JP2003251178A - Nonaqueous absorber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous absorber having high absorbing ability and gelling ability with respect to various kinds of organic solvents and capable of absorbing and gelling a large amount of organic solvents with a small amount of addition. <P>SOLUTION: The nonaqueous absorber (B) comprises a polymer (1) crosslinked material (A) containing 20-100 wt.% of a constitutuent unit having carboxy group and/or a sulfonic acid group in the molecular and in which 30-100 mol.% of proton of the carboxyl group and/or the sulfonic acid group is substituted with onium cation, and a nonaqueous gel comprising the nonaqueous absorber (B) and an organic solvent (2), a nonaqueous absorbing sheet containing the nonaqueous absorber (B) and a nonaqueous absorbing agent comprising the absorber (B) are also provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a non-aqueous absorbent comprising a cross-linked product having a specific composition, a non-aqueous absorbent gel thereof, a non-aqueous absorbent sheet, and a non-aqueous absorbent.

[0002]

2. Description of the Related Art Conventionally, crosslinked polyacrylic acid sodium salt has been used as a water-absorbent resin in various applications. With this composition, although the absorption amount for water and urine is high, for organic solvents, Since the resin does not swell at all,
It has not been applied as an absorbent or gelling agent for these organic solvents. As the cross-linked resin that absorbs the organic solvent, dialkylaminoalkyl (meth) acrylate, (meth)
3 such as acryloyltrialkylammonium chloride
Alcohol absorbent consisting of a cross-linked polymer of a monomer containing a secondary or quaternary amino group (Patent Document 1) and a cross-linked product of a copolymer of a monomer containing a tertiary amino group and a vinyl monomer having a carboxyl group (Patent Document 1). 2), carbon number 10-1
No. 6 oil-absorbing agent (patent document 3) consisting of a crosslinked body of a (meth) acrylate of a monohydric aliphatic alcohol or a crosslinked body of a monomer having a solubility parameter of 9 or less, a crosslinked body of an alkoxyalkyl (meth) acrylate, N- A liquid-absorbent resin composed of a crosslinked vinyl lactam (Patent Document 4), a liquid-absorbent resin composed of a crosslinked N-vinylacetamide (Patent Document 5), and the like have been proposed. In the field of lithium batteries and condensers, polar organic solvents such as propylene carbonate and γ-butyrolactone are usually used as electrolytes, which makes batteries thinner (for casingless purposes etc.) and liquid leakage when damaged. There is a strong need for gelling the organic solvent for prevention and the like, and as a polymer for gelling the electrolytic solution, a polyalkylene oxide cross-linked body (hereinafter referred to as PEO type) (Patent Document 6), polyacryl Nitrile-based crosslinked products (hereinafter referred to as PAN-based) (Patent Document 7), polyacrylic acid ester-based crosslinked products, and a method of using a polymer having the same composition as the above as a gelling agent for an electrolytic solution (Patent Document 8), etc. Is proposed.

[0003]

[Patent Document 1] JP-A-58-154709

[Patent Document 2] JP-A-60-179410

[Patent Document 3] JP-A-4-100359

[Patent Document 4] Japanese Patent Laid-Open No. 11-356632

[Patent Document 5] JP-A-4-230250

[Patent Document 6] Japanese Patent Laid-Open No. 62-285954

[Patent Document 7] Japanese Patent Laid-Open No. 8-264205

[Patent Document 8] Japanese Unexamined Patent Publication No. 2000-331533

[0004]

However, although the crosslinked product (1) has a relatively high absorption amount for alcohol, it has a high absorption amount for organic solvents other than alcohol, such as propylene carbonate, γ-butyrolactone and toluene. Not only is it low, but this type of cationic polymer has p
In the region where H is 4 or more, the decomposition of the ester group is very likely to occur, and there is a problem that it is not suitable for the use requiring the durability of the polymer such as the gelling agent of the electrolytic solution. In addition, regarding the cross-linked product of the polymer of ~, since these polymers are basically nonionic polymers, the dissociation of the polymer does not occur in the target organic solvent, and therefore the absorbency and gel for the target organic solvent It is weak in chemical power, and it is uneconomical to add a large amount of polymer in order to absorb and gelate these organic solvents, and it is also uneconomical. As a result, there are problems that the conductivity of the electrolytic solution is lowered and the electrical characteristics are deteriorated. In addition, lithium batteries and capacitors are used in mobile phones, computers, various home appliances, etc., but if organic solvent-based electrolyte leaks, toxic gas is generated and other ICs, semiconductors, etc. There are problems such as pollution and ignition in some cases. Regarding the prevention of leakage of these electrolytes, only nonwoven fabric sheets and the like have been practically proposed, and in the nonwoven fabrics, the amount of liquid retained against these electrolytes is extremely small, and if a large amount of leakage occurs, no protection can be provided. There was a strong demand for development of a sheet or the like that can retain a large amount of these organic solvents.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above situation, and as a result, a non-aqueous absorbent comprising a cross-linked product having a specific composition has extremely high absorbency / gelling power for the organic solvent, It has been found that a small amount of addition can absorb a large amount of an organic solvent or can gel, and that a sheet containing the non-aqueous absorber has an extremely high liquid retention amount of the organic solvent and can retain a large amount of the organic solvent. The invention was reached. That is, the present invention has a carboxyl group and /
Or a polymer (1) having 20 to 100% by weight of a structural unit having a sulfonic acid group, and 30 to 100 mol% of protons of the carboxyl group and / or the sulfonic acid group being substituted with an onium cation. A non-aqueous absorber (B) comprising a crosslinked body (A); and the (B)
And a non-aqueous gel (C) comprising the organic solvent (2); a non-aqueous absorbent sheet (D) containing the (B); a non-aqueous absorbent (E) comprising the (B); is there.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the non-aqueous absorbent (B) absorbs and gels the target organic solvent,
A polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group in the molecule, and the proton of the carboxyl group and / or the sulfonic acid group is substituted with a predetermined amount of an onium cation It is characterized by comprising the cross-linked body (A). As the structural unit (a) having a carboxyl group and / or a sulfonic acid group, a monomer having a carboxyl group [eg (meth) acrylic acid,
Ethacrylic acid, crotonic acid, sorbic acid, maleic acid, itaconic acid, fumaric acid, cinnamic acid, and their anhydrides]; sulfonic acid group-containing monomers [eg aliphatic vinyl sulfonic acid [vinyl sulfonic acid, allyl sulfone Acid, vinyltoluenesulfonic acid, styrenesulfonic acid, etc.], (meth) acrylate-type sulfonic acid [sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, etc.] and (meth) acrylamide-type sulfonic acid [acrylamido-2-methylpropane] Sulfonic acid and the like]] and the like, and one or more of these can be used as the structural unit in the polymer (1). It is preferably a structural unit having a C3 to C30 carboxyl group and / or a sulfonic acid group.

Further, as a method for obtaining a polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group in the molecule, a monomer (a ') which forms the structural unit (a) is obtained. In addition to the method of polymerizing a predetermined amount, for example, by polymerizing a monomer that can be easily converted into a carboxyl group or a sulfonic acid group, such as an esterified product or an amidated product of the above-mentioned carboxyl group, a sulfonic acid group-containing monomer, hydrolysis, etc. By introducing a predetermined amount of a structural unit of a carboxyl group or a sulfonic acid group into the molecule, a carboxyl group represented by carboxymethyl cellulose, a sulfonic acid group-containing polysaccharide polymer and the polysaccharide and other polysaccharides. Although it is possible to exemplify a graft copolymer with a monomer,
There is no particular limitation as long as a polymer finally containing a predetermined amount of structural units of a carboxyl group and / or a sulfonic acid group can be obtained. In the present invention, the content of the structural unit having a carboxyl group and / or a sulfonic acid group in the polymer (1) is usually 20 to 20 based on the weight of the polymer (1).
It is 100% by weight, preferably 40 to 100% by weight, more preferably 60 to 100% by weight. When the content is less than 20%, the absorption amount of the target organic solvent is lowered even if the proton of carboxylic acid or sulfonic acid is replaced with an onium cation described later, or the target organic solvent cannot be gelated with a small amount. There are cases.

In the present invention, the copolymerizable monomer (b) forming a structural unit other than a structural unit having a carboxyl group and / or a sulfonic acid group is, for example, an alkyl (meth) acrylate (having 1 to 30 carbon atoms). ) Esters [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, (meth)
Octyl acrylate, dodecyl (meth) acrylate,
Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, etc .; oxyalkyl (meth) acrylates (having 1 to 4 carbon atoms) [hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth ) Acrylic acid mono (polyethylene glycol) ester (PEG number average molecular weight: 100 to 4000), (meth) acrylic acid mono (polypropylene glycol) ester (PPG number average molecular weight: 100 to 4000), (meth) acrylic acid monomethoxypolyethylene Glycol (PEG number average molecular weight: 100 to 4000), (meth)
Monomethoxy propylene glycol acrylate (PPG
Number average molecular weight: 100 to 4000), etc.], (meth) acrylamides [(meth) acrylamide, (di) methyl (meth) acrylamide, (di) ethyl (meth) acrylamide, (di) propyl (meth) acrylamide, etc.] , Allyl ethers [methyl allyl ether, ethyl allyl ether, propyl allyl ether, glycerol monoallyl ether, trimethylolpropane triallyl ether, pentaerythritol monoallyl ether, etc.], α-olefins having 4 to 20 carbon atoms [isobutylene, 1-hexene, 1-octene, isooctene,
1-nonene, 1-decene, 1-dodecene, etc.], carbon number 8
To 20 aromatic vinyl compounds [styrene, t-butylstyrene, octylstyrene, etc.], other vinyl compounds [N-vinylacetamide, vinyl caproate, vinyl laurate, vinyl stearate, etc.], amino group-containing monomers [ Dialkyl (carbon number of alkyl: 1 to 5) aminoethyl (meth) acrylate, metha (acryloyl) oxyethyltrialkyl (alkyl carbon number: 1 to 1)
5) Ammonium chloride, bromide, sulfate and the like] and alkali metal salts, primary to tertiary amine salts or alkanolamine salts of the above-mentioned monomers having a carboxyl group and a sulfonic acid group. These monomers (b) may be used alone or in combination of two or more, if necessary, within the range of the above (a ') and a predetermined amount (80% of the polymer constitutional unit).
(Less than 1).

Among the above-mentioned monomers (b), from the viewpoints of the polymerizability of the monomers and the stability of the produced polymer, (meth) acrylic acid alkyl esters, (meth) acrylic acid oxyalkyls, allyl ethers, α-Olefins and aromatic vinyl compounds are preferable. Further, in the present invention, since the absorption and gelation of various organic solvents are targeted, the SP of the organic solvent and the monomer (b) are adjusted in accordance with the SP value (solubility-parameter) of the targeted organic solvent. Monomer (b) whose difference from the value is 5 or less
Is preferable because the absorption amount and gelling power are easily increased, and it is more preferable that the SP value of the target organic solvent and the SP value of the monomer (b) are 3 or less.

In the present invention, the proton of the carboxyl group and / or the sulfonic acid group is replaced by an onium cation.
Substitution of 0 to 100 mol% is essential. The onium cation includes a quaternary ammonium cation (I),
One or more selected from the group of cations consisting of a tertiary phosphonium cation (II), a quaternary phosphonium cation (III) and a tertiary oxonium cation (IV).
As the quaternary ammonium cation (I), the following (I-1)
(I-11) is mentioned (the word cation is omitted below). (I-1) an aliphatic quaternary ammonium having an alkyl and / or alkenyl group having 4 to 30 or more carbon atoms;
Tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethylpropylammonium, dimethylpropylammonium, ethylmethyldipropylammonium, tetrapropylammonium, butyltrimethylammonium, dimethyldibutylammonium, tetrabutylammonium, etc .;

(I-2) Aromatic quaternary ammonium having 6 to 30 or more carbon atoms; trimethylphenylammonium, dimethylethylphenylammonium, triethylphenylammonium, etc .;

(I-3) alicyclic quaternary ammonium having 3 to 30 or more carbon atoms; N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N, N-
Diethylpyrrodinium, N, N dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N, N diethylmorpholinium, N, N dimethylpiperidinium, N, N-diethylpiperidinium, etc .;

(I-4) Imidazolinium having 3 to 30 or more carbon atoms; 1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,
3,4-trimethyl-2-ethylimidazolinium, 1,
3-dimethyl-2,4-diethylimidazolinium, 1,
2-dimethyl-3,4-diethylimidazolinium, 1,
2-dimethyl-3-ethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1-methyl-3-ethylimidazolinium, 1,2,3,4-tetraethylimidazolinium, 1,2, 3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 2-cyanomethyl-1,3-dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazolinium, 4-methylcarboxymethyl-1,2,3-
Trimethylimidazolium, 3-methoxy-1,2-dimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium, 4-formyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2 ，
3-trimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium and the like;

(I-5) Imidazolium having 3 to 30 or more carbon atoms; 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1, 2,3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium,
1,3-dimethyl-2-ethylimidazolium, 1,2-
Dimethyl-3-ethylimidazolium, 1-ethyl-3
-Methyl imidazolium, 1-methyl-3-ethyl imidazolium, 1,2,3-triethyl imidazolium,
1,2,3,4-tetraethylimidazolium, 1,3-
Dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl-
2,3-dimethylimidazolium, 4-cyano-1,
2,3-Trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazolium, 4-acetyl-
1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-carboxymethyl-1,2,3-trimethylimidazolium,
3-Methylcarboxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium, 3-formylmethyl-1,2 -Dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 2-hydroxyethyl-1,3-
Dimethylimidazolium, N, N′-dimethylbenzimidazolazolim, N, N′-diethylbenzimidazolim, N-methyl-N′-ethylbenzimidazolium and the like;

(I-6) Tetrahydropyrimidinium having 4 to 30 or more carbon atoms; 1,3-dimethyltetrahydropyridinium, 1,2,3-trimethyltetrahydropyridinium, 1,2,3,4-tetramethyl Tetrahydropyridinium, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium, 5-methyl-
1,5-diazabicyclo [4,3,0] -5-nonenium, 4-cyano-1,2,3-trimethyltetrahydropyrimidinium, 3-cyanomethyl-1,2-dimethyltetrahydropyrimidinium, 4-acetyl -1, 2,
3-trimethyltetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyltetrahydropyrimidinium, 4-methylcarboxymethyl-1,2,3-trimethyl-tetrahydropyrimidinium, 4-methoxy-
1,2,3-trimethyltetrahydropyrimidinium,
3-methoxymethyl-1,2-dimethyltetrahydropyrimidinium, 4-hydroxymethyl-1,2,3-trimethyltetrahydropyrimidinium, 4-hydroxymethyl-1,3-dimethyltetrahydropyrimidinium and the like;

(I-7) Dihydrohydropyrimidinium having 4 to 30 or more carbon atoms; 1,3-dimethyl-2,4
-Or -2,6-dihydropyrimidinium [These are described as 1,3-dimethyl-2,4, (6) -dihydropyrimidinium, and the same expressions are used below. ], 1,
2,3-trimethyl-2,4, (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-2,4
(6) -dihydropyrimidinium, 1,2,3,5-tetramethyl-2,4, (6) -dihydropymidinium,
8-methyl-1,8-diazacyclo [5,4,0]-
7,9 (10) -undecanedienium, 5-methyl-
1,5-diazacyclo [4,3,0] -5,7 (8)-
Nonadienium, 2-cyanomethyl-1,3-dimethyl-2,4, (6) -dihydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-2,4, (6) -dihydropyrimidinium, 4 -Methylcarboxymethyl-
1,2,3-Trimethyl-2,4, (6) -dihydropyrimidinium, 4-methoxy-1,2,3-trimethyl-2,4, (6) -dihydropyrimidinium, 4-formyl- 1,2,3-Trimethyl-2,4, (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2-
Dimethyl-2,4, (6) -dihydropyrimidinium,
2-hydroxyethyl-1,3-dimethyl-2,4
(6) -dihydropyrimidinium and the like;

(I-8) Guanidium having an imidazolinium skeleton having 3 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethylimidazolinium, 2
-Diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-
Ethyl imidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, 2-diethylamino-1,3,4-triethylimidazolinium,
2-Dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-diethylimidazolinium, 1,5,6,7-tetrahydro- 1,2-
Dimethyl-2H-imide [1,2a] imidazolinium, 1,5,6,7-tetrahydro-1,2-dimethyl-
2H-pyrimido [1,2a] imidazolinium, 1,5
-Dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 2-dimethyl-3-cyanomethyl-1-methylimidazolinium 2-dimethylamino-3-methylcarboxymethyl-1-methyl Imidazolinium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolinium, 2-dimethylamino-4-formyl-1,3-dimethylimidazolinium,
2-dimethylamino-3-hydroxyethyl-1-methylimidazolinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolinium and the like;

(I-9) Guanidium having an imidazolium skeleton having 3 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethyl Imidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-diethylamino-1-methyl-
3,4-diethylimidazolium, 2-diethylamino-1,3,4-triethylimidazolium, 2-dimethylamino-1,3-dimethylimidazolium, 2-dimethylamino-1-ethyl-3-methylimidazolium,
2-Diethylamino-1,3-diethylimidazolium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5
6,7-Tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 1,5-dihydro-
1,2-Dimethyl-2H-pyrimido- [1,2a] imidazolium, 2-dimethylamino-3-cyanomethyl-
1-methylimidazolium, 2-dimethylamino-acetyl-1,3-dimethylimidazolium, 2-dimethylamino-4-methylcarboxymethyl-1,3-dimethylimidazolium, 2-dimethylamino-4-methoxy-1 , 3-dimethylimidazolium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolium,
2-dimethylamino-3-formylmethyl-1-methylimidazolium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolium and the like;

(I-10) Guanidium having a tetrahydropyrimidinium skeleton having 4 to 30 or more carbon atoms; 2
-Dimethylamino-1,3,4-trimethyltetrahydropyrimidinium, 2-diethylamino-1,3,4-
Trimethyltetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyltetrahydropyrimidinium, 2-diethylamino-1-methyl-3,
4-diethyltetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyltetrahydropyrimidinium, 2-diethylamino-1,3-dimethyltetrahydropyrimidinium, 2-diethylamino-1,3-diethyltetrahydropyrimidinium , 1, 3, 4, 6,
7,8-Hexahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6,7,
8-Hexahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2,3,4,6-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2]
a] Pyrimidinium, 2-dimethylamino-3-cyanomethyl-1-methyltetrahydropyrimidinium, 2-
Dimethylamino-4-acetyl-1,3-dimethyltetrahydropyrimidinium 2-dimethylamino-4-methylcarboxymethyl-1,3-dimethyltetrahydropyrimidinium, 2-dimethylamino-3-methylcarboxymethyl-1- Methyltetrahydropyrimidinium,
2-Dimethylamino-3-methoxymethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino-4
-Formyl-1,3-dimethyltetrahydropyrimidinium, 2-dimethylamino-3-hydroxyethyl-1
-Methyltetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyltetrahydropyrimidinium and the like;

(I-11) Guanidium having a dihydropyrimidinium skeleton having 4 to 30 carbon atoms or more; 2-dimethylamino-1,3,4-trimethyl-2,4 (6)
-Dihydropyrimidinium, 2-diethylamino-1,
3,4-trimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-methyl-3,4-diethyl-2,4 (6) -dihydropyrimidinium, 2-
Diethylamino-1-methyl-3,4-diethyl-2,
4 (6) -dihydropyrimidinium, 2-diethylamino-1,3,4-triethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-2,4 (6) -Dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-
3-methyl-2,4 (6) -dihydropyrimidinium,
1,6,7,8-tetrahydro-1,2-dimethyl-2
H-imido [1,2a] pyrimidinium, 1,6-dihydro-1,2-dimethyl-2H-imido [1,2a] pyrimidinium, 1,6-dihydro-1,2-dimethyl-
2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino-4-cyano-1,3-dimethyl-2,4
(6) -Dihydropyrimidinium, 2-dimethylamino-4-acetyl-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl- 2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-methylcarboxymethyl-1-methyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-methoxy-1, Three
-Dimethyl-2,4 (6) -dihydropyrimidinium,
2-Dimethylamino-4-formyl-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-2,4
(6) -Dihydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-2,4
(6) -dihydropyrimidinium and the like;

As the tertiary phosphonium cation (II),
The following (II-1) to (II-3) can be mentioned. (II-1) Aliphatic tertiary phosphonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; trimethylsulfonium, triethylsulfonium, ethyldimethylsulfonium, diethylmethylsulfonium, etc .; (II-2) carbon Aromatic tertiary phosphonium having a number of 6 to 30 or more; phenyldimethylsulfonium, phenylethylmethylsulfonium, phenylmethylbenzylsulfonium, etc .; (II-3) alicyclic tertiary phosphonium having a carbon number of 3 to 30 or more Methylthiolanium, phenylthiolanium,
Methyl thianium, etc .;

Examples of the quaternary phosphonium cation (III) include the following (III-1) to (III-3). (III-1) alkyl having 1 to 30 or more carbon atoms and / or
Or an aliphatic quaternary phosphonium having an alkenyl group; tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, methyltriethylphosphonium, methyltripropylphosphonium, methyltributylphosphonium, dimethyldiethylphosphonium, dimethyldipropylphosphonium, Dimethyldibutylphosphonium, trimethylethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, etc .; (III-2) aromatic quaternary phosphonium having 6 to 30 or more carbon atoms; triphenylmethylphosphonium, diphenyldimethylphosphonium, triphenylbenzyl Phosphonium, etc .; (III-3) Alicyclic quaternary phosphonium having 3 to 30 or more carbon atoms; 1,1-Dimethy Ruphosphoranium, 1-methyl-1-ethylphosphoranium, 1,1-diethylphosphoranium, 1,1-dimethylphosphorinanium, 1-
Methyl-1-ethylphosphorinanium, 1,1-diethylphosphorinanium, 1,1-pentaethylenephosphorinanium and the like;

Examples of the quaternary oxonium cation (IV) include the following (IV-1) to (IV-3). (IV-1) Aliphatic tertiary oxonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; trimethyloxonium, triethyloxonium, ethyldimethyloxonium, diethylmethyloxonium, etc .; (IV -2) aromatic tertiary oxonium having 6 to 30 or more carbon atoms; phenyldimethyloxonium, phenylethylmethyloxonium, phenylmethylbenzyloxonium, etc .; (IV-3) having 3 to 30 carbon atoms or more Alicyclic tertiary oxonium; methyloxoranium, phenyloxolanium, methyloxanium, etc .;

Of these, preferred onium cations are (I), and more preferred are (I-1), (I-4) and (I-
5), and particularly preferred are (I-4) and (I-5). These onium cations may be used alone or in combination of two or more.

In the present invention, the method of introducing the onium cation into the polymer includes, for example, a method of substituting the proton of the carboxyl group and / or the sulfonic acid group of the polymer with the onium cation. As a method for substituting a proton with an onium cation, any method may be used as long as it can be substituted with a predetermined amount of an onium cation. For example, a hydroxide salt of the onium cation (for example, tetraethylammonium hydroxide) Or monomethyl carbonate salt (eg 1, 2, 3, 4
-Trimethylimidazolinium monomethyl carbonate, etc.) can be easily replaced by adding dehydration, decarboxylation, or demethanol to the polymer having a carboxyl group and / or a sulfonic acid group. Moreover, you may substitute similarly at the stage of a monomer. Regarding the step of substituting with an onium cation, for example, a method of substituting a monomer containing a carboxyl group and / or a sulfonic acid group with an onium cation and then polymerizing, or a polymer having a carboxyl group and / or a sulfonic acid group is prepared. After that, a method of substituting the proton of the acid with an onium cation and the like can be mentioned, but any step may be performed as long as the proton of the carboxylic acid and / or sulfonic acid of the final polymer is replaced. ..

The degree of substitution (degree of substitution) of the carboxyl group and / or sulfonic acid group protons with the above-mentioned onium cation is such that the final product is used (for example, a non-aqueous absorbent sheet or a non-aqueous water absorbent, a gelling agent for an electrolytic solution). However, the degree of substitution is usually 30 to 100 mol%, preferably 50 to 100 mol%, more preferably 70 to 1 mol%.
It is 00 mol%. Further, in the case where the application is a gelling agent for a lithium battery containing a lithium salt, the substitution degree is preferably as high as 90 to 100 mol% from the viewpoint of reducing active protons. When the degree of substitution with the onium cation is less than 30 mol%, the dissociation of the carboxyl group, sulfonic acid group and onium cation of the polymer (1) is too low, resulting in low swelling power and gelling power, and depending on the application, there are many active protons. There is a case where the electrical characteristics are deteriorated due to excess.

In the present invention, the polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group, and having a predetermined amount of the carboxyl group and / or the sulfonic acid group substituted with an onium cation. ) Is finally crosslinked at any stage to form a crosslinked product. The method of crosslinking may be a known method, and examples thereof include the following methods. Cross-linking with a copolymerizable cross-linking agent; the carboxyl group- and / or sulfonic acid group-containing monomer (a '), an onium cation substitution product of the monomer, and a monomer or a molecule which is copolymerizable with another monomer (b) which is optionally copolymerized. Copolymerizable cross-linking agent having two or more double bonds inside [polyvalent vinyl cross-linking agent such as divinylbenzene, (meth) acrylamide cross-linking agent such as N, N'-methylenebisacrylamide, pentaerythritol triallyl ether And a polyvalent (meth) acrylic acid ester type cross-linking agent such as trimethylolpropane triacrylate].

Cross-linking with a reactive cross-linking agent; two functional groups capable of reacting with a functional group of a monomer having a carboxyl group and / or a sulfonic acid group or an onium cation substitution product thereof, a monomer to be copolymerized if necessary, in the molecule. Reactive crosslinking agent having the above [polyvalent isocyanate type crosslinking agent such as 4,4′-diphenylmethane diisocyanate, polyvalent epoxy type crosslinking agent such as polyglycerol polyglycidyl ether, polyhydric alcohol type crosslinking agent such as glycerin, hexamethylenetetramine Or a polyvalent amine such as polyethyleneimine, an imine-type crosslinking agent, a haloepoxy-type crosslinking agent such as epichlorohydrin, a polyvalent metal salt-type crosslinking agent such as aluminum sulfate, and the like]. Cross-linking with a polymerization-reactive cross-linking agent; a carboxyl group- and / or sulfonic acid group-containing monomer (a '), an onium cation substitution product of the monomer, and optionally a copolymerizable or molecule with another monomer (b) Polymerization having a functional group capable of reacting with a functional group of a monomer having a double bond in the interior and having a carboxyl group and / or a sulfonic acid group or an onium cation substitution product thereof, a monomer to be copolymerized if necessary, in the molecule Reactive cross-linking agent [glycidyl (meth) acrylate type cross-linking agent such as glycidyl methacrylate,
Crosslinking using an allylepoxy type crosslinking agent such as allylglycidyl ether].

Crosslinking by irradiation: A method for crosslinking the polymer (1) by irradiating the polymer (1) with radiation such as ultraviolet rays, electron beams, γ rays, microwaves, etc., and ultraviolet rays and electron beams for the monomers. , Irradiation with radiation such as γ-rays and microwaves to simultaneously carry out polymerization and crosslinking. Crosslinking by heating: The polymer (1) is heated to 100 ° C. or higher to thermally crosslink between the molecules of the polymer (1) [crosslinking between carbons due to generation of radicals by heating or crosslinking between functional groups]. Method etc. Among these cross-linking methods, preferable ones are and, though comprehensively considering, depending on the use and form of the final product.

Among the above-mentioned copolymerizable cross-linking agents, preferred are polyvalent (meth) acrylamide type cross-linking agents, allyl ether type cross-linking agents, and polyvalent (meth) acrylic acid ester type cross-linking agents, and more preferred ones. , An allyl ether type cross-linking agent. Among the reactive cross-linking agents, preferred are polyvalent isocyanate type cross-linking agents and polyvalent epoxy type cross-linking agents, and more preferable ones are polyvalent isocyanate type cross-linking agents having 3 or more functional groups in the molecule or It is a polyvalent epoxy type crosslinking agent. The degree of crosslinking can be appropriately selected depending on the purpose of use, but when a copolymerizable crosslinking agent is used, 0.001 to 10% by weight based on the total weight of the monomers.
Is preferred, and 0.01 to 5% by weight is more preferred. The addition amount when using a reactive cross-linking agent, the preferred addition amount depends on the type of what is created using the cross-linked body of the present invention, when creating a non-aqueous absorbent sheet or non-aqueous absorbent described below, 0.001-1 based on total polymer weight
0% by weight is preferable, and 0.01 to 50% by weight is preferable when forming an integrated gel containing an organic solvent described later.

In the present invention, the method of polymerizing the above-mentioned carboxyl group- and / or sulfonic acid group-containing monomer, the onium cation substitution product of the monomer, and optionally the other monomer (b) to be copolymerized may be a known method. Solution polymerization method in a solvent in which each of the monomers and the polymer to be produced are dissolved, a bulk polymerization method in which polymerization is performed without using a solvent,
Examples thereof include emulsion polymerization method. Of these, the solution polymerization method is preferable. The organic solvent by solution polymerization can be appropriately selected depending on the solubility of the monomer or polymer used, but examples thereof include alcohols such as methanol and ethanol, carbonates such as ethylene carbonate, propylene carbonate and dimethyl carbonate, and γ-butyrolactone. Lactones, lactones such as ε-caprolactam, ketones such as acetone and methyl ethyl ketone, carboxylic acid esters such as ethyl acetate, ethers such as tetrahydrofuran and dimethoxyethane, aromatic hydrocarbons such as toluene and xylene, and water, etc. Can be mentioned. These solvents may be used alone or in combination of two or more. The polymerization concentration in the solution polymerization is also not particularly limited and varies depending on the intended use, but is preferably 1 to 80% by weight, more preferably 5 to 60% by weight.

The polymerization initiator may also be a conventional one, such as azo initiators [azobisisobutyronitrile, azobiscyanovaleric acid, azobis (2,4-dimethylvaleronitrile),
Azobis (2-amidinopropane) dihydrochloride, azobis {2-methyl-N- (2-hydroxyethyl} proropionamide), etc.], peroxide initiators [benzoyl peroxide, di-t-butyl peroxide] , Cumene hydroperoxide, succinic acid peroxide, di (2-ethoxyethyl) peroxydicarbonate, hydrogen peroxide, etc.], redox initiator [the above-mentioned peroxide-based initiator and reducing agent (ascorbic acid or persulfate And the like]] can be exemplified. As another polymerization method,
Examples thereof include a method of adding a photosensitization initiator [benzophenone and the like] and irradiating with ultraviolet rays, a method of irradiating with radiation such as γ-rays and electron beams, and polymerizing. When the polymerization initiator is used, the amount of the initiator added is not particularly limited, but is preferably 0.0001 to 5%, more preferably 0.001 to 2%, based on the total weight of the monomers used. The polymerization temperature also varies depending on the desired molecular weight, the decomposition temperature of the initiator, the boiling point of the solvent used, etc., but is preferably -20 to 200 ° C, more preferably 0 to 100 ° C.

The non-aqueous absorber (B) of the present invention is characterized by comprising the cross-linked product (A) obtained as described above, and it can be processed into various forms depending on its purpose, but is not particularly limited, but a preferred form. Examples thereof include a particulate form and a sheet form. Hereinafter, a description will be given of a creation method of a preferable mode. However, since the creation method and the like, the preferred method, and the like are slightly different depending on the mode, each will be described.
When the non-aqueous absorber (B) composed of the crosslinked product (A) of the present invention is made into particles, the particle diameter thereof is 1 to 5,0 in terms of average particle diameter.
00 μm is preferable, and more preferably 50 to 2,000.
μm. The method for obtaining a particulate form is not particularly limited as long as it finally becomes a particulate form, for example, the following (i)
Methods such as ~ (iv) are mentioned. The liquid retention amount of (B) of the present invention varies depending on the kind of the target organic solvent, the polymer composition, gel strength, etc., but is selected from propylene carbonate, γ-butyrolactone, methanol, and ethanol. The liquid retention amount for the solvent is 10
It is preferably designed to 1,000 g / g, more preferably 30 to 900 g / g, and particularly preferably 50 to
It is 500 g / g. When the liquid retention amount is 10 g / g or more,
Compared with conventional non-aqueous absorbers, the liquid retention is significantly larger.
When it is 000 g / g or less, there is no problem that the gel strength of the non-aqueous absorber holding the organic solvent is too weak.

(I); a non-aqueous absorber (B) consisting of the cross-linked body (A) of the polymer (1) is prepared by copolymerizing the above-mentioned copolymerizable cross-linking agent using a solvent, if necessary. The solvent is distilled off by a method such as drying, and the particles are pulverized into particles by a known pulverization method. (ii); Polymer is polymerized by using a solvent if necessary (1)
After preparing the above, after cross-linking the polymer (1) by means of the reactive cross-linking agent or irradiation, if necessary, the solvent is distilled off by a method such as drying, and crushed by a known crushing method. How to make particles. (iii); The carboxyl group- and / or sulfonic acid group-containing monomer (a ') and, if necessary, another monomer (b) are copolymerized in the presence of the copolymerizable crosslinking agent, if necessary, with a solvent to crosslink. After polymerizing, the onium cation compound is added, and the proton of the acid group is replaced with a predetermined amount of onium cation, and then the solvent is distilled off by a method such as drying, if necessary, and crushed by a known crushing method. To make particles.

(Iv); copolymerizing the carboxyl group- and / or sulfonic acid group-containing monomer (a ') and optionally other monomer (b) in the presence of the copolymerizable cross-linking agent and optionally using a solvent. After the uncrosslinked polymer is polymerized, the onium cation compound and the reactive crosslinking agent and irradiation are carried out to replace the proton of the acid group and simultaneously crosslink the polymer, and, if necessary, to remove the solvent by a method such as drying. A method of distilling off and pulverizing into particles by a known pulverizing method. In the process of making the shape of the non-aqueous absorber (B) composed of the crosslinked body (A) into particles, the drying that is performed as necessary may be a known drying method, for example, aeration drying (circulation dryer, etc.), Air-permeable drying (band type dryer etc.), reduced pressure drying (vacuum dryer etc.), contact drying (drum dryer etc.), etc. can be mentioned. The drying temperature in the case of drying is not particularly limited as long as the polymer or the like is not deteriorated or excessively crosslinked, but is preferably 0 to 200 ° C., more preferably 50.
~ 150 ° C. When the shape is particulate, a known pulverization method may be used. For example, impact pulverization (pin mill,
A cutter mill, a ball mill type crusher, a high-speed rotary crusher such as an ACM palperizer, etc.), air crushing (jet crusher etc.), freeze crushing and the like can be mentioned.

The non-aqueous absorbent (B) comprising the cross-linked product (A) thus particulate is capable of absorbing an organic solvent and can be used as the non-aqueous absorbent (E). When used as the non-aqueous absorbent (E), the liquid retention amount with respect to an organic solvent selected from propylene carbonate, γ-butyrolactone, methanol, and ethanol is 10 to 1,000.
It is preferably designed to be 0 g / g, more preferably 30
To 900 g / g, particularly preferably 50 to 500 g
/ G. When the liquid holding amount is 10 g / g or more, the liquid holding amount is significantly larger than that of the conventional nonionic absorbent, and
When it is 0 g / g or less, there is no problem that the gel strength of the absorbent holding the organic solvent is too weak.

Next, the case where the shape (B) of the present invention is a sheet will be described. Examples of the method for forming a sheet include the following methods (v) to (vii). (v); A method of sandwiching the particulate non-aqueous absorber (B) between a non-woven fabric, paper or the like to form a sandwich sheet. (vi); a non-crosslinked body of the polymer (1) is a non-woven fabric, a woven fabric,
After impregnating and / or coating one or more base materials selected from the group consisting of paper and film, crosslinking with the above-mentioned crosslinking agent, crosslinking by irradiation with radiation such as ultraviolet rays, electron beams, γ rays, and heating. A method of cross-linking the polymer (1) using one or more cross-linking means selected from the group of cross-linking according to 1. and distilling off the solvent if necessary to form a sheet. (vii); 20 to 100% by weight of a carboxyl group- and / or sulfonic acid group-containing monomer in which 30 to 100 mol% of the proton is substituted with the onium cation, 0 to 80% by weight of another copolymerizable monomer, and the above-mentioned crosslinking After impregnating and / or coating the mixed solution containing the agent on one or more base materials selected from the group consisting of non-woven fabric, woven cloth, paper and film, the base material is polymerized with a polymerization initiator and / or Alternatively, polymerization is carried out using one or more crosslinking means selected from the group consisting of crosslinking by irradiation of ultraviolet rays, electron beams, γ rays and the like and crosslinking by heating, and a solvent is distilled off if necessary to form a sheet. Method.

Among these methods, (vi) or (vii) is preferable from the viewpoint of the ease of adjusting the thickness of the formed sheet and the absorption rate of the formed sheet. When the shape is a sheet, the thickness of the sheet is preferably 1 to 5,000 μm, more preferably 5 to 2,000, and 10 to 1,000.
μm is particularly preferred. When the thickness of the sheet is 1 μm or more, the basis weight of the above (B) becomes sufficient, and 5,000 μ
If it is m or less, the thickness of the sheet is sufficient. The length and width of the sheet can be appropriately selected depending on the purpose and application of use and are not particularly limited, but the preferable length is 0.01 to 1
0000 m, preferred width is 0.1 to 300 cm. The basis weight of (B) of the present invention in the sheet (C) is not particularly limited, but considering the absorption / retention capacity of the target organic solvent and the fact that the thickness does not become too thick, etc. the amount is preferably from 10~3,000g / m ^2, more preferably 20~1,000g / m ^2.

In the present invention, a substrate such as a non-woven fabric, a woven fabric, a paper or a film, which is optionally used for forming a sheet, may be a known one, for example, a basis weight of 10 to 10.
Examples are non-woven fabrics or woven fabrics made of about 500 g of synthetic fibers and / or natural fibers, paper (fine paper, thin paper, Japanese paper, etc.), films made of synthetic resin, two or more substrates of these, and composites thereof. be able to. Among these substrates, preferred are non-woven fabrics and composites of non-woven fabrics and films, and particularly preferred are composites consisting of non-woven fabrics on one side and non-liquid permeable one side. In the present invention, the thickness of these base materials is preferably 1 to
5,000 μm, more preferably 10 to 2,000 μm
Is. When the thickness is 1 μm or more, impregnation and coating with a predetermined amount of the polymer (1) are easy to perform, while when the thickness is 5,000 μm or less, the sheet is not too thick and easy to use. The polymer (1) of the present invention may be applied to or impregnated on the substrate by a known method, for example, a conventional coating or padding method may be applied. After that, the solvent used for polymerization, dilution, viscosity adjustment, etc. may be distilled off by a method such as drying, if necessary.

The sheet containing the non-aqueous absorbent body (B) of the present invention thus produced efficiently absorbs an organic solvent, and thus is used as the non-aqueous absorbent sheet (D).
It is mainly used for the purpose of non-aqueous absorption sheet and leakage prevention sheet for organic solvent electrolytes for organic solvents, lithium primary batteries, secondary batteries and capacitors. The non-aqueous absorbent sheet (D) has an absorption amount that varies depending on the purpose of use, but has a liquid retention amount (absorption amount after centrifugal dehydration) of 0.1 to 10 relative to propylene carbonate, which is a typical solvent for lithium batteries.
A sheet of 0 g / cm ² is preferable, and 1 to 100 g / cm ²
Are more preferred. When the liquid holding amount is 0.1 g / cm ² or more, the electrolytic solution and the like can be sufficiently held, and when the liquid holding amount is 100 g or less, the sheet absorbing the organic solvent does not become too thick.

Another aspect of the present invention is a non-aqueous gel (C) comprising a non-aqueous absorber (B) and an organic solvent (2). The ratio of the non-aqueous absorber (B) / non-aqueous organic solvent in the non-aqueous gel (C) is preferably 0.1 to 99/1 to 99.9% by weight, more preferably 0.5 to 50/50 to 99.5% by weight, particularly preferably 1 to 30/70 to 99% by weight, and most preferably 1 to 20/80 to 99% by weight. When the ratio of (B) is 0.1% by weight or more, the gel strength of the non-aqueous gel produced is sufficient and the entire gel can be obtained, while the content is 9%.
When it is 9.9% by weight or less, the content of the (B) is sufficient, and when it is used for gelation of the electrolytic solution, the conductivity of the gel is lowered, and the required electrolytic solution and the electrolyte described later are not used. The added amount will not be too low and the capacity will not be insufficient.

As the organic solvent (2) used in the non-aqueous gel (C) of the present invention, the same organic solvents as mentioned above can be mentioned, for example, methanol, ethanol, propanol,
Alcohol-based organic solvent such as butanol, glycol-based organic solvent such as ethylene glycol and propylene glycol, carbonate-based organic solvent such as dimethyl carbonate, ethylene carbonate and propylene carbonate, ketone-based organic solvent such as acetone, dimethyl ketone and methyl ethyl ketone, diethyl ether , Ether organic solvents such as ditoxyethane, tetrahydrofuran and dioxane, aliphatic hydrocarbon organic solvents such as hexane and octane, aromatic hydrocarbon organic solvents such as toluene and xylene, methyl acetate, ethyl acetate and propyl acetate Examples thereof include carboxylic acid ester organic solvents, lactone organic solvents such as γ-butyrolactone, and lactam organic solvents such as ε-caprolactam. Among these, preferred organic solvents are propylene carbonate, ethylene carbonate, dimethyl carbonate, dimethoxyethane, which are solvents for lithium batteries, γ-butyrolactone, ε-caprolactam, which are solvents for capacitors, and solvents for solid fuels and ignition agents. Specific examples include methanol, ethanol, propanol; and also one or a mixture of two or more of toluene, xylene, propylene glycol and the like.

In the present invention, the non-aqueous organic solvent may be a solvent containing a salt such as Li, which is an electrolyte used in a lithium battery or the like, in the solvent, if necessary. Examples of preferable types of Li salt contained in the organic solvent include LiClO ₄ , LiBF ₄ , and Li.
PH ₆ , LiAsF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ S
One or more of O ₂ ) ₂ and more preferred salts are LiBF ₄ and / or LiPH ₆ . The content of the Li salt added as necessary can be variously selected depending on the purpose and necessity, Li solubility, etc., but the content of 0.5 to 50% by weight in the weight of the organic solvent is preferable, and more preferable. Is a solvent containing 1 to 20% by weight. still,
In the present invention, when the organic solvent containing the lithium salt is used, the proton of the carboxyl group and / or the sulfonic acid group may react with the lithium salt. Therefore, the degree of substitution of the proton by the onium cation in this case is Is preferably 90 to 100 mol%, more preferably 98 to 100 mol%.

As a method for producing the non-aqueous gel (C),
For example, (viii) to (xi) below are listed, but (x) and (xi)
It is preferable to prepare an integrated gel by the method mentioned above. (viii) A method of adding a predetermined amount of (2) to the above-mentioned particulate non-aqueous absorber (B) of the present invention; (ix) Adding (2) to a sheet containing (B). Method: (x); The polymer (1) is dissolved in the (2), and the (1)
(Xi); a method of forming an integrated gel by cross-linking with any of the above-mentioned cross-linking agents, cross-linking by irradiation with ultraviolet rays, radiation such as electron beam or γ-ray, and cross-linking by heating; In 2), the onium cation is 30 to 1
Carboxyl groups substituted with 00 mol% of protons and /
Alternatively, 20 to 100% by weight of the sulfonic acid group-containing monomer, and optionally 0 to 80% by weight of another copolymerizable monomer are polymerized in the presence of the copolymerizable cross-linking agent to form an integrated gel. Method.

The form of the gel composed of the non-aqueous absorber (B) and the organic solvent can be appropriately selected according to the purpose and application, and examples of the form include a sheet, a block, a sphere, and a circle. A columnar shape or the like can be exemplified. Among these, the preferred shape is a sheet shape or a block shape, and particularly when used as a gel battery of a mobile phone or a computer, a sheet shape is preferred. The thickness of the gel in the case of a sheet gel is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm. Regarding the width and length of the sheet gel, its purpose and place,
It may be appropriately selected according to the purpose of use. There is no particular limitation on the method for producing the gel in these shapes, for example, a method of gelling in a container or a cell according to the shape to be produced, release paper, film, non-woven fabric, etc., and the polymer (1) Examples thereof include a method of forming a sheet-like gel by a method such as laminating or coating a mixture of (2) with a monomer or the like.

The non-aqueous absorbent (B) or the non-aqueous absorbent (E) and / or the non-aqueous gel (C) of the present invention can gelate a large amount of a large amount of organic solvent for a lithium battery.
Therefore, the ratio of the electrolytic solution can be increased, and as a result, the ionic conductivity can be increased, and thus the gelling agent can be preferably used as a gelling agent for a lithium battery.
When the (B), (C), (D) and (E) are used as a gelling agent for a lithium battery, a sheet-like cross-linked product from the viewpoint of contactability with an electrode (interfacial interface). A non-aqueous gel (C) formed by absorbing an organic solvent containing the above lithium electrolyte, or an integrated non-aqueous gel (C) consisting of the above-mentioned non-aqueous absorber (B) and the above organic solvent containing a lithium electrolyte. Can be used as From the above, not only organic solvent-based non-aqueous absorbents (E), non-aqueous gels (C) and non-aqueous absorbent sheets (D), but also organic solvent-based batteries and capacitors for electronic and electric devices and automobiles,
It is useful for a wide range of applications such as leakage-preventing sheets for capacitors and liquid-stopping agents, organic solvent-based batteries and gel electrolyte batteries for capacitors, alcohol-based solid fuels, and ignition agents.

[0047]

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% means% by weight.

Example 1 360 g (5 mol) of acrylic acid, 1.08 g of pentaerythritol triallyl ether and 1140 g of water were placed in a 2-liter adiabatic polymerization tank. The temperature of the monomer solution is 0
After cooling to 0 ° C and passing dissolved nitrogen through the solution to reduce dissolved oxygen, 0.36 g of 2,2'-azobis (2-amidinopropane) hydrochloride as a polymerization initiator and 35
% Hydrogen peroxide water 3.1 g and L-ascorbic acid 0.38
g was added to initiate the polymerization. After polymerization, the resulting hydrous gel was subdivided into gels using a meat chopper, and 60% of methyl carbonate (molecular weight: 203) of 1,2,3,4-trimethylimidazolinium cation was added to the gel. 1353 g of methanol solution (manufactured by Sanyo Kasei Co., Ltd.)
When (4 mol) was added, decarboxylation and demethanol were observed to occur. The gel containing the imidazolinium cation was passed through a band-type dryer (aeration dryer, manufactured by Inoue Metal Co., Ltd.) to pass hot air of 100 ° C. through the gel, and water used as a solvent and a by-product. The methanol formed was distilled off and dried. The dried product is crushed using a cutter mill, and the cross-linked product of the present invention (A having an average particle diameter of 400 μm) is used.
A non-aqueous absorber (B1) consisting of 1) was obtained.

Example 2 Instead of the methyl carbonate of the 1,2,3,4-trimethylimidazolinium cation used in Example 1, triethylammonium hydroxide (molecular weight: 14
3307 g of a 20% aqueous solution of 7) (manufactured by Sanyo Chemical Industry Co., Ltd.)
The same operation as in Example 1 was carried out except that (4.5 mol) was added to obtain a non-aqueous absorber (B2) comprising the particulate cross-linked product (A2) of the present invention.

Example 3 184 g (1 mol) of p-styrenesulfonic acid, 104 g (1 mol) of styrene and 1.8 g of divinylbenzene were dissolved in 500 g of ethyl acetate. In this monomer solution,
332 g (0.8 mol) of a 45% ethanol solution of 1-ethyl-3-methylimidazolium cation monomethyl carbonate (molecular weight: 187) (manufactured by Sanyo Kasei Co., Ltd.) was added, and a part of protons of sulfonic acid was added. Substituted with imidazolium cation. After reducing dissolved oxygen by passing nitrogen through this monomer solution, the monomer solution was heated to 60 ° C. using a water bath, and 0.6 g of azobis-2,4-dimethylvaleronitrile was diluted with 12 g of a polymerization initiator. The solution was dropped and polymerized. The generated gel containing toluene was subdivided, and was dried using a vacuum dryer to obtain 10
The solvent dried at 50 ° C. under reduced pressure of 0 hectopascals was distilled off. The dried product was crushed using a cutter mill to obtain a non-aqueous absorber (B3) consisting of the cross-linked product (A3) of the present invention in the form of particles having an average particle diameter of 400 μm.

Comparative Example 1 The method described in Example 3 of JP-A-58-154709, that is, 100 g of an 80% aqueous solution of methacryloxyoxyethyltrimethylammonium chloride, which is a monomer having a quaternary amino group, and N--N were used. 0.06 g of methylenebisacrylamide was mixed, and 0.8 g of 2,2'-azobis (2-amidinopropane) hydrochloride was further added and mixed as an initiator. Add this solution to 8
Polymerization was carried out by placing in a box-shaped container heated in a constant temperature water bath of 5 ° C. Take out the polymer, crush it with a cutter mill,
A non-aqueous absorber (B'-1) made of a comparative cationic crosslinked body (A'-1) having an average particle diameter of 400 μm was obtained.

Comparative Example 2 The method described in Example 1 of JP-A-60-179410, that is, 5 equipped with a stirrer, a cooler, and a dropping funnel.
230 ml of cyclohexane in a 00 ml round bottom flask,
Ethyl cellulose (1.0 g) was charged and the temperature was raised to 75 ° C. Separately, 12 g of acrylic acid, 26.2 g of dimethylaminoethyl methacrylate, which is a monomer containing a tertiary amino group, and 70 g of distilled water were mixed in an Erlenmeyer flask, and further 3
5 g of 5% hydrochloric acid and 0.5 g of N, N-methylenebisacrylamide were added and uniformly dissolved. To this monomer solution, 0.02 g of ammonium persulfate was added as an initiator, and this solution was added dropwise to the round bottom flask over 1.5 hours for polymerization. After the polymerization, cyclohexane was removed by decantation, and the resulting bead-shaped particles were dried at 90 ° C. using a vacuum dryer to obtain a non-comprised comparative crosslinked product (A′-2) having an average particle size of about 200 μm. An aqueous absorber (B'-2) was obtained.

Comparative Example 3 The method described in Example 1 of JP-A-3-221582,
That is, 50 equipped with a thermometer, a gas introduction pipe and a cooler
In a 0 ml round-bottomed flask, 2 g of complete valence Poval and 0.8 g of partial valence Poval (degree of valence of about 80%) (300 g) were put into water, and the dissolved oxygen was replaced with nitrogen.
Heated to 40 ° C. Thereafter, 99.823 g of a monomer, dodecyl acrylate, 0.177 g of a ethylene glycol diacrylate, which is a cross-linking agent, and azobis-2,4-dimethylvaleronitrile, which is a polymerization initiator, 0.1.
A solution consisting of 5 g was added at once to the flask,
Stir vigorously at a stirring speed of pm. Then, the temperature inside the flask was raised to 70 ° C., and polymerization was performed at that temperature for 2 hours.
Thereafter, the temperature inside the flask was raised to 80 ° C. and maintained for 2 hours to complete the polymerization. After the polymerization, the bead-shaped cross-linked polymer is separated by filtration, the particles are washed with water and then dried,
A comparative cross-linked product (A′−) having an average particle size of about 300 μm
A non-aqueous absorber (B'-3) consisting of 3) was obtained.

Comparative Example 4 The method described in Example 1 of JP-A-11-356632,
That is, in a glass casting polymerization vessel (thickness 1 cm) equipped with a thermometer and a gas introduction tube, 99.827 g of methoxyethyl acrylate and 0.173 g of hexanediol diacrylate as a cross-linking agent and azobis (2,2) as an initiator. A mixed solution of 0.1 g of 4-dimethylvaleronitrile) was injected and the mixture was heated at 50 ° C. for 4 hours in a nitrogen stream to carry out polymerization. Then, the temperature was raised to 80 ° C. and maintained for 2 hours to complete the polymerization. After cooling the polymer to 0 ° C., the polymer was pulverized with a cutter mill, and a non-aqueous absorber (B′-4) made of a comparative crosslinked product (A′-4) having an average particle size of about 500 μm.
Got

Comparative Example 5 The method described in Example 8 of JP-A-4-230250,
That is, 40 g of N-vinylacetamide and N, N'-1 which is a cross-linking agent were placed in a 200 ml separable flask equipped with a nitrogen inlet tube, a thermometer and an exhaust port in a bath kept at 30 ° C. , 4-butylene bisacetamide 2.
0 mg was dissolved in 150 g of water, and nitrogen was introduced into the system at 1 l / min to degas dissolved oxygen. Then, 120 mg of 2,2'-azobis (2-amidinopropane) hydrochloride dissolved in 10 ml of degassed water was added, and 12
The soil was leveled and polymerized. The obtained hydrous gel is cut with a mixer equipped with a cutter and washed with acetone,
It was vacuum dried at 12 ° C for 12 hours. The dried particles were further pulverized with a cutter mill to obtain a non-aqueous absorber (B'-5) made of a comparative crosslinked product (A'-5) having an average particle diameter of 400 μm.

Comparative Example 6 The polymer gel obtained in Example 1 was mixed with 60% of methyl carbonate of 1,2,3,4-trimethylimidazolinium cation.
% Methanol solution (manufactured by Sanyo Kasei Co., Ltd.)
% Aqueous ammonia solution 226.7 g (4 mol) was used, the same operation as in Example 1 was carried out to obtain an average particle size of 400 μm.
A non-aqueous absorber (B'-6) consisting of the comparative crosslinked product (A'-6) of m was obtained.

Non-aqueous absorbers (B1) to (B3) made of the particulate cross-linked body of the present invention and non-aqueous absorbers (B'-1) to (B'-6) made of the comparative particulate cross-linked body. The amount of liquid absorption and the amount of liquid retention with respect to various organic solvents of 1) were measured by the following methods. The results are shown in Table 1. [Measurement of liquid absorption and liquid retention] Measurement of liquid absorption; width 10c
m, 20 cm long nylon mesh bag (opening: 7
5 μm) to which 1.00 g of a particulate non-aqueous absorber is added,
After the bag was immersed in propylene carbonate for 3 hours, excess propylene carbonate was drained for 30 minutes. The same operation was performed using an empty bag, and the liquid absorption amount (g / g) was measured by the following formula. Liquid absorption amount (g / g) = weight of sample bag after swelling-weight of empty bag after immersion Measurement of liquid retention amount: Nylon mesh bag whose absorption amount was measured was centrifugal dehydrator (manufactured by Kokusan Co. It was placed in a centrifuge diameter of 15 cm and centrifuged and dehydrated for 5 minutes at a rotation speed of 1,500 rpm.The same operation was carried out for an empty bag after immersion, and the liquid retention amount was measured by the following formula. g) = weight of sample bag after dehydration-weight of empty bag after dehydration, instead of propylene carbonate, γ-butyrolactone, methanol and toluene were used to perform the same operation,
The amount of liquid absorbed and the amount of liquid retained for each solvent were measured.

[0058]

[Table 1]

Example 4 A 1-liter round bottom flask equipped with a stirrer, nitrogen inlet tube, condenser, dropping funnel, and thermometer was charged with 72 g of acrylic acid and monomethoxypolyethylene glycol acrylate (Blemmer AME-400, manufactured by NOF Corporation). , PEG (number molecular weight: about 400) 28 g and methanol 100 g were put, and the content of the flask was purged with nitrogen to replace the dissolved oxygen, and the temperature of the content was raised to 50 ° C. using a water bath. Separately, the polymerization initiator azobis-2,4-
Dimethyl valeronitrile 0.1 g, methanol 9.9 g
The solution dissolved in was added dropwise with a dropping funnel over a period of about 2 hours to polymerize while stirring under a nitrogen stream, and the polymerization was continued at 50 ° C. for 2 hours after completion of the dropping, and then the temperature was raised to 70 ° C. The polymerization was completed for 2 hours to complete the polymerization. The resulting polymer solution was cooled to room temperature and then used in Example 1,
Using a dropping funnel, 322 g (corresponding to about 0.95 mol) of a 60% methanol solution of a methyl carbonate (molecular weight 203) of 1,2,3,4-trimethylimidazolinium cation was added to a polymer in a round bottom flask. When added dropwise to the solution, decarboxylation was observed to occur with the addition. After the entire amount of the imidazolinium cation solution was dropped, stirring was continued for about 2 hours to obtain a polymer solution (polymer concentration: about 42%) substituted with the imidazolinium cation. To 100 g of this polymer solution, 798 g of γ-butyrolactone was added, and the mixture was heated at 60 ° C. under reduced pressure to distill off methanol to obtain a γ-butyrolactone solution having a polymer concentration of 5%. This γ-
0.5 g of polyglycerol polyglycidyl ether used in Example 4 was added to 100 g of butyrolactone solution, put in a 100 ml sample bottle, the sample bottle was sealed, and heated in a constant temperature bath at 70 ° C. for 1 hour for gelation. Then, a non-aqueous gel (C1) comprising a non-aqueous absorber comprising the crosslinked product of the present invention and an organic solvent was obtained.

Comparative Example 7 In order to prepare a PEO (polyethylene oxide) -based organic solvent-containing gel, polyethylene glycol (molecular weight: 400) mono was used as a monomer and a cross-linking agent described in Examples of JP-A-6-68906. 3 g of acrylate, 2 g of polyethylene glycol diacrylate, and 95 g of γ-butyrolactone as a solvent were mixed. To this γ-butyrolactone solution having a monomer concentration of 5%, azobis (2,4-dimethylvaleronitrile) 0.0
After 5 g was added and dissolved, the mixture was placed in a 100 ml sample bottle and polymerized at 60 ° C. for 5 hours under a nitrogen stream, and a non-aqueous gel (C′-1) composed of a comparative cross-linked non-aqueous absorber and an organic solvent was used. ) Got.

Comparative Example 8 5 g of acryloyltrimethylammonium chloride and 0.
1 g was dissolved in 95 g of γ-butyrolactone. Azobis (2,4-dimethylvaleronitrile), which is a polymerization initiator, was added to a γ-butyrolactone solution having a monomer concentration of 5%.
After adding and dissolving 0.05 g, the mixture was placed in a 100 ml sample bottle and polymerized under a nitrogen stream at 60 ° C. for 5 hours to obtain a non-aqueous gel consisting of a cross-linked comparative product and an organic solvent (C ′). -2) was obtained.

Regarding the non-aqueous gel (C1) of the present invention prepared in Example 4 and the comparative non-aqueous gels (C'-1) and (C'-2) prepared in Comparative Examples 7 and 8, immediately after preparation and The gelled state after aging was measured by the following method. The results are shown in Table 2. [Measurement Method of Gelled State Immediately after Preparation and After Aging] The prepared gel was observed and evaluated according to the following criteria to obtain a gelled state immediately after preparation. ⊚: The whole gelled completely, and the gel strength was strong. ◯: The whole gelled completely, but the gel strength was weak. Δ: The gel is in a semi-dissolved state, and the gel flows when the sample bottle is tilted. X: The whole is liquid and not gelled. Completely seal the sample bottle containing the created gel,
The gel was heated for 30 days in a constant temperature bath at 0 ° C., and the gel state after heating was changed to a gelled state.

Example 5 18.4 g (0.1 mol) of styrene sulfonic acid and 4% of a 45% ethanol solution of the monomethyl carbonate of the 1-ethyl-3-methylimidazolium cation used in Example 3 were used.
After adding 1.8 g (corresponding to 0.102 mol) and completely replacing the sulfonic acid protons with imidazolium cations, the mixture was heated under reduced pressure using a rotary evaporator to distill off the solvent ethanol and by-produced methanol. I left. In a glove box under an argon gas stream, 10 g of a styrene sulfonic acid monomer whose proton was completely replaced by an imidazolium cation was added to a LiPF6 at a concentration of 1
Mol / L (7.2 g / L) dissolved in 90 g of dissolved propylene carbonate, 0.1 g of trimethylolpropane triallyl ether as a copolymerizable cross-linking agent and azobis (2,4-dimethylvaleronitrile) as a polymerization initiator. )
0.1 g was added and dissolved. This monomer solution (monomer concentration: 10%) was placed in a 100 ml sample bottle and argon gas was injected into the monomer solution to replace the dissolved oxygen,
The sample bottle was completely sealed and heated in a constant temperature bath at 60 ° C. for 5 hours to obtain a non-aqueous gel (C2) composed of the non-aqueous absorber of the present invention and the organic solvent. Monomer concentration of 5%, and LiPF6 concentration of 1.5 mol / L
(10.8 g / L) The same operation as above was carried out except that dissolved propylene carbonate was used, and the non-aqueous gel (C3) of the present invention consisting of the non-aqueous absorber composed of the cross-linked product of the present invention and an organic solvent was used. Got

Comparative Example 9 Example 5 was repeated except that polyethylene glycol (molecular weight: 400) monoacrylate was used in place of styrenesulfonic acid having a proton substituted with an imidazolium cation.
The same operation as above was performed to obtain a non-aqueous gel (C′-3) and a non-aqueous gel (C′-4) each containing a non-aqueous absorber composed of a cross-linked product and an organic organic solvent for comparison.

Comparative Example 10 The same operation as in Example 5 was carried out except that acrylonitrile was used in place of styrenesulfonic acid having a proton substituted with an imidazolium cation, and a non-aqueous absorber composed of a crosslinked body and an organic solvent were used. A non-aqueous gel (C'-
5) and a non-aqueous gel (C'-6) were obtained.

Comparative Example 11 The same operation as in Example 5 was carried out except that acryloyltrimethylammonium chloride was used in place of styrenesulfonic acid having a proton substituted with an imidazolium cation, and a non-aqueous absorber composed of a crosslinked product for comparison. And non-aqueous gel (C'-7) and non-aqueous gel (C'-)
8) was obtained.

A non-aqueous gel (C which comprises the non-aqueous absorber made of the crosslinked material of the present invention obtained by the method of Example 5 and an organic solvent)
2) to (C3) and non-aqueous gels (C'-3) to (C'-8) composed of the cross-linked non-aqueous absorbers and organic solvents obtained by the methods of Comparative Examples 9 to 11, The gelled state immediately after preparation and after the aging was measured by the above method, and the ionic conductivity of the gel was measured by the following method. The results are shown in Table 2. [Measurement of ionic conductivity of gel] The prepared gel has a diameter of 1 cm.
The sample was cut out into a cylindrical shape, and the gel was sandwiched between platinum electrode disks having a diameter of 1 cm, and the ionic conductivity at 25 ° C. was measured using an impedance analyzer under the conditions of an applied voltage of 0.5 mV and a sweep frequency of 5 to 13 MHz.

[0068]

[Table 2]

Example 6 A 1-liter round-bottomed flask equipped with a stirrer, a nitrogen inlet tube, a condenser, a dropping funnel, and a thermometer was charged with 72 g of acrylic acid and monomethoxy polyethylene glycol acrylate (Blemmer AME-400, manufactured by NOF Corporation). , PEG (number molecular weight: about 400) 28 g and methanol 100 g were put, and the content of the flask was purged with nitrogen to replace the dissolved oxygen, and the temperature of the content was raised to 50 ° C. using a water bath. Separately, the polymerization initiator azobis-2,4-
Dimethyl valeronitrile 0.1 g was added to methanol 9.9.
The solution dissolved in g was added dropwise using a dropping funnel over a period of about 2 hours to polymerize while stirring under a nitrogen stream, and after the completion of dropping, the polymerization was continued at 50 ° C for 2 hours, and then the temperature was raised to 70 ° C. Then, it was polymerized for 2 hours to complete the polymerization. The resulting polymer solution was cooled to room temperature and then used in Example 1,
271 g (corresponding to about 0.8 mol) of a 60% methanol solution of methyl carbonate (molecular weight 203) of 1,2,3,4-trimethylimidazolinium cation was added to the polymer in the round bottom flask using a dropping funnel. When added dropwise to the solution, decarboxylation was observed to occur with the addition. After the entire amount of the imidazolinium cation solution was dropped, stirring was continued for about 2 hours to obtain a polymer solution (polymer concentration: about 47%) substituted with the imidazolinium cation. To 100 g of the polymer solution substituted with this imidazolinium cation, 0.047 g of polyglycerol polyglycidyl ether (Denacol 521, manufactured by Nagase Chemkex Corp., number of epoxy: about 5) which is a reactive cross-linking agent was added and mixed. Then, using a knife coater, a thickness of 200μ on the release paper.
After coating with a thickness of m, the polymer was crosslinked and the used methanol was distilled off by heating and drying for 10 minutes using a circulating air dryer at 100 ° C. After drying, the release paper was removed from the polymer to obtain a non-aqueous absorbent sheet (D1) having a thickness of about 80 μm and composed of the crosslinked product of the present invention. When the weight per unit area of this sheet was measured, the weight per unit area was about 100 g / m ² .

Example 7 A polyester / polyethylene non-woven fabric having a thickness of 47 μm (Alsima A0404WTO, manufactured by Unitika Ltd.) was immersed in a mixed solution of the polymer solution of the imidazolinium cation obtained in Example 4 and polyglycerol polyglycidyl ether. After that, the impregnation amount of the polymer solution is about 100 g
/ M ² and made like, squeezing the nonwoven fabric impregnated with a mangle, then in a circulating air dryer at 90 ° C. for 15 minutes heating and drying, the weight per unit area of about 4 nonaqueous absorber comprising a crosslinked body of the present invention
A composite non-aqueous absorbent sheet (D2) of the present invention of 7 g / m ² was obtained. When the thickness of this sheet was measured, it was about 65 μm.
Met.

Example 8 A laminated sheet (total thickness: about 55 μm) was prepared by sand-laminating polyethylene on one surface of the nonwoven fabric used in Example 7 so that the thickness was about 10 μm.
On the surface of the non-woven fabric on which polyethylene was not laminated, the weight of the mixed solution was about 100 g / m ^{2 in the} mixed solution of the polymer solution of the imidazolinium cation obtained in Example 6 and polyglycerol polyglycidyl ether. Was coated using a knife coater. Then 90
The mixture was heated and dried for 15 minutes in a circulating air dryer at ℃ to obtain a composite non-aqueous absorbent sheet (D3) having a basis weight of the non-aqueous absorbent of the cross-linked product of the present invention of about 47 g / m ² . When the thickness of this sheet was measured, it was about 75 μm.

Example 9 Methacrylic acid 84 g (1 mol) used in Example 3 1-
Monomethyl of ethyl-3-methylimidazolium cation
332g of a 45% ethanolic solution of
Equivalent) to add methacrylic acid protons to the imidazole
Substituted with um cation. (Monomer concentration: about 41%) This monomer solution was added to the copolymerizable cross-linking agent trimethylo
Propane triacrylate 0.1g and polymerization initiator
Some t-butyl peroxy neodecanoate (perbutyl
Le ND, NOF Corporation, 10-hour half-life temperature: 46.5
C.) 0.3 g was added. In this monomer solution, the thickness
Polyester non-woven fabric of about 400 μm (Appeal AN06
0), and the impregnation amount of the monomer solution is 500 g / m²
And squeezed the non-woven fabric using mangle. This monomer solution
The non-woven fabric impregnated with was heated to 80 ° C. and the blowing was stopped.
When placed in a normal air dryer, the polymerization immediately started. this
After polymerizing for 30 minutes at temperature, start blowing air for 1 hour.
By heating, the polymerization is completed and the solvent
Non-aqueous system consisting of the crosslinked product of the present invention
A composite non-aqueous absorbent sheet (D4) containing an absorber is obtained.
It was The thickness of this absorbent sheet and the non-comprising crosslinked body of the present invention
When the weight per unit area of the water-based absorber was measured, the thickness was about 450.
Micron, non-aqueous absorber weight is about 200g / m ²so
there were.

Comparative Example 12 Nonwoven fabric used in Example 7 (Alsima A0404WT
O) was used as it was as a comparative sheet (D′-1).

Comparative Example 13 The nonwoven fabric (Appeal AN040) used in Example 5 was directly used as a comparative sheet (D'-2).

Regarding the absorbent sheets (D1) to (D4) of the present invention described in Examples 6 to 9 and the comparative sheets (D'-1) (D'-2) described in Comparative Examples 12 to 13, the following will be described. The liquid absorption amount and liquid retention amount, the liquid absorption speed, the strike-through property and the strike-through rate of the non-aqueous absorbent sheet with respect to the organic solvent were measured by the following method. [Measurement of liquid absorption amount and liquid retention amount of non-aqueous absorption sheet] Measurement of liquid absorption amount of non-aqueous absorption sheet; a sheet cut into 5 x 5 cm was immersed in propylene carbonate for 3 hours, and then the sheet was clipped. After fixing with, the excess propylene carbonate was drained off for 30 minutes, and the liquid absorption amount (g /
cm ² ) was measured. Liquid absorption of sheet (g / cm ² ) = weight of sheet after swelling / 25 (cm ² ) Measurement of liquid retention of sheet: Put the sheet whose absorption has been measured into a nylon mesh bag and centrifuge. Dehydration device (manufactured by Kokusan Co., Ltd., put in a centrifugal diameter of 15 cm, centrifugally dehydrated at a rotation speed of 1,500 rpm for 5 minutes, and the liquid retention amount was measured by the following formula. Liquid retention amount (g / cm ² ) = sample after dehydration Weight of bag (g) -weight of empty bag (g) / 25 (cm ² ) Instead of propylene carbonate, γ-butyrolactone was used to perform the same operation, and the amount of liquid absorbed and retained in each solvent. Was measured.

[Measurement of liquid absorption speed] 5 × 5 on a glass plate
The cut sheet was placed in cm, and the edge of the sheet was fixed with Cellotape (registered trademark) so that the sheet was in close contact with the glass plate. 1.0 g of propylene carbonate was added to the center of the sheet using a dropper, and the time until the total amount of the added propylene carbonate was absorbed by the sheet was defined as the liquid absorption rate. [Measurement of strike-through property and strike-through rate] Five pieces of filter paper (No. 2 manufactured by Advantech Toyo Co., Ltd.) having a diameter of 12.5 cm were stacked, a sheet cut into 5 x 5 cm was placed thereon, and colored with a dye. 1.0 g of propylene carbonate was added to the center of the sheet with a dropper, and the strike-through property of the propylene carbonate absorbed by the filter paper through the sheet to the back surface of the sheet was evaluated by the following index. ◎: No strike-through, ○: Almost no strike-through, △: A little strike-through, ×: A lot of strike-through Also, by measuring the weight of the filter paper before and after the test, the strike-through rate is calculated by the following formula. It was Strikethrough rate (%) = {weight of filter paper after test (g) -weight of filter paper before test (g)} / weight of added propylene carbonate (g) x 100

[0077]

[Table 3]

The following is clear from Table 1. Non-aqueous absorbers (B1) to (B comprising the cross-linked product of the present invention
3) is a non-aqueous absorbent (B'-) composed of a cross-linked product for comparison.
Compared with 1) to (B′-6), the amount of liquid absorption and the amount of liquid retention with respect to polar solvents such as propylene carbonate, γ-butyrolactone and methanol are remarkably high. In particular, the difference is remarkable with respect to propylene carbonate, γ-butyrolactone, etc. used as the solvent of the electrolytic solution. By approaching the structure of the solvent that absorbs the polymer structure, it is possible to absorb and retain liquid even for an organic solvent having a relatively low polarity such as toluene.

The following is clear from Table 2. The non-aqueous gels (C1) to (C3) of the present invention have a small concentration of the non-aqueous absorber composed of a crosslinked product as compared with the comparative non-aqueous gels (C'-1) to (C'-8). It is possible to prepare a solid gel containing a solvent such as γ-butyrolactone or propylene carbonate and having high gel strength. The non-aqueous gels (C1) to (C3) of the present invention are remarkably excellent in stability of the gel after aging, as compared with the comparative non-aqueous gels (C′-1) to (C′-8). Non-aqueous gel (C2) (C2) composed of a non-aqueous absorber comprising the cross-linked product of the present invention containing Li ions and an organic solvent
In 3), the ionic conductivity of the gel is higher than that of the non-aqueous gel (C'-3) to (C'-8) made of a non-aqueous absorber made of a cross-linked product and an organic solvent for comparison. In particular, a non-aqueous gel (C3) comprising a non-aqueous absorbent comprising the crosslinked product of the present invention and an organic solvent
Since a solid gel having high gel strength can be prepared even in a system having a low cross-linking agent concentration and a high lithium ion concentration, the ionic conductivity of the gel can be significantly increased.

The following are clear from Table 3. The non-aqueous absorbent sheets (D1) to (D4) of the present invention have significantly higher liquid absorption and retention than propylene carbonate, γ-butyrolactone, etc., as compared with the comparative sheets (D′-1) and (D′-2). The liquid volume is high. Especially, regarding the liquid retention amount, the difference is remarkable. Furthermore, the non-aqueous absorbent sheets (D1) to (D4) of the present invention.
Has a significantly lower strike-through property and strike-through rate than the comparative sheets (D′-1) and (D′-2). In particular, the absorbent sheet (D3) of the present invention using a nonwoven fabric laminated with a polyethylene sheet as a base material does not show strikethrough at all.

[0081]

The non-aqueous absorbent material, non-aqueous absorbent sheet, non-aqueous gel and non-aqueous absorbent of the present invention have the following effects. The non-aqueous absorbent comprising the crosslinked product of the present invention has a remarkably high liquid absorption amount with respect to various organic solvents as compared with conventional non-aqueous absorbents, and therefore, a large amount of an organic solvent should be gelated by adding a very small amount. You can Also, since the liquid retention is high,
Even if some pressure is applied, the absorbed organic solvent will not be extruded. The non-aqueous absorbent sheet of the present invention, compared to conventional sheets,
A large amount of organic solvent is used even if the sheet thickness or total area is small, because the amount of liquid absorbed or retained by the organic solvent is extremely high, and the absorbed organic solvent is hardly extruded even if some pressure is applied. Can be absorbed or retained in a short time. When the non-aqueous absorption sheet of the present invention is used as an electrolyte leakage prevention sheet for organic solvent batteries and capacitors, etc., it can absorb / hold a large amount of organic solvent in a short time with an extremely thin sheet of small area. In addition, since the strike-through property of the sheet is low, even if leakage of the electrolytic solution or the like occurs, there is no risk that the electrolytic solution will contaminate other parts or be exposed to the outside. By using a non-aqueous absorbent comprising the cross-linked product of the present invention or a non-aqueous absorbent and an organic solvent, it is also possible to create an integrated non-aqueous gel, so that it is package-less such as solid fuel and gel battery. It can be used for various purposes. Furthermore, the non-aqueous gel of the present invention can form a solid gel having a high gel strength even if the pure content of the crosslinked product is low, and is capable of gelation even in a system containing a large amount of an electrolyte such as lithium ion. It is possible to create highly functional gels. Moreover, the non-aqueous gel consisting of the cross-linked non-aqueous absorber and the organic solvent is extremely stable even in the long term,
There is no risk that the gel will deteriorate and the electrolyte will be exposed.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/24 C08J 5/24 H01G 9/02 301 H01G 9/02 301 9/035 H01M 10/40 B / / H01M 10/40 C08L 101: 02 C08L 101: 02 H01G 9/02 311 F Term (reference) 4F070 AA17 AA29 AA30 AA32 AA37 AC40 AE08 GA04 GA06 GC02 HA02 HA04 4F072 AA08 AB29 AB31 AD03 AD09 AG03 4G066 AB05A10A AB07A AB07A AB07A AB07A AB07A AB07A AB07A AB09A AC13B AC14A AC14B AC17A AC17B BA03 BA20 CA04 CA56 DA10 FA07 FA37 4J100 AB07P AJ01P AJ02P AJ08P AJ09P AL08P AP01P BA33H BA33P BA58P BA64H BA64P CA01 CA04 HA31 HA61 JA15 5H029 AJ15 AM11 AM12 C04 C02

Claims (12)

[Claims] 1. Containing 20 to 100% by weight of a structural unit having a carboxyl group and / or a sulfonic acid group in the molecule, and 30 to 100 mol% of protons of the carboxyl group and / or the sulfonic acid group is onium. A non-aqueous absorber (B) comprising a cross-linked body (A) of a polymer (1) substituted with a cation. 2. The absorber (B) according to claim 1, wherein the onium cation is a quaternary ammonium cation. 3. The absorption according to claim 1 or 2, wherein the quaternary ammonium cation is one or more selected from the group consisting of an aliphatic ammonium cation, an imidazolinium cation, and an imidazolium cation. Body (B). 4. The content of the structural unit having a carboxyl group and / or a sulfonic acid group of the polymer (1) is 40 to 1
The absorber (B) according to any one of claims 1 to 3, which has an amount of 00 mol% and in which 50 to 100 mol% of the protons of the carboxyl group and / or the sulfonic acid group are substituted with onium cations. 5. The absorbent according to claim 1, wherein the (A) is obtained by the substitution with the onium cation at a stage before or after the polymerization of the polymer (1). (B). 6. A liquid retention amount for an organic solvent selected from the group consisting of propylene carbonate, γ-butyrolactone, methanol, and ethanol is 10 g to 1,000 g.
/ G, The absorber (B) according to any one of claims 1 to 5. 7. A non-aqueous gel (C) comprising the absorber (B) according to any one of claims 1 to 6 and an organic solvent (2). 8. The organic solvent (2) is an alcohol organic solvent, a glycol organic solvent, a carbonate organic solvent, a ketone organic solvent, an ether organic solvent, an aliphatic hydrocarbon organic solvent, an aromatic hydrocarbon. 1 or 2 selected from the group consisting of organic solvents, carboxylic acid ester organic solvents, lactone organic solvents, and lactam organic solvents
The gel (C) according to claim 7, which comprises more than one kind. 9. Containing 20 to 100% by weight of a structural unit having a carboxyl group and / or a sulfonic acid group in the molecule, and 30 to 100 mol% of protons of the carboxyl group and / or the sulfonic acid group is onium. One or two selected from the group consisting of a polymer (1) substituted with a cation dissolved in the organic solvent (2), cross-linked with a cross-linking agent, cross-linked by irradiation of ultraviolet rays or radiation, and cross-linked by heating. Crosslink using the above crosslinking means, or 30 to 1
Carboxylic acid group- and / or sulfonic acid group-containing monomer 20 in which 00 mol% of the proton is replaced by an onium cation
The method for producing the gel (C) according to claim 7 or 8, wherein 100% by weight and optionally 0 to 80% by weight of another copolymerizable monomer are polymerized in the presence of a crosslinking agent in the above (2). 10. A non-aqueous absorbent sheet (D) comprising the absorbent body (B) according to any one of claims 1 to 8 and a base material selected from the group consisting of non-woven fabric, woven fabric, paper and film. 11. Containing 20 to 100% by weight of a structural unit having a carboxylic acid group and / or a sulfonic acid group in the molecule, and 30 to 100 mol% of protons of the carboxylic acid group and / or the sulfonic acid group. After impregnating and / or coating the polymer (1) in which is substituted with an onium cation on one or more base materials selected from the group consisting of non-woven fabrics, woven fabrics, papers and films, a crosslinking agent Cross-linking, UV light,
The (1) is crosslinked by using one or two or more crosslinking means selected from the group consisting of crosslinking by irradiation with electron beams, gamma rays and the like, crosslinking by heating, or 30 to 100 mol% of protons are crosslinked. The above-mentioned substrate was impregnated with a mixed solution containing 20 to 100% by weight of a carboxylic acid- and / or sulfonic acid-containing monomer substituted with an onium cation, 0 to 80% by weight of another copolymerizable monomer, and a crosslinking agent. 11. The sheet according to claim 10, wherein after coating, the substrate is polymerized by using one or more means selected from the group consisting of use of a polymerization initiator, irradiation of ultraviolet rays / radiation, and heating. Method D). 12. The absorbent body (B) according to any one of claims 1 to 8, which has an average particle size of 1 to 5,000 μm.
The non-aqueous absorbent (E) in the form of particles of m.