JPH04224133A - Ir and uv absorbing glass and its manufacture - Google Patents
Ir and uv absorbing glass and its manufactureInfo
- Publication number
- JPH04224133A JPH04224133A JP40584090A JP40584090A JPH04224133A JP H04224133 A JPH04224133 A JP H04224133A JP 40584090 A JP40584090 A JP 40584090A JP 40584090 A JP40584090 A JP 40584090A JP H04224133 A JPH04224133 A JP H04224133A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- infrared
- cao
- al2o3
- sio2
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000002834 transmittance Methods 0.000 claims description 30
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 32
- 239000000203 mixture Substances 0.000 abstract description 17
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 abstract description 2
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004576 sand Substances 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- 241000283986 Lepus Species 0.000 abstract 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 14
- 230000009467 reduction Effects 0.000 description 14
- 239000005357 flat glass Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000005728 strengthening Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 230000002787 reinforcement Effects 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 238000004031 devitrification Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000005340 laminated glass Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000019402 calcium peroxide Nutrition 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 231100000075 skin burn Toxicity 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は比較的高い透視性をもち
赤外線紫外線を吸収して高居住性、高安全性となって軽
量化ができ得る赤外線紫外線吸収ガラスおよびその製法
に関し、建築用窓ガラスや各種ガラス物品はもちろん、
殊に車両用窓ガラスに有用な前記ガラスとその製法を提
供するものである。[Industrial Application Field] The present invention relates to infrared and ultraviolet absorbing glass that has relatively high transparency and absorbs infrared and ultraviolet rays, resulting in high livability, safety, and weight reduction, and a method for producing the same. As well as glass and various glass items,
The object of the present invention is to provide the above-mentioned glass, which is particularly useful for vehicle window glasses, and a method for manufacturing the same.
【０００２】0002
【従来技術】近年富みに、冷房負荷の低減等省エネルギ
ー化あるいは有機物における劣化ならびに退色等から、
赤外線や紫外線の反射吸収等多機能化をガラス自体また
はガラス表面に付加することにより、人的にも物的にも
より高居住性に繋がる板ガラス物品のニーズが急激に高
まってきている。[Prior Art] In recent years, energy saving such as reduction of cooling load, deterioration and discoloration of organic substances, etc.
There is a rapidly increasing need for plate glass products that can be made more comfortable for people and property by adding multi-functionality such as reflection and absorption of infrared rays and ultraviolet rays to the glass itself or the glass surface.
【０００３】そこで、従来の赤外線吸収ガラスに加えて
紫外線吸収を意識したガラスがさらに提案されつつあり
、例えば特開昭６４ー１８９３８ 号公報にはＦｅ２Ｏ
３ として表して少なくとも０．４５重量％の鉄を有す
る溶融ガラスの連続流を送り、溶融操作中の酸化還元条
件をＦｅＯ として表される第一鉄状態の鉄を少なくと
も３５％与えるように制御し、そしてガラスを成形操作
で平板ガラス製品へ成形することを含み、しかも前記平
板ガラスが少なくとも６５％の光透過率及び１５％以下
の赤外線透過率を有する、連続的方法でソーダ・石灰・
シリカ平板ガラスを製造する方法が開示され、ガラス中
でＦｅ２Ｏ３ として表して０．６５％より少ない全鉄
含有量が与えられていることあるいは製品ガラスの硫黄
含有量がＳＯ３ として表して０．０２％より少ないこ
と等にすることが好ましいものであると記載され、また
Ｆｅ２Ｏ３ として表して少なくとも０．４５重量％の
全鉄で、そのうち少なくとも５０％がＦｅＯ として表
した第一鉄状態にある鉄、及びＳＯ３ として表して０
．０２重量％より少ない硫黄を有し、少なくとも６５％
の光透過率及び１５％以下の全太陽赤外線透過率を示す
ソーダ・石灰・シリカガラス物品が開示されており、ガ
ラス物品が、重量に基づいて、６６〜７５％のＳｉＯ２
、１２〜２０％のＮａ２Ｏ、７ 〜１２％のＣａＯ 、
０ 〜５ ％のＭｇＯ 、０ 〜４ ％のＡｌ２Ｏ３
、０ 〜３ ％のＫ２Ｏ 、０ 〜１ ％のＦｅ２Ｏ３
、及びＣｅＯ２、ＴｉＯ２、Ｖ２Ｏ５又はＭｏＯ３の
合計０ 〜１．５ ％から本質的になる組成を有するも
のが好ましいことが記載されている。さらに米国特許第
４７０１４２５ 号には重量％で表して、６０〜８０％
のＳｉＯ２、１０〜２０％のＮａ２Ｏ、０ 〜１０％の
Ｋ２Ｏ 、５ 〜１６％のＣａＯ 、０ 〜１０％のＭ
ｇＯ 、０ 〜５ ％のＡｌ２Ｏ３ 、０ 〜０．５
％のＳＯ３ 、０．２９〜０．６ ％のＦｅ２Ｏ３ 、
０．１ 〜１．５ ％のＳｎＯ２、０．１ 〜１．６
％のＴｉＯ２から実質的になる赤外線と紫外線を吸収す
るガラス組成物が開示されている。Therefore, in addition to the conventional infrared absorbing glass, glasses with ultraviolet absorption in mind are being proposed.
3, and controlling the redox conditions during the melting operation to provide at least 35% iron in the ferrous state, expressed as FeO. , and forming the glass into a flat glass product in a molding operation, wherein said flat glass has a light transmission of at least 65% and an infrared transmission of no more than 15%.
A method for producing silica flat glass is disclosed, providing a total iron content in the glass of less than 0.65% expressed as Fe2O3 or a sulfur content of the product glass of less than 0.02% expressed as SO3. and at least 0.45% by weight of total iron, expressed as Fe2O3, of which at least 50% is in the ferrous state, expressed as FeO2; 0 expressed as SO3
．． 0.02% by weight sulfur and at least 65%
A soda-lime-silica glass article is disclosed that exhibits a light transmittance of 66-75% SiO2, by weight, and a total solar infrared transmittance of 15% or less.
, 12-20% Na2O, 7-12% CaO,
0-5% MgO, 0-4% Al2O3
, 0-3% K2O, 0-1% Fe2O3
, and a total of 0 to 1.5% of CeO2, TiO2, V2O5 or MoO3 is preferred. Further, in U.S. Pat. No. 4,701,425, expressed in weight percent, 60 to 80%
SiO2, 10-20% Na2O, 0-10% K2O, 5-16% CaO, 0-10% M
gO, 0-5% Al2O3, 0-0.5
% SO3, 0.29-0.6% Fe2O3,
0.1-1.5% SnO2, 0.1-1.6
An infrared and ultraviolet absorbing glass composition is disclosed consisting essentially of % TiO2.
【０００４】0004
【発明が解決しようとする問題点】前述したような例え
ば特開昭６４ー１８９３８ 号公報に記載のものは、Ｓ
Ｏ３ 成分を０．０２重量％より少なくし、通常のフロ
ート法による板ガラス製造での溶融操作手段では到底所
期の赤外線紫外線吸収ガラスを得ることが困難であって
、種々の複雑な手段工程、例えば液化段階、溶解段階、
清澄段階、攪拌室ならびに攪拌器等が必要となるような
ものであり、また米国特許第４７０１４２５ 号に記載
のものは必ずしも充分易強化のガラス組成物であるとは
言い難く、しかも赤外線の吸収においても必ずしも充分
優れるものとは言い難いものである。Problems to be Solved by the Invention: For example, the problem described in Japanese Unexamined Patent Application Publication No. 18938/1983, as mentioned above, is
It is difficult to reduce the O3 component to less than 0.02% by weight and obtain the desired infrared and ultraviolet absorbing glass using the melting operation means used in the production of sheet glass using the ordinary float method, and various complicated means and processes are required, e.g. liquefaction stage, dissolution stage,
The glass composition described in US Pat. No. 4,701,425 cannot be said to be sufficiently easily strengthened, and moreover, it is difficult to say that the glass composition described in US Pat. No. 4,701,425 is sufficiently easy to strengthen. However, it is difficult to say that it is necessarily sufficiently superior.
【０００５】[0005]
【問題点を解決するための手段】本発明は、従来のかか
る欠点に鑑みてなしたものであって、熱膨張係数、ヤン
グ率およびポアソン比を大きい方にかつ熱伝導率を小さ
い方になるようにするとともに、赤外線と紫外線を充分
所期の吸収を有するものであって、比較的透視性がある
緑系の色調を発現し、しかも耐候性、成形性も充分に有
する易強化性の赤外線紫外線吸収ガラスおよびその製法
を提供するものである。[Means for Solving the Problems] The present invention has been made in view of the above-mentioned drawbacks of the conventional art. In addition, it has sufficient absorption of infrared rays and ultraviolet rays, exhibits a relatively translucent green tone, and has sufficient weather resistance and moldability, and is easily reinforced. The present invention provides an ultraviolet absorbing glass and a method for producing the same.
【０００６】すなわち、本発明は、重量％で表示して、
実質的に下記酸化物であり、６８〜７２％ＳｉＯ２、１
．６ 〜３．０ ％Ａｌ２Ｏ３ 、８．５ 〜１１．０
％ＣａＯ 、２．０ 〜４．２ ％ＭｇＯ 、１２．０
〜１６．０％Ｎａ２Ｏ、０．５ 〜３．０ ％Ｋ２Ｏ
、０．０８〜０．３０％ＳＯ３ 、０．６５〜０．７５
％Ｆｅ２Ｏ３ 、０．２０〜０．３５％ＣｅＯ２、０．
１ 〜０．２ ％ＴｉＯ２、ならびに微量成分としてＭ
ｎＯ ５ 〜３００ｐｐｍを含み、これら成分の総和が
９８％以上であって、かつ７０．０〜７４．０％ＳｉＯ
２＋Ａｌ２Ｏ３ ＋ＴｉＯ２、 １２．０〜１５．０
％ＣａＯ ＋ＭｇＯ 、１３．５〜１７．０％Ｎａ２Ｏ
＋Ｋ２Ｏ であることを特徴とする赤外線紫外線吸収ガ
ラス。ならびに５ｍｍ 厚換算で、Ａ 光源による可視
光線透過率が６７％以上、日射透過率が３７〜４５％、
紫外線透過率が７〜１３％、主波長が５０６ 〜５１８
ｎｍ、刺激純度が３．５ 以下であることを特徴とす
る前記赤外線紫外線吸収ガラス。さらに前記赤外線紫外
線吸収ガラスを製造するに当たり、原料としてイルメナ
イト、あるいは／および微量原料として炭素、Ｚｎ、Ｓ
ｎ等の金属粉または酸化物のうち少なくとも一つを用い
ることを特徴とする赤外線紫外線吸収ガラスの製法を提
供するものである。[0006] That is, in the present invention, expressed in weight%,
Substantially the following oxide, 68-72% SiO2,1
．． 6-3.0% Al2O3, 8.5-11.0
%CaO, 2.0-4.2% MgO, 12.0
~16.0% Na2O, 0.5 ~3.0% K2O
, 0.08-0.30% SO3, 0.65-0.75
%Fe2O3, 0.20-0.35%CeO2, 0.
1 to 0.2% TiO2, as well as M as a minor component
nO 5 to 300 ppm, the sum of these components is 98% or more, and 70.0 to 74.0% SiO
2+Al2O3 +TiO2, 12.0~15.0
%CaO + MgO, 13.5-17.0% Na2O
An infrared and ultraviolet absorbing glass characterized by +K2O. And in terms of 5 mm thickness, visible light transmittance by A light source is 67% or more, solar transmittance is 37-45%,
Ultraviolet transmittance is 7-13%, main wavelength is 506-518
The infrared and ultraviolet absorbing glass has an excitation purity of 3.5 nm or less. Furthermore, in producing the infrared and ultraviolet absorbing glass, ilmenite is used as a raw material, and/or carbon, Zn, and S are used as trace raw materials.
The present invention provides a method for producing an infrared and ultraviolet absorbing glass characterized by using at least one of metal powder or oxide such as metal powder such as n.
【０００７】ここで、ＳｉＯ２成分を重量％で６８〜７
２％としたのは、６８％未満では表面にやけ等が発生し
やすく耐候性が下がり実用上の問題が生じてくるもので
あり、７２％を超えるとその易強化性が下がり、溶融も
難しくなるものであり、Ａｌ２Ｏ３ 成分を重量％で１
．６ 〜３．０ ％としたのは、１．６ ％未満では耐
候性が下がり表面にやけ等が発生しやすく実用上の問題
が生じてくるものであり、３％を超えると失透が生じや
すくなり成形温度範囲が狭くなり製造が難しくなるもの
であり、ＣａＯ 成分を重量％で８．５ 〜１１．０％
としたのは、８．５ ％未満では易強化性が下がり、ま
た融剤として不足気味となり溶融温度も高くなりまた流
動温度を低くしないので製造しにくくなり、１１％を超
えると失透し易くなり、成形作業範囲が狭くなり製造が
難しくなるものであり、ＭｇＯ 成分を重量％で２．０
〜４．２ ％としたのは、２．０ ％未満では溶融温
度が上がり操作範囲を狭めるので製造がしにくくなり、
４．２ ％を超えると易強化性が下がるものであり、Ｎ
ａ２Ｏ成分を重量％で１２．０〜１６．０％としたのは
、１２．０未満では易強化性が下がり、成形性が難しく
なり、失透も生じ易くなるので操作範囲が狭まり製造し
にくくなり、１６％を超えると耐候性が下がり、表面に
やけ等が発生しやすくなり実用上の問題が生じてくるも
のであり、Ｋ２Ｏ 成分を重量％で０．５ 〜３．０
％としたのは、０．５ ％未満では易強化性が下がり、
３．０ ％を超えると耐候性が下がりかつコストも高く
なるものであり、ＳＯ３ 成分を重量％で０．０８〜０
．３０％としたのは、０．０８％未満では例えば通常の
溶融において脱泡あるいは均質性上不充分となり易い程
度にしかできなくなり、０．３０％を超えると特にガラ
スの着色状態に影響を与え、例えば黄色やアンバー色が
かった色調に移行し易くなる等が発現し所期の緑系色調
が得られなくなるためであり、好ましくは０．１５％前
後とどちらかと言えば範囲内でも低いところがよいもの
である。[0007] Here, the SiO2 component is 68 to 7% by weight.
The reason why it is set at 2% is that if it is less than 68%, the surface will easily become burnt, weather resistance will decrease, and practical problems will occur.If it exceeds 72%, its easy strengthening properties will decrease and it will be difficult to melt. The Al2O3 component is 1% by weight.
．． The reason why the content is set at 6 to 3.0% is that if it is less than 1.6%, the weather resistance will deteriorate and the surface will easily become stained, causing practical problems, whereas if it exceeds 3%, devitrification will occur. The CaO content is 8.5 to 11.0% by weight, which makes the molding temperature range narrow and difficult to manufacture.
The reason for this is that if it is less than 8.5%, the ease of strengthening will decrease, and it will tend to be insufficient as a flux, resulting in a high melting temperature and will not lower the flow temperature, making it difficult to manufacture.If it exceeds 11%, it will tend to devitrify. This narrows the molding work range and makes manufacturing difficult, and the MgO component is 2.0% by weight.
-4.2% is because if it is less than 2.0%, the melting temperature will rise and the operating range will be narrowed, making it difficult to manufacture.
If it exceeds 4.2%, the ease of reinforcement decreases, and N
The reason why the a2O component is set to 12.0 to 16.0% by weight is that if it is less than 12.0, the ease of strengthening will decrease, moldability will be difficult, and devitrification will easily occur, so the operating range will be narrowed and manufacturing will be difficult. If the K2O content exceeds 16%, the weather resistance will decrease and the surface will easily become stained, causing practical problems.
% because if it is less than 0.5%, the ease of reinforcement will decrease.
If it exceeds 3.0%, the weather resistance will decrease and the cost will increase.
．． The reason why it is set at 30% is that if it is less than 0.08%, it will only be possible to achieve defoaming or have insufficient homogeneity in normal melting, and if it exceeds 0.30%, it will particularly affect the coloring state of the glass. This is because, for example, the color tone tends to shift to yellow or amber, making it impossible to obtain the desired green color tone. Preferably, it should be around 0.15%, which is rather low within the range. It is something.
【０００８】また、Ｆｅ２Ｏ３ 成分を重量％で０．６
５〜０．７５％したのは、赤外線を吸収するＦｅＯ 成
分量と紫外線を吸収し所期の色調を確保するＦｅ２Ｏ３
成分量との総量として、前述した各種光学特性を安定
して得るために、他のＣｅＯ２、ＴｉＯ２等の各成分量
とともにことに必要であり、０．６５％未満では上述に
対する作用が劣り、０．７５％を超えると特に可視光線
透過率が劣ることとなる等好ましくないからであり、Ｃ
ｅＯ２とＴｉＯ２成分は紫外線の吸収作用を有し、Ｃｅ
Ｏ２成分を０．２０〜０．３５％とし、ＴｉＯ２成分を
０．１ 〜０．２ ％としたのは、ガラスにおける還元
率をほとんど変化させないしかも紫外線吸収能がＣｅＯ
２成分より小さいＴｉＯ２成分と、ガラスにおける還元
率を比較的大きく変化させしかも紫外線吸収能を充分与
えるＣｅＯ２成分とを上述の特定範囲内に限定して組み
合わすことで、僅かの含有量で所期の特性を効率的に得
ることでき、従来の還元率をほとんど変化させないよう
にしつつ、Ｃｅのガラス中での価数をＣｅ４＋、Ｃｅ３
＋のうち、ほぼ無色のＣｅ３＋が主になるようにし、前
述した全鉄におけるＦｅ２Ｏ３ とＦｅＯ との割合を
制御して、可視光領域の透過率を全体的に低下させない
ようにしかつ紫外線吸収や赤外線吸収等所期の光学特性
を達成し得るようにするためであり、さらにＭｎＯ 成
分を５ 〜３００ｐｐｍとしたのは、ＦｅとＭｎとの関
係ではＦｅが酸化される方向でかつ微量ながら還元率が
低い方向になる傾向があり、ＣｅとＭｎとの関係ではＭ
ｎが酸化される方向であって還元率には影響が殆どない
ものである等によって、ＭｎがＦｅとＣｅらとあいまっ
て中性的に相互作用させながら、約５００ｎｍ 付近に
あるＭｎＯ の吸収波長でもって前記色調調整を、大き
な影響を与えないで微力ながら調整できるようにしたも
のであり、またＭｎＯ 成分を多量に用いれば例えばソ
ラリゼーション等の現象を発現するように成り易くなる
などから３００ｐｐｍを超えないようにしたものである
。[0008] Also, the Fe2O3 component is 0.6% by weight.
The content of 5% to 0.75% is FeO, which absorbs infrared rays, and Fe2O3, which absorbs ultraviolet rays and maintains the desired color tone.
In order to stably obtain the various optical properties described above, the total amount of the components is particularly necessary together with the amounts of other components such as CeO2 and TiO2, and if it is less than 0.65%, the above effects will be poor This is because if it exceeds .75%, the visible light transmittance will deteriorate, which is undesirable.
eO2 and TiO2 components have an ultraviolet absorbing effect, and Ce
The reason why the O2 component is set to 0.20 to 0.35% and the TiO2 component is set to 0.1 to 0.2% is that they hardly change the reduction rate in the glass, and the ultraviolet absorption ability is higher than that of CeO2.
By combining the TiO2 component, which is smaller than the two components, and the CeO2 component, which changes the reduction rate in glass relatively significantly and provides sufficient ultraviolet absorption ability, within the above-mentioned specific range, the desired amount can be achieved with a small content. It is possible to efficiently obtain the characteristics of Ce4+ and Ce3 while keeping the conventional reduction rate almost unchanged.
Among the +, the almost colorless Ce3+ is made to be the main one, and the ratio of Fe2O3 and FeO2 in the total iron mentioned above is controlled so as not to reduce the overall transmittance in the visible light region, and to prevent ultraviolet absorption and infrared ray absorption. This was to achieve the desired optical properties such as absorption, and the reason why the MnO content was set at 5 to 300 ppm was that in the relationship between Fe and Mn, Fe would be oxidized and the reduction rate would be reduced, albeit in a small amount. There is a tendency toward lower values, and in the relationship between Ce and Mn, M
Because n is in the direction of oxidation and has little effect on the reduction rate, Mn interacts neutrally with Fe, Ce, etc., and the absorption wavelength of MnO is around 500 nm. Therefore, it is possible to adjust the color tone in a small way without having a large effect, and if a large amount of MnO is used, phenomena such as solarization are likely to occur, so if the amount exceeds 300 ppm. I tried to avoid it.
【０００９】また、ＳｉＯ２、Ａｌ２Ｏ３ 、ＣａＯ
、ＭｇＯ 、Ｎａ２Ｏ、Ｋ２Ｏ 、Ｆｅ２Ｏ３ 、ＳＯ
３ 、ＣｅＯ２、ＴｉＯ２、ＭｎＯ の成分の総和を重
量百分率で９８％以上としたのは、例えばＺｎＯ 、Ｓ
ｎＯ２等微量成分を２ ％を超えない量に制御するため
である。なかでもＶ２Ｏ５成分を任意成分として０ 〜
０．２５％程度添加することがあり、該Ｖ２Ｏ５は還元
率をほとんど変化させることがなくしかも紫外線吸収能
がＣｅＯ２成分より小さく影響が少ないからで微調整に
添加用いるものであり、Ｖ のガラス中での価数を黄色
を呈するＶ５＋ が極力少なくし緑色を呈するＶ３＋
に主になるようにする必要がある等のためである。[0009] Also, SiO2, Al2O3, CaO
, MgO, Na2O, K2O, Fe2O3, SO
3. The sum of the components of CeO2, TiO2, and MnO was made to be 98% or more by weight, for example, ZnO, S
This is to control trace components such as nO2 to an amount that does not exceed 2%. Among them, the V2O5 component is an optional component of 0 ~
Approximately 0.25% of V2O5 is sometimes added, and V2O5 hardly changes the reduction rate, and its ultraviolet absorption ability is smaller than the CeO2 component, so it has less influence, so it is used for fine adjustment. The valence of V5+, which exhibits yellow color, is reduced as much as possible to create V3+, which exhibits green color.
This is mainly because you need to be like that.
【００１０】さらに、ＳｉＯ２＋Ａｌ２Ｏ３ ＋ＴｉＯ
２を重量百分率で７０．０〜７４．０％としたのは、７
０％未満では耐候性が下がり、７４％を超えると易強化
性が下がる問題が生じるものであり、ＣａＯ ＋ＭｇＯ
を重量百分率で１２．０〜１５．０％としたのは、Ｃ
ａＯ およびＭｇＯ 成分は溶融温度を下げるために用
いられるとともに、１２％未満では易強化性が下がり、
１５％を超えると失透しやすくなり製造上難しくなるも
のであり、Ｎａ２Ｏ＋Ｋ２Ｏ を百分率で１３．５〜１
７％としたのは、１３．５％未満では易強化性が下がり
、失透も生じやすくなって成形において作業温度範囲が
狭くなり、製造が難しくなり、１７％を超えると耐候性
が下がり実用上の問題を生じるものであるとともにコス
ト的にも高くなるものである。[0010] Furthermore, SiO2+Al2O3 +TiO
The weight percentage of 2 is 70.0 to 74.0%, which means 7.
If it is less than 0%, the weather resistance will decrease, and if it exceeds 74%, there will be a problem that the easy strengthening property will decrease.
The weight percentage of C was set at 12.0 to 15.0%.
The aO and MgO components are used to lower the melting temperature, and if they are less than 12%, the easy strengthening property decreases,
If it exceeds 15%, devitrification tends to occur, making it difficult to manufacture.
The reason for setting it at 7% is that if it is less than 13.5%, the ease of strengthening will decrease and devitrification will occur easily, and the working temperature range in molding will be narrow, making manufacturing difficult.If it exceeds 17%, the weather resistance will decrease and it will not be practical. This not only causes the above problems, but also increases costs.
【００１１】さらにまた、５ｍｍ 厚換算で、Ａ 光源
による可視光線透過率が６７％以上、日射透過率が３７
〜４５％、紫外線透過率が７ 〜１３％、主波長が５０
６ 〜５１８ ｎｍ、刺激純度が３．５ 以下であるこ
とが好ましいとしたのは、前記可視光線透過率が６７％
未満では特に自動車のフロント窓ガラスにおいてガラス
の透視性、ことに日暮れ、夜間あるいは雨降りなどに際
し、物体の識別性の低下が発現しやすく好ましくなく、
より好ましくは７０％前後、さらに好ましくは７５％前
後であり、日射透過率が４５％を超えると冷房負荷の増
大あるいは車内・室内での居住性を向上することができ
ないこととなり、３７％未満では透視性ことに前述した
識別性の低下あるいは色調にも影響を与え兼ねないこと
となるので好ましくなく、紫外線透過率が１３％を超え
ると車内・室内での物品の脱色・劣化あるいは肌焼け等
人的影響により居住性の悪化に結び付き易く、７％未満
では例えば前記日射透過率が得られなくなる等の弊害が
発生し易くなり、主波長が５１８ｎｍ を超えると黄色
あるいはアンバー色が影響して所期の緑色調系に成らず
、５０６ｎｍ 未満ではブルー色が勝ち過ぎて所期の緑
色調系と成らないためであり、好ましい主波長は５０９
〜５１５ であり、刺激純度が３．５ を超えると物
体の識別性が低下するようになって例えば日暮れやどん
よりした雨降り等で乗員の透視性に支障を来し、安全性
の確保等が困難となるためである。なお紫外線域は２９
０ 〜３９０ｎｍとし、可視域等は従来通りとした。Furthermore, in terms of 5 mm thickness, the visible light transmittance by light source A is 67% or more, and the solar transmittance is 37%.
~45%, UV transmittance 7~13%, dominant wavelength 50%
6 to 518 nm, and the excitation purity is preferably 3.5 or less because the visible light transmittance is 67%.
If it is less than 100%, the transparency of the glass, particularly in the front window of a car, is undesirable, as it tends to reduce the ability to distinguish objects, especially at dusk, at night, or in the rain.
More preferably, it is around 70%, and even more preferably around 75%. If the solar transmittance exceeds 45%, the cooling load will increase or the comfort inside the car will not be improved, and if it is less than 37%, This is undesirable as it may reduce the visibility and distinguishability mentioned above or affect the color tone.If the ultraviolet transmittance exceeds 13%, it may cause discoloration or deterioration of items in the car or interior, or may cause skin burns or other problems for people. If it is less than 7%, problems such as not being able to obtain the above-mentioned solar transmittance are likely to occur, and if the dominant wavelength exceeds 518nm, the yellow or amber color will be affected and the desired This is because if the wavelength is less than 506 nm, the blue color will be too dominant and the desired green tone will not be achieved.The preferable dominant wavelength is 509 nm.
~515, and when the stimulus purity exceeds 3.5, the ability to distinguish objects decreases, and for example, at dusk or in heavy rain, the visibility of the occupants becomes impaired, making it difficult to ensure safety. This is because. The UV range is 29
The wavelength range was 0 to 390 nm, and the visible range remained the same as before.
【００１２】さらにまた、前記赤外線紫外線吸収ガラス
を製造するに当たり、原料としてイルメナイトを用いた
方が好ましいとしたのは、ＦｅＯ ならびにＴｉＯ２か
らほぼ成るため、ＦｅＯ のガラス中への取り込みが少
しでも容易となり、しかも実窯の操業条件等をほぼ不変
とし、ガラスの酸化還元状態を従来と出来るだけ変えな
いように、すなわち実窯で還元率が約０．４５程度であ
るのに対し本発明の赤外線紫外線吸収ガラスの製造に当
たってはＣｅＯ２等種々の作用を加味し０．３ 〜０．
４ 程度（例えば実窯の還元率の約７割前後）とするの
に少しでも役立つためであり、微量原料として炭素、Ｚ
ｎ、Ｓｎ等の金属粉または酸化物のうち少なくともその
一つを用いると好ましいとしたのは、例えば時として芒
硝（Ｎａ２ＳＯ４）等清澄剤の作用効果を助ける必要が
あり、一方では前記所期の色調の確保に悪い影響を与え
ることともなり易く、ＺｎあるいはＳｎ等還元剤もＦｅ
２Ｏ３ とＦｅＯ とのバランスを調整するために必要
な場合もあるためである。Furthermore, in manufacturing the infrared and ultraviolet absorbing glass, it is preferable to use ilmenite as a raw material because it is composed almost of FeO and TiO2, so it is easier to incorporate FeO into the glass. In addition, the operating conditions of the actual kiln are kept almost unchanged, and the oxidation-reduction state of the glass is kept as unchanged as possible from the conventional one. When producing absorbent glass, various effects such as CeO2 are taken into account and the absorption glass is 0.3 to 0.
4 (for example, around 70% of the reduction rate in a real kiln), and carbon and Z are used as trace raw materials.
The reason why it is preferable to use at least one of metal powders or oxides such as n, Sn, etc. is because, for example, sometimes it is necessary to support the action and effect of a fining agent such as sodium sulfate (Na2SO4), and on the other hand, Reducing agents such as Zn or Sn also tend to have a negative effect on securing the color tone.
This is because it may be necessary to adjust the balance between 2O3 and FeO.
【００１３】なお、本発明の赤外線紫外線吸収ガラスは
易強化ガラス組成物であって、板厚１ｍｍ 前後の薄板
ガラスから１０ｍｍ前後の厚板ガラスで、平板または曲
げ板として生板から強度アップしたもの、半強化したも
の、強化したもの等で、単板ガラス、合せガラス、積層
ガラスあるいは複層ガラス等で用いることが、ことに車
両用窓ガラスで用いることが有用である。[0013] The infrared and ultraviolet absorbing glass of the present invention is an easily temperable glass composition, and can be made from a thin plate glass with a plate thickness of about 1 mm to a thick plate glass with a plate thickness of about 10 mm, which has been strengthened from a raw plate as a flat plate or a bent plate. It is semi-strengthened, reinforced, etc., and is useful for use in single-pane glass, laminated glass, laminated glass, double-layered glass, etc., and is particularly useful in vehicle window glass.
【００１４】[0014]
【作用】前述したとおり、本発明の赤外線紫外線吸収ガ
ラスならびにその製法であって、特定酸化物成分を特定
組成範囲で組み合わせたガラスとし、あるいは特異な原
料を易強化性を持たせしかも還元率の低下を抑制するよ
う組み合わせて用い、上述したガラスを製造することに
よって、例えば溶融性、清澄性、耐候性、成形性、失透
性、コスト等を考慮し、従来のフロートガラスの製造条
件ならびにそのガラスの性質等をほとんど変化させず、
加えて易強化性を持ち合わせかつ赤外線ならびに紫外線
を吸収して人的物的に高居住性であって、物体の識別も
優れた透視性を充分持つものとなって高安全性を確保で
き、グリーン色調系で例えば車・室内外と充分調和のあ
るものとなって環境的にも優れたものとなり、さらに、
従来の熱強化方法では得られなかった薄板ガラス等でも
、充分な強化度あるいは充分強度アップが得られるよう
になり、建築用窓ガラスはもちろん家具用ガラス、調理
用ガラス、ことに自動車用等車両用窓ガラス等に有用な
赤外線紫外線吸収ガラスを提供できるものである。[Function] As mentioned above, the infrared and ultraviolet absorbing glass of the present invention and the method for producing the same include a glass that combines specific oxide components in a specific composition range, or a glass that combines specific oxide components in a specific composition range, or uses specific raw materials to have easy strengthening properties and to reduce the reduction rate. By manufacturing the above-mentioned glasses in combination to suppress the deterioration, we can improve the conventional float glass manufacturing conditions and their It hardly changes the properties of glass,
In addition, it is easy to strengthen, absorbs infrared rays and ultraviolet rays, making it highly livable for people and physical objects, and has sufficient transparency with excellent object identification, ensuring high safety and making it green. The color tone is in perfect harmony with the interior and exterior of a car, for example, and is environmentally friendly.Furthermore,
It is now possible to obtain a sufficient degree of strengthening or sufficiently increased strength even for thin glass, etc., which could not be obtained using conventional thermal strengthening methods, and it is now possible to obtain a sufficient degree of reinforcement or increase in strength. It is possible to provide infrared and ultraviolet absorbing glass useful for window glasses and the like.
【００１５】[0015]
【実施例】以下本発明の実施例について説明する。[Examples] Examples of the present invention will be described below.
【００１６】実施例１
通常方法によって、ガラスは特選珪砂（共立窯業製）と
１級試薬であるＡｌ２Ｏ３ 、Ｆｅ２Ｏ３ 、ＣａＣＯ
３ 、ＭｇＣＯ３ 、Ｎａ２ＳＯ３、ＫＮＯ３、ＣｅＯ
２、ＴｉＯ２、ＭｎＯ 、イルメナイト等を用い、粘性
温度が１０９ ポイズで６５０ 〜６８５ ℃、１０１
２ポイズで５５５ 〜５８５ ℃、かつ両者の温度差が
９６〜１０３ ℃になるようになるガラス組成を目標組
成として秤量調合し、ことに実窯と多少低い程度の還元
率（０．３５前後）を得るためカーボンを０．１７５
重量％程度添加調合したものであって、該調合原料をル
ツボに入れ、約１４５０℃前後に保持した電気炉中で約
３時間程度溶融しガラス化して、さらに均質化および清
澄のため、１４２０〜１４３０℃で約２時間程度保持し
た後、型に流し出しガラスブロックとし、大きさ１００
ｍｍ ×１００ｍｍ で厚み約５ｍｍのガラス板に切り
出し、研削研磨し、各試料とした。Example 1 Glass was prepared using specially selected silica sand (manufactured by Kyoritsu Ceramics) and primary reagents such as Al2O3, Fe2O3, and CaCO.
3, MgCO3, Na2SO3, KNO3, CeO
2. Using TiO2, MnO, ilmenite, etc., the viscosity temperature is 109 poise, 650 to 685 °C, 101
We weighed and prepared a glass composition with a target composition that would produce a temperature of 555 to 585 degrees Celsius at 2 poise and a temperature difference of 96 to 103 degrees Celsius, and in particular, the reduction rate was a little lower than that of the actual kiln (around 0.35). 0.175 carbon to obtain
The blended raw material is placed in a crucible, melted and vitrified for about 3 hours in an electric furnace maintained at around 1450°C, and further homogenized and clarified at 1420~ After keeping it at 1430℃ for about 2 hours, it was poured into a mold and made into a glass block with a size of 100℃.
Each sample was cut out into a glass plate measuring 100 mm x 100 mm and approximately 5 mm thick, and ground and polished.
【００１７】この試料について、ガラス成分組成（重量
％）についてはＪＩＳＲ−３１０１に基づく湿式分析法
等で行い、粘性温度（℃）についてはベンディングアー
ム法により粘度曲線を測定して１０９ および１０１２
ポイズの温度を求めるとともに、リリー法によって歪点
、リトルトン法によって軟化点を測定し、光学特性（５
ｍｍ厚みにおける）としての可視光線透過率（Ａ光源に
て、％）、紫外線透過率（％）、および日射透過率、主
波長（ｎｍ）、刺激純度については３４０ 型自記分光
光度計（日立製作所製）とＪＩＳ Ｚ−８７２２、ＪＩ
Ｓ Ｒ−３１０６、ＩＳＯ／ＤＩＳ−９０５０にて測定
計算して求める等を行った。Regarding this sample, the glass component composition (wt%) was determined by a wet analysis method based on JISR-3101, and the viscosity temperature (°C) was determined by measuring the viscosity curve by the bending arm method.
In addition to determining the temperature of the poise, the strain point was measured using the Lilly method, the softening point was measured using the Littleton method, and the optical properties (5
Visible light transmittance (with A light source, %), UV transmittance (%), and solar transmittance, dominant wavelength (nm), and excitation purity as measured using a 340-type self-recording spectrophotometer (Hitachi, Ltd.). ) and JIS Z-8722, JI
Measurement and calculation were performed using SR-3106 and ISO/DIS-9050.
【００１８】その結果、ガラス成分組成は重量表示でＳ
ｉＯ２６９．７％、Ａｌ２Ｏ３１．９％、ＣａＯ９．１
％、ＭｇＯ３．５％、Ｎａ２Ｏ１３．４％、Ｋ２Ｏ１．
０％、Ｆｅ２Ｏ３０．６９５％、ＴｉＯ２０．１５％、
ＣｅＯ２０．２７％、ＳＯ３０．１８ ％、ＭｎＯ １
０８ｐｐｍと成り、成分の総和が９９．９０６％であっ
てかつＳｉＯ２＋Ａｌ２Ｏ３＋ＴｉＯ２７１．７５ ％
、ＣａＯ ＋ＭｇＯ１２．６ ％、Ｎａ２Ｏ＋Ｋ２Ｏ１
４．４ ％であり、還元率（Ｆｅ２＋／Ｆｅ３＋）は０
．３０〜０．３５程度となった。As a result, the glass component composition was expressed as S in terms of weight.
iO269.7%, Al2O31.9%, CaO9.1
%, MgO3.5%, Na2O13.4%, K2O1.
0%, Fe2O30.695%, TiO20.15%,
CeO20.27%, SO30.18%, MnO1
08 ppm, and the sum of the components is 99.906%, and SiO2 + Al2O3 + TiO2 71.75%
, CaO + MgO12.6%, Na2O + K2O1
4.4%, and the reduction rate (Fe2+/Fe3+) is 0.
．． It was about 30 to 0.35.
【００１９】また光学特性は、可視光線透過率が７１．
３％、日射透過率が４３％、主波長が５１２．２ｎｍ
、刺激純度が２．８ であり、所期のグリーン系色調で
あった。As for the optical properties, the visible light transmittance is 71.
3%, solar transmittance 43%, main wavelength 512.2nm
The stimulus purity was 2.8, and the desired green color tone was obtained.
【００２０】さらに易強化性については、上述したガラ
スが前述した粘性温度が所期の特定範囲をクリヤーして
いることならびに軟化点と歪点との温度差が大体２００
〜２４０ ℃の範囲にあることを確認した上、前記試
料を雰囲気温度約７３０ ℃の炉内で約５分間前後加熱
した後、エア圧約１３００Ａｐで通常の風冷強化し、大
きさ１２０ｍｍ ×１００ｍｍ で板厚約３．５ｍｍ
程度の強化ガラス板を得、該強化ガラス板のコーナー部
の角端面から約３０ｍｍの位置で衝撃を与えて破砕し、
全面に破砕された該ガラス板をＪＩＳ Ｒ−３２１１に
従って調べたところ、決められた規格を充分満足する高
易強化性のものであった。Furthermore, regarding ease of strengthening, the above-mentioned glass has a viscosity temperature that is within the desired specific range, and a temperature difference between the softening point and the strain point of approximately 200°C.
After confirming that the temperature is in the range of ~240 °C, the sample was heated in a furnace at an ambient temperature of about 730 °C for about 5 minutes, then strengthened with normal air cooling at an air pressure of about 1300 Ap, and was heated to a size of 120 mm x 100 mm. Plate thickness approximately 3.5mm
A tempered glass plate of about 100 mL was obtained, and the tempered glass plate was crushed by impact at a position approximately 30 mm from the corner end face of the corner portion,
When the glass plate, which had been completely crushed, was examined in accordance with JIS R-3211, it was found to be easily strengthenable, fully satisfying the established standards.
【００２１】なお、本発明の約２．５ｍｍ 板厚の曲げ
赤外線紫外線吸収ガラスを外側に用い、内側に約２ｍｍ
板厚の熱線反射膜被覆曲げガラス板を配し、該膜側を内
側にしてＰＶＢ 中間膜を介して積層した合せガラスを
試作し、自動車の窓ガラスに用いたところ、本発明の作
用効果を高めるとともにさらに多機能化され、車内外の
居住性なよびに安全性がより優れたものと成るものであ
った。The bent infrared and ultraviolet absorbing glass of the present invention with a thickness of about 2.5 mm is used on the outside, and the bent infrared and ultraviolet absorbing glass with a thickness of about 2 mm is used on the inside.
We fabricated a prototype laminated glass in which thick bent glass plates coated with a heat ray reflective film were laminated with a PVB interlayer between them with the film side facing inside, and used it in an automobile window glass. It was designed to increase the height of the vehicle, make it even more functional, and improve comfort and safety both inside and outside the vehicle.
【００２２】実施例２
前記実施例１と同様なガラス原料を用い、秤量調合し、
溶融操作をし、得たガラスを同様に試料化した。Example 2 Using the same glass raw materials as in Example 1, weighing and mixing,
A melting operation was performed, and the resulting glass was sampled in the same manner.
【００２３】得られた試料について前記実施例１と同様
に分析、測定、評価した結果、ガラス成分組成は重量表
示でＳｉＯ２７０．６％、Ａｌ２Ｏ３１．６％、ＣａＯ
９．５％、ＭｇＯ ２．５ ％、Ｎａ２Ｏ１３．５％、
Ｋ２Ｏ０．９％、Ｆｅ２Ｏ３０．６８７％、ＴｉＯ２０
．１７％、ＣｅＯ２０．３１％、ＳＯ３０．１３ ％、
ＭｎＯ ８０ｐｐｍ と成り、成分の総和が９９．９０
５％であって、ＳｉＯ２＋Ａｌ２Ｏ３ ＋ＴｉＯ２７２
．３７ ％、ＣａＯ ＋ＭｇＯ １２．０％、Ｎａ２Ｏ
＋Ｋ２Ｏ １４．４％であり、還元率は前記と同様に０
．３０〜０．３５程度となった。光学特性は可視光線透
過率が７０．６％、日射透過率が４２％、主波長が５０
９．２ｎｍ 、刺激純度が３．０ であり、所期のグリ
ーン系色調であった。The obtained sample was analyzed, measured, and evaluated in the same manner as in Example 1. As a result, the glass component composition was 70.6% SiO2, 1.6% Al2O3, and CaO2 in terms of weight.
9.5%, MgO 2.5%, Na2O 13.5%,
K2O0.9%, Fe2O30.687%, TiO20
．． 17%, CeO20.31%, SO30.13%,
MnO is 80ppm, and the sum of the components is 99.90.
5%, SiO2 + Al2O3 + TiO272
．． 37%, CaO + MgO 12.0%, Na2O
+K2O 14.4%, and the reduction rate is 0 as above.
．． It was about 30 to 0.35. Optical properties include visible light transmittance of 70.6%, solar transmittance of 42%, and dominant wavelength of 50%.
It had a wavelength of 9.2 nm, an excitation purity of 3.0, and the expected green color tone.
【００２４】さらに易強化性についても、前記実施例１
と同様に実施したところ、前記実施例１と同様にＪＩＳ
で決められた規格を充分満足するものであって、薄い
ガラス板でも高効率、高歩留りで前記規格に合格するも
のが得れるようになるものであった。[0024] Furthermore, regarding easy reinforcement, the above-mentioned Example 1
When carried out in the same manner as in Example 1, JIS
It fully satisfies the standards set by the above standards, and even thin glass plates that meet the standards can be obtained with high efficiency and high yield.
【００２５】実施例３
前記実施例１と同様なガラス原料を用い、秤量調合し、
溶融操作をし、得たガラスを同様に試料化した。Example 3 Using the same glass raw materials as in Example 1, weighing and mixing,
A melting operation was performed, and the resulting glass was sampled in the same manner.
【００２６】得られた試料について前記実施例１と同様
に分析、測定、評価した結果、ガラス成分組成は重量表
示でＳｉＯ２６９．３％、Ａｌ２Ｏ３１．８％、ＣａＯ
９．８％、ＭｇＯ ３．３ ％、Ｎａ２Ｏ１３．４
％、Ｋ２Ｏ１．０％、Ｆｅ２Ｏ３０．６８５％、ＴｉＯ
２０．１２％、ＣｅＯ２０．３０％、ＳＯ３０．１５
％、ＭｎＯ ５５ｐｐｍ と成り、成分の総和が９９．
９１９％であって、ＳｉＯ２＋Ａｌ２Ｏ３ ＋ＴｉＯ２
７１．２３ ％、ＣａＯ ＋ＭｇＯ １３．１％、Ｎａ
２Ｏ＋Ｋ２Ｏ １４．４％ であり、還元率は前記と
同様に０．３０〜０．３５程度となった。光学特性は可
視光線透過率が７１．０％、日射透過率が４２．７％、
主波長が５１４．９ｎｍ 、刺激純度が２．８ であり
、所期のグリーン系色調であった。The obtained sample was analyzed, measured, and evaluated in the same manner as in Example 1. As a result, the glass component composition was 69.3% SiO2, 1.8% Al2O3, and CaO2 in terms of weight.
9.8%, MgO 3.3%, Na2O 13.4
%, K2O1.0%, Fe2O30.685%, TiO
20.12%, CeO20.30%, SO30.15
%, MnO is 55 ppm, and the total of the components is 99.
919%, SiO2 + Al2O3 + TiO2
71.23%, CaO + MgO 13.1%, Na
2O+K2O 14.4%, and the reduction rate was about 0.30 to 0.35 as above. Optical properties include visible light transmittance of 71.0%, solar transmittance of 42.7%,
The dominant wavelength was 514.9 nm, the stimulus purity was 2.8 nm, and the desired green color tone was obtained.
【００２７】さらに易強化性についても、前記実施例１
と同様に実施したところ、前記実施例１と同様にＪＩＳ
で決められた規格を充分満足するものであって、薄い
ガラス板でも高効率、高歩留りで前記規格に合格するも
のが得れるようになるものであった。[0027] Furthermore, as for easy reinforcement, the above-mentioned Example 1
When carried out in the same manner as in Example 1, JIS
It fully satisfies the standards set by the above standards, and even thin glass plates that meet the standards can be obtained with high efficiency and high yield.
【００２８】比較例１
前記イルメナイトを使用しない以外は前記実施例１と同
様なガラス原料を用い、秤量調合し、溶融操作をし、得
たガラスを同様に試料化した。Comparative Example 1 The same glass raw materials as in Example 1 were used, except that the ilmenite was not used, and the glass materials were weighed and prepared, followed by a melting operation, and the resulting glass was made into a sample in the same manner.
【００２９】得られた試料について前記実施例１と同様
に分析、測定、評価した結果、ガラス成分組成は重量表
示でＳｉＯ２７２．１％、Ａｌ２Ｏ３１．５％、ＣａＯ
７．７５ ％、ＭｇＯ ３．５６％、Ｎａ２Ｏ１２．５
％、Ｋ２Ｏ１．１％、Ｆｅ２Ｏ３０．７５３％、ＴｉＯ
２０．２５％、ＣｅＯ２０．３０％、ＳＯ３０．１８
％と成り、成分の総和が９９．９９３％であって、Ｓｉ
Ｏ２＋Ａｌ２Ｏ３ ＋ＴｉＯ２７３．８５ ％、ＣａＯ
＋ＭｇＯ１１．３１％、Ｎａ２Ｏ＋Ｋ２Ｏ １３．６
％ であり、還元率は前記と同様に０．３０〜０．３
５程度となった。光学特性は可視光線透過率が６８．４
％、日射透過率が３９．３％、主波長が５１０．５ｎｍ
、刺激純度が３．３ であり、所期のグリーン系色調
であるとは 必ずしも言えなかった。As a result of analyzing, measuring and evaluating the obtained sample in the same manner as in Example 1, the glass component composition was expressed by weight: SiO272.1%, Al2O31.5%, CaO
7.75%, MgO 3.56%, Na2O12.5
%, K2O1.1%, Fe2O30.753%, TiO
20.25%, CeO20.30%, SO30.18
%, the sum of the components is 99.993%, and Si
O2+Al2O3 +TiO273.85%, CaO
+MgO11.31%, Na2O+K2O 13.6
%, and the return rate is 0.30 to 0.3 as above.
It was about 5. Optical properties include visible light transmittance of 68.4
%, solar transmittance is 39.3%, dominant wavelength is 510.5nm
The stimulus purity was 3.3, and it could not necessarily be said that the desired green color tone was obtained.
【００３０】さらに易強化性についても、前記実施例１
と同様に実施したところ、前記各実施例とは差異がある
ものであってＪＩＳ で決められた規格を必ずしも満足
するものではなかった。また強化処理等で必ずしも効率
や歩留りを向上させるものではなかった。[0030] Furthermore, with regard to easy reinforcement, Example 1
When carried out in the same manner as above, it was found that there were differences from each of the above-mentioned examples, and the results did not necessarily satisfy the standards determined by JIS. Furthermore, strengthening treatments and the like do not necessarily improve efficiency or yield.
【００３１】比較例２
前記比較例１と同様にして得られたガラスを同様に試料
化した。得られた試料について前記実施例１と同様に分
析、測定、評価した結果、ガラス成分組成は重量表示で
ＳｉＯ２６７．０％、Ａｌ２Ｏ３１．７％、ＣａＯ９．
４５ ％、ＭｇＯ ３．０ ％、Ｎａ２Ｏ１６．１％、
Ｋ２Ｏ１．０％、Ｆｅ２Ｏ３０．５７２％、ＴｉＯ２０
．７３％、ＣｅＯ２０．２２％、ＳＯ３０．２２ ％と
成り、成分の総和が９９．９９２％であって、ＳｉＯ２
＋Ａｌ２Ｏ３ ＋ＴｉＯ２６９．４３ ％、ＣａＯ ＋
ＭｇＯ１２．４５％、Ｎａ２Ｏ＋Ｋ２Ｏ １７．１％
であり、還元率は多少増え約０．４ 前後となった。
光学特性は可視光線透過率が７０．９％、日射透過率が
４２．８％、主波長が５３８．６ｎｍ 、刺激純度が４
．２ であり、所期のグリーン系色調であるとは必ずし
も 言えなかった。Comparative Example 2 Glass obtained in the same manner as in Comparative Example 1 was similarly prepared as a sample. As a result of analyzing, measuring and evaluating the obtained sample in the same manner as in Example 1, the glass component composition was 67.0% SiO2, 1.7% Al2O3, and 9.9% CaO in terms of weight.
45%, MgO 3.0%, Na2O 16.1%,
K2O1.0%, Fe2O30.572%, TiO20
．． 73%, CeO20.22%, SO30.22%, and the total of the components is 99.992%, and SiO2
+Al2O3 +TiO269.43%, CaO +
MgO 12.45%, Na2O+K2O 17.1%
The return rate increased slightly to around 0.4. Optical properties include visible light transmittance of 70.9%, solar transmittance of 42.8%, dominant wavelength of 538.6 nm, and excitation purity of 4.
．． 2, and it could not necessarily be said that it was the expected green tone.
【００３２】さらに易強化性についても、前記実施例１
と同様に実施したところ、前記各実施例とは差異がある
ものであってＪＩＳ で決められた規格を必ずしも満足
するものではなかった。また強化処理等で必ずしも効率
や歩留りを向上させるものではなかった。[0032] Furthermore, with regard to easy reinforcement, Example 1
When carried out in the same manner as above, it was found that there were differences from each of the above-mentioned examples, and the results did not necessarily satisfy the standards determined by JIS. Furthermore, strengthening treatments and the like do not necessarily improve efficiency or yield.
【００３３】なお、上述した各実施例は本発明の一例を
示すものであって、これら実施例に限られるものではな
い。It should be noted that each of the above-mentioned embodiments shows an example of the present invention, and the present invention is not limited to these embodiments.
【００３４】[0034]
【発明の効果】本発明によれば、特定酸化物成分を特定
組成範囲で組み合わせた赤外線紫外線吸収ガラスとし、
しかも特異な原料を組み合わせて用いることで、還元率
の低下を抑制し、赤外線の吸収と紫外線の吸収とをバラ
ンス良く、充分透視性を持ち、易強化性を保持させ、所
期のグリーン系色調を呈するガラスを、実窯の操業条件
を大幅に変更することなく製造することができ、人的物
的両面で高居住性、高安全性、高環境性を有し軽量化も
可能であるものと成り、建築用窓ガラス等はもちろん、
ことに自動車用窓ガラスに適用して有用なものと成る赤
外線紫外線吸収ガラスとその製法を提供するものである
。Effects of the Invention According to the present invention, an infrared and ultraviolet absorbing glass in which specific oxide components are combined in a specific composition range,
In addition, by using a combination of unique raw materials, we can suppress the reduction rate, have a good balance between infrared and ultraviolet absorption, have sufficient transparency, maintain easy reinforcement, and achieve the desired green color tone. glass that can be manufactured without significantly changing the operating conditions of the actual kiln, and has high livability, high safety, and high environmental friendliness in terms of both human and material aspects, and is also lightweight. As a result, it can be used not only for architectural window glass, etc.
The object of the present invention is to provide an infrared and ultraviolet absorbing glass that is particularly useful when applied to automobile window glasses, and a method for producing the same.
Claims (3)
物であり、ＳｉＯ２６８〜７２％、Ａｌ２Ｏ３ １．６
〜３．０ ％、ＣａＯ ８．５ 〜１１．０％、Ｍｇ
Ｏ ２．０ 〜４．２ ％、Ｎａ２Ｏ１２．０〜１６．
０％、Ｋ２Ｏ ０．５ 〜３．０ ％、ＳＯ３ ０．０
８〜０．３０％、Ｆｅ２Ｏ３ ０．６５〜０．７５％、
ＣｅＯ２０．２０〜０．３５％、ＴｉＯ２０．１ 〜０
．２ ％、ならびに微量酸化物としてＭｎＯ ５ 〜３
００ｐｐｍを少なくとも含み、これら成分の総和が９８
％以上であって、かつＳｉＯ２＋Ａｌ２Ｏ３ ＋ＴｉＯ
２７０．０〜７４．０％、ＣａＯ ＋Ｍｇ０ １２．０
〜１５．０％、Ｎａ２Ｏ＋Ｋ２Ｏ １３．５〜１７．０
％であることを特徴とする赤外線紫外線吸収ガラス。Claim 1: Substantially the following oxides, expressed in weight%: SiO268-72%, Al2O3 1.6%
~3.0%, CaO 8.5 ~11.0%, Mg
O2.0-4.2%, Na2O12.0-16.
0%, K2O 0.5-3.0%, SO3 0.0
8-0.30%, Fe2O3 0.65-0.75%,
CeO20.20-0.35%, TiO20.1-0
．． 2%, as well as MnO 5 ~3 as trace oxides.
00 ppm, and the total of these components is 98
% or more, and SiO2 + Al2O3 + TiO
270.0-74.0%, CaO + Mg0 12.0
~15.0%, Na2O+K2O 13.5-17.0
% infrared and ultraviolet absorbing glass.
光源による可視光線透過率が６７％以上、日射透過率
が３７〜４５％、紫外線透過率が７〜１３％、主波長が
５０６ 〜５１８ ｎｍ、刺激純度が３．５ 以下であ
ることを特徴とする請求項１記載の赤外線紫外線吸収ガ
ラス。[Claim 2] The glass has a thickness of A when converted to a thickness of 5 mm.
The visible light transmittance of the light source is 67% or more, the solar transmittance is 37-45%, the ultraviolet transmittance is 7-13%, the dominant wavelength is 506-518 nm, and the stimulus purity is 3.5 or less. The infrared and ultraviolet absorbing glass according to claim 1.
外線吸収ガラスを製造するに当たり、原料としてイルメ
ナイト、あるいは／および微量原料として炭素、Ｚｎ、
Ｓｎ等の金属粉または酸化物のうち少なくとも一つを用
いることを特徴とする赤外線紫外線吸収ガラスの製法。3. In producing the infrared and ultraviolet absorbing glass according to claim 1 or 2, ilmenite is used as a raw material, and/or carbon, Zn,
A method for producing infrared and ultraviolet absorbing glass, characterized by using at least one of a metal powder such as Sn or an oxide.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40584090A JPH0694377B2 (en) | 1990-12-25 | 1990-12-25 | Infrared UV absorbing glass and its manufacturing method |
| EP91120063A EP0488110B1 (en) | 1990-11-26 | 1991-11-25 | Infrared and ultraviolet ray absorbing glass |
| DE69120509T DE69120509T2 (en) | 1990-11-26 | 1991-11-25 | Infrared and ultraviolet radiation absorbing glass |
| US08/112,913 US5362689A (en) | 1990-11-26 | 1993-08-27 | Infrared and ultraviolet ray absorbing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40584090A JPH0694377B2 (en) | 1990-12-25 | 1990-12-25 | Infrared UV absorbing glass and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04224133A true JPH04224133A (en) | 1992-08-13 |
| JPH0694377B2 JPH0694377B2 (en) | 1994-11-24 |
Family
ID=18515449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP40584090A Expired - Lifetime JPH0694377B2 (en) | 1990-11-26 | 1990-12-25 | Infrared UV absorbing glass and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694377B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06166536A (en) * | 1992-04-17 | 1994-06-14 | Guardian Ind Corp | Infrared ray and ultraviolet ray absorbing green glass |
| US5683804A (en) * | 1994-04-28 | 1997-11-04 | Central Glass Company, Limited | Glass plate with ultraviolet and infrared absorbing film |
| JP2001036102A (en) * | 1999-07-15 | 2001-02-09 | Sanyo Electric Co Ltd | Solar cell module |
| JP2019517986A (en) * | 2016-06-23 | 2019-06-27 | ケーシーシー コーポレーション | Green glass composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101809336B1 (en) | 2012-12-28 | 2017-12-14 | 니혼 이타가라스 가부시키가이샤 | Reduced pressure double glazed glass panel |
-
1990
- 1990-12-25 JP JP40584090A patent/JPH0694377B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06166536A (en) * | 1992-04-17 | 1994-06-14 | Guardian Ind Corp | Infrared ray and ultraviolet ray absorbing green glass |
| US5683804A (en) * | 1994-04-28 | 1997-11-04 | Central Glass Company, Limited | Glass plate with ultraviolet and infrared absorbing film |
| JP2001036102A (en) * | 1999-07-15 | 2001-02-09 | Sanyo Electric Co Ltd | Solar cell module |
| JP2019517986A (en) * | 2016-06-23 | 2019-06-27 | ケーシーシー コーポレーション | Green glass composition |
| US11066318B2 (en) | 2016-06-23 | 2021-07-20 | Kcc Glass Corporation | Green glass composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0694377B2 (en) | 1994-11-24 |
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