JP6283511B2 - Temperature-responsive resin composition - Google Patents

Description

  The present invention relates to a temperature-responsive resin composition, a hydrophilicity / hydrophobicity control agent using the resin composition, a method for controlling hydrophilicity / hydrophobicity, and a temperature-responsive resin support in which the resin composition is supported on a substrate.

  Some polymer compounds exhibit a phase transition in response to external stimuli such as heat, pH, and light. Temperature sensors, separation membranes, adsorbents, drug release agents, water absorption using this phase transition phenomenon Materials, water retention agents, humidity control agents, indicator agents, etc. are being actively developed.

  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.

  As means for solving such a problem, introduction of an azo group into a temperature-responsive polymer has been studied. For example, by using a diblock copolymer of vinyl ether containing oxyethylene chain and vinyl ether containing azobenzene structure, surface modification of various general-purpose resin films can be performed to provide temperature responsiveness related to hydrophilicity / hydrophobicity. It has been studied (Patent Document 1, Non-Patent Document 1).

  However, as a result of studies by the present inventors, it has been found that the diblock copolymers described in Patent Document 1 and Non-Patent Document 1 cannot impart temperature responsiveness to fibrous substrates such as nonwoven fabrics. did.

JP 2005-154603 A International Publication No. 2013/099427

Yuya Tsuchida, “Development of polymer materials for collecting harmful substances”, Shiga Prefecture Tohoku Industrial Technology Center 2005 Report (http://www.hik.shiga-irc.go.jp/kenkyu/ken_kako/kenk_nag/ H17ken / report / H17_tsuchida.pdf)

Under such a background, the present applicant has obtained a triblock copolymer of a vinyl ether containing an oxyethylene chain, a vinyl ether containing an azobenzene structure, and oxystyrene (Patent Document 2) or an azobenzene structure at the end of the polymer chain. It has been found that by using a temperature-responsive vinyl ether polymer (Japanese Patent Application No. 2013-040947), it is possible to impart hydrophilic and hydrophobic temperature responsiveness to a fibrous base material. Applied for a patent.
However, as a result of the study by the present inventors, the above triblock copolymer and the temperature-responsive vinyl ether polymer containing an azobenzene structure at the end of the polymer chain were supported on a highly permeable fibrous base material such as a woven fabric or a knitted fabric. It has been found that there is room for improvement in the temperature responsiveness of the case, and further, it becomes difficult to adjust the hydrophilicity / hydrophobicity when supported on a highly hydrophilic fibrous base material.

  The problem to be solved by the present invention is that the temperature responsiveness when supported on a base material is less affected by the type of the base material, and the temperature responsive resin composition is easy to adjust hydrophilicity / hydrophobicity. Another object of the present invention is to provide a hydrophilicity / hydrophobicity control agent and a hydrophilicity / hydrophobicity control method using the resin composition, and a temperature-responsive resin carrier having the resin composition supported on a substrate.

  Therefore, as a result of intensive studies to solve the above problems, the present inventor contains a water-repellent polymer containing a water-repellent group such as a fluorine atom or a silyl group, and a specific vinyl ether polymer having a temperature-responsive group. Even when the temperature-responsive resin composition is supported on a highly permeable fibrous base material such as a fabric, the temperature responsiveness can be expressed, and when temperature-responsive resin composition is supported on the base material, It is not easily affected by the type of the base material. Furthermore, depending on the blending ratio of each polymer, it is easily hydrophilic / hydrophobic for both highly hydrophilic fiber base materials and highly hydrophobic fiber base materials. The present invention has been completed.

That is, the present invention provides <1> the following polymers (A) and (B):
(A) a water-repellent polymer;
(B) a temperature-responsive group-containing vinyl ether polymer having a group (b1) containing a diaryldiazene structure and a repeating unit (b2) derived from a temperature-responsive group-containing vinyl ether monomer;
The temperature responsive resin composition containing this is provided.

Moreover, this invention provides the hydrophilicity / hydrophobicity control agent containing the resin composition of <2> said <1>.
Furthermore, the present invention provides <3> a method for controlling hydrophilicity / hydrophobicity using the resin composition according to <1> above.
Furthermore, the present invention provides a temperature-responsive resin carrier in which the resin composition of <4> and <1> is carried on a substrate.

  Furthermore, the present invention provides a water repellent group-containing vinyl ether polymer (A1) having a group (a1) containing a <5> diaryldiazene structure and a repeating unit (a2) derived from a water repellent group-containing vinyl ether monomer. A method comprising a step of living cationic polymerization of a water-repellent group-containing vinyl ether monomer, and a step of stopping the living cationic polymerization using a reaction terminator having a group (a1) containing a diaryldiazene structure. Is to provide.

The temperature-responsive resin composition of the present invention can exhibit temperature responsiveness even when supported on a highly permeable fibrous base material such as a woven fabric, and the temperature response when supported on the base material. Is less affected by the type of base material, and it is possible to easily adjust the hydrophilicity / hydrophobicity of both highly hydrophilic fibrous base materials and highly hydrophobic fibrous base materials. And temperature responsiveness can be imparted to a wide range of substrates.
Therefore, according to the present invention, it is possible to provide a hydrophilicity / hydrophobicity control agent and a hydrophilicity / hydrophobicity control method capable of imparting temperature responsiveness to a wide range of substrates.
Further, the resin carrier of the present invention has temperature responsiveness.

  Moreover, according to the method for producing a water-repellent group-containing vinyl ether polymer of the present invention, a water-repellent group-containing vinyl ether polymer useful as a raw material for the temperature-responsive resin composition of the present invention can be produced simply and easily.

<Water repellent polymer (A)>
First, the water-repellent polymer (A) contained in the temperature-responsive resin composition of the present invention will be described.
The water-repellent polymer (A) is not particularly limited, and polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene- A fluorine-containing resin such as an ethylene copolymer, polyvinyl fluoride, and polyvinylidene fluoride; a group (a1) including a diaryldiazene structure such as a silicone resin such as a pure silicone resin, silicone rubber, fluorine-modified silicone resin, and alkyl-modified silicone resin; The water-repellent group-containing vinyl ether polymer (A1) having the repeating unit (a2) derived from the water-repellent group-containing vinyl ether monomer may be mentioned, and these may be used alone or in combination of two or more.
Among the water-repellent polymers (A) as described above, from the viewpoint of temperature responsiveness when supported on a highly permeable fibrous base material or when supported on a highly hydrophilic base material, fluororesin, vinyl ether Polymer (A1) is preferable, and vinyl ether polymer (A1) is more preferable from the viewpoint of temperature responsiveness when the resin composition is supported on a highly hydrophilic fibrous base material.

  Moreover, as said fluororesin, what has a repeating unit represented by a following formula (F1) is preferable.

[In formula (F1), R ^{a to} R ^d each independently represent a hydrogen atom or a fluorine atom, and at least one of R ^{a to} R ^d is a fluorine atom. ]
The repeating unit (F1) is preferably one in which 2 to 4 of R ^{a to} R ^d are fluorine atoms, and more preferably 3 or 4 are fluorine atoms.

(Group (a1) containing diaryldiazene structure)
In the vinyl ether polymer (A1), the group (a1) containing a diaryldiazene structure is not limited as long as it exhibits an action of imparting permeability to a substrate, but the following formula (1)

[In formula (1), Y represents an ether bond, a thioether bond, a group —NH— or a group —OR ¹ — * (R ¹ represents an alkylene group, * represents a position bonded to Ar ¹ ), Ar ¹ represents a substituted or unsubstituted divalent aromatic hydrocarbon group, and Ar ² represents a substituted or unsubstituted monovalent aromatic hydrocarbon group. ]
The thing represented by these is preferable.

Here, each symbol in the above formula (1) will be described.
In the above formula (1), Y is preferably an ether bond (—O—) or a thioether bond (—S—), and more preferably an ether bond.
The number of carbon atoms of the alkylene group represented by R ¹ is preferably 1 to 10, more preferably from 1 to 6, more preferably 1 to 4, particularly preferably 1 to 2. The alkylene group may be linear or branched. Specific examples include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

In the formula (1), Ar ¹ represents a substituted or unsubstituted divalent aromatic hydrocarbon group. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, and an anthracylene group. From the viewpoint of the temperature responsiveness of the resin composition and the permeation diffusibility to the base material, the phenylene group and the naphthylene group. And a phenylene group is particularly preferable. The binding site of the divalent aromatic hydrocarbon group may be on any carbon on the aromatic ring.

Moreover, as a substituent which the said bivalent aromatic hydrocarbon group may have, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, Examples thereof include an alkoxyalkyl group having 2 to 6 carbon atoms, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group, and an aminosulfonyl group, and an alkyl group having 1 to 4 carbon atoms is preferable.
In addition, the position and number of these substituents are arbitrary, and when they have two or more substituents, the substituents may be the same or different.

  As carbon number of the said C1-C4 alkyl group, 1 or 2 is preferable. 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 tert-butyl group, and an isobutyl group.

In the present invention, the haloalkyl group means a linear or branched alkyl group substituted with a halogen atom such as a chlorine atom, a bromine atom, or a fluorine atom.
In addition, the number and position of the halogen atom substituted on the haloalkyl group having 1 to 4 carbon atoms is arbitrary, and 1 or 2 is preferable as the carbon number of the haloalkyl group having 1 to 4 carbon atoms. 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 said C1-C4 alkoxy group, 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.

Moreover, as carbon number of the said C2-C6 alkoxyalkyl group, 2-4 are preferable. 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.
Moreover, as said halogen atom, the thing similar to the halogen atom contained in the said haloalkyl group is mentioned.

Moreover, as a suitable specific example of Ar < ¹ > in the said Formula (1), following formula (2) or (3)

[In Formula (2), each R ² 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 an alkoxy group having 2 to 6 carbon atoms. An alkyl group, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group or an aminosulfonyl group; ** represents a position bonded to Y; *** represents a position bonded to a nitrogen atom; 1 is an integer of 0-4. ]

Wherein (3), p-2 is an integer of 0~6, R ^2, ** and *** have the same meanings as defined above. ]

In view of the temperature responsiveness of the resin composition and the permeation diffusibility into the substrate, the one represented by the above formula (2) is preferable.

In the above formulas (2) and (3), specific examples of each group represented by R ² are the same as the substituents that the divalent aromatic hydrocarbon group may have.
Moreover, the integer of 0-2 is preferable as p-1 in Formula (2), and the integer of 0-4 is preferable as p-2 in Formula (3).

In formula (1), Ar ² represents a substituted or unsubstituted monovalent aromatic hydrocarbon group. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group. From the viewpoint of the temperature responsiveness of the resin composition and the osmotic diffusion property to the substrate, the phenyl group and the naphthyl group are Preferred is a phenyl group. The binding site of the monovalent aromatic hydrocarbon group may be on any carbon on the aromatic ring.
The substituent that the monovalent aromatic hydrocarbon group may have is the same as the substituent that the divalent aromatic hydrocarbon group may have.

In addition, preferred specific examples of Ar ² include the following formula (4) or (5).

[In Formula (4), each R ³ 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 an alkoxy group having 2 to 6 carbon atoms. An alkyl group, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group or an aminosulfonyl group; *** indicates a position bonded to a nitrogen atom; and p-3 is an integer of 0 to 5. ]

Wherein (5), p-4 is an integer of 0 to 7, R ³ and **** are as defined above. ]
In view of the temperature responsiveness of the resin composition and the penetrability and diffusibility into the substrate, those represented by the above formula (4) are preferred.

In the above formulas (4) and (5), specific examples of each group represented by R ³ are the same as the substituents that the divalent aromatic hydrocarbon group may have.
Moreover, the integer of 0-3 is preferable as p-3 in Formula (4), and the integer of 0-5 is preferable as p-4 in Formula (5).

Further, the vinyl ether polymer (A1) may have a group (a1) containing the diaryldiazene structure in the side chain, or may be at the terminal of the polymer chain (main chain). Furthermore, a star polymer having a group (a1) containing a diaryldiazene structure in the central core may be used.
That is, the vinyl ether polymer (A1) includes
(A1-1) a water-repellent group-containing vinyl ether polymer having a repeating unit having a group (a1) containing a diaryldiazene structure in the side chain and a repeating unit (a2) derived from a water-repellent group-containing vinyl ether monomer;
(A1-2) Water repellent group having a group (a1) containing a diaryldiazene structure at at least one end of a polymer chain (main chain) and having a repeating unit (a2) derived from a water repellent group-containing vinyl ether monomer Contains vinyl ether polymers and the like.
Among these, the vinyl ether polymer (A1-2) is preferable from the viewpoint of easy production and easy loading on the substrate.

Moreover, as a repeating unit which has group (a1) containing the said diaryl diazene structure in a side chain, what is represented by following formula (6) is mentioned.

[In the formula (6), R ⁴ represents a linear or branched alkylene group having 2 to 6 carbon atoms, n is an average value of 1 to 5, and other symbols are represented by the formula (1). It is synonymous with. ]
The alkylene group represented by R ⁴ is the same as the alkylene group represented by R ⁵ described later.

(Repeating unit (a2))
The repeating unit (a2) is not particularly limited as long as it is derived from a vinyl ether monomer containing a water repellent group, and the water repellent group is preferably a fluorine-containing group or a silicon-containing group, a fluorine atom, A fluoroalkyl group and a silyl group are more preferable, and those represented by —SiR ⁶ R ⁷ R ⁸ are more preferable (R ⁶ , R ⁷ and R ⁸ are R ⁶ , R ⁷ and R ⁷ in the following formula (7), respectively. the same meaning as R ^8).
As a repeating unit derived from a vinyl ether monomer containing such a water repellent group, the following formula (7):

[In Formula (7), R ⁵ represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group or a haloalkyl group. , A cycloalkyl group, or a cycloalkyl group having a halogen atom as a substituent, k is an average value of 1 to 10. ]
Is particularly preferred.

In said formula (7), carbon number of the alkylene group shown by R < ⁵ > becomes like this. Preferably it is 2-4, Most preferably, it is 2. Specific examples include an ethylene group, a propylene group, and a trimethylene group, and an ethylene group is particularly preferable. In the case where R ⁵ is more, R ⁵ may be the same or different.

The number of carbon atoms of the alkyl group represented by R ^6, R ⁷ and R ⁸ is preferably 1 to 10, more preferably from 1 to 8, particularly preferably 1 to 6. The alkyl group may be linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and an isobutyl group.
The number of carbon atoms of the cycloalkyl group represented by R ^6, R ⁷ and R ⁸ is preferably 3 to 10, more preferably 4 to 8. Specifically, a cyclohexyl group etc. are mentioned.

Further, the cycloalkyl group having a haloalkyl group represented by R ^6, R ⁷ and R ^8, a halogen atom as a substituent, the alkyl group represented by R ^6, R ⁷ and R ^8, are included in the cycloalkyl group Examples include groups in which some or all of the hydrogen atoms are substituted with halogen atoms, and the number and position of the substituted halogen atoms are arbitrary.
In addition, examples of the halogen atom include a chlorine atom, a bromine atom, and a fluorine atom. From the viewpoint of improving water repellency, a fluorine atom is preferable. Specifically, trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl Group, perfluoropropyl group, 1- (trifluoromethyl) ethyl group, di (trifluoromethyl) methyl group, 2-fluorocyclohexyl group and the like.

Moreover, although k is an average value, it is 1-10, 1-6 are preferable at an average value, 1-4 are more preferable at an average value, and 1-3 are especially preferable at an average value.
Each “average value” in the present invention can be measured by NMR.

Moreover, as content of a repeating unit (a2), 10-100 mol% is preferable with respect to all the repeating units in a vinyl ether polymer (A1), 40-100 mol% is more preferable, and 60-100 mol% is further. Preferably, 80 to 100 mol% is particularly preferable.
Further, the molar ratio [(a1) :( a2)] of the group (a1) containing the diaryldiazene structure and the repeating unit (a2) in the vinyl ether polymer (A1) is 0.01: 99.99 to 10: 90 is preferable, 0.1: 99.9 to 7.5: 92.5 is more preferable, and 0.5: 99.5 to 5:95 is particularly preferable.
In addition, the said content and molar ratio can be measured by NMR etc.

  The vinyl ether polymer (A1) may further have a repeating unit (a3) other than the repeating unit having a group (a1) containing a diaryldiazene structure in the side chain and the repeating unit (a2).

Examples of the repeating unit (a3) include repeating units derived from a cationically polymerizable vinyl monomer. Examples of the vinyl monomer include vinyl aromatic compounds, aliphatic unsaturated hydrocarbons, alkyl vinyl ethers, and N-vinyl carbazole.
Examples of the vinyl aromatic compound include styrene such as styrene, α-methylstyrene, p-methylstyrene, and trimethylstyrene, or alkylstyrene; p-hydroxystyrene, p-isopropenylphenol, p-methoxystyrene, p-tert-butoxy. Examples thereof include oxystyrene such as styrene and p-acetoxystyrene.
Moreover, isobutene etc. are mentioned as said aliphatic unsaturated hydrocarbon.
Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and isobutyl vinyl ether.

  When the vinyl ether polymer (A1) has a repeating unit (a3), the molar ratio of the repeating unit (a2) to the repeating unit (a3) [(a2) :( a3)] is 99.9: 0.00. 1-80: 20 is preferable, 99.75: 0.25-90: 10 is more preferable, and 99.5: 0.5-95: 5 is still more preferable.

Moreover, as a weight average molecular weight (Mw) of water-repellent polymer (A), the range of 5000-1 million is preferable, The range of 7500-100000 is more preferable, The range of 10000-50000 is still more preferable. By setting the weight average molecular weight (Mw) to 5000 or more, hydrophobicity is improved when the temperature is raised, and by setting it to 100,000 or less, solubility in a solvent can be improved.
The water repellent polymer (A) is preferably narrowly dispersed from the viewpoint of the temperature responsiveness of the resin composition, and the molecular weight distribution (Mw / Mn) is preferably in the range of 1.0 to 2.0. The range of 1.0 to 1.5 is more preferable.
The 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 the case where the vinyl ether polymer (A1) has a repeating unit or a repeating unit (a3) having a group (a1) containing a diaryldiazene structure in the side chain, the copolymer is a block copolymer, graft copolymer. Any of a copolymer, a random copolymer, and an alternating copolymer may be sufficient.

Next, taking the vinyl ether polymer (A1) as an example, a method for producing the water repellent polymer (A) will be described in detail. In addition, water-repellent polymer (A) other than vinyl ether polymer (A1) can be manufactured in accordance with a conventional method, and a commercial item can also be used.
Although the manufacturing method of a vinyl ether polymer (A1) is not specifically limited, For example, the said vinyl ether polymer (A1-1) is a vinyl ether which has the group (a1) containing a diaryl diazene structure according to the method of patent document 1 and 2. It can be obtained by a method (PA-I) in which a monomer, a water repellent group-containing vinyl ether monomer, and a monomer that derives an optional repeating unit (a3) are polymerized by living cationic polymerization.

In addition, in a method of living cationic polymerization of a water-repellent group-containing vinyl ether monomer and a monomer that derives an optional additional repeating unit (a3), a starting species having a group (a1) containing a diaryl diazene structure and a diaryl diazene The said vinyl ether polymer (A1-2) can be obtained by using 1 or more types chosen from the reaction terminator which has group (a1) containing a structure (PA-II).
Such a method (PA-II) is a novel production method by which a vinyl ether polymer (A1-2) useful as a raw material for the resin composition of the present invention can be easily obtained. Since living cationic polymerization does not involve a side reaction of chain transfer reaction, a desired functional group can be easily introduced at the end of the polymer chain. Further, according to living cationic polymerization, the molecular weight and composition ratio can be controlled, and a narrowly dispersed polymer can be obtained.

In addition, the specific method of the above method (PA-II) includes a step of subjecting the water-repellent group-containing vinyl ether monomer to living cationic polymerization in the presence of an initiating species having a group (a1) containing a diaryldiazene structure. Method (PA-II-I), a step of living cationic polymerization of a water-repellent group-containing vinyl ether monomer, and a step of stopping the living cationic polymerization using a reaction terminator having a group (a1) containing a diaryl diazene structure (PA-II-II) including
The above method (PA-II-I) is carried out in the same manner as in the conventional living cationic polymerization except that a water-repellent group-containing vinyl ether monomer and a starting species having a group (a1) containing a diaryldiazene structure are used. The above method (PA-II-II) is a conventional method of living cationic polymerization except that a water-repellent group-containing vinyl ether monomer and a reaction terminator having a group (a1) containing a diaryldiazene structure are used. The same can be done.
Among these methods (PA-II), the method (PA-II-II) is preferred because the reaction terminator is easily available and the reaction can be easily controlled.
Hereinafter, the methods (PA-I) and (PA-II-II) will be specifically described.

(Method (PA-I))
As the vinyl ether monomer having the group (a1) containing a diaryldiazene structure used in the method (PA-I), the following formula (8)

[Each symbol in Formula (8) is synonymous with said Formula (6). ]
The thing represented by is mentioned.

Specifically, phenyl (4- (2-vinyloxyethoxy) phenyl) diazene, 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) benzoic acid, 2-((4- (2-vinyloxyethoxy) phenyl) diazenyl) aniline, (2-nitrophenyl) (4 -(2-vinyloxyethoxy) phenyl) diazene, 2-((4- (2-vinyloxyethoxy) phenyl) diazenyl) benzene Etc. sulfonic acid and the like, may be used alone or in combination of two or more thereof.
Among these, phenyl (4- (2-vinyloxyethoxy) phenyl) diazene is preferable.

  In addition, as the water-repellent group-containing vinyl ether monomer used in the method (PA-I), the following formula (9)

[In formula (9), each symbol is synonymous with said formula (7). ]
And silyl group-containing vinyl ether monomers.

Specifically, trimethyl (2- (vinyloxy) ethoxy) silane, triethyl (2- (vinyloxy) ethoxy) silane, t-butyldimethyl (2- (vinyloxy) ethoxy) silane, triisopropyl (2- (vinyloxy) ethoxy) ) Silane, trifluoromethyldimethyl (2- (vinyloxy) ethoxy) silane, bis (trifluoromethyl) methyl (2- (vinyloxy) ethoxy) silane, and the like. You may use the above together.
Among these, from the viewpoint of improving water repellency, t-butyldimethyl (2- (vinyloxy) ethoxy) silane and triisopropyl (2- (vinyloxy) ethoxy) silane are preferable.

The living cationic polymerization in the method (PA-I) is preferably carried out in the presence of an initiating species, a Lewis acid, a solvent, and a Lewis base as necessary. The starting species, Lewis acid, solvent, and Lewis base may be the same as those used in the method (PA-II-II) described later.
The reaction temperature for living cationic polymerization is usually in the range of −80 ° C. to 150 ° C., preferably in the range of −78 ° C. to 80 ° C. The reaction time is usually in the range of 0.5 hours to 250 hours.
The living cationic polymerization can be stopped by adding a reaction terminator such as a compound acting as a terminal terminator and / or a compound having a function of deactivating the activity of Lewis acid to the reaction system. Examples of the reaction terminator include alcohols such as methanol, ethanol and propanol; amines such as dimethylamine and diethylamine; water, aqueous ammonia and aqueous sodium hydroxide.

(Method (PA-II-II))
Examples of the water repellent group-containing vinyl ether monomer used in the method (PA-II-II) include the same water repellent group-containing vinyl ether monomers as used in the method (PA-I).

The living cationic polymerization in the method (PA-II-II) is preferably carried out in the presence of an initiating species, and more preferably carried out in the presence of a Lewis acid and a solvent.
Examples of the starting species used include cations such as adducts of compounds that generate protons such as water, alcohol, and protonic acids, and compounds that generate carbocations such as alkyl halides, as well as compounds that generate vinyl ether and protons. Examples of the compound include carbocations.
Examples of the compound that generates such a carbocation include 1-alkoxyalkyl acetates such as 1-isobutoxyethyl acetate; bis (acetoxyalkoxy) alkanes such as 1,4-bis (1-acetoxyethoxy) butane, and the like. Can be mentioned.
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 vinyl ether polymer.

The Lewis acid is not particularly limited as long as it 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 , VCl ₅ , FeCl ₃ , ZnBr ₂ , ZnCl ₄ , AlCl ₃ , AlBr _3, etc. are preferably used. be able to. Note that the Lewis acid may be used alone or in combination.

  Among such Lewis acids, the following formula (10)

[In the formula (10), R ⁹ represents a monovalent organic group, X represents a halogen atom, r and s are 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 (10), the monovalent organic group represented by R ⁹ 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 May have 7 to 13 carbon atoms, an alkenyl group (preferably 2 to 8 carbon atoms), and an alkoxy group (preferably 1 to 8 carbon atoms).
Moreover, as a halogen atom shown by X, a chlorine atom, a bromine atom, a fluorine atom, etc. are mentioned, r becomes like this. Preferably it is the range of 1-2, s becomes like this.

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

  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 0.1 to 500 moles with respect to 100 moles of the total amount of vinyl ether monomers.

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

  In living cationic polymerization, a Lewis base may be used as an inhibitor of side reactions such as termination reaction. Specific examples include ester compounds such as ethyl acetate and n-butyl acetate.

  The reaction temperature of the living cationic polymerization is usually in the range of −80 ° C. to 150 ° C., but is preferably in the range of −78 ° C. to 80 ° C. The reaction time is usually in the range of 0.5 hours to 250 hours.

  In the method (PA-II-II), a reaction terminator having a group (a1) containing a diaryldiazene structure is added to the reaction system to terminate the living cationic polymerization. As a terminator, the following formula (11)

[In the formula (11), Z represents a hydrogen atom or an alkali metal atom, and other symbols are as defined in the formula (1). ]
What is represented by these is mentioned as a suitable example.
Examples of the alkali metal atom include lithium and sodium.

Specifically, 4- (phenyldiazenyl) phenol, 2- (phenyldiazenyl) phenol, 1-((2,4-dimethylphenyl) diazenyl) naphthalen-2-ol, 4- (phenyldiazenyl) benzenethiol, 2 -(Phenyldiazenyl) benzenethiol, 1-((2,4-dimethylphenyl) diazenyl) naphthalene-2-thiol, 4- (phenyldiazenyl) aniline, 2- (phenyldiazenyl) aniline, 1-((2,4 -Dimethylphenyl) diazenyl) naphthalen-2-amine, (4- (phenyldiazenyl) phenyl) methanol, (2- (phenyldiazenyl) phenyl) methanol, (1-((2,4-dimethylphenyl) diazenyl) naphthalene- 2-yl) methanol and the like.
Among these, 4- (phenyldiazenyl) phenol is particularly preferable in terms of reactivity and easy industrial availability.
Moreover, although the usage-amount of the said reaction terminator is the same mol or more normally as a starting seed | species, the range of 100-500 mol is preferable with respect to 100 mol of starting seeds.

In both methods (PA-I) and (PA-II-II), after adding a reaction terminator, trapping free protons generated by adding a proton scavenger (basic compound) to the reaction system. Further, after removing the catalyst residue, the desired vinyl ether polymer (A1) can be obtained by purifying and isolating the polymer.
In addition, as a method of removing the catalyst residue, a method of treating with an aqueous solution containing water such as hydrochloric acid, nitric acid, sulfuric acid or water; a method of treating with an inorganic oxide such as silica gel, alumina, silica-alumina; an ion exchange resin And the like.
Examples of the method for isolating the polymer include a method of distilling off volatile components from the polymer solution; a method of adding a large amount of a poor solvent to precipitate and separate the polymer;

In addition, the content of the water-repellent polymer (A) in the temperature-responsive resin composition of the present invention may be appropriately adjusted according to the use and the base material, but the hydrophobicity and temperature when the temperature is raised are decreased. From the viewpoint of achieving both hydrophilicity at the time of heating and imparting temperature responsiveness to a wide range of substrates, it is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, based on the total amount of the polymer. Yes, more preferably 5 to 92.5% by mass, still more preferably 5 to 90% by mass.
And when carrying | supporting to a highly permeable fibrous base material or a highly hydrophilic base material, More preferably, it is 10-90 mass%, More preferably, it is 20-90 mass%, Most preferably, it is 30- 90% by mass. On the other hand, when it is supported on a highly hydrophobic substrate, it is more preferably 5 to 70% by mass, further preferably 5 to 50% by mass, further preferably 5 to 30% by mass, and particularly preferably. 5 to 15% by mass.

<Vinyl ether polymer (B)>
Next, the vinyl ether polymer (B) contained in the temperature-responsive resin composition of the present invention will be described.
The vinyl ether polymer (B) is a temperature-responsive group-containing vinyl ether polymer having a group (b1) containing a diaryldiazene structure and a repeating unit (b2) derived from a temperature-responsive group-containing vinyl ether monomer.

  Examples of the group (b1) containing a diaryl diazene structure include the same groups as the group (a1) containing a diaryl diazene structure in the vinyl ether polymer (A1). In addition, (a1) in the vinyl ether polymer (A1) and (b1) in the vinyl ether polymer (B) may be the same or different.

Further, the vinyl ether polymer (B) may have a group (b1) containing the diaryldiazene structure in the side chain, or may be at the terminal of the polymer chain (main chain). Further, it may be a star polymer having a group (b1) containing a diaryldiazene structure in the central core.
That is, the vinyl ether polymer (B) includes
(B1) a temperature-responsive group-containing vinyl ether polymer having a repeating unit having a group (b1) containing a diaryldiazene structure in the side chain and a repeating unit (b2) derived from a temperature-responsive group-containing vinyl ether monomer;
(B2) A temperature-responsive group having a group (b1) containing a diaryldiazene structure at at least one end of the polymer chain (main chain) and having a repeating unit (b2) derived from a temperature-responsive group-containing vinyl ether monomer Containing vinyl ether polymers are included.
Among these, the vinyl ether polymer (B2) is preferable from the viewpoint of easy production, easy loading on the substrate, and temperature responsiveness of the resin composition.

  Moreover, as a repeating unit which has group (b1) containing the said diaryl diazene structure in a side chain, what is represented by the said Formula (6) is mentioned.

  The repeating unit (b2) is not particularly limited as long as it has a temperature-responsive group that reversibly changes from hydrophilic to hydrophobic depending on the temperature, but the following formula (12) or (13)

Wherein (12), R ¹⁰ represents a linear or branched alkylene group having 2 to 6 carbon atoms, R ¹¹ represents an alkyl group or a carboxyphenyl group having 1 to 6 carbon atoms, m Is 1 to 10 on average. ]

[In Formula (13), R < ¹² > shows a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group. ]
What is represented by these is preferable and what is represented by the said Formula (12) is more preferable.
The critical temperature at which the hydrophilicity / hydrophobicity changes can be adjusted by appropriately changing the chain length in such a repeating unit or by using two or more repeating units having different chain lengths.

In the above formula (12), the alkylene group represented by R ¹⁰ is the same as the alkylene group represented by R ^5, when there are a plurality of R ¹⁰ s, R ¹⁰ may be the same or different.
Also, R ^11, from the viewpoint is an alkyl group or carboxyphenyl group having 1 to 6 carbon atoms, the temperature response of the viewpoint of the resin composition, thereby particularly improving the hydrophilicity when it becomes equal to or lower than a predetermined temperature, A C1-C6 alkyl group is preferable. The carbon number of such an alkyl group is preferably 1 to 4, more preferably 1 or 2, from the viewpoint of the temperature at which it responds. The alkyl group may be linear or branched. Preferable specific examples include a methyl group and an ethyl group.

  Moreover, in formula (12), although m is 1-10 in average value, 1-6 are preferable in average value, 1-4 are more preferable in average value, and 1-3 are especially preferable in average value.

In the above formula (13), the alkyl chain of the alkyl group having 1 to 4 carbon atoms and the hydroxyalkyl group having 1 to 4 carbon atoms represented by R ¹² may be linear or branched. Specific examples of the alkyl chain are the same as those exemplified as the substituent that the divalent aromatic hydrocarbon group represented by Ar ¹ may have.

Moreover, as content of a repeating unit (b2), 10-100 mol% is preferable with respect to all the repeating units in a vinyl ether polymer (B), 40-100 mol% is more preferable, and 60-100 mol% is further. Preferably, 80 to 100 mol% is particularly preferable.
The molar ratio [(b1) :( b2)] of the group (b1) containing the diaryldiazene structure and the repeating unit (b2) in the vinyl ether polymer (B) is 0.01: 99.99-10: 90 is preferable, 0.1: 99.9 to 7.5: 92.5 is more preferable, and 0.5: 99.5 to 5:95 is particularly preferable.
In addition, the said content and molar ratio can be measured by NMR etc.

  The vinyl ether polymer (B) may further have a repeating unit (b3) other than the repeating unit having a group (b1) containing a diaryldiazene structure in the side chain and the repeating unit (b2).

  Examples of the repeating unit (b3) include those similar to the repeating unit (a3). Preferred examples include the following formula (14).

[In Formula (14), R < ¹³ > shows a hydrogen atom or a C1-C4 alkyl group, R < ¹⁴ > is a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkoxyalkyl group, An alkanoyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group or an alkylsilyl group, q is an integer of 1 to 3; ]
The repeating unit derived from the oxystyrene monomer represented by these is mentioned. When the repeating unit is contained, the water repellency of the polymer at a temperature higher than the critical temperature is improved.

In Formula (14), as a carbon number of a C1-C4 alkyl group shown by R < ¹³ >, 1 or 2 is preferable. Moreover, as carbon number of a C1-C6 alkyl group shown by R < ¹⁴ >, 1-4 are preferable.
These alkyl groups 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.

In addition, the alkoxyalkyl group having 2 to 6 carbon atoms represented by R ¹⁴ is linear, branched or cyclic (the two alkyl chains together with the oxygen atom form an oxygen-containing heterocycle. For example, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group and the like.

Moreover, as carbon number of the alkanoyl group shown by R < ¹⁴ >, 2-6 are preferable. Such an alkanoyl group may be linear or branched, and examples thereof include an acetyl group, a propionyl group, and a tert-butylcarbonyl group.

Moreover, as carbon number of the alkoxycarbonyl group shown by R < ¹⁴ >, 2-6 are preferable. 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.

Moreover, as carbon number of the alkoxycarbonylalkyl group shown by R < ¹⁴ >, 2-6 are preferable. Such an alkoxycarbonylalkyl group may be linear or branched, and examples thereof include a tert-butoxycarbonylmethyl group.

Moreover, as carbon number of the alkylsilyl group shown by R < ¹⁴ >, 2-6 are preferable. Examples of such an alkylsilyl group include a trimethylsilyl group and a tert-butyldimethylsilyl group.
Moreover, in Formula (14), as q, 1 or 2 is preferable and 1 is more preferable. In addition, when q is 2 or 3, q pieces of —OR ¹⁴ may be the same or different.

  When the vinyl ether polymer (B) has a repeating unit (b3), the molar ratio of the repeating unit (b2) to the repeating unit (b3) [(b2) :( b3)] From the viewpoint of achieving both excellent water repellency when the temperature is exceeded, 99.9: 0.1 to 80:20 is preferable, 99.75: 0.25 to 90:10 is more preferable, and 99.5: 0.5 to 95: 5 is more preferable.

Moreover, as a weight average molecular weight (Mw) of a vinyl ether polymer (B), the range of 5000-1 million is preferable, The range of 7500-100000 is more preferable, The range of 10000-50000 is still more preferable. By setting the weight average molecular weight (Mw) to 5000 or more, hydrophobicity is improved when the temperature is raised, and by setting it to 100,000 or less, solubility in a solvent can be improved.
The vinyl ether polymer (B) is preferably narrowly dispersed from the viewpoint of the temperature responsiveness of the resin composition, and the molecular weight distribution (Mw / Mn) is preferably in the range of 1.0 to 2.0. A range of 1.0 to 1.5 is more preferable.
The 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, when the vinyl ether polymer (B) has a repeating unit or a repeating unit (b3) having a group (b1) containing a diaryldiazene structure in the side chain, the copolymer is a block copolymer or graft copolymer. Any of a copolymer, a random copolymer, and an alternating copolymer may be sufficient.

Next, the manufacturing method of the said vinyl ether polymer (B) is demonstrated.
The production method of the vinyl ether polymer (B) is not particularly limited. For example, the vinyl ether polymer (B1) is a vinyl ether monomer having a group (b1) containing a diaryldiazene structure according to the methods described in Patent Documents 1 and 2. The temperature-responsive group-containing vinyl ether monomer and the monomer that induces the optional repeating unit (b3) can be obtained by a living cationic polymerization method (PB-I).

In the method of living cationic polymerization of a temperature-responsive group-containing vinyl ether monomer and a monomer that derives an optional repeating unit (b3), a starting species having a group (b1) containing a diaryldiazene structure and a diaryldia The vinyl ether polymer (B2) can be obtained by using (PB-II) one or more selected from a reaction terminator having a group (b1) containing a Zen structure. Such a method (PB-II) comprises a temperature-responsive group-containing vinyl ether monomer, a starting species having a group (b1) containing a diaryl diazene structure, and a reaction stopper having a group (b1) containing a diaryl diazene structure. What is necessary is just to perform like the living cation polymerization of a conventional method except using 1 or more types chosen.
Among these, since it is easy to obtain a reaction terminator and the control of the reaction is also easy, a living cation polymerization is performed on the temperature-responsive group-containing vinyl ether monomer, and the living cation polymerization is converted to a diaryldiazene structure. The method of stopping using the reaction terminator which has group (b1) to contain is especially preferable.
Since living cationic polymerization does not involve a side reaction of chain transfer reaction, a desired functional group can be easily introduced at the end of the polymer chain. Further, according to living cationic polymerization, the molecular weight and composition ratio can be controlled, and a narrowly dispersed polymer can be obtained.

The vinyl ether monomer having the group (b1) containing a diaryl diazene structure used in the method (PB-I) is a group (a1) containing a diaryl diazene structure used in the method (PA-I). The same vinyl ether monomer as can be used.
Moreover, as a reaction terminator having the group (b1) containing a diaryl diazene structure used in the method (PB-II), the diaryl diazene structure used in the method (PA-II-II) is used. The thing similar to the reaction terminator which has group (a1) to contain can be used.

  Further, as the temperature-responsive group-containing vinyl ether monomer used in the methods (PB-I) and (PB-II), the following formula (15) or (16)

[In formulas (15) and (16), each symbol is as defined above. ]
The thing represented by is mentioned.

Specifically, 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, 4- [2- (vinyloxy) Ethoxy] benzoic acid, 4- (vinyloxy) -1-butanol, isobutyl vinyl ether and the like may be mentioned, and one kind may be used alone, or two or more kinds may be used in combination.
Among these, from the viewpoint of improving hydrophilicity when the temperature is lower than a predetermined temperature, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2- (2-ethoxyethoxy) ethyl vinyl ether, 2- (2- ( 2-Methoxyethoxy) ethoxy) ethyl vinyl ether is preferred.

  When a repeating unit derived from an oxystyrene monomer is introduced as the repeating unit (b3), the following formula (17)

[Wherein each symbol has the same meaning as described above. ]
It is preferable to copolymerize the oxystyrene monomer represented by these.

Specifically, hydroxystyrenes such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol; p-methoxystyrene, m- Methoxy styrene, o-methoxy styrene, p-ethoxy styrene, m-ethoxy styrene, o-ethoxy styrene, p-propoxy styrene, m-propoxy styrene, o-propoxy styrene, p-isopropoxy styrene, m-isopropoxy styrene, o-isopropoxystyrene, pn-butoxystyrene, mn-butoxystyrene, on-butoxystyrene, p-isobutoxystyrene, m-isobutoxystyrene, o-isobutoxystyrene, p-tert-butoxys Alkoxy, styrene such as len, m-tert-butoxystyrene, o-tert-butoxystyrene; p-methoxymethoxystyrene, m-methoxymethoxystyrene, o-methoxymethoxystyrene, p- (1-ethoxyethoxy) styrene, m -(1-ethoxyethoxy) styrene, o- (1-ethoxyethoxy) styrene, p- (2-tetrahydropyranyl) oxystyrene, m- (2-tetrahydropyranyl) oxystyrene, o- (2-tetrahydropyrani) L) Alkoxyalkyloxystyrenes such as oxystyrene; p-acetoxystyrene, m-acetoxystyrene, o-acetoxystyrene, p-tert-butylcarbonyloxystyrene, m-tert-butylcarbonyloxystyrene, o-tert-butyl Alkanoyloxystyrenes such as rubonyloxystyrene; alkoxycarbonylalkyloxystyrenes such as p-tert-butoxycarbonylmethyloxystyrene, m-tert-butoxycarbonylmethyloxystyrene, o-tert-butoxycarbonylmethyloxystyrene; p- Alkylsilyloxy such as trimethylsilyloxystyrene, m-trimethylsilyloxystyrene, o-trimethylsilyloxystyrene, p-tert-butyldimethylsilyloxystyrene, m-tert-butyldimethylsilyloxystyrene, o-tert-butyldimethylsilyloxystyrene Styrenes etc. are mentioned, 1 type may be used independently and 2 or more types may be used together.
Among these, hydroxystyrenes and alkoxystyrenes are preferable, and p-hydroxystyrene, p-isopropenylphenol, and p-tert-butoxystyrene are particularly preferable.

In the methods of (PB-I) and (PB-II), the living cation polymerization method may be carried out in accordance with a conventional method except using the above-mentioned compounds. It is preferably carried out in the presence.
The starting species, Lewis acid, solvent and Lewis base used, the living cationic polymerization reaction conditions, the purification / isolation method, and the like are the same as in the methods (PA-I) and (PA-II-II).
In the case of copolymerizing an oxystyrene monomer, it is preferable to use a metal halogen compound or an organometallic halogen compound other than Al as a Lewis acid.
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 and ZnCl ₄ . Among this, SnCl _4, FeCl ₃ and the like are preferable.

In addition, the content of the vinyl ether polymer (B) in the temperature-responsive resin composition of the present invention includes a wide range of base materials from the viewpoint of achieving both hydrophobicity when the temperature is raised and hydrophilicity when the temperature is lowered. From the viewpoint of imparting temperature responsiveness to the polymer, it is preferably 1 to 99% by mass, more preferably 5 to 99% by mass, and still more preferably 7.5 to 95% by mass, based on the total amount of the polymer. More preferably, it is 10-95 mass%.
And when carrying | supporting to a highly permeable fibrous base material or a highly hydrophilic base material, More preferably, it is 10-90 mass%, More preferably, it is 10-85 mass%, More preferably, it is 10- It is 75 mass%, Most preferably, it is 10-65 mass%. On the other hand, when supported on a highly hydrophobic substrate, it is more preferably 30 to 95% by mass, further preferably 50 to 95% by mass, further preferably 70 to 95% by mass, and particularly preferably. It is 85-95 mass%.

Moreover, as mass ratio [(A) :( B)] of content of water-repellent polymer (A) and vinyl ether polymer (B) in the temperature-responsive resin composition of the present invention, From the viewpoint of achieving both hydrophobicity and hydrophilicity when the temperature is lowered, and from the viewpoint of imparting temperature responsiveness to a wide range of substrates, 1:99 to 99: 1 is preferable, and 3:97 to 97: 3 is more preferable. 5:95 to 95: 5 is more preferable, and 5:95 to 90:10 is more preferable.
And when carrying | supporting to a highly permeable fibrous base material or a highly hydrophilic base material, 10: 90-90: 10 is still more preferable, 20: 80-90: 10 is still more preferable, 30: 70-90 : 10 is particularly preferable. On the other hand, when supported on a highly hydrophobic substrate, 5:95 to 70:30 is more preferable, 5:95 to 50:50 is more preferable, 5:95 to 30:70 is further preferable, and 5:95. ~ 15: 85 is particularly preferred.

  Further, the total content of the polymers (A) and (B) in the temperature-responsive resin composition of the present invention is preferably 25 to 100% by mass, more preferably 40 to 100% by mass with respect to the total amount of the polymer. 75-100 mass% is still more preferable, and 90-100 mass% is especially preferable.

<Other components (C)>
The temperature-responsive resin composition of the present invention may contain components other than the polymers (A) and (B) such as a solvent, a thickener, and a surfactant.
Examples of such a solvent include those listed above as solvents for use in the polymerization reaction, ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and n-butyl acetate, preferably ketone solvents. It is. These solvents may be used alone or in combination of two or more.
The total content of the polymers (A) and (B) when the temperature-responsive resin composition of the present invention includes a solvent is not particularly limited, but is preferably 0.01 to 75% by mass as a nonvolatile content, -50 mass% is preferable, 0.5-25 mass% is more preferable, 1-15 mass% is still more preferable.

  Examples of the thickener include synthetic polymer compounds such as polyacrylic acid, sodium polyacrylate, polyvinyl alcohol, carboxymethylcellulose, polyacrylamide, and polyvinylpyrrolidone; carrageenan, sodium alginate, agarose, gelatin, pectin, chitansan gum, mannan Any one or two or more of natural polysaccharides such as starch can be suitably used without any particular limitation. When using a thickener, there is no restriction | limiting in particular in the usage-amount, Usually, about 0.01-20 mass% is mix | blended.

  Furthermore, the type of the surfactant is not particularly limited, but at least one of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used. Examples of anionic surfactants include carboxylates, sulfonates and sulfates, and examples of cationic surfactants include amine salts and quaternary ammonium salts, and nonionic surfactants. May include ethers such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether. When using a surfactant, there is no restriction | limiting in particular in the usage-amount, Usually, about 0.1-10 mass% is mix | blended.

  Furthermore, you may add a conventional additive, for example, a coloring agent, antioxidant, a ultraviolet absorber, an antistatic agent, a flame retardant, etc. to the temperature-responsive resin composition of this invention.

  The temperature-responsive resin composition of the present invention can be obtained by mixing the water-repellent polymer (A), the vinyl ether polymer (B) and other components (C) as necessary. The water repellent polymer (A) and the vinyl ether polymer (B) may be mixed as they are, or may be mixed by dissolving or dispersing in a solvent.

The temperature-responsive resin composition of the present invention can exhibit temperature responsiveness even when it is supported on a fibrous substrate, particularly a highly permeable fibrous substrate such as a woven fabric. Temperature responsiveness when supported is not easily affected by the type of base material, and is easily hydrophilic to both highly hydrophilic fiber bases and hydrophobic fiber bases. -Hydrophobicity can be adjusted, and temperature responsiveness can be imparted to a wide range of substrates.
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.

  Therefore, the temperature-responsive resin composition of the present invention is extremely useful as a hydrophilicity / hydrophobicity control agent, and can control the hydrophilicity / hydrophobicity of a substrate to be applied using the temperature-responsiveness. Moreover, the resin carrier provided with temperature responsiveness can be provided by making the base material carry | support the temperature responsive resin composition of this invention. The temperature-responsive resin carrier refers to a resin carrier having a temperature responsiveness among the resin carriers in which the resin composition is supported on a base material.

  The hydrophilicity / hydrophobicity control agent and the resin carrier of the present invention are used as, for example, a temperature sensor, a separation membrane, an adsorbent, a drug release agent, a water absorbing material, a water retention agent, a humidity control agent, an indicator agent, and these materials. be able to.

  Examples of the base material to be controlled for hydrophilicity / hydrophobicity include resins, plant fibers, animal fibers, and inorganic fibers. Examples of the resin include a synthetic resin and a natural resin. The synthetic resin is preferably a synthetic resin fiber, and the natural resin is preferably a natural resin fiber.

  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, high density Polyolefin resins such as 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 polyurethane 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 and the like. These fibers may be used alone or in combination, and may be used in combination with a synthetic resin or a natural resin.

Moreover, it does not specifically limit as a form of a base material, A bead, a film, a fibrous base material, a sheet | seat, a tube, a pipe, or these composites etc. are mentioned.
Examples of the form of the fiber sheet include woven fabric, knitted fabric, and non-woven fabric. Nonwoven fabrics and composite nonwoven fabrics manufactured by various nonwoven fabric manufacturing 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 temperature-responsive resin composition of the present invention can control the hydrophilicity / hydrophobicity of the substrate as described above, but includes an azo group having permeability to the resin, and fixes the temperature-responsive resin composition to the resin surface. It is particularly suitable for controlling hydrophilicity / hydrophobicity of the surface of the resin.

  The hydrophilicity / hydrophobicity control method of the present invention includes a method of dissolving or dispersing the temperature-responsive resin composition of the present invention in the above solvent and applying or impregnating the solution to a substrate. The method of application or impregnation is not particularly limited, and examples thereof include a method of applying the solution or dispersion of the temperature-responsive resin composition of the present invention using a spray, a roll, a brush, a dipping method, and the like.

In addition, the temperature-responsive resin carrier of the present invention 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.
In addition, what is necessary is just to perform the manufacture of the temperature-responsive resin carrier of this invention similarly to the said hydrophilicity / hydrophobicity control method. Moreover, it can also obtain by forming a woven fabric, a knitted fabric, a nonwoven fabric, etc. using the fiber which fixed the temperature-responsive resin composition on the surface.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In addition, unless otherwise indicated, a compounding quantity etc. are a mass reference | standard in an Example.
The physical properties of each polymer 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, it was determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC) (column: Shodex (registered trademark) KF-804L x 3 manufactured by Showa Denko KK, eluent: tetrahydrofuran ).

[Synthesis Example 1]
The following silyl group-containing vinyl ether polymer (hereinafter referred to as “polymer a”) was obtained by the procedure described below.

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, t-butyldimethyl (2- (vinyloxy) ethoxy) silane (hereinafter referred to as “SiOVE”) 0.3M (12.1 g), ethyl acetate 1M (17.6 g), 1-isobutoxyethyl Acetate (hereinafter referred to as “IBEA”) 4.0 mM (0.12 g) and 166 mL of toluene were added, the inside of the reaction system was cooled, and when the temperature reached 0 ° C., a toluene solution of Et _1.5 AlCl _1.5 (Et _1.5 as AlCl _1.5 14.0 mm) and was as a toluene solution (SnCl ₄ of SnCl ₄ 30 mM) added to initiate polymerization of.
When the conversion of SiOVE was completed, a small amount of reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained SiOVE polymer was a monodisperse polymer having Mw = 1600 and Mw / Mn = 1.04.
Subsequently, an ethyl acetate solution (12.0 mM (0.48 g) as PDP) of 4- (phenyldiazenyl) phenol (hereinafter referred to as “PDP”) was added to the reaction system to stop the polymerization reaction. Furthermore, methanol containing sodium methoxide (1M as sodium methoxide) was added to the reaction system to trap free protons.
Thereafter, 5% by mass of aluminum oxide was added to the solution in which the reaction was stopped, and the mixture was 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 using an evaporator to obtain the target polymer a. The obtained polymer a was Mw = 12,500 and Mw / Mn = 1.05.

[Synthesis Example 2]
The following temperature-responsive vinyl ether polymer (hereinafter referred to as “polymer b”) was obtained by the procedure described below.

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”) 0.72M (35.9 g), 2- (2-ethoxyethoxy) ethyl vinyl ether (hereinafter referred to as “EOEOVE”) 0.72M (49.5 g), ethyl acetate 0.90 M (33.9 g), IBEA 3.6 mM (0.25 g) and toluene 261 mL were added, the reaction system was cooled, and when the temperature reached 0 ° C., Et _1.5 AlCl _1.5 toluene solution (13.4 mM as Et _1.5 AlCl _1.5 ) was added to initiate the polymerization.
When the conversion of EOVE and EOEOVE was completed, a small amount of reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained EOVE-ran-EOEOVE polymer was a monodisperse polymer with Mw = 15200 and Mw / Mn = 1.41.
Next, an ethyl acetate solution of PDP (10.7 mM (0.92 g) as PDP) was added to the reaction system to stop the polymerization reaction. Furthermore, methanol containing sodium methoxide (1M as sodium methoxide) was added to the reaction system to trap free protons.
Thereafter, 5% by mass of aluminum oxide was added to the solution in which the reaction was stopped, and the mixture was 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 obtain the desired polymer b. The obtained polymer b was Mw = 15700 and Mw / Mn = 1.37.

[Examples 1-3]
The polymer a obtained in Synthesis Example 1 and the polymer b obtained in Synthesis Example 2 were mixed in the proportions shown in Table 1, and acetone was added thereto so that the nonvolatile content of each composition was 1% by mass. And passed through a filter having a pore diameter of 1 μm. In this solution, a polyethylene terephthalate fabric (3 × 10 cm (woven fabric)) and a nylon fabric (3 × 10 cm) are immersed for 1 hour and thoroughly washed to obtain various fabrics carrying the resin composition of the present invention. Obtained. All of the various doughs obtained had no stickiness or unevenness derived from the polymer on the surface, and maintained the same form as the dough before impregnation.

[Comparative Examples 1-3]
The solution for dipping the dough was changed to an acetone solution (Comparative Example 1) containing only polymer a (1% by mass) as a nonvolatile content or an acetone solution (Comparative Example 2) containing only polymer b (1% by mass) as a nonvolatile content. Except that, various fabrics carrying each polymer were obtained in the same manner as in Examples 1 to 3.
Further, after impregnating various doughs with an acetone solution containing only polymer a (1% by mass) as a non-volatile content, and further impregnating various doughs with an acetone solution containing only polymer b (1% by mass) as a non-volatile content. Various fabrics carrying both polymers were obtained (Comparative Example 3).

[Test Example 1: Permeability Evaluation Test (1)]
100 μL of water droplets are arranged at 15-point equidistant intervals on the surfaces of the various fabrics obtained in Examples 1 to 3 and Comparative Examples 1 to 3, and 3 minutes at a temperature of 19 ° C. and 55 ° C. under a humidity of 43%. By counting the number of water droplets after the lapse of time, the water permeability and changes due to the temperature of the water permeability were confirmed.
Table 1 shows the results of water permeability evaluation of various fabrics. For comparison, Table 1 also shows the results of a similar evaluation performed on the fabric that was not impregnated.

[Examples 4 to 6]
The polymer a obtained in Synthesis Example 1 and the polymer b obtained in Synthesis Example 2 were mixed in the proportions shown in Table 2, and acetone was added thereto so that the nonvolatile content of each composition was 1% by mass. And passed through a filter having a pore diameter of 1 μm. In this solution, a polyurethane fabric (3 × 10 cm (woven fabric)) was immersed for 1 hour and allowed to permeate and washed thoroughly to obtain various fabrics carrying the resin composition of the present invention. All of the various doughs obtained had no stickiness or unevenness derived from the polymer on the surface, and maintained the same form as the dough before impregnation.

[Comparative Examples 4 and 5]
The solution for immersing the dough was changed to an acetone solution (Comparative Example 4) containing only polymer a (1% by mass) as a nonvolatile content or an acetone solution (Comparative Example 5) containing only polymer b (1% by mass) as a nonvolatile content. Except that, various fabrics carrying each polymer were obtained in the same manner as in Examples 4-6.

[Test Example 2: Water permeability evaluation test (2)]
100 μL of water droplets are arranged at 15 points equidistantly on the surfaces of various fabrics obtained in Examples 4 to 6 and Comparative Examples 4 and 5, and 3 minutes at a temperature of 19 ° C. and 55 ° C. under a humidity of 43%. By counting the number of water droplets after the lapse of time, the water permeability and changes due to the temperature of the water permeability were confirmed.
Table 2 shows the results of water permeability evaluation of various fabrics. For comparison, Table 2 also shows the results of a similar evaluation performed on dough that has not been impregnated.

Example 7
90 parts by mass of a mixture containing polytetrafluoroethylene (PTFE) and a cellulose binder (PTFE / cellulose binder = 1 / 1.3) and 10 parts by mass of polymer b are mixed, and the nonvolatile content of the composition is 1 Acetone was blended so as to be the mass% and passed through a filter having a pore size of 1 μm. In this solution, a polyethylene terephthalate fabric (3 × 10 cm (woven fabric)) was immersed for 1 hour and allowed to permeate, and washed thoroughly to obtain a fabric carrying the resin composition of the present invention. The obtained dough had no stickiness or irregularities derived from the polymer on the surface, and maintained the same form as the dough before impregnation.

[Comparative Examples 6 and 7]
The solution in which the dough is immersed is a non-volatile content, and an acetone solution (Comparative Example 6) containing only the mixture (1% by mass) containing PTFE and cellulose binder used in Example 7 or the non-volatile polymer b (1% by mass) ), A variety of fabrics carrying the respective polymers were obtained in the same manner as in Example 7, except that the acetone solution was changed to an acetone solution (Comparative Example 7).

[Test Example 3: Water permeability evaluation test (3)]
100 μL of water droplets are arranged at 15 points equidistantly on the surfaces of various fabrics obtained in Example 7 and Comparative Examples 6 and 7, and after 3 minutes have passed under conditions of humidity of 43% and temperatures of 19 ° C. and 55 ° C. By counting the number of water droplets, water permeability and changes in the water permeability due to temperature were confirmed.
Table 3 shows the results of water permeability evaluation of various fabrics. For comparison, Table 3 also shows the results of a similar evaluation performed on dough that has not been impregnated.

As shown in Tables 1 to 3, a fabric (Comparative Example 1, Comparative Example 4 and Comparative Example 1) in which a water-repellent polymer (polymer a or PTFE) was supported but a temperature-responsive vinyl ether polymer (polymer b) was not supported. In Example 6), the water repellency in the low temperature region was strong and the temperature responsiveness was not exhibited.
On the other hand, the dough (Comparative Example 2, Comparative Example 5 and Comparative Example 7) carrying only the temperature-responsive vinyl ether polymer (Polymer b) was highly hydrophilic even in the high temperature region and did not show temperature responsiveness.
Similarly, when the silyl group-containing vinyl ether polymer (Polymer a) and the temperature-responsive vinyl ether polymer (Polymer b) are sequentially supported (Comparative Example 3), the hydrophilicity is strong and the temperature responsiveness is high in the high temperature range. Not shown.
On the other hand, the fabric in which both polymers are simultaneously supported using the resin composition of the present invention exhibits temperature responsiveness under any conditions, and particularly in fabrics with strong hydrophilicity such as nylon, It was shown that hydrophobicity (water repellency) can be expressed, and hydrophilicity can be expressed even in a highly hydrophobic fabric such as polyurethane in a low temperature range. It can also be seen that the degree of hydrophilicity and hydrophobicity can be controlled by changing the blending ratio of both polymers.

Claims (16)

The following polymers (A) and (B):
(A) a water-repellent polymer;
(B) a temperature-responsive group-containing vinyl ether polymer having a group (b1) containing a diaryldiazene structure and a repeating unit (b2) derived from a temperature-responsive group-containing vinyl ether monomer;
Containing a temperature-responsive resin composition.   The polymer (A) is one selected from a water-repellent group-containing vinyl ether polymer having a fluororesin and a group (a1) containing a diaryldiazene structure and a repeating unit (a2) derived from the water-repellent group-containing vinyl ether monomer The temperature-responsive resin composition according to claim 1, which is as described above. The groups (a1) and (b1) containing a diaryldiazene structure are the same or different, and have the following formula (1)

[In formula (1), Y represents an ether bond, a thioether bond, a group —NH— or a group —OR ¹ — * (R ¹ represents an alkylene group, * represents a position bonded to Ar ¹ ), Ar ¹ represents a substituted or unsubstituted divalent aromatic hydrocarbon group, and Ar ² represents a substituted or unsubstituted monovalent aromatic hydrocarbon group. ]
The resin composition according to claim 2, which is represented by: Ar ¹ in formula (1) is the following formula (2) or (3)

[In Formula (2), each R ² 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 an alkoxy group having 2 to 6 carbon atoms. An alkyl group, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group or an aminosulfonyl group; ** represents a position bonded to Y; *** represents a position bonded to a nitrogen atom; 1 is an integer of 0-4. ]

Wherein (3), p-2 is an integer of 0~6, R ^2, ** and *** have the same meanings as defined above. ]
Ar ² is represented by the following formula (4) or (5)

[In Formula (4), each R ³ 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 an alkoxy group having 2 to 6 carbon atoms. An alkyl group, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group or an aminosulfonyl group; *** indicates a position bonded to a nitrogen atom; and p-3 is an integer of 0 to 5. ]

Wherein (5), p-4 is an integer of 0 to 7, R ³ and **** are as defined above. ]
The resin composition according to claim 3, which is represented by: The following polymers (A) and (B):
(A) One or more repellents selected from a water-repellent group-containing vinyl ether polymer having a fluororesin and a group (a1) containing a diaryldiazene structure and a repeating unit (a2) derived from the water-repellent group-containing vinyl ether monomer. Aqueous polymer;
(B) a temperature-responsive group-containing vinyl ether polymer having a group (b1) containing a diaryldiazene structure and a repeating unit (b2) derived from a temperature-responsive group-containing vinyl ether monomer;
And the fluororesin is polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, polyfluoroethylene. A temperature-responsive resin composition, which is at least one selected from vinyl chloride and polyvinylidene fluoride. The following polymers (A) and (B):
(A) A fluororesin and a water repellent group-containing vinyl ether polymer having a repeating unit (a2) derived from a water repellent group-containing vinyl ether monomer having a group (a1) containing a diaryldiazene structure at at least one of the polymer chain ends One or more water-repellent polymers selected from:
(B) a temperature-responsive group-containing vinyl ether polymer having a group (b1) containing a diaryldiazene structure and a repeating unit (b2) derived from a temperature-responsive group-containing vinyl ether monomer;
Containing a temperature-responsive resin composition. The following polymers (A) and (B):
(A) group (a1) containing a fluororesin and a diaryldiazene structure, and the following formula (7)

[In Formula (7), R ⁵ represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group or a haloalkyl group. , A cycloalkyl group, or a cycloalkyl group having a halogen atom as a substituent, k is an average value of 1 to 10. ]
One or more water-repellent polymers selected from water-repellent group-containing vinyl ether polymers having a repeating unit (a2) represented by :
(B) a temperature-responsive group-containing vinyl ether polymer having a group (b1) containing a diaryldiazene structure and a repeating unit (b2) derived from a temperature-responsive group-containing vinyl ether monomer;
Containing a temperature-responsive resin composition. The following polymers (A) and (B):
(A) a water-repellent polymer;
(B) a thermoresponsive group-containing vinyl ether polymer having a group (b1) containing a diaryldiazene structure at at least one of the polymer chain ends and having a repeating unit (b2) derived from a thermoresponsive group-containing vinyl ether monomer;
Containing a temperature-responsive resin composition. The repeating unit (b2) is represented by the following formula (12) or (13)

Wherein (12), R ¹⁰ represents a linear or branched alkylene group having 2 to 6 carbon atoms, R ¹¹ represents an alkyl group or a carboxyphenyl group having 1 to 6 carbon atoms, m Is 1 to 10 on average. ]

[In Formula (13), R < ¹² > shows a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group. ]
It is represented by these. The resin composition of any one of Claims 1-8 . A hydrophilicity / hydrophobicity control agent containing the resin composition according to any one of claims 1 to 9 . A method for controlling hydrophilicity / hydrophobicity using the resin composition according to any one of claims 1 to 9 . A temperature-responsive resin carrier in which the resin composition according to any one of claims 1 to 9 is supported on a substrate. The resin carrier according to claim 12 , wherein the substrate is a fibrous substrate.   A method for producing a water-repellent group-containing vinyl ether polymer having a group (a1) containing a diaryldiazene structure and a repeating unit (a2) derived from the water-repellent group-containing vinyl ether monomer, wherein the water-repellent group-containing vinyl ether monomer is living A production method comprising a step of cationic polymerization, and a step of terminating the living cationic polymerization using a reaction terminator having a group (a1) containing a diaryldiazene structure. The reaction terminator is represented by the following formula (11)

[In the formula (11), Z represents a hydrogen atom or an alkali metal atom, Y represents an ether bond, a thioether bond, a group —NH— or a group —OR ¹ — * (R ¹ represents an alkylene group, * indicates the position at which the group bonds to Ar ^1), Ar ¹ represents substituted or unsubstituted divalent aromatic hydrocarbon group, Ar ² represents a monovalent aromatic hydrocarbon group substituted or unsubstituted. ]
The production method according to claim 14 , which is represented by: The water repellent group-containing vinyl ether monomer is represented by the following formula (9):

[In Formula (9), R ⁵ represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group or a haloalkyl group. , A cycloalkyl group, or a cycloalkyl group having a halogen atom as a substituent, k is an average value of 1 to 10. ]
The production method according to claim 14 or 15 , which is a silyl group-containing vinyl ether monomer represented by the formula: