WO2016084627A1 - Glass powder, composite powder, and low expansion substrate with decorative layer - Google Patents

Glass powder, composite powder, and low expansion substrate with decorative layer Download PDF

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Publication number
WO2016084627A1
WO2016084627A1 PCT/JP2015/081982 JP2015081982W WO2016084627A1 WO 2016084627 A1 WO2016084627 A1 WO 2016084627A1 JP 2015081982 W JP2015081982 W JP 2015081982W WO 2016084627 A1 WO2016084627 A1 WO 2016084627A1
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Prior art keywords
powder
glass
picture layer
glass powder
low expansion
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PCT/JP2015/081982
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French (fr)
Japanese (ja)
Inventor
石原　健太郎
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日本電気硝子株式会社
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Priority claimed from JP2015034943A external-priority patent/JP6701541B2/en
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Publication of WO2016084627A1 publication Critical patent/WO2016084627A1/en

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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
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
    • F24C15/00—Details
    • F24C15/10—Tops, e.g. hot plates; Rings

Definitions

  • the present invention relates to a glass powder, a composite powder and a low expansion substrate with a picture layer, and more specifically, to a glass powder, a composite powder and a low expansion board with a picture layer suitable for a top plate for a cooker having a picture layer.
  • a low-expansion crystallized glass substrate is widely used as a top plate for cooking appliances because of its high heat durability and thermal shock resistance.
  • the surface of the top plate for a cooker may be decorated with a picture layer in order to enhance aesthetics.
  • the picture layer is generally a sintered body of composite powder containing glass powder and inorganic pigment powder.
  • SiO 2 55 to 70% B 2 O 3 15 to 25%, Al 2 O 3 3 to 10%, BaO 0.1 to 4.9%, ZnO 0. 1-5%, CaO 0-3%, MgO 0-3%, Li 2 O 0.1-5%, Na 2 O 0-10%, K 2 O 0.3-15%, F 2 0-2
  • a lead-free glass powder for forming a picture layer is disclosed, which has a softening point of 600 ° C. or higher and lower than 700 ° C.
  • the method for forming a picture layer on the surface of a crystallized glass substrate is as follows. First, glass powder and inorganic pigment powder are mixed to obtain a composite powder. Next, the obtained composite powder is dispersed in a vehicle containing an organic binder, a solvent and the like to form a paste. Subsequently, the obtained composite powder paste is transferred onto a crystallized glass substrate by screen printing or the like, dried, and then fired under appropriate firing conditions. When the composite powder is fired, the composite powder (glass powder) softens and flows and then sinters. As a result, the composite powder is firmly fixed on the crystallized glass substrate to form a picture layer.
  • the glass powder described in Patent Document 1 softens and flows at a low temperature, but has a high coefficient of thermal expansion, so it is difficult to reduce the coefficient of thermal expansion of the picture layer.
  • the coefficient of thermal expansion of the picture layer is high, cracks are likely to occur in the crystallized glass substrate with the picture layer. This tendency becomes more obvious as the thermal expansion coefficient of the crystallized glass substrate is lower.
  • this crack not only deteriorates characteristics such as water resistance and acid resistance, but also causes a problem that dirt stays in the interior and impairs the appearance.
  • the top plate for cooking appliances is exposed to hot water, fruit juice, and seasoning during use. For this reason, high water resistance and acid resistance may be calculated
  • the present invention has been made in view of the above circumstances, and its technical problem is to create glass powders and composite powders that soften and flow at low temperatures, have a low coefficient of thermal expansion, and have high water resistance and acid resistance. It is.
  • the present inventor has introduced a predetermined amount of Li 2 O and increased the content of SiO 2 in the SiO 2 —B 2 O 3 —Al 2 O 3 glass powder,
  • the present inventors have found that the above technical problem can be solved by reducing the content of B 2 O 3 and propose as the present invention.
  • the glass powder of the present invention has a glass composition of mol%, SiO 2 48 to 75%, B 2 O 3 5 to 23%, Al 2 O 3 5 to 25%, Li 2 O 5 to 30%, It is characterized by containing 0 to 25% of ZnO and having a molar ratio SiO 2 / B 2 O 3 of 3.23 or more.
  • SiO 2 / B 2 O 3 is a value obtained by dividing the content of SiO 2 by the content of B 2 O 3 .
  • Glass powder of the present invention the SiO 2 48 ⁇ 75 mol% in the glass composition, B 2 O 3 of 5 to 23 mol%, the Al 2 O 3 5 ⁇ 25 mol%, Li 2 O 5-30 mole % Is included. This makes it possible to deposit a low expansion ⁇ -quartz solid solution after good softening and flow during firing. As a result, it is possible to achieve both softening fluidity and a low expansion coefficient.
  • the glass powder of the present invention regulates the molar ratio SiO 2 / B 2 O 3 in the glass composition to 3.23 or more.
  • the glass powder of the present invention it is preferable that the content of B 2 O 3 in the glass composition is less than 16 mol%.
  • the glass powder of the present invention preferably has a ZnO content in the glass composition of 0.1 to 7.6 mol%. In this way, it is possible to increase the amount of ⁇ -quartz solid solution deposited while suppressing the precipitation of foreign crystals during firing. As a result, it becomes possible to reduce the firing temperature dependence of the thermal expansion coefficient, and it is easy to prevent a situation where locally distorted stress remains after firing or a place where the thermal expansion coefficient is locally different occurs. Become. In addition, it is easy to prevent a situation in which the thermal expansion coefficient of the picture layer differs between production lots.
  • the glass powder of the present invention preferably further contains 0.1 to 15 mol% of TiO 2 and ZrO 2 in the total amount in the glass composition.
  • the glass powder of the present invention does not substantially contain PbO and Bi 2 O 3 in the glass composition.
  • substantially free of is intended to allow the case where an explicit component is mixed at an impurity level, and specifically, the content of the explicit component is less than 0.1% by mass. Refers to the case.
  • the glass powder of the present invention preferably has a thermal expansion coefficient of 25 ⁇ 10 ⁇ 7 / ° C. or lower after firing at 700 ° C. for 10 minutes.
  • the “thermal expansion coefficient” is a value measured in a temperature range of 30 to 350 ° C. using a TMA apparatus.
  • a glass powder green compact was sintered precisely at 700 ° C. for 10 minutes and then processed into a predetermined shape.
  • the main crystal refers to a crystal having the highest peak intensity when measured by the X-ray diffraction method.
  • the glass powder of the present invention preferably has a softening point of 550 to 700 ° C. measured with a macro DTA apparatus.
  • the softening point measured by the macro DTA apparatus indicates the temperature (Ts) at the fourth bending point shown in FIG.
  • the measurement by a macro type DTA apparatus is performed in the air, and the temperature rising rate is 10 ° C./min.
  • the composite powder of the present invention is a composite powder containing glass powder 55 to 100% by mass, inorganic pigment powder 0 to 45% by mass, refractory filler powder 0 to 40% by mass, It is preferable that it is said glass powder.
  • the inorganic pigment powder is preferably a Cr—Cu composite oxide.
  • ⁇ system complex oxide refers to a complex oxide containing an explicit component as an essential component.
  • the low expansion substrate with a picture layer of the present invention is a low expansion substrate with a picture layer having a picture layer on the surface of the low expansion board, the picture layer being a sintered body of composite powder, and a composite It is preferable that the powder is the above composite powder.
  • the “low expansion substrate” refers to a substrate having a thermal expansion coefficient of 35 ⁇ 10 ⁇ 7 / ° C. or less in a temperature range of 30 to 350 ° C.
  • ⁇ -quartz solid solution is preferably deposited on the picture layer.
  • the low expansion substrate with a picture layer according to the present invention it is preferable that the low expansion substrate is a transparent crystallized glass substrate, and ⁇ -quartz solid solution is precipitated as a main crystal.
  • the low expansion substrate is preferably a quartz substrate.
  • the low expansion substrate with a picture layer of the present invention is preferably used for a top plate for a cooker.
  • the glass powder of the present invention has a glass composition of mol%, SiO 2 48 to 75%, B 2 O 3 5 to 23%, Al 2 O 3 5 to 25%, Li 2 O 5 to 30%, ZnO 0. It is characterized by containing ⁇ 25% and having a molar ratio SiO 2 / B 2 O 3 of 3.23 or more.
  • the reason for limiting the content range of each component as described above will be described below.
  • SiO 2 is a component that forms a glass skeleton, is a crystal component of ⁇ -quartz solid solution, and is a component that enhances the water resistance and acid resistance of the glass matrix after crystal precipitation.
  • the content of SiO 2 is 48 to 75%, preferably 50 to 68%, 52 to 66%, 54 to 64%, particularly 56 to 62%. If the content of SiO 2 is too small, the thermal stability becomes unduly low, and crystals tend to precipitate before the glass powder is sufficiently sintered. In addition, the ⁇ -quartz solid solution is difficult to precipitate during firing, and as a result, it is difficult to reduce the thermal expansion coefficient of the painted layer. Furthermore, the water resistance and acid resistance of the glass matrix after crystal precipitation tend to decrease. On the other hand, if the content of SiO 2 is too large, the softening point is raised, softening and fluidization of the glass powder is liable to lower.
  • B 2 O 3 is a component that forms a glass skeleton, and is a component that lowers the softening point without increasing the thermal expansion coefficient.
  • the content of B 2 O 3 is 5 to 23%, preferably 7 to 19%, 9 to 16%, 10 to 14%, particularly 10 to 12%. If the content of B 2 O 3 is too small, the thermal stability is unduly lowered, and crystals tend to precipitate before the glass powder is sufficiently sintered. Furthermore, the softening point rises and the softening fluidity of the glass powder tends to decrease. On the other hand, when the content of B 2 O 3 is too large, the water resistance of the glass matrix after crystal precipitation, acid resistance tends to decrease.
  • the molar ratio SiO 2 / B 2 O 3 is 3.23 or more, preferably 3.5 or more, 3.9 or more, 4.2 to 10, 4.5 to 8, 4.8 to 7, especially 5 to 6. It is. If the molar ratio SiO 2 / B 2 O 3 is too small, the water resistance and acid resistance of the glass matrix after crystal precipitation are likely to decrease, and the water resistance and acid resistance of the picture layer are likely to decrease. On the other hand, when the molar ratio SiO 2 / B 2 O 3 is too large, different types of crystals such as ⁇ -spodumene are precipitated, and the amount of ⁇ -quartz solid solution deposited tends to decrease.
  • Al 2 O 3 is a crystal component of ⁇ -quartz solid solution and a component that improves acid resistance.
  • the content of Al 2 O 3 is 5 to 25%, preferably 6 to 20%, 7 to 16%, 8 to 13%, particularly 9 to 11%. If the content of Al 2 O 3 is too small, ⁇ -quartz solid solution is difficult to precipitate during firing, and as a result, it is difficult to reduce the thermal expansion coefficient of the painted layer. When the content of Al 2 O 3 is too large, the softening point is raised, softening and fluidization of the glass powder is liable to lower.
  • Li 2 O is a crystal component of ⁇ -quartz solid solution and a component that lowers the softening point without increasing the thermal expansion coefficient.
  • the content of Li 2 O is 5 to 30%, preferably 7 to 25%, 10 to 22%, 12 to 20%, 13 to 18%, particularly 14 to 16%.
  • the softening point is raised, softening and fluidization of the glass powder is liable to lower.
  • the ⁇ -quartz solid solution is difficult to precipitate during firing, and as a result, it is difficult to reduce the thermal expansion coefficient of the painted layer.
  • the content of Li 2 O is too large, the acid resistance is likely to decrease.
  • ZnO is a component that lowers the softening point without significantly increasing the thermal expansion coefficient. It is a component that promotes crystallization.
  • the content of ZnO is 0 to 25%, preferably 0 to 20%, 0 to 16%, 1 to 14%, 2 to 12%, 3 to 10%, particularly 4 to 7.6%.
  • the content of ZnO is 0.1 to 7.6%, 1 to 5%, particularly 1.5 to 3%. It is.
  • Na 2 O and K 2 O are components that lower the softening point. However, if the content is too large, ⁇ -quartz solid solution is difficult to precipitate during firing, resulting in a decrease in the thermal expansion coefficient of the painted layer. It becomes difficult. Furthermore, acid resistance tends to decrease. Therefore, the total amount of Na 2 O and K 2 O is preferably 0 to less than 8%, 0 to 6%, 0 to 4%, 0 to 2%, particularly 0 to less than 1%.
  • the content of Na 2 O is preferably 0-8%, 0-6%, 0-4%, 0-2%, especially 0-1%.
  • the content of K 2 O is preferably 0-8%, 0-6%, 0-4%, 0-2%, especially 0-1%.
  • the molar ratio Li 2 O / (Li 2 O + Na 2 O + K 2 O) is preferably 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, particularly 0.9 or more.
  • Li 2 O / (Li 2 O + Na 2 O + K 2 O)” is a value obtained by dividing the content of Li 2 O by the total amount of Li 2 O, Na 2 O and K 2 O.
  • TiO 2 and ZrO 2 are components that increase crystallinity, and are components that increase the water resistance and acid resistance of the glass matrix after crystal precipitation, but if its content is excessive, the softening point increases, The softening fluidity of the glass powder tends to decrease. Furthermore, the thermal stability is unduly lowered, and crystals tend to precipitate before the glass powder is sufficiently sintered.
  • the total amount of TiO 2 and ZrO 2 is preferably 0-15%, 0-12%, 0.1-10%, 1-8%, especially 2-6%.
  • the content of TiO 2 is preferably 0 to 15%, 0 to 12%, 0.1 to 10%, 1 to 8%, in particular 2 to 6%.
  • the content of ZrO 2 is preferably 0 to 10%, 0 to 5%, 0 to less than 3%, 0 to 2%, especially 0 to 1%.
  • MgO is a component that enhances thermal stability.
  • the content of MgO is preferably 0-7%, 0-5%, 0-3%, especially 0-1%.
  • a softening point will raise and the softening fluidity
  • liquidity of glass powder will fall easily.
  • BaO is a component that enhances thermal stability.
  • the content of BaO is preferably 0 to 7%, 0 to 5%, in particular 0.1 to 3%. When there is too much content of BaO, a thermal expansion coefficient will rise unduly and it will become difficult to reduce the thermal expansion coefficient of a painting layer.
  • CuO is a component for coloring the glass black.
  • the CuO content is preferably 0-7%, 0-5%, 0-3%, especially 0-1%.
  • thermal stability will become low unreasonably and it will become easy to precipitate a crystal
  • other components can be introduced, for example, up to 15%, 10%, 5%, particularly 1%, if necessary.
  • CaO, SrO, Cr 2 O 3 , MnO, SnO 2 , CeO 2 , P 2 O 5 , La 2 O 3 , Nd 2 O 3 , Co 2 O 3 , F, Cl, etc. are combined or It can be introduced individually, for example up to 15%, 10%, 5%, in particular 1%.
  • substantially PbO which preferably does not substantially Bi 2 O 3 is also contained.
  • the average particle diameter D 50 of the glass powder is 15 ⁇ m or less, 0.5 ⁇ 10 [mu] m, particularly 0.7 ⁇ 5 [mu] m is preferred. If the particle size of the glass powder is too large, the screen printability tends to be lowered, and the color tone of the picture layer tends to be uneven.
  • the “average particle diameter D 50” refers to a value measured with a laser diffractometer, and in the cumulative particle size distribution curve based on volume when measured by the laser diffraction method, the accumulated amount is from the smaller particle.
  • the particle diameter is 50% cumulatively (hereinafter the same).
  • the softening point of the glass powder measured with a macro DTA apparatus is preferably 550 to 700 ° C., 570 to 695 ° C., 590 to 690 ° C., particularly 620 to 685 ° C.
  • the softening point is lower, it becomes possible to lower the firing temperature and improve the color developability of the inorganic pigment powder, but if the softening point is too low, other characteristics, particularly the water resistance of the glass matrix after crystal precipitation, Acid resistance tends to decrease.
  • the softening point is too high, the firing temperature is unduly increased, which may increase the firing cost.
  • the crystallization temperature of the glass powder measured with a macro type DTA apparatus is preferably 650 to 750 ° C., 660 to 740 ° C., particularly 670 to 730 ° C.
  • the crystallization temperature measured with the macro type DTA apparatus refers to the exothermic peak temperature (Tc) due to crystal precipitation shown in FIG.
  • the thermal expansion coefficient of the sintered body after firing the glass powder at 700 ° C. for 10 minutes is preferably 25 ⁇ 10 ⁇ 7 / ° C. or less, 15 ⁇ 10 ⁇ 7 / ° C. or less, 10 ⁇ 10 ⁇ 7 /
  • the temperature is not higher than ° C., particularly ⁇ 10 ⁇ 10 ⁇ 7 to 5 ⁇ 10 ⁇ 7 / ° C. If the thermal expansion coefficient of the sintered glass powder is too high, it is difficult to lower the thermal expansion coefficient of the picture layer, and cracks are likely to occur in the low expansion substrate with the picture layer. In addition, dropping off of the picture layer is likely to occur.
  • ⁇ -quartz solid solution is preferably precipitated as the main crystal.
  • the composite powder of the present invention includes at least a glass powder and an inorganic pigment powder, and includes a refractory filler powder as necessary.
  • Glass powder is a component for dispersing inorganic pigment powder and fixing it to a low expansion substrate.
  • the inorganic pigment powder is a component for enhancing decoration by coloring black or the like.
  • the refractory filler powder is an optional component, a component that increases mechanical strength, and a component for adjusting the thermal expansion coefficient.
  • a metal powder such as Cu powder may be added in order to improve the color developability.
  • the composite powder of the present invention preferably contains 55 to 100% by mass of glass powder, 0 to 45% by mass of inorganic pigment powder, and 0 to 40% by mass of refractory filler powder.
  • the content of the glass powder is preferably 55 to 100% by mass, 55 to 95% by mass, 55 to 90% by mass, 55 to 85% by mass, 60 to 80% by mass, particularly 65 to 75% by mass.
  • substrate will fall easily.
  • inorganic pigment powder will decrease relatively and the decoration property of a painting layer will fall easily.
  • the content of the inorganic pigment powder is preferably 0 to 45% by mass, 5 to 45% by mass, 10 to 45% by mass, 13 to 45% by mass, particularly 15 to 30% by mass. If the content of the inorganic pigment powder is too small, the decorative property tends to be lowered. On the other hand, when the content of the inorganic pigment powder is too large, the glass powder becomes relatively small, and the adhesion between the picture layer and the low expansion substrate tends to be lowered. Furthermore, when there is too much content of inorganic pigment powder, the surface smoothness of a painting layer will fall and the water resistance and acid resistance of a painting layer will fall easily.
  • the inorganic pigment powder can be used as the inorganic pigment powder.
  • NiO green
  • MnO 2 black
  • CoO black
  • Fe 2 O 3 brown
  • Cr 2 O 3 green
  • TiO 2 White oxide
  • Cr—Al spinel pink
  • Sn—Sb—V rutile gray
  • Ti—Sb—Ni rutile yellow
  • Zr—V badelite yellow
  • silicates which are to obtain the desired color can be mixed in the above ratio.
  • an appropriate amount of ZrSiO 4 or talc may be mixed in order to improve the concealability and abrasion resistance of the painting layer.
  • the average particle diameter D 50 of the inorganic pigment powder is 9 ⁇ m or less, particularly 0.5 ⁇ 4 [mu] m is preferred.
  • the maximum particle diameter Dmax of the inorganic pigment powder is preferably 10 ⁇ m or less, particularly preferably 2 to 8 ⁇ m. If the particle size of the inorganic pigment powder is too large, the screen printability tends to be lowered, and the color developability of the coated layer tends to be lowered.
  • the content of the refractory filler powder is preferably 0 to 40% by mass, 0 to 20% by mass, 0 to 15% by mass, 0 to 10% by mass, 0 to 5% by mass, 0 to 1% by mass, especially 0 to It is less than 0.1% by mass.
  • the content of the refractory filler powder is preferably 0 to 40% by mass, 0 to 20% by mass, 0 to 15% by mass, 0 to 10% by mass, 0 to 5% by mass, 0 to 1% by mass, especially 0 to It is less than 0.1% by mass.
  • cordierite willemite, alumina, zirconium phosphate, zircon, zirconia, tin oxide, mullite, silica, ⁇ -eucryptite, ⁇ -spodumene, ⁇ -quartz solid solution, zirconium tungstate phosphate, etc. Can be used.
  • the composite powder of the present invention is mixed with a vehicle and used as a composite powder paste.
  • the vehicle is mainly composed of a solvent and a resin.
  • the solvent is added for the purpose of uniformly dispersing the composite powder while dissolving the resin.
  • the resin is added for the purpose of adjusting the viscosity of the paste.
  • surfactant, a thickener, etc. can also be added as needed.
  • acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used.
  • acrylic acid ester and ethyl cellulose are preferable because they have good thermal decomposability.
  • Solvents include pine oil, N, N′-dimethylformamide (DMF), ⁇ -terpineol, higher alcohol, ⁇ -butyllactone ( ⁇ -BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl Ether, diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , Tripropylene glycol monobutyl ether, propylene carbonate, N-methyl-2-pyrrolidone There can be used. In particular, ⁇ -terpineol is preferable because it is highly viscous and has good solubility in resins and the like.
  • the composite powder paste is produced, for example, by mixing the composite powder and the vehicle and then uniformly kneading with a three-roll mill.
  • the composite material paste is applied to a low expansion substrate using a coating machine such as a screen printer, and then subjected to a drying process and a baking process. As a result, a picture layer can be formed on the surface of the low expansion substrate.
  • the drying process is generally performed at 70 to 150 ° C. for 10 to 60 minutes.
  • the firing step is a step in which the resin is decomposed and volatilized and the composite powder is sintered to adhere the picture layer to the surface of the low expansion substrate.
  • the conditions for the firing step are generally 650 to 850 ° C. and 5 to 30 minutes. The lower the calcination temperature in the calcination step, the better the production efficiency and the color developability of the inorganic pigment powder. On the other hand, the adhesion between the picture layer and the low expansion substrate decreases.
  • the low-expansion substrate with a picture layer of the present invention is a low-expansion board with a picture layer having a picture layer on the surface of the low-expansion board, wherein the picture layer is a sintered body of a composite powder, and the composite powder is the above composite A powder is preferred.
  • substrate with a painting layer of this invention contains the technical feature of the composite powder of this invention, since the content has already been described, the description is abbreviate
  • a ⁇ -quartz solid solution is deposited on the picture layer.
  • the coefficient of thermal expansion of the picture layer is significantly reduced, so that it is possible to accurately prevent the occurrence of cracks in the low expansion substrate with the picture layer.
  • the low expansion substrate is preferably a crystallized glass substrate (especially a transparent crystallized glass substrate), and it is also preferable that a ⁇ -quartz solid solution is precipitated as the main crystal. In this way, heat durability and thermal shock resistance can be improved.
  • the thermal expansion coefficient of the crystallized glass substrate is preferably ⁇ 10 ⁇ 10 ⁇ 7 to 30 ⁇ 10 ⁇ 7 / ° C., particularly preferably ⁇ 5 ⁇ 10 ⁇ 7 to 10 ⁇ 10 ⁇ 7 / ° C. Decreasing the thermal expansion coefficient of the crystallized glass substrate improves the heat durability and thermal shock resistance of the crystallized glass substrate. As a result, it is suitable for a top plate for a cooker to which a thermal shock due to rapid heating and rapid cooling is applied during use.
  • the cooking device include an electromagnetic cooking device, an electric cooking device, and a gas cooking device.
  • the thickness of the picture layer is preferably 1 to 30 ⁇ m, particularly preferably 2 to 10 ⁇ m. If the thickness of the picture layer is too small, the picture pattern may become unclear. On the other hand, if the thickness of the picture layer is too thick, cracks may occur in the picture pattern.
  • Table 1 shows Examples (Sample Nos. 1 to 9) and Comparative Examples (Sample Nos. 10 and 11) of the present invention.
  • raw materials were blended and mixed uniformly so as to have the glass composition described in the table.
  • the glass batch was placed in a platinum crucible and melted at 1400 ° C. for 3 hours. Thereafter, the molten glass was formed into a film. Subsequently, the obtained glass film was pulverized in a ball mill, and air classification, the average particle diameter D 50 was obtained glass powder 2.5 [mu] m.
  • the softening point and the crystallization temperature were measured using a macro DTA apparatus. Here, the measurement was performed in air, and the rate of temperature increase was 10 ° C./min.
  • the softening point indicates the temperature of the fourth inflection point, and the crystallization temperature indicates the exothermic peak temperature due to crystal precipitation.
  • the main crystal has a peak intensity when measured by X-ray diffractometry using a glass powder compact that has been densely sintered at 700 ° C. for 10 minutes and then processed into a predetermined shape. The largest crystal.
  • the thermal expansion coefficient of the glass powder is a value measured in a temperature range of 30 to 350 ° C. using a TMA apparatus.
  • a green powder compact was sintered precisely at 700 ° C. for 10 minutes and then processed into a predetermined shape.
  • the water resistance of the glass powder was evaluated as follows. That is, a glass powder green compact is sintered precisely at 700 ° C. for 10 minutes and then processed into a predetermined shape as a measurement sample, and water in 100 ° C. ( ⁇ corrected, 90 ° C.) for 2 hours. When immersed, the case where the appearance change was not recognized was evaluated as “ ⁇ ”, and the case where the appearance change was recognized was evaluated as “x”.
  • the glass powder and the inorganic pigment powder were mixed at a ratio (100% in total) described in the table to obtain a composite powder.
  • the inorganic pigment powder Cr—Cu—Mn composite oxide (average particle diameter D 50 is 1.5 ⁇ m, maximum particle diameter D max is 4.0 ⁇ m) was used.
  • the obtained composite powder and vehicle were mixed and then uniformly kneaded with a three-roll mill to obtain a composite powder paste.
  • vehicle ethyl cellulose dissolved in ⁇ -terpineol was used, and the composite powder / vehicle was adjusted to 2 to 3 by mass ratio.
  • the composite powder paste was screen-printed on the entire surface of a 10 cm square transparent crystallized glass substrate (N-0 manufactured by Nippon Electric Glass Co., Ltd., main crystal: ⁇ -quartz solid solution) and then dried at 120 ° C. for 20 minutes. Above, it put into the 700 degreeC electric furnace, baked for 10 minutes, and naturally cooled to room temperature, and obtained the transparent crystallized glass substrate with a 10-micrometer-thick painting layer.
  • N-0 manufactured by Nippon Electric Glass Co., Ltd., main crystal: ⁇ -quartz solid solution
  • the presence / absence of cracks was evaluated by observing a transparent crystallized glass substrate with a picture layer, with “ ⁇ ” indicating that no crack was observed and “ ⁇ ” indicating that a crack was observed.
  • Abrasion resistance is “ ⁇ ” when the coated layer did not peel off after reciprocating 100 times with a load of 1.3 kg and a speed of 100 mm / second one way using # 1000 sandpaper. What peeled was evaluated as "x".
  • the water resistance of the pictured layer is “ ⁇ ” when the appearance change was not observed in the pictured layer when immersed in water at 90 ° C. for 24 hours, and “ ⁇ ” when the appearance change was slightly recognized. Was clearly recognized as “ ⁇ ”.
  • the acid resistance of the pictured layer is “ ⁇ ” when no change in appearance was observed in the pictured layer when immersed in a 0.1% by mass HCl aqueous solution at 40 ° C. for 1 hour, and a slight change in appearance was observed. “ ⁇ ” and those with a clear change in appearance were evaluated as “x”.
  • sample No. Nos. 1 to 9 had a low coefficient of thermal expansion and good evaluation of water resistance and acid resistance.
  • sample No. No. 10 was poor in evaluation of water resistance and acid resistance because the molar ratio SiO 2 / B 2 O 3 was small.
  • Sample No. In No. 11 no crystal precipitated after firing, and cracks occurred when a transparent crystallized glass substrate with a picture layer was used.
  • Table 2 shows examples (sample Nos. 12 to 16) of the present invention.
  • raw materials were blended and mixed uniformly so as to have the glass composition described in the table.
  • the glass batch was placed in a platinum crucible and melted at 1400 ° C. for 3 hours. Thereafter, the molten glass was formed into a film. Subsequently, the obtained glass film was pulverized in a ball mill, and air classification, the average particle diameter D 50 was obtained glass powder 2.5 [mu] m.
  • the softening point and the crystallization temperature were measured using a macro DTA apparatus. Here, the measurement was performed in air, and the rate of temperature increase was 10 ° C./min.
  • the softening point indicates the temperature of the fourth inflection point, and the crystallization temperature indicates the exothermic peak temperature due to crystal precipitation.
  • the main crystal has a peak intensity when measured by X-ray diffractometry using a glass powder compact that has been densely sintered at 700 ° C. for 10 minutes and then processed into a predetermined shape. The largest crystal.
  • the thermal expansion coefficient of the glass powder is a value measured in a temperature range of 30 to 350 ° C. using a TMA apparatus.
  • a green powder compact was sintered precisely under the firing conditions in the table and then processed into a predetermined shape.
  • the water resistance of the glass powder was evaluated as follows. That is, when a green powder compact is densely sintered at 700 ° C. for 10 minutes and then processed into a predetermined shape as a measurement sample, the appearance changes when immersed in water at 90 ° C. for 2 hours. Those that were not recognized were evaluated as “ ⁇ ”, and those that had a change in appearance were evaluated as “ ⁇ ”.
  • the glass powder and the inorganic pigment powder were mixed at a ratio (100% in total) described in the table to obtain a composite powder.
  • the inorganic pigment powder Cr—Cu—Mn composite oxide (average particle diameter D 50 is 1.5 ⁇ m, maximum particle diameter D max is 4.0 ⁇ m) was used.
  • the obtained composite powder and vehicle were mixed and then uniformly kneaded with a three-roll mill to obtain a composite powder paste.
  • vehicle ethyl cellulose dissolved in ⁇ -terpineol was used, and the composite powder / vehicle was adjusted to 2 to 3 by mass ratio.
  • the composite powder paste was screen-printed on the entire surface of a 10 cm square transparent crystallized glass substrate (N-0 manufactured by Nippon Electric Glass Co., Ltd., main crystal: ⁇ -quartz solid solution) and then dried at 120 ° C. for 20 minutes. Above, it put into the 700 degreeC electric furnace, baked for 10 minutes, and naturally cooled to room temperature, and obtained the transparent crystallized glass substrate with a 10-micrometer-thick painting layer.
  • N-0 manufactured by Nippon Electric Glass Co., Ltd., main crystal: ⁇ -quartz solid solution
  • the presence / absence of cracks was evaluated by observing a transparent crystallized glass substrate with a picture layer, with “ ⁇ ” indicating that no crack was observed and “ ⁇ ” indicating that a crack was observed.
  • Abrasion resistance is “ ⁇ ” when the coated layer did not peel off after reciprocating 100 times with a load of 1.3 kg and a speed of 100 mm / second one way using # 1000 sandpaper. What peeled was evaluated as "x".
  • the water resistance of the pictured layer is “ ⁇ ” when the appearance change was not observed in the pictured layer when immersed in water at 90 ° C. for 24 hours, and “ ⁇ ” when the appearance change was slightly recognized. Was clearly recognized as “ ⁇ ”.
  • the acid resistance of the pictured layer is “ ⁇ ” when no change in appearance was observed in the pictured layer when immersed in a 0.1% by mass HCl aqueous solution at 40 ° C. for 1 hour, and a slight change in appearance was observed. “ ⁇ ” and those with a clear change in appearance were evaluated as “x”.
  • sample No. Nos. 11 to 15 had low thermal expansion coefficients and good evaluations of water resistance and acid resistance.
  • sample no. Since 11, 13 and 15 contained a small amount of ZnO in the glass composition the fluctuation range of the thermal expansion coefficient was small even if the firing temperature fluctuated. That is, the firing temperature dependence of the thermal expansion coefficient was small.
  • the glass powder, the composite powder, and the low-expansion substrate with a picture layer are suitable for a top plate for a cooker having a picture layer, but the coating, sealing and sealing of a low-expansion board such as a quartz substrate and an Si 3 N 4 substrate are possible. It can also be applied to uses such as wearing.
  • a low-expansion board such as a quartz substrate and an Si 3 N 4 substrate
  • it can also be applied to uses such as wearing.

Abstract

The present invention addresses the technical problem of devising a glass powder and a composite powder which soften and become fluid at a low temperature, have a low coefficient of thermal expansion, and exhibit high water resistance and acid resistance. This glass powder is characterized by having a glass composition that contains, in terms of mol.%, 48-75% of SiO2, 5-23% of B2O3, 5-25% of Al2O3, 5-30% of Li2O, and 0-25% of ZnO, with the SiO2/B2O3 molar ratio being 3.23 or higher.

Description

ガラス粉末、複合粉末及び絵付層付き低膨張基板Low expansion substrate with glass powder, composite powder and picture layer
　本発明は、ガラス粉末、複合粉末及び絵付層付き低膨張基板に関し、具体的には、絵付層を有する調理器用トッププレート等に好適なガラス粉末、複合粉末及び絵付層付き低膨張基板に関する。 The present invention relates to a glass powder, a composite powder and a low expansion substrate with a picture layer, and more specifically, to a glass powder, a composite powder and a low expansion board with a picture layer suitable for a top plate for a cooker having a picture layer.
　低膨張の結晶化ガラス基板は、加熱耐久性や耐熱衝撃性が高いため、調理器用トッププレートとして広く使用されている。 A low-expansion crystallized glass substrate is widely used as a top plate for cooking appliances because of its high heat durability and thermal shock resistance.
　また、調理器用トッププレートの表面は、美感を高めるために、絵付層で装飾されることがある。絵付層は、一般的に、ガラス粉末と無機顔料粉末等を含む複合粉末の焼結体である。例えば、特許文献１には、質量％で、ＳｉＯ２　５５～７０％、Ｂ２Ｏ３　１５～２５％、Ａｌ２Ｏ３　３～１０％、ＢａＯ　０．１～４．９％、ＺｎＯ　０．１～５％、ＣａＯ　０～３％、ＭｇＯ　０～３％、Ｌｉ２Ｏ　０．１～５％、Ｎａ２Ｏ　０～１０％、Ｋ２Ｏ　０．３～１５％、Ｆ２　０～２％を含有し、軟化点が６００℃以上７００℃未満であることを特徴とする絵付層形成用無鉛ガラス粉末が開示されている。 In addition, the surface of the top plate for a cooker may be decorated with a picture layer in order to enhance aesthetics. The picture layer is generally a sintered body of composite powder containing glass powder and inorganic pigment powder. For example, in Patent Document 1, in terms of mass%, SiO 2 55 to 70%, B 2 O 3 15 to 25%, Al 2 O 3 3 to 10%, BaO 0.1 to 4.9%, ZnO 0. 1-5%, CaO 0-3%, MgO 0-3%, Li 2 O 0.1-5%, Na 2 O 0-10%, K 2 O 0.3-15%, F 2 0-2 A lead-free glass powder for forming a picture layer is disclosed, which has a softening point of 600 ° C. or higher and lower than 700 ° C.
　結晶化ガラス基板の表面に絵付層を形成する方法は、以下の通りである。まずガラス粉末と無機顔料粉末等を混合して、複合粉末を得る。次に、得られた複合粉末を有機バインダー、溶剤等を含むビークル中に分散させて、ペースト化する。続いて、得られた複合粉末ペーストをスクリーン印刷法等により結晶化ガラス基板上に転写、乾燥した後、適正な焼成条件により焼成する。複合粉末を焼成すると、複合粉末（ガラス粉末）が軟化流動した後、焼結する。これにより、複合粉末が結晶化ガラス基板上で強く固着されて、絵付層になる。 The method for forming a picture layer on the surface of a crystallized glass substrate is as follows. First, glass powder and inorganic pigment powder are mixed to obtain a composite powder. Next, the obtained composite powder is dispersed in a vehicle containing an organic binder, a solvent and the like to form a paste. Subsequently, the obtained composite powder paste is transferred onto a crystallized glass substrate by screen printing or the like, dried, and then fired under appropriate firing conditions. When the composite powder is fired, the composite powder (glass powder) softens and flows and then sinters. As a result, the composite powder is firmly fixed on the crystallized glass substrate to form a picture layer.
特開２００７－３９２９４号公報JP 2007-39294 A
　ところで、特許文献１に記載のガラス粉末は、低温で軟化流動するが、熱膨張係数が高いため、絵付層の熱膨張係数を低下させることが困難である。絵付層の熱膨張係数が高いと、絵付層付き結晶化ガラス基板にクラックが発生し易くなる。この傾向は、結晶化ガラス基板の熱膨張係数が低い程、顕在化し易くなる。なお、このクラックは、耐水性、耐酸性等の特性を劣化させるだけでなく、その内部に汚れが滞留して、美観を損ねるという問題も発生させる。 Incidentally, the glass powder described in Patent Document 1 softens and flows at a low temperature, but has a high coefficient of thermal expansion, so it is difficult to reduce the coefficient of thermal expansion of the picture layer. When the coefficient of thermal expansion of the picture layer is high, cracks are likely to occur in the crystallized glass substrate with the picture layer. This tendency becomes more obvious as the thermal expansion coefficient of the crystallized glass substrate is lower. In addition, this crack not only deteriorates characteristics such as water resistance and acid resistance, but also causes a problem that dirt stays in the interior and impairs the appearance.
　更に、絵付層の熱膨張係数が高いと、絵付層に過大な引張応力が入り、外力により絵付層の機械的強度が劣化し易くなる。 Furthermore, if the coefficient of thermal expansion of the picture layer is high, an excessive tensile stress is applied to the picture layer, and the mechanical strength of the picture layer tends to deteriorate due to external force.
　また、調理器用トッププレートは、使用時に熱湯、果汁、調味料に曝される。このため、絵付層には、高い耐水性、耐酸性が求められることがある。具体的には、絵付層が調理器用トッププレートの調理面側に配置される場合、調理面とは反対側に絵付層が配置される場合であっても、ガス器具等を通すために穴開け加工がなされる場合等は、高い耐水性、耐酸性が求められる。これに伴い、ガラス粉末にも高い耐水性、耐酸性が求められる。 Also, the top plate for cooking appliances is exposed to hot water, fruit juice, and seasoning during use. For this reason, high water resistance and acid resistance may be calculated | required by the layer with a picture. Specifically, when the picture layer is arranged on the cooking surface side of the cooking utensil top plate, even if the picture layer is arranged on the opposite side of the cooking surface, a hole is made to allow gas appliances to pass through. When processing is performed, high water resistance and acid resistance are required. Along with this, high water resistance and acid resistance are also required for glass powder.
　本発明は、上記事情に鑑みなされたものであり、その技術的課題は、低温で軟化流動すると共に、熱膨張係数が低く、しかも耐水性、耐酸性が高いガラス粉末及び複合粉末を創案することである。 The present invention has been made in view of the above circumstances, and its technical problem is to create glass powders and composite powders that soften and flow at low temperatures, have a low coefficient of thermal expansion, and have high water resistance and acid resistance. It is.
　本発明者は、種々の検討を行った結果、ＳｉＯ２－Ｂ２Ｏ３－Ａｌ２Ｏ３系ガラス粉末において、Ｌｉ２Ｏを所定量導入すると共に、ＳｉＯ２の含有量を増加させると共に、Ｂ２Ｏ３の含有量を低下させることにより、上記技術的課題を解決し得ることを見出し、本発明として、提案するものである。すなわち、本発明のガラス粉末は、ガラス組成として、モル％で、ＳｉＯ２　４８～７５％、Ｂ２Ｏ３　５～２３％、Ａｌ２Ｏ３　５～２５％、Ｌｉ２Ｏ　５～３０％、ＺｎＯ　０～２５％を含有し、モル比ＳｉＯ２／Ｂ２Ｏ３が３．２３以上であることを特徴とする。ここで、「ＳｉＯ２／Ｂ２Ｏ３」は、ＳｉＯ２の含有量をＢ２Ｏ３の含有量で割った値である。 As a result of various studies, the present inventor has introduced a predetermined amount of Li 2 O and increased the content of SiO 2 in the SiO 2 —B 2 O 3 —Al 2 O 3 glass powder, The present inventors have found that the above technical problem can be solved by reducing the content of B 2 O 3 and propose as the present invention. That is, the glass powder of the present invention has a glass composition of mol%, SiO 2 48 to 75%, B 2 O 3 5 to 23%, Al 2 O 3 5 to 25%, Li 2 O 5 to 30%, It is characterized by containing 0 to 25% of ZnO and having a molar ratio SiO 2 / B 2 O 3 of 3.23 or more. Here, “SiO 2 / B 2 O 3 ” is a value obtained by dividing the content of SiO 2 by the content of B 2 O 3 .
　本発明のガラス粉末は、ガラス組成中にＳｉＯ２を４８～７５モル％、Ｂ２Ｏ３を５～２３モル％、Ａｌ２Ｏ３を５～２５モル％、Ｌｉ２Ｏを５～３０モル％含む。これにより、焼成時に、良好に軟化流動した後に低膨張のβ－石英固溶体を析出させることができる。結果として、軟化流動性と低膨張係数を両立させることが可能になる。 Glass powder of the present invention, the SiO 2 48 ~ 75 mol% in the glass composition, B 2 O 3 of 5 to 23 mol%, the Al 2 O 3 5 ~ 25 mol%, Li 2 O 5-30 mole % Is included. This makes it possible to deposit a low expansion β-quartz solid solution after good softening and flow during firing. As a result, it is possible to achieve both softening fluidity and a low expansion coefficient.
　一方、ガラス組成中のＳｉＯ２の含有量を低下させつつ、Ｂ２Ｏ３の含有量を増加させると、ガラス粉末の軟化流動性が向上するものの、β－石英固溶体が析出した後にガラスマトリクスの耐水性、耐酸性が低下し易くなる。そこで、本発明のガラス粉末は、ガラス組成中のモル比ＳｉＯ２／Ｂ２Ｏ３を３．２３以上に規制している。これにより、結晶析出後のガラスマトリクスの耐水性、耐酸性が向上するため、絵付層の耐水性、耐酸性を的確に高めることができる。 On the other hand, when the content of B 2 O 3 is increased while the content of SiO 2 in the glass composition is decreased, the softening fluidity of the glass powder is improved, but the β-quartz solid solution is precipitated and the glass matrix Water resistance and acid resistance are likely to decrease. Therefore, the glass powder of the present invention regulates the molar ratio SiO 2 / B 2 O 3 in the glass composition to 3.23 or more. Thereby, since the water resistance and acid resistance of the glass matrix after crystal precipitation improve, the water resistance and acid resistance of a painting layer can be improved exactly.
　第二に、本発明のガラス粉末は、ガラス組成中のＢ２Ｏ３の含有量が１６モル％以下であることが好ましい。 Second, the glass powder of the present invention, it is preferable that the content of B 2 O 3 in the glass composition is less than 16 mol%.
　第三に、本発明のガラス粉末は、ガラス組成中のＺｎＯの含有量が０．１～７．６モル％であることが好ましい。このようにすれば、焼成時に、異種結晶の析出を抑制しつつ、β－石英固溶体の析出量を増加させることができる。結果として、熱膨張係数の焼成温度依存性を低下させることが可能になり、焼成後に局所的に歪な応力が残留したり、局所的に熱膨張係数が異なる箇所が発生する事態を防止し易くなる。また製造ロット間で絵付層の熱膨張係数が異なる事態を防止し易くなる。 Third, the glass powder of the present invention preferably has a ZnO content in the glass composition of 0.1 to 7.6 mol%. In this way, it is possible to increase the amount of β-quartz solid solution deposited while suppressing the precipitation of foreign crystals during firing. As a result, it becomes possible to reduce the firing temperature dependence of the thermal expansion coefficient, and it is easy to prevent a situation where locally distorted stress remains after firing or a place where the thermal expansion coefficient is locally different occurs. Become. In addition, it is easy to prevent a situation in which the thermal expansion coefficient of the picture layer differs between production lots.
　第四に、本発明のガラス粉末は、ガラス組成中に更にＴｉＯ２とＺｒＯ２を合量で０．１～１５モル％含むことが好ましい。 Fourth, the glass powder of the present invention preferably further contains 0.1 to 15 mol% of TiO 2 and ZrO 2 in the total amount in the glass composition.
　第五に、本発明のガラス粉末は、ガラス組成中に実質的にＰｂＯとＢｉ２Ｏ３を含まないことが好ましい。ここで、「実質的に～を含まない」とは、明示の成分が不純物レベルで混入する場合を許容する趣旨であり、具体的には、明示の成分の含有量が０．１質量％未満の場合を指す。 Fifth, it is preferable that the glass powder of the present invention does not substantially contain PbO and Bi 2 O 3 in the glass composition. Here, “substantially free of” is intended to allow the case where an explicit component is mixed at an impurity level, and specifically, the content of the explicit component is less than 0.1% by mass. Refers to the case.
　第六に、本発明のガラス粉末は、７００℃１０分間の条件で焼成した後の熱膨張係数が２５×１０－７／℃以下であることが好ましい。ここで、「熱膨張係数」は、ＴＭＡ装置を用いて、３０～３５０℃の温度範囲で測定した値である。なお、測定試料として、ガラス粉末の圧粉体を７００℃１０分間の焼成条件で緻密に焼結させた後、所定形状に加工したものを用いた。 Sixth, the glass powder of the present invention preferably has a thermal expansion coefficient of 25 × 10 −7 / ° C. or lower after firing at 700 ° C. for 10 minutes. Here, the “thermal expansion coefficient” is a value measured in a temperature range of 30 to 350 ° C. using a TMA apparatus. In addition, as a measurement sample, a glass powder green compact was sintered precisely at 700 ° C. for 10 minutes and then processed into a predetermined shape.
　第七に、本発明のガラス粉末は、７００℃１０分間の条件で焼成すると、主結晶としてβ－石英固溶体が析出することが好ましい。ここで、「主結晶」は、Ｘ線回折法で測定した時に、ピーク強度が最も大きい結晶を指す。 Seventh, when the glass powder of the present invention is fired at 700 ° C. for 10 minutes, β-quartz solid solution is preferably precipitated as the main crystal. Here, the “main crystal” refers to a crystal having the highest peak intensity when measured by the X-ray diffraction method.
　第八に、本発明のガラス粉末は、マクロ型ＤＴＡ装置で測定した軟化点が５５０～７００℃であることが好ましい。ここで、マクロ型ＤＴＡ装置で測定した軟化点は、図１に示す第四屈曲点の温度（Ｔｓ）を指す。なお、マクロ型ＤＴＡ装置による測定は、空気中で行い、昇温速度を１０℃／分とする。 Eighth, the glass powder of the present invention preferably has a softening point of 550 to 700 ° C. measured with a macro DTA apparatus. Here, the softening point measured by the macro DTA apparatus indicates the temperature (Ts) at the fourth bending point shown in FIG. In addition, the measurement by a macro type DTA apparatus is performed in the air, and the temperature rising rate is 10 ° C./min.
　第九に、本発明の複合粉末は、ガラス粉末　５５～１００質量％、無機顔料粉末　０～４５質量％、耐火性フィラー粉末　０～４０質量％を含有する複合粉末であって、ガラス粉末が、上記のガラス粉末であることが好ましい。 Ninth, the composite powder of the present invention is a composite powder containing glass powder 55 to 100% by mass, inorganic pigment powder 0 to 45% by mass, refractory filler powder 0 to 40% by mass, It is preferable that it is said glass powder.
　第十に、本発明の複合粉末は、無機顔料粉末がＣｒ-Ｃｕ系複合酸化物であることが好ましい。ここで、「～系複合酸化物」とは、明示の成分を必須成分として含む複合酸化物を指す。 Tenth, in the composite powder of the present invention, the inorganic pigment powder is preferably a Cr—Cu composite oxide. Here, “˜system complex oxide” refers to a complex oxide containing an explicit component as an essential component.
　第十一に、本発明の絵付層付き低膨張基板は、低膨張基板の表面に絵付層を有する絵付層付き低膨張基板であって、絵付層が複合粉末の焼結体であり、且つ複合粉末が上記の複合粉末であることが好ましい。ここで、「低膨張基板」は、３０～３５０℃の温度範囲における熱膨張係数が３５×１０－７／℃以下の基板を指す。 Eleventh, the low expansion substrate with a picture layer of the present invention is a low expansion substrate with a picture layer having a picture layer on the surface of the low expansion board, the picture layer being a sintered body of composite powder, and a composite It is preferable that the powder is the above composite powder. Here, the “low expansion substrate” refers to a substrate having a thermal expansion coefficient of 35 × 10 −7 / ° C. or less in a temperature range of 30 to 350 ° C.
　第十二に、本発明の絵付層付き低膨張基板は、絵付層にβ－石英固溶体が析出していることが好ましい。 Twelfth, in the low expansion substrate with a picture layer of the present invention, β-quartz solid solution is preferably deposited on the picture layer.
　第十三に、本発明の絵付層付き低膨張基板は、低膨張基板が透明結晶化ガラス基板であり、且つ主結晶としてβ－石英固溶体が析出していることが好ましい。 Thirteenthly, in the low expansion substrate with a picture layer according to the present invention, it is preferable that the low expansion substrate is a transparent crystallized glass substrate, and β-quartz solid solution is precipitated as a main crystal.
　第十四に、本発明の絵付層付き低膨張基板は、低膨張基板が石英基板であることが好ましい。 Fourteenth, in the low expansion substrate with a picture layer of the present invention, the low expansion substrate is preferably a quartz substrate.
　第十五に、本発明の絵付層付き低膨張基板は、調理器用トッププレートに用いることが好ましい。 Fifteenth, the low expansion substrate with a picture layer of the present invention is preferably used for a top plate for a cooker.
マクロ型ＤＴＡ装置で測定した軟化点、結晶化温度を示すチャートである。It is a chart which shows the softening point and crystallization temperature which were measured with the macro type DTA apparatus.
　本発明のガラス粉末は、ガラス組成として、モル％で、ＳｉＯ２　４８～７５％、Ｂ２Ｏ３　５～２３％、Ａｌ２Ｏ３　５～２５％、Ｌｉ２Ｏ　５～３０％、ＺｎＯ　０～２５％を含有し、モル比ＳｉＯ２／Ｂ２Ｏ３が３．２３以上であることを特徴とする。上記のように各成分の含有範囲を限定した理由を下記に示す。なお、各成分の含有範囲の説明において、％表示はモル％を指す。 The glass powder of the present invention has a glass composition of mol%, SiO 2 48 to 75%, B 2 O 3 5 to 23%, Al 2 O 3 5 to 25%, Li 2 O 5 to 30%, ZnO 0. It is characterized by containing ˜25% and having a molar ratio SiO 2 / B 2 O 3 of 3.23 or more. The reason for limiting the content range of each component as described above will be described below. In addition, in description of the containing range of each component,% display points out mol%.
　ＳｉＯ２は、ガラス骨格を形成する成分であり、またβ－石英固溶体の結晶構成成分であり、更に結晶析出後のガラスマトリクスの耐水性、耐酸性を高める成分である。ＳｉＯ２の含有量は４８～７５％であり、好ましくは５０～６８％、５２～６６％、５４～６４％、特に５６～６２％である。ＳｉＯ２の含有量が少な過ぎると、熱的安定性が不当に低くなり、ガラス粉末が十分に焼結する前に結晶が析出し易くなる。また焼成時にβ－石英固溶体が析出し難くなり、結果として絵付層の熱膨張係数を低下させ難くなる。更に結晶析出後のガラスマトリクスの耐水性、耐酸性が低下し易くなる。一方、ＳｉＯ２の含有量が多過ぎると、軟化点が上昇して、ガラス粉末の軟化流動性が低下し易くなる。 SiO 2 is a component that forms a glass skeleton, is a crystal component of β-quartz solid solution, and is a component that enhances the water resistance and acid resistance of the glass matrix after crystal precipitation. The content of SiO 2 is 48 to 75%, preferably 50 to 68%, 52 to 66%, 54 to 64%, particularly 56 to 62%. If the content of SiO 2 is too small, the thermal stability becomes unduly low, and crystals tend to precipitate before the glass powder is sufficiently sintered. In addition, the β-quartz solid solution is difficult to precipitate during firing, and as a result, it is difficult to reduce the thermal expansion coefficient of the painted layer. Furthermore, the water resistance and acid resistance of the glass matrix after crystal precipitation tend to decrease. On the other hand, if the content of SiO 2 is too large, the softening point is raised, softening and fluidization of the glass powder is liable to lower.
　Ｂ２Ｏ３は、ガラス骨格を形成する成分であり、また熱膨張係数を上昇させずに、軟化点を低下させる成分である。Ｂ２Ｏ３の含有量は５～２３％であり、好ましくは７～１９％、９～１６％、１０～１４％、特に１０～１２％である。Ｂ２Ｏ３の含有量が少な過ぎると、熱的安定性が不当に低くなり、ガラス粉末が十分に焼結する前に結晶が析出し易くなる。更に軟化点が上昇して、ガラス粉末の軟化流動性が低下し易くなる。一方、Ｂ２Ｏ３の含有量が多過ぎると、結晶析出後のガラスマトリクスの耐水性、耐酸性が低下し易くなる。 B 2 O 3 is a component that forms a glass skeleton, and is a component that lowers the softening point without increasing the thermal expansion coefficient. The content of B 2 O 3 is 5 to 23%, preferably 7 to 19%, 9 to 16%, 10 to 14%, particularly 10 to 12%. If the content of B 2 O 3 is too small, the thermal stability is unduly lowered, and crystals tend to precipitate before the glass powder is sufficiently sintered. Furthermore, the softening point rises and the softening fluidity of the glass powder tends to decrease. On the other hand, when the content of B 2 O 3 is too large, the water resistance of the glass matrix after crystal precipitation, acid resistance tends to decrease.
　モル比ＳｉＯ２／Ｂ２Ｏ３は３．２３以上であり、好ましくは３．５以上、３．９以上４．２～１０、４．５～８、４．８～７、特に５～６である。モル比ＳｉＯ２／Ｂ２Ｏ３が小さ過ぎると、結晶析出後のガラスマトリクスの耐水性、耐酸性が低下し易くなり、絵付層の耐水性、耐酸性が低下し易くなる。一方、モル比ＳｉＯ２／Ｂ２Ｏ３が大き過ぎると、β－スポジュメン等の異種結晶が析出して、β－石英固溶体の析出量が低下し易くなる。 The molar ratio SiO 2 / B 2 O 3 is 3.23 or more, preferably 3.5 or more, 3.9 or more, 4.2 to 10, 4.5 to 8, 4.8 to 7, especially 5 to 6. It is. If the molar ratio SiO 2 / B 2 O 3 is too small, the water resistance and acid resistance of the glass matrix after crystal precipitation are likely to decrease, and the water resistance and acid resistance of the picture layer are likely to decrease. On the other hand, when the molar ratio SiO 2 / B 2 O 3 is too large, different types of crystals such as β-spodumene are precipitated, and the amount of β-quartz solid solution deposited tends to decrease.
　Ａｌ２Ｏ３は、β－石英固溶体の結晶構成成分であり、また耐酸性を高める成分である。Ａｌ２Ｏ３の含有量は５～２５％であり、好ましくは６～２０％、７～１６％、８～１３％、特に９～１１％である。Ａｌ２Ｏ３の含有量が少な過ぎると、焼成時にβ－石英固溶体が析出し難くなり、結果として絵付層の熱膨張係数を低下させ難くなる。Ａｌ２Ｏ３の含有量が多過ぎると、軟化点が上昇して、ガラス粉末の軟化流動性が低下し易くなる。 Al 2 O 3 is a crystal component of β-quartz solid solution and a component that improves acid resistance. The content of Al 2 O 3 is 5 to 25%, preferably 6 to 20%, 7 to 16%, 8 to 13%, particularly 9 to 11%. If the content of Al 2 O 3 is too small, β-quartz solid solution is difficult to precipitate during firing, and as a result, it is difficult to reduce the thermal expansion coefficient of the painted layer. When the content of Al 2 O 3 is too large, the softening point is raised, softening and fluidization of the glass powder is liable to lower.
　Ｌｉ２Ｏは、β－石英固溶体の結晶構成成分であり、また熱膨張係数を上昇させずに、軟化点を低下させる成分である。Ｌｉ２Ｏの含有量は５～３０％であり、好ましくは７～２５％、１０～２２％、１２～２０％、１３～１８％、特に１４～１６％である。Ｌｉ２Ｏの含有量が少な過ぎると、軟化点が上昇して、ガラス粉末の軟化流動性が低下し易くなる。更に焼成時にβ－石英固溶体が析出し難くなり、結果として絵付層の熱膨張係数を低下させ難くなる。一方、Ｌｉ２Ｏの含有量が多過ぎると、耐酸性が低下し易くなる。 Li 2 O is a crystal component of β-quartz solid solution and a component that lowers the softening point without increasing the thermal expansion coefficient. The content of Li 2 O is 5 to 30%, preferably 7 to 25%, 10 to 22%, 12 to 20%, 13 to 18%, particularly 14 to 16%. When the Li 2 O content is too small, the softening point is raised, softening and fluidization of the glass powder is liable to lower. Furthermore, the β-quartz solid solution is difficult to precipitate during firing, and as a result, it is difficult to reduce the thermal expansion coefficient of the painted layer. On the other hand, when the content of Li 2 O is too large, the acid resistance is likely to decrease.
　ＺｎＯは、熱膨張係数をあまり上昇させずに、軟化点を低下させる成分である。また結晶化を促進させる成分である。ＺｎＯの含有量は０～２５％であり、好ましくは０～２０％、０～１６％、１～１４％、２～１２％、３～１０％、特に４～７．６％である。また、異種結晶の析出を抑制しつつ、β－石英固溶体の析出量を増加させたい場合、ＺｎＯの含有量は０．１～７．６％、１～５％、特に１．５～３％である。ＺｎＯの含有量が多過ぎると、結晶析出後のガラスマトリクスの耐水性、耐酸性が低下し易くなり、更にＬｉ－Ｓｉ－Ｚｎ系の異種結晶が析出し易くなり、β－石英固溶体の析出量が低下し易くなる。 ZnO is a component that lowers the softening point without significantly increasing the thermal expansion coefficient. It is a component that promotes crystallization. The content of ZnO is 0 to 25%, preferably 0 to 20%, 0 to 16%, 1 to 14%, 2 to 12%, 3 to 10%, particularly 4 to 7.6%. Further, when it is desired to increase the precipitation amount of β-quartz solid solution while suppressing the precipitation of different crystals, the content of ZnO is 0.1 to 7.6%, 1 to 5%, particularly 1.5 to 3%. It is. If the ZnO content is too large, the water resistance and acid resistance of the glass matrix after crystal precipitation tend to decrease, and Li-Si-Zn-based heterogeneous crystals tend to precipitate, resulting in the precipitation of β-quartz solid solution. Tends to decrease.
　上記成分以外にも、例えば、以下の成分を導入してもよい。 In addition to the above components, for example, the following components may be introduced.
　Ｎａ２ＯとＫ２Ｏは、軟化点を低下させる成分であるが、その含有量が多過ぎると、焼成時にβ－石英固溶体が析出し難くなり、結果として絵付層の熱膨張係数を低下させ難くなる。更に耐酸性が低下し易くなる。よって、Ｎａ２ＯとＫ２Ｏの合量は、好ましくは０～８％未満、０～６％、０～４％、０～２％、特に０～１％未満である。Ｎａ２Ｏの含有量は、好ましくは０～８％未満、０～６％、０～４％、０～２％、特に０～１％未満である。Ｋ２Ｏの含有量は、好ましくは０～８％未満、０～６％、０～４％、０～２％、特に０～１％未満である。モル比Ｌｉ２Ｏ／（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）は、好ましくは０．５以上、０．６以上、０．７以上、０．８以上、特に０．９以上である。なお、「Ｌｉ２Ｏ／（Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ）」は、Ｌｉ２Ｏの含有量をＬｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの合量で割った値である。 Na 2 O and K 2 O are components that lower the softening point. However, if the content is too large, β-quartz solid solution is difficult to precipitate during firing, resulting in a decrease in the thermal expansion coefficient of the painted layer. It becomes difficult. Furthermore, acid resistance tends to decrease. Therefore, the total amount of Na 2 O and K 2 O is preferably 0 to less than 8%, 0 to 6%, 0 to 4%, 0 to 2%, particularly 0 to less than 1%. The content of Na 2 O is preferably 0-8%, 0-6%, 0-4%, 0-2%, especially 0-1%. The content of K 2 O is preferably 0-8%, 0-6%, 0-4%, 0-2%, especially 0-1%. The molar ratio Li 2 O / (Li 2 O + Na 2 O + K 2 O) is preferably 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, particularly 0.9 or more. “Li 2 O / (Li 2 O + Na 2 O + K 2 O)” is a value obtained by dividing the content of Li 2 O by the total amount of Li 2 O, Na 2 O and K 2 O.
　ＴｉＯ２とＺｒＯ２は、結晶性を高める成分であり、また結晶析出後のガラスマトリクスの耐水性、耐酸性を高める成分であるが、その含有量が多過ぎると、軟化点が上昇して、ガラス粉末の軟化流動性が低下し易くなる。更に熱的安定性が不当に低くなり、ガラス粉末が十分に焼結する前に結晶が析出し易くなる。ＴｉＯ２とＺｒＯ２の合量は、好ましくは０～１５％、０～１２％、０．１～１０％、１～８％、特に２～６％である。ＴｉＯ２の含有量は、好ましくは０～１５％、０～１２％、０．１～１０％、１～８％、特に２～６％である。ＺｒＯ２の含有量は、好ましくは０～１０％、０～５％、０～３％未満、０～２％、特に０～１％である。 TiO 2 and ZrO 2 are components that increase crystallinity, and are components that increase the water resistance and acid resistance of the glass matrix after crystal precipitation, but if its content is excessive, the softening point increases, The softening fluidity of the glass powder tends to decrease. Furthermore, the thermal stability is unduly lowered, and crystals tend to precipitate before the glass powder is sufficiently sintered. The total amount of TiO 2 and ZrO 2 is preferably 0-15%, 0-12%, 0.1-10%, 1-8%, especially 2-6%. The content of TiO 2 is preferably 0 to 15%, 0 to 12%, 0.1 to 10%, 1 to 8%, in particular 2 to 6%. The content of ZrO 2 is preferably 0 to 10%, 0 to 5%, 0 to less than 3%, 0 to 2%, especially 0 to 1%.
　ＭｇＯは、熱的安定性を高める成分である。ＭｇＯの含有量は、好ましくは０～７％、０～５％、０～３％、特に０～１％である。ＭｇＯの含有量が多過ぎると、軟化点が上昇して、ガラス粉末の軟化流動性が低下し易くなる。 MgO is a component that enhances thermal stability. The content of MgO is preferably 0-7%, 0-5%, 0-3%, especially 0-1%. When there is too much content of MgO, a softening point will raise and the softening fluidity | liquidity of glass powder will fall easily.
　ＢａＯは、熱的安定性を高める成分である。ＢａＯの含有量は、好ましくは０～７％、０～５％、特に０．１～３％である。ＢａＯの含有量が多過ぎると、熱膨張係数が不当に上昇して、絵付層の熱膨張係数を低下させ難くなる。 BaO is a component that enhances thermal stability. The content of BaO is preferably 0 to 7%, 0 to 5%, in particular 0.1 to 3%. When there is too much content of BaO, a thermal expansion coefficient will rise unduly and it will become difficult to reduce the thermal expansion coefficient of a painting layer.
　ＣｕＯは、ガラスを黒色に着色させるための成分である。ＣｕＯの含有量は、好ましくは０～７％、０～５％、０～３％、特に０～１％である。ＣｕＯの含有量が多過ぎると、熱的安定性が不当に低くなり、ガラス粉末が十分に焼結する前に結晶が析出し易くなる。 CuO is a component for coloring the glass black. The CuO content is preferably 0-7%, 0-5%, 0-3%, especially 0-1%. When there is too much content of CuO, thermal stability will become low unreasonably and it will become easy to precipitate a crystal | crystallization before glass powder fully sinters.
　上記成分以外にも、必要に応じて、他の成分を例えば１５％、１０％、５％、特に１％まで導入することができる。具体的には、ＣａＯ、ＳｒＯ、Ｃｒ２Ｏ３、ＭｎＯ、ＳｎＯ２、ＣｅＯ２、Ｐ２Ｏ５、Ｌａ２Ｏ３、Ｎｄ２Ｏ３、Ｃｏ２Ｏ３、Ｆ、Ｃｌ等を合量又は個別に、例えば１５％、１０％、５％、特に１％まで導入することができる。 In addition to the above components, other components can be introduced, for example, up to 15%, 10%, 5%, particularly 1%, if necessary. Specifically, CaO, SrO, Cr 2 O 3 , MnO, SnO 2 , CeO 2 , P 2 O 5 , La 2 O 3 , Nd 2 O 3 , Co 2 O 3 , F, Cl, etc. are combined or It can be introduced individually, for example up to 15%, 10%, 5%, in particular 1%.
　なお、環境的観点から、実質的にＰｂＯを含有させないことが好ましく、実質的にＢｉ２Ｏ３も含有させないことが好ましい。 Incidentally, from the environmental point of view, it is preferable to not contained substantially PbO, which preferably does not substantially Bi 2 O 3 is also contained.
　ガラス粉末の平均粒子径Ｄ５０は１５μｍ以下、０．５～１０μｍ、特に０．７～５μｍが好ましい。ガラス粉末の粒度が大き過ぎると、スクリーン印刷性が低下し易くなり、また絵付層の色調が不均一になり易い。ここで、「平均粒子径Ｄ５０」」とは、レーザー回折装置で測定した値を指し、レーザー回折法により測定した際の体積基準の累積粒度分布曲線において、その積算量が粒子の小さい方から累積して５０％である粒子径を表す（以下、同様）。 The average particle diameter D 50 of the glass powder is 15μm or less, 0.5 ~ 10 [mu] m, particularly 0.7 ~ 5 [mu] m is preferred. If the particle size of the glass powder is too large, the screen printability tends to be lowered, and the color tone of the picture layer tends to be uneven. Here, the “average particle diameter D 50” refers to a value measured with a laser diffractometer, and in the cumulative particle size distribution curve based on volume when measured by the laser diffraction method, the accumulated amount is from the smaller particle. The particle diameter is 50% cumulatively (hereinafter the same).
　マクロ型ＤＴＡ装置で測定したガラス粉末の軟化点は、好ましくは５５０～７００℃、５７０～６９５℃、５９０～６９０℃、特に６２０～６８５℃である。軟化点が低い程、焼成温度を低下させることが可能になり、無機顔料粉末の発色性が向上するが、軟化点が低過ぎると、他の特性、特に結晶析出後のガラスマトリクスの耐水性、耐酸性が低下し易くなる。一方、軟化点が高過ぎると、焼成温度が不当に上昇し、焼成コストを高騰させる虞がある。 The softening point of the glass powder measured with a macro DTA apparatus is preferably 550 to 700 ° C., 570 to 695 ° C., 590 to 690 ° C., particularly 620 to 685 ° C. As the softening point is lower, it becomes possible to lower the firing temperature and improve the color developability of the inorganic pigment powder, but if the softening point is too low, other characteristics, particularly the water resistance of the glass matrix after crystal precipitation, Acid resistance tends to decrease. On the other hand, if the softening point is too high, the firing temperature is unduly increased, which may increase the firing cost.
　マクロ型ＤＴＡ装置で測定したガラス粉末の結晶化温度は、好ましくは６５０～７５０℃、６６０～７４０℃、特に６７０～７３０℃である。結晶化温度が低過ぎると、焼成時にガラス粉末が十分に焼結する前に、結晶が析出してしまい、絵付層の緻密性が低下し易くなる。一方、結晶化温度が高過ぎると、焼成時に絵付層に結晶が析出し難くなり、絵付層の熱膨張係数を低下させることが困難になる。ここで、マクロ型ＤＴＡ装置で測定した結晶化温度は、図１に示す結晶析出による発熱ピーク温度（Ｔｃ）を指す。 The crystallization temperature of the glass powder measured with a macro type DTA apparatus is preferably 650 to 750 ° C., 660 to 740 ° C., particularly 670 to 730 ° C. When the crystallization temperature is too low, crystals are precipitated before the glass powder is sufficiently sintered at the time of firing, and the denseness of the painted layer is likely to be lowered. On the other hand, if the crystallization temperature is too high, it becomes difficult for crystals to precipitate in the painted layer during firing, and it becomes difficult to reduce the thermal expansion coefficient of the painted layer. Here, the crystallization temperature measured with the macro type DTA apparatus refers to the exothermic peak temperature (Tc) due to crystal precipitation shown in FIG.
　７００℃１０分間の焼成条件でガラス粉末を焼成した後の焼結体の熱膨張係数は、好ましくは２５×１０－７／℃以下、１５×１０－７／℃以下、１０×１０－７／℃以下、特に－１０×１０－７～５×１０－７／℃である。ガラス粉末の焼結体の熱膨張係数が高過ぎると、絵付層の熱膨張係数を低下させ難くなり、絵付層付き低膨張基板にクラックが発生し易くなる。また絵付層の脱落等も発生し易くなる。 The thermal expansion coefficient of the sintered body after firing the glass powder at 700 ° C. for 10 minutes is preferably 25 × 10 −7 / ° C. or less, 15 × 10 −7 / ° C. or less, 10 × 10 −7 / The temperature is not higher than ° C., particularly −10 × 10 −7 to 5 × 10 −7 / ° C. If the thermal expansion coefficient of the sintered glass powder is too high, it is difficult to lower the thermal expansion coefficient of the picture layer, and cracks are likely to occur in the low expansion substrate with the picture layer. In addition, dropping off of the picture layer is likely to occur.
　７００℃１０分間の条件でガラス粉末を焼成すると、主結晶としてβ－石英固溶体が析出することが好ましい。このようにすれば、絵付層の熱膨張係数が大幅に低下するため、絵付層付き低膨張基板にクラックが発生する事態を的確に防止することができる。 When the glass powder is fired at 700 ° C. for 10 minutes, β-quartz solid solution is preferably precipitated as the main crystal. By doing so, the coefficient of thermal expansion of the picture layer is significantly reduced, so that it is possible to accurately prevent the occurrence of cracks in the low expansion substrate with the picture layer.
　本発明の複合粉末は、少なくともガラス粉末と無機顔料粉末を含み、必要に応じて、耐火性フィラー粉末等を含む。ガラス粉末は、無機顔料粉末を分散させて、低膨張基板に固着させるための成分である。無機顔料粉末は、黒色等に着色させて、装飾性を高めるための成分である。耐火性フィラー粉末は、任意成分であり、機械的強度を高める成分であり、また熱膨張係数を調整するための成分である。なお、上記以外にも、発色性を高めるために、Ｃｕ粉末等の金属粉末を添加してもよい。 The composite powder of the present invention includes at least a glass powder and an inorganic pigment powder, and includes a refractory filler powder as necessary. Glass powder is a component for dispersing inorganic pigment powder and fixing it to a low expansion substrate. The inorganic pigment powder is a component for enhancing decoration by coloring black or the like. The refractory filler powder is an optional component, a component that increases mechanical strength, and a component for adjusting the thermal expansion coefficient. In addition to the above, a metal powder such as Cu powder may be added in order to improve the color developability.
　本発明の複合粉末は、ガラス粉末　５５～１００質量％、無機顔料粉末　０～４５質量％、耐火性フィラー粉末　０～４０質量％を含有することが好ましい。 The composite powder of the present invention preferably contains 55 to 100% by mass of glass powder, 0 to 45% by mass of inorganic pigment powder, and 0 to 40% by mass of refractory filler powder.
　ガラス粉末の含有量は、好ましくは５５～１００質量％、５５～９５質量％、５５～９０質量％、５５～８５質量％、６０～８０質量％、特に６５～７５質量％である。ガラス粉末の含有量が少な過ぎると、絵付層と低膨張基板の固着性が低下し易くなる。なお、ガラス粉末の含有量が多過ぎると、無機顔料粉末が相対的に少なくなり、絵付層の装飾性が低下し易くなる。 The content of the glass powder is preferably 55 to 100% by mass, 55 to 95% by mass, 55 to 90% by mass, 55 to 85% by mass, 60 to 80% by mass, particularly 65 to 75% by mass. When there is too little content of glass powder, the adhesiveness of a painting layer and a low expansion board | substrate will fall easily. In addition, when there is too much content of glass powder, inorganic pigment powder will decrease relatively and the decoration property of a painting layer will fall easily.
　無機顔料粉末の含有量は、好ましくは０～４５質量％、５～４５質量％、１０～４５質量％、１３～４５質量％、特に１５～３０質量％である。無機顔料粉末の含有量が少な過ぎると、装飾性が低下し易くなる。一方、無機顔料粉末の含有量が多過ぎると、ガラス粉末が相対的に少なくなり、絵付層と低膨張基板の固着性が低下し易くなる。更に無機顔料粉末の含有量が多過ぎると、絵付層の表面平滑性が低下して、絵付層の耐水性、耐酸性が低下し易くなる。 The content of the inorganic pigment powder is preferably 0 to 45% by mass, 5 to 45% by mass, 10 to 45% by mass, 13 to 45% by mass, particularly 15 to 30% by mass. If the content of the inorganic pigment powder is too small, the decorative property tends to be lowered. On the other hand, when the content of the inorganic pigment powder is too large, the glass powder becomes relatively small, and the adhesion between the picture layer and the low expansion substrate tends to be lowered. Furthermore, when there is too much content of inorganic pigment powder, the surface smoothness of a painting layer will fall and the water resistance and acid resistance of a painting layer will fall easily.
　無機顔料粉末は、種々の材料が使用可能であり、例えばＮｉＯ（緑色）、ＭｎＯ２（黒色）、ＣｏＯ（黒色）、Ｆｅ２Ｏ３（茶褐色）、Ｃｒ２Ｏ３（緑色）、ＴｉＯ２（白色）等の着色酸化物、Ｃｒ－Ａｌ系スピネル（ピンク色）、Ｓｎ－Ｓｂ－Ｖ系ルチル（グレー色）、Ｔｉ－Ｓｂ－Ｎｉ系ルチル（黄色）、Ｚｒ－Ｖ系バデライト（黄色）等の酸化物、Ｃｏ－Ｚｎ－Ａｌ系スピネル（青色）、Ｚｎ－Ｆｅ－Ｃｒ系スピネル（茶色）、Ｃｒ－Ｃｕ－Ｍｎ系スピネル等の複合酸化物、Ｃａ－Ｃｒ－Ｓｉ系ガーネット（ビクトリアグリーン色）、Ｃａ－Ｓｎ－Ｓｉ－Ｃｒ系スフェイン（ピンク色）、Ｚｒ－Ｓｉ－Ｆｅ系ジルコン（サーモンピンク色）、Ｃｏ－Ｚｎ－Ｓｉ系ウイレマイト（紺青色）、Ｃｏ－Ｓｉ系カンラン石（紺青色）等のケイ酸塩があり、これらは所望の色を得るように、上記の割合で混合することができる。また、上記無機顔料粉末の他に、例えば、絵付層の隠蔽性及び耐磨耗性を向上させるために、ＺｒＳｉＯ4やタルク等を適量混合させてもよい。 Various materials can be used as the inorganic pigment powder. For example, NiO (green), MnO 2 (black), CoO (black), Fe 2 O 3 (brown), Cr 2 O 3 (green), TiO 2 ( White oxide), Cr—Al spinel (pink), Sn—Sb—V rutile (gray), Ti—Sb—Ni rutile (yellow), Zr—V badelite (yellow), etc. Oxides, Co—Zn—Al spinel (blue), complex oxides such as Zn—Fe—Cr spinel (brown), Cr—Cu—Mn spinel, Ca—Cr—Si garnet (Victoria Green color) ), Ca—Sn—Si—Cr sphene (pink), Zr—Si—Fe zircon (salmon pink), Co—Zn—Si willemite (dark blue), Co—Si olivine (dark blue) )etc There are silicates, which are to obtain the desired color can be mixed in the above ratio. In addition to the above inorganic pigment powder, for example, an appropriate amount of ZrSiO 4 or talc may be mixed in order to improve the concealability and abrasion resistance of the painting layer.
　無機顔料粉末の平均粒子径Ｄ５０は９μｍ以下、特に０．５～４μｍが好ましい。無機顔料粉末の最大粒子径Ｄｍａｘは１０μｍ以下、特に２～８μｍが好ましい。無機顔料粉末の粒度が大き過ぎると、スクリーン印刷性が低下し易くなり、また絵付層の発色性が低下し易くなる。 The average particle diameter D 50 of the inorganic pigment powder is 9μm or less, particularly 0.5 ~ 4 [mu] m is preferred. The maximum particle diameter Dmax of the inorganic pigment powder is preferably 10 μm or less, particularly preferably 2 to 8 μm. If the particle size of the inorganic pigment powder is too large, the screen printability tends to be lowered, and the color developability of the coated layer tends to be lowered.
　耐火性フィラー粉末の含有量は、好ましくは０～４０質量％、０～２０質量％、０～１５質量％、０～１０質量％、０～５質量％、０～１質量％、特に０～０．１質量％未満である。耐火性フィラー粉末の含有量が多過ぎると、絵付層と低膨張基板の固着性が低下し易くなる。 The content of the refractory filler powder is preferably 0 to 40% by mass, 0 to 20% by mass, 0 to 15% by mass, 0 to 10% by mass, 0 to 5% by mass, 0 to 1% by mass, especially 0 to It is less than 0.1% by mass. When there is too much content of a refractory filler powder, the adhesiveness of a picture layer and a low expansion board will fall easily.
　耐火性フィラー粉末として、コーディエライト、ウイレマイト、アルミナ、リン酸ジルコニウム、ジルコン、ジルコニア、酸化スズ、ムライト、シリカ、β－ユークリプタイト、β－スポジュメン、β－石英固溶体、リン酸タングステン酸ジルコニウム等が使用可能である。 As refractory filler powder, cordierite, willemite, alumina, zirconium phosphate, zircon, zirconia, tin oxide, mullite, silica, β-eucryptite, β-spodumene, β-quartz solid solution, zirconium tungstate phosphate, etc. Can be used.
　本発明の複合粉末は、ビークルと混合して、複合粉末ペーストとして使用に供される。ビークルは、主に溶媒と樹脂で構成される。溶媒は、樹脂を溶解させつつ、複合粉末を均一に分散させる目的で添加される。樹脂は、ペーストの粘性を調整する目的で添加される。また、必要に応じて、界面活性剤、増粘剤等を添加することもできる。 The composite powder of the present invention is mixed with a vehicle and used as a composite powder paste. The vehicle is mainly composed of a solvent and a resin. The solvent is added for the purpose of uniformly dispersing the composite powder while dissolving the resin. The resin is added for the purpose of adjusting the viscosity of the paste. Moreover, surfactant, a thickener, etc. can also be added as needed.
　樹脂として、アクリル酸エステル（アクリル樹脂）、エチルセルロース、ポリエチレングリコール誘導体、ニトロセルロース、ポリメチルスチレン、ポリエチレンカーボネート、メタクリル酸エステル等が使用可能である。特に、アクリル酸エステル、エチルセルロースは、熱分解性が良好であるため、好ましい。 As the resin, acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used. In particular, acrylic acid ester and ethyl cellulose are preferable because they have good thermal decomposability.
　溶媒として、パインオイル、Ｎ、Ｎ’－ジメチルホルムアミド（ＤＭＦ）、α－ターピネオール、高級アルコール、γ－ブチルラクトン（γ－ＢＬ）、テトラリン、ブチルカルビトールアセテート、酢酸エチル、酢酸イソアミル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ベンジルアルコール、トルエン、３－メトキシ－３－メチルブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、プロピレンカーボネート、Ｎ－メチル－２－ピロリドン等が使用可能である。特に、α－ターピネオールは、高粘性であり、樹脂等の溶解性も良好であるため、好ましい。 Solvents include pine oil, N, N′-dimethylformamide (DMF), α-terpineol, higher alcohol, γ-butyllactone (γ-BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl Ether, diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , Tripropylene glycol monobutyl ether, propylene carbonate, N-methyl-2-pyrrolidone There can be used. In particular, α-terpineol is preferable because it is highly viscous and has good solubility in resins and the like.
　複合粉末ペーストは、例えば、複合粉末とビークルを混合した後、３本ロールミルで均一に混練することにより作製される。 The composite powder paste is produced, for example, by mixing the composite powder and the vehicle and then uniformly kneading with a three-roll mill.
　複合材料ペーストは、スクリーン印刷機等の塗布機を用いて低膨張基板上に塗布された後、乾燥工程、焼成工程に供される。これにより、低膨張基板の表面に絵付層を形成することができる。乾燥工程の条件は、７０～１５０℃で１０～６０分間が一般的である。焼成工程は、樹脂を分解揮発させると共に、複合粉末を焼結させて、低膨張基板の表面に絵付層を固着させる工程である。焼成工程の条件は、６５０～８５０℃で５～３０分間が一般的である。焼成工程で焼成温度が低い程、生産効率が向上すると共に、無機顔料粉末の発色性が向上するが、その一方で絵付層と低膨張基板の固着性が低下する。 The composite material paste is applied to a low expansion substrate using a coating machine such as a screen printer, and then subjected to a drying process and a baking process. As a result, a picture layer can be formed on the surface of the low expansion substrate. The drying process is generally performed at 70 to 150 ° C. for 10 to 60 minutes. The firing step is a step in which the resin is decomposed and volatilized and the composite powder is sintered to adhere the picture layer to the surface of the low expansion substrate. The conditions for the firing step are generally 650 to 850 ° C. and 5 to 30 minutes. The lower the calcination temperature in the calcination step, the better the production efficiency and the color developability of the inorganic pigment powder. On the other hand, the adhesion between the picture layer and the low expansion substrate decreases.
　本発明の絵付層付き低膨張基板は、低膨張基板の表面に絵付層を有する絵付層付き低膨張基板であって、絵付層が複合粉末の焼結体であり、且つ複合粉末が上記の複合粉末であることが好ましい。本発明の絵付層付き低膨張基板は、本発明の複合粉末の技術的特徴を含むが、その内容は記載済みであるため、便宜上、その説明を省略する。 The low-expansion substrate with a picture layer of the present invention is a low-expansion board with a picture layer having a picture layer on the surface of the low-expansion board, wherein the picture layer is a sintered body of a composite powder, and the composite powder is the above composite A powder is preferred. Although the low expansion board | substrate with a painting layer of this invention contains the technical feature of the composite powder of this invention, since the content has already been described, the description is abbreviate | omitted for convenience.
　本発明の絵付層付き低膨張基板は、絵付層にβ－石英固溶体が析出していることが好ましい。このようにすれば、絵付層の熱膨張係数が大幅に低下するため、絵付層付き低膨張基板にクラックが発生する事態を的確に防止することができる。 In the low expansion substrate with a picture layer of the present invention, it is preferable that a β-quartz solid solution is deposited on the picture layer. By doing so, the coefficient of thermal expansion of the picture layer is significantly reduced, so that it is possible to accurately prevent the occurrence of cracks in the low expansion substrate with the picture layer.
　本発明の絵付層付き低膨張基板において、低膨張基板は、結晶化ガラス基板（特に透明結晶化ガラス基板）が好ましく、また主結晶としてβ－石英固溶体が析出していることも好ましい。このようにすれば、加熱耐久性、耐熱衝撃性を高めることができる。 In the low expansion substrate with a picture layer of the present invention, the low expansion substrate is preferably a crystallized glass substrate (especially a transparent crystallized glass substrate), and it is also preferable that a β-quartz solid solution is precipitated as the main crystal. In this way, heat durability and thermal shock resistance can be improved.
　結晶化ガラス基板の熱膨張係数は、－１０×１０－７～３０×１０－７／℃、特に－５×１０－７～１０×１０－７／℃が好ましい。結晶化ガラス基板の熱膨張係数を低下させると、結晶化ガラス基板の加熱耐久性、耐熱衝撃性が向上する。その結果、使用時に急加熱、急冷却による熱衝撃が加わる調理器用トッププレートに好適となる。なお、調理器としては、電磁調理器、電気調理器、ガス調理器等がある。 The thermal expansion coefficient of the crystallized glass substrate is preferably −10 × 10 −7 to 30 × 10 −7 / ° C., particularly preferably −5 × 10 −7 to 10 × 10 −7 / ° C. Decreasing the thermal expansion coefficient of the crystallized glass substrate improves the heat durability and thermal shock resistance of the crystallized glass substrate. As a result, it is suitable for a top plate for a cooker to which a thermal shock due to rapid heating and rapid cooling is applied during use. Note that examples of the cooking device include an electromagnetic cooking device, an electric cooking device, and a gas cooking device.
　本発明の絵付層付き低膨張基板において、絵付層の厚みは１～３０μｍ、特に２～１０μｍが好ましい。絵付層の厚みが小さ過ぎると、絵付の模様が不明確になる虞がある。一方、絵付層の厚みが厚過ぎると、絵付の模様にクラックが発生する虞がある。 In the low expansion substrate with a picture layer of the present invention, the thickness of the picture layer is preferably 1 to 30 μm, particularly preferably 2 to 10 μm. If the thickness of the picture layer is too small, the picture pattern may become unclear. On the other hand, if the thickness of the picture layer is too thick, cracks may occur in the picture pattern.
　以下、実施例に基づいて、本発明を説明する。なお、以下の実施例は、単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, the present invention will be described based on examples. The following examples are merely illustrative. The present invention is not limited to the following examples.
　表１は、本発明の実施例（試料Ｎｏ．１～９）及び比較例（試料Ｎｏ．１０、１１）を示している。 Table 1 shows Examples (Sample Nos. 1 to 9) and Comparative Examples (Sample Nos. 10 and 11) of the present invention.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　まず表中に記載のガラス組成になるように、原料を調合し、均一に混合し、ガラスバッチを得た後、ガラスバッチを白金坩堝に入れて、１４００℃で３時間溶融した。その後、溶融ガラスをフィルム状に成形した。続いて、得られたガラスフィルムをボールミルにて粉砕した後、空気分級して、平均粒子径Ｄ５０が２．５μｍのガラス粉末を得た。 First, raw materials were blended and mixed uniformly so as to have the glass composition described in the table. After obtaining a glass batch, the glass batch was placed in a platinum crucible and melted at 1400 ° C. for 3 hours. Thereafter, the molten glass was formed into a film. Subsequently, the obtained glass film was pulverized in a ball mill, and air classification, the average particle diameter D 50 was obtained glass powder 2.5 [mu] m.
　各ガラス粉末について、マクロ型ＤＴＡ装置を用いて、軟化点及び結晶化温度を測定した。ここで、測定は、空気中で行い、昇温速度を１０℃／分とした。なお、軟化点は、第四変曲点の温度を指しており、結晶化温度は、結晶析出による発熱ピーク温度を指している。 For each glass powder, the softening point and the crystallization temperature were measured using a macro DTA apparatus. Here, the measurement was performed in air, and the rate of temperature increase was 10 ° C./min. The softening point indicates the temperature of the fourth inflection point, and the crystallization temperature indicates the exothermic peak temperature due to crystal precipitation.
　主結晶は、ガラス粉末の圧粉体を７００℃１０分間の焼成条件で緻密に焼結させた後、所定形状に加工したものを測定試料とし、Ｘ線回折法で測定した時に、ピーク強度が最も大きかった結晶である。 The main crystal has a peak intensity when measured by X-ray diffractometry using a glass powder compact that has been densely sintered at 700 ° C. for 10 minutes and then processed into a predetermined shape. The largest crystal.
　ガラス粉末の熱膨張係数は、ＴＭＡ装置を用いて、３０～３５０℃の温度範囲で測定した値である。ここで、測定試料として、ガラス粉末の圧粉体を７００℃１０分間の焼成条件で緻密に焼結させた後、所定形状に加工したものを用いた。 The thermal expansion coefficient of the glass powder is a value measured in a temperature range of 30 to 350 ° C. using a TMA apparatus. Here, as a measurement sample, a green powder compact was sintered precisely at 700 ° C. for 10 minutes and then processed into a predetermined shape.
　以下のようにしてガラス粉末の耐水性を評価した。すなわち、ガラス粉末の圧粉体を７００℃１０分間の焼成条件で緻密に焼結させた後、所定形状に加工したものを測定試料とし、１００℃（←更正、９０℃）の水に２時間浸漬した時に、外観変化が認められなかったものを「○」、外観変化が認められたものを「×」として評価した。 The water resistance of the glass powder was evaluated as follows. That is, a glass powder green compact is sintered precisely at 700 ° C. for 10 minutes and then processed into a predetermined shape as a measurement sample, and water in 100 ° C. (← corrected, 90 ° C.) for 2 hours. When immersed, the case where the appearance change was not recognized was evaluated as “◯”, and the case where the appearance change was recognized was evaluated as “x”.
　次に、ガラス粉末と無機顔料粉末を表中に記載の割合（合計１００％）で混合し、複合粉末を得た。ここで、無機顔料粉末として、Ｃｒ－Ｃｕ－Ｍｎ系複合酸化物（平均粒径Ｄ５０が１．５μｍ、最大粒径Ｄｍａｘが４．０μｍ）を用いた。 Next, the glass powder and the inorganic pigment powder were mixed at a ratio (100% in total) described in the table to obtain a composite powder. Here, as the inorganic pigment powder, Cr—Cu—Mn composite oxide (average particle diameter D 50 is 1.5 μm, maximum particle diameter D max is 4.0 μm) was used.
　更に、得られた複合粉末とビークルを混合後、３本ロールミルで均一に混練し、複合粉末ペーストを得た。なお、ビークルとして、エチルセルロースをα－テルピネオールに溶解させたものを用い、質量比で複合粉末／ビークルを２～３に調整した。 Furthermore, the obtained composite powder and vehicle were mixed and then uniformly kneaded with a three-roll mill to obtain a composite powder paste. As the vehicle, ethyl cellulose dissolved in α-terpineol was used, and the composite powder / vehicle was adjusted to 2 to 3 by mass ratio.
　続いて、複合粉末ペーストを１０ｃｍ角の透明結晶化ガラス基板（日本電気硝子株式会社製Ｎ－０、主結晶：β－石英固溶体）の片面全体にスクリーン印刷した後、１２０℃で２０分間乾燥した上で、７００℃の電気炉に投入して、１０分間焼成し、室温まで自然冷却することにより、厚み１０μｍの絵付層付き透明結晶化ガラス基板を得た。 Subsequently, the composite powder paste was screen-printed on the entire surface of a 10 cm square transparent crystallized glass substrate (N-0 manufactured by Nippon Electric Glass Co., Ltd., main crystal: β-quartz solid solution) and then dried at 120 ° C. for 20 minutes. Above, it put into the 700 degreeC electric furnace, baked for 10 minutes, and naturally cooled to room temperature, and obtained the transparent crystallized glass substrate with a 10-micrometer-thick painting layer.
　クラックの有無は、絵付層付き透明結晶化ガラス基板を観察して、クラックが認められなかったものを「○」、クラックが認められたものを「×」として評価した。 The presence / absence of cracks was evaluated by observing a transparent crystallized glass substrate with a picture layer, with “◯” indicating that no crack was observed and “×” indicating that a crack was observed.
　耐摩耗性は、＃１０００のサンドペーパーを用いて、絵付層を荷重１．３ｋｇ、片道１００ｍｍ／秒の速度で１００回往復した後、絵付層が剥離しなかったものを「○」、絵付層が剥離したものを「×」として評価した。 Abrasion resistance is “○” when the coated layer did not peel off after reciprocating 100 times with a load of 1.3 kg and a speed of 100 mm / second one way using # 1000 sandpaper. What peeled was evaluated as "x".
　絵付層の耐水性は、９０℃の水に２４時間浸漬した時に、絵付層に外観変化が認められなかったものを「○」、外観変化が僅かに認められたものを「△」、外観変化が明確に認められたものを「×」として評価した。 The water resistance of the pictured layer is “○” when the appearance change was not observed in the pictured layer when immersed in water at 90 ° C. for 24 hours, and “△” when the appearance change was slightly recognized. Was clearly recognized as “×”.
　絵付層の耐酸性は、４０℃の０．１質量％ＨＣｌ水溶液に１時間浸漬した時に、絵付層に外観変化が認められなかったものを「○」、外観変化が僅かに認められたものを「△」、外観変化が明確に認められたものを「×」として評価した。 The acid resistance of the pictured layer is “○” when no change in appearance was observed in the pictured layer when immersed in a 0.1% by mass HCl aqueous solution at 40 ° C. for 1 hour, and a slight change in appearance was observed. “△” and those with a clear change in appearance were evaluated as “x”.
　表１から明らかなように、試料Ｎｏ．１～９は、熱膨張係数が低く、耐水性、耐酸性の評価が良好であった。一方、試料Ｎｏ．１０は、モル比ＳｉＯ２／Ｂ２Ｏ３が小さかったため、耐水性、耐酸性の評価が不良であった。また、試料Ｎｏ．１１は、焼成後に結晶が析出せず、絵付層付き透明結晶化ガラス基板とした場合に、クラックが発生した。 As is clear from Table 1, sample No. Nos. 1 to 9 had a low coefficient of thermal expansion and good evaluation of water resistance and acid resistance. On the other hand, sample No. No. 10 was poor in evaluation of water resistance and acid resistance because the molar ratio SiO 2 / B 2 O 3 was small. Sample No. In No. 11, no crystal precipitated after firing, and cracks occurred when a transparent crystallized glass substrate with a picture layer was used.
　表２は、本発明の実施例（試料Ｎｏ．１２～１６）を示している。 Table 2 shows examples (sample Nos. 12 to 16) of the present invention.
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　まず表中に記載のガラス組成になるように、原料を調合し、均一に混合し、ガラスバッチを得た後、ガラスバッチを白金坩堝に入れて、１４００℃で３時間溶融した。その後、溶融ガラスをフィルム状に成形した。続いて、得られたガラスフィルムをボールミルにて粉砕した後、空気分級して、平均粒子径Ｄ５０が２．５μｍのガラス粉末を得た。 First, raw materials were blended and mixed uniformly so as to have the glass composition described in the table. After obtaining a glass batch, the glass batch was placed in a platinum crucible and melted at 1400 ° C. for 3 hours. Thereafter, the molten glass was formed into a film. Subsequently, the obtained glass film was pulverized in a ball mill, and air classification, the average particle diameter D 50 was obtained glass powder 2.5 [mu] m.
　各ガラス粉末について、マクロ型ＤＴＡ装置を用いて、軟化点及び結晶化温度を測定した。ここで、測定は、空気中で行い、昇温速度を１０℃／分とした。なお、軟化点は、第四変曲点の温度を指しており、結晶化温度は、結晶析出による発熱ピーク温度を指している。 For each glass powder, the softening point and the crystallization temperature were measured using a macro DTA apparatus. Here, the measurement was performed in air, and the rate of temperature increase was 10 ° C./min. The softening point indicates the temperature of the fourth inflection point, and the crystallization temperature indicates the exothermic peak temperature due to crystal precipitation.
　主結晶は、ガラス粉末の圧粉体を７００℃１０分間の焼成条件で緻密に焼結させた後、所定形状に加工したものを測定試料とし、Ｘ線回折法で測定した時に、ピーク強度が最も大きかった結晶である。なお、試料Ｎｏ．１１～１５の内、試料Ｎｏ．１５がβ－石英固溶体の析出量が最も多く、異種結晶（β－スポジュメン）の析出量が最も少なかった。 The main crystal has a peak intensity when measured by X-ray diffractometry using a glass powder compact that has been densely sintered at 700 ° C. for 10 minutes and then processed into a predetermined shape. The largest crystal. Sample No. Among samples 11 to 15, sample no. No. 15 had the highest precipitation amount of β-quartz solid solution and the lowest precipitation amount of heterogeneous crystals (β-spodumene).
　ガラス粉末の熱膨張係数は、ＴＭＡ装置を用いて、３０～３５０℃の温度範囲で測定した値である。ここで、測定試料として、ガラス粉末の圧粉体を表中の焼成条件で緻密に焼結させた後、所定形状に加工したものを用いた。 The thermal expansion coefficient of the glass powder is a value measured in a temperature range of 30 to 350 ° C. using a TMA apparatus. Here, as a measurement sample, a green powder compact was sintered precisely under the firing conditions in the table and then processed into a predetermined shape.
　以下のようにしてガラス粉末の耐水性を評価した。すなわち、ガラス粉末の圧粉体を７００℃１０分間の焼成条件で緻密に焼結させた後、所定形状に加工したものを測定試料とし、９０℃の水に２時間浸漬した時に、外観変化が認められなかったものを「○」、外観変化が認められたものを「×」として評価した。 The water resistance of the glass powder was evaluated as follows. That is, when a green powder compact is densely sintered at 700 ° C. for 10 minutes and then processed into a predetermined shape as a measurement sample, the appearance changes when immersed in water at 90 ° C. for 2 hours. Those that were not recognized were evaluated as “◯”, and those that had a change in appearance were evaluated as “×”.
　次に、ガラス粉末と無機顔料粉末を表中に記載の割合（合計１００％）で混合し、複合粉末を得た。ここで、無機顔料粉末として、Ｃｒ－Ｃｕ－Ｍｎ系複合酸化物（平均粒径Ｄ５０が１．５μｍ、最大粒径Ｄｍａｘが４．０μｍ）を用いた。 Next, the glass powder and the inorganic pigment powder were mixed at a ratio (100% in total) described in the table to obtain a composite powder. Here, as the inorganic pigment powder, Cr—Cu—Mn composite oxide (average particle diameter D 50 is 1.5 μm, maximum particle diameter D max is 4.0 μm) was used.
　更に、得られた複合粉末とビークルを混合後、３本ロールミルで均一に混練し、複合粉末ペーストを得た。なお、ビークルとして、エチルセルロースをα－テルピネオールに溶解させたものを用い、質量比で複合粉末／ビークルを２～３に調整した。 Furthermore, the obtained composite powder and vehicle were mixed and then uniformly kneaded with a three-roll mill to obtain a composite powder paste. As the vehicle, ethyl cellulose dissolved in α-terpineol was used, and the composite powder / vehicle was adjusted to 2 to 3 by mass ratio.
　続いて、複合粉末ペーストを１０ｃｍ角の透明結晶化ガラス基板（日本電気硝子株式会社製Ｎ－０、主結晶：β－石英固溶体）の片面全体にスクリーン印刷した後、１２０℃で２０分間乾燥した上で、７００℃の電気炉に投入して、１０分間焼成し、室温まで自然冷却することにより、厚み１０μｍの絵付層付き透明結晶化ガラス基板を得た。 Subsequently, the composite powder paste was screen-printed on the entire surface of a 10 cm square transparent crystallized glass substrate (N-0 manufactured by Nippon Electric Glass Co., Ltd., main crystal: β-quartz solid solution) and then dried at 120 ° C. for 20 minutes. Above, it put into the 700 degreeC electric furnace, baked for 10 minutes, and naturally cooled to room temperature, and obtained the transparent crystallized glass substrate with a 10-micrometer-thick painting layer.
　クラックの有無は、絵付層付き透明結晶化ガラス基板を観察して、クラックが認められなかったものを「○」、クラックが認められたものを「×」として評価した。 The presence / absence of cracks was evaluated by observing a transparent crystallized glass substrate with a picture layer, with “◯” indicating that no crack was observed and “×” indicating that a crack was observed.
　耐摩耗性は、＃１０００のサンドペーパーを用いて、絵付層を荷重１．３ｋｇ、片道１００ｍｍ／秒の速度で１００回往復した後、絵付層が剥離しなかったものを「○」、絵付層が剥離したものを「×」として評価した。 Abrasion resistance is “○” when the coated layer did not peel off after reciprocating 100 times with a load of 1.3 kg and a speed of 100 mm / second one way using # 1000 sandpaper. What peeled was evaluated as "x".
　絵付層の耐水性は、９０℃の水に２４時間浸漬した時に、絵付層に外観変化が認められなかったものを「○」、外観変化が僅かに認められたものを「△」、外観変化が明確に認められたものを「×」として評価した。 The water resistance of the pictured layer is “○” when the appearance change was not observed in the pictured layer when immersed in water at 90 ° C. for 24 hours, and “△” when the appearance change was slightly recognized. Was clearly recognized as “×”.
　絵付層の耐酸性は、４０℃の０．１質量％ＨＣｌ水溶液に１時間浸漬した時に、絵付層に外観変化が認められなかったものを「○」、外観変化が僅かに認められたものを「△」、外観変化が明確に認められたものを「×」として評価した。 The acid resistance of the pictured layer is “○” when no change in appearance was observed in the pictured layer when immersed in a 0.1% by mass HCl aqueous solution at 40 ° C. for 1 hour, and a slight change in appearance was observed. “△” and those with a clear change in appearance were evaluated as “x”.
　表２から明らかなように、試料Ｎｏ．１１～１５は、熱膨張係数が低く、耐水性、耐酸性の評価が良好であった。特に、試料Ｎｏ．１１、１３、１５は、ガラス組成中にＺｎＯを少量含むため、焼成温度が変動しても、熱膨張係数の変動幅が小さかった。つまり熱膨張係数の焼成温度依存性が小さかった。 As is clear from Table 2, the sample No. Nos. 11 to 15 had low thermal expansion coefficients and good evaluations of water resistance and acid resistance. In particular, sample no. Since 11, 13 and 15 contained a small amount of ZnO in the glass composition, the fluctuation range of the thermal expansion coefficient was small even if the firing temperature fluctuated. That is, the firing temperature dependence of the thermal expansion coefficient was small.
　本発明は、ガラス粉末、複合粉末及び絵付層付き低膨張基板は、絵付層を有する調理器用トッププレート等に好適であるが、石英基板、Ｓｉ３Ｎ４基板等の低膨張基板の被覆、封着等の用途にも応用可能である。なお、本発明の複合粉末を封着、被覆等の用途に適用する場合は、無機顔料粉末を導入しなくてもよく、代わりに、機械的強度を高めるために、耐火性フィラー粉末を０．１質量％以上導入してもよい。 In the present invention, the glass powder, the composite powder, and the low-expansion substrate with a picture layer are suitable for a top plate for a cooker having a picture layer, but the coating, sealing and sealing of a low-expansion board such as a quartz substrate and an Si 3 N 4 substrate are possible. It can also be applied to uses such as wearing. In addition, when applying the composite powder of the present invention to applications such as sealing and coating, it is not necessary to introduce inorganic pigment powder. 1% by mass or more may be introduced.

Claims (15)

  1. 　ガラス組成として、モル％で、ＳｉＯ２　４８～７５％、Ｂ２Ｏ３　５～２３％、Ａｌ２Ｏ３　５～２５％、Ｌｉ２Ｏ　５～３０％、ＺｎＯ　０～２５％を含有し、モル比ＳｉＯ２／Ｂ２Ｏ３が３．２３以上であることを特徴とするガラス粉末。 As a glass composition, it contains SiO 2 48 to 75%, B 2 O 3 5 to 23%, Al 2 O 3 5 to 25%, Li 2 O 5 to 30%, ZnO 0 to 25% in mol%. A glass powder having a molar ratio SiO 2 / B 2 O 3 of 3.23 or more.
  2. 　ガラス組成中のＢ２Ｏ３の含有量が１６モル％以下であることを特徴とする請求項１に記載のガラス粉末。 The glass powder according to claim 1, wherein the content of B 2 O 3 in the glass composition is 16 mol% or less.
  3. 　ガラス組成中のＺｎＯの含有量が０．１～７．６モル％であることを特徴とする請求項１又は２に記載のガラス粉末。 The glass powder according to claim 1 or 2, wherein the content of ZnO in the glass composition is 0.1 to 7.6 mol%.
  4. 　ガラス組成中に更にＴｉＯ２とＺｒＯ２を合量で０．１～１５モル％含むことを特徴とする請求項１～３の何れかに記載のガラス粉末。 The glass powder according to any one of claims 1 to 3, wherein the glass composition further contains TiO 2 and ZrO 2 in a total amount of 0.1 to 15 mol%.
  5. 　ガラス組成中に実質的にＰｂＯとＢｉ２Ｏ３を含まないことを特徴とする請求項１～４の何れかに記載のガラス粉末。 The glass powder according to any one of claims 1 to 4, wherein the glass composition is substantially free of PbO and Bi 2 O 3 .
  6. 　７００℃１０分間の条件で焼成した後の熱膨張係数が２５×１０－７／℃以下であることを特徴とする請求項１～５の何れかに記載のガラス粉末。 6. The glass powder according to claim 1, wherein the glass powder has a thermal expansion coefficient of 25 × 10 −7 / ° C. or less after firing at 700 ° C. for 10 minutes.
  7. 　７００℃１０分間の条件で焼成すると、主結晶としてβ－石英固溶体が析出することを特徴とする請求項１～６の何れかに記載のガラス粉末。 The glass powder according to any one of claims 1 to 6, wherein β-quartz solid solution is precipitated as a main crystal when fired at 700 ° C for 10 minutes.
  8. 　マクロ型ＤＴＡ装置で測定した軟化点が５５０～７００℃であることを特徴とする請求項１～７の何れかに記載のガラス粉末。 The glass powder according to any one of claims 1 to 7, wherein the softening point measured with a macro DTA apparatus is 550 to 700 ° C.
  9. 　ガラス粉末　５５～１００質量％、無機顔料粉末　０～４５質量％、耐火性フィラー粉末　０～４０質量％を含有する複合粉末であって、
    　ガラス粉末が、請求項１～８の何れかに記載のガラス粉末であることを特徴とする複合粉末。     A composite powder containing 55 to 100% by weight of glass powder, 0 to 45% by weight of inorganic pigment powder, and 0 to 40% by weight of refractory filler powder,
    A composite powder, wherein the glass powder is the glass powder according to any one of claims 1 to 8.
  10. 　無機顔料粉末がＣｒ-Ｃｕ系複合酸化物であることを特徴とする請求項９に記載の複合粉末。 The composite powder according to claim 9, wherein the inorganic pigment powder is a Cr—Cu composite oxide.
  11. 　低膨張基板の表面に絵付層を有する絵付層付き低膨張基板であって、
    　絵付層が複合粉末の焼結体であり、且つ複合粉末が請求項９又は１０に記載の複合粉末であることを特徴とする絵付層付き低膨張基板。     A low expansion substrate with a picture layer having a picture layer on the surface of the low expansion board,
    A low expansion substrate with a picture layer, wherein the picture layer is a sintered body of the composite powder, and the composite powder is the composite powder according to claim 9 or 10.
  12. 　絵付層にβ－石英固溶体が析出していることを特徴とする請求項１１に記載の絵付層付き低膨張基板。 The low expansion substrate with a picture layer according to claim 11, wherein β-quartz solid solution is deposited on the picture layer.
  13. 　低膨張基板が透明結晶化ガラス基板であり、且つ主結晶としてβ－石英固溶体が析出していることを特徴とする請求項１１又は１２に記載の絵付層付き低膨張基板。 13. The low expansion substrate with a picture layer according to claim 11 or 12, wherein the low expansion substrate is a transparent crystallized glass substrate, and β-quartz solid solution is precipitated as a main crystal.
  14. 　低膨張基板が石英基板であることを特徴とする請求項１１又は１２に記載の絵付層付き低膨張基板。 The low expansion substrate with a picture layer according to claim 11 or 12, wherein the low expansion substrate is a quartz substrate.
  15. 　調理器用トッププレートに用いることを特徴とする請求項１１～１３の何れかに記載の絵付層付き低膨張基板。 The low expansion substrate with a picture layer according to any one of claims 11 to 13, which is used for a top plate for a cooking device.
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JP2018035008A (en) * 2016-08-29 2018-03-08 日本電気硝子株式会社 Joined body and production method thereof
WO2019177112A1 (en) * 2018-03-16 2019-09-19 デンカ株式会社 Powder and mixed powder

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JPWO2019177112A1 (en) * 2018-03-16 2021-03-11 デンカ株式会社 Powder and mixed powder
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