JP2020196642A - Composite powder material, composite powder material paste, printer head for laser printer, and thermal printer head - Google Patents

Abstract

To provide a composite powder material from which such a coating layer can be formed that exhibits sufficient development of sintering at 830°C or lower, that is environmentally friendly, that prevents significant foaming during calcination even when the material contains a silicon carbide powder, and that has good wear resistance and thermal conductivity.SOLUTION: The composite powder material contains a glass powder comprising, in terms of mol% based on oxides, 31 to 42% of SiO2, 16 to 26% of B2O3, 2 to 10% of ZnO, 20 to 30% of CaO, 1 to 10% of BaO, 1 to 10% of SrO and 1 to 10% of Al2O3, a silicon carbide powder and an alumina powder, in which a volume ratio of the content of the silicon carbide powder with respect to the total content of the silicon carbide powder and the alumina powder ((silicon carbide powder)/(alumina powder+silicon carbide powder)) is 1 to 65%.SELECTED DRAWING: None

Description

The present invention relates to a composite powder material and a composite powder material paste containing the composite powder material. The present invention also relates to a printer head for a laser printer and a thermal printer head having a coating layer formed by using the composite powder material.

Conventionally, a coating layer containing glass as a main component has been used in various applications.

For example, in a printer such as a laser printer in which a toner image is transferred to a printed matter such as paper and fixed, the transferred toner is melted and coated by applying pressure while the printed matter is heated in the fixing device. Fixes on printed matter. The fixing device includes a fixing heater for heating the printed matter and a pressurizing roller for feeding the printed matter in one direction while pressing the printed matter toward the fixing heater. As one type of such a fixing device, a fixing film made of heat-resistant resin that is rotated by the rotation of the pressure roller is provided between the flat plate long-shaped fixing heater and the pressure roller to form the fixing device. Some have been miniaturized and their heat capacity has been reduced.
The fixing heater in this type is provided with a heat generation resistance layer made of an Ag / Pd alloy or the like provided on the surface of a flat substrate made of, for example, glass or ceramics by an appropriate method such as printing or transfer. For example, both ends of the heat generation resistance layer are connected to electrode terminals made of Ag or the like, and heat is generated when energized. An insulating film containing glass as a main component is formed on the surface of such a heat-generating resistance layer for the purpose of ensuring insulation and improving abrasion resistance. Such an insulating film is not limited to a flat plate-shaped fixing heater, but is also provided on a fixing roller in which a heat generation resistance layer is provided on the outer peripheral surface of a cylindrical insulating base material.

In addition, the thermal printer forms an image on the recording paper by heating the recording paper while feeding it in one direction in the printing unit. In particular, in the type using a thermal recording paper (heat-sensitive printer), the heat-sensitive dye in the heat-sensitive layer provided on the thermal recording paper is heated to develop a color and form an image. Further, in the type using the thermal transfer ink ribbon (thermal transfer printer), the ink melted or sublimated by heating is transferred to the recording paper to form an image. In this format, plain paper is used as the recording paper.
In any of the above formats, the printing unit includes a thermal printer head for heating the thermal recording paper and the thermal transfer ink ribbon, and a thermal printer head for pressing the recording paper toward the thermal printer head and feeding the recording paper in one direction. It is equipped with a pressure roller. In this thermal printer head, for example, an electrode layer is formed on a line-shaped heat generation resistance layer provided on one surface of a ceramic substrate via a heat storage layer, and these are covered with a protective layer containing glass as a main component. It has a basic structure. As the electrode layer, for example, an Au lead electrode, an Ag external electrode, or the like is formed, and as a heat generation resistance layer, for example, a RuO ₂ layer or the like is formed.

Further, for example, also in a circuit board, an insulating film containing glass as a main component is formed for the purpose of protecting a conductor film such as an electrode provided on the surface thereof and an electronic component.
Hereinafter, these insulating films and protective layers are collectively referred to as "coating layer".

Special Fair 04-002533

The coating layer as described above is generally formed by firing a powder material containing glass powder. The firing temperature is preferably 900 ° C. or lower in order to prevent deterioration of the characteristics of the electrodes and the like, but it is required to be further lowered depending on the type of the electrodes and the like, for example, 830 ° C. or lower. Will be done.
However, if the firing temperature is low, sintering may not proceed sufficiently depending on the powder material, the denseness of the obtained coating layer may decrease, and the surface smoothness may deteriorate. If the surface smoothness deteriorates, the printed matter may be damaged when it is used as a coating layer of a printer.
Therefore, there is a demand for a powder material in which sintering proceeds sufficiently even when fired at 830 ° C. or lower, and a coating layer having sufficient surface smoothness can be obtained.

In addition, the powder material containing glass powder includes ceramic powders such as alumina, silicon carbide, zirconia, mullite, silica, cordierite, titania, and tin oxide for the purpose of improving thermal expansion coefficient, thermal conductivity, and abrasion resistance. May be contained. In particular, silicon carbide is an effective ceramic powder having high Vickers hardness, excellent wear resistance, and high thermal conductivity. By containing this, a coating layer having high thermal conductivity and high wear resistance Is expected to be obtained.

As a conventional coating layer material, PbO-B ₂ O ₃ -SiO ₂ glass containing lead as an essential component is often used, and Patent Document 1 also discloses such glass. Further, Patent Document 1 discloses that alumina or silicon carbide is contained as a ceramic powder.
In recent years, from the viewpoint of environmental protection, reduction of environmentally hazardous substances, for example, reduction of PbO has been promoted, and glass that does not contain lead as an essential component is required instead of PbO-B ₂ O _3- SiO ₂ system glass. There is. However, when the lead-free glass and the silicon carbide powder are combined, the silicon carbide powder foams during firing, so that there is a problem that the silicon carbide powder cannot be substantially used.

The present invention has been made in view of the above, and is good because sintering proceeds sufficiently at 830 ° C. or lower, the load on the environment is small, and even if silicon carbide powder is contained, there is no significant foaming during firing. An object of the present invention is to provide a composite powder material capable of forming a coating layer having abrasion resistance and thermal conductivity.
Another object of the present invention is to provide a composite powder material paste containing the composite powder material.
Another object of the present invention is to provide a printer head for a laser printer provided with an insulating film formed by using the composite powder material.
Another object of the present invention is to provide a thermal printer head provided with a protective layer formed by using the composite powder material.

The present inventors have found that the above problems can be solved by combining a glass composition having a glass composition in a specific range with alumina powder as a reaction inhibitor and combining it with silicon carbide powder, and completed the present invention. ..
The present invention provides a composite powder material, a composite powder material paste, a printer head for a laser printer, and a thermal printer head having the following configurations.

The composite powder material of the present invention contains 31 to 42% of SiO ₂ , 16 to 26% of B ₂ O ₃ , 2 to 10% of Zn O, 20 to 30% of Ca O, and BaO in terms of molar% based on oxides. 1-10%, SrO 1-10%, Al ₂ O ₃ 1-10%, contains glass powder, silicon carbide powder, and alumina powder, relative to the total content of silicon carbide powder and alumina powder. The volume ratio of the content of the silicon carbide powder (silicon carbide powder / alumina powder + silicon carbide powder) is 1 to 65%.
In one aspect of the composite powder material of the present invention, the glass powder contains 35 to 40% SiO ₂ , 18 to 24% B ₂ O ₃ , 4 to 6% Zn O, and CaO in terms of oxide-based molar%. the 23 to 27%, a BaO 4 to 6 percent, SrO 4 to 6% of _Al 2 _{O 3} may be contained 2-5%.
In one aspect of the composite powder material of the present invention, the volume ratio of the content of the silicon carbide powder to the total content of the silicon carbide powder and the alumina powder (silicon carbide powder / alumina powder + silicon carbide powder) is 15 to 45%. There may be.
In one aspect of the composite powder material of the present invention, the volume ratio of the content of the silicon carbide powder to the total content of the silicon carbide powder and the alumina powder (silicon carbide powder / alumina powder + silicon carbide powder) is 20 to 40%. There may be.
In one aspect of the composite powder material of the present invention, the content of the glass powder is 40 to 90% by volume, the content of the silicon carbide powder is 3 to 16% by volume, and the content of the alumina powder is 5 to 45% by volume. May be good.

The composite powder material paste of the present invention contains the composite powder material of the present invention and a vehicle.

The printer head for a laser printer of the present invention includes a substrate, a heat generation resistance layer formed on the surface of the substrate, at least a part of the surface of the substrate, and the entire surface of the heat generation resistance layer opposite to the substrate. A printer head for a laser printer provided with a covering insulating film, the substrate containing alumina, the insulating film in mass% display, SiO ₂ 16 to 24%, B ₂ O _{3 9} to 17%, ZnO. 2 to 5%, CaO 9 to 14%, BaO 5 to 8%, SrO 3 to 5%, Al ₂ O _{3 20} to 48%, and SiC ₃ to 15%.
In one aspect of the printer head for a laser printer of the present invention, the mass ratio of the content of SiC to the total content of SiC and Al ₂ O ₃ in the insulating film (SiC / Al ₂ O ₃ + SiC) is 5 to 50. May be%.
In one aspect of the printer head for a laser printer of the present invention, the mass ratio of the content of SiC to the total content of SiC and Al ₂ O ₃ in the insulating film (SiC / Al ₂ O ₃ + SiC) is 20 to 45. May be%.

The thermal printer head of the present invention has a substrate, a glaze layer formed on the surface of the substrate, a heat generation resistance layer formed on the surface of the glaze layer opposite to the substrate, and a glaze layer of the heat generation resistance layer. A thermal printer head for a thermal printer including an electrode layer formed on the side surface and a protective layer formed on the surface opposite to the heat generation resistance layer of the electrode layer, and the protective layer displays mass%. So, SiO ₂ is 16 to 24%, B ₂ O ₃ is 9 to 17%, ZnO is 2 to 5%, CaO is 9 to 14%, BaO is 5 to 8%, SrO is 3 to 5%, and Al ₂ It contains 20 to 48% of O3 and ₃ to 15% of SiC.
In one aspect of the thermal printer head of the present invention, the mass ratio of the content of SiC to the total content of SiC and Al ₂ O ₃ in the protective layer (SiC / Al ₂ O ₃ + SiC) is 5 to 50%. You may.
In one aspect of the thermal printer head of the present invention, the mass ratio of the content of SiC to the total content of SiC and Al ₂ O ₃ in the protective layer (SiC / Al ₂ O ₃ + SiC) is 20 to 45%. You may.
In one aspect of the thermal printer head of the present invention, a barrier layer may be provided between the glaze layer and the heat generation resistance layer.
In one aspect of the thermal printer head of the present invention, the substrate may be made of glass or ceramics.
In one aspect of the thermal printer head of the present invention, the heat generation resistance layer may be made of metal.
In one aspect of the thermal printer head of the present invention, the heat generation resistance layer may be made of an alloy containing Ag and Pd.

The composite powder material of the present invention sufficiently progresses sintering at 830 ° C. or lower, has a low burden on the environment, does not cause significant foaming even if it contains silicon carbide powder, and has good wear resistance and thermal conductivity. It is possible to form a coating layer having a coating layer.

FIG. 1 is a schematic view of an embodiment of a printer head for a laser printer including an insulating film containing the glass composition of the present invention. FIG. 2 is a schematic view of an embodiment of a thermal printer head including an insulating film containing the glass composition of the present invention.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the embodiments described below. Further, in the following drawings, members / parts having the same action may be described with the same reference numerals, and duplicate description may be omitted or simplified. In addition, the embodiments described in the drawings are schematically for the purpose of clearly explaining the present invention, and do not necessarily accurately represent the actual size and scale.

<Glass composition>
First, a glass composition constituting the glass powder contained in the composite powder composition of the present embodiment (hereinafter, also referred to as “glass composition of the present embodiment”) will be described.
The glass composition of the present embodiment contains 31 to 42% of SiO ₂ , 16 to 26% of B ₂ O ₃ , 2 to 10% of Zn O, and 20 to 30% of Ca O in terms of molar% based on oxides. It contains 1 to 10% of BaO, 1 to 10% of SrO, and 1 to 10% of Al ₂ O ₃ . The reason for restricting the content range of each component as described above will be described below. In the description of the content of each component contained in the glass composition of the present specification, the% indication means the molar% indication based on the oxide unless otherwise specified.

SiO ₂ is a component that forms a glass skeleton and contributes to suppression of foaming due to an excessive reaction with silicon carbide powder. Further, if the reactivity of the glass composition with the electrode is high, the glass composition may react with the electrode during firing and the electrode may be broken. Therefore, the glass composition may have low reactivity with the electrode. Although required, SiO ₂ is also a component that suppresses reactivity with the electrode. Further, the coating layer obtained by firing the glass composition may be required to have water resistance from the viewpoint of long-term stability depending on its use, but SiO ₂ is a component that also contributes to the improvement of water resistance. is there. If the content of SiO _{2 in} the glass composition of the present embodiment is small, the above effects cannot be sufficiently obtained.
On the other hand, when the content of SiO _{2 in} the glass composition of the present embodiment is large, the softening point of the glass composition rises. When the softening point of the glass composition rises, the temperature required for firing rises. Therefore, when firing at a temperature of 830 ° C. or lower, sintering does not proceed sufficiently, and the resulting coating layer has a denseness and surface smoothness. The sex may deteriorate.
For the above reasons, the content of SiO _{2 in} the glass composition of the present embodiment is 31 to 42%. Further, the content of SiO _{2 in} the glass composition of the present embodiment is preferably 33% or more, more preferably 35% or more, preferably 41% or less, and more preferably 40% or less.

B ₂ O ₃ is a component that forms a glass skeleton and expands the vitrification range. B ₂ O ₃ has a weaker skeleton than SiO ₂ and is a low softening component.
When the content of B ₂ O _{3 in} the glass composition of the present embodiment is small, the softening point of the glass composition rises, and by extension, the denseness and surface smoothness of the coating layer obtained when firing at a temperature of 830 ° C. or lower The sex may deteriorate.
On the other hand, when the content of B ₂ O _{3 in} the glass composition of the present embodiment is large, the reaction with the silicon carbide powder proceeds and foaming occurs, the water resistance deteriorates, and the reactivity with the electrode becomes high.
For the above reasons, the content of B ₂ O _{3 in} the glass composition of the present embodiment is set to 16 to 26%. Further, the content of B ₂ O _{3 in} the glass composition of the present embodiment is preferably 17% or more, more preferably 18% or more. Further, 25% or less is preferable, and 24% or less is more preferable.

In addition, the total content of SiO ₂ and B ₂ O ₃ (hereinafter also referred to as "SiO ₂ + B ₂ O ₃ ") also suppresses the reaction with the silicon carbide powder (and thus suppresses foaming), improves water resistance, and , Important for reducing softening points.
From the viewpoint of suppressing foaming of the obtained coating layer and improving water resistance, the SiO ₂ + B ₂ O ₃ in the glass composition of the present embodiment is preferably 53% or more, more preferably 54% or more, and 56%. The above is more preferable.
On the other hand, from the viewpoint of reducing the softening point of the glass composition, the SiO ₂ + B ₂ O ₃ in the glass composition of the present embodiment is preferably 60% or less, more preferably 59% or less, still more preferably 58% or less. ..

ZnO is a component that lowers the softening point of the glass composition. When the ZnO content of the glass composition of the present embodiment is small, the softening point of the glass composition increases.
On the other hand, if the content of ZnO in the glass composition of the present embodiment is large, the chemical durability of the obtained coating layer, particularly acid resistance, is lowered.
For the above reasons, the ZnO content of the glass composition of the present embodiment is set to 2 to 10%. The ZnO content of the glass composition of the present embodiment is preferably 3% or more, more preferably 4% or more, and preferably 6% or less.

CaO, SrO and BaO are components that stabilize the glass. In the glass composition of the present embodiment, if the content of each of these components is too small, crystals tend to precipitate when the paste is formed and fired, the softening point becomes high, and the surface smoothness of the obtained coating layer becomes high. It tends to decrease.
On the other hand, in the glass composition of the present embodiment, when the content of each of these components is too large, crystals are likely to precipitate when the paste is formed and fired, and the surface smoothness of the obtained coating layer is lowered. It will be easier.
For the above reasons, the CaO content of the glass composition of the present embodiment is 20 to 30%, the SrO content is 1 to 10%, and the BaO content is 1 to 10%.
The CaO content of the glass composition of the present embodiment is preferably 21% or more, more preferably 23% or more, and preferably 28% or less, more preferably 27% or less.
The content of SrO in the glass composition of the present embodiment is preferably 3% or more, more preferably 4% or more, and preferably 8% or less, more preferably 6% or less.
The content of BaO in the glass composition of the present embodiment is preferably 3% or more, more preferably 4% or more, and preferably 8% or less, more preferably 6% or less.
It is also important to control the total content of these components (hereinafter, also referred to as "CaO + SrO + BaO") in order to improve the surface smoothness.
The CaO + SrO + BaO of the glass composition of the present embodiment is preferably 26% or more, more preferably 30% or more, still more preferably 33% or more, and preferably 40% or less, more preferably 38% or less, still more preferable. Is 37% or less.

Among CaO, SrO, and BaO, CaO is a component having a large effect on surface smoothness. In order to particularly improve the surface smoothness of the coating layer, it is effective to adjust the total content of CaO and the contents of SrO and BaO in a well-balanced manner, and it is effective to adjust the content of CaO in the glass composition. It is effective to control the ratio of the total contents of SrO and BaO (hereinafter, also referred to as “CaO / (BaO + SrO)”) to be within a predetermined range.
Therefore, in the glass composition of the present embodiment, CaO / (BaO + SrO) is preferably 1 or more, more preferably 1.4 or more, preferably 5 or less, and more preferably 4.7 or less.

Al ₂ O ₃ is a component that enhances the wear resistance and water resistance of the obtained coating layer. If the content of Al ₂ O _{3 in} the glass composition of the present embodiment is small, the above effects cannot be sufficiently obtained.
On the other hand, if the content of Al ₂ O _{3 in} the glass composition of the present embodiment is large, crystals tend to precipitate when the glass composition is made into a paste and fired, and the softening point rises, so that the surface of the obtained coating layer is obtained. Smoothness tends to decrease.
For the above reasons, the content of Al ₂ O _{3 in} the glass composition of the present embodiment is set to 1 to 10%. Further, the content of Al ₂ O _{3 in} the glass composition of the present embodiment is preferably 2% or more, preferably 7% or less, and more preferably 5% or less.

The glass composition of the present embodiment may contain components other than the above as long as the effects of the present invention are exhibited. Examples of other components contained in the glass composition of the present embodiment will be described below. The other components contained in the glass composition of the present embodiment other than the above components are not limited to those exemplified below.

The glass composition of the present embodiment may contain MgO, but when it is made into a paste having a large MgO content and fired, crystals are likely to precipitate, and the surface smoothness of the obtained coating layer is lowered. It will be easier. Therefore, the MgO content of the glass composition of the present embodiment is preferably 3% or less, more preferably 1% or less. Further, it is most preferable that the glass composition of the present embodiment substantially does not contain MgO.
The fact that the glass composition of the present embodiment does not substantially contain a certain component means that it does not contain any impurities other than unavoidable impurities, that is, it means that the glass composition is not intentionally added.

In addition, the glass composition of the present embodiment may contain Cs ₂ O, Rb ₂ O and the like in a total amount of 5% or less, preferably 1% or less, in order to lower the softening point. In addition, in order to stabilize the glass, Y ₂ O ₃ , La ₂ O ₃ , Ta ₂ O ₅ , SnO ₂ , TiO ₂ , Nb ₂ O ₅ , P ₂ O ₅ , CeO ₂ , V ₂ O _5, etc. are combined. It may be contained in an amount of 10% or less, preferably 1% or less.

Since PbO and Bi ₂ O ₃ are components that lower the softening point, the glass composition of the present embodiment may contain these components, but since these components are also environmentally hazardous substances, this embodiment It is preferable that the glass composition in the form does not contain these components substantially. For example, in the glass composition of the present embodiment, the contents of PbO and Bi ₂ O ₃ are preferably 0.3% or less, more preferably 0.1% or less, respectively.

Further, it is preferable that the glass composition of the present embodiment substantially does not contain alkali metals such as Li ₂ O, Na ₂ O and K ₂ O and halogens such as F and Cl. For example, in the glass composition of the present embodiment, the total content of the alkali metal is preferably 0.3% or less, more preferably 0.1% or less, and the total halogen content is 0.3% or less. Is preferable, and 0.1% or less is more preferable.

The softening point of the glass composition of the present embodiment is preferably 730 to 760 ° C. When the softening point is 760 ° C. or higher, sintering tends to proceed when the paste is formed and fired at a temperature of 830 ° C. or lower, so that a coating layer having excellent denseness and surface smoothness can be easily obtained. Further, when the softening point is 730 ° C. or lower, the reactivity between the glass composition and the electrode is unlikely to increase.

<Composite powder material>
The composite powder material of the present embodiment is a composite powder material containing a glass powder composed of the above glass composition, a silicon carbide powder, and an alumina powder.

Glass powder is a material that forms a dense coating layer by melting during firing and then solidifying.
Silicon carbide powder is a material that contributes to improving the wear resistance, thermal conductivity, and withstand voltage of the coating layer, and is a more preferable material among many ceramic powders.
In the printer, it is necessary to efficiently transfer the heat generated from the heat generation resistance layer to the printed matter, and in the circuit board, it is necessary to efficiently release the heat generated from the electronic components to the outside. Is required to have high thermal conductivity. Further, depending on the application, the coating layer is required to have withstand voltage resistance. Further, the coating layer of the printer is required to have high wear resistance (scratch resistance) and high Vickers hardness because it is not damaged by the printed matter. In the composite powder material of the present embodiment, silicon carbide powder is contained in order to obtain these properties.

However, when the silicon carbide powder is fired at the same time as the glass powder, it may react with the glass powder and foam. If the coating layer contains bubbles, the properties deteriorate.
Therefore, in the composite powder material of the present embodiment, alumina powder is contained as a reaction inhibitor. The alumina powder is a material that functions as a reaction inhibitor that suppresses an excessive reaction between the silicon carbide powder and the glass powder in combination with the glass powder of the present embodiment, and is contained in the composite powder material of the present embodiment. By doing so, foaming due to the addition of the silicon carbide powder can be suppressed.
Alumina powder, like silicon carbide powder, is also a material that contributes to improving the wear resistance, thermal conductivity, and withstand voltage of the coating layer. Therefore, by incorporating the silicon carbide powder and the alumina powder into the composite powder material of the present embodiment, the glass powder and the carbonized material can be carbonized while obtaining the effects of improving the wear resistance, thermal conductivity, and withstand voltage of these materials. Foaming due to the reaction with the silicon powder can be suppressed, and a preferable coating layer can be obtained.

In the composite powder material of the present embodiment, if the content of the silicon carbide powder is too large with respect to the total content of the silicon carbide powder and the alumina powder, the function of suppressing foaming by the alumina powder cannot be obtained. Therefore, in the composite powder of the present embodiment, the volume ratio of the content of the silicon carbide powder to the total content of the silicon carbide powder and the alumina powder (silicon carbide powder / alumina powder + silicon carbide powder) is preferably 1% or more. Is 10% or more, more preferably 20% or more.
On the other hand, if the content of the silicon carbide powder is too small with respect to the total content of the silicon carbide powder and the alumina powder, the wear resistance, thermal conductivity, and voltage resistance of the obtained coating layer become insufficient. Therefore, in the composite powder of the present embodiment, the volume ratio of the content of the silicon carbide powder to the total content of the silicon carbide powder and the alumina powder (silicon carbide powder / alumina powder + silicon carbide powder) is preferably 65% or less. Is 50% or less, more preferably 40% or less.

In the composite powder material of the present embodiment, the contents of the glass powder, the silicon carbide powder, and the alumina powder are not particularly limited, but by setting these in a suitable range, foaming can be particularly suppressed, and foaming can be suppressed. In particular, a coating layer having high surface smoothness and also excellent wear resistance, thermal conductivity, and withstand voltage can be obtained.
From the above viewpoint, the content of the glass powder in the composite powder material of the present embodiment is preferably 40% by volume or more, more preferably 45% by volume or more, further preferably 50% by volume or more, and 90% by volume or less. Preferably, it is 85% by volume or less, more preferably 65% by volume or less.
Further, the content of the silicon carbide powder in the composite powder material of the present embodiment is preferably 3% by volume or more, more preferably 4% by volume or more, preferably 18% by volume or less, and more preferably 16% by volume or less. More preferably, it is 15% by volume or less.
The content of alumina powder in the composite powder material of the present embodiment is preferably 5% by volume or more, more preferably 10% by volume or more, further preferably 14% by volume or more, and preferably 45% by volume or less, 42. By volume or less is more preferable, and 40% by volume or less is further preferable.

The average particle size D50 and the maximum particle size Dmax of the glass powder in the composite powder material of the present embodiment are not particularly limited, but if they are too large for the thickness of the coating layer formed by them, the surface smoothness of the coating layer deteriorates. In addition, large bubbles are likely to remain in the coating layer.
The thickness of the insulating film in the printer head for a laser printer is 40 to 80 μm, and when the insulating film is formed using the composite powder material of the present embodiment, the average particle size D50 of the glass powder is preferably 2.5 μm or less. The maximum particle size Dmax is preferably 15 μm or less.
The thickness of the protective layer of the thermal printer head is about 10 μm, and when the protective layer is formed using the composite powder material of the present embodiment, the average particle size D50 of the glass powder is preferably 1.5 μm or less, and the maximum particle size. The Dmax is preferably 10 μm or less.
The method for producing the glass powder is not particularly limited, and for example, the glass powder can be produced by forming the molten glass into a film and then pulverizing the obtained glass film. At this time, a glass powder having a desired particle size can be obtained by adjusting the pulverization conditions and classifying the obtained glass powder as needed.
In the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the particle size in which the accumulated amount is 50% cumulative from the smallest particle is defined as "average particle size D50", and the particle size is 99%. Is "maximum particle size Dmax".

The average particle size D50 of the silicon carbide powder in the present embodiment is preferably 0.2 μm or more, more preferably 0.3 μm or more, further preferably 0.4 μm or more, preferably 8 μm or less, more preferably 3 μm or less, 1 More preferably, it is 5.5 μm or less.
The maximum particle size Dmax of the silicon carbide powder in the present embodiment is preferably 20 μm or less, more preferably 5 μm or less. If the particle size of the silicon carbide powder is too large, the surface smoothness of the coating layer tends to decrease. If the particle size of the silicon carbide powder is too small, the surface area of the silicon carbide powder becomes large, and defects due to aggregation of the silicon carbide powder and insufficient sintering tend to occur.
Further, as the shape of the silicon carbide powder, the closer it is to a spherical shape, the more preferable it is.

The average particle size D50 of the alumina powder in the present embodiment is preferably 0.2 μm or more, more preferably 0.3 μm or more, further preferably 0.4 μm or more, and preferably 2.0 μm or less, more preferably 1.0 μm or less. It is preferable, and 0.8 μm or less is more preferable. The maximum particle size Dmax of the alumina powder in the present embodiment is preferably 20 μm or less, more preferably 5 μm or less. If the particle size of the alumina powder is too large, the surface smoothness of the coating layer tends to decrease. If the particle size of the alumina powder is too small, the surface area of the alumina powder becomes large, and defects due to aggregation of the alumina powder and insufficient sintering tend to occur.
Further, as the shape of the alumina powder, the closer it is to a spherical shape, the more preferable it is.

The composite powder material of the present embodiment may contain components other than the above glass powder, silicon carbide powder, and alumina powder as long as the effects of the present invention are exhibited. For example, an inorganic pigment or an inorganic pigment may be used to identify the appearance. It may contain an organic dye.

The content of the inorganic pigment or organic dye is preferably 0.01% by mass or more, more preferably 0.1% or more, and preferably 3% by mass or less, more preferably 2% by mass or less. If the content of the inorganic pigment or organic dye is too large, it becomes difficult to ensure surface smoothness.

Further, the composite powder material of the present embodiment may contain 10% by mass or less, preferably 8% by mass or less of other ceramic powders in addition to the alumina powder. Various materials can be used as other ceramic powders. For example, zirconia, mullite, silica, cordierite, titanium, tin oxide, etc. can be used to adjust the coefficient of thermal expansion and abrasion resistance of the coating layer. Of these, one or more may be contained.

The composite powder material of the present embodiment contains, for example, 16 to 24% of SiO ₂ , 9 to 17% of B ₂ O ₃ , 2 to 5% of Zn O, 9 to 14% of Ca O, and Ba O in terms of mass%. 5-8%, the SrO 3 to 5% of _Al 2 _{O 3} 20 to 48% containing 3% to 15% of SiC. Further, the mass ratio of the content of SiC to the total content of SiC and Al ₂ O ₃ in the composite powder material of the present embodiment (SiC / Al ₂ O ₃ + SiC) is preferably 5% from the viewpoint of suppressing firing. Above, more preferably 20% or more. Further, from the viewpoint of improving the abrasion resistance, thermal conductivity, and voltage resistance of the obtained coating layer, it is preferably 50% or less, more preferably 45% or less.

The average coefficient of thermal expansion in the temperature range of 50 to 350 ° C., which is measured after firing the composite powder material of the present embodiment, is preferably 55 × ^10-7 from the viewpoint of preventing warpage of the substrate on which the coating layer is formed. It is / ° C. or higher, more preferably 60 × ^10-7 / ° C. or higher, and preferably 75 × ^10-7 / ° C. or lower, more preferably 72 × ^10-7 / ° C. or lower. Here, the "coefficient of thermal expansion" is a value measured by a thermomechanical analyzer (TMA), and can be measured by the method described in the column of Examples.

<Composite powder material paste>
The composite powder material paste of the present embodiment contains the above-mentioned composite powder material and a vehicle. The vehicle is a material for dispersing a composite powder material and forming a paste, and is usually composed of a thermoplastic resin, a plasticizer, a solvent, or the like. The composite powder material paste can be prepared by mixing and kneading the composite powder material and the vehicle at a predetermined ratio.

The thermoplastic resin is a component that enhances the strength of the coating layer after drying and is a component that imparts flexibility to the coating layer. The content of the thermoplastic resin in the composite powder material paste is preferably 0.1 to 20% by mass. As the thermoplastic resin, polybutyl methacrylate, polyvinyl butyral, polymethyl methacrylate, polyethyl methacrylate, ethyl cellulose and the like are preferable, and one or more of these are preferably used.

The plasticizer is a component that adjusts the leveling property after printing and smoothes the surface roughness of the coating layer. The content of the plasticizer in the composite powder material paste is preferably 1 to 20% by mass. As the plasticizer, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, etc. are preferable, and one or more of these are preferably used.
The solvent is a component for dissolving the thermoplastic resin. The content of the solvent in the composite powder material paste is preferably 10 to 30% by mass. As the solvent, tarpineol, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate and the like are preferable, and one or more of these are preferably used.

<Printer head for laser printer>
FIG. 1 is a schematic view of a printer head for a laser printer of the present embodiment (hereinafter, also simply referred to as “laser printer head”). The laser printer head 10 of the present embodiment includes a substrate 11, a heat generation resistance layer 12 formed on the surface of the substrate 11, at least a part of the surface of the substrate, and a surface of the heat generation resistance layer 12 opposite to the substrate 11. An insulating film 13 that covers the entire surface of the above is provided.

The substrate 11 in this embodiment is a substrate containing alumina.

The heat generation resistance layer 12 in the present embodiment is not particularly limited, but is preferably a layer made of metal, more preferably a layer made of an alloy containing Ag and Pd, and a layer made of an alloy made of Ag and Pd. It is more preferable to have. Further, in the present embodiment, electrodes (not shown) such as Ag external electrodes are connected to the heat generation resistance layer 12.

The insulating film 13 in the present embodiment is, for example, coated with the above-mentioned composite powder material paste on a substrate 11 on which a heat generation resistance layer 12 and electrodes are formed to form a coating layer having a predetermined thickness, and then dried. It is obtained by obtaining a dry film and then firing the dry film at a temperature of 800 to 830 ° C. for 5 to 20 minutes. The insulating film 13 of the present embodiment has a SiO ₂ of 16 to 24%, a B ₂ O ₃ of 9 to 17%, a ZnO of 2 to 5%, a CaO of 9 to 14%, and a BaO of 5 to 5 in terms of mass%. 8%, 3-5% of SrO, and _Al 2 _{O 3} 20 to 48% containing 3% to 15% of SiC.
The mass ratio of the content of SiC to the total content of SiC and Al ₂ O ₃ in the insulating film (SiC / Al ₂ O ₃ + SiC) is preferably 5% or more, more preferably 20% from the viewpoint of suppressing firing. That is all. Further, from the viewpoint of improving wear resistance, thermal conductivity, and withstand voltage, it is preferably 50% or less, more preferably 45% or less.
If the firing temperature is too low or the firing time (holding time) is too short, the dried film is not sufficiently sintered, and the denseness and surface smoothness of the coating layer tend to decrease. On the other hand, if the firing temperature is too high or the firing time (holding time) is too long, the glass powder reacts with the heat generation resistance layer, the characteristics of the heat generation resistance layer deteriorate, or the glass powder reacts with the electrode. There is a risk of disconnection of the electrodes.

<Thermal printer head>
FIG. 2 is a schematic view of the thermal printer head 20 of the present embodiment. The thermal printer head 20 of the present embodiment includes a substrate 21, a glaze layer 22 formed on the surface of the substrate 21, and a heat generation resistance layer 23 formed on the surface of the glaze layer 22 opposite to the substrate 21. The electrode layer 24 formed on the surface of the heat generation resistance layer 23 opposite to the glaze layer 22 and the protective layer 25 formed on the surface of the electrode layer 24 opposite to the heat generation resistance layer 23 are provided.

The substrate 21 in this embodiment is not particularly limited, and for example, a substrate made of glass or ceramics can be used.
The glaze layer 22 in the present embodiment is not particularly limited, but is, for example, a layer made of glass.
The heat generation resistance layer 23 in the present embodiment is not particularly limited, but is preferably a layer made of metal, more preferably a layer made of an alloy containing Ag and Pd, and a layer made of an alloy made of Ag and Pd. It is more preferable to have.
The electrode layer 24 in the present embodiment is not particularly limited, but can be formed of, for example, a metal such as Ag.
Further, the thermal printer head 20 of the present embodiment may include a barrier layer (not shown) between the glaze layer 22 and the heat generation resistance layer 23. The barrier layer is not particularly limited, but can be formed of, for example, an insulating inorganic oxide such as SiO ₂ , SiON, AlSiO, and Al ₂ O ₃ .

For the protective layer 25 in the present embodiment, for example, the composite powder material paste of the present embodiment is first applied on the substrate 21 on which the glaze layer 22, the heat generation resistance layer 23, and the electrode layer 24 are formed, and the protective layer 25 has a predetermined thickness. After forming the coating layer, it is dried to obtain a dried film, and then the dried film is fired at a temperature of 800 to 830 ° C. for 5 to 20 minutes. In the protective layer 25 of the present embodiment, SiO ₂ is 16 to 24%, B ₂ O ₃ is 9 to 17%, ZnO is 2 to 5%, CaO is 9 to 14%, and BaO is 5 to 5 in terms of mass%. 8%, 3-5% of SrO, and _Al 2 _{O 3} 20 to 48% containing 3% to 15% of SiC.
The mass ratio of the content of SiC to the total content of SiC and Al ₂ O ₃ in the protective layer (SiC / Al ₂ O ₃ + SiC) is preferably 5% or more, more preferably 20% from the viewpoint of suppressing firing. That is all. Further, from the viewpoint of improving wear resistance, thermal conductivity, and withstand voltage, it is preferably 50% or less, more preferably 45% or less.
If the firing temperature is too low or the firing time (holding time) is too short, the dried film is not sufficiently sintered, and the denseness and surface smoothness of the coating layer tend to decrease. On the other hand, if the firing temperature is too high or the firing time (holding time) is too long, the glass powder reacts with the heat generation resistance layer, the characteristics of the heat generation resistance layer deteriorate, or the glass powder reacts with the electrode layer. There is a risk of disconnection of the electrodes.

Hereinafter, the present invention will be described in detail based on Examples. The present invention is not limited to the following examples.

<Manufacturing of glass powder>
First, the glass raw materials were prepared so as to have the glass composition shown in Tables 1 and 2 in terms of molar% based on the oxide, and mixed uniformly. Next, the mixed glass raw material was placed in a platinum crucible and melted at 1350 to 1450 ° C. for 2 hours, and then formed into a film.
Subsequently, the obtained film-shaped glass is crushed by a ball mill and then classified by air flow to be used in the composite powder material of each example having an average particle size D50 of 1.0 μm or less and a maximum particle size Dmax of 5 μm or less. Obtained powder.
<Measurement of glass transition point (Tg) and softening point (Ts)>
The glass transition point (Tg) and softening point (Ts) of the obtained glass powder were measured by a macro differential thermal analyzer (DTA). The results are shown in Tables 1 and 2. The softening point (Ts) is the temperature of the fourth inflection point measured by a macro differential thermal analyzer (DTA).

<Manufacturing of composite powder material>
Subsequently, the obtained glass powder, silicon carbide powder, and alumina powder were sufficiently mixed to obtain composite powder materials of Examples 1 to 10 and Comparative Examples 1 to 8. The contents of the glass powder, the silicon carbide powder, and the alumina powder in the obtained composite powder material are as shown in Tables 1 and 2.
The average particle size D50 of the silicon carbide powder was 1.5 μm or less, and the maximum particle size Dmax was 20 μm or less.
The average particle size D50 of the alumina powder was 2.0 μm or less, and the maximum particle size Dmax was 10 μm or less.

<Evaluation of the presence or absence of foaming>
Each of the obtained composite powder materials was compacted in an amount of 1.5 g and fired at a temperature of 81 to 830 ° C., and the appearance of the obtained sintered body was visually evaluated. "(Defective), and those for which foaming was not confirmed were rated as" ○ "(good).

<Manufacturing of coating layer>
The composite powder materials of Comparative Examples 4 and 8 and Examples 1 to 10 in which good results were obtained without foaming were mixed with a vehicle (tarpineol containing 5% by mass of ethyl cellulose and 3% by mass of tributyl acetylcitrate), and three of them were mixed. The mixture was kneaded with a roll mill to obtain a composite powder material paste. The obtained composite powder material paste was applied on an alumina substrate having an underglaze layer by a screen printing method, # 325, and then the coating film was dried and fired in an electric furnace at a temperature of 810 to 830 ° C. for 10 minutes. A coating layer having a thickness of about 6 to 9 μm was obtained. The surface smoothness and wear resistance (Vickers hardness) of the obtained coating layer were evaluated as shown below.

<Evaluation of surface smoothness>
The maximum height Ra of the surface of the obtained coating layer was measured with Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd., and those with Ra of 0.3 μm or less were “○” (good), and those larger than 0.3 μm were “x” (. Defective). The results are shown in Tables 1 and 2.

<Evaluation of wear resistance>
The Vickers hardness of the obtained coating layer was measured with AVK-G1 manufactured by AKASHI, and those with 600 HV or more were evaluated as "○" (good), and those with less than 600 were evaluated as "x" (insufficient). The results are shown in Tables 1 and 2.

Foaming was confirmed in the sintered body formed by using the composite powder materials of Comparative Examples 1 to 3 and Comparative Examples 5 to 7.
The coating layer formed by using the composite powder material of Comparative Example 4 had a Vickers hardness of less than 600 HV and was inferior in wear resistance. The coating layer formed by using the composite powder material of Comparative Example 8 had a Ra of more than 0.3 μm and was inferior in surface smoothness.
On the other hand, the coating layer formed by using the composite powder materials of Examples 1 to 10 had no foaming, had good surface smoothness, and had excellent wear resistance.

10: Printer head for laser printer (laser printer head)
11: Substrate 12: Heat generation resistance layer 13: Insulating film 20: Thermal printer head 21: Substrate 22: Glaze layer 23: Heat generation resistance layer 24: Electrode layer 25: Protective layer

Claims (16)

In terms of oxide-based mol%, SiO ₂ is 31 to 42%, B ₂ O ₃ is 16 to 26%, ZnO is 2 to 10%, CaO is 20 to 30%, BaO is 1 to 10%, and SrO is SrO. Contains glass powder, silicon carbide powder, and alumina powder containing 1 to 10% and 1 to 10% of Al ₂ O ₃ ,
A composite powder material in which the volume ratio (silicon carbide powder / alumina powder + silicon carbide powder) of the content of the silicon carbide powder to the total content of the silicon carbide powder and the alumina powder is 1 to 65%. The glass powder contains 35 to 40% of SiO ₂ , 18 to 24% of B ₂ O ₃ , 4 to 6% of Zn O, 23 to 27% of Ca O, and 4 to 4 of BaO in terms of molar% based on oxides. The composite powder material according to claim 1, which contains 6%, 4 to 6% of SrO, and 2 to 5% of Al ₂ O ₃ . According to claim 1 or 2, the volume ratio of the content of the silicon carbide powder to the total content of the silicon carbide powder and the alumina powder (silicon carbide powder / alumina powder + silicon carbide powder) is 10 to 50%. The composite powder material described. The third aspect of claim 3, wherein the volume ratio of the content of the silicon carbide powder to the total content of the silicon carbide powder and the alumina powder (silicon carbide powder / alumina powder + silicon carbide powder) is 20 to 40%. Composite powder material. Any one of claims 1 to 4, wherein the content of the glass powder is 40 to 90% by volume, the content of the silicon carbide powder is 3 to 16% by volume, and the content of the alumina powder is 5 to 45% by volume. The composite powder material described in the section. A composite powder material paste containing the composite powder material according to any one of claims 1 to 5 and a vehicle. A laser including a substrate, a heat generation resistance layer formed on the surface of the substrate, and an insulating film covering at least a part of the surface of the substrate and the entire surface of the heat generation resistance layer opposite to the substrate. A printer head for a printer
The substrate contains alumina and
The insulating film is expressed in mass%, SiO ₂ is 16 to 24%, B ₂ O ₃ is 9 to 17%, ZnO is 2 to 5%, CaO is 9 to 14%, BaO is 5 to 8%, and SrO is SrO. A printer head for a laser printer containing ₃ to 5%, ₂₀ to 48% of Al ₂ O _3, and ₃ to 15% of SiC. The laser according to claim 7, wherein the mass ratio (SiC / Al ₂ O ₃ + SiC) of the content of the SiC to the total content of the SiC and Al ₂ O ₃ in the insulating film is 5 to 50%. Printer head for printers. The laser according to claim 8, wherein the mass ratio (SiC / Al ₂ O ₃ + SiC) of the content of the SiC to the total content of the SiC and Al ₂ O ₃ in the insulating film is 20 to 45%. Printer head for printers. A substrate, a glaze layer formed on the surface of the substrate, a heat generation resistance layer formed on the surface of the glaze layer opposite to the substrate, and a surface of the heat generation resistance layer opposite to the glaze layer. A thermal printer head for a thermal printer including an electrode layer formed on the electrode layer and a protective layer formed on a surface of the electrode layer opposite to the heat generation resistance layer.
The protective layer is expressed in mass%, SiO ₂ is 16 to 24%, B ₂ O ₃ is 9 to 17%, ZnO is 2 to 5%, CaO is 9 to 14%, BaO is 5 to 8%, and SrO is SrO. A thermal printer head containing ₃ to 5%, ₂₀ to 48% of Al ₂ O _3, and ₃ to 15% of SiC. The thermal according to claim 10, wherein the mass ratio of the content of the SiC to the total content of the SiC and Al ₂ O ₃ in the protective layer (SiC / Al ₂ O ₃ + SiC) is 5 to 50%. Printer head. The thermal according to claim 11, wherein the mass ratio (SiC / Al ₂ O ₃ + SiC) of the content of the SiC to the total content of the SiC and Al ₂ O ₃ in the protective layer is 20 to 45%. Printer head. The thermal printer head according to any one of claims 10 to 12, wherein a barrier layer is provided between the glaze layer and the heat generation resistance layer. The thermal printer head according to any one of claims 10 to 13, wherein the substrate is made of glass or ceramics. The thermal printer head according to any one of claims 10 to 14, wherein the heat generation resistance layer is made of metal. The thermal printer head according to any one of claims 10 to 15, wherein the heat generation resistance layer is made of an alloy containing Ag and Pd.

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