CN109790062B - Borosilicate glass, composite powder material, and composite powder material paste - Google Patents
Borosilicate glass, composite powder material, and composite powder material paste Download PDFInfo
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- CN109790062B CN109790062B CN201780058625.5A CN201780058625A CN109790062B CN 109790062 B CN109790062 B CN 109790062B CN 201780058625 A CN201780058625 A CN 201780058625A CN 109790062 B CN109790062 B CN 109790062B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The borosilicate glass of the present invention is characterized by containing SiO in mol% as a glass composition220～40％、B2O325～45％、CaO 3～15％、SrO+BaO+ZnO 5～30％、ZrO20～6％、Al2O30 to 8% of CuO, 0 to 1% of CuO, in a molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) is greater than 0.50.
Description
Technical Field
The present invention relates to a borosilicate glass, a composite powder material, and a composite powder material paste, and more particularly, to a borosilicate glass, a composite powder material, and a composite powder material paste used for coating an electrode and a resistor of a thermal head.
Background
The thermal printer heats, for example, thermal paper while conveying the thermal paper in one direction, and develops color of a thermal dye provided in a thermal layer of the thermal paper, thereby forming an image.
A printing unit of a thermal printer includes: a thermal head for heating the thermal paper, and a pressing roller for conveying the thermal paper in a single direction while pressing the thermal paper against the thermal head thereof. The thermal head has a basic laminated structure in which a heat storage layer, a linear resistor layer, an electrode layer, a coating layer (protective layer), and the like are formed on a ceramic substrate such as alumina.
The coating layer of the thermal head is formed for the purpose of protecting the electrodes and the resistors from contact with the thermal paper. Further, as the electrodes, for example, Au lead electrodes, Ag external electrodes, and the like are formed, and as the resistor, for example, RuO is formed2A resistor, and the like.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication (Kokoku) No. 04-002533
Patent document 2: japanese laid-open patent publication No. 2008-150269
Disclosure of Invention
Problems to be solved by the invention
The coating layer is generally formed by firing a powder material (glass powder). In order to prevent the deterioration of the characteristics of the electrodes and the like, the firing temperature is limited to 900 ℃ or lower. Therefore, the powder material is required to be capable of being fired at a temperature of 900 ℃ or less.
Further, the powder material is required to have low reactivity with Au lead electrodes and Ag external electrodes. When the reactivity with the Au lead electrode and the Ag external electrode is high, the electrode may be disconnected after firing.
Further, the coating layer of the thermal head repeatedly comes into contact with the thermal paper. Therefore, the powder material is required to easily produce a coating layer having high abrasion resistance and surface smoothness.
As a powder material satisfying these required characteristics, PbO-SiO has been used so far2Is glass (see patent document 1).
In recent years, from the viewpoint of environmental protection, reduction of environmental load substances, for example, reduction of PbO, has been advanced, and replacement of PbO — B with various lead-free glasses has been proposed2O3-SiO2Is a glass. For example, patent document 2 describes ZnO-B2O3-BaO-based glass.
However, the ZnO-B described in patent document 22O3the-BaO glass has a problem of high reactivity with Ag external electrodes and the like.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a glass that can be fired at a temperature of 900 ℃ or lower even without containing PbO, has low reactivity with an electrode such as an Ag external electrode, and can contribute to improvement in wear resistance and surface smoothness of a coating layer.
Means for solving the problems
The inventors of the present invention conducted various experiments and found that: the above technical problem can be solved by selecting a predetermined borosilicate glass as a glass system, and the present invention proposes the borosilicate glass. That is, the borosilicate glass of the present invention is characterized by containing SiO in mol% as a glass composition2 20～40％、B2O3 25～45％、CaO 3～15％、SrO+BaO+ZnO 5～30％、ZrO2 0～6％、Al2O30 to 8% of CuO, 0 to 1% of CuO, in a molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) is greater than 0.50. Here, "SrO + BaO + ZnO" is the total amount of SrO, BaO, and ZnO. Further, "(SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) "means SiO2The total amount of CaO divided by B2O3A total amount of SrO, BaO and ZnO.
Borosilicate glass is generally highly reactive with Ag external electrodes. However, in the borosilicate glass of the present invention, SiO is contained in2Is limited to 20 mol% or more, B2O3The content of (b) is limited to 45 mol% or less and the content of CaO is limited to 3 mol% or more, so that the reactivity with Ag external electrodes is low.
In addition, in borosilicate glass, SiO is used2When the content of (b) is large, if the contents of SrO, BaO and ZnO are large, feldspar crystals precipitate during firing, and it may be difficult to ensure desired surface smoothness. Thus, the borosilicate-based glass of the present invention is obtained by mixing the molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) is limited to more than 0.50, thereby suppressing the precipitation of feldspar crystals.
Secondly, the borosilicate glass of the present invention preferably contains SiO in mol% as a glass composition2 25～40％、B2O3 25～40％、CaO 5～15％、SrO 0.1～10％、BaO 0.1～10％、ZnO 5～15％、ZrO20.1～4％、Al2O30.1 to 7% of CuO, 0.005 to 0.09% of CuO, and the molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) is 0.55 or more, and the borosilicate glass is used for coating a thermal head.
Third, the borosilicate glass of the present invention preferably contains SiO in mol% as a glass composition2 25～40％、B2O3 25～40％、CaO 5～15％、SrO 1～10％、BaO 1～10％、ZnO 5～15％、ZrO2 0.5～4％、Al2O31 to 7% of CuO, 0.01 to 0.09% of CuO, in a molar ratio of (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) is 0.55 or more, and the borosilicate glass is used for coating a thermal head.
Fourth, the borosilicate glass of the present invention preferably contains substantially no PbO and Bi in the glass composition2O3. Here, "substantially free of PbO" means that PbO is allowed to be mixed at an impurity level but active introduction is avoided, and specifically, it means that the content of PbO in the glass composition is less than 1000ppm (less than 0.1 mol%). Further, "substantially no Bi2O3"means that incorporation of Bi at impurity level is permitted2O3However, the meaning of avoiding active introduction specifically means Bi in the glass composition2O3A content of less than 1000ppm (less than 0.1 mol%).
Fifth, the composite powder material of the present invention is preferably a composite powder material containing a glass powder and an alumina powder, wherein the glass powder is formed of the borosilicate glass, and the content of the glass powder is 60 to 90 vol% and the content of the alumina powder is 10 to 30 vol%.
Sixthly, the composite powder material of the invention preferably has a softening point of 650-850 ℃. Here, the "softening point" refers to a temperature at the fourth inflection point measured by a micro Differential Thermal Analyzer (DTA).
Seventh, the composite powder material paste of the present invention is preferably a powder material paste containing a composite powder material and a vehicle, and the composite powder material is the above-mentioned composite powder material.
Detailed Description
Characteristics of the borosilicate-based glass of the present inventionIn that, as described above, SiO is contained in mol% as the glass composition2 20～40％、B2O3 25～45％、CaO 3～15％、SrO+BaO+ZnO 5～30％、ZrO2 0～6％、Al2O30 to 8% of CuO, 0 to 1% of CuO, in a molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) is greater than 0.50. The reason why the content ranges of the respective components are limited as described above will be described below. In the description of the content ranges of the respective components,% represents mol%.
SiO2Is a component forming a glass skeleton and also a component suppressing reactivity with the Ag external electrode. SiO 22The content of (b) is 20 to 40%, preferably 25 to 40%, more preferably 27 to 38%. If SiO2When the content (b) is less, the reactivity with the Ag external electrode becomes higher. On the other hand, if SiO2When the content (B) is too large, the softening point is not properly increased, and it is difficult to perform firing at a temperature of 900 ℃ or lower.
B2O3The glass skeleton is formed to widen the vitrification range, but when the content thereof is increased, the reactivity with the Ag external electrode is increased. Thus, B2O3The content of (b) is 25 to 45%, preferably 25 to 40%, more preferably 27 to 38%.
CaO is a component for stabilizing glass and also a component for suppressing reactivity with Ag external electrodes. The content of CaO is 3 to 15%, preferably 5 to 15%, more preferably 6 to 14%. When the content of CaO is increased, feldspar-based crystals are likely to precipitate, and the surface smoothness of the coating layer is likely to be lowered.
SrO, BaO and ZnO are components for stabilizing the glass. The total amount of SrO, BaO and ZnO is 5-30%, preferably 10-25%. The SrO content is preferably 0 to 12%, more preferably 0.1 to 11%, still more preferably 1 to 10%, and particularly preferably 3 to 9%. The content of BaO is preferably 0 to 12%, more preferably 0.1 to 10%, further preferably 1 to 10%, particularly preferably 3 to 8%. The content of ZnO is preferably 0 to 15%, more preferably 1 to 15%, further preferably 3 to 15%, further preferably 5 to 14%, and particularly preferably 6 to 12%. When the contents of SrO, BaO and ZnO are increased, feldspar series crystals are likely to precipitate, and the surface smoothness of the coating layer is likely to be lowered.
ZrO2Is a component for improving the abrasion resistance. ZrO (ZrO)2The content of (B) is 0 to 6%, preferably 0.1 to 5%, more preferably 0.5 to 4%, and particularly preferably 1 to 4%. If ZrO of2When the content (b) is small, the abrasion resistance tends to be low. On the other hand, if ZrO2When the content (B) is too large, the softening point is not properly increased, and it is difficult to perform firing at a temperature of 900 ℃ or lower.
Al2O3Is a component for improving the abrasion resistance. Al (Al)2O3The content of (b) is 0 to 8%, preferably 0.1 to 7%, more preferably 1 to 7%, and further preferably 2 to 6%. If Al is present2O3When the content (b) is small, the abrasion resistance tends to be low. On the other hand, if Al2O3When the content of (b) is more than the above range, feldspar type crystals are likely to precipitate, and the surface smoothness of the coating layer is likely to be lowered.
CuO is a component that significantly suppresses reactivity with Ag external electrodes. The content of CuO is 0 to 1%, preferably 0.005 to 0.09%, more preferably 0.01 to 0.08%. When the content of CuO is increased, feldspar-based crystals are likely to precipitate, and the surface smoothness of the coating layer is likely to be lowered.
Molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) is greater than 0.50, preferably 0.55 or greater, more preferably 0.60 or greater. Molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO), feldspar series crystals are likely to precipitate, and the surface smoothness of the coating layer is likely to decrease.
In addition to the above components, for example, the following components may be introduced.
In addition to the above components, various components may be introduced within a range not significantly impairing the characteristics of the thermal head. For example, to lower the softening point, Cs may be added2O、Rb2O and the like may be introduced in a total amount of 5%, particularly 1%, or individually. Further, Y may be added for stabilizing the glass2O3、La2O3、Ta2O5、SnO2、TiO2、Nb2O5、P2O5、CeO2、V2O5Etc. are introduced in total amounts or individually up to 10%, in particular up to 1%.
PbO and Bi2O3Is a component that lowers the softening point, but is also an environmental load substance, and therefore, it is preferable to avoid substantial introduction.
The composite powder material of the present invention is preferably a composite powder material containing a glass powder and an alumina powder, wherein the glass powder is formed from the borosilicate glass, and the content of the glass powder is 60 to 90 vol% and the content of the alumina powder is 10 to 30 vol%.
The glass powder is a material that melts during firing and forms a coating layer. The glass powder can be produced, for example, by forming molten glass into a film, and then crushing and classifying the obtained glass film.
The content of the glass powder is preferably 60 to 90 vol%, preferably 70 to 88 vol%, and more preferably 76 to 85 vol%. When the content of the glass powder is small, it is difficult to form a dense coating layer and to ensure desired surface smoothness. On the other hand, when the content of the glass powder is increased, the content of the alumina powder is relatively decreased, and therefore, the wear resistance and the thermal conductivity of the coating layer are likely to be decreased.
Average particle diameter D of glass powder50Preferably 2.0 μm or less, and a maximum particle diameter DmaxPreferably 10 μm or less. When the particle size of the glass powder is too large, the surface smoothness of the coating layer is likely to be lowered, and large bubbles are likely to remain in the coating layer. Here, the "average particle diameter D50"means a value measured by a laser diffraction apparatus, and indicates a particle size at which the cumulative amount of particles becomes 50% by accumulation from the start of particle size in a volume-based cumulative particle size distribution curve measured by a laser diffraction method. Further, "maximum particle diameter Dmax"means a value measured by a laser diffraction apparatus, and indicates that the cumulative particle size distribution curve based on a volume measured by a laser diffraction method shows that the cumulative amount of particles is 99% from the beginning of the accumulation of small particlesAnd (4) the particle size.
The alumina powder is a material for improving the wear resistance of the coating layer and for improving the thermal conductivity of the coating layer. The content of the alumina powder is preferably 10 to 30 vol%, and preferably 15 to 23 vol%. When the content of the alumina powder is increased, feldspar-based crystals are likely to precipitate, and the surface smoothness of the coating layer is likely to be lowered. Further, when the content of the alumina powder is increased, the ratio of the glass powder is relatively decreased, and thus it is difficult to form a dense coating layer and to ensure desired surface smoothness.
Average particle diameter D of alumina powder50Preferably 2.0 μm or less, and a maximum particle diameter DmaxPreferably 10 μm or less. When the particle size of the alumina powder is too large, the surface smoothness of the coating layer tends to be lowered.
In addition to the alumina powder, other ceramic powder may be introduced in an amount of 0 to 10 vol%, particularly 0 to 8 vol%. As the other ceramic powder, various materials can be used, and for example, one or two or more kinds of zirconia, mullite, silica, cordierite, titania, tin oxide, and the like can be added in order to adjust the thermal expansion coefficient, wear resistance, and the like of the coating layer.
The softening point of the composite powder material of the present invention is preferably 650 to 850 ℃, more preferably 670 to 830 ℃, and still more preferably 690 to 810 ℃. If the softening point is too high, it becomes difficult to form a dense coating layer at a firing temperature of 900 ℃ or lower, and it becomes difficult to ensure desired surface smoothness. On the other hand, if the softening point is too low, the reactivity with the Ag external electrode becomes high.
The average thermal expansion coefficient of the composite powder material of the invention is preferably 53 x 10 in the temperature range of 30-300 DEG C-7～70×10-7/° C, more preferably 55X 10-7～68×10-7V. C. With such a configuration, the alumina substrate can be easily prevented from warping after firing. Here, the "coefficient of thermal expansion" is a value measured by a thermomechanical analyzer (TMA).
The composite powder material paste of the present invention is a powder material paste containing a composite powder material and a vehicle, and the composite powder material is preferably the composite powder material. Here, the vehicle is a material for dispersing the composite powder material to form a paste, and is generally composed of a thermoplastic resin, a plasticizer, a solvent, and the like.
The composite powder material paste can be prepared by preparing a composite powder material and a vehicle, and mixing and kneading them at a predetermined ratio.
The thermoplastic resin is a component for improving the strength of the dried film and imparting flexibility. The content of the thermoplastic resin in the composite powder material paste is preferably 0.1 to 20 mass%. The thermoplastic resin is preferably polybutylmethacrylate, polyvinylbutyral, polymethylmethacrylate, polyethylmethacrylate, ethylcellulose and the like, and one or two 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 mass%. The solvent is preferably terpineol, diethylene glycol monobutyl ether acetate, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, or the like, and one or two or more of these are preferably used.
A coating layer of a thermal head is formed by forming Au lead electrodes, Ag external electrodes, and RuO2A composite powder material paste is applied onto an alumina substrate such as a resistor, a coating layer having a predetermined thickness is formed thereon, and then dried to obtain a dry film. Thereafter, the dried film is fired at a temperature of 800 to 900 ℃ for 5 to 20 minutes to form a coating layer (fired film). When the firing temperature is too low or the firing time (holding time) is too short, the dried film is not sufficiently sintered, and the density and surface smoothness of the coating layer are likely to be reduced. On the other hand, if the firing temperature is too high or the firing time (holding time) is too long, the glass powder and RuO will be mixed2The characteristics of the resistor are likely to deteriorate due to the reaction with the resistor or the like, or the reactivity with the Ag external electrode or the like becomes high, and there is a risk that the electrode is broken.
Examples
The present invention will be described in detail below based on examples. The present invention is not limited to the following examples. The following examples are merely illustrative.
Table 1 shows an example of the present invention (sample N)o1 to 4) and comparative example (sample N)o.5)。
[ Table 1]
Each sample was prepared as follows. First, raw materials were blended and uniformly mixed so as to have a glass composition shown in the table. Then, the molten alloy is put into a platinum crucible, melted at 1350 to 1450 ℃ for 2 hours, and then formed into a film.
Next, the glass film was pulverized by a ball mill and then subjected to air classification to obtain an average particle diameter D50Has a maximum particle diameter D of 2.0 μm or lessmaxGlass powder of 10 μm or less. The obtained glass powder and alumina powder were weighed so that they became 80 vol% and 20 vol%, respectively, and then sufficiently mixed to obtain a composite powder material. The softening point and the thermal expansion coefficient were evaluated for the obtained composite powder material. The average particle diameter D of the alumina powder50Has a maximum particle diameter D of 2.0 μm or lessmaxIs 10 μm or less.
The softening point is the temperature at the fourth inflection point measured by a micro Differential Thermal Analyzer (DTA).
The thermal expansion coefficient is as follows: each composite powder material was press-molded, fired at (softening point +10) ° C, processed into a diameter of 5mm and a length of 20mm to obtain measurement samples, and the average values obtained were measured at a temperature range of 30 to 300 ℃ by a thermomechanical analyzer (TMA).
Next, the composite powder was mixed with a vehicle (terpineol containing 5 mass% of ethyl cellulose and 3 mass% of acetyl tributyl citrate) and kneaded by a three-roll mill to obtain a composite powder material paste. Further, a composite powder material paste was applied onto the alumina substrate with a heat storage layer having an electrode layer (Ag external electrode layer) and a resistor layer by a screen printing method, and then the resultant applied film was dried and baked at 800 ℃ for 20 minutes in an electric furnace to obtain a baked film (coating layer) having a thickness of about 10 μm. The surface smoothness and reactivity with an Ag external electrode were evaluated for the obtained alumina substrate with a laminated film.
The surface smoothness was evaluated as follows: the surface of the fired film was observed with a microscope, and evaluated as "X" when there was crystal precipitation and "O" when there was no crystal precipitation.
The reactivity with Ag external electrodes was evaluated as follows: when the sintered Ag external electrode was observed, the electrode was evaluated as "x" when yellowing was observed and as "o" when yellowing was not observed. The yellowing of the Ag external electrode is related to the reactivity with the Ag external electrode, and if the Ag external electrode is yellowed, it can be said that the reactivity with the Ag external electrode is high.
As is clear from table 1: the glass compositions of the glass powders of samples nos. 1 to 4 were limited to the predetermined ranges, and therefore the softening points were low, and the surface smoothness and reactivity with Ag external electrodes were evaluated well. On the other hand, sample No.5 had a low softening point but a molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) was small, and therefore evaluation of surface smoothness was poor.
Claims (7)
1. A borosilicate glass characterized by containing SiO in mol% as a glass composition2 20％～40％、B2O3 25％～45％、CaO 3％～15％、SrO+BaO +ZnO 5％～30％、ZrO2 0％～6％、Al2O30 to 8 percent of CuO, 0.005 to 0.09 percent of CuO, and the molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) is greater than 0.50.
2. The borosilicate glass according to claim 1, wherein the glass composition contains SiO in mol%2 25％～40％、B2O3 25％～40％、CaO 5％～15％、SrO 0.1％～10％、BaO 0.1％～10％、ZnO 5％～15％、ZrO20.1％～4％、Al2O30.1-7 percent of CuO, 0.005-0.09 percent of CuO, and the molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) of 0.55 or more, the borosilicate glass being used for coating a thermal head.
3. The borosilicate glass according to claim 1, wherein the glass composition contains SiO in mol%2 25％～40％、B2O3 25％～40％、CaO 5％～15％、SrO 1％～10％、BaO 1％～10％、ZnO 5％～15％、ZrO20.5％～4％、Al2O31 to 7 percent of CuO, 0.01 to 0.09 percent of CuO, and the molar ratio (SiO)2+CaO)/(B2O3+ SrO + BaO + ZnO) of 0.55 or more, the borosilicate glass being used for coating a thermal head.
4. The borosilicate glass according to any one of claims 1 to 3, wherein the glass composition contains substantially no PbO and Bi2O3。
5. A composite powder material comprising a glass powder and an alumina powder, wherein the glass powder is formed from the borosilicate-based glass according to any one of claims 1 to 4, and the composite powder material is characterized in that the content of the glass powder is 60 to 90 vol% and the content of the alumina powder is 10 to 30 vol%.
6. The composite powder material according to claim 5, characterized in that the softening point is 650-850 ℃.
7. A composite powder material paste comprising a composite powder material and a vehicle, wherein the composite powder material is the composite powder material according to claim 5 or 6.
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| JP2016-196284 | 2016-10-04 | ||
| JP2016196284A JP6952949B2 (en) | 2016-10-04 | 2016-10-04 | Borosilicate glass, composite powder material and composite powder material paste |
| PCT/JP2017/032164 WO2018066295A1 (en) | 2016-10-04 | 2017-09-06 | Borosilicate glass, composite powder material, and composite powder material paste |
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| CN109790062B true CN109790062B (en) | 2021-11-26 |
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| JP7247825B2 (en) * | 2018-12-17 | 2023-03-29 | Ａｇｃ株式会社 | Glass composition, composite powder material, composite powder material paste, printer head for laser printer, and thermal printer head |
| CN110550864B (en) * | 2019-09-29 | 2022-09-02 | 长沙新材料产业研究院有限公司 | Low-expansion-coefficient insulating medium slurry and preparation method thereof |
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| US20080187730A1 (en) * | 2007-02-06 | 2008-08-07 | Mitsubishi Electric Corporation | Ceramic powder for a green sheet and multilayer ceramic substrate |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018066295A1 (en) | 2018-04-12 |
| JP6952949B2 (en) | 2021-10-27 |
| JP2018058716A (en) | 2018-04-12 |
| CN109790062A (en) | 2019-05-21 |
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