JP2000098655A - Metallic toner for forming conductive pattern, method for producing metallic toner for forming conductive pattern, and method of using metallic toner for forming conductive pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive pattern forming metal toner having a high charge level and excellent image characteristics, a conductive pattern forming metal toner capable of efficiently manufacturing such a metal toner, and a method for manufacturing the conductive pattern forming metal toner. A method of using a metal toner using such a metal toner for forming a conductive pattern is provided. SOLUTION: The surface of metal particles or metal oxide particles is coated with an insulating resin or an easily chargeable insulating resin by using a mechanical surface treatment method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal toner for forming a conductive pattern (hereinafter, may be simply referred to as a metal toner), a method for producing the metal toner, and a method for using the metal toner. More specifically, a metal toner having a high charge level, a uniform coating state, and excellent image characteristics, a method of manufacturing a metal toner capable of efficiently manufacturing such a metal toner, and a method of manufacturing such a metal toner using a conductive material The present invention relates to a method of using a metal toner used for forming a pattern.

[0002]

2. Description of the Related Art Conventionally, a screen printing method has been used to form a conductor pattern (electrode) in a multilayer capacitor. Specifically, a conductive pattern is formed by applying a paste containing predetermined metal particles on a ceramic green sheet composed of a ceramic powder and an organic binder using a screen printing machine. However, such a forming method using the screen printing method has a problem that the productivity (production efficiency) of the conductor pattern is low. In the screen printing method,
Since a mesh-like net is used as a screen, so-called screen drooping occurs, and there are problems that printing accuracy is reduced and that it is difficult to form a fine conductor pattern.

[0003] In order to solve such a problem, Japanese Patent Laid-Open Publication Nos.
JP-A-02682, JP-A-60-137886 and JP-A-60-160690 disclose a toner (developer) in which conductive particles are covered with an insulating resin by electrophotography. A method for forming a conductor pattern that prints on a ceramic sheet is disclosed.

Here, a method of forming a conductor pattern by using electrophotography will be briefly described with reference to FIG. First, the charger 1 is placed on the rotating photosensitive drum 11.
3 and an image signal exposure device 15 to form an electrostatic latent image.
Next, a toner (metal toner) for forming a conductor pattern is supplied from the developing device 17 in accordance with the electrostatic latent image to form a toner image. Further, the formed toner image is transferred onto a ceramic sheet (not shown) using the transfer roll 19, and then heated to form a conductor pattern. The toner not transferred to the ceramic sheet is removed using the cleaning blade 21.

However, in the conventional method of forming a conductor pattern, there is a problem that the charging characteristics of the metal toner (developer) are insufficient, and it is difficult to stably form a fine conductor pattern. Was. In addition, in the formed conductor pattern, there was a problem that edges blurred, image characteristics (sharpness) were poor, and image density was low.

[0006]

Therefore, the inventors of the present invention diligently studied the problems in the prior art, and found that the insulating resin covering the metal toner was insufficient in chargeability and that the insulating resin had poor chargeability. It has been found that the reason is that the resin coating state is not uniform. That is, the inventors of the present invention, the surface of the metal particles or metal oxide particles, using a mechanical surface treatment method, by coating an insulating resin or an easily chargeable insulating resin, the charging level is high It is possible to obtain a metal toner having a uniform covering state. Therefore, by using such a metal toner, the image characteristics (sharpness and image density) are excellent, and as a result, a fine conductor pattern can be stably formed. And found that the present invention has been completed.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a conductive pattern forming metal toner having a high charge level, a uniform covering state, and excellent image characteristics. Another object of the present invention is to provide a method for producing a metal toner capable of efficiently producing a metal toner having a high charge level, a uniform covering state, and excellent image characteristics. Still another object of the present invention is to provide a method of using a metal toner having a high charge level, a uniform coating state, and excellent image characteristics for forming a conductive pattern.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a metal toner for forming a conductor pattern, which is formed on a surface of a metal particle or a metal oxide particle by using a mechanical surface treatment method. It is characterized by being coated with a conductive resin. As described above, since the insulating resin is not only electrically insulating but also easily charged, it is possible to provide a metal toner for forming a conductive pattern having a high charging level and excellent image characteristics. In addition, even if a general insulating resin other than an easily chargeable insulating resin is used, since it is uniformly coated by a mechanical surface treatment method, the charge level is high and the conductive pattern is formed with excellent image characteristics. A metal toner can be provided.

In the present invention, the term “insulating resin has both electric insulating properties and chargeability” (hereinafter referred to as easily chargeable insulating resin) means that the insulating resin has a certain electrical insulation property, for example, in accordance with JIS K6911. The metal toner to a fixed charge level, for example, a value within a range of 10 to 30 μC / g as a charge amount by a blow-off method, as a specific volume resistivity of 1 × 10 ¹⁰ Ω · cm or more. It means that it is a chargeable resin. Therefore, the easily chargeable insulating resin may be a mixture of the insulating resin and the chargeable material, or may have a chargeable functional group in a molecule constituting the insulating resin, for example, having a carboxyl group. It may be a resin, or a copolymer of an insulating resin and a chargeable material.

In the present invention, when referring to metal particles or metal oxide particles, they may be used alone or in combination. Therefore, hereinafter, metal particles or metal oxide particles may be abbreviated as metal particles or the like. However, when a conductor pattern is formed, a more uniform conductor resistance can be obtained.
The metal particles or metal oxide particles are preferably used as mononuclear particles. Therefore, in this case, the surface of each metal particle or metal oxide particle is covered with an easily chargeable insulating resin.

Further, in constituting the metal toner of the present invention, it is preferable that the easily chargeable insulating resin comprises an insulating resin and a chargeable material. By using an insulating resin and a chargeable material in combination in this manner, excellent electrical insulation can be obtained, and the chargeability can be easily controlled, and the charge balance between the electrical insulation and the chargeability can be obtained. An easy insulating resin can be obtained.

In constituting the metal toner of the present invention, the chargeable material is selected from the group consisting of a fluorine resin, a styrene resin, an acrylic resin, an ethylene resin, a propylene resin, an ester resin and a metal complex. It preferably contains at least one material selected. By including such a chargeable material, the charge level of the metal toner is adjusted, and the charge amount is adjusted to 1
Values in the range of 0-30 μC / g can be easily obtained. Further, these chargeable materials are easy to handle, can be uniformly contained in the insulating resin, and are inexpensive and economical.

In constituting the metal toner of the present invention, at least one selected from the group consisting of a styrene resin, an acrylic resin, an ethylene resin and a propylene resin, other than the chargeable material, is used as the insulating resin. It is preferable to contain two resins. These insulating resins have a high value of 1 × 10 ¹⁶ Ω · cm or more as a volume resistivity, and excellent electrical insulation can be obtained even with a metal toner. An insulating resin layer having a uniform thickness can be easily provided.
These insulating resins are easy to handle, inexpensive, and economical. Note that the insulating resin is preferably a resin that can be distinguished from a chargeable material and can obtain a charge amount of less than 10 μC / g as a charge level in the metal toner.

In constituting the metal toner of the present invention, when the volume of the insulating resin is 100 parts by volume,
It is preferable that the amount of the chargeable material be in the range of 1 to 200 parts by volume. By limiting the amount of the chargeable material as described above, the charge level of the metal toner can be easily adjusted, and when the conductor pattern is formed, the value of the conductor resistance can be made more uniform. .

In constituting the metal toner of the present invention, when the volume of metal particles and the like is 100 parts by volume,
It is preferable that the coating amount of the easily charging insulating resin is set to a value within a range of 20 to 250 parts by volume. By limiting the coating amount of the insulating resin layer that is easily charged in this way, it becomes easier to adjust the charging level of the metal toner, and when a conductor pattern is formed, the value of the conductor resistance is made lower. be able to.

In constituting the metal toner of the present invention, the average particle diameter of the metal particles or metal oxide particles is 2
It is preferable to set the value within the range of 20 μm to 20 μm. By limiting the average particle diameter of the metal particles and the like in this manner, it becomes easier to adjust the charge level of the metal toner,
As a result, a fine conductor pattern can be formed more stably.

Further, in constituting the metal toner of the present invention, the chargeable material is constituted to contain the chargeable particles, and the average particle diameter of the chargeable particles is adjusted to the average particle diameter of the metal particles or the metal oxide particles. Is preferably 1/10 to 1/1000. By using the chargeable particles as the chargeable material in this way, and by limiting the average particle size of the chargeable particles, not only can the aggregation of the chargeable particles be effectively prevented, but also the chargeable particles It can be more uniformly contained in the insulating resin.

In constituting the metal toner of the present invention, the metal particles or the metal oxide particles have a particle size distribution of 70 to 70 in the volume conversion of the metal particles or the metal oxide particles.
It is preferable that 100 vol% is within the range of 40% of the average particle diameter ± the average particle diameter. By limiting the average particle diameter of the metal particles or the metal oxide particles in consideration of the particle size distribution, the image characteristics of the conductor pattern can be further improved.

In constituting the metal toner of the present invention, the sphericity of the metal particles or metal oxide particles is set to 0.1.
The value is preferably 5 or more. By limiting the sphericity of the metal particles and the like in this manner, the developability in so-called electrophotography is improved. Therefore, it is possible to obtain a sharp image conductor pattern with little bleeding.

In constituting the metal toner of the present invention, it is preferable to use metal particles produced by a wet method. By using such metal particles, an insulating resin layer or a charge providing layer having a more uniform thickness can be formed on the surface. Therefore, the particle size distribution of the obtained metal toner can be narrowed.

Another aspect of the present invention is a method for producing a metal toner for forming a conductive pattern, wherein the surface of metal particles or metal oxide particles is subjected to a mechanical surface treatment method.
It is characterized by being coated with an insulating resin or an easily chargeable insulating resin. By manufacturing the metal toner in this way, a metal toner having a high charge level and excellent image characteristics (sharpness and image density) can be efficiently (shortly) and economically obtained. That is, in order to increase the charge level of the metal toner, for example, when the insulating resin is thickened and coated by a direct polymerization method of a monomer, the required time tends to be significantly long. Further, when the thickness of the insulating resin is increased by only the direct polymerization method of the monomer, the thickness of the insulating resin layer tends to be non-uniform, and as a result, image characteristics tend to be poor.

In carrying out the method for producing a metal toner of the present invention, an insulating resin and a chargeable material are used as the easily chargeable insulation resin, and the insulating resin and the chargeable material are used. It is preferable to carry out a mechanical surface treatment method simultaneously or separately. By using not only the insulating resin but also a separately chargeable material, the chargeability can be easily controlled, and a well-balanced and easily chargeable insulating resin layer can be obtained. Also, an insulating resin,
If a mechanical surface treatment method is applied to the chargeable material at the same time, a single-layer coating layer having a uniform thickness can be obtained and can be manufactured in a short time. On the other hand, if the mechanical surface treatment method is performed separately for the insulating resin and the chargeable material, only the surface can be coated with the chargeable material having a high chargeability. The amount of the chargeable material to be obtained can be small.

In carrying out the method for producing a metal toner of the present invention, before the mechanical surface treatment method, the surface of the metal particles or metal oxide particles is treated with a saturated fatty acid, an unsaturated fatty acid, a titanium coupling agent, It is preferable to treat with at least one surface treatment agent selected from the group consisting of a silane coupling agent and an aluminum coupling agent. The surface treatment of the metal particles or the like in this way can suppress oxidation of the metal particles or the like. Therefore, a low-resistance conductive pattern can be obtained without forming the conductive pattern in a reducing atmosphere.
In addition, by treating the metal particles and the like in this manner, the adhesion between the metal particles and the like and the easily chargeable insulating resin is improved, and a coating layer having a uniform thickness is formed on the surface of the metal particles and the like. It can be easily provided.

In carrying out the method for producing a metal toner of the present invention, it is preferable that the mechanical surface treatment method is carried out using a Henschel mixer, a super Henschel mixer, a mechanomill, an ongmill or a hybridizer. By using these mechanical processing machines, an insulating resin or an easily chargeable insulating resin can be formed in a short time as a coating layer having a uniform thickness.

In carrying out the method for producing a metal toner of the present invention, an amorphous polymer is used as an insulating resin or a charging material, and the glass transition point of the insulating resin or the charging material is determined by Q (° C.). ), The treatment temperature in the mechanical surface treatment method is preferably set to a value within the range of Q ± 20 (° C.). By performing the mechanical surface treatment under such a temperature condition, the insulating resin or the chargeable material can be sufficiently softened, and an appropriate viscosity can be obtained. Therefore, the chargeable material can be uniformly contained in the easily chargeable insulating resin.

The glass transition point of the chargeable material can be measured by using a differential scanning calorimeter (DSC).

In carrying out the method for producing a metal toner of the present invention, the processing time of the mechanical surface treatment method is set to 5 times.
It is preferable to set the value within a range of up to 20 minutes. By manufacturing the metal toner while limiting the processing time, a metal toner having a higher charge level can be efficiently obtained.

In carrying out the method for producing a metal toner of the present invention, it is preferable to carry out the mechanical surface treatment method a plurality of times. By performing the mechanical surface treatment a plurality of times as described above, a relatively thick insulating resin layer can be formed. Therefore, a metal toner having a higher charge level can be efficiently obtained. Further, even if an insulating resin layer having the same thickness is formed, a more uniform thickness can be obtained by performing the mechanical surface treatment a plurality of times. Note that the mechanical surface treatment method is performed a plurality of times (for example, 2
In the case of performing the first and second times, it is also preferable to coat the same easily chargeable insulating resin in the first and second times. Or 1
It is also preferable to coat each with a different resin so that only the insulating resin is coated the second time, and the easily chargeable insulating resin is coated the second time.

Still another embodiment of the present invention relates to a method of using a metal toner for forming a conductor pattern, wherein the metal toner for forming a conductor pattern has an insulating resin or an easily-chargeable metal particle. Metallic toner coated with a suitable insulating resin is used. The present invention is characterized in that a conductive pattern is formed by applying the metal toner to a ceramic thin film sheet by using an electrophotographic method and then heating the metal thin film sheet. By using metal toner in this way, image characteristics (sharpness and image density)
And a conductor pattern having a low conductor resistance can be obtained.

In carrying out the method of using the metal toner of the present invention, it is preferable to use a one-component developing method when the metal toner is adhered to the ceramic thin film sheet. In this case, since the developing electric field is very high, a sharp image without bleeding can be obtained.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The metal toner (first
Embodiment), a method for producing a metal toner (second and third methods)
Embodiment) and an embodiment relating to a method of using a metal toner (Fourth Embodiment), while appropriately referring to the drawings.
This will be specifically described.

[First Embodiment] The metal toner of the first embodiment is obtained by applying an insulating resin or an easily chargeable insulating resin to the surface of metal particles or metal oxide particles by using a mechanical surface treatment method. Is a coated metallic toner for forming a conductive pattern. The metal particles or metal oxide particles constituting the metal toner and the easily chargeable insulating resin will be specifically described. However, the easily chargeable insulating resin in the first embodiment is mainly composed of an insulating resin that secures electrical insulation and a chargeable material that mainly secures chargeability. Therefore, in the following description of the easily chargeable insulating resin, the insulating resin and the chargeable material will be further divided and described.

(1) Metal Particles or Metal Oxide Particles The metal particles and the like used in the first embodiment are not particularly limited, but, for example, preferred types of metal particles include copper, tungsten, nickel, and silver. And the like.
Preferred types of metal oxide particles include ruthenium oxide, (RuO ₂ ), lead ruthenate, and (Pb ₂ Ru _2).
O _7-n and n are the total value of the valences of Pb and Ru). Conductive patterns obtained from these metal particles and metal oxides are characterized by low conductor resistance and excellent pattern accuracy.

A preferred type of metal particles is a metal particle produced by a wet method. The metal particles produced by the wet method have a narrow particle size distribution, and can form an insulating resin layer or a charge imparting layer having a uniform thickness on the surface. Therefore, the particle size distribution of the obtained metal toner can be narrowed, and as a result, sharp image characteristics with less bleeding can be obtained.

Here, the wet method is a production method compared with the dry method, and is characterized by using water or an organic solvent to produce metal particles. Therefore, if it is a metal particle manufactured using water or an organic solvent,
Although the type is not particularly limited, for example, metal particles obtained by an atomizing method or a precipitation method are more preferable. The metal particles produced by these methods are particularly characterized by a narrow particle size distribution and a high sphericity. In addition, the atomization method is a method in which a metal is formed into droplets and then sprayed into water or the like to make physically fine particles.On the other hand, the precipitation method is a method in which fine particles are formed from an inorganic metal solution in water or the like. This is a method of chemically depositing metal particles.

Further, preferred types of metal particles include:
Those having a sphericity of 0.5 or more are exemplified. The reason is that when the sphericity of the metal particles is less than 0.5, the thickness of the insulating resin layer and the chargeability-imparting layer becomes poor in uniformity, and further, the developability tends to decrease. Therefore, it is more preferable to set the sphericity of the metal particles to a value of 0.7 or more, since more excellent developability and the like can be obtained. The sphericity is represented by a ratio (Da / Ds) obtained by reducing the particle diameter (Da) obtained from the particle area in the micrograph by the particle diameter (Ds) similarly obtained from the particle circumference. Therefore, when the metal particles are true spheres, the sphericity is 1.

In this regard, the effect of the sphericity of the metal particles will be described in detail with reference to Table 1. Table 1 shows that copper powder was used as the metal particles, and the sphericity of the copper powder was 0.4 to 0.9.
The metal toner was manufactured in the following manner, and its image characteristics were evaluated according to the following criteria. Detailed production conditions and evaluation conditions for metal toner are described in Example 1 below.
8 to 22 will be described. 〇: The conductor pattern has no blur and the conductor pattern is sharp. Δ: Slight bleeding is observed in the conductor pattern. X: Remarkable bleeding is observed in the conductor pattern.

As understood from the results, when the sphericity of the copper powder is 0.5 or more, sharp image characteristics with little bleeding can be obtained in the initial evaluation. Further, when the sphericity of the copper powder is 0.7 or more, sharp image characteristics with little bleeding can be obtained even after printing 3000 sheets of conductor patterns as well as initial evaluation.

[0039]

[Table 1]

Further, as a preferred metal particle or metal oxide particle, 70 to 100 vol% of the metal particle or metal oxide particle in the volume-converted particle size distribution is within a range of average particle diameter ± 40% of the average particle diameter. Some are preferred. Such types of metal particles and the like can further improve the image characteristics of the conductor pattern and obtain a sharp image. Therefore, more excellent image characteristics can be obtained, so that the metal particles or metal oxide particles have a particle size of 70 to 100.
It is more preferable that vol% is within a range of 30% of the average particle diameter ± the average particle diameter.

In this regard, the effect of the particle size distribution on the metal particles will be described in detail with reference to Table 2. Table 2 uses sieved copper powder as the metal particles so that 70 to 100 vol% of the copper powder in the volume-converted particle size distribution falls within the range of 30 to 70% of the average particle diameter ± the average particle diameter. After adjusting each of them, a metal toner was manufactured, and its image characteristics were evaluated based on the same evaluation criteria as in Table 1.
Detailed production conditions and evaluation conditions of the metal toner will be described in Examples 1 and 15 to 17 described later. As understood from the results, when the particle size distribution falls within the range of the average particle diameter ± 60% of the average particle diameter, sharp image characteristics with little bleeding can be obtained in the initial evaluation. Also,
When the average particle diameter is within the range of 40% of the average particle diameter, not only initial evaluation but also sharp image characteristics with little bleeding can be obtained even after printing 3000 conductor patterns.

[0042]

[Table 2]

The particle size of the metal particles and the like is not particularly limited, but the average particle size is preferably in the range of 2 to 20 μm. The reason for this is that if the average particle diameter of the metal particles or the like is less than 2 μm, the particles tend to aggregate, which makes it difficult to handle and makes it difficult to adjust the charge level of the metal toner. On the other hand, when the average particle diameter exceeds 20 μm, it is still difficult to adjust the charge level of the metal toner, and so-called ground fogging tends to occur. Therefore, it is more preferable that the average particle diameter of the metal particles or the like is set to a value within the range of 3 to 10 μm because the charge level of the metal toner can be adjusted better and a fine conductor pattern can be formed.

Further, oxidation of metal particles and the like is effectively suppressed,
In addition, since the adhesion between metal particles and the like and the easily chargeable insulating resin can be improved, the surfaces of the metal particles or metal oxide particles can be saturated fatty acids, unsaturated fatty acids, titanium coupling agents, silane coupling agents. It is preferable to pre-treat with at least one surface treatment agent selected from the group consisting of aluminum coupling agents. In addition, it is more preferable to use a silane coupling agent because an excellent antioxidant effect and an effect of improving adhesion can be obtained particularly with a small amount of surface treatment.

Here, preferred saturated fatty acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,
Enanthic acid, caprylic acid, pelargonic acid, capric acid,
Undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid,
Stearic acid, nonadecanoic acid, arachidic acid, behenic acid,
Lignoceric acid, lacceric acid and the like.

A saturated fatty acid having 1 to 8 carbon atoms such as propionic acid is preferable because it is liquid at room temperature and can be more uniformly surface-treated. Also, saturated fatty acids having 9 to 22 carbon atoms, such as myristic acid and stearic acid, can be easily liquefied by heating, and
It is preferable because the antioxidant effect can be obtained continuously. Furthermore, a higher saturated fatty acid having 23 to 32 carbon atoms such as lacquer acid is preferable because a more excellent antioxidant effect can be continuously obtained. Preferred unsaturated fatty acids include:
Acrylic acid, crotonic acid, oleic acid, linoleic acid, propiolic acid, stearolic acid and the like can be mentioned.

Preferred titanium coupling agents are γ-aminopropyltrimethoxytitanium, γ-aminopropyltriethoxytitanium, γ-aminopropyldimethoxymethyltitanium, γ-glycidoxypropyltrimethoxytitanium, γ-glycidyl Xypropyltriethoxytitanium, γ-glycidoxypropyldimethoxymethyltitanium and the like.

Preferred silane coupling agents are γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidyl Xypropyltriethoxysilane, γ-glycidoxypropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane, γ-mercaptopropyldimethoxymethylsilane, and the like.

Preferred aluminum coupling agents are γ-aminopropyltrimethoxyaluminum, γ-aminopropyltriethoxyaluminum, γ
-Aminopropyldimethoxymethylaluminum, γ-
Glycidoxypropyltrimethoxyaluminum, γ-
Glycidoxypropyltriethoxyaluminum, γ-
Glycidoxypropyldimethoxymethylaluminum and the like.

When a titanium coupling agent, a silane coupling agent and an aluminum coupling agent are used, it is preferable to carry out a hydrolysis treatment or a condensation reaction on these coupling agents in advance. . By performing a hydrolysis treatment or the like, these coupling agents can react with metal particles or the like in a shorter time. Therefore, the adhesive force between the metal particles and the like and the easily-chargeable insulating resin can be further improved. In addition, since the coupling agent has a high molecular weight or a three-dimensional structure, an excellent antioxidant effect and an excellent effect of improving adhesion can be obtained for a long time.

The amount of the surface treatment agent is not particularly limited, but it may be, for example, 100 parts such as metal particles.
It is preferable to set the value within the range of 0.01 to 20 parts by weight with respect to parts by weight. The reason for this is that if the amount of the surface treatment agent is less than 0.01 part by weight, the antioxidant effect and the effect of improving the adhesion tend not to be reliably obtained. This is because there is a tendency that the adhesive force with the insulating resin tends to decrease. Therefore, the amount of the surface treatment agent used, 100 parts by weight of metal particles and the like,
The value is more preferably in the range of 0.1 to 10 parts by weight, and even more preferably in the range of 0.5 to 5 parts by weight.

(2) Insulating resin easily charged Next, the insulating resin easily charged will be described. Acrylic resins (including styrene-acrylic resins), styrene resins, fluororesins (including fluoroacrylic resins), ethylene resins, propylene resins and esters include such easily chargeable insulating resins. And the like. Further, the easily chargeable insulating resin may be formed of an insulating resin described later and a chargeable material, or a resin having a chargeable functional group in a molecule constituting the insulating resin. Or a copolymer of an insulating resin and a chargeable material.

The coating amount of the easily chargeable insulating resin is not particularly limited. For example, when the volume of the metal particles and the like is 100 parts by volume, the coating amount of the easily chargeable insulating resin is set. Is preferably in the range of 20 to 250 parts by volume. The reason is that if the coating amount of the insulating resin that is easily charged is less than 20 parts by volume, it becomes difficult to adjust the charging level of the metal toner, and the insulation resistance value is low, for example, a value of less than 1 × 10 ¹⁴ Ω · cm. This is because it is easy to become. Therefore, when the developability of the metal toner is reduced and the conductor pattern is formed, it tends to bleed and it is difficult to obtain a sharp image. On the other hand, if the coating amount of the easily chargeable insulating resin exceeds 250 parts by volume, the conductor resistance of the conductor pattern significantly increases,
This is because disconnection is likely to occur.

Accordingly, a higher insulation resistance value is obtained, the charge level is improved, and the conductor resistance of the conductor pattern is lower. It is more preferable that the coating amount is within a range of 30 to 240 parts by volume,
More preferably, the value is in the range of 30 parts by volume.

With reference to Table 3 and FIG. 4, the effect of the amount of the easily chargeable insulating resin (particle) in the metal toner will be described in detail. Table 3 and FIG.
With respect to 100 parts by volume of metal particles constituting an easily chargeable insulating resin, a volume ratio of the chargeable material was changed within a range of 10 to 200 parts by volume to prepare a metal toner, and a charge amount,
This is an evaluation of Macbeth image density and occurrence of fog. The fog was evaluated based on the following criteria. In addition, detailed production conditions and evaluation conditions for metal toner
This will be described in Examples 1 to 6 described later. 〇: No fogging is observed at all. Δ: Fogging is slightly observed. X: Remarkable fogging is observed.

As understood from the results, when the amount of the easily chargeable insulating resin is reduced to 10 parts by volume, the charge amount is reduced, and the image density tends to be reduced or fog tends to occur. is there. Conversely, when the chargeable material is added in an amount of 200 parts by volume, the charge level tends to decrease slightly, fogging occurs, or the image density tends to decrease.

[0057]

[Table 3]

Next, when particles are used as the easily chargeable insulating resin, the average particle diameter of the resin is determined in consideration of the charge level and the like in the obtained metal toner. It is preferably within a range of 0.01 to 1 μm. The reason for this is that if the average particle diameter of the easily chargeable insulating resin is less than 0.01, the particles are likely to aggregate, and it is difficult to form a coating layer having a uniform thickness. On the other hand, if the average particle size of the easily chargeable insulating resin exceeds 1 μm, the charge level is reduced,
Alternatively, the fixability of the chargeable particles is reduced, and the thickness of the chargeability-imparting layer is likely to be non-uniform. Accordingly, a higher charge level is obtained, and excellent image characteristics are obtained.
More preferably, the value is in the range of 0.9 μm to 0.9 μm.

With reference to Table 4 and FIG. 5, the effect of the average particle diameter of the easily chargeable insulating resin in the metal toner will be described in detail. The data shown in Table 4 and FIG. 5 show that the metal toner was manufactured after changing the average particle size of the easily-chargeable insulating particles in the metal toner within the range of 0.1 to 5.0 μm, and the charge amount and image Characteristics (initial and 30
(After printing 00 sheets) was evaluated in the same manner as the evaluation in Table 3, and the coating state of the chargeability-imparting layer was evaluated using a microscope according to the following criteria. Detailed production conditions and evaluation conditions of the metal toner are described in Examples 11 to 11 described later.
This will be described at 14. 〇: The entire particles are uniformly coated, and no uncoated portions are observed. Δ: Slightly non-uniform, uncovered part observed. ×: Non-uniform, many uncoated portions observed.

As understood from the results, even when the average particle diameter of the easily-chargeable insulating particles is 0.1 μm,
A high charge amount can be obtained, and excellent image characteristics can be obtained. On the other hand, when the average particle diameter of the easily-chargeable insulating particles is 1 μm, the coating state becomes slightly non-uniform,
There was a tendency for the charge amount to slightly decrease and for the image characteristics after printing 3,000 sheets to decrease, but this was a level that was not problematic in practical use. Furthermore, when the average particle diameter of the easily-chargeable insulating particles was 5 μm, the coating state became non-uniform, the charge amount was reduced, and the image characteristics tended to be poor from the beginning. Therefore, it is more preferable that the average particle size of the easily-chargeable insulating particles is in the range of 0.01 to 1 μm, and more preferably 0.1 to 0.9 μm.
m within the range of m.

[0061]

[Table 4]

Next, the thickness of the coating layer made of an easily chargeable insulating resin will be described. The thickness of the coating layer is determined in consideration of the charge level of the metal toner and the like, and specifically, is preferably set to a value within a range of 0.01 to 3 μm. The reason for this is that if the thickness of the coating layer is less than 0.01 μm, the charge level of the metal toner tends to decrease, while the thickness of the coating layer becomes 3 μm.
If the thickness exceeds μm, on the contrary, the charge level tends to decrease, fogging occurs, or the image density tends to decrease. Therefore, from the viewpoint of obtaining a higher charging level, the thickness of the coating layer is more preferably set to a value within the range of 0.05 to 2 μm, and 0.1 to 1.5 μm.
More preferably, the value is in the range of μm.

(2) Insulating resin As the insulating resin constituting the easily chargeable insulating resin,
Styrene resin, acrylic resin, other than chargeable material,
At least one insulating resin selected from the group consisting of ethylene-based resins and propylene-based resins is included. By using such an insulating resin, a thin resin layer having a uniform thickness on the surface of metal particles or the like can be easily and economically provided by using a mechanical surface treatment method or the like. Therefore, a high insulation resistance value, for example, a value of 1 × 10 ¹⁴ Ω · cm or more can be obtained in the metal toner.

In particular, when an ethylene-based resin and a propylene-based resin are used, a thin film coating layer having a more uniform thickness can be provided. Therefore, in a metal toner, a higher insulation resistance value, for example, 1 × 10 ¹⁵ Ω · cm
The above values can be obtained, and when a conductor pattern is formed, a lower conductor resistance value can be obtained. In addition, when a styrene-acrylic insulating resin in which a styrene-based resin and an acrylic resin are combined is used, not only a high insulation resistance value of 1 × 10 ¹⁵ Ω · cm or more can be obtained, but also excellent adhesion to a chargeable resin. You can gain power.

(3) Chargeable Material When the easily chargeable insulating resin is composed of an insulating resin and a chargeable material, the chargeable material may be a material which improves the charge level of the metal toner, for example, a metal toner. It is preferable to use a material that can be charged to a value within the range of 10 to 30 μC / g as the charge amount in the blow-off method. By charging in such a range, excellent image characteristics can be obtained while preventing fog.

Specific examples of such a chargeable material include fluorine-based resins (vinylidene difluoride resin, vinylidene trifluoride resin, vinylidene tetrafluoride resin, polyethylene difluoride resin, polyethylene trifluoride resin, tetrafluoroethylene resin). Polyethylene resin, fluorinated acrylic resin, etc.), polystyrene resin (polystyrene, ABS resin, etc.), polyacrylic resin (MMA, MA, etc.), polyethylene resin (polyethylene, EVE, etc.), polypropylene resin (polypropylene, etc.) At least one material selected from the group consisting of polymethylpentane, a polyester-based resin, and a metal complex (such as a metal salicylate complex and a metal-containing azo complex). In particular, the addition of a small amount of a fluorine-based resin is preferable for use as a chargeable material because the charge level of a metal toner can be improved.

Further, azine compounds, quaternary ammonium salt compounds, nigrosine compounds, triphenylmethane, carboxylate compounds, phenol resin condensates, vinyl chloride resins, and celluloid resins are also preferably used as chargeable materials. Can be used together. By using or using such a charging material, the charging level on the plus (+) side or the minus (-) side can be increased, and the charging level can be easily and quickly adjusted within a desired range. You can also.

Among these chargeable materials, a preferable chargeable material for charging the metal toner to the plus (+) side is, specifically, pyridazine as an azine compound;
Pyrimidine, pyrazine, orthooxazine, methoxazine, paraoxazine, orthothiazine, metathiazine, parathiazine, 1,2,3-triazine, 1,2,2
4-triazine, 1,3,5-triazine, 1,2,4
-Oxadiazine, 1,3,4-oxadiazine, 1,
2,6-oxadiazine, 1,3,4-thiadiazine,
1,3,5-thiadiazine, 1,2,3,4-tetrazine, 1,2,4,5-tetrazine, 1,2,3,5-tetrazine, 1,2,4,6-oxatriazine, 1 ,
Azin Fast Red FC, Azin Fast Red 12BK, Azin Violet BO, Azin Brown 3 as direct dye consisting of 3,4,5-oxatriazine, phthalazine, quinazoline, quinoxaline, azine compound
G, azine light brown GR, azine dark green BH / C, azine deep black EW and azine deep black 3RL, nigrosine as a nigrosine compound, a nigrosine salt, a nigrosine derivative, nigrosine BK as an acidic dye composed of a nigrosine compound, nigrosine NB, Nigrosine Z, Nigrosine bases and nigrosine derivatives as azine-based compounds, benzylmethylhexyldecylammonium chloride and decyltrimethylammonium chloride as quaternary ammonium salts, naphthenic acid or higher fatty acid salts as metal salts, alkoxylated amines , An alkylamide, triphenylmethane, a quaternary ammonium salt-containing copolymer zone, a basic dye, and a lake pigment of a basic dye.

Among the chargeable materials described above, preferable chargeable materials for charging the metal toner to the minus (-) side include metal complexes of monoazo dyes, salicylic acid, naphthoic acid, and dicarboxylic acids such as Co, Cr and Fe. Metal complexes such as sulfonated copper phthalocyanine pigments, nitro group-introduced styrene oligomers, halogen group-introduced styrene oligomers, chlorinated paraffins, carboxylate compounds, fluororesins, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, alkyls Amides and the like.

The above-mentioned quaternary ammonium salt compound or carboxylate compound specifically includes a quaternary ammonium salt-containing polystyrene resin, a quaternary ammonium salt-containing acrylic resin, and a quaternary ammonium salt. Styrene-acrylic resin, polyester resin having quaternary ammonium salt, polystyrene resin having carboxylate, acrylic resin having carboxylate, styrene-acrylic resin having carboxylate, having carboxylate One or a combination of two or more of a polyester resin, a polystyrene resin having a carboxyl group, an acrylic resin having a carboxyl group, a styrene-acrylic resin having a carboxyl group, and a polyester resin having a carboxyl group are exemplified. .

The form of the chargeable material to be used is not particularly limited. For example, it is preferable to use chargeable particles. By using the chargeable particles as described above, a coating layer having a uniform thickness can be formed together with the insulating resin. In addition, the chargeable particles can be easily fixed around or inside the insulating resin layer by mechanical surface treatment.

When chargeable particles are used as the chargeable material, it is preferable to determine the average particle diameter of the chargeable particles in consideration of the average particle diameter of the metal particles or metal oxide particles. Specifically, the average particle diameter of the chargeable particles is preferably set to 1/10 to 1/1000 of the average particle diameter of metal particles or the like. The reason is that, when the average particle diameter of the chargeable particles is less than 1/1000 of that of the metal particles, the chargeable particles are likely to aggregate, and it becomes difficult to form a chargeability-imparting layer having a uniform thickness. That's why. on the other hand,
When the average particle diameter of the chargeable particles exceeds 1/10 of that of the metal particles or the like, the charge level is reduced, or the fixability of the chargeable particles is reduced, and the thickness of the chargeability-imparting layer tends to be uneven. That's why. Therefore, a higher charging level can be obtained, and the charging particles can be more easily fixed around or inside the insulating resin layer. 1 /
It is more preferable to be 20 to 1/500.

Next, the addition amount (volume amount) of the chargeable material in the easily chargeable insulating resin will be described. Although there is no particular limitation on the amount of the chargeable material, for example, when the volume of the insulating resin layer is 100 parts by volume, the volume of the chargeable material is in the range of 1 to 200 parts by volume. Is preferable. The reason is that if the amount of the chargeable material is less than 1 part by volume, it is easy to adjust the charge level of the metal toner. Therefore, the developability of the metal toner decreases, and the image density tends to decrease. On the other hand, when the added amount of the charging material exceeds 200 parts by volume, the charging level is reduced, fog is generated, or the image density is apt to be reduced. Therefore, a higher charge level is obtained, and a higher image density is obtained.
It is more preferable that the amount of the chargeable material to be added falls within a range of 5 to 150 parts by volume relative to 0 parts by volume.
More preferably, the value is in the range of 50 parts by volume.

[Second Embodiment] A method for manufacturing a metal toner according to a second embodiment includes the following steps (A) and (B).
, Respectively. Note that as a modification of the second embodiment, it is also preferable to simultaneously perform the following fixing (A) and step (B). (A) A step of coating the surface of metal particles or metal oxide particles with an insulating resin by mechanical surface treatment. (B) A method of mechanically forming a charge-imparting layer made of a chargeable material around or inside the insulating resin layer. Step of coating by surface treatment.

(1) Step (A) As the mechanical surface treatment of the insulating resin in the step (A), for example, it is preferable to use a Henschel mixer, a super Henschel mixer, a mechano mill, an ang mill or a hybridizer. It is more preferable to use an ang mill. By using these mechanical processing devices, an insulating resin layer having a uniform thickness can be formed around or inside the insulating resin layer in a short time.

FIG. 7 shows an Angular mill as an example of a mechanical processing apparatus. This angmill 51 is a container 37
And an inner piece 45 composed of a semicircular head 41 and a shaft 43 fixed therein. Therefore, the container 37 which rotates in the direction of arrow F
The two or more kinds of powders (metal particles and chargeable particles having an insulating resin layer) 39 charged into the container are pressed against the inner surface of the container by centrifugal force, rotate together with the container 37, and rotate with the head 41 of the inner piece 45. Between, subject to strong compressive and shearing action. Therefore, the two or more types of powders 39 are each subjected to the compounding process, and the uniformly layered charged particles can be fixed on the metal particles having the insulating resin layer.

(2) Step (B) The apparatus for carrying out the mechanical surface treatment method in the step (B) is not particularly limited, but as in the step (A), a Henschel mixer, a super Henschel mixer, a mechanomill, an angmill Alternatively, it is preferable to use a hybridizer. By using these mechanical processing devices, a charge-imparting layer having a uniform thickness (charged particle diameter) can be formed in a short time around or inside the insulating resin layer.

Further, for example, the ongmill shown in FIG.
The degree of the compounding process can be changed depending on the rotation speed of the container 37, the pressing force of the inner piece 45, or the processing time. Therefore, a metal toner as shown in FIGS. 2 and 3 can be easily obtained. The metal toner shown in FIG. 2 is composed of metal particles 25 and the like, an insulating resin layer 27 and a charge-imparting layer 29 sequentially from the inside, and the metal toner shown in FIG.
5, an insulating resin layer 27 and a charge-imparting layer 31 embedded in the insulating resin layer 27.

Next, the effect of the processing temperature in the step (B) will be described. It is desirable to determine the processing temperature in consideration of the charge level of the metal toner,
As partially described above, when the glass transition point or melting point of the chargeable material is Q (° C.), the mechanical surface treatment in the step (B) is performed at a temperature within the range of Q ± 20 (° C.). Is preferred. By performing the mechanical surface treatment under such a temperature condition, a charge-imparting layer having a uniform thickness can be easily formed, and the charge level of the metal toner can be increased.

The effect of the processing temperature in the step (B) will be described in detail with reference to Table 5 and FIG. 6A. Table 5 and FIG. 6 (a) show that the metal toner was manufactured by changing the processing temperature (saturation temperature of the processing tank in an ang mill) when manufacturing the metal toner within the range of 30 to 90 ° C., and the charge amount and image characteristics (Initial and after printing 3000 sheets)
Was evaluated in the same manner as the evaluation criteria shown in Table 1.
Detailed production conditions and evaluation conditions of the metal toner will be described in Examples 1 and 22 to 25 described later.

As can be understood from the results, the charging amount of the metal toner greatly changes depending on the processing temperature, and the metal toner has an optimum processing temperature with respect to the charging level. That is,
The treatment temperature is in the range of 30 to 90 ° C, more preferably 4
Within the range of 0 to 80 ° C, more preferably 50 to 70 ° C
Within this range, a tendency to obtain a higher charge amount was observed. Conversely, when the processing temperature is out of the range of 30 to 90 ° C., the charge level tends to suddenly decrease. Therefore, it is understood that the charge amount of the metal toner can be easily adjusted by changing the processing temperature within such a range.

[0082]

[Table 5] * Cell rotation speed: 20 m / s, processing time: 10 minutes

Next, the effect of the cell rotation speed (vessel rotation speed) in the step (B) will be described. Although it is desirable to determine the cell rotation speed in consideration of the charge level of the metal toner, it is preferable that the cell rotation speed at the time of performing the mechanical surface treatment be a value within a range of 1 to 50 m / s. . By performing the mechanical surface treatment at such a cell rotation speed, a charge-imparting layer having a uniform thickness can be easily formed, and the charge level of the metal toner can be further increased.

The effect of the cell rotation speed in the step (B) will be described in detail with reference to Table 6 and FIG. 6B. Table 6 and FIG. 6B show that the cell rotation speed (using an ang mill, in this case, the cell rotation speed may be the rotation speed of the processing blade) when producing the metal toner is 5 to 50 m.
/ S was changed within the range of / s to evaluate the charge amount and image characteristics (initial and after printing 3000 sheets). Detailed production conditions and evaluation conditions of the metal toner will be described in Examples 1 and 26 to 28 described later.

As can be understood from the results, the amount of charge in the metal toner greatly changes depending on the cell rotation speed, and the charge level has an optimum cell rotation speed. That is, the cell rotation speed is in the range of 1 to 50 m / s, more preferably in the range of 5 to 40 m / s, and still more preferably 1 to 50 m / s.
Within the range of 0 to 40 m / s, a tendency to obtain a higher charge amount was observed. Conversely, when the cell rotation speed is 1 to
Outside the range of 50 m / s, the charge level tends to suddenly decrease. Therefore, it is understood that the charge amount of the metal toner can be easily adjusted by changing the cell rotation speed within such a range.

[0086]

[Table 6] * Treatment temperature: 60 ° C, treatment time: 10 minutes

Next, the effect of the processing time in the step (B) will be described. Although it is desirable to determine the processing time in consideration of the charge level of the metal toner,
For example, the processing time for performing the mechanical surface treatment is 5-2
It is preferable to set the value within a range of 5 minutes. By performing the mechanical surface treatment for such a treatment time, a charge imparting layer having a uniform thickness can be easily formed, and the charge level of the metal toner can be further increased.

The effect of the processing time in the step (B) will be described in detail with reference to Table 7 and FIG. 6C. Table 7 and FIG. 6C show that the processing time (using an ang mill) for producing the metal toner was 5 minutes, 10 minutes, and 15 minutes.
The results are obtained by producing a metal toner and evaluating the charge amount and the image characteristics (initial and after printing 3000 sheets), respectively. Detailed production conditions and evaluation conditions for the metal toner are described in Examples 1 and 29 to be described later.
This will be described at 31.

As can be understood from the results, the charge amount of the metal toner greatly changes depending on the processing time, and the processing time has an optimum processing time with respect to the charge level. That is,
Processing time is in the range of 5 to 25 minutes, more preferably 5 to 25 minutes.
Within the range of 20 m / s, more preferably 10 to 15 m
In the range of / s, a tendency to obtain a higher charge amount was observed. Conversely, when the processing time is outside the range of 5 to 25 minutes, the charge level tends to suddenly decrease. Therefore, it is understood that the amount of charge in the metal toner can be easily adjusted by limiting the processing time to a value within a certain range.

[0090]

[Table 7] * Treatment temperature: 60 ° C, cell rotation speed: 20m / s

[Third Embodiment] A method for manufacturing a metal toner according to a third embodiment includes the following steps (A) and (B), and performs step (B) a plurality of times, for example, from 2 to 10
It is characterized in that it is performed separately. As a modified example of the third embodiment, it is preferable that the following steps (A) and (B) are simultaneously performed, and the steps (A) and (B) are performed a plurality of times. (A) A step of coating the surface of metal particles or metal oxide particles with an insulating resin by mechanical surface treatment. (B) A method of mechanically forming a charge-imparting layer made of a chargeable material around or inside the insulating resin layer. Step of coating by surface treatment.

Hereinafter, a case where the mechanical surface treatment method is performed a plurality of times in the step (B), for example, three times will be specifically described. In addition, the configuration of the step (A) in the third embodiment can basically adopt the same configuration as that of the second embodiment, and thus the description thereof will be omitted as appropriate.

First, in the first time, 1/3 of the amount of the chargeable material to be finally laminated is reduced by a mechanical surface treatment machine,
For example, the surface of the metal particles or the like coated with the insulating resin after the step (A) is further coated using an on-mill. In addition, the processing conditions of the ongmill can adopt the conditions that are preferable in the second embodiment, and specifically,
Preferably, the temperature is 60 ° C., the cell rotation speed is 20 m / s, and the processing time is 10 minutes. However, the processing time may be set to a value in the range of 1 to 9 minutes because the amount of the charging material added is relatively small.

Next, in the second time, similarly, 1/3 of the added amount of the chargeable material to be finally laminated is further coated by using a mechanical surface treatment machine. In this case, the processing conditions of the Ongmill were set to a temperature of 60 ° C. and a cell rotation speed of 20 m.
/ S and a processing time of 10 minutes. And
Finally, in the third time, similarly, 1/3 of the added amount of the chargeable material to be finally laminated is further reduced by using a mechanical surface treatment machine under the same processing conditions as the first and second times. Cover.

As described above, by separately charging the chargeable material, the chargeable material can be coated more uniformly. Therefore, the chargeability and image characteristics of the obtained metal toner are further improved.

In this regard, with reference to Table 8 and FIG.
(B) The advantage of performing the step in a plurality of times will be described in detail. Table 8 and FIG. 7 show that the step (B)
, Twice and three times, the metal toner was manufactured, and the coating state, the charge amount, and the image characteristics (initial and after printing 3000 sheets) were evaluated. Detailed production conditions and evaluation conditions for metal toner are described in Example 1 below.
And 32-33.

As can be understood from the results, by performing the step (B) a plurality of times, the coating of the chargeable material becomes uniform, and the charge amount of the metal toner increases by 10% or more. Image characteristics after printing are improved.
For example, when the step (B) is performed once, the coating state of the chargeable material was observed to be slightly non-uniform,
(B) In the case where the number of steps is two or three, this is eliminated. Therefore, it can be said that the advantage of performing the step (B) a plurality of times is large.

[0098]

[Table 8] * Treatment temperature: 60 ° C., cell rotation speed: 20 m / s, treatment time: 10 minutes

[Fourth Embodiment] A method for using a metal toner (a method for forming a conductor pattern) according to a fourth embodiment will be specifically described with reference to the drawings as appropriate. In the fourth embodiment, as the metal toner, the metal particles or the surface of the metal particles are coated with an insulating resin layer formed by an on-mill as shown in FIG. 2 and a charge providing layer also formed by an on-mill. A metal toner is used. The present invention is characterized in that a conductive pattern is formed by applying the metal toner to a ceramic thin film sheet by using an electrophotographic method and then heating the sheet. Therefore, it is preferable that the method of using the metal toner includes the following steps (C) to (F).

(C) The metal toner in the first embodiment is
Step prepared by the manufacturing method of the second embodiment. (D) a step of forming an image using an electrophotographic method and transferring a metal toner to a ceramic green sheet corresponding to the formed image; (E) A step of fixing the metal toner to the ceramic green sheet by heating using a flash discharge. (F) A step of forming a conductive pattern by heating at a temperature equal to or higher than the melting point of metal particles or the like constituting the metal toner.

In the step (D), a one-component developing method or a two-component developing method can be used for attaching the metal toner to the ceramic thin film sheet. When the one-component developing method is used, it is not necessary to use a carrier, and the conductor resistance of the obtained conductor pattern can be further reduced. On the other hand, when the two-component developing method is used, it is necessary to use a carrier. However, even when the charging characteristics of the metal toner are low, a conductive pattern can be stably formed.

[0102]

Hereinafter, the present invention will be described in more detail with reference to examples. Needless to say, the following description is an exemplification of the present invention, and the scope of the present invention is not limited to the following description without any particular reason.

Example 1 (Preparation of Metal Toner) 200 g of copper powder and acrylic fine particles N-30 as an easily-chargeable insulating resin were placed in a treatment tank of Angmill AM-15F (manufactured by Hosokawa Micron Corporation).
(Nippon Paint Co., Ltd., average particle diameter 0.1 μm, glass transition temperature 60 ° C.) 20 g. Next, mechanical processing was performed under the conditions of a processing temperature (saturation temperature) of 60 ° C., a cell rotation speed of 20 m / s, and a processing time of 10 minutes to form a coating layer. The obtained coating layer is based on 100 parts by volume of the copper particles.
It was about 100 parts by volume.

The copper particles used were obtained by the precipitation method, and the average particle diameter of the copper particles was 5 μm.
70 to 100 vol% in the particle size distribution in terms of volume,
Those that exist within a range of ± 30% of the average particle diameter were used.

(Evaluation of Metal Toner) The obtained metal toner was used as a non-magnetic one-component developer and housed in a printer for negative (-) charged toner mounted on an OPC drum. Next, an image evaluation pattern (solid pattern) was output, and the following amounts of charge, Macbeth image density, and occurrence of fog were measured. The obtained results are shown in Table 3 and the like.

(1) Charge Amount According to the blow-off method, after mixing 5 parts by weight of the obtained metal toner and 100 parts by weight of a ferrite carrier,
Under normal environmental conditions (20 ° C., 65% RH), triboelectric charging was performed by vibrating in a container for 60 minutes. The charge amount (μC / g) of the metal toner at that time was measured using a blow-off powder charge amount measuring device (manufactured by Toshiba Chemical Corporation).

(2) Macbeth Image Density and Fog The obtained metal toner was used as a magnetic one-component developer, housed in the printer described above, and then printed to evaluate the image density. That is, normal environment (20 ° C, 65% RH)
The image evaluation pattern (solid pattern) obtained in (1) is used as an initial image, and then 3000 sheets are continuously printed.
A conductive pattern was printed to obtain a durable image. Then, using a Macbeth reflection densitometer (using a monochrome filter), the image densities of the initial image and the durable image were measured. Further, fog of the obtained initial image and durable image was visually observed based on the criteria shown in the description of Table 5 above.

[Examples 2 to 6] In Example 1, a charge-imparting layer (chargeable particles) was added to 100 parts by volume of copper particles.
Instead of 100 parts by volume, 10 parts by volume (Example 2), 30 parts by volume (Example 3), 50 parts by volume (Example 4), 150 parts by volume (Example 5) and 200 parts by volume
Example 1 except that the volume part (Example 6) was changed.
In the same manner as in the above, a metal toner was produced. The obtained metal toner was evaluated in the same manner as in Example 1 for the charge amount, image density and fog. Table 3 shows the results.

Examples 7 to 10 (Preparation of Metal Toner) (1) Formation of Insulating Resin Layer Ongmill AM-15F (manufactured by Hosokawa Micron Corporation)
, A 200 g copper powder and styrene-based acrylic resin particles N32 as insulating resin particles (Nippon Paint Co., Ltd., average particle diameter 0.1 μm, glass transition temperature 10)
(0 ° C.) 20 g. Next, mechanical processing was performed under the conditions of a processing temperature (saturation temperature) of 90 ° C., a cell rotation speed of 20 m / s, and a processing time of 10 minutes to form an insulating resin layer.
The obtained insulating resin layer was about 100 parts by volume with respect to 100 parts by volume of the copper particles. The copper particles used are the same as those in Example 1.

(2) Formation of charge-imparting layer Next, 200 g of copper powder on which an insulating resin layer had been formed, and a fluorine-based chargeable particle were placed in a treatment tank of Angmill AM-15F (manufactured by Hosokawa Micron Corporation). Acrylic fine particles F570 (manufactured by Nippon Paint Co., Ltd., average particle size 0.1
μm, glass transition temperature 70 ° C.). Then, a processing temperature (saturation temperature) of 60 ° C. and a cell rotation speed of 20 m /
s, mechanical processing was performed under the conditions of a processing time of 10 minutes to form a chargeability-imparting layer to obtain a metal toner. The volume ratio (addition amount) of the chargeability-imparting layer (chargeable particles) in the obtained metal toner was 100 parts by volume of the insulating resin.
It was about 30 parts by volume.

(Evaluation of Metal Toner) The obtained metal toner was evaluated in the same manner as in Example 1 for the charge amount and the image characteristics. Table 9 shows the obtained results.

[0112]

[Table 9]

[Examples 11 to 14] The average particle diameter of the chargeable particles was 0.1 μm (Example 11), 0.5 μm (Example 12), 1.0 μm (Example 13) and 5.0 μm.
A metal toner was produced in the same manner as in Example 1, except that each was changed to (Example 14). With respect to the obtained metal toner, the charge amount, the coating state, and the image characteristics were evaluated in the same manner as in Example 1. Table 4 shows the obtained results.

[Examples 15 to 17] In Example 1, 70 to 100% by volume of the copper powder in the particle size distribution in terms of volume.
Is, instead of the average particle diameter ± 30% of the average particle diameter,
Average particle diameter ± 40% of average particle diameter (Example 15), average particle diameter ± 60% of average particle diameter (Example 16) and average particle diameter ± 70% of average particle diameter (Example 17) Otherwise, in the same manner as in Example 1, a metal toner was produced. The obtained metal toner was evaluated for only the image characteristics in the same manner as in Example 7 and the like. Table 2 shows the obtained results.

[Examples 18 to 22] The sphericity of copper powder was set at 0.
4 or less (Example 18), more than 0.4 to 0.5 or less (Example 19), more than 0.5 to 0.6 or less (Example 20), 0.6
Exceeding to 0.7 or less (Example 21), and exceeding 0.7 to 0.
Except having changed each to 9 or less (Example 22), it carried out similarly to Example 1, and produced the metal toner. Example 22
Is a reproducibility test of Example 1. The obtained metal toner was evaluated for only the image characteristics in the same manner as in Example 7 and the like. Table 1 shows the obtained results.

Examples 23 to 31 As shown in Tables 5 to 7, similar to Example 1, except that the production conditions (processing temperature, cell rotation speed, processing time) of the metal toner were partially changed. A metal toner was prepared. The obtained metal toner was evaluated for only the image characteristics in the same manner as in Example 7 and the like.
The obtained results are shown in Tables 5 to 7 and FIGS. 6 (a) to 6 (c).
Shown in

Examples 32 to 33 Example 1 was repeated except that the number of times of supply of the easily chargeable insulating resin was changed to twice (Example 32) and three times (Example 32) to produce metal toner. In the same manner as in the above, a metal toner was produced. Example 32
Then, the first and second mechanical surface treatment amounts were each 50 parts by volume with respect to 100 parts by volume of the copper particles. Further, in Example 33, the first to third mechanical surface treatment amounts were respectively set to 100 parts by volume of the copper particles.
33 parts by volume. The obtained metal toner was evaluated for only the image characteristics in the same manner as in Example 7 and the like.
The results obtained are shown in Table 8 and FIG.

[0118]

According to the present invention, the surface of metal particles or metal oxide particles is coated with an insulating resin or an easily chargeable insulating resin by using a mechanical surface treatment method, so that the charge level can be reduced. It has become possible to provide a metal toner for forming a conductor pattern which is high and has excellent image characteristics.

Further, according to the method for producing a metal toner for forming a conductor pattern of the present invention, a mechanical surface treatment method is used.
Efficient (short-time) production of metal toner with high charge level and excellent image characteristics by coating the surface of metal particles or metal oxide particles with insulating resin or easily chargeable insulating resin. Became possible.

Further, by forming a conductor pattern using the method of using the metal toner of the present invention, a conductor pattern having excellent image characteristics (including image density), low fog, and low conductor resistance can be formed. You can now.

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus for forming a conductor pattern using electrophotography.

FIG. 2 is a cross-sectional view of a metal toner for forming a conductive pattern (part 1).

FIG. 3 is a cross-sectional view of a metal toner for forming a conductive pattern (part 2).

FIG. 4 is a diagram showing the relationship between the addition amount of an easily chargeable insulating resin, the charge amount, and the image density.

FIG. 5 is a diagram showing the relationship between the average particle size of an easily chargeable insulating resin and the charge amount.

FIG. 6A is a diagram illustrating a relationship between a processing temperature and a charge amount. FIG. 3B is a diagram illustrating a relationship between a cell rotation speed and a charge amount. (B) is a diagram showing the relationship between the processing time and the charge amount.

FIG. 7 is a diagram illustrating a relationship between the number of times of processing by a mechanical processing device and a charge amount.

FIG. 8 is a diagram showing an example of a mechanical processing device (mechano mill).

[Explanation of symbols]

 REFERENCE SIGNS LIST 11 photoconductor drum 13 charger 15 image signal exposure device 17 developing device 19 transfer roll 21 cleaning blade 23 full-surface exposure device 25 metal particles or metal oxide particles 27 insulating resin layer 29, 31 chargeability imparting layer 39 powder 45 inner Peace 51 Angmir

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[Procedure amendment]

[Submission date] October 2, 1998 (1998.10.
2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0110

[Correction method] Change

[Correction contents]

(2) Formation of charge-imparting layer Next, 200 g of copper powder on which an insulating resin layer was formed and a fluorine-based charge Acrylic fine particles F70 (Nippon Paint Co., Ltd., average particle diameter 0.1μ)
m, glass transition temperature 70 ° C.) 5 g. Then, a processing temperature (saturation temperature) of 60 ° C. and a cell rotation speed of 20 m /
s, mechanical processing was performed under the conditions of a processing time of 10 minutes to form a chargeability-imparting layer to obtain a metal toner. The volume ratio (addition amount) of the chargeability-imparting layer (chargeable particles) in the obtained metal toner was 100 parts by volume of the insulating resin.
It was about 30 parts by volume.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H05K 1/09 C09C 1/62 3/12 630 G03G 9/08 321 // C09C 1/62 325 371 381 H01G 1/1

Claims (20)

[Claims] 1. A metal for forming a conductive pattern, wherein a surface of a metal particle or a metal oxide particle is coated with an insulating resin or an easily chargeable insulating resin by using a mechanical surface treatment method. toner. 2. The metal toner for forming a conductive pattern according to claim 1, wherein the easily chargeable insulating resin contains an insulating resin and a chargeable material. 3. The chargeable material is at least one material selected from the group consisting of a fluorine resin, a styrene resin, an acrylic resin, an ethylene resin, a propylene resin, an ester resin and a metal complex. 3. The metal toner for forming a conductive pattern according to claim 2, wherein: 4. The insulating resin is a resin other than the chargeable material, and is at least one resin selected from the group consisting of a styrene resin, an acrylic resin, an ethylene resin and a propylene resin. The metal toner for forming a conductor pattern according to claim 2 or 3, wherein: 5. The method according to claim 2, wherein when the volume of the insulating resin is 100 parts by volume, the amount of the chargeable material is set to a value within a range of 1 to 200 parts by volume. The metal toner for forming a conductor pattern according to any one of the above. 6. When the volume of the metal particles or metal oxide particles is 100 parts by volume, the coating amount of the easily chargeable insulating resin is set to a value within a range of 20 to 250 parts by volume. The metal toner for forming a conductor pattern according to any one of claims 1 to 5. 7. The conductive pattern for forming a conductive pattern according to claim 1, wherein the average particle diameter of the metal particles or the metal oxide particles is set to a value within a range of 2 to 20 μm. Metal toner. 8. The chargeable material is in the form of chargeable particles, and has an average particle diameter of 1/10 to 1/1/1 of the average particle diameter of the metal particles or metal oxide particles.
The metal toner for forming a conductive pattern according to any one of claims 2 to 6, wherein the number is set to 1,000. 9. 70% to 100% by volume of the metal particles or metal oxide particles in the volume-converted particle size distribution is within the range of the average particle diameter of the metal particles or metal oxide particles ± 40% of the average particle diameter. 9. The method according to claim 1, wherein
The metal toner for forming a conductor pattern according to any one of the above. 10. The metal toner for forming a conductive pattern according to claim 1, wherein the sphericity of the metal particles or the metal oxide particles is set to a value of 0.5 or more. . 11. The metal toner for forming a conductive pattern according to claim 1, wherein the metal particles are metal particles manufactured by a wet method. 12. A metal toner for forming a conductive pattern, wherein the surface of metal particles or metal oxide particles is coated with an insulating resin or an easily chargeable insulating resin by using a mechanical surface treatment method. Production method. 13. The conductive pattern forming method according to claim 12, wherein an insulating resin and a charging material are used as the insulating resin, and a mechanical surface treatment method is performed simultaneously or separately. Manufacturing method of metal toner. 14. Before the mechanical surface treatment method, the surface of the metal particles or metal oxide particles is treated with a saturated fatty acid,
14. The conductive pattern formation according to claim 12, wherein the treatment is performed with at least one surface treatment agent selected from the group consisting of an unsaturated fatty acid, a titanium coupling agent, a silane coupling agent, and an aluminum coupling agent. Of producing metal toner for automobiles. 15. The conductor pattern according to claim 12, wherein the mechanical surface treatment method is performed using a Henschel mixer, a super Henschel mixer, a mechano mill, an ang mill, or a hybridizer. A method for producing a forming metal toner. 16. The mechanical surface treatment method, wherein the insulating resin or the chargeable material is an amorphous polymer, and the glass transition point of the insulating resin or the chargeable material is Q (° C.). The method for producing a metal toner for forming a conductive pattern according to any one of claims 13 to 15, wherein the treatment temperature is set to a value within a range of Q ± 20 (° C). 17. The metal for forming a conductive pattern according to claim 12, wherein a treatment time of the mechanical surface treatment method is set to a value within a range of 5 to 20 minutes. Manufacturing method of toner. 18. The method for producing a metal toner for forming a conductive pattern according to claim 12, wherein the mechanical surface treatment method is performed a plurality of times. 19. A metal toner for forming a conductive pattern, wherein a metal particle or a metal toner whose surface is coated with an insulating resin or an easily chargeable insulating resin by a mechanical surface treatment method is used. A method of using the metal toner for forming a conductor pattern, wherein the metal toner is adhered to a ceramic thin film sheet by electrophotography and then heated to form a conductor pattern. 20. The method according to claim 19, wherein a one-component developing method is used when attaching the metal toner to the ceramic thin film sheet.