JPH10208542A - Ion conductor and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ion conductor and its manufacture where base material can effectively be endowed with ion conduction performance, excellent in adhesion with the base material, in mechanical strength, and in transparency. SOLUTION: The ion conductor is formed out of base material such as an acrylic resin plate and the like, a polymer layer containing photo-polymerization initiation groups having been formed over the polymer layer, and of an ion conductive film having been formed over the polymer layer. The ion conductive film is formed by letting activated energy beams be irradiated on the composition of ion conductive monomer after the composition of ion conductive monomer, which contains ion conductive monomer, soluble electrolyte salt compounds, or electrolyte salt monomer, has been coated over the polymer layer containing photopolymerization initiation groups. As ion conductive monomer, polyethylene glycol diacrylate and the like are used, as a soluble electrolyte salt compound, lithium perchlorate and the like are used, and as an electrolyte salt monomer, lithium methacrylate and the like are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ionic conductor applied to a solid electrolyte, a conductive film and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, ion conductive polymer electrolytes include, for example, diacrylate of a random copolymer of polyethylene glycol and polypropylene glycol, lithium perchlorate, and a photopolymerization initiator, and are cured by active energy rays. Polymer electrolyte (Japanese Patent Publication No. 8-32754)
Is known. Furthermore, a polymer electrolyte comprising an ethylene glycol copolymer containing an ionic compound in a dissolved state (JP-A-61-83249), and a homopolymer or a copolymer having no thermoplastic cross-linking. Ion-conducting polymer electrolyte using a polymer solid material having plasticity substantially consisting of branches (Japanese Patent Laid-Open No.
5-98480) and the like.

[0003] However, although the ion-conductive polymer electrolyte obtained by these methods exhibits excellent ionic conductivity at room temperature or higher, there is a problem that the ionic conductivity sharply decreases at room temperature or lower. Also,
There is a problem that it is difficult to obtain a material having a sufficient shape retention required for practical use.

As a method for solving these problems, an ion-conductive polymer electrolyte using a polyether obtained by ring-opening polymerization of methyl polyethylene glycol glycidyl ether (JP-A-4-36347) and a domain A polymer solid electrolyte in which rubber latex is dispersed has been proposed [Preprints of the Society of Polymer Science, vol. 43, pp. 749-750 (1993)]. The ion-conductive polymer electrolyte obtained by these methods stably exhibits excellent ionic conductivity even at a low temperature, and has excellent shape retention.

[0005]

However, the ion-conductive polymer electrolyte obtained by these methods is generally used as a solution of an organic solvent such as methyl ethyl ketone, which is applied or cast on a substrate such as a glass plate. For this reason, there has been a problem that the adhesion to the base material is still insufficient.

In addition, there is a problem that the mechanical strength is still insufficient due to the fact that the ion-conductive polymer electrolyte obtained by these methods contains polyalkylene glycol as a main component.

Further, there is another problem that the transparency of the obtained ion-conductive film is reduced due to dispersion of the rubber latex to obtain a predetermined mechanical strength. The present invention has been made by paying attention to the problems existing in the prior art as described above. Its purpose is to have excellent ion conduction performance, as well as adhesion to the substrate,
An object of the present invention is to provide an ion conductor excellent in mechanical strength and transparency.

[0008]

Means for Solving the Problems In order to achieve the above object, an ionic conductor according to the first invention comprises a base material and a polymer layer having a photopolymerization initiation group formed on the base material. And an ion conductive film formed from a cured product of a composition containing an ion conductive monomer and a soluble electrolyte salt compound on the polymer layer, and the ion conductive film is formed of It is bonded to the polymer layer via a photopolymerization initiator group fragment derived from the polymerization initiator.

According to a second aspect of the present invention, there is provided an ion conductor comprising a substrate, a polymer layer having a photopolymerization initiating group formed on the substrate, and an ion-conductive monomer and an electrolyte salt formed on the polymer layer. An ion-conductive film formed from a cured product of a composition containing a monomer, wherein the ion-conductive film overlaps via a photopolymerization initiation group fragment derived from the photopolymerization initiation group of the polymer layer. It is bonded to the coalescing layer.

[0010] The ion conductor of the third invention comprises a substrate, a polymer layer having a photopolymerization initiating group formed on the substrate, an ion-conductive monomer and a soluble electrolyte on the polymer layer. A photopolymerization initiation group derived from a photopolymerization initiation group of the polymer layer, comprising an ion-conductive film formed from a cured product of a composition containing a salt compound and an electrolyte salt monomer. It is bonded to the polymer layer via fragments.

According to a fourth aspect of the present invention, there is provided an ionic conductor comprising:
In any one of the inventions, the polymer forming the polymer layer having a photopolymerization initiating group is a polymer composed of a monomer having at least one selected from the group of photopolymerization initiating groups shown below. It is a polymer having segments.

Photopolymerization initiation group:

[0013]

Embedded image Where φ ₁ is a phenylene group and A is

[0014]

Embedded imageφ_TwoRepresents a phenyl group;₁, R_TwoHas 1 to 4 carbon atoms
Alkyl group or R₁, R ₁And R_Two, R_TwoDue to the carbon between
A cycloalkyl group having 5 to 7 carbon atoms formed, R _ThreeIs water
Acid group or amino group, R_Four, R_FiveIs an alk having 1 to 4 carbon atoms
Represents a hydroxyl group.

According to a fifth aspect of the present invention, there is provided a method for manufacturing an ion conductor, comprising:
A polymer layer having a photopolymerization initiation group is formed on a substrate, and a composition containing an ion conductive monomer and a soluble electrolyte salt compound is brought into contact with the polymer layer, and an active energy ray is applied to the composition. Irradiation forms an ion-conductive film.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The ionic conductor includes a base material, a polymer layer having a photopolymerization initiation group formed on the base material, and an ionic conductive monomer and a soluble electrolyte salt compound, or an ionic conductive compound formed on the polymer layer. Cured product of a composition containing a monomer and an electrolyte salt monomer, or an ion conductive monomer, a soluble electrolyte salt compound and an electrolyte salt monomer (hereinafter referred to as a composition of an ion conductive monomer) And an ion-conductive film formed by the method. The ion conductive membrane is bonded to the polymer layer via a photopolymerization initiation group fragment derived from the photopolymerization initiation group of the polymer layer.

That is, the ion-conductive film is obtained by irradiating the composition of the ion-conductive monomer in contact with the polymer layer having a photopolymerization initiating group with active energy rays to cause photograft polymerization. Cured. More specifically, the photopolymerization initiation group bonded to the polymer layer formed on the base material generates radicals upon irradiation with active energy rays, and the radicals of the photopolymerization initiation group fragments generated from the radicals generate ion-conductive monomers. Alternatively, a cured layer of an ion conductive polymer or a copolymer of an ion conductive monomer and an electrolyte salt monomer is formed by graft polymerization of the electrolyte salt monomer. Therefore, the resulting ion-conductive membrane is formed from a graft-polymerized chain of an ion-conductive monomer or an ion-conductive monomer and an electrolyte salt monomer bonded to the polymer layer via a photopolymerization initiation group fragment. It has a two-layer structure in which layers are formed.

FIG. 1 conceptually shows a manufacturing process of such an ion conductor. In FIG. 1, the solid line is the main chain of a polymer having a photopolymerization initiation group, -CD is a photopolymerization initiation group, -C. Is an initiator group fragment radical in which the photopolymerization initiation group is cleaved, and -C- is photopolymerization initiation The base fragment and the broken line represent an ion-conductive polymer obtained by polymerizing the ion-conductive monomer, or a graft polymer chain of a copolymer of the ion-conductive monomer and the electrolyte salt monomer.

Next, the base material is not particularly limited, but a colorless transparent or colored transparent material or a colored material such as glass, synthetic resin molding material or film is used. For example, an acrylic resin plate or polyethylene terephthalate (P
ET) film or the like is used.

Next, the polymer layer having a photopolymerization initiating group is a polymer layer having a group capable of generating a radical upon irradiation with active energy rays, particularly a hydrophobic polymer layer. It can be obtained in various ways. (i) A method of forming a polymer layer by applying a composition containing a homopolymer or a copolymer of a monomer having a photopolymerization initiating group alone or both to a substrate. (ii) A method of forming a polymer layer by applying a composition containing a monomer having a photopolymerization initiating group to a substrate and then polymerizing the composition with heat or light. (iii) A method in which a photopolymerization initiating group is introduced by a chemical reaction onto the surface of a polymer having no functional group and having no photopolymerization initiating group. Specifically, European Polymer Journal (Eur. Polym. J.), Vol. 29,
63, 1993, and Polymer Material Science and Engineering (Polym. M.
ater. Sci. Eng. ), 60 volumes, 1 page, 198
This is the method described in nine years. That is, for example, a method in which a photopolymerization initiator having an alkoxysilyl group is reacted with a substrate having a hydroxyl group.

Among them, the method (i) is preferred because it is simple. When applying the composition, the composition may be diluted with a solvent if necessary. Here, the monomer having a photopolymerization initiating group is a group that generates a radical upon irradiation with an active energy ray, that is, a monomer having at least one photopolymerization initiating group and one or more polymerizable double bonds in one molecule. Say.

Specific examples of the monomer having a photopolymerization initiating group include S- (meth) acryloyl-O-methylxanthate, S- (meth) acryloyl-O-ethylxanthate, and S- (meth) Xanthates such as acryloyl-O-propylxanthate, 2,2′-azobis [2
-(Acryloyloxymethyl) propionitrile],
Examples include azo compounds such as 2,2′-azobis [2- (methacryloyloxymethyl) propionitrile] and ketone compounds represented by the following chemical formula (5).

[0023]

Embedded image Wherein R ₁ is

[0024]

Embedded imageAnd φ₁Is a phenylene group, R_TwoIs hydrogen, R₆Or Z
And R_ThreeIs hydrogen or R₁₃And R_Four, R_FiveAre each
Independently hydrogen, an alkyl group having 1 to 12 carbon atoms, 1 carbon atom
To 12 alkoxy groups, phenyl groups, or R_FourOnly,
Or R_FourAnd R _FiveC5-C7 cyclo formed by
An alkyl group;₆Is OR_Fifteen, SR_Fifteen, N (R
₁₆)_Two, Piperidino group, morpholino group, SO_TwoR₁₇Or Z
And R ₇Each represents a halogen, an alkyl having 1 to 6 carbon atoms.
Substituted by a kill group or an alkoxy group having 1 to 6 carbon atoms
Optionally, an alkyl group having 1 to 6 carbon atoms, phenyl
A benzoyl group;₈, R₉Is hydrogen, hydroxyl,
An alkyl group having 1 to 6 carbon atoms or Z;_TenIs hydrogen
Or Z and R₁₁Is an alkyl group having 1 to 3 carbon atoms or
A phenyl group;₁₂Represents an alkyl group, an acyl group or Z
Represents, R₁₃Is hydrogen,

[0025]

Embedded image Or —O— or —S— attached to the ortho position together with R ₃ , R ₁₄ is hydrogen, Z or R ₁₃ , R ₁₅ is hydrogen, an alkyl group having 1 to 6 carbon atoms or Z And R ₁₆ ,
R ₁₇ is an alkyl group having 1 to 6 carbon hydrogen or carbon, R ₁₈
Represents a tertiary alkyl or aralkyl group having 4 to 10 carbon atoms.

The Z is

[0027]

Embedded image A, B and D are each independently a single bond,

[0028]

Embedded image And X and Y are unsubstituted or hydroxyl-substituted carbon atoms of 1
Represents an alkylene group of 4 to 4, p and q are 0 or an integer of 1 to 10, W is

[0029]

Embedded image Represents φ ₁ is a phenylene group, R ₁₉ is a hydrogen or methyl group, R ₂₀ is an alkyl group having 1 to ₂₀ carbon atoms, R ₂₁ is hydrogen,
Represents an alkyl group having 1 to 6 carbon atoms or a hydroxy-substituted alkyl group having 1 to 3 carbon atoms. When W is divalent, it indicates that two groups having the same structure are bonded. In addition, one or more Z groups are contained in R _{1 to} R ₃ .

Specific examples of the monomer having a photopolymerization initiating group represented by Chemical Formula 5 are as follows: 1- (4-vinylphenyl) -2-hydroxy-2-methylpropane-
1-one, 1- (4-isopropenylphenyl) -2-
Hydroxy-2-methylpropan-1-one, 1- (4
-Allyloxybenzoyl) -1-hydroxycyclohexane, 1- {4- (2-acryloyloxyethoxy) phenyl} -2-hydroxy-2-methylpropan-1-one, 1- [4- {2- (3- Acryloyloxy-2-hydroxypropyloxy) ethoxy {phenyl] -2-hydroxy-2-methylpropan-1-one, 1- {4- (2-methacryloyloxyethoxy)
Phenyl} -2-hydroxy-2-methylpropane-1
-One, 1- [4- {2- (2- (methacryloyloxy) ethoxycarbonyloxy) ethoxy} phenyl]
-2-hydroxy-2-methylpropan-1-one, 2
-Acryloyloxy-1-phenyl-2-methylpropan-1-one, 1- {4- (2-acryloyloxyethylthio) phenyl} -2-morpholino-2-methylpropan-1-one, methyl [2- {4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy}
Ethyl] malate, isopropyl [2- {4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy} ethyl] fumarate, butyl [2- {4- (2-hydroxy-2-methyl-1-oxo) Propyl) phenoxydiethyl] itaconate, octyl [2- {4- (2
-Hydroxy-2-methyl-1-oxopropyl) phenoxydiethyl] mesaconate, bis [2- {4- (2
-Hydroxy-2-methyl-1-oxopropyl) phenoxydiethyl] fumarate, bis [2- {4- (2-
Hydroxy-2-methyl-1-oxopropyl) phenoxydiethyl] itaconate, bis [2- {4- (2-
Hydroxy-2-methyl-1-oxopropyl) phenoxy {ethyl] mesaconate, 1- {4- (2-methacryloylethoxy) phenyl} -2,2-dimethoxy-
2-phenylethane-1-one, 2- {4- (2-acryloylbutoxy) phenyl} -2,2-dimethoxy-
2-phenylethane-1-one, 1,2-bis {4-
(2-acryloylethoxy) phenyl} -2,2-dimethoxy-2-phenylethane, 2,2-bis (2-methacryloyloxyethoxy) -1,2-diphenylethan-1-one, 2-allyl-2- Isopropyloxy-1,2-diphenylethan-1-one, 2-acryloyloxymethyl-2-methoxy-1,2-diphenylethan-1-one, 2-acryloyloxy-1,2-
Diphenylethan-1-one, 1,2-diphenyl-
1,2-ethanedione-2-O-acryloyloxime, 4-vinylbenzoyldiphenylphosphine oxide, 4-vinyl-4 ′-(t-butylperoxycarbonyl) benzophenone, 3,3′-bis (2-methacryloyloxyethoxy) Carbonyl) -4,4′-bis (t-butylperoxycarbonyl) benzophenone, 4,4 ′-(3-methacryloyloxy-2-hydroxypropyloxycarbonyl) -3,3′-bis (t-hexylperoxycarbonyl) Benzophenone, 3,3'-bis (methacryloyloxyethoxycarbonyl) -4,4'-bis (t-butylperoxycarbonyl) benzophenone, 4- (meth) acryloyloxybenzophenone, 4- {2- (acryloyloxy) ethoxy} Benzophenone, Styryl-methoxybenzophenone, 4 (meth) acryloyloxy thioxanthone and the like.

Of these, monomers having a photopolymerization initiation group represented by the following chemical formulas 11 and 12 are preferred from the viewpoint of good photopolymerization initiation efficiency and easy production.

[0032]

Embedded image Where φ ₁ is a phenylene group and A is

[0033]

Embedded image Wherein φ ₂ is a phenyl group, R ₁ and R _{2 each} have 1 to 4 carbon atoms.
Alkyl group or R ₁ only, or R ₁ and cycloalkyl groups having 5 to 7 carbon atoms formed by R _2, R ₃ is a hydroxyl group or amino group, R _4, R ₅ is alkyl of 1 to 4 carbon atoms Represents a group.

The phenylene group of φ ₁ is usually bonded at the para position, but may be bonded at the meta or ortho position. As the monomer having a photopolymerization initiating group, specifically, 1- {4- (2- (meth)
(Acryloyloxyethoxy) phenyl} -2-hydroxy-2-methylpropan-1-one, {4- (2-
(Meth) acryloyloxyethoxy) phenyl} (1
-Hydroxycyclohexyl) ketone, 1- {4- (2
-(Meth) acryloyloxyethoxy) phenyl｝-
2-morpholino-2-methylpropan-1-one, 1-
{4- (2- (meth) acryloyloxyethoxy) phenyl} -2-dimethylamino-2-methylpropane-
1-one, 1- [4- {2- (2-((meth) acryloyloxy) ethoxycarbonyloxy) ethoxy} phenyl] -2-hydroxy-2-methylpropane-1-
On, 1- {4- (2- (meth) acryloylethoxy) phenyl} -2,2-dimethoxy-2-phenylethan-1-one and the like are preferred.

The polymer having a photopolymerization initiating group is formed by using one or more monomers having no photopolymerization initiating group in addition to the monomer having a photopolymerization initiating group. It may be something. Such a monomer having no photopolymerization initiating group is not particularly limited, and specifically, alkyl (meth) acrylates such as methyl (meth) acrylate and butyl (meth) acrylate, and 2-hydroxyethyl (meth) ) Acrylates, hydroxyl-containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate,
(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N, N-dialkylaminoalkyl (meth) acrylate, fumaric acid esters, glycidyl (meth) acrylate, maleic acid esters,
Examples include itaconic esters, (meth) acrylic acid, maleic anhydride, styrene, vinyl acetate, N-vinylpyrrolidone, N-vinylpyridine, fluorine-containing monomers, silicon-containing monomers, phosphorus-containing monomers, and the like. Can be

In particular, in the case of a polymer having a photopolymerization initiating group consisting of only a monomer having a photopolymerization initiating group, if the adhesion to the substrate and the mechanical strength are insufficient, the photopolymerization initiating group is insufficient. It is preferable to use a monomer having no appropriate photopolymerization initiating group during the synthesis of the polymer having

For example, in order to improve the adhesion to a substrate shown below, it is preferable to use a monomer having no photopolymerization initiation group. When using glass as the base material, use γ-methacryloxypropyltrimethoxysilane; when using a methacrylic resin plate or a vinyl chloride sheet as the base material, use methyl methacrylate; when using the epoxy resin as the base material, use methacrylic acid. Glycidyl, stearyl methacrylate when a polyolefin sheet is used as a base material, and styrene when a polystyrene plate is used as a base material.

The polymer having a photopolymerization initiating group can be obtained by polymerization using a usual radical polymerization initiator. In this case, the polymer is obtained by polymerizing one or more of monomers having a photopolymerization initiating group alone, or one or more of other monomers having no photopolymerization initiating group. And obtained by copolymerization.

The amount of the monomer component having a photopolymerization initiating group in the polymer having a photopolymerization initiating group is preferably from 5 to 100% by weight, and if it is less than 5% by weight, the polymerization of the ion-conductive monomer by light irradiation. Becomes inefficient.

In the composition containing a polymer having a photopolymerization initiating group, in addition to the polymer having a photopolymerization initiating group, a monomer having an unreacted photopolymerization initiating group, and a general coating film May be added to form an additive. Examples of such additives include, for example, other monofunctional or polyfunctional monomers and their polymers, photopolymerization initiators, curing agents, ultraviolet absorbers, leveling agents, surfactants, and colloidal silica. Inorganic fillers and the like. In addition, a silane coupling agent, a titanate coupling agent, or the like, which is generally used, may be added to improve the adhesion to the substrate.

Next, the composition of the ion conductive monomer will be described. As described above, the composition of the ion conductive monomer refers to the ion conductive monomer and the soluble electrolyte salt compound, or the ion conductive monomer and the electrolyte salt monomer, or the ion conductive monomer. Body, a composition containing a soluble electrolyte salt compound and an electrolyte salt monomer, if necessary,
It contains other solvents and additives. The total concentration of the ion conductive monomer, the soluble electrolyte salt compound and the electrolyte salt monomer in the composition of the ion conductive monomer is 100
%, But diluted with a solvent in which the ion-conductive monomer, the soluble electrolyte salt compound or the electrolyte salt monomer is dissolved, and the layer of the polymer having a photopolymerization initiation group is not dissolved. Is also good.

Although the solvent is not particularly limited,
Polar solvents such as water, methanol, acetone and methyl ethyl ketone are preferred. Also, in the composition of the ion conductive monomer, other monofunctional or polyfunctional monomer, a surfactant,
An additive such as a thickener may be contained. The total concentration of the ion-conductive monomer, the soluble electrolyte salt compound and the electrolyte salt monomer in the composition of the ion-conductive monomer is 1 to 100% by weight, more preferably 20 to 100% by weight.

The ionic conductive monomer includes at least one of a functional group consisting of a polyether group, a polyester group, a polyurethane group, a polyimino group, a pyridyl group, a 4-butyllactam ring, a hydroxyl group, an acetamido group and a nitrile group. Is used.

Specific examples of the ion conductive monomer include the following monomers (1) to (20), and one of these monomers may be used alone or as appropriate. Two or more kinds can be used as a mixture. (1) Polyethylene glycol mono (meth) acrylate having an addition mole number of ethylene glycol of 2 to 98, methoxypolyethylene glycol (meth) acrylate having an addition mole number of ethylene glycol of 2 to 98, and an addition mole number of ethylene glycol of 2 to 98 Mono (meth) acrylates of polyethylene glycol, such as phenoxy polyethylene glycol (meth) acrylate, nonylphenol polyethylene glycol (meth) acrylate, methoxyethyl acrylate, and ethoxydiethylene glycol (meth) acrylate having 1 to 4 moles of added ethylene glycol. (2) Di (meth) acrylates of polyethylene glycol such as polyethylene glycol di (meth) acrylate and ethylene glycol di (meth) acrylate in which the number of moles of ethylene glycol added is from 2 to 98. (3) The addition mole number of propylene glycol is 2 to 98
Polypropylene glycol mono (meth) acrylate, methoxyglycol glycol (meth) acrylate having an addition mole number of propylene glycol of 2-98, phenoxypolypropylene glycol (meth) acrylate having an addition mole number of propylene glycol of 2-98, propylene glycol Mono (meth) acrylates of polypropylene glycol such as nonylphenol polypropylene glycol (meth) acrylate, methoxypropyl acrylate, and ethoxydipropylene glycol (meth) acrylate having an addition mole number of 1 to 4. (4) The addition mole number of propylene glycol is 2 to 98
Polypropylene glycol di (meth) acrylate,
Di (meth) acrylates of polypropylene glycol such as propylene glycol di (meth) acrylate. (5) Random (or block) of polyethylene glycol and polypropylene glycol in a total added mole of 2-98 ethylene glycol and propylene glycol
Total addition moles of copolymer mono (meth) acrylate, ethylene glycol and propylene glycol 2 to 9
(Meth) acrylates of polyethylene glycol / polypropylene glycol copolymers, such as di (meth) acrylate of polyethylene glycol / polypropylene glycol block copolymer of No. 8. (6) The side chain obtained by ring-opening polymerization of (poly) alkylene glycol glycidyl ether having one or both of ethylene glycol and propylene glycol having an addition mole number of 1 to 10 alone or together with another glycidyl compound is also included in ( A poly (ether) mono (meth) acrylate or di (meth) acrylate having a weight average molecular weight of 5,000 or less and having an alkylene glycol group. (7) fumaric acid, maleic acid, itaconic acid and citraconic acid of a random (or block) copolymer of polyethylene glycol and polypropylene glycol having a total added mole number of one or both of ethylene glycol and propylene glycol of 1 to 98; Ester. (8) The side chain obtained by ring-opening polymerization of (poly) alkylene glycol glycidyl ether having an addition mole number of one or both of ethylene glycol and propylene glycol, alone or together with another glycidyl compound, is also (poly). ) Esters of polyether having an alkylene glycol group and having a weight average molecular weight of 5,000 or less with fumaric acid, maleic acid, itaconic acid and citraconic acid. (9) Allyl ethers, methallyl ethers and vinyl ethers of random (or block) copolymers of polyethylene glycol and polypropylene glycol in a total addition mole of one or both of ethylene glycol and propylene glycol of 1 to 98. (10) A styrene sulfonic acid ester of a polyethylene glycol polypropylene glycol random (or block) copolymer having a total added mole of one or both of ethylene glycol and propylene glycol of 1 to 98. (11) Polyester mono (meth) acrylate and di (meth) acrylate obtained by polycondensation of (poly) ethylene glycol having 1 to 98 addition moles of ethylene glycol and dicarboxylic acid having 3 to 12 carbon atoms Kind. (12) Esters of fumaric acid, maleic acid and itaconic acid of polyester obtained by polycondensation of (poly) ethylene glycol having an addition mole number of ethylene glycol of 1 to 98 and dicarboxylic acid having 3 to 12 carbon atoms . (13) Mono (meth) acrylate and di (meth) acrylate of polyurethane obtained by polyaddition of (poly) ethylene glycol having 1 to 98 moles of ethylene glycol and diisocyanic acid having 3 to 12 carbon atoms Kind. (14) Polyethyleneimine (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, glycidyl (meth) acrylate, methacryloyl isocyanate, isocyanatoethyl methacrylate, sulfoethyl methacrylate, acrylamide-t-butylsulfonic acid, 2 -Adducts with (meth) acryloyloxyethyl acid phosphate and methallylsulfonic acid. (15) Hydroxy group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 2,3-dihydroxypropyl (meth) acrylate. (16) Completely and partially saponified polyvinyl alcohol (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, glycidyl (meth) acrylate, methacryloyl isocyanate, isocyanatoethyl methacrylate, sulfoethyl methacrylate, acrylamide- t-
Adducts with butylsulfonic acid, 2- (meth) acryloyloxyethyl acid phosphate and methallylsulfonic acid. (17) Monomers having a 4-butanelactam ring such as vinylpyrrolidone. (18) Monomers having a pyridyl group such as vinylpyridine. (19) Monomers having an acetamide group such as N-vinylacetamide. (20) Nitrile compounds such as acrylonitrile and methacrylonitrile.

Among these, one or both of a polyethylene glycol group and a polypropylene glycol group are used as an ion conductive group, and a (meth) acryloyl group is used as a polymerizable group, since the ion conductivity and the radical polymerizability are particularly good. Is preferable. Specifically, the addition mole number of ethylene glycol is 2 to 98, and the addition mole number of polyethylene glycol mono (meth) acrylate and di (meth) acrylate is 2 to 98.
Methoxypolyethylene glycol (meth) acrylate, propylene glycol having an addition mole number of 2-98 propylene glycol mono (meth) acrylate and di (meth) acrylate, and propylene glycol having an addition mole number of 2-98 methoxypolypropylene glycol (meth) A) acrylate and the like.

Next, the soluble electrolyte salt compound is a salt compound having the following structure which is soluble in the ion conductive polymer film formed from the above ion conductive monomer.

[0047]

XY X: Li, Na, K, Rb, Cs, Ca, Mg, Ag,
Cu, NH ₄ Y: I, Cl, Br, ClO ₄ , ClO ₃ , SCN, B
F ₄ , AsF ₆ , CF ₃ SO ₃ , OH Specific examples of the soluble electrolyte salt compounds include lithium iodide, lithium perchlorate, potassium chlorate, ammonium thiocyanate, lithium boron tetrafluoride, and lithium hexafluoride. Antimony fluoride, sodium chloride, sodium bromide, sodium perchlorate, potassium iodide, potassium thiocyanate, copper (II) chloride, silver chloride magnesium chloride, lithium trifluoromethanesulfonic acid, calcium hydroxide, rubidium hydroxide, water Cesium oxide and the like can be mentioned. Among these, lithium perchlorate, potassium chlorate, lithium boron tetrafluoride, lithium antimony hexafluoride, sodium chloride or lithium trifluoromethanesulfonic acid is preferable in that coloring of the ion conductor can be prevented.

The proportion of the soluble electrolyte salt compound in the composition of the ion-conductive monomer greatly varies depending on the ion conductivity of the intended ion-conductive membrane and the type of the ion-conductive monomer and the soluble electrolyte salt compound. Therefore, it cannot be specified uniquely, but 0.5 to 1900 parts by weight per 100 parts by weight of the ion conductive monomer is appropriate. More specifically, when obtaining a membrane having an ion conductivity of 10 ^-5 to 10 ^-7 S (Siemens) / cm, 0.5 to 20 parts by weight and 1 to 5 parts by weight are required.
When obtaining a membrane having an ion conductivity of 0 ^-3 to 10 ^-5 S / cm, 20 to 400 parts by weight is further added, and 10 ^-2 to 10 ^-3 S / c is further added.
m to obtain a membrane having an ionic conductivity of 400 to 190 m.
0 parts by weight are preferred.

Next, the electrolyte salt monomer is soluble in the ion-conductive polymer membrane formed from the above-mentioned ion-conductive monomer, and is radically copolymerized with the ion-conductive monomer. A possible monomer, and in its molecule at least one electrolyte base selected from the group consisting of a carboxylate group, a sulfonate group, a phosphate group, a sulfate group, a pyridyl base, and a phenoxide group, and a radical polymerizable group. That have both.

Specific examples of the electrolyte salt monomer include the following monomers (a) to (f). Of these monomers, one of them may be used alone or as appropriate. A mixture of more than one species can be used. (A) lithium methacrylate, potassium acrylate,
Sodium methacrylate, ammonium acrylate, dilithium fumarate, monopotassium fumarate, disodium maleate, monolithium maleate, monopotassium itaconate, diammonium citraconic acid, β-methacryloyloxyethylpotassium phthalate and β-acryloyl Salts of monomers having a carbonyl acid group such as oxyethyl sodium succinate. (B) lithium salt of sulfoethyl methacrylate, potassium salt of sulfoethyl acrylate, acrylamide-t
Lithium salt of butyl sulfonic acid, acrylamide-t
-Salts of monomers having a sulfonic acid group, such as ammonium salts of butylsulfonic acid and potassium salts of p-styrenesulfonic acid. (C) Salts of monomers having a phosphate group such as 2-acryloyloxyethyl sodium phosphate and 2-methacryloyloxyethylpotassium phosphate. (D) Polyethylene glycol methacrylate sodium sulfate having an addition mole number of ethylene glycol (hereinafter abbreviated as EG) of 2 to 98, and an EG addition mole number of 2 to 98
And salts of monomers having a sulfate group, such as lithium polyethylene glycol allyl ether sulfate and sodium polyethylene glycol fumarate having an EG addition mole number of from 2 to 98. (E) A salt of a monomer having a pyridyl group such as 4-vinyl-N-butylpyridinium bromide. (F) Monomers containing a metal phenoxide group such as sodium-p-vinylphenoxide, potassium-potassium-p-vinylphenoxide, and potassium or lithium phenoxide of N-4-hydroxyphenylmaleimide.

Among these, salts of a monomer having a carboxylic acid group, a salt of a monomer having a sulfonic acid group, and a monomer of a monomer having a pyridyl group, which have particularly good radical polymerizability and can prevent coloring. Salts are preferred. The proportion of the electrolyte salt monomer cannot be unambiguously defined because the ion conductivity of the intended ion-conductive membrane greatly differs depending on the type of the ion-conductive monomer and the electrolyte salt monomer. It is 0.5 to 1900 parts by weight per 100 parts by weight of the conductive monomer. More specifically, when obtaining a membrane having an ion conductivity of 10 ^-5 to 10 ^-7 S / cm, 0.5 to 20 parts by weight is required.
When a film having an ion conductivity of 10 ⁻³ to 10 ⁻⁵ S / cm is obtained, 20 to 400 parts by weight is further added, and 10 ⁻² to 10 ⁻³ is further used.
When obtaining a membrane having an ion conductivity of S / cm, 400 to
1900 parts by weight are each preferred.

For the purpose of controlling the film properties such as further improving the mechanical strength, the composition of the ion-conductive monomer may contain other monofunctional or non-functional monomers other than the ion-conductive monomer and the electrolyte salt monomer. A polyfunctional radical polymerizable monomer may be contained.

Other monofunctional radical polymerizable monomers include, for example, (meth) acrylic acid, methyl (meth) acrylate, dimethylacrylamide, itaconic acid, dimethylaminoethyl fumarate (meth) acrylate, maleic acid Anhydride, itaconic anhydride and the like can be mentioned.

Other polyfunctional radically polymerizable monomers include, for example, di (meth) acrylate, reaction product of bisphenol A and polyethylene glycol, trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate. Tri (meth) of the reaction product of acrylate, glycerin and polyethylene glycol
Acrylate, (trishydroxyethyl isocyanurate) di (meth) acrylate, and the like.

The ratio of the other radically polymerizable monomer having one or both of monofunctionality and polyfunctionality in the composition of the ionically conductive monomer depends on the ratio of the ionically conductive monomer to the other radically polymerizable monomer. It is preferably at most 80% by weight based on the total weight of the monomer. The ratio of other radical polymerizable monomers is 8
If it exceeds 0% by weight, sufficient ion conductivity cannot be obtained, which is not preferable.

In preparing the composition of the ion conductive monomer, both the soluble electrolyte salt compound and the electrolyte salt monomer can be used as described above. In this case, the total amount of the soluble electrolyte salt compound and the electrolyte salt monomer used is determined by the ion conductivity of the target ion-conductive membrane, the ion-conductive monomer, the type of the electrolyte salt compound and the electrolyte salt monomer. Can not be unambiguously defined, but 0.5% per 100 parts by weight of the ion-conductive monomer.
~ 1900 parts by weight are suitable. More specifically, 10
0.5 to 20 parts by weight to obtain a membrane having an ion conductivity of ^-5 to 10 ^-7 S / cm, and to obtain a membrane having an ion conductivity of 10 ^-3 to 10 ^-5 S / cm. Is preferably 20 to 400 parts by weight, and more preferably 400 to 1900 parts by weight when obtaining a membrane having an ion conductivity of 10 ^-2 to 10 ^-3 S / cm. The thickness of the polymer layer having a photopolymerization initiation group,
In order to promptly polymerize the ion-conductive monomer, the amount of 0.1.
001 to 10 μm, preferably 0.1 to 10 μm.
More preferably, it is in the range of 5 to 5 μm. Further, the thickness of the ion-conductive film formed from the composition containing the ion-conductive monomer is preferably in the range of 0.01 to 10 μm in order to achieve good ion conductivity of the ion conductor. , 0.1 to 5 μm. Furthermore, the total thickness of the polymer layer having a photopolymerization initiating group and the ion conductive film is preferably in the range of 0.02 to 10 μm, and more preferably in the range of 0.2 to 6 μm.

Next, the ionic conductor as described above is manufactured, for example, according to the following manufacturing procedure. (A) A composition containing a polymer having a photopolymerization initiating group is applied to a substrate, and drying and heat curing are performed, if necessary, to form a polymer layer having a photopolymerization initiating group. (B) A substrate on which a polymer layer having a photopolymerization initiating group is formed is immersed in the composition of the ion-conductive monomer described above, and if necessary, an inert gas such as nitrogen is used to immerse the inside of the composition and the atmosphere. Perform the replacement. Alternatively, the composition of the ion-conductive monomer is applied and formed to a predetermined thickness on the substrate on which the polymer layer having a photopolymerization initiating group is formed. (C) Active energy rays to the polymer layer having a photopolymerization initiating group immersed in the composition of the ion-conductive monomer or to the polymer layer coated with the composition of the ion-conductive monomer. To generate radicals from the photopolymerization initiating group,
Graft polymerization of the ion conductive monomer is performed to form a film of the ion conductive polymer. (D) When there is an unreacted ion-conductive monomer or a homopolymer of the ion-conductive monomer, it is washed and removed with water as necessary. (E) Drying is performed as necessary in order to remove water remaining on the film by washing or the like.

The above-mentioned production procedure (B) aims at bringing the polymer layer having a photopolymerization initiation group into contact with the composition of the ion-conductive monomer. When applying the composition of the ion conductive monomer on the polymer layer having a photopolymerization initiation group,
The composition may be diluted with a solvent if necessary. As a coating method, a conventionally known method using a bar coater or a roll coater can be adopted. In addition, as a method of contacting, a conventionally known method other than the immersion method or the coating method may be used.

Further, in order to prevent a decrease in polymerizability due to oxygen, a material that transmits active energy rays and blocks oxygen, such as glass, quartz, or transparent plastic, is placed on the composition of the ion-conductive monomer. May be covered with a plate, film or the like.

When the composition of the ion-conductive monomer is brought into contact with the polymer layer having a photopolymerization-initiating group, the polymer layer having the photopolymerization-initiating group dissolves in the composition of the ion-conductive monomer. If they do, adverse effects may occur. That is, the appearance of the obtained ion conductive film may be deteriorated due to whitening or the like, or the ion conduction performance of the ion conductor may be deteriorated because the surface layer does not become a uniform layer of the ion conductive polymer. For this reason, it is preferable that the composition of the ion conductive monomer does not dissolve the polymer layer having a photopolymerization initiation group.

The active energy ray used in the production procedure (C) is not particularly limited as long as it promotes the decomposition of the photopolymerization initiating group used, and ultraviolet rays, visible rays, electron beams and the like are used. Preferably, 200-800n
m, more preferably 300 to 600 nm ultraviolet or visible light. As the light source, a high pressure mercury lamp,
Examples include a low-pressure mercury lamp, a halogen lamp, a xenon lamp, an excimer laser, a dye laser, a YAG laser, an electron beam irradiation device, and sunlight.

In the case where the composition of the ion-conductive monomer contains a crosslinking component such as a bifunctional acrylate or an ion-conductive polymer such as polyvinylpyrrolidone,
When the entire composition becomes a coating film having sufficient strength by irradiation with active energy rays, an ion conductive monomer, a homopolymer of the ion conductive monomer, an electrolyte salt monomer, an electrolyte salt monomer And a copolymer of an ion conductive monomer and an electrolyte salt monomer may be included. In such a case, the manufacturing steps (D) and (E) can be omitted.

The ionic conductor having the polymer layer having a photopolymerization initiating group and the ionic conductive film formed on the surface of the base material as described above can be used as a solid electrolyte for a lightweight sheet battery, a separator for a lithium secondary battery, A solid electrolyte for a chromic element, a sensor responding to various stimuli such as mechanical, light or humidity, a conductive film, an antistatic film, and an electromagnetic wave are suitably used for applications such as a shielding material.

According to the embodiment described in detail above, the following effects are exhibited. (1) A polymer layer having a photopolymerization initiating group is formed on a substrate surface, and an ion-conductive monomer and a soluble electrolyte salt compound, or an ion-conductive monomer and an electrolyte salt monomer are formed thereon.
Or, after applying a composition containing an ion-conductive monomer, a soluble electrolyte salt compound and an electrolyte salt monomer, by irradiating the composition with an active energy ray, it has an ion-conducting performance on the polymer layer. An ion conductive film can be easily formed. (2) Since the mechanism for initiating the polymerization is not a mechanism in which the photopolymerization initiator withdraws hydrogen from the substrate to initiate the polymerization, it is possible to prevent the possibility that the usable substrate is limited. (3) Since the composition layer containing the ion-conductive polymer, the soluble electrolyte salt compound or the electrolyte salt polymer is oriented on the surface of the ion-conductive film, the ion-conductive film on the substrate surface is excellent. Can exhibit high ionic conductivity. (4) The ion-conductive membrane containing the ion-conductive polymer, the soluble electrolyte salt compound or the electrolyte salt polymer is bonded to the polymer layer via the photopolymerization initiator fragment,
Since the polymer layer is in close contact with the substrate, the adhesion and mechanical strength of the ion-conductive film can be maintained for a long time. (5) Since the ion-conductive film containing the ion-conductive polymer, the soluble electrolyte salt compound or the electrolyte salt polymer has good uniformity, the performance can be sufficiently exhibited with a thin film having a thickness of 10 μm or less, and the transparency is high. Is excellent. (6) Further, the ion conductive film is hardly swelled due to its properties, is less likely to be damaged or peeled off, and can exhibit practical coating film strength.

[0065]

Next, the present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In addition,% in a text and a table represents weight%. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

Abbreviations in the text and tables are as follows. PI1: 1- [4- {2- (2- (methacryloyloxy) ethoxycarbonyloxy) ethoxy} phenyl] -2-hydroxy-2-methylpropan-1-one PI2: methyl [2- {4- (2- Hydroxy-2-
Methyl-1-oxopropyl) phenoxydiethyl] fumarate PI3: Bis [2- {4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy} ethyl] itaconate PI4: 1- {4- (2- Methacryloyl ethoxy)
Phenyl {-2,2-dimethoxy-2-phenylethan-1-one PI5: 1,2-diphenyl-1,2-ethanedione-2-O-acryloyloxime PI6: 3,3'-bis (methacryloyloxyethoxycarbonyl ) -4,4′-Bis (t-butylperoxycarbonyl) benzophenone MMA: Methyl methacrylate BMA: Butyl methacrylate LMA: Lauryl methacrylate ST: Styrene DBF: Dibutyl fumarate HEMA: Hydroxyethyl methacrylate MAA: Methacrylic acid DMAEMA: N, N -Dimethylaminoethyl methacrylate GMA: Glycidyl methacrylate KBM503: Trimethoxysilylpropyl methacrylate ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.) PPZ: Phosphaze System 6-functional methacrylate (“Idemitsu PPZ” manufactured by Idemitsu Petrochemical Co., Ltd.) 3002A: Bifunctional epoxy acrylate (“Epolite 3002A” manufactured by Kyoeisha Chemical Co., Ltd.) MEK: methyl ethyl ketone PGM: propylene glycol monomethyl ether THF: tetrahydrofuran PVA: partially saponified polyacetic acid Vinyl ("Gohsenol KH-17" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) TTA: Triethylenetetramine ACS: Colloidal silica ("Snowtex O" manufactured by Nissan Chemical Co., Ltd.) trimethoxysilylpropyl methacrylate ("KBM-" manufactured by Shin-Etsu Chemical Co., Ltd.) 503 ") treated with a 20% MEK solution of acrylic-modified coidal silica LPO: lauroyl peroxide (" Perloyl L "manufactured by NOF Corporation) A-200: polyethylene glycol diacrylate (E A-400: Polyethylene glycol diacrylate (number of added moles of EG: 9) A-600: Polyethylene glycol diacrylate (number of added moles of EG: 14) NK-14G: Polyethylene glycol dimethacrylate (Number of moles of added EG: 14) A-1000: Polyethylene glycol diacrylate (Number of moles of added EG: 23) NK-23G: Polyethylene glycol dimethacrylate (Number of moles of added EG: 23) PP-800: Polypropylene glycol di Methacrylate (number of moles of added PG: 12) PESDA: Diacrylate of polyester (weight average molecular weight: 5000) obtained by reacting adipic acid with polyethylene glycol (number of added moles of EG: 23) PUDA: Hexamethylene diisocyanate Polyurethane (weight average molecular weight: 5000) obtained by the reaction of anate and polyethylene glycol (number of moles of EG added: 23)
VP: Vinylpyrrolidone VPy: Vinylpyridine VAcAm: N-vinylacetamide PVAMA: Partially saponified polyvinyl acetate ("Goselan L-302", manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) treated with glycidyl methacrylate. 20% by weight methanol solution of functionalized polyvinyl acetate AN: Acrylonitrile PIA: Polyethyloxazoline having a weight average molecular weight of 5 × 10 ⁵ (manufactured by Dow Chemical Co.) was added to Macromolecules, Vol. 20, 968.
Page, 1987, treated with hydrochloric acid and dried, and then treated with acryloyl isocyanate ("MAI" manufactured by Nippon Paint Co., Ltd.) in chloroform to obtain a 20% by weight chloroform solution AN: acrylonitrile PET-30: pentane Erythritol triacrylate (“KAYARAD PET-30” manufactured by Nippon Kayaku Co., Ltd.) GE-3A: Triacrylate of ethyleneglycol-modified glycerin (“GE-3A” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) MAA: methacrylic acid DMAAm: N, N -Dimethylacrylamide LiClO ₄ : Lithium perchlorate KClO ₃ : Potassium chlorate KI: Potassium iodide NH ₄ SCN: Ammonium thiocyanate CuCl ₂ : Copper chloride (II) MAAK: Potassium methacrylate MAACe: Cesium methacrylate MAS E: potassium salt of 2-sulfoethyl methacrylate AOEPP: 2-acryloyloxyethylpotassium phosphate POEMS: polyoxyethylene (number of moles of EO added: 9) sodium methacryloyl sulfate (“Eleminol RS-30” manufactured by Sanyo Chemical Industries, Ltd.) VPy: Vinyl pyridine MAAm: Ammonium methacrylate D2959: Photopolymerization initiator, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropan-1-one ("Daro" manufactured by Ciba Geigy)
cure2959 ") PVPy: polyvinylpyrrolidone (" L "manufactured by BASF)
20% by weight aqueous solution of UVISOL K90) (Reference Example 1, Production of Photopolymerization Initiating Group-Containing Polymer)
50 g of MEK was charged into a 1-liter reaction vessel equipped with a thermometer, a purge gas inlet, and a water-cooled condenser, and heated to 80 ° C. under nitrogen gas flow. Then, with stirring, 90 g of methyl methacrylate, 10 g of PI1, M
A mixture of 50 g of EK and 5 g of LPO was added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued for 4 hours to complete the polymerization. The resulting solution was poured into petroleum ether to precipitate a polymer, which was then dried to obtain a photopolymerization-initiating group-containing polymer a. Its weight average molecular weight (Mw) is 210
00. Further, it was confirmed from the ultraviolet (UV) absorption spectrum that the same amount of the photopolymerization initiating group as the charged amount was introduced into the polymer. (Reference Examples 2 to 12) Polymerization was carried out in the same manner as in Reference Example 1 except that the monomers were changed to the types and amounts shown in Tables 1 and 2, and photopolymerization group-containing polymers bl were obtained.

[0067]

[Table 1]

[0068]

[Table 2] (Example 1, Production of coating film) Reference Example 1 as a coating liquid (a)
Using a 20% MEK solution of the polymer a obtained in
It is applied to an acrylic resin plate having a thickness of 10 cm and a thickness of 2 mm using a bar coater so that the dry film thickness becomes 5 μm.
Dry at 10 ° C. for 10 minutes. A-600 10 as a composition (b) containing an ion-conductive monomer on the obtained coating film
After applying 0 g and 10 g of LiClO ₄ uniformly mixed in advance, the mixture was irradiated with light for 1 minute using a 1 kW high-pressure mercury lamp. The light irradiation amount at this time was 5 J / cm ² . After irradiation with light, washing with water and drying were performed to obtain an ion conductor having a colorless and transparent ion conductive film on the coating film of the polymer a.

Next, the physical properties of the obtained ionic conductor were evaluated by the following evaluation methods. (1) Graft thickness The thickness before and after the graft polymerization is measured by a digital thickness meter (Sheen).
Instrument Inc.) and the increase was expressed as a graft thickness (μm). (2) Adhesion According to the grid tape method of JIS K-5400, the coating film is cut vertically and horizontally using a cutter knife to make 100 cross cuts (cut pieces) reaching the base material. A cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) was affixed and peeled in a direction perpendicular to the adhesive surface, and the number of crosscuts remaining without peeling was represented by the following symbol.

：: 100/100, Δ: 80/100 or more, ×: less than 80/100 (3) Surface resistivity: Conducted according to JIS K-6911.

Using an electric conductivity measuring device SS-608H manufactured by Shibayama Kagaku Kikai Seisakusho, at an applied voltage of 10 V under an atmosphere of a temperature of 25 ° C. and a relative humidity of 50%.
The value after minutes was measured. (4) Bendability (90 ° and 180 °) The appearance of the film when bent at 90 ° and 180 ° was visually observed.

○: No peeling or cracking, Δ: Peeling, ×: Cracking (5) Tensile strength and elongation The peeled ion conductive film formed on the Teflon plate was peeled off according to JISK-7113, Shimadzu Corporation. The test was carried out using AUTOGRAPH DSS-500 manufactured by Toshiba Corporation. (6) Total light transmittance The total light transmittance was measured using a “direct reading haze meter” manufactured by Toyo Seiki Seisaku-Sho, Ltd. in accordance with JIS-K-7105.

Table 7 shows the above results. Among these evaluation items, “surface resistivity” is an index of ionic conductivity, “bending property” and “tensile strength and elongation” are mechanical strength, and “total light transmittance” is an index of transparency. Becomes (Examples 2 to 10) An ion conductor was produced by the method described in Example 1 except that the coating liquid (a) described in Table 3 was used, and the physical properties were evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 7 and 8.

[0074]

[Table 3] (Examples 11 to 20) Except for using those described in Tables 4 to 6 as the composition (b) containing an ion conductive monomer, an ionic conductor was produced by the method described in Example 1,
Physical properties were evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 9 and 10.

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

[0079]

[Table 8]

[0080]

[Table 9]

[0081]

[Table 10] (Example 21) Polymer solution k20 g, TTA5 g, PG
A mixture of 30 g of M was applied to a polycarbonate plate so that the dry film thickness became 5 μm, and heated at 120 ° C. for 1 hour. Then, A-600 91 g and LiClO ₄ 9 g
Example 1 after applying a mixture in which the parts were uniformly mixed in advance,
Light irradiation, washing with water and drying were performed in the same manner as in the above to obtain an ion conductor.
The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. Table 11 shows the evaluation results. (Example 22) A mixture of 120 g of the polymer solution and 20 g of MEK was applied to a glass plate so as to have a dry film thickness of 2 µm, and heated at 80 ° C for 30 minutes. Then, A-2005
After applying ₃ g, 42 g of NK-23G and 5 g of KClO ₃ uniformly beforehand, light irradiation, washing with water and drying were carried out in the same manner as in Example 1 to obtain an ion conductor. And
The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. Table 11 shows the evaluation results. (Example 23) A mixture of 20 g of the polymer solution a and 20 g of MEK was applied to a PET film (“Tetron HP” manufactured by Teijin Limited).
7 ", a film thickness of 100 μm) and a dried film thickness of 2 μm, and heated at 80 ° C. for 30 minutes. Then, A-40
0 30 g, A-1000 30 g, NK-14G 1
1 g, 10 g of PET-30, 10 g of DMAAm, and 9 g of KI were uniformly mixed in advance, and then applied, light-irradiated, washed with water and dried in the same manner as in Example 1 to obtain an ion conductor. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. Table 11 shows the evaluation results. (Example 24) PI6 10 g, PPZ 10 g, 300
A mixture of 5 g of 2A and 25 g of MEK was applied to an acrylic resin plate so as to have a dry film thickness of 5 μm.
After drying for 5 minutes, an electron beam of 5 Mrad was irradiated for 1 second. Then, after applying 91 g of A-600 and 9 g of LiClO ₄ uniformly in advance, the mixture was applied, irradiated with light, washed with water and dried in the same manner as in Example 1 to obtain an ion conductor. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. Table 11 shows the evaluation results. (Example 25) A mixture of 20 g of the polymer solution b and 20 g of MEK was applied to an acrylic resin plate so as to have a dry film thickness of 5 µm, and dried at 60 ° C for 10 minutes. This is A-600
91 g and 9 g of LiClO ₄ were placed in a well-mixed state in advance, and irradiated with light for 1 minute from a coating surface side with a 1 kW high-pressure mercury lamp. After the light irradiation, washing with water and drying were performed to obtain an ion conductor. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. Table 11 shows the evaluation results. (Example 26) A mixture of 20 g of the polymer solution a and 20 g of MEK was applied to an acrylic resin plate so as to have a dry film thickness of 5 µm, and dried at 60 ° C for 10 minutes. Then, A-20
0 53 g, NK-23G 42 g and KClO ₃ 5 g
Was uniformly mixed in advance, and a glass plate was directly placed thereon, and then irradiated with light, washed with water and dried in the same manner as in Example 1 to obtain an ion conductor. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. Table 11 shows the evaluation results.

[0082]

[Table 11] Comparative Example 1 90 g of polyethylene glycol (23 moles of EG added), LiClO ₄ 10 on an acrylic resin plate
g and 100 g of MEK were uniformly mixed in advance and applied so that the dry film thickness was 5 μm.
After drying for 0 minutes, an ion conductor was obtained. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. Table 12 shows the evaluation results. (Comparative Example 2) 20 g of A-1000 and 0.2 of a photopolymerization initiator ("Darocure 2959" manufactured by Ciba-Geigy)
g, 1 g of LiClO ₄ and 30 g of MEK were applied to an acrylic resin plate so as to have a dry film thickness of 5 μm, dried, and then irradiated with light for 1 minute with a 1 kW high-pressure mercury lamp to obtain an ion conductor. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. The results are shown in Table 12. Comparative Example 3 20 g of A-1000 and LiClO ₄ 1
g of the mixture was applied to an acrylic resin plate so as to have a dry film thickness of 5 μm, dried, and then irradiated with an electron beam to obtain an ion conductor. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. The results are shown in Table 12. (Comparative Example 4) A 20% MEK solution of the polymer a obtained in Reference Example 1 was used as a coating liquid (a) on an acrylic resin plate having a size of 10 cm x 10 cm and a thickness of 2 mm so that the dry film thickness was 5 µm. It was applied using a bar coater and dried at 60 ° C. for 10 minutes. As a monomer solution (b) on the obtained coating film,
A mixture of 20 g of A-1000 and 30 g of MEK was applied so as to have a dry film thickness of 5 μm, dried, and then irradiated with light with a 1 kW high pressure mercury lamp for 1 minute to obtain an ion conductor. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. The results are shown in Table 12.

[0083]

[Table 12] (Comparative Example 5) A 20% MEK solution of the polymer a obtained in Reference Example 1 was used as a coating liquid (a) on an acrylic resin plate having a size of 10 cm × 10 cm and a thickness of 2 mm so that the dry film thickness was 5 µm. It was applied using a bar coater and dried at 60 ° C. for 10 minutes. As a monomer solution (b) on the obtained coating film,
A mixture of 20 g of MAA, 1 g of LiClO ₄ and 30 g of MEK was applied so as to have a dry film thickness of 5 μm, and after drying,
Light irradiation was performed for 1 minute with a 1 kW high-pressure mercury lamp to obtain an ion conductor. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. The results are shown in Table 13. (Comparative Example 6) A 20% MEK solution of the polymer a obtained in Reference Example 1 was used as a coating liquid (A) on an acrylic resin plate having a size of 10 cm × 10 cm and a thickness of 2 mm so that the dry film thickness was 5 µm. It was applied using a bar coater and dried at 60 ° C. for 10 minutes. As a monomer solution (b) on the obtained coating film,
A mixture of 20 g of MMA, 1 g of LiClO ₄ and 30 g of MEK was applied to an acrylic resin plate so as to have a dry film thickness of 5 μm, dried, and then irradiated with light for 1 minute with a 1 kW high-pressure mercury lamp,
An ionic conductor was obtained. The physical properties of the ionic conductor were evaluated in the same manner as in Example 1. The results are shown in Table 13. (Comparative Example 7) 20 in a 1-liter screw-in pressure-resistant bottle
% PVP aqueous solution (“LUVISKOL K” manufactured by BASF)
90 ") 252 g, disproportionated potassium rosinate 5 g, sodium salt of naphthalenesulfonic acid-formalin condensate 0.2 g, potassium chloride 0.6 g tetraethylenepentamine 0.2 g, styrene 30 g, nododecyl mercaptan 0.3 g Was charged.

Next, after 100 g of butadiene was charged, a gasket and a stopper having three 1 mm holes were attached to the pressure-resistant bottle, attached to a rotary polymerization layer at 5 ° C., and stirred for 30 minutes. After the stirring, a solution of 0.3 g of cumene hydroperoxide and 20 g of styrene was injected using a syringe to start polymerization. After reaction at 5 ° C. for 10 hours, 7 g of a 10% aqueous solution of sodium dimethyldithiocarbamate was injected to terminate the polymerization, thereby obtaining a latex. The obtained latex was applied to an acrylic resin plate so as to have a dry film thickness of 5 μm, dried, immersed in a 10% LiClO ₄ aqueous solution for 1 hour, and vacuum dried to obtain a PVP / latex polymer solid electrolyte. This was evaluated for physical properties in the same manner as in Example 1. Table 13 shows the results.

[0085]

[Table 13] The following can be seen from the results of Examples and Comparative Examples shown in Tables 7 to 13. That is, the ion conductors of Examples 1 to 26 vary the type and amount of the polymer forming the polymer layer having a photopolymerization initiating group, or change the composition of the ion conductive monomer. However, it has excellent ion conduction performance, and also has excellent adhesiveness to a substrate, mechanical strength, and transparency.

On the other hand, a uniform mixture of the ion-conductive polymer of Comparative Example 1 and the soluble electrolyte salt compound was applied, and the ion-conductive monomer of Comparative Examples 2 and 3 and the soluble electrolyte salt were applied. The cured product of the mixture with the compound exhibits good ionic conductivity and transparency, but has poor adhesion and mechanical strength, and easily peels or cracks.

In the case where only the ion-conductive monomer of Comparative Example 4 was graft-polymerized on a layer of a hydrophobic polymer having a photopolymerization initiating group, good ion conductivity was not obtained. Comparative Example 5
And a mixture of a monomer having no ion conductivity of Comparative Example 6 and a soluble electrolyte salt compound graft-polymerized on a layer of a hydrophobic polymer having a photopolymerization initiating group have good ionic conductivity. , Mechanical strength and transparency cannot be obtained. Comparative Example 7
A rubber latex blended with the above-mentioned ion conductive polymer has good ionic conductivity and mechanical strength, but does not have good adhesion and transparency.

The technical ideas grasped from the above embodiment will be described below. Forming a polymer layer having a photopolymerization initiating group on a substrate,
The composition according to claim 2, wherein a composition containing an ion conductive monomer and an electrolyte salt monomer is brought into contact with the polymer layer, and the composition is irradiated with an active energy ray to form an ion conductive film. A method for producing an ion conductor.

According to this method, an ionic conductor having excellent adhesion to a substrate and excellent mechanical strength can be quickly and efficiently manufactured while maintaining the ionic conductivity and transparency. Forming a polymer layer having a photopolymerization initiating group on a substrate,
A composition comprising an ion conductive monomer, a soluble electrolyte salt compound and an electrolyte salt monomer is brought into contact with the polymer layer, and the composition is irradiated with active energy rays to form an ion conductive membrane. Item 4. The method for producing an ionic conductor according to Item 3.

According to this method, an ion conductor excellent in adhesion to a substrate, mechanical strength, and transparency can be rapidly and efficiently produced while maintaining ion conduction performance. The ion conductor according to any one of claims 1 to 4, wherein the ion conductive film forms a graft polymer chain on a polymer layer having a photopolymerization initiating group.

In such a configuration, since the ion conductive film has an integral structure with the polymer layer, the adhesion and the mechanical strength of the ion conductive film to the polymer layer can be improved. -The ion-conductive monomer is one or both of a polyethylene glycol group and a polypropylene glycol group,
2. A monomer having a (meth) acryloyl group.
5. The ionic conductor according to any one of items 1 to 4.

With such a constitution, it is possible to exhibit excellent ionic conductivity of the ionic conductor and good radical polymerization of the ionic conductive monomer. The electrolyte salt monomer is a salt of a monomer having a carboxylic acid group, a sulfonic acid group or a pyridyl group.
5. The ionic conductor according to any one of 4.

With this configuration, it is possible to exhibit excellent radical polymerizability of the electrolyte salt monomer and anti-coloring performance of the ion conductive film. The thickness of the ion conductive membrane is 0.01 to 10 μm;
The ionic conductor according to any one of claims 1 to 4, wherein

With such a configuration, it is possible to achieve good ion conductivity of the ion conductor.

[0095]

As described above in detail, according to the present invention, the following excellent effects can be obtained. According to the ionic conductor of the first aspect, excellent ionic conduction performance can be exhibited based on the ionic conductive monomer and the soluble electrolyte salt compound. In addition, since the ion conductive membrane is bonded to the polymer layer via the photopolymerization initiation fragment, excellent adhesion to the substrate and mechanical strength can be maintained for a long period of time. In addition, the ion conductive film is excellent in transparency because of its good uniformity.

According to the ionic conductor of the second aspect,
By the ion conductive monomer and the electrolyte salt monomer forming the ion conductive film, the adhesion to the substrate and the mechanical strength can be improved while maintaining the ion conductive performance and the transparency.

According to the ionic conductor of the third aspect,
Due to the synergistic effect of the ion-conductive monomer, soluble electrolyte salt compound and electrolyte salt monomer forming the ion-conductive film, adhesion to the substrate, mechanical strength and transparency while maintaining ion-conducting performance Can be improved.

According to the ionic conductor of the fourth aspect,
Photopolymerization initiation efficiency of the polymer having a photopolymerization initiation group is good,
Further, the polymer can be easily produced. According to the method for producing an ion conductor according to the fifth aspect, the ion conductor having excellent ion conduction performance, excellent adhesion to a substrate, mechanical strength, and transparency can be quickly and efficiently produced. Can be manufactured well.

[Brief description of the drawings]

FIG. 1 is an explanatory view conceptually showing a manufacturing process of an ion conductor.

Claims (5)

[Claims] 1. Curing of a composition comprising a substrate, a polymer layer having a photopolymerization initiation group formed on the substrate, and an ion-conductive monomer and a soluble electrolyte salt compound on the polymer layer An ion-conductive film formed from a material, and the ion-conductive film is bonded to the polymer layer via a photopolymerization initiation group fragment derived from the photopolymerization initiation group of the polymer layer. body. 2. A composition comprising a base material, a polymer layer having a photopolymerization initiation group formed on the base material, and an ion-conductive monomer and an electrolyte salt monomer on the polymer layer. An ion conductive film formed from a cured product, wherein the ion conductive film is bonded to the polymer layer via a photopolymerization initiation group fragment derived from the photopolymerization initiation group of the polymer layer. Conductor. 3. A base material, a polymer layer having a photopolymerization initiation group formed on the base material, and an ion conductive monomer, a soluble electrolyte salt compound and an electrolyte salt monomer on the polymer layer. An ion conductive film formed from a cured product of a composition containing the polymer layer, the ion conductive film and the polymer layer via a photopolymerization initiation group fragment derived from the photopolymerization initiation group of the polymer layer. Bound ionic conductor. 4. The method according to claim 1, wherein the polymer layer having a photopolymerization initiating group is formed.
The polymer to be formed is selected from the group of photopolymerization initiation groups shown below.
Consists of at least one selected monomer
The polymer according to claim 1, which is a polymer having a polymer segment.
The ionic conductor according to any one of the above. Photopolymerization initiator group:Where φ₁Is a phenylene group, and A isφ_TwoRepresents a phenyl group;₁, R_TwoHas 1 to 4 carbon atoms
Alkyl group or R₁, R ₁And R_Two, R_TwoDue to the carbon between
A cycloalkyl group having 5 to 7 carbon atoms formed, R _ThreeIs water
Acid group or amino group, R_Four, R_FiveIs an alk having 1 to 4 carbon atoms
Represents a hydroxyl group. 5. A composition comprising a polymer layer having a photopolymerization initiating group formed on a substrate, and a composition containing an ion-conductive monomer and a soluble electrolyte salt compound being brought into contact with the polymer layer. The method for producing an ion conductor according to claim 1, wherein the ion conducting film is formed by irradiating the ion conductive film with an active energy ray.