JPS63245457A - Acrylic elastomer composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has a high polarity, does not cause phase separation and has good electrical conductivity, consisting of a specific acrylic copolymer, an electrolyte material compatible with said acrylic copolymer and a water-soluble high-molecular material. CONSTITUTION:The title compsn. consists of a copolymer obtd. by copolymerizing an alkyl acrylate (A) having a 1-4C alkyl group (e.g., ethyl acrylate) and/or an alkoxyalkyl acrylate (B) having a 2-8C alkoxyalkyl group (e.g. 2-methoxyethyl acrylate) with a monomer (C) selected from the group consisting of vinyl monomers having an epoxy group (e.g., glycidyl acrylate), vinyl monomers having a carboxyl group (e.g., methacrylic acid), reactive halogen-contg. vinyl monomers (e.g., 2-chloroethylvinyl ether), diene monomers (e.g., divinylbenzene), vinyl monomers having a hydroxyl group (e.g., hydroxyalkyl methacrylate) and vinyl monomers having an amide group (e.g., methacrylamide), an electrolyte material compatible with said copolymer (e.g., lithium perchlorate) and a water-soluble high-molecular material (e.g., polyethylene glycol).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to acrylic elastomer compositions. More specifically, the present invention relates to an acrylic elastomer composition that is excellent in electrical conductivity.

[Conventional technology]

JP-A-59-206,444 describes a conductive polymer material composition in which a water-soluble inorganic salt electrolyte material and a water-soluble polymer material are blended into a base polymer material made of thermoplastic resin or rubber. ing.

However, in this composition, there is insufficient compatibility between the base polymeric substance and the water-soluble polymeric substance, and if the water-soluble polymeric substance is used in a proportion exceeding a certain level, phase separation may occur. , the mechanical degradation is reduced, and for these reasons the amount of electrolyte that can be dissociated is also limited, so that as a result the conductivity cannot be increased as much as expected.

[Problem that the invention seeks to solve]

Therefore, the present inventors conducted various studies in search of a method for increasing the conductivity of a base polymer material in the coexistence of an electrolyte material and a water-soluble polymer material. An acrylic elastomer, which is not exemplified in , is selected as the base polymer material, and this acrylic elastomer has strong polarity and has good compatibility with the water-soluble polymer material in the coexistence of an electrolyte material or a plasticizer. By discovering this property, we were able to effectively solve this problem.

Means for Solving Problem C] Therefore, the present invention relates to an acrylic elastomer composition,
This acrylic elastomer composition has (a) a carbon number of 1 to
Alkyl acrylate having 8 alkyl groups and/or
or (b) an alkoxyalkyl acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms; and (c) at least one of the following monomers: (i) an epoxy group-containing vinyl monomer; and (ii) a carboxyl group-containing vinyl monomer. (3) Reactive halogen-containing vinyl monomer (d) Diene monomer (e) Hydroxyl group-containing vinyl monomer (f) A copolymer of amide group-containing vinyl monomer, which is compatible with the copolymer. It is made of a water-soluble electrolyte material and a water-soluble polymer material, preferably with a plasticizer added thereto.

Forming the acrylic elastomer used in the present invention (
Examples of the alkyl acrylate component a) include methyl acrylate, ethyl acrylate, n- or iso-propyl acrylate, n- or iso-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, Alkyl acrylates having an alkyl group having 1 to 8 carbon atoms (including those having a substituent such as a cyano group) such as n-octyl acrylate and 2-cyanoethyl acrylate are used, and preferably ethyl acrylate or n-butyl acrylate is used. used.

(b) Component alkoxyalkyl acrylates include methoxymethyl acrylate, ethoxymethyl acrylate, 2-methoxyethyl acrylate, 2-
An alkoxyalkyl acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms such as ethoxyethyl acrylate and 2-ptoxyethyl acrylate 1- is used,
Preferably, 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate are used.

These (a) components and/or (b) components are about 9
It is copolymerized and used in a proportion of 9.9 to 90 mol%.

When both components (a) and (b) are used, the former is about 10 to 90 mol%, and the latter is about 90 to 10 mol%.
Commonly used in mole % proportions.

A part of these components (a) and/or (b), specifically up to about 10 mol %, may be substituted with other copolymerizable monomers and copolymerized. Examples of such copolymerizable monomers include vinyl chloride, vinylidene chloride, acrylonitrile, styrene, vinyl acetate, ethyl vinyl ether, butyl vinyl ether, alkyl methacrylate, and alkoxyalkyl methacrylate.

The following crosslinking agents are used depending on the type of component (c) forming the crosslinking points of the copolymer and its reactive group.

(a) Epoxy group-containing vinyl monomer allyl glycidyl ether, glycidyl acrylate,
Glycidyl methacrylate is exemplified, and examples of crosslinking agents include polyamines such as diethylenetriamine and metaphenylenediamine, polycarboxylic acids such as adipic acid, acid anhydrides such as pyromellitic anhydride and maleic anhydride, and polyamides. and sulfonamides are used.

(b) Carboxyl group-containing vinyl monomers such as acrylic acid, methacrylic acid, itaconic acid, etc., and crosslinking agents for these include polyepoxides such as ethylene glycol diglycidyl ether, 6-hexanesiol diglycidyl ether, etc. Polyols such as 2, 4-butanediol, and 1,1.1-trimethylolpropane are used. Instead of using these crosslinking agents, crosslinking may be performed only by heating.

(c) Reactive halogen-containing vinyl monomers 2-chloroethyl vinyl ether, monochloroacetic acid, etc. are exemplified, and crosslinking agents for these include, for example, diethylenetriamine,
Polyamines such as triethylenetetramine, polycarbamates such as hexamethylene diamine carbamate, etc. are used.

(d) Diene monomer Divinylbenzene, piperylene, isoprene.

Pentagene, vinylcyclohexene, chloroprene,
butadiene, methylbutadiene, cyclopentadiene,
Examples include methyl pentadiene, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, and propylene glycol dimethacrylate. Examples of crosslinking agents for these include sulfur, benzoyl peroxide,
Organic peroxides such as dicumyl peroxide, azo compounds such as azobisisobutyronitrile, divinylbenzene, triallyl ciaslate, triallyl isocyanurate, etc. are used. Instead of using these crosslinking agents, crosslinking may be performed only by heating.

(e) Hydroxyl group-containing vinyl monomers Examples include hydroxyalkyl methacrylate, hydroxyalkoxy acrylate, and N-methylol acrylamide. Examples of crosslinking agents for these include polyisocyanates such as hexamethylene diisocyanate and tolylene diisocyanate, and adipine. Polycarboxylic acids such as acids, alkoxymethylmelamines such as methoxymethylmelamine, and the like are used.

(f) Amide group-containing vinyl monomers such as acrylamide and methacrylamide are exemplified, and as a crosslinking agent for these, aminoformaldehyde and the like are used, for example. Alternatively, crosslinking may be effected only by heating.

The copolymerization reaction of each component of the above copolymerizable monomers may be carried out by any method such as bulk polymerization, emulsion polymerization, barrier polymerization, or solution polymerization, but specifically, for example, as follows. It will be done. 100 parts by weight of solvent (an amount accounting for about 5 to 98 weight X in the copolymer solution to be formed) is charged into a flask equipped with a reflux condenser, dropping row 1 and a stirrer, and maintained at a predetermined temperature. do. In the dropping funnel, about 1 to 10 parts by weight of a polymerization initiator is added to about 10 to 900 parts by weight of the monomer mixture.
A solution in which parts by weight are dissolved is added dropwise over about 0.5 to 5 hours, and the reaction is continued for about 1 to 5 hours after the dropwise addition is completed. Under such reaction conditions, the polymerization rate is about 80 to 95%.

In order to further increase the polymerization rate, approximately 1 to 5 parts by weight of a polymerization initiator is added after the monomer mixture has been added dropwise, thereby increasing the polymerization rate to 99% or more.

Adoption of such a dropwise polymerization method has the advantage that the copolymerization ratio of reactive monomers that are different from each other is not significantly different between the start and end of polymerization, and a copolymer elastomer with a uniform composition can be obtained. In addition, when copolymerizing monomers with extremely different reactivities, it is recommended to increase the concentration of the monomer with low reactivity at the beginning of the dropwise addition and lower the concentration at the later stage of the dropwise addition to achieve a relatively uniform composition. A copolymer elastomer is obtained.

When the copolymerization reaction is carried out using a mercapto compound as a chain transfer agent in the polymerization reaction carried out in this manner, the resulting copolymer elastomer provides a crosslinked product with excellent vulcanization properties.

As the mercapto compound, ω-mercaptoalkanol, alkylmercaptancaptan, mercaptocarboxylic acid, alkyl dithiol, dithioglycerin, trithioglycerin, etc. are used, but preferably 2-mercaptoethanol, 3-mercaptopropanol, 4-mercapto An omega-mercaptoalkanol such as butanol is used. These mercapto compounds have a concentration of about 0.1 to
It is used in a proportion of 3 mol I, preferably about 0.15 to 1 mol %.

Another advantage of using these compounds for mercap 1 is that the copolymerization ratio of the crosslinkable group-containing monomer can be increased. Generally, gelation becomes easier when the copolymerization ratio is increased, but by using this chain transfer agent, a relatively large amount of the crosslinkable group-containing monomer of about 0.1 to 10 mol% can be added. Even when copolymerized, the effect of copolymerization without gelation can be obtained.

Electrolyte substances which are added to the copolymer elastomer copolymerized in this way and which are compatible with it include hydrohalic acid, perhalogenated oxyacid, halogenated oxyacid, subhalogenated oxyacid, Oxyhalous acid, tetrahaloboric acid, hexahalogenated phosphoric acid, trihalogenated metasulfonic acid, thiocyanic acid, nitric acid, sulfuric acid, phosphoric acid,
Alkali metal salts such as carbonic acid, alkaline earth metal salts, transition metal salts, ammonium salts, organic carboxylates, organic sulfonates, various onium salts, quaternary ammonium salts, etc. are used, preferably perchloric acid. Perchlorates such as lithium, quaternary ammonium salts such as penzylpyridinium t1 chloride, thiocyanates such as sodium thiocyanate, and lithium thiocyanate are used.

These electrolyte substances are used in a proportion of about 0.1 to 100 parts by weight per 100 parts by weight of the acrylic elastomer, and their dispersion into the transparent acrylic elastomer is carried out according to each of the following (a) to (c). method, preferably (,) or (
This can be done by method b).

(a) The crosslinking agent and the like are dissolved together in a solvent in which both are soluble, stirred to homogenize, and then the solvent is distilled off. At this time, heat within a range that does not cause crosslinking reaction.

Alternatively, these treatments can be carried out under reduced pressure.

(b) If a suitable solvent is not available, the electrolyte material is preferably made into fine particles of 0.1 μm or less, and the fine particles are kneaded and dispersed in the transparent acrylic elastomer.

(c) A cross-linked acrylic elastomer is immersed in an electrolyte solution, sufficiently swollen, and then taken out and dried.

Further, as the plasticizer preferably used together with the electrolyte substance, any colorless and transparent plasticizer can be used as long as it has a polarity that dissociates the electrolyte, is nonvolatile, and is compatible with the transparent acrylic elastomer. For example, monovalent or polyvalent carboxylic acid esters, phosphine oxide triesters, sulfamide compounds, alkylene glycols or alkyl etherified products thereof, etc. can also be used, but alkylene carbonate compounds such as ethylene carbonate and propylene carbonate are preferable. used.

These plasticizers are used in a proportion of about 0.1 to 100 parts by weight per 100 parts by weight of acrylic elastomer, and their dispersion into the acrylic elastomer is generally carried out simultaneously with the electrolyte material.

Examples of water-soluble polymer substances include starch, its acetic acid,
Grafted with derivatives such as phosphoric acid and hydroxyl, formalin, epichlorohydrin, phosphate, glycerine dichlorohydrin, dichloropentane, propylene dichloride, cross-linked starch cross-linked with vinyl sulfone, etc., acrylonitrile, acrylic acid ester, acrylamide, etc. Polymerized grafted starch, pullulan, its esterified or etherified products, carboxymethylcellulose, methylcellulose, its hydroxypropyl,
Derivatives such as hydroxyethyl and carboxymethyl, hydroxyethylcellulose, hydroxypropylcellulose, alginic acid, guar gum, gum arabic, gum tragacanth, tamarind seed, gelatin, casein, polyacrylate, polyacrylamide, polyvinyl alcohol, polyethylene glycol, cross-linked acrylic acid combination, polyvinylpyridine salt, polydimethylaminoethyl methacrylate salt, polystyrene sulfonate, polyvinylpyrrolidone, amylose, methylated methylolmelamine, water-soluble urethane resin, acrylic resin,
Epoxy compounds, polyesters, alkyd resins, maleated oils, maleated polybutadiene, polyamidoamines, etc. are used, preferably polyvinyl alcohol,
Polyethylene glycol and the like are used.

These water-soluble polymer substances include acrylic elastomer 1
About 0.1 to 20 parts by weight per 00 parts by weight, preferably about 5 parts by weight
~10 parts by weight, and its dispersion into the acrylic elastomer is generally carried out simultaneously with the electrolyte material.

Crosslinking of the acrylic elastomer thus prepared is carried out using various crosslinking agents as described above or by heating. Note that during crosslinking, the mechanical strength of the crosslinked product can be increased by filling it with fine particles (eg, Aerosil) whose refractive index does not differ that much.

〔Effect of the invention〕

The acrylic elastomer composition according to the present invention has the following characteristics.

(1) The acrylic elastomer used in the present invention has strong polarity compared to other elastomers, so it is not only capable of dissolving a large amount of F11M substances, but also has good compatibility with water-soluble polymer substances. Even if the latter is used in an amount of 10 times the weight of the former, no phase separation is observed.

(2) By blending water-soluble polymer substances that do not undergo phase separation in this way, the electrical conductivity can be increased approximately twice. This can be considered to be because the water-soluble polymer substance absorbs humidity in the air, thereby promoting the dissociation of the electrolyte substance, but in the composition of the present invention,
Since the acrylic elastomer itself or both the acrylic elastomer and the plasticizer have the effect of accelerating the dissociation of the electrolyte substance, the effect is doubled and, for example, the acrylic elastomer exhibits conductivity even in a dry atmosphere.

(3) Acrylic elastomer has a viscosity so low that it can flow by itself in an uncrosslinked state, so it can be used to mold products with high conductivity and complex shapes.

〔Example〕

Next, the present invention will be explained with reference to examples.

Example 1 100 parts of ethyl acrylate (weight, same below), 4.4 parts of hydroxyethyl acrylate, 0.4 part of 2-mercaptoethanol, and 0 parts of azobisisobutyronitrile
．． Two parts were copolymerized by the method described above.

To 100 parts of the obtained transparent acrylic elastomer, add 1
-2100 parts, 1.6 parts of hexamethylene diisocyanate trimer as a crosslinking agent, lithium perchlorate (A), lithium thiocyanate (B), benzylpyridinium chloride (c,) or lithium ethyl carboxylate as an electrolyte Add a predetermined amount of (D), a predetermined amount of propylene carbonate 1 as a plasticizer, and a predetermined amount of polyethylene glycol (PEG) as a water-soluble polymer substance, stir and mix, and then distill acetone. I left.

The acrylic elastomer composition thus prepared was heated at 120°C for 1 hour under normal pressure to give 100×10
After cross-linking molding into a sheet of 0 x 3 mm, the refractive index and wavelength of the cross-linked product at a temperature of 20°C and 55% RH were 66.
Light transmittance and conductivity at 0 nm (frequency 5-13
The values obtained from the complex impedance plot at 10'Hz) were measured. The results obtained are below 3.
7 Shown in Nos. 011 to 25 of Table 1.

(Left below) Table 1! ``parallel understanding''
AIOO05,0X10 bow 2 AIO1006,8X10 bow 3 A20 10 0 1.9xtO
Bow 4 AIOO59,7X10-' 5 A], 0 10 5 2. lXl
0-56 A20 10 to 4
．． 8X10zu 7 BIOOO2,3X10-' 8 BIO1003,4X10-' 9 B20 10 0 7.8X10
-'10 BIO057,2xlO-" 11 [110105g, 1X10-'12 [1
2010101, 5X10-513 CIOOO3,
8xlO-” 14 CIOIo 0 7.0xlO-”
15 C20,1003,lX10”716 CI
OO58,3X10-" 17 CIOto 5 '3.7X10
-718 G20 10 10 5.
0XIO-719010003,8X10-' 20 DIo 10 0 3.8X
10-721 020 10 0 4.
8X10-722 010 0 5 7
．． 5X1o-'23 010 10 5
7.6X10-'24 B20 10
10 1.0X10 bow 25 0 0
0 2, lX1O-” Example 2 100 parts of ethyl acrylate, 4.4 parts of glycidyl acrylate, and 0.2 parts of azobisisobutyronitrile were copolymerized by the method described above. 100 parts of the resulting transparent acrylic elastomer A composition was prepared in the same manner as in Example 1 using 100 parts of acetone, 1.5 parts of diethylenetriamine as a crosslinking agent, and predetermined amounts of lithium perchlorate, propylene carbonate, and polyvinyl alcohol (pvA).

Crosslinking molding and measurement were performed. The obtained results are shown in Nos. 001 to 7 of Table 2 below.

Table 2 Electrolytes (Group Plasticizers)
1,0006,7X10-6 2 10 10 0 9.5X10-
'3 20 10 0 3.2XlO
-'4 1.0 0 5 1.7xt
O-'5 10 10 5 2, lX
l0-56 20 10 10 4.
6X10-'7 0 0 0 5.
9X10-'' Comparative Example 100 parts of SBR, predetermined amounts of polyvinyl alcohol as a water-soluble polymer substance, and sodium thiocyanate as an electrolyte substance were uniformly kneaded with a roll heated to 90°C, and then pressed at 180°C for 5 minutes. 120 x 2
The same measurements as in the examples were carried out on a sheet formed into a 40 x 2+n+n sheet. The results obtained are shown in Table 3 below.

Table 3 No 1 calculation p Hafu 1ge Mi 1 笈Ω” (Yu 1 0
0 1, lXl0-162 3
1 1.3X10-'3 6 3
2.7XlO-'4 10 5 4.
9X10-”□ Agent

Claims (1)

[Scope of Claims] 1. (a) an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and/or (b) an alkoxyalkyl acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms; and (c) at least one The following monomers (a) Epoxy group-containing vinyl monomer (b) Carboxyl group-containing vinyl monomer (c) Reactive halogen-containing vinyl monomer (d) Diene monomer (e) Hydroxyl group-containing vinyl An acrylic elastomer composition comprising a copolymer of a (h)amide group-containing vinyl monomer, an electrolyte material compatible with the copolymer, and a water-soluble polymer material. 2. Approximately 0.1 to 100 parts by weight of acrylic elastomer
The acrylic elastomer composition according to claim 1, wherein 100 parts by weight of electrolyte material is used. 3. Approximately 0.1 to 100 parts by weight of acrylic elastomer
The acrylic elastomer composition according to claim 1, wherein 20 parts by weight of a water-soluble polymeric substance is used. 4, (a) an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and/or (b) an alkoxyalkyl acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms; and (c) at least one of the following monomers ( (a) Epoxy group-containing vinyl monomer (b) Carboxyl group-containing vinyl monomer (c) Reactive halogen-containing vinyl monomer (d) Diene monomer (e) Hydroxyl group-containing vinyl monomer (f) An acrylic elastomer composition comprising a copolymer of an amide group-containing vinyl monomer, a plasticizer, an electrolyte material compatible with at least one of these, and a water-soluble polymer material. 5. Approximately 0.1 to 100 parts by weight of acrylic elastomer
5. The acrylic elastomer composition according to claim 4, wherein 100 parts by weight of electrolyte material is used. 6. The acrylic elastomer composition according to claim 4, wherein about 100 parts by weight or less of plasticizer is used per 100 parts by weight of the acrylic elastomer. 7. Approximately 0.1 to 100 parts by weight of acrylic elastomer
The acrylic elastomer composition according to claim 4, wherein 20 parts by weight of a water-soluble polymeric substance is used.