JPS60215546A - Infrared absorption glass - Google Patents

Abstract

PURPOSE:The titled glass that is composed of SiO2, as a major component, and BaO, is suitably used as window panes for automobiles or green houses, due to having increased infrared absorption as the transmission of visible rays are kept high. CONSTITUTION:The objective infrared absorption glass has a basic composition of 60-72wt% of SiO2, 4-15wt% of BaO, 0-3wt% of Al2O3, 0-10wt% of ZnO, 0-4wt% of MgO, 3-15wt% of Na2O, 4-9wt% of CaO, 0-13wt% of K2O and 0-13wt% of iron oxide (calculated as Fe2O3). The addition of BaO as a constituent, shifts the absorption peak of FeO toward longer wave side to increase transmission in the visible region. Iron oxide exists in glass in the form of Fe2O3 and FeO and the FeO absorbs infrared rays. It can be suitably used as glass panes for automobile windows and green houses, because of its high visible ray transmission and low solar radiation transmission.

Description

Translated fromJapanese

【発明の詳細な説明】本発明は可視光透過率を高く維持しながら赤外吸収を大
きくすることができる赤外線吸収ガラスに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an infrared absorbing glass that can increase infrared absorption while maintaining high visible light transmittance.

建築用・車輌用などに使用されている赤外義眼１■ガラ
スには、青緑色・茶褐色・灰褐色のものがある。これら
はデザイン効果を満すとともに、近赤外線を吸Ｑ　Ｌで
冷房負荷を減少させる省エネルギー効果も有している。Infrared prosthetic eye glass used for construction and vehicles comes in blue-green, brown-brown, and gray-brown colors. These not only satisfy the design effect, but also have the energy-saving effect of reducing the cooling load by absorbing near-infrared rays.

しかし自動車用窓ガラスなどでは、視腎の明るさを確保
するために可視光線透過率が７０％以上であることが規
格で定められており、その条件を満すためには赤外線吸
収ガラスを低くせざるを得ないという問題がある。例え
ば現在自動車用窓に使用されている青緑色ガラスの組成
は重量％で表示して大略Ｓｊ、０２７２．ｊＵ２０３２
　＋ＭｇＯ４’　、　ＧａＯｒ　、　Ｎａ２Ｏ／’ｌ　
、　Ｆｅ２Ｏ３０，ＩＩ”’Ｃあり、その厚さｔｍｍの
ときの可視光線透過率は７６．３％であるが、冷房負荷
算定の基礎数値となる太陽放射透過率はｔ３．ｌ１％も
あり、近年自動車の窓とか温室などの可視光線透過率が
高く、かつ太陽放射透過率の低いガラスの要求に対して
十分に応えることができない。However, in order to ensure the brightness of the optic kidneys, the standards for automobile window glass require visible light transmittance of 70% or more, and in order to meet this condition, infrared absorbing glass must be made with low infrared absorbing glass. The problem is that you have no choice but to get used to it. For example, the composition of the blue-green glass currently used in automobile windows is approximately Sj, 0272. jU2032
+MgO4', GaOr, Na2O/'l
, Fe2O30,II"'C, and its visible light transmittance when the thickness is tmm is 76.3%, but the solar radiation transmittance, which is the basic value for calculating the cooling load, is as high as t3.l1%, and in recent years It cannot fully meet the demand for glass with high visible light transmittance and low solar radiation transmittance, such as for automobile windows and greenhouses.

本発明はかかる要求に応えることのできるガラスを提供
することを目的とし、その構成は、重量％で表示して次
の基本成分を有する赤外線吸収ガラスからなる。The object of the present invention is to provide a glass that can meet such demands, and its composition consists of an infrared absorbing glass having the following basic components expressed in weight percent.

５ｉ０２　１．０〜７２　ＢａＯｕ　〜／３ＡＩ２０３
０〜３ｚｎ００−１ＯＩＭｇ０　０−４Ｚ　Ｎａ２Ｏ３〜／　ｊａａｏ　’ｌ〜
ｑ　Ｒ２００−／３酸化鉄（全量をＦｅ２ｏ３に換算して）０．２〜．２以
下に成分限定の理由を述べる。5i02 1.0~72 BaOu~/3AI203
0~3zn00-1OI Mg0 0-4Z Na2O3~/jaao'l~
q R200-/3 Iron oxide (total amount converted to Fe2o3) 0.2~. The reasons for limiting the ingredients are explained below.

５１０２はガラスの骨格を形成する酸化物で、に０％未
満ではガラスの耐久性が劣り、７２％を越えるとガラス
の粘性が高くなり溶解性が悪くなる。5102 is an oxide that forms the skeleton of glass, and if it is less than 0%, the durability of the glass will be poor, and if it exceeds 72%, the viscosity of the glass will increase and its solubility will deteriorate.

１２０３はガラスの耐久性を高めるが３％を越えるとガ
ラスの溶解性が著しく悪くなる。1203 improves the durability of the glass, but if it exceeds 3%, the meltability of the glass deteriorates significantly.

ＭｇＯはＣａＯと共にガラスの粘性調節に使われるが、
１１％を越えるとガラスに失透が生じ易くなる。MgO is used together with CaO to adjust the viscosity of glass.
If it exceeds 11%, devitrification tends to occur in the glass.

ＣａＯは溶解性促進、耐候性向上、粘性の調節に使われ
、１１％未満ではガラスの耐候性が低下し、９％を越え
るとガラスに失透を生じ易くなる。CaO is used to promote solubility, improve weather resistance, and adjust viscosity. If it is less than 11%, the weather resistance of the glass decreases, and if it exceeds 9%, it tends to cause devitrification in the glass.

Ｂａ、Ｏ１赤外線吸収ガラスに通常酸化鉄が含まれるの
は、２価の酸化鉄（Ｆｅｄ）が波長１０００ｍｍ　付近
に光吸１■のピータを有し、そのピークは２２□ｏ、ｏ
、’ｍｍ付近にかけてゆるやかに広がっており、溜る近
赤外線をよく吸収するからである。ＦｅＯの吸収ピーク
の波長および吸光係数がガラス組成に依存することはソ
ルベージョン効果表して知られており、ガラスの地基性
１９に関係すると考えらねているが、ＦｅＯなどの遷移
金属による吸ＩＩＭスペクトルとガラスの塩基仕度との
関係は複雑で、ガラス組成から吸１■スペクトルを予想
することは困ヴｆｆ［であり、現、在では試行り１シ誤
によって赤外義眼１［１７に適した組成を見つけざるを
得ない。Ba, O1 Infrared absorbing glass usually contains iron oxide because divalent iron oxide (Fed) has a light absorption peak of 1■ around a wavelength of 1000 mm, and its peak is 22□o, o.
, 'mm, and absorbs accumulated near-infrared rays well. It is known that the absorption peak wavelength and extinction coefficient of FeO depend on the glass composition, which is known as the solvation effect, and is thought to be related to the basicity of the glass. The relationship between the spectrum and the basic preparation of the glass is complicated, and it is difficult to predict the absorption spectrum from the glass composition. We have no choice but to find a composition that

本願発明者はガラス成分の７つとしてＢａ、０を加エル
トＦｅ０）吸収ピークを長波長側にずら刊？Ｕることを
発見した。このことは可視域の透過率向上に寄与する。The inventor of this application added Ba and 0 as the seven glass components, and shifted the absorption peak to the longer wavelength side. I discovered that. This contributes to improving the transmittance in the visible range.

ＢａＯがｌＩ％未ｔ）もでは前記効果が乏しく、また１
５％を越えても効果に差がないばかりかガラスの粘性を
高め溶解・成形を困難にする。The above effect is poor when BaO is less than lI%;
Even if it exceeds 5%, there is no difference in effectiveness, and the viscosity of the glass increases, making melting and molding difficult.

ＺｎＯは必須成分ではないが以下に述べるようなガラス
のアンバー着色を防市する効果を有する。Although ZnO is not an essential component, it has the effect of preventing amber coloring of glass as described below.

前述したようにガラスの赤ダ１線１１に収はＦｅ０Ｋよ
る。As mentioned above, the intensity of the red 1 line 11 of the glass depends on Fe0K.

したがってガラスの溶解はガラス中の酸化鉄に占めるＦ
ｅＯの比率が高くなるよう還元性雰囲気で行うことが望
ましい。しかしガラス原料に添加する清澄剤としての硫
酸塩や燃料重油中の硫黄が、通常はＳｏ３としてガラス
中に溶は込むが、還元性雰即気下テハカラス中で還元さ
れガラスにアンバー着色を生ずる。Therefore, the melting of glass is caused by F occupying iron oxide in glass.
It is desirable to carry out the process in a reducing atmosphere so that the ratio of eO is high. However, sulfate as a refining agent added to the glass raw material and sulfur in heavy fuel oil are normally dissolved into the glass as So3, but are reduced in the Tejacaras under a reducing atmosphere and cause the glass to be colored amber.

ガラス中のＺｎＯは前記還元される硫黄を無色透明力゛のＺｎＳとして固定する効果を有する。ヘラス清澄剤と
して原料中に硫酸塩等硫黄化合物を加えない場合はｚｎ
ｏ　ｉは３％もあれば十分であるが、加える場合には１
０％程度必要なこともある。ZnO in the glass has the effect of fixing the reduced sulfur as colorless and transparent ZnS. If sulfur compounds such as sulfates are not added to the raw material as a Hellas clarifier, use zn.
It is sufficient for o i to be 3%, but when adding 1
In some cases, about 0% is necessary.

Ｎａ２Ｏは７ラソクスとしてガラスの溶解性を向上させ
る。３％未満ではその効果が乏しく、１３；％を越える
とガラスの化学的耐久性を低下させる。Na2O improves the solubility of glass as a 7 lasox. If it is less than 3%, the effect is poor, and if it exceeds 13%, the chemical durability of the glass will be reduced.

Ｒ２０ハＮａ２Ｏと較へて原料価格が大ではあるが、Ｎ
ａ２Ｏと同様の効果を有する他に、Ｆｅｏの吸収ピーク
を長波長側に移行させる効果を有する。一方に２０　Ｋ
　Ｌｉ　５ｉ０２−Ｒ２０２成分系ガラスの場合Ｆｅｏ
の吸光係数を小さくするという欠点もあるが、本発明の
ケースではＢａＯと共存することによってその欠点は解
消されている。Ｒ２０の含有量が７３％を越えても効果
の向上はなく、むしろガラスの粘性を高める。R20 has a higher raw material price compared to Na2O, but N
In addition to having the same effect as a2O, it also has the effect of shifting the absorption peak of Feo to the longer wavelength side. 20K on one side
For Li 5i02-R20 binary glass, Feo
However, in the case of the present invention, this drawback is solved by coexisting with BaO. Even if the content of R20 exceeds 73%, there is no improvement in the effect, but rather increases the viscosity of the glass.

アルカリ金属酸化物としてＮａ２Ｏ−１−に２０は７０
〜．２０％　が好ましい。１０％未満ではガラスの溶解
性向上のための７ラツクスの量として不足し、２０％を
越えるとガラスの化学的耐久性が低下する。20 is 70 for Na2O-1- as an alkali metal oxide
~． 20% is preferred. If it is less than 10%, the amount of 7 lux is insufficient to improve the solubility of the glass, and if it exceeds 20%, the chemical durability of the glass will decrease.

酸化鉄はガラス中で３価（Ｆｅ！２０．、）と２価（Ｆ
ｅｄ）の形で共存し、Ｆｅｏが赤外線を吸１１Ｙする。Iron oxide is trivalent (Fe!20.,) and divalent (F
ed), and Feo absorbs infrared radiation.

酸化鉄が全量をＦｅ２Ｏ３に換算して。０．２％未満で
はガラス中のＦｅＯ濃度が不足し、太陽放射透過率が高
くなり、２％を越えるとガラス中のＦｅ２Ｏ３濃度が高
くなり、可視光線透過率が低くなってしまう。The total amount of iron oxide is converted to Fe2O3. If it is less than 0.2%, the FeO concentration in the glass will be insufficient and the solar radiation transmittance will be high, and if it exceeds 2%, the Fe2O3 concentration in the glass will be high and the visible light transmittance will be low.

以上の基本成分の他に、着色剤として通常用いられる成
分、例えばＮ］−０１ｃｏｏ　、ＭｎＯｌ　ｃｒ２ｏ３
．ｓｅ　すどが通常着色剤として使用される濃度に、ま
た清澄剤として通常用いら第１る成分、例えばＳＯ３。In addition to the above basic components, components commonly used as colorants, such as N]-01coo, MnOl cr2o3
．． The first ingredient, such as SO3, is added to the concentrations commonly used as a coloring agent and as a clarifying agent.

５ｂ２０ａ＋ＡＳｇＯ３，Ｆ、ＣＩ！Ｑ　とカｉｍ常ｍ
ＩＭ剤トｌ、　Ｔ使用される濃度に、さらＫｔたＺｒＯ
２，Ｔｊ０２，５ｎ０２゜ＭｏＯ３，Ｗｏ３など本発明
の主旨を損ねない成分は本発明の主旨を損ねない程度に
含有し得る。5b20a+ASgO3,F,CI! Q and Kai
IM agent Tol, T to the concentration used, further Kt to ZrO
Components such as 2, Tj02, 5n02°MoO3, Wo3, etc. that do not impair the gist of the present invention may be contained to the extent that they do not impair the gist of the present invention.

実施例１（７）第１表の試料番号／〜乙のガラス成分となるようガラス
原料を調合し、還元剤を加えてルツボ中で／’ｌ！；０
°Ｃで３時間加熱溶解し、室温まで徐冷して得たガラス
ブロックを所要寸法に切断し、ＪＩＳＺざ７２．２によ
る標準光Ａに対する可視光透過率が７０％になるような
厚さに研磨して得た各試料を波長、２　ｌｒＯｎｍ−２
，２０Ｏｒａｍ　の間の分光透過率を測定し、ＪＩＳＲ
３２０Ｉｒにしたがって太陽放射透過率を計算した。本
発明の成分範囲内の試料番号ｌ−グのガラスは太陽放射
透過率がいずれも３０％台であり、赤外線をよく吸１ベ
シているが、本発明の成分範囲外の試料番号ｊ〜乙のガ
ラスは実施例７〜ｌのガラスに較べて同じ可視光線透過
率でありながら、太陽放射透過率が犬であることが判る
。Example 1 (7) Glass raw materials were prepared so as to have the glass components of sample numbers /~B in Table 1, a reducing agent was added, and the mixture was added in a crucible /'l! ;0
The glass block obtained by heating and melting at °C for 3 hours and cooling slowly to room temperature is cut into the required dimensions, and the thickness is such that the visible light transmittance for standard light A according to JIS Z 72.2 is 70%. The wavelength of each sample obtained by polishing was 2 lrOnm-2.
, 20Oram, and JISR
Solar radiation transmittance was calculated according to 320Ir. The glasses with sample numbers l-g, which are within the composition range of the present invention, all have solar radiation transmittances of 30% and absorb infrared rays well, but the glasses with sample numbers j-g, which are outside the composition range of the present invention, It can be seen that although the glasses of Examples 7 to 1 have the same visible light transmittance as the glasses of Examples 7 to 1, their solar radiation transmittance is lower than that of the glasses of Examples 7 to 1.

実施例２第２表の試料番号７〜９について、実施例１と同様にガ
ラスブロックを製作し、ｔｍｍの厚さとなるよう切断研
磨して試料を得た。Example 2 For sample numbers 7 to 9 in Table 2, glass blocks were produced in the same manner as in Example 1, and the samples were cut and polished to a thickness of tmm.

この試料について実施例／と同様に分光透過率を測定し
、近赤外部における吸収ピークの波長とそ（ざ）の波長における透過率をめた。試料番号９は本発明の成
分範囲外のガラスで、Ｋ２Ｏを多量に含むために吸収ビ
ータはＦｅＯの吸収ピークの１１０００ｎヨリモカナり
長波長側にずれているが、Ｂａｏヲ含有していないため
にそのピークにおける透過率は本発明成分範囲内の実施
例番号７〜ｇと較べて２倍以上である。The spectral transmittance of this sample was measured in the same manner as in Example 1, and the wavelength of the absorption peak in the near-infrared region and the transmittance at that wavelength were determined. Sample No. 9 is a glass outside the composition range of the present invention, and because it contains a large amount of K2O, the absorption beater is shifted to the longer wavelength side of 11,000n than the absorption peak of FeO, but since it does not contain BaOwo, The transmittance at the peak is more than twice that of Example Nos. 7 to g within the range of the components of the present invention.

Claims (1)

Translated fromJapanese

【特許請求の範囲】重量％で表示して下記基本成分を有する赤外線吸収ガラ
ス。５ｉ０２　Ａ　Ｏ〜７２　ＢａＯ’ＩＰ−／　！；Ａｌ
２Ｏ３０〜３　ｚｎｏ　Ｏ〜ｌ０Ｍｇ０　Ｏ〜４’　Ｎａ２Ｏ３〜／！；ｃａｏ　’ｌ−
９Ｋ２Ｏ０／−／　３酸化鉄（全量をｐｅ２ｏ３　Ｋ換算して）０．２〜２[Claims] An infrared absorbing glass having the following basic components expressed in weight %. 5i02 AO~72 BaO'IP-/! ;Al
2O30~3 zno O~l0 Mg0 O~4'Na2O3~/!;cao'l-
9K2O0/-/ 3 Iron oxide (total amount converted to pe2o3 K) 0.2-2