JP2001181499A - Electroconductive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electroconductive composition capable of exhibiting a high electroconductivity even by a small amount of an added conductive material. SOLUTION: This electroconductive composition comprises a conductive material and a compound represented by the general formula (I) [X is a hydrogen atom, a 1-42C hydrocarbon group, a carboxyl group or an ester group; Y is a 1-42C hydrocarbon group, a carboxyl group, an ester group or CH2OR1 (R1 is a hydrogen atom, a 1-42C hydrocarbon group or the like); Z is a polymerization unit derived from a monomer copolymerizable with CH(X)CH(Y)O; (a) is >=4; and b is >=0].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive composition which exhibits high conductivity even when a small amount of a conductive material is added.

[0002]

2. Description of the Related Art Resins,
Rubber, paint and wax are usually insulators. Therefore,
As a method of imparting conductivity to these, a method of adding a conductive substance (hereinafter referred to as a conductive material) such as carbon or metal particles is known. However, with the method of adding conductive material,
In order to exhibit conductivity, it is necessary to add a large amount of a conductive material to a resin or rubber, so that it is difficult to uniformly mix the conductive material, and it is difficult to exhibit sufficient conductivity. Also, even if mixed, a large amount of conductive material
The problem is that the mechanical properties are greatly reduced.

[0003] An object of the present invention is to provide a conductive composition which exhibits high conductivity even when the amount of a conductive material added is small.

[0004]

The present invention relates to a conductive material and a compound represented by formula (I) (hereinafter referred to as compound (I)).
And a conductive composition comprising:

[0005]

Embedded image

[Wherein, X represents a hydrogen atom or has 1 carbon atom.
~ 42 hydrocarbon groups, carboxyl groups or ester groups. Y represents a hydrocarbon group having 1 to 42 carbon atoms,
Represents a carboxyl group or an ester group, or -CH
₂ OR ¹か where R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 42 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or a fluoroaryl group having 6 to 24 carbon atoms ,
Or showing a siloxy silyl propyl group having a silicon atom number 1 to 50, or - (AO) _n -R ² (wherein R ² represents a hydrocarbon group having 1 to 20 carbon atoms, A is 2-3 carbon atoms Represents an alkylene group, and n represents a number of 1 to 100). ｝
Represents a group represented by Z represents a polymerized unit derived from a monomer copolymerizable with the polymerized unit represented by -CH (X) CH (Y) O-.
a and b represent the number of repetitions of each polymerization unit, and a
≧ 4 and b ≧ 0. The conductive composition of the present invention can uniformly disperse the conductive material by the compound (I), and can impart high conductivity to resins, rubbers, paints, waxes and the like even with a small amount of the conductive material added.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound (I), when X and Y are a hydrocarbon group, preferred examples thereof are those having 1 to carbon atoms.
Examples thereof include an alkyl group or alkenyl group having 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an arylalkyl group or alkylaryl group having 7 to 18 carbon atoms. More preferred examples include methyl, n-propyl, isopropyl, n-butyl, t-butyl, octyl, decyl, dodecyl, cetyl, stearyl, phenyl, nonylphenyl, and the like. . X and Y are-
_They may be bonded by a linking group represented by (CH ₂ ) _s —, in which case s is an integer of 3 to 6, and is preferably 4. Also, X
And when Y is a hydrocarbon group, it may have a substituent, but as a substituent, a hydroxy group, an alkoxy group (1 to 18 carbon atoms), an amino group, a dimethylamino group, a diethylamino group, an amide group ( C1-C18), trialkyl (C1-C12) ammonium group, dialkyl (C1-C12), alkyl (C1-C12) ammonium Group, ammonium group, methyl ester group, ethyl ester group, carboxyl group (including its salt), acyl group (having 1 to 1 carbon atoms)
8), silyl group or siloxy group, chloro group, bromo group,
Examples thereof include a cyano group (hereinafter, referred to as “substituent of the present invention”).

When X and Y are carboxyl groups, a part or all of the carboxyl groups in the general formula (I) may form a salt with one or more cations such as lithium, sodium, potassium and ammonium. It may be formed. Of these, sodium or ammonium salts are preferred.

When X and Y are ester groups, the bond direction of the ester group may be either -COO- or -OCO-. Preferred examples thereof include methyl ester, ethyl ester, propyl ester, butyl ester, octyl ester, phenyl ester, allyl ester,
Examples thereof include methacrylate groups.

Y is the above hydrocarbon group, carboxyl group,
In addition to the ester group, a group represented by —CH ₂ OR ¹ may be used, and among them, a group represented by —CH ₂ OR ¹ is more preferable.

When R ¹ is a hydrocarbon group, preferred examples thereof include an alkyl or alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a 7 to 18 carbon atom.
Arylalkyl group or alkylaryl group. More preferred examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples thereof include a t-butyl group, an octyl group, a decyl group, a dodecyl group, a cetyl group, a stearyl group, a phenyl group and a nonylphenyl group. When R ¹ is a hydrocarbon group, it may have a substituent, and examples of the substituent include the aforementioned “substituents of the present invention”.

When R ¹ is a fluoroalkyl group, a preferred example is a perfluoroalkyl group having 1 to 22 carbon atoms, an ω-H-perfluoroalkyl group, or a fluoroalkyl group represented by -E-Rf. No. Here, E represents an alkylene group having 1 to 3 carbon atoms, and Rf has 1 to 22 carbon atoms.
Represents a perfluoroalkyl group or an ω-H-perfluoroalkyl group. Preferred examples of these fluoroalkyl groups R ¹ include a perfluorobutyl group, a perfluorohexyl group, a perfluorododecyl group, a perfluoro-3-methylbutyl group, a 4H-octafluorobutyl group, a 6H-dodecafluorohexyl group, and an 8H- Hexadecafluorooctyl group, 1H, 1H, 2H, 2H-nonafluorohexyl group, 1H, 1H, 2
H, 2H-heptadecafluorodecyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 7H-dodecafluoroheptyl group, 1H, 1H, 9H-hexadecafluorononyl group and the like.

When R ¹ is a fluoroaryl group, a preferred example is a perfluorophenyl group.

When R ¹ is a siloxysilylpropyl group, it preferably has 1 to 30 silicon atoms, more preferably 1 silicon atom.
-20 linear or branched siloxysilylpropyl groups. The alkyl substituents bonded to the silicon atom of the siloxysilylpropyl group may be the same or different, and examples thereof include a methyl group, a butyl group, a vinyl group, and a phenyl group.

When R ¹ is a group represented by — (AO) _n —R ² , the hydrocarbon group R ² may be methyl, ethyl, n-butyl, t-butyl, octyl, dodecyl, Groups, a cetyl group, a stearyl group, a phenyl group, a nonylphenyl group and the like are preferably exemplified. R ² may have a substituent,
Examples of the substituent include the aforementioned “substituent of the present invention”. Examples of the A group include an ethylene group and a trimethylene group, and n is preferably 1 to 50, and more preferably 2 to 10.

In the compound (I), X and Y may be plural types. In that case, their arrangement in the polyether main chain may be block, alternate, or random. When the compound (I) has a polymerized unit Z, the arrangement of the polymerized unit represented by -CH (X) CH (Y) O- may be any of block, alternating, and random. .

Here, as the polymerized unit Z, -CH (X) CH (Y) O-
Polymerized units derived from epoxides other than epoxide, or polymerized units derived from anionic polymerizable monomers other than epoxide are exemplified. Preferred _{examples, -CH 2 CH 2 O -,} - C (X) 2 CH (Y) O-
(X and Y indicate the foregoing _{groups), - CH 2 CH (CF} 3) O -, - CH 2
CH ₂ CH ₂ O−, −CH ₂ CH ₂ C (= O) O−, −CH ₂ CH ₂ CH ₂ CH ₂ C (= O) O
_{-, - CH 2 CH (Y} ) OC (= O) O- (Y represents the above groups), - C
_{H 2 CH 2 CH (Y)} OC (= O) O- (Y denotes the aforementioned group) or a group such as,
Examples include groups derived from monomers such as lactams, (meth) acrylates such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and methyl methacrylate, styrene, butadiene, isoprene, and terminal olefins having 5 to 22 carbon atoms. You.

A represents an integer of 4 or more, preferably 5
22,000,000, more preferably 5-1,000,000, particularly preferably 10-100,000.

B represents 0 (in this case, compound (I) is composed of only polymerized unit -CH (X) CH (Y) O-) or an integer of 1 or more, preferably 0 or 1 to 100,000, Preferably it is 0 or 5 to 10,000.

The conductive material used in the present invention may be any conductor or semiconductor (electrical conductivity of 10 ⁻⁸ S · cm ⁻¹ or more).

Specific examples of the conductive material include carbon compounds such as carbon black, graphite, tubular graphite, and fullerenes, metals such as iron, copper, silver, and aluminum; triiron tetroxide, tin oxide, and indium oxide. Metal oxides, inorganic compounds such as titanium nitride and silicon carbide, polymer compounds such as polyaniline, polypyrrole, and polyacetylene, and clay minerals. Among them, carbon black, graphite, tubular graphite, iron, copper, aluminum, polyacetylene and clay are preferred, and carbon black, tubular graphite, iron and clay are particularly preferred. These may be used alone or in any combination.

The shape of these conductive materials is not limited. That is, it may be spherical, ellipsoidal, plate-like, rod-like, tube-like, needle-like, or irregular. There is no limitation on the size of the conductive material.

In the present invention, the amount of the conductive material used is not limited, and can be appropriately adjusted according to the desired conductivity. Among them, conductive material is used for 100 parts by weight of the object to be given conductivity.
Addition of 0.001 to 500 parts by weight is preferred, more preferably
It is 0.005 to 100 parts by weight, most preferably 0.01 to 50 parts by weight.

In the present invention, the amount of compound (I) used is not limited at all. However, depending on the particle size and surface area of the conductive material to be used, compound (I) is added to 100 parts by weight of conductive material.
01 to 100 parts by weight are preferable, and 0.003 to 50 is more preferable.
Parts by weight, most preferably 0.005 to 10 parts by weight.

The type of medium in which the conductive material is dispersed is not particularly limited, and resins, rubbers, solvents, oils, waxes and the like can be used.

Specific examples of the resin include polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polybutadiene, polycarbonate, polyacrylonitrile, ABS resin, AES resin,
Polyamide 6, polyamide 66, polyamide 12, polyetherimide, polyetheretherketone, polysulfone, polyallylamine, polyphenylene oxide,
Petroleum resins, polytetrafluoroethylene, polyvinyl fluoride, polydimethyl silicone, thermoplastic resins such as polydiphenyl silicone and derivatives thereof, and copolymers containing them, and epoxy resins, phenol resins, phthalic resins, polyimides, Examples thereof include thermosetting resins such as polyurethane, furan resin, xylene-formaldehyde resin, melamine resin, urea resin, polyester resin, and unsaturated polyester resin, and derivatives thereof.

Specific examples of rubber include natural rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, isoprene rubber, nitrile-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, chloroprene rubber, neoprene rubber, urethane rubber, Norbornene rubber, epichlorohydrin rubber, fluoro rubber,
Synthetic rubbers such as silicone rubber and thermoplastic elastomer are exemplified.

There is no limitation on the type of pigment or vehicle as the paint. Specific examples of the pigment include inorganic pigments such as carbon black, titanium oxide, and metal lakes, and organic pigments such as nitroso-based, azo-based, and phthalocyanine-based pigments. Further, specific examples of the vehicle include a phenol resin, an alkyd resin, a melamine resin, a vinyl chloride resin, and a vinyl chloride resin.
Examples include vinyl acetate resin, acrylic resin, unsaturated polyester resin, polyurethane resin and the like. Further, there is no limitation on the solvent and oil contained in the vehicle, and toluene, acetone, ethyl acetate, ethanol, butanol,
Dry oils such as linseed oil, drill oil, eno oil, hemp seed oil, soybean oil, sardine oil and the like, boil oil and stand oil obtained by treating the dry oils, and the like. Also, silicone oil,
Hydrocarbon oils such as liquid paraffin and oils such as butadiene oligomers can also be used.

As the wax, a solid or semi-solid wax at normal temperature (for example, 25 ° C.) is used. For example, natural waxes such as candelilla wax, carnauba wax, rice wax, wood wax, beeswax, and lanolin; Examples include petroleum wax such as paraffin wax, microwax, petrolatum, polyethylene wax, and hardened castor oil.

In the present invention, there are no particular restrictions on the mixing order during the production of the composition. That is, the compound (I) and the conductive material may be mixed first, and then mixed with the medium. The mixture of the medium and the compound (I) may be mixed with the conductive material later. The compound (I) may be mixed with the mixture of the conductive materials, or they may be mixed together. At this time, there is no limitation on the mixing method,
Any known technique can be used. Specifically, mechanical mixing methods such as rolls, kneaders, mixers, mills,
Examples include a wet mixing method using an organic solvent.

The conductive composition according to the present invention can contain any additive. Examples of specific additives include plasticizers, stabilizers, fillers, reinforcing agents, antioxidants,
Examples include a curing agent, a viscosity modifier, an ultraviolet absorber, a flame retardant, a pigment, a matting agent, and a lubricant. What kind of additive is used is appropriately selected depending on the purpose of using the conductive composition obtained by the present invention.

[0032]

EXAMPLES The GPC measurement of the synthesis example was carried out by using Waters 15
Using a 0C type column, Shodex HT-806M x 1
Two ShodexHT-803 × 2 were used. For the measurement of the volume resistivity in the examples, R8340A manufactured by Advantest was used.

Synthesis Example 1 4 g of cetyl glycidyl ether was placed in a vessel purged with nitrogen, and 5.7 mL of toluene was added and dissolved. To this was added a catalyst prepared from 0.5192 g of samarium trisacetylacetonate and 0.22 mL (1 equivalent) of a toluene solution of methylalumoxane, and the vessel was sealed and polymerized at 130 ° C. with stirring. After completion of the polymerization, the reaction solution is added to acetone to which a small amount of dilute hydrochloric acid is added, and the precipitated white solid is dried under reduced pressure at 80 ° C. for 24 hours to obtain a compound represented by the general formula (II) (hereinafter, referred to as compound (II)) I got 95% yield. According to GPC analysis (130 ° C., o-dichlorobenzene, molecular weight in terms of polystyrene),
The number average molecular weight (Mn) was 130,000, and the weight average molecular weight (Mw) was 1.05 million.

[0034]

Embedded image

Example 1 Polypropylene resin (manufactured by Nippon Polychem Co., Ltd., BC03B, hereinafter abbreviated as PP), carbon black (manufactured by Mitsubishi Chemical Corporation, Ketjen Black EC), and compound (II) were prepared at composition ratios as shown in Table 1. They were mixed and kneaded with a twin screw extruder to form pellets.
A test piece was molded using an injection molding machine using the pellet, and the volume resistivity was measured.

Example 2 Instead of PP, polyethylene resin (manufactured by Nippon Polychem Co., Ltd.
A test piece was prepared in the same manner as in Example 1 except that L350 (hereinafter abbreviated as LDPE) was used, and the volume resistivity was measured. Table 1 shows the results.

Example 3 Iron powder (average particle size 150 μm) instead of carbon black
A test piece was prepared in the same manner as in Example 1 except that
The volume resistivity was measured. Table 1 shows the results.

Example 4 Iron powder instead of carbon black (average particle size 150 μm)
A test piece was prepared in the same manner as in Example 2 except that
The volume resistivity was measured. Table 1 shows the results.

Comparative Examples 1-4 Test pieces were prepared in the same manner as in Examples 1-4 except that no compound (II) was used, and the volume resistivity was measured. Table 1 shows the results.

[0040]

[Table 1]

Example 5 Natural rubber (RSS1), carbon black (Tokai Carbon Co., Ltd., Seast 300), tubular graphite, zinc white
(Manufactured by Wako Pure Chemical Industries), stearic acid (manufactured by Wako Pure Chemical Industries),
Compound (II), sulfur (manufactured by Wako Pure Chemical Industries, Ltd.), and a vulcanization accelerator (manufactured by Sumitomo Chemical Co., Ltd., Succinol D) were kneaded with a biaxial roll in a composition ratio as shown in Table 2. The obtained composition was pressed to a thickness of 2 mm to form a 5 cm × 5 cm test piece, and the volume resistivity was measured. Table 2 shows the results.

The tubular graphite was synthesized as follows. 1 kg of a 9: 1 copolymer of butyl methacrylate and vinyl ferrocene and 1 kg of petroleum pitch were mixed well, and pyrolyzed at 1000 ° C. in a silicone knit tube furnace under a nitrogen stream. After allowing to cool, the carbon compound precipitated on the inner wall of the end of the furnace was collected, and sufficiently washed with hexane and then with toluene. This was wet-ground in a ball mill in ethanol and dried. It was confirmed by a transmission electron microscope that the present compound was a tubular graphite having a diameter of 10 to 20 nm.

Comparative Example 5 A test piece was prepared in the same procedure as in Example 5 except that no compound (II) was used, and the volume resistivity was measured. Table 2 shows the results.

[0044]

[Table 2]

Example 6 A phenol resin (manufactured by Sumitomo Bakelite Co., Ltd.), carbon black (manufactured by Mitsubishi Chemical Corporation, Ketjen Black EC), and compound (II) were mixed in a composition ratio shown in Table 3 using three rolls. And apply it in a 2 mm line on the polyester sheet.
Cured at 50 ° C. for 30 minutes. Cured coating thickness is 25
μm. The electrical resistance of the linear coating film between 25 mm was measured. Table 3 shows the results.

Comparative Example 6 A linear coating film was prepared in the same procedure as in Example 6 except that no compound (II) was used, and the electric resistance was measured. Table 3 shows the results.

[0047]

[Table 3]

Example 7 Polyethylene wax (Polywax 655, manufactured by Toyo Petrolite Co.), n-butyl myristate, clay (Kunipia F, manufactured by Kokumine Kogyo) and compound (II) were biaxially mixed at a composition ratio as shown in Table 4. Mix with a roll, heat and melt to form a test piece,
The volume resistivity was measured. Table 4 shows the results. .

Comparative Example 7 A test piece was prepared in the same procedure as in Example 7 except that no compound (II) was used, and the volume resistivity was measured. Table 4 shows the results.

[0050]

[Table 4]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Taku Oda 1334 Minato, Wakayama-shi, Wakayama F-term in the Kao Research Laboratory (reference) 4J002 AA011 AC011 AE031 BB031 BB121 CC031 CH022 DA026 DA036 DA066 DE096 FD116

Claims (5)

[Claims] 1. A conductive composition containing a conductive material and a compound represented by the general formula (I). Embedded image [In the formula, X represents a hydrogen atom, a hydrocarbon group having 1 to 42 carbon atoms, a carboxyl group or an ester group.
Y represents a hydrocarbon group having 1 to 42 carbon atoms, a carboxyl group or an ester group, or -CH ₂ OR ¹
R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 42 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms or a fluoroaryl group having 6 to 24 carbon atoms, or a silicon atom having 1 to 42 carbon atoms. Indicates a siloxysilylpropyl group of 50, or-(A
O) _n -R ² (where R ² represents a hydrocarbon group having 1 to 20 carbon atoms, A represents an alkylene group having 2 to 3 carbon atoms, and n represents 1 to 10
Indicates the number of 0. ). Represents a group represented by｝. Z represents a polymerized unit derived from a monomer copolymerizable with the polymerized unit represented by -CH (X) CH (Y) O-. a and b represent the number of repetitions of each polymerization unit, and a ≧ 4, b ≧ 0
It is. ] 2. A conductive resin composition comprising a conductive material and a compound represented by the general formula (I). 3. A conductive rubber composition comprising a conductive material and a compound represented by the general formula (I). 4. A conductive coating composition comprising a conductive material and a compound represented by the general formula (I). 5. A conductive wax composition comprising a conductive material and a compound represented by the general formula (I).