JPH0312447A - Polymer solid electrolyte - Google Patents

Abstract

PURPOSE:To obtain a polymer solid electrolyte suitable as transmission type electrochromic display element of large area, etc., having high setting properties, a long pot life and excellent workability, usable in one-pack type, comprising a crosslinking type resin prepared by reacting a specific compound with an amino resin and an alkali metallic salt. CONSTITUTION:(A) A crosslinking type resin prepared by reacting A1: a compound (e.g. ethylene glycol) which contains two or more reactive groups selected from among hydroxyl group, carboxyl group and glycidyl group and has a bond shown by formula I (m>=1) and/or bond shown by formula II (n>=1) with A2: an amino resin (e.g. urea-formaldehyde resin) in the ratio of the component A2/A1=(1/9)-(9/1) is blended with (B) an alkali metallic salt (e.g. lithium perchlorate).

Description

[Detailed Description of the Invention] [Objective of the Invention] (Industrial Application Field) The present invention can be used in places where electrolytes have been conventionally used, such as secondary batteries, secondary batteries, and electrocomic display elements. The present invention relates to a polymer electrolyte having high electrical conductivity and particularly suitable for large-area transmission type electrochromic display elements.

(Prior art) As a solid polymer electrolyte, one consisting of a crosslinked resin 1 obtained by reacting trifunctional polyoxyalkylene glycerin and an aliphatic diisocyanate and an inorganic ionic salt such as an alkali metal salt has been known. (Unexamined Japanese Patent Publication No. 62-4
8716, JP-A-63-55811, etc.).

(Problems to be Solved by the Invention) Although these solid polymer electrolytes using aliphatic diisocyanates have good yellowing resistance, they have high reactivity between the trifunctional polyoxyalkylene glycerin and the aliphatic diisocyanate, and are difficult to use in pots. Because of its short life, it was used as a two-component type, and the trifunctional polyoxyalkylene glycerin and aliphatic diisocyanate had to be mixed immediately before use, resulting in extremely poor workability.

The present invention solves various problems with conventional polymer solid electrolytes using aliphatic isocyanates, and provides a polymer solid with high curability, long pot life, and good workability because it can be used as a one-component type. It provides electrolytes.

[Structure of the invention]

(Means for Solving the Problems) The present invention has two or more reactive groups selected from a hydroxyl group, a carboxyl group, and a glycidyl group, and.

Ha (-CH-CH, -0su, bond [however, 1m≧1] and (or) +CH! CHz O)-bond [however, n≧1]
This is a polymer solid electrolyte consisting of a crosslinked resin (A) obtained by reacting a compound (a) having the above and an amino resin (b), and an alkali metal salt (B).

In the present invention, it has two or more reactive groups selected from a hydroxyl group, a carboxyl group, and a glycidyl group, and.

and (or) -(-CH2-CH2-O-)-1 bond [however, n≧
1] as the compound (a), ethylene glycol, polyethylene glycol, propylene glycol,
Polypropylene glycol, poly(oxyethylene-
(oxypropylene) copolymer, butanediol, oxyethylene glycerin, polyoxyethylene glycerin,
Glycols and glycerin such as oxypropylene glycerin, polyoxypropylene glycerin, poly(oxyethylene-oxypropylene) copolymer glycerin, butanediol monoglycidyl ether, ethylene glycol monoglycidyl ether, polyethylene glycol monoglycidyl ether, propylene glycol mono Glycidyl ether, polypropylene glycol monoglycidyl ether, poly(oxyethylene-
monoglycidyl ethers such as (oxypropylene) copolymer monoglycidyl ether, butanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether,
Diglycidyl ethers such as propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly(oxyethylene-oxypropylene) copolymer diglycidyl ether, or mixtures thereof, or their terminal hydroxyl groups and/or terminal glycidyl groups. 1. Polybasic acids such as phthalic acid, hexahydrophthalic acid, maleic acid, trimellitic acid, and pyromellitic acid or their anhydrides are ester bonded.

In the present invention, the amino resin (b) includes urea formaldehyde resin, melamine formaldehyde resin, guanamine formaldehyde resin, benzoguanamine formaldehyde resin, spiroguanamine formaldehyde resin, aniline formaldehyde resin, sulfonamide formaldehyde resin, thiourea formaldehyde resin, etc. These include derivatives such as alkylated products and etherified products, copolymer resins thereof, and mixtures thereof.

The compound (a) and the amino resin (b) are
)/total amount of compound (a) = 1/9 to 9/1 (weight ratio).

In the present invention, as the alkali metal salt (B).

Lithium, sodium, and potassium perchlorates, thiocyanates, and phosphates, including but not limited to lithium, sodium, and potassium perchlorates.

Tetrafluorobaltate, trifluoroacetate, trifluoromethanesulfonate, hexafluorophosphate,
and halide 1 It is particularly preferable to use lithium perchlorate or lithium thiocyanate, and when using thorium carbonate, sodium carbonate, sodium monochloroacetate, or acidic sodium sulfite, which have strong deliquescent properties, It is preferable to keep the amount used to a minimum.

Compound (a) and alkali metal salt (B) are compound H3! I! Ratio Z/
Y is.

0.001:52/Y≦0.4. Especially 0.01≦Z/Y
It is preferable to use the ratio such that ≦0.1. The compound (a) and the alkali metal salt (B) are mixed in such a manner that Z/Y is 0.
When used at a ratio that is smaller than 001.

The conductivity of the resulting polymer solid electrolyte is small (sometimes it becomes low), and when Z/Y is used at a ratio larger than 0.4, the excess alkali metal salt does not dissociate. There are cases where the conductivity of the obtained solid polymer electrolyte becomes low because the elements are simply mixed together.

The polymer solid electrolyte of the present invention is.

(2) It may also be obtained by simultaneously mixing the compound (a), the amino resin (b), and the alkali metal salt (B), and then reacting the compound (a) with the amino resin (I).

■ Mix the alkali metal salt (B) with the compound (a).

Next, the amino resin (b) may be mixed and the compound (a) and the amino resin (b) may be reacted.

(2) It may also be obtained by mixing the alkali metal salt (B) with the amino resin (b), then mixing the compound (a), and reacting the compound (a) with the amine resin (b).

■ Mix compound (a) and amine resin (b).

Next, the alkali metal salt (B) may be mixed and the compound <a> and the amino resin (b) may be reacted.

(2) The crosslinked resin (A) may be obtained by reacting the compound (a) with the amino resin (b), and the alkali metal salt (B) may be impregnated or adsorbed into the crosslinked resin (A). The reaction between compound (a) and amine resin (b) is usually carried out at 100 to 210°C.
This is done by heating for ~25 minutes. In addition, when the polymer solid electrolyte of the present invention is obtained by the above methods ① to ②, it is combined as an alkali metal salt! Furthermore, using lithium perchlorate, which also acts as a reaction catalyst between lk (a) and amine resin (b).

Good curability and long pot life can be achieved.

The solid polymer electrolyte of the present invention may contain, as necessary, within a range that does not impede its performance.
Water, acetone, methyl ethyl ketone, methanol, ethanol, propatool, butanol.

Ethyl acetate, butyl acetate, acetonitrile, cellosolve, butyl cellosolve, cellosolve acetate.

Butyl cellosolve acetate, xylene, toluene conductive agent, flame retardant, inorganic filler, flammability agent, antistatic agent. Antifogging agent, deterioration prevention side, tackifier, lubricant, surfactant 1 foaming agent, antifoaming agent, leveling agent, silane coupling agent,
Additives such as a curing catalyst other than perchlorate can be added as appropriate. There is no particular restriction on the timing of addition of these additives as long as they do not impede the performance of the solid polymer electrolyte of the present invention.

The solid polymer electrolyte of the present invention can be formed into a film, a vibrator, a tube, etc. by a molding method such as casting or extrusion, or can be coated by coating such as roll coating, spray coating, or screen printing. The method is used to coat and print onto substrates of various shapes and put into practical use.

(Example) The present invention will be explained below using one example. Note that in the two examples, 1 part represents part by weight.

Example 1 100 parts of polyethylene glycol with a molecular weight of 400 and 10 parts of hexamethoxymethylolmelamine (molecular weight 600)
Add 5 parts of lithium perchlorate and add 2 parts of lithium perchlorate.
Add 58 parts of 0% methyl ethyl ketone solution and mix well until X/W is 0.7. A liquid composition with Z/Y of 0°05 was obtained. Note that X/W is the ratio of the amino resin (b) to the sum W of the number of moles of the compound (a) in the obtained liquid compound.
It is the ratio of the sum of the number of moles of

The obtained liquid composition was heated and cured at 140°C for 15 minutes,
Got the film. The electrical conductivity of the obtained film at 25°C was measured using the complex impedance method and was found to be 1.2.
X 10-'S/am.

Further, the obtained liquid composition was stored at 50° C. for 7 days, but no change occurred.

Example 2 The same procedure as Example 1 was carried out except that the amount of lithium perchlorate was changed to 11.6 parts, and X/W was 0.7. A liquid composition having Z/Y of 0101 was obtained, and the electrical conductivity of the obtained liquid composition was measured to be OX10-'S/cm.

In addition, the obtained liquid composition was stored at 50° C. for 7 days, but no change occurred.

Example 3゜X/W
is 0.3. A liquid composition with Z/Y of 0.05 was obtained, and the conductivity of the obtained liquid composition was measured.

It was 2.5 x 10-'S/cm.

Further, the obtained liquid composition was stored at 50° C. for 7 days, but no change occurred.

Example 4 The procedure of Example 1 was repeated except that butylated benzoguanamine (molecular weight 600) was used instead of hexamethoxymethylolmelamine (molecular weight 600), except that X/W was 0.7.
When a liquid composition with 2/Y of 0.05 was obtained and the conductivity of the obtained liquid composition was measured, it was found to be 3.2XIO-'S/c.
It was m.

Further, the obtained liquid composition was stored at 50° C. for 7 days, but no change occurred.

Example 5 Same as Example 1 except that 132 parts of polypropylene glycol having a molecular weight of 425 was used instead of 100 parts of polyethylene glycol having a molecular weight of 400.

A liquid composition with X/W of 0.7.2/Y of 0.05 was obtained.

When the conductivity of the obtained liquid composition was measured, it was found to be 2゜l.
It was X10-'S/cm.

Further, the obtained liquid composition was stored at 50° C. for 7 days, but no change occurred.

Example 6 70 parts of hexamethoxymethylolmelamine (molecular weight 600) was added to 100 parts of polyethylene glycol with a molecular weight of 600.
of lithium thiocyanate, and to this, 2 parts of lithium thiocyanate.
Add 35 parts of 0% by weight methyl ethyl ketone solution and mix well until X/W is 0.7. A liquid composition with Z/Y of 0.05 was obtained.

The obtained liquid composition was heated and cured at 200°C for 15 minutes,
Got the film. When the conductivity of the obtained film at 25°C was measured using the complex impedance method, it was found that 9
．． OX 10-7S/cm.

Further, the obtained liquid composition was stored at 50° C. for 7 days, but no change occurred.

Comparative example.

25 parts of hexamethylene diisocyanate was added to 70 parts of poly(oxypropylene)glycerin having a molecular weight of 700, and 29 parts of a 20% by weight solution of lithium perchlorate in methyl ethyl ketone was added thereto and mixed well to form compound (a). The ratio of the number of moles of hexamethylene diisocyanate to the number of moles is 1.5. A liquid composition with Z/Y of 0.05 was obtained.

The obtained liquid composition was heated and cured at 80° C. for 24 hours to obtain a film. The electrical conductivity of the obtained film at 25° C. was measured using the complex impedance method.1.
IXIO"'S/cm.

Moreover, when the obtained liquid composition was stored at 50° C. for 7 days, it was found to be gelatinous.

〔Effect of the invention〕

The present invention has a long pot life and can be used as a one-liquid type, resulting in good two-way workability.Also, since it has good curability, it can be cured in a short time only by heating.

Polymer solid electrolytes with high conductivity can now be obtained. Furthermore, in the present invention, lithium perchlorate is used as the alkali metal salt.

Furthermore, it has become possible to obtain solid polymer electrolytes with high curability and a long pot life.

Claims (1)

[Scope of Claims] 1. has two or more reactive groups selected from hydroxyl group, carboxyl group, and glycidyl group, and ▲ has a numerical formula, chemical formula, table, etc. ▼ bond [however, m≧1]; and (or) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼Bond [However, n≧
1] A solid polymer electrolyte comprising a crosslinked resin (A) obtained by reacting a compound (a) having the following and an amino resin (b), and an alkali metal salt (B).