JP4860986B2 - Adhesive, binder for electrode preparation, and composition for solid electrolyte - Google Patents

Description

  The present invention relates to an adhesive containing a star polymer having an arm portion having a specific structure, a binder for producing an electrode, and a composition for a solid electrolyte.

  Conventionally, various adhesives have been developed for various applications. For example, Patent Document 1 includes (A) an organic compound composed of an organic skeleton containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) at least in one molecule. An adhesive composition comprising a silicon compound containing two SiH groups and (C) a hydrosilylation catalyst as essential components, wherein the component (A) is a carbon-carbon double bond having reactivity with SiH groups. (A) The adhesive for electronic materials which is an organic compound containing 0.001 mol or more per 1 g of component is disclosed. Patent Document 2 discloses a conductive adhesive containing a curable resin composition.

  In addition, as an adhesive for batteries, for example, Patent Document 3 discloses a non-conductive powder, a dispersant that dissolves the non-conductive powder in the solvent, a solvent that dissolves in the solvent, and an adhesive property. And an adhesive resin that dissolves in the solvent, and an adhesive for a lithium secondary battery is disclosed. Patent Document 4 discloses an acrylic adhesive or pressure-sensitive adhesive for a lithium secondary battery having a functional group-containing monomer as a constituent monomer, and the residual amount of the functional group-containing monomer in the adhesive or pressure-sensitive adhesive. An adhesive or pressure-sensitive adhesive for lithium secondary batteries, characterized by being less than 0.01% by weight, is disclosed.

  In recent years, development of high-performance batteries has been actively promoted in response to demands for electronic devices to be reduced in size and weight, multifunctional, and cordless. These batteries can be classified into a single-use primary battery and a secondary battery that can be repeatedly used by charging. Examples of the former include manganese batteries and alkaline manganese batteries. Examples of the latter include alkaline secondary batteries (nickel-cadmium batteries) obtained using cadmium and alkaline batteries obtained using hydrogen storage alloys. Secondary batteries (Ni-MH batteries), non-aqueous electrolyte secondary batteries (lithium ion batteries) using lithium compounds, and the like can be given.

  Among these, the lithium ion battery has a positive electrode, a negative electrode, and a separator sandwiched between the positive electrode and the negative electrode as main components, and the positive electrode, the negative electrode, and the separator are impregnated with an electrolytic solution. In a lithium ion battery currently in practical use, a positive electrode active material made of a powder such as lithium cobalt oxide is applied to a positive electrode current collector to form a plate, and the negative electrode is used as a negative electrode. A negative electrode active material made of a carbon-based powder is applied to a negative electrode current collector to form a plate. In addition, a nonaqueous solvent such as propylene carbonate is used for the electrolytic solution, and a supporting electrolytic salt is usually added. Further, a porous film such as polyethylene or polypropylene is used for the separator.

  However, since many separators shrink due to heat, the separator shrinks under high temperature environment such as when the battery is overcharged or abnormally heated due to an internal short circuit. In some cases, the separator melts or breaks. As a result of the film not functioning as a separator between the electrodes, the decomposition reaction of the electrolytic solution and the positive electrode proceeds, and the battery may ignite or the battery may burst.

  As such an adhesive, polyvinylidene fluoride (PVDF) or the like is usually used (for example, see Patent Document 5).

  The positive electrode of the lithium ion battery is a paste prepared by adding a conductive material made of metal powder or carbon and a binder to lithium cobaltate, which is an active material, and kneading and preparing in the presence of N-methyl-2-pyrrolidone. By applying with a doctor blade and drying, lithium cobaltate and a conductive material are alternately bound by a binder and further bound to a metal current collector. On the other hand, in the negative electrode, a binder is added to a carbon material that is an active material, and a paste kneaded and prepared is applied with a doctor blade in the presence of water, etc., and dried, so that the carbon material is collected into a metal current collector by the binder. It is bound to the body. Here, a nonaqueous solvent such as propylene carbonate is used for the electrolyte solution of the lithium ion battery, and a supporting electrolytic salt is usually added.

  In addition, the positive electrode of the Ni-MH battery is formed by alternately binding nickel hydroxide and nickel oxyhydroxide as active materials, carbon as a conductive material, and cobalt powder and the like with a binder, It is formed by binding to a current collector. On the other hand, the negative electrode is a punched metal, a metal porous plate, a metal foam plate, a net-like paste made by adding a conductive material made of nickel powder or carbon and a binder to a hydrogen storage alloy and kneading and adjusting it in the presence of water. By applying to a metal current collector such as a metal fiber sintered plate and drying, the hydrogen storage alloy and the conductive material are alternately bound by the binder, and further bound to the metal current collector. It is. Here, a strong alkaline aqueous solution such as potassium hydroxide is used as the electrolytic solution of the Ni-MH battery.

  Therefore, the binder of these batteries includes (1) a current collector, an active material, a conductive material, and a polymer having a high binding property between the materials, and (2) a voltage within the battery. In addition to being a stable substance in a harsh environment, (3) excellent corrosion resistance to the electrolyte is required.

  As these binders for secondary batteries, those usually used include, for example, fluorine-containing polymers such as polytetrafluoroethylene (PTFE) and water-insoluble such as styrene-ethylene-butene-styrene (SEBS). Polymers are used, and mixtures with water-soluble polymers such as polyvinyl alcohol, water-soluble cellulose derivatives, polyethylene oxide, and polyvinylpyrrolidone are used as necessary (for example, Patent Document 7, Patent Document 8, and Patent Document 9). , See Patent Document 10).

  However, the binding force of the active material to the active material on the current collector is still insufficient with only the binder as described in the above publications. Therefore, the problem that the active material gradually drops from the current collector due to the swelling / shrinkage of the electrodes accompanying the progress of the charge / discharge cycle, and the battery performance deteriorates, that is, sufficient cycle characteristics cannot be obtained. There was a problem.

  Conventionally, as a polymer solid electrolyte, XYX type triblock copolymer obtained by copolymerizing methoxypolyethylene glycol monomethacrylate (X component) and styrene (Y component) by a living anion polymerization method. A solid polymer electrolyte having a matrix base material is proposed (Non-patent Document 1). In the matrix substrate described in this document, the X component is a component that forms a PEO domain as a diffusion transport space for lithium ions. Therefore, in order to increase ion conductivity, it is preferable to increase the content of the X component in the matrix substrate.

However, since the homopolymer of methoxypolyethyleneglycol monomethacrylate, which is the X component, is a liquid substance at room temperature even if it becomes a high molecular weight substance, in order to use the XYX type copolymer as a matrix base material for a solid electrolyte Is limited in the content of the X component. This also means that the shape and size of the PEO domain as a lithium ion diffusion transport space are limited. In fact, the ionic conductivity of the matrix substrate at 40 ° C. was not satisfactory at 10 ⁻⁶ S / cm.

  Patent Document 11 also proposes a polymer solid electrolyte having flexibility utilizing a hydrogen bond between poly (ethylene glycol) bis (carboxymethyl) ether and a nitrogen-containing heterocyclic compound such as pyrazine.

  However, the polymer solid electrolyte described in this document uses hydrogen bonding with a polymer having a hydrogen bonding site at the polymer terminal, and is a bond with a hydrogen bonding functional group in a repeating unit in the polymer main chain. It does not use hydrogen bonding. In addition, since ionic conductivity is lower than that of poly (ethylene glycol) bis (carboxymethyl) ether alone, it has not been put into practical use.

  Further, Patent Document 11 discloses that a repeating unit in a polymer main chain has a hydrogen bonding site in an ion conductive polymer having a hydrogen-filling functional group or an ion conductive cyclic compound having a hydrogen bonding functional group. It has been disclosed that inclusion of a compound that forms a hydrogen bond with a low molecular weight compound improves control of the chain structure of the polymer and ionic conductivity. There, a compound having a hydroxyl group, a carboxyl group, or an amino group is disclosed as a low molecular weight compound.

  However, the polymer solid electrolyte described in this document does not have characteristics that both ionic conductivity and shape stability are practically satisfactory. Accordingly, there has been a demand for the development of a solid polymer electrolyte having both excellent thermal and physical properties and ionic conductivity.

JP 2001-98248 A JP 2005-113059 A Japanese Patent Laid-Open No. 2004-214042 JP 2002-260667 A JP-A-10-172606 JP 2004-107641 A JP-A-3-283362 JP-A-4-206345 JP-A-4-272656 Japanese Patent Laid-Open No. 9-63589 WO02 / 40594 Macromol.Chem190, 1069 (1989)

  An object of the present invention is to provide an adhesive particularly excellent in adhesive strength, film strength, conductivity, solvent resistance (electrolytic solution resistance) and heat shrinkage resistance. Another object of the present invention is to provide a binder for electrode preparation that is particularly excellent in binding strength, film strength, conductivity, solvent resistance (electrolytic solution resistance) and heat shrinkage resistance. Furthermore, it is providing the composition for solid electrolytes which was excellent especially in film | membrane intensity | strength, electroconductivity, solvent resistance, and heat shrink resistance.

  The present inventors have proposed a polymer having excellent properties as an adhesive, a binder for electrode preparation and a composition for solid electrolyte (Japanese Patent Application Nos. 2005-204969, 2005-213933, and Japanese Patent Application No. 2005-213933). 2005-014195). As a result of intensive research for the development of a polymer that retains the characteristics of such a polymer and has further excellent characteristics, the present inventors have found that adhesion is achieved by using a star polymer having such a linear polymer as an arm part. As a result, it has been found that it is possible to exhibit further excellent characteristics as a composition for an agent, a binder for electrode preparation and a composition for a solid electrolyte, and the present invention has been completed.

  That is, the present invention relates to (1) an adhesive comprising a star polymer having a polymer chain containing a random repeating structure (C) composed of a repeating unit (A) and a repeating unit (B) as an arm part.

(In the repeating unit (A), R _{100 to} R ₃₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₀₀ and R ₃₀₀ may combine to form a ring. R ^400a and R _400b each independently represent a hydrogen atom or a methyl group, R ₅₀₀ represents a hydrocarbon group, an acyl group, or a silyl group, and s ₁ represents an integer of 1 to 100 And when s ₁ is 2 or more, the groups represented by the formula: —CH (R _400a ) —CH (R _400b ) —O— may be the same or different.

(In the repeating unit (B), R ₁₁₀ and R ₃₁₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₁₀ and R ₃₁₀ may combine to form a ring. Well, R ₂₁₀ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a hydrocarbon oxy group, a carboxyl group, an acid anhydride group, an amino group, an ester group, or a hydroxyl group, a carboxyl group, an epoxy group, an acid. Represents an organic group having at least one functional group selected from the group consisting of an anhydride group and an amino group, and R ₄₁₀ is selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group. Represents an organic group having at least one functional group.)

  The present invention also relates to (2) the adhesive described in (1) above, wherein the repeating unit (B) is any one of the repeating units (B-1) to (B-3).

(In the repeating unit (B-1), R _410a and R _410b each independently represent a hydrogen atom or a methyl group, s ₂ represents an integer of 1 to 100, and s ₂ is 2 or more. The groups represented by the formula: —CH (R _410a ) —CH (R _410b ) —O— may be the same or different.)

(In the repeating unit (B-2), R _410c is an alkylene group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms. Group or a divalent organic group obtained by _combining these groups, R _410d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(In the repeating unit (B-3), R _410e is a hydrogen atom or —R ₅₁₀ —COOH (R ₅₁₀ is an alkylene group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, Represents a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent organic group obtained by combining these groups.)

  In addition, the present invention provides (3) the adhesive according to (1) or (2) above, wherein the arm part is composed of a polymer chain containing the repeating structure (D) together with the random repeating structure (C). About.

(In the repeating unit (D), R _{600 to} R ₈₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ₉₀₀ represents an aryl group or a heteroaryl group, h represents Represents any integer of 20 to 300.)

The present invention also relates to (4) the adhesive according to (3) above, wherein R ₉₀₀ of the repeating structure (D) is a phenyl group, and (5) R _{900 of the} repeating structure (D). Is a p- (1-ethoxyethoxy) phenyl group or a p-tert-butoxyphenyl group, and relates to the adhesive described in (4) above.

  Moreover, (6) this invention relates to the adhesive agent in any one of said (3)-(5), wherein an arm part consists of a polymer chain represented by Formula (I).

(In Formula (I), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₁ represents a halogen atom, and Z ₁ represents at least one of Represents a group having a carbon atom.)

  Moreover, this invention relates to the adhesive agent in any one of said (3)-(5) characterized by (7) an arm part consisting of a polymer chain represented by Formula (II).

(In Formula (II), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₂ represents a halogen atom, and Z ₂ represents at least one of Represents a group having a carbon atom.)

  The present invention also relates to (8) the adhesive according to any one of (3) to (5) above, wherein the arm portion is composed of a polymer chain represented by the formula (III).

(In Formula (III), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₃ represents a halogen atom, and R _a and R _b are Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Z ₃ represents a group having at least one carbon atom, and k represents any integer of 1 or more.)

  Further, the present invention provides (9) the adhesive according to any one of (1) to (8) above, wherein the core has a benzene ring skeleton, and (10) the core is represented by the formula ( The adhesive according to (9) above, characterized in that it has a structure represented by (IV), and (11) the core part comprising the structure represented by formula (V) It relates to the adhesive described in 9).

(In the formula (V), F is _{(CH 2)} represents _q or p- phenylene, q represents an integer of 0 to 3.)

In the present invention, the adhesive according to any one of (1) to (11) above, wherein (12) the star polymer is a star polymer represented by the formula (VI); ) The adhesive according to any one of (1) to (11) above, wherein the star polymer is a star polymer represented by the formula (VII).

(In the formula (VI), G represents an arm portion, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, _{t 1} represents an integer of 2-6.)

(In the formula (VII), G represents an arm portion, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, F is, represents _{(CH 2) q} or p- phenylene, q is And any one of 0 to 3 is represented, and n ^{1 to} n ⁴ each represents any one of 1 to 5)

  The present invention also relates to (14) the adhesive according to any one of (1) to (13) above, wherein the number average molecular weight (Mn) of the star polymer is 50,000 to 1,000,000, The repeating structure (E) in the repeating unit (A) is contained in an amount of 40 to 80% by weight in the polymer chain constituting the arm part, according to any one of the above (1) to (14), It relates to adhesives.

  Further, in the present invention, (16) in the polymer chain constituting the arm part, the repeating unit (A) is 40 to 70% by weight, the repeating unit (B) is 5 to 15% by weight, and the repeating structure (D) is 20 to 20%. The adhesive according to any one of the above (3) to (15), characterized in that it is contained in an amount of 50% by weight, and (17) further comprising a metal salt (1) to (1) above The present invention relates to the adhesive described in (16).

  In addition, the present invention includes (18) a star polymer having a polymer chain containing a random repeating structure (C) composed of a repeating unit (A) and a repeating unit (B) as an arm part. It relates to a binder.

(In the repeating unit (A), R _{100 to} R ₃₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₀₀ and R ₃₀₀ may combine to form a ring. R _400a and R _400b each independently represent a hydrogen atom or a methyl group, R ₅₀₀ represents a hydrocarbon group, an acyl group, or a silyl group, and s ₁ represents an integer of 1 to 100 And when s ₁ is 2 or more, the groups represented by the formula: —CH (R _400a ) —CH (R _400b ) —O— may be the same or different.

(In the repeating unit (B), R ₁₁₀ and R ₃₁₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₁₀ and R ₃₁₀ may combine to form a ring. Well, R ₂₁₀ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a hydrocarbon oxy group, a carboxyl group, an acid anhydride group, an amino group, an ester group, or a hydroxyl group, a carboxyl group, an epoxy group, an acid. Represents an organic group having at least one functional group selected from the group consisting of an anhydride group and an amino group, and R ₄₁₀ is selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group. Represents an organic group having at least one functional group.)

  In addition, the present invention provides (19) the electrode-forming link as described in (18) above, wherein the repeating unit (B) is any one of the repeating units (B-1) to (B-3). It relates to the dressing.

(In the repeating unit (B-1), R _410a and R _410b each independently represent a hydrogen atom or a methyl group, s ₂ represents an integer of 1 to 100, and s ₂ is 2 or more. The groups represented by the formula: —CH (R _410a ) —CH (R _410b ) —O— may be the same or different.)

(In the repeating unit (B-2), R _410c is an alkylene group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms. Group or a divalent organic group obtained by _combining these groups, R _410d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(In the repeating unit (B-3), R _410e is a hydrogen atom or —R ₅₁₀ —COOH (R ₅₁₀ is an alkylene group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, Represents a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent organic group obtained by combining these groups.)

  Further, the present invention provides the electrode production as described in (18) or (19) above, wherein (20) the arm part is composed of a polymer chain containing the repeating structure (D) together with the random repeating structure (C). It relates to a binder.

(In the repeating unit (D), R _{600 to} R ₈₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ₉₀₀ represents an aryl group or a heteroaryl group, h represents Represents any integer of 20 to 300.)

In addition, the present invention provides (21) the binder for electrode preparation as described in (20) above, wherein R ₉₀₀ of the repeating structure (D) is a phenyl group, and (22) the repeating structure (D Wherein R ₉₀₀ is a p- (1-ethoxyethoxy) phenyl group or a p-tert-butoxyphenyl group, or (23) an arm for producing an electrode according to (21) above, The part is composed of a polymer chain represented by the formula (I), and relates to the binder for electrode preparation according to any one of the above (20) to (22).

(In Formula (I), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₁ represents a halogen atom, and Z ₁ represents at least one of Represents a group having a carbon atom.)

  In the present invention, (24) the binder for producing an electrode according to any one of the above (20) to (22), wherein the arm portion comprises a polymer chain represented by the formula (II) About.

(In Formula (II), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₂ represents a halogen atom, and Z ₂ represents at least one of Represents a group having a carbon atom.)

  In the present invention, (25) The binder for producing an electrode according to any one of the above (20) to (22), wherein the arm portion is composed of a polymer chain represented by the formula (III). About.

(In Formula (III), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₃ represents a halogen atom, and R _a and R _b are Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Z ₃ represents a group having at least one carbon atom, and k represents any integer of 1 or more.)

  The present invention also relates to (26) the binder for electrode preparation according to any one of (18) to (25) above, wherein the core portion has a benzene ring skeleton, and (27) the core portion. Is a structure represented by formula (IV), and relates to the binder for electrode preparation as described in (26) above.

  The present invention also relates to (28) the binder for producing an electrode according to the above (26), wherein the core part includes a structure represented by the formula (V).

(In the formula (V), F is _{(CH 2)} represents _q or p- phenylene, q represents an integer of 0 to 3.)

  The present invention also relates to (29) the binder for electrode preparation as described in any one of (18) to (28) above, wherein the star polymer is a star polymer represented by the formula (VI). .

(In the formula (VI), G represents an arm portion, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, _{t 1} represents an integer of 2-6.)

  In the present invention, (30) the binder for producing an electrode according to any one of (18) to (28), wherein the star polymer is a star polymer represented by the formula (VII) About.

(In the formula (VII), G represents an arm portion, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, F is, represents _{(CH 2) q} or p- phenylene, q is And any one of 0 to 3 is represented, and n ^{1 to} n ⁴ each represents any one of 1 to 5)

  In addition, the present invention provides (31) a binder for electrode preparation as described in any one of (18) to (30) above, wherein the number average molecular weight (Mn) of the star polymer is 50,000 to 1,000,000. (32) Any one of (18) to (31) above, wherein the repeating structure (E) in the repeating unit (A) is contained in an amount of 40 to 80% by weight in the polymer chain constituting the arm part. It relates to the binder for electrode preparation as described above.

  In the polymer chain constituting the (33) arm portion, the present invention is such that the repeating unit (A) is 40 to 70% by weight, the repeating unit (B) is 5 to 15% by weight, and the repeating structure (D) is 20 to 20%. The binder for electrode preparation according to any one of the above (20) to (32), characterized in that it is contained in an amount of 50% by weight, and (34) further comprising a metal salt (18) It is related with the binder for electrode preparation as described in (33).

  In addition, the present invention includes (35) a star polymer having a polymer chain containing a random repeating structure (C) composed of a repeating unit (A) and a repeating unit (B) as an arm part. Relates to the composition.

(In the repeating unit (A), R _{100 to} R ₃₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₀₀ and R ₃₀₀ may combine to form a ring. R _400a and R _400b each independently represent a hydrogen atom or a methyl group, R ₅₀₀ represents a hydrocarbon group, an acyl group, or a silyl group, and s ₁ represents an integer of 1 to 100 And when s ₁ is 2 or more, the groups represented by the formula: —CH (R _400a ) —CH (R _400b ) —O— may be the same or different.

(In the repeating unit (B), R ₁₁₀ and R ₃₁₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₁₀ and R ₃₁₀ may combine to form a ring. Well, R ₂₁₀ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a hydrocarbon oxy group, a carboxyl group, an acid anhydride group, an amino group, an ester group, or a hydroxyl group, a carboxyl group, an epoxy group, an acid. Represents an organic group having at least one functional group selected from the group consisting of an anhydride group and an amino group, and R ₄₁₀ is selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group. Represents an organic group having at least one functional group.)

  Further, the present invention provides the composition for solid electrolyte as described in (35) above, wherein (36) the repeating unit (B) is any one of the repeating units (B-1) to (B-3). Related to things.

(In the repeating unit (B-1), R _410a and R _410b each independently represent a hydrogen atom or a methyl group, s ₂ represents an integer of 1 to 100, and s ₂ is 2 or more. The groups represented by the formula: —CH (R _410a ) —CH (R _410b ) —O— may be the same or different.)

(In the repeating unit (B-2), R _410c is an alkylene group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms. Group or a divalent organic group obtained by _combining these groups, R _410d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(In the repeating unit (B-3), R _410e is a hydrogen atom or —R ₅₁₀ —COOH (R ₅₁₀ is an alkylene group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, Represents a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent organic group obtained by combining these groups.)

  In the present invention, (37) the solid electrolyte according to the above (35) or (36), wherein the arm portion is composed of a polymer chain containing the repeating structure (D) together with the random repeating structure (C). It relates to a composition for use.

(In the repeating unit (D), R _{600 to} R ₈₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ₉₀₀ represents an aryl group or a heteroaryl group, h represents Represents any integer of 20 to 300.)

The invention also relates to (38) repeatedly R ₉₀₀ of the structure (D) is, or the solid electrolyte composition according to the above (37), which is a phenyl group, (39) repeating structure (D) Wherein R ₉₀₀ is a p- (1-ethoxyethoxy) phenyl group or a p-tert-butoxyphenyl group, and (40) the arm part is The solid electrolyte composition according to any one of (37) to (39) above, comprising a polymer chain represented by formula (I).

(In Formula (I), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₁ represents a halogen atom, and Z ₁ represents at least one of Represents a group having a carbon atom.)

  Moreover, this invention relates to the composition for solid electrolytes in any one of said (37)-(39) characterized by (41) arm part consisting of a polymer chain represented by Formula (II). .

(In Formula (II), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₂ represents a halogen atom, and Z ₂ represents at least one of Represents a group having a carbon atom.)

  The present invention also relates to the solid electrolyte composition according to any one of the above (37) to (39), wherein the (42) arm portion is composed of a polymer chain represented by the formula (III). .

(In Formula (III), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₃ represents a halogen atom, and R _a and R _b are Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Z ₃ represents a group having at least one carbon atom, and k represents any integer of 1 or more.)

  The present invention also provides the solid electrolyte composition according to any one of the above (35) to (42), wherein the (43) core portion has a benzene ring skeleton, and (44) the core portion is The composition for solid electrolyte according to (43) above, which has a structure represented by formula (IV).

  The present invention also relates to (45) the solid electrolyte composition as described in (43) above, wherein the core part includes a structure represented by the formula (V).

(In the formula (V), F is _{(CH 2)} represents _q or p- phenylene, q represents an integer of 0 to 3.)

  Moreover, this invention relates to the composition for solid electrolytes in any one of said (35)-(45) characterized by the (46) star polymer being a star polymer represented by Formula (VI). .

(In the formula (VI), G represents an arm portion, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, _{t 1} represents an integer of 2-6.)

  Moreover, this invention relates to the composition for solid electrolytes in any one of said (35)-(45) characterized by the (47) star polymer being a star polymer represented by Formula (VII). .

(In the formula (VII), G represents an arm portion, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, F is, represents _{(CH 2) q} or p- phenylene, q is And any one of 0 to 3 is represented, and n ^{1 to} n ⁴ each represents any one of 1 to 5)

  In addition, the present invention provides (48) the composition for a solid electrolyte according to any one of the above (35) to (47), wherein the number average molecular weight (Mn) of the star polymer is 50,000 to 1,000,000, (49) Any of (35) to (48) above, wherein the repeating structure (E) in the repeating unit (A) is contained in an amount of 40 to 80% by weight in the polymer chain constituting the arm part. It relates to the composition for solid electrolytes as described in above.

  In the polymer chain constituting the (50) arm portion, the present invention is such that the repeating unit (A) is 40 to 70% by weight, the repeating unit (B) is 5 to 15% by weight, and the repeating structure (D) is 20 to 20%. The solid electrolyte composition according to any one of the above (37) to (49), characterized in that it is contained in an amount of 50% by weight, and (51) further comprising a metal salt ( 35) to (50).

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive agent which has the very outstanding characteristic, the binder for electrode production, and the composition for solid electrolytes can be provided.

  As the adhesive, the electrode-forming binder, and the solid electrolyte composition of the present invention, a star provided with a random repeating structure (C) composed of a repeating unit (A) and a repeating unit (B). It is not particularly limited as long as it is an adhesive containing a polymer, and each of the repeating unit (A) and the repeating unit (B) may be a single repeating unit or a plurality of repeating units. There may be. The number average molecular weight of the random repeating structure (C) is about 2000 to 50000.

In the repeating unit (A), R _{100 to} R ₃₀₀ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₀₀ and R ₃₀₀ may combine to form a ring. . Examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, phenyl group, naphthyl group, A benzyl group etc. can be mentioned. R _400a and R _400b each independently represent a hydrogen atom or a methyl group.

R ₅₀₀ represents a hydrocarbon group, an acyl group, or a silyl group. Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-hexyl group, phenyl group, substituted phenyl group, A naphthyl group etc. are mentioned. Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group and the like. Examples of the silyl group include a trimethylsilyl group, a t-butyldimethylsilyl group, and a dimethylphenylsilyl group.

Further, the hydrocarbon group of R ₁₀₀ to R ₅₀₀ may have a substituent on an appropriate carbon atom. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; hydrocarbon groups such as methyl group, ethyl group, n-propyl group, phenyl group, naphthyl group and benzyl group; acetyl group, benzoyl group and the like Cyano group; nitro group; hydrocarbon oxy group such as methoxy group and phenoxy group; alkylthio group such as methylthio group; alkylsulfinyl group such as methylsulfinyl group; alkylsulfonyl group such as methylsulfonyl group; amino group; An optionally substituted amino group such as a dimethylamino group; an anilino group;

s ₁ represents an integer of 1 to 100, and is preferably an integer of 2 to 50. When s ₁ is 2 or more, the _{formula: -CH (R 400a) -CH (} R 400b) groups represented by the -O- may be also different and the same. This repeating structure (E)

Is preferably contained in the polymer chain constituting the arm part in an amount of 20 to 90% by weight, and more preferably in an amount of 35 to 70% by weight. By containing the repeating structure (E) within the above range, the adhesion (binding) strength, film strength, conductivity, solvent resistance (electrolytic solution resistance) and heat shrink resistance are extremely excellent.

In the repeating unit (B), R ₁₁₀ and R ₃₁₀ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₁₀ and R ₃₁₀ may combine to form a ring. . Examples of the hydrocarbon group having 1 to 10 carbon atoms include those similar to those in the repeating unit (A).

R ₂₁₀ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a hydrocarbon oxy group, a carboxyl group, an acid anhydride group, an amino group, an ester group, or a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride. An organic group having at least one functional group selected from the group consisting of a group and an amino group. Examples of the hydrocarbon group having 1 to 10 carbon atoms include those similar to those in the repeating unit (A), and examples of the hydrocarbon oxy group include methoxy group, ethoxy group, and phenoxy group. Examples of the acid anhydride group include a maleic anhydride group and a phthalic anhydride group. _R410 represents an organic group having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group.

R _{110 to} R ₄₁₀ may have a substituent on an appropriate carbon atom. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; hydrocarbon groups such as methyl group, ethyl group, n-propyl group, phenyl group, naphthyl group and benzyl group; acetyl group, benzoyl group and the like Cyano group; nitro group; hydrocarbon oxy group such as methoxy group and phenoxy group; alkylthio group such as methylthio group; alkylsulfinyl group such as methylsulfinyl group; alkylsulfonyl group such as methylsulfonyl group; amino group; An optionally substituted amino group such as a dimethylamino group; an anilino group;

  Specifically, as the repeating unit (B), repeating units (B-1) to (B-3) can be preferably exemplified, and the repeating unit (B-1) is particularly preferable.

In the repeating unit (B-1), R _410a and R _410b each independently represent a hydrogen atom or a methyl group. s ₂ represents an integer of 1 to 100, and is preferably an integer of 2 to 50. When s ₂ is 2 or more, groups represented by the formula: —CH (R _410a ) —CH (R _410b ) —O— may be the same or different.

In the repeating unit (B-2), R _410c is an alkylene group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms. Or a divalent organic group in which these are combined. R _410d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, Examples thereof include a t-butyl group. R _410d may have a substituent on an appropriate carbon atom. Examples of such a substituent include halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; a methyl group, an ethyl group, and n-propyl. Group, phenyl group, naphthyl group, benzyl group and other hydrocarbon groups; acetyl group, benzoyl group and other acyl groups; cyano group; nitro group; methoxy group, phenoxy group and other hydrocarbon oxy groups; methylthio group and other alkylthio groups An alkylsulfinyl group such as a methylsulfinyl group; an alkylsulfonyl group such as a methylsulfonyl group; an optionally substituted amino group such as an amino group and a dimethylamino group; an anilino group; and the like.

In the repeating unit (B-3), R _410e represents a hydrogen atom or a group represented by —R ₅₁₀ —COOH. As R ₅₁₀ , an alkylene group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent compound thereof. Represents an organic group.

  Moreover, it is preferable that the polymer chain which comprises the arm part of the star polymer of this invention contains a repeating structure (D) with the said random repeating structure (C). As the repeating structure (D), one type of repeating structure may be used, or two or more types of block repeating structures or random repeating structures may be used.

In the repeating unit (D), R _{600 to} R ₈₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include those similar to those in the repeating unit (A). _R900 represents an aryl group or a heteroaryl group, specifically, an aryl group such as a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, or a 2-pyridyl group And heteroaryl groups such as 4-pyridyl group, among which aryl groups are preferable, and phenyl group, p- (1-ethoxyethoxy) phenyl group, and p-tert-butoxyphenyl group are particularly preferable. . h represents an integer of 20 to 300, and preferably an integer of 30 to 150.

R _{600 to} R ₉₀₀ may have a substituent on an appropriate carbon atom. As such substituents, halogen atoms such as fluorine atom, chlorine atom, bromine atom; hydrocarbon groups such as methyl group, ethyl group, n-propyl group, phenyl group, naphthyl group, benzyl group; acetyl group, benzoyl group Cyano group; nitro group; hydrocarbon oxy group such as methoxy group and phenoxy group; alkylthio group such as methylthio group; alkylsulfinyl group such as methylsulfinyl group; alkylsulfonyl group such as methylsulfonyl group; amino group And an optionally substituted amino group such as a dimethylamino group; an anilino group; and the like.

  Specifically, the polymer chain represented by the formula (I), the formula (II) and the formula (III) is used as the polymer chain containing the repeating structure (D) together with the random repeating structure (C) constituting the arm portion. It can illustrate suitably.

In the formula (I), (C) represents the random repeating structure (C), (D) represents the repeating structure (D), and X ₁ represents a halogen atom. Z ₁ represents a group having at least one carbon atom, and is a group in which a part of the polymerization initiator is bonded through the one carbon atom. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.

In formula (II), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), and X ₂ represents a halogen atom. Z ₂ represents a group having at least one carbon atom, and is a group in which a part of the polymerization initiator is bonded through the one carbon atom. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.

In formula (III), (C) represents a random repeating structure (C), (D) represents a repeating structure (D), X ₃ represents a halogen atom, and R _a and R _b are respectively Independently, it represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Z ₃ represents a group having at least one carbon atom, and is a group in which a part of the polymerization initiator is bonded through the one carbon atom. k represents any integer of 1 or more, and examples thereof include any integer of 1 to 300. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group having 1 to 10 carbon atoms include those similar to those in the repeating unit (A).

  When the polymer constituting the arm part contains the repeating unit (A), the repeating unit (B), and the repeating structure (D), the repeating unit (A) is 40 to 70 weights in the polymer chain constituting the arm part. %, The repeating unit (B) is contained in an amount of 5 to 15% by weight, and the repeating structure (D) is preferably contained in an amount of 20 to 50% by weight. The repeating unit (A) is contained in an amount of 55 to 70% by weight and the repeating unit (B). Is more preferably 5 to 15% by weight and the repeating structure (D) is more preferably 20 to 40% by weight.

  The core part of the star polymer contained in the adhesive, the electrode-forming binder, and the solid electrolyte composition of the present invention may be any one that has three or more bonds and can form a star polymer. It is not particularly limited, and examples thereof include a chain or cyclic aliphatic compound, an aromatic compound, a heterocyclic compound, and the like, and a structure having a benzene ring skeleton is preferable. Specifically, as the core part, the formula (IV)

The core part of the structure represented by the formula (V)

The core part containing the structure represented by can be mentioned. Wherein (V), F represents _{(CH 2) q} or p- phenylene, q represents an integer of 0 to 3. In addition, examples of structures having a large number of benzene rings in the skeleton include those described in J. Am. Chem. Soc., Vol. 118, No. 37, 8647, 1996.

  Specifically, examples of the core portion including the structure represented by the formula (V) include the following.

  More specifically, as the star polymer in the adhesive of the present invention, for example, a star polymer represented by the formula (VI) and a star polymer represented by the formula (VII) can be preferably exemplified, The star polymer which provided the arm part similar to these to the benzene ring of the outermost shell of the said core part can be mentioned.

Wherein (VI), G represents an arm portion, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, t ₁ represents an integer of 2-6.

In formula (VII), G represents an arm part, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, F represents (CH ₂ ) _q or a p-phenylene group, and q represents Any one of 0 to 3 is represented, and n ^{1 to} n ⁴ each represents any one of 1 to 5.

  The number average molecular weight (Mn) of the star polymer contained in the present invention is, for example, about 50,000 to 1,000,000. Moreover, as ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn), it is preferable that it is 1.01-1.50, for example.

  The star polymer of the present invention preferably has a microphase separation structure, and particularly preferably has a network type microphase separation structure. By having such a structure, ionic conductivity, physical characteristics, thermal characteristics, particularly strength can be improved. The “microphase separation structure” in the present invention includes structures such as cylinders, lamellae, and spheres, and can have a stable phase separation structure as appropriate depending on conditions such as the primary structure, molecular weight, and molecular weight distribution of the polymer.

  It is preferable that the adhesive, the electrode preparation binder, and the solid electrolyte composition of the present invention containing the star polymer as described above contain a metal salt. By containing a metal salt together with the star polymer, the conductivity can be improved and the adhesive strength can be further improved. The reason why the adhesive strength is improved is that the metal salt is coordinated to an oxygen atom or the like of the repeating unit (E) in the repeating unit (A) to form pseudo-crosslinking, and as a result, the crosslinking density of the polymer is increased. Conceivable.

  Examples of the method for containing the metal salt include, for example, contacting the star polymer with a solution containing the metal salt, in addition to a method in which the star polymer and the metal salt are mixed and uniform in a solvent. The solvent is not particularly limited as long as it can dissolve the star polymer, but a polar solvent is preferable, for example, acetonitrile, tetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, chloroform, N-methylpyrrolidone, methanol and the like. Can be mentioned.

The metal salt is not particularly limited, but is preferably an electrolyte salt. Electrolyte salts include alkali metal salts, quaternary ammonium salts such as (CH ₃ ) ₄ NBF ₆ , quaternary phosphonium salts such as (CH ₃ ) ₄ PBF ₆ , transition metal salts such as AgClO ₄ , hydrochloric acid, perchlorine Examples thereof include proton acids such as acid and borohydrofluoric acid, and alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts are preferable, and alkali metal salts are more preferable. Multiple metal salts may be used in combination.

Specific examples of the alkali metal salt include LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC (CH ₃ ) (CF ₃ SO ₂ ) ₂ , LiCH (CF ₃ SO ₂ ). _{2) 2, LiCH 2 (CF} 3 SO 2), LiC 2 F 5 SO 3, LiN (C 2 F 5 SO 2) 2, LiB (CF 3 SO 2) 2, LiPF 6, LiClO 4, LiI, LiBF 4 _{, LiSCN, LiAsF 6, NaCF 3} SO 3, NaPF 6, NaClO 4, NaI, NaBF 4, NaAsF 6, KCF 3 SO 3, KPF 6, KI, LiCF 3 CO 3, NaClO 3, NaSCN, KBF 4, Mg ( ClO ₄ ) ₂ , Mg (BF ₄ ) _{2 and the} like can be mentioned, and lithium salt is particularly preferable.

  In the case of an adhesive or a binder for making an electrode, the metal salt is 0.005 to 80 mol% with respect to the repeating unit (E) in the repeating unit (A) in the polymer chain constituting the arm portion of the star polymer. It is preferable to make it contain in the range, and it is more preferable to make it contain in the range of 0.01-30 mol%. By containing in this range, a metal salt can be disperse | distributed uniformly and the uniform adhesive effect can be acquired. Moreover, in the case of the composition for solid electrolytes, a metal salt is contained in 1-10 mol% with respect to the repeating unit (E) in the repeating unit (A) in the polymer chain which comprises the arm part of a star polymer. It is preferable to make it contain in 2-6 mol%. By containing in this range, the metal salt can be uniformly dispersed, and very high characteristics can be exhibited as a solid electrolyte.

  Although it does not restrict | limit especially as a manufacturing method of the star polymer in the adhesive agent of this invention, For example, it can manufacture by making the polymer which has an anion polymerization active terminal used as an arm part, and the compound used as a core part react. That is, after completion of the arm polymer synthesis reaction, it can be carried out by further adding a compound that becomes a core part to the reaction solution. In addition, the synthesized arm polymer can be added to the solution of the compound to be the core part.

  This reaction can usually be carried out in an organic solvent in an inert gas atmosphere such as nitrogen or argon at a temperature of -100 ° C to 50 ° C, preferably -70 ° C to 40 ° C. A polymer having a controlled structure and a narrow molecular weight distribution can be obtained. In addition, the star polymer formation reaction can be performed continuously in the solvent used to form the arm polymer, the composition is changed by adding a solvent, or the solvent is replaced with another solvent. It can also be done. As such a solvent, the same solvent as that used in the arm polymer synthesis reaction can be used.

  In such a method for producing a star polymer, it is preferable to use a compound having two or more ester groups as a compound to be a core part, whereby the anionic polymerization active terminal attacks twice with respect to one ester group. Thus, two arms can be formed for one ester group, and a narrowly dispersed star polymer can be obtained easily and reliably. As the addition ratio of the compound having two or more ester groups and the polymer having an anionic polymerization active terminal, the active terminal (D) of the polymer having an anionic polymerization active terminal is the number of ester groups of the compound having two or more ester groups ( It may be calculated and added in advance so as to be twice the amount of P), or it may be added so that (D) is an excess amount exceeding twice the amount of (P).

  The compound having two or more ester groups is not particularly limited, such as a chain or cycloaliphatic compound, an aromatic compound, a heterocyclic compound, etc., and a benzene ring such as an aromatic compound or an aromatic hydrocarbon group It is preferable that it is a compound which has in a frame | skeleton. Specific examples include a compound represented by the formula (VIII) and a compound represented by the formula (IX).

In formula (VIII), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and t represents an integer of 2 to 6. (In Formula (IX), R ^{2 to} R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms, and p ^{2 to} p ⁵ are each independently an integer of 1 to 5) , F represents (CH ₂ ) _q or a p-phenylene group, and q represents an integer of 0 to 3.

  As a method for synthesizing a polymer having an anionic polymerization active terminal as an arm part, a method of dropping an anionic polymerization initiator into a monomer (mixed) solution or a method of dropping a monomer (mixed) solution into a solution containing an anionic polymerization initiator However, since the molecular weight and molecular weight distribution can be controlled, a method of dropping a monomer (mixed) solution into a solution containing an anionic polymerization initiator is preferable. This arm polymer synthesis reaction is usually carried out in an organic solvent under an inert gas atmosphere such as nitrogen or argon at a temperature in the range of −100 to 50 ° C., preferably −100 to 40 ° C.

  Specifically, as a method for synthesizing a polymer having an anion polymerization active terminal as an arm part, for example, 1) a mixture of a compound capable of deriving a repeating unit (A) and a compound capable of deriving a repeating unit (B) is used. And a method of producing a polymer having an anionic polymerization active terminal containing a random repeating structure (C) composed of a repeating unit (A) and a repeating unit (B), and 2) a repetition obtained by the method of (1) above. A method of producing a polymer having a polymerization active terminal in the repeating structure (D) by mixing a polymer having a polymerization active terminal containing the structure (C) and a compound capable of forming the repeating structure (D); Using a monomer capable of forming the structure (D), a polymer having a polymerization active terminal containing the repeating structure (D) is produced, the polymer and the repeating unit A mixture of a compound capable of deriving A) and a compound capable of deriving the repeating unit (B) is mixed, and the random repeating structure (C) comprising the repeating unit (A) and the repeating unit (B) has a polymerization active terminal. Mention may be made of methods for producing polymers.

  Examples of the anionic polymerization initiator used in producing the arm polymer can include alkali metals or organic alkali metals. Examples of the alkali metals include lithium, sodium, potassium, cesium, and the like. Examples of the metal include alkylated products, allylated products, arylated products and the like of the above alkali metals. Specifically, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, ethyl sodium, Examples include lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, α-methylstyrene sodium dianion, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, and the like.

  Examples of the organic solvent used in producing the arm polymer include aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane and cyclopentane, and aromatic hydrocarbons such as benzene and toluene. In addition to ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane, organic solvents usually used in anionic polymerization such as anisole and hexamethylphosphoramide can be mentioned. It can be used as the above mixed solvent. Among these, from the viewpoints of polarity and solubility, a mixed solvent of tetrahydrofuran and toluene, tetrahydrofuran and hexane, tetrahydrofuran and methylcyclohexane can be preferably exemplified.

  Moreover, the polymer which has an anion polymerization active terminal used as an arm part can be manufactured by using the compound represented by Formula (X) as a polymerization initiating compound.

  In formula (X), W and W ′ each independently represent a functional group that can be substituted with a hydroxyl group or a halogen atom without inhibiting polymerization. Specific examples include silyloxy groups such as trimethylsilyloxy group, t-butyldimethylsilyloxy group and dimethylphenylsilyloxy group, and aryloxy groups such as phenoxy group and naphthoxy group. Is preferred.

  That is, first, a compound represented by the formula (X) is converted into a compound having a polymerization initiating species by an anionic polymerization initiator, and then a compound capable of deriving the repeating unit (A) in the compound having the polymerization active species and A mixture of compounds capable of deriving the repeating unit (B), a polymerizable monomer such as a monomer capable of forming the repeating structure (D) is added, anion polymerization is performed, and the compound serving as the core part is further reacted to form a formula. After producing a star polymer in which the compound represented by (X) is the outermost shell (hereinafter referred to as star polymer (X)), W and W ′ of the compound represented by formula (X) are halogenated. A group having an atom or a halogen atom is substituted (hereinafter, W and W ′ are substituted with a halogen atom or a group having a halogen atom is referred to as a star polymer (X ′)). By adding a polymerizable monomer such as a mixture of a monomer capable of forming the structure (D), a compound capable of deriving the repeating unit (A), and a compound deriving the repeating unit (B), and performing polymerization. The star polymer in this invention can be manufactured.

  Among the above star polymer production methods, the compound represented by the formula (X) is converted into a compound having a polymerization initiating species by an anionic polymerization initiator, and then the compound having the polymerization active species is converted into a repeating structure (D). The star polymer (X) in which the compound represented by the formula (X) is the outermost shell was produced by adding a monomer capable of forming an anion, and further reacting the compound serving as the core. Thereafter, W and W ′ of the compound represented by the formula (X) are substituted with a halogen atom or a group having a halogen atom to form a star polymer (X ′), and further a compound capable of deriving the repeating unit (A) And a method of performing living radical polymerization by adding a mixture of compounds capable of deriving the repeating unit (B) is preferable from the viewpoint of easy polymerization.

  For example, in a star polymer having an arm part composed of a polymer chain represented by the formula (II), W and W ′ of the star polymer (X) are substituted with hydroxyl groups, and then reacted with bromoisobutyl butyrate, Furthermore, it can be produced by living radical polymerization of a mixture of a compound capable of deriving the repeating unit (A) and a compound deriving the repeating unit (B).

  In addition, the star polymer having an arm portion composed of a polymer chain represented by the formula (III) is obtained by substituting the halogen atom for W and W ′ of the star polymer (X), and then converting the (meth) acrylic acid compound into a living radical. Furthermore, it can be produced by polymerizing and living radical polymerization of a mixture of a compound capable of deriving the repeating unit (A) and a compound deriving the repeating unit (B). Examples of (meth) acrylic acid compounds include (meth) acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, and n-acrylate. Acrylic acid ester compounds such as hexyl, cyclopentyl acrylate, cyclohexyl acrylate, phenyl acrylate, 2-pyridyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Methacrylic acid ester compounds such as t-butyl methacrylate, n-hexyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-pyridyl methacrylate;

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, methoxypolyethylene glycol (the number of units of ethylene glycol is 2 to 100) (Meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (propylene glycol has 2 to 100 units) (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, phenoxypolypropylene Glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, poly Propylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) Acrylate, “Blenmer PME series; manufactured by NOF Corporation”, acetyloxypolyethylene glycol (meth) acrylate, benzoyloxypolyethylene glycol (meth) acrylate, trimethylsilyloxypolyethylene glycol (meth) acrylate, t-butyldimethylsilyloxypolyethylene glycol (Meth) acrylate, methoxypolyethylene glycol cyclo Cyclohexene-1-carboxylate, methoxy polyethylene glycol - like can be exemplified cinnamate, it can be used as a mixture of two or more.

  Living radical polymerization using a star polymer (X ′) includes (A) a living radical polymerization method in which a polymerization reaction is performed using a star polymer (X ′) as a polymerization initiator and a transition metal complex as a catalyst; ) Living radical polymerization method using a stable radical initiator, and the like. From the viewpoint of obtaining a target star polymer more efficiently, the living radical polymerization method (A) is preferred.

  As the central metal constituting the transition metal complex used in the living radical polymerization method of (A), Group 7-11 elements of the periodic table such as manganese, rhenium, iron, ruthenium, rhodium, nickel, copper, etc. (edited by the Chemical Society of Japan) Preferably, the chemical handbook basic edition I revised 4th edition (according to the periodic table described in 1993) is used. Of these, ruthenium is preferable.

  The ligand that forms a complex by coordinating with these metals is not particularly limited, but examples thereof include phosphorus-based ligands, halogen atoms, carbon monoxide, hydrogen atoms, hydrocarbon-based ligands, oxygen-containing ligands. Examples thereof include system ligands, other chalcogenides, and nitrogen-containing ligands. The transition metal complex may have two or more of these ligands.

  Preferred specific examples of the transition metal complex include dichlorotris (triphenylphosphine) ruthenium, chloroindenylbis (triphenylphosphine) ruthenium, dihydrotetrakis (triphenylphosphine) ruthenium, chlorocyclopentadienylbis (triphenylphosphine). Ruthenium, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium; dicarbonylcyclopentadienylruthenium iodide (II), dicarbonylcyclopentadienyliron iodide (II), carbonylcyclopentadienyl iodide Nickel (II); (1-ethoxycarbonyl-1-methylethyl) methyltellurium, (1-cyano-1-methylethyl) methyltellurium, α-methylbenzylmethyltellurium, benzylmethylte Le, and a tellurium complex such as methyl benzoyl tellurium. These transition metal complexes can be used alone or in combination of two or more.

  In the living radical polymerization, an activator that promotes radical polymerization by acting on the transition metal complex can be used in combination. As such activators, Lewis acids and / or amines can be used.

  The kind of Lewis acid is not particularly limited, and for example, aluminum-based Lewis acid, scandium-based Lewis acid, titanium-based Lewis acid, zirconium-based Lewis acid, tin-based Lewis acid and the like can be used. The amine is not particularly limited as long as it is a nitrogen-containing compound such as a secondary amine, tertiary amine, or nitrogen-containing aromatic heterocyclic compound, but a secondary amine or tertiary amine is preferable. These Lewis acids and amines can be used alone or in combination of two or more. The usage-amount of a Lewis acid and / or amine is 0.1-20 mol normally with respect to 1 mol of transition metal complexes, Preferably it is 0.2-10 mol.

  In the method for producing a star polymer by the living radical polymerization method (A), the star polymer (X ′) serves as a polymerization initiator. That is, the bonding site of the active halogen atom in the functional group represented by W and W ′ of the star polymer (X ′) becomes a radical species by the action of the transition metal complex, thereby becoming a polymerization active site. The compound having a living radical polymerizable unsaturated bond is polymerized.

As a method of forming the arm portion by the living radical polymerization method,
(1) A method of forming an arm portion composed of a homopolymer using a compound having a kind of living radical polymerizable unsaturated bond,
(2) A method in which a compound having a plurality of living radical polymerizable unsaturated bonds is simultaneously added to the reaction system to form an arm portion made of a random copolymer,
(3) A method in which a compound having a plurality of living radically polymerizable unsaturated bonds is sequentially added to a reaction system to form an arm portion composed of a block copolymer,
(4) A method of changing the composition ratio of a compound having a plurality of living radical polymerizable unsaturated bonds over time to form an arm portion made of a gradient copolymer,
Etc.

  The polymerization method is not particularly limited, and for example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like can be adopted, but solution polymerization is preferable.

  When the solution polymerization method is adopted, the star polymer (X ′), the compound having a polymerizable unsaturated bond, a transition metal complex, and optionally Lewis acid and / or amines are mixed in an organic solvent and heated. The desired star polymer can be obtained by stirring while stirring.

  Examples of the stable radical initiator used in the living radical polymerization method (B) include a mixture of a stable free radical compound and a radical polymerization initiator, or various alkoxyamines.

  The adhesive, the electrode-forming binder, and the solid electrolyte composition of the present invention may contain an optional component in addition to the star polymer and the metal salt as long as the effects of the present invention are not hindered. Examples of such optional components include a crosslinking agent, a filler, a sensitizer, and a storage stabilizer. Examples of the sensitizer include urea, nitrile compounds (N, N-disubstituted-P-aminobenzonitrile and the like), phosphorus compounds (tri-n-butylphosphine and the like), and examples of the storage stabilizer include the fourth. Examples include quaternary ammonium chloride, benzothiazole, hydroquinone and the like.

  The crosslinking agent is preferably used in an amount of 0.01 to 2 mol, more preferably 0.1 to 1 mol, per 1 mol of the repeating unit (B) of the star polymer in the present invention. Although it does not restrict | limit especially as a crosslinking agent to be used, The polyisocyanate compound which has a 2 or more isocyanate group in a molecule | numerator, and the polyepoxy compound which has a 2 or more epoxy group in a molecule | numerator can be mentioned.

  The adhesive of the present invention has high adhesion to plastics such as olefin resins, metals, inorganic compounds, ceramics, and coating substrates thereof, and also has high conductivity and high film strength. is doing. Moreover, since the adhesive of this invention is excellent in solvent resistance, the use in a solvent is also possible. From these properties, the adhesive of the present invention can be preferably used for a battery regardless of whether it is a solid battery or a liquid battery, and is particularly useful for adhesion between an electrode and a separator. For example, it can be used for adhesion between an electrode and a separator in a lithium ion battery. Further, since it does not shrink against heat, it can sufficiently withstand the temperature rise during battery use, and the separator can be prevented from being deformed. Therefore, it is possible to prevent the electrodes from coming into contact and short-circuiting.

  The binder for producing an electrode of the present invention can be used for holding an electrode active substance on the surface of a current collector, and is excellent in binding between electrode active substances and binding with a current collector. . In addition, it has high conductivity and high film strength. Furthermore, the binder of the present invention is also excellent in electrolytic solution resistance, and can be preferably used regardless of whether it is a solid battery or a liquid battery. Moreover, since it does not shrink against heat, it can sufficiently withstand the temperature rise during battery use.

  As an electrode manufacturing method using the binder for electrode preparation of the present invention, for example, the electrode preparation binder of the present invention is formed on a layer containing an electrode active material prepared on a support (current collector). A method of casting or coating an agent and drying it can be mentioned. The coating method is not particularly limited, and methods such as a roll coater method, a curtain coater method, a spin coat method, a dip method, and a cast method can be used.

  The composition for solid electrolyte of the present invention can produce a solid electrolyte, and examples of the shape of the solid electrolyte include a sheet shape, a film shape, and a film shape. The composition for solid electrolytes of the present invention can form a highly strong sheet, membrane, or film having high conductivity. The solid electrolyte can be produced by forming a coating film of the solid electrolyte composition on a carrier and curing the coating film by heating or the like. As a carrier to be used, the material, size, shape and the like are not particularly limited as long as they can support a solid electrolyte. Of these, those excellent in chemical resistance, heat resistance and peelability, such as those made of polytetrafluoroethylene, are desirable.

  As a method for applying the solid electrolyte composition onto the carrier, a known application method can be employed. For example, a method of pouring the solid electrolyte composition onto the carrier, a roll coater method, a screen coating method, a doctor blade method, a bar Various coating means such as a coating method, a curtain coater method, a spin coating method, a dip method, and a casting method may be mentioned.

  After the casting or application of the solid electrolyte composition, the solvent is removed by a method such as distillation at normal pressure or reduced pressure, heat drying, etc., but it is preferable to include a heat treatment step in a state containing at least the solvent. As pre-processing or post-processing steps other than this step, steps such as distillation under reduced pressure and heat drying may be further included. Here, the state containing the solvent is a state before the solvent is completely removed, and is 10 to 50% by weight, further 15 to 30% by weight, based on the solid content in the cast or applied solution. It is preferable that the solvent remains in the range. The heating temperature is not particularly limited, but is preferably near or above the glass transition temperature.

  The obtained solid electrolyte such as a sheet can be suitably used as a solid electrolyte layer of a solid electrolyte battery having a positive electrode, a negative electrode, and a solid electrolyte composition layer. That is, a polymer solid electrolyte battery can be obtained by sandwiching a solid electrolyte sheet between a positive electrode and a negative electrode. In addition, the solid electrolyte of the present invention has excellent mechanical strength to such an extent that a self-supporting film can be formed, and excellent ionic conductivity over a wide temperature range. Moreover, it is excellent also in solvent resistance and can also be used by impregnating electrolyte solution.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.

<Production of star polymer according to example (Example star polymer (1))>
[Synthesis of arm having OTBDMS group (t-butyldimethylsilyloxy group)]
To a nitrogen-substituted 2000 mL four-necked flask, 113 g of dehydrated tetrahydrofuran (hereinafter abbreviated as THF), 1020 g of dehydrated toluene, and 13.75 g (29.3 mmol) of DPE (diphenylethylene)-(m-OTBDMS) ₂ were added. The reaction system was kept at −40 ° C. with stirring. To the reaction system, 11.35 g (26.7 mmol) of a n-butyllithium / hexane 1.6 mol / L solution was added and stirred for 30 minutes. Thereafter, 200 g (1920.3 mmol) of styrene was added to the reaction system for polymerization. Sampling was performed 20 minutes after the completion of the dropping, and the completion of polymerization was confirmed by gas chromatography (hereinafter abbreviated as GC). When this polymer solution was analyzed by gel filtration chromatography (hereinafter abbreviated as GPC), it was a unimodal polymer having a molecular weight Mn = 9400 and a dispersity Mw / Mn = 1.49.

[Starization reaction]
To this reaction system, 1.56 g (2.5 mmol) of 1,1,2,2-tetrakis- (4-ethoxycarbonylphenyl) ethane dissolved in 25 ml of dehydrated THF was added, and the reaction was continued for 30 minutes. Was used to stop the reaction. The polymer solution was poured into a large amount of methanol to precipitate a polymer, filtered and washed, and then dried under vacuum at 50 ° C. for 5 hours to obtain 205 g of a white powdery polymer (yield 97%).

  By using preparative GPC, an excess amount of the arm polymer was removed to obtain a white powdery star polymer. When this polymer was analyzed by GPC, it was a unimodal polymer having a molecular weight Mn = 46800 and a dispersity Mw / Mn = 1.021. The molecular weight Mw was 81100 and the degree of dispersion Mw / Mn was 1.013 as measured by a multi-angle light scattering detector (hereinafter abbreviated as GPC-MALLS).

[Conversion of functional group (OTBDMS group) to OH group)]
To a 2000 mL flask purged with nitrogen, 1500 ml of dehydrated THF, 200 g of the 8-arm star polymer produced above, and 100 ml of tetra-n-butylammonium fluoride (TABF) (1.0 M in THF) were added and stirred overnight at room temperature. The solvent was concentrated to half, and this solution was poured into a large amount of methanol to precipitate a polymer. After filtration and washing, the polymer was dried at 50 ° C. for 5 hours under vacuum to obtain 195 g of a white powdery polymer (yield 98%) )

[Functional group conversion (conversion of OH group to OBiB group (bromoisobutylbutyrate))]
To a nitrogen-substituted 2000 mL four-necked flask, 1200 ml of dehydrated THF, 190 g (2.3 mmol) of 8-arm star polymer (OH group) converted to the OH group, and 5.70 g (56.3 mmol) of triethylamine were added, and the mixture was stirred. The reaction system was kept at 0 ° C. To the reaction system, 11.2 g (48.7 mmol) of bromoisobutyryl bromide was gradually added. After completion of the dropwise addition, the mixture was returned to room temperature and stirred overnight. After removing the TEA odorate by filtration, the solvent was concentrated to half, and this solution was poured into a large amount of methanol to precipitate a polymer, followed by filtration and washing. The obtained polymer was subjected to fractional purification with THF / methanol, reprecipitated with a large amount of methanol, and then dried under vacuum at 50 ° C. for 5 hours to obtain 140 g (yield 74%) of a white powdery polymer. Obtained.

  When this polymer solution was analyzed by GPC, it was a unimodal polymer having a molecular weight Mn = 45700 and a dispersity Mw / Mn = 1.026. Moreover, it was molecular weight Mw = 82500 and dispersion degree Mw / Mn = 1.020 when it measured by GPC-MALLS.

[Living radical polymerization]
In a 100 ml flask, 2.05 g (0.025 mmol) of the 8-arm star polymer converted into the bromoisobutyl butyrate group, 7.79 g (7.00 mmol) of methoxypolyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Bremer PME-1000) Then, 0.41 g (3.15 mmol) of hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) and 40 g of toluene were charged and degassed. By adding 0.04 g (0.04 mmol) of dichlorotris (triphenylphosphine) ruthenium and dissolving uniformly, 0.02 g (0.16 mmol) of di-n-butylamine is added and heated to 80 ° C. The polymerization reaction was started. Four hours after the start of the polymerization reaction, the reaction solution was cooled to 0 ° C. to stop the polymerization reaction. When the conversion rate was calculated | required from NMR, PME-1000 was 46% and HEMA was 90%. The reaction solution was applied to a column to remove the metal complex and unreacted monomers. The solvent was concentrated under reduced pressure, and N-methylpyrrolidone (hereinafter abbreviated as NMP) was added to prepare a 10% NMP solution. PME-1000: HEMA: St = 60: 6: 34 (wt% ratio), PEO (polyethylene oxide) (repeated structure (E)) content = 54 wt%.

<Production of star polymer according to example (Example star polymer (2))>
[Living radical polymerization]
In a 200 ml flask, 4.10 g (0.05 mmol) of 8-arm star polymer converted to the bromoisobutyl butyrate group, 14.76 g (13.26 mmol) of PME-1000, 1.64 g (12.60 mmol) of hydroxyethyl methacrylate, 80 g of toluene was charged and deaerated. By adding 0.08 g (0.008 mmol) of dichlorotris (triphenylphosphine) ruthenium and dissolving uniformly, 0.04 g (0.32 mmol) of di-n-butylamine is added and heated to 80 ° C. The polymerization reaction was started. Five hours after the initiation of the polymerization reaction, the polymerization reaction was stopped by cooling the reaction solution to 0 ° C. When the conversion rate was calculated | required from NMR, PME-1000 was 66% and HEMA was 97%. The reaction solution was applied to a column to remove the metal complex and unreacted monomers. The solvent was concentrated under reduced pressure and NMP was added to prepare a 10% NMP solution. PME-1000: HEMA: St = 63: 11: 26 (wt% ratio), PEO (repeated structure (E) content = 57 wt%).

<Production of Polymer According to Comparative Example (Comparative Example Polymer (1))>
Under an argon atmosphere, 135.0 g (121.3 mmol) of PME-1000, 15.0 g (115.3 mmol) of HEMA, and 450.0 g of toluene were placed in a flask and uniformly mixed, followed by deaeration treatment.

  To this mixed solution, 0.72 g (0.75 mmol) of dichlorotris (triphenylphosphine) ruthenium and 0.39 g (3.0 mmol) of di-n-butylamine were added, and 0.28 g (1) of 2,2-dichloroacetophenone was further added. .5 mmol) was added, and the polymerization reaction was started by heating to 80 ° C. with stirring. After 47 hours from the start of the polymerization reaction, the temperature of the reaction system was cooled to 0 ° C. to stop the polymerization reaction. Column purification of the reaction solution was performed to remove metal complexes and unreacted monomers. The viscous residue obtained by removing volatiles under reduced pressure was dried under reduced pressure at 60 ° C. for 5 hours.

  As described above, a random copolymer of PME-1000 and HEMA was obtained. When the GPC-MALLS analysis of the obtained copolymer was conducted, they were Mw = 215,000 and Mw / Mn = 2.15.

  Under an argon atmosphere, 50.0 g (0.23 mmol) of P- (PME1000 / HEMA) synthesized earlier, 75.0 g (720 mmol) of styrene, and 300 g of toluene were collected in a flask and mixed uniformly. After degassing this mixed solution, 0.12 g (0.15 mmol) of chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium and 0.07 g (0.5 mmol) of di-n-butylamine were added, and the mixture was heated to 100 ° C. The polymerization reaction was started by heating.

  68 hours after the start of the polymerization reaction, the reaction solution was cooled to 0 ° C. to stop the polymerization reaction. The polymerization rate of styrene was 21%. It was reprecipitated with a large amount of cold hexane, and the obtained polymer was dried under reduced pressure at 30 ° C. for 20 hours.

  As described above, a block copolymer of (PME-1000 / HEMA) and St was obtained. When the GPC-MALLS analysis of the obtained copolymer was conducted, they were Mw = 329,000 and Mw / Mn = 2.02. PME-1000: HEMA: St = 68: 8: 24 (wt% ratio) and PEO content = 62 wt%.

<Production of polymer according to Comparative Example 2 (Comparative Example Polymer (2))>
Under an argon atmosphere, 90.0 g (80.8 mmol) of PME-1000, 10.0 g (76.8 mmol) of HEMA, and 300.0 g of toluene were placed in a flask and mixed uniformly, and then degassed.

  To this mixed solution, 0.48 g (0.5 mmol) of dichlorotris (triphenylphosphine) ruthenium and 0.26 g (2.0 mmol) of di-n-butylamine were added, and further 0.19 g (1 of 2,2-dichloroacetophenone) 0.0 mmol) was added and heated to 80 ° C. with stirring to initiate the polymerization reaction. After 45 hours from the start of the polymerization reaction, the temperature of the reaction system was cooled to 0 ° C. to stop the polymerization reaction. Column purification of the reaction solution was performed to remove metal complexes and unreacted monomers. The viscous residue obtained by removing volatiles under reduced pressure was dried under reduced pressure at 60 ° C. for 5 hours.

  As described above, a random copolymer of PME-1000 and HEMA was obtained. When the GPC-MALLS analysis of the obtained copolymer was conducted, they were Mw = 155,000 and Mw / Mn = 1.54.

  Under an argon atmosphere, 28.0 g (0.18 mmol) of P- (PME1000 / HEMA) synthesized earlier, 84.0 g (807 mmol) of styrene, and 110 g of toluene were collected in a flask and mixed uniformly. After degassing this mixed solution, chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium 0. 06 g (0.08 mmol) and di-n-butylamine 0.05 g (0.37 mmol) were added, and the polymerization reaction was started by heating to 100 ° C.

  28 hours after the start of the polymerization reaction, the reaction solution was cooled to 0 ° C. to stop the polymerization reaction. The polymerization rate of styrene was 19%. It was reprecipitated with a large amount of cold hexane, and the obtained polymer was dried under reduced pressure at 30 ° C. for 20 hours.

  As described above, a block copolymer of (PME-1000 / HEMA) and St was obtained. When the GPC-MALLS analysis of the obtained copolymer was conducted, they were Mw = 445,000 and Mw / Mn = 2.07. PME-1000: HEMA: St = 57: 7: 34 (wt% ratio) and PEO content = 54 wt%.

<Evaluation>
[Evaluation of conductivity]
1. Sample preparation (Sample 1-1)
Example 1 g of the star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 56 mg of LiPF ₆ ([Li] / [EO] = 0.03) was added. The polymer composition was obtained by uniform dissolution.

(Sample 1-2 (containing crosslinking agent))
Example 1 g of star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 40 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 100%). (Conversion) After adding and sufficiently stirring, 56 mg of LiPF ₆ ([Li] / [EO] = 0.03) was added and uniformly dissolved to obtain a polymer composition.

(Sample 2-1 (containing crosslinking agent))
Example 1 g of the star polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 70 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 100%). (Converted) After adding and stirring sufficiently, 59 mg of LiPF ₆ ([Li] / [EO] = 0.03) was added and uniformly dissolved to obtain a polymer composition.

(Comparative sample 1-1)
Comparative Example Polymer (1) 1 g was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 64 mg of LiPF ₆ ([Li] / [EO] = 0.03) was added uniformly. To obtain a polymer composition.

(Comparative sample 1-2)
Comparative Example Polymer (1) 1 g was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 53 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (in terms of 100% crosslinking rate). ) And sufficiently stirred, 64 mg of LiPF ₆ ([Li] / [EO] = 0.03) was added and dissolved uniformly to obtain a polymer composition.

2. Measurement of conductivity Apply each sample prepared above on a polytetrafluoroethylene plate in an argon atmosphere and heat and vacuum dry (25 ° C x 0.5 hours, 70 ° C x 4 hours) to measure uniform conductivity. An evaluation film was obtained (film thickness 100 μm). The obtained evaluation film was sandwiched between platinum plates, and ion conductivity was measured by complex impedance analysis using an impedance analyzer (Solartron-1260 type) having a frequency of 5 to 10 MHz.

3. Results The results are shown in Table 1 and FIG.

  As is clear from Table 1 and FIG. 1, the comparative sample also shows good ionic conductivity, and is a material useful as an adhesive, a binder for electrode preparation, and a solid electrolyte, but contains the star polymer of the present invention. Regardless of cross-linking and non-cross-linking, the material showed better ionic conductivity, and was found to be a very useful material as an adhesive, a binder for electrode preparation, and a solid electrolyte.

[Evaluation of film strength]
1. Preparation of polymer film for measurement (Sample 1-1)
Example A polymer composition prepared by dissolving 1 g of star polymer (1) in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g) was applied on a polytetrafluoroethylene plate in an argon atmosphere and heated. Vacuum drying (25 ° C. × 0.5 hours, 65 ° C. × 4 hours) gave a polymer film (film thickness 100 μm).

(Sample 1-2 (containing crosslinking agent))
Example 1 g of star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 40 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (in terms of 100% crosslinking rate). ) The added and dissolved polymer composition was applied onto a polytetrafluoroethylene plate in an argon atmosphere, and heated and vacuum dried (25 ° C. × 0.5 hours, 65 ° C. × 4 hours) to obtain a polymer film. (Film thickness 100 μm).

(Sample 2-1)
Example A polymer composition prepared by dissolving 1 g of star polymer (2) in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g) was applied onto a polytetrafluoroethylene plate under an argon atmosphere. Heat drying under vacuum (25 ° C. × 0.5 hours, 70 ° C. × 4 hours) gave a polymer film (film thickness 100 μm).

(Sample 2-2 (containing crosslinking agent))
Example 1 g of the star polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 70 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 100%). Conversion) The polymer composition added and dissolved is applied on a polytetrafluoroethylene plate in an argon atmosphere, and heated and vacuum dried (25 ° C. × 0.5 hours, 70 ° C. × 4 hours) to form a polymer film. Obtained (film thickness 100 μm).

(Comparative sample 2-1)
A polymer composition prepared by dissolving 1 g of Comparative Example Polymer (2) in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g) was applied on a polytetrafluoroethylene plate in an argon atmosphere and heated. The polymer film was obtained by vacuum-drying (25 degreeC x 0.5 hour, 70 degreeC x 4 hours) (film thickness of 100 micrometers).

(Comparative sample 2-2 (containing a crosslinking agent))
Comparative Example Polymer (2) 1 g was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 46 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (in terms of 100% crosslinking rate). ) And dissolved to obtain a polymer composition. The obtained polymer composition was applied onto a polytetrafluoroethylene plate in an argon atmosphere, and heated and vacuum dried (25 ° C. × 0.5 hours, 70 ° C. × 4 hours) to obtain a polymer film (film) Thickness 100 μm).

2. Measurement of film strength Each of the obtained polymer films was cut into strips having a width of 1 cm and a length of 3 cm to obtain test specimens for evaluation. Set both ends of the test piece 5mm on a tension jig of Autograph (manufactured by Shimadzu Corporation), measure at a pulling rate of 20mm / min at 25 ° C, and determine the stress (MPa) -elongation (%) curve from the measurement results. Asked.

3. Results Table 2 shows the maximum stress and elongation at break of each test piece. A stress-elongation curve is shown in FIG.

  As is clear from Table 2 and FIG. 2, the comparative sample also shows good strength and flexibility, and is a material useful as an adhesive, a binder for electrode preparation, and a solid electrolyte, but contains the star polymer of the present invention. Compared with the comparative sample, the material exhibits excellent film physical properties that are stronger and more flexible, and is found to be a very useful material as an adhesive, a binder, and a solid electrolyte.

[Evaluation of bonding (binding) strength]
1. Sample preparation (Sample 1-1)
Example 1 g of the star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g) to obtain a polymer composition.

(Sample 1-2)
Example 1 g of star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 20 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 50%). Conversion) was added and sufficiently stirred to obtain a polymer composition.
(Sample 1-3)
The amount of the crosslinking agent (TDI) was increased, and the same operation as in Sample 1-2 preparation was performed to obtain a polymer composition in terms of a crosslinking rate of 100%.

(Sample 1-4)
Example 1 g of star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 40 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 100%). (Conversion) After adding and sufficiently stirring, 56 mg of LiPF ₆ ([Li] / [EO] = 0.03) was added and uniformly dissolved to obtain a polymer composition.

(Sample 2-1)
Example 1 g of star polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g) to obtain a polymer composition.

(Sample 2-2)
Example 1 g of the star polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 35 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 50%). Conversion) was added and sufficiently stirred to obtain a polymer composition.

(Sample 2-3)
The amount of the crosslinking agent (TDI) was increased, and the same operation as in the preparation of Sample 2-2 was performed to obtain a polymer composition in terms of a crosslinking rate of 100%.

(Sample 2-4)
Example 1 g of the star polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 70 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 100%). (Conversion) After addition and stirring sufficiently, 59 mg of LiPF ₆ ([Li] / [EO] = 0.03) was further added and uniformly dissolved to obtain a polymer composition.

(Comparative sample)
Polyvinylidene fluoride (hereinafter abbreviated as “PVDF”) was prepared as a polymer of the comparative example (Comparative Sample 3-1). Further, 0.3 g of PVDF was dissolved in 4.7 g of NMP solution, and 21 mg of LiPF ₆ was further added and uniformly dissolved to obtain a polymer composition (Comparative Sample 3-2).

2. Measurement of Adhesion (Binding) Strength 2-1 Preparation of Specimen An aluminum plate (100 mm × 25 mm × 1.0 mm) was prepared, and the polymer composition solution was applied to one end portion (12.5 mm × 25 mm). Separately, a polyethylene porous film (100 mm × 25 mm × 0.02 mm) is prepared, and one end portion (12.5 mm × 25 mm) is overlapped with the portion to which the binder of the aluminum plate is applied. Pasted together. Next, it was heated and vacuum-dried (25 ° C. × 0.5 hours, 65 ° C. × 4 hours) to prepare a binding test body.

2-2 Strength measurement Both ends of the obtained binding test specimen were set in an autograph (manufactured by Shimadzu Corporation), and a tensile test was performed at 25 ° C. The tensile test speed was 10 mm / min. The tensile test was performed based on JISK6850: 1999. The breaking stress (MPa) was calculated from the result of the tensile test.

3. Results The measurement results are shown in Table 3.

  From the results of Table 3, the material containing the star polymer of the present invention is a material that exhibits a high breaking stress and a good adhesive (binding) strength as compared with a comparative sample containing polyvinylidene fluoride. all right.

[Solvent resistance test]
1. Sample preparation (Sample 1-1)
Example 1 g of the star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g) to obtain a polymer composition.

(Sample 1-2)
Example 1 g of star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 20 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 50%). Conversion) was added and sufficiently stirred to obtain a polymer composition.

(Sample 1-3)
The amount of the crosslinking agent (TDI) was increased, and the same operation as in Sample 1-2 preparation was performed to obtain a polymer composition in terms of a crosslinking rate of 100%.

(Sample 1-4)
Example 1 g of star polymer (1) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 40 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 100%). (Conversion) After adding and sufficiently stirring, 56 mg of LiPF ₆ ([Li] / [EO] = 0.03) was added and uniformly dissolved to obtain a polymer composition.

(Sample 2-1)
Example 1 g of star polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g) to obtain a polymer composition.

(Sample 2-2)
Example 1 g of the star polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 35 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 50%). Conversion) was added and sufficiently stirred to obtain a polymer composition.

(Sample 2-3)
The amount of the crosslinking agent (TDI) was increased, and the same operation as in the preparation of Sample 2-2 was performed to obtain a polymer composition in terms of a crosslinking rate of 100%.

(Sample 2-4)
Example 1 g of the star polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 70 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (crosslinking rate: 100%). (Conversion) After addition and stirring sufficiently, 59 mg of LiPF ₆ ([Li] / [EO] = 0.03) was further added and uniformly dissolved to obtain a polymer composition.

(Comparative sample 2-1)
1 g of Comparative Example polymer (2) was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g) to obtain a polymer composition.

(Comparative Sample 2-2)
Comparative Example Polymer (2) 1 g was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 23 mg of TDI (tolylene-2,4-diisocyanate) was used as a cross-linking agent (in terms of cross-linking rate of 50%). ) And dissolved to obtain a polymer composition.

(Comparative sample 2-3)
The amount of the crosslinking agent (TDI) was increased, and the same operation as the preparation of Comparative Sample 2-2 was performed to obtain a polymer composition in terms of a crosslinking rate of 100%.

(Comparative sample 2-4)
Comparative Example Polymer (2) 1 g was dissolved in 9 g of a mixed solvent of THF and acetonitrile (THF / acetonitrile = 4 g / 5 g), and 46 mg of TDI (tolylene-2,4-diisocyanate) was used as a crosslinking agent (in terms of 100% crosslinking rate). ) And sufficiently stirred, 56 mg of LiPF ₆ ([Li] / [EO] = 0.03) was further added and uniformly dissolved to obtain a polymer composition.

(Comparative Sample 3-1)
Polyvinylidene fluoride (hereinafter abbreviated as “PVDF”) was prepared.

2. Solvent Resistance Test A graphite electrode was prepared, and a polymer composition was applied thereon. Separately, a polyethylene porous film (20 mm × 20 mm × 0.02 mm) was prepared, and was laminated and pasted on the portion where the polymer composition solution of the graphite electrode was applied. Next, it was heated and vacuum-dried (25 ° C. × 0.5 hours, 65 ° C. × 4 hours) to prepare a test specimen.

A mixed solvent of ethylene carbonate / diethylene carbonate = 3/7 (volume ratio) having a lithium (LiPF ₆ ) salt concentration of 1M was prepared, and the test specimen was immersed in 20 ml of the mixed solvent to improve the solvent resistance of the polymer. Observed. The test conditions are standing at room temperature × 12 h, 60 ° C. × 2 h, 80 ° C. × 2 h, 100 ° C. × 2 h.

3. Results As a result of measurement, ◎ indicates that the polyethylene porous film is well adhered in the mixed solvent, ◯ indicates that the polyethylene film is partially peeled, △ indicates that the film is peeled off by about 50%, and is completely made of polyethylene. The case where the film was peeled off was evaluated as x.

  From the results of the above table, it can be seen that all the systems according to the examples hold the polyethylene porous film without peeling off even in the mixed solution and show good solvent resistance as compared with the comparative sample, and performance comparable to PVDF. It was found that Furthermore, it was found that the star polymer contained in the present invention satisfactorily adheres and retains without removing the polyethylene porous film without performing TDI crosslinking.

It is a graph which shows the result of electrical conductivity measurement. It is a graph which shows the stress-elongation curve of a polymer film.

Claims (3)

An adhesive comprising: a star polymer having a polymer chain containing a random repeating structure (C) composed of a repeating unit (A) and a repeating unit (B) as an arm part.

(In the repeating unit (A), R _{100 to} R ₃₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₀₀ and R ₃₀₀ may combine to form a ring. R _400a and R _400b each independently represent a hydrogen atom or a methyl group, R ₅₀₀ represents a hydrocarbon group, an acyl group, or a silyl group, and s ₁ represents an integer of 1 to 100 And when s ₁ is 2 or more, the groups represented by the formula: —CH (R _400a ) —CH (R _400b ) —O— may be the same or different.

(In the repeating unit (B), R ₁₁₀ and R ₃₁₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₁₀ and R ₃₁₀ may combine to form a ring. Well, R ₂₁₀ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a hydrocarbon oxy group, a carboxyl group, an acid anhydride group, an amino group, an ester group, or a hydroxyl group, a carboxyl group, an epoxy group, an acid. Represents an organic group having at least one functional group selected from the group consisting of an anhydride group and an amino group, and R ₄₁₀ is selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group. Represents an organic group having at least one functional group.) A binder for electrode preparation, comprising a star polymer having a polymer chain containing a random repeating structure (C) composed of a repeating unit (A) and a repeating unit (B) as an arm part.

(In the repeating unit (A), R _{100 to} R ₃₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₀₀ and R ₃₀₀ may combine to form a ring. R _400a and R _400b each independently represent a hydrogen atom or a methyl group, R ₅₀₀ represents a hydrocarbon group, an acyl group, or a silyl group, and s ₁ represents an integer of 1 to 100 And when s ₁ is 2 or more, the groups represented by the formula: —CH (R _400a ) —CH (R _400b ) —O— may be the same or different.

(In the repeating unit (B), R ₁₁₀ and R ₃₁₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₁₀ and R ₃₁₀ may combine to form a ring. Well, R ₂₁₀ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a hydrocarbon oxy group, a carboxyl group, an acid anhydride group, an amino group, an ester group, or a hydroxyl group, a carboxyl group, an epoxy group, an acid. Represents an organic group having at least one functional group selected from the group consisting of an anhydride group and an amino group, and R ₄₁₀ is selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group. Represents an organic group having at least one functional group.) A composition for solid electrolyte, comprising a star polymer having a polymer chain containing a random repeating structure (C) comprising a repeating unit (A) and a repeating unit (B) as an arm part.

(In the repeating unit (A), R _{100 to} R ₃₀₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₀₀ and R ₃₀₀ may combine to form a ring. R _400a and R _400b each independently represent a hydrogen atom or a methyl group, R ₅₀₀ represents a hydrocarbon group, an acyl group, or a silyl group, and s ₁ represents an integer of 1 to 100 And when s ₁ is 2 or more, the groups represented by the formula: —CH (R _400a ) —CH (R _400b ) —O— may be the same or different.

(In the repeating unit (B), R ₁₁₀ and R ₃₁₀ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₁₁₀ and R ₃₁₀ may combine to form a ring. Well, R ₂₁₀ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a hydrocarbon oxy group, a carboxyl group, an acid anhydride group, an amino group, an ester group, or a hydroxyl group, a carboxyl group, an epoxy group, an acid. Represents an organic group having at least one functional group selected from the group consisting of an anhydride group and an amino group, and R ₄₁₀ is selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group. Represents an organic group having at least one functional group.)