JP6241399B2 - Block copolymer, method for producing the same, and film - Google Patents

Description

  The present invention relates to a block copolymer, a method for producing the same, and a film. More specifically, the present invention relates to a block copolymer having high transparency and useful in the optical field, a method for producing the same, and a film containing the block copolymer.

  Cyclic olefin resins such as thermoplastic norbornene resins have high glass transition temperature, high light transmittance, and low birefringence compared to conventional optical films due to low refractive index anisotropy. have. Therefore, it attracts attention as a transparent thermoplastic resin excellent in heat resistance, transparency and optical properties. And utilizing such characteristics, for example, in the optical field such as optical materials such as optical disks, optical lenses, optical fibers, transparent plastic substrates, sealing materials such as optical semiconductor sealing, cyclic olefin-based resins are applied. It is being considered.

In particular, low birefringence is an important performance in the optical field, and attempts have been made to further lower the birefringence of conventional thermoplastic norbornene resins.
Thermoplastic norbornene resins generally have “positive” birefringence, which is due to the fact that the orientation-derived (glass state) birefringence is “positive”. Therefore, as a further attempt to lower birefringence, by introducing a unit with negative orientation birefringence into the norbornene-based resin, low birefringence and zero birefringence are achieved, so that lens applications and zero phase difference can be achieved. Attempts to develop films, reverse wavelength dispersion films, and the like have been studied.

  For example, a copolymer with a norbornene-based monomer whose orientation birefringence is “negative” (see Patent Document 1 and Patent Document 2, etc.) and a compatible blend with a non-norbornene-based resin whose orientation birefringence is “negative” (See Non-Patent Document 1) Copolymerization and grafting (see Patent Document 3) with a non-norbornene-based resin whose orientation birefringence is “negative” have been studied.

  When synthesizing a norbornene-based monomer having an orientation birefringence of “negative”, a norbornene-based monomer is produced by a Diels-Alder reaction between dicyclopentadiene (or pyrolyzed cyclopentene) and dienophile because of the advantage that it can be carried out without solvent from the production cost. It is usual to produce monomers. However, it is generally difficult to separate dicyclopentadiene and its multimers in the purification step, and there is a problem that the purification cost increases (for example, see Patent Document 4).

  In addition, a non-norbornene-based resin having an orientation birefringence of “negative” and a resin compatible with the norbornene-based resin has a disadvantage that extrusion film formation is difficult because many resins are easily colored by heating. Non-norbornene-based resin having a negative orientation birefringence that seems to be the lowest cost includes the styrene-maleic anhydride random copolymer described in Non-Patent Document 1, and is available at a relatively low cost. . However, since the compatibility with the norbornene resin is not sufficient, spinodal decomposition occurs in a molten state such as injection molding or extrusion film formation. A transparent film can be produced if it is cast film formation, but there are many cast solvents that are expensive in the process and are not put into practical use.

  On the other hand, as a measure for suppressing spinodal decomposition, there is an attempt to use oligomers (lower molecular weights) whose orientation birefringence is “negative”, such as inexpensive styrene oligomers, but the orientation is saturated in the case of oligomers. In practical use, birefringence can hardly be erased (for example, Non-Patent Document 2 describes the relationship between the molecular weight of a negative birefringent polymer and the degree of orientation birefringence erasure). Furthermore, the glass transition temperature is lowered and the practicality is small.

Therefore, an attempt has been made to perform a block copolymerization method of a norbornene monomer and a styrene monomer (Patent Document 3).
However, since separation from the homopolymer is difficult, purification must be repeated many times, resulting in high costs. Furthermore, since the introduction rate of styrenes is unstable and there is a problem in quality, it is not a method capable of mass production. Moreover, the obtained block body also has poor practicality. For example, when a stretching operation often performed with an optical film is performed, there is a problem that the block body is whitened and loses transparency.

JP 2006-265176 A JP 2008-222663 A JP-A-8-92357 Japanese Patent Application Laid-Open No. 2002-173452

Polymer Papers, Vol. 61, no. 1, pp. 89-94 Journal of Polymer Science, Part A: Polymer Chemistry, 2013, 51, 3140. Figure7

  This invention is made | formed in view of the said situation, and it aims at providing the block copolymer which is excellent in transparency, its manufacturing method, and a film.

〔一般式（１）において、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、又はメチル基を表し、Ｒ^３及びＲ^４は、それぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、水酸基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、シクロアルキル基、アルキルエステル基又はアルコキシ基を表す。ｐは０〜３の整数であり、ｑは０〜４の整数であり、ｒは０又は１である。〕

〔一般式（２）において、ｍは０〜３の整数であり、ｎは０又は正の整数であり、Ｘは、メチレン基、酸素原子又は硫黄原子を表し、Ａ^１〜Ａ^４は、それぞれ独立に、下記（ｉ）〜（ｉｖ）のいずれかを表すか、下記（ｖ）又は（ｖｉ）の形態を表す。但し、前記Ｘが、メチレン基である場合には、前記Ａ^１〜Ａ^４のうちの少なくとも１つは下記（ｉｉｉ）を表す。
（ｉ）水素原子、
（ｉｉ）ハロゲン原子、
（ｉｉｉ）アルコキシ基、水酸基、エステル基、カルボキシル基、シアノ基、アミド基、アミノ基及びチオール基の群から選ばれる極性基、
（ｉｖ）ハロゲン原子若しくは前記極性基（ｉｉｉ）により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基又は芳香族炭化水素基、
（ｖ）Ａ^１とＡ^２、又は、Ａ^３とＡ^４が、相互に結合してアルキリデン基を形成し、該結合に関与しないＡ^１〜Ａ^４は、相互に独立に、前記（ｉ）〜（ｉｖ）のいずれかを表す、
（ｖｉ）Ａ^１とＡ^３、Ａ^１とＡ^４、Ａ^２とＡ^３、又は、Ａ^２とＡ^４が、相互に結合して、それぞれが結合している炭素原子と共に環状構造を形成し、該結合に関与しないＡ^１〜Ａ^４は、相互に独立に、前記（ｉ）〜（ｉｖ）のいずれかを表す。〕
［２］一般式（１）で表される構造単位を含んでいると共に、主鎖の少なくとも１つの末端部分にエチレン性不飽和結合を有するマクロモノマーの存在下において、
一般式（３）で表される化合物を含有する原料モノマーをメタセシス重合触媒により開環重合した後、該開環重合された重合物中に存在するエチレン性不飽和結合に水素添加することを特徴とするブロック共重合体の製造方法。

〔一般式（１）において、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、又はメチル基を表し、Ｒ^３及びＲ^４は、それぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、水酸基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、シクロアルキル基、アルキルエステル基又はアルコキシ基を表す。ｐは０〜３の整数であり、ｑは０〜４の整数であり、ｒは０又は１である。〕

〔一般式（３）において、ｍは０〜３の整数であり、ｎは０又は正の整数であり、Ｘは、メチレン基、酸素原子又は硫黄原子を表し、Ａ^１〜Ａ^４は、それぞれ独立に、下記（ｉ）〜（ｉｖ）のいずれかを表すか、下記（ｖ）又は（ｖｉ）の形態を表す。但し、前記Ｘが、メチレン基である場合には、前記Ａ^１〜Ａ^４のうちの少なくとも１つは下記（ｉｉｉ）を表す。
（ｉ）水素原子、
（ｉｉ）ハロゲン原子、
（ｉｉｉ）アルコキシ基、水酸基、エステル基、カルボキシル基、シアノ基、アミド基、アミノ基及びチオール基の群から選ばれる極性基、
（ｉｖ）ハロゲン原子若しくは前記極性基（ｉｉｉ）により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基又は芳香族炭化水素基、
（ｖ）Ａ^１とＡ^２、又は、Ａ^３とＡ^４が、相互に結合してアルキリデン基を形成し、該結合に関与しないＡ^１〜Ａ^４は、相互に独立に、前記（ｉ）〜（ｉｖ）のいずれかを表す、
（ｖｉ）Ａ^１とＡ^３、Ａ^１とＡ^４、Ａ^２とＡ^３、又は、Ａ^２とＡ^４が、相互に結合して、それぞれが結合している炭素原子と共に環状構造を形成し、該結合に関与しないＡ^１〜Ａ^４は、相互に独立に、前記（ｉ）〜（ｉｖ）のいずれかを表す。〕
［３］前記［１］に記載のブロック共重合体を含むことを特徴とするフィルム。 The present invention is as follows.
[1] A block part (A) containing a structural unit represented by the general formula (1);
And a block part (B) containing a structural unit represented by the general formula (2).

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. , A hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkyl ester group or an alkoxy group. p is an integer of 0 to 3, q is an integer of 0 to 4, and r is 0 or 1. ]

In [general formula (2), m is an integer of 0 to 3, n is 0 or a positive integer, X is a methylene group, an oxygen atom or a sulfur ^atom, A 1 to A ⁴ are each Independently, any one of the following (i) to (iv) is represented, or the following (v) or (vi) is represented. However, the X is, if a methylene group is at least one of the ^A 1 to A ⁴ represents the following (iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, an amide group, an amino group, and a thiol group;
(Iv) a C1-C10 aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group which may be substituted by a halogen atom or the polar group (iii);
(V) A ¹ and A ² , or A ³ and A ⁴ are bonded to each other to form an alkylidene group, and A ^{1 to} A ⁴ not participating in the bonding are independently of each other (i) Represents any one of (iv),
(Vi) A ¹ and A ³ , A ¹ and A ⁴ , A ² and A ³ , or A ² and A ⁴ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are bonded. A ^{1 to} A ⁴ not involved in the bond represent any of the above (i) to (iv), independently of each other. ]
[ 2 ] In the presence of a macromonomer containing the structural unit represented by the general formula (1) and having an ethylenically unsaturated bond in at least one terminal portion of the main chain,
A raw material monomer containing a compound represented by the general formula (3) is subjected to ring-opening polymerization using a metathesis polymerization catalyst, and then hydrogenated to ethylenically unsaturated bonds present in the ring-opened polymer. A method for producing a block copolymer.

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. , A hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkyl ester group or an alkoxy group. p is an integer of 0 to 3, q is an integer of 0 to 4, and r is 0 or 1. ]

In [Formula (3), m is an integer of 0 to 3, n is 0 or a positive integer, X is a methylene group, an oxygen atom or a sulfur ^atom, A 1 to A ⁴ are each Independently, any one of the following (i) to (iv) is represented, or the following (v) or (vi) is represented. However, the X is, if a methylene group is at least one of the ^A 1 to A ⁴ represents the following (iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, an amide group, an amino group, and a thiol group;
(Iv) a C1-C10 aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group which may be substituted by a halogen atom or the polar group (iii);
(V) A ¹ and A ² , or A ³ and A ⁴ are bonded to each other to form an alkylidene group, and A ^{1 to} A ⁴ not participating in the bonding are independently of each other (i) Represents any one of (iv),
(Vi) A ¹ and A ³ , A ¹ and A ⁴ , A ² and A ³ , or A ² and A ⁴ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are bonded. A ^{1 to} A ⁴ not involved in the bond represent any of the above (i) to (iv), independently of each other. ]
[ 3 ] A film comprising the block copolymer according to [1].

The block copolymer of this invention is equipped with the specific block part (A) and the specific block part (B) provided with a polar site | part, and is equipped with the outstanding transparency. Therefore, it can be suitably used in the optical field such as optical materials such as optical disks, optical lenses, optical fibers and transparent plastic substrates, and sealing materials such as optical semiconductor sealing.
Moreover, according to the method for producing a block copolymer of the present invention, a block copolymer having excellent transparency can be obtained efficiently.
Furthermore, the film of this invention is equipped with the specific block part (A) and the outstanding transparency by including the block copolymer provided with the specific block part (B) provided with a polar site | part. Therefore, it can be suitably used as an optical material such as a transparent plastic substrate such as a retardation film.

Hereinafter, the present invention will be described in detail.
[1] Block Copolymer The block copolymer of the present invention comprises a block part (A) and a block part (B).

(1-1) Block part (A)
The block part (A) includes a structural unit represented by the following general formula (1) (hereinafter also referred to as “structural unit (a1)”).

〔一般式（１）において、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、又はメチル基を表し、Ｒ^３及びＲ^４は、それぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、水酸基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、シクロアルキル基、アルキルエステル基又はアルコキシ基を表す。ｐは０〜３の整数であり、ｑは０〜４の整数であり、ｒは０又は１である。〕

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. , A hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkyl ester group or an alkoxy group. p is an integer of 0 to 3, q is an integer of 0 to 4, and r is 0 or 1. ]

R ³ and R ⁴ in the general formula (1) are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl. Group, an alkyl ester group or an alkoxy group, preferably an alkyl group.
The ^{R 3} and the carbon number of the linear or branched alkyl group for ^{R 4} is 1 to 10, preferably 1 to 7, more preferably 1-4.
Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, and an n-pentyl group. , N-hexyl group, n-octyl group and the like.

The number of carbon atoms of the cycloalkyl group represented by R ³ and R ⁴ is not particularly limited, but is preferably 3-10, more preferably 4-6, more preferably 5 or 6.
Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The number of carbon atoms of the alkyl ester group in R ³ and R ⁴ is not particularly limited, but is preferably 2 to 10, more preferably 2 to 5, and still more preferably 2 to 4. The alkyl moiety in the alkyl ester group may be any of linear, branched and cyclic.
Specific examples of the alkyl ester group include methyl ester group, ethyl ester group, n-propyl ester group, i-propyl ester group, n-butyl ester group, i-butyl ester group, s-butyl ester group, t -Butyl ester group, n-pentyl ester group, n-hexyl ester group, n-octyl ester group and the like.

Although carbon number of the alkoxy group in said R < ³ > and R < ⁴ > is not specifically limited, It is preferable that it is 1-10, More preferably, it is 1-6, More preferably, it is 1-4. In addition, the alkyl part in this alkoxy group may be linear, branched or cyclic.
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, and n-pentyloxy. Group, n-hexyloxy group, cyclopentyloxy group, cyclohexyloxy group and the like.

Moreover, p in the said Formula (1) is an integer of 0-3, Preferably it is 0 or 1, More preferably, it is 0.
Q is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
The r is 0 or 1, preferably 0.

  In the block copolymer of the present invention, the block part (A) may contain only one type of the above structural unit (a1), or may contain two or more types. Moreover, this block part (A) may contain other structural units (a2) besides the structural unit (a1).

Examples of the other structural unit (a2) in the block part (A) include structural units derived from conjugated dienes such as diolefins such as butadiene and isoprene, and polar substituents of diolefins such as chloroprene. be able to.
In addition, the said block part (A) may contain only 1 type of the other structural units (a2) mentioned above, and may contain 2 or more types.

  Here, when the entire structural unit constituting the block part (A) [that is, the sum of the structural unit (a1) and the structural unit (a2)] is 100 parts by weight, the structural unit (a1 in the block part (A)) ) Content is preferably 25 to 100 parts by weight, more preferably 50 to 100 parts by weight, and still more preferably 75 to 100 parts by weight. When the content ratio is within the above range, it is preferable because birefringence can be effectively erased.

  Moreover, when the whole block copolymer of this invention is 100 weight part, it is preferable that the content rate of the said block part (A) is 10-90 weight part, More preferably, 15-70 weight part, More preferably, it is 25-50 weight part. When the content ratio is within the above range, it is preferable because birefringence can be effectively erased.

Moreover, the number average molecular weight (Mn) of the block part (A) in the block copolymer of the present invention is preferably 3000 to 200000, more preferably 4000 to 100000, in terms of polystyrene by gel permeation chromatography. More preferably, it is 5000-30000. When the number average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be obtained.
Furthermore, the weight average molecular weight (Mw) in this block part (A) is a polystyrene conversion value by GPC, preferably 3000 to 200000, more preferably 5000 to 100,000, and still more preferably 8000 to 50000. When the weight average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be obtained.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the block part (A) in this block copolymer is usually 1 to 10, more preferably 1 to 3, and further preferably 1 to 1.5. .

(1-2) Block part (B)
The block part (B) in the block copolymer of the present invention contains a structural unit represented by the following general formula (2) (hereinafter also referred to as “structural unit (b1)”).

〔一般式（２）において、ｍは０〜３の整数であり、ｎは０又は正の整数であり、Ｘは、メチレン基、酸素原子又は硫黄原子を表し、Ａ^１〜Ａ^４は、それぞれ独立に、下記（ｉ）〜（ｉｖ）のいずれかを表すか、下記（ｖ）又は（ｖｉ）の形態を表す。但し、前記Ｘが、メチレン基である場合には、前記Ａ^１〜Ａ^４のうちの少なくとも１つは下記（ｉｉｉ）を表す。
（ｉ）水素原子、
（ｉｉ）ハロゲン原子、
（ｉｉｉ）アルコキシ基、水酸基、エステル基、カルボキシル基、シアノ基、アミド基、アミノ基及びチオール基の群から選ばれる極性基、
（ｉｖ）ハロゲン原子若しくは前記極性基（ｉｉｉ）により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基又は芳香族炭化水素基、
（ｖ）Ａ^１とＡ^２、又は、Ａ^３とＡ^４が、相互に結合してアルキリデン基を形成し、該結合に関与しないＡ^１〜Ａ^４は、相互に独立に、前記（ｉ）〜（ｉｖ）のいずれかを表す、
（ｖｉ）Ａ^１とＡ^３、Ａ^１とＡ^４、Ａ^２とＡ^３、又は、Ａ^２とＡ^４が、相互に結合して、それぞれが結合している炭素原子と共に環状構造を形成し、該結合に関与しないＡ^１〜Ａ^４は、相互に独立に、前記（ｉ）〜（ｉｖ）のいずれかを表す。〕

In [general formula (2), m is an integer of 0 to 3, n is 0 or a positive integer, X is a methylene group, an oxygen atom or a sulfur ^atom, A 1 to A ⁴ are each Independently, any one of the following (i) to (iv) is represented, or the following (v) or (vi) is represented. However, the X is, if a methylene group is at least one of the ^A 1 to A ⁴ represents the following (iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, an amide group, an amino group, and a thiol group;
(Iv) a C1-C10 aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group which may be substituted by a halogen atom or the polar group (iii);
(V) A ¹ and A ² , or A ³ and A ⁴ are bonded to each other to form an alkylidene group, and A ^{1 to} A ⁴ not participating in the bonding are independently of each other (i) Represents any one of (iv),
(Vi) A ¹ and A ³ , A ¹ and A ⁴ , A ² and A ³ , or A ² and A ⁴ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are bonded. A ^{1 to} A ⁴ not involved in the bond represent any of the above (i) to (iv), independently of each other. ]

M in General formula (2) is an integer of 0-3, Preferably it is an integer of 0-2, More preferably, it is 0 or 1.
The n is 0 or a positive integer, preferably an integer of 0 to 3, more preferably an integer of 0 to 2.

Examples of the halogen atom (ii) in A ^{1 to} A ⁴ of the above formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferable.

The polar group of (iii) in A ^{1 to} A ⁴ of the above formula (2) is selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, an amide group, an amino group, and a thiol group. It is.
Although carbon number of the said alkoxy group is not specifically limited, It is preferable that it is 1-10, More preferably, it is 1-5, More preferably, it is 1-3. In addition, the alkyl part in this alkoxy group may be linear, branched or cyclic.
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, and n-pentyloxy. Group, n-hexyloxy group, cyclopentyloxy group, cyclohexyloxy group and the like.

Although carbon number of the said ester group is not specifically limited, It is preferable that it is 2-10, More preferably, it is 2-8, More preferably, it is 2-5.
Specific examples of the ester group include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aryloxycarbonyl groups such as phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl group, and biphenylyloxycarbonyl group. Etc.

Examples of the amide group include a primary amide group, a secondary amide group, and a tertiary amide group. Of these, primary amide groups are preferred.
Examples of the amino group include a primary amino group, a secondary amino group, and a tertiary amino group. Among these, a primary amino group is preferable.

The carbon number of the aliphatic hydrocarbon group (iv) in A ^{1 to} A ⁴ of the above formula (2) is 1 to 10, preferably 1 to 4, more preferably 1 to 2. Specific examples of the aliphatic hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and alkenyl groups such as a vinyl group, an allyl group, and a propenyl group.
It is preferable that carbon number of the alicyclic hydrocarbon group of said (iv) is 5-10, More preferably, it is 5-8, More preferably, it is 5 or 6. Specific examples of the alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. In addition, this alicyclic hydrocarbon group does not have a double bond in the ring.
Although carbon number of the aromatic hydrocarbon group of said (iv) is not specifically limited, It is preferable that it is 6-20, More preferably, it is 6-14, More preferably, it is 6-10. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an indenyl group, a fluorenyl group, and an anthracenyl group.

  In the block copolymer of the present invention, the block part (B) may contain only one type of the above structural unit (b1) or may contain two or more types. Moreover, this block part (B) may contain another structural unit (b2) besides the structural unit (b1).

Examples of the other structural unit (b2) in the block portion (B) include, for example, JP-A-51-80400, JP-A-60-26024, JP-A-1-168725, and JP-A-1-190726. Known in Japanese Patent Laid-Open No. 3-14882, Japanese Patent Laid-Open No. 3-12137, Japanese Patent Laid-Open No. 4-63807, Japanese Patent Laid-Open No. 2-227424, and Japanese Patent Laid-Open No. 2-276842. Mention may be made of structural units derived from norbornene monomers.
Furthermore, examples of the other structural unit (b2) include a structural unit derived from a monomer capable of chain transfer (excluding the structural unit (a1) described above). Specifically, for example, cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclooctene, 1-methylcyclooctene, 5-methylcyclo Monocyclic cycloolefins such as octene, cyclooctatetraene, 1,5-cyclooctazine, and cyclododecene; acetylenes that are substituted acetylenes such as acetylene, propyne, and 1-butene; both ends of 1,6-heptadiene, etc. Examples thereof include structural units derived from dienes having a double bond.
In addition, the said block part (B) may contain only 1 type of the other said structural unit (b2), and may contain 2 or more types.

  Here, when the entire structural unit constituting the block part (B) [that is, the sum of the structural unit (b1) and the structural unit (b2)] is 100 mol%, the structural unit (b1 in the block part (B)) ) Content is preferably 20 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 60 to 100 mol%. When the content ratio is within the above range, it is preferable because practical transparency of the block body can be expressed.

  Moreover, when the whole block copolymer of this invention is 100 weight part, it is preferable that the content rate of the said block part (B) is 10-90 weight part, More preferably, it is 30-85 weight part, More preferably, it is 50-75 weight part. When the content ratio is within the above range, it is preferable because birefringence can be effectively erased.

Further, the number average molecular weight (Mn) of the block part (B) in the block copolymer of the present invention is preferably 3000 to 100,000, more preferably 4000 to 50000, and still more preferably, in terms of polystyrene converted by GPC. 5,000 to 30,000. When the number average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be obtained.
Furthermore, the weight average molecular weight (Mw) in this block part (B) is preferably from 3,000 to 150,000, more preferably from 5,000 to 100,000, and even more preferably from 8,000 to 75,000 in terms of polystyrene by GPC. When the weight average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be obtained.
Moreover, ratio (Mw / Mn) of Mw and Mn in this block part (B) is 1-10 normally, More preferably, it is 1-5, More preferably, it is 1-2.5.

(1-3) Block copolymer The arrangement | sequence of each block part which comprises the block copolymer of this invention, etc. are not specifically limited.
Specific examples include sequences of AB type, ABA type, BAB type, ABAB type, and the like.

The number average molecular weight (Mn) in the block copolymer of the present invention is a polystyrene equivalent value by GPC, preferably 3000 to 200000, more preferably 5000 to 100,000, and still more preferably 8000 to 50000. When the number average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be obtained.
Moreover, it is preferable that the weight average molecular weight (Mw) in this block copolymer is a polystyrene conversion value by GPC, and it is preferable that it is 5000-200000, More preferably, it is 10000-100,000, More preferably, it is 20000-80000. When the weight average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be obtained.
Furthermore, the ratio (Mw / Mn) of Mw and Mn in this block copolymer is usually 1 to 10, more preferably 1 to 5, and further preferably 1 to 2.5.

The block copolymer in the present invention preferably has one glass transition temperature peak. In this case, it is preferable because there is no bias in the development of retardation (birefringence) of each block portion generated during stretching, and birefringence can be effectively erased.
The glass transition temperature is preferably 80 to 300 ° C, more preferably 100 to 200 ° C, still more preferably 120 to 180 ° C.
The glass transition temperature can be obtained by a method according to JIS K 7121 using a DSC (differential scanning calorimeter).

  The block copolymer in the present invention has a property that the absolute value of the phase difference becomes higher as the wavelength becomes longer, that is, reverse wavelength dispersion, contrary to a general polymer material. Can do.

Moreover, the block copolymer in this invention has the haze (Haze) of the stretched film obtained by performing 1.5 time extending | stretching by the free end uniaxial stretching with respect to the unstretched film obtained from this polymer. % Or less (particularly 3% or less, and further 2% or less).
In addition, the thickness of the unstretched film at the time of measuring this cloudiness shall be 20-500 micrometers. This measurement is performed in accordance with JIS K 7105.

  Furthermore, in the block copolymer of the present invention, the haze of an unstretched film (thickness: 20 to 500 μm) obtained from this polymer is 5% or less (particularly 3% or less, more preferably 2% or less). ).

  The block copolymer of the present invention can be suitably used in the optical field such as optical materials such as optical disks, optical lenses, optical fibers and transparent plastic substrates, and sealing materials such as optical semiconductor sealing.

  Although the method for producing the block copolymer of the present invention is not particularly limited, for example, it can be produced by a production method described later.

[2] Method for Producing Block Copolymer The method for producing a block copolymer of the present invention includes a structural unit represented by the above general formula (1), and at least one terminal portion of the main chain has ethylene. In the presence of a macromonomer having an ionic unsaturated bond, the raw material monomer is subjected to ring-opening polymerization with a metathesis polymerization catalyst, and then hydrogenated to the ethylenically unsaturated bond existing in the ring-opened polymerized product. It can manufacture with the manufacturing method of the block copolymer made into.

(2-1) Macromonomer The macromonomer includes the structural unit (a1) represented by the general formula (1) and has an ethylenically unsaturated bond at at least one terminal portion of the main chain. It is.
The macromonomer may contain only one type of structural unit (a1) or may contain two or more types. In addition to the structural unit (a1), this macromonomer may contain one or more of the above-mentioned other structural units (a2).

  Here, when the whole structural unit constituting the macromonomer [that is, the sum of the structural unit (a1) and the structural unit (a2)] is 100 parts by weight, the content ratio of the structural unit (a1) in the macromonomer is: It is preferable that it is 25-100 weight part, More preferably, it is 50-100 weight part, More preferably, it is 75-100 weight part. When the content ratio is within the above range, it is preferable because birefringence can be effectively erased.

In addition, the number average molecular weight (Mn) of the macromonomer is preferably 3000 to 200000, more preferably 4000 to 100000, and still more preferably 5000 to 30000, in terms of polystyrene by gel permeation chromatography. When the number average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be obtained.
Furthermore, the weight average molecular weight (Mw) in this macromonomer is preferably 3000 to 200000 in terms of polystyrene by GPC, more preferably 4000 to 100000, still more preferably 5000 to 30000. When the weight average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be obtained.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the block part (A) in this macromonomer is usually 1 to 10, more preferably 1 to 3, and further preferably 1 to 1.5.

(2-2) Synthesis of Macromonomer The macromonomer includes a monomer represented by the following general formula (4) corresponding to the structural unit (a1) represented by the general formula (1), and if necessary. Synthesize | combining by introduce | transducing an ethylenically unsaturated bond in the at least 1 terminal part of the principal chain in the polymer obtained by superposing | polymerizing using the raw material containing the monomer corresponding to the said structural unit (a2) Can do.
Incidentally, ^R 1 ^{to R} 4, p, the q, and r in the general formula (4), respectively, the general formula in ^(1), R 1 ^{to R} 4, p, can be directly applied to the description of q and r Can do.

〔一般式（４）において、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、又はメチル基を表し、Ｒ^３及びＲ^４は、それぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、水酸基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、シクロアルキル基、アルキルエステル基又はアルコキシ基を表す。ｐは０〜３の整数であり、ｑは０〜４の整数であり、ｒは０又は１である。〕

[In General Formula (4), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. , A hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkyl ester group or an alkoxy group. p is an integer of 0 to 3, q is an integer of 0 to 4, and r is 0 or 1. ]

In the synthesis of the macromonomer, the method for polymerizing the monomer is not particularly limited, and a normal method for producing a hydrocarbon polymer can be used. Specifically, for example, radical polymerization methods such as solution polymerization, emulsion polymerization and bulk polymerization; anionic polymerization methods using organic alkali metal compounds as catalysts; cations using BF ₃ , AlCl ₃ , TiCl _{4 and the} like as catalysts Examples thereof include a polymerization method. Among these, a method that easily introduces a non-conjugated ethylenically unsaturated bond is preferable in order to obtain a macromonomer. Specifically, living anionic polymerization and living radical polymerization are preferable, and living anionic polymerization is particularly preferable.

  Furthermore, in the synthesis of the macromonomer, a method for introducing an ethylenically unsaturated bond into at least one terminal portion of the main chain is not particularly limited, and can be performed using a known method. Specifically, for example, the method described in Chapter 2 of “Macromonomer Chemistry and Industry” (edited by Yuya Yamashita) published by IPC Publishing Department (IPC Co., Ltd.) can be mentioned.

Moreover, the said raw material monomer used for ring-opening polymerization contains the compound represented by following General formula (3).
Incidentally, in the general formula (3), X, m, n, for the and ^A 1 to A ^4, respectively, the general formula in (2), X, m, n, and of ^A 1 to A ⁴ description It can be applied as it is.

〔一般式（３）において、ｍは０〜３の整数であり、ｎは０又は正の整数であり、Ｘは、メチレン基、酸素原子又は硫黄原子を表し、Ａ^１〜Ａ^４は、それぞれ独立に、下記（ｉ）〜（ｉｖ）のいずれかを表すか、下記（ｖ）又は（ｖｉ）の形態を表す。但し、前記Ｘが、メチレン基である場合には、前記Ａ^１〜Ａ^４のうちの少なくとも１つは下記（ｉｉｉ）を表す。
（ｉ）水素原子、
（ｉｉ）ハロゲン原子、
（ｉｉｉ）アルコキシ基、水酸基、エステル基、カルボキシル基、シアノ基、アミド基、アミノ基及びチオール基の群から選ばれる極性基、
（ｉｖ）ハロゲン原子若しくは前記極性基（ｉｉｉ）により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基又は芳香族炭化水素基、
（ｖ）Ａ^１とＡ^２、又は、Ａ^３とＡ^４が、相互に結合してアルキリデン基を形成し、該結合に関与しないＡ^１〜Ａ^４は、相互に独立に、前記（ｉ）〜（ｉｖ）のいずれかを表す、
（ｖｉ）Ａ^１とＡ^３、Ａ^１とＡ^４、Ａ^２とＡ^３、又は、Ａ^２とＡ^４が、相互に結合して、それぞれが結合している炭素原子と共に環状構造を形成し、該結合に関与しないＡ^１〜Ａ^４は、相互に独立に、前記（ｉ）〜（ｉｖ）のいずれかを表す。〕

In [Formula (3), m is an integer of 0 to 3, n is 0 or a positive integer, X is a methylene group, an oxygen atom or a sulfur ^atom, A 1 to A ⁴ are each Independently, any one of the following (i) to (iv) is represented, or the following (v) or (vi) is represented. However, the X is, if a methylene group is at least one of the ^A 1 to A ⁴ represents the following (iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, an amide group, an amino group, and a thiol group;
(Iv) a C1-C10 aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group which may be substituted by a halogen atom or the polar group (iii);
(V) A ¹ and A ² , or A ³ and A ⁴ are bonded to each other to form an alkylidene group, and A ^{1 to} A ⁴ not participating in the bonding are independently of each other (i) Represents any one of (iv),
(Vi) A ¹ and A ³ , A ¹ and A ⁴ , A ² and A ³ , or A ² and A ⁴ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are bonded. A ^{1 to} A ⁴ not involved in the bond represent any of the above (i) to (iv), independently of each other. ]

As a specific compound represented by the general formula (3), for example,
5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene,
5-hydroxy-bicyclo [2.2.1] hept-2-ene,
5-cyano-bicyclo [2.2.1] hept-2-ene,
5-amino-bicyclo [2.2.1] hept-2-ene,
7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-bromo-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7,8-dichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-hydroxy-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-amino-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-hydroxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-cyano-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-amino-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition, the raw material monomer contains one or more known norbornene monomers described in the other structural unit (b2) in the block (B) of the above-mentioned block copolymer and monomers capable of chain transfer. You may do it.

  The metathesis polymerization catalyst used for the ring-opening polymerization is not particularly limited, and a known catalyst can be used. Specifically, for example, Japanese Patent Publication No. 41-20111, Japanese Patent Publication No. 46-14910, Japanese Patent Publication No. 57-17883, Japanese Patent Publication No. 57-61044, Japanese Patent Publication No. 54-86600, Examples thereof include those described in JP-A-58-127728 and JP-A-1-240517.

  The amount of the metathesis polymerization catalyst used is preferably 0.00000001 to 0.005 mol, more preferably 0.00000005 to 0.001 mol, based on 1 mol of the total amount of monomers. When the usage-amount of a catalyst is the said range, while being able to fully advance reaction, a catalyst can be removed easily.

Examples of the reaction solvent used for the ring-opening polymerization include alkanes such as pentane, hexane, heptane, octane, nonane and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; benzene , Toluene, xylene, ethylbenzene, cumene and other aromatic hydrocarbons; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene and other halogenated alkanes, aryl halides and other compounds; ethyl acetate And saturated carboxylic acid esters such as n-butyl acetate, isobutyl acetate and methyl propionate; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane.
These reaction solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the reaction solvent used in the ring-opening polymerization is preferably 1: (0.5 to 5), more preferably the mass ratio of all monomers to the solvent (total monomers: solvent). 1: (1-3).

Although the method of hydrogenation is not particularly limited, it is usually performed by a hydrogenation reaction in which a hydrogenation catalyst and hydrogen gas are added to a solution of a block polymer after ring-opening polymerization.
As the solvent at this time, the same solvent as the reaction solvent used in the above-described ring-opening polymerization can be used, and it is not particularly limited as long as it is not hydrogenated. Therefore, the block copolymer solution obtained by ring-opening polymerization can be directly subjected to a hydrogenation reaction.

  As said hydrogenation catalyst, the well-known compound used when hydrogenating a normal olefinic unsaturated bond can be used. Specifically, for example, a so-called Ziegler type homogeneous catalyst in which an organic acid salt such as titanium, cobalt or nickel or an acetylacetone salt and an organic metal compound such as lithium, magnesium, aluminum or tin are combined; palladium, platinum, Examples include supported noble metal catalysts in which a noble metal such as ruthenium or rhodium is supported on a carrier such as carbon, alumina, silica alumina, silica magnesia, or diatomaceous earth; a noble metal complex catalyst such as rhodium, rhenium, or ruthenium. Among these, a metal hydride complex compound in which the metal element is ruthenium is preferable because of excellent hydrogenation reactivity.

As the metal hydride complex compound in which the metal element is ruthenium, specifically, for example,
RuH (OCOPh) (CO) (PPh ₃ ) ₂ ,
_{RuH (OCOPh-CH 3) (} CO) (PPh 3) 2,
_{RuH (OCOPh-C 2 H 5} ) (CO) (PPh 3) 2,
_{RuH (OCOPh-C 5 H 11} ) (CO) (PPh 3) 2,
_{RuH (OCOPh-C 8 H 17} ) (CO) (PPh 3) 2,
_{RuH (OCOPh-OCH 3) (} CO) (PPh 3) 2,
_{RuH (OCOPh-OC 2 H 5} ) (CO) (PPh 3) 2,
RuH (OCOPh) (CO) (P (cyclohexyl) ₃ ) 2,
_{RuH (OCOPh-NH 2) (} CO) (PPh 3) 2,
RuHF (CO) (PPh ₃ ) ₃ ,
RuHCl (CO) (PPh ₃ ) ₃ ,
RuHBr (CO) (PPh ₃ ) ₃ ,
RuHI (CO) (PPh ₃ ) _{3 and the} like.
Among _{these, RuH (OCOPh-C 5 H} 11) (CO) (PPh 3) 2 is preferred. In addition, “Ph” in each formula represents a phenyl group (—C ₆ H ₅ ) or a phenylene group (—C ₆ H ₄ —).

  The amount of the hydrogenation catalyst used is preferably 5 to 200 ppm by mass, more preferably 10 to 100 ppm by mass, when the total amount of raw material monomers is 100% by mass (1000000 ppm by mass).

The supply amount of the hydrogen gas is preferably 0.0001 to 0.01 MPa / s, more preferably 0.001 to 0.005 MPa / s.
Moreover, it is preferable that the pressure of the reaction system in hydrogenation reaction is 1-25 Mpa, More preferably, it is 3-20 Mpa, More preferably, it is 5-15 Mpa.
Furthermore, the temperature of the solution in the hydrogenation reaction is preferably 100 to 200 ° C, more preferably 120 to 200 ° C, still more preferably 140 to 180 ° C.
The reaction system temperature is maintained at the target reaction temperature, and the time from when the hydrogen gas pressure reaches the target pressure until the reaction is completed is usually 1 to 9 hours, preferably 2 to 5 hours. is there. If it is time of the said range, while being able to perform sufficient hydrogenation, the side reaction which arises when time is too long can be suppressed.

The hydrogenation by this hydrogenation reaction is a reaction with respect to the ethylenically unsaturated bond present in the ring-opened polymer, and the other unsaturated bonds may not be hydrogenated.
The hydrogenation rate of the ethylenically unsaturated bonds in the main chain by this hydrogenation reaction is preferably 90 to 100%, more preferably 95 to 100%, and still more preferably 97 to 100%. When the hydrogenation rate is within the above range, it is preferable because higher transparency can be exhibited.
In addition, this hydrogenation rate can be calculated from, for example, the integral ratio of the peaks of the olefin part and the alicyclic structure part in the NMR spectrum obtained by ¹ H-NMR measurement.

Here, a specific scheme for synthesizing the block copolymer of the present invention will be described.
First, a polymer (macromonomer) having an ethylenically unsaturated bond at the terminal is obtained from a raw material containing a monomer corresponding to the structural unit (a1) [see the following scheme (X)].
Thereafter, in the presence of the obtained macromonomer, the raw material monomer containing the compound represented by the general formula (3) is subjected to ring-opening copolymerization [see the following scheme (Y)].
Subsequently, the target block copolymer can be synthesized by hydrogenation [see the following scheme (Z)].
In the following formula, R represents a monovalent organic group, and examples of the monovalent organic group include a methyl group, an n-butyl group, a s-butyl group, a t-butyl group, and an n-hexyl group. It is done. B represents a divalent linking group, and examples of the divalent linking group include a methylene group, an ethylene group, a propylene group, and an ethoxyethylene group.

[3] Film The film of the present invention is characterized by including the above-described block copolymer of the present invention.
Since this film contains the block copolymer having excellent transparency, it can be suitably used in the optical field such as an optical material such as a transparent plastic substrate.

The said film may be comprised only from the said block copolymer, and may contain another polymer, an additive, etc.
Examples of the other polymer include a cyclic olefin polymer and polystyrene. In addition, these other polymers may be used individually by 1 type, and may be used in combination of 2 or more type.
Moreover, as said additive, a well-known anti-aging agent, a ultraviolet absorber, a mold release agent, a lubricant, etc. can be used. In addition, these additives may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, when the said film is 100 weight part, it is preferable that the content rate of the said block copolymer is 50-100 weight part, More preferably, it is 80-100 weight part, More preferably, it is 90-100 weight Part. When this content rate is in the above range, it is preferable because higher transparency can be exhibited.

  Although the thickness of the said film is not specifically limited, For example, it can be set to 1-500 micrometers (especially 5-200 micrometers, Furthermore, 10-100 micrometers).

  Further, when the film is an unstretched film having a thickness of 20 to 500 μm, the haze (Haze) can be 5% or less (particularly 3% or less, and further 2% or less).

Further, when the film is an unstretched film having a thickness of 20 to 500 μm, the haze (Haze) of the stretched film obtained when stretched 1.5 times by free end uniaxial stretching is 5% or less ( In particular, it may be 3% or less, and further 2% or less).
In addition, this measurement shall be performed based on JISK7105.

  Moreover, since the said film contains the said block copolymer, contrary to a general polymer film, what has a property which becomes high, so that the absolute value of phase difference becomes a long wavelength side, ie, reverse wavelength It can have dispersibility.

  The method for producing the film of the present invention is not particularly limited, and examples thereof include known methods such as a solution casting method, a melt extrusion method, and a calendar method.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, “part” and “%” are based on mass unless otherwise specified.

The following measurements in the following synthesis examples and the like were performed in the following manner.
<Mw, Mn, and Mw / Mn>
Monodispersed polystyrene using Tosoh Corporation GPC columns (G2000HXL; 2, G3000HXL; 1, G4000HXL; 1), flow rate 1.0 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. Was measured by gel permeation chromatography (GPC). Further, the degree of dispersion Mw / Mn was calculated from the measurement results.
^<1 H-NMR analysis>
¹ H-NMR analysis was performed using a model number “JNM-ECX400” manufactured by JEOL Ltd.
<Glass transition temperature>
The glass transition temperature was measured by a method according to JIS K 7121 using DSC (Differential Scanning Calorimeter, Seiko Instruments, model number “EXSTAR6000”).

[1] Production of block copolymer (1-1) Synthesis of macromonomer <Polystyrene macromonomer (A) having an ethylenically unsaturated bond at the terminal>
Tetrahydrofuran (THF) 1500 parts and sec-butyllithium 1.9 parts were mixed and the mixture was cooled to an internal temperature of -78 ° C. with stirring, and then 300 parts of styrene was added dropwise over 20 minutes. And after maintaining the reaction liquid at -78 degreeC for 1 hour, 4.9 parts of 5-bromo- 1-pentene was added to the reaction liquid, and it stirred for 30 minutes, heating up to room temperature.
After completion of the reaction, the precipitate obtained by dropping the reaction solution into 8000 parts of methanol was collected, filtered, and dried to obtain a terminal vinyl group-modified styrenic polymer having the following structure [ethylenic at the terminal] 290 parts of polystyrene-based macromonomer (A)] having an unsaturated bond were obtained.
The macromonomer (A) had a weight average molecular weight (Mw) of about 16,000, a number average molecular weight (Mn) of about 12,000, and a molecular weight distribution (Mw / Mn) of 1.3.

[Macromonomer (A)]

<Polystyrene-based macromonomer (B) having an ethylenically unsaturated bond at the terminal>
The macromonomer (A) except that the blending amount of sec-butyllithium in the synthesis of the macromonomer (A) is 2.4 parts and the blending amount of 5-bromo-1-pentene is 6.1 parts. In the same manner as above, 288 parts of a terminal vinyl group-modified styrene polymer [polystyrene macromonomer (B) having an ethylenically unsaturated bond at the terminal] having the following structure was obtained.
The macromonomer (B) had a weight average molecular weight (Mw) of about 12,000, a number average molecular weight (Mn) of about 9,000, and a molecular weight distribution (Mw / Mn) of 1.3.

[Macromonomer (B)]

(1-2) Production of block copolymer <Example 1>
The macromonomer (A) 35 parts of the following compound (m-1) (8- methyl-8-methoxycarbonyl - tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodeca-3-ene) After 65 parts and 150 parts of toluene were mixed in an autoclave, the internal temperature was heated to 100 ° C., and a metathesis polymerization catalyst represented by the following formula ([1,3-bis (2,4,6-trimethylphenyl) -2-imidazo 0.00116 part of lysinylidene] dichloro [[2- (1-methylacetoxy) phenyl] methylene] ruthenium (II)) was added and stirred for 1 hour. Next, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

[Compound (m-1)]

[Metathesis polymerization catalyst]

Then, 110 parts of toluene and hydrogenation reaction catalyst (Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) _{3] 2} ) was added at 20 ppm, the pressure was increased to 10 MPa at 165 ° C., and the mixture was stirred for 3 hours to carry out a hydrogenation reaction.
Subsequently, the precipitate obtained by dropping the reaction solution into 3000 parts of methanol was collected, filtered, and dried to obtain 97 parts of a block copolymer of Example 1 having the following structure.
The block copolymer of Example 1 had a weight average molecular weight (Mw) of about 64,000, a number average molecular weight (Mn) of about 38,000, and a molecular weight distribution (Mw / Mn) of 1.7. Further, the hydrogenation rate of the main chain by ¹ H-NMR analysis was 99.9%, and the hydrogenation rate of the side chain (styrene-based site) was 0%. Furthermore, the glass transition temperature (Tg) by DSC measurement was one peak of only 125 ° C.

[Hydrogenation catalyst]

[Block copolymer (Example 1)]

<Example 2>
The macromonomer (B) 35 parts of the above compound (m-1) (8- methyl-8-methoxycarbonyl - tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodeca-3-ene) After 65 parts and 150 parts of toluene were mixed in an autoclave, the internal temperature was heated to 100 ° C., and the above-mentioned metathesis polymerization catalyst ([1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) was added. Dichloro [[2- (1-methylacetoxy) phenyl] methylene] ruthenium (II)) was added in an amount of 0.00116 parts and stirred for 1 hour. Next, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Thereafter, 110 parts of toluene and the hydrogenation reaction catalyst (Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] _{2 are} added to the reaction solution. ) Was added at 20 ppm, the pressure was increased to 10 MPa at 165 ° C., and the mixture was stirred for 3 hours to carry out a hydrogenation reaction.
Next, the precipitate obtained by dropping the reaction solution into 3000 parts of methanol was collected, filtered, and dried to obtain 96 parts of a block copolymer of Example 2 having the following structure.
The block copolymer of Example 2 had a weight average molecular weight (Mw) of about 39,000, a number average molecular weight (Mn) of about 21,000, and a molecular weight distribution (Mw / Mn) of 1.9.
Further, the hydrogenation rate of the main chain by ¹ H-NMR analysis was 99.9%, and the hydrogenation rate of the side chain (styrene-based site) was 0%. Furthermore, Tg by DSC measurement was one peak only at 121 ° C.

[Block copolymer (Example 2)]

<Example 3>
The macromonomer (B) 30 parts of the above compound (m-1) (8- methyl-8-methoxycarbonyl - tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodeca-3-ene) After 70 parts and 150 parts of toluene were mixed in an autoclave, the internal temperature was heated to 100 ° C. and the above-mentioned metathesis polymerization catalyst ([1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) was added. Dichloro [[2- (1-methylacetoxy) phenyl] methylene] ruthenium (II)) was added in an amount of 0.00116 parts and stirred for 1 hour. Next, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Thereafter, 110 parts of toluene and the hydrogenation reaction catalyst (Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] _{2 are} added to the reaction solution. ) Was added at 20 ppm, the pressure was increased to 10 MPa at 165 ° C., and the mixture was stirred for 3 hours to carry out a hydrogenation reaction.
Next, the precipitate obtained by dropping the reaction solution into 3000 parts of methanol was collected, filtered, and dried to obtain 96 parts of a block copolymer of Example 3 having the following structure.
The block copolymer of Example 3 had a weight average molecular weight (Mw) of about 51,000, a number average molecular weight (Mn) of about 25,000, and a molecular weight distribution (Mw / Mn) of 2.0.
Further, the hydrogenation rate of the main chain by ¹ H-NMR analysis was 99.9%, and the hydrogenation rate of the side chain (styrene-based site) was 0%. Furthermore, Tg by DSC measurement was one peak only at 127 ° C.

[Block copolymer (Example 3)]

<Example 4>
The macromonomer (B) 35 parts of the above compound (m-1) (8- methyl-8-methoxycarbonyl - tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodeca-3-ene) 30 parts, 20 parts of the following compound (m-2) (5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene), the following compound (m-3) (6-methyl-1) , 4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene), 12 parts of the following compound (m-4) (tricyclopentadiene), 1 part of the following compound ( m-5) 1 part of (dicyclopentadiene), 1 part of the following compound (m-6) (2-norbornene) and 150 parts of toluene were mixed in an autoclave, and the internal temperature was then heated to 100 ° C. Catalyst ([1,3-bis (2, 4,116 parts of 4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro [[2- (1-methylacetoxy) phenyl] methylene] ruthenium (II)) was added and stirred for 1 hour. Next, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

[Compounds (m-2) to (m-6)]

Thereafter, 110 parts of toluene and the hydrogenation reaction catalyst (Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] _{2 are} added to the reaction solution. ) Was added at 200 ppm, the pressure was increased to 10 MPa at 165 ° C., and the mixture was stirred for 3 hours to carry out a hydrogenation reaction.
Subsequently, the precipitate obtained by dropping the reaction solution into 3000 parts of methanol was collected, filtered, and dried to obtain 98 parts of a block copolymer of Example 4 having the following structure.
The block copolymer of Example 4 had a weight average molecular weight (Mw) of about 60,000, a number average molecular weight (Mn) of about 30,000, and a molecular weight distribution (Mw / Mn) of 2.0.
Further, the hydrogenation rate of the main chain by ¹ H-NMR analysis was 99.9%, and the hydrogenation rate of the side chain (styrene-based site) was 0%. Furthermore, the glass transition temperature (Tg) by DSC measurement was 1 peak only at 110 degreeC.

[Block copolymer (Example 4)]

<Comparative Example 1>
After 35 parts of the macromonomer (A), 65 parts of the compound (m-5) (dicyclopentadiene) and 150 parts of toluene were mixed in an autoclave, the internal temperature was heated to 100 ° C., and the metathesis polymerization catalyst ([ 0.00116 parts of 1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro [[2- (1-methylacetoxy) phenyl] methylene] ruthenium (II)) was added. Stir for 1 hour. Next, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Thereafter, 350 parts of toluene and the hydrogenation reaction catalyst (Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] _{2 were} added to the reaction solution. ) Was added at 20 ppm, the pressure was increased to 10 MPa at 165 ° C., and the mixture was stirred for 3 hours to carry out a hydrogenation reaction.
Next, the precipitate obtained by dropping the reaction solution into 4000 parts of methanol was collected, filtered, and dried to obtain a block copolymer.
Since the obtained block copolymer was mixed with macromonomer homopolymer, it was further dissolved in 500 parts of toluene, the reaction solution was dropped into 4000 parts of methanol, and the precipitate was collected and filtered. The operation was repeated 3 times.
Thereafter, by drying, 90 parts of a block copolymer of Comparative Example 1 having the following structure was obtained.
The weight average molecular weight (Mw) of the block copolymer of Comparative Example 1 was about 54,000, the number average molecular weight (Mn) was about 31,000, and the molecular weight distribution (Mw / Mn) was 1.7.
Further, the hydrogenation rate of the main chain by ¹ H-NMR analysis was 99.9%, and the hydrogenation rate of the side chain (styrene-based site) was 0%. Furthermore, the glass transition temperature (Tg) by DSC measurement was two peaks of 98 ° C. and 105 ° C.

[Block Copolymer (Comparative Example 1)]

<Comparative example 2>
35 parts of the macromonomer (B), the compound (m-3) (6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene ) 65 parts and cyclohexane 150 parts were mixed in an autoclave, and then the internal temperature was heated to 100 ° C., and the above-mentioned metathesis polymerization catalyst ([1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidini 0.0016 parts of redene] dichloro [[2- (1-methylacetoxy) phenyl] methylene] ruthenium (II)) was added and stirred for 1 hour. Next, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Thereafter, 350 parts of toluene and the hydrogenation reaction catalyst (Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] _{2 were} added to the reaction solution. ) Was added at 20 ppm, the pressure was increased to 10 MPa at 165 ° C., and the mixture was stirred for 3 hours to carry out a hydrogenation reaction.
Subsequently, the deposit obtained by dripping a reaction liquid to 4000 parts isopropanol was collect | recovered, it filtered and dried, and the block copolymer was obtained.
Since the obtained block copolymer was mixed with a homopolymer of macromonomer, it was further dissolved in 500 parts of cyclohexane, the reaction solution was dropped into 4000 parts of isopropanol, and the precipitate was collected and filtered. The operation was repeated 3 times.
Thereafter, by drying, 88 parts of a block copolymer of Comparative Example 2 having the following structure were obtained.
The weight average molecular weight (Mw) of the block copolymer of Comparative Example 2 was about 50,000, the number average molecular weight (Mn) was about 21,000, and the molecular weight distribution (Mw / Mn) was 2.3.
Further, the hydrogenation rate of the main chain by ¹ H-NMR analysis was 99.9%, and the hydrogenation rate of the side chain (styrene-based site) was 0%. Furthermore, the glass transition temperature (Tg) by DSC measurement was two peaks of 105 ° C. and 151 ° C.

[Block Copolymer (Comparative Example 2)]

<Comparative Example 3>
1.5 parts of 1-butene, the above compound (m-1) (8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 7.1 ^7,10 ] dodec-3-ene) 100 And 150 parts of toluene in an autoclave, the internal temperature was heated to 100 ° C., and the above-mentioned metathesis polymerization catalyst ([1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] 0.00116 parts of dichloro [[2- (1-methylacetoxy) phenyl] methylene] ruthenium (II)) was added and stirred for 1 hour. Next, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Thereafter, 110 parts of toluene and the hydrogenation reaction catalyst (Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] _{2 are} added to the reaction solution. ) Was added at 20 ppm, the pressure was increased to 10 MPa at 165 ° C., and the mixture was stirred for 3 hours to carry out a hydrogenation reaction.
Next, the precipitate obtained by dropping the reaction solution into 3000 parts of methanol was collected, filtered, and dried to obtain 95 parts of a block copolymer of Comparative Example 3 having the following structure.
The polymer of Comparative Example 3 had a weight average molecular weight (Mw) of about 64,000, a number average molecular weight (Mn) of about 34,000, and a molecular weight distribution (Mw / Mn) of 1.9.
The hydrogenation rate of the main chain was 99.9% by analysis of ¹ H-NMR. Furthermore, the glass transition temperature (Tg) by DSC measurement was 1 peak of only 174 degreeC.

[Block Copolymer (Comparative Example 3)]

[2] Characteristics of the block copolymer Using a vacuum press, unstretched films were prepared from the block copolymers of Examples 1 to 4 and Comparative Examples 1 to 3. Thereafter, using a stretching apparatus (Instron, model number “5567”), the film was stretched 1.5 times by free end uniaxial stretching at a temperature 5 ° C. higher than each glass transition temperature to obtain a stretched film. . Table 1 shows the thickness of each film when unstretched and when stretched.
Further, the haze (cloudiness) of the unstretched film and the stretched film was measured as follows, and the results are shown in Table 1.
Furthermore, in the stretched film, retardation [Re (450), Re (550), Re (650)] at each wavelength (450 nm, 550 nm, 650 nm), retardation development [ΔNxy (550)], wavelength dispersion [Re (450) / Re (550), Re (650) / Re (550)] were measured and calculated as follows, and the results are shown in Table 1.

<Measurement method of Haze when not stretched>
Using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., model number “HM-150”), the haze was measured when unstretched.
<Measurement method of Haze after 1.5 times stretching>
Using a haze meter (manufactured by Murakami Color Research Laboratory, model number “HM-150”), the haze after 1.5-fold stretching was measured.
<Measurement of Re (450), Re (550), and Re (650) and calculation of Re (450) / Re (550) and Re (650) / Re (550)>
Re (450), Re (550) and Re (650) are measured using a retardation film / optical material inspection apparatus (manufactured by Otsuka Electronics Co., Ltd., model number “RETS-100”), and Re (450) / Re (550) and Re (650) / Re (550) were calculated.
<Calculation of phase difference expression [ΔNxy (550)]>
Retardation at 550 nm: ΔNxy (550) was calculated from Re (550) and film thickness.

As is clear from Table 1, in Comparative Examples 1 and 2 that did not contain the block part (B) having a polar site, the unstretched Haze was 15% and 23%, which was inferior in transparency and stretched. In some cases, the film was whitened to form a non-uniform film. The haze was 85% and 103%, and the measurement of retardation was impossible.
Further, as in Comparative Examples 1 and 2, in Comparative Example 3 that does not contain the block part (B) having a polar site, the retardation value becomes smaller toward the longer wavelength side, and has reverse wavelength dispersion. It wasn't.

On the other hand, each film of Examples 1-4 which consists of a block copolymer containing the block part (B) which has a polar site | part has 1% or less Haze at the time of unstretched, and is at the time of extending | stretching, Was 1% or less, and it was confirmed that the film was excellent in transparency.
In addition, each stretched film of Examples 1 to 4 had a larger retardation value toward the longer wavelength side, and it was confirmed that the film had reverse wavelength dispersibility.
Further, each stretched film of Examples 1 to 4 has practically sufficient retardation development properties from the results of ΔNxy (550), Re (450) / Re (550) and Re (650) / Re (550). -It was confirmed that it has reverse wavelength dispersion.

  From the above, the block copolymers of Examples 1 to 4 are excellent in transparency and have inverse wavelength dispersion, and are made of optical materials such as optical disks, optical lenses, optical fibers, transparent plastic substrates, and optical semiconductor encapsulation. It can be suitably used in the optical field such as a sealing material such as a stopper. In particular, the film containing the block copolymer of Examples 1 to 4 can be suitably used in the field of optical materials such as a transparent plastic substrate such as a retardation film.

Claims (3)

A block part (A) containing a structural unit represented by the general formula (1);
And a block part (B) containing a structural unit represented by the general formula (2).

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. , A hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkyl ester group or an alkoxy group. p is an integer of 0 to 3, q is an integer of 0 to 4, and r is 0 or 1. ]

In [general formula (2), m is an integer of 0 to 3, n is 0 or a positive integer, X is a methylene group, an oxygen atom or a sulfur ^atom, A 1 to A ⁴ are each Independently, any one of the following (i) to (iv) is represented, or the following (v) or (vi) is represented. However, the X is, if a methylene group is at least one of the ^A 1 to A ⁴ represents the following (iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, an amide group, an amino group, and a thiol group;
(Iv) a C1-C10 aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group which may be substituted by a halogen atom or the polar group (iii);
(V) A ¹ and A ² , or A ³ and A ⁴ are bonded to each other to form an alkylidene group, and A ^{1 to} A ⁴ not participating in the bonding are independently of each other (i) Represents any one of (iv),
(Vi) A ¹ and A ³ , A ¹ and A ⁴ , A ² and A ³ , or A ² and A ⁴ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are bonded. A ^{1 to} A ⁴ not involved in the bond represent any of the above (i) to (iv), independently of each other. ] In the presence of a macromonomer containing the structural unit represented by the general formula (1) and having an ethylenically unsaturated bond at least at one terminal portion of the main chain,
A raw material monomer containing a compound represented by the general formula (3) is subjected to ring-opening polymerization using a metathesis polymerization catalyst, and then hydrogenated to ethylenically unsaturated bonds present in the ring-opened polymer. A method for producing a block copolymer.

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. , A hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkyl ester group or an alkoxy group. p is an integer of 0 to 3, q is an integer of 0 to 4, and r is 0 or 1. ]

In [Formula (3), m is an integer of 0 to 3, n is 0 or a positive integer, X is a methylene group, an oxygen atom or a sulfur ^atom, A 1 to A ⁴ are each Independently, any one of the following (i) to (iv) is represented, or the following (v) or (vi) is represented. However, the X is, if a methylene group is at least one of the ^A 1 to A ⁴ represents the following (iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, an amide group, an amino group, and a thiol group;
(Iv) a C1-C10 aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group which may be substituted by a halogen atom or the polar group (iii);
(V) A ¹ and A ² , or A ³ and A ⁴ are bonded to each other to form an alkylidene group, and A ^{1 to} A ⁴ not participating in the bonding are independently of each other (i) Represents any one of (iv),
(Vi) A ¹ and A ³ , A ¹ and A ⁴ , A ² and A ³ , or A ² and A ⁴ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are bonded. A ^{1 to} A ⁴ not involved in the bond represent any of the above (i) to (iv), independently of each other. ]   A film comprising the block copolymer according to claim 1.