JPS6042447A - Electrically conductive resin composition - Google Patents

Abstract

PURPOSE:To provide the titled. compsn. which is moldable and has high electrical conductivity, by dissolving a metal salt in a polymer of a polyoxyalkylene(meth)acrylate or itaconate with a polymerizable vinyl monomer. CONSTITUTION:20-100wt% polyoxyalkylene(meth)acrylate or itaconate of the formula [wherein R<1> is H, methyl, CH2COO(CmH2mO)nR<2>; R<2> is H, a C1-28 hydrocarbon group; n is the mean number of C2-4 alkylene groups and 2-200] and 80-0wt% other polymerizable vinyl monomer such as methyl methacrylate are polymerized in the presence of a polymn. initiator in a solvent to obtain a polymer. 0.01-0.5g equivalent (per one oxyalkylene group in the polymer) of an alkali metal salt such as KSCN is added to the polymer. If desired, the mixture is heated to dissolve the salt.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to ionically conductive conductive 114 fat compositions.

Conventionally, polyether-based electrolyte compositions with ionic conductivity have been prepared by combining polyoxyethylene glycol, polypropylene oxide, polyoxypropylene glycol, polypropylene oxide, etc. with alkali metal hydrohalides, thiocyanate groups, perhalogen oxygen acids, etc. Salt, 4.
・Compositions containing dissolved boronates, etc., are known.

These electrolyte compositions are liquid or semicircular at room temperature, and cannot be used for measuring electrical conductivity as a solid electrolyte due to national circumstances, and cannot be used for forming or plastic processing into sheets. Electrolytes made from polyethylene oxide, polypropylene oxide, and alkaline metals remain solid even at high temperatures of up to 80°C, but they are extremely deliquescent and absorb moisture when stored at room temperature, becoming liquid after one day. Furthermore, when measured in a solid state without moisture absorption, the electrical conductivity is about 100 (7F+) at room temperature (20° C.), which is not so large.

The present inventors have carried out extensive studies aimed at developing a conductive resin composition that can be molded and has high electrical conductivity, and as a result, they have arrived at the present invention.

That is, the present invention is a polyoxyalkylene acrylate, methacrylate or itaconate 20 to 100 polymer resin composition represented by formula (1) and other polymeric resin compositions.

(Here, R is a hydrogen atom, a methyl group, or a CH3COO
(CmI2mO)n R2, R2 is a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms, m is an integer of 2 to 4, n
The average number of carbon atoms is 2 to 200. )(1)
The compound represented by the formula is a monoether type polyodialkylene obtained by addition polymerizing an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran to an alcohol or phenol having 1 to 28 carbon atoms in the presence of a catalyst. Esterification reaction of glycol with acrylic acid, methacrylic acid or itaconic acid, or hydroxyalkyl acrylate,
It is obtained by adding the alkylene oxide to methacrylate or itaconate.

To obtain the polymer (A), the formula (1) compound 20 to 100
1% by weight and, if necessary, 0 to 80% by weight of other polymerizable vinyl monomers, by a known method, using a peroxide, an azo compound, etc. as a polymerization initiator, or by using light energy. 1 trtt in the presence of a solvent of
It can be obtained by polymerization, but it can also be obtained by emulsion polymerization, suspension polymerization or bulk polymerization.

In order to sufficiently dissolve the metal salt (B) and obtain high electrical conductivity in the polymer (A), it is necessary to contain at least 20% by weight of the compound of formula (1).

Other polymerizable vinyl monomers that copolymerize with the compound of formula (1) are not particularly limited, but include acrylic acid alkyl esters, hydroxyalkyl acrylates, methacrylic acid alkyl esters, hyaluronan hydroxyalkyl methacrylates, itaconic acid monoalkyl esters, Itaconic acid dialkyl ester, hydroxyalkyl itaconate, acrylonitrile, acrylamide, vinyl acetate, styrene, vinylbenzene, glycidyl acrylate, glycidyl methacrylate, maleic acid monoalkyl ester, maleic acid dialkyl ester, ψ fumaric acid monoalkyl ester, moalkyl fumarate These include esters, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

The metal salt (B) that dissolves in the polymer (A) is not particularly limited as long as it dissolves in the polymer (A).
), sulfates, phosphates, halide oxygen salts, perhalogen oxygen salts, and tetrahalogenated borates are preferred, and lithium, sodium or potassium salts are particularly preferred.

The amount of the metal salt (B) added is 0.000000000000000000000000000000000000000000,000,000,0000,0000,0000,0000,0000,0000, f11~5 grams]? f is preferable; if the amount is less than 0.01 grams, it is difficult to obtain high electrical conductivity, and if it is more than 5 grams, it is difficult to uniformly dissolve.

The method for dissolving gold 4 salt (B) is to directly add K metal salt (B) to polymer (A), heat if necessary, and stir.
Therefore, it is possible to dissolve the metal salt (B) in a polar solvent such as methanol, ethanol, methoxyethylene glycol, ethoxy-diethylene glycol, dimethylformamide, dimethyl sulfoxide, water, etc., and then add it to the polymer (A). , after mixing to make a homogeneous solution,
A conductive resin composition is obtained by heating under reduced pressure to 60 to 100° C. to remove the solvent, if necessary.

The α-conducting resin composition of the present invention has a uniform metal salt (B) dissolved in a polymer (A), and exhibits a uniform solid state in a temperature range of about -20°C to 120°C. In addition, it has ionic conductivity as a solid electrolyte, and when measuring electrical conductivity, it is more than 2 × lOΩ α at 20 °C, and 4 × 1 at 80 °C.
Indicates a value of 0 Ω-1゛α or more.

[2] The conductive resin composition of the present invention is easily molded and has excellent electrical conductivity, and can be used for conductive sheet films, conductive coatings, etc.
G%, it can be applied as a material for battery electrolytes or internal palators, ion sensors, display elements, capacitors, etc.

Examples will be explained below.

Example (+) Production of polymer (A) Methoxypolyoxyethylene (n=23) methacrylate 32. Of, methyl methacrylate8. Or,N,
N-azobisisobutyronitrile 0081 and methyl isobutyl keto/160F were placed in a 500 ml four-bottle flask, and a polymerization reaction was carried out at 100°C for 20 hours in a nitrogen gas atmosphere to obtain a polymer (A) (Ya 1) solution. I got it.

Place a small amount of this polymer solution on a glass/yare surface and
The solvent was distilled off at 0° C. under reduced pressure of 1 mHg for 4 hours. The obtained polymer was a soft solid at 20°C and 80°C. The number average molecular weight determined by gel permeation chromatography was 41,300, and the weight average molecular weight was 127°00.

Polymers (A) used in the present invention (A2-
A solution of &11) and a solution of comparative polymers (Y12-17) not containing the monomer of formula (1) were obtained.

Table 1 shows these monomer compositions and properties of the polymers.

The formula (1) compound used as a raw material for the polymer (A) used in the present invention is shown below.

I Methoxypolyoxyethylene (n=za)7+Tacrylate CH3 CH2-CC00(C21140)23CH3 "Methoxypolyoxyethylene (n=9) Methacrylate CH3 CH2=CC00(C2H40)9CH3111 Pholyoxyethylene glycol (n=8) Monomethacrylate CI(3 CH2=CC00(C2H40)sH ■ Polyoxypropylene glycol (n=iz) monomethacrylate ft3 1 ・CH2(:Coo(C3HsO)12HV Methoxypolyoxypropylene (n=10) Polyoxyethylene (
n=10) Acrylate (block adduct) CH2=CHC00(C2H40) to (Ca Hs
0) toC) Ia ■ Di[methoxypolyoxyethylene (n=to)) itaconate CH2C00 (C2H40) toc, H3・l CH2-CC00 (CzH40) tocHa・(2) m-product and electrical conductivity of conductive resin composition A 5M timethanol solution of an alkali metal salt and a solution of the polymer (A) or comparative polymer are mixed at a predetermined ratio under a nitrogen atmosphere,
Place a portion of this mixture on a polytetrafluoroethylene plate,
The solvent was distilled off at 80° C. for 24 hours under a reduced pressure of 1 wHg to obtain a conductive resin composition.

In addition, conduction was conducted in a similar manner using a 5% methanol solution of an alkali metal salt and polyoxyethylene glycol (20,000 molecules), polyethylene oxide (1 million molecules), or polyoxypropylene glycol (6000 molecules). A synthetic resin composition was obtained.

Table 2 shows the composition, electrical conductivity at 20°C and 80°C, and properties of the conductive resin composition obtained.

Note that the electrical conductivity was measured by the following method.

After adding 611 to the thickness of the sheet of the sample 4it resin composition using a micrometer, a diameter of 15W was added to both sides of the sheet.
The circular tin base of No. 5 was attached in close contact. Measuring electrodes are connected to the tin bases on both sides, and the whole is temperature controlled (2,
The electrodes and series lead wires were taken out and connected to the transformer bridge. Connect this bridge to an external AC oscillator with a frequency of 10” to 105Hz.
We applied an alternating current of 100 Ω, calculated the complex impedance from its equilibrium position, and calculated the degree of conductivity by extrapolation with respect to the frequency.

According to Table 2, the weight conductivity of the conductive resin composition of the present invention is 2.
2.7X10 to 7.2X10'Ω α at 0℃,
4.3X10 ~ 8.8X100 α at 80℃
whereas the comparative composition had a temperature of 1.6 at 20°C.
X10 Ω m or less, 3.2X10 at 80℃
Ω. It is clear that the electrical conductivity of the composition of the present invention is high.

In addition, the compositions of polymer point 1 and flat plate 2 of the present invention are flexible solids and are therefore suitable for plastic working.
Since the composition of No. 1 is in the form of a film, it is suitable for use in conductive sheets, films, conductive coatings, battery electrolytes, internal separators, and the like.

The comparative compositions of Polymer 1G 12 to 17 not only had low electrical conductivity, but also were cloudy and had fine crystals of inorganic salts dispersed in the pancreas of the composition, making them unsuitable as conductive resin compositions. be.

Comparative compositions using polyoxyethylene glycol or polyoxypropylene glycol as the polymer are semi-solid or liquid, making it impossible to measure K'4 gas conductivity; Although Composition 1 forms a solid 11'8, it absorbs moisture indoors and becomes a viscous liquid after one day, indicating that it is of no practical use.

(3) Antistatic property A thin sheet of a conductive resin composition of polymer A4 was formed on a polytetrafluoroethylene plate in the same manner as in (2). Peel off this sheet and remove the polymethyl methacrylate plate (10a
nX 10crn) and then left in a dusty room for one day. When the dust adhering to the surface of this board was blown away by an air flow, most of the dust #1 remained on the surface where the sheet was pasted, but there was a lot of #1 dust remaining on the surface where the sheet was not pasted. dust remained.

It has been found that the conductive resin composition of the present invention is also effective as an antistatic sheet.

Patent applicant: NOF Corporation

Claims (1)

[Claims] 1. Polyoxyalkylene acrylate, methacrylate or itaconate represented by formula (1) 20 to 100
Heavily decomposed chi and other polymerizable vinyl monomers 0 to 80 wk%
A conductive resin composition obtained by dissolving a metal salt (B) in a polymer (A) of . 1 CH2=CH2=CC00(C)nH2R2++++++
・++++++” (1) (Here, R” is a hydrogen atom, a methyl group, or CH3COO(CmJI2mO)nR2t
lI, R2 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, m is an integer of 2 to 4, and n is the average number of oxyalkylene groups having 2 to 4 carbon atoms, which is 2 to 200. ) 2. The conductive resin according to claim 1, which is obtained by dissolving 0.01 to 0.5 grams of the metal salt (B) per oxyalkylene group of the polymer (A). Composition. 3. The conductive resin composition according to claim 2, wherein the metal salt (I3) is an alkali metal salt. 4. A patent claim in which the alkali metal salt is a lithium salt, sodium salt, or potassium salt of a hydrohalic acid, thiocyanic acid, nitric acid, sulfuric acid, phosphoric acid, a halogen oxyacid, a perhalogen oxyacid, or a tetrahalogenoboric acid. Range Wc
The conductive resin composition according to item 3.