TWI649338B - Block copolymer, method of producing the same, and film - Google Patents

Abstract

The present invention provides a block copolymer which is highly transparent and useful in the field of optics, a method for producing the same, and a film. The block copolymer of the present invention comprises a block portion (A) comprising a structural unit represented by the following formula (1), and a block portion (B) comprising a structural unit represented by the following formula (2). Further, in the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, and R ³ and R ⁴ represent a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkyl ester group or an alkane. Oxy group, X represents a methylene group, an oxygen atom or a sulfur atom, A ¹ to A ⁴ represent a specific group or an atom, etc., p is an integer of 0 to 3, q is an integer of 0 to 4, and r is 0 or 1. m is an integer from 0 to 3, and n is 0 or a positive integer.

Description

Block copolymer, method of producing the same, and film

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 which is highly transparent and useful in the field of optics, a method for producing the same, and a film comprising the block copolymer.

The cyclic olefin-based resin such as a thermoplastic norbornene-based resin has a high glass transition temperature and a high light transmittance, and has a small refractive index anisotropy. Therefore, it exhibits characteristics such as low birefringence and the like compared with the conventional optical film. Therefore, it has attracted attention as a transparent thermoplastic resin excellent in heat resistance, transparency, and optical characteristics. Further, it has been studied to use a cyclic olefin resin in the optical field such as an optical material such as an optical disk, an optical lens, an optical fiber, or a transparent plastic substrate, or a sealing material such as an optical semiconductor seal.

In particular, low birefringence is an important performance in the field of optics, and attempts have been made to further reduce the birefringence of existing thermoplastic norbornene-based resins.

The thermoplastic norbornene-based resin generally has a "positive" birefringence because the birefringence derived from the orientation is "positive". Therefore, as an attempt to further reduce the birefringence, attempts have been made to introduce low birefringence and zero birefringence by introducing a unit having an orientation birefringence of "negative" into a norbornene-based resin, and at the lens. Use or zero phase difference film • Reverse wavelength dispersion film, etc.

For example, a copolymer of a norbornene-based monomer having a "negative" orientation birefringence (see Patent Document 1 and Patent Document 2) and a non-norbornene-based resin having an orientation birefringence of "negative" are started. The compatibility blend (see Non-Patent Document 1) and the non-norbornene-based resin having an orientation birefringence of "negative" are copolymerized or grafted (see Patent Document 3) and the like.

In the case of synthesizing a norbornene-based monomer whose orientation birefringence is "negative", in terms of production cost, it is usually inexpensive dicyclopentadiene (or heat) due to the advantage that it can be carried out without solvent. The deinomerized monomer is produced by a Diels-Alder reaction of decomposed cyclopentene and dienophile. However, it is generally difficult to separate dicyclopentadiene or a polymer thereof in the purification step, and there is a problem that the purification cost is high (for example, refer to Patent Document 4).

Further, a non-norbornene-based resin having an orientation birefringence of "negative" and a resin compatible with a norbornene-based resin are often disadvantageous in that it is easy to heat the colored resin, and thus it is difficult to perform extrusion film formation. The non-norbornene-based resin which is considered to be "negative" in the lowest cost, and the styrene-maleic anhydride random copolymer described in Non-Patent Document 1 can be obtained at a relatively low cost. However, since compatibility with a norbornene-based resin is not sufficient, spinodal decomposition occurs in a molten state such as injection molding or extrusion film formation. In the case of a cast film, a transparent film can be produced. However, the current situation is that the casting solvent is often high in cost, and has not been put into practical use.

On the other hand, as a spinodal decomposition inhibition scheme, attempts have been made to use an oligomer (lower molecular) having an orientation birefringence such as an inexpensive styrene-based oligomer, but if it is an oligomer, Since the orientation is saturated, it is practically impossible to eliminate birefringence (for example, Non-Patent Document 2 describes the relationship between the molecular weight of the negative birefringent polymer and the degree of elimination of the orientation birefringence). Further, the glass transition temperature is lowered, and the practicality is also small.

Therefore, block copolymerization of a norbornene-based monomer and a styrene-based monomer has been attempted (Patent Document 3).

However, separation from a homopolymer is difficult, and therefore it is necessary to repeat the purification a plurality of times, resulting in high cost. Further, since the introduction rate of styrene is unstable and there is a problem in quality, it is not a method which can be mass-produced. Further, the obtained block body also lacks practicality. For example, in the case of performing an stretching operation which is often performed by an optical film, there is a problem that whitening occurs and transparency is lost. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-173452 [Non-Patent Document] [Non-Patent Document 1] "Collection of Polymers", Vol. 61, No. 1, pp. 89-94 [Non-Patent Document 2] Journal of Polymer Science, Part A: Polymer Chemistry, 2013, No. 51, page 3140, Figure 7

[Problems to be solved by the invention]

The present invention has been made in view of the above circumstances, and an object thereof is to provide a block copolymer excellent in transparency, a method for producing the same, and a film. [Technical means to solve the problem]

The invention is as follows. [1] A block copolymer comprising: a block portion (A) comprising a structural unit represented by the formula (1); and a block portion comprising the structural unit represented by the formula (2) ( B), [Chemical 1] In the 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, an iodine atom, a hydroxyl group, and a carbon number of 1. a linear or branched alkyl group, a cycloalkyl group, an alkyl ester group or an alkoxy group of ～10; p is an integer of 0 to 3, q is an integer of 0 to 4, and r is 0. Or 1] [Chemical 2] In the formula (2), m is an integer of 0 to 3, n is 0 or a positive integer, X represents a methylene group, an oxygen atom or a sulfur atom, and A ¹ to A ⁴ each independently represent the following (i) to Any one of (iv) or the form of (v) or (vi) below; wherein, in the case where X is a methylene group, at least one of A ¹ to A ⁴ represents the following (iii); (i) a hydrogen atom; (ii) a halogen atom; (iii) selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, a decylamino group, an amine group, and a thiol group. a polar group; (iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group or an 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 alkylene group, and A ¹ to A ⁴ which do not participate in the bonding independently represent any of the above (i) to (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 bonded thereto, and A ¹ to A ⁴ not participating in the bonding are independent of each other. Said (i) (Iv) any one]. [2] The block copolymer according to [1], which has a reverse wavelength dispersibility. [3] The block copolymer according to [1] or [2], wherein the unstretched film obtained from the block copolymer is 1.5-fold extended by uniaxial stretching at the free end. The haze of the stretched film is 5% or less. [4] A method for producing a block copolymer, which comprises a macromonomer having not only a structural unit represented by the formula (1) but also an ethylenically unsaturated bond at at least one terminal portion of the main chain. In the presence of a ring-forming polymerization of a raw material monomer containing a compound represented by the general formula (3) by a metathesis polymerization catalyst, the ethylenically unsaturated bond present in the ring-opened polymerized polymer Hydrogenation, In the 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, an iodine atom, a hydroxyl group, or a carbon number of 1 to 1; a linear or branched alkyl group, 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 general formula (3), m is an integer of 0 to 3, n is 0 or a positive integer, X represents a methylene group, an oxygen atom or a sulfur atom, and A ¹ to A ⁴ each independently represent the following (i) to Any one of (iv) or the form of (v) or (vi) below; wherein, in the case where X is a methylene group, at least one of A ¹ to A ⁴ represents the following (iii); (i) a hydrogen atom; (ii) a halogen atom; (iii) selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, a decylamino group, an amine group, and a thiol group. a polar group; (iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group or an 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 alkylene group, and A ¹ to A ⁴ which do not participate in the bonding independently represent any of the above (i) to (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 bonded thereto; and A ¹ to A ⁴ not participating in the bonding are independent of each other; Said (i) (Iv) any one]. [5] A film comprising the block copolymer according to any one of [1] to [3].

[Effects of the Invention] The block copolymer of the present invention has excellent transparency by including a specific block portion (A) and a specific block portion (B) having a polar portion. Therefore, it can be suitably used in optical fields such as optical materials such as optical disks, optical lenses, optical fibers, and transparent plastic substrates, and sealing materials such as optical semiconductor seals. Further, according to the method for producing a block copolymer of the present invention, a block copolymer having excellent transparency can be obtained efficiently. Further, the film of the present invention has excellent transparency by including a block copolymer including a specific block portion (A) and a specific block portion (B) having a polar portion. Therefore, it can be suitably used as an optical material, such as a transparent plastic substrate, such as a retardation film.

The above described features and advantages of the invention will be apparent from the following description.

Hereinafter, the present invention will be described in detail. [1] Block Copolymer The block copolymer of the present invention includes a block portion (A) and a block portion (B). (1-1) Block portion (A) The block portion (A) includes a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (a1)"). [Chemical 5] In the 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, an iodine atom, a hydroxyl group, and a carbon number of 1. a linear or branched alkyl group, a cycloalkyl group, an alkyl ester group or an alkoxy group of ～10; 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 formula (1) each independently represent 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 cycloalkane. A group, an alkyl ester group or an alkoxy group is preferably an alkyl group. The linear or branched alkyl group in R ³ and R ⁴ has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, an n-octyl group and the like.

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

The carbon number 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 particularly preferably 2 to 4. Further, the alkyl moiety in the alkyl ester group may be any of a linear chain, a branched chain, and a cyclic chain. Specific examples of the alkyl ester group include a methyl ester group, an ethyl ester group, a n-propyl ester group, an isopropyl ester group, a n-butyl ester group, an isobutyl ester group, a sec-butyl ester group, a tert-butyl ester group, and a n-pentyl group. Ester group, n-hexyl ester group, n-octyl ester group, and the like.

The carbon number of the alkoxy group in R ³ and R ⁴ is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. Further, the alkyl moiety in the alkoxy group may be any of a linear chain, a branched chain, and a cyclic chain. Specific alkoxy groups include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy Base, n-hexyloxy, cyclopentyloxy, cyclohexyloxy and the like.

Further, p in the formula (1) is an integer of 0 to 3, preferably 0 or 1, and particularly preferably 0. The q is an integer of 0 to 4, preferably 0 or 1, and particularly preferably 0. The r is 0 or 1, preferably 0.

In the block copolymer of the present invention, the block portion (A) may contain only one type of the structural unit (a1), or may contain two or more types. Further, the block portion (A) may contain other structural units (a2) in addition to the structural unit (a1).

The other structural unit (a2) in the block portion (A) may, for example, be a conjugated diene such as a diene such as butadiene or isoprene or a diene such as chloroprene. a structural unit derived from an ene. Further, the block portion (A) may contain only one type of the other structural unit (a2), or may contain two or more types.

Here, in the case where the entire structural unit constituting the block portion (A) [that is, the total of the structural unit (a1) and the structural unit (a2)] is 100 parts by weight, the block portion (A) The content ratio of the structural unit (a1) in the range of preferably 25 parts by weight to 100 parts by weight, more preferably 50 parts by weight to 100 parts by weight, particularly preferably 75 parts by weight to 100 parts by weight. When the content ratio is within the above range, birefringence can be effectively eliminated, which is preferable.

In the case where the entire block copolymer of the present invention is 100 parts by weight, the content of the block portion (A) is preferably 10 parts by weight to 90 parts by weight, and more preferably 15 parts by weight to 70 parts by weight. The part by weight is particularly preferably 25 parts by weight to 50 parts by weight. When the content ratio is within the above range, birefringence can be effectively eliminated, which is preferable.

In addition, the number average molecular weight (Mn) of the block portion (A) in the block copolymer of the present invention is preferably from 3,000 to 200,000, more preferably from 4,000 to 20,000 in terms of polystyrene equivalent value by gel permeation chromatography. 100000, particularly preferably 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 formed. Further, the weight average molecular weight (Mw) of the block portion (A) is preferably from 3,000 to 200,000, more preferably from 5,000 to 100,000, in terms of polystyrene equivalent value by gel permeation chromatography (GPC). It is especially preferably 8,000 to 50,000. When the weight average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be formed. Further, the ratio (Mw/Mn) of Mw to Mn of the block portion (A) in the block copolymer is usually from 1 to 10, more preferably from 1 to 3, particularly preferably from 1 to 1.5.

(1-2) Block portion (B) The block portion (B) in the block copolymer of the present invention contains a structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit ( B1)").

[Chemical 6] In the formula (2), m is an integer of 0 to 3, n is 0 or a positive integer, X represents a methylene group, an oxygen atom or a sulfur atom, and A ¹ to A ⁴ each independently represent the following (i) to Any one of (iv) or the form of (v) or (vi) below; wherein, in the case where X is a methylene group, at least one of A ¹ to A ⁴ represents the following (iii); (i) a hydrogen atom; (ii) a halogen atom; (iii) selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, a decylamino group, an amine group, and a thiol group. a polar group; (iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group or an 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 alkylene group, and A ¹ to A ⁴ which do not participate in the bonding independently represent any of the above (i) to (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 bonded thereto, and A ¹ to A ⁴ not participating in the bonding are independent of each other. Said (i) (Iv) any one]

m in the formula (2) is an integer of 0 to 3, preferably an integer of 0 to 2, and particularly preferably 0 or 1. The n is 0 or a positive integer, preferably an integer of 0 to 3, and particularly preferably an integer of 0 to 2.

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

Further, the polar group of (iii) in A ¹ to A ⁴ of the formula (2) is selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, a decylamino group, an amine group, and a thiol group. In the group. The carbon number of the alkoxy group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Further, the alkyl moiety in the alkoxy group may be any of a linear chain, a branched chain, and a cyclic chain. Specific alkoxy groups include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy Base, n-hexyloxy, cyclopentyloxy, cyclohexyloxy and the like.

The carbon number of the ester group is not particularly limited, but is preferably 2 to 10, more preferably 2 to 8, and particularly preferably 2 to 5. Specific examples of the ester group include an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, an aryloxycarbonyl group such as a phenoxycarbonyl group, a naphthyloxycarbonyl group, a decyloxycarbonyl group or a biphenyloxycarbonyl group. .

The guanamine group may be exemplified by a primary guanamine group, a second guanamine group, and a tertiary amide group. Among these guanamine groups, a primary guanamine group is preferred. The amine group may, for example, be a primary amino group, a secondary amino group or a tertiary amino group. Among these amine groups, a primary amine group is preferred.

The aliphatic hydrocarbon group of (iv) in A ¹ to A ⁴ of the formula (2) has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. Specific examples of the aliphatic hydrocarbon group include an alkyl group such as a methyl group, an ethyl group or a propyl group; and an alkenyl group such as a vinyl group, an allyl group or a propenyl group. The alicyclic hydrocarbon group of the above (iv) preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and particularly preferably 5 or 6 carbon atoms. Specific examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Further, the alicyclic hydrocarbon group does not have a double bond in the ring. The carbon number of the aromatic hydrocarbon group (iv) is not particularly limited, but is preferably 6 to 20, more preferably 6 to 14, and particularly preferably 6 to 10. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, an anthracenyl group, and an anthracenyl group.

In the block copolymer of the present invention, the block portion (B) may contain only one type of the structural unit (b1), or may contain two or more types. Further, the block portion (B) may contain other structural units (b2) in addition to the structural unit (b1).

The other structural unit (b2) in the block portion (B) is exemplified by Japanese Patent Laid-Open No. 51-80400, Japanese Patent Laid-Open Publication No. SHO 60-26024, and Japanese Patent Laid-Open No. Hei No. Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. A structural unit derived from a known norbornene-based monomer, such as Japanese Laid-Open Patent Publication No. Hei 2-276842. Further, the other structural unit (b2) may be a structural unit derived from a monomer capable of chain transfer (excluding the structural unit (a1)). Specific examples include, for example, structural units derived from cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, and a ring. Pentene, 3-methylcyclopentene, cyclooctene, 1-methylcyclooctene, 5-methylcyclooctene, cyclooctatetraene, 1,5-cyclooctadiene, cyclododecene, etc. Monocyclic cycloolefin; acetylene or propyne, 1-butyne or the like as an acetylene of a substituted acetylene; 1,6-heptadiene or the like having a double bond at both end portions. Further, the block portion (B) may include only one type of the other structural unit (b2), or may include two or more types.

Here, in the case where the entire structural unit constituting the block portion (B) [that is, the total of the structural unit (b1) and the structural unit (b2)] is set to 100 mol%, the block portion (B) The content ratio of the structural unit (b1) in the ) is preferably from 20 mol% to 100 mol%, more preferably from 40 mol% to 100 mol%, and particularly preferably from 60 mol% to 100 mol%. When the content ratio is within the above range, practical transparency of the block can be exhibited, which is preferable.

In addition, when the entire block copolymer of the present invention is 100 parts by weight, the content of the block portion (B) is preferably 10 parts by weight to 90 parts by weight, and more preferably 30 parts by weight to 85 parts by weight. The part by weight is particularly preferably from 50 parts by weight to 75 parts by weight. When the content ratio is within the above range, birefringence can be effectively eliminated, which is preferable.

In addition, the number average molecular weight (Mn) of the block portion (B) in the block copolymer of the present invention is preferably from 3,000 to 100,000, more preferably from 4,000 to 50,000, in terms of polystyrene equivalent value of GPC, and particularly preferably It is 5000 to 30000. When the number average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be formed. Further, the weight average molecular weight (Mw) of the block portion (B) is preferably 3,000 to 150,000, more preferably 5,000 to 100,000, and particularly preferably 8,000 to 75,000, in terms of polystyrene equivalent value 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 formed. Further, the ratio (Mw/Mn) of Mw to Mn of the block portion (B) is usually from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 2.5.

(1-3) Block copolymer The arrangement of the respective block portions constituting the block copolymer of the present invention and the like are not particularly limited. Specifically, for example, an arrangement of AB type, ABA type, BAB type, or ABAB type may be mentioned.

The number average molecular weight (Mn) of the block copolymer of the present invention is preferably from 3,000 to 200,000, more preferably from 5,000 to 100,000, still more preferably from 8,000 to 50,000, based on the polystyrene equivalent value of GPC. When the number average molecular weight is within the above range, a block copolymer having high transparency and sufficient impact resistance can be formed. In addition, the weight average molecular weight (Mw) of the block copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 80,000, in terms of polystyrene equivalent value 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 formed. Further, the ratio (Mw/Mn) of Mw to Mn of the block copolymer is usually from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 2.5.

The peak temperature of the glass transition temperature of the block copolymer of the present invention is preferably one. In this case, the phase difference (birefringence) of each block portion generated during stretching does not vary, and birefringence can be effectively eliminated, which is preferable. The glass transition temperature is preferably from 80 ° C to 300 ° C, more preferably from 100 ° C to 200 ° C, and particularly preferably from 120 ° C to 180 ° C. Further, the glass transition temperature can be obtained by a method according to JIS K 7121 using a differential scanning calorimeter (DSC).

The block copolymer of the present invention can be formed to have a property in which the absolute value of the phase difference is higher as it is closer to the long wavelength side than the general polymer material, that is, it has a reverse wavelength dispersion property.

Further, the block copolymer of the present invention can be formed such that the haze of the stretched film obtained by stretching the unstretched film obtained from the polymer by 1.5 times by uniaxial stretching at the free end is 5% or less (particularly It is 3% or less, and further 2% or less. Further, the thickness of the unstretched film when the haze is measured is set to be 20 μm to 500 μm. In addition, this measurement was performed in accordance with JIS K 7105.

Further, in the block copolymer of the present invention, the haze of the unstretched film (thickness: 20 μm to 500 μm) obtained from the polymer is 5% or less (particularly 3% or less, and further For those below 2%).

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

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

[2] Method for Producing Block Copolymer The method for producing a block copolymer of the present invention can be produced by the following method for producing a block copolymer, which is characterized in that not only the above formula (1) is contained The structural unit represented, and in the presence of a macromonomer having an ethylenically unsaturated bond in at least one terminal portion of the main chain, the ring-opening polymerization is carried out after ring-opening polymerization of the raw material monomer by a metathesis polymerization catalyst The ethylenically unsaturated bonds present in the polymer are hydrogenated.

(2-1) Giant Monomer The macromonomer contains not only the structural unit (a1) represented by the above formula (1) but also an ethylenically unsaturated bond at at least one terminal portion of the main chain. The macromonomer may contain only one structural unit (a1), or may contain two or more types. Further, the macromonomer may contain one or two or more of the other structural units (a2) in addition to the structural unit (a1).

Here, in the case where the entire structural unit constituting the macromonomer [that is, the total of the structural unit (a1) and the structural unit (a2)] is 100 parts by weight, the structural unit in the macromonomer (a1) The content ratio is preferably 25 parts by weight to 100 parts by weight, more preferably 50 parts by weight to 100 parts by weight, and particularly preferably 75 parts by weight to 100 parts by weight. When the content ratio is within the above range, birefringence can be effectively eliminated, which is preferable.

Further, the number average molecular weight (Mn) of the macromonomer is preferably from 3,000 to 200,000, more preferably from 4,000 to 100,000, particularly preferably from 5,000 to 30,000, in terms of polystyrene equivalent value 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 formed. Further, the weight average molecular weight (Mw) of the macromonomer is preferably from 3,000 to 200,000, more preferably from 4,000 to 100,000, still more preferably from 5,000 to 30,000, in terms of polystyrene equivalent value 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 formed. Further, the ratio (Mw/Mn) of Mw to Mn of the block portion (A) in the macromonomer is usually from 1 to 10, more preferably from 1 to 3, particularly preferably from 1 to 1.5.

(2-2) Synthesis of a macromonomer The monolithic body represented by the following general formula (4) corresponding to the structural unit (a1) represented by the general formula (1) can be used, and The raw material of the unitary body corresponding to the structural unit (a2) is polymerized as needed, and at least one terminal portion of the main chain in the obtained polymer is introduced into an ethylenically unsaturated bond to be synthesized. Further, regarding the general formula ^{R 1 ~ R 4, p,} q and r (. 4) in, respectively, can be applied directly in the general formula ¹ ~ R ^4, p, q and r Description (1) R.

[Chemistry 7] In the 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, an iodine atom, a hydroxyl group, and a carbon number of 1. a linear or branched alkyl group, a cycloalkyl group, an alkyl ester group or an alkoxy group of ～10; 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 of polymerizing the monolith is not particularly limited, and a usual method for producing a hydrocarbon-based polymer can be used. Specific examples thereof include a radical polymerization method such as solution polymerization, emulsion polymerization, and bulk polymerization; an anionic polymerization method using an organic alkali metal compound or the like as a catalyst; and a cation using BF ₃ , AlCl ₃ , TiCl ₄ or the like as a catalyst. Polymerization method, etc. Among these polymerization methods, in order to form a macromonomer, a method of easily introducing a non-conjugated ethylenically unsaturated bond is preferred. Specifically, it is preferably a living anionic polymerization or a living radical polymerization method, and particularly preferably a living anionic polymerization.

Further, in the synthesis of the macromonomer, a method of introducing an ethylenically unsaturated bond to at least one terminal portion of the main chain is not particularly limited, and it can be carried out by a known method. Specifically, for example, the method described in Chapter 2 of "Chemicals and Industries of Giant Monomers" (edited by Yamashita Hideo) issued by the IPC Publishing Department (IPC Co., Ltd.) is exemplified.

Further, the raw material monomer used in the ring-opening polymerization contains a compound represented by the following formula (3). Further, the descriptions of X, m, n and A ¹ to A ⁴ in the above formula (2) can be directly applied to X, m, n and A ¹ to A ⁴ in the above formula (3).

[化8] In the general formula (3), m is an integer of 0 to 3, n is 0 or a positive integer, X represents a methylene group, an oxygen atom or a sulfur atom, and A ¹ to A ⁴ each independently represent the following (i) to Any one of (iv) or the form of (v) or (vi) below; wherein, in the case where X is a methylene group, at least one of A ¹ to A ⁴ represents the following (iii); (i) a hydrogen atom; (ii) a halogen atom; (iii) selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, a decylamino group, an amine group, and a thiol group. a polar group; (iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group or an 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 alkylene group, and A ¹ to A ⁴ which do not participate in the bonding independently represent any of the above (i) to (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 bonded thereto, and A ¹ to A ⁴ not participating in the bonding are independent of each other. Said (i) (Iv) any one]

Specific examples of the compound represented by the above formula (3) include 5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene and 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]heptane- 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 ]non-3-ene, 7-Bromo-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7,8-dichloro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-chloromethyl-three Ring [4.3.0.1 ^2,5 ]non-3-ene, 7-hydroxy-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-cyano-tricyclo[4.3.0.1 ^2,5 ] Indole-3-ene, 7-amino-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Di-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-benzene Ylcarbonyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene, 8-hydroxy - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene , 8-hydroxyethyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^dode -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. Further, these compounds may be used alone or in combination of two or more.

Further, the raw material monomer may contain one or two or more kinds of known norbornene-based monomers described in the other structural unit (b2) in the block (B) of the block copolymer, or may be A monomer that undergoes chain transfer.

The metathesis polymerization catalyst used in the ring-opening polymerization is not particularly limited, and a known one can be used. Specifically, for example, Japanese Patent Publication No. Sho 41-50111, Japanese Patent Laid-Open No. SHO 46-14910, Japanese Patent Publication No. Sho 57-17883, Japanese Patent Publication No. Sho 57-61044, Japan It is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The metathesis polymerization catalyst is preferably used in an amount of from 0.00000001 mol to 0.005 mol, more preferably from 0.00000005 mol to 0.001 mol, based on 1 mol of the total amount of the monomer. In the case where the amount of the catalyst used is in the above range, the reaction can be sufficiently carried out, and the catalyst can be easily removed.

Further, examples of the reaction solvent used in the ring-opening polymerization include alkanes such as pentane, hexane, heptane, octane, decane, and decane; cyclohexane, cycloheptane, cyclooctane, and ten. Naphthenes such as hydrogen naphthalene and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutane, bromohexane, dichloromethane, dichloroethane and hexamethylene a compound such as a halogenated alkane such as bromine, chlorobenzene, chloroform or tetrachloroethylene; or a halogenated aryl group; a saturated carboxylic acid ester such as ethyl acetate, n-butyl acetate, isobutyl acetate or methyl propionate; dibutyl ether or tetrahydrofuran; An ether such as dimethoxyethane. These reaction solvents may be used singly or in combination of two or more.

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

The method of the hydrogenation is not particularly limited, and it is usually carried out by adding a hydrogenation catalyst and a hydrogenation reaction of hydrogen to a solution of the block polymer after ring-opening polymerization. The solvent used in this case may be the same solvent as the reaction solvent used in the ring-opening polymerization, and is not particularly limited as long as it is not hydrogenated by itself. Therefore, the block copolymer solution obtained by ring-opening polymerization can also be directly supplied to the hydrogenation reaction.

As the hydrogenation catalyst, a known compound used for hydrogenating a usual olefinic unsaturated bond can be used. Specifically, for example, a so-called Ziegler type in which an organic acid salt such as titanium, cobalt or nickel or an acetoacetone salt is combined with an organometallic compound such as lithium, magnesium, aluminum or tin may be mentioned. a homogeneous catalyst; a supported noble metal catalyst obtained by supporting a noble metal such as palladium, platinum, rhodium or ruthenium on a carrier such as carbon, alumina, cerium oxide alumina, cerium oxide magnesia or diatomaceous earth; A noble metal complex catalyst such as ruthenium, osmium or iridium. Among these catalysts, since the reactivity of hydrogenation is excellent, a metal hydride complex compound in which the metal element is ruthenium is preferable.

Specifically, the metal hydride complex compound in which the metal element is ruthenium may, for example, be RuH(OCOPh)(CO)(PPh ₃ ) ₂ or 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 so on. Among these compounds, RuH(OCOPh-C ₅ H ₁₁ )(CO)(PPh ₃ ) ₂ is preferable. Further, "Ph" in each formula means a phenyl group (-C ₆ H ₅ ) or a phenylene group (-C ₆ H ₄ -).

When the total amount of the raw material monomers is 100% by mass (1,000,000 ppm by mass), the amount of the hydrogenation catalyst used is preferably 5 ppm by mass to 200 ppm by mass, and more preferably 10 ppm by mass to 100 ppm by mass.

The supply amount of the hydrogen gas is preferably 0.0001 MPa/s to 0.01 MPa/s, and more preferably 0.001 MPa/s to 0.005 MPa/s. Further, the pressure of the reaction system in the hydrogenation reaction is preferably from 1 MPa to 25 MPa, more preferably from 3 MPa to 20 MPa, even more preferably from 5 MPa to 15 MPa. Further, the temperature of the solution in the hydrogenation reaction is preferably from 100 ° C to 200 ° C, more preferably from 120 ° C to 200 ° C, and still more preferably from 140 ° C to 180 ° C. Further, the time from the temperature in the reaction system to the target reaction temperature, and the time until the pressure of the hydrogen gas reaches the target pressure until the end of the reaction is usually from 1 hour to 9 hours, preferably from 2 hours to 5 hours. If it is the time of the said range, sufficient hydrogenation can be performed, and the side reaction by the time too long can be suppressed.

The hydrogenation by the hydrogenation reaction is a reaction with an ethylenically unsaturated bond present in the ring-opening polymerized polymer, and the other unsaturated bond may be unhydrogenated. The hydrogenation ratio of the ethylenically unsaturated bond of the main chain obtained by the hydrogenation reaction is preferably from 90% to 100%, more preferably from 95% to 100%, particularly preferably from 97% to 100%. When the hydrogenation ratio is within the above range, higher transparency can be exhibited, which is preferable. In addition, the hydrogenation ratio can be calculated, for example, from the integral ratio of the peaks of the olefin portion to the alicyclic structure portion in the NMR spectrum obtained by measurement of ¹ H-nuclear magnetic resonance (NMR).

Here, a specific procedure 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 single body corresponding to the structural unit (a1) [refer to the following scheme (X)]. Then, a raw material monomer containing the compound represented by the above formula (3) is subjected to ring-opening copolymerization in the presence of the obtained macromonomer [refer to the following scheme (Y)]. Then, by performing hydrogenation, the target block copolymer can be synthesized [refer to the following scheme (Z)]. Further, R in the following formula represents a monovalent organic group, and examples of the monovalent organic group include a methyl group, a n-butyl group, a sec-butyl group, a t-butyl group, a n-hexyl group and the like. Further, B represents a divalent linking group, and examples of the divalent linking group include a methylene group, an ethylene group, a propylene group, an ethoxyethylene group and the like.

[Chemistry 9]

[化10]

[11]

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

The film may be composed only of the block copolymer, and may also contain other polymers or additives. Examples of the other polymer include a cyclic olefin polymer, polystyrene, and the like. Further, these other polymers may be used alone or in combination of two or more. Further, as the additive, a known anti-aging agent, ultraviolet absorber, mold release agent, lubricant or the like can be used. Further, these additives may be used alone or in combination of two or more.

In addition, when the entire film is 100 parts by weight, the content of the block copolymer is preferably 50 parts by weight to 100 parts by weight, more preferably 80 parts by weight to 100 parts by weight, and particularly preferably 90 parts by weight to 100 parts by weight. When the content ratio is within the above range, higher transparency can be exhibited, which is preferable.

The thickness of the film is not particularly limited, and may be, for example, 1 μm to 500 μm (particularly 5 μm to 200 μm, and further 10 μm to 100 μm).

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

Further, in the case where the film is an unstretched film having a thickness of 20 μm to 500 μm, the haze of the stretched film obtained when the film is stretched 1.5 times by the uniaxial stretching at the free end is 5%. The following film (particularly 3% or less, further 2% or less). Further, the measurement was carried out in accordance with JIS K 7105.

Further, since the film contains the block copolymer, it can be formed to be opposite to a general polymer film, and has a property in which the absolute value of the phase difference is higher as it is closer to the longer wavelength side, that is, has a reverse wavelength dispersion. Sex.

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

[Examples] Hereinafter, the present invention will be further specifically described by way of examples. However, the invention is not limited by these examples. In addition, in the following, unless otherwise indicated, a part and % are a mass basis.

The following measurements in the following synthesis examples and the like were carried out in accordance with the following procedures. <Mw, Mn, and Mw/Mn> GPC column (G2000HXL: 2, G3000HXL: 1 and G4000HXL: 1) manufactured by Tosoh Corporation was used, and the flow rate was 1.0 ml/min, and the solvent was dissolved in tetrahydrofuran. The analysis conditions of the column temperature of 40 ° C were measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. Further, the degree of dispersion Mw/Mn was calculated from the measurement results. ^<1 H-NMR analysis> ¹ H-NMR analysis was performed using JEOL () manufactured model "JNM-ECX400" is determined. <Glassification temperature> The glass transition temperature was measured by a method according to JIS K 7121 using DSC (differential scanning calorimeter, manufactured by Seiko Instruments, model "Exstar 6000").

[1] Production of block copolymer (1-1) Synthesis of macromonomer <Polystyrene macromonomer having ethylenic unsaturated bond at the terminal (A)> 1500 parts of tetrahydrofuran (THF) Then, 1.9 parts of sec-butyllithium was mixed, and the mixture was cooled to an internal temperature of -78 ° C while stirring, and then 300 parts of styrene was added dropwise over 20 minutes. Next, while stirring the reaction liquid for 1 hour while maintaining the reaction liquid at -78 ° C, 4.9 parts of 5-bromo-1-pentene was added to the reaction liquid, and the mixture was stirred for 30 minutes while warming to room temperature. After the completion of the reaction, the reaction liquid was added dropwise to 8000 parts of methanol, and the precipitate thus obtained was recovered, filtered, and dried, whereby 290 parts of a terminal vinyl-modified styrene-based polymerization having the following structure was obtained. Body [polystyrene macromonomer (A) having an ethylenically unsaturated bond at the end]. Further, 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.

[巨单单(A)] [化12]

<Polystyrene macromonomer (B) having an ethylenically unsaturated bond at the terminal> The amount of sec-butyllithium in the synthesis of the macromonomer (A) is set to 2.4 parts, and 5 In the same manner as the above-mentioned macromonomer (A), 288 parts of a terminal vinyl-modified styrene-based polymer having the following structure was obtained in the same manner as in the above-mentioned macromonomer (A). A polystyrene macromonomer (B) having an ethylenically unsaturated bond at its end. Further, 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.

[巨单单(B)] [化13]

(1-2) Production of Block Copolymer <Example 1> 35 parts of the macromonomer (A) and 65 parts of the following compound (m-1) (8-methyl-8-methoxy group) After the carbonyl group-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^dode -3-ene) and 150 parts of toluene are mixed in an autoclave, the internal temperature is heated to 100 ° C, and 0.00116 parts is added. Metathesis polymerization catalyst of the formula ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidine subunit]dichloro[[2-(1-methylethyl oxime) Phenyl]methylene]phosphonium (II)), stirred for 1 hour. Then, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

[compound (m-1)] [Chemical 14]

[Translocation polymerization catalyst] [Chemical 15]

Then, 110 parts of toluene and 20 ppm of a catalyst for hydrogenation reaction of the following formula (Ru[4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ]H(CO) [P (C) were added to the reaction liquid. ₆ H ₅ ) ₃ ] ₂ ), the pressure was raised to 10 MPa of hydrogen at 165 ° C, and the mixture was stirred for 3 hours to carry out a hydrogenation reaction. Then, the reaction liquid was added dropwise to 3,000 parts of methanol, and the precipitate obtained therefrom was recovered, filtered, and dried, whereby 97 parts of the block copolymer of Example 1 having the following structure was obtained. Further, 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 ratio of the main chain obtained by ¹ H-NMR analysis was 99.9%, and the hydrogenation ratio of the side chain (styrene-based site) was 0%. Further, the glass transition temperature (Tg) obtained by DSC measurement was only one peak at 125 °C.

[Catalyst for Hydrogenation Reaction] [Chem. 16]

[Block Copolymer (Example 1)] [Chem. 17]

<Example 2> 35 parts of the macromonomer (B), 65 parts of the compound (m-1) (8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^{2, 5} .1 ^7,10 ]dodec-3-ene), and 150 parts of toluene were mixed in an autoclave, and the internal temperature was heated to 100 ° C, and 0.00116 parts of the metathesis polymerization catalyst was added ([1, 3 - bis(2,4,6-trimethylphenyl)-2-imidazolidine subunit]dichloro[[2-(1-methylethyloxy)phenyl]methylene]anthracene (II) ), stirring for 1 hour. Then, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Then, 110 parts of toluene and 20 ppm of the catalyst for hydrogenation reaction (Ru[4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ]H(CO) [P(C ₆ H) were added to the reaction liquid. ₅ ) ₃ ] ₂ ), the pressure was raised to 10 MPa of hydrogen at 165 ° C, and the mixture was stirred for 3 hours to carry out a hydrogenation reaction. Then, the reaction liquid was added dropwise to 3,000 parts of methanol, and the precipitate obtained thereby was collected, filtered, and dried, whereby 96 parts of the block copolymer of Example 2 having the following structure was obtained. Further, 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 ratio of the main chain obtained by ¹ H-NMR analysis was 99.9%, and the hydrogenation ratio of the side chain (styrene-based site) was 0%. Further, the Tg obtained by DSC measurement was only one peak at 121 °C.

[Block Copolymer (Example 2)] [Chem. 18]

<Example 3> 30 parts of the macromonomer (B), 70 parts of the compound (m-1) (8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^{2, 5} .1 ^7,10 ]dodec-3-ene), and 150 parts of toluene were mixed in an autoclave, and the internal temperature was heated to 100 ° C, and 0.00116 parts of the metathesis polymerization catalyst was added ([1, 3 - bis(2,4,6-trimethylphenyl)-2-imidazolidine subunit]dichloro[[2-(1-methylethyloxy)phenyl]methylene]anthracene (II) ), stirring for 1 hour. Then, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Then, 110 parts of toluene and 20 ppm of the catalyst for hydrogenation reaction (Ru[4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ]H(CO) [P(C ₆ H) were added to the reaction liquid. ₅ ) ₃ ] ₂ ), the pressure was raised to 10 MPa of hydrogen at 165 ° C, and the mixture was stirred for 3 hours to carry out a hydrogenation reaction. Then, the reaction liquid was added dropwise to 3,000 parts of methanol, and the precipitate thus obtained was collected, separated by filtration, and dried to obtain 96 parts of the block copolymer of Example 3 having the following structure. Further, 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 ratio of the main chain obtained by ¹ H-NMR analysis was 99.9%, and the hydrogenation ratio of the side chain (styrene-based site) was 0%. Further, the Tg obtained by DSC measurement was only one peak at 127 °C.

[Block Copolymer (Example 3)] [Chem. 19]

<Example 4> 35 parts of the macromonomer (B), 30 parts of the compound (m-1) (8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^{2, 5} .1 ^7,10 ]dodec-3-ene), 20 parts of the following compound (m-2) (5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene ), 12 parts of the following compound (m-3) (6-methyl-1,4:5,8-dimethyl bridge-1,4,4a,5,6,7,8,8a-octahydronaphthalene) 1 part of the following compound (m-4) (tricyclopentadiene), 1 part of the following compound (m-5) (dicyclopentadiene), 1 part of the following compound (m-6) (2-norbornene), and 150 parts of toluene are mixed in an autoclave, and the internal temperature is heated to 100 ° C, and 0.00116 parts of the metathesis polymerization catalyst is added ([1,3-double (2, 4) ,6-Trimethylphenyl)-2-imidazolidine subunit]dichloro[[2-(1-methylethyloxy)phenyl]methylene]phosphonium (II)), stirred for 1 hour. Then, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

[Compound (m-2) to Compound (m-6)] [Chemical 20]

Then, 110 parts of toluene and 200 ppm of the catalyst for hydrogenation reaction (Ru[4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ]H(CO) [P(C ₆ H) were added to the reaction liquid. ₅ ) ₃ ] ₂ ), the pressure was raised to 10 MPa of hydrogen at 165 ° C, and the mixture was stirred for 3 hours to carry out a hydrogenation reaction. Then, the reaction liquid was added dropwise to 3,000 parts of methanol, and the precipitate obtained therefrom was recovered, filtered, and dried, whereby 98 parts of the block copolymer of Example 4 having the following structure was obtained. Further, 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 ratio of the main chain obtained by ¹ H-NMR analysis was 99.9%, and the hydrogenation ratio of the side chain (styrene-based site) was 0%. Further, the glass transition temperature (Tg) obtained by DSC measurement was only one peak at 110 °C.

[Block Copolymer (Example 4)] [Chem. 21]

<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 0.00116 parts of the metathesis polymerization catalyst ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidine subunit]dichloro[[2] was added. -(1-Methylethyloxy)phenyl]methylene]phosphonium (II)), stirred for 1 hour. Then, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Then, 350 parts of toluene and 20 ppm of the catalyst for hydrogenation reaction (Ru[4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ]H(CO) [P(C ₆ H) were added to the reaction liquid. ₅ ) ₃ ] ₂ ), the pressure was raised to 10 MPa of hydrogen at 165 ° C, and the mixture was stirred for 3 hours to carry out a hydrogenation reaction. Then, the reaction liquid was added dropwise to 4000 parts of methanol, and the precipitate obtained thereby was recovered, separated by filtration, and dried to obtain a block copolymer. Since the homopolymer of the macromonomer is mixed in the obtained block copolymer, it is further dissolved in 500 parts of toluene, and the reaction liquid is added dropwise to 4000 parts of methanol to recover the precipitate and be separated by filtration. The operation was repeated 3 times. Then, 90 parts of the block copolymer of Comparative Example 1 having the following structure was obtained by drying. Further, the block copolymer of Comparative Example 1 had a weight average molecular weight (Mw) of about 54,000, a number average molecular weight (Mn) of about 31,000, and a molecular weight distribution (Mw/Mn) of 1.7. Further, the hydrogenation ratio of the main chain obtained by ¹ H-NMR analysis was 99.9%, and the hydrogenation ratio of the side chain (styrene-based site) was 0%. Further, the glass transition temperature (Tg) obtained by DSC measurement was two peaks at 98 ° C and 105 ° C.

[Block Copolymer (Comparative Example 1)] [Chem. 22]

<Comparative Example 2> 35 parts of the macromonomer (B) and 65 parts of the compound (m-3) (6-methyl-1,4:5,8-dimethyl bridge-1,4) , 4a, 5, 6, 7, 8, 8a-octahydronaphthalene), and 150 parts of cyclohexane are mixed in an autoclave, and the internal temperature is heated to 100 ° C, and 0.00116 parts of the metathesis polymerization catalyst is added. ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidine subunit]dichloro[[2-(1-methylethyloxy)phenyl]methylene ]钌(II)), stir for 1 hour. Then, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Then, 350 parts of toluene and 20 ppm of the catalyst for hydrogenation reaction (Ru[4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ]H(CO) [P(C ₆ H) were added to the reaction liquid. ₅ ) ₃ ] ₂ ), the pressure was raised to 10 MPa of hydrogen at 165 ° C, and the mixture was stirred for 3 hours to carry out a hydrogenation reaction. Then, the reaction liquid was added dropwise to 4000 parts of isopropyl alcohol, and the precipitate obtained thereby was recovered, separated by filtration, and dried to obtain a block copolymer. Since the homopolymer of the macromonomer is mixed in the obtained block copolymer, it is further dissolved in 500 parts of cyclohexane, and the reaction liquid is added dropwise to 4000 parts of isopropyl alcohol to precipitate the precipitate. The mixture was recovered and separated by filtration, and the operation was repeated 3 times. Then, 88 parts of the block copolymer of Comparative Example 2 having the following structure was obtained by drying. Further, the block copolymer of Comparative Example 2 had a weight average molecular weight (Mw) of about 50,000, a number average molecular weight (Mn) of about 21,000, and a molecular weight distribution (Mw/Mn) of 2.3. Further, the hydrogenation ratio of the main chain obtained by ¹ H-NMR analysis was 99.9%, and the hydrogenation ratio of the side chain (styrene-based site) was 0%. Further, the glass transition temperature (Tg) obtained by DSC measurement was two peaks at 105 ° C and 151 ° C.

[Block Copolymer (Comparative Example 2)] [Chem. 23]

<Comparative Example 3> 1.5 parts of 1-butene and 100 parts of the compound (m-1) (8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^{7] , 10} ] dodeca-3-ene), and 150 parts of toluene were mixed in an autoclave, and the internal temperature was heated to 100 ° C, and 0.00116 parts of the metathesis polymerization catalyst was added ([1,3-double (2) ,4,6-trimethylphenyl)-2-imidazolidine subunit]dichloro[[2-(1-methylethyloxy)phenyl]methylene]phosphonium (II)), stirring 1 hour. Then, 0.00025 parts of ethyl vinyl ether was added to stop the reaction.

Then, 110 parts of toluene and 20 ppm of the catalyst for hydrogenation reaction (Ru[4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ]H(CO) [P(C ₆ H) were added to the reaction liquid. ₅ ) ₃ ] ₂ ), the pressure was raised to 10 MPa of hydrogen at 165 ° C, and the mixture was stirred for 3 hours to carry out a hydrogenation reaction. Then, the reaction liquid was added dropwise to 3,000 parts of methanol, and the precipitate obtained thereby was collected, filtered, and dried, whereby 95 parts of the block copolymer of Comparative Example 3 having the following structure was obtained. Further, 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. Further, the hydrogenation rate of the main chain was 99.9% by ¹ H-NMR analysis. Further, the glass transition temperature (Tg) obtained by DSC measurement was only one peak at 174 °C.

[Block Copolymer (Comparative Example 3)] [Chem. 24]

[2] Characteristics of the block copolymer An unstretched film was produced from each of the block copolymers of Examples 1 to 4 and Comparative Examples 1 to 3 by vacuum pressing. Then, using a stretching device (manufactured by Instron, model "5567"), 1.5 times extension was performed by uniaxial stretching at the free end at a temperature 5 ° C higher than the respective glass transition temperature to obtain a stretched film. . The thickness of each film at the time of non-extension and extension at this time is shown in Table 1. Further, Haze (haze) of the unstretched film and the stretched film was measured in the following manner, and the results are shown in Table 1. Further, the retardation at each wavelength (450 nm, 550 nm, 650 nm) of the stretched film was measured and calculated as follows [Re (450), Re (550), Re (650)], and phase difference expression [ΔNxy] (550)], wavelength dispersibility [Re (450) / Re (550), Re (650) / Re (550)], and the results are shown in Table 1.

<Measurement Method of Haze at the Time of Unexpanded> The haze at the time of non-extension was measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., model "HM-150"). <Measurement Method of Haze after Extension of 1.5 Times> Using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., model "HM-150"), the haze after 1.5-fold extension was measured. <Re (450), Re (550), and Re (650), and Re (450)/Re (550) and Re (650)/Re (550) calculations> Using a retardation film and an optical material inspection device ( Manufactured by Otsuka Electronics Co., Ltd., model "RETS-100"), measured Re (450), Re (550) and Re (650), and calculated Re (450) / Re (550) and Re (650) / Re ( 550). <Calculation of phase difference expression [ΔNxy(550)]> ΔNxy (550) was calculated from the retardation at 550 nm: Re (550) and the film thickness.

[Table 1] Table 1

As shown in Table 1, in Comparative Example 1 and Comparative Example 2, which did not contain the block portion (B) having a polar portion, the haze at the time of not extending was 15% and 23%, and the transparency was poor, and whitening occurred when extended. The film became uneven, and the haze was 85% and 103%, and the retardation could not be measured. Further, in Comparative Example 3, which does not include the block portion (B) having a polar portion, as in Comparative Example 1 and Comparative Example 2, the retardation value is smaller as it is closer to the longer wavelength side, and the reverse wavelength dispersibility is not obtained.

On the other hand, in each of the films of Examples 1 to 4 including the block copolymer having the block portion (B) having a polar portion, the haze at the time of non-expansion is 1% or less, even when it is extended. When it is 1% or less, it is confirmed that the transparency is excellent. Further, the closer the respective stretched films of Examples 1 to 4 are to the longer wavelength side, the larger the retardation value is, and it is confirmed that the reverse wavelength dispersibility is provided. Further, each of the stretched films of Examples 1 to 4 was confirmed to have a sufficient phase in practical use based on the results of ΔNxy (550), Re (450)/Re (550), and Re (650)/Re (550). Poor performance · Reverse wavelength dispersion.

As described above, the block copolymers of Examples 1 to 4 are excellent not only in transparency but also in wavelength dispersion, and can be suitably used for optical materials such as optical disks, optical lenses, optical fibers, and transparent plastic substrates, and optical semiconductor seals. In the field of optics such as sealing materials. In particular, the film containing the block copolymers 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.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

no

no

Claims (5)

A block copolymer comprising: a block portion (A) comprising a structural unit represented by the formula (1); and a block portion (B) comprising a structural unit represented by the formula (2), In the 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, an iodine atom, a hydroxyl group, and a carbon number of 1 to 2; a linear or branched alkyl group, 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 formula (2), m is an integer of 0 to 3, n is 0 or a positive integer, X represents a methylene group, an oxygen atom or a sulfur atom, and A ¹ to A ⁴ each independently represent the following (i) to ( Any one of iv) or a form of the following (v) or (vi); wherein, in the case where X is a methylene group, at least one of A ¹ to A ⁴ represents the following ( Iii); (i) a hydrogen atom; (ii) a halogen atom; (iii) a polarity selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, a decylamino group, an amine group, and a thiol group (iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group or an 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 alkylene group, and A ¹ to A ⁴ not participating in the bonding represent each other independently of (i) to (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, and A ¹ to A ⁴ which do not participate in the bonding Any of the above (i) to (iv) is independently indicated. The block copolymer according to claim 1, which has reverse wavelength dispersion. The block copolymer according to claim 1 or 2, wherein the haze of the stretched film obtained by 1.5-fold extension of the unstretched film obtained from the block copolymer by the free end uniaxial stretching is 5% or less. A method for producing a block copolymer, characterized in that, in the presence of a macromonomer having not only a structural unit represented by the formula (1) but also an ethylenically unsaturated bond in at least one terminal portion of the main chain, After ring-opening polymerization of a raw material monomer containing a compound represented by the general formula (3) by a metathesis polymerization catalyst, hydrogenation of an ethylenically unsaturated bond existing in the ring-opening polymerized polymer is carried out, In the 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, an iodine atom, a hydroxyl group, and a carbon number of 1 to 2; a linear or branched alkyl group, 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 formula (3), m is an integer of 0 to 3, n is 0 or a positive integer, X represents a methylene group, an oxygen atom or a sulfur atom, and A ¹ to A ⁴ each independently represent the following (i) to ( Any one of iv) or a form of the following (v) or (vi); wherein, in the case where X is a methylene group, at least one of A ¹ to A ⁴ represents the following ( Iii); (i) a hydrogen atom; (ii) a halogen atom; (iii) a polarity selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a carboxyl group, a cyano group, a decylamino group, an amine group, and a thiol group (iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group or an 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 alkylene group, and A ¹ to A ⁴ not participating in the bonding represent each other independently of (i) to (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, and A ¹ to A ⁴ which do not participate in the bonding Any of the above (i) to (iv) is independently indicated. A film comprising the block copolymer of item 1 or 2 of the patent application.