JP3391600B2 - Method for producing solid polymer electrolyte - Google Patents

Abstract

PURPOSE: To obtain a solid polymer electrolyte being excellent in properties such as inoic conductivity, film-forming properties, flexibility and strengths and reduced in a volume change in film formation by solidifying a composition containing a specified urethane acrylate, an organic nonaqueous solvent and a supporting electrolyte. CONSTITUTION: A composition containing 100 pts.wt. urethane acrylate having 2-6 polymerizable functional groups in the molecule and a molecular weight of 2,500-30,000 and represented by the formula (wherein R<1> and R<2> are the same or different groups; R<5> to R<7> are each 1-3C alkyl; R<8> is a 1-20C bi- to tetravalent organic residue; R<3> and R<4> are each a 1-20C bivalent hydrocarbon residue; Y is a polyether unit, a polyester unit, a polycarbonate unit or a combination thereof; and n is an integer of 1-100), 100-1,200 pts.wt. organic nonaqueous solvent (e.g. propylene carbonate) and 0.1-30wt.%, based on the solvent, supporting electrolyte (e.g. alkali metal salt) is solidified by photocuring or heating to form a polymer matrix.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a material for an electrochemical device.
The present invention relates to a solid polymer electrolyte useful as a material. Further details
Or cured body useful as a material for electrochemical devices
The present invention relates to a polymer solid electrolyte having a very small product change rate. [0002] 2. Description of the Related Art Conventionally, primary batteries, secondary batteries,
Electrochemical data such as chromic elements and electric double layer capacitors
Dissolve supporting electrolyte in organic solvent as vice electrolyte
Liquid electrolyte is used. But the liquid electrolyte is
Low reliability due to leakage of liquid outside the element, sealing
There are problems such as scattering of the electrolyte at the time and the need for a sealing technique. As a result, liquid leakage is prevented and reliability is further improved.
High polymer conductivity with high ionic conductivity
Development of resolving power is underway. As the polymer solid electrolyte, polyethylene is used.
Oxide-based polymer and alkali metal salt
Focusing on complexes with supporting electrolytes such as quaternary ammonium salts
It has been studied to improve the ionic conductivity of polyethylene.
Copolymerization of ethylene oxide and propylene oxide,
Introducing a polymerizable functional group at the end of polyethylene oxide
Useful by polymerizing the obtained macromonomer, etc.
Attempts have been made to obtain polymer solid electrolytes. [0005] These polymer solid electrolytes are
Incorporate into electrochemical elements such as rhomic elements and capacitors
In this case, a polymer solid electrolyte film is prepared and
Method or a polymer solid containing a polymerizable monomer in the device.
Method of injecting body electrolyte component and curing with heat, light, etc.
And the like, but using the conventional polymer solid electrolyte,
Attempts to fabricate the electrochemical device by these methods
In this case, there are various problems described below. [0006] A film of the polymer solid electrolyte is prepared.
Fabricating electrochemical devices by sandwiching them between electrodes
In this case, the conventional polymer solid electrolyte has a uniform thin film filter.
Lum, especially in large areas.
There is a problem that. For example, polyethylene oxide-alkali gold
The ionic conductivity of the genus salt polymer solid electrolyte is 10 at room temperature.
~⁶S / cm, which is not enough for practical use
Propylene
Improvements are made by adding organic solvents such as carbonates. I
Add organic solvent to the linear matrix polymer
Then, a film having good film-forming properties cannot be obtained. Especially polyethylene
Transparent due to high crystallinity when using lenoxide
And it cannot be used for devices that require transparency.
Another problem is that In order to improve the film forming property, a matrix is used.
Introduce a crosslinked structure of polyether as a polymer
Has been attempted. For example, glycerin derivative polye
-The system of tertriol and tolylene isocyanate
Although this system takes several hours to cure,
It is difficult to enlarge the area and it is easy to color brown
There are drawbacks such as limited use. Also disclosed in Japanese Patent Application Laid-Open No. 4-53872.
Polyalkylene glycol
In the case of solid polymer electrolyte with a structure to which coal is added,
Since a solvent is required during formation, remove the solvent before
Must be manufactured, making it difficult to increase the area.
Cause. [0010] In addition, the device may contain a polymerizable monomer.
Inject molecular solid electrolyte components and cure with heat, light, etc.
When manufacturing an electrochemical device by the method described above,
All solid electrolytes have the property of contracting during the solidification process.
Therefore, there is a problem that it is difficult to obtain a high quality product. For example, in the case of application to a battery, polymerization shrinkage
If they do, they will crack, increase interface resistance, and
The flow cannot be drawn. In adoption for capacitors,
When polymerization shrinkage occurs, the interface resistance between the electrode and the solid polymer electrolyte is reduced.
Resistance and the rapid charge / discharge characteristic of capacitors
No longer. Odor in electrochromic devices
When polymerization shrinkage occurs, internal stress is applied to the element,
Therefore, cracks may occur when driving the element,
There is a risk of losing product value. [0012] SUMMARY OF THE INVENTION The object of the present invention is to
Ion conductivity, high film forming properties, extremely small during film formation
High volume change rate, high flexibility, strength, etc.
An object of the present invention is to provide a polymer solid electrolyte. [0013] According to the present invention, the following is provided.
Urethane acrylate represented by general formula 2, organic non-water-soluble
Solidifying a composition comprising a medium and a supporting electrolyteEspecially
SignPolymer solid electrolyteManufacturing methodIs provided. [0014] Embedded image Hereinafter, the present invention will be described in more detail.
You. The solid polymer electrolyte of the present invention has the general formula
A urethane acrylate represented by Chemical formula 2, an organic non-aqueous solvent,
And a composition containing a supporting electrolyte (hereinafter abbreviated as composition A)
Is solidified. R in Formula 2^Five~ R⁷Are the same or different groups
Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
You. Specific examples of the alkyl group include a methyl group,
A butyl group or a propyl group, and a methyl group is particularly preferred.
Good. R in Formula 2⁸Has 1 to 20 carbon atoms, preferably
Represents 2 to 8 divalent to tetravalent organic residues. As the organic residue
Specifically, specifically, alkyl tolyl group, alkyl tetra
Carbon such as an alkylene group represented by the following general formula 3:
And a hydride residue. [0019] Embedded image In the hydrocarbon residue, a part of a hydrogen atom is
An alkoxy group having 1 to 6, preferably 1 to 3 carbon atoms, carbon
By a hydrocarbon group such as an aryloxy group of the formulas 6 to 12
It may be a substituted group. R in the above formula 2⁸As
Is preferably a group represented by the following formula 4
Can be mentioned. [0021] Embedded image R in Formula 2^ThreeAnd R^FourAre the same or different
Group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms.
Indicates a divalent hydrocarbon residue. As the hydrocarbon residue,
Chain divalent hydrocarbon group, aromatic hydrocarbon group, alicyclic hydrocarbon
And a hydrogen group. As the chain divalent hydrocarbon group
Is, for example, an alkylene group represented by the following general formula 5.
be able to. [0023] Embedded image The above aromatic hydrocarbon group and alicyclic ring
As the hydrocarbon group, a hydrocarbon represented by the following general formula 6
Element groups and the like. [0025] Embedded image In the above formula 2, R^ThreeAnd R^FourAs a tool
Physically, a group represented by the following formula 7 is preferably exemplified.
be able to. [0027] Embedded imageIn Formula 2, Y is a polyether unit,
Steal units, polycarbonate units or a mixture of these
Indicates the unit. The polyether unit and the polyester unit
And polycarbonate units are as follows:
Represented by formulas (a), (b) and (c) in general formula 8
Units and the like can be mentioned. [0029] Embedded image In Formula 8, R¹⁶~ R^{twenty one}Are the same or different
A group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms.
Shows a monovalent hydrocarbon residue. Especially R¹⁹Is about 2 to 6 carbon atoms
Is preferred. The R¹⁶~ R^{twenty one}As a linear or branched
And the like, and specifically,¹⁸As
Are methylene, ethylene, trimethylene, tetrame
Tylene group, pentamethylene group, hexamethylene group, pro
A pyrene group is preferred. Also, R¹⁶, R¹⁷, And R¹⁹
~ R^{twenty one}Are preferably ethylene, propylene, etc.
No. In the formula 8, m is 2 to 300, preferably 10 to
Represents an integer of 200, and r is 1 to 300, preferably 2 to
Represents an integer of 200, and s is 1 to 200, preferably 2
Represents an integer of 100, and t is 1 to 200, preferably 2
An integer of 100, u is 1 to 300, preferably 10 to 20
Indicates an integer of 0. In Formula 8, each unit is the same.
Alternatively, a copolymer of different units may be used. That is, a plurality of R¹⁶~ R
^{twenty one}If exists, then R¹⁶Comrade, R¹⁷Comrade, R¹⁸Comrade, R
¹⁹Comrade, R²⁰Comrade and R^{twenty one}Comrades may be the same or different
Good. Examples of the copolymerization include, for example, the case of the formula (a)
In the case of ethylene oxide and propylene oxide
A combined unit is particularly preferred. In Formula 2, n is 1 to 100, preferably 1
And 50, more preferably an integer of 1 to 20. A urethane aclay represented by the above formula (2)
Molecular weight of 2,500 to 30,000, preferably
3,000-20,000 is desirable. 2,5 molecular weight
If it is less than 00, the degree of crosslinking is large, depending on the number of polymerized functional groups.
It is preferable because ionic conductivity may be too low.
Not good. When the molecular weight exceeds 30,000,
Flexibility during curing may decrease, which is not preferable
No. Polymerization in one molecule of the urethane acrylate
The number of functional groups is preferably 2 to 6, more preferably 2
4 is desirable. Examples of the urethane acrylate include:
Specifically, compounds represented by the following formulas 9 to 15 may be mentioned.
It is. In addition, urethane that can be used in the present invention
The acrylate is not limited to the following specific examples.
No. [0036] Embedded image [0037] Embedded image[0038] Embedded image[0039] Embedded image[0040] Embedded image[0041] Embedded image[0042] Embedded imageThe urethane acrylate used in the present invention is:
It can be easily manufactured by a known method.
Is not particularly limited, the following methods are preferred methods
No. That is, first, a polymer having hydroxyl groups at both ends
Ethers, polycarbonates, polyesters and
Reacts these mixtures with diisocyanates,
Acrylate having a hydroxyl group is further added to the product.
Reaction. The above polyether having a hydroxyl group at both ends
, Polycarbonate or polyester molecules
Although the amount is not particularly limited, it is generally 500 to 2000, preferably
More preferably, it is about 1,000 to 10,000. The polyethers include the urethane
It is not particularly limited as long as it induces acrylate.
For example, polyethylene glycol, polyethylene glycol
Coal triol, polypropylene glycol, polyp
Propylene glycol triol, polytetramethylene
Silicide diol, ethylene oxa of bisphenol A
Use of oxides or propylene oxide adducts
Specifically, a compound represented by the following general formula 16
And the like. [0046] Embedded imageThe polyesters and the polycarbonate
As the nitrates, the urethane acrylate is derived.
Is not particularly limited so long as it is, for example, polycaprolact
Use tondiol, polycarbonate diol, etc.
Can be. Adipic acid, succinic acid, terephthalic acid
Dicarboxylic acids such as acid and isophthalic acid, and ethylene glycol
, Diethylene glycol, propylene glycol,
1,4-butanediol, neopentyl glycol and the like
Dehydration condensates such as diols can also be used. Concrete
Specifically, compounds represented by the following general formula 17 are preferably listed.
I can do it. [0048] Embedded image As the diisocyanate, for example,
Rylene diisocyanate, methylene bisphenyl isocyanate
Anate, methylenebisdiethylphenyl isocyanate
G, hexamethylene diisocyanate, methylene bis
Clohexyl isocyanate, α, α, α ', α'-te
Tramethyl-1,3-xylylene diisocyanate, i
Sophorone diisocyanate or a mixture thereof
Can be used. As the acrylate having a hydroxyl group,
Is a compound represented by the following general formula (18).
You. [0051] Embedded imageSpecific examples of the acrylate having a hydroxyl group
As 2-hydroxyethyl acrylate,
Droxyethyl methacrylate, 2-hydroxypropyl
Acrylate, 4-hydroxybutyl acrylate,
2- (2-hydroxyethoxy) ethyl acrylate,
2- (2-hydroxyethoxy) ethyl methacrylate
G, 2-hydroxycyclohexyl acrylate, 2-
Hydroxycyclohexyl methacrylate, 1-hydro
Xycyclohexyl acrylate, 1-hydroxycycl
Rohexyl methacrylate, 2- (2-hydroxy-
1,1-dimethylethoxy) -1,1-dimethylethyl
Acrylate, 2- (2-hydroxy-1,1-dimethyl)
Ruethoxy) -1,1-dimethylethyl acrylate,
2-hydroxy-3-piperidinopropyl acrylate
G, 2-hydroxy-3-piperidinopropyl methacrylate
Rate, 2-hydroxy-2-phenylethyl acryle
, 2-hydroxy-2-phenylethyl methacrylate
, 2-hydroxy-2-methoxypropyl acryle
, 2-hydroxy-2-methoxypropyl methacrylate
Rate, polyethylene glycol monomethacrylate,
2-hydroxy-1,3-dimethacryloxypropane,
2-hydroxy-1-acryloxy-3-methacryloxy
Cypropane, 2,3-diacryloylpropanol,
2,3-dimethacryloylpropanol, tetramethylo
Methane triacrylate, tetramethylol methane
Trimethacrylate and the like. When using,
They can be used alone or as a mixture. In preparing the urethane acrylate,
Or polyethers having hydroxyl groups at both ends,
Recarbonates, polyesters or mixtures thereof
The compounding ratio of the compound and the diisocyanate is usually 1:
0.1 to 10, preferably 1 to 1 to 2. Also
The reaction is carried out in a solvent, preferably in a dehydrated solvent.
Is desirable. The solvent is not particularly limited.
Hydrogen-free ones are preferred, for example, toluene, benzene
Various aromatics such as zen and xylene, methyl ethyl ketone, etc.
Ketones, dimethyl sulfoxide and the like.
In addition, the reaction is carried out in the presence of a catalyst such as dibutyltin dilaurate.
It is desirable to do it in the presence. The amount of the catalyst
Usually 0.001 to 1 with respect to 100 mol% of the cyanate
0 mol%, preferably 0.01 to 5 mol% is desirable.
The reaction temperature and time can be appropriately selected, but the reaction temperature is
Usually 0 to 150 ° C, preferably 20 to 120 ° C, during reaction
The period is usually 10 minutes to 10 hours, preferably 20 minutes to 5 hours.
It can be performed in about an hour. Then the said hydroxy
The reaction for adding the acrylate having a group is not particularly limited.
For example, for one mole of the reactant,
Usually 1 to 10 mol of acrylate, preferably 2 to 3 mol
Can be added. Having this hydroxyl group
In the reaction of the acrylate,
Addition of polymerization inhibitor such as hydroquinone monomethyl ether
You can also. The reaction temperature is usually 0 to 150 ° C, preferably
The reaction time is usually 10 minutes to 10 minutes.
Time, preferably about 20 minutes to 5 hours
be able to. After the reaction is completed, alcohol such as methanol
To react unreacted isocyanate by adding
To obtain the desired urethane acrylate.
Wear. The above-mentioned composition constituting the composition A used in the present invention
Non-aqueous solvents that have polarity and can dissolve the supporting electrolyte
Is not particularly limited as long as it is suitable as
Physically, propylene carbonate, ethylene carbonate
, Butylene carbonate, γ-butyrolactone,
Ruphoran, 1,3-dioxane, N, N-dimethylform
Muamide, 1,2-dimethoxyethane, acetonitrile
And tetrahydrofuran. this
Can be used alone or as a mixture when used.
You. The mixing ratio of the organic non-aqueous solvent is
100 to 120 parts by weight of acrylate
0 parts by weight, preferably 200 to 900 parts by weight
Is desirable. Less than 100 parts by weight of organic non-aqueous solvent
In this case, the ionic conductivity may not be sufficient.
Not good. In addition, when it exceeds 1200 parts by weight, it is obtained.
When the mechanical strength of the polymer solid electrolyte is reduced
There is not preferred. The support constituting the composition A used in the present invention is described above.
Uses of the obtained polymer solid electrolyte as a supported electrolyte
Can be selected as appropriate, and unless the object of the present invention is impaired.
Although not limited to, for example, alkali metal salts, quaternary anions
Monium salts, alkaline earth metal salts and the like. Said
As the alkali metal salt, for example, LiClO_Four, Li
SCN, LiBF_Four, LiAsF₆, LiCF_ThreeSO_Three, N
aI, NaSCN, NaClO_Four, NaBF_Four, NaAs
F₆, Sodium or potassium such as KSCN
And the like. Also the 4th grade ammonium
As the salt, (CH_Three)_FourNBF_Four, (C_TwoH_Five)_FourNBF
_Four, (N-C_FourH₉)_FourNBF_Four, (C_TwoH_Five)_FourNBr, (C
_TwoH_Five)_FourNCLO_Four, (N-C_FourH₉)_FourNCLO_Four, Ring 4
Secondary ammonium salts and the like. Also, the alkali
Examples of the earth metal salt include, for example, Mg (ClO_Four)_Two, Ca
(ClO_Four)_Two, Mg (BF_Four)_Two, Ca (BF_Four)_TwoEtc.
Various ion salts such as gnesium or calcium are mentioned.
It is. These supporting electrolytes may be used alone or in combination.
Can be used as compound. The mixing ratio of the supporting electrolyte is not particularly limited.
Not included, but 0.1 to 30% by weight of the total amount of the organic non-aqueous solvent
%, Preferably 1 to 20% by weight. The composition A is basically composed of the urethane
Including acrylates, organic non-aqueous solvents and supporting electrolytes,
In addition to these, as an optional component, the object of the present invention is impaired.
Unless otherwise, additional ingredients can be added as needed
Wear. Examples of the optional component include a crosslinking agent and a polymerization initiator.
And the like. The crosslinking agent is a polymer solid electrolyte
It can be added for the purpose of further improving the strength. Said
The crosslinking agent is not particularly limited, but may be a bifunctional or more functional crosslinking agent.
A bridging agent, preferably a bifunctional or higher acrylate compound
Suitable examples include, specifically, for example,
Lenglycol dimethacrylate, diethylene glycol
Ludi methacrylate, tetraethylene glycol dimeth
Acrylate, ethylene glycol diacrylate, die
Tylene glycol diacrylate, triethylene glyco
Diacrylate, polyethylene glycol dimethac
Relate, polyethylene glycol diacrylate, ne
Opentyl glycol diacrylate, 1,6-hexa
Diol diacrylate, trimethylol proppant
Remethacrylate, trimethylolpropane triacrylate
Rate, tetramethylolmethanetetraacrylate,
Tetramethylolmethanetetramethacrylate and the like
Can be These may be used alone or as a mixture when used.
Can be used. The mixing ratio of the crosslinking agent is
0.01 to 10 mol%, preferably 100 mol%,
More preferably, the content is 0.01 to 5 mol%. The polymerization initiator may be a photopolymerization initiator.
Initiators or thermal polymerization initiators can be used. The photopolymerization initiator is not particularly limited.
No benzoin, acetophenone, benzyl ketone
Known materials such as a tar system can be used. Specifically
Is acetophenone, benzophenone,
Nzophenone, benzoin methyl ether, 2,2-di
Methoxy-2-phenyldimethoxy-2-phenylace
Tophenone, benzyl, benzoyl, 2-methylbenzo
In, 2-hydroxy-2-methyl-1-phenyl-1
-One, 1- (4-isopropylphenyl-2-hydro
Xy-2-methylpropan-1-one, triphenylpho
It is possible to use sphin, 2-chlorothioxanthone, etc.
it can. These may be used alone or as a mixture when used.
Can be used. The thermal polymerization initiator is not particularly limited.
But peroxide-based polymerization initiator or azo-based polymerization initiator
Can be used. Specifically, peracid
For example, benzoyl peroxy
Side, methyl ethyl peroxide, t-butyl per
Oxypivalate, diisopropyl peroxycarbonate
And azo compounds such as 2,2'-
Azobis (2-isobutyronitrile), 2,2'-azo
Bisisobutyronitrile, 2,2'-azobis (2,4
-Dimethylvaleronitrile), 1,1'-azobis (cy
Chlorohexane-1-carbonitrile) and the like.
These may be used alone or as a mixture when used.
Can be The solid polymer electrolyte of the present invention is characterized in that
It is obtained by solidifying A. Solidification in the present invention
Is a polymerizable or crosslinkable component, such as urethane
Relate and the like are cured with the progress of polymerization and crosslinking, and the composition
Substantially no fluid at room temperature as a whole
That means. In this case, the normal urethane
Has a network-like basic structure. As a preferred method of the solidification, the composition
The product A is cured by light or heat to form a polymer matrix.
There is a method of solidifying by forming. The photo-curing is usually performed using the photo-polymerization initiator.
Can be done. Mixing ratio of the photopolymerization initiator
Is 0.1 parts by weight based on 100 parts by weight of urethane acrylate.
10 to 10 parts by weight, preferably 0.1 to 5 parts by weight is desired.
No. The light at the time of the photocuring is not particularly limited.
But far ultraviolet light, ultraviolet light, visible light and the like. Light source and
Use high-pressure mercury lamps, fluorescent lamps, xenon lamps, etc.
be able to. The irradiation amount is not particularly limited, but is high.
When using a pressure mercury lamp, usually 100 to 50,000 mJ
/ Cm^Two, Preferably 1000 to 20000 mJ / cm^Two
Is desirable. The thermal curing usually uses the thermal polymerization initiator.
Can be done. The mixing ratio of the thermosetting agent,
0.1 to 1 based on 100 parts by weight of urethane acrylate
0 parts by weight, preferably 0.1 to 5 parts by weight is desirable. The thermal curing reaction conditions are as follows:
The reaction temperature is selected depending on the agent and is not particularly limited.
Usually 0 to 130 ° C, preferably 20 to 80 ° C is desirable.
No. The curing time is usually 30 minutes to 100 hours, preferably
Or 1 to 40 hours is desirable. The progress of the solidification is doubled by IR, NMR, etc.
It can be confirmed by detecting a decrease in binding. Also cured
The fact that the material has a cross-linked structure means that the solid
-Extraction method to confirm residual solids, IR, N
It can be confirmed by MR or the like. The solid polymer electrolyte of the present invention is a solid polymer
When the product shrinkage is 0 to 0.5%, preferably 0 to 0.3%
is there. Further, the solid polymer electrolyte of the present invention has a composition
By appropriate selection, a substantially colorless and transparent polymer solid
It can also be a body electrolyte. [0072] As described above, the solid polymer electrolyte of the present invention
No or minimal volume changes, especially volume shrinkage
Small, and dimensionally stable even if left at low temperatures for a long time
Excellent in nature. Therefore, used in electrochemical devices
Cracking due to shrinkage during curing, volume when left at low temperature
Electrification of large area with less occurrence of voids due to shrinkage
It is useful for fabrication of scientific devices. Further, the solid polymer electrolyte of the present invention is high.
It has ionic conductivity and excellent flexibility and strength
Therefore, when used in electrochemical devices, its adhesion is improved.
Of reliable and reliable electrochemical devices
Useful for From the above points, the polymer solid electrolyte of the present invention
Are electrochromic devices, batteries, electric double layer
Use as a material for various electrochemical devices such as pasita
Can be expected. [0075] The present invention will be described in more detail with reference to the following examples and comparative examples.
Although described, the present invention is not limited to these.
No. [0076] EXAMPLE 1 1 liter of dry methyl ethyl ketone
Propylene glycol (Aldrich, molecular weight 4,
000) 400 g (0.1 mol) and hexamethylenediyl
22.4 g (0.133 mol) of cyanate were added,
Further, 0.1 g of dibutyltin dilaurate was added as a catalyst.
Then, the mixture was reacted at 80 ° C. for 3 hours with vigorous stirring. Next
Then, 0.5 g of hydroquinone monomethyl ether and
7.78 g of droxyethyl acrylate (0.067
) And reacted at 60 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was washed with cold hexane and depressurized.
Hexane was removed. The structure of the obtained substance was
And IR, which is a compound represented by the following formula:
It was confirmed. [0078] Embedded image 10 g of the above product and γ-butyrolactone 4
0g and LiClO_Four4g and a photopolymerization initiator daro.
Cure 1173 (trade name, Ciba-Geigy) 100
mg and 3000 J / cm under high pressure mercury lamp^TwoIrradiation
And cured. The volume shrinkage was 0.1% or less.
Is volume shrinkage a change in height before and after curing in the tube?
Determined). Ionic conduction by complex impedance analysis
5 × 10 ~ at room temperature^ThreeS / cm. [0080] Example 2 1 liter of dry methyl ethyl ketone
Propylene glycol (Aldrich, molecular weight 4,
000) 400 g (0.1 mol) and hexamethylenediyl
25.2 g (0.15 mol) of socyanate are added.
Further, 0.1 g of dibutyltin dilaurate was added as a catalyst.
Then, the mixture was reacted at 80 ° C. for 3 hours with vigorous stirring. Next
Then, 0.5 g of hydroquinone monomethyl ether and
7.78 g of droxyethyl acrylate (0.067
) And reacted at 60 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was washed with cold hexane and depressurized.
Hexane was removed. The structure of the obtained substance was
And a compound represented by Formula 20 below
It was confirmed. [0082] Embedded image 10 g of the above product and γ-butyrolactone 4
0g and LiClO_Four4g and a photopolymerization initiator daro.
Cure 1173 (trade name, Ciba-Geigy) 100
mg was added and photocured in the same manner as in Example 1. Example
When physical properties of the obtained cured product were measured in the same manner as in Example 1,
The product shrinkage is 0.1% or less and the ionic conductivity is
5.3 × 10 ~^ThreeS / cm. [0084] [0085] Example 3 1 liter of dry methyl ethyl ketone
Propylene glycol (Aldrich, molecular weight 4,
000) 400 g (0.1 mol) and hexamethylenediyl
33.6 g (0.2 mol) of socyanate were added, and
0.1 g of dibutyltin dilaurate was added as a catalyst to
The reaction was carried out at 80 ° C. for 3 hours with vigorous stirring. Next
With 0.5 g of hydroquinone monomethyl ether and hydr
7.78 g of roxyethyl acrylate (0.067
) And reacted at 60 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was washed with cold hexane and depressurized.
Hexane was removed. The structure of the obtained substance was
And IR, and is a compound represented by the following formula:
It was confirmed. [0087] Embedded image 10 g of the above product and γ-butyrolactone 4
0g and LiClO_Four4g and a photopolymerization initiator daro.
Cure 1173 (trade name, Ciba-Geigy) 100
mg was added and photocured in the same manner as in Example 1. Example
When physical properties of the obtained cured product were measured in the same manner as in Example 1,
The product shrinkage is 0.1% or less and the ionic conductivity is
4.1 × 10 ~^ThreeS / cm. [0089] Example 4 1 liter of dry methyl ethyl ketone
(Propylene glycol-b-ethylene glycol)
(Propylene glycol and ethylene glycol
Block copolymer, manufactured by Aldrich, molecular weight 2,800)
280 g (0.1 mol) with hexamethylene diisocyanate
22.4 g (0.133 mol) were added.
0.1 g of dibutyltin dilaurate was added as a medium,
The reaction was carried out at 80 ° C. for 3 hours with good stirring. Then, c
0.5 g of hydroquinone monomethyl ether and hydroxy
7.78 g (0.067 mol) of ethyl acrylate
In addition, the reaction was performed at 60 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was washed with cold hexane and depressurized.
Hexane was removed. The structure of the obtained substance was
And a compound represented by the following formula:
It was confirmed. [0091] Embedded image 10 g of the above product and γ-butyrolactone 4
0g and LiClO_Four4g and a photopolymerization initiator daro.
Cure 1173 (trade name, Ciba-Geigy) 100
mg was added and photocured in the same manner as in Example 1. Example
When physical properties of the obtained cured product were measured in the same manner as in Example 1,
The product shrinkage is 0.1% or less and the ionic conductivity is
5.5 × 10 ~^ThreeS / cm. [0093] [Example 5] Polyethylene was added to 1 liter of dry methyl ethyl ketone.
Propylene glycol (Aldrich, molecular weight 4,
000) 400 g (0.1 mol) and hexamethylenediyl
22.4 g (0.133 mol) of cyanate were added,
Further, 0.1 g of dibutyltin dilaurate was added as a catalyst.
Then, the mixture was reacted at 80 ° C. for 3 hours with vigorous stirring. Next
Then, 0.5 g of hydroquinone monomethyl ether and
8.71 g of droxyethyl methacrylate (0.067
Mol) and reacted at 60 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was washed with cold hexane and depressurized.
Hexane was removed. The structure of the obtained substance was
And a compound represented by the following formula:
It was confirmed. [0095] Embedded image10 g of the above product and γ-butyrolactone 4
0g and LiClO_Four4g and a photopolymerization initiator daro.
Cure 1173 (trade name, Ciba-Geigy) 100
mg was added and photocured in the same manner as in Example 1. Example
When physical properties of the obtained cured product were measured in the same manner as in Example 1,
The product shrinkage is 0.1% or less and the ionic conductivity is
5 × 10 ~^ThreeS / cm. [0097] Embodiment 6 Commercially available in 1 liter of dry methyl ethyl ketone
Polycaprolactone diol (molecular weight 2,000) 2
00g (0.1 mol) and hexamethylene diisocyanate
And 22.4 g (0.133 mol) of the catalyst
Add 0.1 g of dibutyltin dilaurate as
The reaction was carried out at 80 ° C. for 3 hours with stirring. Then high
0.5 g of droquinone monomethyl ether and hydroxye
7.78 g (0.067 mol) of butyl acrylate was added.
At 60 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was washed with cold hexane and depressurized.
Hexane was removed. The structure of the obtained substance was
And a compound represented by the following formula 24
It was confirmed. [0099] Embedded image 10 g of the above product and γ-butyrolactone 4
0g and LiClO_Four4g and a photopolymerization initiator daro.
Cure 1173 (trade name, Ciba-Geigy) 100
mg was added and photocured in the same manner as in Example 1. Example
When physical properties of the obtained cured product were measured in the same manner as in Example 1,
The product shrinkage is 0.1% or less and the ionic conductivity is
5.1 × 10 ~^ThreeS / cm. [0101] Comparative Example 1 Methoxy polyethylene ethylene glycol
10 g of methacrylate (molecular weight: 570), γ-butyrol
40 g of coutone and polyethylene glycol (molecular weight 4
00) 0.2 g of dimethacrylate is mixed and photopolymerization is started
Agent Darocur 1173 (Ciba-Geigy) 100m
g and photocured in the same manner as in Example 1. Example 1 and
When the physical properties of the obtained cured product were measured,
The shrinkage was 1.9%.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI H01M 10/40 H01G 9/00 301G (56) References JP-A-3-84807 (JP, A) JP-A-8-167415 ( JP, A) JP-A-8-295711 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 299/06 C08F 290/06 G02F 1/15 H01B 1/06 H01G 9 / 025 H01M 6/18 H01M 10/40

Claims (1)

(57) [Claim 1] A polymer solid electrolyte characterized by solidifying a composition comprising a urethane acrylate represented by the following general formula 1, an organic non-aqueous solvent, and a supporting electrolyte . Manufacture
How . Embedded image