Conductive Liquid Composition

Abstract

A conductive liquid composition includes: for a binder resin, 5 to 25 mass % of hydroxyl-containing resin with hydroxyl value 3 to 100 and weight-average molecular weight 4000 to 20000, for a solvent, at least one solvent with a boiling point 170 C., 70 mass % of the total solvent, for a curing agent, 1.5 to 10.0 mass % of polyisocyanate, (D) for a curing accelerator, 0.005 to 0.1 mass % of an organometallic compound, (E) for an adhesion reinforcing agent, 0.2 to 2.5 mass % of coupling agent, (F) for conducting materials: (f1) 2.0 to 10.0 mass % of graphite, (f2) 5.0 to 15.0 mass % of conductive carbon black, and (f3) 20.0 to 50.0 mass % of silica particles with a mean particle size 1.0 to 7.0 m and surface-coated with silver, and (G) a surface resistivity 1 to 1000 /sq. when the thickness of the cured film of the conductive liquid composition is 8 m.

Claims

1. A conductive liquid composition comprising: (A) for a binder resin, from 5 to 25 mass % of a hydroxyl-containing resin with a hydroxyl value from 3 to 100 and a weight-average molecular weight from 4000 to 20000, (B) for a solvent, at least one type of solvent, each with a boiling point of not less than 170 C. selected from the group consisting of isophorone, dibasic acid esters, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, ethyleneglycol monobutyl ether acetate, coal tar naphtha with a boiling point of more than 170 C., diethyleneglycol monoethyl ether, diethyleneglycol monoethyl ether acetate, diethyleneglycol monobutyl ether, diethyleneglycol monobutyl ether acetate, triethyleneglycol monobutyl ether, triethyleneglycol monobutyl ether acetate, polyethyleneglycol dimethyl ether, tetraethyleneglycol dimethyl ether and polyethyleneglycol monomethyl ether, at not less than 70 mass % of the total solvent, (C) for a curing agent, from 1.5 to 10.0 mass % of polyisocyanate, (D) for a curing accelerator, from 0.005 to 0.1 mass % of an organometallic compound, (E) for an adhesion reinforcing agent, from 0.2 to 2.5 mass % of a coupling agent, (F) for conducting materials: (f1) from 2.0 to 10.0 mass % of graphite, (f2) from 5.0 to 15.0 mass % of conductive carbon black, and (f3) from 20.0 to 50.0 mass % of silica particles with a mean particle size from 1.0 to 7.0 m and surface-coated with silver, and (G) having a surface resistivity from 1 to 1000 /sq. when the thickness of the cured film of the conductive liquid composition is 8 m.

2. The conductive liquid composition according to claim 1, wherein the conductive liquid composition has a viscosity from 0.1 to 100 Pa.Math.s when measured at 251 C. by a BH-type rotating viscosimeter at 20 rpm/min, and the composition is adapted to be used for an ink for screen printing.

3. The conductive liquid composition according to claim 1, wherein the conductive liquid composition has a viscosity from 1.0 to 60 Pa.Math.s when measured at 251 C. by a BH-type rotating viscosimeter at 20 rpm/min, and the composition is adapted to be used for an ink for pad printing.

4. The conductive liquid composition according to claim 1, wherein the organometallic compound is a dibutyltin compound.

5. The conductive liquid composition according to claim 1, wherein the coupling agent is a silane coupling agent.

6. The conductive liquid composition according to claim 1, wherein the polyisocyanate is a block polyisocyanate having a curing reaction starting temperature of not less than 90 C.

7. The conductive liquid composition according to claim 1, wherein the conductive liquid composition further contains dimethylsilicon oil at from over 0 to 0.02 mass %.

8. An article having a coating layer of the conductive liquid composition according to claim 1.

9. A method for producing an article comprising the step of producing the article by coating the conductive liquid composition according to claim 1 onto a material for coating.

Description

EXAMPLES

[0105] Examples and Comparative Examples of the invention are shown in [Table 1] below. However, the invention is not limited to these examples.

[0106] The conductive liquid compositions of the examples and comparative examples in Table 1 were produced by precisely measuring out the materials in the amounts listed in the table into a production vessel, subsequently stirring with a propeller rotating stirrer until the material became thoroughly uniform, and then forming a dispersion by 2 passes with a triple roll mill.

TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 ple 9 ple 10 <Resin> Polyester resin (hydroxyl value: 15) 15.000 13.000 10.000 15.000 5.000 15.000 25.000 Epoxy resin (hydroxyl value: 3) 5.000 5.000 15.000 Amic acid resin (hydroxyl value: 100) 10.000 15.000 Acryl resin (hydroxyl value: 120) Solvent DBE (boiling point: 203-245 C.) 10.000 21.960 20.000 15.000 10.000 10.000 Coal tar naphtha (boiling point: 195-245 C.) 4.000 6.000 10.000 Ethyleneglycol monobutyl ether acetate (boiling 20.000 3.400 16.982 5.000 point: 190-195 C.) Isophorone (boiling point: 216 C.) 20.000 14.000 18.982 10.000 10.000 Polyethylene glycol dimethyl ether 6.500 3.295 6.585 4.920 (boiling point: 264-294 C.) Cyclohexanone (boiling point: 156 C.) 19.795 3.000 5.579 1.000 Diacetone alcohol (boiling point: 168 C.) 1.000 3.460 <Curing agent> Non-blocked polyisocyanate (hexamethylene 10.000 5.000 1.500 diisocyanate) 120 C. Block polyisocyanate (hexamethylene 1.500 3.000 4.000 5.000 5.000 4.000 2.500 diisocyanate) <Curing accelerator> Dibutyltin compound 0.005 0.100 0.015 0.020 0.020 0.020 0.005 0.015 0.015 0.050 <Coupling agent> Silane coupling agent 0.200 2.500 0.500 1.000 0.400 0.500 0.200 0.500 0.400 0.500 <Conductive material> Graphite (mean particle size: 8 m) 2.000 10.000 4.500 2.000 5.000 2.000 10.000 5.000 4.000 2.000 Conductive Ketjen carbon black 5.000 15.000 10.000 5.000 5.000 10.000 15.000 10.000 10.000 5.000 (mean structure length: 50 m) Surface silver-coated silica (mean particle size: 7 20.000 27.000 35.000 50.000 20.000 25.000 20.000 10.000 m) Surface silver-coated silica 20.000 50.000 25.000 14.500 40.000 30.000 (mean particle size: 1 m) <Antifoaming agent> Dimethylsilicone oil 0.003 0.020 0.001 0.020 0.003 0.030 <Total content (mass %)> 100.000 100.000 100.000 100.000 100.000 100.000 100.000 100.000 100.000 100.000 Viscosity [Pa .Math. s] 0.10 100.00 29.00 60.00 35.00 75.00 70.00 30.00 35.00 25.00 Measured electric resistivity [/sq.] 1000.00 537.43 23.77 3.65 20.95 96.28 8.68 53.45 70.55 65.70 Measured surface roughness [m] 0.79 0.43 0.58 0.75 0.70 0.49 0.56 0.51 0.48 0.77 <Performance evaluation> Adhesion on polyimide film substrate G G G G G G G G G G Adhesion on glass substrate G G G G G G G G G G Flexibility G G G G G G G G G G Surface smoothness G G G G G G G G G G MEK rinsing resistance G G G G G G G G G G Conductive function G G VG G VG VG G VG VG VG Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 <Resin> Polyester resin (hydroxyl value: 15) 3.000 10.000 5.000 15.000 10.000 10.000 Epoxy resin (hydroxyl value: 3) 15.000 5.000 10.000 10.000 Amic acid resin (hydroxyl value: 100) 10.000 Acryl resin (hydroxyl value: 120) 15.000 Solvent DBE (boiling point: 203-245 C.) 30.000 20.000 21.960 15.000 34.470 34.470 Coal tar naphtha (boiling point: 195-245 C.) 4.000 4.000 Ethyleneglycol monobutyl ether acetate (boiling 5.000 3.400 point: 190-195 C.) Isophorone (boiling point: 216 C.) 18.982 2.400 Polyethylene glycol dimethyl ether 3.297 (boiling point: 264-294 C.) Cyclohexanone (boiling point: 156 C.) 4.870 5.579 1.000 Diacetone alcohol (boiling point: 168 C.) 10.000 <Curing agent> Non-blocked polyisocyanate (hexamethylene 5.000 1.000 1.500 10.000 diisocyanate) 120 C. Block polyisocyanate (hexamethylene 4.000 5.000 5.000 5.000 diisocyanate) <Curing accelerator> Dibutyltin compound 0.100 0.020 0.015 0.020 0.003 0.100 0.030 0.030 <Coupling agent> Silane coupling agent 2.000 0.400 0.500 1.000 0.200 0.100 0.500 0.500 <Conductive material> Graphite (mean particle size: 8 m) 5.000 5.000 5.000 2.000 10.000 10.000 10.000 5.000 Conductive Ketjen carbon black 10.000 5.000 10.000 5.000 15.000 15.000 15.000 3.000 (mean structure length: 50 m) Surface silver-coated silica (mean particle size: 7 40.000 20.000 20.000 50.000 25.000 30.000 10.000 20.000 m) Surface silver-coated silica 20.000 14.500 25.000 5.000 20.000 (mean particle size: 1 m) <Antifoaming agent> Dimethylsilicone oil 0.030 0.001 0.003 0.020 <Total content (mass %)> 100.000 100.000 100.000 100.000 100.000 100.000 100.000 108.000 Viscosity [Pa .Math. s] 5.00 31.00 35.00 62.00 70.00 100.00 25.00 30.00 Measured electric resistivity [/sq.] 25.33 28.48 55.00 4.50 8.68 595.00 1500.00 65.00 Measured surface roughness [m] 0.61 0.71 1.15 0.78 0.56 0.48 0.49 1.53 <Performance evaluation> Adhesion on polyimide film substrate G G G P G G G G Adhesion on glass substrate F G G P F P G G Flexibility G G G G G G G G Surface smoothness G G F G G G G F MEK rinsing resistance P F G P F P G G Conductive function VG VG VG G G G F VG

[0107] The evaluated properties and evaluation methods are described below.

[0108] The coated film was formed by screen printing (coating area: 80 mm50 mm rectangle, coated film thickness after drying curing: 8 m), and dry curing was carried out at 150 C. for 30 minutes.

Adhesion onto Polyimide Film Substrate

[0109] The coated film on a flexible polyimide substrate with a thickness of 125 m was subjected to a crosscut cellophane tape peeling test on a grid with 100 pieces of 1 mm-squares (hereunder referred to simply as grid peeling test), and to a scratch peeling test with the fingernail (hereunder referred to simply as fingernail peeling test, with an evaluation of G to be satisfactory.

[0110] G: Absolutely no peeling in grid peeling test or fingernail peeling test.

[0111] F: Slight peeling occurred in grid peeling test or fingernail peeling test.

[0112] P: Obvious peeling occurred in grid peeling test or fingernail peeling test.

Adhesion onto Glass Substrate

[0113] The coated film on a 2 mm-thick glass substrate was subjected to a gridpeeling test and a fingernail peeling test, with an evaluation of G being considered satisfactory.

[0114] G: Absolutely no peeling in grid peeling test or fingernail peeling test.

[0115] F: Slight peeling occurred in grid peeling test or fingernail peeling test.

[0116] P: Obvious peeling occurred in grid peeling test or fingernail peeling test.

Flexibility

[0117] The coated film on a flexible polyimide substrate with a thickness of 125 m was subjected to 180 folding three times, together with a polyimide substrate, and the outer appearance of the coated film was observed while changes in the electric resistivity were measured, with an evaluation of G being considered satisfactory.

[0118] G: No abnormal outer appearance, change in electric resistivity of less than 5%.

[0119] F: No abnormal outer appearance, but change in electric resistivity of not less than 5%.

[0120] P: Abnormalities in outer appearance such as cracking.

Surface Smoothness

[0121] The surface roughness of the coated film on a flexible polyimide substrate with a thickness of 125 m was measured with a surface roughness measuring instrument SV-600 by Mitsutoyo Corporation.

[0122] G: Less than 0.8 m.

[0123] F: Less than from 0.8 to 2.0 m.

[0124] P: Not less than 2.0 m.

MEK Rinsing Resistance

[0125] The coated film on a flexible polyimide substrate with thickness of 125 m was immersed for 1 hour in an MEK solution, and then the outer appearance of the coated film was observed while changes in the electric resistivity were measured, with an evaluation of G to be satisfactory.

[0126] G: No abnormal outer appearance, change in electric resistivity of less than 5%.

[0127] F: No abnormal outer appearance, but change in electric resistivity of not less than 5%.

[0128] P: Abnormalities in outer appearance such as dissolution, blistering, notable change in luster.

Conductive Function (Surface Resistivity)

[0129] The coated film on a flexible polyimide substrate with a thickness of 125 m was subjected to potential resistivity measurement by a K-705RS four-point probe meter of Kyowa Riken Co., Ltd. using the direct-current four-point probe method, with an evaluation of VG or G to be satisfactory.

[0130] VG: From 10 to 100 /sq.

[0131] G: From 1 to less than 10 /sq., or over 100 to 1000 /sq.

[0132] F: Less than 1 /sq., or more than 1000 /sq.

[0133] As shown in Table 1, with the conductive liquid compositions of the examples, it was possible to manufacture articles simultaneously satisfying the required performance aspects mentioned in paragraph [0056] above, and having satisfactory electromagnetic wave shield functions and antistatic functions.

[0134] In addition, when the conductive liquid resin composition of Example 5 was used to form a coating layer with a dry cured film thickness of 8 m on a flexible imide film substrate by pad printing, it was possible to manufacture articles simultaneously satisfying the required performance aspects mentioned in [0056], and having a satisfactory electromagnetic wave shield functions and antistatic functions, similar to Example 5.