JPS5929302A - Conductive resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention provides a conductive resin that can obtain sufficient conductivity with a small amount of conductivity imparting agent and has excellent flexibility, weather resistance (water resistance), coating film adhesion, etc. Regarding the composition.

Conventionally, resins for conductive compositions include epoxy resin,
Silicone resin, phenol resin, polyester resin, etc. are used. However, in the case of these resins, it is necessary to use a large amount of a conductivity imparting agent, and in the case of epoxy resin, phenol resin, and polyester resin, flexibility is poor, so It has the disadvantage that cracks and peeling are more likely to occur due to stress VC such as vibration and bending, and in the case of silyl-y-resin, it has the disadvantage of poor weather resistance (water resistance) and coating film adhesion.

As a result of various studies on methods for overcoming the above-mentioned drawbacks, the present inventors have found that the above-mentioned drawbacks can be overcome when a certain type of polybutadiene derivative is used as a polymerizable monolithic gold resin component having at least 1115 double bonds. , and the amount of expensive conductivity imparting agent used can be reduced, leading to the completion of the present invention.

That is, the present invention provides (A) (a) a 1,4 or 1,2-, which has do-D+cy groups at both ends, has a molecular weight of 500-'d, and is defined by C'OQ;
The do D+ groups at both ends of the polybutadiene group and (b) the isocyanate group of the di- or trifunctional isocyanate compound are bonded by a urethane bond, and the remaining isocyanate group and (t) acrylic acid or methacrylic acid. Noshido 0
A polybutadiene derivative in which the lower alkyl ester and the 1D+ radicals are bonded via urethane bonds, or the above (a) with the radicals at both ends, and (d) at least one double bond in the molecule. (B) a polymerizable monomer having at least one double bond capable of polymerization; (C) a polymerization catalyst that is a radical generator; and LD). It consists of a conductivity imparting agent, and the blending amount thereof is 25-1000 parts by weight of component (B) and 0.2-15 parts by weight of component (C) per 100 parts by weight of component (A), and ( D) The components are 10-. It relates to a conductive resin composition characterized in that the content is 85% by weight.

In the present invention, as a raw material for component (a) 1, 4 or 1,2 having do0+C groups at both ends and having a molecular weight of 500-sooo, preferably 1000-4000.
- using polybutadiene. As such component (a)
C is, for example, the commercially available product "R-45NOIT",
"l?-45nJ, rR-45D", r(
1”S-15J, [LM-10J, rL&-15J(
The above is 1,4-polybutadiene manufactured by Idemitsu Petrochemical Co., Ltd.)
, rG-1000J, "G-2000,, l, rG-3
000J (1,2-polybutadiene manufactured by Nippon Gita Co., Ltd.), etc. can also be used. Also, the same <(A)
(b) is a di- or tri-functional isocyanate compound which is a raw material of the component, and -C is, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, ■, 6-
to↑+t methylene:) diisocyanate, 1,12-dodecane diisocyanate, Schiff 0 butane-1,3-diisocyanate, Schiff 0 to ten sun: i-1.3 or 1,4
- diisocyanate or mixtures thereof, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methyl-schiff, 1.34 or L4-phenylene diisocyanate or mixtures thereof, 2,4 or 2. Diisocyanates such as 6-dodecane diisocyanate or mixed isocyanates or mixtures thereof, isophorone diisocyanate, naphthalene:J-1,5-diisocyanate, triphenylnate g can also be obtained. As the raw material (C) of acrylic acid or methacrylic acid, for example, 2-hydro+diethyl acrylate, 2-hydro+diethyl methacrylate, 2-hydro+diethyl methacrylate, Examples include ShidoD↑Syptyl acrylate, 2-Sido+Syptyl acrylate, 2-Sido0+diptyl methacrylate, 4-Human0+cyptyl methacrylate, and the like.

Each of the above components ('), (b), and (and) is usually used one at a time and subjected to a urethane bond forming reaction in a conventional manner to obtain a polybutadiene derivative, which is component (A) of the present invention.

Examples of such components include commercially available [R-45A]
CRJ, [R-45ACR-LCJ, “R-45ACR
-LV", "R-45ACR-Xl" (all manufactured by Idemitsu Petrochemical Co., Ltd.), etc. can also be used.

In addition, as the acid anhydride having at least one double bond in the molecule (tf) which is the raw material for the same <(A) component,
For example, maleic anhydride can be used as a substitute for maleic anhydride.

Usually, one type of each of the above-mentioned (a) component and the above-mentioned (d) component is used and subjected to an ester bond forming reaction by a conventional method to obtain a polybutadiene derivative which is the (A) component of the present invention. As such component (A), for example, commercially available 1"R-45
It is also possible to use MAJC Idemitsu Petrochemical Co., Ltd.'s Fu and the like.

The polybutadiene long chains and urethane bonds or ester bonds of the component (A) impart sustainability, toughness, water resistance, heat resistance, etc. to the polymerized composition.

Examples of the polymerizable monomer having at least one double bond which is component ([3)] used in the present invention include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and hesyl acrylate. Acrylate, cyclosyl acrylate, 2-ethyl + syl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Schiff 0 + syl methacrylate, syl methacrylate, 2-ethyl + syl methacrylate , lauryl methacrylate, glycidyl methacrylate, ethylene silicold diacrylate, methylene diglycol dimethacrylate, tetramethylene diglycol diacrylate,
Tetramethylegitalicol dimethacrylate, trimethyl 0-20 pantriacrylate, trimethyl 0-10
Pantorimethacrylate, neopentyl sili-sil acrylate, Fo + neopentyl glycol diacrylate, amber m-L6-↑Sandio-
Silacrylate, tri-1,3-poFf.

Range recall diacrylate, itaconic acid, acrylic 0
Nitrile, methacrylate trile, methacrylic mP trid,
Acrylic acid amide, styrene, α-methylstyrene, etc., and commercially available acrylates [AONIX &-
5500j, [A0nix”-5700J (A0nix M-6100J, [A0nix M-6300J
(The above are manufactured by Toagosei Co., Ltd.) 4,
One or more of these may be used.

The blending amount of component (B) is usually 25-1000 parts by weight, preferably 10-4 parts by weight per 100 parts by weight of component (A).
00 parts by weight. If it is less than 25 parts by weight, the viscosity will be high and workability will be poor, and if it exceeds 1,000 parts by weight, it will take a long time to cure.

Polymerizes with the curd component) to impart coating film adhesion, continuity, heat resistance, solvent resistance, etc.

Examples of the polymerization catalyst which is a radical generator for component (C) used in the present invention include cumene hito 0 pero 1 side, baylyyl l 1 1 sai 1 side, l-butyl parve υ lyate, lauroyl 1 2 side, and 1 -Organic peroxides such as butyl perphthalate, di-l-butyl peracetate, l-butyl peracetate, l-butyl hydroxide, Bread) shear tate, 2,2-p dihydrochloride, 2,2-p dihydrochloride, 2,2-p dihydrochloride, 1,1-p dihydrochloride, 1,1-p dihydrochloride, 1,1-p dihydrochloride 2,2-azidisu (2゜4-dimethylbenzene nitrile), 2,2'-azidisu (4-dimethylbenzene 2,4-dimethylvalenitrile) ), etc., and at least one of these compounds is used.

The blending amount of component (C) is usually 0.2-15 parts by weight, preferably 1-7 parts by weight, per 100 parts by weight of component (A). If it is less than 0.2 parts by weight, it will take a long time to cure;
If it exceeds parts by weight, flexibility will be insufficient.

In the present invention, in addition to the above component (C), a reaction accelerator may be used in combination as necessary. Such reaction accelerators include organic salts of transition metals, such as cobalt, nickel,
May 75, iron naphthinate, copper octylate, hef
'Iron gunate, prodione, iron I acid, etc. are used.

As the conductivity imparting agent of component (i) used in the present invention,
For example, metals such as gold, silver, copper, nickel, lead, lead, palladium, aluminum, titanium, etc., metal oxides such as titanium dioxide, tin dioxide, zinc oxide, carbon , silicon carbide, carbon or carbon compounds such as ter-J Tasten carbide, etc.
One or more of these may be used. These are usually used in the form of powder, flakes, or fibers, and the average particle size is not particularly limited, but is usually 0.01-
The thickness is about 100 μm, preferably about 0.1-10 μm.

The amount of component (D) varies depending on the type of component (D) used and the degree of conductivity required, but is usually 10-85 times the total composition. If it is less than 10% by weight, it is difficult to obtain sufficient conductivity.

(D) Specific resistance 10-5 depending on the selection of components and their blending amounts
Desired conductivity can be obtained within a range of about -1001.

In the composition of the present invention, in addition to the above-mentioned components, (i))
Various thixotropy agents are added to prevent sedimentation of components7.
Also, silica, clay, calcium carbonate,
Fillers such as talc, mica, aluminum hydroxide, magnesium hydroxide, zirconium oxide, zirconium hydroxide, titanium white, phthalocyanide green, chromium oxide + guidgilici, i:, / Tastorene blue, Konyoi, ultramarine, li Pigments such as D Mouillet []-, cadmium red, anthlanthrone, +nactory, and other additives commonly used in this type of composition can also be used.

The method for preparing the composition of the present invention is not particularly limited, and any known method can be applied. For example, component (5) and component (B) are dissolved, and component (C) and optionally Add and mix the reaction accelerator, etc. to be used, and then <D
) components are added and mixed using an 0-ru, 2+ goo, etc. to form a composition. It is also preferable that the component (C) and the reaction accelerator used if necessary are added separately at the time of use.

When using the composition of the present invention, it may be diluted with a solvent depending on the intended use. As the solvent in this case, any solvent used for this type of use can be used, such as toluene, +sile), 1" OD ethylene, tric 0 loethane, butyl calditol, butyl calditol ahitate, etc. be able to.

By using a specific polybutadiene derivative and a specific monomer as resin components, the conductive resin composition of the present invention has improved flexibility and weather resistance after curing compared to conventional ones.
Not only has the water resistance (water resistance) and adhesion of the coating film been significantly improved, but the amount of conductivity imparting agent required to obtain the same level of conductivity has been greatly reduced! It has the advantage of being able to strike down. In addition, the composition of the present invention has a lower viscosity than conventional compositions and cures in a short time.
C for about 100 minutes), and has a long pot life (more than 24 hours at room temperature, so it is easy to work with).

The application of the composition of the present invention is not particularly limited, and can be used in a wide range of applications that require electrical conductivity.In particular, due to its excellent flexibility, it can be suitably used in areas subject to repeated bending fatigue. Specifically, as an alternative to soldering, adhesives or caulking agents for integrated circuits, electronic and electrical parts, anti-static coatings for diode equipment, microphone D, :]yjiniters, cathode ray tubes, etc. It can be suitably used as a conductive paste for electric circuits, impregnation of cloth, paper, etc., and molded products such as conductive sheets, pressure-sensitive conductive sheets, crosses, hoses, etc.

The present invention will now be described in more detail with reference to Examples and Comparative Examples. For each of the cured products obtained in Examples and Comparative Examples, specific resistance was used as an indicator of conductivity, elongation and hardness were used as indicators of flexibility, water absorption was used as an indicator of water resistance, and coating film adhesion was measured using specific resistance as an indicator of conductivity. Each of the Erichsen tests was examined as an index.

Each test method is as follows.

Specific resistance...on a glass plate, thickness 50μ2n, width 4mm,
The product was coated and cured with a length of 7 cm and 1 g, and then the JIS (
According to the method of 1”-13Ql, the resistivity at 23°C (0
) was measured.

Elongation: Measured with an elongation trowel according to the method of JIS/(-63Ql).

Hardness -- Shore D hardness was measured according to the method of ASTM D-224Q, and D Tsukwell hardness was measured according to the method of ASTM D-185. Shore D hardness of 60 corresponds to about 14.1 in D Tsukwell hardness. ...Prepared a test piece with a length of 50mm, a width of 50fl, and a thickness of 3mm, and immersed it in water at 23°C for 24 hours, and the weight before and after was increased by 2 (%)
was measured.

Eriksen test... Hard coated on a mild steel plate with a thickness of 50μm 5 on one side in the center of the extrusion part in advance. Make an n square cut. Then apply it to the Erichsen tester. Insert it with the membrane side outside, and insert it directly from the inside. Push it out with a diameter 15 silk punch and Pressure when the center cut part peels off The ejection distance (ff) was measured.

Example 1-10r Polybutadiene derivative CrR-45MA] or “R-4
5ACR, both manufactured by Idemitsu Petrochemical Co., Ltd.) and polymerizable monomers [Styrene υ and [POnics &-5701]
J (manufactured by Toagosei@)) or trimethyl 0-ru 0 pantriacrylic 1 note] is mixed with 1 agent (resin component), and 1 agent and a blackout property imparting agent (silver powder or niraguru powder, either (average particle size: 1 μm) were mixed and kneaded using three rolls. This contaminant and ■ agent (polymerization catalyst) [
Lucidor 50PJ (Penriil Pao + Gate's 5
0% by weight paste (manufactured by Kayaku Thule Co., Ltd.) was mixed with a needle,
Various test materials were prepared by heating and curing at 100'C for 30 minutes. (Example 1-7) Next, as a polymerizable monomer, ethyl acrylate, 2-
Various test pieces were prepared in the same manner as above, except that ethyl silacrylate or dilycidyl methacrylate was used alone. (Example 8-10) The amounts of each component of the l agent, the conductivity imparting agent, and the additive are listed in Table 1 (Example 1-7) and Table 2 (Example 8-10).
In addition, the results of each test are shown in Table 3.

Table 2 (Note) In Tables 1 and 2, the values in the columns of silver powder and nickel powder indicate MJIt% relative to the entire composition. All other numbers indicate parts by weight.

Comparative Example 1-5 For comparison, one drug was prepared as shown in Table 4,
A conductivity imparting agent (same as that used in the example) and a conductive agent were mixed, and the curing conditions were 80°C for 2 hours and l20'.
Same as Example except that C was used for two-step curing for 4 hours.
A mixture and a test piece were prepared.

The results of each test are shown in Table F.

Table 4 (Note) The values in the columns of silver powder and nickel powder indicate the weight % based on the entire composition. All values of flh indicate parts by weight.

*“Kogo Coat 828” No. 5 manufactured by Yuka Shell Co., Ltd.
As is clear from Tables 3 and 5, when the same conductivity imparting agent is used in equal proportions, the composition of the present invention exhibits significantly superior conductivity compared to the comparative composition. It is also found that the composition of the present invention has significantly superior flexibility, water resistance, and coating adhesion compared to comparative compositions (see above) 11-

Claims (1)

[Scope of Claims] ■(A) (a) A 1,4 or 1,2-polybutadiene having a dolo+shi group at both ends and a molecular structure of 5oo-sooo. , <b> The isocyanate groups of the di- or trifunctional isocyanate compound are bonded via a urethane bond, and the remaining isocyanate group and (C) the bond of acrylic acid or i methacrylic acid. A polybutadiene derivative in which the do0+Ci groups are bonded through urethane bonds, or the above (a) in which the do0+Ci groups at both ends and the acid anhydride having at least one double bond in the molecule form an ester bond. A polybutadiene derivative bound by (B) a polymerizable monomer having at least one double bond, (C) a polymerization catalyst as a radical generator, and (D) a conductivity imparting agent; The blending amount is 25-1000 parts by weight of component (B) and 0.2-15 parts by weight of component (C) per 100 parts by weight of component (A), and the total amount of component (D) is +
7) A conductive resin composition characterized in that the content is 10-85% by weight.