JP2002198093A - Electrolyte composition, polymeric solid-state electrolyte, polymeric gel electrolyte and lithium polymer cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolyte composition having high ionic conductivity and excellent safety and suitably for use in a lithium ion secondary cell. SOLUTION: The electrolyte composition comprises a compound represented by the general formula (1), R1-(A)m-(Y)n-X-.Li+ and/or (2), Li+.X--(Y1)e-(A)p-(Y2)f- X-.Li, and a matrix polymer. In the general formula (1), R1 is an unsubstituted or fluorine-substituted alkyl or alkoxy group having 1-4 carbon atoms, A is a perfluoroalkylene component, polyoxyalkylene component or polyfluorooxyalkylene component, Y is, for example, CH2 or CF2, m is 0 or an integer of 1-70, n is 0 or an integer 1-2, and X is SO3, SO2NSO2R4 or COO. In the general formula (2), Y1 is, for example, CH2 or CF2, Y2 is, for example, OCH2 or OCF2, e and f are individually 0 or an integer of 1-2, p is 0 or an integer 1-70, and X and A have the same meanings as defined in the formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrolyte composition, a polymer solid electrolyte, and a polymer gel having high ionic conductivity and excellent safety, and particularly suitable for lithium secondary batteries or lithium ion secondary batteries. It relates to an electrolyte and a lithium polymer battery.

[0002]

2. Description of the Related Art Conventionally, a polymer battery using a non-aqueous electrolyte, particularly a lithium polymer battery, has a high withstand voltage and a high energy density.
Because of its excellent storage properties, it is widely used as a power source for consumer electronic devices.However, despite its excellent characteristics, lithium secondary batteries using metallic lithium Sufficient charge / discharge cycle life cannot be obtained due to precipitation, and it has not yet been put to practical use. Therefore, instead of using metallic lithium as it is for the negative electrode,
In addition to using a carbonaceous material capable of inserting and extracting lithium ions, various studies have been made on a non-aqueous solvent (plasticizer) constituting an electrolytic solution suitable for this.

[0003] Such plasticizers include low molecular weight organic solvents such as propylene carbonate (PC), ethyl carbonate (EC), ethyl methyl carbonate, and the like.
γ-butyrolactone, sulfolane and the like have been used.

[0004] However, low molecular weight solvents such as PC and EC have relatively low flash points, are flammable, and have high temperatures.
There is a problem in safety when the battery is used repeatedly at room temperature. That is, when a current is short-circuited, a large current suddenly flows into the battery to generate heat, thereby causing the electrolytic solution containing the organic solvent to vaporize or decompose, thereby generating gas, thereby causing damage, rupture or ignition of the battery. Can occur. In addition, even if the battery is excessively charged, the battery may ignite due to internal heat generation. Furthermore,
There is a risk that a short circuit may occur due to a nail or the like piercing the charged battery, causing fire.

For this reason, various plasticizers having a relatively large molecular weight have been proposed (JP-A-10-25140).
0, JP-A-10-251401, JP-A-1
0-251182, JP-A-2000-260467
According to these publications, although the safety is improved, such a plasticizer having a relatively large molecular weight has no function as an electrolyte salt.

On the other hand, low-molecular-weight electrolyte salts include Li
ClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (SO ₂
CF ₃ ) _{2 and the} like are used.

However, these low-molecular-weight electrolyte salts have a problem that the anion component also moves in the electrolyte, so that the lithium ion transport rate becomes low and a sufficient ion conductivity cannot be obtained.

The present invention has been made in view of the above circumstances, and has both high ionic conductivity and safety, and is particularly suitable for a lithium secondary battery and a lithium ion secondary battery. Polymer gel electrolyte,
And a lithium polymer battery using the same.

[0009]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, have found that a relatively high-molecular-weight compound having both functions as a plasticizer and an electrolyte is obtained. By using it as an electrolyte salt, the high molecular weight anion component functions as a plasticizer and hardly moves in the electrolyte, so that only a lithium ion becomes a single ion conductor that can move in the electrolyte, and the lithium ion transport rate Has been dramatically improved, and it has been found that a high-performance lithium polymer battery having both high ionic conductivity and safety, which has been a conventional problem, can be obtained, and the present invention has been accomplished.

That is, the present invention provides the following electrolyte composition:
Polymer solid electrolyte, polymer gel electrolyte and lithium polymer
-Provide batteries. Claim 1: represented by the following general formulas (1) and / or (2)
And a matrix polymer.
Electrolyte composition. R¹-(A)_m-(Y)_n-X^-・ Li⁺ ... (1) [wherein, R¹Is an unsubstituted or fluorine-substituted alkyl group having 1 to 4 carbon atoms.
Alkyl group or unsubstituted or fluorine-substituted alkoxy group,
A is a perfluoroalkylene component, polyoxyalkylene
Components and polyfluorooxyalkylene components
Represents one or more kinds, wherein Y is CH_Two, CF_Two, CF
_TwoCH_TwoOr OCONHR^TwoNHCOOR^Three(However, R^TwoPassing
And R^ThreeAre the same or different divalent hydrocarbons having 1 to 18 carbon atoms
Represents a group), m is 0 or an integer of 1 to 70, and n is 0 or 1.
X is SO_Three, SO_TwoNSO _TwoR^Four(However, R^Four
Represents an unsubstituted or fluorine-substituted alkyl group having 1 to 4 carbon atoms.
) Or COO. ] Li⁺・ X^-− (Y¹)_e-(A)_p− (Y^Two)_f-X^-・ Li⁺ ... (2) [wherein, Y¹Is CH_Two, CF_Two, CH_TwoCF_Two, R^FiveOCH_Two
CF_TwoOr R^TwoOCONHR^TwoNHCO, Y^TwoIs OC
H_Two, OCF_Two, OCF_TwoCH_Two, OCF_TwoCH_TwoOR^Five,or
Is OCONHR^TwoNHCOOR^Three(However, R^FiveIs 1 carbon
Alkylene group, R^TwoAnd R^ThreeHas the same meaning as above
E) and f are 0 or an integer of 1-2, and p is 0 or 1-7.
Indicates an integer of 0. X and A have the same meaning as described above. Claim 2: The polyoxyalkylene component represented by A
The minute is-(OCH_TwoCH_Two)-And / or-(OCH_TwoCH_Two
CH_Two3. The electric cell according to claim 1, which comprises a) as a repeating unit.
Decomposition composition. Claim 3: The polyfluorooxyal represented by the above A
The kilen component is-(OCF_Two)-,-(OCF_TwoCF_Two)
-,-(OCF_TwoCF (CF_Three))-And-(OCF_TwoC
F_TwoCF_Two)-One or two types of repeating units selected from
The electrolyte composition according to claim 1, which contains the above. Claim 4: The amount of the matrix polymer is small in (A) molecule.
At least one (meth) acryloyl group and hydroxyl group
And (B) an unsaturated alcohol having the following general formula:
A polyol compound represented by (3);
A cyanate compound and, if necessary, (D) a chain extender
An unsaturated polyurethane compound obtained by reacting
The electrolyte composition according to any one of claims 1 to 3. HO-[(R⁶)_h-(Y)_i− (R⁷)_j]_q-OH (3) [wherein, R⁶And R⁷Are the same or different amino groups, nitro
May contain a group, a carbonyl group or an ether group
A divalent hydrocarbon group having 1 to 10 carbon atoms, wherein Y is -COO
-, -OCOO-, -NR⁸CO- (R⁸Is a hydrogen atom or
Represents an alkyl group having 1 to 8 carbon atoms), -O- or aryl
H, i, j are each 0 or 1 to 10,
q represents an integer of 1 or more. Claim 5: The matrix polymer has an interpenetrating network structure or
2. A polymer material having a semi-interpenetrating network structure.
An electrolyte composition according to any one of claims 1 to 3. Claim 6: An interpenetrating network structure or a semi-interpenetrating network structure
Having a hydroxyalkyl polysaccharide derivative
Body, polyvinyl alcohol derivative, or polyglycidol
And a compound having a crosslinkable functional group.
A part of the compound having a crosslinkable functional group or
All the unsaturated polyurethane compounds according to claim 4
The electrolyte composition according to claim 5. Claim 7: The matrix polymer is represented by the following general formula (4).
4. A thermoplastic resin containing the above units.
The electrolyte composition according to any one of the above.

Embedded image (Wherein, r represents an integer of 3 to 5 and s represents an integer of 5 or more.) Claim 8: The electrolyte composition according to any one of Claims 1 to 3, wherein the matrix polymer is a fluorine-based polymer material. . (9) A solid polymer electrolyte comprising the electrolyte composition according to any one of (1) to (8). [10] The polymer solid electrolyte according to [9], wherein the ionic conductivity at 25 ° C. by the AC impedance method is 1 × 10 ⁻⁵ S / cm or more. [11] A polymer gel electrolyte obtained by swelling the electrolyte composition according to any one of [1] to [8] with an organic solvent. In a twelfth aspect, the ionic conductivity at 25 ° C. according to the AC impedance method is 1 × 10 ⁻³ S / cm or more.
The polymer gel electrolyte according to the above. In a thirteenth aspect, in a lithium polymer battery including a positive electrode, a negative electrode, and an electrolyte, the polymer solid electrolyte according to the ninth or tenth aspect or the eleventh or the first aspect is used as the electrolyte.
A lithium polymer battery using the polymer gel electrolyte according to 2.

Hereinafter, the present invention will be described in more detail. <Electrolyte Composition of the Present Invention> The electrolyte composition of the present invention contains a compound represented by the following general formula (1) and / or (2) and a matrix polymer. _{^{R 1 - (A) m -}} (Y) n -X - · Li + ... (1) Li + · X - - (Y 1) e - (A) p - (Y 2) f -X - · Li + … (2)

Here, in the above formula (1), R ¹ has ¹ carbon atom.
Represents an unsubstituted or fluorine-substituted alkyl group or an unsubstituted or fluorine-substituted alkoxy group, for example, a methyl group,
Examples include an ethyl group, a propyl group, a methoxy group, an ethoxy group, and a propoxy group.

A represents one or more selected from a perfluoroalkylene component, a polyoxyalkylene component and a polyfluorooxyalkylene component.

As the perfluoroalkylene component, a linear or branched perfluoroalkyl group represented by C _z F _{2z + 1} (where z is 1 to 10) is preferable.

In the polyoxyalkylene component, A is-(OCH ₂ CH ₂ )-and / or-(OCH ₂ CH ₂ CH).
₂ ) Those containing one or more kinds of-as a repeating unit are preferable.

As the polyfluorooxyalkylene component, A is-(OCF ₂ )-,-(OCF ₂ CF ₂ )-,-
_{(OCF 2 CF (CF 3)} ) - and - (OCF ₂ CF ₂ CF
₂ ) A compound containing one or more kinds of repeating units selected from-is preferable.

M represents 0 or an integer of 1 to 70, particularly 3 to 40, and n represents an integer of 0 or 1 to 2.

Y is CH ₂ , CF ₂ , CF ₂ CH ₂ or OCO
NHR ² NHCOOR ³ (provided that R ² and R ³ are the same or different and are a divalent hydrocarbon group having 1 to 18 carbon atoms, particularly
8 represents a linear alkylene group, an alicyclic group-containing alkylene group having 6 to 18 carbon atoms, and an aromatic group-containing alkylene group having 6 to 18 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, and a propylene group. Arylene groups such as alkylene group, phenylene group, tolylene group and xylylene group, and aralkylene groups such as benzylene group, phenylethylene group and phenylpropylene group.

X is SO ₃ , SO ₂ NSO ₂ R ⁴ (where R ⁴
Represents an unsubstituted or fluorine-substituted alkyl group having 1 to 4 carbon atoms) or COO.

In the above formula (2), Y¹Is CH_Two, CF_Two, C
H_TwoCF_Two, R^FiveOCH_TwoCF_TwoOr R ^TwoOCONHR^TwoN
HCO, Y^TwoIs OCH_Two, OCF_Two, OCF_TwoC
H_Two, OCF_TwoCH_TwoOR^FiveOr OCONHR^TwoNHCO
OR^Three(However, R^FiveIs an alkylene group having 1 to 8 carbon atoms, R^Two
And R^ThreeHas the same meaning as above)

E and f are 0 or an integer of 1 to 2, and p is 0 or 1 to 70, particularly 3 to 40.

In this case, the compounds represented by the above general formulas (1) and (2) have a weight average molecular weight of 200 or more, preferably 200 to 8000, more preferably 200 to 400.
0, more preferably 200 to 2000. If the weight average molecular weight is too small, the anion component also moves in the electrolyte, and the transport rate of Li ions may decrease.
On the other hand, if it is too large, it may not be possible to increase the amount of electrolyte salt added in the electrolyte composition.

The compound represented by the above general formula (1)
Include, for example, a compound represented by the following formula:
You. CF_Three(CF_Two)_mCO_Two ^-・ Li⁺, CF_Three(CF_Two)_m
CH_TwoSO_Three ^-・ Li⁺, CF_Three(CF_Two)_mCH_TwoSO_TwoN^-S
O_TwoCF_Three・ Li⁺, CH_Three(OCH_TwoCH_Two)_mSO_TwoN^-S
O_TwoCF_Three・ Li⁺, CH_Three(OCH_TwoCH_Two)_mSO_TwoN^-S
O_TwoC_FourF₇・ Li⁺, CH_Three(OCH_TwoCH_Two)_mOCONH
(CH_Two)₆NHCO_Two(CH_Two)_TwoSO_TwoN^-SO_TwoCF_Three・
Li⁺, CH_Three(OCH_TwoCH_Two)_mOCONHC₆H_FourCH_Two
C₆H_FourNHCO_Two(CH_Two)_TwoSO _TwoN^-SO_TwoCF_Three・ L
i⁺, CH_Three(OCH_TwoCH_Two)_mOCONHC₆H_Three(C
H_Three) NHCO_Two(CH_Two)_TwoSO_TwoN^-SO_TwoCF_Three・ Li⁺
In the above formula, m is an integer of 1 to 70.

The compound represented by the above general formula (2)
Include, for example, a compound represented by the following formula:
You. Li⁺・^-O_TwoC (CF_Two)_nCO_Two ^-・ Li⁺, Li⁺・^-
O_TwoCCF_Two(OCF_TwoCF_Two)_x(OCF_Two)_yOCF_TwoCO
_Two ^-・ Li⁺, Li⁺・^-O_ThreeSCH_TwoCF_Two(OCF_TwoCF_Two)
_x(OCF_Two)_yOCF_TwoCH_TwoSO_Three ^-・ Li⁺, Li⁺・ C
F_ThreeSO_TwoN^-SO_TwoCH_TwoCH_TwoOCH_TwoCF_Two(OCF_TwoC
F_Two)_x(OCF _Two)_yOCF_TwoCH_TwoOCH_TwoCH_TwoSO_TwoN^-
SO_TwoCF_Three・ Li⁺, Li⁺・ C_TwoF_FiveSO_TwoN^-SO_TwoCH_Two
CF_Two(OCF_TwoCF_Two)_x(OCF_Two)_yOCF_TwoCH_TwoSO
_TwoN^-SO_TwoC_TwoF_Five・ Li⁺, Li⁺・ CF_ThreeSO_TwoN^-SO_Two
CH_TwoCH_TwoOCONHC₆H_Three(CH_Three) NHCO (OC
F_TwoCF_Two)_x(OCF_Two)_yOCONHC₆H_Three(CH_Three) N
HCO_TwoCH_TwoCH_TwoSO_TwoN^-SO_TwoCF_Three・ Li⁺, Li⁺
・ CF_ThreeSO_TwoN^-SO_TwoCH_TwoCH_Two(OCH_TwoCH_Two)_nS
O_TwoN^-SO_TwoCF_Three・ Li⁺, Li⁺・ C_FourF₉SO_TwoN^-SO
_TwoCH_TwoCH_Two(OCH_TwoCH_Two)_nSO_TwoN^-SO_TwoC_FourF₉・
Li⁺, Li⁺・ CF_ThreeSO_TwoN^-SO_Two(CH_Two)_TwoOCON
HC₆H_Three(CH_Three) NHCO (OCH_TwoCH_Two)_nOCON
HC₆H_Three(CH_Three) NHCO_Two(CH_Two)_TwoSO_TwoN^-SO_Two
CF_Three・ Li⁺, Li⁺・ CF_ThreeSO_TwoN^-SO_Two(CH_Two)_Two
OCONH (CH_Two)₆NHCO (OCH_TwoCH_Two)_nOC
ONH (CH_Two)₆NHCO_Two(CH_Two)_TwoSO_TwoN^-SO_TwoC
F_Three・ Li⁺, Li⁺・ CF_ThreeSO_TwoN^-SO_Two(CH_Two)_FourO
CONHC₆H_FourCH_TwoC₆H_FourNHCO (OCH_TwoCH_Two)_n
OCONHC₆H_FourCH_TwoC₆H_FourNHCO_Two(CH_Two)_FourSO
_TwoN^-SO_TwoCF_Three・ Li⁺ In the above formula, n is 1 to 70, x is 1 to 40, and y is 1 to
An integer of 60 is shown.

The compounding amount of the compound represented by the above general formula (1) and / or (2) of the present invention is 0.1 to 5.0M, preferably 1. 0-3.0M.

In the electrolyte composition of the present invention, the compounds represented by the general formulas (1) and (2) have both functions as a plasticizer and an electrolyte, but do not impair the object of the present invention. Then, if necessary, other electrolyte salts and plasticizers can be added.

The electrolyte salt can be used without any particular limitation as long as it is used for lithium polymer batteries such as lithium secondary batteries and lithium ion secondary batteries. For example, alkali metal salts, quaternary ammonium salts and the like can be mentioned. As the alkali metal salt, a lithium salt, a sodium salt, and a potassium salt are preferable. Specifically, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium salts of sulfonylimide represented by the following general formula (5), and the following general formula (6) Lithium salts of sulfonyl methide represented by the formula: lithium salts such as lithium acetate, lithium trifluoroacetate, lithium benzoate, lithium p-toluenesulfonate, lithium nitrate, lithium bromide, lithium iodide and lithium phenylborate; Sodium salts such as sodium chlorate, sodium iodide, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium trifluoromethanesulfonate, and sodium bromide; potassium iodide, potassium tetrafluoroborate, potassium hexafluorophosphate; Potassium salts such as potassium trifluoromethanesulfonate And the like. _{^{(R 9 -SO 2) (R}} 10 -SO 2) NLi ... (5) (R 11 -SO 2) (R 12 -SO 2) (R 13 -SO 2) CLi ... (6) [Equation (4) , (5), R ^{9 to} R ¹³ each represent a C 1 to C 4 perfluoroalkyl group which may contain one or two ether groups. ]

The sulfonyluy represented by the above general formula (5)
Specifically, the lithium salt of amide is represented by the following formula:
And the like. (CF_ThreeSO_Two)_TwoNL
i, (C_TwoF_FiveSO_Two)_TwoNLi, (C_ThreeF₇SO_Two)_TwoNL
i, (C_FourF₉SO_Two)_TwoNLi, (CF_ThreeSO_Two) (C_TwoF_Five
SO_Two) NLi, (CF_ThreeSO _Two) (C_ThreeF₇SO_Two) NL
i, (CF_ThreeSO_Two) (C_FourF₉SO_Two) NLi, (C_TwoF_Five
SO_Two) (C_ThreeF₇SO_Two) NLi, (C_TwoF_FiveSO_Two) (C_Four
F₉SO_Two) NLi, (CF_ThreeOCF_TwoSO_Two)_TwoNLi

Specific examples of the lithium salt of sulfonylmethide represented by the general formula (6) include those represented by the following formula. (CF ₃ SO ₂ ) ₃ CL
i, (C ₂ F ₅ SO ₂ ) ₃ CLi, (C ₃ F ₇ SO ₂ ) ₃ CL
i, (C ₄ F ₉ SO ₂ ) ₃ CLi, (CF ₃ SO ₂ ) ₂ (C ₂ F
₅ SO ₂ ) CLi, (CF ₃ SO ₂ ) ₂ (C ₃ F ₇ SO ₂ ) CL
i, (CF ₃ SO ₂ ) ₂ (C ₄ F ₉ SO ₂ ) CLi, (CF ₃
SO ₂ ) (C ₂ F ₅ SO ₂ ) ₂ CLi, (CF ₃ SO ₂ ) (C ₃
F ₇ SO ₂ ) ₂ CLi, (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) ₂
CLi, (C ₂ F ₅ SO ₂ ) ₂ (C ₃ F ₇ SO ₂ ) CLi,
(C ₂ F ₅ SO ₂ ) ₂ (C ₄ F ₉ SO ₂ ) CLi, (CF ₃ OC
F ₂ SO ₂ ) ₃ CLi

The quaternary ammonium salts include, for example, tetramethylammonium / 6-fluorophosphate, tetraethylammonium / 6-fluorophosphate, tetrapropylammonium / 6-fluorophosphate, methyltriethylammonium / 6-fluoride Phosphate, tetraethylammonium / 4-fluoroborate, tetraethylammonium / perchlorate, etc., or chain amidines, cyclic amidines (imidazoles, imidazolines, pyrimidines,
1,5-diazabicyclo [4,3,0] nonene-5 (D
BN), 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) and the like, pyrroles, pyrazoles,
Oxazoles, thiazoles, oxadiazoles,
And quaternary salts such as thiadiazoles, triazoles, pyridines, pyrazines and triazines, pyrrolidines, morpholines, piperidines, and piperazines.

Among these, lithium tetrafluoroborate,
Lithium hexafluorophosphate, a lithium salt of sulfonylimide represented by the above general formula (5) and a lithium salt of sulfonylmethide represented by the above general formula (6) show particularly high ionic conductivity and thermal stability It is preferable because the electrolyte salt is also excellent. In addition, these electrolyte salts can be used individually by 1 type or in combination of 2 or more types.

When other electrolyte salts as described above are used in combination, the compounds represented by the general formulas (1) and (2) of the present invention: other electrolyte salts (molar ratio) = 1: 99-99: 1, preferably 5:95 to 50:50.

As the plasticizer, for example, a compound such as a cyclic or chain carbonate, a chain carboxylate, a cyclic or chain ether, a phosphate, a lactone compound, a nitrile compound, an amide compound, or a mixture thereof is used. be able to.

As the cyclic carbonate, for example, propylene carbonate (PC), ethylene carbonate (E
C) and alkylene carbonates such as butylene carbonate. Examples of the chain carbonate include dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), and diethyl carbonate (DEC).
And the like. Examples of the chain carboxylate include methyl acetate and methyl propionate. Examples of the cyclic or chain ether include tetrahydrofuran, 1,3-dioxolan, 1,2-dimethoxyethane and the like. Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, ethyldimethyl phosphate, diethylmethyl phosphate, tripropyl phosphate, tributyl phosphate, tri (trifluoromethyl) phosphate, and tri (trichloromethyl) phosphate. , Tri (trifluoroethyl) phosphate, tri (triplefluoroethyl) phosphate, 2-ethoxy-1,
3,2-dioxaphospholane-2-one, 2-trifluoroethoxy-1,3,2-dioxaphospholane-2-
And 2-methoxyethoxy-1,3,2-dioxaphospholane-2-one. Examples of the lactone compound include γ-butyrolactone. Examples of the nitrile compound include acetonitrile. Examples of the amide compound include dimethylformamide. Among these,
It is preferable to use a cyclic carbonate, a chain carbonate, a phosphate, or a mixture thereof, since the battery performance such as high charge / discharge characteristics and output characteristics is exhibited.

When another plasticizer as described above is used in combination, the compound represented by the general formulas (1) and (2) of the present invention: another plasticizer (mass ratio) = 50: 50-99. 9:
0.1, preferably 80:20 to 98: 2.

Next, as the matrix polymer constituting the electrolyte composition of the present invention, a polymer having a high affinity for a plasticizer and a property of not syneresis or re-dissolution even after gelation is preferably used. For example, (I) an unsaturated polyurethane compound, (II) a polymer material having an interpenetrating network structure or a semi-interpenetrating network structure, (III) a thermoplastic resin containing a unit represented by the general formula (4), or (IV) ) A fluorine-based polymer material or the like can be used.

Further, among the matrix polymers (I) to
The use of the polymer material of (III) has high adhesiveness, so that the physical strength of the polymer gel electrolyte can be improved. Further, the polymer material having the interpenetrating network structure or semi-interpenetrating network structure (II) has a high affinity for an electrolyte solvent molecule and an ionic molecule, has a high ion mobility, and has a high concentration of an electrolyte salt. And has high ionic conductivity. The above general formula (4) of (III)
Since the thermoplastic resin containing the unit represented by the formula (1) is thermoplastic, it can be easily molded, swells appropriately by absorbing an organic electrolyte solution, and exhibits high ionic conductivity. The fluorine-based polymer material (IV) has excellent thermal and electrical stability.

Specifically, the unsaturated polyurethane compound (I) includes (A) an unsaturated alcohol having at least one (meth) acryloyl group and a hydroxyl group in a molecule; Those obtained by reacting the polyol compound represented by the general formula (2), the (C) polyisocyanate compound, and, if necessary, the (D) chain extender are preferable. HO-[(R ⁶ ) _h- (Y) _i- (R ⁷ ) _j ] _q -OH (3) [wherein R ⁶ and R ⁷ are the same or different amino group, nitro group, carbonyl group or A divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an ether group, and Y is -COO
—, —OCOO—, —NR ⁸ CO— (R ⁸ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), —O— or an arylene group, and h, i, j are each 0 or 1 to 10,
q represents an integer of 1 or more. ]

As the unsaturated alcohol of the component (A),
There is no particular limitation as long as it has at least one (meth) acryloyl group and a hydroxyl group in the molecule.
For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
Examples thereof include diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, and triethylene glycol monomethacrylate.

As the polyol compound of the component (B),
For example, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, ethylene glycol / propylene glycol copolymer, ethylene glycol / oxytetramethylene glycol copolymer, and polyester polyols such as polycaprolactone can be used. But,
Particularly, those represented by the following general formula (2) are preferable. HO - _{^{[(R 6) h - (Y}} ) i - (R 7) j ] _q -OH ... (3)

In the above formula (2), R ⁶ and R ^{7 each} have the same or different amino group, nitro group, carbonyl group or ether group and may have 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
And 6 represents a divalent hydrocarbon group, particularly an alkylene group, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, an ethylene oxide group, and a propylene oxide group.

Y is -COO-, -OCOO-, -NR ⁸
CO- (R ⁸ is an alkyl group of 1 to 8 carbon hydrogen atom or a carbon), - O-or an arylene group such as phenylene group.

H, i, j are 0 or an integer of 1 to 10, and q is 1 or more, preferably 5 or more, more preferably 10 to 20.
Indicates the number of 0.

In this case, the number average molecular weight of the polyol compound (B) is preferably in the range of from 400 to 10,000, more preferably from 1,000 to 5,000.

As the polyisocyanate compound of the component (C), for example, tolylene diisocyanate, 4,4'-
Aromatic diisocyanates such as diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dichloro-4,4′-diphenylmethane diisocyanate, xylylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, Examples thereof include aliphatic or alicyclic diisocyanates such as 4′-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate.

The unsaturated polyurethane compounds of the present invention include:
In addition to the components (A) to (C), it is preferable to add a chain extender as necessary. As such a chain extender, those usually used for the synthesis of a thermoplastic polyurethane resin can be used. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol Aliphatic diols such as 1,1,9-nonanediol;
1,4-bis (β-hydroxyethoxy) benzene,
Aromatic diols or alicyclic diols such as 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, hexamethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, Diamines such as piperazine derivatives, phenylenediamines and tolylenediamines; adipic hydrazide;
Examples thereof include amino alcohols such as isophthalic hydrazide and the like, and one of these can be used alone or in combination of two or more.

It is also possible to use a urethane prepolymer obtained by previously reacting the polyol component (B) and the polyisocyanate compound (C).

In the present invention, the polyol compound (B) is used in an amount of 100 to 20,000 parts by mass, preferably 1,2 parts by mass, per 100 parts by mass of the unsaturated alcohol (A).
000 to 10,000 parts by mass, the polyisocyanate compound of the component (C) is 80 to 5,000 parts by mass, preferably 300 to 2,000 parts by mass, and if necessary, the chain extender of the component (D) is 5 to 5 parts by mass. ~ 1,000 parts by mass, preferably 10
It is preferable to add 〜500 parts by mass.

Specific examples of the unsaturated polyurethane compound of the present invention obtained as described above include the following compounds and the like. One of these compounds may be used alone, or two or more may be used in combination. Can be. _{CH 2 = C (CH 3)} COO-C 2 H 4 O-CONH-C
_{6 H 4 -CH 2 C 6 H} 4 -NHCOO - _{[(C 2 H 4 O) h} (C
_{H 2 CH (CH 3) O} ) j ] _{q -CONH-C 6 H 4 -CH} 2
_{C 6 H 4 -NHCOO-C 2} H 4 O-COC (CH 3) = C
H ₂ (where h = 7, j = 3, q = 5 to 7) (A) Component: hydroxyethyl methacrylate (B) Component: Ethylene oxide / propylene oxide random copolymer diol (in the above general formula (2)) , H
/ J = 7/3, a number average molecular weight of about 3000) (C) component: 4,4'-diphenylmethane diisocyanate _{CH 2 = C (CH 3)} COO-C 2 H 4 O-CONH-C
_{6 H 4 -CH 2 C 6 H} 4 -NHCOO - { [(C ₂ H ₄ O)
_{h (CH 2 CH (CH 3} ) O) j ] _q -CONH-C ₆ H ₄ -
_{CH 2 C 6 H 4 -NHCOO-} C 4 H 8 O} r -CONH-C 6
_{H 4 -CH 2 C 6 H 4} -NHCOO-C 2 H 4 O-COC (C
H ₃ ) = CH ₂ (where h = 7, j = 3, q = 5-7, r = 2-20) (A) component: hydroxyethyl methacrylate (B) component: ethylene oxide / propylene oxide random copolymer Polymerized diol (in the above general formula (2), h
/ J = 7/3, number average molecular weight about 3000) (C) component: 4,4′-diphenylmethane diisocyanate (D) component: 1,4-butanediol CH ₂ ＣC (CH ₃ ) COO—C ₂ H ₄ O-CONH-C
_{6 H 7 (CH 3) 3} -CH 2 -NHCOO - [(C _{2 H 4} O) _{h
(CH 2 CH (CH 3)} O) j ] _{q -CONH-C 6 H 7 (} C
_{H 3) 3 -CH 2 -NHCOO-} C 2 H 4 O-COC (C
H ₃ ) = CH ₂ (however, h = 7, j = 3, q = 5 to 7) (A) component: hydroxyethyl methacrylate (B) component: ethylene oxide / propylene oxide random copolymerized diol (the above general formula In (2), h
/ J = 7/3, a number average molecular weight of about 3000) (C) component: isophorone diisocyanate _{CH 2 = C (CH 3)} COO-C 2 H 4 O-CONH-C
_{6 H 4 -CH 2 C 6 H} 4 -NHCOO-CH 2 CH 2 O- (C
_{OC 5 H 10 O) s -CH} 2 CH 2 O-CONH-C 6 H 4 -C
_{H 2 C 6 H 4 -NHCOO-} C 2 H 4 O-COC (CH 3) =
CH ₂ (where s is 20 to 30) (A) Component: hydroxyethyl methacrylate (B) Component: polycaprolactone diol (number average molecular weight: about 3000) (C) Component: 4,4′-diphenylmethane diisocyanate

The number average molecular weight of the obtained unsaturated polyurethane compound is preferably in the range of 1,000 to 50,000, more preferably in the range of 3,000 to 30,000. If the number average molecular weight is too small, the molecular weight between cross-linking points of the cured gel may be small, and the flexibility of the polymer gel electrolyte may be too low. On the other hand, if it is too large, the viscosity of the polymer electrolyte solution before gel hardening increases, which may make it difficult to incorporate the polymer electrolyte solution into a secondary battery or an electric double layer capacitor.

In the present invention, a monomer copolymerizable with the unsaturated polyurethane compound may be used in combination.
As monomers copolymerizable with the unsaturated polyurethane compound, for example, acrylonitrile, methacrylonitrile,
Acrylic esters, methacrylic esters, N-
And vinylpyrrolidone. Acrylonitrile,
When methacrylonitrile is used in combination, the ionic conductivity is not hindered, and the strength of the film can be improved, which is preferable. In this case, the compounding ratio of the monomer component copolymerizable with the unsaturated polyurethane compound is such that the molar equivalent of the unsaturated double bond group in 1 liter of the electrolyte composition solution before gel curing is 0.5 to 5.0, preferably 1.0 to 2.5. If the molar equivalent is too small, a sufficient crosslinking reaction does not occur and gelation may not occur. On the other hand, if it is too large, the molecular weight between crosslink points may be too small and the flexibility of the electrolyte composition may be too low.

The amount of the unsaturated polyurethane compound (I) is 0.5 to 30% by mass, preferably 1 to 20% by mass, based on the whole electrolyte composition.

Next, as the polymer material having the interpenetrating network structure or the semi-interpenetrating network structure of the above (II), two or more kinds capable of forming an interpenetrating network structure or a semi-interpenetrating network structure with each other (Polymers, reactive monomers, etc.) can be used.

As such two or more compounds,
(A) (a) a hydroxyalkyl polysaccharide derivative and (d)
A polymer matrix combining a compound having a crosslinkable functional group, a polymer matrix combining a (b) (b) polyvinyl alcohol derivative and (d) a compound having a crosslinkable functional group, or (c) ( Polymer matrix in which c) a polyglycidol derivative and (d) a compound having a crosslinkable functional group are combined.
In this case, it is preferable to use the unsaturated polyurethane compound of the present invention (I) as a part or all of the compound having a crosslinkable functional group of the component (d) from the viewpoint of improving physical strength.

The hydroxyalkyl polysaccharide derivative of the component (a) constituting the matrix polymer of the above (a) includes hydroxyethyl obtained by reacting a naturally occurring polysaccharide such as cellulose or starch with ethylene oxide. Polysaccharides, hydroxypropyl polysaccharides obtained by reacting propylene oxide, glycidol or dihydroxypropyl polysaccharides obtained by reacting 3-chloro-1,2-propanediol, and the like. These hydroxyalkyl polysaccharides A part or all of the hydroxyl groups are blocked with a substituent via an ester bond or an ether bond.

Examples of the polysaccharide include cellulose,
Examples include starch, amylose, amylopectin, pullulan, curdlan, mannan, glucomannan, arabinan, chitin, chitosan, alginic acid, carrageenan, dextran, etc. There are no restrictions on the arrangement and the like, but cellulose and starch are particularly preferred from the viewpoint of availability.

A method for synthesizing dihydroxypropylcellulose is described in US Pat. No. 4,096,326. Further, other dihydroxypropyl polysaccharides can be synthesized by a known method [Sato et al., M.
akromol. Chem. , 193, 647 (199).
2) or Macromolecules 24, 46
91 (1991)].

The hydroxyalkyl polysaccharide that can be used in the present invention has a degree of molar substitution of 2 or more. When the molar substitution degree is less than 2, the ability to dissolve the ion-conductive metal salts is too low to be used. The upper limit of the degree of molar substitution is 30, preferably 20 ,. It is sometimes difficult to industrially synthesize a hydroxyalkyl polysaccharide having a degree of molar substitution higher than 30 in view of the industrial production cost and the complexity of the synthesis operation. Further, even if it is manufactured by force and the molar substitution degree is increased from 30, the increase in conductivity due to the increase in the molar substitution degree is not expected to be so much expected.

In the present invention, the component (a)
10 of the terminal OH group of the molecular chain of the hydroxyalkyl polysaccharide
% Or more is a halogen atom, unsubstituted or substituted monovalent hydrocarbon
Group, R ¹⁴CO-group (R¹⁴Is unsubstituted or substituted monovalent hydrocarbon
Group), R¹⁴ _ThreeSi-group (R¹⁴Is the same as above), amino
Group, alkylamino group, H (OR¹⁵)_m-Group (R¹⁵Is charcoal
An alkylene group having a prime number of 2 to 5, m is an integer of 1 to 100) and
One or two or more selected from groups containing
Of hydroxyalkyl polysaccharides blocked by a divalent group
Use conductor.

R ¹⁴ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl,
Butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group,
Aryl groups such as phenyl group, tolyl group and xylyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group and cyclohexenyl group An alkenyl group such as octenyl group, or a part or all of the hydrogen atoms of these groups, a halogen atom such as fluorine, bromine or chlorine, a cyano group, a hydroxyl group, H (OR ¹⁵ ) _z −
Group (R ¹⁵ is an alkylene group having 2 to 5 carbon atoms, z is 1 to 10
0), those substituted with an amino group, an aminoalkyl group, a phosphono group, and the like, for example, a cyanoethyl group, a cyanobenzyl group, a substituent in which a cyano group is bonded to another alkyl group, a chloromethyl group, a chloropropyl group, Examples thereof include a bromoethyl group and a trifluoropropyl group, and one of these can be used alone or in combination of two or more.

The substituent can be blocked by a known method for introducing various groups into the terminal OH group.

The compounding amount of the hydroxyalkyl polysaccharide derivative of the above-mentioned component (a) is 0.5 to the entire electrolyte composition.
-30% by mass, preferably 1-20% by mass.

Next, the (b) component (b) of the polyvinyl alcohol derivative constituting the matrix polymer is a hydroxyl group of a polymer compound having a polyvinyl alcohol unit having an oxyalkylene chain (the remaining hydroxyl group derived from the polyvinyl alcohol unit, And the total of the introduced hydroxyl groups derived from the oxyalkylene-containing group).

The polymer compound having a polyvinyl alcohol unit is a polymer compound having a polyvinyl alcohol unit in a molecule and having an average degree of polymerization of 20 or more, preferably 30 or more, more preferably 50 or more. Some or all of the hydroxyl groups therein are substituted by oxyalkylene-containing groups.
The upper limit of the average degree of polymerization is 2,000 or less, especially 20.
It is preferably 0 or less. The average degree of polymerization here is a number average degree of polymerization. A polymer having an excessively high degree of polymerization has an excessively high viscosity and is difficult to handle. Therefore, the preferable range of the degree of polymerization is 20 to 500 mer.

Here, the polyvinyl alcohol unit constitutes the main chain of the polyvinyl alcohol derivative of the present invention, and is represented by the following general formula (7).

[0066]

Embedded image

In the above formula (7), n is 20 or more, preferably 30 or more, more preferably 50 or more, and the upper limit thereof is preferably 2000 or less, particularly preferably 200 or less.

The high molecular compound having a polyvinyl alcohol unit is preferably a homopolymer which satisfies the above average polymerization degree range and has a polyvinyl alcohol unit fraction of 98 mol% or more in the molecule, but is not particularly limited. A polymer compound which satisfies the above average polymerization degree range and has a polyvinyl alcohol content of preferably at least 60 mol%, more preferably at least 70 mol%, for example, a part of the hydroxyl group of the polyvinyl alcohol is formal. For example, modified polyvinyl formal, modified polyvinyl alcohol in which a part of hydroxyl groups of polyvinyl alcohol is alkylated, poly (ethylene vinyl alcohol), partially saponified polyvinyl acetate, and other modified polyvinyl alcohol can be used.

The polymer compound is an oxyalkylene-containing group in which a part or all of the hydroxyl groups in the polyvinyl alcohol unit has an average degree of molar substitution of 0.3 or more (this oxyalkylene group is a part of the hydrogen atom). May be substituted with a hydroxyl group), and preferably at least 30 mol%, more preferably at least 50 mol%.

The average molar substitution degree (MS) can be calculated by accurately measuring the charged mass and the mass of the reaction product. For example, consider a case where 10 g of PVA is reacted with ethylene oxide, and the amount of the obtained PVA derivative is 15 g. PVA is a unit of _{- (CH 2 CH (OH)} )
Therefore, the unit molecular weight is 44. On the other hand, PVA derivative is a reaction _{product, - (CH 2 CH (OH} ))
- because those -OH groups becomes _{-O- (CH 2 CH 2 O)} n -H group, their unit molecular weight is 44 + 44n. Accordingly, the mass increase accompanying the reaction corresponds to 44n, and is as follows.

[0071]

(Equation 1)

Therefore, in the above example, it can be calculated that MS = 0.5. Note that this value merely represents the average degree of molar substitution. That is, the amount of unreacted PVA units and the length of oxyethylene groups introduced by the reaction cannot be specified.

[0073]

Embedded image

Here, the method of introducing an oxyalkylene-containing group into the polymer compound having a polyvinyl alcohol unit includes a method of reacting an oxirane compound such as ethylene oxide with a polymer compound having a polyvinyl alcohol unit, or a method of introducing a polyvinyl alcohol unit. A method in which a polymer compound having a unit is reacted with a polyoxyalkylene compound having a substituent having reactivity with a hydroxyl group at a terminal.

In the above method, one kind selected from ethylene oxide, propylene oxide and glycidol can be used alone or in combination of two or more kinds as the oxirane compound.

In this case, when ethylene oxide is reacted, an oxyethylene chain is introduced as shown by the following formula.

Embedded image [However, a = 1 to 10, especially 1 to 5 is preferable. ]

When propylene oxide is reacted, an oxypropylene chain is usually introduced as shown by the following formula.

Embedded image [However, b = 1 to 10, especially 1 to 5 is preferable. ]

Further, when glycidol is reacted, two branched chains are introduced as shown by the following formula.

The reaction between the hydroxyl group of PVA and glycidol is as follows:
There are two types of attack, a attack and b attack. When one glycidol reacts, two new hydroxyl groups are generated,
The hydroxyl groups react with glycidol again. as a result,
The following two branched chains are introduced on the hydroxyl group of the PVA unit.

[0080]

Embedded image

The value of x + y is preferably 1 to 10,
More preferably, it is 1-5. The ratio between x and y is not particularly limited, but generally, x: y = 0.4: 0.6 to .0.
6: 0.4 is often in the range.

The reaction between the polymer compound having a polyvinyl alcohol unit and the above oxirane compound can be carried out using a basic catalyst such as sodium hydroxide, potassium hydroxide and various amine compounds.

Specifically, a reaction between polyvinyl alcohol and glycidol will be described as an example. A solvent and polyvinyl alcohol are charged in a reaction vessel. In this case, the polyvinyl alcohol does not necessarily need to be dissolved in the solvent, and may be uniformly dissolved or the polyvinyl alcohol may be in a suspended state in the solvent. A predetermined amount of a basic catalyst, for example, an aqueous solution of sodium hydroxide is added to this solution, and the mixture is stirred for a while, and then glycidol diluted with a solvent is added. After reacting at a predetermined temperature for a predetermined time, polyvinyl alcohol is taken out. If the polyvinyl alcohol is not dissolved, it is filtered off using a glass filter or the like. In the case of dissolution, an alcohol or the like is poured to cause precipitation, and the precipitate is separated by filtration using a glass filter or the like. For purification, neutralization by dissolving in water and passing through an ion exchange resin or dialysis and freeze-drying can be performed to obtain dihydroxypropylated polyvinyl alcohol.

The reaction ratio between the polyvinyl alcohol and the oxirane compound is preferably 1:10, more preferably 1:20 in molar ratio.

As the polyoxyalkylene compound having a substituent having reactivity with a hydroxyl group at the terminal, a compound represented by the following general formula (8) can be used.

[0086]

Embedded image

In the formula (8), A is a monovalent substituent having a reactivity with a hydroxyl group, for example, isocyanate group, epoxy group, carboxylic acid group, carboxylic acid chloride group, ester group, amide group, fluorine, Halogen atoms such as bromine and chlorine,
Examples include a silicon-containing reactive substituent and a monovalent substituent capable of reacting with another hydroxyl group. Among these, an isocyanate group, an epoxy group, and a carboxylic acid chloride group are preferable from the viewpoint of reactivity.

The carboxylic acid group may be an acid anhydride. Further, as the ester group, a methyl ester group,
Ethyl ester groups are preferred. Examples of the silicon-containing reactive substituent include those having a SiH group, a SiOH group, or the like at a terminal.

Further, the above isocyanate groups and epoxy groups
The reactive group with a hydroxyl group such as ¹⁵O oxyalkyl
May be bonded to an oxygen group, an oxygen atom, a sulfur atom,
Rubonyl group, carbonyloxy group, NH group, N (C
H_Three) Group, N (C_TwoH_Five) Groups, such as nitrogen-containing groups, SO_TwoGroup
Intervening, preferably 1-10 carbon atoms, especially 1-carbon
6, alkylene group, alkenylene group, arylene group, etc.
Through R¹⁵May be bonded to the oxyalkylene group of O
No.

For example, as the polyoxyalkylene group having the substituent A, a substance obtained by reacting a terminal hydroxyl group of a polyoxyalkylene group with a polyisocyanate compound can be used. In this case, as the compound having an isocyanate group, for example, two or more in a molecule such as tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, biphenylene diisocyanate, diphenyl ether diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Can be used. For example, a compound obtained by the following reaction can be used.

[0091]

Embedded image

R ¹⁵ O is an oxyalkylene group having 2 to 5 carbon atoms, for example, —CH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ O
_{-, - CH 2 CH (CH} 3) O -, - CH 2 CH (CH 2 C
H ₃ ) O— and —CH ₂ CH ₂ CH ₂ CH ₂ O—. m represents the number of added moles of the oxyalkylene group, and the number of added moles (m) is preferably 1 to 100, and more preferably 1 to 50.

In this case, the polyoxyalkylene chain represented by the above formula (R ¹⁵ O) _m is, in particular, a polyethylene glycol chain, a polypropylene glycol chain, or polyethylene oxide (EO) / polypropylene oxide (P
O) Copolymer chains are preferred. The weight average molecular weight of these polyoxyalkylene chains is preferably 100 to 3000,
More preferably, those having a weight average molecular weight in the range of 200 to 1,000, which is a molecular region in a liquid state at room temperature, are preferable.

R ¹⁴ is a one-terminal blocking group, and is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or an R ¹⁴ CO— group (R ¹⁴ is the same as above having 1 to 1 carbon atoms). 10 unsubstituted or substituted monovalent hydrocarbon groups).

As the R ¹⁴ CO— group, for example, R ¹⁴ may be the same unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms as described above. Preferably, R ¹⁴ may be substituted with a cyano group. A good alkyl or phenyl group, an acyl group,
Benzoyl and cyanobenzoyl are preferred.

The reaction between the polymer compound having a polyvinyl alcohol unit and the polyoxyalkylene compound having a substituent having reactivity with the hydroxyl group at the terminal can be carried out in the same manner as in the case of the oxirane compound.

The reaction ratio between the polyvinyl alcohol and the polyoxyalkylene compound having a substituent having reactivity with the hydroxyl group at the terminal is preferably 1: 1 to 1 in molar ratio.
The ratio is 1:20, more preferably 1: 1 to 1:10.

The polymer compound of the present invention having an oxyalkylene-containing group introduced into the polyvinyl alcohol unit has the structure
It can be confirmed by ¹³ C-NMR.

In this case, the number of oxyalkylene groups of the polymer compound having a polyvinyl alcohol unit having an oxyalkylene chain of the present invention can be measured by various methods such as NMR and elemental analysis. However, a method of obtaining from the mass increase of the polymer produced by the reaction with the charged polymer is simple. For example, the method for obtaining from the yield is to accurately measure the charged amount of the polymer compound having a polyvinyl alcohol unit and the mass of the polymer compound having a polyvinyl alcohol unit having an oxyalkylene group obtained by the reaction, and introduce the mass from the difference. The amount (average molar substitution degree) of the oxyalkylene chain thus obtained can be determined as described above.

The average molar substitution (MS) is an index indicating how many oxyalkylene groups are introduced per vinyl alcohol unit. In the polymer of the present invention, the average molar substitution is 0.3 Or more, preferably 0.5 or more, more preferably 0.1 or more.
It is preferably 7 or more, more preferably 1.0 or more. In this case, the upper limit of the average molar substitution degree is not particularly limited, but is preferably at most 20 or less. If the average molar substitution degree is too small, the ionic conductive salt does not dissolve,
The mobility of ions is also low, and the ionic conductivity may be low.On the other hand, if it is higher than a certain level, the solubility and mobility of the ionic conductive salt will not change,
It is useless if it is too large.

The polymer compound having a polyvinyl alcohol unit having an oxyalkylene chain according to the present invention has an apparent shape from a syrupy liquid having a high viscosity at room temperature (20 ° C.) to a rubbery solid state, depending on the average degree of polymerization. Changes,
The larger the average degree of polymerization, the lower the fluidity at room temperature (20 ° C.), so-called solids (soft paste solids).

Further, the polymer compound of the present invention is not a linear polymer but an amorphous (amorphous) polymer formed by entanglement of highly branched molecular chains, regardless of the average degree of polymerization.

The polyvinyl alcohol derivative of the present invention comprises
A part or all, preferably 10 mol% or more, of a hydroxyl group (total of a residual hydroxyl group derived from a polyvinyl alcohol unit and a hydroxyl group derived from an introduced oxyalkylene-containing group) in the molecule is a halogen atom, An unsubstituted or substituted monovalent hydrocarbon group, an R ¹⁴ CO— group (R ¹⁴ is the same unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms), R
^It is one blocked by one or more monovalent substituents selected from a ¹⁴ ₃ Si— group (R ¹⁴ is the same as described above), an amino group, an alkylamino group and a group having a phosphorus atom.

The substituent can be blocked by a known method for introducing various groups into the terminal OH group.

The blending amount of the polyvinyl alcohol derivative of the component (b) is 0.5 to 3 with respect to the whole electrolyte composition.
0 mass%, preferably 1 to 20 mass%.

Next, the polyglycidol derivative of the component (c) constituting the polymer matrix of the above (c) comprises a unit represented by the following formula (9) (hereinafter referred to as A unit) and a unit represented by the following formula (10) (Hereinafter, referred to as a B unit), and each terminal of the molecular chain is blocked at the terminal of the molecular chain by a predetermined substituent.

Embedded image

The above polyglycidol can be obtained by polymerizing glycidol or 3-chloro-1,2-propanediol.
It is recommended to carry out the polymerization using glycidol as raw material.

As the above-mentioned polymerization reaction, there are known a method using a basic catalyst such as sodium hydroxide, potassium hydroxide and various amine compounds, and a method using a Lewis acid catalyst (Andrzej Dwork).
et al. , Macromol. Chem. Phys
s. 196, 1963-1970 (1995); T
oker. , Macromolecules 27,3
20-322 (1994)).

The polyglycidol has A, B in the molecule.
It is preferable that there are two or more, preferably six or more, and more preferably ten or more of the two units. In this case, although the upper limit is not particularly limited,
The number is preferably 0 or less. When fluidity as a liquid is required for polyglycidol, it is preferable that the total of the A and B units is small. On the other hand, when high viscosity is required, the total of the A and B units is preferably large.

The appearance of these A and B units has no regularity and is random, for example, -AAAA-, -AA
-B-, -ABBA-, -BAA-, -AB-
B-, -BABB-, -BBAA-, -BBB
Any combination such as-is possible.

The polyglycidol preferably has a weight average molecular weight (Mw) in terms of polyethylene glycol using gel filtration chromatography (GPC) of 200.
~ 730,000, more preferably 200 ~ 100,0
00, more preferably 600 to 20,000. In this case, polyglycidol having a weight-average molecular weight of up to about 2000 is a high-viscosity liquid that flows at room temperature, while polyglycidol having a weight-average molecular weight exceeding 3000 is a soft paste-like solid at room temperature. Further, the average molecular weight ratio (Mw / Mn) is 1.1 to 20, more preferably 1.1.
It is preferably from 10 to 10.

The apparent shape of the polyglycidol changes from a syrupy liquid having a high viscosity at room temperature (20 ° C.) to a rubbery solid state depending on the molecular weight, and the larger the molecular weight, the higher the molecular weight at room temperature (20 ° C.). It has low fluidity, so-called solid (soft paste solid).

Further, polyglycidol is not a linear polymer, regardless of the molecular weight, but is an amorphous (amorphous) polymer formed by entanglement of highly branched molecular chains. This is recognized because the result of wide-angle X-ray diffraction does not show any peak indicating the presence of crystals.

Further, the ratio of A unit to B unit in the molecule is
A: B = 1 / 9-9 / 1, preferably 3 / 7- by molar ratio
7/3.

This polyglycidol is colorless and transparent and has no toxicity. Therefore, electrochemical materials such as binder materials for various active materials (for example, binders for electroluminescence), thickeners, substitutes for alkylene glycol, etc. It can be used for a wide range of applications.

In the present invention, as the component (c), at least 10% of the terminal OH groups in the molecular chain of the polyglycidol are halogen atoms, unsubstituted or substituted monovalent hydrocarbon groups, R ¹⁴ C
O- group (R ¹⁴ is the same unsubstituted or substituted monovalent hydrocarbon groups as above), R ¹⁴ ₃ Si- groups (R ¹⁴ is as defined above), an amino group, an alkylamino group, H (OR ¹⁵⁾ _m - A polyglycidol derivative blocked by one or more monovalent groups selected from a group (R ¹⁵ is an alkylene group having 2 to 5 carbon atoms, m is an integer of 1 to 100) and a group containing a phosphorus atom; Used.

The substituent can be blocked by a known method for introducing various groups into the terminal OH group.

The blending amount of the polyglycidol derivative of the component (c) is 0.5 to 30% by mass, preferably 1 to 20% by mass based on the whole electrolyte composition.

Next, the compound having a crosslinkable functional group of the component (d) includes a compound having an epoxy group in a molecule and a compound having two or more active hydrogen groups capable of reacting with the epoxy group. A compound having an isocyanate group in the molecule, a compound having two or more active hydrogen groups capable of reacting with the isocyanate group, and a compound having two or more reactive double bonds in the molecule can be used.

Examples of the compound having an epoxy group in the molecule include sorbitol polyglycidyl ether,
Sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylpropane polyglycidyl ether,
Resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diglycidyl ether of ethylene / propylene glycol copolymer, polytetramethylene glycol diglycidyl ether, adipic acid Compounds having two or more epoxy groups in the molecule, such as glycidyl ether, are mentioned.

Compounds having two or more active hydrogen groups, such as amine compounds,
An alcohol compound, a carboxylic acid compound, and a phenol compound can be reacted to form a three-dimensional network structure. When these are exemplified, high molecular polyols such as polyethylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymer, ethylene glycol, 1,2-propylene glycol, 1,3
-Propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 2,2-dimethyl-1,3
-Propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 1,4-bis (β-hydroxyethoxy) benzene,
p-xylylenediol, phenyldiethanolamine, methyldiethanolamine, polyethyleneimine,
Other polyfunctional amines, polyfunctional carboxylic acids and the like can be mentioned.

As the compound having an isocyanate group in the molecule, for example, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate,
Diphenylmethane diisocyanate, biphenylene diisocyanate, diphenyl ether diisocyanate,
2 in the molecule of trizine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.
Compounds having at least two isocyanate groups are exemplified.

Further, an isocyanate-terminated polyol compound obtained by reacting the above isocyanate compound with a polyhydric polyol compound can also be used. These can be obtained by reacting an isocyanate compound such as diphenylmethane diisocyanate or tolylene diisocyanate with the following polyol compounds.

In this case, the isocyanate compound [NC
O] and the stoichiometric ratio of [OH] of the polyol compound are [NCO]> [OH], and specifically, [NCO]:
[OH] = 1.03 / 1 to 10/1, preferably 1.10 / 1 to 5/1.

Examples of the polyol compound include high molecular polyols such as polyethylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymer, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3
-Butanediol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 2,2
-Dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 1,4-bis- (β-hydroxyethoxy) benzene, p-xylylenediol, phenyldiethanolamine, methyldiethanolamine, 3 ,
9-bis- (2-hydroxy-1,1-dimethyl)-
2,4,8,10-tetraoxaspiro [5,5] -undecane and the like.

Further, instead of the polyol compound, an amine compound having two or more active hydrogen groups may be reacted with the isocyanate compound. As the amine compound,
A compound having a primary or secondary amino group can be used, but a compound having a primary amino group is more preferable.
For example, ethylenediamine, 1,6-diaminohexane,
Diamines such as 1,4-diaminobutane and piperazine,
Examples thereof include polyamines such as polyethyleneamine, and amino alcohols such as N-methyldiethanolamine and aminoethanol. Of these, more preferred are diamines having the same reactivity of functional groups. Also in this case, the stoichiometric ratio of [NCO] of the isocyanate compound to [NH ₂ ] and [NH] of the amine compound is [NCO]> [N
H ₂ ] + [NH].

A compound having an isocyanate group alone cannot form a three-dimensional network structure. In order to form a three-dimensional network structure, these compounds must have two
A three-dimensional network structure can be formed by reacting a compound having two or more active hydrogen groups, for example, an amine compound, an alcohol compound, a carboxylic acid compound, and a phenol compound. Such compounds having two or more active hydrogen groups include, for example, polyethylene glycol, polypropylene glycol, ethylene glycol.
Polymer polyols such as propylene glycol copolymers,
Ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-
1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 1,4-bis (β-hydroxyethoxy) benzene, p-xylylenediol, phenyldiethanolamine, methyldiethanolamine, polyethyleneimine, and others Examples include polyfunctional amines and polyfunctional carboxylic acids.

Compounds having a reactive double bond include divinylbenzene, divinylsulfone, allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate ( Weight average molecular weight 200 to 1000), 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate (weight average molecular weight 400), 2-hydroxy -1,3
-Dimethacryloxypropane, 2,2-bis- [4-
(Methacryloxyethoxy) phenyl] propane, 2,
2-bis- [4- (methacryloxyethoxydiethoxy) phenyl] propane, 2,2-bis- [4- (methacryloxyethoxy / polyethoxy) phenyl] propane, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene diacrylate Ethylene glycol, polyethylene glycol diacrylate (weight average molecular weight 200 to 1000), 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polypropylene glycol diacrylate (weight average molecular weight 40)
0), 2-hydroxy-1,3-diacryloxypropane, 2,2-bis- [4- (acryloxyethoxy) phenyl] propane, 2,2-bis- [4- (acryloxyethoxydiethoxy) Phenyl] propane, 2,2
-Bis- [4- (acryloxyethoxy / polyethoxy) phenyl] propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetetraacrylate, tricyclodecanedimethanolacrylate, hydrogenated Two reactive double bonds are present in the molecule of dicyclopentadiene diacrylate, polyester diacrylate, polyester dimethacrylate, the unsaturated polyurethane compound of the above (I), etc.
Compounds having at least one compound.

Further, if necessary, acrylic acid or methacrylic acid ester such as glycidyl methacrylate, glycidyl acrylate, tetrahydrofurfuryl methacrylate, methacryloyl isocyanate, 2-hydroxymethyl methacrylic acid, N, N-dimethylaminoethyl methacrylic acid, etc. A compound having one acrylic acid group or methacrylic acid group in the molecule can be added. Further, acrylamide compounds such as N-methylolacrylamide, methylenebisacrylamide and diacetoneacrylamide, vinyl compounds such as vinyloxazolines and vinylene carbonate, and other compounds having a reactive double bond can be added.

Also in this case, in order to form a three-dimensional network structure, it is necessary to add a compound having two or more reactive double bonds in the molecule. That is, since a compound having only one reactive double bond such as methyl methacrylate alone cannot form a three-dimensional network structure, a compound partially having at least two reactive double bonds is used. It must be added.

Among the compounds containing a reactive double bond, particularly preferred reactive monomers include those described in the above (I).
Or an unsaturated polyurethane compound represented by the following general formula (11):
And a diester compound containing a polyoxyalkylene component represented by the following general formula (12). It is recommended to use these in combination with a monoester compound containing a polyoxyalkylene component represented by the following general formula (12).

[0132]

Embedded image

(Wherein, in the formula, R¹⁶, R¹⁷, R¹⁸Is hydrogen field
Or a methyl group, an ethyl group, an n-propyl group, an i-
Propyl group, n-butyl group, i-butyl group, s-butyl
Group, t-butyl group, etc.
A kill group which satisfies the condition of X ≧ 1 and Y ≧ 0
Or satisfy the condition of X ≧ 0 and Y ≧ 1
X + Y is preferably 100 or less, more preferably 1 to 30.
Good. Especially R¹⁶, R¹⁷, R ¹⁸Is a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
Butyl, s-butyl and t-butyl are preferred. )

[0134]

Embedded image

(Wherein, in the formula, R¹⁹, R²⁰, R^{twenty one}Is hydrogen field
Or a methyl group, an ethyl group, an n-propyl group, an i-
Propyl group, n-butyl group, i-butyl group, s-butyl
Group, t-butyl group, etc.
A kill group that satisfies the condition of A ≧ 1 and B ≧ 0
Or satisfying the condition of A ≧ 0 and B ≧ 1
A + B is preferably 100 or less, particularly preferably 1 to 30.
Good. Especially R¹⁹, R²⁰, R ^{twenty one}Is a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
Butyl, s-butyl and t-butyl are preferred. )

The unsaturated polyurethane compound of the above (I),
Or a diester compound containing a polyoxyalkylene component and a monoester compound containing a polyoxyalkylene component are heated or electron beam in a polymer electrolyte composition,
The three-dimensional network structure can be formed by irradiating a microwave, a high frequency wave, or the like, or by heating the mixture.

In this case, generally, the unsaturated polyurethane compound of the above (I) or the diester compound containing a polyoxyalkylene component can form a three-dimensional network structure by reacting it alone. To
It is preferable to further add a monoester compound containing a polyoxyalkylene component which is a monofunctional monomer to the unsaturated polyurethane compound or a diester compound containing a polyoxyalkylene component. This is because a polyoxyalkylene branched chain can be introduced onto a three-dimensional network by adding this monoester compound.

The composition ratio of the unsaturated polyurethane compound or the diester compound containing the polyoxyalkylene component to the monoester compound containing the polyoxyalkylene component is not particularly limited. Diester compound containing oxyalkylene component / monoester compound containing polyoxyalkylene component] = 0.2 to 10, particularly 0.1 to 0.1.
The range of 5 to 5 is preferable from the viewpoint of improving the film strength.

The compounding amount of the compound having a crosslinkable functional group of the component (d) is 1% by mass or more, preferably 5 to 40% by mass, more preferably 1% by mass based on the whole electrolyte composition.
0 to 20% by mass.

The matrix polymer containing the components (a) to (c) and (d) is heated or irradiated with an electron beam, microwave, high frequency, or the like, so that the crosslinkable functional group of the component (d) is (A) to the three-dimensional network structure of a polymer obtained by reacting (polymerizing) a compound having
It forms a semi-interpenetrating polymer network in which the molecular chains of the polymer (c) are entangled with each other.

Next, as the matrix polymer of the above (III), it is preferable to use a thermoplastic resin containing a unit represented by the following general formula (4).

[0142]

Embedded image (In the formula, r represents 3 to 5, and s represents an integer of 5 or more.)

Examples of such a thermoplastic resin include (E)
It is preferable to use a thermoplastic polyurethane resin obtained by reacting a polyol compound, (F) a polyisocyanate compound, and (G) a chain extender. The thermoplastic polyurethane-based resin includes a polyurethane urea resin having a urethane bond and a urea bond in addition to a polyurethane resin having a urethane bond.

As the polyol compound as the component (E), those obtained by a dehydration reaction or a dealcoholization reaction of the following compounds (i) to (vi) are preferable. Particularly, polyester polyols, polyester polyether polyols, and polyester polycarbonate polyols , Polycaprolactone polyol, or a mixture thereof. (I) a polyester polyol obtained by ring-opening polymerization of one or more cyclic esters (lactones); (ii) (a) a polyester polyol obtained by ring-opening polymerization of the cyclic ester (lactone) and a carboxylic acid;
(B) a dihydric aliphatic alcohol, a carbonate compound,
Polyester polyol obtained by reacting at least one selected from a polycarbonate polyol and a polyether polyol, respectively. (Iii) Polyester polyol obtained by reacting one or more carboxylic acids with one or more dihydric aliphatic alcohols (iv ) Polyester polycarbonate polyol obtained by reacting one or more carboxylic acids with one or more polycarbonate polyols (v) Polyester polyether polyol obtained by reacting one or more carboxylic acids with one or more polyether polyols (vi) One kind Polyester polyol obtained by reacting the above carboxylic acid with two or more kinds selected from dihydric aliphatic alcohols, polycarbonate polyols and polyether polyols

In this case, examples of the cyclic ester (lactone) include γ-butyrolactone, δ-valerolactone, ε-caprolactone and the like.

As the carboxylic acid, for example, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
5-1 carbon atoms such as sebacic acid and dodecanedicarboxylic acid
4 linear aliphatic dicarboxylic acids; 2-methylsuccinic acid,
2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-
C5-14 branched aliphatic dicarboxylic acids such as dimethyldecandioic acid and 3,7-dimethyldecandioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and orthophthalic acid; or esters thereof. Derivatives and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, carbon number 5-14
Are preferred, and adipic acid, azelaic acid and sebacic acid are particularly preferably used.

Examples of the dihydric aliphatic alcohol include ethylene glycol, 1,3-propanediol,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol,
C2-C14 linear aliphatic diols such as 1,10-decanediol; 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl C3 to C14 branched aliphatic diols such as -1,8-octanediol; cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; and the like, alone or in combination of two or more. Can be used in combination. Among them, a branched or chain aliphatic diol having 4 to 10 carbon atoms is preferable, and 3-methyl-1,5-pentanediol is particularly preferable.

As the carbonate compound, for example, dialkyl carbonate, alkylene carbonate, diaryl carbonate and the like can be mentioned. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate. Examples of the alkylene carbonate include ethylene carbonate. Examples of the diaryl carbonate include, for example, diphenyl carbonate.

The polycarbonate polyol is selected from polyhydric alcohols and the above-mentioned carbonate compounds.
And those obtained by a dealcoholation reaction with at least one carbonate compound. Examples of the polyhydric alcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octane. Examples include diol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, 1,4-cyclohexanedimethanol, and the like.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol,
EO / PO copolymer, polyoxytetramethylene glycol and the like can be mentioned, and one of these can be used alone or in combination of two or more.

The number average molecular weight of the polyol compound (E) is preferably from 1,000 to 5,000, more preferably from 1,500 to 3,000. Heat resistance of the thermoplastic polyurethane resin film obtained when the number average molecular weight of the polyol compound is too small,
Physical properties such as tensile elongation may be reduced. On the other hand, if it is too large, the viscosity at the time of synthesis increases, and the production stability of the obtained thermoplastic polyurethane resin may decrease. In addition, the number average molecular weight of the polyol compound referred to herein means a number average molecular weight calculated based on a hydroxyl value measured according to JIS K1577.

Examples of the polyisocyanate compound of the component (F) include tolylene diisocyanate,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate And aliphatic or alicyclic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate.

As the chain extender of the component (G), it is preferable to use a low molecular weight compound having two active hydrogen atoms reactive with an isocyanate group in the molecule and having a molecular weight of 300 or less.

Examples of such low molecular weight compounds include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, 1,7-heptanediol, 1,8
Aliphatic diols such as octanediol and 1,9-nonanediol; 1,4-bis (β-hydroxyethoxy)
Benzene, 1,4-cyclohexanediol, bis (β
Aromatic diols or alicyclic diols such as -hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, hexamethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, piperazine derivatives, phenylenediamine, tolylenediamine, etc. Diamines; amino alcohols such as adipic hydrazide and isophthalic hydrazide; one of these can be used alone or two or more can be used in combination.

In the thermoplastic polyurethane resin of the present invention, 5 to 20 parts by weight of the polyisocyanate compound of the component (F) is added to 100 parts by mass of the polyol compound of the component (E).
0 parts by weight, preferably 20 to 100 parts by weight,
It is preferable to add 1 to 200 parts by mass, preferably 5 to 100 parts by mass of the chain extender of the component (G).

The amount of the thermoplastic resin (III) is from 0.5 to 30% by mass, preferably from 1 to 20% by mass, based on the whole electrolyte composition.

Further, the swelling ratio of the thermoplastic resin of the present invention is in the range of 150 to 800% by mass, preferably 250 to 500% by mass, more preferably 250 to 500% by mass.
４００400% by mass.

[0158]

(Equation 2)

Next, as the fluorine-based polymer material which is the matrix polymer of the above (IV), for example, polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene (HFP) copolymer [P (VDF- H
FP)], vinylidene fluoride-ethylene trifluoride chloride (CTFE) copolymer [P (VDF-CTFE)], vinylidene fluoride-hexafluoropropylene fluororubber [P (VDF-HFP)], vinylidene fluoride- Tetrafluoroethylene-hexafluoropropylene fluoro rubber [P (VDF-TFE-HFP)], vinylidene fluoride-tetrafluoroethylene-perfluoroalkyl vinyl ether fluoro rubber, and the like. As the vinylidene fluoride-based polymer, a polymer in which vinylidene fluoride is 50% by mass or more, particularly 70% by mass or more (the upper limit is about 97% by mass) is preferable. Among these, polyvinylidene fluoride (PVDF), a copolymer of vinylidene fluoride and hexafluoropropylene [P (VDF-H
FP)], and a copolymer of vinylidene fluoride and ethylene chloride trifluoride [P (VDF-CTFE)] is preferred.

In this case, the weight average molecular weight of the fluoropolymer is at least 500,000, preferably 500,000.
0 to 2,000,000, more preferably 500,00
0 to 1,500,000. If the weight average molecular weight is too small, the physical strength may be significantly reduced.

The compounding amount of the fluorine-based polymer material is 0.5 to 30% by mass, and preferably 1 to 20% by mass, based on the whole electrolyte composition.

The electrolyte composition of the present invention is suitably used as a solid polymer electrolyte, and has an ionic conductivity of 1 × 10 ⁻⁵ S / cm or more at 25 ° C. by an AC impedance method.

The polymer gel electrolyte obtained by swelling the electrolyte composition of the present invention with an organic solvent has an ionic conductivity of 1 × 10 ⁻³ S / c at 25 ° C. by an AC impedance method.
m or more. In this case, as the organic solvent, propylene carbonate (PC), ethyl carbonate (EC),
Examples include ethyl methyl carbonate, γ-butyrolactone, sulfolane, diethyl carbonate, and dimethyl carbonate.

<Lithium Polymer Battery of the Present Invention> The lithium polymer battery of the present invention includes a positive electrode, a negative electrode, and an electrolyte. In this case, the polymer solid electrolyte or polymer gel electrolyte of the present invention is used as the electrolyte.

The positive electrode is obtained by applying a positive electrode binder composition containing a binder resin and a positive electrode active material as main components on both front and rear surfaces or one surface of a positive electrode current collector. The positive electrode can also be formed by melt-kneading a binder composition for a positive electrode containing a binder resin and a positive electrode active material as main components, extruding, and forming a film.

As the binder resin, the matrix polymers (I) to (IV) used in the electrolyte composition of the present invention and other resins commonly used as electrode binder resins for secondary batteries can be used as appropriate. In particular, it is preferable to use the same polymer material as the matrix polymer of the electrolyte composition of the present invention as the binder resin in that the internal resistance can be reduced.

As the positive electrode current collector, stainless steel, aluminum, titanium, tantalum, nickel or the like can be used. Among these, aluminum is preferred from both the viewpoint of performance and cost. As the positive electrode current collector, various forms such as a three-dimensional structure such as a foil shape, an expanded metal shape, a plate shape, a foamed shape, a wool shape, and a net shape can be adopted.

The positive electrode active material is appropriately selected according to the use of the electrode, the type of battery, and the like. For example, when the positive electrode of a lithium secondary battery is used, CuO, Cu ₂ O,
Group I metal compounds such as Ag ₂ O, CuS, CuSO ₂ , Ti
Group IV metal compounds such as S, SiO ₂ and SnO, V ₂ O ₅ ,
V such as V ₆ O ₁₃ , VO _x , Nb ₂ O ₅ , Bi ₂ O ₃ , Sb ₂ O ₃
Group metal compounds, CrO ₃ , Cr ₂ O ₃ , MoO ₃ , Mo
Group VI metal compounds such as S ₂ , WO ₃ and SeO ₂ , MnO ₂ ,
Group VII metal compounds such as Mn ₂ O ₄ , Fe ₂ O ₃ , FeO,
Group VIII metal compounds such as Fe ₃ O ₄ , Ni ₂ O ₃ , NiO, and CoO ₂ ; conductive polymer compounds such as polypyrrole, polyaniline, polyparaphenylene, polyacetylene, and polyacene-based materials.

In the case of a lithium ion secondary battery, a chalcogen compound or a lithium ion-containing chalcogen compound capable of adsorbing and desorbing lithium ions is used as a positive electrode active material.

Examples of the chalcogen compound capable of adsorbing and desorbing lithium ions include, for example, FeS ₂ , Ti
Examples include S ₂ , MoS ₂ , V ₂ O ₅ , V ₆ O ₁₃ , and MnO ₂ .

Examples of the lithium ion-containing chalcogen compound include, for example, LiCoO ₂ , LiMnO ₂ , LiMn
₂ O ₄ , LiMo ₂ O ₄ , LiV ₃ O ₈ , LiNiO ₂ , Li _x
Ni _y M _1-y O ₂ (where M is Co, Mn, Ti, C
represents at least one metal element selected from the group consisting of r, V, Al, Sn, Pb, and Zn;
0, 0.5 ≦ y ≦ 1.0).

[0172] In addition to the binder resin and the positive electrode active material, a conductive material can be added to the positive electrode binder composition as required. Conductive materials include carbon black, Ketjen black, acetylene black,
Examples thereof include carbon whiskers, carbon fibers, natural graphite, and artificial graphite.

In the positive electrode binder composition of the present invention,
The addition amount of the positive electrode active material is 1000 to 5000 parts by mass, preferably 1200 to 500 parts by mass with respect to 100 parts by mass of the binder resin.
3500 parts by mass, and the amount of the conductive material added is 20 to 500 parts.
It is part by mass, preferably 50 to 400 parts by mass.

The positive electrode binder composition of the present invention has a high binding property to the positive electrode active material particles and a high adhesiveness to the positive electrode current collector, so that the positive electrode can be prepared by adding a small amount of the binder resin. Since the electrolyte solution has high ionic conductivity when swollen, the internal resistance of the battery can be reduced.

The binder composition for a positive electrode of the present invention is usually
It is used in the form of a paste by adding a dispersion medium. Examples of the dispersion medium include polar solvents such as N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, and dimethylsulfonamide. In this case, the addition amount of the dispersion medium is about 30 to 300 parts by mass with respect to 100 parts by mass of the binder composition for the positive electrode.

The method for thinning the positive electrode is not particularly limited. For example, the positive electrode may be dried using a roller coating such as an applicator roll, a screen coating, a doctor blade method, a spin coating, or a bar coater. The thickness of the active material layer is 10 to 2
It is preferably formed to a uniform thickness of 00 μm, particularly 50 to 150 μm.

The negative electrode is obtained by applying a binder composition for a negative electrode containing a binder resin and a negative electrode active material as main components on both front and rear surfaces or one surface of a negative electrode current collector. The same binder resin as that used for the positive electrode can be used. The binder resin for the negative electrode containing the binder resin and the negative electrode active material as main components is melt-kneaded, and then extruded and formed into a negative electrode by forming a film. You can also.

As the negative electrode current collector, copper, stainless steel,
Titanium, nickel and the like can be mentioned. Among them, copper is preferable from both the viewpoint of performance and cost. This current collector is in the form of foil, expanded metal, plate, foam, wool,
Various forms such as a three-dimensional structure such as a net shape can be adopted.

The negative electrode active material is appropriately selected depending on the use of the electrode, the type of the battery, and the like. For example, when the negative electrode active material is used as a negative electrode of a lithium secondary battery, an alkali metal, an alkali alloy, a carbon material, the positive electrode active material, The same material as the substance can be used.

In this case, as the alkali metal, Li,
Examples of the alkali metal alloy include, for example, metal Li, Li-Al, Li-Mg, and Li-Al-.
Ni, Na, Na-Hg, Na-Zn and the like can be mentioned.

The carbon material may be graphite,
Examples thereof include carbon black, coke, glassy carbon, carbon fiber, and a sintered body thereof.

In the case of a lithium ion secondary battery, a material capable of reversibly occluding and releasing lithium ions can be used. As a material capable of reversibly occluding and releasing lithium ions, a carbon material such as a non-graphitizable carbon-based material and a graphite-based material can be used. More specifically,
Pyrolytic carbons, cokes (pitch coke, needle coke, petroleum coke), graphites, glassy carbons,
Organic polymer compound fired body (phenol resin, furan resin etc. fired at appropriate temperature and carbonized), carbon fiber,
A carbon material such as activated carbon can be used. In addition, materials that can reversibly occlude and release lithium ions include polymers such as polyacetylene and polypyrrole and S
An oxide such as nO ₂ can also be used.

In addition to the binder resin and the negative electrode active material, a conductive material can be added to the negative electrode binder composition as required. Examples of the conductive material include carbon black, Ketjen black, acetylene black, carbon whiskers, carbon fibers, natural graphite, and artificial graphite.

In the binder composition for a negative electrode of the present invention,
The addition amount of the negative electrode active material is 500 to 1700 parts by mass, preferably 700 to 13 parts by mass, based on 100 parts by mass of the binder resin.
00 parts by mass, the amount of the conductive material added is 0 to 70 parts by mass,
Preferably it is 0 to 40 parts by mass.

The binder composition for a negative electrode of the present invention is usually
It is used in the form of a paste by adding a dispersion medium. Examples of the dispersion medium include polar solvents such as N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, and dimethylsulfonamide. In this case, the addition amount of the dispersion medium is about 30 to 300 parts by mass with respect to 100 parts by mass of the binder composition for a negative electrode.

The method of thinning the negative electrode is not particularly limited. For example, the negative electrode may be dried by using a roller coating such as an applicator roll, a screen coating, a doctor blade method, a spin coating, or a bar coater. The thickness of the active material layer is 10 to 2
It is preferably formed to a uniform thickness of 00 μm, particularly 50 to 150 μm.

The separator interposed between the positive electrode and the negative electrode to be obtained is a separator obtained by impregnating a separator base material with a polymer electrolyte solution and then curing the mixture, the above-mentioned solid polymer electrolyte of the present invention, or the above-mentioned solid electrolyte of the present invention. It is preferable to use the polymer gel electrolyte of the above.

The above-mentioned separator substrate is not particularly restricted but includes, for example, fluoropolymers, polyethers such as polyethylene oxide and polypropylene oxide,
Polyolefins such as polyethylene and polypropylene, polyacrylonitrile, polyvinylidene chloride, polymethyl methacrylate, polymethyl acrylate, polyvinyl alcohol, polymethacrylonitrile, polyvinyl acetate, polyvinyl pyrrolidone, polyethylene imine,
One selected from polybutadiene, polystyrene, polyisoprene, polyurethane polymers, and derivatives thereof can be used alone or in combination of two or more. Among these, a fluoropolymer is preferred.

Examples of the fluorine-based polymer include (I)
The same fluoropolymer material as the matrix polymer of V) can be used.

A filler can be added to the separator substrate. Such a filler is not particularly limited as long as it forms a matrix together with the polymer constituting the separator and can form micropores capable of impregnating the electrolyte solution at the interface with the polymer.
The physical properties such as the particle shape, particle diameter, density, and surface condition are not particularly limited. As such a filler, for example, as an inorganic powder, silicon oxide, titanium oxide, aluminum oxide,
Zinc oxide, calcium carbonate, calcium sulfate, tin oxide,
In addition to oxides such as chromium oxide, iron oxide, magnesium oxide, magnesium carbonate, and magnesium sulfate, carbonates and sulfates, carbides such as silicon carbide and calcium carbide, nitrides such as silicon nitride and titanium nitride, and the like. Examples of the powder include various polymer particles that are incompatible with the polymer matrix constituting the separator.

The particle size of the filler is not particularly limited, but is preferably 10 μm or less, more preferably 0.005 to 1 μm, and particularly preferably 0.01 to 0.8 μm. The amount added to the polymer,
5 to 100 parts by weight per 100 parts by weight of the polymer, depending on the type of the polymer and the filler to be used,
In particular, it is preferably 30 to 100 parts by mass.

The lithium polymer battery of the present invention is obtained by laminating, folding, or winding a battery structure having a separator between the positive electrode and the negative electrode obtained as described above, and further forming a laminate type battery. Or coin-shaped, and this is stored in a battery container such as a battery can or a laminate pack, filled with the polymer electrolyte solution of the present invention, and cured by reaction. If there is, it is assembled into a battery by heat sealing.

The obtained lithium polymer battery of the present invention can operate at a high capacity and a high current without impairing excellent characteristics such as charge / discharge efficiency, energy density, output density, and life, and has a wide operating temperature range. Yes, it is particularly suitable as a lithium secondary battery or a lithium ion secondary battery.

The lithium polymer battery such as a lithium secondary battery and a lithium ion secondary battery of the present invention can be used for a main power supply of a video camera, a notebook computer, a portable terminal such as a portable telephone and a PHS, and a backup power supply for a memory. It can be suitably used for various applications such as a power supply for countermeasures against momentary power failure such as a personal computer, an application to an electric vehicle or a hybrid vehicle, and a solar power generation energy storage system used in combination with a solar cell.

[0195]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1 Synthesis of CF ₃ (CF ₂ ) ₈ COO ⁻ .Li ⁺ 10 g of nonadecafluorodecanoic acid (manufactured by ACROSS) was added to 100 mL of methanol, and while stirring well, lithium hydroxide (Merck) was added. 0.47 g). The reaction solution was initially in a suspended state, but dissolved in about 5 minutes to form a uniform solution. After 30 minutes, the stirring was stopped, and the solvent was distilled off to obtain 9.2 g of crystals. Recrystallization from ethanol yielded 5.4 g of the desired product. The molecular weight of the obtained compound was 520.02.

[0197] [Synthesis Example 2] _{^{Li + · - OOC (CF 2}} ) 6
Synthesis of COO ⁻ .Li ⁺ Synthesis was performed in the same manner as in Synthesis Example 1 except that the starting material was perfluorosebacic acid (manufactured by ACROSS) and the amount of the reagent was adjusted to the equivalent amount of the carboxylic acid group. The molecular weight of the obtained compound was 501.96.

[Synthesis Example 3] Li⁺・^-OOCCF^Two(O
CF_TwoCF_Two)_x(OCF_Two)_yOCF _TwoCOO^-・ Li⁺If
The starting material was poly (tetrafluoroethylene oxide-c
o-Difluoromethylene oxide) α, ω-dicarboxylic
Acid (Aldrich, weight average molecular weight about 2000,
(Tylene: methylene = 1: 1) and the amount of reagent
Synthesis was performed in the same manner as in Synthesis Example 1 except that the acid group equivalent was adjusted.
Was. The molecular weight of the obtained compound was about 2,000.

Synthesis Example 4 CH ₃ (OCH ₂ CH ₂ ) ₄ S
Synthesis of O ₂ N ^— SO ₂ CF ₃ .Li ⁺ Triethylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 6.57 g of anhydrous tetrahydrofuran 5
4.48 g of potassium-t-butoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the 0 mL solution, and the mixture was stirred for 30 minutes.
Next, 1,3-propane sultone (Wako Pure Chemical Industries, Ltd.)
4.89 g), and after stirring for 5 hours, the solvent was distilled off. 20 mL of anhydrous acetonitrile was added to the residue, and the mixture was stirred well, and 5.64 g of chloromethylene dimethylammonium chloride (manufactured by Aldrich) was added, followed by stirring for 2 hours.
6.56 g of trifluoromethanesulfonamide and 4.94 g of DABCO were further added to the reaction solution. After stirring for about 5 hours, the reaction solution was filtered to remove precipitates, and then 6.80 g of lithium phosphate was added to the reaction mixture.
Stirred for a day. After filtering the reaction solution, the reaction solution was added dropwise to 500 mL of diethyl ether, and the precipitate was recovered and dried to obtain 6.89 g of the desired product. The molecular weight of this compound is 409.
It was 3.

[Synthesis Example 5] Li ⁺ · CF ₃ SO ₂ N ^- SO
₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₇ SO ₂ N ^— SO ₂ CF ₃ .L
Synthesis of i ⁺ Synthesis was performed in the same manner as in Synthesis Example 4 except that the starting material was hexaethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), and the amount of the reagent was adjusted to the hydroxyl equivalent. The molecular weight of this compound was 756.7.

[Synthesis Example 6] Li ⁺ · CF ₃ SO ₂ N ^- SO
₂ CH ₂ CH ₂ OCH ₂ CF ₂ (OCF ₂ CF ₂ ) _x (OC
F ₂ ) _y OCF ₂ CH ₂ OCH ₂ CH ₂ SO ₂ N ^— SO ₂ CF _3.
Synthesis of Li ⁺ Starting material is poly (tetrafluoroethylene oxide-c
o-Difluoromethylene oxide) α, ω-diol (manufactured by Aldrich Co., Ltd., molecular weight: about 3800, ethylene: methylene ratio = 1: 1), and the synthesis was performed in the same manner as in Synthesis Example 4 except that the reagent input amount was adjusted to the hydroxyl equivalent. did. The molecular weight of the obtained compound was about 3,800.

Synthesis Example 7 CH ₃ (OCH ₂ CH ₂ ) ₃ O
CONH (CH ₂ ) ₆ NHCO ₂ (CH ₂ ) ₂ SO ₂ N ^— SO ₂
CF ₃ · Li ⁺ of synthetic hexamethylene diisocyanate (Wako Pure Chemical Industries, Ltd.
16.82 g of anhydrous tetrahydrofuran 100 mL
1.64 g of triethylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the solution over about 1 hour, and after stirring for 1 hour, the solvent was distilled off. Was distilled off.
100 mL of anhydrous tetrahydrofuran was added again to the residue to dissolve it, and then 0.81 g of 2-chloroethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by stirring for 2 hours. After distilling off the solvent, an aqueous solution 5 containing 1.30 g of sodium bisulfite was added.
0 mL was added, and the mixture was reacted under reflux with vigorous stirring for 1 day. When the temperature was lowered to room temperature, tetrohydrofuran was added to carry out liquid separation. After taking the aqueous solution component and making it acidic, tetrahydrofuran was added again to carry out liquid separation. After magnesium sulfate was added to the organic component and dried, this was separated by filtration and the solvent was distilled off to obtain a crude sulfonic acid component. Add 100 mL of anhydrous acetonitrile to the sulfonic acid component of this crude
And stirred well, and 1.41 g of chloromethylene dimethylammonium chloride (manufactured by Aldrich) was added.
Stirred for hours. To this reaction solution, 1.41 g of trifluoromethanesulfonamide (synthesized by the method described in Example 1 of Japanese Patent Publication No. 12-508678) and 1,4-
1.24 g of diazabicyclo [2.2.2] octane (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After stirring for about 5 hours, the reaction solution was filtered to remove precipitates, and then 1.70 g of lithium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction mixture, followed by stirring for 1 day. After filtering the reaction solution, the reaction solution was dropped into 500 mL of diethyl ether, and the precipitate was collected and dried to obtain 1.57 g of the desired product. The molecular weight of the obtained compound was 814.

[Synthesis Example 8] Li⁺・ CF_ThreeSO_TwoN^-SO
_Two(CH_Two) 2OCONHC₆H_Three(CH_Three) NHCO (O
CH_TwoCH_Two)_nOCONHC₆H_Three(CH_Three) NHCO
_Two(CH _Two)_TwoSO_TwoN^-SO_TwoCF_Three・ Li⁺Synthesis of polyethylene glycol 600 (Wako Pure Chemical Industries, Ltd.)
3.00 g of anhydrous tetrahydrofuran
Dissolve in 200 mL of run and add toluene diisocyanate
Add 1.74 g of Nate (manufactured by Wako Pure Chemical Industries, Ltd.)
Stirred well. One hour later, 2-chloroethanol (Wako Jun
0.81 g of Yakuhin Kogyo Co., Ltd.) was added, and the mixture was stirred for 2 hours.
After evaporating the solvent, 1.30 g of sodium bisulfite was added to the residue.
Add 50 mL of an aqueous solution containing and reflux with vigorous stirring
Allowed to react for one day under. After cooling to room temperature,
Lofran was added to carry out liquid separation. Aqueous solution component was acidified
Thereafter, tetrahydrofuran was added again to carry out liquid separation. Organic
The mixture was dried over magnesium sulfate and filtered.
The solvent was distilled off to obtain a crude sulfonic acid component. The following is a trial
Synthetic Example 7 except that the drug input amount was adjusted to the sulfonic acid group equivalent.
Synthesis was performed in the same manner. The molecular weight of the obtained compound is about
1500.

Synthesis Example 9 Synthesis of Cellulose Derivative 8 g of hydroxypropyl cellulose [molar substitution degree (M
S) = 4.65, manufactured by Nippon Soda Co., Ltd.] in 400 mL of acrylonitrile, 1 mL of a 4% by mass aqueous sodium hydroxide solution was added, and the mixture was stirred at 30 ° C. for 4 hours.

After the above reaction mixture was neutralized with acetic acid, the mixture was poured into a large amount of methanol to obtain cyanoethylated hydroxypropylcellulose.

To remove impurities, cyanoethylated hydroxypropylcellulose was dissolved in acetone, filled in a dialysis membrane tube, and purified by dialysis using ion-exchanged water. The cyanoethylated hydroxypropyl cellulose precipitated during dialysis was collected and dried.

The obtained cyanoethylated hydroxypropylcellulose was subjected to elemental analysis, and it was found that N% was 7.3% by mass. From this value, the capping ratio of the hydroxyl groups in the hydroxypropyl cellulose by the cyanoethyl groups was 94%.

Synthesis Example 10 Synthesis of Unsaturated Polyurethane Compound In a reactor equipped with a stirrer, a thermometer and a cooling pipe, a random copolymer of ethylene oxide (EO) and propylene oxide (PO) having a hydroxyl value of 36.1 was previously dehydrated. 870 parts by mass of a diol (provided that EO / PO = 7/3 (molar ratio))
4,4'-diphenylmethane diisocyanate 107.
4 parts by mass and 100 parts by mass of methyl ethyl ketone as a solvent were charged and stirred and mixed at 80 ° C. for 3 hours to obtain a polyurethane prepolymer having an isocyanate group end. Thereafter, the whole reactor was cooled to 50 ° C., and 0.3 parts by mass of benzoquinone, 5 parts by mass of dibutyltin laurate, 16.3 parts by mass of hydroxyethyl acrylate, and 6.3 parts by mass of 1,4-butanediol were added thereto. After reacting at 3 ° C. for 3 hours, methyl ethyl ketone was removed under reduced pressure to obtain an unsaturated polyurethane compound. When the weight average molecular weight of the obtained unsaturated polyurethane compound was measured by GPC, it was found to have distributions of 17,300 and 6,200.

Synthesis Example 11 Synthesis of Polyglycidol Derivative In a flask, methylene chloride was used as a solvent so that the concentration of glycidol was 4.2 mol / L, and the reaction temperature was set at −10 ° C.

As a catalyst (reaction initiator), trifluoroborate / diethyl etherate (BF ₃ · OEt ₂ ) was added at a concentration of 1.2 × 10 ^-2 mol / L, and the mixture was added under a nitrogen gas stream for 3 hours. The reaction was carried out with stirring. After completion of the reaction, methanol was added to stop the reaction. afterwards,
Methanol and methylene chloride were distilled off under reduced pressure.

After dissolving the obtained crude polymer in water and neutralizing with sodium hydrogen carbonate, the solution was passed through a column filled with an ion exchange resin (trade name: Amberlite IRC-76; manufactured by Organo Corporation). Was. The solution after passing through the column was separated by filtration through a 5C filter paper, and the filtrate was distilled under reduced pressure and dried.

The obtained purified polyglycidol was used in 0.1 M
Gel filtration chromatography using saline as the mobile phase (G
PC), and the weight average molecular weight in terms of polyethylene glycol was determined to be 6,250. When the crystallinity was evaluated by wide-angle X-ray diffraction, it was amorphous, and the state at room temperature was a soft paste solid.

3 parts by mass of the obtained polyglycidol were mixed with 20 parts by mass of dioxane and 14 parts by mass of acrylonitrile. A sodium hydroxide solution obtained by dissolving 0.16 parts by mass of sodium hydroxide in 1 part by mass of water was added to the mixed solution, and the mixture was stirred at 25 ° C. for 10 hours. After completion of the reaction, 20 parts by mass of water was added to the mixed solution, and then neutralized with an ion exchange resin (trade name: Amberlite IRC-76; manufactured by Organo Corporation). After filtering off the ion exchange resin,
50 parts by mass of acetone was added to the solution, and the insoluble portion was separated by filtration. The filtered solution was concentrated under reduced pressure to obtain a crude cyanoethylated polyglycidol. The crude cyanoethylated polyglycidol was dissolved in acetone, filtered through 5A filter paper, and then precipitated in water to collect the precipitated components. After repeating the operation of dissolving acetone and precipitating in water twice, 50
Drying under reduced pressure at ℃ gave purified cyanoethylated polyglycidol.

When the infrared absorption spectrum of the obtained purified cyanoethylated polyglycidol was measured, no absorption of hydroxyl group was observed, and it was found that all hydroxyl groups were substituted with cyanoethyl groups. When the crystallinity was evaluated by wide-angle X-ray diffraction, it was amorphous at room temperature. Furthermore, the state at room temperature was a soft paste solid.

Synthesis Example 12 Synthesis of Polyvinyl Alcohol Derivative In a reaction vessel equipped with stirring blades, 10 parts by mass of polyvinyl alcohol (average degree of polymerization: 500, vinyl alcohol fraction = 98% or more) and 70 parts by mass of acetone were charged and stirred. An aqueous solution in which 1.81 parts by mass of sodium hydroxide was dissolved in 2.5 parts by mass of water was gradually added, and the mixture was stirred at room temperature for 1 hour.
A solution prepared by dissolving 67 parts by mass of glycidol in 100 parts by mass of acetone was gradually added to this solution over 3 hours.
The mixture was stirred and reacted at 8 ° C. for 8 hours. After completion of the reaction, when the stirring is stopped, the polymer precipitates. The precipitate is collected, dissolved in 400 parts by mass of water, neutralized with acetic acid, purified by dialysis, and lyophilized to dihydroxypropylated solution. Polyvinyl alcohol was obtained. The yield was 22.50 parts by mass.

3 parts by mass of the obtained PVA polymer was mixed with 20 parts by mass of dioxane and 14 parts by mass of acrylonitrile. An aqueous solution of sodium hydroxide in which 0.16 part by mass of sodium hydroxide was dissolved in 1 part by mass of water was added to this mixed solution, and the mixture was stirred at 25 ° C. for 10 hours. Next, neutralization was performed using an ion exchange resin (trade name: Amberlite IRC-76, manufactured by Organo Corporation). After filtering off the ion exchange resin, 50 parts by mass of acetone was added to the solution, and the insoluble portion was filtered off. The acetone solution was placed in a dialysis membrane tube, and dialyzed against running water. The polymer precipitated in the dialysis membrane tube was collected, dissolved again in acetone, filtered, and the acetone was evaporated to obtain a cyanoethylated PVA polymer derivative of Synthesis Example 1. In the obtained polymer derivative, absorption of a hydroxyl group in an infrared absorption spectrum could not be confirmed, and the hydroxyl group was completely blocked by a cyanoethyl group (blocking rate: 100).
%).

[Synthesis Example 13] In a reactor equipped with a thermoplastic polyurethane resin stirrer, a thermometer and a cooling pipe, polycaprolactone diol (Placcel 22
0N, manufactured by Daicel Chemical Industries, Ltd.) and 4,4'-diphenylmethane diisocyanate 2
8.57 parts by mass and charged at 120 ° C.
After stirring and mixing for an hour, 1,4-butanediol 7.0
9 parts by mass were added, and the mixture was reacted at 120 ° C. in a nitrogen stream in the same manner. When the reaction proceeded and the reaction product became rubbery, the reaction was stopped. Thereafter, the reaction product was taken out of the reactor and heated at 100 ° C. for 12 hours. After confirming that the absorption peak of the isocyanate group had disappeared in the infrared absorption spectrum, the heating was stopped to obtain a solid polyurethane resin.

The weight average molecular weight (Mw) of the obtained polyurethane resin was 1.71 × 10 ⁵ . This polyurethane resin is immersed in an electrolyte solution in which 1 mol of LiClO ₄ is dissolved as a supporting salt in a total volume of 1 liter of a mixed solvent of ethylene carbonate: diethyl carbonate = 1: 1 (volume ratio) at 20 ° C. for 24 hours. The determined swelling ratio was 320%.

Example 1 Solid polymer electrolyte (1) 32.5 parts by mass of the compound of Synthesis Example 1, 20 parts by mass of the unsaturated polyurethane compound of Synthesis Example 10, and methoxypolyethylene glycol monomethacrylate (the number of oxyethylene units = 9) ) (Ie, 1 molar equivalent (L
(equivalent) / 1000 parts by mass (electrolyte salt + matrix resin)], and 0.15 parts by mass of azobisisobutyronitrile was further added to obtain a polymer electrolyte solution. The obtained polymer electrolyte solution was applied with a doctor blade so that the film thickness became 30 μm, and then heated at 80 ° C. for 1 hour using a thermostat and cured to prepare a polymer solid electrolyte of Example 1. .

[Example 2] Polymer solid electrolyte (2) In the same manner as in Example 1, except that 10.1 parts by mass of the compound of Synthesis example 2 was added instead of the compound of Synthesis example 1, The solid polymer electrolyte of Example 2 was prepared.

Example 3 Solid Polymer Electrolyte (3) In Example 1, 8.5 parts by mass of the compound of Synthesis Example 3 and 3.6 parts by mass of LiClO ₄ were mixed instead of the compound of Synthesis Example 1. A solid polymer electrolyte of Example 3 was prepared in the same manner as in Example 1 except that the electrolyte solution was used.

[Comparative Example 1] Polymer solid electrolyte (4) In Example 1, LiC was used instead of the compound of Synthesis Example 1.
Add 3.6 parts by mass of IO ₄ [ie, 1 molar equivalent (Li equivalent) / 1000 parts by mass (electrolyte salt + matrix resin)
In the same manner as in Example 1 except that
A solid polymer electrolyte of Comparative Example 1 was prepared.

Example 4 Polymer solid electrolyte (5) 22.2 parts by mass of the compound of Synthesis example 4, 2 parts by mass of the cellulose derivative of Synthesis example 9, 20 parts by mass of the unsaturated polyurethane compound of Synthesis example 10, and methoxy Polyethylene glycol monomethacrylate (oxyethylene unit number = 9) 1
0 parts by mass [that is, 1 molar equivalent (Li equivalent) / 1
000 parts by mass (electrolyte salt + matrix resin)], and azobisisobutyronitrile 0.1
5 parts by mass were added and mixed to obtain a polymer electrolyte solution.
After applying the obtained polymer electrolyte solution with a doctor blade so that the film thickness becomes 30 μm, the solution is heated to 80 μm using a thermostat.
The polymer solid electrolyte of Example 4 was prepared by heating at 1 ° C. for 1 hour and curing.

[Comparative Example 2] Polymer solid electrolyte (6) In Example 4, LiC was used instead of the compound of Synthesis Example 4.
A solid polymer electrolyte of Comparative Example 2 was prepared in the same manner as in Example 4, except that 3.8 parts by mass of 10 ₄ was added.

Example 5 Polymer solid electrolyte (7) 70 parts by mass of the polyglycidol derivative of Synthesis Example 11, 20 parts by mass of the unsaturated polyurethane compound of Synthesis Example 10, and methoxypolyethylene were added to 61 parts by mass of the compound of Synthesis Example 5. Glycol monomethacrylate (oxyethylene unit number =
9) Add 10 parts by mass [that is, 1 molar equivalent (Li equivalent) / 1000 parts by mass (electrolyte salt + matrix resin)
Azobisisobutyronitrile was further added and mixed to obtain a polymer electrolyte solution. The obtained polymer electrolyte solution was applied with a doctor blade so that the film thickness became 30 μm, and then heated at 80 ° C. for 1 hour using a thermostat and cured to prepare a polymer solid electrolyte of Example 5. .

Comparative Example 3 Solid Polymer Electrolyte (8) In Example 5, LiC was used instead of the compound of Synthesis Example 5.
A solid polymer electrolyte of Comparative Example 3 was prepared in the same manner as in Example 5, except that 11.9 parts by mass of 10 ₄ was added.

Example 6 Polymer solid electrolyte (9) 68.8 parts by mass of the compound of Synthesis example 6 and LiBF ₄
In an electrolyte solution obtained by mixing 8 parts by mass, 70 parts by mass of the polyvinyl alcohol derivative of Synthesis Example 12, 20 parts by mass of the unsaturated polyurethane compound of Synthesis Example 10, and 10 parts by mass of methoxypolyethylene glycol monomethacrylate (oxyethylene unit number = 9). [That is, 1 molar equivalent (Li equivalent) / 1000 parts by mass (electrolyte salt + matrix resin)], and 0.15 parts by mass of azobisisobutyronitrile are further added and mixed. Thus, a polymer electrolyte solution was obtained. The resulting polymer electrolyte solution is
The solution was applied with a doctor blade so as to have a thickness of 0 μm, and then heated at 80 ° C. for 1 hour using a thermostat and cured to prepare a polymer solid electrolyte of Example 6.

Comparative Example 4 Polymer solid electrolyte (10) In Example 6, LiB was used instead of the compound of Synthesis example 6.
Except that F ₄ was added 10.3 parts by weight in the same manner as in Example 6 to prepare a polymer solid electrolyte of Comparative Example 4.

Example 7 Polymer Gel Electrolyte (1) The thermoplastic polyurethane resin solution obtained in Synthesis Example 13 was applied by a doctor blade so as to have a dry film thickness of 30 μm, and then the pressure was reduced at 120 ° C. for 2 hours. After drying, a polyurethane resin film was formed.

A 1 M electrolyte solution of the compound of Synthesis Example 7 (ethylene carbonate: diethylene carbonate = 1: 1)
The above-mentioned polyurethane resin film is immersed at 20 ° C. for 24 hours,
A polymer gel electrolyte of Example 7 was prepared.

[Comparative Example 5]Polymer gel electrolyte (2) In Example 7, a 1M electrolyte solution of the compound of Synthesis Example 7
LiClO instead of _Four1M electrolyte solution (ethylene
-Carbonate: diethylene carbonate = 1: 1)
The same procedure as in Example 7 was repeated except that the polymer gel of Comparative Example 5 was used.
An electrolyte was made.

Example 8 Polymer Gel Electrolyte (3) In Example 7, the compound of Synthesis Example 7 and LiPF ₆ were used instead of the 1M electrolyte solution of the compound of Synthesis Example 7 [Compound of Synthesis Example 7: LiPF ₆ = [1: 1 (molar ratio)] A polymer gel electrolyte of Example 8 was prepared in the same manner as in Example 7, except that a 1M electrolyte solution (ethylene carbonate: diethylene carbonate = 1: 1) was used.

Comparative Example 6 Polymer Gel Electrolyte (4) In Example 7, a 1 M electrolyte solution of LiPF ₆ (ethylene carbonate: diethylene carbonate = 1: 1) was used instead of the 1 M electrolyte solution of the compound of Synthesis Example 7. A polymer gel electrolyte of Comparative Example 6 was prepared in the same manner as in Example 7, except for using the same.

Example 9 Polymer solid electrolyte (11) In Example 4, 6.6 parts by mass of the compound of Synthesis example 8 and 5.3 parts by mass of LiPF ₆ were mixed instead of the compound of Synthesis example 4. A polymer electrolyte solution was prepared in the same manner as in Example 4 except that the electrolyte solution was used, and cured in the same manner as in Example 4 to prepare a polymer solid electrolyte of Example 9.

[Comparative Example 7] Polymer solid electrolyte (12) The same procedures as in Example 9 were carried out except that 5.7 parts by mass of LiPF ₆ was added instead of the electrolyte solution in which the compound of Synthesis Example 8 and LiPF ₆ were mixed. In the same manner as in Example 9, a polymer solid electrolyte of Comparative Example 7 was produced.

Next, the obtained polymer solid electrolyte or polymer gel electrolyte was sandwiched between two copper plates, and the ionic conductivity at 25 ° C. was measured by the AC impedance method.
Table 1 shows the results.

[0237]

[Table 1]

Example 10 Secondary Battery <Preparation of Positive Electrode> 90 parts by mass of LiCoO ₂ as a positive electrode active material, 6 parts by mass of Ketjen black as a conductive material, and 8% by mass of a thermoplastic polyurethane resin of Synthesis Example 13 -Methyl-2-pyrrolidone solution was stirred and mixed to obtain a paste-like binder composition for a positive electrode. The positive electrode binder composition was applied on an aluminum foil by a doctor blade so that the dry film thickness became 100 μm,
For 2 hours to prepare a positive electrode.

<Preparation of Negative Electrode> MCMB was used as the negative electrode active material.
(MCMB6-28; manufactured by Osaka Gas Chemical Co., Ltd.) 94
The mass part and the thermoplastic polyurethane resin 8 mass% N-methyl-2-pyrrolidone solution of Synthesis Example 13 were stirred and mixed to obtain a paste-like binder composition for a negative electrode. This negative electrode binder composition is coated on a copper foil with a dry film thickness of 100
After applying with a doctor blade so that
It dried at 80 degreeC for 2 hours, and produced the negative electrode.

Using the obtained positive electrode and negative electrode, a separator base material (three-layer structure film of PP / PE / PP) is interposed between the positive and negative electrodes, and this battery structure is inserted into an aluminum laminate outer bag. After decompressing the inside of the laminate outer bag,
After the laminate material and the battery structure were brought into close contact with each other, the polymer electrolyte solution of Example 4 was injected from the hole passed through the needle,
After sealing the laminate, at 80 ° C for 1
After heating for a time, the laminated secondary battery of Example 10 shown in FIG. 1 was prepared. In FIG. 1, 1 is a positive electrode current collector, 2 is a negative electrode current collector, 3 is a positive electrode, 4 is a negative electrode, 5 is a separator, 6
Indicates a tab, and 7 indicates a laminated outer bag.

With respect to the laminated secondary battery of Example 10, the upper limit voltage at the time of charging was set at 4.2 V, the cut-off voltage at the time of discharging was set at 3 V, and the cycle was performed at a constant current of 0.5 mA / cm ² for 50 cycles. Was subjected to a charge / discharge test. After the completion of the charge / discharge test, no leakage of the electrolyte solution or swelling of the battery pack due to generation of gas was observed in the laminated secondary battery.
There was no change in capacity before and after the 0 cycle, and no cycle deterioration occurred.

[0242]

According to the present invention, an electrolyte composition and a polymer solid having high ionic conductivity and excellent safety, and particularly suitable for lithium polymer batteries such as lithium secondary batteries or lithium ion secondary batteries. An electrolyte and a polymer gel electrolyte are obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a laminated lithium polymer battery of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/098 C08K 5/098 5H029 5/42 5/42 C08L 75/04 C08L 75/04 101/00 101 / 00 H01B 1/06 H01B 1/06 A 1/12 1/12 Z F term (reference) 4J002 AA001 AB012 AB042 AB052 BD121 BD141 BE022 CH022 CH053 CK021 EG026 EV256 4J011 PA29 PA45 PA53 PA67 PA90 PB40 4J027 AC03 AC06 AG03 AG04 AG09 AG12 AG13 AG14 AG23 AG24 AG27 AJ08 BA01 CA05 CA10 CA24 CA26 CB09 CC02 CD00 4J034 BA08 CA04 CA15 CB03 CB07 CB08 CC12 CC26 CC45 CC52 CC62 CC65 CD04 CD06 DA01 DB03 DB04 DF12 DG03 DG04 DG06 DG10 FA02 FB01 HC01 HC03 HC12 HC01 HC07 HC12 HC61 HC64 HC67 HC71 HC73 JA24 KA04 MA12 MA15 MA22 MA24 RA14 5G301 CA16 CD01 5H029 AJ06 AJ12 AJ15 AK02 AK03 AK05 AK16 AL06 AL07 AL08 AL12 AL13 AL16 AM0 2 AM03 AM04 AM05 AM07 AM16 BJ02 BJ03 BJ04 BJ12 BJ14 DJ04 DJ09 EJ12 HJ02 HJ14 HJ16

Claims (13)

[Claims] 1. A compound represented by the following general formula (1) and / or (2)
And a matrix polymer.
Electrolyte composition to be characterized. R¹-(A)_m-(Y)_n-X^-・ Li⁺ ... (1) [wherein, R¹Is an unsubstituted or fluorine-substituted alkyl group having 1 to 4 carbon atoms.
Alkyl group or unsubstituted or fluorine-substituted alkoxy group,
A is a perfluoroalkylene component, polyoxyalkylene
Components and polyfluorooxyalkylene components
Represents one or more kinds, wherein Y is CH_Two, CF_Two, CF
_TwoCH_TwoOr OCONHR^TwoNHCOOR^Three(However, R^TwoPassing
And R^ThreeAre the same or different divalent hydrocarbons having 1 to 18 carbon atoms
Represents a group), m is 0 or an integer of 1 to 70, and n is 0 or 1.
X is SO_Three, SO_TwoNSO _TwoR^Four(However, R^Four
Represents an unsubstituted or fluorine-substituted alkyl group having 1 to 4 carbon atoms.
) Or COO. ] Li⁺・ X^-− (Y¹)_e-(A)_p− (Y^Two)_f-X^-・ Li⁺ ... (2) [wherein, Y¹Is CH_Two, CF_Two, CH_TwoCF_Two, R^FiveOCH_Two
CF_TwoOr R^TwoOCONHR^TwoNHCO, Y^TwoIs OC
H_Two, OCF_Two, OCF_TwoCH_Two, OCF_TwoCH_TwoOR^Five,or
Is OCONHR^TwoNHCOOR^Three(However, R^FiveIs 1 carbon
Alkylene group, R^TwoAnd R^ThreeHas the same meaning as above
E) and f are 0 or an integer of 1-2, and p is 0 or 1-7.
Indicates an integer of 0. X and A have the same meaning as described above. ] 2. The polyoxyalkylene represented by the above A.
Component is-(OCH _TwoCH_Two)-And / or-(OCH_Two
CH_TwoCH_Two2. The method according to claim 1, wherein
Electrolyte composition. 3. The polyfluorooxyalkylene component represented by A is-(OCF ₂ )-,-(OCF ₂ C
F ₂ )-,-(OCF ₂ CF (CF ₃ ))-and-(OC
F ₂ CF ₂ CF ₂₎ - electrolyte composition of claim 1 wherein a repeating unit containing one or more selected from. 4. A matrix polymer comprising: (A) an unsaturated alcohol having at least one (meth) acryloyl group and a hydroxyl group in a molecule; and (B) a polyol compound represented by the following general formula (3). The electrolyte composition according to any one of claims 1 to 3, which is an unsaturated polyurethane compound obtained by reacting (C) a polyisocyanate compound and (D) a chain extender as needed. HO-[(R ⁶ ) _h- (Y) _i- (R ⁷ ) _j ] _q -OH (3) [wherein R ⁶ and R ⁷ are the same or different amino group, nitro group, carbonyl group or A divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an ether group, and Y is -COO
—, —OCOO—, —NR ⁸ CO— (R ⁸ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), —O— or an arylene group, and h, i, j are each 0 or 1 to 10,
q represents an integer of 1 or more. ] 5. The electrolyte composition according to claim 1, wherein the matrix polymer is a polymer material having an interpenetrating network structure or a semi-interpenetrating network structure. 6. A polymer material having an interpenetrating network structure or a semi-interpenetrating network structure, comprising a hydroxyalkyl polysaccharide derivative, a polyvinyl alcohol derivative, or a polyglycidol derivative, and a compound having a crosslinkable functional group, The electrolyte composition according to claim 5, wherein a part or all of the compound having a crosslinkable functional group is the unsaturated polyurethane compound according to claim 4. 7. The matrix polymer according to the following general formula (4)
The electrolyte composition according to any one of claims 1 to 3, which is a thermoplastic resin containing a unit represented by the following formula: Embedded image (In the formula, r represents 3 to 5, and s represents an integer of 5 or more.) 8. The electrolyte composition according to claim 1, wherein the matrix polymer is a fluoropolymer material. 9. A solid polymer electrolyte comprising the electrolyte composition according to any one of claims 1 to 8. 10. The polymer solid electrolyte according to claim 9, which has an ionic conductivity of 1 × 10 ⁻⁵ S / cm or more at 25 ° C. by an AC impedance method. 11. A polymer gel electrolyte obtained by swelling the electrolyte composition according to claim 1 with an organic solvent. 12. The polymer gel electrolyte according to claim 11, which has an ionic conductivity of 1 × 10 ⁻³ S / cm or more at 25 ° C. by an AC impedance method. 13. A lithium polymer battery including a positive electrode, a negative electrode, and an electrolyte, wherein the polymer solid electrolyte according to claim 9 or 10 or the polymer gel electrolyte according to claim 11 or 12 is used as the electrolyte. Lithium polymer battery.