JP2000306605A - High polymer solid electrolyte for hardening active energy line and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid electrolyte forming material which dispenses with using a photopolymerization agent, which handens at practical light strength and light radiation amount and is liquid at ordinary temperature and provide such a hardening method by providing a (poly)alkylene glycol derivative with at least one maleimide group in its electrolyte and a molecule. SOLUTION: This is a compound represented by a formula, In the formula, m and n are respectively independently integers of 0-6, and m+n is an integer of 1-6. R11 and R12 are respectively independently hydrocarbon linkages containing an aliphatic group and/or an aromatic group. G1 and G2 are respectively independently ether linkage, ester linkage, urethane linkage, or carbonate linkage. R2 is an ether linkage chain or a (poly)ether residue with 44-10000 average molecular weight where straight chain or branch alkylene groups are coupled by the ether linkage. It is preferable that (poly)alkylene glycol derivative has two or more polymeric functional groups in molecule, and at least one of the polymeric functional groups is a maleimide group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid polymer electrolyte or a gel polymer solid electrolyte useful for lithium ion batteries, lithium metal batteries, electric double layer capacitors, electrochromic devices, solar cells, and the like. , An active energy ray-curable polymer solid electrolyte forming material containing a specific maleimide derivative which is cured by a practical irradiation amount of ultraviolet light in the absence of a photopolymerization initiator; The present invention relates to a polymer solid electrolyte made of a material and a method for curing the active energy ray-curable polymer solid electrolyte forming material.

[0002]

2. Description of the Related Art Conventionally, liquid electrolytes have been used for electrochemical devices such as primary batteries, secondary batteries, capacitors, electrochromic displays, and wet solar cells. However, there is a problem that a liquid electrolyte leaks and lacks long-term reliability. In addition, all-solidification is being studied due to demands such as downsizing, and solid electrolytes are attracting attention as a new ionic conductor instead of conventional electrolyte solutions, and their application to all-solid primary batteries, secondary batteries, and electric double layer capacitors is flourishing. (JP-A-55-98480, etc.).

On the other hand, Japanese Patent Application Laid-Open No. 55-35420 and the like propose a gel polymer solid electrolyte in which an electrolyte solution is confined in a polymer matrix for the purpose of improving ionic conductivity. As a method for producing these, JP-A-63-94501, JP-A-63-94563 and JP-A-5-109310 disclose a method of mixing and dissolving an electrolyte in a polymer, a radical polymerizable initiator. There is disclosed a method of adding an electrolyte or an electrolyte solution to a polymerizable monomer or oligomer containing, and thermally polymerizing, a method of adding an electrolyte or an electrolyte solution to a polymerizable monomer or oligomer containing a photoradical polymerization initiator, and performing ultraviolet polymerization. ing.

[0004] However, the solid polymer electrolyte has problems such as the charge / discharge capacity being rapidly reduced when charge / discharge is repeated due to the polymerization initiator. Japanese Patent Application Laid-Open No. 10-158418 discloses a method for removing a residual polymerization initiator by heat treatment or ultrasonic treatment. However, this method involves subjecting the polymer solid electrolyte once polymerized to ultrasonic cleaning or heat treatment at a temperature of 100 to 300 ° C., and has a problem of low productivity.

[0005] When a gel polymer solid electrolyte is formed, a polymerizable composition, an electrolyte solution, and a composition containing a heat or photopolymerization initiator are generally polymerized by heat or active energy rays to crosslink. A gel-like polymer solid electrolyte that forms a network (JP-A-10-251318, etc.)
In general, a battery is constructed by sandwiching it between two types of electrodes or forming it on one of the electrodes, and after forming a crosslinked network by polymerizing with heat or active energy rays, It is difficult to insert a step of removing the remaining polymerization initiator by the method disclosed in JP-A-158418.

On the other hand, as a method for forming a polymer solid electrolyte, a method without using a polymerization initiator is disclosed in
No. 0885, JP-A-5-326019, JP-A-9-17449, JP-A-9-17450, JP-A-10-112321 and the like, polymerization and crosslinking by irradiation with an electron beam. A method for forming an electrolyte by the method is disclosed. According to electron beam irradiation, polymerization and cross-linking of the polymer solid electrolyte forming material can be performed without using heat or a photoinitiator, and the above-mentioned drawbacks caused by the initiator can be solved. ,
There are problems such as restrictions on manufacturing conditions and securing of operational safety.

[0007]

An electrolyte or an electrolyte solution is added to a conventionally known polymerizable monomer or oligomer containing a thermal or photoradical initiator to obtain a solid electrolyte by thermal polymerization or ultraviolet polymerization. No.
JP-A-63-94501, JP-A-63-9456
No. 3, JP-A-5-109310 and the like have a problem that the charge / discharge capacity is rapidly reduced at the time of repeated charge / discharge due to the polymerization initiator and the like.

In the method disclosed in JP-A-10-158418 for removing the remaining polymerization initiator by performing a heat treatment or an ultrasonic treatment after the polymerization, the productivity is poor, or the gel-like polymer is poor. There is a problem that application to a solid electrolyte is difficult.

On the other hand, as a method for forming a polymer solid electrolyte without using a polymerization initiator, JP-A-5-290885, JP-A-5-326019, and JP-A-9-174.
No. 49, JP-A-9-17450, JP-A-10
JP-A-112321 and the like propose a method of polymerizing and crosslinking by irradiation with an electron beam. However, although the above-mentioned drawbacks caused by the initiator can be solved, when an electron beam is used, there are restrictions on manufacturing conditions and work. There is a new problem of ensuring the above safety.

[0010] The problem to be solved by the present invention is to use a photopolymerization initiator which causes effluent from a cured coating film,
Another object of the present invention is to provide an active energy ray-curable solid electrolyte-forming material which is liquid at ordinary temperature and which can be cured with a practical light intensity and light irradiation amount, and an active energy ray curing method.

[0011]

The inventors of the present invention disclose in European Patent Publication No. 878,482 that a maleimide derivative having a specific structure can be converted to a UV light having a practical light intensity without using a general-purpose photoinitiator. , And copolymerization with (meth) acrylate or vinyl ether.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the use of a specific maleimide derivative-maleimide derivative having a (poly) oxyalkylene bond-provides a general-purpose photoinitiator with charge / discharge characteristics. The present inventors have found that a solid electrolyte exhibiting an ion conductivity of a practical level superior to that of a solid electrolyte system obtained by polymerizing the polymer can be formed, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the present invention is characterized in that it comprises (I) an (1) electrolyte and (2) a (poly) alkylene glycol derivative having at least one maleimide group in a molecule. To provide a solid polymer electrolyte forming material.

In order to solve the above problems, the present invention provides (II) a (poly) alkylene glycol derivative having at least one maleimide group in a molecule having two or more polymerizable functional groups in the molecule ( The polymer solid electrolyte forming material according to the above item (I), comprising a (poly) alkylene glycol derivative, wherein the (poly) alkylene glycol derivative has at least one of a polymerizable functional group being a maleimide group.

In order to solve the above problems, the present invention provides (III) (1) an electrolyte, (2) a (poly) alkylene glycol derivative having one maleimide group in the molecule, and
(3) The above-mentioned (I), which comprises a (poly) alkylene glycol derivative having two or more polymerizable functional groups in the molecule, wherein at least one of the polymerizable functional groups is a maleimide group. The present invention provides a polymer solid electrolyte-forming material according to the above item.

In order to solve the above-mentioned problems, the present invention provides (IV) a (poly) alkylene glycol derivative having at least one maleimide group in a molecule represented by the general formula (1):

[0017]

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(Wherein m and n each independently represent 0-6
Where m + n represents an integer of 1 to 6. R
₁₁ and R ₁₂ each independently represent a hydrocarbon bond containing an aliphatic group and / or an aromatic group. G ₁ and G ₂ each independently represent an ether bond, an ester bond, a urethane bond, or a carbonate bond. R ₂ has an average molecular weight of 4 in which a linear or branched alkylene group is connected by an ether bond.
Represents 4 to 10,000 (poly) ether linking chains or (poly) ether residues. The present invention provides the material for forming a solid polymer electrolyte according to the above (I), (II) or (III), which is a compound represented by the formula (1).

In order to solve the above-mentioned problems, the present invention provides a compound (V) containing a compound other than the (poly) alkylene glycol derivative having a maleimide group, the compound having a copolymerizability with the maleimide group. I), (I
A material for forming a solid polymer electrolyte according to the item (I), (III) or (IV).

In order to solve the above-mentioned problems, the present invention provides (VI) a compound having copolymerizability with a maleimide group, wherein the (meth) acrylic acid ester having a (poly) alkylene glycol chain and the (poly) alkylene glycol chain 1 selected from the group consisting of vinyl ether compounds having
The polymer solid electrolyte forming material according to the above (V), which is a compound of at least one kind, is provided.

In order to solve the above-mentioned problems, the present invention provides (VII) an electrolyte containing at least one electrolyte selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. (I)-(VI)
13. A material for forming a solid polymer electrolyte according to any one of the above items.

In order to solve the above-mentioned problems, the present invention provides the above-mentioned (I), which further comprises (VIII) a non-aqueous organic solvent.
-The solid polymer electrolyte forming material according to any one of the items (VII) to (VII).

In order to solve the above-mentioned problems, the present invention provides (IX) the above-mentioned (VIII), wherein the non-aqueous organic solvent is at least one non-aqueous solvent selected from the group consisting of carbonate, lactone and ether. The solid polymer electrolyte forming material according to the above is provided.

Furthermore, the present invention provides a polymer solid comprising a cured product of the polymer solid electrolyte forming material according to any one of the above (I) to (X). Provide electrolyte.

In order to solve the above-mentioned problems, the present invention further provides (XI) a polymerized solid electrolyte forming material according to any one of the above (I) to (IX), Provided is a method for curing a polymer solid electrolyte forming material in which the polymer solid electrolyte forming material is polymerized by irradiating an active energy ray in the absence.

Further, the present invention provides the curing method according to the above item (XI), wherein (XII) the active energy ray is ultraviolet rays.

[0027]

DETAILED DESCRIPTION OF THE INVENTION The (poly) alkylene glycol derivative having at least one maleimide group in the molecule used for the polymer solid electrolyte forming material of the present invention is a straight-chain alkylene glycol having 1 to 6 carbon atoms in the molecule. It refers to a compound in which one or both of a group and / or a branched alkylene group bonded by an ether bond or a compound containing a repeating unit thereof and a compound having at least one maleimide group are chemically bonded. Among such derivatives, (poly) alkylene glycol derivatives having two or more polymerizable functional groups in the molecule and at least one of the polymerizable functional groups being a maleimide group are preferable, and particularly, the above-mentioned general formula (1) (Poly) alkylene glycol derivatives having a maleimide group represented by

The polymerizable functional group other than the maleimide group in the (poly) alkylene glycol derivative having two or more polymerizable functional groups in the molecule and at least one of the polymerizable functional groups is a maleimide group includes, for example, ( Examples thereof include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and a vinyl ether group.

In the compound represented by the above general formula (1) which is preferably used as a (poly) alkylene glycol derivative having at least one maleimide group in the molecule, m and n each independently represent an integer of 0 to 6. Where m + n is an integer of 1 to 6. R ₁₁ and R
Each ₁₂ independently represents a hydrocarbon bond having an aliphatic group and / or an aromatic group, and is preferably an aliphatic group. Here, the aliphatic group may be linear or branched, and may have a branched ether group or the like.

Examples of such R ₁₁ and R ₁₂ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group,
Linear alkylene groups such as decamethylene group, undecamethylene group and dodecamethylene group; 1-methylethylene group,
1-methyl-trimethylene group, 2-methyl-trimethylene group, 1-methyl-tetramethylene group, 2-methyl-tetramethylene group, 1-methyl-pentamethylene group, 2-
Alkylene group having a branched alkyl group such as methyl-pentamethylene group, 3-methyl-pentamethylene group, neopentyl group; cycloalkylene group such as cyclopentylene group and cyclohexylene group; benzylene group, 2,2-diphenyl-trimethylene Group, 1-phenyl-ethylene group, 1-phenyl-tetraethylene group, 2-phenyl-
An arylalkylene group having an aryl group in a main chain or side chain such as a tetraethylene group; a main chain such as a cyclohexylmethylene group, 1-cyclohexyl-ethylene group, 1-cyclohexyl-tetraethylene group, or 2-cyclohexyl-tetraethylene group; A cycloalkyl-alkylene group having a cycloalkyl group in a side chain; and the like, but is not limited thereto.

In the compound represented by the general formula (1), G ₁ and G ₂ each independently represent an ether bond, an ester bond, a urethane bond, or a carbonate bond.
R ₂ represents a (poly) ether-linked chain or a (poly) ether residue having an average molecular weight of 44 to 10,000 in which a linear or branched alkylene group is connected by an ether bond.

As such R ₂ , for example, (a)
An average molecular weight of 44 to 10.0 having one or a repeating unit in which a linear alkylene group and / or a branched alkylene group having 1 to 6 carbon atoms are bonded by an ether bond.
A connecting chain composed of a (poly) ether (poly) ol residue of 00: (b) one in which a linear alkylene group and / or a branched alkylene group having 1 to 6 carbon atoms are bonded by an ether bond or (Poly) ether (poly) ol having an average molecular weight of 44 to 10,000 and having these repeating units, is a linked chain in which two to six branched ether groups are linked:
(C) a linear alkylene group having 1 to 6 carbon atoms and / or a branched alkylene group having one or a repeating unit thereof linked by an ether bond or an average molecular weight of 44 to 1;
20,000 (poly) ether (poly) ol groups
Examples include, but are not limited to, a linking chain linked by a 6-branched ester bond.

Examples of the (poly) ether (poly) ol constituting the linking chain (a) include ethylene glycol, propanediol, propylene glycol,
Alkylene glycols such as -methyl-1,3-diol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol; Monoalkyl ethers and monocarboxylic acid esters; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol; these monoalkyl ethers and monocarboxylic acid esters; No.

Examples of the linking chain in which the (poly) ether (poly) ol constituting the linking chain (b) is linked by a 2- to 6-branched ether group include ethylene glycol and
Ethylene oxide-modified alkylene glycols such as propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol; Modified propylene oxide, modified butylene oxide, modified tetrahydrofuran, and the like.

Further, the (poly) ether (poly) ol constituting the connecting chain (a) or (b) includes, for example, a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, Hydrocarbon polyols such as copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, and polytetramethylene hexaglyceryl ether (tetrahydrofuran modified hexaglycerin) Examples include, but are not limited to, polyvalent hydroxyl group compounds.

Examples of the connecting chain in which the (poly) ether (poly) ol group constituting the connecting chain (c) is connected by a 2- to 6-branched ester bond include, for example, (1) succinic acid, adipic acid, Phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid, isophthalic acid, itaconic acid,
Adipic acid, sebacic acid, maleic acid, trimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, citric acid, polycarboxylic acid such as tetrahydrofurantetracarboxylic acid, cyclohexanetricarboxylic acid, and (2) the above ( Examples include esterified products with (poly) ether (poly) ol shown in a) or (b), but are not limited thereto.

The maleimide derivative represented by the general formula (1) used in the polymer solid electrolyte forming material of the present invention is:
For example, (d) a maleimide compound (d-1) having a carboxyl group and a compound (d
-2) or from (e) a maleimide compound (e-1) having a hydroxyl group and a compound (e-2) that reacts with a hydroxyl group using a known technique.

The maleimide compound (d-1) having a carboxyl group can be prepared, for example, by reacting with a reaction formula

[0039]

Embedded image

As shown in the above, the compound can be synthesized from maleic anhydride and a primary aminocarboxylic acid using a known technique (for example, European Patent Publication No. 878,482).

Further, the maleimide compound (e-1) having a hydroxyl group can be prepared, for example, by the following reaction scheme.

[0042]

Embedded image

As shown in the above, from maleimide and formaldehyde, or from the reaction formula

[0044]

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As shown in the above, the compound can be synthesized from maleic anhydride and a primary amino alcohol using a known technique (for example, European Patent Publication No. 878,482).

The primary aminocarboxylic acid used in the above reaction includes, for example, asparagine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, tryptophan, threonine, valine, phenylalanine, homophenylalanine, α-methyl-phenylalanine , Lysine, leucine, cycloleucine, 3-
Aminopropionic acid, α-aminobutyric acid, 4-aminobutyric acid, aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 2-aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-amino Caprylic acid,
2-aminononanoic acid, 4-aminononanoic acid, 9-aminononanoic acid, 2-aminocapric acid, 9-aminocapric acid, 10-aminocapric acid, 2-aminoundecanoic acid, 10-aminoundecanoic acid, 11-aminoundecanoic acid 2-aminolauric acid, 11-aminolauric acid, 12-aminolauric acid, 2-aminotridecanoic acid, 13-aminotridecanoic acid, 2-aminomistinic acid, 14-aminomistinic acid, 2-aminopentadecanoic acid, 15-amino Pentadecanoic acid, 2-aminopalmitic acid, 16-aminopalmitic acid, 2-aminoheptadecanoic acid, 17-aminoheptadecanoic acid, 2-aminostearic acid, 18-aminostearic acid, 2-aminoeicosanonic acid, 20 -Aminoeicosanonic acid, aminocyclohexanecarboxylic acid, Examples include nomethylcyclohexanecarboxylic acid, 2-amino-3-propionic acid, 3-amino-3-phenylpropionic acid, and the like, but are not limited thereto, and any primary aminocarboxylic acid may be used. Can also be used. Also, pyrrolidone, δ-
Lactams such as valerolactam and ε-caprolactam can also be used.

The primary amino alcohol used in the above reaction includes, for example, 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-
Amino-3-phenyl-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-
Amino-3-methyl-1-butanol, 2-amino-4
-Methylthio-1-butanol, 2-amino-1-pentanol, 5-amino-1-pentanol, (1-aminocyclopentane) methanol, 6-amino-1-hexanol, 2-amino-1-hexanol, 7-amino-1-heptanol, 2- (2-aminoethoxy) ethanol, N- (2-aminoethyl) ethanolamine,
4-amino-1-piperazineethanol, 2-amino-
1-phenylethanol, 2-amino-3-phenyl-
Examples thereof include 1-propanol, 1-aminomethyl-1-cyclohexanol, and aminotrimethylcyclohexanol, but are not limited thereto, and any primary amino alcohol can be used.

Compounds which react with carboxyl groups (d-
As 2), for example, a linear alkylene group and / or a branched alkylene group has an average molecular weight of 44 to 1 having one or a repeating unit thereof bonded by an ether bond.
And 000 1-6 functional polyols or polyepoxides.

The compound (e-
As 2), for example, a linear alkylene group and / or a branched alkylene group has an average molecular weight of 44 to 1 having one or a repeating unit thereof bonded by an ether bond.
Examples of the compound include 000 1-6 functional polyols or polyepoxides whose terminals are a hydroxyl group, a carboxyl group, an ester group, an isocyanate group, a carbonate group, a halogen atom, or the like.

A maleimide compound (d-1) having a carboxyl group and a compound (d-
The reaction with the polyol which is one of 2) is not particularly limited, but may be performed by a known technique (for example, European Patent No. 878,
482) can be used to synthesize a maleimide derivative represented by the general formula (1).

A maleimide compound (d-1) having a carboxyl group and a compound (d-
The reaction with polyepoxide, which is one of 2), is not particularly limited, but may be carried out by a known technique (for example, European Patent No. 87
No. 8,482), a maleimide derivative represented by the general formula (1) can be synthesized.

A maleimide compound (e-1) having a hydroxyl group and a compound (e-
The reaction with 2) is not particularly limited, but the maleimide derivative represented by the general formula (1) can be synthesized by using a known technique (for example, European Patent Publication No. 878,482).

Compounds which react with carboxyl groups (d-
Examples of the polyol used as 2) include ethylene glycol, propanediol, propylene glycol, butanediol, butylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, Alkylene glycols such as pentaerythritol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol; ethylene glycol, propanediol, propylene glycol, butanediol, butylene glycol, hexanediol, neopentyl glycol , Glycerin, trimethylolpropane, pentaerythritol, Modified ethylene oxide, propylene oxide, modified butylene oxide, tetrahydrofuran, modified ε-caprolactone, modified γ-butyrolactone, modified δ-valerolactone of alkylene glycols such as glycerin, ditrimethylolpropane, dipentaerythritol Product, methyl valerolactone modified product;

Copolymers such as copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol Hydrogen-based polyols; polycarbonate polyols; acrylic polyols; polyvalent hydroxyl compounds such as polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin); mono- and polyvalent terminal ether groups of the above-mentioned polyvalent hydroxyl-containing compounds A hydroxyl group-containing compound; and the like, but is not limited thereto. If it is a (poly) ether (poly) ol having 1 to 6 hydroxyl groups in one molecule, Shift can also be used.

Compounds that react with carboxyl groups (d-
As the polyepoxide used as 2), for example,
Glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol and the like, and polyglycidyl ethers of alkylene oxide modified products thereof; trimethylolpropane, trimethylol Ethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4
Aliphatic polyhydric alcohols such as -butanediol and 1,6-hexanediol; and glycidyl ethers of alkylene oxide-modified products thereof.

The compound (e-
The terminal used as 2) is a hydroxyl group, a carboxyl group, an ester group, an isocyanate group, a carbonate group, or
Examples of the compound such as a halogen atom include (poly) ether (poly) ol, condensates thereof with di-hexa-carboxylic acid or ester, condensates with di-polyisocyanate, phosgene, etc. And carbonates and chlorocarbonates, terminal halides, and the like obtained by condensation with the above.

Examples of the dicarboxylic acid to hexacarboxylic acid include fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid, succinic acid, adipic acid, hexahydrophthalic acid, tetrahydrophthalic acid, Examples include, but are not limited to, dicarboxylic acids such as pyromellitic acid.

Examples of the diisocyanate to polyisocyanate include aliphatic diisocyanate compounds such as methylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, and dimer diisocyanate; Isocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4′-diphenylmethane diisocyanate,
Aromatic diisocyanate compounds such as 1,5-naphthylene diisocyanate and 3,3′-dimethylbiphenyl-4,4′-diisocyanate; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 ( Or 2,
6) diisocyanates, alicyclic diisocyanates such as 1,3- (isocyanatomethylene) cyclohexane,
And the like, but are not limited thereto.

Examples of the compound used for the esterification with (poly) ether (poly) ol include diethyl carbonate, dipropyl carbonate, phosgene and the like. In addition, polycarbonate can be obtained by alternate polymerization of epoxide and carbon dioxide, but is not limited thereto.

The maleimide derivative represented by the general formula (1) used in the polymer solid electrolyte forming material of the present invention can be obtained by the above-described production method. The production method of the compound used in the present invention is as follows. It is not limited.

Further, a compound other than the (poly) alkylene glycol derivative having a maleimide group and having a copolymerizability with the maleimide group can be used in combination with the polymer solid electrolyte forming material of the present invention.

The compound having copolymerizability with such a maleimide group is, specifically, a compound having various unsaturated double bonds. For example, a compound having at least one maleimide group in a molecule (poly) Maleimide derivatives other than alkylene glycol derivatives, (meth) acryloyl derivatives, (meth) acrylamide derivatives, vinyl ether derivatives, vinyl carboxylate derivatives, styrene derivatives, unsaturated polyesters, and the like.

Examples of the maleimide derivative other than the (poly) alkylene glycol derivative having at least one maleimide group in the molecule include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
Nn-butylmaleimide, N-tert-butylmaleimide, N-pentylmaleimide, N-hexylmaleimide, N-laurylmaleimide, 2-maleimidoethyl-ethylcarbonate, 2-maleimidoethyl-isopropylcarbonate, N-ethyl- ( Monofunctional aliphatic maleimides such as 2-maleimidoethyl) carbamate;
Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N-phenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, N- (2,6-diethylphenyl) maleimide;
Aromatic monofunctional maleimides such as -2-chlorophenylmaleimide, N- (4-hydroxyphenyl) maleimide, N-2-trifluoromethylphenylmaleimide;

N, N'-methylene bismaleimide, N, N
N′-ethylene bismaleimide, N, N′-trimethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N′-dodecamethylene bismaleimide,
Alicyclic bismaleimides such as 1,4-dimaleimidecyclohexane; N, N '-(4,4'-diphenylmethane) bismaleimide, N, N'-(4,4'-diphenyloxy) bismaleimide; N′-p-phenylenebismaleimide, N, N′-m-phenylenebismaleimide, N, N′-2,4-tolylenebismaleimide,
N, N'-2,6-tolylenebismaleimide, N, N '
Aromatic bis such as-[4,4'-bis (3,5-dimethylphenyl) methane] bismaleimide and N, N '-[4,4'-bis (3,5-diethylphenyl) methane] bismaleimide Maleimides, and the like,
It is not limited to these.

Compounds having an acryloyloxy group or a methacryloyloxy group which can be used in combination with the polymer solid electrolyte forming material of the present invention are roughly classified into (A-1); (poly) ester (meth) acrylate, (A- 2); urethane (meth) acrylate, (A-3); epoxy (meth) acrylate, (A-4); (poly) ether (meth) acrylate, (A-5); alkyl (meth) acrylate or alkylene ( (Meth) acrylate, (A-
6); (meth) acrylate having an aromatic ring, (A-
7); (meth) acrylates having an alicyclic structure, and the like, but are not limited thereto. Among these, a (meth) acrylate compound having a (poly) alkylene glycol chain is particularly recommended.

The (poly) ester (meth) acrylate (A-A) which can be used in combination with the polymer solid electrolyte forming material of the present invention.
1) is a general term for (meth) acrylates having one or more ester bonds in the main chain, and urethane (meth) acrylate (A-2) is a (meth) acrylate having one or more urethane bonds in the main chain. Epoxy acrylate (A-3) is a general term for (meth) acrylate obtained by reacting monofunctional or higher epoxide with (meth) acrylic acid, and is a general term for (poly) ether (meth) acrylate (A- 4) is a general term for (meth) acrylates having one or more ether bonds in the main chain, and alkyl (meth) acrylate or alkylene (meth) acrylate (A-5) is a main chain having a straight-chain alkyl, branched Alkyl, a linear alkylene group or a branched alkylene group,
(Meth) acrylate having an aromatic ring (A-6) is a general term for (meth) acrylates which may have a halogen atom and / or a hydroxyl group at the side chain or at the terminal. (Meth) acrylate having an alicyclic structure (A-
7) is used as a general term for a (meth) acrylate having an alicyclic structure which may contain an oxygen atom or a nitrogen atom in a constitutional unit in a main chain or a side chain. Among them, (meth) acrylates having a (poly) alkylene glycol chain are particularly preferable from the viewpoint of ionic conductivity.

Examples of the (poly) ester (meth) acrylate (A-1) include (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol,
Diol components such as (poly) pentanediol, (poly) methylpentanediol, (poly) hexanediol, and maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, itaconic acid Citraconic acid, hetonic acid, hymic acid, chlorendic acid, dimer acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, -Sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid,
5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid,
(Meth) acrylates of polyester polyols composed of polybasic acids such as oxalic acid, malonic acid, glutanic acid, trimellitic acid, and pyromellitic acid; the diol component and the polybasic acid, ε-caprolactone, γ-butyrolactone, δ
And polyfunctional (poly) ester (meth) acrylates such as (meth) acrylate of a cyclic lactone-modified polyester diol comprising valerolactone or methylvalerolactone, but are not limited thereto.

Urethane (meth) acrylate (A-2)
Is a general term for (meth) acrylates obtained by reacting a hydroxy compound (A-2-1) having at least one (meth) acryloyloxy group with an isocyanate compound (A-2-2).

Examples of the hydroxy compound (A-2-1) having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth)
Acrylate or glycidyl (meth) acrylate-
(Meth) acrylic acid adduct, (meth) acrylate compound having a hydroxyl group such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, ring opening of the above-mentioned (meth) acrylate compound having a hydroxyl group and ε-caprolactone Reactants, and the like.

An isocyanate compound (A-2-2), for example, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate,
m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
4,4′-diphenylmethane diisocyanate, 3,
Aromatic diisocyanates such as 3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexyl Aliphatic or alicyclic diisocyanates such as methane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and lysine diisocyanate; polyisocyanates such as one or more burettes of isocyanate monomers or isocyanurates obtained by trimerizing the diisocyanate compound A polyisocyanate obtained by a urethanization reaction of the above isocyanate compound and various polyols (A-2-3).

Examples of the polyol (A-2-3) used for producing the polyisocyanate include (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol and (poly) tetramethylene glycol. (Poly) alkylene glycols; ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol Alkylene glycols such as ethylene oxide-modified, propylene oxide-modified, butylene oxide-modified, tetrahydrofuran-modified, ε-capro Lactone-modified products, .gamma.-butyrolactone modified products, .delta.-valerolactone-modified products, and methyl valerolactone-modified product;

Copolymers such as ethylene oxide and propylene oxide copolymers, propylene glycol and tetrahydrofuran copolymers, ethylene glycol and tetrahydrofuran copolymers, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol Hydrogen-based polyols; aliphatic polyester polyols which are esterification products of aliphatic dicarboxylic acids such as adipic acid and dimer acid with polyols such as neopentyl glycol and methylpentanediol; aromatic dicarboxylic acids such as terephthalic acid Aromatic polyester polyols which are esterification products of phenol and polyols such as neopentyl glycol; polycarbonate polyols; acrylic polyols; Polyhydric hydroxyl compounds such as methylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin); mono- and polyhydric hydroxyl-containing compounds having terminal ether groups of the above-mentioned polyhydric hydroxyl-containing compounds; polyhydric hydroxyl-containing compounds described above, and fumaric acid , Polyphthalic acid-containing compounds obtained by esterification with dicarboxylic acids such as phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid and maleic acid; polyhydric hydroxyl compounds such as glycerin; and fatty acid esters of animals and plants And a polyvalent hydroxyl group-containing compound such as monoglyceride obtained by transesterification with thiol, but are not limited thereto.

The epoxy (meth) acrylate (A-3) which can be used in combination with the polymer solid electrolyte forming material of the present invention comprises:
It is a generic term for (meth) acrylates obtained by reacting an epoxide having more than one functionality with (meth) acrylic acid. Epoxide (A) which is a raw material of epoxy (meth) acrylate
Examples of -3-1) include, for example, epichlorohydrin-modified hydrogenated bisphenol synthesized from (methyl) epichlorohydrin, hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, and ethylene oxide and propylene oxide modified products thereof. Epoxy resin; 3,4-epoxycyclohexylmethyl-3,4-
Epoxy cyclohexane carboxylate, bis-
Alicyclic epoxides such as (3,4-epoxycyclohexyl) adipate; alicyclic epoxy resins such as triglycidyl isocyanurate;

Epichlorohydrin-modified bisphenol type epoxy resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, ethylene oxide and propylene oxide modified products thereof; phenol novolak type epoxy resin; cresol novolak type epoxy resin Epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol, and aromatic epoxides such as phenylglycidyl ether Such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol, etc. (Poly) glycidyl ether of coals; (poly) glycidyl ether of alkylene oxide-modified glycols; trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, (Poly) glycidyl ethers of aliphatic polyhydric alcohols such as 1,6-hexanediol; and alkylene-type epoxides such as (poly) glycidyl ether of alkylene oxide modified products of aliphatic polyhydric alcohols. It is not limited.

The (poly) ether (meth) acrylate (A-A) which can be used in combination with the polymer solid electrolyte forming material of the present invention.
Examples of 4) include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate. ,
Ethyl carbitol (meth) acrylate, 2-methoxy (poly) ethylene glycol (meth) acrylate,
Methoxy (poly) propylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, phenoxy hydroxypropyl (meth) acrylate, phenoxy (poly) ethylene glycol (meth) acrylate, polyethylene glycol Monofunctional (poly) ether (meth) acrylates such as mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate;

Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate; ethylene oxide Propylene oxide copolymer, propylene glycol and tetrahydrofuran copolymer, ethylene glycol and tetrahydrofuran copolymer, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrocarbon polyols such as hydrogenated polybutadiene glycol, A polyvalent hydroxyl compound such as polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin); Polyfunctional (meth) acrylates derived from crylic acid; di (meth) acrylates of diols obtained by adding one or more moles of a cyclic ether such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mole of neopentyl glycol )
Acrylate;

Dialkylene oxide modified di (meth) acrylates of bisphenols such as bisphenol A, bisphenol F and bisphenol S; alkylenes of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S Oxide-modified di (meth) acrylate; Trisphenol alkylene oxide-modified di (meth) acrylate; Hydrogenated trisphenol alkylene oxide-modified di (meth) acrylate; p, p′-biphenol Alkylene oxide modified di (meth) acrylate; hydrogenated biphenol alkylene oxide modified di (meth) acrylate; p, p'-dihydroxybenzophenone alkylene oxide modified di (meth) acrylate
Acrylates; mono-, di- or tri (meth) acrylates of triols obtained by adding one or more moles of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mole of trimethylolpropane or glycerin;

Triol mono-, di-, tri- or tetra (meth) triol obtained by adding one or more moles of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mole of pentaerythritol or ditrimethylolpropane Acrylates: Triol mono- or poly (meth) acrylate triols, tetraols, pentals obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mol of dipentaerythritol Monofunctional (poly) ether (meth) acrylates or polyfunctional (poly) ether (meth) acrylates of polyhydric alcohols such as all and hexaol, but are not limited thereto. Not shall.

Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (A-5) usable in combination with the polymer solid electrolyte forming material of the present invention include ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate. A) acrylate, 1,2-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Di (meth) acrylates of hydrocarbon diols such as neopentyl glycol di (meth) acrylate; mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, di, tri, Tetra,
"Poly" is used as a generic term for multifunctionality such as. ), Mono (meth) acrylate or poly (meth) acrylate of glycerin, mono (meth) acrylate or poly (meth) acrylate of pentaerythritol, mono (meth) acrylate or poly (meth) acrylate of ditrimethylolpropane, dipentaerythritol And mono (meth) acrylates or poly (meth) acrylates of polyhydric alcohols such as triol, tetraol and hexaol of mono (meth) acrylate or poly (meth) acrylate.

Next, a compound having a vinyl ether group which can be used in combination with the polymer solid electrolyte forming material of the present invention is roughly classified into (B-1): a compound in which the other end is substituted with a halogen atom, a hydroxyl group or an amino group. (B-2): a cycloalkyl vinyl ether whose other terminal may be substituted with a halogen atom, a hydroxyl group or an amino group, (B-3): a vinyl ether group is bonded to an alkylene group, and further a substituent And at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aromatic group, which may have, and at least one bond selected from the group consisting of an ether bond, a urethane bond, and an ester bond. Monovinyl ether, divinyl ether and polyvinyl ether having a bonding structure, and the like. In particular, it is recommended vinyl ether compound having a (poly) alkylene glycol chain.

Examples of the compound having an ether bond include ethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol methyl vinyl ether, triethylene glycol divinyl ether, and polyethylene glycol. Monovinyl ether, polyethylene glycol methyl vinyl ether, polyethylene glycol divinyl ether, propylene glycol methyl vinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol methyl vinyl ether, dipropylene glycol divinyl ether, tripropylene glycol monobi Ether, tripropylene glycol methyl ether, tripropylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol methyl ether, polypropylene glycol divinyl ether, tetramethylene glycol methyl ether,
Di (tetramethylene glycol) monovinyl ether,
Di (tetramethylene glycol) methyl vinyl ether, di (tetramethylene glycol) divinyl ether, tri (tetramethylene glycol) monovinyl ether, tri (tetramethylene glycol) methyl vinyl ether, tri (tetramethylene glycol) divinyl ether, poly (tetramethylene glycol) ) Monovinyl ether, poly (tetramethylene glycol) methyl vinyl ether, poly (tetramethylene glycol) divinyl ether, 1,6-hexanediol methyl vinyl ether, di (hexamethylene glycol) monovinyl ether, di (hexamethylene glycol) methyl vinyl ether, (Hexamethylene glycol) divinyl ether, tri (hexamethylene glycol) monovinyl ether, tri ( Hexamethylene glycol) methyl ether, tri (hexamethylene glycol)
Divinyl ether, poly (hexamethylene glycol)
Monovinyl ether, poly (hexamethylene glycol) methyl vinyl ether, poly (hexamethylene glycol) divinyl ether, and the like can be mentioned.

The vinyl ether compound having a urethane bond includes (f) a monovinyl ether of (poly) alkylene glycol having at least one hydroxyl group in one molecule and (g) a compound having at least one isocyanate group in one molecule. Can be obtained by a urethanation reaction of

Among these, the monovinyl ether (f) of (poly) alkylene glycol having at least one hydroxyl group in one molecule includes, for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, -Hydroxypropyl vinyl ether, 2-hydroxy-2-methylethyl vinyl ether, dipropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 1,6-hexanediol monovinyl ether, and the like.

On the other hand, the compound (g) having at least one isocyanate group in one molecule includes, for example, m
-Isopropenyl-α, α-dimethylbenzyl isocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4, 4'-diphenylmethane diisocyanate,
Aromatic isocyanates such as 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, naphthalenediisocyanate; propyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Aliphatic and alicyclic isocyanates such as 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and lysine diisocyanate.

Among the compounds having a vinyl ether group,
The compound having an ester bond is obtained by an esterification reaction of (h) a monovinyl ether of an alkylene glycol having at least one hydroxyl group in one molecule and (i) a compound having at least one carboxyl group in one molecule. Can be.

The monovinyl ether (h) of the alkylene glycol having at least one hydroxyl group in one molecule includes the materials described as the component (f) of the compound having a urethane bond.

As the compound (i) having at least one carboxyl group in one molecule, known carboxylic acids and acid anhydrides thereof can be used. Such compounds include, for example, formic acid, acetic acid, propionic acid, valeric acid, benzoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, hetonic acid, hymic acid, chlorendic acid, dimer Acid, adipic acid, succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyladipic acid, 1,4
-Cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid; dimethyl of 5-sodium-sulfoisophthalic acid or Di-lower alkyl esters of 5-sodium-sulfoisophthalic acid such as diethyl ester; orthophthalic acid;
Sulfophthalic acid, 1,10-decamethylene dicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, or these Acid anhydride, and the like. Further, among these carboxylic acids, a compound having two or more carboxyl groups in one molecule and various alcohols used as an isocyanate adduct of component (g) of the compound having a urethane bond described above are used. A carboxylic acid obtained by the reaction can also be used.

Examples of other compounds which can be used in combination with the polymer solid electrolyte forming material of the present invention and which can be copolymerized with a maleimide group include (meth) acrylamide derivatives, for example,
Monofunctional (meth) acrylamides such as N-isopropyl (meth) acrylamide and acryloylmorpholine; and polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide.

Examples of the vinyl carboxylate derivatives include vinyl acetate and vinyl cinnamate. Examples of the styrene derivative include styrene and divinylstyrene.

Examples of unsaturated polyesters include maleic esters such as dimethyl malate and diethyl malate, fumaric esters such as dimethyl fumarate and diethyl fumarate; and polyunsaturated esters such as maleic acid and fumaric acid. And esterification products of carboxylic acids and polyhydric alcohols.

Among the compounds copolymerizable with the maleimide group, (meth) acrylate having a (poly) alkylene glycol chain and / or vinyl ether having a (poly) alkylene glycol chain are particularly preferred from the viewpoint of ionic conductivity. Recommended.

The curable compound which can be used in combination with the polymer solid electrolyte forming material of the present invention is not limited to the above-mentioned compounds, but has a copolymerizability with the maleimide group of the (poly) alkylene glycol derivative having a maleimide group. As long as it has a compound, one or more of the compounds can be used in combination without particular limitation.

The (poly) alkylene glycol derivative having a maleimide group according to the present invention, particularly preferably, the polymer solid electrolyte-forming material containing the maleimide derivative represented by the general formula (1) is copolymerizable with the maleimide group. When the compounds are used in combination, the ratio of the compounds used is not particularly limited, but from the viewpoint of the curing rate, the ratio of the compound having a maleimide group is preferably 10% by weight or more, more preferably 20% by weight, in the polymerization component of the electrolyte forming material. % Or more is recommended.

From the viewpoint of ionic conductivity, the content of the (poly) alkylene glycol derivative is preferably 20% by weight or more, and more preferably 50% by weight, based on all the polymerization components.
It is recommended that it be greater than or equal to weight percent.

On the other hand, a monomer or oligomer having a copolymerizable property with a maleimide group which does not react with the electrolyte or the electrode can be used for forming the matrix of the solid polymer electrolyte. The content is preferably 50% by weight or less, more preferably 20% by weight or less, based on the total amount of the polymerization components, because the property is deteriorated.

Further, the combined use of a monofunctional polymerizable (poly) alkylene glycol derivative and a polyfunctional polymerizable (poly) alkylene glycol derivative is preferable from the viewpoint of improving ionic conductivity. In order for the polymer solid electrolyte to have sufficient rigidity and complete separation of the negative electrode and the positive electrode, the combined ratio of the monofunctional polymerizable (poly) alkylene glycol derivative is
The content is preferably in the range of 5 to 50% by weight based on all the polymerizable components. Although trifunctional or higher polyfunctional polymerizable (poly) alkylene glycol derivatives are useful for forming a three-dimensional matrix, from the same viewpoint, it is recommended that the content be in the range of 2 to 30% by weight.

The electrolyte used in the polymer solid electrolyte forming material of the present invention can be used without any particular limitation as long as it is used as a normal electrolyte. Examples thereof include alkali metal salts, quaternary ammonium salts, and quaternary phosphonium. Salts, transition metal salts, and the like.

When the polymer solid electrolyte forming material of the present invention is used for a lithium ion battery or a lithium metal battery, a salt containing a lithium ion is preferable. Examples of the salt containing lithium ions include LiPF ₆ and LiSb.
F ₆ , LiAsF ₆ , LiBF ₄ , LiClO ₄ , CF
₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, C ₄ F ₉ SO ₃ L
i, C ₈ F ₁₇ SO ₃ Li, LiAlCl ₄ , and the like.

Electric double layer condenser, electrochromic
Polymer solid electrolyte of the present invention for mic devices, solar cells, etc.
When using a forming material, ions used as carriers by electric charge
And in addition to the above-mentioned lithium salt, Na
ClO_Four , NaI, KCLO _Four , KI, (CH_Three)_FourNB
F_Four , (CH_Three)_FourPBF_Four , AgCLO_Four , Etc.
It is.

In the case of using a solvent for the polymer solid electrolyte of the present invention to form a gel polymer solid electrolyte, any solvent that is usually used for a gel polymer solid electrolyte can be used without any particular limitation. Such solvents include, for example,
Carbonate-based solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate and diethyl carbonate; γ-butyrolactone, γ-valerolactone, δ-valerolactone, 3-
Lactone solvents such as methyl-1,3-oxazolin-2-one; methylal, 1,2-dimethoxyethane,
1,2-diethoxyethane, diethylene glycol diethyl ether, alkoxy polyalkylene glycol,
Ether-based solvents such as tetrahydrofuran and 2-methyltetrahydrofuran;

The electrolyte can be used in a range that does not exceed the limit of the solubility of the electrolyte in the polymerizable compound constituting the polymer solid electrolyte forming material or the solvent used. The solubility varies depending on the polymerizable compound constituting the polymer solid electrolyte forming material and the solvent used, and cannot be unconditionally specified. However, usually, the solubility limit of the electrolyte is used to maximize the ionic conductivity. Generally, 0.1 to 70 to the polymerizable compound or the solvent constituting the polymer solid electrolyte forming material.
% Is preferred, and a range of 1 to 60% by weight is particularly preferred.

When used as a polymer solid electrolyte containing no solvent, the electrolyte and the polymerizable compound constituting the polymer solid electrolyte forming material are dissolved in a solvent having a low boiling point among the above non-aqueous solvents. The polymer solid electrolyte of the present invention can be obtained by casting an electrode or a peelable polymer film, evaporating the solvent under reduced pressure, and irradiating with an active energy ray. In this case, after the solvent is distilled off, it is necessary to adjust the concentration so that the electrolyte does not precipitate. Further, the electrolyte may be dissolved in a polymerizable compound constituting the polymer solid electrolyte forming material without using a solvent.

When used as a gelled polymer solid electrolyte, the larger the amount of the electrolyte solution added, the better the ionic conductivity. However, if the amount is too large, the mechanical strength of the polymer solid electrolyte tends to decrease. It is not preferable. The amount of the electrolyte solution to be added is preferably 12 times by weight or less, particularly preferably 8 times or less, of the polymerizable compound constituting the solid polymer electrolyte forming material.

When the polymer solid electrolyte forming material of the present invention is used as an electric double layer capacitor or a lithium battery, an alkali metal ion such as an alkali metal, an alkali metal alloy or a carbon material is used as a carrier as a negative electrode active material. Low oxidation-reduction potential electrode; lithium metal, lithium aluminum alloy, lithium lead alloy, lithium antimony alloy, carbon material; natural graphite, artificial graphite, vapor phase graphite,
Petroleum coke, coal coke, pitch-based carbon, polyacene, fullerene such as C60, and the like are used.

When the polymer solid electrolyte forming material of the present invention is used as an electric double layer capacitor or a lithium battery, the positive electrode active material may be a metal oxide, a metal sulfide, a conductive polymer, or a carbon material. Electrode materials having a redox potential; cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, molybdenum oxide, molybdenum sulfide, titanium sulfide, vanadium sulfide, and the like are used.

Further, a conductive polymer can also be used as a positive and / or negative electrode active material. Examples of conductive polymers that can be used for such purposes include, for example, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polyparaphenylene vinylene and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, polyaniline and its derivatives , Polyacene, and the like.

When the polymer solid electrolyte forming material of the present invention is used for an electrochromic display, tungsten oxide, methyl viologen and its derivatives, polypyrrole and its derivatives can be used as one of the electrode active materials.

When the polymer solid electrolyte forming material of the present invention is used as a wet solar cell, one of the electrode active materials is an inorganic semiconductor such as silicon, zinc oxide, titanium oxide or cadmium sulfide, methyl viologen, ruthenium bipyridyl. Complexes, thin films containing organic dyes such as inorganic semiconductors, perylene and derivatives thereof, porphyrin and derivatives thereof, phthalocyanine and derivatives thereof sensitized with organic dyes such as porphyrin and phthalocyanine, and conductive polymers described above , Etc. are used.

The methods for constructing these devices using the polymer solid electrolyte forming material of the present invention include, for example, (1) coating the polymer solid electrolyte forming material of the present invention on a positive electrode active material, After curing by irradiation with an active energy ray, a method of building a device by laminating a negative electrode active material layer, (2) After applying the polymer solid electrolyte forming material of the present invention on the negative electrode active material, the active energy ray After curing by irradiation, a method of constructing a device by laminating a positive electrode active material layer, (3) impregnating the polymer solid electrolyte forming material of the present invention into a nonwoven fabric, polyethylene mesh, etc., and irradiating with an active energy ray After curing, a method of building a device by laminating the positive and negative electrode active material layers, (4) facing the positive and negative electrode active material layers at regular intervals, during which the solid polymer electrolyte of the present invention is formed Inject material You. Then, the polymer solid electrolyte forming material of the present invention is cured by irradiating the active energy ray through the positive or negative electrode active material layer, a method of building a device, (5) cast on a peelable film, A method of irradiating an active energy ray to cure the polymer solid electrolyte forming material of the present invention, and then sandwiching the material between the positive and negative electrode active material layers to construct a device.

As the method for applying the polymer solid electrolyte forming material, known and commonly used methods such as a doctor blade method, a spin coating method, an impregnation method, an injection method, and a casting method can be used.

The polymer solid electrolyte forming material of the present invention comprises
It has an inherent spectral sensitivity of 00 to 400 nm, and in the absence of a photopolymerization initiator, can be polymerized by irradiating ultraviolet light or visible light having a wavelength of 180 to 500 nm,
In particular, light having wavelengths of 254 nm, 308 nm, 313 nm, and 365 nm is effective for curing the polymer solid electrolyte forming material of the present invention. Further, the polymer solid electrolyte forming material of the present invention can be cured by irradiation with energy rays other than ultraviolet rays or by heat. Further, the polymer solid electrolyte forming material of the present invention can be cured in air and / or in an inert gas.

Examples of light sources of ultraviolet or visible light having a wavelength of 180 to 500 nm include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, and excimer lamps. Lamps, short arc lamps,
Helium / cadmium laser, argon laser,
Excimer laser and sunlight.

The polymer solid electrolyte forming material of the present invention is cured by irradiation of ultraviolet light or visible light in the absence of a photopolymerization initiator. In order to carry out the curing reaction more efficiently, a conventional photopolymerization initiator is used. It can be cured by adding an agent. Photopolymerization initiators can be broadly classified into two types: an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type.

Examples of the intramolecular bond cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 1- (4-isopropylphenyl). ) -2-Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-
(Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether;
Acylphosphine oxides such as 6-trimethylbenzoindiphenylphosphine oxide; benzyl, methylphenylglyoxyester, and the like.

On the other hand, examples of the intramolecular hydrogen abstraction type photopolymerization initiator include, for example, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate,
4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4
Benzophenones such as 4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone,
Thioxanthones such as 4-diethylthioxanthone and 2,4-dichlorothioxanthone; Michler's ketone;
Aminobenzophenones such as 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like.

When the photopolymerization initiator is used, the compounding amount is as follows:
0.0 to the polymerization component in the polymer solid electrolyte forming material
A range of 1 to 10.00% by weight is preferred. In particular, for the purpose of the present invention, the smaller the amount used, the better.
% By weight is recommended.

The polymer solid electrolyte forming material of the present invention is cured by the irradiation of ultraviolet rays, but a photosensitizer may be used in combination in order to carry out the curing reaction more efficiently.

Examples of such a photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4-dimethylaminobenzoic acid (n-
Amines such as butoxy) ethyl and 2-ethylhexyl 4-dimethylaminobenzoate.

When the photosensitizer is used, the amount thereof is preferably in the range of 0.01 to 10.00% by weight in the polymer solid electrolyte forming material.

Further, various non-reactive compounds and the like can be appropriately used in combination with the polymer solid electrolyte forming material of the present invention depending on the use.

Next, a lithium ion secondary battery will be described as an example of a device constituted by using the polymer solid electrolyte forming material of the present invention. The schematic cross-sectional view shown in FIG. 1 is an example of a thin lithium secondary battery, in which the polymer solid electrolyte forming material of the present invention 2 was cured by irradiation with ultraviolet light, and was sandwiched between a positive electrode active material 1 and a negative electrode active material 3. Structure. The positive and negative electrode active materials are formed on the current collector 4,
The thickness of the electrolyte is adjusted to 0.1 mm by the spacer 5 and is sealed by the insulating resin sealing agent 6. The lithium ion secondary battery thus constructed is further sealed with an insulating resin sealant 7. 8 is a lead wire. This example is an example of an all solid-state device constructed using the polymer solid electrolyte forming material of the present invention, and the application range of the present invention is not limited by this.

The polymer solid electrolyte forming material of the present invention can form a cured coating film and the like without using a photopolymerization initiator at the time of photopolymerization. Therefore, by using the polymer solid electrolyte forming material of the present invention, it is possible to prevent the degradation of device characteristics caused by the conventional photopolymerization initiator, primary batteries, secondary batteries, capacitors, It is useful for applications such as electrochemical devices such as electrochromic displays and wet solar cells.

[0123]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples. In the following example,
“%” Represents “% by weight” unless otherwise specified.

Example 1 As an active energy ray-curable compound, polyethylene glycol (average molecular weight: 40
0) Bismaleimide acetate (abbreviation: MIAPEG4
00) to which 0.5 mol / L of LiP was added.
After adding the same weight of an F ₆ / ethylene carbonate / propylene carbonate (50/50 volume ratio) solution to make a uniform solution, it was applied on a polyethylene terephthalate film (hereinafter referred to as a PET film) to a thickness of 100 μm. did.

The composition was irradiated with 900 J / m ² ultraviolet rays from a high-pressure mercury lamp of 120 W / cm to obtain a transparent self-supporting film made of a gel polymer solid electrolyte having a thickness of about 50 μm.

(Example 2) In Example 1, the MIAP
Example 1 Example 1 was repeated except that polytetramethylene glycol (average molecular weight: 250) bismaleimide acetate (abbreviation: MIAPTMG250) was used instead of EG400.
In the same manner as in the above, a transparent self-supporting film made of a gel polymer solid electrolyte having a thickness of about 50 μm was obtained.

(Embodiment 3) In the embodiment 1, the MIAP
Example 1 was repeated except that polytetramethylene glycol (average molecular weight: 650) bismaleimide acetate (abbreviation: MIAPTMG650) was used instead of EG400.
In the same manner as in the above, a transparent self-supporting film made of a gel polymer solid electrolyte having a thickness of about 50 μm was obtained.

(Embodiment 4) In the first embodiment, the MIAP
A gel having a thickness of about 50 μm was obtained in the same manner as in Example 1, except that a mixture of MIAPEG400 and polyethylene glycol (average molecular weight: 400) diacrylate (abbreviation: PEG400DA) in a weight ratio of 1/1 was used instead of EG400. A transparent free-standing film composed of a solid polymer electrolyte was obtained.

(Comparative Example 1) In Example 1, the MIAP
Except that PEG400DA was used instead of EG400, UV irradiation was performed after application in the same manner as in Example 1, but no polymerization occurred, and a free-standing film was not obtained.

From Examples 1 to 4 and Comparative Example 1, when the polymer solid electrolyte forming material of the present invention was used, a gel polymer solid electrolyte was obtained, and it was found that the material of the present invention was excellent. it is obvious.

Example 5 A glass substrate having a 0.1 μm-thick indium tin oxide (ITO) -deposited film as an electrode was used to fabricate a cell through a 0.14 mm spacer. As the photopolymerizable compound, polyethylene glycol (average molecular weight: 400) bismaleimide acetate (abbreviation: MIAPEG400) was used.
5 mol / L concentration of LiPF ₆ / ethylene carbonate
Propylene carbonate (50/50 volume ratio) solution
An equal weight of the dissolved solution was prepared and injected into the cell.

After the photopolymerizable compound was cured by irradiating ultraviolet rays having a dose of 24000 J / m ² through a glass with ITO using a 120 W / cm high pressure mercury lamp, the cell was placed in a glove box filled with dry argon. At 25 ° C. by applying an impedance method of 100 mV,
The conductivity at a frequency of 1 KHz was measured. The frequency of the solid polymer electrolyte whose resistance value of the ITO electrode has been corrected is 1 KHz
The conductivity at that time is shown in Table 1.

(Embodiment 6) In Embodiment 5, the MIAP
Example 5 except that polytetramethylene glycol (average molecular weight: 250) bismaleimide acetate (abbreviation: MIAPTMG250) was used instead of EG400.
The conductivity of the solid polymer electrolyte was measured in the same manner as described above, and the results are shown in Table 1.

(Example 7) In Example 5, the MIAP
Example 5 was repeated except that polytetramethylene glycol (average molecular weight: 650) bismaleimide acetate (abbreviation: MIAPTMG650) was used instead of EG400.
The conductivity of the solid polymer electrolyte was measured in the same manner as described above, and the results are shown in Table 1.

(Eighth Embodiment) In the fifth embodiment, the MIAP
In the same manner as in Example 5, except that a mixture of MIAPTMG250 and polyethylene glycol (average molecular weight: 400) diacrylate (abbreviation: PEG400DA) in a weight ratio of 1/1 was used instead of EG400, the conductivity of the polymer solid electrolyte was changed. Was measured, and the results are shown in Table 1.

(Comparative Example 2) In Example 5, the MIAP
The conductivity of the polymer solid electrolyte was measured in the same manner as in Example 5, except that PEG400DA containing 2% by weight of "Irgacure 184" (photoinitiator) was used instead of EG400. The results are shown in Table 1.

[0137]

[Table 1]

From the results shown in Table 1, the conductivity of the gelled solid electrolyte obtained by subjecting the polymer solid electrolyte-forming material of the present invention to UV polymerization was determined using a general-purpose photopolymerization initiator, polyethylene glycol (average molecular weight). 400) It is apparent that the value is higher than the conductivity of the solid electrolyte prepared using diacrylate as a polymerization component.

(Examples 9 to 12, Comparative Example 3) Instead of measuring the change in the electrolyte during the repetition of the charge / discharge cycle, the change in the conductivity during the application of an alternating current was observed.

The cells obtained in the same manner as in Examples 5 to 8 and Comparative Example 2 were placed in a glove box kept at 25 ° C. in which dry argon was sealed, 100 mV and 1 KHz were applied, and the conductivity after 24 hours was measured. The measurement was performed, and the results are summarized in Table 2.

[0141]

[Table 2]

From the results shown in Table 2, the conductivity of the cell formed using the material for forming a solid polymer electrolyte of the present invention hardly changed between the start of the measurement and 24 hours after the start of the measurement. It is clear that the conductivity of the cell of Comparative Example 3 formed using the agent is reduced to almost 1/10.

Therefore, the lithium ion secondary battery formed using the polymer solid electrolyte forming material of the present invention has excellent stability of the conductive characteristics at the time of repetition of the charge / discharge cycle. Conceivable.

Similarly, when another electrochemical element is formed using the polymer solid electrolyte forming material of the present invention, it is considered to be excellent in stability.

[0145]

Since the photopolymerization initiator is not used, the charge / discharge capacity of the solid polymer electrolyte is unlikely to be reduced by repeating charge / discharge.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a lithium ion secondary battery using a polymer solid electrolyte forming material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Polymer solid electrolyte 3 Negative electrode 4 Current collector 5 Spacer 6 Insulating resin sealing agent 7 Insulating resin sealing agent 8 Lead wire

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 290/06 C08F 290/06 5F051 C08G 65/329 C08G 65/329 5G301 C08L 71/00 C08L 71/00 5H024 H01B 1/06 H01B 1/06 A 5H029 H01G 9/035 H01M 6/18 E 5H032 9/00 6/22 C H01L 31/04 14/00 P H01M 6/18 H01G 9/02 311 6/22 9/24 A 14/00 H01L 31/04 Z F term (reference) 4J002 BH021 DD036 DD086 DE196 DH006 DK006 ED017 EL067 EL087 EL107 EV256 FD206 FD207 GQ00 4J005 AA04 BD02 BD03 BD05 4J011 PA06 PA09 PA10 PA14 PA26 PA30 PA35 QB QA QA Q QA23 QA24 QA39 QB05 QB12 QB14 QB15 QB20 QB22 QB24 UA01 UA06 WA10 4J027 AA03 AB02 AB03 AB06 AB07 AB15 AB16 AB18 AB1 9 AB23 AB25 AB26 AB28 AB32 AC02 AC03 AC04 AC06 AC07 AC09 AE01 AE02 AE03 AE04 AE05 AE07 AG03 AG04 AG05 AG09 AG12 AG13 AG14 AG15 AG23 AG24 AG27 BA04 BA05 BA07 BA09 BA14 BA18 BA20 BA21 BA26 BA28 CC04 CC05 CD00 ALJQ AL63Q AL67Q AM45Q AM47Q AM48Q AM49Q AM55P AM55Q BA02P BA02Q BA03Q BA04Q BA05Q BA08P BA08Q BA15P BA21Q BA22P BA34P BA39Q BB01Q BC04P BC04Q BC28Q BC43P BC43Q BC44P BC45P BC45Q BC60Q CA01 CA04 ACO5 CA01 ACOA 5A01 FF15 FF18 FF19 FF23 FF31 GG01 HH01 5H029 AJ02 AJ05 AJ14 AM03 AM04 AM05 AM07 AM16 BJ04 BJ12 CJ11 EJ12 HJ02 5H032 AA06 AS01 AS06 AS17 AS19 BB07 BB10 CC17 EE02 EE04 HH00

Claims (12)

[Claims] (1) at least one compound in (1) an electrolyte and (2) a molecule;
A polymer solid electrolyte forming material comprising a (poly) alkylene glycol derivative having two maleimide groups. 2. A (poly) alkylene glycol derivative having two or more polymerizable functional groups in a molecule, wherein at least one of the polymerizable functional groups is a maleimide group. The polymer solid electrolyte forming material according to claim 1. 3. A (poly) alkylene glycol derivative having one maleimide group in a molecule, and (2) a (poly) alkylene glycol derivative having two or more polymerizable functional groups in a molecule, The polymer solid electrolyte forming material according to claim 1, comprising a (poly) alkylene glycol derivative in which at least one of the polymerizable functional groups is a maleimide group. 4. A (poly) alkylene glycol derivative having at least one maleimide group in the molecule is represented by the general formula (1): (In the formula, m and n each independently represent an integer of 0 to 6, but m + n represents an integer of 1 to 6. R ₁₁ and R ₁₁
Each ₁₂ independently represents a hydrocarbon bond containing an aliphatic group and / or an aromatic group. G ₁ and G ₂ each independently represent an ether bond, an ester bond, a urethane bond, or a carbonate bond. R ₂ has an average molecular weight of 44 to 10, in which a linear or branched alkylene group is connected by an ether bond;
000 (poly) ether linking chains or (poly) ether residues. The polymer solid electrolyte forming material according to any one of claims 1 to 3, which is a compound represented by the formula: 5. (Poly) having a maleimide group
The polymer solid electrolyte forming material according to any one of claims 1 to 4, further comprising a compound other than the alkylene glycol derivative and having a copolymerizability with a maleimide group. 6. A compound having a maleimide group and copolymerizability having a (poly) alkylene glycol chain (meth)
6. The polymer solid electrolyte forming material according to claim 5, which is at least one compound selected from the group consisting of an acrylate ester and a vinyl ether compound having a (poly) alkylene glycol chain. 7. The polymer solid according to claim 1, wherein the electrolyte contains at least one electrolyte selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. Electrolyte forming material. 8. The polymer solid electrolyte forming material according to claim 1, further comprising a non-aqueous organic solvent. 9. The polymer solid electrolyte forming material according to claim 8, wherein the non-aqueous organic solvent is at least one non-aqueous solvent selected from the group consisting of carbonate, lactone and ether. 10. A solid polymer electrolyte comprising a cured product of the material for forming a solid polymer electrolyte according to any one of claims 1 to 9. 11. The polymer solid electrolyte forming material according to claim 1, which is irradiated with an active energy ray in the absence of a photopolymerization initiator. A method for curing a polymer solid electrolyte forming material, comprising polymerizing a material. 12. The curing method according to claim 11, wherein the active energy rays are ultraviolet rays.