JP2002105151A - Film and sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film or sheet having high heat resistance, transparency and mechanical strength. SOLUTION: This film or sheet is obtained by forming a block copolymer composed of [A] polymer block having recurring unit of alicyclic structure and [B] polymer block having vinyl compound-derived recurring unit(s); wherein the polymer block [B] maybe composed of two kinds of recurring unit, and the molar fraction of each of the two kinds of recurring unit to the polymer block [A] fall preferably within a specific range. This film or sheet can be used as an optical or packaging material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a film and a sheet obtained by molding a block copolymer having an alicyclic structure.

[0002]

2. Description of the Related Art Styrene-ethylene-butylene-styrene block copolymer (SE) which is a hydride of styrene-butadiene-styrene block copolymer (SBS)
BS) has been studied for various applications as an improved SBS having improved heat resistance, weather resistance, oil resistance and the like. Recently, for example, it has been used as a sheet for civil engineering and construction, and its use in the medical field has begun to be studied. But,
SEBS is not high in elasticity, so it can be used only as a relatively thick sheet, and it is difficult to use it for optical applications because it is not transparent.

[0003] On the other hand, WO 98/55886 discloses that an aromatic ring has a hydrogenation rate of 97% or more, a weight average molecular weight of 100,000 to 300,000, and a molecular weight distribution of 2.0 or less. It describes that a hydrogenated product of an aromatic vinyl polymer can be used for a polarizing film, a retardation film, or the like. However, this polymer was invented as a suitable material for a plastic lens excellent in low birefringence, and only disclosed the possibility of use in a special optical film as described above. . Under these circumstances, in recent years, the demand for polymer film materials in the information field, the medical field, the food field, and the like is high, and transparency,
There has been a demand for films and sheets that are excellent in heat resistance, mechanical strength, and the like, and that can be used for various applications.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide films and sheets having excellent transparency, heat resistance and mechanical strength.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, hydrogenation is carried out up to the aromatic ring portion of the block copolymer of styrene and butadiene or isoprene. By that, transparency, heat resistance,
Since a block copolymer excellent in mechanical strength such as elastic modulus can be obtained, it has been found that a film or sheet excellent in transparency and the like can be formed by using the polymer. The present invention has been obtained based on this finding.

Thus, according to the present invention, a polymer block [A] containing a repeating unit [1] represented by the following formula (1) and a repeating unit [2] represented by the following formula (2) or And / or a film or sheet obtained by molding a block copolymer having a polymer block [B] containing a repeating unit [3] represented by the following formula (3).

[0007]

Embedded image (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{2 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, and a carbon atom having 1 carbon atom. To 20 alkoxy groups or halogen groups.)

[0008]

Embedded image (In the formula, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

[0009]

Embedded image (In the formula, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

According to the present invention, the polymer block [B] further contains the repeating unit [1], and the mole fraction a (mol%) of the repeating unit [1] in the block [A]. And the repeating unit [1] in the block [B]
Wherein the molar fraction b (mol%) is a> b. Further, according to the present invention, the content of the repeating unit [1] in the polymer block [A] is 50 mol% or more, and the mole fraction of the repeating unit [2] in the polymer block [B]. m ₂ (mol%), and
The molar fraction m ₃ (mol%) of the repeating unit [3] is 2 ×
The aforementioned film and sheet having a relationship of m ₂ + m ₃ ≧ 2 (mol%) are provided. Further, according to the present invention, the block copolymer, the mole number m _b of all repeating units constituting the mole number m _a of all repeating units constituting the block [A], block [B] ratio ( _{m a:} m _b) 4
A film and sheet as described above, wherein the ratio is from 0:60 to 90:10. Further, according to the present invention, there are provided the above-mentioned films and sheets which are optical or packaging materials.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The film and sheet of the present invention
A polymer block [A] containing a repeating unit [1] represented by the following formula (1) and a polymer block [B] containing a repeating unit [2] represented by the following formula (2): It is obtained by molding the following block copolymer. 1. Block copolymer polymer block [A] containing a repeating unit [1] represented by the following formula (1). The content of the repeating unit [1] in the polymer block [A] is preferably 50 mol%.
It is more preferably at least 70 mol%, most preferably at least 90 mol%.

[0012]

Embedded image (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{2 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, and a carbon atom having 1 carbon atom. To 20 alkoxy groups or halogen groups.
The above [R ² -R ¹² ] represents R ² , R ³ , R ⁴ ,
^{R 5, R 6, R 7} , R 8, R 9, R 1 0, R 11, and a ^{R 12.} Hereinafter the same)

A preferred structure of the repeating unit [1] represented by the above formula (1) is that R ¹ is hydrogen or a methyl group,
R ² -R ¹² are all those of hydrogen. When the content of the repeating unit [1] in the polymer block [A] is in the above range, transparency and mechanical strength are excellent. The remainder other than the repeating unit [1] in the polymer block [A] is a repeating unit derived from a chain conjugated diene or a chain vinyl compound.

The polymer block [B] contains a repeating unit [2] represented by the following formula (2) and / or a repeating unit [3] represented by the following formula (3). It is preferable that the polymer block [B] further contains the above-mentioned repeating unit [1]. The content of the repeating unit [1] in the polymer block [B] is preferably 40 to 95 mol%, more preferably 50 to 90 mol%. When the content of the repeating unit [1] is within the above range, transparency and mechanical strength are excellent. When the mole fraction of the repeating unit [2] in the block [B] is m ₂ (mol%) and the mole fraction of the repeating unit [3] is m ₃ (mol%), 2
× m ₂ + m ₃ is preferably 2 mol% or more, more preferably 5 to 60 mol%, and most preferably 10 to 50 mol%.
It is.

[0015]

Embedded image (In the formula, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

A preferred structure of the repeating unit [2] represented by the above formula (2) is that wherein R ¹³ is hydrogen or a methyl group.

[0017]

Embedded image (In the formula, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

A preferred structure of the repeating unit [3] represented by the above formula (3) is that wherein R ¹⁴ is hydrogen and R ¹⁵ is a methyl group or an ethyl group.

When the content of the repeating unit [2] or the repeating unit [3] in the polymer block [B] is too small, the mechanical strength decreases. Therefore, when the content of the repeating unit [2] and the content of the repeating unit [3] are in the above ranges, transparency and mechanical strength are excellent. The polymer block [B] may further contain a repeating unit [X] represented by the following formula (X). Repeat unit [X]
Is an amount which does not impair the properties of the block copolymer of the present invention, and is usually 30 mol% or less, preferably 20 mol% or less, based on the whole block copolymer.

[0020]

Embedded image (Wherein, R ²⁵ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ²⁶ represents a nitrile group, an alkoxycarbonyl group, a formyl group, a hydroxycarbonyl group, or a halogen group, and R ²⁷ represents a hydrogen atom. Or R ²⁶ and R ²⁷ are mutually bonded to form an acid anhydride group,
Alternatively, an imide group may be formed. )

In the block copolymer of the present invention, the mole fraction of the repeating unit [1] in the polymer block [A] is a, and the mole fraction of the repeating unit [1] in the polymer block [B] is a When the ratio is b, it is preferable that a> b. By setting a> b, transparency and mechanical strength are excellent.

Furthermore, the block copolymer of the present invention, when the molar number m _a of all repeating units constituting the block _[A], the number of moles of all repeating units constituting the block [B] was m _b The ratio (m _a : m _b ) is preferably 5:95 to 95: 5, more preferably 30:70.
９５95: 5, most preferably 40:60 to 90:10. When (m _a : m _b ) is within the above range, excellent mechanical strength and heat resistance are obtained.

The molecular weight of the block copolymer of the present invention can be determined by gel permeation chromatography (hereinafter referred to as G
PC) as 10,000 to 300,000, preferably 15,000 to 250,000, more preferably 2 in terms of polystyrene equivalent weight average molecular weight (Mw) measured by PC).
It is in the range of 000 to 200,000. When the weight average molecular weight (Mw) of the block copolymer is within the above range,
Excellent balance of mechanical strength, heat resistance and moldability.

The molecular weight distribution of the block copolymer can be appropriately selected according to the purpose of use, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by GPC. ), Usually in the range of 5 or less, preferably 4 or less, more preferably 3 or less.
When Mw / Mn is within this range, mechanical strength and heat resistance are excellent.

The glass transition temperature of the block copolymer (T
g) may be appropriately selected according to the purpose of use, and is a value measured on a high temperature side by a differential scanning calorimeter (DSC),
Usually 70 ° C to 150 ° C, preferably 80 ° C to 140 ° C,
More preferably, the temperature is from 90C to 130C.

The above block copolymer used in the present invention comprises:
Even if it has a polymer block [A] and a polymer block [B] and is a diblock copolymer of ([A]-[B]) type, ([A]-[B]-[A] ) Type and ([B]-
[A]-[B]) type triblock copolymer is a block copolymer in which a total of four or more polymer blocks [A] and polymer blocks [B] are alternately connected. You may.

[0027] 2. Method for Producing Block Copolymer The block copolymer of the present invention is a monomer mixture containing an aromatic vinyl compound and / or an alicyclic vinyl compound having an unsaturated bond in a ring, and a monomer containing a vinyl monomer. The mixture is polymerized to form a polymer block containing a repeating unit derived from an aromatic vinyl compound and / or an alicyclic vinyl compound, and a block copolymer having a polymer block containing a repeating unit derived from a vinyl monomer. Can be obtained by a method including hydrogenating the aromatic ring and / or the aliphatic ring of the block copolymer. Among them, more preferred as the block copolymer used in the present invention are, for example, It can be obtained by the following method.

That is, (1) a monomer mixture [a '] containing 50 mol% or more of an aromatic vinyl compound and / or an alicyclic vinyl compound having an unsaturated bond in a ring is polymerized to obtain an aromatic vinyl compound or / And a polymer block [A ′] containing a repeating unit derived from an alicyclic vinyl compound having an unsaturated bond in a ring
And the ratio of an aromatic vinyl compound or / and an alicyclic vinyl compound having an unsaturated bond to a ring containing at least 2 mol% of a vinyl monomer as compared with the ratio in the monomer mixture [a ′]. Polymerization of a monomer mixture [b '] containing a small amount of a polymer block containing a repeating unit derived from an aromatic vinyl compound or / and the alicyclic vinyl compound and a repeating unit derived from a vinyl monomer [ B ′], a block copolymer having the polymer block [A ′] and the polymer block [B ′] is obtained, and an aromatic ring and / or an aliphatic ring of the block copolymer is obtained. A method comprising hydrogenating.

(2) Step of polymerizing a monomer mixture [a] containing at least 50 mol% of a saturated alicyclic vinyl compound to obtain a polymer block [A] containing a repeating unit derived from an alicyclic vinyl compound. And a vinyl monomer
The monomer mixture [b] containing at least mol% and containing the saturated alicyclic vinyl compound in an amount smaller than the ratio in the monomer mixture [a] is polymerized to repeat the alicyclic vinyl compound-derived repeating unit. A method for obtaining a block copolymer having the polymer block [A] and the polymer block [B] through at least a step of obtaining a polymer block [B] containing a unit and a repeating unit derived from a vinyl monomer.

Among the above methods, the availability of monomers,
The method (1) is more preferable from the viewpoints of polymerization yield, ease of introducing the repeating unit [1] into the polymer block [B '], and the like.

Specific examples of the aromatic vinyl compound used in the method (1) include styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, and α-t-butylstyrene. , 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,
4-dimethylstyrene, 4-t-butylstyrene, 5-
t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, 4-phenylstyrene, and the like, and those having a substituent such as a hydroxyl group or an alkoxy group.
Methylstyrene, 3-methylstyrene, 4-methylstyrene and the like are preferred.

Specific examples of the saturated alicyclic vinyl compound used in the above method (2) include cyclohexenyl ethylene, α-methylcyclohexenyl ethylene, -α-t-butylcyclohexenyl ethylene, halogen, and the like. And those having a substituent such as a group, an alkoxy group or a hydroxyl group.

These aromatic vinyl compounds and alicyclic vinyl compounds can be used alone or in combination of two or more. In the present invention, the monomer mixtures [a '] and [b' ], It is preferable to use an aromatic vinyl compound, and it is more preferable to use styrene or α-methylstyrene.

The vinyl monomer used in the above method is
A chain vinyl compound and a chain conjugated diene compound.

Specific examples of the chain vinyl compound include chain olefin monomers such as ethylene, propylene, 1-butene, 1-pentene, and 4-methyl-1-pentene. Monomers are preferred, with ethylene, propylene and 1-butene being most preferred.

The chain conjugated diene includes, for example, butadiene (1,3-butadiene, 1,2-butadiene), isoprene, 2,3-dimethyl-1,3-butadiene, 1,3
-Pentadiene, 1,3-hexadiene and the like. Among these chain vinyl compounds and chain conjugated dienes, chain conjugated dienes are preferred, and butadiene and isoprene are particularly preferred. These chain vinyl compounds and chain conjugated dienes can be used alone or in combination of two or more.

In the case of polymerizing a monomer mixture containing the above monomers, the polymerization reaction may be carried out by any method such as radical polymerization, anionic polymerization and cationic polymerization.
In order to obtain the block copolymer of the present invention, anionic polymerization is preferable, and living anionic polymerization is most preferably performed in the presence of an inert solvent.

The anionic polymerization is carried out in the presence of a polymerization initiator at a temperature of usually 0 ° C. to 200 ° C., preferably 20 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C. Examples of the initiator include n-butyllithium, sec-
Monoorganic lithium such as butyllithium, t-butyllithium, hexyllithium, phenyllithium, dilithiomethane, 1,4-dibutane, 1,4-dilithio-2
-Polyfunctional organolithium compounds such as ethylcyclohexane can be used.

Examples of the inert solvent used include, for example, n
-Aliphatic hydrocarbons such as butane, n-pentane, isopentane, n-hexane, n-heptane, isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, decalin; benzene, Examples thereof include aromatic hydrocarbons such as toluene, and among them, when an aliphatic hydrocarbon or an alicyclic hydrocarbon is used, the solvent can be used as it is as an inert solvent for the hydrogenation reaction. These solvents can be used alone or in combination of two or more. Usually, 200 to 1 part by weight based on 100 parts by weight of all monomers used.
It is used in such a ratio that it becomes 000 parts by weight.

When each polymer block is polymerized, a polymerization accelerator or a randomizer may be used in order to prevent a chain of one component from becoming long in each block. In particular, when the polymerization reaction is performed by anionic polymerization, a Lewis base compound or the like can be used as a randomizer. Specific examples of Lewis base compounds include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, and ethylene glycol methyl phenyl ether; tetramethyl ethylene diamine;
Tertiary amine compounds such as trimethylamine, triethylamine and pyridine; alkali metal alkoxide compounds such as potassium-t-amyl oxide and potassium-t-butyl oxide; and phosphine compounds such as triphenylphosphine. These Lewis base compounds can be used alone or in combination of two or more.

As a method for obtaining a block copolymer by living anionic polymerization, a conventionally known sequential addition polymerization reaction method and coupling method can be mentioned. In the present invention, it is preferable to use a sequential addition polymerization reaction method. .

When the block copolymer having a polymer block [A '] and a polymer block [B'] is obtained by a sequential addition polymerization method, a step of obtaining a polymer block [A ']; The step of obtaining the polymer block [B '] is performed sequentially and continuously. Specifically, in an inert solvent, in the presence of the living anionic polymerization catalyst, the monomer mixture [a '] is polymerized to obtain a polymer block [A'], and then the monomer mixture [b '] is added to the reaction system. Is added to continue the polymerization to obtain a polymer block [B '] connected to the polymer block [A'].

The obtained block copolymer is recovered by a known method such as a steam stripping method, a direct desolvation method and an alcohol coagulation method. In the polymerization reaction, when an inert solvent is used in the hydrogenation reaction, the polymerization solution itself can be used in the hydrogenation reaction step, so that the block copolymer need not be recovered from the polymerization solution. .

Among the block copolymers obtained by the above method (1) and having a polymer block [A '] and a polymer block [B'] (hereinafter referred to as pre-hydrogenated block copolymer), the following: Those having a repeating unit having the following structure are preferred.

The polymer block [A ′] constituting the preferred block copolymer before hydrogenation is a polymer block containing at least 50 mol% of the repeating unit [4] represented by the following formula (4).

[0046]

Embedded image (Wherein, R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹⁷ -R ²¹ each independently represent
A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, and a halogen group. Incidentally, the ^{[R 1} 7 ^{-R 21] is,} R ^{17, R 18,}
..., and it represents the ^{R 21.} )

Further, a preferred polymer block [B ']
Always includes the repeating unit [4] and has the following formula (5)
And a polymer block containing at least one of the repeating unit [5] represented by the following formula (6) and the repeating unit [6] represented by the following formula (6). When the mole fraction of the repeating unit [4] in the polymer block [A '] is a' and the mole fraction of the repeating unit [4] in the block [B '] is b', a '> b ′.

[0048]

Embedded image (In the formula, R ²² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

[0049]

Embedded image (In the formula, R ²³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ²⁴ represents a hydrogen atom, an alkyl group or an alkenyl group having 1 to 20 carbon atoms.)

Further, the block [B '] may contain a repeating unit [Y] represented by the following formula (Y).

[0051]

Embedded image (Wherein, R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ²⁹ represents a nitrile group, an alkoxycarbonyl group, a hydrocarbonyl group, a hydroxycarbonyl group, or a halogen group, and R ³⁰ represents a hydrogen atom. Represents an atom, or R ²⁹ and R ³⁰ may be mutually bonded to form an acid anhydride group or an imide group.)

Further, a preferred block copolymer before hydrogenation is such that the number of moles of all the repeating units constituting the block [A '] is m _a and the number of moles of all the repeating units constituting the block [B'] is _mb. in case of a, the ratio _{(m a} ':
m _b ') is 5:95 to 95: 5, preferably 30: 7
0 to 95: 5, more preferably 40:60 to 90:10
It is. _{If: (m a 'm b'} ) is in the above range,
Excellent mechanical strength and heat resistance.

The preferred molecular weight of the block copolymer before hydrogenation is from 12,000 to 400,000 in terms of polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter, GPC).
0, preferably from 19,000 to 350,000, more preferably from 25,000 to 300,000.
If the weight average molecular weight (Mw) of the block copolymer is too small, the mechanical strength decreases, and if it is too large, the hydrogenation rate decreases.

The preferred molecular weight distribution of the block copolymer before hydrogenation can be appropriately selected according to the purpose of use.
C and weight average molecular weight (Mw) and number average molecular weight (M) in terms of polystyrene (or polyisoprene).
The ratio (Mw / Mn) to n) is usually 5 or less, preferably 4 or less, more preferably 3 or less. Mw / M
When n is in this range, the hydrogenation rate is improved.

The glass transition temperature (Tg) of the preferred block copolymer before hydrogenation may be appropriately selected according to the purpose of use, and is determined on the high-temperature side by a differential scanning calorimeter (DSC). Usually 70 ° C to 150 ° C, preferably 80 ° C
C. to 140C, more preferably 90C to 130C.

Method for hydrogenating unsaturated bond The above-mentioned carbon-carbon unsaturated bond of unsaturated ring such as aromatic ring or cycloalkene ring of the block copolymer before hydrogenation,
There is no particular limitation on the method and reaction form for hydrogenating unsaturated bonds of the main chain or side chains, and the method may be performed according to a known method, but the hydrogenation rate can be increased and the polymer chain scission reaction is reduced. A hydrogenation method is preferable, and examples thereof include a method in which an organic solvent is used using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, and rhenium. As the hydrogenation catalyst, any of a heterogeneous catalyst and a homogeneous catalyst can be used.

The heterogeneous catalyst can be used as it is as a metal or a metal compound, or supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbide, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, and the like. The amount of the supported catalyst is usually 0.01 to 80% by weight, preferably 0.1 to 80% by weight. 05-
It is in the range of 60% by weight. The homogeneous catalyst is a catalyst obtained by combining a nickel, cobalt, titanium or iron compound with an organometallic compound (for example, an organoaluminum compound or an organolithium compound), or an organometallic complex catalyst such as rhodium, palladium, platinum, ruthenium, or rhenium. Can be used. As the nickel, cobalt, titanium or iron compound, for example, acetylacetone salts of various metals, naphthenates, cyclopentadienyl compounds, cyclopentadienyldichloro compounds and the like are used. As the organic aluminum compound, alkyl aluminum such as triethylaluminum and triisobutylaluminum, aluminum halide such as diethylaluminum chloride and ethylaluminum dichloride, and alkylaluminum hydride such as diisobutylaluminum hydride are preferably used.

Examples of the organometallic complex catalyst include metal complexes such as γ-dichloro-π-benzene complex, dichloro-tris (triphenylphosphine) complex and hydride-chloro-triphenylphosphine) complex of each of the above metals. Is done. These hydrogenation catalysts can be used alone or in combination of two or more, and the amount of use is usually 0.01 to 100 parts by weight of the polymer.
100 parts by weight, preferably 0.05 to 50 parts by weight, more preferably 0.1 to 30 parts by weight.

The hydrogenation reaction is usually carried out at a temperature of from 10 ° C. to 250 ° C., but preferably from 50 ° C. to 20 ° C., because the hydrogenation rate can be increased and the polymer chain scission reaction can be reduced.
0 ° C, more preferably 80 ° C to 180 ° C. The hydrogen pressure is usually 0.1 MPa to 30 MPa, but from the viewpoint of operability in addition to the above reasons, preferably 1 MPa.
-20 MPa, more preferably 2-10 MPa.

The hydrogenation rate of the block copolymer thus obtained was measured by ¹ H-NMR to determine the carbon-carbon unsaturated bonds of the main chain and side chain, the carbon number of the aromatic ring and the cycloalkene ring. Each of the carbon unsaturated bonds is usually 90
% Or more, preferably 95% or more, more preferably 97%
That is all. When the hydrogenation rate is low, the resulting copolymer has low birefringence, thermal stability, and the like.

After the completion of the hydrogenation reaction, the block copolymer is
For example, by removing the hydrogenation catalyst from the reaction solution by a method such as filtration and centrifugation, a method of directly removing the solvent by drying, a method of pouring the reaction solution into a poor solvent for the block copolymer, and a method of coagulation. Can be collected.

The block copolymer of the present invention obtained by the above method can be blended with various additives as required. There is no particular limitation on the compounding agent that can be compounded in the block copolymer, but stabilizers such as antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, ultraviolet absorbers, and near infrared absorbers; Resin modifiers such as plasticizers; coloring agents such as dyes and pigments; antistatic agents, flame retardants, fillers and the like. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention.

In the present invention, the block copolymer
Among the above-mentioned compounding agents, it is preferable to compound an antioxidant, an ultraviolet absorber, and a light stabilizer. Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. Among these, a phenol-based antioxidant, particularly an alkyl-substituted phenol-based antioxidant, is preferable. By blending these antioxidants, it is possible to prevent coloring and strength reduction of films and sheets due to oxidative deterioration during molding without reducing transparency, heat resistance and the like. These antioxidants can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention. Parts by weight, usually 0.001 to 5 parts by weight, preferably 0.01 to 5 parts by weight.
1 part by weight.

Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,2'-disidoxy-4,4'-.
Dimethoxybenzophenone, 2-hydroxy-4-methoxy-2′-benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2
-Hydroxy-4-n-octoxybenzophenone,
Benzophenone-based ultraviolet absorbers such as 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane; 2- ( 2'-hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6
-Tetrahydrophthalimidylmethyl) phenol,
2- (2H-benzotriazol-2-yl) -4-6
-Bis (1-methyl-1-phenylethyl) phenol, 2- (2'-hydroxy-3 ', 5'-di-tert-
Butyl-phenyl) benzotriazole, 2- (2'-
(Hydroxy-3′-tert-butyl-5′-methyl-phenyl) -5-chlorobenzotriazole, 2- (2′-
Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
Tertiary-amylphenyl) benzotriazole, 2-
[2'-hydroxy-3 '-(3 ", 4", 5 ", 6"
-Tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6
(2H-benzotriazol-2-yl) phenol]
And the like. Among them, among these, 2- (2'-hydroxy-5'-
Methyl-phenyl) benzotriazole, 2- (2H-
Benzotriazol-2-yl) -4-methyl-6
(3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2H-benzotriazole-2)
-Yl) -4-6-bis (1-methyl-1-phenylethyl) phenol and the like are preferable from the viewpoint of heat resistance, low volatility and the like.

Examples of the light stabilizer include a benzophenone-based light stabilizer, a benzotriazole-based light stabilizer, a hindered amine-based light stabilizer, and the like. From the viewpoint, it is preferable to use a hindered amine light stabilizer. Hindered amine light stabilizer (hereinafter HALS)
Abbreviations), number average molecular weight (Mn) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
Is preferably from 1,000 to 10,000, and 200
It is more preferably 0 to 5000, and 2800 to 3
A value of 800 is most preferred. When Mn is too small, when blending the HALS into the block copolymer by heat-melt kneading, it volatilizes and cannot be mixed in a predetermined amount, or causes foaming and silver streaks during heat-melt molding such as injection molding. As a result, the processing stability decreases. Also,
When a film and a sheet are used for a long time with the lamp turned on, volatile components are generated as gas from the film and the sheet. Conversely, if Mn is too large, the dispersibility in the block copolymer decreases, the transparency of films and sheets decreases, and the effect of improving light resistance decreases.
Therefore, in the present invention, by setting the Mn of HALS within the above range, films and sheets excellent in processing stability, low gas generation properties, and transparency can be obtained.

As a specific example of such a HALS,
N, N ', N ", N"'-tetrakis- (4,6-
Bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine And 1,3,5-triazine and N,
Polycondensate with N'-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1,
1,3,3-tetramethylbutyl) amino-1,3,5
-Triazine-2,4-diyl {{(2,2,6,6-
Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], 1,6-hexanediamine-N, N '
-Bis (2,2,6,6-tetramethyl-4-piperidyl) and morpholine-2,4,6-trichloro-1,
Polycondensate with 3,5-triazine, poly [(6-morpholino-s-triazine-2,4-diyl) [(2,
Piperidine ring such as 2,6,6, -tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] via a triazine skeleton Multiple high molecular weight HAL
S: dimethyl succinate and 4-hydroxy-2,2,6
Polymerization with 6-tetramethyl-1-piperidineethanol, 1,2,3,4-butanetetracarboxylic acid and 1,
2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5
5] High molecular weight HALS having a piperidine ring bonded through an ester bond, such as a mixed esterified product with undecane
And the like.

Among these, dibutylamine and 1,1
3,5-triazine and N, N'-bis (2,2,6,6
Polycondensation product with -tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2 , 2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 4-hydroxy-2,2 , 6,6-tetramethyl-
Mn of a polymer with 1-piperidineethanol is 20
It is preferably from 00 to 5000.

The amount of the ultraviolet absorber and HALS to be added to the block copolymer is usually 0.01 to 20 parts by weight, preferably 0.02 parts by weight, per 100 parts by weight of the polymer.
To 15 parts by weight, more preferably 0.05 to 10 parts by weight. If the addition amount of the ultraviolet absorber and HALS is too small, the effect of improving the light resistance cannot be sufficiently obtained, and if the film and the sheet are left outdoors for a long time, coloring occurs. Part of the gas is generated as a gas, or dispersibility in the block copolymer is reduced, and the transparency of the film or sheet is reduced.

Further, in the present invention, by blending a soft polymer with a block copolymer, it is possible to maintain a high temperature and high humidity environment for a long time without deteriorating various properties such as transparency, heat resistance and mechanical strength. Prevents white turbidity below.

The soft polymer is a polymer having the lowest glass transition temperature of 30 ° C. or lower. Specific examples of the flexible polymer include polyethylene, polypropylene, and ethylene.
Olefin-based soft polymers such as α-olefin copolymer, ethylene-propylene-diene copolymer (EPDM); Isobutylene-based soft polymers such as polyisobutylene, isobutylene / isoprene rubber, isobutylene / styrene copolymer; polybutadiene; Polyisoprene,
Butadiene / styrene random copolymer, isoprene /
Styrene random copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / butadiene / styrene copolymer, butadiene / styrene / block copolymer, styrene / butadiene / styrene / block copolymer, isoprene / styrene / block copolymer And diene-based soft polymers such as styrene / isoprene / styrene / block copolymers;

Silicon-containing soft polymers such as dimethylpolysiloxane and diphenylpolysiloxane; acrylic soft polymers such as polybutyl acrylate, polybutyl methacrylate and polyhydroxyethyl methacrylate; polyethylene oxide, polypropylene oxide,
Epoxy soft polymers such as epichlorohydrin rubber; fluorine soft polymers such as vinylidene fluoride rubber and ethylene tetrafluoride-propylene rubber; natural rubber;
Other soft polymers such as polypeptides, proteins, polyester-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers are included. These soft polymers may have a crosslinked structure, or may have a functional group introduced by a modification reaction.

Among the above-mentioned soft polymers, diene-based soft polymers are preferable, and hydrides obtained by hydrogenating carbon-carbon unsaturated bonds of the soft polymers are particularly preferred in terms of rubber elasticity, mechanical strength, flexibility and dispersibility. Excellent. The amount of the soft polymer varies depending on the type of the compound, but in general, if the amount is too large, the glass transition temperature and the transparency of the block copolymer are greatly reduced, and it may be used as a film and a sheet. Can not. If the amount is too small, the molded product may become cloudy under high temperature and high humidity. The amount is usually 0.01 to 10 parts by weight based on 100 parts by weight of the block copolymer.
Parts by weight, preferably 0.02 to 5 parts by weight, particularly preferably 0.05 to 2 parts by weight.

A method for blending the above compounding agent with the block copolymer is, for example, a method in which the block copolymer is melted and kneaded with the compounding agent using a mixer, a twin screw kneader, a roll, a Brabender, an extruder, or the like. And a method of dissolving and dispersing in an appropriate solvent to coagulate. When a twin-screw kneader is used, it is often used after being kneaded, usually extruded in a molten state into strands, and cut into pellets by a pelletizer.

[0074] 3. Film and Sheet The film and sheet of the present invention can be obtained by molding the above-mentioned block copolymer obtained by the above method. The thickness of the film and sheet is usually 1 μm to 10 m
m. Although there is no special definition for the distinction between a film and a sheet, usually, a film having a thickness of about 5 to 500 μm and a sheet having a thickness of 500 μm or more are used.
Those having a range of 0 to 500 μm may be used as sheets. For the film or sheet of the present invention, the optimum thickness range can be appropriately selected depending on the purpose of use and the like in the above thickness range, but is preferably 5 μm to 5 mm, more preferably 10 μm to 2 mm. Choose the optimal range.

The method for forming the film and sheet is not particularly limited, and any of a heat-melt molding method and a solution casting method can be used. The heat-melt molding method can be further classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method and the like. Among these methods, an extrusion method, an inflation molding method, and a press molding method are preferable in order to obtain a film and a sheet having excellent mechanical strength, surface accuracy and the like. The molding conditions are appropriately selected depending on the purpose of use and the molding method. In the case of the heat-melt molding method, the melting temperature of the block copolymer is usually 150 to 400 ° C., preferably 200 to 350 ° C., more preferably 230. ~ 330
It is appropriately selected in the range of ° C. If the resin temperature is too low, the fluidity will deteriorate, causing sinks and distortions in the film and sheet.If the resin temperature is too high, voids and silver streaks will occur due to thermal decomposition of the resin, and the film and sheet will turn yellow. There is a possibility that molding defects such as rubbing may occur.

The films and sheets of the present invention obtained as described above are excellent in heat resistance, transparency, and mechanical strength.
It can be used for various applications. Among them, it can be suitably used for optics and packaging. For optical applications, liquid crystal display (LCD) components such as retardation films, polarizing films, liquid crystal substrates, etc .: LCD backlight components, such as light diffusion sheets and condensing sheets: for optical information media such as optical cards and optical disks Substrate: An optical film or an optical sheet such as a planar lens such as a Fresnel lens or a Lenticular lens is exemplified. For packaging, wrap films, stretch films, shrink films, press-through package films, blister package films, and the like can be mentioned. In addition, the film and sheet of the present invention can be used for pharmaceuticals such as infusion bags, infusion bags, and drug bags.

[0077]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples, Examples, and Comparative Examples. [Parts] and [%] in these examples are by weight unless otherwise specified. However, the present invention is not limited to only these production examples and examples.

Various physical properties were measured according to the following methods. (1) Molecular Weight of Block Copolymer Measured by GPC using tetrahydrofuran (THF) as a solvent, and a weight average molecular weight (Mw) in terms of standard polystyrene.
I asked. (2) Molecular weight distribution Weight average molecular weight (Mw) measured by GPC using tetrahydrofuran (THF) as a solvent and converted to standard polystyrene
And the number average molecular weight (Mn) are determined, and the weight average molecular weight (M
w) and the number average molecular weight (Mn) ratio (Mw / Mn) was calculated. (3) Glass transition temperature (Tg) Measured by DSC based on JIS K7121 and the value obtained from the high-temperature side displacement point is calculated as the T of the block copolymer.
g. (4) Hydrogenation rate The hydrogenation rate of the main chain and aromatic ring of the block copolymer is as follows:
¹ H-NMR was measured and calculated.

(5) Film Thickness The film was fixed between metal clamps, and cut with a sharp cutter so that the cross section became flat. The thickness of each layer was measured by observing the cross section with an optical microscope (200 times). (6) Heat resistance of film The softening temperature was measured according to JIS-K7196. 10
× below 0 ° C, ○ over 100 ° C and below 120 ° C, 12
0 ° C. or higher was evaluated as ◎. (7) Transparency of film The light transmittance (%) is measured with a spectrophotometer while continuously changing the wavelength in the wavelength range of 400 to 900 nm, and the minimum transmittance is defined as the light transmittance of the film. It was measured. The higher the light transmittance, the better the transparency. Evaluation criteria: 92% or more: （(very good), 88%
Those with less than 92% were rated as ○ (good), and those with less than 88% were rated as x (bad). (8) Tear strength Measured according to JIS K7128. 10kgf / m
x less than 10 kgf / mm, 20 kgf / mm
Is less than ○ and 20 kgf / mm or more is ◎. (9) Tensile modulus Measured according to JIS K7127. 10,000kg
x less than f / cm ² , 10,000 kgf / cm ² or more,
○ for less than 20,000 kgf / cm ^2, 20,000 kgf / cm ²
/ Cm ² or more was evaluated as ◎.

[Production Example 1]
A stainless steel reactor equipped with a stirrer was charged with 320 parts of dehydrated cyclohexane, 60 parts of styrene monomer, and 0.38 part of dibutyl ether, and stirred at 60 ° C. while n-butyllithium solution (hexane solution containing 15%).
The polymerization reaction was started by adding 0.36 parts. After conducting the polymerization reaction for one hour, a mixed monomer 2 composed of 8 parts of styrene monomer and 12 parts of isoprene monomer was added to the reaction solution.
After adding 0 parts and performing a polymerization reaction for 1 hour, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained block copolymer were measured, it was Mw = 102,100 and Mw / Mn = 1.11.

Next, 400 parts of the polymerization reaction solution was transferred to a pressure-resistant reactor equipped with a stirrer, and used as a hydrogenation catalyst was a silica-alumina-supported nickel catalyst (manufactured by Nikki Chemical Co., Ltd .; E22U, nickel support amount 60%). %) And mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution, and a hydrogenation reaction was performed at a temperature of 160 ° C. and a pressure of 4.5 MPa for 8 hours. After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and 800 parts of cyclohexane was added for dilution. The reaction solution was diluted with 3500 parts of isopropanol (in a class 1000 clean room using a filter having a pore diameter of 1 μm). The mixture was poured into a filtered solution to precipitate a block copolymer, separated and recovered by filtration, and dried at 80 ° C. for 48 hours under reduced pressure. The obtained block copolymer is a block containing a repeating unit derived from styrene (hereinafter abbreviated as St),
And a block containing a repeating unit derived from styrene and isoprene (hereinafter abbreviated as St / Ip).
And the molar ratio of each block is St: St / Ip = 69: 31 (St: Ip = 1
0:21). Mw of the block copolymer is 85
100, Mw / Mn was 1.17, the degree of hydrogenation of the main chain and the aromatic ring was 99.9%, and Tg was 126.5 ° C.

[Production Example 2] Dehydrated cyclohexane 320 was placed in the same stainless steel reactor used in Production Example 1.
Parts, 37.5 parts of a styrene monomer, and 0.38 parts of dibutyl ether, and 0.36 part of an n-butyllithium solution (hexane solution containing 15%) was added while stirring at 60 ° C. to start a polymerization reaction. . After conducting the polymerization reaction for 1 hour, 20 parts of a mixed monomer composed of 8 parts of styrene monomer and 12 parts of isoprene monomer was added to the reaction solution, and the polymerization reaction was further conducted for 1 hour.
After adding 37.5 parts of a styrene monomer and further performing a polymerization reaction for 1 hour, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction. The weight average molecular weight (Mw) and molecular weight distribution (M
w / Mn), Mw = 101000, M
w / Mn = 1.13. Next, a hydrogenation reaction was performed in the same manner as in Production Example 1. The obtained block copolymer is represented by S
It is a ternary block copolymer consisting of t, St / Ip, and St, and the molar ratio of each block is St: St /
Ip: St = 34.5: 31 (St: Ip = 10/2
1): 34.5. Mw of the block copolymer was 84900, Mw / Mn was 1.20, and the hydrogenation ratio was 99.
9%, Tg was 127.1 ° C.

[Production Example 3] Dehydrated cyclohexane 320 was placed in the same stainless steel reactor used in Production Example 1.
, A mixed monomer consisting of 28.8 parts of a styrene monomer and 28.8 parts of an isoprene monomer and 5 parts of dibutyl ether were charged, and stirred at 60 ° C. while stirring n-butyllithium solution (hexane solution containing 15%). )
The polymerization reaction was started by adding 0.36 parts. After polymerization for 1 hour, 22.4 parts of a mixed monomer composed of 8.8 parts of styrene monomer and 13.6 parts of isoprene monomer were added, and after further reacting for 1 hour, 0.2 part of isopropyl alcohol was added. To stop the reaction. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained block copolymer were measured, Mw = 1050
0, Mw / Mn = 1.07. Next, Production Example 1
A hydrogenation reaction was performed in the same manner. The obtained block copolymer is a binary block copolymer composed of St / Ip and St / Ip, and the molar ratio of each block is St / Ip.
Ip: St / Ip = 28/42: 9/21. Mw of the block copolymer is 83500, Mw / Mn is 1.16, hydrogenation rate is 99.9%, and Tg is 123.5 ° C.
Met.

[Production Example 4] Dehydrated cyclohexane 320 was placed in the same stainless steel reactor as used in Production Example 1.
Parts, styrene monomer 56 parts and dibutyl ether 0.38 part, and while stirring at 60 ° C., 0.36 part of an n-butyllithium solution (hexane solution containing 15%) was added to initiate a polymerization reaction. After conducting the polymerization reaction for 1 hour, a mixed monomer 2 composed of 23.92 parts of a styrene monomer and 0.08 part of an isoprene monomer was added to the reaction solution.
After adding 4 parts and conducting a polymerization reaction for 1 hour, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained block copolymer were measured, it was Mw = 102000 and Mw / Mn = 1.11. Next, a hydrogenation reaction was performed in the same manner as in Production Example 1. The obtained block copolymer is a binary block copolymer composed of St and St / Ip, and the molar ratio of each block is St: St / Ip = 70: 30 (St: Ip
= 29.85 / 0.15). The block copolymer had Mw of 85300, Mw / Mn of 1.17, a hydrogenation ratio of 99.9%, and a Tg of 132.1 ° C.

[Production Example 5] Dehydrated cyclohexane 320 was placed in the same stainless steel reactor used in Production Example 1.
Parts, styrene monomer 72 parts, and dibutyl ether 0.38 part were charged, and while stirring at 60 ° C., 0.36 part of an n-butyllithium solution (hexane solution containing 15%) was added to initiate a polymerization reaction. After conducting the polymerization reaction for 1 hour, 8 parts of isoprene monomer is added to the reaction solution,
After the polymerization reaction was further performed for 1 hour, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction.
When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained block copolymer were measured, Mw = 1
01300, Mw / Mn = 1.12. Then
A hydrogenation reaction was performed as in Production Example 1. The obtained block copolymer is a binary block copolymer composed of St and Ip, and the molar ratio of each block is St: Ip
= 85:15. Mw of the block copolymer is 8
3300, Mw / Mn 1.18, hydrogenation rate 99.9
%, Tg was 138.1 ° C.

[Production Example 6] Dehydrated cyclohexane 320 was placed in the same stainless steel reactor as used in Production Example 1.
Parts, 80 parts of styrene monomer and 0.1 part of dibutyl ether.
38 parts were charged, and while stirring at 60 ° C., 0.36 part of an n-butyllithium solution (hexane solution containing 15%) was added to initiate a polymerization reaction. After polymerization for 2 hours, 0.2 parts of isopropyl alcohol was added to stop the reaction. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained polystyrene were measured, Mw = 1
29000, Mw / Mn = 1.04. Then
A hydrogenation reaction was performed as in Production Example 1. Mw of the obtained hydrogenated polystyrene resin was 84700, and Mw / Mn was 1.
10, the hydrogenation rate was 99.9%, and the Tg was 145 ° C.

Example 1 0.1 part of a soft polymer (manufactured by Kuraray; Septon 2002) and an antioxidant (Ciba Specialty Chemicals) were used for 100 parts of the block copolymer obtained in Production Example 1. Made by Irganox 101
0) 0.1 part, and 0.1 part of 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole (manufactured by Ciba Specialty Chemicals: TINUVIN P) as a benzotriazole-based ultraviolet absorber Further, as HALS, dibutylamine, 1,3,5-triazine.N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- ( Polycondensate with 2,2,6,6-tetramethyl-4-piperidyl) butylamine (HALS (A): M
n = 3000), and 0.1 parts of each were added, and a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd .; TEM-35B, screw diameter 37 m)
m, L / D = 32, screw rotation speed 150 rpm, resin temperature 240 ° C., field rate 10 kg / hour) and extruded into strands. This was cooled with water, cut with a pelletizer, and pelletized.

The obtained pellets were dried at 70 ° C. for 2 hours using a hot-air dryer through which air was circulated to remove moisture, and then a T-die film having a resin melt kneader equipped with a 65 mmφ screw was used. Using a melt extrusion machine,
Under the molding conditions of a molten resin temperature of 220 ° C. and a T-die width of 500 mm, a thickness of 300 μm, 500 mm × 1000 mm
Was extruded. The heat resistance, transparency and mechanical strength of the obtained film were evaluated. The results are shown in Table 1.

[0089]

[Table 1]

Examples 2 to 5 Films and sheets were formed in the same manner as in Example 1 except that the block copolymers obtained in Production Examples 2 to 5 were used, and heat resistance, transparency and mechanical strength were measured. It was measured and evaluated. The results are shown in Table 1.

Comparative Example 1 Films and sheets were formed in the same manner as in Example 1 except that the hydrogenated polystyrene resin obtained in Production Example 6 was used, and the heat resistance, transparency and mechanical strength were measured and evaluated. did. The results are shown in Table 1.

Comparative Example 2 Using a styrene-butadiene-styrene block copolymer (Clayton KX408P: manufactured by Shell Chemical Co., Ltd.), a T-die film melt extruder having a resin melt kneader equipped with a screw of 65 mmφ. Using a molten resin temperature of 220 ° C and a T-die width of 5
Under the molding conditions of 00 mm, 500 m
An mx 1000 mm base film was extruded.
The heat resistance, transparency and mechanical strength of the obtained film were evaluated. The results are shown in Table 1.

[0093]

According to the present invention, films and sheets excellent in heat resistance, transparency and mechanical strength are provided.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toru Murata 1-2-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa F-term in the Zeon Corporation General Development Center (reference) 2H049 BA02 BA06 BB42 BB47 BC09 4F071 AA12X AA14X AA22X AA23X AA30X AA39X AA75 AA78 AF14 AF30 AF45 AH04 AH19 BC01 4J026 HA06 HA08 HA09 HA13 HA16 HA20 HA26 HA32 HA38 HA39 HA48 HA49 HB02 HB03 HB04 HB06 HB09 HB11 HB14 HB15 HB16 HB19 HB20 HB38 HB20 HB20

Claims (6)

[Claims] 1. A polymer block [A] containing a repeating unit [1] represented by the following formula (1), and a repeating unit [2] represented by the following formula (2) or / and Films and sheets obtained by molding a block copolymer having a polymer block [B] containing the repeating unit [3] represented by 3). Embedded image (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{2 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, and a carbon atom having 1 carbon atom. To 20 alkoxy groups or halogen groups.) (In the formula, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) (In the formula, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) 2. The polymer block [B] further contains the repeating unit [1], and the mole fraction a (mol%) of the repeating unit [1] in the block [A] and the block [B] ], The mole fraction b (mol%) of the repeating unit [1]
The film and sheet according to claim 1, wherein a> b. 3. The content of the repeating unit [1] in the polymer block [A] is 50 mol% or more, and the molar fraction m of the repeating unit [2] in the polymer block [B] is m.
₂ (mol%) and the molar fraction m of the repeating unit [3]
_3. The film and sheet according to claim 1, wherein ₃ (mol%) has a relationship of 2 × m ₂ + m ₃ ≧ 2 (mol%). Wherein in the block copolymer, the mole number m _b of all repeating units constituting the mole number m _a of all repeating units constituting the block [A], block [B] ratio (m _a: m _b) is 40: 60 to 90: 10, according to any one of claims 1 to 3 films and sheets. 5. The film and sheet according to claim 1, which is for optical use. 6. The film or sheet according to claim 1, which is a packaging material.