JPS6351467B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a conductive resin composition, and particularly to a conductive resin composition that can impart high conductivity with a small amount of carbon black. Specifically, by mixing carbon black treated with a titanate coupling agent with resin, or by adding a titanate coupling agent in the process of mixing carbon black with resin, high conductivity can be imparted with a small amount of carbon black. The present invention relates to a resin composition. Conventionally, it has been known to impart conductivity to a resin by blending carbon black into the resin. Conductive resins are conductive materials for high-voltage cables, conductive materials for heating elements, electromagnetic shielding materials for ICs, etc.
It is widely used as a conductive material for video discs, an antistatic material for packaging materials, conductive printing inks, conductive paints, conductive adhesives, etc. As the carbon black that imparts conductivity to the resin, acetylene black, by-product carbon black, or conductive furnace black is usually used. However, in order to blend these carbon blacks into a resin and impart sufficient electrical conductivity, a considerable amount of carbon black must be blended. For example, to reduce the volume resistivity of polyethylene to 10 ⁴ Ω・cm or less, add 15 parts of Kettien Black EC (manufactured by Lion Akzo Co., Ltd., secondary carbon black) to 100 parts by weight of polyethylene.
It is necessary to mix more than 1 part by weight. However, blending a considerable amount or more of carbon black into a resin requires a long time and high temperature during blending and kneading, which tends to cause resin deterioration. The moldability is poor because of the increased Therefore, in order to provide the same level of conductivity, it is preferable to incorporate as little carbon black as possible, but such a resin composition has not yet been found. As a result of extensive research, the present inventor has found that by adding a titanate coupling agent to a composition in which conductive carbon black treated with a titanate coupling agent is blended with a resin, or when blending conductive carbon black with a resin, In the case of polyethylene, the conductive carbon black was found to have a high conductivity equal to or higher than that of conventional materials even when the amount of conductive carbon black is 8 to 13 parts by weight per 100 parts of polyethylene. The invention has been achieved. An object of the present invention is to provide a resin composition that has high conductivity even when the amount of conductive carbon black is small. That is, the present invention is a conductive resin composition comprising 3 to 60% by weight of conductive carbon black and 0.01 to 10% by weight of a titanate coupling agent based on the conductive carbon black. Next, the present invention will be explained in detail. In the present invention, it is necessary to treat the conductive carbon black blended with the resin with a titanate coupling agent. There are two methods for treating the titanate coupling agent: one is to first treat the conductive carbon black with the titanate coupling agent and then blend it into the resin, and the other is to add the titanate coupling agent at the same time when blending the resin and the conductive carbon black. There is a way to handle this. The former method involves dissolving the titanate coupling agent or titanate coupling agent with a solvent from the top of the stirrer while stirring the conductive carbon black at high speed in a high-speed stirring mixer (for example, Henschel mixer manufactured by Mitsui Miike Manufacturing Co., Ltd.). The solution is dripped or sprayed to uniformly adhere the titanate coupling agent to the conductive carbon black, then taken out from the stirrer and dried with hot air. A conductive resin composition is obtained by kneading with a kneader such as a kneader or an extruder. In the latter method, a resin, conductive carbon black, and a titanate coupling agent are blended and kneaded using a kneading machine such as a two-roll mixer, a Banbury mixer, a kneader, or an extruder to form a conductive resin composition. In the present invention, various known conductive carbon blacks can be used as the conductive carbon black treated with the titanate coupling agent, such as Ketsuen Black EC (manufactured by Lion Akzo),
vulcan
etc. Next, in the present invention, the resins in which the conductive carbon black treated with a titanate coupling agent is mixed include polyethylene, polypropylene, ethylene-acrylate copolymer,
Ethylene-vinyl acetate copolymer, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, nylon 6, nylon 66, thermoplastic polyurethane resin, polyester resin, polyether resin, polycarbonate, polyvinyl chloride, ethylene-salt vinyl polymer, Various known resins can be used, including thermoplastic resins such as propylene-vinyl chloride copolymers, thermosetting resins such as phenolic resins, urethane resins, epoxy resins, unsaturated polyester resins, and alkyd resins. In addition, these resins may contain antioxidants, ultraviolet absorbers, inorganic fillers, reinforcing agents, crosslinking agents, colorants,
Additives such as plasticizers and heat stabilizers may also be added. Next, in the present invention, the titanate coupling agent for treating conductive carbon black has the general formula:

[Formula] {where R ₁ is an optionally substituted alkyl group, x is an integer of 1 to 3, m and n are integers of 0 to 3, and satisfies x+m+n=4, A and B
is −OCOR ₂ , −OSO ₂ R ₃ , −OPO(OH−O−PO−
(OR ₄ ) ₂ , -O-R ₅ (where R ₂ , R ₃ , R ₄ , R ₅ represent an alkyl group, an alkenyl group, a cumyl phenyl group, an allyl group, a methacrylic group, etc.)] Coupling agents, or titanate coupling agents with coordination bonds such as tetraisopropyl di(dilauryl phosphite) titanate, diisostearoyloxyacetate titanate, di(dioctylpyrophosphate)
A titanate coupling agent having a heterocycle such as oxyacetate titanate can be used. Next, in the present invention, when processing with a titanate coupling agent, the solvent used is an aliphatic hydrocarbon, an aromatic hydrocarbon, a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, etc., or an ester solvent. Various known materials can be used. If the amount of the titanate coupling agent used in the treatment of conductive carbon black in the present invention is small, the treatment will not be effective, and if it is too large, the effect will be saturated. , the throughput of titanate coupling agents for conductive carbon black is usually
0.01% to 10% by weight, preferably 0.1% to 5% by weight
A titanate-based coupling agent is blended into the conductive carbon black so that the following results are obtained. If the amount of conductive carbon black treated in the present invention is incorporated into the resin, if it is extremely small, it will not have the effect of imparting conductivity, and if it is too large, the effect will be saturated, so it will vary depending on the type of resin etc. However, carbon black is blended into the resin so that the carbon black content is usually 3 to 60% by weight, preferably 5 to 50% by weight. After the conductive carbon black treated with a titanate coupling agent, or the conductive carbon black and the titanate coupling agent are blended with a resin, this is thoroughly kneaded and then molded into a suitable shape. As a kneading device, a known device such as a two-roll mill, a Banbury mixer, a kneader, or an extruder type kneader can be used. The conductive resin composition of the present invention thus obtained is excellent as a conductive material, an antistatic material, etc. even if the amount of carbon black incorporated is extremely small compared to conventional compositions. By appropriately selecting the processing conditions for conductive carbon black in the present invention, the amount of conductive carbon black added to the resin, etc., it is possible to reduce the volume resistivity to 10 ² Ωcm or less without deteriorating moldability. Therefore, it is very useful as a conductive material. As described in detail above, according to the present invention, compared to conventional conductive carbon black resin compositions, it has a low conductive carbon black content and has almost the same or higher conductivity. A resin composition can be provided. The conductive resin composition of the present invention can be used not only for molded articles as described above, but also for conductive paints, inks, and adhesives. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the spirit thereof is changed. Examples 1 to 21, Comparative Examples 1 to 9 300g of various carbon blacks shown in Table 1 below
While stirring in a 10-capacity Henschel mixer (manufactured by Mitsui Miike Seisakusho), a solution of various titanate coupling agents dissolved in 100 parts by weight of mineral spirits was mixed from the top of the Henschel mixer using the treatment shown in Table 1 below. After spraying, 100℃,
After drying for 5 hours, each conductive carbon black treated with a titanate coupling agent was prepared. This was blended with various resins shown in Table 1 below in various contents and thoroughly kneaded using a two-roll mill heated to 100°C to 180°C. After kneading, the same composition was molded at 150° C. to 180° C. and a pressure of 200 Kg/cm ² to prepare a flat plate of 40×100×3 (mm), and the volume resistivity was measured. For comparison, the volume resistivity of a conventional carbon black-containing resin that was not treated with a titanate coupling agent was also measured in the same manner as in the above example. The results are shown in Table 1. In addition, the volume resistivity is
Measured by the method of ASTMD-991.

【table】

[Table] Examples 22 to 31, Comparative Examples 10 to 14 Various conductive carbon blacks, resins, and titanate coupling agents shown in Table 2 below were blended in various contents and thoroughly kneaded using a Banbury mixer. did. After kneading, the same composition was heated at 150°C to 180°C,
A flat plate of 40×100×3 (mm) was formed by molding at a pressure of 200 Kg/cm ² and the volume resistivity was measured. For comparison, the volume resistivity of a resin containing conventional conductive carbon black that was not treated with a titanate coupling agent was also measured in the same manner as in the above example. The results are shown in Table 2.

【table】

[Table] Examples 32 to 37, Comparative Examples 15 to 17 Silicone rubber SH-1820 (manufactured by Torray Silicone), conductive carbon black, and isopropyl triisostearoyl titanate were mixed in three rolls in the amounts shown in Table 3 below. After kneading, 1% by weight of benzoyl peroxide was mixed uniformly, and then pressure molded at 70℃, 100Kg/cm ² for 4 hours,
A flat plate of ×100 × 3 (mm) was prepared, and the volume resistivity value was measured. For comparison, the volume resistivity value of a resin composition containing no titanate coupling agent was also measured in the same manner. The results are shown in Table 3.

[Table] Example 38, Comparative Example 18 100 parts by weight of Acrydik A-801 (manufactured by Dainippon Ink & Chemicals, acrylic polyol) and Vulcan
Blending 7 parts by weight of XC-7C (manufactured by Cabot Corporation, USA) and 0.07 parts by weight of tetra-n-butyl titanate,
After kneading with 3 rolls, Desmodille N-75
Add 12 parts by weight of hexamethylene diisocyanate (manufactured by Sumitomo Bayer), adjust the viscosity to Ordkap #4.20 seconds with thinner, and spray paint on polyester film to a coating thickness of 50 μm.
℃ for 1 hour to prepare a 40 x 100 x 3 (mm) coated film, and its surface resistance was measured. For comparison, the surface resistance of a composition containing no titanate coupling agent was also measured in the same manner as in the above example. Example 38 is 2×10 ⁵ and comparative example 18 is 9×10 ⁵
It was hot. The surface resistance was measured using an electrometer TR-8651 manufactured by Takeda Riken.

Claims (1)

[Scope of Claims] 1. A conductive resin composition comprising 3 to 60% by weight of conductive carbon black and 0.01 to 10% by weight of a titanate coupling agent based on the conductive carbon black. 2 Claim 1 using conductive carbon black treated with a titanate coupling agent
The conductive resin composition described in .