JP2003217340A - Gel-like polymer electrolyte and electrochemical element using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gel-like polymer electrolyte simultaneously satisfying both of ion conductivity and mechanical strength and a secondary battery using it. <P>SOLUTION: In the gel-like polymer electrolyte comprising a matrix polymer (A) and a non-aqueous electrolytic solution (B), the gel-like polymer electrolyte in which (A) contains a polymer (A1) obtained by polymerizing an ethylenic unsaturated bond-containing polyol (a) represented by the following general formula (1): (HO)<SB>m</SB>R<SP>1</SP>(OX)<SB>r-m</SB>(1) [wherein R<SP>1</SP>is residual group of an r-valent polyol, X is an organic group having an ethylenic unsaturated bond, r is an integer of 3-10, m is an integer of 2-9 and r-m is an integer of 1-8], other polyol (b), an organic polyisocyanate (c) and if necessary, a monomer (d) having other ethylenic unsaturated bond is used. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel gel polymer electrolyte and its use. More specifically, the present invention relates to a gel polymer electrolyte having high ionic conductivity and excellent mechanical strength, and an electrochemical element or electrochemical device using the gel polymer electrolyte.

[0002]

2. Description of the Related Art Electrochemical devices such as aluminum electrolytic capacitors, electric double layer capacitors and batteries are widely used in consumer electronic devices such as mobile phones and notebook computers. The electrochemical device using the conventional electrolyte solution has a problem in long-term reliability because liquid leakage easily occurs. recent years,
Gel-like polymer electrolytes have been studied as electrolytes without such problems. Generally, a gel-like polymer electrolyte has a structure in which an electrolyte solution in which an electrolyte salt such as a lithium salt is dissolved is held in a polymer. Therefore, in order to increase the mechanical strength, it is sufficient to increase the proportion of the polymer, but the proportion of the electrolytic solution decreases, so that the ion conductivity deteriorates. On the contrary, if the amount of electrolyte is increased, the ionic conductivity is improved but the mechanical strength is deteriorated. In the case of batteries using gelled polymer electrolytes, ionic conductivity is an important factor that directly affects battery performance, and mechanical strength is an important factor that directly affects battery safety. Has been done.

In recent years, a gel-type polyelectrolyte using a urethane (meth) acrylate-based polymer obtained by addition-polymerizing a (meth) acryloyl group at the end of a polyurethane chain as a gel-type polyelectrolyte having improved mechanical strength ( For example, JP-A-8-295715 or JP-A-2001-35251)
Is proposed.

[0004]

However, the above-mentioned gel polymer electrolyte is not satisfactory in terms of mechanical strength because of insufficient crosslink density. The problem to be solved by the present invention is to provide a gel-like polymer electrolyte that satisfies both ionic conductivity and mechanical strength at the same time, and an electrochemical device using the same.

[0005]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides a gel polymer electrolyte comprising a matrix polymer (A) and a non-aqueous electrolyte solution (B),
(A) is an ethylenically unsaturated bond-containing polyol (a) represented by the following general formula (1), another polyol (b),
A gel polymer electrolyte containing an organic polyisocyanate (c), and optionally a polymer (A1) obtained by polymerizing another monomer (d) having an ethylenically unsaturated bond, (HO) _m R ¹ (OX) _rm (1) [wherein, R ¹ is a residue of an r-valent polyol, X is an organic group having an ethylenically unsaturated bond, r is an integer of 3 to 10, m
Is an integer of 2 to 9, and r-m is an integer of 1 to 8. ] And an electrochemical device, an electrochemical device, and a secondary battery using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylenically unsaturated bond-containing polyol compound (a) used in the present invention is a compound represented by the following general formula (1). (HO) _m R ¹ (OX) _rm (1) In the formula, R ¹ is a residue of an r-valent polyol, X is an organic group having an ethylenically unsaturated bond, r is an integer of 3 to 10, and m is 2 ~ 9, r-m is an integer of 1-8. In the general formula (1), R ¹ excludes all OH groups from an alkylene oxide adduct (hereinafter abbreviated as novolak AOA) of a r-valent polyol having a hydroxyl equivalent of 30 to 200 and / or a condensate of phenol and formaldehyde. It is a residue. From the viewpoint of mechanical strength of the polymer electrolyte, R
The hydroxyl equivalent of ¹ is preferably 30 to 200. Substituted H in place of X in the general formula (1),
Examples of R ¹ (HO) _r include r-valent polyols and novolac AO adducts. 3 for polyol
Examples thereof include a 10-valent polyhydric alcohol, an alkylene oxide (hereinafter abbreviated as AO) adduct of the polyhydric alcohol, and a polyhydric phenol (trivalent) AO adduct.

Specific examples of the polyhydric alcohol having 3 to 10 valences include trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylolpropane,
Trimethylolethane, alkanetriols such as hexanetriol; and alicyclic triols such as cyclohexanetriol, C4 to C8 polyhydric alcohols (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, Alkane polyols such as sorbitan, diglycerin, dipentaerythritol and their intramolecular or intermolecular dehydrated products;
And sugars such as sucrose, glucose, mannose, lactose, and methylglucoside, and derivatives thereof). Examples of AO adducts of polyhydric phenols (trivalent) include AO adducts of trivalent monocyclic phenols (pyrogallol, phloroglucin, etc.). Examples of the AOA of novolac include ethylene oxide adducts of trivalent to 10-valent novolac.

The above AO includes ethylene oxide (hereinafter abbreviated as EO) and propylene oxide (hereinafter referred to as PO).
Abbreviated), 1,2-, 1,4- and 2,3-butylene oxide (hereinafter abbreviated as BO), α-olefin oxide, styrene oxide, epichlorohydrin, etc.,
And combinations of two or more of these. Among these, EO and / or EO and other AO [C3 or C4 alkylene oxides such as PO, 1,2-B
One or more of O, 1,4-BO and the like. Below other A
Abbreviated as O. ] Co-adduct (random or block)
Is preferred.

In the general formula (1), X is a group having an ethylenically unsaturated bond. 1 as the number of unsaturated bonds
-4 is preferable and 2 is more preferable. Examples of X include groups represented by the following general formulas (3) and (4). —Q ₁ (3) —COQ ₂ (4) [In the formula, Q ₁ is an alkenyl group having 2 to 24 carbon atoms, an alkadienyl group, an alkatrienyl group or an alkatetraenyl group, and Q ₂ is Q ₁ or carbon. It is a residue obtained by removing one COOH group from the unsaturated polycarboxylic acid of the number 4 to 24 or its partial ester forming derivative. ]

As a specific example of X, in the general formula (3), X =
It becomes Q ₁ and has a linear, branched or cyclic alkenyl group having 2 to 24 carbon atoms, such as vinyl group, allyl group, isopropenyl group, oleyl group, cyclohexenyl group: 2 carbon atoms.
24 linear or branched or cyclic alkadienyl groups,
Examples thereof include a linole group; a linear, branched, or cyclic alkatrienyl group having 2 to 24 carbon atoms, such as a linolene group.

When Q ₂ = Q _{1 in} the general formula (4), X = CO
It becomes Q _{1 and} is an unsaturated acyl group having 3 to 25 carbon atoms, such as an acryloyl group, a methacryloyl group and an oleoyl group. When Q ₂ is a residue obtained by removing one COOH group from an unsaturated polycarboxylic acid having 4 to 24 carbon atoms or a partial ester-forming derivative thereof, examples of the unsaturated polycarboxylic acid include (anhydrous) maleic acid and fumaric acid. , Crotonic acid, itaconic acid, citraconic acid and the like. The partial ester forming derivative is an ester of the above-mentioned unsaturated polycarboxylic acid having at least one carboxyl group, an acid anhydride and an acid halide, for example, a monoalkyl maleic acid (having 1 to 12 carbon atoms) ester, a monoalkyl fumarate. (C1-12) ester, itaconic acid monoalkyl (C1-12) ester, and citraconic acid monoalkyl (C1-12) ester are mentioned. Among X, preferred are an acryloyl group and a methacryloyl group.

The number m of hydroxyl groups in the general formula (1) is usually 2
It is an integer of -9, preferably 2-4. Further, in order to introduce an ethylenically unsaturated bond into (A), rm is 1 to
It must be 8, preferably 1 to 4, more preferably 1 or 2, and particularly preferably 2. When m is 0 or 1, sufficient strength cannot be given to the polymer electrolyte, and when m exceeds 9, the polymer electrolyte becomes brittle and may cause cracks or chips, which is not preferable. Further, when r-m is 0, the cross-linking of the polymer electrolyte is not sufficiently performed and the strength tends to be insufficient, and when it exceeds 4, the polymer electrolyte becomes brittle and may cause cracks or chips, which is not preferable.

The following are specific examples of (a). (I) The above-mentioned trihydric alcohol having 3 to 20 carbon atoms and unsaturated alcohol having 2 to 24 carbon atoms (vinyl alcohol, allyl alcohol, isopropenyl alcohol, oleyl alcohol, etc.) or its AO (as described above) adduct. Partial ether (for example, obtained by jumping with an alkylene dihalide having 1 to 4 carbon atoms such as methylene bromide, dibromoethane, dibromopropane, dibromobutane, ethylene diiodide).

(Ii) Trivalent alcohol having 3 to 20 carbon atoms and unsaturated carboxylic acid having 3 to 25 carbon atoms (acrylic acid, methacrylic acid, oleic acid, etc.), or 4 carbon atoms
To 24 unsaturated polycarboxylic acids or partial ester-forming derivatives thereof (maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, citraconic acid monoalkyl ester, etc.) by partial esterification reaction .

(Iii) 4 to 8 having 5 to 20 carbon atoms as described above
Partial ethers of a polyhydric polyhydric alcohol with an unsaturated alcohol having 2 to 24 carbon atoms or its AO adduct (for example, obtained by jumping with an alkylene dihalide having 1 to 4 carbon atoms).

(Iv) C4 to C4 polyhydric alcohol having 5 to 20 carbons and unsaturated carboxylic acid having 3 to 25 carbons or unsaturated polycarboxylic acid having 4 to 24 carbons. Alternatively, a partially acylated product obtained by a partial esterification reaction with a partial ester forming derivative thereof.

(V) Partial ether of the above trivalent monocyclic phenol and the above novolac AOA and the above unsaturated alcohol having 2 to 24 carbon atoms or its AO adduct (for example, 1 to above carbon atoms). Obtained by jumping with an alkylene dihalide of 4).

(Vi) The above trivalent monocyclic phenol, the above novolac AOA and the above unsaturated carboxylic acid having 3 to 25 carbon atoms, or the above unsaturated polycarboxylic acid having 4 to 24 carbon atoms or a portion thereof. A partially acylated product by a partial esterification reaction with an ester-forming derivative.

Preferred as (a) is a polyol compound in which X is a (meth) acryloyl group in the general formula (1). Specific examples thereof include the above-mentioned trihydric alcohol having 3 to 20 carbon atoms or 4 to 4 having 5 to 20 carbon atoms.
It is a partial (meth) acryloyl compound obtained by a partial esterification reaction of a 10-valent polyhydric alcohol and (meth) acrylic acid or its ester-forming derivative.

As a specific example, glycerin mono (meta)
Acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate,
Examples thereof include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, and sorbitol tetra (meth) acrylate. Moreover, these can be used individually or as a mixture of 2 or more types. The number average molecular weight of (a) is 130 to 200 from the viewpoint of mechanical strength of the polymer electrolyte.
0 is preferable, and 140-1500 is more preferable.

As (b), the hydroxyl equivalent is 200 to 5
There is no particular limitation as long as it is 000 polyols (valence 2 to 4 and 5 or more), "Polyurethane resin handbook" (edited by Keiji Iwata, September 25, 1987, published by Nikkan Kogyo Shimbun), page 99. To polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polybutadiene polyols and the like described on page 117. Among them, the preferred one is
It is a polyether polyol. Examples of the polyether polyol include the following (b-1) to (b-3) EO adducts of low molecular weight active hydrogen-containing compounds and / or EO and other A
O co-adducts (random or block) are mentioned.

The low molecular weight active hydrogen-containing compound includes (b-1) low molecular weight polyols: dihydric alcohols having 2 to 20 carbon atoms (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1 , 4-
Alkyl glycols such as butanediol, 1,6-hexanediol and neopentyl glycol; and alicyclic diols such as cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol), trihydric alcohols having 3 to 20 carbon atoms (the above Those exemplified in the explanation of the general formula (1)], 4 to 5 having 20 to 20 carbon atoms
Octahydric polyhydric alcohol [exemplified in the description of the general formula (1)] and the like. (B-2) Polyphenols: monocyclic phenols such as hydroquinone, resorcin, catechol, pyrogallol and phloroglucin; bisphenols such as bisphenol A, bisphenol B, bisphenol F and bisphenol S; and a condensate of phenol and formaldehyde. (Novolak); eg US Pat. No. 32
Polyphenols and the like described in the specification of 65641. (B-3) Low-molecular-weight amines: ammonia; as aliphatic amines, alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine and isopropanolamine), and 1 to 20 carbon atoms. Alkylamines (eg, n
-Butylamine and octylamine), carbon number 2-6
Alkylenediamine (for example, ethylenediamine, propylenediamine, and hexamethylenediamine), polyalkylenepolyamines having 4 to 20 carbon atoms (dialkylenetriamine having 2 to 6 carbon atoms in the alkylene group to hexaalkyleneheptamine, such as diethylenetriamine and Triethylenetetramine); aromatic mono- or polyamines having 6 to 20 carbon atoms (for example, aniline,
Phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine), carbon number 4 to 2
0 cycloaliphatic amines (isophoronediamine, cyclohexylenediamine and dicyclohexylmethanediamine), heterocyclic amines having 4 to 20 carbon atoms (for example, piperazine and aminoethylpiperazine) and the like.

Further preferred as (b) is the EO of the above low molecular weight polyols and the above polyhydric phenols.
Adducts and / or co-adducts of EO with other AO (random or block). Particularly preferred are aliphatic diols [exemplified in the above (b-1)] and aliphatic polyols [exemplified in the explanation of the above general formula (1)] and aliphatic triols [of the above general formula (1)]. Exemplified in the description] EO adduct and / or EO and other A
O-coadducts (random or block), and electrolytes using them are preferable because they have excellent flexibility and good ionic conductivity.

The hydroxyl equivalent of (b) is preferably 200 to 5,000, more preferably 250 to 3,000, and particularly preferably 300 to 2,000. The hydroxyl equivalent is preferably 250 or more from the viewpoint of mechanical properties of the polymer electrolyte, and 50 from the viewpoint of curability and shape retention of the polymer electrolyte.
00 or less is preferable. The amount of EO used in the AO adduct is preferably 5% by mass or more, more preferably 15% by mass or more, and particularly preferably 25% by mass or more based on the total mass of AO used for the addition. When two or more kinds of (b) are used, the weighted average EO content is preferably within the above range.

Examples of (c) include aliphatic polyisocyanates having 2 to 18 carbon atoms (excluding carbon in the isocyanate group, the same applies hereinafter), such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate. 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl)
Fumarate, bis (2-isocyanatoethyl) carbonate and the like; alicyclic polyisocyanates having 8 to 15 carbon atoms, such as isophorone diisocyanate (IPDI),
Dicyclohexylmethane diisocyanate (hydrogenated MD
I), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) 4-cyclohexene-
1,2-dicarboxylate and the like; araliphatic polyisocyanates having 8 to 15 carbon atoms, such as xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate (TMXDI); and modified products of these polyisocyanates (carbodiimide group). , Uretdione group, uretoimine group, urea group, buret group, isocyanurate group and the like) and the like.

From the viewpoints of chemical resistance and weather resistance, preferred among these are aliphatic or alicyclic polyisocyanates, more preferred are aliphatic or alicyclic diisocyanates, and particularly preferred are HDI. , I
PDI and hydrogenated MDI.

(C) has an isocyanate group content of 2. with respect to 1.0 equivalent of active hydrogen in (a) and (b).
It is used in an amount of 0 equivalent or less, preferably 1.0 to 1.8 equivalents, and more preferably 1.0 to 1.5 equivalents.
(A) is 1.0 mol% or more, preferably 2.0 mol% to 50 mol%, and more preferably 2.
It is 5 to 25 mol%.

(D) is a monomer having an ethylenically unsaturated bond and includes the following. Moreover, these can be used individually or as a mixture of 2 or more types. (D-1) Vinyl-based hydrocarbons (having 2 to 20 carbon atoms); Aliphatic vinyl-based hydrocarbons such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, α-olefins other than the above; alicyclic vinyl hydrocarbons such as cyclohexene, (di) cyclopentadiene, pinene, limonene,
Indene, vinylcyclohexene, ethylidenebicycloheptene, etc .; aromatic vinyl hydrocarbons such as styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene , Benzylstyrene, crotylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, divinylketone, trivinylbenzene, etc. (d-2) hydroxyl group-containing vinyl monomer (having 2 to 20 carbon atoms), for example, hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) Ryl alcohol, crotyl alcohol, isocrotyl alcohol, 1-butene-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl Ethers, etc. (d-3) Nitrogen-containing vinyl monomers (C2-C2)
0); vinyl monomers containing amino groups, such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethylmethacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl ( Meta)
Acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole and the like; amide group-containing vinyl monomers such as (meth) acrylamide, N-methyl (Meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N'-methylene-bis (meth) acrylamide, cinnamic acid amide, N, N-dimethyl acrylamide, N, N- Dibenzyl acrylamide,
Methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone and the like. (D-4) Epoxy group-containing vinyl monomer (having 2 carbon atoms
To 20), for example, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like (d-5) halogen-containing vinyl monomer (having 2 to 4 carbon atoms).
20), for example, vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, dichlorostyrene, chloroprene and the like (d-6) vinyl ester, vinyl ether, vinyl ketones (each having 2 to 20 carbon atoms), for example vinyl formate, Vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl acylate, vinyl methacrylate, vinyl methoxyacetate, vinyl benzoate, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, Vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2-butoxy ethyl ether, 3, - dihydro 1,2 pyran, 2-butoxy-2'-vinyloxy diethyl ether, vinyl 2
Ethyl mercaptoethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide,
Dimethyl fumarate, dimethyl maleate, poly (meth) allyloxyalkanes [diaryloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc.], etc. . (D-7) alkyl (meth) acrylate (having 1 to 7 carbon atoms
Alkyl (meth) acrylate having 50 alkyl groups, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth). ) Acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate and the like. (D-8) A (meth) acrylic acid ester having a polyalkylene glycol chain, for example, a polyalkylene glycol mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate or polypropylene glycol mono (meth) acrylate. Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, EO-modified bisphenol A
Type di (meth) acrylate, PO-modified bisphenol A
Type di (meth) acrylate of polyalkylene glycol such as di (meth) acrylate. Alkoxyl ethylene glycol (meth) acrylates such as methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxytetraethylene glycol (meth) acrylate. Alkoxyl propylene glycol (meth) acrylates such as ethoxy polypropylene glycol (meth) acrylate, butoxy polypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate. (D-9) Poly (meth) acrylate of polyhydric (2 to 8) alcohols such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate and the like. (D-10) Other vinyl-based monomer (having 2 to 3 carbon atoms)
0), for example, acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene, cyclohexyl methacrylate, benzyl methacrylate, ethyl α-ethoxy acrylate, phenyl (meth) acrylate, isocyanatoethyl (meth) acrylate, cyanoacrylate, m-isopropenyl-. α, α-dimethylmethylbenzyl isocyanate and the like.

Preferred as (d) is the above (d-
7), (d-8) and (d-9), and particularly (meth) acrylic acid ester (d) represented by the following general formula (2).
1). ^{_{{CH 2 = C (R 2}} ) COO (R 3 0) y -} z R ⁴ (2), R ² is hydrogen or a methyl group, R ³ is - (CH _{2)
2 -, - CH (CH 3} ) CH 2 -, and -CH ₂ CH (C
H ₃₎ - represents at least one selected from the group of, y is an integer of 0 or 1 to 40, z is an integer of 1-8. R
⁴ is a residue obtained by removing all OH groups from a z-valent monool or polyol having a molecular weight of 90 or more and less than 500.

As the compound represented by the general formula (2),
The following are preferred. Moreover, these can be used individually or as a mixture of 2 or more types.

(D1-1) (meth) acrylic acid ester having a polyalkylene glycol chain, for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, EO-modified bisphenol A type di (meth) acrylate, propylene Di (meth) acrylate of polyalkylene glycol such as oxide-modified bisphenol A type di (meth) acrylate. Alkoxyl ethylene glycol (meth) acrylates such as methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxytetraethylene glycol (meth) acrylate. Alkoxyl propylene glycol (meth) acrylates such as ethoxy polypropylene glycol (meth) acrylate, butoxy polypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate.

(D1-2) Poly (meth) acrylate of polyhydric (2 to 8) alcohols, for example, the above (d-9)
The ones listed in.

Of these, particularly preferred are:
Alkoxyl polyethylene glycol (meth) acrylates such as methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol acrylate and trimethylolpropane tri (meth) acrylate are mentioned.

(A1) is obtained by polymerizing (a), (b), (c) and optionally (d), and preferably (a),
(B), (c) and (d) are copolymerized, and more preferably (a), (b), (c) and (d1) are copolymerized.

(A1) is obtained by the urethanization reaction of (a), (b) and (c) and the reaction of the ethylenically unsaturated bond of (a) and, if necessary, (d).
For the manufacturing method of (A1), (a), (b),
The method is not particularly limited as long as it is a method of reacting (c) and (d) if necessary, and a known method is adopted.

For example, (1) a method of subjecting (a), (b), and (c) to a urethanization reaction, and then (a) reacting an unsaturated bond of (d) if necessary. (2) (a), (b),
A method of simultaneously advancing the urethane-forming reaction of (c) and (a) the reaction of the unsaturated bond of (d). (3)
(A) A method of reacting the unsaturated bond possessed by (d), if necessary, and then carrying out the urethanization reaction of (a), (b) and (c) can be mentioned.

As the method for carrying out the urethanization reaction of (1) and (3), for example, (1-i) (b) and (c) are reacted to contain one or more isocyanate groups per molecule. A method of reacting the intermediate with (a) after forming the urethane isocyanate intermediate, (1-ii)
A method of reacting (a) and (c) to form a urethane isocyanate intermediate containing one or more isocyanate groups per molecule, and then reacting the intermediate with (b), (1-iii) ( Examples thereof include a method in which the three components of a), (b), and (c) are reacted together.

In the urethanization reaction, a crosslinking agent and / or a stretching agent can be used if necessary. As the crosslinking agent and / or the stretching agent, water can be used in addition to the polyhydric alcohols and polyamines described on pages 122 to 123 of "Polyurethane Resin Handbook". Of these, polyhydric alcohols such as ethylene glycol are preferable. Further, in the urethanization reaction, the reaction temperature is 5
0-150 degreeC is preferable. A catalyst may be used in this reaction system in order to shorten the reaction time and lower the heating temperature. Examples of the catalyst include tertiary amines (triethylamine, triethanolamine, triethylenediamine, etc.) and organic tin compounds (dibutyltin laurate, dibutyltin diacetate, etc.).

The reaction of the ethylenically unsaturated bond is not particularly limited and can be carried out by a known method. For example,
A method of directly irradiating radiation such as electron beam or γ ray without adding an initiator, a method of irradiating ultraviolet rays by adding an ultraviolet polymerization initiator such as a photosensitizer, a thermal polymerization initiator such as an organic peroxide And a heating method, and a redox type room temperature reaction using a redox type initiator. In particular, the method of irradiating with ultraviolet rays is preferably used in that low temperature reaction is possible and the reaction time is short, and the method of heating is simple in that it requires no special equipment and is simple.

Further, the simultaneous progress of the urethanization reaction and the ethylenically unsaturated reaction described in the above (2) means that heating is performed after adding a thermal polymerization initiator, or while the urethanization reaction is performed by heating, It is achieved by irradiating the above-mentioned radiation or ultraviolet rays.

Examples of the ultraviolet polymerization initiator include the following. (A) Benzoin ether-based polymerization initiator benzoin alkyl ether, etc. (b) Benzophenone-based polymerization initiator: benzophenone, benzyl, methyl orthobenzoylbenzoate, etc. (c) Acetophenone-based polymerization initiator benzyl dimethyl ketal, 2,2-diethoxyacetophenone 2-hydroxy-2-methylpropiophenone,
4'-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, etc. (d) Thioxanthone-based polymerization initiator 2-chlorothioxanthone, 2-methylthioxanthone,
2-isopropylthioxanthone and the like. Of the above, a benzoin ether type polymerization initiator is preferable. The amount of the sensitizer used is 0.01 to 10% by weight, preferably 0.05 to 6 based on the total amount of (A1).
%, And more preferably 0.1 to 4%.

The following may be mentioned as the thermal polymerization initiator. (I) Peroxide-based polymerization initiator acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, t-butyl peroxy Vivarate, 3, 5, 5-
Trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexa Noate, benzoyl peroxide, parachlorobenzoyl peroxide, t
-Butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoylper Oxyhexane, t-butylperoxyacetate, t-butylperoxybenzoate, diisobutyldiperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butyl cumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, pinane hydroperoxide, 2,5- Methyl-2,5-dihydro peroxide, cumene peroxide, etc.

(Ii) Azo polymerization initiator: 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexane 1-carbonitrile, 2,2'-azobis-4
-Methoxy-2,4-dimethylvaleronitrile, 2,
2'-azobis-2,4-dimethylvaleronitrile, etc.

Of these, hydroperoxides or peroxyesters are preferred, and more specifically di (4-t-butyl) cyclohexylperoxydicarbonate or cumene hydroperoxide is preferred. The amount of the polymerization initiator used is (A1) as a whole,
It is 0.1 to 10% by weight, preferably 0.1 to 6%, more preferably 1 to 4%.

In the polymer electrolyte of the present invention, (a),
The proportion of each of the components (b) and (c) should be in the following range based on the total weight of (a), (b) and (c) from the viewpoint that the mechanical strength of the polymer electrolyte is sufficient. Is preferred. (A) 0.2 to 20% by weight (b) 50 to 95% by weight (c) 5 to 50% by weight

Further, (d) which is optionally used is
0 to 90% by weight in (A1), preferably 0 to
It is 75% by weight. When the proportion is 90% by weight or less, the mechanical strength of the polymer electrolyte is sufficient, which is preferable.

(A) can be a mixture of (A1) and another polymer. The polymer to be mixed is not particularly limited, but for example, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.), vinyl resin (polyacrylonitrile, polybutadiene, poly (meth) acrylic acid esters, polystyrene, etc.),
Examples thereof include silicon-containing resins (polysiloxane, polysilane), fluororesins (polyvinylidene fluoride, polytetrafluoroethylene, etc.), and polyphosphazenes.

The content of (A1) in (A) is 30% by weight or more, preferably 40% by weight or more, and more preferably 50% by weight or more.

Examples of (B) used in the present invention include those obtained by dissolving the electrolyte salt (B1) in the non-aqueous solvent (B2). The component (B1) is not particularly limited as long as it is used for a normal non-aqueous electrolyte solution. Examples thereof include alkali metal salts, quaternary ammonium salts, amidinium salts, alkaline earth metal salts and the like. These electrolyte salts can be used alone or as a mixture upon use.

Examples of the alkali metal salt include lithium salt, sodium salt and potassium salt. For example, (i)
Examples of the lithium salt include lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide, lithium bistetrafluoroethylenesulfonylimide, lithium tristrifluoromethanesulfonylmethyi. Lithium salt such as lithium chloride, lithium acetate, lithium trifluoroacetate, lithium benzoate, lithium p-toluenesulfonate, lithium nitrate, lithium bromide, lithium iodide, and lithium 4-phenylborate;
i) As sodium salt, sodium perchlorate, sodium iodide, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium trifluoromethanesulfonate, sodium bromide and the like; (iii) As potassium salt, Examples thereof include potassium iodide, potassium tetrafluoroborate, potassium hexafluorophosphate, potassium trifluoromethanesulfonate, and the like.

Further, as the quaternary ammonium salt, tetramethylammonium / 4 fluoroborate, tetraethylammonium / 4fluoroborate, tetrapropylammonium / 4fluoroborate, tetrabutylammonium / 4fluoroborate Salt, methyltriethylammonium / 4
Fluoroborate, tetraethylammonium / 6-fluorophosphate, tetraethylammonium / perchlorate, etc., or pyridine ring, pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring, pyrimidine ring, 1,5-diazabicyclo [4 , 3,0] Nonene-5 (DBN), 1,
8-diazabicyclo [5,4,0] undecene-7 (D
BU) and other quaternary ammonium salts having a cyclic or bicyclic structure.

As the amidinium salt, 1-ethyl-3-methylimidazolium / 4 fluoroborate, 1,
3-Dimethylimidazolium / 6-fluorophosphate, 1,3
Examples include-dimethyl-1,4,5,6-tetrahydropyrimidinium / perchlorate.

Examples of the alkaline earth metal salt include magnesium salt and calcium salt. For example, (i)
Mg (ClO ₄ ) ₂ and magnesium salts of Mg (BF ₄ ) ₂ ;
(Ii) Ca (ClO ₄ ) ₂ , Ca (BF ₄ ) _{2 and} other calcium salts.

Among these, lithium tetrafluoroborate, 6
Lithium fluorophosphate, lithium bistrifluoromethanesulfonylimide, and lithium tristrifluoromethanesulfonylmethide are preferred because they are electrolytes exhibiting particularly high ionic conductivity and excellent thermal stability.

Examples of the non-aqueous solvent (B2) include carbonate solvents (propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate), amide solvents (N-methylformamide, N-ethylformamide, N, N-). Dimethylformamide, N-methylacetamide, N-ethylacetamide, N-methylpyrrolidinone), lactone solvent (γ-butyl lactone, γ-valerolactone, 5-valerolactone, 3-methyl-1,3 oxazolidine-2)
-On, etc.), alcohol solvent (ethylene glycol, propylene glycol, glycerin, methyl cellosolve,
1,2 butanediol, 1,3 butanediol, 1,4
Butanediol, diglycerin, polyoxyalkylene glycol cyclohexanediol, xylene glycol, etc.), ether solvent (methylal, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-ethoxy-
2-methoxyethane, alkoxy polyalkylene ether, etc.), nitrile solvent (benzonitrile, acetonitrile, 3-methoxypropionitrile, etc.), phosphoric acid and phosphoric acid ester solvent (orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid) , Trimethyl phosphate, etc.), 2-imidazolidinones (1,3-dimethyl-2-imidazolidinone, etc.), pyrrolidones, sulfolane solvents (sulfolane,
Tetramethylene sulfolane), a furan solvent (tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran), dioxolane, dioxane, dichloroethane, or a mixed solvent of two or more thereof can be used. Among these, preferred are carbonate solvents, ether solvents and furan solvents.

From the viewpoint of ionic conductivity, the concentration of (B1) in (B) is preferably in the range of 0.25 to 3 mol / liter, particularly preferably 0.5 to 2.
It is 5 mol / liter.

As a method for producing a gel-like polymer electrolyte, (a), (b), (c) in the absence of (i) and (B) is used.
And a method of impregnating with (B) after polymerizing (d) if necessary, (ii) in the presence of (B), (a), (b),
The method of polymerizing (c) and (d) as needed is mentioned.

In (i), (a), (b), (c) and optionally (d) synthesized by a known method were polymerized in the presence of a solvent, if necessary, and used as required. (A1) is obtained by vacuum-drying and removing the solvent. Then, (A1) is impregnated with (B). (A
The impregnation of (B) into 1) is usually carried out by immersing (A1) in (B) for 1 to 24 hours in a temperature range of 20 to 80 ° C.

The method for polymerizing (A1) in both (i) and (ii) is as described above. Use (A)
And the ratio of (B) is (A) / (B) = 1/99 to 70
/ 30% by weight is preferable. From the viewpoint of mechanical strength, (A) is preferably 1% by weight or more, and from the viewpoint of ionic conductivity, it is preferably 70% by weight or less.

The gel-like polymer electrolyte of the present invention exhibits high ionic conductivity and is therefore suitable as an electrolyte for electrochemical devices such as electrolytic capacitors, electric double layer capacitors, batteries, or electrochemical devices.

The gel-like polymer electrolyte of the present invention comprises (a) and (b) by using the polyol compound (a) having at least two or more hydroxyl groups and at least one or more ethylenically unsaturated bond at the same time. , (C) and optionally (d) have an unsaturated double bond in the branch portion of the molecular chain, and the crosslink density of the polymer (A1) can be increased. For this reason, the mechanical strength is higher than that of the conventional one, and the thickness can be reduced particularly when used in a secondary battery.

The secondary battery of the present invention comprises a positive electrode, a negative electrode,
The gel polymer electrolyte having the above composition is used.
Generally, a battery includes a positive electrode made of a positive electrode active material, a negative electrode made of a negative electrode active material, a diaphragm, and an electrolyte. When the gel polymer electrolyte of the present invention is applied to a battery, the gel polymer electrolyte itself of the present invention can also function as a diaphragm. When using a partition,
This membrane and the gel-like polymer electrolyte of the present invention can be easily integrated, and the gel-like polymer electrolyte can be directly formed in the battery container having the membrane or the composition for forming the gel-like polymer electrolyte in the membrane. It can be achieved by impregnating the product and carrying out a polymerization reaction. As a partition,
Low resistance to ionic migration of the electrolyte solution, and
Those having excellent solution retention are used, for example, polyester, polytetrafluoroethylene, polypropylene,
Examples include non-woven fabrics and woven fabrics selected from one or more materials such as polyethylene, polyvinyl alcohol, and saponified ethylene-vinyl acetate copolymer. These are not necessary when the gel polymer electrolyte of the present invention itself has a function as a separator.

Positive electrode of battery using the polymer electrolyte of the present invention
(I) LiCoO 2 as its active material₂, LiNi
O₂, Li_xNi_yCo_1-yO₂(Where x and y are battery charges
Depends on the discharge state, usually 0 <x <1, 0.7 <y
<1.02), LiMnO₂, LiMn₂O_FourEtc.
Complex oxidation of lithium with one or more transition metals
Thing; (II) MnO₂, V₂O_FiveTransition metal oxides such as;
(III) MoS₂, TiS ₂Transition metal sulfides, such as (I
V) Polyaniline, polypyrrole, polyacene, polyti
Offen, polyacetylene, poly-p-phenylene, po
Conductive polymer such as licarbazole; (V) disulfide
Compounds that reversibly undergo electrolytic polymerization and depolymerization like compounds
Can be used. Among these, lithium and transition
Complex oxides with metals improve battery capacity and reduce energy consumption.
-It is preferable because it has excellent density.

When forming a positive electrode using such a positive electrode active material, known conductive agents and binders can be added and used in combination.

The negative electrode of the battery using the polymer electrolyte of the present invention uses light metal or light metal ion as its active material. Examples of such a light metal include lithium, sodium, potassium, cesium, aluminum and the like, and likewise, light metal ions include lithium ion, sodium ion, potassium ion, cesium ion, aluminum ion and the like. Of these, lithium and lithium ions are particularly preferable in terms of battery output and energy density.

The negative electrode is composed of the above-mentioned negative electrode active material itself or a material capable of occluding and releasing the active material. As the constituent material of such a negative electrode, (I) a light metal itself; (II) a compound having a light metal ion itself;
(III) The alloy itself containing these light metals may be used, or (IV) such a light metal or a material capable of occluding and releasing the ions thereof may be used.

Among the constituent materials of such a negative electrode, (I
Examples of the material V) which can occlude and release lithium or its ions include, for example, (1) graphites, organic polymer compound fired bodies (phenolic resins, furan resins, etc., fired at an appropriate temperature to be carbonized) , Carbonaceous materials such as cokes (pitch coke, needle coke, petroleum coke, etc.), carbon fibers, glassy carbons, pyrolytic carbons, activated carbon; (2) polyacetylene showing conductivity by absorbing lithium ions Polymers such as polypyrrole can be used. In addition, (II
As the light metal alloy of I), for example, a lithium-aluminum alloy or the like can be used.

As the constituent material of the negative electrode, these (I) to
Among (IV), it is preferable to use the carbonaceous material of (IV) (1) from the viewpoint of improving the charge / discharge characteristics and the self-discharge characteristics. When forming the negative electrode from such a material, a known binder and the like can be added.

The shape, form, etc. of the battery using the gel polymer electrolyte of the present invention are not particularly limited.
A sheet, a cylinder or the like can be arbitrarily selected within the scope of the present invention.

The lithium secondary battery of the present invention uses the gel polymer electrolyte having the above composition together with the positive electrode and the negative electrode. A composite oxide of lithium and a transition metal is used for the positive electrode of this battery. Lithium and lithium ions are used as the active material of the negative electrode, and lithium or a material capable of absorbing and releasing lithium ions is used as the constituent material.

[0071]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the following, parts and% mean parts by weight and% by weight, respectively.
In addition, the non-aqueous solvent and the electrolyte salt were sufficiently refined to have a water content of 20 ppm or less and further deoxidized and denitrified, and battery-grade ones were used, and all the experimental operations were performed in an argon gas atmosphere. . The ionic conductivity of the gel polymer electrolyte and the polymer electrolyte strength were evaluated according to the following methods.

<Measurement of Ionic Conductivity> At 25 ° C.,
An electrochemical cell is constructed by sandwiching the gel-like polymer electrolyte between cylindrical electrodes made of stainless steel, and an alternating current impedance method in which an alternating current is applied between the electrodes to measure the resistance component is used. Calculated from real impedance intercept.

<Evaluation of compressive rupture strength> Creep meter (Yamaden Co., Ltd. RE-3305, plunger diameter 3 m)
m, sample table moving speed of 0.05 mm / min), and the compression rupture strength of the polymer electrolyte was measured.

Example 1 Propylene carbonate and 1,2-dimethoxyethane
LiBFn in a non-aqueous solvent in which the volume ratio is 7: 3._Four3
Electrolyte solution 800.00 dissolved to be mol / L
Parts, sorbitol diacrylate; 0.66 parts, poly
Ethylene glycol (number average molecular weight 2000); 90.
71 parts, HDI; 8.38 parts and dibutyltin laure
0.10 parts and ethoxydiethylene glycol activator
Relate; 99.75 parts, benzo as photo radical initiator
In-isopropyl ether; 0.40 parts are uniformly dissolved,
A gel-like polymer electrolyte-forming composition (C-1) was obtained. Thickness
1mm Silicone rubber sheet is used as a spacer
For forming gel-like polymer electrolyte between two glass plates
Put the composition (C-1), heat at 80 ° C for 3 hours, and
30 minutes after high pressure halogen lamp after tanning reaction
It was exposed to light and photopolymerized. The resulting gel-like polymer electrolyte
The ionic conductivity of the solution was measured to be 3.5 x 10^-3
S / cm, and when the compression breaking strength was measured,
1.5 x 10 ⁷dyn / cm²And sufficient solid strength
Indicated.

Example 2 To 800.00 parts of the electrolytic solution used in Example 1, 0.17 parts of sorbitol diacrylate and polyethylene glycol used in Example 1; 45.65 parts, HDI; 4.0
3 parts and dibutyltin laurate; 0.05 parts and ethoxydiethylene glycol acrylate;
Part, trimethylolpropane triacrylate; 5.9
8 parts, benzoyl peroxide as a thermal polymerization initiator;
0.60 parts was uniformly dissolved to obtain a gel polymer electrolyte-forming composition (C-2). Between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer,
Put the gel-like polymer electrolyte forming composition (C-2),
Polymerization was performed by heating at 0 ° C for 12 hours. When the ionic conductivity of the obtained gel-like polymer electrolyte was measured, 3.
It was 3 × 10 ⁻³ S / cm, and the compression rupture strength was measured and found to be 1.4 × 10 ⁷ dyn / cm ² , showing a sufficient solid strength.

Example 3 1 mol of LiPF ₆ was added to a non-aqueous solvent prepared by mixing ethylene carbonate and dimethyl carbonate in a volume ratio of 5: 5.
/ L dissolved electrolyte; 800.00 parts, sorbitol diacrylate; 2.45 parts and EO (50%) / PO (50%) adduct of glycerin (manufactured by Sanyo Kasei Co., Ltd., Newpol GEP-2800, number average molecular weight 2600); 175.67 parts, HDI; 21.
28 parts and dibutyltin laurate; 0.2 parts were uniformly dissolved to obtain a gel polymer electrolyte forming composition (C-3). After the gel polymer electrolyte forming composition (C-3) was put between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer and heated at 80 ° C. for 1 hour to cause a urethanization reaction. Then, light was irradiated with a high-pressure halogen lamp for 30 minutes for photopolymerization. The ionic conductivity of the obtained gel polymer electrolyte was measured to be 4.1.
× a 10 ^-3 S / cm, also the compressive fracture strength was measured to be ^{2.8 × 10 7 dyn / cm 2} , it showed sufficient solid strength.

Example 4 Electrolyte used in Example 3; 800.00 parts, sorbitol diacrylate; 4.51 parts and Newpol GEP-2800 used in Example 3; 161.87 parts, HD
I; 25.15 parts and dibutyltin laurate;
19 parts and diethylene glycol monoacrylate; 8.
07 parts, benzoin isopropyl ether; 0.20 parts were uniformly dissolved, and a gel polymer electrolyte forming composition (C-
4) was obtained. The gel polymer electrolyte forming composition (C-4) was put between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by shining light for 10 minutes with a high pressure halogen lamp. Also, 80 ℃
The gel-like polymer electrolyte was obtained by heating for 6 hours. The ionic conductivity of this product is 5.4 × 10 ⁻³ S / cm,
The compression rupture strength was measured to be 1.7 × 10 ⁷ d
It was yn / cm ² and showed sufficient solid strength.

Example 5 Methoxytriethylene glycol acrylate; 49
4.70 parts with sorbitol diacrylate; 20.6
0 parts and polyethylene glycol (PEG-600 number average molecular weight 600); 340.98 parts, HDI; 143.2
1 part and dibutyltin laurate; 0.50 part were dissolved, charged into a reaction vessel, and a urethanization reaction was carried out at 80 ° C. with stirring while blowing dry air. 3 hours later, IR
The disappearance of isocyanate was confirmed by the measurement results, and the reaction was terminated to obtain a mixture (D-1) of a polyurethane compound and methoxytriethylene glycol acrylate. The resulting mixture (D-1) was a high viscosity liquid. The electrolytic solution used in Example 3; 800.00 parts, (D-1); 1
97.61 parts and trimethylolpropane triacrylate; 2.00 parts, benzoin isopropyl ether;
0.40 part was uniformly dissolved to obtain a gel polymer electrolyte-forming composition (C-5). Between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer,
The gel polymer electrolyte-forming composition (C-5) was added, and light was irradiated with a high-pressure halogen lamp for 30 minutes for photopolymerization.
The ionic conductivity of the obtained gel polymer electrolyte was measured to be 5.5 × 10 ⁻³ S / cm, and the compression rupture strength was measured to be 1.6 × 10 ⁷ dyn / c.
m ² and showed sufficient solid strength.

Example 6 Sorbitol diacrylate; 10.67 parts and Example 1
Polyethylene glycol used in No. 883.22 parts, H
DI; 105.10 parts and dibutyltin laurate;
1.0 part was charged into a reaction vessel, and a urethanization reaction was carried out at 80 ° C. under stirring. After 3 hours, the disappearance of isocyanate was confirmed by the result of IR measurement, and the reaction was terminated to obtain a polyurethane compound (A1-6). Electrolyte used in Example 1; 800.00 parts by weight (A1-6); 99.85 parts by weight, methoxytriethylene glycol acrylate; 95.7
6 parts, trimethylolpropane triacrylate; 3.
99 parts, benzoin isopropyl ether; 0.40 parts were dissolved to form a gel polymer electrolyte-forming composition (C-6).
Got The gel polymer electrolyte-forming composition (C-6) was put between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by irradiating light for 30 minutes with a high pressure halogen lamp. . When the ionic conductivity of the obtained gel-like polymer electrolyte was measured,
It was 3.1 × 10 ⁻³ S / cm, and the compression rupture strength was measured and found to be 1.8 × 10 ⁷ dyn / cm ² , showing a sufficient solid strength.

Example 7 Methyl ethyl ketone; 800.00 parts pentaerythritol diacrylate; 0.51 parts and Newpol GEP-2800 used in Example 3; 43.37 parts, HD
I; 5.96 parts, dibutyltin laurate; 0.05
Part, ethoxydiethylene glycol acrylate; 14
8.02 parts, trimethylolpropane triacrylate; 1.50 parts and benzoin isopropyl ether;
0.60 parts was dissolved to obtain a gel polymer electrolyte-forming composition (C-7). The composition (C-7) was put between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer, and light was irradiated with a high pressure halogen lamp for 30 minutes for photopolymerization, and then at 80 ° C. for 6 hours. It was heated to cause a urethane reaction. 10 sheets of the obtained polymer
It was dried in a vacuum dryer at 0 ° C. for 12 hours to remove methyl ethyl ketone used for polymerization, and immersed in the electrolytic solution used in Example 1 at room temperature for 24 hours to impregnate the electrolytic solution. Excessive electrolytic solution was removed by adsorbing with a filter paper to obtain a gel polymer electrolyte. The ionic conductivity of the obtained gel polymer electrolyte was measured to be 2.7 × 10 ⁻³ S / cm, and the compression rupture strength was measured to be 1.8 × 10 3.
^{It was 7} dyn / cm ² and showed sufficient solid strength.

Example 8 Methyl ethyl ketone; pentaerythritol diacrylate in 800.00 parts; 0.54 parts and polyethylene glycol used in Example 1; 44.11 parts, HDI; 5.1
9 parts, dibutyltin laurate; 0.05 parts, ethoxydiethylene glycol acrylate; 143.53 parts,
Dissolve 5.98 parts of trimethylolpropane triacrylate and 0.60 parts of benzoin isopropyl ether,
A gel polymer electrolyte-forming composition (C-8) was obtained. The composition (C-8) was placed between two glass plates sandwiching a 1 mm-thick silicone rubber sheet as a spacer and heated at 80 ° C. for 1 hour to cause a urethanization reaction, followed by a high pressure halogen lamp for 30 minutes. It was exposed to light and photopolymerized.
The obtained sheet-shaped polymer was dried in a vacuum dryer at 100 ° C. for 12 hours to remove methyl ethyl ketone used for polymerization, and immersed in the electrolytic solution used in Example 3 at room temperature for 24 hours to form an electrolytic solution. Impregnated. Excessive electrolytic solution was removed by adsorbing with a filter paper to obtain a gel polymer electrolyte. The ionic conductivity of the obtained gel polymer electrolyte was measured to be 5.2 × 10 ⁻³ S / cm, and the compression rupture strength was measured to be 1.8 × 10 ⁷ dyn / cm. ² , which was a sufficient solid strength. .

Example 9 Methyl ethyl ketone; sorbitol diacrylate in 800.00 parts; 0.14 part and Newpol GEP-2800 used in Example 3; 53.41 parts, HDI; 6.0
2 parts, dibutyltin laurate 0.06 parts, diethylene glycol acrylate; 0.25 parts, ethoxydiethylene glycol acrylate; 136.78 parts, trimethylolpropane triacrylate; 2.79 parts, benzoyl peroxide 0.56 parts are uniformly dissolved. Then, a gel-like polymer electrolyte forming composition (C-9) was obtained. 1m thick
m Silicone rubber sheets sandwiched as spacers 2
The gel-like polymer electrolyte-forming composition (C-9) was put between the glass plates and heated at 80 ° C. for 12 hours for polymerization. The obtained sheet-shaped polymer was dried in a vacuum dryer at 100 ° C. for 12 hours to remove methyl ethyl ketone used for polymerization, and immersed in the electrolytic solution used in Example 1 at room temperature for 24 hours to form an electrolytic solution. Impregnated. Excessive electrolytic solution was removed by adsorbing with a filter paper to obtain a gel polymer electrolyte. When the ionic conductivity of the gel polymer electrolyte was measured, 3.
It was 1 × 10 ⁻³ S / cm, and the compression rupture strength was measured and found to be 1.4 × 10 ⁷ dyn / cm ² , showing a sufficient solid strength.

Example 10 To 800.00 parts of the electrolytic solution used in Example 3, 4.22 parts of sorbitol diacrylate and Newpol GEP-2800 used in Example 3; 151.21 parts, hydrogenated MD
I; 36.65 parts and dibutyltin laurate;
19 parts and diethylene glycol monoacrylate;
54 parts, benzoin isopropyl ether; 0.20 parts were uniformly dissolved, and a gel polymer electrolyte forming composition (C-
10) was obtained. The gel polymer electrolyte forming composition (C-10) was placed between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer, and the temperature was adjusted to 80 ° C. while shining light with a high pressure halogen lamp. . Light irradiation was completed for 30 minutes and heating was completed for 3 hours to obtain a gel-like polymer electrolyte. The ionic conductivity of this product is 4.3 × 10 ^-3.
S / cm, and when the compression breaking strength was measured,
It was 1.4 × 10 ⁷ dyn / cm ² , showing a sufficient solid strength.

Example 11 Methyl ethyl ketone; pentaerythritol diacrylate in 800.00 parts; 0.48 part and Newpol GEP-2800 used in Example 3; 40.66 parts, hydrogenated M
DI; 8.71 parts, dibutyltin laurate; 0.05
Part, ethoxydiethylene glycol acrylate; 14
8.02 parts, trimethylolpropane triacrylate; 1.50 parts and benzoin isopropyl ether;
0.60 parts was dissolved to obtain a gel polymer electrolyte-forming composition (C-11). The composition (C-11) was placed between two glass plates sandwiching a 1 mm-thick silicone rubber sheet as a spacer, and light was irradiated with a high-pressure halogen lamp for 30 minutes for photopolymerization, and then at 80 ° C for 6 hours. It was heated to cause a urethane reaction. The obtained sheet-shaped polymer was dried in a vacuum dryer at 100 ° C. for 12 hours to remove methyl ethyl ketone used for polymerization, and immersed in the electrolytic solution used in Example 1 at room temperature for 24 hours to form an electrolytic solution. Impregnated.
Excessive electrolytic solution was removed by adsorbing with a filter paper to obtain a gel polymer electrolyte. The ionic conductivity of the obtained gel polymer electrolyte was measured to be 2.7 × 10 ⁻³ S / c.
m, and the compression breaking strength was measured to be 1.7
It was × 10 ⁷ dyn / cm ² , showing a sufficient solid strength.

Comparative Example 1 The electrolytic solution used in Example 1; 800.00 parts, 195.22 parts of methoxytriethylene glycol acrylate and 3.98 parts of trimethylolpropane triacrylate,
0.80 part of benzoin isopropyl ether was uniformly dissolved to obtain a gel polymer electrolyte forming composition (C-1 ′). A gel polymer electrolyte-forming composition (C-1 ') was put between two glass plates sandwiching a rubber sheet made of silicone with a thickness of 1 mm as a spacer, and photopolymerized by applying light for 10 minutes with a high pressure halogen lamp. It was When the ionic conductivity of the obtained gel-like polymer electrolyte was measured, 1.
It was 1 × 10 ⁻³ S / cm, and the compression rupture strength was 3.0 × 10 ⁶ dyn / cm ² , which was easy to tear.

Comparative Example 2 2-hydroxyethyl acrylate; 3.91 parts and polyethylene glycol used in Example 1; 33.75 parts,
HDI; 5.67 parts and dibutyltin laurate;
0.04 part was charged into a reaction vessel, and a urethanization reaction was carried out at 80 ° C. under stirring. After 3 hours, the disappearance of isocyanate was confirmed by the result of IR measurement, and the reaction was terminated to obtain a polyurethane compound (A1-2 ′). The obtained polyurethane compound (A1-2 ') was a high viscosity liquid. Example 3
The electrolytic solution used in (1) was added to 800.00 parts (A1-2 ');
43.38 parts, ethoxydiethylene glycol acrylate; 156.00 parts, and benzoin isopropyl ether; 0.62 parts were uniformly dissolved to obtain a gel polymer electrolyte forming composition (C-2 ′). The gel polymer electrolyte forming composition (C-2 ') was put between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by irradiating with a high pressure halogen lamp for 10 minutes. It was The ionic conductivity of the obtained gel polymer electrolyte was measured and found to be 3.5 × 10 ⁻³ S / cm,
Also, when the compression rupture strength was measured, it was 9.8 × 10 ⁶ d
Since it was yn / cm ² , sufficient solid strength was not obtained.

Comparative Example 3 Pentaerythritol triacrylate; 8.81 parts and the polyethylene glycol used in Example 1; 29.56
Parts, HDI; 4.97 parts and dibutyltin laurate; 0.04 parts were charged in a reaction vessel, and a urethanization reaction was carried out at 80 ° C. under stirring. After 3 hours, the disappearance of isocyanate was confirmed by the result of IR measurement, and the reaction was terminated to obtain a polyurethane compound (A1-3 ′). The obtained polyurethane compound (A1-3 ') was a high viscosity liquid. The electrolytic solution used in Example 1; 800 parts, (A1-3 ′); 4
3.38 parts, ethoxydiethylene glycol acrylate; 156.00 parts, and benzoin isopropyl ether; 0.62 parts were uniformly dissolved to obtain a gel polymer electrolyte-forming composition (C-3 '). The gel-like polymer electrolyte forming composition (C-3 ′) was put between two glass plates sandwiching a 1 mm thick silicone rubber sheet as a spacer, and photopolymerized by shining light for 10 minutes with a high pressure halogen lamp. It was The ionic conductivity of the obtained gel-like polymer electrolyte was measured and found to be 1.5 × 10 ⁻³ S / cm,
Also, when the compression rupture strength was measured, it was 1.0 × 10 ⁷ d
Since it was yn / cm ² , sufficient solid strength was not obtained.

[0088]

The gel polymer electrolyte of the present invention has higher ionic conductivity and mechanical strength than conventional ones, and has electrochemical elements or electrochemical devices such as electrolytic capacitors, electric double layer capacitors and batteries. Thin film when used for
It is possible to form a laminate, simplify the package, and reduce the weight. Therefore, when used in the electrolyte of the secondary battery, thinning of the secondary battery, especially when used in the gel electrolyte of the lithium secondary battery, despite the small size, high voltage, large electric capacity, A thin lithium battery which has a flat discharge characteristic and a good low temperature characteristic and can be used in a wide temperature range becomes possible. Since it has the above effects, the gel polymer electrolyte of the present invention is suitable as an electrolyte for an electrolytic capacitor, an electric double layer capacitor, an electrochemical element such as a battery, or an electrochemical device, and particularly a material for a secondary battery. And is suitably used as a gel polymer electrolyte for a lithium secondary battery.

Continued front page    F term (reference) 4J034 DA01 DB03 DB07 DF01 DF02                       DG03 DG04 DG08 DG10 DG12                       DG14 DG15 DG16 DG22 DG25                       DG27 DJ02 DJ08 DJ12 DP18                       FA01 FA02 FC03 FC04 FC05                       FD01 FD03 FD04 FD07 FE01                       FE04 GA05 GA33 GA65 GA73                       HA01 HA07 HA18 HB06 HB08                       HB09 HB13 HC03 HC09 HC12                       HC17 HC22 HC25 HC26 HC34                       HC35 HC46 HC52 HC61 HC64                       HC67 HC71 HC73 JA21 JA22                       KA01 KA02 KB04 KC17 KD02                       KD06 KD08 KD11 KD12 KD21                       KD24 KE02 MA18 RA14                 5G301 CA30 CD01                 5H029 AJ02 AK02 AK03 AK05 AK16                       AL06 AL07 AL08 AL12 AL16                       AM07 AM16 DJ09 HJ02

Claims (9)

[Claims] 1. A gel polymer electrolyte comprising a matrix polymer (A) and a non-aqueous electrolytic solution (B), wherein (A)
Is an ethylenically unsaturated bond-containing polyol (a) represented by the following general formula (1), another polyol (b), an organic polyisocyanate (c), and optionally a monomer having another ethylenically unsaturated bond. A gel polymer electrolyte comprising a polymer (A1) obtained by polymerizing (d). (HO) _m R ¹ (OX) _rm (1) [In the formula, R ¹ is the residue of an r-valent polyol, X is an organic group having an ethylenically unsaturated bond, r is an integer of 3 to 10, m
Is an integer of 2 to 9, and r-m is an integer of 1 to 8. ] 2. The electrolyte according to claim 1, wherein in the general formula (1), X is a (meth) acryloyl group. 3. The method according to claim 1, wherein (c) is an aliphatic polyisocyanate and / or an alicyclic polyisocyanate.
The described electrolyte. 4. The (meth) acrylic acid ester (d1) represented by the following general formula (2):
3. The electrolyte according to any one of 3 above. {CH ₂ ═C (R ² ) COO (R ³ 0) _y −} _z R ⁴ (2) [wherein R ² is hydrogen or a methyl group, and R ³ is — (CH ₂ ) _{2
-, - CH (CH 3)} CH 2 -, and -CH ₂ CH (C
H ₃₎ - represents at least one selected from the group of, y is an integer of 0 or 1 to 40, z is an integer of 1-8. R
⁴ is a residue in which all OH groups have been removed from a z-valent monool or polyol having a molecular weight of 90 or more and less than 500. ]
5. The electrolyte according to claim 1, which comprises polymerizing (A) in the absence of (B) and then impregnating (A) with (B). 6. The electrolyte according to claim 1, which is obtained by polymerizing (A) in the presence of (B). 7. An electrochemical device or an electrochemical device using the electrolyte according to claim 1. 8. A secondary battery comprising a positive electrode, a negative electrode, and the electrolyte according to claim 1. 9. The secondary battery according to claim 8, which is a lithium secondary battery.