polymerization initiator)
The anionic polymerization initiator used in the present invention contains a bifunctional anionic polymerization initiator as a main component. Here, monofunctional means having one polymerization site, and difunctional means having two polymerization sites. That is, the bifunctional anionic polymerization initiator means an initiator having two polymerization sites. In the present invention, the bifunctional anionic polymerization initiator may be used alone as the anionic polymerization initiator, or may be used in combination with the monofunctional anionic polymerization initiator. However, since the monofunctional anionic polymerization initiator has only one polymerization site, coupling does not occur at one end of the polymer polymerized by the monofunctional anionic polymer. Therefore, when the bifunctional anionic polymerization initiator and the monofunctional anionic polymerization initiator are used in combination, when the content of the bifunctional anionic polymerization initiator is low, the polymer polymerized by the monofunctional anionic polymerization initiator is By increasing the proportion, the proportion of the polymer in which three or more polymers are linearly coupled decreases, and as a result, the proportion of the anionic polymer A2 decreases. In the present invention, the bifunctional anionic polymerization initiator is contained in an amount of preferably 60 mol% or more, more preferably 70 mol% or more, based on the total amount of the polymerization initiators. The upper limit is not particularly limited and can be 100 mol% or less, 98 mol% or less, or 95 mol% or less.
二官能性アニオン重合開始剤としては、分子中に２個のリチウム原子が結合した有機リチウム化合物が挙げられ、例えば、１，３−イソプロペニルベンゼンにｔ−ブチルリチウムを付加させた化合物や、１，３−ジ（１−フェニルエテニル）ベンゼンにｓｅｃ−ブチルリチウムを付加させた化合物等が使用できる。このように、二官能性アニオン重合開始剤は、ジビニル芳香族化合物と有機リチウム化合物を反応させることにより調製できる。 Examples of the bifunctional anionic polymerization initiator include organolithium compounds having two lithium atoms bonded in the molecule. For example, a compound obtained by adding t-butyllithium to 1,3-isopropenylbenzene or 1 A compound obtained by adding sec-butyllithium to 3,3-di(1-phenylethenyl)benzene can be used. Thus, the bifunctional anionic polymerization initiator can be prepared by reacting the divinyl aromatic compound and the organolithium compound.
二官能性アニオン重合開始剤の調製方法の具体例としては、炭化水素溶媒中で、有機リチウム化合物とジビニル芳香族化合物とを反応させる方法、有機リチウム化合物と共役ジエン化合物とを反応させた後にジビニル芳香族化合物を反応させる方法、有機リチウム化合物とモノビニル芳香族化合物とを反応させた後にジビニル芳香族化合物を反応させる方法、共役ジエン化合物及び／又はモノビニル芳香族化合物と、ジビニル芳香族化合物との二者又は三者の存在下で有機リチウム化合物を反応させる方法等が挙げられる。特に、炭化水素溶媒中で、有機リチウム化合物とジビニル芳香族化合物とを反応させる方法で調製された二官能アニオン開始剤が好ましい。 Specific examples of the method for preparing the bifunctional anion polymerization initiator include a method of reacting an organolithium compound and a divinyl aromatic compound in a hydrocarbon solvent, and a method of reacting an organolithium compound and a conjugated diene compound with divinyl. A method of reacting an aromatic compound, a method of reacting an organolithium compound with a monovinyl aromatic compound and then a divinyl aromatic compound, a method of reacting a conjugated diene compound and/or a monovinyl aromatic compound with a divinyl aromatic compound. And a method of reacting an organolithium compound in the presence of the three parties. In particular, a bifunctional anion initiator prepared by a method of reacting an organic lithium compound and a divinyl aromatic compound in a hydrocarbon solvent is preferable.
単官能性アニオン重合開始剤は、分子中に１個以上のリチウム原子が結合した化合物であり、例えばエチルリチウム、ｎ−プロピルリチウム、イソプロピルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウムのような化合物等が使用できる。 The monofunctional anionic polymerization initiator is a compound in which one or more lithium atoms are bonded in the molecule, and examples thereof include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl. A compound such as lithium can be used.
アニオン重合開始剤の合計添加量は、本発明の重合体が得られれば制約されず、モノマーの総和１ｍｏｌ％に対し、０．９×１０−４〜９．５×１０−３ｍｏｌ％であることが好ましく、１．１×１０−３〜５．０×１０−３ｍｏｌ％であることがより好ましい。重合開始剤の添加量をこの範囲に調整することで、数平均分子量を本発明の範囲に調整し易くなる。 The total addition amount of the anionic polymerization initiator is not limited as long as the polymer of the present invention is obtained, and is 0.9×10 −4 to 9.5×10 −3 mol% based on 1 mol% of the total amount of the monomers. It is preferably 1.1×10 −3 to 5.0×10 −3 mol %. By adjusting the addition amount of the polymerization initiator within this range, it becomes easy to adjust the number average molecular weight within the range of the present invention.
＜アニオン重合体Ａ２＞
アニオン重合体Ａ２は、二官能性カップリング剤によりアニオン重合体Ａ１がカップリングした重合体である。
<Anionic polymer A2>
The anionic polymer A2 is a polymer obtained by coupling the anionic polymer A1 with a bifunctional coupling agent.
本発明のアニオン重合体Ａ２の数平均分子量は１４万〜４０万が好ましく、２５万〜３５万がより好ましい。数平均分子量が１４万以上とすることで、成形性を良好に維持することができる。一方、数平均分子量が４０万以下とすることで、低分子量成分が少ない場合に生じる場合がある押出時のメルトフラクチャーの発生を抑制し、外観を良好に保つことができる。 The number average molecular weight of the anionic polymer A2 of the present invention is preferably 140,000 to 400,000, more preferably 250,000 to 350,000. By setting the number average molecular weight to 140,000 or more, good moldability can be maintained. On the other hand, by setting the number average molecular weight to 400,000 or less, it is possible to suppress the occurrence of melt fracture at the time of extrusion which may occur when the low molecular weight component is small, and maintain a good appearance.
（二官能性カップリング剤）
二官能性カップリング剤の添加量は、アニオン重合体Ａ１のモル数に対して７０〜１５０ｍｏｌ％とすることができる。７０ｍｏｌ％以上とすることで、カップリングしない重合体が多くなることを防いで、アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対するアニオン重合体Ａ２に由来する面積Ｓ２の面積比率が少なくなるのを抑制できる。また、１５０ｍｏｌ％以下とすることで、アニオン重合末端にカップリング剤がそれぞれ導入されることを防いで、アニオン重合体Ａ２に由来する面積Ｓ２の面積比率が少なくなるのを抑制できる。
(Bifunctional coupling agent)
The addition amount of the bifunctional coupling agent can be 70 to 150 mol% with respect to the number of moles of the anionic polymer A1. By setting the content to 70 mol% or more, it is possible to prevent an increase in the amount of uncoupling polymer and reduce the area ratio of the area S2 derived from the anionic polymer A2 to the total area of the anionic polymer A1 and the anionic polymer A2. Can be suppressed. Further, when the content is 150 mol% or less, it is possible to prevent the coupling agent from being introduced into each terminal of the anionic polymerization and suppress the reduction of the area ratio of the area S2 derived from the anionic polymer A2.
二官能性カップリング剤は公知のものから選ぶことができるが、例えばジハロゲン化合物、ジエポキシ化合物、ジカルボン酸エステル、珪素またはスズのジアルコキシ化合物、珪素またはスズのジハロゲン化合物、等を挙げることができる。中でもジエポキシ化合物が好ましい。ジエポキシ類の例としては、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル等のグリコールジグリシジルエーテル類；グリセリンジグリシジルエーテル；水添ビスフェノールＡジグリシジルエーテル等の脂環式系ジグリシジルエーテル類；グリシジルフェニルエーテル、ビスフェノールＡポリエチレンオキシド付加物ジグリシジルエーテル等の芳香族系ジグリシジルエーテル類、１，７−オクタジエンジエポキシド、１，５−ヘキサジエンジエポキシド、リモネンジエポキシド等が挙げられる。 The bifunctional coupling agent can be selected from known ones, and examples thereof include a dihalogen compound, a diepoxy compound, a dicarboxylic acid ester, a dialkoxy compound of silicon or tin, a dihalogen compound of silicon or tin, and the like. Of these, diepoxy compounds are preferred. Examples of diepoxys, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Glycol diglycidyl ethers such as 1,6-hexanediol diglycidyl ether; glycerin diglycidyl ether; alicyclic diglycidyl ethers such as hydrogenated bisphenol A diglycidyl ether; glycidyl phenyl ether, bisphenol A polyethylene oxide adduct Examples thereof include aromatic diglycidyl ethers such as diglycidyl ether, 1,7-octadiene diepoxide, 1,5-hexadiene diepoxide and limonene diepoxide.
本発明のビニル芳香族炭化水素系重合体は、ゲル・パーミネーション・クロマトグラフィー法により測定され、ポリスチレン換算で求められる数平均分子量曲線において、アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対し、前記アニオン重合体Ａ２に由来する面積が４０％以上であり、数平均分子量が５０万以上の重合体の面積が１５％以上である。 The vinyl aromatic hydrocarbon-based polymer of the present invention has a number average molecular weight curve measured by gel permeation chromatography and determined in terms of polystyrene, and shows the total area of the anionic polymer A1 and the anionic polymer A2. On the other hand, the area derived from the anionic polymer A2 is 40% or more, and the area of the polymer having a number average molecular weight of 500,000 or more is 15% or more.
［ゲルパーミエーションクロマトグラフィー（ＧＰＣ）］
重合体の濃度が１ｍｇ／１ｍＬのテトラヒドロフラン（ＴＨＦ）溶液を調製し、ＧＰＣ測定装置において、４０℃のヒートチャンバ中でカラムを安定化させ、この温度におけるカラムに溶媒としてＴＨＦを毎分１ｍＬの流速で流し、ＴＨＦ試料溶液を約１００μＬ注入することで重合体の分子量分布を測定することができる。
[Gel permeation chromatography (GPC)]
A tetrahydrofuran (THF) solution having a polymer concentration of 1 mg/1 mL was prepared, and the column was stabilized in a heat chamber at 40° C. in a GPC measuring device, and THF was used as a solvent for the column at this temperature at a flow rate of 1 mL per minute. Then, the molecular weight distribution of the polymer can be measured by injecting about 100 μL of the THF sample solution.
ＧＰＣを用いて、重合体の分子量分布の測定を行う場合、溶出体積（溶出速度×溶出時間）が増大するにしたがって、検出器を通過する溶離液中の重合体の分子量の対数が単調に減少する。すなわち分子量が大きいほど、カラムからの溶出が早い。また信号強度は、検出器を通過する溶離液中における重合体の存在量に比例する。標準ポリスチレンを用いて溶出時間と分子量との関係を表す較正曲線を作成することにより、示差屈折率計によって検出される溶出曲線を、縦軸に信号強度、横軸にポリスチレン換算の分子量の対数を持った曲線（以下、分子量曲線と呼ぶ）に変換することができる。検量線作成用の標準ポリスチレン試料としては、東ソー社製の分子量が１０２〜１０７程度のものを用いる。例えば、ベースラインの数値から０．２以上の数値を示す時間をピークの始点とし、最少の分子量を示すピークの後のベースラインの数値から０．２以上の数値を示す時間をピークの終点とすることができる。 When measuring the molecular weight distribution of a polymer using GPC, the logarithm of the molecular weight of the polymer in the eluent passing through the detector monotonically decreases as the elution volume (elution rate x elution time) increases. To do. That is, the higher the molecular weight, the faster the elution from the column. The signal intensity is also proportional to the amount of polymer present in the eluent passing through the detector. By creating a calibration curve that shows the relationship between elution time and molecular weight using standard polystyrene, the elution curve detected by the differential refractometer is plotted, the vertical axis represents the signal intensity, and the horizontal axis represents the logarithm of polystyrene-equivalent molecular weight. It can be converted into a curve (hereinafter, referred to as a molecular weight curve). As the standard polystyrene sample for preparing the calibration curve, a molecular weight of about 10 2 to 10 7 manufactured by Tosoh Corporation is used. For example, the time at which the numerical value of the baseline is 0.2 or more is the start point of the peak, and the time at which the numerical value of the baseline after the peak showing the minimum molecular weight is 0.2 or more is the end point of the peak. can do.
分子量曲線を微分することで、アニオン重合体Ａ２由来の極大値及び極小値と、アニオン重合体Ａ１由来の極大値及び極小値を得ることができる。アニオン重合体Ａ１由来の極大値が０以上の場合は、アニオン重合体Ａ２由来の極小値からアニオン重合体Ａ１由来の極大値の間にある０を示す点に対応する分子量曲線の点から垂直にベースラインに下した線で分割し、分子量曲線から得られる高分子側の面積をＳ２、低分子側の面積をＳ１とする。アニオン重合体Ａ１由来の極大値が０未満の場合は、アニオン重合体Ａ１由来の極大値を示す点に対応する分子量曲線の点から垂直にベースラインに下した線で分割し、高分子側の面積をＳ２、低分子側の面積をＳ１とする（図１及び図２）。 By differentiating the molecular weight curve, the maximum value and the minimum value derived from the anion polymer A2 and the maximum value and the minimum value derived from the anion polymer A1 can be obtained. When the maximum value derived from the anionic polymer A1 is 0 or more, it is perpendicular to the point of the molecular weight curve corresponding to the point showing 0 between the minimum value derived from the anionic polymer A2 and the maximum value derived from the anionic polymer A1. The area on the polymer side obtained from the molecular weight curve is divided into S2 and the area on the low molecule side is divided into S1 by dividing the line by the line drawn to the baseline. When the maximum value derived from the anionic polymer A1 is less than 0, it is divided by a line perpendicular to the baseline from the point of the molecular weight curve corresponding to the point showing the maximum value derived from the anionic polymer A1, The area is S2, and the area on the low molecular side is S1 (FIGS. 1 and 2).
アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対し、前記アニオン重合体Ａ２に由来する面積が４０％以上であるとは、以下の式Ｉを満たすことを意味する。
（式Ｉ）
Ｓ２／（Ｓ１＋Ｓ２）≧０．４
That the area derived from the anionic polymer A2 is 40% or more with respect to the total area of the anionic polymer A1 and the anionic polymer A2 means that the following formula I is satisfied.
(Formula I)
S2/(S1+S2)≧0.4
アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対するアニオン重合体Ａ２に由来する面積は、５０％以上又は６０％以上とすることもできる。上限値は特に限定されず、９０％以下、８０％以下又は７０％以下とすることができる。 The area derived from the anionic polymer A2 with respect to the total area of the anionic polymer A1 and the anionic polymer A2 can be 50% or more or 60% or more. The upper limit is not particularly limited and can be 90% or less, 80% or less, or 70% or less.
分子量曲線の始点から５０万を示す分子量までの総面積を、数平均分子量が５０万以上の重合体の面積とした。アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対し、数平均分子量が５０万以上の重合体の面積が１５％以上であるとは、以下の式ＩＩを満たすことを意味する。
（式ＩＩ）
５０万以上の重合体の面積／（Ｓ１＋Ｓ２）≧０．１５
The total area from the starting point of the molecular weight curve to the molecular weight showing 500,000 was defined as the area of the polymer having a number average molecular weight of 500,000 or more. That the area of the polymer having a number average molecular weight of 500,000 or more is 15% or more with respect to the total area of the anionic polymer A1 and the anionic polymer A2 means that the following formula II is satisfied.
(Formula II)
Area of polymer of 500,000 or more/(S1+S2)≧0.15
ＧＰＣから得られる分子量曲線中において、数平均分子量が５０万以上の重合体の面積比率を１５％以上に調節することによって、重合体組成物を成形した際、厚み斑が改善される。数平均分子量が５０万以上の重合体の面積は、２０％以上、３０％以上又は４０％以上とすることもできる。一方、数平均分子量が５０万以上の重合体の面積比率を８０％以下とすることで、反応溶液の粘度が高くなることにより低濃度でしか生産できなくなり生産性が低下することを抑制することができる。数平均分子量が５０万以上の重合体の面積比率は、８０％以下、７０％以下又は６０％以下とすることもできる。 By adjusting the area ratio of the polymer having a number average molecular weight of 500,000 or more in the molecular weight curve obtained from GPC to 15% or more, uneven thickness can be improved when the polymer composition is molded. The area of the polymer having a number average molecular weight of 500,000 or more can be 20% or more, 30% or more, or 40% or more. On the other hand, by controlling the area ratio of the polymer having a number average molecular weight of 500,000 or more to 80% or less, it is possible to prevent the productivity from being lowered because the viscosity of the reaction solution is increased and the reaction solution can be produced only at a low concentration. You can The area ratio of the polymer having a number average molecular weight of 500,000 or more can be 80% or less, 70% or less, or 60% or less.
得られた重合体は、水、アルコール、二酸化炭素などの重合停止剤を、活性末端を不活性化させるのに充分な量を添加することにより、不活性化される。得られた重合体溶液より重合体を回収する方法としては、メタノール等の貧溶媒により析出させる方法、加熱ロール等により溶媒を蒸発させて析出させる方法（ドラムドライヤー法）、濃縮器により溶媒を濃縮した後にベント式押出機で溶媒を除去する方法、溶液を水に分散させ、水蒸気を吹き込んで溶媒を加熱除去して共重合体を回収する方法（スチームストリッピング法）等、任意の方法が使用される。 The obtained polymer is inactivated by adding a polymerization terminator such as water, alcohol or carbon dioxide in an amount sufficient to inactivate the active terminal. As a method of recovering the polymer from the obtained polymer solution, a method of precipitating with a poor solvent such as methanol, a method of evaporating and precipitating the solvent with a heating roll or the like (drum dryer method), and a method of concentrating the solvent with a concentrator After that, any method can be used, such as a method of removing the solvent with a vented extruder, a method of dispersing the solution in water and blowing steam to remove the solvent by heating to recover the copolymer (steam stripping method). To be done.
（ランダム化剤）
本発明の重合体の製造において、ランダム化剤を添加することもできる。ランダム化剤の添加量としては、重合体を構成するモノマーの総和１００質量部に対し、０．００１〜８質量部が好ましい。添加時期は重合反応の開始前でも良い。また、必要に応じて追加添加することもできる。ランダム化剤を前記の添加量で添加することにより、重合速度を改善することができる。ランダム化剤としては、テトラヒドロフラン、テトラメチルエチレンジアミンなどが使用できる。
(Randomizing agent)
A randomizing agent may be added in the production of the polymer of the present invention. The addition amount of the randomizing agent is preferably 0.001 to 8 parts by mass with respect to 100 parts by mass as the total of the monomers constituting the polymer. It may be added before the start of the polymerization reaction. In addition, it can be added additionally as required. The polymerization rate can be improved by adding the randomizing agent in the above-mentioned addition amount. Tetrahydrofuran, tetramethylethylenediamine or the like can be used as the randomizing agent.
（有機溶媒）
本発明の重合体を製造する際の有機溶剤としてはブタン、ペンタン、ヘキサン、イソペンタン、ヘプタン、オクタン、イソオクタン等の脂肪族炭化水素、シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環式炭化水素、あるいは、ベンゼン、トルエン、エチルベンゼン、キシレン等の芳香族炭化水素などが使用できる。
(Organic solvent)
Examples of the organic solvent when producing the polymer of the present invention include butane, pentane, hexane, isopentane, heptane, octane, aliphatic hydrocarbons such as isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like. Alicyclic hydrocarbons or aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used.
［第二実施形態］
本発明に係る第二実施形態のビニル芳香族炭化水素系重合体は、加工の容易さを付与したり、強度の向上のために、予め重合された第二のビニル芳香族炭化水素系重合体や添加剤等を押出機で溶融ブレンドしたり、ペレット状態でドライブレンドして、重合体組成物として用いることもできる。
[Second embodiment]
The vinyl aromatic hydrocarbon-based polymer of the second embodiment according to the present invention is a second vinyl aromatic hydrocarbon-based polymer pre-polymerized for imparting processability and improving strength. It is also possible to melt-blend the additives, additives and the like with an extruder or dry-blend them in a pellet state to use as a polymer composition.
（第二のビニル芳香族炭化水素重合体）
第二のビニル芳香族炭化水素系重合体としては、流動性の改良のための汎用ポリスチレン重合体や強度向上のためのゴム質を含有する耐衝撃性ポリスチレン重合体、メタクリル酸メチル−ブタジエン−スチレン（ＭＢＳ）重合体等のゴム強化芳香族ビニル系重合体やスチレン−ブタジエン−スチレン（ＳＢＳ）等の芳香族ビニル系熱可塑性エラストマーが挙げられる。
(Second vinyl aromatic hydrocarbon polymer)
The second vinyl aromatic hydrocarbon-based polymer includes a general-purpose polystyrene polymer for improving fluidity and an impact-resistant polystyrene polymer containing rubber for improving strength, methyl methacrylate-butadiene-styrene. Examples thereof include rubber-reinforced aromatic vinyl-based polymers such as (MBS) polymers and aromatic vinyl-based thermoplastic elastomers such as styrene-butadiene-styrene (SBS).
（添加剤）
添加剤としては、安定剤、滑剤、顔料等が挙げられ、本発明の効果を阻害しない範囲で配合することができる。
(Additive)
Examples of the additives include stabilizers, lubricants, pigments and the like, and the additives can be added within a range that does not impair the effects of the present invention.
安定剤としては、２，６−ジ−ｔ−ブチル−４−メチルフェノール、２−ｔ−ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート、２−［１−（２−ヒドロキシ−３，５−ジ−ｔ−ペンチルフェニル）−エチル］−４，６−ジ−ペンチルフェニルアクリレート、ｎ−オクタデシル−３−（４’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）プロピオネート等のフェノール系酸化防止剤、２，２−メチレンビル（４，６−ジ−ｔ−ブチルフェニル）オクチルフォスファイト、トリスノニルフェニルフォスファイト等の燐系酸化防止剤等が挙げられる。 As the stabilizer, 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate , 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)-ethyl]-4,6-di-pentylphenyl acrylate, n-octadecyl-3-(4'-hydroxy-3'. ,5'-di-t-butylphenyl)propionate and other phenolic antioxidants, 2,2-methylenebiyl(4,6-di-t-butylphenyl)octyl phosphite, trisnonylphenyl phosphite and other phosphorus Examples include system antioxidants and the like.
（滑剤）
滑剤としては、メチルフェニルポリシロキサン、脂肪酸、脂肪酸グリセリンエステル、脂肪酸アマイド、炭化水素系ワックス等が挙げられる。
(Lubricant)
Examples of the lubricant include methylphenyl polysiloxane, fatty acid, fatty acid glycerin ester, fatty acid amide, hydrocarbon wax and the like.
（顔料）
顔料としては、酸化チタン、カーボンブラック等が挙げられる。
(Pigment)
Examples of the pigment include titanium oxide and carbon black.
［第三実施形態］
本発明の重合体組成物は、公知の成形方法により、成形体として用いることができる。具体的な成形方法としては射出成形、押出し成形、中空成形、シートあるいはフィルム成形等が挙げられる。本発明の重合体組成物をシート化したあと、一般的な真空成形、圧空成形やこれらの応用として、シートの片面にプラグを接触させて成形を行うプラグアシスト法、又、シートの両面に一対をなす雄雌型を接触させて成形を行う、いわゆるマッチモールド成形と称される方法等が挙げられるが、これに限定されるものではない。また成形前にシートを加熱軟化させる方法として非接触加熱である赤外線ヒーター等による輻射加熱等、公知のシート加熱方法を適応することができる。また、各種発泡成形技術と組み合わせて、発泡成型体を成型することもできる。
[Third embodiment]
The polymer composition of the present invention can be used as a molded product by a known molding method. Specific molding methods include injection molding, extrusion molding, hollow molding, sheet or film molding and the like. After forming the polymer composition of the present invention into a sheet, general vacuum forming, pressure forming, and the application thereof include a plug assist method in which a plug is brought into contact with one side of the sheet to form a sheet, and a pair of sheets are formed on both sides of the sheet. Examples of the method include so-called match mold forming, in which the male and female molds forming the above are brought into contact with each other, but the present invention is not limited thereto. As a method of heating and softening the sheet before molding, a known sheet heating method such as radiant heating using an infrared heater which is non-contact heating can be applied. Further, it is also possible to mold a foam molded body by combining with various foam molding techniques.
本発明の成形体は、その特長、即ち加熱時の剛性、耐熱性、印刷性、成型性、透明性を生かす各種の成形品用途に用いることができる。例えば電気製品材料、雑貨材料、玩具材料、住宅の発泡断熱材、食品容器材料、食品包装材料等のスチレン系重合体の使用が公知の各種用途に好ましく用いることができる。ビニル芳香族炭化水素の単量体、ビニル芳香族炭化水素の低分子量体の含有量が少ないことを生かして、食品と直接接触するような食品容器、食品包装用途に特に好ましく使用できる。例えば各種の食品包装、食品容器、また発泡成形して発泡食品容器、発泡食品包装を好ましく成形できる。 The molded product of the present invention can be used for various molded product applications that take advantage of its features, namely rigidity upon heating, heat resistance, printability, moldability, and transparency. For example, the use of styrene polymers such as electric appliance materials, miscellaneous goods materials, toy materials, foam insulation materials for houses, food container materials, food packaging materials and the like can be preferably used for various known applications. Due to the low content of vinyl aromatic hydrocarbon monomers and low-molecular weight vinyl aromatic hydrocarbons, it can be particularly preferably used for food containers and food packaging that are in direct contact with foods. For example, various food packages, food containers, and foamed food containers and foamed food packages can be preferably molded by foam molding.
食品容器、包装の具体例としては、例えば射出成形、射出中空成形あるいはシート状に二軸延伸加工する等して得られる乳酸飲料容器、プリン容器、ゼリー容器、醤油さし等の食品容器、発泡成形して得られる食品トレー、インスタント麺のどんぶり、弁当箱、飲料、カップ等の食品容器、あるいはシートあるいはフィルム成形して得られる青果物包装、水産物包装等の食品包装が挙げられる。 Specific examples of food containers and packaging include, for example, injection molding, injection hollow molding, lactic acid beverage containers obtained by biaxially stretching into a sheet, pudding containers, jelly containers, soy sauce bottles and other food containers, foaming. Examples include food trays such as molded food trays, instant noodle bowls, lunch boxes, beverages, and food containers such as cups, and food packages such as fruit and vegetable packaging and seafood packaging obtained by molding sheets or films.
以上、本発明の低分子量体が低減され、拡大された分子量分布を有するビニル芳香族炭化水素系重合体、重合体組成物及び成形体について説明したが、これらは本発明の一実施形態であり、本発明はこれらに限定されるものではない。 As described above, the low molecular weight product of the present invention is reduced, and the vinyl aromatic hydrocarbon polymer, the polymer composition and the molded product having an expanded molecular weight distribution have been described, but these are one embodiment of the present invention. However, the present invention is not limited to these.
以下に、実施例に基づいて、本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
実施例等で用いた各種原料は以下の通りである。 Various raw materials used in Examples and the like are as follows.
（１）単量体
市販のスチレンモノマーをビニル芳香族炭化水素の単量体として使用した。
市販のブタジエンモノマーを購入し、共役ジエンの単量体として使用した。
（２）アニオン重合開始剤
二官能性重合開始剤「１，３−Ｂｉｓ−［９−ｌｉｔｈｉｏ−１，４，８−ｔｒｉｍｅｔｈｙｌ−１−（２−ｍｅｔｈｙｌ−ｂｕｔｙｌ）−ｎｏｎａ−３，７−ｄｉｅｎｙｌ］−ｂｅｎｚｅｎｅ」（０．１４ｍｍｏｌ／ｍＬシクロヘキサン溶液、ロックウッドリチウム社製）を購入し、使用した。以下Ｂｉｓ−Ｌｉ−ＤＩＰＢと示す。
単官能性重合開始剤として、ｎ−ブチルリチウム（１０質量％シクロヘキサン溶液、（ロックウッドリチウム）社製）を使用した。
（３）二官能性カップリング剤
二官能性カップリング剤として、１，６−ヘキサンジオールジグリシジルエーテル「ＥＸ−２１２Ｌ」（ナガセケムテックス社製）及び１，７−オクタジエンジエポキシド（東京化成社製）を使用した。
(1) Monomer A commercially available styrene monomer was used as a monomer of vinyl aromatic hydrocarbon.
A commercially available butadiene monomer was purchased and used as a monomer of the conjugated diene.
(2) Anionic polymerization initiator Bifunctional polymerization initiator "1,3-Bis-[9-lithio-1,4,8-trimethyl-1-(2-methyl-butyl)-nona-3,7-dienyl]. ]-Benzene" (0.14 mmol/mL cyclohexane solution, manufactured by Rockwood Lithium Co., Ltd.) was purchased and used. Hereinafter referred to as Bis-Li-DIPB.
N-Butyllithium (10 mass% cyclohexane solution, manufactured by (Rockwood lithium)) was used as a monofunctional polymerization initiator.
(3) Bifunctional coupling agent As a bifunctional coupling agent, 1,6-hexanediol diglycidyl ether "EX-212L" (manufactured by Nagase Chemtex) and 1,7-octadiene diepoxide (Tokyo Kasei). Manufactured by the company) was used.
実施例等で作製したビニル芳香族炭化水素系重合体の数平均分子量及び分子量分布は以下の通りに測定した。
ＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用いて標準ポリスチレン換算の数平均分子量を求めた。重合体を１ｍｇ／ｍＬの濃度でＴＨＦに溶解させ、ＴＨＦを溶媒とし、送液速度０．１ｍＬ／ｍｉｎ、カラムはＴＳＫ−ＧＥＬ ＭｕｌｔｉｐｏｒｅＨＸＬ-Ｍ φ７．８×３００ｍｍ（東ソ−社製）を２本直列に繋いで用いた。ディテクターは示差屈折率計を用いた。
データ処理はシステムインスツルメンツ社製のＳＩＣ４８０データステーションを用い処理を行い、数平均分子量を算出した。
The number average molecular weight and molecular weight distribution of the vinyl aromatic hydrocarbon polymer produced in Examples and the like were measured as follows.
The number average molecular weight in terms of standard polystyrene was determined using GPC (gel permeation chromatography). The polymer was dissolved in THF at a concentration of 1 mg/mL, THF was used as a solvent, the liquid feed rate was 0.1 mL/min, and the column was TSK-GEL Multipore HXL-M φ7.8×300 mm (manufactured by Toso Corporation). It was used by connecting in series. A differential refractometer was used as a detector.
Data processing was performed using a SIC480 data station manufactured by System Instruments, and the number average molecular weight was calculated.
［実施例１］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、２５０ｇのスチレンモノマーを添加し攪拌を行いながら、内温５０℃で８．９ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、１．３×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに０．３７１ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Example 1]
1170 g of cyclohexane was charged into the reaction vessel. Next, while adding 250 g of styrene monomer and stirring, 8.9 mL of Bis-Li-DIPB was added and polymerized at an internal temperature of 50° C. (1.3×10 −3 mol% based on the total amount of monomers). Polymerization initiator). After sampling 10 mL of the polymerization liquid, 0.371 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added, and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［実施例２］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、２５０ｇのスチレンモノマーを添加し攪拌を行いながら内温５０℃で０．４ｍＬのｎ−ブチルリチウム（１０質量％シクロヘキサン溶液）と１３．４ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、２．１×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに０．９９０ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Example 2]
1170 g of cyclohexane was charged into the reaction vessel. Next, 250 g of a styrene monomer was added, and 0.4 mL of n-butyllithium (10% by mass cyclohexane solution) and 13.4 mL of Bis-Li-DIPB were added and polymerized at an internal temperature of 50° C. while stirring (( 2.1×10 −3 mol% of polymerization initiator based on the total amount of monomers). After 10 mL of the polymerization liquid was sampled, 0.990 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［実施例３］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。内温８０℃で２２．９ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加した。総量３５０ｇのスチレンモノマーと総量５０ｇのブタジエンモノマーをそれぞれ４６６ｇ／ｈ、６６ｇ／ｈの一定添加速度で両者を同時に添加し、ビニル芳香族炭化水素と共役ジエンのランダム共重合体を重合させた（モノマーの総和に対し、６．７×１０−４ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに０．８２１ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Example 3]
1170 g of cyclohexane was charged into the reaction vessel. At an internal temperature of 80° C., 22.9 mL of Bis-Li-DIPB was added. A total of 350 g of styrene monomer and a total of 50 g of butadiene monomer were simultaneously added at a constant addition rate of 466 g/h and 66 g/h, respectively, to polymerize a random copolymer of vinyl aromatic hydrocarbon and conjugated diene (monomer Of 6.7×10 −4 mol% of the polymerization initiator). After sampling 10 mL of the polymerization liquid, 0.821 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added, and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［実施例４］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、１３０ｇのスチレンモノマーを添加し攪拌を行いながら内温５０℃で７．８ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、２．１×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに０．１３４ｇの１，７−オクタジエンジエポキシドに溶解させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Example 4]
1170 g of cyclohexane was charged into the reaction vessel. Next, 130 g of a styrene monomer was added, and 7.8 mL of Bis-Li-DIPB was added and polymerized at an internal temperature of 50° C. with stirring (2.1×10 −3 mol% of the total amount of the monomers). Polymerization initiator). After 10 mL of the polymerization liquid was sampled, 0.134 g of 1,7-octadiene diepoxide was dissolved in 30 mL of dehydrated cyclohexane, added and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［実施例５］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、２５０ｇのスチレンモノマーを添加し攪拌を行いながら、内温５０℃で０．４ｍＬのｎ−ブチルリチウム（１０質量％シクロヘキサン溶液）と１３．４ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、２．１×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに０．４９５ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Example 5]
1170 g of cyclohexane was charged into the reaction vessel. Next, while adding 250 g of styrene monomer and stirring, 0.4 mL of n-butyllithium (10 mass% cyclohexane solution) and 13.4 mL of Bis-Li-DIPB were added and polymerized at an internal temperature of 50°C. (2.1×10 −3 mol% of polymerization initiator based on the total amount of monomers). After sampling 10 mL of the polymerization liquid, 0.495 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［比較例１］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、２５０ｇのスチレンモノマーを添加し攪拌を行いながら、内温５０℃で０．４ｍＬのｎ−ブチルリチウム（１０質量％シクロヘキサン溶液）と１３．４ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、２．１×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに０．２８９ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Comparative Example 1]
1170 g of cyclohexane was charged into the reaction vessel. Next, while adding 250 g of styrene monomer and stirring, 0.4 mL of n-butyllithium (10 mass% cyclohexane solution) and 13.4 mL of Bis-Li-DIPB were added and polymerized at an internal temperature of 50°C. (2.1×10 −3 mol% of polymerization initiator based on the total amount of monomers). After sampling 10 mL of the polymerization liquid, 0.289 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［比較例２］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、２５０ｇのスチレンモノマーを添加し攪拌を行いながら、内温５０℃で０．４ｍＬのｎ−ブチルリチウム（１０質量％シクロヘキサン溶液）と１３．４ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、２．３×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに０．３７１ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Comparative example 2]
1170 g of cyclohexane was charged into the reaction vessel. Next, while adding 250 g of styrene monomer and stirring, 0.4 mL of n-butyllithium (10 mass% cyclohexane solution) and 13.4 mL of Bis-Li-DIPB were added and polymerized at an internal temperature of 50°C. (2.3×10 −3 mol% of polymerization initiator based on the total amount of monomers). After sampling 10 mL of the polymerization liquid, 0.371 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added, and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［比較例３］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、２５０ｇのスチレンモノマーを添加し攪拌を行いながら、内温５０℃で２４．６ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、３．５×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに１．７１０ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Comparative Example 3]
1170 g of cyclohexane was charged into the reaction vessel. Next, while adding 250 g of styrene monomer and stirring, 24.6 mL of Bis-Li-DIPB was added and polymerized at an internal temperature of 50° C. (3.5×10 −3 mol% based on the total amount of monomers). Polymerization initiator). After 10 mL of the polymerization liquid was sampled, 1.710 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［比較例４］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、２５０ｇのスチレンモノマーを添加し攪拌を行いながら、内温５０℃で１．４ｍＬのｎ−ブチルリチウム（１０質量％シクロヘキサン溶液）と８．１ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、１．８×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに０．６１１ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Comparative Example 4]
1170 g of cyclohexane was charged into the reaction vessel. Next, while adding 250 g of styrene monomer and stirring, 1.4 mL of n-butyllithium (10 mass% cyclohexane solution) and 8.1 mL of Bis-Li-DIPB were added and polymerized at an internal temperature of 50°C. (1.8×10 −3 mol% of polymerization initiator based on the total amount of monomers). After sampling 10 mL of the polymerization liquid, 0.611 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added, and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
［比較例５］
反応容器中に１１７０ｇのシクロヘキサンを仕込んだ。次いで、２５０ｇのスチレンモノマーを添加し攪拌を行いながら、内温５０℃で１３．８ｍＬのＢｉｓ−Ｌｉ−ＤＩＰＢを添加し重合させた（モノマーの総和に対し、２．２×１０−３ｍｏｌ％の重合開始剤）。重合液を１０ｍＬサンプリングした後、３０ｍＬの脱水シクロヘキサンに１．８５ｇの１，６−ヘキサンジオールジグリシジルエーテルを分散させ、添加しカップリングさせた。ＧＰＣによりカップリング前後の重合体の分子量測定を実施した。
[Comparative Example 5]
1170 g of cyclohexane was charged into the reaction vessel. Next, while adding 250 g of styrene monomer and stirring, 13.8 mL of Bis-Li-DIPB was added and polymerized at an internal temperature of 50° C. (2.2×10 −3 mol% based on the total amount of monomers). Polymerization initiator). After 10 mL of the polymerization liquid was sampled, 1.85 g of 1,6-hexanediol diglycidyl ether was dispersed in 30 mL of dehydrated cyclohexane, added and coupled. The molecular weight of the polymer before and after coupling was measured by GPC.
実施例等で作製したビニル芳香族炭化水素系重合体のアニオン重合体Ａ１のモル数／カップリング剤のモル数、カップリング前の数平均分子量、カップリング後の数平均分子量、カップリング後の分子量分布（重量平均分子量／数平均分子量）、数平均分子量が５０万以上の重合体の面積比率、アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対するアニオン重合体Ａ２の面積比率、使用されたモノマーを表１に記載する。 Number of moles of anionic polymer A1 of vinyl aromatic hydrocarbon-based polymer/number of moles of coupling agent, number average molecular weight before coupling, number average molecular weight after coupling, after coupling, and after coupling Molecular weight distribution (weight average molecular weight/number average molecular weight), area ratio of polymers having a number average molecular weight of 500,000 or more, area ratio of anionic polymer A2 to total area of anionic polymer A1 and anionic polymer A2, used The monomers are listed in Table 1.
前記実施例１〜５、比較例１〜５で得られた重合液をメタノールに添加することにより、重合体を析出させ、回収し、乾燥した。 Polymers were precipitated by adding the polymerization solutions obtained in Examples 1 to 5 and Comparative Examples 1 to 5 to methanol, recovered, and dried.
実施例１〜５、比較例１〜５の重合体３０質量％と耐衝撃性ポリスチレン（Ｅ６４０ 東洋スチレン社製）７０質量％をそれぞれドライブレンドした後、ラボプラストミルμ（東洋精機社製）を使用し、回転数１５ｒｐｍ、ダイス温度２１０℃でペレット化を行った。 After 30% by mass of the polymers of Examples 1 to 5 and Comparative Examples 1 to 5 and 70% by mass of high-impact polystyrene (E640 Toyo Styrene Co., Ltd.) were dry-blended, Labo Plastomill μ (Toyo Seiki Co., Ltd.) was used. It was used and pelletized at a rotation speed of 15 rpm and a die temperature of 210°C.
＜一軸伸長粘度の測定＞
［伸長粘度の傾き：Ｓ］を算出するための一軸伸長粘度の測定は以下の機器及び条件で測定した。得られたペレットを２００℃で溶融させ直径１ｍｍの円柱状にしたものを用いた。
測定機器：東洋精機製作所社製 マイスナー型 メルテンレオメータ
使用オイル：東レ・ダウ コーニングシリコーン株式会社製 ＳＲＸ３１０
測定条件：一定歪速度伸長 歪み速度０．１［ｓｅｃ−１］
測定温度：１４０℃
<Measurement of uniaxial extensional viscosity>
The uniaxial extensional viscosity for calculating [Slope of extensional viscosity: S] was measured by the following equipment and conditions. The obtained pellets were melted at 200° C. and formed into a cylindrical shape having a diameter of 1 mm.
Measuring instrument: Toyo Seiki Seisakusho's Meissner type melten rheometer Oil used: Toray Dow Corning Silicone SRX310
Measurement conditions: constant strain rate extension strain rate 0.1 [sec-1]
Measurement temperature: 140℃
一軸伸長粘度の測定結果は、横軸を測定開始からの伸長時間［ｓｅｃ］、縦軸を一軸伸長粘度η［Ｐａ・ｓｅｃ］の常用対数（ＬＯＧ）値としてプロットした。そして、伸長開始後７．０ｓｅｃのときと、１４．０ｓｅｃのときの一軸伸長粘度をそれぞれη７．０及びη１４．０とし、２点間の傾きＳを以下の式ＩＩＩに従い算出し、表１に「伸長粘度の傾き：Ｓ」として示した。
（式ＩＩＩ）
Ｓ＝（ＬＯＧη１４．０−ＬＯＧη７．０）／（１４．０−７．０）
この傾きが大きいということは、フィルムの延伸に大きな力を要することを表し、その結果シートが過膨張しづらくなり成形体の肉厚が均一になりやすいことを意味する。表１に示されるように、本発明の重合体組成物の伸長粘土の傾きは、０．０４８以上が好ましく、０．０５以上がより好ましい。
The measurement result of the uniaxial extensional viscosity was plotted by plotting the horizontal axis as the extension time [sec] from the start of the measurement and the vertical axis as the common logarithm (LOG) value of the uniaxial extensional viscosity η [Pa·sec]. Then, the uniaxial elongation viscosities at 7.0 seconds and 14.0 seconds after the start of elongation are respectively η 7.0 and η 14.0, and the slope S between the two points is calculated according to the following formula III, It was shown as "Slope of extensional viscosity: S" in Table 1.
(Formula III)
S=(LOG η 14.0 −LOG η 7.0 )/(14.0-7.0)
The large inclination means that a large force is required for stretching the film, and as a result, the sheet is less likely to be overexpanded and the thickness of the molded body tends to be uniform. As shown in Table 1, the slope of the extended clay of the polymer composition of the present invention is preferably 0.048 or more, more preferably 0.05 or more.
＜偏肉性の評価＞
ペレット化した重合体は加熱プレス法（温度２００℃、時間３分間、圧力５０ｋｇ／ｃｍ２）により成形し、厚さ１．０ｍｍ、３００ｍｍ角のシ−トを得た。
<Evaluation of uneven thickness>
The pelletized polymer was molded by a hot pressing method (temperature 200° C., time 3 minutes, pressure 50 kg/cm 2 ) to obtain a sheet having a thickness of 1.0 mm and 300 mm square.
得られたシートを、真空成形機（（株）浅野研究所ＦＫ−０４３１−１０）を用いて開口部直径６５ｍｍ、底部直径４０ｍｍ、高さ８０ｍｍのコップに成形した。 The obtained sheet was formed into a cup having an opening diameter of 65 mm, a bottom diameter of 40 mm, and a height of 80 mm by using a vacuum forming machine (FK-0431-10, Asano Laboratory Co., Ltd.).
成形したコップを縦に半分に切断し、１０ｍｍ間隔で１７か所の肉厚を測定した。成形品の偏肉性については、成形品開口部より１０ｍｍ底部側の箇所の肉厚を基準肉厚として、それに対する最少肉厚で評価した。
良：最少肉厚/基準肉厚≧０．７０
可：０．７０＞最少肉厚/基準肉厚≧０．５０
不可：０．５０＞最少肉厚/基準肉厚、もしくはシートの破裂
The molded cup was cut in half lengthwise, and the wall thickness was measured at 17 places at 10 mm intervals. The uneven thickness of the molded product was evaluated with the minimum thickness relative to the standard thickness, which is 10 mm from the opening of the molded product.
Good: Minimum wall thickness/standard wall thickness ≧ 0.70
Acceptable: 0.70> minimum wall thickness/standard wall thickness ≧ 0.50
Impossible: 0.50> minimum wall thickness/standard wall thickness or sheet rupture
表１に示されるように、本発明の重合体を含有する重合体組成物を用いて成形される成形体は、肉厚が均一な成形体であることが分かる。 As shown in Table 1, it can be seen that the molded product molded using the polymer composition containing the polymer of the present invention is a molded product having a uniform wall thickness.
Claims (9)
ゲル・パーミネーション・クロマトグラフィー法により測定され、ポリスチレン換算で求められる分子量曲線において、アニオン重合体Ａ１とアニオン重合体Ａ２との総面積に対し、
前記アニオン重合体Ａ２に由来する面積が４０％以上であり、
分子量が５０万以上の重合体の面積が１５％以上である、重合体。 An anionic polymer A1 in which a monomer containing a vinyl aromatic hydrocarbon is anionically polymerized by a polymerization initiator containing a bifunctional polymerization initiator as a main component, and the anionic polymer A1 is cupped by a bifunctional coupling agent. A vinyl aromatic hydrocarbon-based polymer containing a ring anionic polymer A2,
As measured by gel permeation chromatography method, in the molecular weight curve obtained in terms of polystyrene, relative to the total area of the anionic polymer A1 and an anionic polymer A2,
The area derived from the anionic polymer A2 is 40% or more,
Area of molecular weight of 500,000 or more polymers is 15% or more, the polymer.
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