JP3232280B2 - 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

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 and excellent image characteristics, a method of manufacturing a metal toner capable of efficiently manufacturing such a metal toner, and a metal using such a metal toner for forming a conductive pattern The present invention relates to a method for using a toner.

[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 using electrophotography will be briefly described with reference to FIG. First, an electrostatic latent image is formed on the rotating photosensitive drum 11 by using the charger 13 and the image signal exposure unit 15. Next, a 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 transfer roll 19
By transferring the formed toner image onto a ceramic sheet (not shown) using
A conductor pattern is formed. The toner not transferred to the ceramic sheet is removed using the cleaning blade 21.

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

[0005]

SUMMARY OF THE INVENTION The inventors of the present invention
In a metal toner in which the surface of metal particles or metal oxide particles is coated with an insulating resin layer obtained by a direct polymerization method of a monomer, a charge-imparting layer made of a chargeable material is provided around or inside the insulating resin layer. It has been found that by providing a toner, a metal toner having a high charge level and excellent image characteristics (sharpness and image density) can be efficiently obtained, and as a result, a fine conductor pattern can be stably formed. The invention has been completed. That is, an object of the present invention is to provide a metal toner for forming a conductive pattern having a high charge level and excellent image characteristics. Another object of the present invention is to provide a method for producing a metal toner which can efficiently produce a metal toner having a high charge level 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 and excellent image characteristics for forming a conductive pattern.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a metal toner for forming a conductive pattern, wherein metal particles or metal oxide particles are coated with an insulating resin layer obtained by a direct polymerization method of a monomer. A charge-imparting layer made of a chargeable material (provided by a method other than the direct polymerization method of a monomer) is provided around or inside the insulating resin layer. 100 volumes of resin
The volume ratio of the charge-imparting layer is 1 to 2
When the volume of the metal particles or the metal oxide particles is set to 100 parts by volume, the coating amount of the insulating resin layer is set to a value within the range of 20 to 250 parts by volume. Features. By providing not only the insulating resin layer but also the chargeability-imparting layer separately, a metal toner for forming a conductor pattern having a high charge level and excellent image characteristics can be provided. In addition, by limiting the volume ratio of the chargeability-imparting layer in this way, it becomes easier to adjust the charge level in the metal toner, and when a conductor pattern is formed, the value of the conductor resistance is made more uniform. be able to. Further, by limiting the coating amount of the insulating resin layer in this way, it becomes easier to adjust the charge level of the metal toner, and when the conductor pattern is formed, the value of the conductor resistance is reduced. Can be.

In the present invention, the charge-imparting layer is
It is not necessary to have a layered structure, and the chargeable particles may be scattered around or inside the insulating resin layer. 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.

In constituting the metal toner of the present invention, the chargeable material includes a fluororesin, a polystyrene resin, a polyacrylic resin, a polyethylene resin, a polypropylene resin, a polyester resin and a metal complex. It is preferable to use at least one material selected from By using such a chargeable material, the charge level of the metal toner can be further increased. Further, these chargeable materials are easy to handle and inexpensive, and the chargeability-imparting layer can be provided uniformly and economically.

In constituting the metal toner of the present invention, at least one insulating resin material selected from the group consisting of a styrene monomer, an acrylic monomer, an ethylene monomer and a propylene monomer is used as a monomer. Is preferred. By using such a monomer, a thin insulating resin layer having a uniform thickness can be easily provided on the surface of metal particles or the like. These insulating materials are easy to handle and inexpensive, and the insulating resin layer can be provided economically.

[0010]

[0011]

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.

In constituting the metal toner of the present invention, the charge-imparting layer is constituted to contain the chargeable particles, and the average particle diameter of the chargeable particles is adjusted to the average particle size of the metal particles or the metal oxide particles. The diameter is preferably set to 1/10 to 1/1000 of the diameter. As described above, by using the chargeable particles in the chargeability-imparting layer, and by limiting the average particle diameter of the chargeable particles, not only can the aggregation of the chargeable particles be effectively prevented, but also the chargeability impartation is provided. The formation of the layer becomes easier.

In constituting the metal toner of the present invention, the metal particles or the metal oxide particles have a particle size distribution in terms of volume of 70 to 70% 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-imparting layer having a 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, which is characterized by including the following steps (A) and (B). (A) A step of coating an insulating resin layer on the surface of metal particles or metal oxide particles by a direct polymerization method of a monomer. (B) A charge-imparting layer made of a chargeable material is provided around or inside the insulating resin layer. Step of providing by mechanical surface treatment. 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 and economically obtained. That is, when the thickness of the insulating resin layer is increased by the direct polymerization method of the monomer in order to increase the charge level of the metal toner, the required time tends to be extremely long. Further, when the thickness of the insulating resin layer is increased by the direct polymerization method of the monomer, the thickness of the insulating resin layer tends to be uneven, and as a result, the image characteristics tend to be poor.

In carrying out the method for producing a metal toner of the present invention, it is preferable that the mechanical surface treatment in the step (B) is performed using a Henschel mixer, a super Henschel mixer, a mechano mill, an ang mill or a hybridizer. By using these mechanical processing machines, 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.

In carrying out the method for producing a metal toner of the present invention, when the chargeable material is an amorphous polymer and the glass transition point of the chargeable material is Q (° C.),
The mechanical surface treatment in the step (B) is preferably performed at a temperature within the range of Q ± 20 (° C.). By performing the mechanical surface treatment under such a temperature condition, the chargeable material can be sufficiently softened and an appropriate viscosity can be obtained. Therefore, a charge-imparting layer having a uniform thickness (charged particle diameter) can be easily formed around or inside the insulating resin layer. Note that the glass transition point of the chargeable material can be measured using a differential scanning calorimeter (DSC).

In carrying out the method for producing a metal toner of the present invention, it is preferable to perform the mechanical surface treatment in the step (B) for a treatment time within a range of 5 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.

Still another aspect of the present invention is a method of using a metal toner for forming a conductor pattern. First, as a metal toner, the surface of metal particles or metal oxide particles is:
It is covered with an insulating resin layer obtained by a direct polymerization method of a monomer, and around or inside the insulating resin layer,
A metal toner provided with a chargeability-imparting layer made of a chargeable material 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,
A conductor pattern having excellent image characteristics (sharpness and image density) and low conductor resistance can be obtained.

In practicing 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.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The metal toner (first
Embodiment), a method for manufacturing a metal toner (second embodiment), and a method for using a metal toner (third embodiment) will be specifically described with reference to the drawings as appropriate.

[First Embodiment] Metal particles or metal oxide particles constituting a metal toner according to the first embodiment, an insulating resin layer obtained by a direct polymerization method of a monomer, and a chargeable material The charge-imparting layer will be described.

(1) Metal Particles or Metal Oxide Particles The metal particles and the like used in the first embodiment are not particularly limited. 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 using an atomizing method or a precipitation method are more preferable. Metal particles produced by these methods,
In particular, it is 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.

Also, as a preferred type of metal particles,
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 from the viewpoint of obtaining more excellent developability and the like. 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.

[0031]

[Table 1]

Further, as a preferable 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 the 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, from the viewpoint of obtaining better image characteristics, 70 to 100 particles of metal particles or metal oxide particles are used.
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.

[0034]

[Table 2]

The particle size of the metal particles and the like is not particularly limited, but it is preferable that the average particle size is in a 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, from the viewpoint that the charge level of the metal toner is better adjusted and a fine conductor pattern can be formed, it is more preferable that the average particle diameter of the metal particles and the like be in the range of 3 to 10 μm.

(2) Insulating Resin Layer The insulating resin layer in the first embodiment is particularly applicable as long as the monomer is polymerized by a direct polymerization method (sometimes called a gas phase polymerization method) and coated. Although not limited, for example, preferred monomers to be used include at least one insulating resin material selected from the group consisting of styrene-based monomers, acrylic-based monomers, ethylene-based monomers and propylene-based monomers. . When such a monomer is used in the direct polymerization method, a thin insulating resin layer having a uniform thickness can be easily and economically provided on the surface of metal particles 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 monomer and a propylene-based monomer are used for polymerizing the insulating resin layer, a thin insulating resin layer having a more uniform thickness can be provided. Therefore, in the metal toner, a higher insulation resistance value, for example, a value of 1 × 10 ¹⁵ Ω · cm or more can be obtained, and a low conductor resistance value can be obtained. Further, when a styrene-based monomer and an acrylic-based monomer are used in combination for polymerizing the insulating resin layer, not only a high insulation resistance value of 1 × 10 ¹⁵ Ω · cm or more can be obtained, but also an excellent chargeability-imparting layer can be obtained. High adhesion can be obtained.

Next, the coverage of the insulating resin layer will be described. There is no particular limitation on the coating amount of the insulating resin layer.
When the volume is 00 volume parts, the coating amount of the insulating resin layer is 20
It is preferable to set the value within the range of ~ 250 parts by volume. The reason for this is that if the coating amount of the insulating resin layer is less than 20 parts by volume, it is difficult to adjust the charge level of the metal toner, and the insulation resistance value is low, for example, it tends to be less than 1 × 10 ¹⁴ Ω · cm. That's why. 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, when the coating amount of the insulating resin layer exceeds 250 parts by volume, the conductor resistance of the conductor pattern is significantly increased and disconnection is likely to occur. Therefore, a higher insulation resistance value is obtained, the charging level is improved, and the conductor resistance of the conductor pattern is lower,
For a volume of 100 parts by volume of metal particles or the like, the coating amount of the insulating resin layer is more preferably set to a value within a range of 30 to 240 parts by volume, and to a value within a range of 50 to 230 parts by volume. Is more preferred.

With reference to Table 3 and FIG. 5, the effect of the coating amount of the insulating resin layer on the metal toner (the amount of the insulating resin) will be described in detail. Table 3 and FIG. 5 show that the metal toner was manufactured after changing the coating amount of the insulating resin constituting the insulating resin layer in the metal toner within a range of 10 to 300 parts by volume, and the charge amount, the coating state, The image characteristics and the conductor resistance were evaluated. The coat state is
It was evaluated according to the following criteria using a microscope,
The image characteristics were evaluated based on the same criteria as the evaluation criteria in Table 1. Detailed production conditions and evaluation conditions of the metal toner will be described in Examples 1 and 8 to 9 and Reference Examples 1 and 2 described later. 〇: The entire particles are uniformly coated, and no uncoated portions are observed. Δ: Slightly non-uniform, uncovered part observed. ×: Notably non-uniform, many uncoated portions are observed.

As will be understood from the results, when the coating amount of the insulating resin layer is 10 parts by volume, the charge amount is significantly reduced, and the image characteristics tend to be reduced. Further, when the coating amount of the insulating resin layer exceeds 300 parts by volume and exceeds 300 parts by volume, the conductor resistance of the conductor pattern sharply increases, and disconnection is observed. Therefore, the coating amount of the insulating resin layer is set to 20
By setting the value in the range of up to 250 parts by volume, the charge amount of the metal toner increases, and the value of the conductor resistance can be reduced.

[0041]

[Table 3]

Next, the thickness of the insulating resin layer will be described. The thickness of the insulating resin layer is determined in consideration of the charging level and the like of the metal toner, and specifically, is preferably set to a value in the range of 0.01 to 3 μm. The reason is that when the thickness of the insulating resin layer is less than 0.01 μm, metal parts (metal particles and the like) are exposed on the surface,
The charge level of the metal toner tends to decrease,
On the other hand, if the thickness of the insulating resin layer exceeds 3 μm, on the contrary, the charge level tends to decrease, fogging occurs, or the image density tends to decrease. In addition, at the time of debinding before the main firing of the sheet (for example, heating temperature: 30)
(0-500 ° C.), the insulating resin cannot be completely removed, and there is also a tendency to increase the resistance of the conductor pattern. Therefore, from the viewpoint of obtaining a higher charging level, the thickness of the insulating resin layer is more preferably set to a value within the range of 0.05 to 2 μm, and to a value within the range of 0.1 to 1.5 μm. More preferably,

(3) Chargeability-imparting layer The chargeability-imparting layer in the first embodiment is not particularly limited as long as it can enhance the insulating property of the metal toner and improve the charge level. Fluorine resin (vinylidene fluoride resin, polyethylene tetrafluoride resin, etc.), polystyrene resin (polystyrene, ABS resin, etc.), polyacrylic resin (MMA, MA, etc.), polyethylene resin (polyethylene, EVE, etc.), polypropylene It is preferable that the recording medium be made of at least one chargeable material selected from the group consisting of a resin based on a resin (such as polypropylene and polymethylpentane), a polyester resin, and a metal complex.

Further, azine compounds, quaternary ammonium salt compounds, nigrosine compounds, triphenylmethane, carboxylate compounds, phenol resin condensates, vinyl chloride resins, and celluloid resins are also suitably used as the chargeable material. 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, as a preferable chargeable material for charging the metal toner to the positive (+) side, 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.

Further, as a preferable charging material for charging the metal toner to the minus (-) side, a metal complex of a monoazo dye, salicylic acid, naphthoic acid and C of dicarboxylic acid are preferable.
o, Cr, metal complexes such as Fe, sulfonated copper phthalocyanine pigment, nitro group-introduced styrene oligomer, halogen group-introduced styrene oligomer, chlorinated paraffin, carboxylate compound, fluororesin, metal salts of naphthenic acid or higher fatty acid, Examples include alkoxylated amines and alkylamides.

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 used to form the chargeability-imparting layer is not particularly limited. For example, it is preferable to use chargeable particles. By using such chargeable particles, a chargeability-imparting layer having a uniform thickness can be formed. Also,
Chargeable particles can be easily fixed around or inside the insulating resin layer by mechanical treatment.

When the chargeable particles are used, 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. 1/10 to 1/1 of average particle diameter
000 is preferable. 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, the average particle size of the chargeable particles is one such as metal particles.
If the ratio exceeds / 10, 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. Therefore, from the viewpoint that a higher charging level can be obtained and the charging particles can be more easily fixed around or inside the insulating resin layer, the average particle diameter of the charging particles is set to an average particle size such as metal particles. It is more preferable to set the diameter to 1/20 to 1/500.

When chargeable particles are used, it is preferable that the average particle size of the chargeable particles be in the range of 0.01 to 1 μm. The reason for this is that if the average particle size of the chargeable particles is less than 0.01, the chargeable particles are likely to aggregate with each other, and it is difficult to form a chargeability-imparting layer having a uniform thickness. On the other hand, if the average particle diameter of the chargeable particles exceeds 1 μm, 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 non-uniform. Therefore, from the viewpoint that a higher charging level can be obtained and the charging particles can be more easily fixed around or inside the insulating resin layer, the average particle diameter of the charging particles is 0.1 to 0.1.
More preferably, it is 9 μm.

In this regard, the influence of the average particle diameter of the chargeable particles in the metal toner will be described in detail with reference to Table 4. Table 4 shows that, after changing the average particle diameter of the chargeable particles in the metal toner within the range of 0.1 to 5.0 μm, the metal toner was manufactured, the charge amount, the coating state in the chargeability-imparting layer, and the image characteristics. Table 3 (initial and after printing 3000 sheets)
The evaluation was performed in the same manner as the evaluation. 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.

As understood from the results, even when the average particle size of the chargeable 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 size of the chargeable particles is 1 μm,
The coating state becomes slightly uneven, the charge amount slightly decreases,
Further, the image characteristics after printing 3000 sheets tended to decrease, but this was at a level that was not problematic in practical use. Furthermore, when the average particle diameter of the chargeable particles was 5 μm, the coating state became nonuniform, the charge amount was reduced, and the image characteristics tended to be poor from the beginning. Therefore,
More preferably, the average particle size of the chargeable particles is in the range of 0.01 to 1 μm, and more preferably 0.1 to 0.9 μm.
By setting it in the range of m, a charge-imparting layer having a uniform thickness can be obtained, the charge amount of the metal toner increases, and excellent image characteristics can be obtained.

[0053]

[Table 4]

Next, the volume ratio (amount of chargeable particles) of the chargeability-imparting layer will be described. Although there is no particular limitation on the volume ratio of such a charge imparting layer, for example,
When the volume of the insulating resin layer (insulating resin) is set to 100 parts by volume, the volume ratio of the chargeability-imparting layer is preferably set to a value within the range of 1 to 200 parts by volume. The reason is that when the volume ratio of the chargeability-imparting layer 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 volume ratio of the chargeability-imparting layer exceeds 200 parts by volume, on the contrary, the charge level decreases, fogging occurs, or the image density tends to decrease. Therefore, a higher charging level is obtained, and a higher image density is obtained, so that the volume ratio of the chargeability-imparting layer to the volume of the insulating resin layer is in the range of 20 to 150 parts by volume. It is more preferable to set the value within a range of 30 to 150 parts by volume.

The effect of the volume ratio (the amount of charged particles) of the charge-imparting layer in the metal toner will be described in detail with reference to Table 5 and FIG. Table 5 and FIG. 4 show that, with respect to a volume of 100 parts by volume of the insulating resin layer (insulating resin),
The metal toner was manufactured after changing the volume ratio of the chargeability-imparting layer (chargeable material) in the metal toner within the range of 10 to 100 parts by volume, and the charge amount, Macbeth image density, and occurrence of fog were evaluated. is there. The fog was evaluated based on the following criteria. Further, detailed production conditions and evaluation conditions of the metal toner 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 volume ratio of the chargeability-imparting layer is reduced to 10 parts by volume, the charge amount is reduced, and the image density tends to decrease or fog tends to occur. On the other hand, when the volume ratio of the chargeability-imparting layer is 100 parts by volume, the charge level tends to decrease, fogging occurs, or the image density tends to decrease.

[0056]

[Table 5]

Next, the thickness of the chargeability-imparting layer will be described. The thickness of the charge-imparting layer is determined in consideration of the charge level of the metal toner and the like.
It is preferable that the value be in the range of 0.01 to 3 μm.
The reason is that when the thickness of the charge-imparting layer is less than 0.01 μm, the charge level tends to decrease, while when the thickness of the charge-imparting layer exceeds 3 μm, the charge level decreases. Or fogging occurs, or the image density tends to decrease. Therefore, from the viewpoint of obtaining a higher charge level, the thickness of the chargeability-imparting layer is set to 0.05 to 2
More preferably, the value is in the range of 0.1 μm.
More preferably, the value is in the range of 1.5 μm.

[Second Embodiment] A method of manufacturing a metal toner according to a second embodiment is characterized by including the following steps (A) and (B). (A) A step of coating an insulating resin layer on the surface of metal particles or metal oxide particles by a direct polymerization method of a monomer. (B) A charge-imparting layer made of a chargeable material is provided around or inside the insulating resin layer. Step of providing by mechanical surface treatment.

(1) Step (A) As the direct polymerization method of the monomer in the step (A), known methods such as those disclosed in JP-A-60-10680 and JP-A-2-187770 can be used. A method can be adopted. According to these polymerization methods, the surface of a metal particle or a metal oxide particle is treated with a polymerization catalyst in advance, and the polymerization catalyst is used to convert the surface of the metal particle from an olefin (ethylene or the like) monomer to a molecular weight, for example. Is in the range of 10,000 to 500,000 to polymerize and grow. Therefore, the surface of the metal particles or the like can be coated with an insulating resin layer made of an olefin polymer or the like as a thin film having a uniform thickness. Here, as the polymerization catalyst, titanium and / or zirconium as a main component is preferable. Olefin polymers and the like obtained by using these polymerization catalysts are rich in stereoregularity and high in crystallinity, but are excellent in toughness. Therefore, the obtained insulating resin layer has excellent strength and durability.

(2) Step (B) The apparatus for carrying out the mechanical surface treatment method in the step (B) is not particularly limited. For example, a Henschel mixer, a super Henschel mixer, a mechano mill, an ang mill or a hybridizer is used. Is preferred. 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, among these mechanical processing devices, it is more preferable to use a hybridizer or an ong mill. By using these devices, a charge-imparting layer, which is a thin film having a more uniform thickness, can be formed in a short time around or inside the insulating resin layer.

As an example of the mechanical processing device, an angmill is shown in FIG. 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 kinds of powders 39 are each subjected to the compounding treatment, and the uniformly layered charged particles can be fixed on the metal particles having the insulating resin layer. As a result, a metal toner as shown in FIG. 2 can be obtained. The metal toner 23 shown in FIG. 2 is composed of metal particles 25, an insulating resin layer 27, and a charge-imparting layer 29 sequentially from the inside.

The degree of the compounding process can be changed depending on the number of rotations of the container 37, the pressing force of the inner piece 45, or the processing time. Therefore, by combining more advanced processing, for example, by increasing the processing time,
As shown in FIG. 3, it is possible to obtain a metal toner in which the charging particles are embedded in the insulating resin layer. The metal toner 33 shown in FIG. 3 includes metal particles 25 and the like, an insulating resin layer 27, and a charge-imparting layer 31 embedded in the insulating resin layer 27 in this order from the inside.

Next, the influence 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 described above, when the chargeable material is an amorphous polymer such as styrene or acrylic, the mechanical surface treatment in the step (B) is performed when the glass transition point is defined as Q (° C.). It is preferable to carry out at a temperature within the range of Q ± 20 (° C.). 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 6 and FIG. 6A. Table 6 and FIG. 6A show that an acrylic resin (glass transition point: 60 ° C.) is selected as a charging material, and a processing temperature (saturation temperature of a processing tank in an ang mill) when producing a metal toner is 50 to 50. The metal toner was manufactured by changing the temperature within the range of 80 ° C., and the charge amount and the image characteristics (initial and 300
(After printing 0 sheets) was evaluated in the same manner as in Table 1 and the like. 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 40 to 80 ° C, more preferably 5
Within the range of 0 to 75 ° C, more preferably 55 to 73 ° 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 40 to 80 ° C., the charge level tends to suddenly decrease. That is, if the processing temperature is too low, the chargeable material (chargeable particles) does not adhere and remains as particles, and tends to peel off from the metal toner. Aggregation is likely to occur, and as a result, the metal toners tend to aggregate. Therefore, it can be seen that the charge amount of the metal toner can be easily adjusted by changing the processing temperature within the range of 40 to 80 ° C.

[0068]

[Table 6]

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 7 and FIG. 6B. Table 7 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 40 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 21 to 28 described later.

As can be understood from the results, the amount of charge in the metallic toner greatly changes depending on the cell rotation speed, and the cell 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.

[0072]

[Table 7]

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 8 and FIG. 6C. Table 8 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 metal toner 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 40 m / s, more preferably 10 to 40 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 charge amount of the metal toner can be easily adjusted by changing the processing time within such a range.

[0076]

[Table 8]

Third Embodiment A method of using a metal toner (a method of forming a conductor pattern) according to a third embodiment will be specifically described with reference to the drawings as appropriate. In the third embodiment, as a metal toner, metal particles or metal particle surfaces are covered with an insulating resin layer obtained by a direct polymerization method of a monomer, and around or inside the insulating resin layer, It uses a metal toner provided with a chargeability-imparting layer made of a chargeable material. 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. Therefore, in the method of using the metal toner, the following steps (C) to (F)
It is preferable to include

(C) The metal toner in the first embodiment is
Step of preparing 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), when the metal toner is adhered to the ceramic thin film sheet, a one-component developing method or a two-component developing method can be used. 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.

[0080]

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 Metallic Toner) (1) Preparation of Titanium-Containing Catalyst After sufficiently replacing the inside of a 500-ml container with a stirrer with argon, 200 ml of n-heptane was added.
15 g (25 mmol) of magnesium stearate were contained. Subsequently, 0.44 g (2.3 mmol) of titanium tetrachloride was added dropwise while stirring the inside of the container using a stirrer. Thereafter, the temperature was raised, and the mixture was reacted under reflux at the boiling temperature of n-heptane for 1 hour to obtain a viscous transparent titanium-containing catalyst.

(2) Formation of Insulation-Providing Layer In an autoclave with a stirrer of 2000 ml in inner volume,
After sufficient replacement with argon, the copper particles 1400Y
960 g (manufactured by Mitsui Kinzoku Co., Ltd.) and dehydrated hexane 800
ml, 5.0 mmol of diethylaluminum chloride, and the titanium-containing catalyst obtained in (1) (0.05 mmol in terms of titanium atoms). The copper particles used were obtained by a precipitation method. Also,
The average particle size of the copper particles is 5 μm, and 70 to 100 vol% in the volume-converted particle size distribution is ± 3% of the average particle size.
It is in the range of 0%. Next, while stirring the inside of the autoclave, the mixture was heated at a temperature of 40 ° C. for 30 minutes to perform a treatment for attaching a polymerization catalyst to the surface of the copper particles. Next, after the temperature in the autoclave was raised to 90 ° C., an ethylene monomer was introduced, and the ethylene monomer was polymerized on the surface of the copper particles to obtain a polyethylene resin. Then, while adjusting the polymerization time so that the coating amount of the polyethylene in the metal toner is 80 parts by volume with respect to 100 parts by volume of the copper particles, the surface of the copper particles is coated with a polyethylene resin to form an insulation-imparting layer. Formed.

(3) Formation of charge-imparting layer Ongmill AM-15F (manufactured by Hosokawa Micron Corporation)
200 g of copper powder having an 80 vol% insulating resin layer formed thereon and acrylic fine particles N- as chargeable particles.
30 (manufactured by Nippon Paint Co., Ltd., average particle diameter 0.1 μm,
(Glass transition temperature 60 ° C.) 8 g. Next, a mechanical treatment 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 charge-imparting layer. The volume ratio of the charge-imparting layer (chargeable particles) in the obtained metal toner is determined by the ratio of the insulating resin layer 1
It was 50 parts by volume with respect to 00 parts by volume.

(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. Table 5 shows the obtained results.

(1) Charge Amount 5 parts by weight of the obtained metal toner and ferrite carrier 1
00 parts by weight and mixed under normal environmental conditions (20 ° C., 65%
(RH), and triboelectrically charged for 60 minutes by vibrating in a container. 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] Instead of using 50 parts by volume of the charge imparting layer (chargeable particles) in Example 1, 10 parts by volume (Example 2) and 20 parts by volume (Example) 3) A metal toner was produced in the same manner as in Example 1, except that the volume was changed to 30 parts by volume (Example 4), 70 parts by volume (Example 5), and 100 parts by volume (Example 6). The obtained metal toner was evaluated in the same manner as in Example 1 for the charge amount, image density and fog. Table 5 shows the results
Shown in

Examples 8 to 9 and Reference Examples 1 to 2 Instead of using 80 parts by volume of the insulating layer in Example 1, 10 parts by volume (Reference Example 1) and 20 parts by volume (Example Example 8), 250 parts by volume (Example 9) and 300
Example 1 except that the volume part (Reference Example 2) was changed.
In the same manner as in the above, a metal toner was produced. For the obtained metal toner, the charge amount was measured in the same manner as in Example 1, and the coating state and the image characteristics were newly evaluated. Table 3 shows the obtained results. The evaluation criteria for the coating state and the image characteristics are as described in the description of the influence of the coating amount of the insulating layer.

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)
A metal toner was produced in the same manner as in Example 1, except that the thickness was changed to 5.0 μm (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 Reference Example 1 and the like. Table 4 shows the obtained results.

[Examples 15 to 17] In Example 1, the copper powder having a particle size distribution of 7
0 to 100 vol% is the average particle diameter ± 30 of the average particle diameter.
% Instead of the average particle diameter ± 40% of the average particle diameter
(Example 15) As in Example 1, except that the average particle diameter was changed to ± 60% of the average particle diameter (Example 16) and the average particle diameter was changed to 70% of the average particle diameter (Example 17). And a metal toner was produced. The obtained metal toner was evaluated for only the image characteristics in the same manner as in Reference Example 1 and the like. Table 2 shows the obtained results.

[Examples 18 to 22] The sphericity of copper powder was 0.4 or less (Example 18) and more than 0.4
0.5 or less (Example 19), more than 0.5 to 0.6 or less (Example 20), more than 0.6 to 0.7 or less (Example 21), and more than 0.7 to 0.9 or less A metal toner was produced in the same manner as in Example 1, except that the toner was changed to (Example 22). 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 Reference Example 1 and the like. Table 1 shows the obtained results.

Examples 23 to 31 As shown in Tables 6 to 8, 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 Reference Example 1 and the like. The obtained results are shown in Tables 6 to 8 and FIG.
(A) to FIG. 6 (c).

[0093]

According to the present invention, in a metal toner in which the surface of a metal particle or a metal oxide particle is coated with an insulating resin layer obtained by a direct polymerization method of a monomer, the metal toner or the metal oxide particle is formed around or inside the insulating resin layer. By providing a chargeability-imparting layer made of a chargeable material, a metal toner for forming a conductor pattern having a high charge level and excellent image characteristics can be provided.

Further, according to the method for producing a metal toner for forming a conductive pattern of the present invention, (A) a step of coating an insulating resin layer on the surface of metal particles or metal oxide particles by a direct polymerization method of a monomer; ) Efficient production of a metal toner having a high charge level and excellent image characteristics by including a step of providing a charge-imparting layer made of a chargeable material around or inside the insulating resin layer by mechanical surface treatment. It became possible to do.

Further, by forming a conductive pattern using the method of using the metal toner of the present invention, a conductive pattern having excellent image characteristics (including image density), low fog, and low conductive resistance is 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 conductive pattern forming metal toner (No. 1).

FIG. 3 is a cross-sectional view of a metal toner for forming a conductive pattern (No. 2).

FIG. 4 is a diagram showing the relationship between the amount of charged particles, the amount of charge, and the image density.

FIG. 5 is a diagram showing the relationship between the amount of insulating resin, the amount of charge and the conductor resistance.

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 an example of a mechanical processing device (mechanomill).

[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

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshi Mukotaka 704-19 Noshino, Tamaki-cho, Gakukai-gun, Mie Prefecture Examiner, Mie Tamaki Factory, Kyocera Corporation Susumu Ogawa (56) References JP-A-4-237062 (JP, a) JP flat 10-10840 (JP, a) JP flat 6-19191 (JP, a) JP flat 8-225652 (JP, a) (58 ) investigated the field (Int.Cl. ⁷ , DB name) H01B 5/00 H01B 1/00 G03G 5/14-5/147 504 G03G 9/08-9/113 G03G 15/02 101 G03G 15/08 507 H05K 1/09 H05K 1/16 H05K 3 / 10-3/12 630 H05K 3/46 C08G 81/00

Claims (14)

(57) [Claims] 1. The method according to claim 1, wherein the surface of the metal particles or the metal oxide particles is
In a metal toner coated with an insulating resin layer obtained by a direct polymerization method of a monomer, a charge-imparting layer made of a chargeable material is provided around or inside the insulating resin layer. When the volume of the resin is 100 parts by volume, the volume ratio of the chargeability-imparting layer is a value within the range of 1 to 200 parts by volume, and the volume of the metal particles or the metal oxide particles is 100 parts by volume. The coating amount of the insulating resin layer is 20 to 2
A metal toner for forming a conductive pattern, which has a value within a range of 50 parts by volume. 2. The chargeable material is at least one material selected from the group consisting of a fluororesin, a polystyrene resin, a polyacrylic resin, a polyethylene resin, a polypropylene resin, a polyester resin and a metal complex. 2. The metal toner for forming a conductive pattern according to claim 1, wherein: 3. The method according to claim 1, wherein the monomer is a styrene monomer,
The metal toner for forming a conductive pattern according to claim 1, wherein the metal toner is at least one insulating resin material selected from the group consisting of an acrylic monomer, an ethylene monomer, and a propylene monomer. 4. The 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. 5. The charge-imparting layer comprises chargeable particles, and the average particle diameter of the chargeable particles is 1/10 to 1 times the average particle diameter of the metal particles or metal oxide particles.
The metal toner for forming a conductor pattern according to any one of claims 1 to 4, wherein the ratio is set to / 1000. 6. The method according to claim 1, wherein 70 to 100% by volume of the metal particles or metal oxide particles is in the range of average particle diameter ± 40% of the average particle diameter. 6. The metal toner for forming a conductor pattern according to any one of 5. 7. 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. . 8. The metal toner for forming a conductor pattern according to claim 1, wherein the metal particles are metal particles manufactured by a wet method. 9. A method for producing a metal toner for forming a conductive pattern, comprising the following steps (A) and (B). (A) A step of coating an insulating resin layer on the surface of metal particles or metal oxide particles by a direct polymerization method of a monomer. (B) A charge-imparting layer made of a chargeable material is provided around or inside the insulating resin layer. Step of providing by mechanical surface treatment. 10. The mechanical surface treatment in the step (B) is performed by using a Henschel mixer, a super Henschel mixer,
The method for producing a metal toner for forming a conductive pattern according to claim 9, wherein the method is performed using a mechano mill, an ong mill, or a hybridizer. 11. When the chargeable material is an amorphous polymer and the glass transition point of the chargeable material is Q (° C.), the temperature of the mechanical surface treatment in the step (B) is Q The method for producing a metal toner for forming a conductive pattern according to claim 9, wherein the value is within a range of ± 20 (° C.). 12. The conductor pattern according to claim 9, wherein the time of the mechanical surface treatment in the step (B) is set to a value within a range of 5 to 20 minutes. A method for producing a forming metal toner. 13. The metal particle or the surface of the metal particle is coated with an insulating resin layer obtained by a direct polymerization method of a monomer, and around or inside the insulating resin layer,
A conductive pattern is formed by using a metal toner provided with a charge-imparting layer made of a chargeable material, and attaching the metal toner to a ceramic thin film sheet by using an electrophotographic method, and then heating. A method of using a metal toner for forming a conductor pattern, the method comprising: 14. The method according to claim 13, wherein a one-component developing method is used when attaching the metal toner to the ceramic thin film sheet.