JPS62273273A - Electrically conductive coating composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in economy and electrically conductive effect, by formulating each specific phosphoric ester type surfactant and aminoether type one. CONSTITUTION:The objective composition can be obtained by formulating (A) 100pts.wt. of a phosphoric ester type surfactant of formula I or II (R1 is 8-22C alkyl or alkenyl; R2 is OH or R1O; R3 is 8-22C alkyl, alkenyl-contg. higher alcohol, etc., R4 is OH or R3O) and (B) 20-500pts.wt. of an aminoether type surfactant selected from compounds of respective formulae III-VI {R13 is the same as R1 or 8-22C hydroxyalkyl; R5 is ethylene or propylene, R6 is OH or (R5O)nH; n is integer 1-50; R7 is 7-21C alkyl or alkenyl; R8 is the same as R6 or of formula VII [x is 0 or integer 1-3; R9 is R7CON or (R5O)nH]; R10 is (R5O)nH or of formula VIII (R11 is the same as R5, etc.)}.

Description

[Detailed description of the invention]

The present invention relates to a conductive coating composition, and more particularly to a conductive coating composition that is economical and has excellent conductivity. Metal powder, graphite, and gold R7M fibers are the most common means to prevent problems in handling electronic components caused by the insulating properties of conventional polymer materials. Approaches have been taken to apply conductive coatings in which fillers such as carbon black are dispersed in binder solutions. However, in order to achieve the desired conductivity with these coatings, it is necessary to use an extremely large amount of filler; for example, in the case of the best silver powder-dispersed conductive coating, the amount of filler is four times the solid content of the binder. Unless a certain amount of silver powder is used, the desired conductivity cannot be obtained, which makes the product extremely expensive.At the same time, the low proportion of binder in the coating results in poor physical properties of the coating, which results in a long period of time. It has been pointed out as pressure. The present inventors have arrived at the present invention as a result of various studies to overcome the drawbacks of such conventional conductive coating agents,
The present invention uses the -i formula (
1) or general formula (2) R,0-P-CH...
・(1) ■ R1 (However, R1 is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and R is OH or R, O.) ○ R2O-P-OH... (2) ■ (However, R is an alkyl group having 8 to 22 carbon atoms, a higher alcohol having an alkenyl group, or an alkylphenol having an alkyl group having 4 to 12 carbon atoms, and 1 to 1 mol of ethylene oxide or/and propylene oxide.
00 molar residue, R4 is OH or R,○. ) General formula % Formula % (6) (R13 is the same as R1 or a hydroxyalkyl group having 8 to 22 carbon atoms, R is ethylene or propylene, R is hydrogen Atom or (R,0)nH,n is an integer from 1 to 50.) R1 R, C0NHR, N R, (5) (However, R7 is an alkyl group or alkenyl group having 7 to 21 carbon atoms, and R1 is an alkyl group or alkenyl group having 7 to 21 carbon atoms. R6 or formula % formula % or an integer from 1 to 3, R3 is R, CON or (R,○
)nH). ) N-CH. 〃 R7C1・・(6) R1゜ (where RI 1 is (R,0)nHl or a compound containing 20 to 500 parts by weight of at least one compound represented by the formula % (hereinafter referred to as the compound of the present invention) By adding a small amount of filler (hereinafter referred to as a substance), it exhibits an excellent conductive effect even with a lower filler content than conventional conductive coating agents, thereby reducing costs and improving the physical properties of the coating film. The object of the present invention is to provide a novel conductive coating agent based on the new discovery that the viscosity of the coating agent can be reduced as a secondary effect.The formulation of the present invention can be obtained as follows. Phosphate ester type surfactants represented by formulas (1) and (2) have carbon numbers determined by decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, cetyl alcohol, myristyl alcohol, oleyl alcohol, and Oxon method. 11 to 15 mixed alcohols, secondary alcohols having 12 to 13 carbon atoms, and higher alcohols 1 of these
A nonionic surfactant, butylphenol, to which 1 to 10 moles of ethylene oxide or/and propylene oxide are added by a known method. Oxychloride is added to 1 mol of these raw materials using nonionic surfactants, etc., which are made by adding 1 to 100 mol of ethylene oxide or/and propylene oxide to 1 mol of octylphenol, nonylphenol, dodenylphenol, or dinonylphenol by a known method. It is obtained by reacting phosphorus, phosphorus pentoxide, preferably phosphorus pentoxide, in an amount of 0.3 mol to 1.0 mol by a known method, and is usually obtained as a mixture of a monoester and a diester. Preferred in terms of performance are lauryl alcohol, tridecyl alcohol, oleyl alcohol, and carbon number 11 from the oxo method.
It is preferable to use a phosphate ester type surfactant made from a nonionic surfactant prepared by adding 5 to 15 moles of ethylene oxide to 1 mole of mixed alcohol, octylphenol, or nonylphenol. Aminoether type surfactants represented by general formulas (3), (4), (5), and (6) include decylamine, dodecylamine, myristylamine, valmitylamine, cetylamine, stearylamine, tallow amine, and behenylamine. , lauryl aminopropylamine, tallow aminopropylamine, and higher fatty acids such as lauric acid, myristic acid, valmitic acid, stearic acid, and oleic acid, as well as ethylenediamine, propylenecyamine, aminoethylnitanolamine, diethylenetriamine, and triethylenepentamine. , by reacting with amines such as tetraethylenepentamine by a known method. R, C0NHC, H4NH,,R. C0NHC, H4NH-C, H, ○H, R, C0NHC
2H,NHC,H4NH,,R,C0NHC,H,NH
C, H, NH,, R, CONHC, H4NHC, H4N
HOCR,,R,C0NH(C,H4NHLC,H4N
H2,R,C0NH(C,H4NHLC,H,NHO(
, R7, R, C0NH (C, H4NH), C', H4N
H,,R7CON H'(C=H-NH),C-
H-N HOCR. HC, H, N H. N-CH 〃 R, Cl N-CH. C, H, NHC, H, NH. Amide compounds or imidacillin compounds such as α
A product obtained by using a hydroxyalkylamine compound obtained by reacting an olefin with the above-mentioned polyalkyl polyamines or alkanolamines as a raw material and adding 1 to 3 oO moles of ethylene oxide to 1 mole of these raw materials by a known method. Preferred in terms of performance are dodecylamine, myristylamine, palmitylamine, cetylamine, stearylamine, tallow aminopropylamine, C, H, CONHC, HNHC,
H,NH,,C,,H,,C0NHC,H4NHC,H
4NHC,H,N)■ Occ,,H,,,N-CH□C,84N H. An aminoether type surfactant in which 5 to 20 moles of ethylene oxide is added to 1 mole is preferred. The phosphate ester type surfactant and the amino ether type surfactant thus obtained are used in a ratio of 1:0.2 to 1:5, or preferably, the acid ester type surfactant is The amine value equivalent and the amine value equivalent of the aminoether type surfactant should be mixed to be neutralized, or if the oxidation prevention of metals is expected, the aminoether type surfactant should be mixed in an amount larger than the neutralizing amount. It is preferable to mix them in a weight ratio of 1:0.5 to 1:2. The conductive coating agent of the present invention uses well-known fillers such as silver, platinum, copper, iron, tin, aluminum, nickel, carbon black, etc., and binders such as well-known phenol resins, polyester resins, acrylic resins, urethane resins, Alkyd resin, epoxy resin, etc. are used. The compound of the present invention is usually used in an amount of about 0.5 to 5% based on the filler, and is added at the time of manufacturing the coating agent, or the filler is treated in advance in a solution of the compound of the present invention and dried. Also good. Furthermore, the phosphoric acid ester type surfactant and the aminoether type surfactant of the present invention can be added separately in predetermined amounts at the time of manufacturing the coating agent. Next, the present invention will be explained with examples. Examples 1 to 2 (Synthesis of phosphate ester type surfactant (1) 1 1 mol of poly(8) oxyethylene nonylphenyl ether prepared by adding 8 mol of ethylene oxide to 1 mol of nonyl phenol by a known method) 572g of phosphorus pentoxide was added to a 4-liter diluted liquid, 57g of 0.4mol of phosphorus pentoxide was gradually added with stirring at room temperature, and the mixture was reacted at 9°C for 5 hours. A yellow viscous oily poly(8) oxyethylene nonylphenyl ether phosphate was obtained. [Synthesis of aminoether type surfactant (1) 1 241 g of 1 mole of hexadecylamine was charged into an autoclave, and 0.3 g of sodium succinate was added. was added, and 264 g of 6 moles of ethylene oxide was gradually added at 160°C under 3 atm of N gas.
Poly(6)oxyethylenehexadecylamine No. 11 was obtained as a yellowish brown viscous oil. [Production 1 of compounded product (1) of the present invention Poly(8) oxyethylene nonylphenyl ether phosphate [Phosphate ester type surfactant (1)) io
ng and poly(6)oxyethylenehexadecylamine [
95g of aminoether type surfactant (1)) at 60°C.
A yellowish brown paste-like compounded product (1) of the present invention was obtained. The crystal will be subjected to the test described below.

[Synthesis of phosphate ester type surfactants (2) to (9)] Phosphate ester type surfactants (2) to (9) were synthesized in the same manner as the synthesis of phosphate ester type surfactant (1). The results shown in Table 1 were obtained.

[Synthesis of aminoether type surfactants (2) to (9)]
Aminoether type surfactants (2) to (9) were synthesized in the same manner as the synthesis of aminoether type surfactant (1), and the results shown in Table 2 were obtained. [Coating agent composition of the present invention] 100 g of silver powder with an average tear diameter of 0.35μ, a compounded product of the present invention (
1) - (20) 1.5g, acrylic binder, Kodax LK-704 (solid content 50%, manufactured by Toshi) 100g
and 100 g of xylene were mixed in a mixer to obtain coating compositions (1) to (20) of the present invention. Similarly, silver powder 10
0g, Kodax LK-704 100g, solvent 100g
Comparative example (1) consisting of 100 g of silver powder, Kodax LK-70470 g, and 130 g of solvent (
A coating composition 2) was obtained. These coating compositions were applied to a polyester film with a film thickness of 2
The area electrical resistance was measured after coating to a thickness of 0 micron and air-drying at room temperature for one day, and the results shown in Table 4 were obtained. Furthermore, coating compositions (1) to (2o) of the present invention and Comparative Example (1) had superior coating film strength compared to Comparative Example (2). Table 4 As shown in Table 4, the coating composition of the present invention exhibited excellent conductivity despite the small amount of silver powder. [Examples 21 to 26] Channel carbon black 100g, blended products of the present invention (1), (5), (7), (1o), (16) and (1
), 1.2g of urethane binder UCX-90
1 (solid content: 30%, manufactured by JIMINKA) were mixed in a mixer to obtain coating compositions (21) to (26) of the present invention. Similarly, carbon black loog, UcX-901
A coating composition of Comparative Example (3) containing 330 g was obtained. These coating compositions were applied to a polyvinylidene film to a thickness of 20 microns, and after being air-dried for one day at room temperature, the area electrical resistance was measured, and the results shown in Table 5 were obtained. Table 5 Conductive Effects of the Conductive Coating of the Present Invention and Comparative Examples (2) As shown in Table 5, the coating composition of the present invention exhibited superior conductivity compared to the comparative examples. [Example (27) to Example (30)] 100 g of copper powder with an average particle size of 2 microns, 3 g of the blended products (2), (8), (12) and (2o) of the present invention, polyester binder Vylon 200 (solid content 100%,
Toyobo) 50g, toluene 200g, MIBK
100g of the coating composition of the present invention (
27) to (30) were obtained. Also its powder LOOg,
Comparative Example (4) consisting of 50 g of Vylon 200 and 300 g of solvent was obtained. These coating compositions were applied to a polyester film to a thickness of 20 microns, and after IB air drying at room temperature, the area electrical resistance was measured, and the results shown in Table 6 were obtained. Table 6 Conductive effect of the conductive coating agent of the present invention and comparative examples (3) [Example (31) to Example (33)] 50 g of nickel powder with an average particle size of 2 microns, 50 g of nickel powder with an average particle size of 20 mm, Compounded products (3), (4) of the present invention
), 2 g of (13), 50 g of polyester binder Vylon 200, 200 g of toluene, 1 acetone
00g of the coating composition of the present invention (31
) to (33) were obtained. Similarly, a comparative example (5
) was obtained. These coating compositions were applied to an ABS board to a film thickness of 20 microns, and after air-drying at room temperature for one day, the area electrical resistance was measured, and the results shown in Table 7 were obtained. Further, when the coating composition of the present invention was treated with 40'C for 11 months and the conductive effect was measured, there was almost no change. Table 7 Conductive effect of the conductive coating agent of the present invention and comparative examples (4) Patented by Kenjin Toho Chemical Industry Co., Ltd.

Claims (1)

[Claims] General formula (1) or general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……(1) (However, R_1 is an alkyl group having 8 to 22 carbon atoms, an alkenyl group, R_2 is OH or R_1O) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ...... (2) (However, R_3 is an alkyl group with 8 to 22 carbon atoms, a higher alcohol having an alkenyl group, or an alkyl group with 4 to 12 carbon atoms. 1 to 1 mol of ethylene oxide or/and propylene oxide to 1 mol of alkylphenol having a group
100 mol added residue, R_4 is OH or R_3
It is O. ) General formula (3), (4), (5) or (6) ▲ Numerical formula, chemical formula, table, etc. for 100 parts by weight of at least one type of compound shown in )... (3) {R_1_3 is R_1 or a hydroxyalkyl group with 8 to 22 carbon atoms, R_5 is ethylene or propylene, R_■ is a hydrogen atom or (R_5O)nH, n is an integer from 1 to 50} ▲There are mathematical formulas, chemical formulas, tables, etc. ▼...(4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(5) {However, R_7 is an alkyl group or alkenyl group having 7 to 21 carbon atoms, and R_■ is R_■ or ▲Mathematical formulas, chemical formulas, tables, etc. etc. ▼ [However, x is 0 or an integer from 1 to 3, R_■ is R_7CON or (R_
6O)nH]. } ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(6) {However, R_1_■ is (R_■O)nH, or the following formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R_1_1 is R■, R_5[ N-R_■]yR_1
_2, (y is 0 or an integer from 1 to 2, R_1_2 is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas,
There are tables etc. ▼. } An electrically conductive coating composition comprising 20 to 500 parts by weight of at least one of the following compounds.