JP6260770B2 - Glass, glass powder, composite powder and glass plate with colored layer - Google Patents

Description

  TECHNICAL FIELD The present invention relates to glass, glass powder, composite powder, and a glass plate with a colored layer. Specifically, the inner peripheral edge of an automobile window glass, a train window glass, a residential window glass (hereinafter referred to as an automobile window glass, etc.). The present invention relates to glass, a glass powder, a composite powder, and a glass plate with a colored layer for forming a colored layer in the part.

  A colored layer is formed on the inner peripheral edge of the window glass for automobiles. The colored layer is formed to prevent UV deterioration of the organic adhesive that joins the automobile body and the window glass (soda lime glass plate) and to conceal the protruding portion of the organic adhesive. Furthermore, in recent years, a colored layer in which a minute dot pattern is formed in a gradation is widely used in order to improve design properties.

  The colored layer is formed by pasting the composite powder, applying the obtained composite powder paste to a soda lime glass plate, drying and firing, and sintering the soda lime glass plate. The composite powder includes at least a glass powder and an inorganic pigment powder, and optionally includes a refractory filler powder. The inorganic pigment powder is usually black.

Japanese Patent Laid-Open No. 06-256039

  In recent years, thinning of window glass for automobiles has been promoted. However, in connection with this, there exists a possibility that the intensity | strength of the window glass for motor vehicles may become inadequate. In particular, it is known that window glass with a colored layer has a lower strength than when a colored layer is not formed.

  As a method for increasing the strength of the window glass on which the colored layer is formed, a method for reducing the thermal expansion coefficient of the colored layer is effective. However, it is difficult to apply this method to thin window glass. The reason for this is that as the window glass is made thinner, in order to prevent thermal deformation of the window glass, the firing temperature of the composite powder is lowered, and the glass powder must also have a lower melting point correspondingly. This is because when the melting point of the glass powder is lowered, the thermal expansion coefficient of the glass powder increases.

  As a glass powder that satisfies this requirement, lead-based glass powder is promising, but there is a concern about the environmental impact of lead (for example, see Patent Document 1).

  Therefore, the present invention has been made in view of the above problems, and a technical problem thereof is to create a glass that can achieve both a low melting point and a low thermal expansion coefficient without containing a large amount of lead.

As a result of various studies, the present inventor has found that the above technical problem can be solved by strictly regulating the glass composition of the alkali borosilicate glass, and proposes as the present invention. . That is, the glass of the present invention has a glass composition of mol%, SiO ₂ 35 to 65%, B ₂ O ₃ 1 to 20%, Al ₂ O ₃ 5 to 15%, Li ₂ O 5 to 40%, Na ₂ O + K ₂ O contains 0 to less than 8%. Here, “Na ₂ O + K ₂ O” is the total amount of Na ₂ O and K ₂ O.

The glass of the present invention has a low melting point because the glass composition is regulated as described above. Moreover, when this glass is baked, low-expansion crystals, particularly β-quartz solid solution, is likely to precipitate. For this reason, the glass (crystallized glass) after baking becomes low expansion. As a result, it becomes easy to achieve both a low melting point and a low expansion coefficient. Furthermore, since the glass matrix of the present invention becomes rich in B ₂ O ₃ after the crystals are precipitated, it can be softened and sintered well after the crystals are precipitated. Furthermore, the glass can be softened at a temperature 30 ° C. lower than the softening point even after the crystals are precipitated by the glass matrix rich in B ₂ O ₃ . In general, it is difficult to soften the glass powder at a temperature lower than the softening point.

Second, the glass of the present invention preferably has a Na ₂ O + K ₂ O content of 0.1 mol% or more.

Thirdly, the glass of the present invention preferably further includes a _Bi 2 _{O 3} 0.1 to 15 mol%.

Fourthly, it is preferable that the glass of the present invention further contains 0.1 to 12 mol% of TiO ₂ + ZrO ₂ . Here, “TiO ₂ + ZrO ₂ ” is the total amount of TiO ₂ and ZrO ₂ .

In recent years, acid rain has become a problem in terms of environment. When the colored layer formed on various glass products comes into contact with acid rain, the glass in the colored layer may be discolored to white or the like, and the colored layer may be peeled off. In addition, even when the colored layer comes into contact with the detergent during the cleaning of the window glass for automobiles, the glass in the colored layer may be changed to white or the like, and the colored layer may be peeled off. Therefore, acid resistance is required for the glass powder. As described above, the glass of the present invention becomes B ₂ O ₃ rich after crystals are precipitated, but this B ₂ O ₃ rich layer may reduce acid resistance. Therefore, if a predetermined amount of TiO ₂ + ZrO ₂ is introduced, the decrease in acid resistance can be effectively suppressed.

  Fifth, it is preferable that the glass of the present invention does not substantially contain PbO in the glass composition. Here, “substantially does not contain” is 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.

  Sixth, the glass powder of the present invention is preferably made of the above glass. If it is processed into a powder shape, it becomes easy to soften and flow at low temperatures, and crystals are likely to precipitate during firing.

  Seventh, the glass powder of the present invention preferably has a glass transition point of 550 ° C. or less measured with a macro DTA (differential thermal analysis) apparatus. Here, the measurement with the macro type DTA apparatus is performed in the air, and the heating rate is 10 ° C./min (hereinafter the same).

  Eighth, the glass powder of the present invention preferably has a softening point of 600 ° C. or less 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.

  Ninth, the glass powder of the present invention preferably has a crystallization temperature of 600 to 700 ° C. measured with a macro DTA apparatus. Here, “crystallization temperature” refers to an exothermic peak temperature due to crystal precipitation.

  10thly, it is preferable that the glass powder of this invention has a property which a crystal | crystallization precipitates, when it bakes for 30 minutes at 600 degreeC.

  Eleventh, in the glass powder of the present invention, the main crystal is preferably a β-quartz solid solution. Here, the “main crystal” refers to a crystal having the highest peak intensity when measured by the X-ray diffraction method.

  Twelfth, the composite powder of the present invention is a composite powder containing 55 to 95% by weight of glass powder, 5 to 45% by weight of inorganic pigment powder, and 0 to 20% by weight of refractory filler powder, The above glass powder is preferable.

  13thly, as for the composite powder of this invention, it is preferable that inorganic pigment powder is Cr type complex oxide. Here, “to complex oxide” refers to a complex oxide containing an explicit component as an essential component.

  14thly, the glass plate with a colored layer of the present invention is a glass plate with a colored layer having a colored layer on the surface of the glass plate, the colored layer is a sintered body of the composite powder, and the composite powder is the above It is characterized by being a composite powder.

  15thly, as for the glass plate with a colored layer of this invention, it is preferable that (beta) -quartz solid solution precipitates in the colored layer.

It is a chart which shows the softening point measured with the macro type DTA apparatus.

The glass of the present invention, as a glass composition, in _{mol%, SiO 2 35~65%, B} 2 O 3 1~20%, Al 2 O 3 0~15%, Li 2 O 5~40%, Na 2 O + K ₂ O 0 to less than 8% is contained. 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%.

SiO ₂ is a component that forms a glass skeleton, a crystal component of β-quartz solid solution, and a component that further enhances acid resistance. The content of SiO ₂ is 35 to 65%, preferably 38 to 62%, 41 to 59%, 43 to 57%, particularly 45 to 55%. If the content of SiO ₂ is too small, the thermal stability is unduly lowered, and crystals are likely to precipitate before the glass powder is sufficiently sintered. -Quartz solid solution becomes difficult to precipitate. On the other hand, if the content of SiO ₂ is too large, the softening point is raised, it becomes difficult to firing the glass powder at a low temperature.

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 1 to 20%, preferably ₃ to 18%, 4 to 17%, 4 to 16%, particularly 5 to 15%. 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. On the other hand, when the content of B ₂ O ₃ is too large, the acid resistance is likely to decrease.

Al ₂ O ₃ is a component that enhances acid resistance and is a crystal component of the β-quartz solid solution. The content of Al ₂ O ₃ is 5 to 15%, preferably 5 to 13%, 5 to 11%, 5 to 10%, particularly 6 to 9%. When the content of Al ₂ O ₃ is too large, the softening point is raised, it becomes difficult to firing the glass powder at a low temperature.

Li ₂ O is a component that lowers the softening point without increasing the thermal expansion coefficient, and is a component that can adjust crystallinity. The content of Li ₂ O is 5 to 40%, preferably 7 to 37%, 9 to 33%, 11 to 30%, 13 to 28%, particularly 14 to 25%. If the content of Li ₂ O is too small, the softening point increases and it becomes difficult to fire the glass powder at a low temperature, and it becomes difficult to precipitate low expansion crystals, particularly β-quartz solid solution during firing. On the other hand, when the content of Li 2 _O is too large, the acid resistance is likely to decrease.

Na ₂ O + K ₂ O is a component that lowers the softening point. However, if its content is too large, low-expansion crystals, especially β-quartz solid solution, is difficult to precipitate during firing, resulting in thermal expansion of the colored layer. It becomes difficult to reduce the coefficient. Furthermore, acid resistance tends to decrease. Therefore, the content of Na ₂ O + K ₂ O is 0 to less than 8%, preferably 0 to 7%, 0 to 6%, 0.1 to 6%, particularly 1 to 5%. In addition, if any of Na ₂ O and K ₂ O is introduced, the alkali mixing effect can be enjoyed. As a result, the thermal expansion coefficient can be lowered while lowering the softening point than when only Li ₂ O is introduced alone.

Na ₂ O is a component that lowers the softening point. However, if its content is too large, low-expansion crystals, especially β-quartz solid solution, is difficult to precipitate during firing, and as a result, the thermal expansion coefficient of the colored layer is reduced. It becomes difficult to lower. Furthermore, acid resistance tends to decrease. Therefore, the content of Na ₂ O is preferably 0 to less than 8%, 0 to 7%, 0 to 6%, 0.1 to 6%, particularly 1 to 5%.

K ₂ O is a component that lowers the softening point. However, if its content is too large, low-expansion crystals, particularly β-quartz solid solution, is difficult to precipitate during firing, and as a result, the thermal expansion coefficient of the colored layer is reduced. It becomes difficult to lower. Furthermore, water resistance tends to be lowered. Therefore, the content of K ₂ O is preferably 0 to 5%, 0 to 4%, 0 to 3%, 0 to 2%, particularly 0 to 1%.

The molar ratio Li ₂ O / (Li ₂ O + Na ₂ O + K ₂ O) is preferably 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, or 0.75 to 0.99. In this way, low-expansion crystals, particularly β-quartz solid solution, is likely to precipitate during firing.

  In addition to the above components, for example, the following components may be introduced.

TiO ₂ + ZrO ₂ is a component that increases acid resistance. The content of TiO ₂ + ZrO ₂ is preferably 0-12%, 0.1-12%, 1-10%, 3-8%, in particular 4-6%. When the content of TiO 2 ₊ ZrO ₂ is too high, the softening point is raised, it becomes difficult to firing the glass powder at a low temperature.

TiO ₂ is a component that increases acid resistance. The content of TiO ₂ is preferably 0 to 12%, 0.1 to 12%, 1 to 10%, 3 to 8%, particularly 4 to 6%. When the content of TiO ₂ is too large, the softening point is raised, it becomes difficult to firing the glass powder at a low temperature.

ZrO ₂ is a component that increases acid resistance. The content of ZrO ₂ is preferably 0 to 8%, 0 to 6%, 0 to 4%, 0 to 3%, particularly 0 to 2%. When the content of ZrO ₂ is too high, the softening point is raised, it becomes difficult to firing the glass powder at a low temperature.

  MgO is a component that enhances thermal stability. The content of MgO is preferably 0 to 7%, 0 to 5%, particularly 0.1 to 3%. When there is too much content of MgO, a softening point will raise and it will become difficult to bake glass powder at low temperature.

  BaO is a component that enhances thermal stability. The content of BaO is preferably 0 to 7%, 0 to 5%, particularly 0 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 colored layer.

  ZnO is a component that lowers the softening point without significantly increasing the thermal expansion coefficient. The content of ZnO is preferably 0 to 12%, 0 to 10%, 0 to 8%, 0 to 6%, 0 to 4%, particularly 0 to 2%. When there is too much content of ZnO, acid resistance will fall easily.

  CuO is a component for coloring the glass black. The content of CuO is preferably 0 to 7%, 0 to 5%, 0 to 3%, particularly 0 to 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.

Bi ₂ O ₃ is a component that lowers the softening point. The content of Bi ₂ O ₃ is preferably 0 to 15%, 0.1 to 15%, 1 to 12%, 2 to 9%, particularly 3 to 6%. If the content of Bi ₂ O ₃ is too large, batch cost increases.

In addition to the above components, other components can be introduced, for example, up to 15%, 10%, especially 5%, if necessary. Specifically, introducing 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. Can do.

  In addition, as above-mentioned, it is preferable not to contain PbO substantially in a glass composition.

  It is preferable that the glass powder of this invention consists of said glass. If it is processed into a powder shape, it becomes easy to soften and flow at low temperatures, and crystals with low expansion are likely to precipitate during firing.

The average of the glass powder the particle diameter _{D 50} is 10μm or less, 1 to 7 [mu] m, particularly 2~5μm is preferred. The maximum particle diameter _Dmax of the glass powder is preferably 15 μm or less, particularly preferably 3 to 10 μm. When the particle size of the glass powder is too large, the screen printability tends to be lowered, and the color tone of the colored 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). “Maximum particle diameter D _max ” refers to a value measured by a laser diffractometer. In the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is 99 from the smaller particle. % Represents the particle diameter (hereinafter the same).

  The glass transition point of the glass powder measured with a macro type DTA apparatus is preferably 550 ° C. or lower, 500 ° C. or lower, 495 ° C. or lower, 490 ° C. or lower, particularly 440 to 485 ° C. The lower the glass transition point, the lower the firing temperature and the better the color developability of the inorganic pigment powder. However, if the glass transition point is too low, other properties, especially thermal stability, are unduly reduced. There is a risk of this. On the other hand, if the glass transition point is too high, the firing temperature rises and the soda lime glass plate may be thermally deformed during firing.

  The glass transition point of the sintered body of glass powder measured with a push rod type TMA device is preferably 510 ° C. or lower, 505 ° C. or lower, 500 ° C. or lower, particularly 450 to 495 ° C. The lower the glass transition point of the sintered body of glass powder, the lower the firing temperature and the better the color developability of the inorganic pigment powder, but if the glass transition point of the sintered body of glass powder is too low Other characteristics, particularly thermal stability, may be unduly lowered. On the other hand, if the glass transition point of the sintered body of the glass powder is too high, the firing temperature rises and the soda lime glass plate may be thermally deformed during firing. Here, the “sintered body of glass powder” refers to a glass powder compact that has been densely sintered at 600 ° C. for 30 minutes (hereinafter the same).

  The yield point of the sintered body of glass powder measured with a push rod TMA apparatus is preferably 550 ° C. or lower, 545 ° C. or lower, 540 ° C. or lower, particularly 490 to 535 ° C. The lower the yield point of the sintered glass powder, the lower the firing temperature and the better the color developability of the inorganic pigment powder. These characteristics, particularly thermal stability, may be unduly lowered. On the other hand, if the yield point of the sintered body of glass powder is too high, the firing temperature rises and the soda lime glass plate may be thermally deformed during firing.

  The softening point of the glass powder measured with a macro DTA apparatus is preferably 600 ° C. or lower, 595 ° C. or lower, 590 ° C. or lower, particularly 540 to 585 ° C. The lower the softening point, the lower the firing temperature can be, and the color development of the inorganic pigment powder is improved.However, if the softening point is too low, other properties, especially thermal stability and acid resistance, are unreasonable. There is a risk of lowering. On the other hand, if the softening point is too high, the firing temperature rises and the soda lime glass plate may be thermally deformed during firing.

  The crystallization temperature of the glass powder measured with a macro DTA apparatus is preferably 600 to 700 ° C, 610 to 680 ° C, and particularly 620 to 660 ° 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 colored layer is likely to be lowered. On the other hand, if the crystallization temperature is too high, it is difficult for crystals to precipitate in the colored layer during firing, and it becomes difficult to reduce the thermal expansion coefficient of the colored layer.

The thermal expansion coefficient of the sintered body of the glass powder is preferably 88 × 10 ⁻⁷ / ° C. or less, 80 × 10 ⁻⁷ / ° C. or less, 30 to 75 × 10 ⁻⁷ / ° C., 35 to 70 × 10 ⁻⁷ / ° C., in particular 40 to 65 × 10 ⁻⁷ / ° C. When the thermal expansion coefficient of the sintered body of glass powder is too high, it becomes difficult to reduce the thermal expansion coefficient of the colored layer. If the thermal expansion coefficient of the sintered glass powder is too low, it is difficult to match the thermal expansion coefficient of the colored layer with the thermal expansion coefficient of the soda lime glass plate. If the thermal expansion coefficients of the colored layer and the soda lime glass plate are inconsistent, cracks are likely to occur in the colored layer and / or soda lime glass plate, and the colored layer is likely to fall off.

The glass powder of the present invention preferably has a property that crystals are precipitated when fired at 600 ° C. for 30 minutes (desirably at 600 ° C. for 10 minutes). From the viewpoint of a low thermal expansion coefficient, the precipitated crystal is preferably a crystal mainly composed of SiO ₂ , and particularly preferably β-quartz solid solution.

  The composite powder of the present invention includes at least a glass powder and an inorganic pigment powder, and includes a refractory filler powder and the like as necessary. Glass powder is a component for dispersing inorganic pigment powder and fixing it to a soda lime glass plate or the like. The inorganic pigment powder is a component for increasing the shielding property of ultraviolet rays and visible light by coloring it to 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, an inorganic heat-resistant whisker or the like may be added in order to improve mold release properties, and a metal powder such as Cu powder may be added in order to improve color developability.

  The composite powder of the present invention preferably contains 55 to 95% by weight of glass powder, 5 to 45% by weight of inorganic pigment powder, and 0 to 20% by weight of refractory filler powder.

  The content of the glass powder is preferably 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 fixed property of a soda-lime glass plate and a colored layer will fall easily. On the other hand, when the content of the glass powder is too large, the inorganic pigment powder becomes relatively small, the ultraviolet shielding property is lowered, the organic adhesive is easily deteriorated, and the visible light shielding property is lowered. , The design properties are likely to deteriorate.

  The content of the inorganic pigment powder is preferably 5 to 45 mass%, 10 to 45 mass%, 15 to 45 mass%, 20 to 40 mass%, particularly 25 to 35 mass%. When the content of the inorganic pigment powder is too small, the ultraviolet shielding property is lowered, the organic adhesive is easily deteriorated, the visible light shielding property is lowered, and the design property is easily lowered. On the other hand, when the content of the inorganic pigment powder is too large, the glass powder becomes relatively small, and the sticking property between the soda lime glass plate and the colored layer tends to be lowered.

The inorganic pigment powder is preferably a composite oxide. Since the composite oxide is structurally stable, it has high heat resistance, acid resistance, and water resistance. Examples of such complex oxides include Al—Co complex oxides, Al—Co—Cr complex oxides, Al—Cr—Fe—Zn complex oxides, Al—Co—Li—Ti complex oxides, Al-Cu-Fe-Mn complex oxide, Al-Fe-Mn complex oxide, Al-Si complex oxide, Ba-Ni-Ti complex oxide, Ca-Cr-Si-Sn complex oxide Co-Cr composite oxide, Co-Cr-Fe-Mn composite oxide, Co-Cr-Fe-Ni composite oxide, Co-Cr-Fe-Ni-Si-Zr composite oxide, Co-Cr-Fe complex oxide, Co-Cr-Fe-Mn complex oxide, Co-Cr-Fe-Ni-Zn complex oxide, Co-Fe complex oxide, Co-Fe-Mn- Ni-based composite oxide, Co-Li-P-based composite oxide, Co-Ni-Si Zr composite oxide, Co-Ni-Nb-Ti composite oxide, Co-Ni-Sb-Ti composite oxide, Co-Ni-Ti-Zn composite oxide, Co-Si composite oxide, Co-Si-Zn complex oxide, Co-Ti complex oxide, Cr-Cu complex oxide, Cr-Cu-Mn complex oxide, Cr-Fe complex oxide, Cr-Fe-Mn complex Composite oxide, Cr—Fe—Zn composite oxide, Cr—Nb—Ti composite oxide, Cr—Sb—Ti composite oxide, Fe—Cr composite oxide, Fe—Mn composite oxide, Fe-Ti complex oxide, Fe-Ti-W complex oxide, Fe-Ti-Zn complex oxide, Fe-Zn complex oxide, Ni-Nb-Ti complex oxide, Ni-Sb- Ti complex oxide, Ni-Ti-W complex oxide, Sb-Sn complex oxidation It is preferably be at one or two or more selected from. These inorganic pigments include (Co, Fe, Mn) (Fe, Cr, Mn) ₂ O ₄ , (Ni, Co, Fe) (Fe, Cr) ₂ O ₄ , (Ni, Co, Fe) (Fe , Cr) ₂ O _4. (Zn, Fe) (Fe, Cr) ₂ O ₄ , (Co, Fe, Mn) (Fe, Cr, Mn) ₂ O ₄ , (Fe, Mn) (Fe, Mn) ₂ O ₄ (Manganese ferrite black spinel), (Fe, Mn) (Fe, Cr, Mn) O ₄ , Cu (Cr, Mn) ₂ O ₄ , CuCr ₂ O ₄ , (Co, Fe) (Fe, Cr) ₂ O ₄ , (Co, Ni) O.ZrSiO ₄ , (Sn, Sb) O ₂ , (Ni, Co, Fe) (Fe, Cr) ₂ O ₄ .ZrSiO ₄ , Fe (Fe, Cr) ₂ O ₄ , _{(Zn, Fe) (Fe,} Cr) 2 O 4, (Z _{, Fe) (Fe, Cr,} Al) 2 O 4, (Fe, Co) Fe 2 O 4, (Zn, Fe) Fe 2 O 4, (Ti, Sb, Ni) O 2, (Ti, Sb, Cr ) O ₂ , (Ti, Cr, Nb) O ₂ , (Ti, Sb, Ni, Co) O ₂ , (Ti, Nb, Ni, Co) O ₂ , (Ti, Ni, W) O ₂ , (Ti , Ni, Nb) O ₂ , (Ti, Fe, W) O ₂ , (Ti, Nb, Ni) O ₂ , (Zn, Fe) (Fe, Cr) ₂ O ₄ , (Fe, Zn) Fe ₂ O ₄ : TiO ₂ , (Co, Ni, Zn) TiO ₄ , CoCr ₂ O ₄ , CoAl ₂ O ₄ , CoAl ₂ O ₄ : TiO ₂ : Li ₂ O, CoSi ₂ O ₄ , Co ₂ TiO ₄ , CoLiPO ₄ , Co (Al, Cr) ₂ O ₄ , Fe ₂ TiO ₄ , Cr ₂ O ₃ : Fe ₂ O It can be mentioned _Cr 2 _{O 3} or the _{like: 3, (Co, Zn)} 2SiO 4, 2NiO, 3BaO, 17TiO 2, CaO, SnO 2, SiO 2.

The inorganic pigment powder is preferably black, and as the black inorganic pigment powder, an Al—Cu—Fe—Mn composite oxide, an Al—Fe—Mn composite oxide, a Co—Cr—Fe composite oxide, Co-Cr-Fe-Mn composite oxide, Co-Cr-Fe-Ni composite oxide, Co-Cr-Fe-Mn composite oxide, Co-Cr-Fe-Ni-Zn composite oxide, Co-Fe-Mn-Ni-based composite oxide, Cr-Cu-based composite oxide, Cr-Cu-Mn-based composite oxide, Cr-Fe-Mn-based composite oxide, Fe-Mn-based composite oxide, Ti _n O _2n-1 (n is an integer), Cr ₂ O ₃ , and C are preferable. For example, (Co, Fe, Mn) (Fe, Cr, Mn) ₂ O ₄ , (Ni, Co, Fe) (Fe, Cr ) ₂ O ₄ , (Ni, Co, Fe) (Fe, Cr) ₂ O _4. Zn, Fe) (Fe, Cr) ₂ O ₄ , (Co, Fe, Mn) (Fe, Cr, Mn) ₂ O ₄ , (Fe, Mn) (Fe, Mn) ₂ O ₄ , (Fe, Mn) Examples include (Fe, Cr, Mn) O ₄ , Cu (Cr, Mn) ₂ O ₄ , CuCr ₂ O ₄ , (Co, Fe) (Fe, Cr) ₂ O ₄ , carbon black, and the like.

  As inorganic pigment powders, from the viewpoints of visible light shielding properties, ultraviolet light shielding properties, and black color development properties, Cr-Cu-Mn complex oxides, Cr-Co complex oxides, Cr-Fe-Ni complex oxides Cr-based composite oxides such as products are preferable, and Cr-Cu-Mn-based composite oxides are particularly preferable.

The average particle diameter _{D 50} of the inorganic pigment powder is 9μm or less, particularly 1~4μm is preferred. The maximum particle diameter _Dmax of the inorganic pigment powder is preferably 5 μm or less, particularly preferably 2 to 6 μm. If the particle size of the inorganic pigment powder is too large, the screen printability tends to be lowered, and the color tone of the colored layer tends to be white.

  The content of the refractory filler powder is preferably 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 less than 0.1% by mass. It is. When there is too much content of a refractory filler powder, the fixed property of a soda-lime glass plate and a colored layer will fall easily.

  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.

The thermal expansion coefficient of the sintered body of the composite powder is preferably 100 × 10 ⁻⁷ / ° C. or less, 92 × 10 ⁻⁷ / ° C. or less, 40 to 87 × 10 ⁻⁷ / ° C., 45 to 82 × 10 ⁻⁷ / ° C., in particular 50 to 77 × 10 ⁻⁷ / ° C. When the thermal expansion coefficient of the sintered body of the composite powder is too high, it is difficult to reduce the thermal expansion coefficient of the colored layer. If the thermal expansion coefficient of the sintered compact of the composite powder is too low, it is difficult to match the thermal expansion coefficient of the colored layer with the thermal expansion coefficient of the soda lime glass plate. Here, “sintered body of composite powder” refers to a compact sintered compact of composite powder under conditions of 600 ° C. for 30 minutes (hereinafter the same).

  The composite powder paste according to the present invention is a composite powder paste containing a composite powder and a vehicle, wherein the composite powder is the composite powder described above.

  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.

  As the resin, acrylic ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic ester and the like can be used. In particular, acrylic acid ester and ethyl cellulose are preferable because they have good thermal decomposability.

  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, etc. It is possible to use. In particular, α-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 soda lime glass plate using a coating machine such as a screen printing machine, and then subjected to a drying process and a baking process. Thereby, a colored layer can be formed on the surface of the soda lime glass plate. In the case of the window glass for automobiles, the part to which the composite material paste is applied is the peripheral part of the windshield, side glass, and rear glass. In the case of an automotive window glass, a silver paste layer may be formed so as to cover a part of the composite powder paste after coating. The drying step is a step of volatilizing the solvent. The drying process is generally performed at 70 to 150 ° C. for 10 to 60 minutes. The firing step is a step of decomposing and volatilizing the resin and sintering the composite powder to fix the colored layer on the surface of the soda lime glass plate. The conditions for the firing step are generally 570 to 640 ° C. and 5 to 30 minutes. The lower the firing temperature in the firing step, the better the production efficiency and the color developability of the inorganic pigment powder.

  The glass plate with a colored layer of the present invention is a glass plate with a colored layer having a colored layer on the surface of the glass plate, the colored layer is a sintered body of a composite powder, and the composite powder is the above composite powder. The β-quartz solid solution is preferably deposited in the colored layer. Although the glass plate with a colored layer of the present invention includes the technical features of the composite powder of the present invention, since the contents thereof have been described, the description thereof is omitted for convenience.

  The glass plate with a colored layer of the present invention may be subjected to bending or the like as well as a flat plate shape. In the case of a window glass for automobiles, the glass plate with a colored layer is bent by a molding device such as a press device or a vacuum adsorption molding device. In the bending process, stainless steel covered with a glass fiber cloth is usually used for the mold.

  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.

  Table 1 shows Examples (Sample Nos. 1 to 7) and Comparative Examples (Sample No. 8) of the present invention.

First, the raw materials were prepared so as to have the glass composition described in the table, mixed uniformly, and a glass batch was obtained. Then, the glass batch was placed in a platinum crucible and melted at 1300 ° C. for 2 hours. Thereafter, the molten glass was formed into a bulk shape or a film shape. Subsequently, the obtained glass film was pulverized in a ball mill, and air classification, the average particle diameter _{D 50} of 2.5 [mu] m, maximum particle diameter _{D max} to obtain a glass powder 6.0 .mu.m. The softening point was measured for each glass powder.

  About each glass powder, the glass transition point, the softening point, and the crystallization temperature were measured using the macro type | mold 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.

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. “Cr—Cu—Mn” in the table is a Cr—Cu—Mn composite oxide (average particle size D ₅₀ is 1.5 μm, maximum particle size D _max is 4.0 μm).

  A thermal expansion coefficient is the value measured in the temperature range of 30-300 degreeC with the TMA apparatus. Here, the thermal expansion coefficient of the glass bulk was obtained by pouring molten glass into a bulk shape, performing predetermined annealing, and then processing into a predetermined shape as a measurement sample. The thermal expansion coefficient of the sintered body of glass powder was obtained by subjecting the green compact of glass powder to precise sintering by firing at 600 ° C. for 30 minutes and then processing it into a predetermined shape. The thermal expansion coefficient of the sintered compact of the composite powder was obtained by subjecting a green compact of glass powder to precise sintering by firing at 600 ° C. for 30 minutes and then processing into a predetermined shape.

  Further, the obtained composite powder and vehicle were mixed and then uniformly kneaded with a three-roll mill to obtain a composite powder paste. In addition, as a vehicle, what dissolved ethyl cellulose in alpha-terpineol was used, and mass ratio composite powder / vehicle was adjusted to 2-3.

  Subsequently, the composite powder paste was screen-printed on one side of a 10 cm square soda lime glass plate (manufactured by Nippon Sheet Glass Co., Ltd .: plate thickness 2.8 mm), dried at 150 ° C. for 20 minutes, The glass plate with a colored layer having a thickness of 10 μm was obtained by placing in a furnace, firing for 30 minutes, and naturally cooling to room temperature.

  For the colored layer of each sample, the crystallinity was estimated from the scattering intensity area and the crystal peak area measured in the range of diffraction angle 2θ of 10 to 60 ° using an X-ray diffractometer (manufactured by Rigaku) as follows. As a result, sample no. The crystallinity of 1 to 7 indicates the sample No. It was higher than the crystallinity of 8. The main crystal of the colored layer was identified by an X-ray diffractometer (manufactured by Rigaku). In the table, “α-quartz” refers to α-quartz solid solution, and “β-quartz” refers to β-quartz solid solution.

  As is clear from Table 1, sample No. In Nos. 1 to 7, the thermal expansion coefficient of the sintered body of the glass powder was low, and the thermal expansion coefficient of the sintered body of the composite powder was low. On the other hand, sample No. In No. 8, the main crystal was an α-quartz solid solution and its crystallinity was low, so that the thermal expansion coefficient of the sintered body of the glass powder was high, and the thermal expansion coefficient of the sintered body of the composite powder was high.

  The glass, glass powder and composite powder of the present invention are suitable for forming a colored layer, but are suitable for other applications because they can achieve both a low melting point and a low thermal expansion coefficient. For example, it is also suitable for forming insulating layers, partitions, sealing layers, and protective layers for displays, electronic components, optical components, and the like. In the case of these uses, the composite powder preferably contains 55 to 100% by mass of glass powder and 0 to 45% by mass of refractory filler powder, and 55 to 95% by mass of glass powder and 5 to 45% by mass of refractory filler powder. % Is more preferable.

Claims (12)

As a glass composition, in _{mol%, SiO 2 41 ~65%,} B 2 O 3 1~20%, Al 2 O 3 5~15%, Li 2 O 5~40%, Na 2 O + K 2 O 0~8% glass powder is an, 600 and baked for 30 minutes at ° C., a glass powder characterized by having the property of β- quartz solid solution as the predominant crystalline precipitates containing less than. The glass powder according to claim 1, wherein the content of Na ₂ O + K ₂ O is 0.1 mol% or more. The glass powder according to claim 1, further comprising 0.1 to 15 mol% of Bi ₂ O ₃ . Further glass powder according to claim 1, characterized in that it comprises a _{TiO 2} + ZrO 2 _0.1~12 mol%. The glass powder according to any one of claims 1 to 4, wherein the glass composition does not substantially contain PbO. The glass powder according to any one of claims 1 to 5, wherein the glass transition point measured with a macro type DTA apparatus is 550 ° C or less. The glass powder according to any one of claims 1 to 6, wherein a softening point measured with a macro type DTA apparatus is 600 ° C or less. Glass powder according to any one of claims 1 to 7, the crystallization temperature measured by the macro-type DTA apparatus characterized in that it is a 600 to 700 ° C.. A composite powder containing 55 to 95% by weight of glass powder, 5 to 45% by weight of inorganic pigment powder, and 0 to 20% 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 . The composite powder according to claim 9 , wherein the inorganic pigment powder is a Cr-based composite oxide. A glass plate with a colored layer having a colored layer on the surface of the glass plate,
A glass layer with a colored layer, wherein the colored layer is a sintered body of the composite powder, and the composite powder is the composite powder according to claim 9 or 10 . The glass plate with a colored layer according to claim 11 , wherein β-quartz solid solution is precipitated in the colored layer.