JPH05270855A - Heat ray absorbing glass having neutral gray tone - Google Patents
Heat ray absorbing glass having neutral gray toneInfo
- Publication number
- JPH05270855A JPH05270855A JP6374992A JP6374992A JPH05270855A JP H05270855 A JPH05270855 A JP H05270855A JP 6374992 A JP6374992 A JP 6374992A JP 6374992 A JP6374992 A JP 6374992A JP H05270855 A JPH05270855 A JP H05270855A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- color tone
- ray absorbing
- neutral gray
- heat ray
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 97
- 230000007935 neutral effect Effects 0.000 title claims abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 239000006103 coloring component Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 4
- 238000002834 transmittance Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 31
- 239000005357 flat glass Substances 0.000 claims description 26
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 230000005855 radiation Effects 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 20
- 239000003086 colorant Substances 0.000 description 14
- 238000005728 strengthening Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000011572 manganese Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000000638 stimulation Effects 0.000 description 4
- 239000005341 toughened glass Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006121 base glass Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000005340 laminated glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、比較的高透視性で、熱
線吸収性能および紫外線吸収性能を併せ持ち、中性灰色
系色調を呈し、高居住性かつ高安全性となり、しかも種
々の形状で軽量化をもでき得る中性灰色系色調の熱線吸
収ガラスに関し、建築用窓ガラスや各種ガラス物品はも
ちろん、特に車両用窓ガラス、ことに自動車用窓ガラス
として有用な中性灰色系色調の熱線吸収ガラスを提供す
るものである。INDUSTRIAL APPLICABILITY The present invention has a relatively high transparency, a heat ray absorbing ability and an ultraviolet ray absorbing ability, exhibits a neutral grayish color tone, is highly livable and highly safe, and has various shapes. Neutral gray color tone heat ray absorbing glass that can also be made lighter, useful not only for building window glass and various glass articles, but especially for vehicle window glass, especially automobile window glass, neutral gray color tone heat ray An absorption glass is provided.
【０００２】[0002]
【従来技術】近年富みに、冷房負荷の低減等省エネルギ
ー化等から、建築物ではもちろん自動車窓ガラス等にお
いて、ことに熱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、より安全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。そのなかで、従来の着
色された熱線吸収ガラスのうち、中性灰色系色調の熱線
吸収ガラスにおいても、主に建築物用の着色ガラスとし
て種々提案されてきている。2. Description of the Related Art In recent years, from the viewpoint of energy saving such as reduction of cooling load, in addition to buildings, of course, automobile window glass, etc. There is a rapidly increasing need for flat glass articles that are more comfortable to live in and safer both physically and physically. Among them, among the conventional colored heat ray absorbing glasses, various types of heat ray absorbing glasses having a neutral gray color tone have been proposed mainly as colored glass for buildings.
【０００３】例えば特開平３ー153543号公報には中性灰
色低透過性ガラス組成物が記載されており、基礎ガラス
組成として重量％表示で、SiO268〜75、Na2O10〜18、Ca
O 5〜15、MgO 0 〜5 、Al2O3 0 〜5 、K2O 0 〜5 を有
し、もし必要ならば、微量の溶融及び清澄化助剤を含
み、Fe2O3 （全鉄）0.4 〜0.7 、FeO 0.08〜0.15、Se
0.003〜0.008 、CoO 0.003 〜0.025 、Cr2O3 0.022 〜
0.050 から本質的になる着色剤を含むもので、ガラスが
5.56mm（0.219in ）の厚さで20％より小さい光透過率を
有するものであることが開示され、紫外線及び赤外線透
過率が低く、そのため全太陽エネルギー透過率も低いも
のであることが記載されている。For example, Japanese Unexamined Patent Publication (Kokai) No. 3-153543 describes a neutral gray low-transmissivity glass composition, which is represented by weight% as a basic glass composition, and is SiO 2 68 to 75, Na 2 O 10 to 18, Ca.
O 5 to 15, MgO 0 to 5, Al 2 O 3 0 to 5, K 2 O 0 to 5 and, if necessary, a trace amount of a melting and clarifying aid, Fe 2 O 3 (total (Iron) 0.4 to 0.7, FeO 0.08 to 0.15, Se
0.003~0.008, CoO 0.003 ~0.025, Cr 2 O 3 0.022 ~
0.050 contains a colorant consisting essentially of
It has been disclosed that it has a light transmission of less than 20% at a thickness of 5.56 mm (0.219 in) and that it has low UV and IR transmission and therefore low total solar energy transmission. ing.
【０００４】また例えば特開平２ー64038 号公報には黒
ずんだ、うすい灰色でニッケルを含まないガラス組成物
が記載されており、重量％表示で、SiO268〜75、Na2O10
〜18、CaO 5 〜15、MgO 0 〜5 、Al2O3 0 〜5 、K2O 0
〜5 と、もしあれば溶融及び精製助剤の痕跡を含むアル
カリガラス組成物と、本質的にFe2O3 （全鉄量）0.55〜
1.0 、Se 0.003〜0.02、CoO 0.005 〜0.02が少なくとも
２価の状態の鉄で15％より成る着色剤を有するもので、
そのガラスは5.56mmの厚さで20％以下の光透過率を有す
るものであり、FeO としては全ガラス組成物の0.09〜0.
3 重量％を構成することが記載されている。Further, for example, Japanese Unexamined Patent Publication (Kokai) No. 2-64038 describes a glass composition which is dark, light gray and does not contain nickel. SiO 2 68 to 75 and Na 2 O 10 are represented by weight%.
~ 18, CaO 5 ~ 15, MgO 0 ~ 5, Al 2 O 3 0 ~ 5, K 2 O 0
~ 5 and an alkaline glass composition containing traces of melting and refining aids, if any, and essentially Fe 2 O 3 (total iron content) 0.55 ~
1.0, Se 0.003 to 0.02, CoO 0.005 to 0.02 with at least divalent iron having a colorant of 15%,
The glass has a thickness of 5.56 mm and a light transmittance of 20% or less, and as FeO, 0.09 to 0.
It is stated to make up 3% by weight.
【０００５】さらに例えば特公昭56ー41579 号公報には
熱線吸収灰色ガラスが記載されており、重量％で、SiO2
70〜75、Al2O3 1 〜2 、CaO 5 〜10、MgO 1 〜5 、R2O
10〜15であり、ここにおいてR2O はNa2OとK2O の合計で
ありかつ、モル比で全R2O の3/4 〜1/4 がK2O である基
礎組成のガラスに、着色剤として重量％でFe2O30.1〜0.
2 、NiO 0.02〜0.06、CoO 0.001 〜0.004 、MnO 0.01〜
0.5 を加えたものであることが開示され、青紫色ないし
赤紫色をおびた灰色を呈することが記載されている。[0005] The further example Japanese Patent Publication 56 over 41579 JP describes a heat absorbing gray glass, in weight%, SiO 2
70-75, Al 2 O 3 1-2, CaO 5-10, MgO 1-5, R 2 O
10-15 a and, R 2 O wherein is the total of Na 2 O and K 2 O and the glass of the base composition 3/4 to 1/4 of the total R 2 O is K 2 O in a molar ratio In addition, Fe 2 O 3 0.1 to 0% by weight as a coloring agent.
2, NiO 0.02-0.06, CoO 0.001-0.004, MnO 0.01-
It is disclosed that 0.5 is added, and it is described that it exhibits a bluish purple to magenta grey.
【０００６】さらにまた例えば特公昭55ー23221 号公報
には熱線吸収ガラスが記載されており、重量％表示で、
SiO265〜75、Al2O3 0 〜5 、CaO 5 〜15、MgO 0 〜10、
但しCaO+MgO 6 〜16、Na2O10〜18、K2O 0 〜5 、但しNa
2O+K2O10〜20の組成の基体ガラスに、着色成分としてFe
2O30.05 〜1.0 、MnO20.05〜5.0 、Cr2O30.002〜0.1、C
uO 0.005 〜0.3 を含有せしめ、かつ該着色成分の含有
量と比率を上記範囲内で調節することにより、中性灰色
又はブロンズ色の所望の着色特性を与えたものが開示さ
れている。Further, for example, Japanese Examined Patent Publication No. 55-23221 discloses a heat ray absorbing glass, which is expressed in weight%.
SiO 2 65-75, Al 2 O 3 0-5, CaO 5-15, MgO 0-10,
However CaO + MgO 6 ~16, Na 2 O10~18, K 2 O 0 ~5, except Na
The base glass composition 2 O + K 2 O10~20, Fe as a coloring component
2 O 3 0.05 to 1.0, MnO 2 0.05 to 5.0, Cr 2 O 3 0.002 to 0.1, C
It is disclosed that the desired coloring characteristic of neutral gray or bronze color is provided by containing 0.005 to 0.3 of uO and adjusting the content and ratio of the coloring component within the above range.
【０００７】さらにまた例えば特公昭52ー49010 号公報
には中性灰色ガラスが記載されており、重量％表示で、
SiO268〜75、Al2O3 ０〜５、CaO ５〜15、MgO ０〜10、
CaO+MgO ６〜15、Na2O10〜18、K2O ０〜５、Na2O+K2O10
〜20を基体組成とし、これに着色成分としてFe2O30.1〜
0.5 、CoO 0.003 〜0.02、Se 0.0005 〜0.001 、NiO０
〜0.002 を含有させ、かつ前記着色成分の比率を調整
し、５mm厚換算で可視光透過率57〜63％、太陽輻射熱透
過率57〜63％、透過光色純度1.5 ％以下である中性灰色
の透過光の色調を有するものが開示されている。Further, for example, Japanese Examined Patent Publication No. 52-49010 discloses neutral gray glass, which is expressed in% by weight,
SiO 2 68-75, Al 2 O 3 0-5, CaO 5-15, MgO 0-10,
CaO + MgO 6~15, Na 2 O10~18 , K 2 O 0~5, Na 2 O + K 2 O10
The 20 as a base composition, Fe 2 O 3 0.1~ as a coloring component to
0.5, CoO 0.003 to 0.02, Se 0.0005 to 0.001, NiO0
-0.002 and adjusting the ratio of the coloring components, the neutral gray color has a visible light transmittance of 57 to 63%, a solar radiation heat transmittance of 57 to 63%, and a transmitted light color purity of 1.5% or less in terms of 5 mm thickness. And a color tone of transmitted light is disclosed.
【０００８】[0008]
【発明が解決しようとする問題点】前述したような例え
ば特開平３ー153543号公報ならびに特開平２ー64038 号
公報に記載のものは、確かにガラス製造中に時として特
異な変化をし、強化ガラス等の熱処理時に色の変化ある
いは破壊等に到ることがあると言われるNiO 成分を着色
剤として用いていないものの、板ガラス板厚5.56mmで20
％以下と低い可視光透過率のものであり、70％以上の可
視光透過率を必要とする自動車用窓ガラスには到底採用
することは困難なものである。また特公昭56ー41579 号
公報に記載のものは、前述したNiO 成分を用いること
と、Seに替えてMnを用い、赤紫色のMn2+と無色のMn3+の
両者の量比が種々変化して色むらが生じるのを特定割合
のK2O 成分によって、溶融状況に係わらず一定量のMn2+
に固定しようとする手段等で赤色系の着色を得るMnO 成
分を含有し、これらはなお後工程ならびに基礎ガラス組
成におけるNa2O＋K2O 量に対するK2O 量の割合におい
て、ことに自動車用窓ガラスとして必ずしも満足できる
ものではないものである。The problems described above, for example, those disclosed in Japanese Patent Laid-Open Nos. 3-153543 and 2-64038, certainly make a peculiar change during glass production. Although it does not use the NiO component, which is said to cause color change or destruction during heat treatment of tempered glass, etc.
It has a low visible light transmittance of less than 100%, and it is very difficult to use it for automobile window glass that requires a visible light transmittance of 70% or more. In addition, the one described in Japanese Examined Patent Publication No. 56-41579 uses the above-mentioned NiO component, uses Mn instead of Se, and has various quantitative ratios of both magenta Mn 2+ and colorless Mn 3+. Due to a certain proportion of K 2 O component that changes and causes color unevenness, a certain amount of Mn 2+
Containing MnO component to obtain a colored reddish by a means such as to be secured to, the ratio of K 2 O amount for the Na 2 O + K 2 O contents in these still later step and the base glass composition, in particular a window for automobiles It is not always satisfactory as glass.
【０００９】さらに特公昭55ー23221 号公報に記載のも
のは、Seに替えてMnを用い、ピンク色の発色をするMn3+
が緑色系のFe2+と共存すると無色のMn2+になりMn3+の発
色を妨げ、その発色が減少するので酸化クロムを加える
ことによってMn3+の比率を高め、Fe2+による着色を消色
するための酸化マンガンが加えられ、しかもCu2+の形で
存在し、青色に発色するとともに800 〜900mμの近赤外
部に吸収ピークを有し熱線吸収性能を与える働きをさせ
ようとするものであるから、ことに紫外線透過率を極力
抑制しようとするものではなく、また板ガラスの板厚５
mmで可視光透過率が35〜65％と必ずしも充分自動車用窓
ガラスとして満足し得るものではないものである。Further, the one disclosed in Japanese Examined Patent Publication No. 55-23221 uses Mn in place of Se and develops pink Mn 3+.
Co-exists with green Fe 2+ , it becomes colorless Mn 2+ and interferes with the coloring of Mn 3+ , and the coloring decreases, so the ratio of Mn 3+ is increased by adding chromium oxide and coloring by Fe 2+ Manganese oxide is added to decolorize the compound, and it is present in the form of Cu 2 + .It develops a blue color and has an absorption peak in the near-infrared region of 800 to 900 mμ, so that it tries to exert a function of absorbing heat rays. Therefore, it is not intended to suppress the ultraviolet transmittance as much as possible, and the plate thickness of the plate glass is 5
The visible light transmittance in mm is 35 to 65%, which is not always satisfactory as a window glass for automobiles.
【００１０】さらにまた特公昭52ー49010 号公報に記載
のものは、NiO 成分の含有を可及的減少または廃絶し、
Fe2O3 、CoO およびSeの３成分のみのバランスによって
中性灰色を得、熱線吸収性能も付与しようとするもの
の、可視光透過率が板厚５mmで57〜63％と必ずしも自動
車用窓ガラスとして充分とは言い難く、紫外線吸収性能
も充分とは言い難いものである。Furthermore, the one disclosed in Japanese Examined Patent Publication No. 52-49010 reduces the content of NiO component as much as possible or eliminates it,
Although a neutral gray color is obtained by balancing only three components of Fe 2 O 3 , CoO, and Se, and heat ray absorption is also intended to be imparted, the visible light transmittance is always 57 to 63% at a plate thickness of 5 mm, which is not necessarily a window glass for automobiles. However, it is difficult to say that the ultraviolet absorption performance is sufficient.
【００１１】[0011]
【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、前述したNiO 成分
を着色剤として基本的に用いることなく、紫外線吸収機
能を付与するCeO2成分ならびTi02成分を特定量用いなが
ら、Fe2O3 表示の全鉄を特定量とし、還元率を調整して
Fe2+とFe3+のバランスをとりつつ、特定量の CoO成分と
Se成分で補色的に少なくとも必須着色剤として用いてさ
らにバランスさせ、比較的透視性能を有し中性灰色系色
調を発現せしめるものであって、自動車用窓ガラスとし
て充分使用でき、しかも熱線吸収性能ならびにより高紫
外線吸収性能を兼ね供えるものであり、さらに基礎ガラ
ス組成とては易強化性を発現し、耐候性、成形性も充分
に有するものとし得、高居住性で高安全性、かつ高環境
性である、建築物用はもちろん、ことに自動車等車輌用
窓ガラスとして有用な中性灰色系色調の熱線吸収ガラス
を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and is CeO which imparts an ultraviolet absorbing function without basically using the above NiO component as a colorant. Adjusting the reduction rate by using a specific amount of Fe 2 O 3 while using a specific amount of 2 components and Ti 0 2 component
While balancing Fe 2+ and Fe 3+ , a certain amount of CoO component
It is a Se component that is used as a complementary color and at least is used as an essential colorant to further balance it, and has a relatively transparent property and exhibits a neutral gray color tone, which can be sufficiently used as a window glass for automobiles and has a heat ray absorbing property. In addition, it can also have higher ultraviolet absorption performance, and can be easily strengthened as a basic glass composition, and can have sufficient weather resistance and moldability, and it has high habitability, high safety, and high It is intended to provide a heat absorbing glass having a neutral gray color tone which is environmentally friendly and is particularly useful as a window glass for vehicles such as automobiles as well as for buildings.
【００１２】すなわち、本発明は、ソーダ石灰シリカ系
ガラスを基礎組成とし、着色成分として重量％表示で、
Fe2O3（全鉄）0.15〜0.55、CeO20.2 〜0.6 、Ti020.15
〜0.45、ならびにppm 表示で、 CoO 15 〜35、Se 2〜18
を基本的に含有せしめたことを特徴とする中性灰色系色
調の熱線吸収ガラス。ならびに前記中性灰色系色調の熱
線吸収ガラスにおいて、該ガラスの還元率（Fe2+／F
e3+）が18〜55％であることを特徴とする上述した中性
灰色系色調の熱線吸収ガラス。またならびに前記ソーダ
石灰シリカ系ガラスの基礎組成が、重量％表示で、SiO2
68〜74、Al2O3 0.1〜3.0 、CaO 8 〜11、MgO2〜4.5 、N
a2O11.5〜16、K2O 0.5 〜3.0 、SO30.1〜0.4 、かつSiO
2＋Al2O3 68〜74、CaO ＋Mg0 11〜15、Na2O＋K2O 12〜1
7である基本的に板ガラス組成物であることを特徴とす
る上述した中性灰色系色調の熱線吸収ガラス。That is, the present invention is based on soda-lime-silica glass as a basic composition, and is represented by weight% as a coloring component.
Fe 2 O 3 (total iron) 0.15 to 0.55, CeO 2 0.2 to 0.6, Ti0 2 0.15
~ 0.45, as well as ppm, CoO 15-35, Se 2-18
A heat ray absorbing glass with a neutral gray color tone, which is characterized by containing essentially. In addition, in the heat ray absorbing glass of the neutral gray color tone, the reduction ratio (Fe 2+ / F
e 3+ ) is 18 to 55%, and the above-mentioned neutral gray color tone heat ray absorbing glass is characterized. In addition, the basic composition of the soda-lime-silica-based glass is SiO 2
68~74, Al 2 O 3 0.1~3.0, CaO 8 ~11, MgO2~4.5, N
a 2 O 11.5 to 16, K 2 O 0.5 to 3.0, SO 3 0.1 to 0.4, and SiO
2 + Al 2 O 3 68 ~ 74, CaO + Mg0 11 ~ 15, Na 2 O + K 2 O 12 ~ 1
7. A heat ray absorbing glass having a neutral gray color tone as described above, which is basically a plate glass composition.
【００１３】さらに前記着色成分として重量％表示で、
Fe2O3（全鉄）0.33〜0.45、CeO20.3 〜0.6 、Ti020.2
〜0.4 、ならびにppm 表示で、 CoO 15 〜30、Se 3〜10
を基本的に含有せしめ、かつ該ガラスの還元率（Fe2+／
Fe3+）が20〜30％であることを特徴とする上述した中性
灰色系色調の熱線吸収ガラス。Further, the coloring component is expressed in% by weight,
Fe 2 O 3 (total iron) 0.33 to 0.45, CeO 2 0.3 to 0.6, Ti0 2 0.2
~ 0.4, as well as ppm, CoO 15-30, Se 3-10
Is basically contained, and the reduction rate of the glass (Fe 2+ /
Fe 3+ ) is 20 to 30%, and the above-mentioned neutral gray color tone heat ray absorbing glass.
【００１４】またさらに前記着色成分として重量％表示
で、 Fe2O3（全鉄）0.25〜0.45、CeO20.3 〜0.6 、Ti02
0.2 〜0.4 、ならびにppm 表示で、 CoO 15 〜30、Se 6
〜15を基本的に含有せしめ、かつ該ガラスの還元率（Fe
2+／Fe3+）が30〜40％であることを特徴とする上述した
中性灰色系色調の熱線吸収ガラス。Further, Fe 2 O 3 (total iron) 0.25 to 0.45, CeO 2 0.3 to 0.6, and Ti 0 2 are represented by weight% as the coloring component.
0.2 to 0.4, and ppm display, CoO 15 to 30, Se 6
~ 15 is contained basically, and the reduction ratio (Fe
2 + / Fe 3+ ) is 30 to 40%, and the above-mentioned heat-ray absorbing glass having a neutral gray color tone.
【００１５】またさらに前記着色成分として重量％表示
で、 Fe2O3（全鉄）0.18〜0.35、CeO20.3 〜0.6 、Ti02
0.2 〜0.4 、ならびにppm 表示で、 CoO 15 〜30、Se 6
〜12を基本的に含有せしめ、かつ該ガラスの還元率（Fe
2+／Fe3+）が40〜50％であることを特徴とする上述した
中性灰色系色調の熱線吸収ガラス。Further, as the coloring component, in terms of weight%, Fe 2 O 3 (total iron) 0.18 to 0.35, CeO 2 0.3 to 0.6, Ti 0 2
0.2 to 0.4, and ppm display, CoO 15 to 30, Se 6
To 12 are basically contained, and the reduction ratio (Fe
2 + / Fe3 + ) is 40 to 50%, and the above-mentioned heat-ray absorbing glass having a neutral grayish color tone.
【００１６】さらにまた前記中性灰色系色調の熱線吸収
ガラスにおいて、該板ガラス板厚４mmでの可視光透過率
が70％以上、日射透過率が50〜65％、紫外線透過率が15
〜25％であることを特徴とする上述した中性灰色系色調
の熱線吸収ガラスをそれぞれ提供するものである。Furthermore, in the heat ray absorbing glass of the neutral gray color tone, the visible light transmittance is 70% or more, the solar radiation transmittance is 50 to 65%, and the ultraviolet light transmittance is 15 at a plate thickness of 4 mm.
Each of the above-mentioned neutral-gray-based heat ray absorbing glasses is characterized by being -25%.
【００１７】ここで、前記着色成分として重量％表示
で、 Fe2O3（全鉄）0.15〜0.55、CeO20.2 〜0.6 、Ti02
0.15〜0.45、ならびにppm 表示で、 CoO 15 〜35、Se 2
〜18を基本的に含有せしめることとしたのは、先ず紫外
線の吸収作用するCeO2成分を0.2 〜0.6 ％ならびにTi02
成分を0.15〜0.45重量％として、ガラスにおける還元率
をほとんど変化させないでしかも紫外線吸収能がやや小
さいTi02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
上述した特定範囲内に限定して組み合わせることで、僅
かの含有量で色調に与える影響を極力少なくし、所期の
紫外線吸収機能特性を効率的に付与し得て維持できるよ
うにするとともに、 Fe2O3（全鉄）0.15〜0.55重量％と
して、還元率を調整してFe2+とFe3+のバランスをとり、
赤外線を吸収しどちらかと言えば青色を生じるFeO 成分
と、紫外線を吸収しどちらかと言えば黄色味系を生じる
Fe2O3成分を適宜バランスをとりつつ、板厚４mmでの可
視光透過率を70％以上として比較的透視性能を有するも
のとし、さらに CoO 15 〜35ppm 、Se 2〜18ppm を基本
的に含有せしめ、特定量の CoO成分とSe成分で前記鉄成
分等と補色的に働き、Co2+は約0.52〜0.54 mμの吸収で
どちらかと言えば青色を生じ、Seはガラス中にどちらか
と言えばピンク色を与え鉄と一緒になると褐色を生じる
等を有する両者を、相互作用するように少なくとも必須
着色剤として用いてさらにバランスさせ、安定して中性
灰色系色調を発現せしめ維持するものとするものであっ
て、自動車用窓ガラスとして充分使用でき、しかも所期
の熱線吸収性能ならびにより高紫外線吸収性能を兼ね供
えるものにでき、上述した該光学特性を確保維持するこ
とによって、高居住性、高安全性ならびに高環境性を実
現できるものである。Here, Fe 2 O 3 (total iron) 0.15 to 0.55, CeO 2 0.2 to 0.6, and Ti0 2 are expressed in weight% as the coloring component.
0.15 to 0.45, and ppm display, CoO 15 to 35, Se 2
~ 18 is basically included because the CeO 2 component that absorbs ultraviolet rays is 0.2 to 0.6% and Ti 0 2
The ingredients as 0.15 to 0.45 wt%, most moreover ultraviolet absorptivity without changing and is slightly smaller Ti0 2 component, CeO 2 component that gives sufficiently relatively greatly varied Moreover ultraviolet absorbing ability of the reduction rate of the glass reduction rate of glass By limiting the combination of and within the above-mentioned specific range, it is possible to minimize the influence on the color tone with a small content and to efficiently impart the desired ultraviolet absorbing functional characteristics and to maintain it. , Fe 2 O 3 (total iron) 0.15 to 0.55% by weight, adjusting the reduction rate to balance Fe 2+ and Fe 3+ ,
FeO component that absorbs infrared rays and produces a rather blue color, and that absorbs ultraviolet rays that produces a rather yellowish system
Fe 2 O 3 components should be properly balanced, and the visible light transmittance at a plate thickness of 4 mm should be 70% or more to have a relatively transparent property, and further CoO 15 to 35 ppm and Se 2 to 18 ppm should be basically contained. At the very least, a specific amount of CoO component and Se component acts as a complementary color to the iron component, etc., Co 2+ produces a rather blue color with absorption of about 0.52-0.54 mμ, and Se is rather rather in glass. Both, which impart a pink color and produce a brown color when combined with iron, are used as at least an essential coloring agent so as to interact with each other, and are further balanced to stably maintain a neutral grayish color tone. Which can be sufficiently used as a window glass for automobiles, and can also have expected heat ray absorption performance and higher ultraviolet absorption performance, and by maintaining and maintaining the above-mentioned optical characteristics, high habitability, If high safety It can realize high environmental performance.
【００１８】好ましくは、 Fe2O3（全鉄）としては0.15
〜0.47重量％程度、CeO2成分としては0.25〜0.50重量％
程度ならびにTi02成分としては0.20〜0.40重量％程度、
またCoO成分としては16〜30ppm 程度、Se成分としては
3〜16ppm 程度である。Fe 2 O 3 (total iron) is preferably 0.15
~ 0.47 wt%, 0.25 ~ 0.50 wt% as CeO 2 component
And about 0.20 to 0.40 wt% as Ti0 2 component,
The CoO component is about 16 to 30 ppm and the Se component is
It is about 3 to 16 ppm.
【００１９】なお、MnO 成分、ZnO 成分ならびにNiO 成
分等任意成分として、使用原料あるいはカレット等か
ら、微量の不純物成分が含有することは言うまでもない
し、微量であれば特に問題とはならないものである。Needless to say, trace amounts of impurity components are contained in the raw materials used, cullet, etc. as optional components such as MnO component, ZnO component and NiO component.
【００２０】また、該ガラスの還元率（Fe2+／Fe3+）が
18〜55％であるとしたのは、前述した各着色剤成分およ
びその特定した量において、ガラス原料からガラスにす
る溶融条件をできるだけ変化させないようにして均一性
が高くかつ色むらも発現することなく、中性灰色系色調
および前述した熱線吸収能または紫外線吸収能等の各光
学特性を得、しかもフロート法等の製板工程ならびに強
化ガラスあるいは曲げ板ガラス等の熱処理工程において
より色調等に変化がなく安定せしめるためである。好ま
しくは19〜53％程度、より好ましくは20〜50％程度であ
る。Further, the reduction ratio (Fe 2+ / Fe 3+ ) of the glass is
18-55% means that each colorant component and the specified amount thereof as described above have high uniformity and color unevenness by not changing the melting conditions for converting the glass raw material into glass as much as possible. However, the neutral grayish color tone and each optical characteristic such as the heat ray absorption ability or the ultraviolet ray absorption ability described above are obtained, and the color tone is changed more in the plate making process such as the float method and the heat treatment process such as tempered glass or bent plate glass. This is because it is not stable. It is preferably about 19 to 53%, more preferably about 20 to 50%.
【００２１】さらに、前記ソーダ石灰シリカ系ガラスの
基礎組成が、重量％表示で、SiO268〜74、Al2O3 0.1 〜
3.0 、CaO 8 〜11、MgO2〜4.5 、Na2O11.5〜16、K2O 0.
5 〜3.0 、SO30.1〜0.4 、かつSiO2＋Al2O3 68〜74、Ca
O ＋Mg0 11〜15、Na2O＋K2O12〜17である基本的に板ガ
ラス組成物であることとしたのは、SiO2成分を重量％で
68〜74としたのは、68未満では表面にヤケ等が発生しや
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、74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0.1 〜3.0 とし
たのは、0.1 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って、好
ましくは1.0 以上であり、3.0 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 〜11としたのは、8 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 〜4.5 としたのは、2 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、4.5
を超えると易強化性が下がるものである。Further, the basic composition of the soda-lime-silica type glass is represented by weight% of SiO 2 68-74, Al 2 O 3 0.1-
3.0, CaO 8 ~11, MgO2~4.5, Na 2 O11.5~16, K 2 O 0.
5 to 3.0, SO 3 0.1 to 0.4, and SiO 2 + Al 2 O 3 68 to 74, Ca
O + Mg0 11 to 15, Na 2 O + K 2 O 12 to 17 is basically a plate glass composition because the SiO 2 component is represented by weight%.
The value of 68 to 74 is that when it is less than 68, the surface is liable to be burned and the weather resistance is lowered to cause a problem in practical use, and when it exceeds 74, its easy strengthening property is lowered and melting is also difficult. The content of the Al 2 O 3 component in the range of 0.1 to 3.0 is preferably less than 0.1 because the weather resistance is lowered and the surface is liable to cause burns or the like, which is a practical problem. Is 1.0 or more, and when it exceeds 3.0, devitrification is likely to occur and the molding temperature range is narrowed to make the production difficult.The CaO component in 8 to 11% by weight means that if it is less than 8, it is easy to strengthen. It is difficult to manufacture because the melting temperature becomes low, the melting temperature becomes high and the flow temperature is not lowered, and devitrification tends to occur when it exceeds 11, the molding work range becomes narrow and the manufacturing becomes difficult. , MgO component was set to 2 to 4.5 by weight% because In becomes difficult to manufacture because narrow the operating range melting temperature rises, 4.5
If it exceeds, the ease of strengthening will decrease.
【００２２】また、Na2O成分を重量％で11.5〜16とした
のは、11.5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、表面にヤケ
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0.1 〜0.4 としたのは、0.1 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、好ましくは0.2 程度より以上で
あり、0.4 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中性灰色系色調が得られ難くなる
ためであって、好ましくは0.35前後以下である。The Na 2 O component is set to 11.5 to 16% by weight. When it is less than 11.5, the easy strengthening property is deteriorated, the moldability becomes difficult, and devitrification easily occurs. If it exceeds 16, the weather resistance is lowered, and the surface is liable to be burned, which causes a practical problem.The K 2 O content of 0.5 to 3.0 is 0.5 to 3.0.
If it is less than 3.0, the toughness is lowered, and if it exceeds 3.0, the weather resistance is lowered and the cost is also high.The SO 3 component is set to 0.1 to 0.4% by weight. Or it can only be made to the extent that it becomes inadequate in terms of homogeneity, and it is preferably more than about 0.2, and when it exceeds 0.4, it particularly affects the coloring state of glass, for example, it tends to shift to a yellowish or amberish tone. And the like, which makes it difficult to obtain the desired neutral gray color tone, and is preferably around 0.35 or less.
【００２３】さらに、SiO2＋Al2O3 を重量百分率で68〜
74％としたのは、68％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、Ca
O ＋MgO を重量百分率で11〜15％としたのは、CaO 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、11％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＋K2
O を重量百分率で12〜17％としたのは、12％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。Further, SiO 2 + Al 2 O 3 is contained in a weight percentage of 68 to
The reason why 74% is set is that when it is less than 68%, the weather resistance is deteriorated, and when it exceeds 74%, the problem that the easy strengthening property is deteriorated occurs.
The weight percentage of O + MgO is set to 11 to 15% because CaO and MgO components are used to lower the melting temperature, and if less than 11%, the easy strengthening property decreases, and if it exceeds 15%, devitrification tends to occur. It is difficult to manufacture and Na 2 O + K 2
The weight percentage of O is set to 12 to 17% because if it is less than 12%, the easy strengthening property is lowered, devitrification is likely to occur, the working temperature range is narrowed in molding, and the production becomes difficult. The weather resistance is lowered, causing problems in practical use and increasing the cost.
【００２４】さらにまた、前記着色成分として重量％表
示で、 Fe2O3（全鉄）0.33〜0.45、CeO20.3 〜0.6 、Ti
020.2 〜0.4 、ならびにppm 表示で、 CoO 15 〜30、Se
3〜10を基本的に含有せしめ、かつ該ガラスの還元率
（Fe2+／Fe3+）が20〜30％であるもの、またさらに前記
着色成分として重量％表示で、 Fe2O3（全鉄）0.25〜0.
45、CeO20.3 〜0.6 、Ti020.2 〜0.4 、ならびにppm 表
示で、 CoO 15 〜30、Se6〜15を基本的に含有せしめ、
かつ該ガラスの還元率（Fe2+／Fe3+）が30〜40％である
もの、ならびにまたさらに前記着色成分として重量％表
示で、 Fe2O3（全鉄）0.18〜0.35、CeO20.3 〜0.6 、Ti
020.2 〜0.4 、ならびにppm 表示で、 CoO15 〜30、Se
6〜12を基本的に含有せしめ、かつ該ガラスの還元率（F
e2+／Fe3+）が40〜50％であるものとしたのは、各着色
剤成分とその特定量との組み合わせにおいて、該ガラス
の還元率を適宜特定することで、より好ましい所期の中
性灰色系色調となるとともに、例えば可視光透過率70％
以上とより透視性で、かつより優れた熱線および紫外線
の吸収能等の光学特性を付与することができることとな
って、より有用な中性灰色系色調の熱線吸収ガラスとな
るためである。Further, Fe 2 O 3 (total iron) 0.33 to 0.45, CeO 2 0.3 to 0.6 and Ti are represented by weight% as the coloring component.
0 2 0.2 to 0.4, and ppm display, CoO 15 to 30, Se
3 to 10 are contained basically, and the reduction rate (Fe 2+ / Fe 3+ ) of the glass is 20 to 30%. Further, Fe 2 O 3 All iron) 0.25-0.
45, CeO 2 0.3 to 0.6, Ti0 2 0.2 to 0.4, and ppm display, basically containing CoO 15 to 30, Se6 to 15,
And the reduction ratio (Fe 2+ / Fe 3+ ) of the glass is 30 to 40%, and further, in terms of weight% as the coloring component, Fe 2 O 3 (total iron) 0.18 to 0.35, CeO 2 0.3-0.6, Ti
0 2 0.2 to 0.4, and ppm display, CoO15 to 30, Se
6-12 are basically contained, and the reduction ratio (F
e 2+ / Fe 3+ ) is set to 40 to 50% because the reduction ratio of the glass is appropriately specified in the combination of each colorant component and its specific amount. Neutral gray color tone and visible light transmittance of 70%
This is because the above is more transparent, and more excellent optical properties such as heat ray and ultraviolet ray absorbing ability can be imparted to the heat ray absorbing glass having a more useful neutral gray color tone.
【００２５】さらにまた前記中性灰色系色調の熱線吸収
ガラスにおいて、該板ガラス板厚４mmでの可視光透過率
が70％以上、日射透過率が50〜65％、紫外線透過率が15
〜25％であることとしたのは、各種自動車用窓ガラスと
してより透視性があり、かつ熱線吸収能ならびに紫外線
吸収能が従来品より数段優れ、車内での居住性、例えば
冷暖房効果を高め、かつ紫外線による人的・物的な悪影
響を減じ、車外の環境に優しいものとするためであり、
好ましくは板厚４mmでの可視光透過率が71％以上程度、
日射透過率が50〜62％程度、紫外線透過率が15〜20％程
度である。Furthermore, in the heat-ray absorbing glass of the neutral gray color tone, the visible light transmittance at the plate glass plate thickness of 4 mm is 70% or more, the solar radiation transmittance is 50 to 65%, and the ultraviolet transmittance is 15%.
-25% means that it is more transparent as a window glass for various automobiles, its heat ray absorption ability and ultraviolet ray absorption ability are several times better than conventional products, and it enhances habitability in the vehicle, such as cooling and heating effects. In addition, it is to reduce the harmful effects of humans and materials due to ultraviolet rays, and to make it environmentally friendly outside the vehicle.
Preferably, the visible light transmittance at a plate thickness of 4 mm is about 71% or more,
The solar transmittance is about 50-62%, and the ultraviolet transmittance is about 15-20%.
【００２６】また、例えば主波長としては556nm 〜582n
m 程度で、刺激純度としては1.5 〜5.0 程度である。好
ましくは例えば主波長としては560nm 〜578nm 程度で、
刺激純度としては2.0 〜4.0 程度である。さらに、本発
明の中性灰色系色調の熱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、例えば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、建築物用窓ガラスをはじ
め、ことに車両用、特に自動車用窓ガラスに用いること
が有用である。Further, for example, the main wavelength is 556 nm to 582n
The stimulation purity is about 1.5 to 5.0 at about m. Preferably, for example, the main wavelength is about 560 nm to 578 nm,
The stimulation purity is about 2.0 to 4.0. Further, the neutral gray color heat ray absorbing glass of the present invention is an easily tempered glass composition, which is a thin glass having a thickness of about 1 mm to a thick glass having a thickness of about 10 mm, for example, a flat plate or a bent plate having an increased strength from a green plate. It can be used as single glass, laminated glass, laminated glass, or double glazing, etc., such as window glass for buildings, especially for vehicle, especially automobile window glass. It is useful to use.
【００２７】[0027]
【作用】前述したとおり、本発明の中性灰色系色調の熱
線吸収ガラスは、ソーダ石灰シリカガラスを基礎ガラス
組成として、特定した着色剤成分を特定した組成範囲で
組み合わせた中性灰色系色調の着色ガラスとし、さらに
該基礎ガラス組成に易強化性を持たせ、しかもガラスの
還元率を特定した範囲内に調整したものとすることがで
き、上述した着色剤成分とその量的範囲内において、還
元率等の調整も寄与して、前述した所期の光学特性、す
なわち可視光透過率が板厚４mmで70％以上、日射透過率
が50〜65％ならびにことに紫外線透過率が15〜25％、さ
らに例えば刺激純度が1.5 〜5.0 程度が得られることと
なり、さらにまた例えば溶融性、清澄性、耐候性、成形
性、失透性、コスト等を考慮し、従来のガラス溶融窯で
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熱線ならびに紫
外線を吸収して冷暖房効果を高め、人的物的にも快適と
なって高居住性であって、優れた透視性を充分持ちかつ
ギラつきもなく、物体の識別が優しくできしかも眼の疲
労を防ぐ等高安全性を確保でき、中性灰色系色調で例え
ば車・室内外と充分調和のあるものとなって環境的にも
優しく優れたものとなり、さらに、従来の熱強化方法で
は得られなかった薄板着色ガラス等でも、充分な強化度
あるいは充分強度アップが得られ易くなるようになり、
建築用窓ガラスはもちろん家具用ガラス、調理用ガラ
ス、ことに自動車用などの車両用窓ガラス等に有用な中
性灰色系色調の熱線吸収ガラスを提供できるものであ
る。As described above, the heat-absorbing glass having a neutral gray color tone of the present invention has a neutral gray color tone obtained by combining the specified colorant components in the specified composition range with soda lime silica glass as the basic glass composition. As a colored glass, the basic glass composition further has an easily strengthening property, and the reduction rate of the glass can be adjusted within a specified range, and in the above-mentioned colorant component and its quantitative range, Adjusting the reduction rate, etc. also contributes to the above-mentioned desired optical characteristics, namely, visible light transmittance of 70% or more at a plate thickness of 4 mm, solar radiation transmittance of 50 to 65%, and especially ultraviolet light transmittance of 15 to 25%. %, For example, a stimulation purity of about 1.5 to 5.0 can be obtained. Furthermore, considering the meltability, clarification, weather resistance, moldability, devitrification, cost, etc., the conventional glass melting furnace And the moth The properties of the space are hardly changed, and in addition, it has an easy strengthening property and absorbs heat rays and ultraviolet rays to enhance the cooling and heating effect, which makes it comfortable for humans and people, and has high living comfort. It has sufficient properties and is free from glare, can identify objects gently, and can secure high safety such as preventing eye fatigue, and it has a neutral gray color tone that is in good harmony with, for example, cars and indoors and outdoors. It becomes environmentally friendly and excellent, and further, even with thin plate colored glass etc. which could not be obtained by the conventional heat strengthening method, it becomes easy to obtain a sufficient strengthening degree or a sufficient strength increase,
It is possible to provide a heat absorbing glass having a neutral gray color tone which is useful not only for architectural window glass but also for furniture glass, cooking glass, and in particular window glass for vehicles such as automobiles.
【００２８】[0028]
【実施例】以下本発明の実施例について説明する。実施例１ ガラス原料として例えば珪砂、長石、ソーダ灰、ドロマ
イト、石灰石、芒硝、ベンガラ、酸化チタン、炭酸セリ
ウムあるいはイルメナイト、セレンフリット、酸化コバ
ルトならびにカーボン等を用い、前記着色剤組成成分範
囲内となるようにするとともに、例えば粘性温度が109
ポイズで650 〜685 ℃程度、1012ポイズで555 〜585 ℃
程度、かつ両者の温度差が95〜105 ℃程度になるように
なるガラス組成を目標組成として設定し、該目標組成量
を秤量調合し、小型電気溶融窯で例えば還元剤としてカ
ーボンを相当量用い、また清澄剤として芒硝を相当量用
い、還元率を調整して充分確保しつつ約1400°C 前後程
度で約３時間程度溶融し、均質化および清澄等をした
後、流し出し製板化して板ガラス状とし、充分な徐冷を
行い、厚み約４mm程度に研磨して、大きさ100mm ×100m
m のガラス板とし、ガラス成分組成分析および各種光学
特性等の測定用中性灰色系色調の熱線吸収ガラスを得
た。EXAMPLES Examples of the present invention will be described below. Example 1 As the glass raw material, for example, silica sand, feldspar, soda ash, dolomite, limestone, mirabilite, red iron oxide, titanium oxide, cerium carbonate, ilmenite, selenium frit, cobalt oxide, carbon, etc. are used and fall within the above colorant composition range. The viscosity temperature is 10 9
650-685 ℃ with Poise, 555-585 ℃ with 10 12 Poise
And a glass composition such that the temperature difference between the two becomes 95 to 105 ° C is set as a target composition, the target composition amount is weighed and blended, and a small amount of carbon is used as a reducing agent in a small electric melting kiln. In addition, using a considerable amount of Glauber's salt as a clarifying agent, the reduction rate was adjusted and sufficiently secured to melt at about 1400 ° C for about 3 hours, homogenized and clarified, and then cast into plate. Plate glass, slowly annealed, and polished to a thickness of about 4 mm, size 100 mm x 100 m
Using the m 2 glass plate, a heat-ray absorbing glass with a neutral gray color tone for glass component composition analysis and measurement of various optical properties was obtained.
【００２９】得られた該ガラスについて、JIS R-3101に
基づく湿式分析法等で確認したところ、重量％表示でSi
O270.3％、Al2O31.8、CaO8.9、MgO3.5、Na2O13.0、K2O
1.0、SO30.2の基礎ガラス組成で、表1 に示すように着
色剤はFe2O3 （全鉄） 0.403、TiO20.31、CeO20.41、pp
m 表示でCoO 23.2、Se 7.6程度と成り、成分の総和が約
99.789％であってかつSiO2＋Al2O3 72.1％、CaO ＋MgO
12.4％、Na2O＋K2O 14.0％であった。The obtained glass was confirmed by a wet analysis method based on JIS R-3101, etc.
O 2 70.3%, Al 2 O 3 1.8, CaO8.9, MgO3.5, Na 2 O13.0, K 2 O
With a basic glass composition of 1.0 and SO 3 0.2, as shown in Table 1, the coloring agents are Fe 2 O 3 (total iron) 0.403, TiO 2 0.31, CeO 2 0.41, pp.
In terms of m, CoO is 23.2, Se is 7.6, and the sum of the components is approximately
99.789% and SiO 2 + Al 2 O 3 72.1%, CaO + MgO
They were 12.4% and Na 2 O + K 2 O 14.0%.
【００３０】さらに、還元率（Fe2+／Fe3+）について
は、図１に示す板厚４mmでの透過率曲線において、FeO
量を赤外域約 1.10 μｍでの透過率（光学密度）から求
め、上述した分析値の全鉄量（Fe2O3 ）から計算し、2
4.3％程度となった。Further, regarding the reduction rate (Fe 2+ / Fe 3+ ), in the transmittance curve at a plate thickness of 4 mm shown in FIG.
The amount was calculated from the transmittance (optical density) in the infrared region of about 1.10 μm, and calculated from the total iron amount (Fe 2 O 3 ) in the above-mentioned analysis values,
It was around 4.3%.
【００３１】さらにまた、光学特性（４mm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（n
m）、刺激純度等については340 型自記分光光度計（日
立製作所製）とJIS Z-8722、JISR-3106、ISO/DIS-9050
にて測定計算して求める等を行った。Furthermore, visible light transmittance (at A light source:%), ultraviolet light transmittance (%), solar radiation transmittance (%), and dominant wavelength (n) as optical characteristics (at a thickness of 4 mm).
m) and stimulus purity, etc., 340 type self-recording spectrophotometer (manufactured by Hitachi Ltd.) and JIS Z-8722, JISR-3106, ISO / DIS-9050
Measurements and calculations were carried out at.
【００３２】その結果、表２に示すように、可視光線透
過率が70.3％程度、日射透過率が60.4％程度、主波長が
563.6nm 程度、紫外線透過率が18.4％程度、刺激純度が
2.5程度であり、さらに太陽放射透過率が59.0％程度で
淡灰色すなわち所期の中性灰色系色調の熱線吸収特性を
有するガラスであった。As a result, as shown in Table 2, the visible light transmittance is about 70.3%, the solar radiation transmittance is about 60.4%, and the dominant wavelength is
563.6nm, UV transmittance about 18.4%, stimulation purity
It was about 2.5, and the solar radiation transmittance was about 59.0%, and it was a glass that had a light gray absorption characteristic of a light gray color, that is, a desired neutral gray color tone.
【００３３】さらにまた、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
ーしていること等を確認した上、前記試料を雰囲気温度
約650 〜730 ℃の炉内で約５分間前後加熱した後、通常
の風冷強化を行い強化ガラス板を得、該ガラス板をJIS
R-3211に従って調べたところ、高効率かつ高歩留りで、
決められた規格を充分満足する高易強化性の中性灰色系
色調の熱線吸収ガラスであった。Furthermore, regarding the easiness of strengthening, it was confirmed that the above-mentioned glass had the above-mentioned viscosity temperature clearing a predetermined specific range and the like, and the sample was heated in an oven at an ambient temperature of about 650 to 730 ° C. After heating for about 5 minutes in the inside, tempered by ordinary wind to obtain a tempered glass plate, which is JIS JIS
When examined according to R-3211, high efficiency and high yield,
It was a heat ray-absorbing glass with a neutral gray color tone that was easily toughened and satisfied the specified standards.
【００３４】実施例２〜６ 前記実施例１と同様にして、所期の中性灰色系色調の熱
線吸収ガラスとなるようなガラス調合組成を計算して秤
量調合し、溶融操作をし、得たガラスを同様に試料化し
た。 Examples 2 to 6 In the same manner as in Example 1 above, the glass composition was calculated and weighed to obtain the desired neutral gray color tone heat absorbing glass, and the melting operation was carried out to obtain Another glass was similarly sampled.
【００３５】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、基礎ガラス成分組成の分
析値はほぼ実施例１と同様となり、各着色剤成分組成あ
るいは還元率は表１に示すとおりであり、また前記各光
学特性は表２のとおりとなり、前記実施例１と同様に、
所期の中性灰色系色調であってかつ熱線およびことに紫
外線吸収特性を持つガラスであった。The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1 above. As a result, the analysis values of the basic glass component composition were almost the same as in Example 1, and the respective colorant component compositions or reduction rates are shown in Table 1. And the respective optical characteristics are as shown in Table 2, and as in Example 1,
It was a glass with the desired neutral gray color tone and absorption of heat rays and especially ultraviolet rays.
【００３６】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、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。Further, regarding the easy strengthening property, the above-mentioned Example 1 was used.
Was carried out in the same manner as in Example 1, but similarly to Example 1 described above, the standard determined by JIS was sufficiently satisfied, and high efficiency,
It was possible to obtain a product that passed the above standard with a high yield.
【００３７】なお、ガラスフリットあるいはカレットを
適宜用いてもよいことは言うまでもない。Needless to say, glass frit or cullet may be used as appropriate.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【表２】 [Table 2]
【００４０】[0040]
【発明の効果】本発明によれば、特定した着色剤成分を
特定した組成範囲内で巧みに組み合わせ、さらに還元率
を微妙に調整して適切な還元率を確保維持し、熱線吸収
特性を持たせかつことに紫外線の吸収等をより付与して
バランス良く得、充分透視性を持ち、易強化性を保持さ
せ、所期の中性灰色系色調を呈するガラスを、例えば実
窯の操業条件を大幅に変更することなく、充分安定して
製造することができ、該ガラスは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
とすることができるものと成り、建築用窓ガラス等はも
ちろん、自動車用窓ガラスに適用して有用なものとなる
中性灰色系色調の熱線吸収ガラスを提供するものであ
る。According to the present invention, the specified colorant components are skillfully combined within the specified composition range, and the reduction rate is finely adjusted to ensure and maintain an appropriate reduction rate and to have a heat ray absorbing property. In addition, it is possible to obtain glass in a well-balanced manner by further imparting UV absorption and the like, having sufficient transparency, maintaining easy strengthening, and glass that exhibits the desired neutral gray color tone, for example, in the operating conditions of a real kiln. It shall be possible to manufacture it with sufficient stability without major changes, and the glass shall have high habitability, high safety, high environmental performance in terms of both human and physical properties, and be lightweight. The present invention provides a heat absorbing glass having a neutral gray color tone, which is useful when applied to not only architectural window glass but also automobile window glass.
【図１】本発明の実施例１における中性灰色系色調の熱
線吸収ガラス板の板厚４mmでの分光透過率曲線である。FIG. 1 is a spectral transmittance curve of a neutral gray color tone heat ray absorbing glass plate in Example 1 of the present invention at a plate thickness of 4 mm.
Claims (7)
し、着色成分として重量％表示で、 Fe2O3（全鉄）0.15
〜0.55、CeO20.2 〜0.6 、Ti020.15〜0.45、ならびにpp
m 表示で、 CoO 15 〜35、Se 2〜18を基本的に含有せし
めたことを特徴とする中性灰色系色調の熱線吸収ガラ
ス。1. Fe 2 O 3 (total iron) 0.15 based on soda-lime-silica glass as a basic composition and represented by weight% as a coloring component.
~ 0.55, CeO 2 0.2 ~ 0.6, Ti0 2 0.15 ~ 0.45, and pp
A heat-ray absorbing glass with a neutral gray color tone, characterized in that it basically contains CoO 15 to 35 and Se 2 to 18 in m.
いて、該ガラスの還元率（Fe2+／Fe3+）が18〜55％であ
ることを特徴とする請求項１記載の中性灰色系色調の熱
線吸収ガラス。2. The neutralizing gray-colored heat ray absorbing glass according to claim 1, wherein the reduction ratio (Fe 2+ / Fe 3+ ) of the glass is 18 to 55%. Gray-colored heat ray absorption glass.
が、重量％表示で、SiO268〜74、Al2O3 0.1 〜3.0 、Ca
O 8 〜11、MgO2〜4.5 、Na2O11.5〜16、K2O0.5 〜3.0
、SO30.1〜0.4 、かつSiO2＋Al2O3 68〜74、CaO ＋Mg0
11〜15、Na2O＋K2O 12〜17である基本的に板ガラス組
成物であることを特徴とする請求項１記載の中性灰色系
色調の熱線吸収ガラス。3. The basic composition of the soda-lime-silica based glass is SiO 2 68-74, Al 2 O 3 0.1-3.0, Ca in weight% display.
O 8 ~11, MgO2~4.5, Na 2 O11.5~16, K 2 O0.5 ~3.0
, SO 3 0.1 to 0.4, and SiO 2 + Al 2 O 3 68 to 74, CaO + Mg0
The heat ray absorbing glass having a neutral gray color tone according to claim 1, which is basically a plate glass composition of 11 to 15 and Na 2 O + K 2 O 12 to 17.
（全鉄）0.33〜0.45、CeO20.3 〜0.6 、Ti020.2 〜0.4
、ならびにppm 表示で、 CoO 15 〜30、Se 3〜10を基
本的に含有せしめ、かつ該ガラスの還元率（Fe2+／F
e3+）が20〜30％であることを特徴とする請求項１なら
びに２記載の中性灰色系色調の熱線吸収ガラス。4. Fe 2 O 3 in terms of weight% as the coloring component
(Total iron) 0.33 to 0.45, CeO 2 0.3 to 0.6, Ti0 2 0.2 to 0.4
, And in ppm, it basically contains CoO 15-30, Se 3-10, and the reduction rate of the glass (Fe 2+ / F
e 3+ ) is 20 to 30%, and the heat ray absorbing glass having a neutral gray color tone according to claim 1 or 2.
（全鉄）0.25〜0.45、CeO20.3 〜0.6 、Ti020.2 〜0.4
、ならびにppm 表示で、 CoO 15 〜30、Se 6〜15を基
本的に含有せしめ、かつ該ガラスの還元率（Fe2+／F
e3+）が30〜40％であることを特徴とする請求項１なら
びに２記載の中性灰色系色調の熱線吸収ガラス。5. Fe 2 O 3 in terms of weight% as the coloring component
(Total iron) 0.25 to 0.45, CeO 2 0.3 to 0.6, Ti0 2 0.2 to 0.4
, And in ppm, it basically contains CoO 15 to 30 and Se 6 to 15, and the reduction rate of the glass (Fe 2+ / F
e 3+ ) is 30 to 40%, and the heat-ray absorbing glass having a neutral grayish color tone according to claim 1 or 2.
（全鉄）0.18〜0.35、CeO20.3 〜0.6 、Ti020.2 〜0.4
、ならびにppm 表示で、 CoO 15 〜30、Se 6〜12を基
本的に含有せしめ、かつ該ガラスの還元率（Fe2+／F
e3+）が40〜50％であることを特徴とする請求項１なら
びに２記載の中性灰色系色調の熱線吸収ガラス。6. Fe 2 O 3 in terms of weight% as the coloring component
(Total iron) 0.18 to 0.35, CeO 2 0.3 to 0.6, Ti0 2 0.2 to 0.4
, And in ppm, basically contain CoO 15 to 30 and Se 6 to 12 and reduce the reduction ratio (Fe 2+ / F) of the glass.
e 3+ ) is 40 to 50%, and the heat ray absorbing glass having a neutral gray color tone according to claim 1 or 2.
いて、該板ガラス板厚４mmでの可視光透過率が70％以
上、日射透過率が50〜65％、紫外線透過率が15〜25％で
あることを特徴とする請求項１乃至２ならびに４乃至６
記載の中性灰色系色調の熱線吸収ガラス。7. The heat ray absorbing glass of neutral gray color tone, wherein the visible light transmittance is 70% or more, the solar radiation transmittance is 50 to 65%, and the ultraviolet light transmittance is 15 to 25% when the plate glass plate thickness is 4 mm. 1 to 2 and 4 to 6 characterized in that
Heat-ray absorbing glass with the neutral gray color tone described.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6374992A JPH05270855A (en) | 1992-03-19 | 1992-03-19 | Heat ray absorbing glass having neutral gray tone |
| DE69311197T DE69311197T2 (en) | 1992-03-19 | 1993-03-16 | Infrared and ultraviolet radiation absorbing, neutral gray colored glass |
| EP93104240A EP0565882B1 (en) | 1992-03-19 | 1993-03-16 | Neutral gray-colored infrared and ultraviolet radiation absorbing glass |
| US08/032,597 US5364820A (en) | 1992-03-19 | 1993-03-17 | Neutral gray-colored infrared and ultraviolet radiation absorbing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6374992A JPH05270855A (en) | 1992-03-19 | 1992-03-19 | Heat ray absorbing glass having neutral gray tone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05270855A true JPH05270855A (en) | 1993-10-19 |
Family
ID=13238368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6374992A Pending JPH05270855A (en) | 1992-03-19 | 1992-03-19 | Heat ray absorbing glass having neutral gray tone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05270855A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848540A (en) * | 1993-11-16 | 1996-02-20 | Ppg Ind Inc | Grey glass composition |
| JPH0867526A (en) * | 1993-11-16 | 1996-03-12 | Ppg Ind Inc | Grey glass composition |
| US5763342A (en) * | 1996-02-16 | 1998-06-09 | Asahi Glass Company Ltd. | Ultraviolet ray absorbing colored glass |
| WO1999025660A1 (en) * | 1997-11-13 | 1999-05-27 | Nippon Sheet Glass Co., Ltd. | Ultraviolet/infrared absorbing glass, ultraviolet/infrared absorbing glass sheet, ultraviolet/infrared absorbing glass sheet coated with colored film, and window glass for vehicles |
| JP2003529523A (en) * | 2000-04-04 | 2003-10-07 | グラヴルベル | Colored soda lime glass with high light transmittance |
| WO2008102822A1 (en) | 2007-02-20 | 2008-08-28 | Fujifilm Corporation | Polymer material containing ultraviolet absorbent |
| WO2009022736A1 (en) | 2007-08-16 | 2009-02-19 | Fujifilm Corporation | Heterocyclic compound, ultraviolet ray absorbent, and composition comprising the ultraviolet ray absorbent |
-
1992
- 1992-03-19 JP JP6374992A patent/JPH05270855A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848540A (en) * | 1993-11-16 | 1996-02-20 | Ppg Ind Inc | Grey glass composition |
| JPH0867526A (en) * | 1993-11-16 | 1996-03-12 | Ppg Ind Inc | Grey glass composition |
| US6114264A (en) * | 1993-11-16 | 2000-09-05 | Ppg Industries Ohio, Inc. | Gray glass composition |
| US5763342A (en) * | 1996-02-16 | 1998-06-09 | Asahi Glass Company Ltd. | Ultraviolet ray absorbing colored glass |
| WO1999025660A1 (en) * | 1997-11-13 | 1999-05-27 | Nippon Sheet Glass Co., Ltd. | Ultraviolet/infrared absorbing glass, ultraviolet/infrared absorbing glass sheet, ultraviolet/infrared absorbing glass sheet coated with colored film, and window glass for vehicles |
| US6468934B2 (en) | 1997-11-13 | 2002-10-22 | Nippon Sheet Glass Co., Ltd. | Ultraviolet/infrared absorbent glass |
| JP2003529523A (en) * | 2000-04-04 | 2003-10-07 | グラヴルベル | Colored soda lime glass with high light transmittance |
| WO2008102822A1 (en) | 2007-02-20 | 2008-08-28 | Fujifilm Corporation | Polymer material containing ultraviolet absorbent |
| WO2009022736A1 (en) | 2007-08-16 | 2009-02-19 | Fujifilm Corporation | Heterocyclic compound, ultraviolet ray absorbent, and composition comprising the ultraviolet ray absorbent |
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