WO2013099427A1 - Abc-type azo-based triblock copolymer - Google Patents

Abstract

Provided are: a novel block copolymer capable of manifesting temperature-responsiveness even when supported on a fibrous substrate; a hydrophobicity/hydrophilicity control agent containing the copolymer; a method for controlling hydrophobicity/hydrophilicity in which the polymer is used; and a copolymer/fiber composite in which the polymer is supported. An ABC-type azo-based triblock copolymer, characterized in that a segment (A) comprising repeating vinyl ether-based structural units (a) including a temperature-responsive group, a segment (B) comprising repeating structural units (b) including an azobenzene skeleton, and a segment (C) comprising repeating oxystyrene-based structural units (c) are bonded together in an A-B-C sequence.

Description

ABC type azo triblock copolymer

The present invention relates to an ABC type azo triblock copolymer, a hydrophilicity / hydrophobicity control agent, a hydrophilicity / hydrophobicity control method, and a copolymer-fiber composite.

Some polymer compounds exhibit a phase transition phenomenon in response to external stimuli such as heat, pH, light, etc., and temperature sensors, separation membranes, adsorbents, drug release agents, water absorbing agents that apply this phase transition phenomenon In addition, the development of water retention agents, humidity control agents, indicator agents and the like has been actively conducted.

Among the above-mentioned polymer compounds, those that exhibit a phase transition phenomenon in response to heat are called temperature-responsive polymers, and as such polymers, living polymers of vinyl ethers containing oxyethylene chains are known. Yes. This living polymer exhibits hydrophilicity at a specific temperature or lower, and exhibits hydrophobicity when the temperature is exceeded. However, since it is an oily compound, it does not have moldability and film forming properties, and its use is greatly limited. It had been.

Therefore, a diblock copolymer of a vinyl ether containing an oxyethylene chain and an alicyclic vinyl ether has been developed as a polymer exhibiting temperature responsiveness and having film forming properties and moldability (Patent Document 1). ).
However, the diblock copolymer has a problem that the moldability is not yet sufficient, the formed film has a surface tack, and cracks are generated by contact with water.

As a means for solving such a problem, introduction of an azo group into a temperature-responsive polymer has been studied. For example, a diblock copolymer of a vinyl ether containing an oxyethylene chain and a vinyl ether containing an azobenzene skeleton is known (Patent Document 2). In addition, as a result of surface modification of various general-purpose resin films with the same diblock copolymer, polystyrene and polypropylene are particularly easily surface-modified, and the surface-modified polystyrene film is temperature responsive to hydrophilicity and hydrophobicity. (Non-Patent Document 1).

JP 2006-131805 A JP 2005-154603 A

Then, when this inventor advanced examination about the temperature responsiveness of the diblock copolymer of the vinyl ether containing an oxyethylene chain | strand and the vinyl ether containing an azobenzene skeleton like the patent document 2 and the nonpatent literature 1, It has been found that such a diblock copolymer does not exhibit temperature responsiveness related to hydrophilicity / hydrophobicity when supported on a fibrous base material.
Accordingly, an object of the present invention is to provide a novel block copolymer that can exhibit temperature responsiveness even when supported on a fibrous base material, a hydrophilicity / hydrophobicity control agent containing the copolymer, and a hydrophilicity / hydrophobicity using the polymer. It is an object of the present invention to provide a control method and a copolymer-fiber composite carrying the polymer.

Therefore, as a result of intensive studies to solve the above problems, the present inventor has found that a segment A composed of repeating vinyl ether structural units (a) containing a temperature-responsive group and a repeating structural unit (b) containing an azobenzene skeleton. And an Azo-type triazo group having segments A to C bonded by an ABC sequence, and a segment C composed of repeating oxystyrene-based structural units (c). It has been found that the block copolymer can exhibit temperature responsiveness even if it is supported on a fibrous base material, and the present invention has been completed.

That is, the present invention relates to a segment A composed of repeating vinyl ether structural units (a) containing a temperature-responsive group, a segment B consisting of repeating structural units (b) containing an azobenzene skeleton, and an oxystyrene structural unit ( Provided is an ABC type azo triblock copolymer (hereinafter also referred to as a triblock copolymer) characterized in that the segment C formed by repeating c) is bonded by an ABC sequence. To do.
Moreover, this invention provides the hydrophilicity / hydrophobicity control agent containing the said triblock copolymer.
Furthermore, the present invention provides a method for controlling hydrophilicity / hydrophobicity using the above triblock copolymer.
Furthermore, the present invention provides a copolymer-fiber composite in which the above triblock copolymer is supported on a fibrous base material.

Even if the triblock copolymer of the present invention is supported on a fibrous base material, it exhibits temperature responsiveness and reversibly changes its hydrophilicity / hydrophobicity, so that temperature responsiveness can be imparted to a wide range of base materials. .
Therefore, according to this invention, the hydrophilicity / hydrophobicity control agent and the hydrophilicity / hydrophobicity control method which can provide temperature responsiveness to a fibrous base material can be provided.
Further, the copolymer-fiber composite of the present invention has temperature responsiveness even though the base material is fibrous.

The ABC type azo triblock copolymer of the present invention is composed of a segment A composed of repeating vinyl ether structural units (a) containing a temperature-responsive group and a segment B consisting of repeating structural units (b) containing an azobenzene skeleton. And a segment C composed of repeating oxystyrene-based structural units (c) are bonded by an ABC sequence.
First, the triblock copolymer will be described in detail.

<Segment A>
As the structural unit (a) constituting the segment A, for example, the following general formula (1)

[In the formula (1), R ¹ represents a methyl group or an ethyl group, and k is an integer of 1 to 10. ]
The thing represented by is mentioned. The critical temperature at which the hydrophilicity / hydrophobicity changes can be adjusted by appropriately changing the chain length of the side chain in such a structural unit.

In the formula (1), k is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.

Examples of vinyl ether monomers that induce segment A include 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 2- (2-ethoxyethoxy) ethyl vinyl ether. 2- (2- (2-methoxyethoxy) ethoxy) ethyl vinyl ether, 2- (2- (2-ethoxyethoxy) ethoxy) ethyl vinyl ether, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy ) Ethyl vinyl ether, 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethyl vinyl ether, etc., and segment A is derived using one of such vinyl ether monomers. It may be one that is derived using two or more types .
Among these, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, and 2- (2- (2-methoxyethoxy) ethoxy) ethyl vinyl ether are preferable from the viewpoint of improving hydrophilicity when the temperature is lowered.

<Segment B>
As the structural unit (b) constituting the segment B, for example, the following general formula (2)

[In the formula (2), R ² and R ³ each independently represents an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxyalkyl group, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a nitro group, a sulfo group, a sulfooxy group, or an aminosulfonyl group, n is an integer of 1 to 5, and p is an integer of 0 to 2. Q is an integer from 0 to 3. ]
The thing represented by is mentioned.

In the formula (2), the alkyl group represented by R ² and R ³ preferably has 1 or 2 carbon atoms. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group.

The haloalkyl group represented by R ² and R ³ means a linear or branched alkyl group substituted with a halogen atom such as a chlorine atom, a bromine atom or a fluorine atom, and is substituted. The number and position of halogen atoms are arbitrary. The carbon number of the haloalkyl group is preferably 1 or 2, and the halogen atom is preferably a fluorine atom. Examples of the haloalkyl group include a trifluoromethyl group, a pentafluoroethyl group, and a 2,2,2-trifluoroethyl group.

Moreover, as carbon number of the alkoxy group shown by R < ² > and R < ³ >, 1 or 2 is preferable. The alkoxy group may be linear or branched, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an isobutoxy group. Can be mentioned.
The number of carbon atoms of the alkoxyalkyl group represented by R ² and R ³ is preferably 2-4. The alkoxyalkyl group may be linear or branched, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a 2-methoxyethyl group, and a 2-ethoxyethyl group.

In addition, examples of the halogen atom represented by R ² and R ³ include the same halogen atoms as those contained in the haloalkyl group.

In the formula (2), n is preferably an integer of 1 to 3, particularly preferably 1.
P is an integer from 0 to 2, and q is an integer from 0 to 3. When p is 2, p R ^{2 s} may be the same or different. Similarly, when q is 2 or 3, q R ^{3 s} may be the same or different.
Moreover, as p, 0 or 1 is preferable and 0 is more preferable. On the other hand, q is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

Examples of the monomer containing an azobenzene skeleton for deriving segment B include phenyl (4- (2-vinyloxyethoxy) phenyl) diazene and o-tolyl (4- (2-vinyloxyethoxy) phenyl) diazene. (2- (trifluoromethyl) phenyl) (4- (2-vinyloxyethoxy) phenyl) diazene, (2- (methoxymethyl) phenyl) (4- (2-vinyloxyethoxy) phenyl) diazene, (2 -Chlorophenyl) (4- (2-vinyloxyethoxy) phenyl) diazene, 2-((4- (2-vinyloxyethoxy) phenyl) diazenyl) phenol, 2-((4- (2-vinyloxyethoxy) phenyl ) Diazenyl) benzoic acid, 2-((4- (2-vinyloxyethoxy) phenyl) diazenyl) aniline, (2-ni Rophenyl) (4- (2-vinyloxyethoxy) phenyl) diazene, 2-((4- (2-vinyloxyethoxy) phenyl) diazenyl) benzenesulfonic acid and the like, and segment B includes such an azobenzene skeleton. Among these monomers, one derived from one of them may be used, or two or more may be used.
Of these, phenyl (4- (2-vinyloxyethoxy) phenyl) diazene is particularly preferable.

<Segment C>
As the structural unit (c) constituting the segment C, for example, the following general formula (3)

[In the formula (3), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. , An alkanoyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group or an alkylsilyl group, and m is an integer of 1 to 3. ]
The thing represented by is mentioned.

In the formula (3), the carbon number of the alkyl group represented by R ⁴ is preferably 1 or 2.
The alkyl group represented by R ⁴ and R ⁵ may be linear or branched, and examples thereof include those exemplified as the alkyl group represented by R ² .

In addition, the alkoxyalkyl group having 2 to 6 carbon atoms represented by R ⁵ is linear, branched or cyclic (two alkyl chains together with an oxygen atom form an oxygen-containing heterocycle) Specifically, in addition to those exemplified as the alkoxyalkyl group represented by R ² , 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group and the like can be mentioned.

Further, the number of carbon atoms of the alkanoyl group represented by R ⁵ is preferably 2 to 6. Such an alkanoyl group may be linear or branched, and examples thereof include an acetyl group, a propionyl group, and a tert-butylcarbonyl group.
The number of carbon atoms of the alkoxycarbonyl group represented by R ⁵ is preferably 2-6. Such an alkoxycarbonyl group may be linear or branched, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a tert-butoxycarbonyl group.

The number of carbon atoms of the alkoxycarbonylalkyl group represented by R ⁵ is preferably 2-6. Such an alkoxycarbonylalkyl group may be linear or branched, and examples thereof include a tert-butoxycarbonylmethyl group.
The number of carbon atoms of the alkylsilyl group represented by R ⁵ is preferably 2-6. Examples of such an alkylsilyl group include a trimethylsilyl group and a tert-butyldimethylsilyl group.

In Formula (3), m is preferably 1 or 2, and more preferably 1. When m is 2 or 3, the m —OR ⁵ may be the same or different.

Examples of the oxystyrene monomer for deriving segment C include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol. Hydroxystyrenes such as p-methoxystyrene, m-methoxystyrene, p-ethoxystyrene, m-ethoxystyrene, p-propoxystyrene, m-propoxystyrene, p-isopropoxystyrene, m-isopropoxystyrene, p- alkoxystyrenes such as n-butoxystyrene, mn-butoxystyrene, p-isobutoxystyrene, m-isobutoxystyrene, p-tert-butoxystyrene, m-tert-butoxystyrene; p-methoxymethoxystyrene m-methoxymethoxystyrene, p- (1-ethoxyethoxy) styrene, m- (1-ethoxyethoxy) styrene, p- (2-tetrahydropyranyl) oxystyrene, m- (2-tetrahydropyranyl) oxystyrene, etc. Alkanoyloxystyrenes such as p-acetoxystyrene, m-acetoxystyrene, p-tert-butylcarbonyloxystyrene, m-tert-butylcarbonyloxystyrene; p-tert-butoxycarbonylmethyloxystyrene M-tert-butoxycarbonyloxymethylstyrenes, alkoxycarbonylalkyloxystyrenes; p-trimethylsilyloxystyrene, m-trimethylsilyloxystyrene, p-tert-butyldimethyl Rusilyloxystyrene, m-tert-butyldimethylsilyloxystyrenes, alkylsilyloxystyrenes, etc., and segment C is derived from one of such oxystyrene monomers. Alternatively, it may be derived using two or more kinds.
Among these, hydroxystyrenes and alkoxystyrenes are preferable, and p-hydroxystyrene, p-isopropenylphenol, and p-tert-butoxystyrene are particularly preferable.

Further, in the triblock copolymer of the present invention, segments A to C are bonded by an ABC sequence. With such a configuration, temperature responsiveness can be exhibited even when it is supported on a fibrous base material.

The content of segments A to C in the triblock copolymer of the present invention may be appropriately adjusted according to the use, but the content of segment A is preferably 70 to 99 mol%, more preferably 85. ~ 98 mol%. The hydrophilicity when the temperature is lowered can be improved by setting such content to 70 mol% or more, while the hydrophobicity when the temperature is raised is improved by setting it to 99 mol% or less. Can do.

Further, the content of segment B is preferably 1 to 20 mol%, more preferably 1 to 15 mol%, and further preferably 1 to 10 mol%. By making such content 20 mol% or less, the action of segment A and segment C can be enhanced, while by making it 1 mol% or more, the penetration action of segment B into the fibrous base material is enhanced. Can do.

Further, the content of segment C is preferably 0.1 to 10 mol%, more preferably 0.3 to 5 mol%, and particularly preferably 0.75 to 3 mol%. Hydrophobicity when the temperature is raised can be improved by making the content 0.1 mol% or more, while hydrophilicity when the temperature is lowered by making the content 5 mol% or less. Can be made.

Further, the molar ratio [B / A] of the segments A and B in the triblock copolymer is preferably 0.005 to 1, more preferably 0.01 to 0.5, from the viewpoint of temperature responsiveness. 0.025 to 0.25 is more preferable, and 0.025 to 0.15 is particularly preferable.
In addition, the molar ratio [C / A] of the segments A and C is preferably 0.001 to 0.1, more preferably 0.0025 to 0.05, and more preferably 0.005 to 0 from the viewpoint of temperature responsiveness. 0.025 is more preferable, and 0.0075 to 0.025 is particularly preferable.
In addition, content and ratio of each said segment can be measured by NMR etc.

The weight average molecular weight (M _w ) of the triblock copolymer of the present invention is preferably in the range of 5000 to 100,000, more preferably in the range of 10,000 to 50,000. Temperature responsiveness is improved by setting the weight average molecular weight (M _w ) to 5000 or more, while solubility in a solvent can be improved by setting the weight average molecular weight (M _w ) to 100,000 or less.
The triblock copolymer of the present invention is preferably narrowly dispersed from the viewpoint of temperature responsiveness, and the molecular weight distribution (M _w / M _n ) is in the range of 1.0 to 2.0. preferable.
Each said weight average molecular weight ( _Mw ) and molecular weight distribution ( _Mw / _Mn ) can be measured by the method as described in the Example mentioned later.

In addition, examples of both ends of the triblock copolymer of the present invention include a hydrogen atom, an alkyl group, and an alkoxy group.

Next, the manufacturing method of the triblock copolymer of this invention is demonstrated.
The triblock copolymer of the present invention can be produced by living cationic polymerization. According to living cationic polymerization, control of molecular weight and composition ratio is easy, and a narrowly dispersed polymer can be obtained.
That is, <1> a vinyl ether monomer that induces segment A is subjected to living cationic polymerization in the presence of a starting species, a Lewis acid, and a solvent, and <2> an azobenzene skeleton that induces segment B in this reaction system. A diblock polymer is formed by adding a monomer to be contained and subjecting it to living cationic polymerization. Next, the triblock copolymer of the present invention can be produced by adding an oxystyrene monomer that induces segment C to the reaction system in which the <3> diblock polymer is formed, and performing living cationic polymerization. . In the steps <2> and <3>, a Lewis acid or a solvent may be further added.

As a vinyl ether monomer for deriving segment A used in step <1>, the following general formula (4)

[In formula (4), each symbol is as defined above. ]
The thing represented by is mentioned.
Moreover, as a monomer containing the azobenzene skeleton which induces segment B used in step <2>, the following general formula (5)

[In formula (5), each symbol is as defined above. ]
The thing represented by is mentioned.
Moreover, as an oxystyrene-type monomer which derives the segment C used at process <3>, following General formula (6)

[In formula (6), each symbol is as defined above. ]
The thing represented by is mentioned.

The starting species used in each of the above steps include compounds that generate protons such as water, alcohol, and protonic acids, compounds that generate carbocations such as alkyl halides, and compounds that generate protons with vinyl ether. Cation supplying compounds, such as adducts, are preferable. Among them, compounds that generate carbocations are preferred. Examples of the compound that generates such a carbocation include 1-alkoxyethyl acetate such as 1-isobutoxyethyl acetate.
What is necessary is just to determine suitably the addition amount of the said start seed | species according to the molecular weight of the target triblock copolymer.

In addition, the Lewis acid used in each of the above steps may be any one that is generally used for living cationic polymerization. Specifically, organometallic halides such as Et _1.5 AlCl _1.5 ; TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ .OEt ₂ , SnCl ₂ , SnCl ₄ , SbCl ₅ , SbF ₅ , WCl ₆ , TaCl ₅ , metal halides such as VCl ₅ , FeCl ₃ , ZnBr ₂ , ZnCl ₄ , AlCl ₃ , and AlBr ₃ can be preferably used. Note that the Lewis acid may be used alone or in combination.

Among such Lewis acids, the Lewis acid used in the steps <1> and <2> includes the following general formula (7)

[In the formula (7), R ⁶ represents a monovalent organic group, Y represents a halogen atom, r and s represent r + s = 3, and 0 ≦ r <3 and 0 <s ≦ 3. ]
The organic aluminum halide compound or aluminum halide compound represented by these is preferable.

In formula (7), the monovalent organic group represented by R ⁶ is not particularly limited, but an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 12 carbon atoms), an aralkyl group (preferably Includes an alkenyl group (preferably 2 to 8 carbon atoms) and an alkoxy group (preferably 1 to 8 carbon atoms).
Examples of the halogen atom represented by Y include a chlorine atom, a bromine atom, and a fluorine atom. R is preferably in the range of 1 to 2, and s is preferably in the range of 1 to 2.

Specific examples of the Lewis acid as described above include diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, isobutylaluminum sesquichloride, ethylaluminum sesquibromide, isobutyl. Examples include aluminum sesquichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum difluoride, isobutylaluminum dichloride, octylaluminum dichloride, ethoxyaluminum dichloride, phenylaluminum dichloride.

On the other hand, the Lewis acid used in the step <3> is preferably a metal halogen compound or an organometallic halogen compound other than Al. Such compounds include TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ .OEt ₂ , SnCl ₂ , SnCl ₄ , SbCl ₅ , SbF ₅ , WCl ₆ , TaCl ₅ , VCl ₅ , FeCl ₃ , ZnBr ₂ , ZrCl _{4 and the} like. Among this, SnCl _4, FeCl ₃ and the like are preferable.

The amount of Lewis acid used is not particularly limited, and may be set in consideration of the polymerization characteristics or polymerization concentration of each monomer used. Usually, it is used in the range of 1 to 500 mol% with respect to each monomer.

The solvent used in each of the above steps includes aromatic hydrocarbon solvents such as benzene, toluene and xylene; propane, n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane. Aliphatic hydrocarbon solvents such as isooctane, decane, hexadecane and isopentane; halogenated hydrocarbon solvents such as methylene chloride, ethylene chloride and carbon tetrachloride; tetrahydrofuran (THF), dioxane, diethyl ether, dibutyl ether, ethylene glycol Examples include ether solvents such as diethyl ether. These solvents may be used alone or in combination of two or more.

The polymerization temperature in each step is usually in the range of −80 ° C. to 150 ° C., but is preferably in the range of −78 ° C. to 80 ° C. The polymerization time is usually in the range of 5 to 12 hours.

Further, the triblock copolymer of the present invention, after step <3>, added a reaction terminator at a desired degree of polymerization to stop the polymerization reaction, and removed catalyst residues such as metal compounds as necessary. Thereafter, it can be isolated by (1) a method of distilling off volatile components from the polymer solution, or (2) a method of adding a large amount of poor solvent to precipitate and separate the polymer.
Examples of the reaction terminator include compounds such as alcohols such as methanol, ethanol, and propanol; amines such as dimethylamine and diethylamine; compounds that act as end terminators such as water, aqueous ammonia, and aqueous sodium hydroxide; A compound having a function of deactivating the activity of the Lewis acid is used.
The catalyst residue can be removed by treating with water or an aqueous solution containing an acid such as hydrochloric acid, nitric acid or sulfuric acid; treating with an inorganic oxide such as silica gel, alumina or silica-alumina; ion exchange resin And the like. Among them, a method of treating with alumina that does not cause penetration of azo groups and exhibits metal adsorption ability is preferable.

The triblock copolymer of the present invention obtained as described above exhibits temperature responsiveness and reversibly changes its hydrophilicity / hydrophobicity even when supported on a fibrous base material. Sex can be imparted. Moreover, it can fix | immobilize on base-material surfaces, such as a synthetic resin, and base-material surfaces, such as a synthetic resin to which the triblock copolymer was fix | immobilized, are smooth and do not have a tack. Here, in the present specification, the temperature responsiveness refers to showing hydrophilicity (water permeability) when the temperature is lower than a predetermined temperature, and showing hydrophobicity (water repellency) when the temperature exceeds a predetermined temperature.
Although the reason why the temperature responsiveness can be expressed even if it is supported on the fibrous base material is not necessarily clear, the action of imparting hydrophilicity or hydrophobicity in response to the thermal stimulation of the segment A, and the segment B Both the effect of imparting the permeability to the fibrous base material and the effect of adjusting the hydrophobicity of the segment C are sufficiently expressed by setting the segment sequence to ABC, and the present invention. Guess.

Therefore, by using the triblock copolymer of the present invention, the hydrophilicity / hydrophobicity of the substrate to be applied can be controlled by utilizing its temperature responsiveness. By supporting the coalescence on a fibrous base material, a copolymer-fiber composite having temperature responsiveness can be provided. The hydrophilicity / hydrophobicity control agent and copolymer-fiber composite of the present invention are used as materials such as a temperature sensor, a separation membrane, an adsorbent, a drug release agent, a water absorbing agent, a water retention agent, a humidity control agent, and an indicator agent. Can be used.

Further, the hydrophilicity / hydrophobicity control agent may contain a solvent in addition to the triblock copolymer. Examples of such solvents include those listed above as solvents used in the polymerization reaction, lower alcohols (preferably having 1 to 3 carbon atoms) such as methanol, ethanol, propanol and isopropanol; water, and the like. It may be included, and two or more kinds of combinations may be included.
The content of the triblock copolymer is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 25% by mass in the hydrophilicity / hydrophobicity control agent.

In addition, examples of the base material to be controlled for hydrophilicity / hydrophobicity include synthetic resins, natural resins, plant fibers, animal fibers, and inorganic fibers. Synthetic resins and inorganic fibers are preferable, and synthetic resin fibers and inorganic fibers are more preferable.
Examples of the synthetic resin include polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; polystyrene resins such as polystyrene; vinyl chloride resins; low density polyethylene, Polyolefin resins such as high-density polyethylene and polypropylene; polyether resins such as polyether ketone and polyether ether ketone; polyamide resins such as nylon and aramid; polycarbonate resins such as polycarbonate; polyimide resins such as polyimide; Polyurethane resins such as polytetrafluoroethylene, and the like, and examples of the natural resin include latex and natural rubber. Note that it may be a composite material composed of a plurality of these resins, an alloy, a copolymer, or the like.
Examples of the plant fiber include cotton, hemp, and linen. Examples of the animal fiber include wool, silk, and cashmere. Examples of the inorganic fiber include glass fiber. These fibers may be used alone or in combination, and may be used in combination with a synthetic resin or a natural resin.

In addition, the form of the substrate is not particularly limited, and examples thereof include beads, films, fibrous substrates, sheets, tubes, pipes, and composites thereof. However, fibrous substrates are preferable, and fiber sheets are more preferable. . Examples of the fiber sheet include woven fabrics, knitted fabrics, and non-woven fabrics, and non-woven fabrics are preferred in that the gap between fibers is small. Nonwoven fabrics and composite nonwoven fabrics manufactured by various nonwoven fabric production methods such as air-through method, heat roll method, spun lace method, needle punch method, chemical bond method, airlaid method, melt blown method, and spun bond method (for example, , Spunbond / meltblown nonwoven fabric, spunbond / meltblown / spunbond nonwoven fabric) and the like. The fiber sheet may be a single layer or a laminate of multiple layers.
In addition, the triblock copolymer of the present invention can control the hydrophilicity / hydrophobicity of the substrate as described above, but contains an azo group having permeability to a synthetic resin or inorganic fiber, and the triblock copolymer on the surface of the synthetic resin or inorganic fiber. Since the block copolymer can be immobilized, it is particularly suitable for controlling hydrophilicity / hydrophobicity of the surface of the synthetic resin or inorganic fiber.

Moreover, as a hydrophilicity / hydrophobicity control method, the method which dissolves the triblock copolymer of this invention in the said solvent, and apply | coats or impregnates to a base material is mentioned.
The method of application or impregnation is not particularly limited, and examples thereof include a method in which a solution in which the triblock copolymer is dissolved is applied using a spray, a roll, a brush, a dipping method, and the like.

In the copolymer-fiber composite of the present invention, the triblock copolymer of the present invention is supported on a fibrous base material. The fibrous base material refers to a base material having a fiber assembly as a main constituent component, and examples thereof include the same ones as described above. The copolymer-fiber composite is preferably one in which a triblock copolymer is immobilized on the surface of the fibers constituting the fibrous base material.
Moreover, as said fibrous base material, what consists of 1 or more types chosen from a synthetic resin fiber, a natural resin fiber, a vegetable fiber, an animal fiber, and an inorganic fiber is mentioned, 1 type chosen from a synthetic resin fiber and an inorganic fiber What consists of the above is preferable.
Examples of the synthetic resin constituting the synthetic resin fiber, the natural resin constituting the natural resin fiber, the plant fiber, the animal fiber, and the inorganic fiber include the same as those described above. Among the synthetic resin fibers, among the polyester fibers, Polyolefin fibers, polyamide fibers, polyurethane fibers, and composite fibers thereof are preferable. On the other hand, glass fiber is preferable as the inorganic fiber.

The copolymer-fiber composite may contain a drug or the like, and may be a fiber base material that has been processed. For example, it may be provided with functions such as flame retardancy, antibacterial properties, deodorant properties, insect repellent properties, antifungal properties, aromatic properties, etc., and integrated with a sheet or film having these functions. It may be.
The production of the copolymer-fiber composite of the present invention may be carried out in the same manner as in the above hydrophilicity / hydrophobicity control method. Moreover, you may form a woven fabric, a knitted fabric, a nonwoven fabric, etc. using the fiber which fixed the triblock copolymer on the surface.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The physical properties of each block copolymer were evaluated by the following methods.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)>
Using a RI detector, a standard polystyrene calibration curve was obtained by gel permeation chromatography (GPC) method (column: KF-804L x 3 manufactured by Shodex, eluent: tetrahydrofuran).

Example 1: Preparation of methoxyethyl vinyl ether-b-phenyl (4- (2-vinyloxyethoxy) phenyl) diazene-b-paraisopropenylphenol (hereinafter referred to as “MOVE-b-PVEPD-b-PIPP polymer”) (1)

The MOVE-b-PVEPD-b-PIPP polymer was synthesized according to the following synthesis route.

A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. In this container, 2-methoxyethyl vinyl ether (hereinafter referred to as “MOVE”) 0.71M (32.6 g), ethyl acetate 0.89M (35.3 g), 1-isobutoxyethyl acetate (hereinafter “IBEA”) referred to as) 3.56mM (0.25g), and placed in toluene 270 mL, the reaction system was cooled, 13.2 mm When the temperature reached 0 ° C., as a toluene solution (Et _1.5 AlCl _1.5 of Et _1.5 AlCl _1.5 ) Was added to initiate the polymerization.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE polymer was a monodisperse polymer having Mw = 32800 and Mw / Mn = 1.11.

Next, a toluene solution of phenyl (4- (2-vinyloxyethoxy) phenyl) diazene (hereinafter referred to as “PVEPD”) (0.071 M (8.56 g) as PVEPD) was added to the reaction system, and Et. _1.5 AlCl _1.5 in toluene solution (20.2 mM as Et _1.5 AlCl _1.5 ) was added to continue the reaction.
A small amount of the reaction solution was collected when the conversion of PVEPD was completed, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE-b-PVEPD polymer was a monodisperse polymer with Mw = 35400 and Mw / Mn = 1.12. Further, it was confirmed from the GPC chart of this polymer that the peak derived from the MOVE polymer completely disappeared.

Then, p- isopropenylphenol (hereinafter, referred to as "PIPP") was added an ethyl acetate solution of (7.13MM as PIPP (0.43 g)) to the reaction system of the further SnCl ₄ toluene solution (SnCl ₄ As the reaction was continued.
When the conversion of PIPP is completed, methanol containing sodium methoxide (5M as sodium methoxide) is added to the reaction system to stop the reaction, and the desired MOVE-b-PVEPD-b-PIPP polymer (triblock polymer) a) was obtained. The obtained triblock polymer a was a monodispersed polymer having Mw = 37300 and Mw / Mn = 1.15.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter with celite and a pore size of 1 μm and concentrated under reduced pressure with an evaporator to purify the triblock polymer a. The triblock polymer a after purification had Mw = 38100 and Mw / Mn = 1.18.

Example 2: Preparation of MOVE-b-PVEPD-b-PIPP polymer (2)
A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. In this vessel, MOVE 0.69M (32.6 g), ethyl acetate 0.87M (35.2 g), IBEA 3.46 mM (0.25 g), and 270 mL of toluene were cooled, and the reaction system was cooled to a temperature of 0 ° C. the Upon reaching, polymerization was initiated by the addition of (12.9 mM as Et _1.5 AlCl _1.5) toluene solution of Et _1.5 AlCl _1.5.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE polymer was a monodisperse polymer with Mw = 22600 and Mw / Mn = 1.17.

Then added as a toluene solution (PVEPD of PVEPD 0.039M a (4.91 g) to the reaction system, further continue the reaction by adding 32.6 mm) as a toluene solution (Et _1.5 AlCl _1.5 of Et _1.5 AlCl _1.5 It was.
A small amount of the reaction solution was collected when the conversion of PVEPD was completed, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE-b-PVEPD polymer was a monodisperse polymer with Mw = 24600 and Mw / Mn = 1.29. Further, it was confirmed from the GPC chart of this polymer that the peak derived from the MOVE polymer completely disappeared.

Then, ethyl acetate was added a solution of PIPP (6.9 mM as PIPP (0.43 g)) to the reaction system described above, the reaction was continued by adding further toluene solution of SnCl ₄ (76.0 mm as SnCl _4).
When the conversion of PIPP is completed, methanol containing sodium methoxide (5M as sodium methoxide) is added to the reaction system to stop the reaction, and the desired MOVE-b-PVEPD-b-PIPP polymer (triblock polymer) b) was obtained. The obtained triblock polymer b was a monodispersed polymer having Mw = 26700 and Mw / Mn = 1.29.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter of celite and a pore size of 1 μm, and concentrated under reduced pressure with an evaporator to purify the triblock polymer b. Triblock polymer b after purification was Mw = 27400 and Mw / Mn = 1.27.

Example 3: Preparation of MOVE-b-PVEPD-b-PIPP polymer (3)
A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. In this vessel, MOVE 1.29M (58.6 g), ethyl acetate 0.86M (31.6 g), IBEA 3.2 mM (0.23 g) and toluene 243 mL were placed, the inside of the reaction system was cooled, and the temperature was 0 ° C. the Upon reaching, polymerization was initiated by the addition of (12.0 mM as Et _1.5 AlCl _1.5) toluene solution of Et _1.5 AlCl _1.5.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE polymer was a monodisperse polymer with Mw = 28300 and Mw / Mn = 1.22.

Then added as a toluene solution (PVEPD of PVEPD 0.064M a (7.7 g) to the reaction system, further continue the reaction by adding 18.3 mm) as a toluene solution (Et _1.5 AlCl _1.5 of Et _1.5 AlCl _1.5 It was.
A small amount of the reaction solution was collected when the conversion of PVEPD was completed, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE-b-PVEPD polymer was a monodisperse polymer with Mw = 29800 and Mw / Mn = 1.46. Further, it was confirmed from the GPC chart of this polymer that the peak derived from the MOVE polymer completely disappeared.

Then, ethyl acetate was added a solution of PIPP (6.5 mM as PIPP (0.39 g)) to the reaction system described above, the reaction was continued by adding further toluene solution of SnCl ₄ (30.5 mm as SnCl _4).
When the conversion of PIPP is completed, methanol containing sodium methoxide (5M as sodium methoxide) is added to the reaction system to stop the reaction, and the desired MOVE-b-PVEPD-b-PIPP polymer (triblock polymer) c) was obtained. The obtained polymer c was a monodispersed polymer having Mw = 33800 and Mw / Mn = 1.23.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter of celite and a pore size of 1 μm, and concentrated under reduced pressure with an evaporator to purify the triblock polymer c. The purified triblock polymer c had Mw = 34600 and Mw / Mn = 1.58.

Example 4: Preparation of ethoxyethyl vinyl ether-b-phenyl (4- (2-vinyloxyethoxy) phenyl) diazene-b-paraisopropenylphenol (hereinafter referred to as “EOVE-b-PVEPD-b-PIPP polymer”) (1)

EOOVE-b-PVEPD-b-PIPP polymer was synthesized according to the following synthesis route.

A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. In this container, 2-ethoxyethyl vinyl ether (hereinafter referred to as “EOVE”) 0.68M (37.0 g), ethyl acetate 0.85M (35.2 g), IBEA 3.4 mM (0.25 g), and toluene 270 mL placed, the reaction system was cooled, and when the temperature reached 0 ° C., was added to initiate polymerization of (12.8 mM as Et _1.5 AlCl _1.5) toluene solution of Et _1.5 AlCl _1.5.
When the conversion of EOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained EOVE polymer was a monodisperse polymer with Mw = 29500 and Mw / Mn = 1.14.

Then added as a toluene solution (PVEPD of PVEPD 0.039M a (4.9 g) to the reaction system, further continue the reaction by adding 30.9mm) as a toluene solution (Et _1.5 AlCl _1.5 of Et _1.5 AlCl _1.5 It was.
A small amount of the reaction solution was collected when the conversion of PVEPD was completed, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained EOVE-b-PVEPD polymer was a monodisperse polymer with Mw = 31800 and Mw / Mn = 1.20. Further, it was confirmed from the GPC chart of this polymer that the peak derived from the EOVE polymer completely disappeared.

Then, ethyl acetate was added a solution of PIPP (6.8 mM as PIPP (0.43 g)) to the reaction system described above, the reaction was continued by adding further toluene solution of SnCl ₄ (76.5mM as SnCl _4).
When the conversion of PIPP is completed, methanol containing sodium methoxide (5M as sodium methoxide) is added to the reaction system to stop the reaction, and the desired EOVE-b-PVEPD-b-PIPP polymer (triblock polymer) d) was obtained. The obtained polymer d was a monodisperse polymer with Mw = 34600 and Mw / Mn = 1.16.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter of celite and a pore size of 1 μm and concentrated under reduced pressure with an evaporator to purify the triblock polymer d. The triblock polymer d after purification had Mw = 36500 and Mw / Mn = 1.18.

Comparative Example 1: Production of methoxyethyl vinyl ether-b-phenyl (4- (2-hydroxyethoxy) phenyl) diazene (hereinafter referred to as “MOVE-b-PVEPD polymer”) A glass container with a three-way cock was prepared. After replacing the inside of the container with argon, heating was performed to remove the adsorbed water in the glass container. In this vessel, MOVE 0.66M (32.6 g), ethyl acetate 0.83M (35.2 g), IBEA 3.3 mM (0.25 g), and 270 mL of toluene were cooled, and the reaction system was cooled to a temperature of 0 ° C. the Upon reaching, polymerization was initiated by the addition of (12.5 mM as Et _1.5 AlCl _1.5) toluene solution of Et _1.5 AlCl _1.5.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE polymer was a monodisperse polymer having Mw = 23600 and Mw / Mn = 1.18.

Then added as a toluene solution (PVEPD of PVEPD 0.066 M of (8.56 g) to the reaction system, further continue the reaction by adding 62.5 mM) as a toluene solution (Et _1.5 AlCl _1.5 of Et _1.5 AlCl _1.5 It was.
When the conversion of PVEPD was completed, methanol containing sodium methoxide (0.2 M as sodium methoxide) was added to the reaction system to stop the reaction, and diblock polymer e was obtained. The obtained MOVE-b-PVEPD polymer (diblock polymer e) was a monodispersed polymer having Mw = 25000 and Mw / Mn = 1.30.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter of celite and a pore size of 1 μm, and concentrated under reduced pressure with an evaporator to purify the diblock polymer e. Diblock polymer e after purification was Mw = 24300 and Mw / Mn = 1.36.

Comparative Example 2: Production of phenyl (4- (2-hydroxyethoxy) phenyl) diazene-b-methoxyethyl vinyl ether-b-paraisopropenylphenol (hereinafter referred to as “PVEPD-b-MOVE-b-PIPP polymer”) A glass container with a stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. PVEPD0.069M (8.57g), ethyl acetate 0.87M (35.3g), IBEA 3.49mM (0.25g), and toluene 350mL are put in this container, the inside of a reaction system is cooled, and temperature is 0 degreeC. the Upon reaching, polymerization was initiated by the addition of (32.7 mm as Et _1.5 AlCl _1.5) toluene solution of Et _1.5 AlCl _1.5.
A small amount of the reaction solution was collected when the conversion of PVEPD was completed, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained PVEPD polymer was a monodisperse polymer with Mw = 2800 and Mw / Mn = 1.09.

Next, the addition reaction of MOVE 0.69M was continued to the above reaction system.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained PVEPD-b-MOVE polymer was a monodisperse polymer with Mw = 29800 and Mw / Mn = 1.24. Further, it was confirmed from the GPC chart of this polymer that the peak derived from the PVEPD polymer completely disappeared.

Then, ethyl acetate was added a solution of PIPP (6.9 mM as PIPP (0.43 g)) to the reaction system described above, the reaction was continued by adding further toluene solution of SnCl ₄ (32.6 mm as SnCl _4).
When the conversion of PIPP is completed, methanol containing sodium methoxide (5M as sodium methoxide) is added to the reaction system to stop the reaction, and PVEPD-b-MOVE-b-PIPP polymer (triblock polymer f) is added. Obtained. The obtained polymer f was a monodisperse polymer with Mw = 33500 and Mw / Mn = 1.30.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter of celite and a pore size of 1 μm, and concentrated under reduced pressure with an evaporator to purify the triblock polymer f. Triblock polymer f after purification had Mw = 34700 and Mw / Mn = 1.30.

Examples 5 to 11 and Comparative Examples 3 and 4: Fabrication of Fiber Sheet A 10% by mass methanol solution and a 10% by mass aqueous solution of the polymers a to f obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were prepared, respectively. . Each block copolymer is supported by immersing polyethylene terephthalate nonwoven fabric (2 × 10 cm), glass fiber (47φ filter paper), or polyurethane nonwoven fabric (2 × 10 cm) in this prepared solution for 1 hour and thoroughly washing it. The fiber sheets of Examples 5 to 11 and Comparative Examples 3 and 4 shown in the following table were obtained. All of the obtained fiber sheets were derived from azo groups and colored pale yellow, and it was confirmed that the block copolymer was uniformly supported on the nonwoven fabric. Moreover, the stickiness and unevenness | corrugation originating in a block copolymer were not looked at by the surface of any fiber sheet, but the form similar to the nonwoven fabric before an impregnation was maintained.

Test Example 1: Water Permeability Evaluation Test 100 μL of water droplets were placed at equal intervals on the surface of the fiber sheets of Examples 5 to 11 and Comparative Examples 3 and 4, and 0 ° C., 25 ° C., and 70 at a humidity of 55%. By counting the number of water droplets after 5 minutes under the temperature condition of ° C., the water permeability and the change of the water permeability due to the temperature were confirmed.
Table 1 shows the results of water permeability evaluation of each fiber sheet. For comparison, Table 1 also shows the results of a similar evaluation performed on a non-impregnated nonwoven fabric.

As shown in Table 1, the fiber sheet in which the polymer (polymers a to d) in which the segments A to C are bonded by the sequence ABC is supported on the nonwoven fabric exhibits water permeability at a low temperature and is high. It did not show water permeability at temperature.
From this result, it can be seen that the composite of the present invention has temperature responsiveness and can reversibly achieve hydrophilicity (water permeability) and hydrophobicity (water repellency) in response to thermal stimulation.

On the other hand, although the fiber sheet which carried the copolymer (polymer e) which does not contain the segment C on the nonwoven fabric showed water permeability, it did not show temperature responsiveness.
In addition, even if the segment C is included, it is evaluated if the copolymer (polymer f) in which the segments A to C are bonded by the sequence BAC instead of ABC is evaluated. Water droplets were not permeated at all temperatures subjected to the above, and water permeability could not be imparted.

Claims (9)

1. It consists of a segment A consisting of repeating vinyl ether structural units (a) containing a temperature-responsive group, a segment B consisting of repeating structural units (b) containing an azobenzene skeleton, and a repeating oxystyrene structural unit (c). An ABC type azo triblock copolymer, wherein the segment C is bonded with the sequence ABC.
2. The structural unit (a) is represented by the following general formula (1)
   

   

   [In the formula (1), R ¹ represents a methyl group or an ethyl group, and k is an integer of 1 to 10. ]
   It is represented by
   The structural unit (b) is represented by the following general formula (2)
   

   

   [In the formula (2), R ² and R ³ each independently represents an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxyalkyl group, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a nitro group, a sulfo group, a sulfooxy group, or an aminosulfonyl group, n is an integer of 1 to 5, and p is an integer of 0 to 2. Q is an integer from 0 to 3. ]
   It is represented by
   The structural unit (c) is represented by the following general formula (3)
   

   

   [In the formula (3), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. , An alkanoyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group or an alkylsilyl group, and m is an integer of 1 to 3. ]
   The triblock copolymer according to claim 1, which is represented by:
3. The triblock copolymer according to claim 1 or 2, wherein the content of segment B is 1 to 20 mol% in the triblock copolymer.
4. A hydrophilicity / hydrophobicity control agent containing the triblock copolymer according to any one of claims 1 to 3.
5. A method for controlling hydrophilicity / hydrophobicity using the triblock copolymer according to any one of claims 1 to 3.
6. A copolymer-fiber composite in which the triblock copolymer according to any one of claims 1 to 3 is supported on a fibrous base material.
7. The copolymer-fiber composite according to claim 6, wherein the fibrous base material is one or more selected from synthetic resin fibers, natural resin fibers, plant fibers, animal fibers, and inorganic fibers.
8. The copolymer-fiber composite according to claim 6 or 7, wherein the fibrous base material comprises at least one selected from polyester fiber, polyolefin fiber, polyamide fiber, polyurethane fiber and glass fiber.
9. The copolymer-fiber composite according to any one of claims 6 to 8, wherein the fibrous base material is a woven fabric, a knitted fabric or a non-woven fabric.