JP2018172582A - Cyclic olefin based resin composition and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclic olefin based resin composition capable of achieving a molding excellent even in impact resistance while satisfying transparency required for the molding.SOLUTION: The cyclic olefin based resin composition comprises [A] a cyclic olefin based resin having a specified structure and a softening point temperature (TMA) of 50°C or more and less than 120°C and [B] an aromatic vinyl based polymer. The component [A] of 50-90 pts.mass and the component [B] of 10-50 pts.mass (the total content of the cyclic olefin based resin and the aromatic vinyl-base polymer is 100 pts.mass) are included.SELECTED DRAWING: None

Description

  The present invention relates to a cyclic olefin resin composition and a molded product thereof.

  Cyclic olefin random copolymers obtained by copolymerizing ethylene and cyclic olefins are excellent in transparency, water vapor permeability, gas barrier properties, heat aging resistance, chemical resistance, solvent resistance, rigidity, etc. Although it is known that the balance is good, it is brittle and inferior in impact resistance, and improvement in impact strength is desired for molded products such as injection molding, extrusion molding, and blow molding.

  Patent Document 1 (Japanese Patent Laid-Open No. 1-256548) and Patent Document 2 (Japanese Patent Laid-Open No. 2007-154074) disclose techniques relating to a composition using such a cyclic olefin-based resin composition. Those described are mentioned.

  Patent Document 1 describes a resin composition comprising a specific cyclic olefin resin and an aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydrogenated product thereof.

  Patent Document 2 describes a resin composition comprising a specific cyclic olefin resin and an aromatic vinyl / conjugated diene copolymer or a hydrogenated product thereof.

JP-A-1-256548 JP 2007-154074 A

Here, the cyclic olefin-based resin is excellent in transparency, water vapor permeability, and gas permeability, for example, as a molded body such as a film or sheet, but has insufficient impact properties, and the molding method and application range are limited. It had been.
According to the study by the present inventors, the film / sheet using the cyclic olefin-based resin composition as described in Patent Documents 1 and 2 is excellent in impact properties but the balance between transparency and impact properties. It has become clear that there is room for improvement in terms of improvement.

  The present invention has been made in view of the above circumstances, and provides a cyclic olefin-based resin composition capable of realizing a molded article having more excellent impact properties while satisfying the transparency required for a molded article such as a film or a sheet. To do.

  As a result of intensive investigations on application to various molded products while maintaining the above-described characteristics of a resin comprising a cyclic olefin-based random copolymer (hereinafter referred to as “cyclic olefin-based resin”), the present inventors have softened. By combining an aromatic vinyl polymer with a cyclic olefin resin having a temperature of 50 ° C. or more and less than 120 ° C., the impact property is further improved while maintaining the transparency of the cyclic olefin resin, The present invention has been completed.

  That is, according to the present invention, the following cyclic olefin-based resin composition and molded article are provided.

（上記式［Ｉ］中、ｎは０または１であり、ｍは０または正の整数であり、ｑは０または１であり、Ｒ^１〜Ｒ^１８ならびにＲ^ａおよびＲ^ｂは、それぞれ独立に、水素原子、ハロゲン原子またはハロゲンで置換されていてもよい炭化水素基であり、Ｒ^１５〜Ｒ^１８は互いに結合して単環または多環を形成していてもよく、かつ、該単環または多環は二重結合を有していてもよく、またＲ^１５とＲ^１６とで、またはＲ^１７とＲ^１８とで、アルキリデン基を形成していてもよい。）、

（上記式［ＩＩ］中、ｐおよびｑは０または正の整数であり、ｍおよびｎは０，１または２であり、Ｒ^１〜Ｒ^１９はそれぞれ独立に水素原子、ハロゲン原子、ハロゲン原子で置換されていてもよい炭化水素基またはアルコキシ基であり、Ｒ^９またはＲ^１０が結合している炭素原子と、Ｒ^１３が結合している炭素原子またはＲ１１が結合している炭素原子とは直接あるいは炭素数１〜３のアルキレン基を介して結合していてもよく、またｎ＝ｍ＝０のときＲ^１５とＲ^１２またはＲ^１５とＲ^１９とは互いに結合して単環または多環の芳香族環を形成していてもよい。）、
［Ａ−２］上記式［Ｉ］または［ＩＩ］で示される環状オレフィンの開環重合体または共重合体、
［Ａ−３］上記開環重合体または共重合体［Ａ−２］の水素化物、
［Ａ−４］上記［Ａ−１］、［Ａ−２］または［Ａ−３］のグラフト変成物。
［２］
上記［１］に記載の環状オレフィン系樹脂組成物において、
以下の要件（１）および（２）をすべて満たすことを特徴とする環状オレフィン系樹脂組成物。
（１）２ｍｍ厚の射出成形シートのヘイズ値が３０％以下である
（２）２３℃で測定した高速面衝撃試験（ＨＲＩＴ）の最大衝撃点エネルギーが２０Ｊ以上である
［３］
上記［１］または［２］に記載の環状オレフィン系樹脂組成物からなり、フィルム、シート、ブロー成形体、射出成形体から選ばれる成形体。 [1]
[A] (1) Contains at least one selected from the following [A-1], [A-2], [A-3] and [A-4], and has a softening point temperature (TMA) of 50. A cyclic olefin-based resin that is not lower than 120 ° C. and
[B] an aromatic vinyl polymer,
The component [A] is contained in an amount of 50 to 90 parts by mass, and the component [B] is contained in an amount of 10 to 50 parts by mass (the total amount of the cyclic olefin resin and the aromatic vinyl polymer is 100 parts by mass). A cyclic olefin-based resin composition characterized by:
[A-1] A random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II];

(In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently , A hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or The polycycle may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group).

(In the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom or a halogen atom. An optionally substituted hydrocarbon or alkoxy group, the carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R 11 is bonded are directly Alternatively, they may be bonded via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic ring. An aromatic ring may be formed).
[A-2] A ring-opening polymer or copolymer of a cyclic olefin represented by the above formula [I] or [II],
[A-3] a hydride of the above ring-opening polymer or copolymer [A-2],
[A-4] A graft modified product of the above [A-1], [A-2] or [A-3].
[2]
In the cyclic olefin-based resin composition according to the above [1],
A cyclic olefin-based resin composition characterized by satisfying all of the following requirements (1) and (2).
(1) The haze value of a 2 mm-thick injection molded sheet is 30% or less. (2) The maximum impact point energy of a high-speed surface impact test (HRIT) measured at 23 ° C. is 20 J or more [3]
A molded article comprising the cyclic olefin-based resin composition according to the above [1] or [2] and selected from a film, a sheet, a blow molded article and an injection molded article.

  ADVANTAGE OF THE INVENTION According to this invention, the cyclic olefin resin composition which can implement | achieve the molded object which was excellent also in impact property, satisfying the transparency calculated | required by a molded object can be provided.

  Hereinafter, the present invention will be described based on embodiments. In the present embodiment, “A to B” indicating a numerical range represents A or more and B or less unless otherwise specified.

[Cyclic olefin resin composition (P)]
First, the cyclic olefin resin composition (P) according to this embodiment will be described.
The cyclic olefin-based resin composition (P) according to the present embodiment is a cyclic olefin-based resin composition used for obtaining a molded article, and will be described later [A-1], [A-2], [A- 3] and [A-4], a cyclic olefin resin (A) having a softening point temperature (TMA) of 50 ° C. or more and less than 120 ° C., and an aromatic vinyl polymer (B). And when the total of the cyclic olefin resin and the aromatic vinyl polymer contained in the cyclic olefin resin composition (P) is 100 parts by mass, the content of the cyclic olefin resin (A) is 50 parts by mass or more. 90 parts by mass or less, preferably 60 parts by mass or more and 90 parts by mass or less, more preferably 60 parts by mass or more and 85 parts by mass or less, and the content of the aromatic vinyl polymer (B) is 10 parts by mass or more and 50 parts by mass. Hereinafter, it is preferably 10 parts by mass or more and 40 parts by mass or less, more preferably 15 parts by mass or more and 40 parts by mass or less.

The cyclic olefin-based resin composition (P) according to the present embodiment includes a cyclic olefin-based resin (A) and an aromatic vinyl-based polymer (B) at the above ratio, thereby obtaining a molded body. While satisfying the required transparency, impact properties can be further improved.
Moreover, according to the cyclic olefin-based resin composition (P) according to the present embodiment, it is possible to impart good toughness to the obtained molded body, so that cracking due to impact is less likely to occur, and durability to various processes. It is possible to obtain a molded body that requires properties.
From the above, according to the cyclic olefin-based resin composition (P) according to the present embodiment, it is possible to obtain a molded body having more excellent impact properties while satisfying the transparency required for the molded body.

<Cyclic olefin resin (A)>
The cyclic olefin resin (A) according to the present embodiment contains at least one selected from the following [A-1], [A-2], [A-3] and [A-4].
[A-1] Random copolymer of ethylene and cyclic olefin represented by the following formula [I] or [II] [A-2] Ring opening weight of cyclic olefin represented by the following formula [I] or [II] Copolymer or copolymer [A-3] Hydrogenated product of the above ring-opening polymer or copolymer [A-2] [A-4] [A-1], [A-2] or [A-3] Graft-modified product of the cyclic olefin resin [A-1], [A-2], [A-3] and [A-4] forming the cyclic olefin resin represented by the formula [I] or [II] The olefin will be described.

上記式［Ｉ］中、ｎは０または１であり、ｍは０または正の整数であり、ｑは０または１である。なお、ｑが１の場合には、Ｒ^ａおよびＲ^ｂは、それぞれ独立に、下記の原子または炭化水素基であり、ｑが０の場合には、それぞれの結合手が結合して５員環を形成する。

In the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. In addition, when q is 1, R ^a and R ^b are each independently the following atoms or hydrocarbon groups, and when q is 0, each bond is bonded to form a 5-membered ring. Form.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C3-C15 cycloalkyl group, an aromatic hydrocarbon group etc. are mentioned each independently, for example. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group, and the cycloalkyl group includes a cyclohexyl group. And aromatic hydrocarbon groups include phenyl and naphthyl groups. These hydrocarbon groups may be substituted with a halogen atom.

Furthermore, in the above formula [I], R ^{15 to} R ¹⁸ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed May have a double bond. Specific examples of the monocyclic or polycyclic ring formed here are shown below.

In the above examples, the carbon atom numbered 1 or 2 represents the carbon atom to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded in the above formula [I]. . R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is, for example, an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group, and an isopropylidene group.

上記式［ＩＩ］中、ｐおよびｑは０または正の整数であり、ｍおよびｎは０、１または２である。またＲ^１〜Ｒ^１９はそれぞれ独立に水素原子、ハロゲン原子、炭化水素基またはアルコキシ基である。

In the above formula [II], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

  The halogen atom has the same meaning as the halogen atom in the above formula [I]. The hydrocarbon group is independently, for example, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon. Groups and the like. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group, and the cycloalkyl group includes a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. These hydrocarbon groups and alkoxy groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. It may be connected via. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ or the groups represented by R ¹⁰ and R ¹¹ are combined with each other to form a methylene group (— An alkylene group of any one of CH ₂ —), ethylene group (—CH ₂ CH ₂ —) or propylene group (—CH ₂ CH ₂ CH ₂ —) is formed. Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include the following groups in which R ¹⁵ and R ¹² further form an aromatic ring when n = m = 0.

  Here, q has the same meaning as q in the above formula [II].

  Examples of the cyclic olefin represented by the formula [I] or [II] as described above include:

（上記式中、１〜７の数字は炭素の位置番号を示す。）およびこのビシクロ［２．２．１］−２−ヘプテンに炭化水素基が置換した誘導体等が挙げられる。この炭化水素基としては、例えば、５−メチル、５，６−ジメチル、１−メチル、５−エチル、５−ｎ−ブチル、５−イソブチル、７−メチル、５−フェニル、５−メチル−５−フェニル、５−ベンジル、５−トリル、５−（エチルフェニル）、５−（イソプロピルフェニル）、５−（ビフェニル）、５−（β−ナフチル）、５−（α−ナフチル）、５−（アントラセニル）、５，６−ジフェニル等が挙げられる。

(In the above formula, the numbers 1 to 7 represent the position number of carbon.) And derivatives in which a hydrocarbon group is substituted on this bicyclo [2.2.1] -2-heptene. Examples of the hydrocarbon group include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5. -Phenyl, 5-benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- ( Anthracenyl), 5,6-diphenyl and the like.

  Furthermore, examples of the cyclic olefin represented by the above formula [I] or [II] include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano Bicyclo [2.2.1] -2-heptene derivatives such as -1,4,4a, 5,10,10a-hexahydroanthracene and the like.

Further, examples of the cyclic olefin represented by the above formula [I] or [II] include tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0]. .1 ^2,5] -3-decene, 5-methyl-tricyclo ^[4.3.0.1 2,5] -3-decene such as tricyclo ^[4.3.0.1 2,5] -3 Decyclo derivatives such as tricyclo [4.4.0.1 ^2,5 ] -3-undecene, 10-methyltricyclo [4.4.0.1 ^2,5 ] -3-undecene, etc. 0.1 ^2,5 ] -3-undecene derivative,

(In the above formula, the numbers 1 to 12 indicate the position number of carbon.) And tetracyclo [4.4.0.1 ^2,5 . And a derivative in which a hydrocarbon group is substituted on 1 ^7,10 ] -3-dodecene. As this hydrocarbon group, for example, 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10 -Dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9- Methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8- -Propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8- Benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (Anthracenyl), 5,6-diphenyl and the like.

Furthermore, examples of the cyclic olefin represented by the above formula [I] or [II] include, for example, an adduct of (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13 ] -3-pentadecene and its derivatives, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] 4,10 penta octadecadienoic Penta cyclopentadiene octadecadienoic compounds such as pentacyclo [8.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] -3-hexadecene and derivatives thereof, pentacyclo [6.6.1.1 ^{3, 6.} 0 ^2,7 . 0 ^9,14] -4-hexadecene and derivatives thereof, hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene and its derivatives, heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^{11, 17} . 0 ^3,8 . 0 ^12,16 ] -5-eicosene and its derivatives, heptacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^{11, 18} . 0 ^3,8 . 0 ^12,17 ] -5- ^Heneicosene and derivatives thereof, octacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^{11, 18} . 1 ^13,16 . 0 ^3,8 . 0 ^12,17] -5-docosene and its derivatives, Nonashikuro [10.9.1.1 ^{4, 7.} 1 ^13,20 . 1 ^{15, 18} . 0 ^2,10 . 0 ^3,8 . 0 ^{12, 21} . 0 ^14,19] -5-pentacosene and derivatives thereof, Nonashikuro [10.10.1.1 ^5,8. 1 14, ²¹ . 1 ^{16, 19} . 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20] -6-hexacosenoic and derivatives thereof.

  Specific examples of the cyclic olefin represented by the above formula [I] or [II] are shown above. As a more specific structural example of these compounds, paragraph number [0032] of JP-A-7-145213 is disclosed. ] To [0054], examples of the structure of the cyclic olefin can be given. The cyclic olefin resin (A) according to this embodiment may contain two or more units derived from the cyclic olefin.

  The cyclic olefin represented by the above formula [I] or [II] can be produced, for example, by subjecting cyclopentadiene and an olefin having a corresponding structure to Diels-Alder reaction.

  The cyclic olefin resin (A) according to the present embodiment uses, for example, a cyclic olefin represented by the above formula [I] or [II], for example, JP-A-60-168708, JP-A-61202081, JP 61-115912, JP 61-115916, JP 61-271308, JP 61-272216, JP 62-252406, JP 62-252407 and international publication According to the method described in the gazette of 2008/068888, etc., it can manufacture by selecting conditions suitably, respectively.

([A-1] Random copolymer of ethylene and cyclic olefin)
[A-1] A random copolymer of ethylene and a cyclic olefin represented by the above formula [I] or [II] (hereinafter also referred to as ethylene / cyclic olefin random copolymer [A-1]) is a co-polymer. The content of units derived from ethylene is, for example, 5 mol% or more and 95 mol% or less, preferably 20 mol% or more and 80 mol% or less, when the entire constitutional unit constituting the polymer is 100 mol%, The content of the unit derived from the cyclic olefin is, for example, from 5 mol% to 95 mol%, preferably from 20 mol% to 80 mol%.
The ethylene composition and the cyclic olefin composition can be measured by ¹³ C-NMR.

  The ethylene / cyclic olefin random copolymer [A-1] has a substantially linear structure in which units derived from ethylene and units derived from a cyclic olefin are randomly arranged and bonded. preferable. The fact that this copolymer is substantially linear and does not have a gel-like cross-linked structure means that when this copolymer is dissolved in an organic solvent, this solution contains insoluble matter. It can be confirmed by not. For example, when the intrinsic viscosity [η] is measured, the copolymer can be confirmed by being completely dissolved in decalin at 135 ° C.

  In the ethylene / cyclic olefin random copolymer [A-1], at least a part of the cyclic olefin represented by the formula [I] or [II] constitutes a repeating unit represented by the following formula [III] or [IV]. it seems to do.

上記式［ＩＩＩ］において、ｎ、ｍ、ｑ、Ｒ^１〜Ｒ^１８、Ｒ^ａおよびＲ^ｂは上記式［Ｉ］と同じ意味である。

In the above formula [III], n, m, q, R ^{1 to} R ¹⁸ , R ^a and R ^b have the same meaning as in the above formula [I].

上記式［IＶ］において、ｎ、ｍ、ｐ、ｑおよびＲ^１〜Ｒ^１９は上記式［ＩＩ］と同じ意味である。

In the above formula [IV], n, m, p, q and R ^{1 to} R ¹⁹ have the same meaning as in the above formula [II].

  In addition, the ethylene / cyclic olefin random copolymer [A-1] may have units derived from other copolymerizable monomers as necessary as long as the object of the present invention is not impaired. Specifically, units derived from other monomers may be contained in an amount of usually 20 mol% or less, preferably 10 mol% or less.

Examples of such other monomers include olefins other than ethylene or cyclic olefins as described above, and specifically include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1 -Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl -1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. C3-C20 α-olefin, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, Cycloolefins such as-(2-methylbutyl) -1-cyclohexene, cyclooctene, and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, 1,4-hexadiene, 4-methyl-1 Non-conjugated dienes such as 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2-norbornene.
The ethylene / cyclic olefin random copolymer [A-1] may contain two or more units derived from the other monomers.

  The ethylene / cyclic olefin random copolymer [A-1] can be produced by the production method disclosed in the above publication using ethylene and the cyclic olefin represented by the above formula [I] or [II]. Among these, a copolymerization reaction is performed in a hydrocarbon solvent, and an ethylene / cyclic olefin random copolymer [A-] is used as a catalyst by using a catalyst formed from a vanadium compound soluble in the hydrocarbon solvent and an organoaluminum compound. 1] is preferably produced.

  Moreover, ethylene / cyclic olefin random copolymer [A-1] can also be manufactured using a solid IVA group metallocene catalyst. This solid group IVA metallocene-based catalyst comprises a transition metal compound (metallocene compound) containing a ligand having at least one cyclopentadienyl skeleton, an organoaluminum oxy compound, and, if necessary, an organoaluminum compound. It is formed. Here, the IVA group transition metal is zirconium, titanium, or hafnium. Examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group, which may be substituted with an alkyl group. These groups may be bonded via other groups such as an alkylene group. Examples of the ligand other than the ligand containing a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

  Moreover, what is used for manufacture of an olefin polymer can be used for an organoaluminum oxy compound and an organoaluminum compound, for example. Such solid IVA group metallocene catalysts are described in detail, for example, in JP-A-61-221206, JP-A-64-106 and JP-A-2-173112.

  In addition, the ethylene / cyclic olefin random copolymer [A-1] can also be produced using a phenoxyimine catalyst (FI catalyst) or a pyrrolimine catalyst (PI catalyst). These catalysts include (a) phenoxyimine as described in JP-A No. 2001-72706, JP-A No. 2002-332312, JP-A No. 2003-313247, JP-A No. 2004-107486, and JP-A No. 2004-107563. Alternatively, a transition metal compound having pyrrolimine as a ligand reacts with (b) (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a transition metal compound (a). And at least one compound selected from compounds that form ion pairs. Here, as the transition metal contained in the transition metal compound, a transition metal belonging to Groups 3 to 11 of the periodic table can be used.

([A-2] Ring-opening polymer or copolymer of cyclic olefin)
[A-2] Cyclic olefin ring-opening polymer or copolymer represented by the above formula [I] or [II] (hereinafter also referred to as cyclic olefin ring-opening (co) polymer [A-2]) In the above, at least a part of the units derived from the cyclic olefin represented by the formula [I] or [II] is represented by the following formula [V] or [VI].

上記式［Ｖ］において、ｎ、ｍ、ｑ、Ｒ^１〜Ｒ^１８、Ｒ^ａおよびＲ^ｂは上記式［Ｉ］と同じ意味である。

In the above formula [V], n, m, q, R ^{1 to} R ¹⁸ , R ^a and R ^b have the same meaning as in the above formula [I].

上記式［ＶＩ］において、ｎ、ｍ、ｐ、ｑおよびＲ^１〜Ｒ^１９は上記式［ＩＩ］と同じ意味である。

In the above formula [VI], n, m, p, q and R ^{1 to} R ¹⁹ have the same meaning as in the above formula [II].

  The ring-opening (co) polymer [A-2] of the cyclic olefin can be produced by the production method disclosed in the above publication, for example, the cyclic olefin represented by the above formula [I] is used as a ring-opening polymerization catalyst. It can be produced by polymerization or copolymerization in the presence.

As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, indium and platinum and a reducing agent, or titanium, palladium, zirconium A catalyst comprising a metal halide selected from molybdenum and the like, or an acetylacetone compound and an organoaluminum compound can be used.
The ring-opening (co) polymer [A-2] of cyclic olefin can also be obtained, for example, by the method described in JP-A-7-324108.

([A-3] hydride of cyclic olefin ring-opening (co) polymer [A-2])
Cyclic olefin ring-opening (co) polymer [A-2] hydride (hereinafter also referred to as ring-opening (co) polymer hydride [A-3]) is a cyclic olefin ring-opening (co). The polymer [A-2] can be obtained by hydrogenation in a conventionally known method, for example, in the presence of a hydrogenation catalyst described in JP-A-7-324108.

  In the hydride [A-3] of the ring-opening (co) polymer, at least a part of units derived from the above formula [I] or [II] is considered to be represented by the following formula [VII] or [VIII]. It is done.

上記式［ＶII］において、ｎ、ｍ、ｑ、Ｒ^１〜Ｒ^１８、Ｒ^ａおよびＲ^ｂは上記式［Ｉ］と同じ意味である。

In the above formula [VII], n, m, q, R ^{1 to} R ¹⁸ , R ^a and R ^b have the same meaning as in the above formula [I].

上記式［ＶＩＩＩ］において、ｎ、ｍ、ｐ、ｑおよびＲ^１〜Ｒ^１９は上記式［ＩＩ］と同じ意味である。

In the above formula [VIII], n, m, p, q and R ^{1 to} R ¹⁹ have the same meaning as in the above formula [II].

  As the hydride [A-3] of the ring-opening (co) polymer, for example, Zeonex 1040R, ZF14, ZF16 manufactured by Nippon Zeon Co., Ltd. can be used.

([A-4] Graft modified product)
[A-4] The graft modified product of [A-1], [A-2] or [A-3] (also referred to as graft modified product [A-4]) is an ethylene / cyclic olefin random copolymer. [A-1], a graft modified product of a cyclic olefin ring-opening (co) polymer [A-2] or a ring-opening (co) polymer hydride [A-3].

As the modifier for obtaining the graft modified product [A-4], for example, unsaturated carboxylic acids are used. Specifically, (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, Unsaturated carboxylic acids such as citraconic acid, crotonic acid, isocrotonic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^TM ); derivatives of the above unsaturated carboxylic acids Examples thereof include unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and ester compounds of unsaturated carboxylic acids. Specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, citraconic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like.

Among these modifiers, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic acid anhydrides such as maleic acid, nadic acid and anhydrides of these acids are preferably used. These modifiers may be used alone or in combination of two or more.
The modification rate in the graft modified product [A-4] is usually preferably 10 mol% or less.

  Ethylene / cyclic olefin random copolymer [A-1], cyclic olefin ring-opening (co) polymer [A-2] or ring-opening (co) polymer hydride [A-3], and modifier In order to obtain the graft modified product [A-4] using, conventionally known polymer modification methods can be widely applied. For example, the cyclic olefin random copolymer [A-1], the cyclic olefin ring-opening (co) polymer [A-2] or the ring-opening (co) polymer hydride [A-3] in a molten state A method of graft polymerization (reaction) by adding a modifier; or cyclic olefin random copolymer [A-1], ring-opening (co) polymer of cyclic olefin [A-2], or ring-opening (co) heavy The graft modified product [A-4] can be obtained by a method in which a modifier is added to a solution of the combined hydride [A-3] to cause a graft reaction. Such a grafting reaction is performed at a temperature of 60 to 350 ° C., for example. The grafting reaction can be performed in the presence of a radical initiator such as an organic peroxide and an azo compound.

  Further, the graft-modified product [A-4] having the above-described modification rate includes an unmodified ethylene / cyclic olefin random copolymer [A-1], a cyclic olefin ring-opening (co) polymer [A-2]. Or a hydride of a ring-opening (co) polymer [A-3] and a modifying agent can be directly obtained. Also, ethylene / cyclic olefin random copolymer [A-1], cyclic olefin ring-opening (co) polymer [A-2] or ring-opening (co) polymer hydride [A-3] and modifier A modified product having a high modification rate is prepared in advance by a graft reaction with the unmodified ethylene / cyclic olefin random copolymer [A-1], and the cyclic olefin ring-opening (co) polymer [A]. -2], or a hydride of a ring-opening (co) polymer [A-3] to obtain a desired modification rate.

  In the present embodiment, as the cyclic olefin resin (A), the above-mentioned ethylene / cyclic olefin random copolymer [A-1], cyclic olefin ring-opening (co) polymer [A-2], ring-opening Either a (co) polymer hydride [A-3] or a graft-modified product [A-4] may be used alone, two or more of the same may be used, or a combination thereof may be used. Also good. Among these, as the cyclic olefin resin (A), an ethylene / cyclic olefin random copolymer [A-1] is preferable.

  The degree of crystallinity measured by the X-ray diffraction method of the cyclic olefin resin (A) according to this embodiment is, for example, 0 to 20%, preferably 0 to 2%.

  The softening point temperature (TMA) of the cyclic olefin-based resin (A) according to this embodiment is 50 ° C. or higher from the viewpoint of further improving the heat resistance while maintaining good transparency and impact resistance of the obtained molded product. It is less than 120 ° C, preferably 60 ° C or more and less than 120 ° C, more preferably 60 ° C or more and 110 ° C or less.

  The intrinsic viscosity [η] (in 135 ° C. decalin) of the cyclic olefin resin [A] according to the present embodiment is, for example, 0.05 to 5.0 dl / g, preferably 0.2 to 4.0 dl / g. More preferably, it is 0.3-2.0 dl / g, Most preferably, it is 0.4-1.0 dl / g.

<Aromatic vinyl polymer (B)>
The aromatic vinyl polymer (B) according to this embodiment may be a polymer containing aromatic vinyl or a hydrogenated product thereof, and may be a block copolymer in which an aromatic vinyl block and a conjugated diene block are copolymerized or Examples thereof include a hydrogenated product; a random copolymer obtained by randomly copolymerizing aromatic vinyl with a conjugated diene, or a hydrogenated product thereof.
Among these, an aromatic vinyl / conjugated diene block copolymer or a hydrogenated product thereof is preferable.

The aromatic vinyl polymer (B) is preferably selected so that the difference in refractive index from the cyclic olefin resin (A) falls within a specific range. For example, the aromatic vinyl polymer (B) can be measured according to ASTM D542. When the refractive index of the aromatic vinyl polymer (B) is nD [B] and the refractive index nD [A] of the cyclic olefin resin (A), the difference in refractive index | nD [B] −nD [A] | Is preferably 0.015 or less, more preferably 0.012 or less, and still more preferably 0.010 or less.
When the cyclic olefin resin composition (P) according to the present embodiment contains such an aromatic vinyl polymer (B), the environment changes from a high temperature and high humidity atmosphere to a normal temperature and normal humidity atmosphere. Etc., excellent transparency can be maintained.

  Examples of the aromatic vinyl that forms the aromatic vinyl polymer (B) include styrene, α-methylstyrene, p-methylstyrene, and the like. Examples of the conjugated diene include butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene.

  In the block copolymer obtained by copolymerizing the aromatic vinyl block and the conjugated diene block according to the present embodiment or the hydrogenated product thereof, the content of the unit derived from the aromatic vinyl as described above is, for example, 40% by mass or more. Preferably, it is 40 mass% or more and 70 mass% or less, More preferably, it is 45 mass% or more and 65 mass% or less. The content of units derived from aromatic vinyl can be measured by conventional methods such as infrared spectroscopy and NMR spectroscopy.

  Specific examples of such a block copolymer obtained by copolymerizing an aromatic vinyl block and a conjugated diene block or a hydrogenated product thereof include a styrene / butadiene block copolymer (SB) and a hydrogenated product thereof (SEB). ), Styrene / butadiene / styrene block copolymer (SBS) and hydrogenated product thereof (SEBS; styrene / ethylene / butylene / styrene block copolymer), styrene / isoprene block copolymer (SI) and hydrogenated product thereof (SEP), styrene / isoprene / styrene block copolymer (SIS) and hydrogenated product thereof (SEPS; styrene / ethylene / propylene / styrene block copolymer).

Examples of the SEBS include trade names Clayton G1641H, G1651H, G1657M manufactured by Clayton Japan, trade names TUFTEC H1043, H1051, H1041 manufactured by Asahi Kasei, and trade name Septon 8104 manufactured by Kuraray.
Examples of the SEPS include Kuraray's trade name Septon 2104.

  In the present embodiment, SEBS (hydrogenated SBS) and SEPS (hydrogenated SIS) are particularly preferably used as the aromatic vinyl / conjugated diene block copolymer or a hydrogenated product thereof.

The aromatic vinyl / conjugated diene block copolymer or hydrogenated product thereof according to this embodiment is a thermoplastic elastomer composed of an aromatic vinyl block unit and a conjugated diene rubber block unit (or its hydrogenated rubber block unit). It is preferable.
In such a block copolymer, an aromatic vinyl block unit that is a hard segment exists as a crosslinking point of a rubber block unit that is a soft segment, and forms a physical crosslink (domain).

  The number average molecular weight of the aromatic vinyl / conjugated diene block copolymer or the hydrogenated product thereof according to this embodiment is, for example, preferably 500 to 2,000,000, more preferably 10,000 to 1,000,000. The number average molecular weight (Mn) is obtained by measuring gel permeation chromatography (GPC; o-dichlorobenzene, 140 ° C.) of an aromatic vinyl / conjugated diene block copolymer or a hydrogenated product thereof. Can be sought. In this embodiment, two or more of these compounds may be used in combination.

When the aromatic vinyl polymer (B) according to this embodiment has a refractive index close to that of the cyclic olefin resin (A), the transparency of the cyclic olefin resin composition (P) can be further improved. . The cyclic olefin resin (A) is ethylene and tetracyclo [4.4.0.1 ^2,5 . In the case of a random copolymer with 1 ^7,10 ] -3-dodecene, the refractive index nD [A] of the cyclic olefin resin (A) measured in accordance with ASTM D542 is 1.542 ± 0.005. When the cyclic olefin resin (A) is a random copolymer of ethylene and bicyclo [2.2.1] -2-heptene, the refractive index nD [A] of the cyclic olefin resin (A) is It is preferably 1.530 ± 0.005.

  The cyclic olefin resin composition (P) according to the present embodiment melts the cyclic olefin resin (A) and the aromatic vinyl polymer (B) using a known kneading apparatus such as an extruder and a Banbury mixer. Method of kneading; Method of evaporating solvent after dissolving cyclic olefin resin (A) and aromatic vinyl polymer (B) in a common solvent; or Cyclic olefin resin (A) and aromatic in a poor solvent It can be obtained by a method such as adding a solution of the aromatic vinyl polymer (B) to cause precipitation.

  Further, the cyclic olefin-based resin composition (P) according to this embodiment is, for example, a dye, a pigment, a stabilizer, a plasticizer, an antistatic agent, an ultraviolet absorber, and an antioxidant within a range that does not impair the object of the present invention. You may contain various additives, such as an agent, a lubricant, and a filler, as needed.

  The molded body according to the present embodiment is obtained by molding the cyclic olefin resin composition (P) according to the present embodiment by a known molding method. The molded body according to the present embodiment is, for example, a known one such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. It is obtained by a thermoforming method.

  In the cyclic olefin resin composition (P) according to the present embodiment, an injection molded sheet having a thickness of 2 mm made of the cyclic olefin resin composition (P) is used from the viewpoint of further improving the impact resistance of the obtained molded product. When produced, the maximum impact point energy of the injection molded sheet measured at 23 ° C. in the high-speed surface impact test is preferably 20 J or more and 100 J or less, more preferably 25 J or more and 90 J or less, and further preferably 25 J or more and 80 J or less. It is as follows.

  In addition, in the cyclic olefin resin composition (P) according to this embodiment, from the viewpoint of further improving the transparency of the obtained molded product, an injection molded sheet having a thickness of 2 mm made of the cyclic olefin resin composition (P). The haze of the injection molded sheet measured according to JIS K7136 is preferably 30% or less, more preferably 25% or less, still more preferably 15% or less, particularly preferably. 10% or less.

  The cyclic olefin-based resin composition (P) according to this embodiment is excellent in heat resistance, transparency, chemical resistance, oxygen permeability, gas permeability and water vapor permeability, and further exhibits high surface impact strength and elongation at break. It has good toughness and excellent impact resistance. For this reason, it is suitable for the use of the molded object which requires the durability to various processes.

[Molded body]
The molded body according to the present embodiment includes the cyclic olefin-based resin composition (P) according to the present embodiment. A molded body selected from a film, a sheet, a blow molded body, and an injection molded body is preferable.
Since the molded product according to the present embodiment contains the cyclic olefin resin composition (P), it has excellent heat resistance, transparency, chemical resistance, oxygen permeability, gas permeability and water vapor permeability, and higher surface impact strength. It exhibits elongation at break, good toughness, and excellent impact resistance. For this reason, it is suitable for the use of the molded object which requires the durability to various processes.
Examples of uses of the cyclic olefin-based resin composition according to the present invention include packaging sheets or films, bottles, containers such as containers, spherical lenses, aspherical lenses, Fresnel lenses, prisms, optical components such as light guide plates, Optical recording media such as CD, MD, DVD, MO, and PD, transparent boards, vials, prefilled syringes, pharmaceutical and medical containers such as analysis cells, wide-mouth containers, shampoo containers, coffee containers, seasoning containers, beverages Daily miscellaneous goods such as food containers, food containers, transparent sheets and the like. Especially because it is excellent in moisture resistance, transparency, impact resistance, etc., it is especially solid, liquid drugs such as tablets, capsules, powders, liquids, foods such as rice crackers, snacks, cookies, tobacco, tea It can be suitably used as a packaging material for hygroscopic packages such as bags. Specifically, bags, packs, PTP (press through pack), blister packs, hand twists, wrapping, shrink, easy peel films, etc., containers assembled from sheet-like molded products such as tetra packs, milk packs, medicine bottles And vials, infusion bottles, medical containers such as syringe dialyzers such as prefilled syringes, laboratory instruments such as petri dishes, test tubes and analysis cells, and cosmetic bottles.

  The cyclic olefin-based resin composition according to this embodiment can form a composite laminate with other materials, for example, can be coated on vinylidene chloride to form a laminate, and polyamide, ethylene- It is also possible to form a multilayer laminate with a vinyl alcohol copolymer, a polyolefin such as polyester, polypropylene, or polyethylene.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a scope that can achieve the object of the present invention are included in the present invention.

(Evaluation of cyclic olefin resin composition)
[Pelletization]
With respect to 100 parts by mass of the resin composition obtained by mixing the cyclic olefin resin (A) and the aromatic vinyl polymer (B) in the blending amounts shown in Table 2, tri (2 , 4-di-t-butylphenyl) phosphate, 0.1 parts by weight, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate as a heat stabilizer Was blended in an amount of 0.1 parts by mass. Next, using a twin-screw extruder BT-30 (screw system 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd., granulated under the conditions of a set temperature of 270 ° C., a resin extrusion rate of 80 g / min, and 200 rpm. A pellet for measurement was obtained.

[injection molding]
Using the pellet machine obtained above, an injection molding machine IS-55 manufactured by Toshiba Machine Co., Ltd., cylinder temperature = 250-290 ° C., injection speed = 20-40%, screw rotation speed 70 rpm, mold temperature 80 ° C. The injection molding was performed under the conditions to prepare a 2 mm thick injection square plate specimen.

[Haze (%)]
Based on JIS K7136, using a 2 mm-thick injection square plate as a test piece, the measurement was performed with a digital turbidity meter (NDH-20D) manufactured by Nippon Denshoku Industries Co., Ltd.

[High-speed surface impact test (high-rate test)]
At 23 ° C., a striker with a load cell having a diameter of 1/2 inch was collided with an injection square plate having a thickness of 2 mm at a test speed of 3 m / s. A base with a support base diameter of 3 inches was used on the back of the sample. The energy value from the obtained displacement and test force displacement curve to the maximum point of the test force was calculated as the maximum impact point energy.

(Evaluation of cyclic olefin resin (A) and aromatic vinyl polymer (B))
[Press molding]
Hydraulic heat press machine (NS-50) manufactured by Shindo Metal Industry Co., Ltd., in which the pellet, cyclic olefin resin (A) or aromatic vinyl polymer (B) obtained by the above method was set at 230 to 290 ° C. The sheet was molded at a gauge pressure of 10 MPa. In the case of a sheet having a thickness of 1 to 2 mm (pacer shape; 200 × 200 × 1 to 2 mm on a 240 × 240 × 2 mm thick plate), the residual heat was reduced to about 5 to 7 minutes, and the pressure was applied at a gauge pressure of 10 MPa for 1 to 2 minutes. Thereafter, using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set at 20 ° C., the gauge was compressed at a pressure of 10 MPa and cooled for about 5 minutes to prepare a measurement sample. A 5 mm thick brass plate was used as the hot plate. The samples prepared by the above method were used for various physical property evaluation samples.

[Young's modulus (tensile modulus) (YM), tensile elongation at break (EL), tensile yield stress (YS), and tensile stress at break (TS)]
Evaluations of Young's modulus (YM), tensile elongation at break (EL), tensile yield stress (YS), and tensile stress at break (TS), which are tensile properties, were punched from a 1 mm thick press sheet obtained by the above press molding. JIS K7113 type 2 test piece 1/2 was used as a sample for evaluation, and a precision universal testing machine (AG-XPlus) manufactured by Shimadzu Corporation was used at 23 ° C. and at a tensile speed of 200 mm / min.

[Softening point temperature (TMA)]
Using TMAQ400 manufactured by TA Instruments, the thermal deformation behavior of a sheet having a thickness of 2 mm obtained by the press molding was measured. A quartz needle was placed on the sheet, a load of 16 g was applied, the temperature was raised at a rate of 5 ° C./min, and the temperature at the displacement point obtained from the TMA curve in the penetration mode was defined as TMA.

[Glass transition point (Tg)]
Using a DSC-220C manufactured by Seiko Denshi Co., Ltd., measurement was performed at a heating rate of 10 ° C./min in a nitrogen atmosphere.

[Rubber hardness]
The rubber hardness of the aromatic vinyl polymer (B) was measured according to JISA.

  The cyclic olefin resins and aromatic vinyl polymers used in the examples and comparative examples are shown below.

[Cyclic olefin resin (A)]
A-1: Random copolymer of ethylene and cyclic olefin (ethylene content: 81 mol%, refractive index nD: 1.540 measured according to ASTM D542, TMA: 90 ° C., intrinsic viscosity [η]: 0. 65dl / g)
A-2: Random copolymer of ethylene and cyclic olefin (ethylene content: 66 mol%, refractive index nD: 1.543 measured according to ASTM D542, TMA: 155 ° C., intrinsic viscosity [η]: 0. 60 dl / g)
Here, said cyclic olefin resin (A) was each synthesize | combined by the method according to the synthesis example as described in the Example of international publication 2008/0688897. Here, Table 1 shows the type and content of the comonomer (cyclic olefin monomer) of each cyclic olefin resin (A) and the respective physical properties. In Table 1, TD is tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene and NB represents bicyclo [2.2.1] -2-heptene.

[Aromatic vinyl polymer (B)]
B-1: SEBS (Taftec H1043 manufactured by Asahi Kasei Corporation, refractive index nD: 1.548, styrene content: 67% by mass)
B-2: SEBS (Taftec H1051 manufactured by Asahi Kasei Corporation, refractive index nD: 1.522, styrene content: 42% by mass)
Here, Table 1 shows the styrene content and physical properties of each aromatic vinyl polymer (B).

  As Examples 1 to 2 and Comparative Examples 1 to 3, samples for measurement were prepared with the compositions shown in Table 2, and physical properties were evaluated. The results are shown in Table 2.

Claims (3)

[A] (1) Contains at least one selected from the following [A-1], [A-2], [A-3] and [A-4], and has a softening point temperature (TMA) of 50. A cyclic olefin-based resin that is not lower than 120 ° C. and
[B] an aromatic vinyl polymer,
The component [A] is contained in an amount of 50 to 90 parts by mass, and the component [B] is contained in an amount of 10 to 50 parts by mass (the total amount of the cyclic olefin resin and the aromatic vinyl polymer is 100 parts by mass). A cyclic olefin-based resin composition characterized by:
[A-1] A random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II];

(In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently , A hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or The polycycle may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group).

(In the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom or a halogen atom. A carbon atom to which R ⁹ or R ¹⁰ is bonded and a carbon atom to which R ¹³ is bonded or a carbon atom to which R ¹¹ is bonded are an optionally substituted hydrocarbon group or alkoxy group It may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic ring An aromatic ring may be formed).
[A-2] A ring-opening polymer or copolymer of the cyclic olefin represented by the formula [I] or [II],
[A-3] a hydride of the ring-opening polymer or copolymer [A-2],
[A-4] The graft modified product of [A-1], [A-2] or [A-3]. In the cyclic olefin resin composition according to claim 1,
A cyclic olefin-based resin composition characterized by satisfying all of the following requirements (1) and (2).
(1) The haze value of a 2 mm-thick injection molded sheet is 30% or less. (2) The maximum impact point energy of a high-speed surface impact test (HRIT) measured at 23 ° C. is 20 J or more.   A molded article comprising the cyclic olefin-based resin composition according to claim 1 or 2 and selected from a film, a sheet, a blow molded article, and an injection molded article.