Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
• • 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
  • C03C4/00—Compositions for glass with special properties
  • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
  • C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass

Definitions

• the present invention relates to a heat ray absorbing glass plate and a method for producing the same.
• heat ray absorbing glass plates for automobiles those made of soda lime silica glass having a green or blue color tone by containing a coloring component are known.
• the heat ray absorbing glass plate has low solar transmittance (for example, the 4 mm thickness equivalent value of solar transmittance (hereinafter also referred to as Te) defined in JIS R 3106 (1998) is 42% or less),
• 4 mm thickness equivalent value of visible light transmittance for example, JIS R 3106 (1998) prescribed visible light transmittance (by A light source) (hereinafter also referred to as Tv)
• Tv visible light transmittance
• the heat ray absorbing glass plate when the passenger views the scenery through the glass plate, a heat ray absorbing glass plate having a green color tone which is a more natural color tone of transmitted light tends to be preferred.
• the heat-absorbing glass plate can reduce the types of coloring components as much as possible from the viewpoint of suppressing the contamination of impurities when changing the base material (variety switching) in the melting furnace used for glass production, It is hoped that the unit price of raw materials will be low.
• (1) to (3) As heat ray absorbing glass plates, for example, the following (1) to (3) have been proposed.
• a heat-absorbing glass plate made of soda lime silica glass having a mass ratio of FeO / total Fe 2 O 3 of 0.26 to 0.60 see Patent Document 1.
• Redox is 0.38 to 0.60, SO 3 : 0.005 to 0.18% in terms of mass percentage based on oxide, Made of soda-lime silica glass substantially free of polysulfides, A heat-absorbing glass plate containing any one of I) to V) in terms of mass percentage or mass percentage as a coloring component (see Patent Document 2).
• the heat ray absorbing glass plate of (1) has a green color tone, it does not satisfy Te ⁇ 42% (4 mm thickness conversion) and Tv ⁇ 70% (4 mm thickness conversion) at the same time.
• Te ⁇ 42% (4 mm thickness conversion) and Tv ⁇ 70% (4 mm thickness conversion) In addition to TiO 2 as a coloring component, CeO 2 is contained in a large amount, and there is a problem of impurity contamination (described later) and cost when changing the substrate.
• Some of the heat-absorbing glass plates of (2) satisfy Te ⁇ 42% (4 mm thickness conversion) and Tv ⁇ 70% (4 mm thickness conversion), but they have a blue color tone. is there.
• there are many kinds of coloring components and there are problems of contamination of impurities and cost when changing the substrate.
• Some of the heat-absorbing glass plates of (3) satisfy Te ⁇ 42% (4 mm thickness conversion) and Tv ⁇ 70% (4 mm thickness conversion), but they have a blue color tone. is there.
• CoO is contained, even if a small amount of CoO is used, a blue color tone is generated, so that there is a problem that impurities are mixed when the substrate is changed.
• the heat-absorbing glass has a green tone of transmitted light and has few kinds of coloring components while satisfying Te ⁇ 42% (4 mm thickness conversion) and Tv ⁇ 70% (4 mm thickness conversion). It was difficult to obtain a board.
• the present invention provides a heat-absorbing glass plate that satisfies the low solar transmittance (Te) and the high visible light transmittance (Tv) at the same time while the transmitted light has a green color tone and has few kinds of coloring components. More specifically, it has a green color tone in which the dominant wavelength of transmitted light is 492 to 500 nm while satisfying Te ⁇ 42% (4 mm thickness conversion) and Tv ⁇ 70% (4 mm thickness conversion), And the heat ray absorption glass plate with few kinds of coloring components is provided.
• the heat ray absorbing glass plate of the present invention is made of soda lime silica glass containing a coloring component, and the coloring component is expressed in terms of mass percentage based on the following oxide, Total iron converted to Fe 2 O 3 : 0.45 to 0.61%, TiO 2 : contains 0.2 to 0.6%, Substantially free of CoO, Cr 2 O 3 , V 2 O 5 , MnO and CeO 2 ; Mass percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 is 45 to 60%
• the solar radiation transmittance defined in JIS R 3106 (1998) is 42% or less in terms of 4 mm thickness conversion value
• JIS R 3106 (1998) prescribed visible light transmittance (by A light source) is 70% or more in terms of 4 mm thickness conversion value
• the main wavelength of transmitted light defined in JIS Z 8701 (1982) is 492 to 500 nm.
• the heat ray absorbing glass plate of the present invention is made of soda lime silica glass containing a coloring component, and the coloring component is expressed in mass percentage based on the following oxide, Total iron converted to Fe 2 O 3 : 0.45 to 0.61%, TiO 2 : contains 0.2 to 0.6%, Substantially free of cobalt oxide, chromium oxide, vanadium oxide, manganese oxide and cerium oxide, Mass percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 is 45 to 60%
• the solar radiation transmittance defined in JIS R 3106 (1998) is 42% or less in terms of 4 mm thickness conversion value
• JIS R 3106 (1998) prescribed visible light transmittance (by A light source) is 70% or more in terms of 4 mm thickness conversion value
• the heat-absorbing glass plate has a principal wavelength of transmitted light as defined in JIS Z 8701 (1982) of 492 to 500 nm.
• the heat-absorbing glass plate of the present invention is preferably made of soda lime silica glass having the following composition substantially in terms of mass percentage based on the following oxide. SiO 2 : 65 to 75%, Al 2 O 3 : 0.1 to 5%, Na 2 O + K 2 O: 10-18%, CaO: 5 to 15%, MgO: 2-6% SnO 2 : 0 to 0.5% SO 3 : 0 to 1%, Total iron converted to Fe 2 O 3 : 0.45 to 0.61%, TiO 2 : 0.2 to 0.6%.
• the method for producing a heat-absorbing glass plate of the present invention is a method for producing soda-lime silica glass containing a coloring component that melts a glass raw material and forms it into a plate shape.
• Total iron converted to Fe 2 O 3 0.45 to 0.61%
• TiO 2 contains 0.2 to 0.6%, Substantially free of CoO, Cr 2 O 3 , V 2 O 5 , MnO and CeO 2 ;
• Mass percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 is 45 to 60%
• the glass plate after molding is The solar radiation transmittance defined in JIS R 3106 (1998) is 42% or less in terms of 4 mm thickness conversion value, JIS R 3106 (1998) prescribed visible light transmittance (by A light source) is 70% or more in terms of 4 mm thickness conversion value,
• a heat-absorbing glass plate having a dominant wavelength of transmitted light as defined in JIS Z 8701 (1982) is 492 to 500 nm.
• the method for producing a heat ray absorbing glass plate of the present invention is a method for producing soda lime silica glass containing a coloring component that melts a glass raw material and forms it into a plate shape.
• Total iron converted to Fe 2 O 3 0.45 to 0.61%
• TiO 2 contains 0.2 to 0.6%
• Mass percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 is 45 to 60%
• the glass plate after molding is The solar radiation transmittance defined in JIS R 3106 (1998) is 42% or less in terms of 4 mm thickness conversion value, JIS R 3106 (1998) prescribed visible light transmittance (by A light source) is 70% or more in terms of 4 mm thickness conversion value,
• a heat-absorbing glass plate having a dominant wavelength of transmitted light as defined in JIS Z 8701 (1982) is 492 to 500 n
• the heat ray-absorbing glass plate of the present invention satisfies the low solar transmittance and the high visible light transmittance at the same time, and the transmitted light has a green color tone, and contains few kinds of coloring components.
• the total iron content converted to Fe 2 O 3 is 0.45 to 0.61% in terms of mass percentage based on oxide. If the total iron content converted to Fe 2 O 3 is 0.45% or more, Te can be kept low. Te decreases as the total iron content converted to Fe 2 O 3 decreases, but Tv also decreases. If the total iron content converted to Fe 2 O 3 is 0.61% or less, the decrease in Tv can be prevented and 70% (4 mm thickness conversion) or more can be achieved.
• the total iron content in terms of Fe 2 O 3 is preferably 0.47 to 0.55%, more preferably 0.49 to 0.54% in terms of mass percentage based on oxide.
• the total iron content is expressed as the amount of Fe 2 O 3 according to the standard analysis method, but not all iron present in the glass is present as trivalent iron.
• divalent iron is present in the glass.
• Divalent iron has an absorption peak near a wavelength of 1100 nm
• trivalent iron has an absorption peak near a wavelength of 400 nm. Therefore, when attention is paid to the infrared absorption ability, it is preferable that the amount of divalent iron is larger than that of trivalent iron.
• Redox the mass percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 (hereinafter referred to as Redox.) It is preferable to increase the.
• the Redox in the heat ray absorbing glass plate of the present invention is 45 to 60%. If Redox is 45% or more, Te can be kept low. If Redox is 60% or less, the melting process of the glass raw material does not become complicated, and a heat-absorbing glass plate having a target green color tone with the addition amount of Fe 2 O 3 (described above) and TiO 2 (described later) can be obtained. can get.
• Redox is preferably 48 to 57%, more preferably 50 to 55%.
• the content of TiO 2 is 0.2 to 0.6% in terms of mass percentage based on oxide. If the content of TiO 2 is 0.2% or more, a heat-absorbing glass plate with the desired green color tone can be obtained by adjusting the amount of Fe 2 O 3 (described above) and the above-described Redox. If the content of TiO 2 is 0.6% or less, Tv can be increased.
• the content of TiO 2 is preferably 0.3 to 0.5%, more preferably 0.32 to 0.41% in terms of mass percentage on the basis of oxide.
• the heat ray absorbing glass plate of the present invention is substantially free of CoO, Cr 2 O 3 , V 2 O 5 , MnO and CeO 2 .
• CoO, Cr 2 O 3 , V 2 O 5 , MnO and CeO 2 are substantially free of CoO, Cr 2 O 3 , V 2 O 5 , MnO and CeO 2 , or CoO, It means that Cr 2 O 3 , V 2 O 5 , MnO and CeO 2 may be contained as impurities inevitably mixed in the production. If CoO, Cr 2 O 3 , V 2 O 5 , MnO and CeO 2 are not substantially contained, impurities can be prevented from being mixed during substrate replacement, and the cost of the heat-absorbing glass plate can be reduced.
• the composition of each component is generally determined by conversion to a predetermined oxide. That is, in the composition analysis of the cobalt (Co) component described above, the cobalt component is converted as a CoO oxide to determine the composition ratio, and various cobalt oxides corresponding to the Co valences exist. Even so, the analysis value is calculated as CoO. Therefore, the fact that CoO is not substantially contained indicates that cobalt oxide is not substantially contained.
• the chromium (Cr) component, the vanadium (V) component, the manganese component, and the cerium component are the same as the above-described cobalt component, and substantially not containing Cr 2 O 3 does not substantially contain chromium oxide.
• the mixing of impurities at the time of substrate replacement means the following.
• Commercial production of glass plates for construction, automobiles, and other uses is not usually a batch type, but glass raw materials are put into a large glass melting furnace, melted in the glass melting furnace, and the molten glass is advanced.
• mixing of impurities at the time of changing the substrate means that the glass composition before switching is mixed into the glass after switching when switching to another glass type.
• impurities such as CoO, Cr 2 O 3 , V 2 O 5 , MnO, CeO 2 as coloring components are mixed, the color tone of the glass after switching is greatly affected.
• the heat-absorbing glass plate of the present invention is preferably made of soda lime silica glass having the following composition substantially in terms of mass percentage based on the following oxide. SiO 2 : 65 to 75%, Al 2 O 3 : 0.1 to 5%, Na 2 O + K 2 O: 10-18%, CaO: 5 to 15%, MgO: 2-6% SnO 2 : 0 to 0.5% SO 3 : 0 to 1%, Total iron converted to Fe 2 O 3 : 0.45 to 0.61%, TiO 2 : 0.2 to 0.6%.
• the content of SiO 2 is preferably 67 to 74%, more preferably 69 to 73% in terms of oxide-based mass percentage.
• Al 2 O 3 is a component that improves weather resistance. When the content of Al 2 O 3 is 0.1% or more, the weather resistance is good. If the content of Al 2 O 3 is 5% or less, the meltability will be good.
• the content of Al 2 O 3 is preferably from 0.5 to 4%, more preferably from 1 to 3%, and even more preferably from 1.5 to 2.5% in terms of mass percentage based on oxide.
• Na 2 O and K 2 O are components that promote melting of the glass raw material. If Na 2 O + K 2 O content of 10% or more, a good meltability. When the content of Na 2 O + K 2 O is 18% or less, the weather resistance is good.
• the content of Na 2 O + K 2 O is preferably 11 to 16%, more preferably 12 to 14% in terms of mass percentage based on oxide.
• the content of Na 2 O is preferably 5 to 18%, more preferably 10 to 16%, and further preferably 12 to 14%.
• the content of K 2 O is preferably 0 to 5%, more preferably 0 to 2%, and further preferably 0 to 1%.
• CaO is a component that promotes the melting of the glass raw material and improves the weather resistance.
• the content of CaO is preferably 6 to 12%, more preferably 7 to 10% in terms of mass percentage based on oxide.
• MgO is a component that promotes the melting of the glass raw material and improves the weather resistance. If the content of MgO is 2% or more, the meltability and weather resistance will be good. If the content of MgO is 6% or less, devitrification is difficult.
• the content of MgO is preferably 2 to 5%, more preferably 3 to 4% in terms of mass percentage based on oxide.
• SnO 2 may be used as a reducing agent or a clarifying agent. If the content of SnO 2 is 0.5% or less, the volatilization of SnO 2 is small and the cost can be kept low.
• the content of SnO 2 is preferably 0 to 0.3%, more preferably 0 to 0.1% in terms of mass percentage based on oxide.
• SO 3 may be used as a fining agent. If the content of SO 3 is 1% or less, the SO 2 gas component does not remain in the glass as bubbles.
• the SO 3 content is preferably 0.02 to 0.5%, more preferably 0.05 to 0.2% in terms of mass percentage based on oxide.
• the specific gravity of the heat ray absorbing glass plate of the present invention is preferably 2.49 to 2.55, more preferably 2.50 to 2.53.
• the specific gravity of the heat ray absorbing glass plate of the present invention can be adjusted by adjusting the glass composition.
• the mass ratio of SiO 2 / (MgO + CaO) is preferably 5.0 to 7.0, and more preferably 5.4 to 6.6.
• the mass ratio of CaO / MgO is preferably 1.3 to 2.5, and more preferably 1.5 to 2.3.
• Te (4 mm thickness conversion) of the heat ray absorbing glass plate of the present invention is 42% or less, preferably 40% or less.
• Te is the solar radiation transmittance calculated by measuring the transmittance with a spectrophotometer according to JIS R 3106 (1998) (hereinafter simply referred to as JIS R 3106).
• Tv (4 mm thickness conversion) of the heat ray absorbing glass plate of the present invention is 70% or more, and preferably 71.5% or more.
• Tv is the visible light transmittance calculated by measuring the transmittance with a spectrophotometer in accordance with JIS R 3106. As the coefficient, the standard light A and the value of the 2-degree visual field are used.
• the main wavelength of transmitted light of the heat ray absorbing glass plate of the present invention is 492 to 500 nm, preferably 492 to 495 nm.
• the dominant wavelength is calculated by measuring the transmittance with a spectrophotometer according to JIS Z 8701 (1982). As the coefficient, the standard light C and the value of the 2-degree visual field are used.
• the heat ray absorbing glass plate of the present invention can be used for both vehicles and buildings, and is particularly suitable as a windshield for automobiles.
• a window glass for automobiles it is used as necessary, as laminated glass in which a plurality of glass plates are sandwiched between interlayer films, glass obtained by processing a flat glass into a curved surface, or glass that has been tempered.
• a multilayer glass for construction it uses as a multilayer glass which consists of two sheets of the heat ray absorption glass plate of this invention, or the heat ray absorption glass plate of this invention, and another glass plate.
• the heat ray absorbing glass plate of the present invention is produced, for example, through the following steps (i) to (v) in order.
• a glass raw material is prepared by mixing a glass mother composition raw material such as silica sand, a coloring component raw material such as an iron source and a titanium source, a reducing agent, a clarifying agent and the like so as to achieve a target composition.
• a glass raw material is continuously supplied to a melting kiln, heavy oil or the like is burned and heated, for example, heated to about 1500 ° C. and melted to obtain molten glass.
• After the molten glass is clarified, it is formed into a glass plate having a predetermined thickness by a float method or the like.
• the glass plate After slowly cooling the glass plate, it is cut into a predetermined size to obtain the heat ray absorbing glass plate of the present invention. (V) If necessary, the cut glass plate may be tempered, processed into a laminated glass, or processed into a multilayer glass.
• a glass mother composition raw material what is used as a raw material of normal soda-lime silica glass, such as silica sand, is mentioned.
• the iron source as the coloring component include iron powder, iron oxide powder, and bengara.
• the titanium source include titanium oxide.
• the reducing agent include carbon and coke.
• a reducing agent is for adjusting the oxidation of iron in the molten glass so as to achieve the target Redox.
• SnO 2 may be used as a reducing agent or a clarifying agent
• SO 3 may be used as a clarifying agent.
• Beta-OH of the heat ray absorbing glass plate of the present invention is preferably 0.20 ⁇ 0.35 mm -1, and more preferably 0.23 ⁇ 0.30 mm -1, further preferably 0.25 ⁇ 0.28 mm -1 .
• the Tuv (4 mm thickness conversion) of the heat ray absorbing glass plate of the present invention is preferably low, particularly when used as vehicle glass, specifically 32% or less, more preferably 30% or less. Tuv is the ultraviolet transmittance measured and calculated by a spectrophotometer according to JISO 9050.
• Redox (%) ⁇ log (T 1000 nm /91.4)/(Fe 2 O 3 amount ⁇ t ⁇ 20.79) ⁇ 100
• T 1000 nm is the transmittance at a wavelength of 1000 nm (%)
• t is the thickness of the glass plate (cm)
• the above Redox is a method of obtaining from a spectral curve of glass measured by a spectrophotometer, and this value is divalent iron converted to Fe 2 O 3 in all iron converted to Fe 2 O 3 in the same glass. May be considered to be equal to the mass ratio of
• ⁇ -OH was calculated from the spectrum curve of the glass measured by FT-IR using the following equation.
• ⁇ -OH (mm ⁇ 1 ) ⁇ log 10 (T3500 cm ⁇ 1 / T4000 cm ⁇ 1 ) / t
• T3500cm -1 is the transmittance of the wave number 3500cm -1 (%)
• T4000cm -1 is the transmittance of the wave number 4000cm -1 (%)
• t is the thickness of the glass plate (mm) It is.
• Examples 1 to 39 Each raw material was mixed so as to have the composition shown in Tables 1 to 7, thereby preparing a glass raw material.
• the glass raw material was put in a crucible and heated to 1500 ° C. in an electric furnace to obtain molten glass.
• Molten glass was poured onto a carbon plate and cooled. Both surfaces were polished to obtain a glass plate having a thickness of 4 mm.
• permeability was measured for every 1 nm using the spectrophotometer (the Perkin Elmer company make, Lambda950), and Te, Tv, Tuv, and Dw were calculated
• the glass was polished to a thickness of 2 mm, and the transmittance of this glass plate was measured every 1 cm ⁇ 1 using FT-IR (Thermo Nicolet Avatar 370) to obtain ⁇ -OH.
• FT-IR Thermo Nicolet Avatar 370
• the heat-absorbing glass plates of Examples 1 to 18 and 22 to 39 of the present invention satisfy Te ⁇ 42% (4 mm thickness conversion) and Tv ⁇ 70% (4 mm thickness conversion) while the transmitted light has a green color tone.
• the transmitted light had a blue color tone (Dw of 488).
• Te (4 mm thickness conversion) exceeded 42%.
• the total iron content converted to Fe 2 O 3 is less than 0.45% in terms of oxide-based mass percentage, so Te (4 mm thickness conversion) exceeded 42%. .
• the heat ray absorbing glass plate of the present invention is useful as a glass plate for vehicles and buildings, and is particularly suitable as a glass plate for automobiles.
• the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2009-243284 filed on Oct. 22, 2009 are incorporated herein as the disclosure of the present invention.

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• 2010
  • 2010-10-22 IN IN3331DEN2012 patent/IN2012DN03331A/en unknown
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  • 2010-10-22 WO PCT/JP2010/068744 patent/WO2011049210A1/ja not_active Ceased
  • 2010-10-22 CN CN201080047967.5A patent/CN102596839B/zh active Active
• 2012
  • 2012-04-12 US US13/444,994 patent/US8518843B2/en not_active Expired - Fee Related

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