JPH01297475A - Copper powder for electrically conductive coating material and electrically conductive coating composition - Google Patents

Abstract

PURPOSE:To obtain the subject copper powder capable of giving electrical conductivity and environmental resistance comparable to those of silver coating using an inexpensive coating material by coating the surface of copper powder with a mixture of an organic zirconate compound and an organic titanate compound. CONSTITUTION:The objective copper powder can be produced by coating the surface of copper powder with a mixture of an organic zirconate compound [e.g., isopropyl triisostearoyl zirconate or bis(dioctyl pyrophosphate)ethylene zirconate] and an organic titanate compound [e.g., isopropyl triisostearoyl titanate or isopropyl tris(dioctyl pyrophosphate) titanate]. An electrically conductive coating composition can be produced by compounding the coated copper powder with a resin binder and a solvent.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to copper powder for conductive paint, and more specifically, the present invention relates to copper powder for conductive paint, and more specifically, the present invention relates to copper powder for use in conductive paints, and more specifically, the present invention relates to copper powder for use in conductive paints. The present invention relates to a copper powder for conductive paint and a conductive paint composition that has improved storage stability and environmental resistance of the powder itself and the conductive paint.

[Prior art] Conductive paints, which are made by kneading conductive fillers such as nickel powder, silver powder, copper powder, and carbon powder into various resin binders, have been used as electromagnetic shielding materials to protect electronic devices from electromagnetic interference. This paint is applied to the surface of plastic molded products by spraying or brushing to shield them from electromagnetic waves. Among various conductive paints, copper-based conductive paints are cheaper than paints using silver powder or nickel powder, and have excellent shielding effects.

However, copper-based conductive paints have poor storage stability because the copper powder aggregates in the paint, making it difficult to obtain a good dispersion state. Furthermore, they are easily oxidized in environments such as heat and humidity, and therefore have poor environmental resistance. There is a problem in that conductivity tends to deteriorate (shielding effect attenuates). Various proposals have been made in the past to solve this problem. For example, a conductive coating composition (Japanese Unexamined Patent Publication No. 60-2582
73 Publication), surface treatment of steel powder with a coupling agent (Japanese Patent Laid-Open No. 60-30200), and coating electrolytic copper powder with organic titanate (Japanese Patent Laid-open No. 59-174661).
In addition to a method for producing silver-coated copper powder in which metallic silver is precipitated by substitution on the surface of metallic copper powder (Japanese Patent Application Laid-Open No. 60-243277), there are various other proposals (Japanese Patent Application Laid-Open No. 60-243277). 59-17961, JP 57-113505, JP 60-35405, JP 60-6
3239, JP 58-145769, JP 61-163975, JP 60-2021
66, JP 56-103260, JP 58-74759, JP 56-163166, JP 56-163165, JP 59-
36170, JP 57-34606, JP 55-102332).

[Problems to be Solved by the Invention] However, although conventional silver-coated copper powder exhibits low resistance and good environmental resistance, it is significantly costly, and copper powder treated with organic carboxylic acids, etc. After that, copper powder deteriorates rapidly, and copper powder coated with metal-organic compounds such as silane, titanium, and aluminum can achieve a certain degree of conductivity, but its environmental resistance, especially heat aging resistance, deteriorates significantly. Alloy plating such as solder impedes the conductivity of the copper powder itself, and even if a conductive paint is obtained by blending conventional copper powder with a resin binder, a solvent, and various organic compounds, the effect is was temporary and not sustainable.

This invention has been made based on the above-mentioned background, and its purpose is to eliminate the drawbacks of the conventional copper powder for conductive paints and conductive paint compositions, and to improve the conductivity of copper powder and electromagnetic shielding. An object of the present invention is to provide a copper powder for a conductive paint and a conductive paint composition in which the environmental resistance, chemical and physical strength, etc. of the copper powder itself and the paint composition are significantly improved without reducing the effectiveness.

[Means for Solving the Problems] As a result of conducting various tests and research on copper powder for conductive paint, the present inventor achieved the object of the present invention by coating the surface of steel powder with a mixture of organic zirconate and organic titanate. The present inventors have found that this method is effective and have completed this invention.

That is, the copper powder for conductive paint of the present invention is characterized in that the surface of the copper powder is coated with a mixture of an organic zirconate compound and an organic titanate compound.

In a preferred embodiment of the invention, the organic zirconate compound and the organic titanate compound have at least one easily hydrolyzable hydrophilic group and at least one hardly hydrolyzable hydrophobic group.

A first conductive coating composition according to the present invention is characterized by containing copper powder coated with a mixture of an organic zirconate compound and an organic titanate compound, a resin binder, and a solvent.

In a preferred embodiment of the first conductive coating composition according to the present invention, the coating amount of the mixture is 0.05 to 1
It can be reduced to 0% by weight.

A second conductive coating composition according to the present invention is characterized by containing a mixture of an organic zirconate compound and an organic titanate compound, copper powder, a resin binder, and a solvent.

In a preferred embodiment of the second conductive coating composition according to the present invention, the content of the mixture is 0.0% relative to the solid content composition.
05 to 10% by weight.

This invention will be explained in more detail below.

Copper powder The shape of the copper powder used in this invention can be obtained by electrolytic method, reduction method,
There are dendritic, granular, acicular, and spherical shapes obtained by the atomization method, and there are also flake shapes obtained by mechanically processing these with a ball mill or the like.

Further, dendritic copper powder, flaky copper powder, granular copper powder, and spherical copper powder can be mixed and used using a V-type mixer or the like.

Furthermore, as the raw material copper powder that can be used in this invention, metals such as silver, nickel, zinc, platinum, and palladium, alloys such as semi-Ill, and organic compounds such as amines, amino acids, carboxylic acids, and their derivatives are pre-prepared. It may be covered.

The copper powder to be treated can be pretreated to remove the oxidized coating from the surface of the copper powder using reagents such as inorganic acids, organic acids, various reducing agents, etc., or by hydrogen reduction, as necessary. . Additionally, the copper powder to be treated can be dried as a pretreatment.

Copper powder for conductive paint according to the present invention has a surface y
It is coated with a coating agent. This preferred zirconium compound has at least one easily hydrolyzable hydrophilic group and at least ] hardly hydrolyzable hydrophobic groups, and specifically, an organic zirconate compound represented by the following formula. be.

(RO) -Zr-(○")4-x (wherein, RO is an easily hydrolyzable organic group, OR' is an organic group that is hardly hydrolyzable and exhibits lipophilicity, and X is an organic group of 1 to 3 (integer) Such compounds include, for example, isopropyl triisostearoyl zirconate, isopropyl tridodecylbenzenesulfonyl zirconate, isopropyl tris(dioctyl pyrophosphate) zirconate, tetraisopropyl bis(dioctyl phosphate) zirconate, tetraoctyl bis(dioctyl pyrophosphate) zirconate, decyl phosphite) zirconate, tetra(2,2-diallyloxymethyl-1-butyl) bis(di-tridecyl) phosphite zirconate, bis(dioctyl pyrophosphate) oxyacetate zirconate, bis(dioctyl pyrophosphate) ethylene zirconate Isopropyltrioctanoylzirconate, Isopropyltrioctanoylzirconate, Isopropyldimethacryliisostearoylzirconate, Isopropylisostearoyldiacrylzirconate, Isopropyltri(dioctylphosphate)zirconate, Isopropyltricumylphenylzirconate, Isopropyltri(N-aminoethyl-aminoethyl) ) zirconate, dicumylphenyloxyacetate zirconate, diisostearoyl ethylene zirconate, etc.

Zirconate compounds preferred in terms of performance are obtained by reacting zirconium alkoxides with carboxylic acids, especially higher fatty acids. For example, per 1 mole of tetraisopropyl zirconium, several moles of higher saturated fatty acids such as stearic acid, balmitic acid, mystiric acid, lauric acid, capric acid, their isomers, and oleic acid, linoleic acid, lylunic acid, etc. React higher unsaturated fatty acids and their isomers. At this time, fatty acid ester is quantitatively produced as a by-product as acylated zirconium condenses with each other.

Organic Titanate Compound The copper powder for conductive paint according to the present invention is coated with a surface coating agent comprising a mixture of an organic titanate compound and an organic zirconate compound. This preferred titanate compound has both at least one easily hydrolyzable hydrophilic group and at least one hardly hydrolyzable hydrophobic group, and specifically, an organic titanate compound represented by the following formula. be.

(RO) T i (OR') 4-X (in the formula, R
(O is an easily hydrolyzable organic group, OR' is an organic group that is hardly hydrolyzable and lipophilic, and X is an integer from 1 to 3) Examples of such compounds include isopropyl triisostearoyl titanate. , isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphate) titanate,
Tetraoctylbis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-
butyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyltitanate, isopropyldimethacrylylisostearoyltitanate, isopropylisostearoyldiacryltitanate , isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate, and the like.

Titanate compounds preferred in terms of performance are obtained by reacting titanium alkoxides with carboxylic acids, especially higher fatty acids. For example, for 1 mole of tetraisopropyl titanium, several moles of higher saturated fatty acids such as stearic acid, valmitic acid, mystyric acid, lauric acid, capric acid, and their isomers, oleic acid, linoleic acid, etc.
React higher unsaturated fatty acids such as lylunic acid and their isomers. At this time, fatty acid ester is quantitatively produced as a by-product as the acylated titanium condenses with each other.

Surface Coating Agent The surface coating agent used in this invention consists of a mixture of an organic titanate compound and an organic zirconate compound.

The mixing ratio of the organic titanate compound and the organic zirconate compound is 90 to 10% by weight of the organic zirconate compound to 10 to 90% by weight of the organic titanate compound.

This is because if the content falls outside of this range, the environmental resistance of the copper powder and its composition will drop significantly.

In this invention, the amount of surface coating agent used is 0.01 to 15% by weight, preferably 0.05 to 10% by weight based on the copper powder.
Weight%. If the amount used is less than the lower limit, oxidation resistance is poor and patina occurs, discoloration and agglomeration of copper powder are likely to occur. This is because if the upper limit is exceeded, an excessive hydrophobic film is formed on the surface of the copper powder, which impairs conductivity.

The coating treatment method involves adding an organic zirconate compound and an organic titanate compound dissolved in a solvent to the copper powder, and then removing the solvent, adding a required amount of an organic zirconate compound and an organic titanate compound to the copper powder,
There are methods such as mixing and stirring.

Conductive Coating Composition There are two embodiments of the conductive coating composition of the present invention.

A first conductive coating composition according to the present invention includes copper powder coated with a mixture of an organic zirconate compound and an organic titanate compound, a resin binder, and a solvent.

The second conductive coating composition according to the present invention contains a mixture of an A-type zirconate compound and an A-type titanate compound, copper powder, a resin binder, and a solvent.

The amount of the mixture added in the second embodiment is 0.01 to 15% by weight, preferably 0.01 to 15% by weight, based on the composition excluding the solvent.
．． 05-10 weight 96. This is 0.05% by weight
If it is less than that, the surface of the copper powder in the composition will be insufficiently coated, and the composition will have poor conductivity, heat resistance, moisture resistance, environmental resistance such as storage stability, chemical strength such as chemical resistance, and adhesion to the substrate. This is because physical strength such as elasticity begins to decrease, and this tendency becomes remarkable when the weight is less than 0.01%. Also, 10
If it exceeds 15% by weight, the surface of the copper powder in the composition will be excessively coated, and the physical strength such as conductivity and adhesion to the base material will begin to decrease, and if it exceeds 15% by weight, this tendency will become significant. It is.

The resin binder that can be used in the present invention is one that has good adhesion to plastics that are commonly used in electronic devices. For example, ABS,
Acrylic resins, polyurethane resins, polyester resins, styrene resins, phenol resins, epoxy resins, and the like can be used for electronic device housing plastics such as polystyrene, PPO, and polycarbonate.

In addition, examples of solvents that can be used in this invention include toluene, hexane, and
Benzene, methyl ethyl ketone, xylene, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, methyl isobutyl ketone, ethyl acetate,
It is preferable to use one type or a mixture of two or more organic solvents such as butyl acetate, methyl cellosolve, and ethyl cellosolve.

The amount of copper powder added to the conductive coating composition is 40 to 95% by weight, preferably 50 to 90% by weight, based on the solid content of the conductive composition.

The resin binder blended into this composition is 5 to 60% by weight, preferably 10 to 50% by weight, based on the solid content of the composition.

In addition to the above components, various additives can be included depending on the purpose. Such agents include reducing agents, surfactants, antisettling agents, antifoaming agents, thickeners, thixotropic agents, rust preventives, and flame retardants.

In the method for producing a conductive coating composition of the present invention, a resin binder and a solvent are added to copper powder that has already been coated with a mixture of an organic zirconate compound and an organic titanate compound of the present invention. Alternatively, a mixture of organozirconate and organotitanate compounds may be added to the mixture of uncoated copper powder, resin binder and/or solvent to coat the copper powder during preparation of the composition.

[Function] In the present invention having the above-described structure, the mixture of the organic zirconate compound and the organic titanate compound has an organic group centered on a zirconium atom or a titanium atom, which exhibits hydrophilic properties that are easily hydrolyzed, and an organic group that exhibits hydrophilic properties that are difficult to be hydrolyzed. Since it has a lipophilic organic group and a hydrophilic part and a hydrophobic part in the molecule, the hydrophilic group causes a displacement reaction with the water adsorbed on the surface of the copper powder, and the hydrophilic part is placed on the surface of the copper powder and the hydrophobic part is inside. An organic zirconate compound and an organic titanate compound are arranged on the outside to form a monomolecular film. Therefore, a monomolecular film can be firmly and favorably formed on the surface of the copper powder, and high hydrophobicity can be imparted to the surface of the copper powder.

This hydrophobic film acts to protect the copper powder from external environments such as heat and humidity without compromising conductivity. Also,
The organic group moiety that is difficult to hydrolyze and exhibits lipophilic properties is skillfully entangled with the resin binder molecules in the composition through van der Waals forces, hydrogen bonds, ionic bonds, covalent bonds, etc., and the shear stress generated during the stirring and kneading process. In this way, a good dispersion state of copper powder is formed. Furthermore, by-products such as fatty acid esters also contribute to the formation of a hydrophobic film on the surface of the copper powder and to improving the dispersibility of the copper powder in the composition.

[Effects of the Invention] As demonstrated from the following examples, the copper powder of claim 1 is coated with a mixture of an organic zirconate compound and an organic titanate compound, so that silver can be coated with a relatively low-cost coating material. Conductivity and environmental resistance comparable to coatings can be obtained.

In the conductive coating compositions according to claims 3 and 5, since a mixture of an organic zirconate compound and an organic titanate compound is added or coated, the storage stability can be greatly improved. Furthermore, excellent heat resistance and environmental resistance can be imparted to this coating film.

[Example code] This invention will be specifically explained by the following examples.

experimental materials The materials used in the examples are shown below.

Organic zirconate compounds are shown in Table 1 below.

Table 1 Organic zirconate compound material No. Organic zirconate compound 1-1.
Isopropyl triisostearoyl zirconate 1-2. 1' Sopropyl tridodecylbenzenesulfonyl zirconate 1-3 Isopropyl tris(dioctylpyrophosphate) zirconate 1-4. Tetraisopropylbis(dioctylphosphite)zirconate 1-5. Tetraoctyl bis(ditridecyl phosphite) zirconate 1-6. Tetra(2,2-diallyloxymethyl-
1-Butyl)bis(di-tridecyl)phosphite zirconate 1-7. Bis(dioctylpyrophosphate)oxyacetate zirconate 1-8. Bis(dioctylpyrophosphate) ethylene zirconate 1-9. Isopropyltrioctanoylzirconate 1-10. Isopropyl dimethacrylic isostearoyl zirconate 1-11. Isopropyl isostearoyl diacryl zirconate 1-12. Isopropyl tri(dioctylphosphate) zirconate 1-13. Isopropyl tricumylphenyl zirconate 1-14. Isopropyl tri(N-aminoethyl-
aminoethyl) zirconate 1-15. Dicumylphenyloxyacetate zirconate 1-16. Diisostearoylethylene zirconate Table 2 below shows the organic titanate compounds used in this example.

Table 2 Organic titanate compound material No. Organic titanate compound 2-1. Isopropyl triisostearoyl titanate 2-2. Isopropyl tridodecylbenzenesulfonyl titanate 2-3. Isopropyl tris(dioctylpyrophosphate) titanate 2-4. Tetraisopropyl bis(dioctyl phosphate) titanate 2-5. Tetraoctyl bis(ditridecyl phosphite) titanate 2-6. Tetra(2,2-diallyloxymethyl-
1-Butyl)bis(di-tridecyl)phosphite titanate 2-7. Bis(dioctylpyrophosphate)oxyacetate titanate 2-8. Bis(dioctylpyrophosphate) ethylene titanate 2-9. Isopropyltrioctanoyl titanate 2-10. Isopropyl dimethacrylic isostearoyl titanate 2-11. Isopropyl isostearoyldiacryl titanate 2-12. Isopropyltri(dioctylphosphate)titanate 2-13. Isopropyl tricumylphenyl titanate 2-14. Isopropyl tri(N-aminoethyl-aminoethyl) titanate 2-15. Dicumylphenyloxyacetate titanate 2-16. Diisostearoyl Ethylene Titanate The mixture of organic zirconate and organic titanate compounds used in this example is shown in Table 3 below.

Table 3 Mixture No. according to the invention Titanate ('ldt%) Zirconate (wt%) 3-3 1-:3 50 2-3
503-25 1-9 90 2-8
1.03-26 1-10 10 2-7.
903-28 1-1.2 10 2-
5 903-36 1-7 '70
2-8 30 Comparative samples used in this example are shown in Tables 4 and 5.

Table 4 Comparative Sample No. I No. Titanate (wt%) Zirconate (Sot%) Table 5 Comparative Sample No. 32 No. Comparative Sample 5-I No. Organic Titanate 5-2 of 2-1 to 16
Citric acid 5-3 Acetalkoxyaluminum diisopropylate 5-4 7-methacryloxypropyltrimethoxysilane 5-5 7-gelicidoxypropyltrimethoxysilane 5-6 Anthrazine 5-7 Anthranilic acid 5-8 Glycerolporate Stearate 5-9
Polyoxyethylene glycerol borate laurate The dendritic electrolytic copper powder used in this example is shown in Table 6.

Table 6 Characteristic apparent density of copper powder 0.8-1. 1g/cIII specific surface area 0.4i/g average particle size
8.0□□Purity 99
．． If 2% or more HNO does not dissolve, less than 0.03% reduction! Less than 0.80% The resin binders used in this example are shown in Table 7 below.

Table 7 Resin binder type Product name Manufacturer Acrylic resin Acrybond Mitsubishi Rayon BC-415B Phenolic resin Pl, -2210 Gunei Kagaku Kogyo Experimental Example 1 Heat-resistant, moisture-resistant and aging properties of copper powder The coating materials of the present invention shown in Table 3 and the comparative coating materials shown in Tables 4 and 5 were each added in small amounts to a copper powder dispersion bath, and the coating materials were stirred and dispersed in a solvent. A film was formed. After drying, temperature of 85℃, 60℃/95%
The copper powder was left in a humid environment of RH for 1,350 hours, and the appearance of discoloration and patina of the copper powder was observed.

The processing amount of each coating material is 0.01.
Experiments were conducted by changing the amount to 0.1.0, 5.1.0.5.0.10% by weight.

As a result, the coating material of the present invention (No. 3-
1 to 40), the treatment amount was 0.1 to 10% by weight, and there was no discoloration or generation of patina.

On the other hand, the copper powder treated with the coating materials shown in Table 4 (Nos. 4-1 to 13) and Table 5 (Nos. 5-1 to 9) showed significant brownish discoloration and patina. there were.

From the above results, it is clear that the coated copper powder of the present invention has excellent heat resistance, moisture resistance, and aging characteristics at high temperatures and high humidity.

Experimental Example 2 Electroconductivity of Paint Film The surface-coated copper powder used in Experimental Example 1 was
A conductive paint was prepared using the acrylic resin shown in Table 7 in weight percent and toluene as a solvent.

A conductive circuit with a length of 10 cm, a width of 0.3 cm, and a film thickness of 50 ± 10 μm was formed using the obtained conductive paint on an acrylic plate using a screen printing machine, and after drying in the air at 25 ± 5 ° C for 24 hours, this circuit was Volume resistivity was measured.

As a result, the coatings of Table 3 according to the invention (No,
The circuit obtained from the conductive paint containing coated copper powder treated in 3-1 to 40) has a resistance of approximately 3.0 x 10 to 6 x 10'Ω.
・It had a volume resistivity of the mark.

On the other hand, circuits obtained from conductive paints containing copper powder treated with comparative coatings ranged from approximately lX10' to 5X10-3
It had a volume resistivity of Ω.

This result shows that the conductive paint of the present invention exhibits good conductivity.

Experimental Example 3 Storage stability of paint The conductive paint prepared in Experimental Example 2 was heated at 25±5°C and 60±10°C.
After leaving the conductive paint in an environment of %RH for 3 months, a conductive circuit with 10 vertical marks, 0.3 cm width, and 50 ± 10 μm film thickness was formed on an acrylic plate using a screen printing machine, and then printed at 25 ± 5 °C for 2 months.
After drying in the air for 4 hours, the volume resistivity of this circuit was determined to be 11Ilj.

As a result, the coatings of Table 3 according to the invention (No,
The circuit obtained from the conductive paint containing coated copper powder treated in 3-1 to 40) is approximately 3.0 x 10 to 6 x 10-4
It had a volume resistivity of Ω.

On the other hand, in the conductive paint containing copper powder treated with the comparative coating material, the copper powder, resin binder, and solvent separated, and the copper powder solidified, making it difficult to form into a paint.

The circuit obtained from the part that was made into paint is approximately 8x10
It had a volume resistivity of ˜2×10 −3 Ω·mark.

This result shows that the conductive paint of the present invention exhibits good storage stability.

Experimental Example 4 Conductivity of Paint Film The surface coating treated copper powder used in Experimental Example 1 was
A conductive paint was prepared using a phenolic resin in Table 7 in weight percent and methylcarpitol as a solvent.

A conductive circuit with a length of 20 cm, a width of 0.1 cm, and a film thickness of 40 ± 10 μm was formed using the obtained conductive paint on a phenol board using a screen printing machine, and after drying at 150 ° C. for 30 minutes (in air, circulation oven), The volume resistivity of this circuit was measured.

As a result, the coating material of Table 3 according to the present invention (No. 3-
The circuit obtained from the conductive paint containing coated copper powder treated in 1 to 40) has a resistance of approximately 2.0 × 10 to 5 × 10'Ω・(1
).

On the other hand, circuits obtained from conductive paints containing copper powder treated with comparative coatings were approximately 1 x 10-3 to 3 x 10-3
It had a volume resistivity of Ω·−.

This result shows that the conductive paint of the present invention exhibits good conductivity.

Experimental Example 5 Storage stability of paint The conductive paint prepared in Experimental Example 4 was heated at 20±5°C and 60±10°C.
After leaving it in an environment of %RH for 5 months, the conductive paint was applied to a phenol board using a screen printing machine to form a conductor circuit with a length of 20 (to) and a width of 0.1, and a film thickness of 40 ± 10 μm.
After drying for 30 minutes (in a circulating oven), the volume resistivity of the circuit was measured.

As a result, the coatings of Table 3 according to the invention (No,
Coated copper powder treated with 3-1 to 40) (processing amount 0.1
The circuit obtained from the conductive paint containing ~10% by weight)
．． It had a volume resistivity of 0XIO to 6X10'Ω·■.

On the other hand, it was observed that the conductive paint containing copper powder treated with the comparative coating agent had a brown resin film on the paint surface and a marked increase in viscosity. The circuits obtained from the usable parts had a volume resistivity of approximately 5.times.10@-3 to 8.times.10' ohms.

This result shows that the conductive paint of the present invention exhibits good storage stability.

Experimental Example 6 The dendritic copper powder shown in Table 6 from which the conductive oxide film of the coating film was removed, the acrylic resin shown in Table 7 in an amount of 45% by weight based on the copper powder, and the inventive resin shown in Table 3 A conductive paint was prepared using additives, comparative additives shown in Tables 4 and 5, and 70% by volume of toluene/30% by volume of n-butanol as a solvent.

The amount of each additive added is 0.01.
Experiments were conducted by changing the weight to 0.1, 0.5.1, 0.5, 0.10 weight ff1%.

The obtained conductive paint was used to form a conductive circuit on an acrylic plate with a length of 10 cm, a width of 0.3 cm, and a film thickness of 50 ± 10 μm. After drying in the air at 25 ± 5 ° C for 24 hours, this circuit was printed. Volume resistivity was measured.

As a result, the additives of Table 3 according to the invention (No. 3-
1 to 40) (Additional amount 0.1 to 10ffi)
The circuit obtained from 3.0XIO~6X10=
It had a volume resistivity of Ω.

On the other hand, circuits obtained from conductive paints with comparative additives had volume resistivities of 1 x 10 to 5 x 10 -3 ohms.

This result shows that the conductive paint of the present invention exhibits good conductivity.

Experimental Example 7 Storage stability of paint The conductive paint prepared in Experimental Example 6 was heated at 25±5°C/60±1
After leaving it in an environment of 0% RH for 3 months, conductive paint was printed on an acrylic board with a screen printing machine in a size of 10 cm long and 0.3 cm wide.
, a conductor circuit with a film thickness of 50±10μm was formed, and the temperature was 25±5℃.
After drying in the atmosphere for 24 hours, the volume resistivity of this circuit was determined.

As a result, the additives of Table 3 according to the invention (No. 3-
1 to 40) added (addition amount 0.1 to 10)
The circuit obtained from approximately 3X10''4~
It had a volumetric resistance of 6×10 −4 Ω·mark.

On the other hand, in the conductive paint to which comparative additives were added, the copper powder, resin binder, and solvent separated, and the copper powder solidified, making it difficult to form into a paint. The circuit obtained from the painted part had a volume resistivity of approximately 8.times.10' to 2.times.10@-3 ohm.

This result shows that the conductive paint of the present invention exhibits good storage stability.

Experimental Example 8 The dendritic copper powder shown in Table 6 from which the conductive oxide film of the paint film has been removed, the phenolic resin shown in Table 7 in a total amount of 45% by weight based on the steel powder, and the phenolic resin shown in Table 3
A conductive paint was prepared using the additives of the present invention shown in the table, the comparative additives shown in Tables 4 and 5, and 80% by volume of methylcarpitol/20% by volume of butyl cellosolve as a solvent.

The amount of each additive added is 0.01.
An experiment was conducted by changing the amount to 061.0, 5.1.0.5.0.10% by weight.

The obtained conductive paint was used to form a conductive circuit on a phenol board with a length of 2Qcm and a width of 0.1cm and a film thickness of 40±10μm. After drying at 150°C for 130 minutes (in air, circulation oven), this circuit was formed. The volume resistivity was measured.

As a result, the additives of Table 3 according to the invention (No. 3-
1 to 40) (Additional amount 0.1 to 10%)
The circuit obtained from the total amount is 2×10−4 to 5×10−4 Ω
' It had a volume resistivity of Cm.

On the other hand, circuits obtained from conductive paints with comparative additives had volume resistivities of lXlO'~3xlO-''Ω·.

This result shows that the conductive paint of the present invention exhibits good conductivity.

Experimental Example 9 Storage stability of paint I! Paint at 25±5℃/60
After leaving it in an environment of ±10%RH for 5 months, the conductive paint was printed with phenol using a screen printing machine.
1c+n, a conductor circuit with a film thickness of 40±10 μm was formed, and 1
After drying at 50° C. for 30 minutes (in air, circulation oven), the volume resistivity of this circuit was measured.

As a result, the additives of Table 3 according to the invention (No. 3-
1 to 40) added (addition amount 0.1 to 10)
The circuit obtained from (wt%) is approximately 3 X 10'
It had a volume resistivity of ˜6×10′Ω·mark.

On the other hand, it was observed that in the conductive paint to which the comparative additive was added, a brown resin film was formed on the paint surface and the viscosity increased significantly. The circuit obtained from the available parts is 5X1
It had a volume resistivity of 0' to 8 x 10' Ω·mark.

This result shows that the conductive paint of the present invention exhibits good storage stability.

Experimental Example 10 Heat-resistant, moisture-resistant and aging properties of copper powder Acylated titanium condensate obtained from 1 mol of tetraisopropyl titanium and 3 mol of isostearic acid (50%
1m%) and isopropyl isostearate (50% by weight)
) and a mixture of an acylated zirconium condensate obtained from 1 mole of tetraisopropyl zirconium and 3 moles of oleic acid (51% by weight) and isopropyl oleate (49% by weight) were mixed in equimolar amounts. In the same manner as in Experimental Example 1, the dendritic copper powder shown in Table 6 above was coated. After drying, the copper powder was left to stand for 1350 hours at a temperature of 85° C. and a humidity of 60° C./95% RH, and the appearance of discoloration and patina of the copper powder was observed.

The amount of coating material to be treated is 0.01.0 per steel powder.
．． 1.0.5.1.0.5.0, 10 parts and 2 parts were used for the experiment.

As a result, when treated with equimolar mixtures of coating materials,
At a treatment amount of 0.1 to 101% by weight, no discoloration occurred and no patina occurred.

From the above results, it can be seen that the coated copper powder according to the present invention has excellent heat resistance, humidity resistance, and aging characteristics at high temperatures and high humidity.

Experimental Example 11 Conductivity of coating film The surface coating treated copper powder used in Experimental Example 10 was
A conductive paint was prepared using 5% by weight of the acrylic resin shown in Table 7 and 70% by volume of toluene/96% by volume of n-butanol/20% by volume of methylcarpitol/10% by volume of methylcarpitol.

The obtained conductive paint was used to form a conductive circuit on an acrylic plate with a length of 10C1, a width of 0.3cm, and a film thickness of 50cm and 10μm using a screen printing machine. After drying at 25±5°C for 24 hours in an oven, this circuit was printed. Volume resistivity was measured.

As a result, conductive paints containing coated copper powder treated with equimolarly mixed coating agents according to the present invention (coverage amount 0.1 to 10
The circuit obtained from 3×10 to 6×10″′
It had a volume resistivity of 4Ω·mark.

This result shows that the conductive paint of the present invention exhibits good conductivity.

Experimental Example 12 Storage stability of paint The conductive paint prepared in Experimental Example 11 was heated at 25±5°C/60±
After leaving it in an environment of 10% RH for 3 months, conductive paint was applied to the acrylic board using a screen printing machine by 10cm long and 0.3cm wide.
Form a conductor circuit with a m5 film thickness of 50±10μm,
After drying in the air for 24 hours at 0.degree. C., the volume surface H-resistance of this circuit was measured.

As a result, a conductive paint containing coated copper powder treated with the coating agent mixed in equimolar proportions according to the present invention (coating amount 0.1-10
The circuit obtained from (wt%) is approximately 3X10 to 6X1
It had a volume resistivity of 0'Ω·cm.

Experimental Example 13 An equimolar mixture of the dendritic copper powder of Table 6 from which the conductive oxide film of the paint film has been removed, the phenolic resin of Table 7 at 45% by weight based on the copper powder, and the equimolar mixture of Experimental Example 10. Additives and 80% by volume of methylcarpitol/20% by volume of butyl cellosolve as solvent
A conductive paint was prepared using

The amount of each additive added is 0.01.
An experiment was conducted by changing the amount to 0.1.0.5.1.0.5.0.10% by weight.

The obtained conductive paint was used to form a conductor circuit on a phenol board with a length of 20cm5FfIO, 1cm and a film thickness of 40±10μm, and after drying at 150°C for 30 minutes (in air, circulation oven), this circuit was Volume resistivity was measured.

As a result, the circuit obtained from the conductive paint containing the equimolar mixture of additives of Experimental Example 10 according to the present invention (the total amount added is 0.1 to 10%) was The resistance was set to H.

This result shows that the conductive paint of the present invention exhibits good conductivity.

Experimental Example 14 The dendritic copper powder shown in Table 6 coated with 5% by weight of silver by the conductive displacement plating method of the coating film, or the dendritic copper powder shown in Table 6 from which the oxide film was removed, and the copper powder 45% by weight of the acrylic resin from Table 7, the additives of the invention shown in Table 3, the comparative additives shown in Tables 4 and 5, and 70% by volume/n- toluene as a solvent. A conductive paint was prepared using 30% by volume of butanol.

The amount of each additive added is 0.01.
An experiment was conducted by changing the amount to 0.1.0°5.1.0.5.0.10% by weight.

The obtained conductive paint was used to form a conductive circuit on an acrylic board with a length of 10 cm, width of 0.3 cm, and film thickness of 50 ± 10 μIn, and after drying in a heated oven at 25 ± 5 ° C for 24 hours, this circuit was printed. Volume resistivity was measured.

As a result, the additives (No. 3-1 to
40) containing conductive paint (addition amount 0.1 to 10 weight fj19
6) The circuit obtained from
・It had a volume resistivity of the mark.

On the other hand, the circuits obtained from the conductive paints to which comparative additives were added were 5X10' to 8X10-4 Ω for silver-coated copper powder, and 1x10' to 5X1O' Ω for copper powder with oxide film removed.
It had a volume resistivity of (to).

This result shows that the conductive paint of the present invention exhibits good conductivity.

Experimental example 15 Heat resistance, moisture resistance and aging properties of coating film Experimental example 2.4
．． The coated substrate of the conductive paint prepared in 6.8.11 was
At a temperature of 5℃ and a humidity environment of 60℃/9596RH, 20
The coating film was left to stand for 00 hours and the rate of change in resistance of the coating film was measured.

As a result, it was found that the coating film obtained from the conductive paint containing the additive or coating agent (No. 3-1 to 40) in Table 3 according to the present invention (coating amount or additive amount 0.1 to 10% by weight) ,
At a temperature of 85° C., it was mostly around 10%, at least 5%, and at most 15%. 60℃/95%R
The humidity of H was mostly around 5%, at least -10%, and at most 10%.

On the other hand, coating films obtained from conductive paints containing comparative additives or coatings had a temperature of 50-50°C at a temperature of 85°C.
It was 100%, not less than 150%. 60℃/
At a humidity of 95% RH, most of the humidity was 40 to 7026, and some were 100% or more.

These results show that the conductive paint of the present invention exhibits excellent heat resistance and moisture aging resistance.

Experimental example 16 Heat shock resistance of coating film Experimental example 2.4.
The coated substrate of the conductive paint prepared in 6.8.11 was heated to -5
A heat shock test was conducted under the conditions of 100 repetitions of 5° C./1 hour and 75° C./1 hour, and the rate of change in resistance of the coating film was measured.

As a result, in the coating film obtained from the conductive paint (coating amount or addition amount 0.1 to 10% by weight) containing the additive or coating agent (No. 3-1 to 40) in Table 3 according to the present invention, The resistance change rate was around -10%, at least 15%, and at most 120%.

On the other hand, the resistance change rate of coating films obtained from conductive paints containing comparative additives or coating agents was mostly 20 to 30%, and often 40% or more.

These results show that the conductive paint of the present invention exhibits excellent heat shock resistance.

Experimental example 17 Heat cycle resistance of coating film Experimental example 2.4.
The coated substrate of the conductive paint prepared in 6.8.11 was heated to -2
5℃/1 hour - 1 hour (temperature increase) - 20℃/1 hour - 1 hour (temperature increase) = 65℃/1 hour - 1 hour (temperature decrease) → 20℃
A heat cycle test was conducted under the conditions of /1 hour - 1 hour (temperature fall) -25°C/1 hour, repeated 20 times, and the rate of change in resistance of the coating film was measured.

As a result, it was found that the coating film obtained from the conductive paint (coating amount or addition ff 10.1 to 10% by weight) containing the additives or coating agents (No. 3-1 to 40) listed in Table 3 according to the present invention has a resistance The rate of change is around 0%, at least 15%.
%, at most 10%.

On the other hand, the resistance change rate of coating films obtained from conductive paints containing comparative additives or coating agents is often 40 to 60%,
It was more than 80%.

This result shows that the conductive paint of the present invention exhibits excellent neat cycle resistance.

Experimental Example 18 Salt water resistance of coating film The coating substrate of the conductive paint prepared in Experimental Example 2.4.6.8.11 was treated with a 5% by weight sodium chloride aqueous solution at 35% by weight.
A salt water spray test was conducted at a liquid temperature of ℃ for 72 hours, and the discoloration of the coating film
The development of patina was observed and the resistance change rate was determined as IP+.

As a result, in the coating film obtained from the conductive paint (coating amount or addition amount 0.1 to 10% by weight) containing the additive or coating agent (No. 3-1 to 40) of Table 3 according to the present invention,
The resistance change rate is around -20%, at least -7
%, at most -32%. In addition, although there was slight discoloration on the surface of the paint film, there was no occurrence of verdigris at all.

On the other hand, the resistance change rate of coating films obtained from conductive paints containing comparative additives or coating agents is mostly 100 to 3009
6. It was more than 1000%. In addition, the surface of the paint film was discolored to brownish-brown, and a significant amount of verdigris had developed.

This result shows that the conductive paint of the present invention exhibits excellent salt water resistance.

One experimental example Soldering heat resistance of coating film The conductive paint coating substrate prepared in Experimental Example 2.4.6.8.11 was placed in a soldering bath (Sb63/Pb3) at 260°C.
7) for 5 seconds 10 times to perform a heat resistance test and measure the rate of change in resistance of the coating film.

As a result, in coating films obtained from conductive paints (coating amount or addition 10.1 to 10% by weight) containing additives or coating agents (No. 3-1 to 40) of Table 3 according to the present invention,
The resistance change rate is around -5%, at least 0%,
It was at most 10%.

On the other hand, the resistance change rate of coating films obtained from conductive paints containing comparative additives or coating agents is often 50 to 100%,
It was more than 150%.

This result shows that the conductive paint of the present invention exhibits excellent soldering heat resistance.

Experimental Example 20 Chemical resistance of coating film The coating substrate of the conductive paint prepared in Experimental Example 2.4.6.8.11 was treated with 2N diluted hydrochloric acid, 3N diluted sodium hydroxide, methanol, and a fluorine-based cleaning solution. ``Freon'', chlorine-based cleaning liquid ``Chlorocene NUJ'', ``Chlorocene VGJ''
A chemical resistance test was conducted by immersing the product at ±5℃ for 5 hours.
The rate of change in resistance of the coating film was measured.

As a result, conductive paints (N o, 3-L to 40) containing additives or coatings of Table 3 according to the invention
For coatings obtained from coatings or additives of 0.1 to 10% by weight, the rate of change in resistance is 30 to 60% for dilute sodium hydroxide and methanol, and approximately 15% for other coatings. ~5%, at least 0%, and at most -10%.

On the other hand, the rate of change in resistance of coating films obtained from conductive paints containing comparative additives or coating agents was 500% or more in most cases with sodium hydroxide and methanol, and was not a little infinite, and in other cases it was much higher (but not less). It was 300 to 60096 or more, not less than 700%.

This result shows that the conductive paint of the present invention exhibits excellent chemical resistance.

Experimental Example 21 Adhesion of Paint Film The conductive paint prepared in Experimental Example 2.4.6.8.11 was
Paper phenol board, glass epoxy board, acrylic board, AB
2 using a screen printing machine on S plate and alumina plate
A X211II11 pad coating film is formed, and after drying, a room temperature curing epoxy resin (two-component type) is used to coat the coating film with 0.
A 90° pool test was conducted by bonding 5φmn+suzmeteki copper wire. The thickness of the coating film was 50±10 μm, and the number of test pads was 20.

As a result, in the coating film obtained from the conductive paint (coating amount or addition amount 0.1 to 10% by weight) containing the additive or coating agent (No. 3-1 to 40) of Table 3 according to the present invention,
Peel strength is 0.7 to 1.4 kg/for all base materials
It was IMA.

On the other hand, the peel strength of coatings obtained from conductive paints containing comparative additives or coatings was 0 for all substrates.
3-0,6 kg/mtA.

These results show that the conductive paint of the present invention exhibits excellent adhesion to all base materials.

Experimental Example 22 Coating film structure The cross section and surface of a coating film formed from a conductive paint according to the present invention and a coating film obtained from a conductive paint containing a comparative additive or coating agent were observed using a scanning electron microscope. did.

Reference photo 1 and reference photo A3 show the cross section (700x magnification) and surface (500x magnification) of the coating film according to the present invention, respectively. This electron micrograph shows that in this coating film, the copper powder is well dispersed in the resin binder, and it has a dense structure with no pinholes.

On the other hand, Reference Photo 1 and Reference Photo 3 show the cross section (magnification: 700 times) and surface (magnification: 500 times) of a comparative coating film, respectively. This electron micrograph shows that in the comparative coating film, copper powder is unevenly distributed in the resin binder, and it has a structure with many pinholes.

Manual continuation supplementary book Commissioner of the Patent Office Yoshi [Mr. H-bun Takeshi] 1 Display of incident 1986 Patent Application No. 128069 2 Name of the invention Copper powder for conductive paints and conductive paint compositions 3 Person making the amendment Relationship to the incident Patent applicant (618) Mitsui Metal Mining Co., Ltd. Shipping date: Month, Day, Heisei 6 Number of claims to be amended 7 Target of correction “Detailed description of the invention” column in the specification 8 Contents of amendment The specification shall be amended as indicated in C.

(1) Page 9, lines 9-10, "tetraisopropylzirconium" was corrected to "tetraisopropoxyzirconium".

(2) Page 11, No. 13-. Line 14 "Tetraisopropyltitanium" is corrected to "Tetraisopropoxytitanium".

(3) On page 38, line 7, "tetraisopropyl titanium" was corrected to "tetraisopropoxytitanium."

(4) Page 38, line 11, "tetraisopropylzirconium" was corrected to "tetraisopropoxyzirconium".

(5) Page 46, line 3 Corrected "neat cycleability" to "heat cycleability".

Claims (3)

[Claims] 1. A copper powder for conductive paints whose surface is coated with a mixture of an organic zirconate compound and an organic titanate compound. 2. A conductive coating composition comprising copper powder coated with a mixture of an organic zirconate compound and an organic titanate compound, a resin binder, and a solvent. 3. A conductive coating composition comprising a mixture of an organic zirconate compound and an organic titanate compound, copper powder, a resin binder, and a solvent.