JPH11217234A - Deep gray color glass - Google Patents

Deep gray color glass

Info

Publication number
JPH11217234A
JPH11217234A JP1975598A JP1975598A JPH11217234A JP H11217234 A JPH11217234 A JP H11217234A JP 1975598 A JP1975598 A JP 1975598A JP 1975598 A JP1975598 A JP 1975598A JP H11217234 A JPH11217234 A JP H11217234A
Authority
JP
Japan
Prior art keywords
weight
glass
parts
less
thickness
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.)
Withdrawn
Application number
JP1975598A
Other languages
Japanese (ja)
Inventor
Mizuki Sasage
みずき 捧
Toru Kudo
透 工藤
Shiro Tanii
史朗 谷井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP1975598A priority Critical patent/JPH11217234A/en
Publication of JPH11217234A publication Critical patent/JPH11217234A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass

Abstract

PROBLEM TO BE SOLVED: To obtain glass that has low visible light transmission, largely low solar radiation and ultraviolet transmission with reduced excitation purity. SOLUTION: This glass composition contains, based on the 100 pts.wt. of the mother components of soda lime silicate glass, 0.7-0.9 pt.wt. of Fe2 O3 (the whole iron are calculated as Fe2 O3 ), 0.8-3.0 pts.wt. of TiO2 , 0.001-0.0035 pt.wt. of Se; 0.01-0.035 pt.wt. of CoO, 0-0.05 pt.wt. of Cr2 O3 , 0-0.5 pt.wt. of CeO2 and 0-0.5 pt.wt. of V2 O5 in which the proportion of divalent iron is 22-30 wt.% calculated the whole irons as Fe2 O3 . The visible light transmission is <=30%, calculating as the 4 mm thickness using the standard A light source.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、低い可視光透過
率、低い紫外線透過率および低い刺激純度を有し、自動
車のリヤガラスやサイドガラスに適した濃グレー色ガラ
スに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dark gray glass having a low visible light transmittance, a low ultraviolet light transmittance and a low stimulating purity, and suitable for a rear glass or a side glass of an automobile.

【０００２】[0002]

【従来の技術】Ｆｅ2 Ｏ3 、Ｓｅ、ＣｏＯ、ＮｉＯ、Ｃ
ｒ2 Ｏ3 等を含む典型的な中性灰色熱線吸収ガラスはす
でに知られている。しかし、このうち、ニッケルは、ガ
ラス中でときどき硫化ニッケルの形成をもたらすので好
ましくない。硫化ニッケルは、目視ではほとんど確認で
きず、通常の状態ではガラスに害を与えないが、熱膨張
係数が大きいので、ガラスの急冷強化時などにガラスを
破壊するのに充分な熱的応力を発生させることがある。
ニッケルを含まず、かつ自動車のサンルーフやリヤガラ
スに適用できる程度に可視光透過率の低いグレー色ガラ
スとしては、以下のようなものがある。 2. Description of the Related Art Fe 2 O 3 , Se, CoO, NiO, C
Typical neutral gray heat ray absorbing glasses containing r 2 O 3 etc. are already known. However, of these, nickel is not preferred because it sometimes causes the formation of nickel sulfide in the glass. Nickel sulfide can hardly be confirmed visually and does not harm the glass under normal conditions, but has a large thermal expansion coefficient, so it generates enough thermal stress to break the glass when quenching and strengthening the glass May be caused.
The following are examples of gray glass that does not contain nickel and has low visible light transmittance such that it can be applied to a sunroof or a rear glass of an automobile.

【０００３】特開平２−６４０３８には、Ｆｅ2 Ｏ3 換
算で０．６〜１．０重量％の全鉄、およびＳｅ、ＣｏＯ
を含有し、ニッケル、クロムを含有しないガラスが開示
されている。しかし、このガラスは紫外線透過率が充分
に低くないため、乗用車のガラスとして使用した場合
に、紫外線による内装の劣化を抑制できない。JP-A-2-64038 discloses that 0.6 to 1.0% by weight of total iron in terms of Fe 2 O 3 , Se, CoO
And a glass containing no nickel or chromium is disclosed. However, since this glass does not have a sufficiently low ultraviolet transmittance, deterioration of the interior due to ultraviolet rays cannot be suppressed when used as glass for a passenger car.

【０００４】また、特開平４−２７５９４３（対応米国
特許明細書第５３９３５９３号）には、Ｆｅ2 Ｏ3 換算
で１．０〜１．７重量％の全鉄、およびＳｅ、ＣｏＯを
含有し、ニッケル、クロムを含有しないガラスが開示さ
れている。しかし、このガラスは、大量の鉄を含有する
ため、熔融時の熱効率が悪い。したがって、加熱源から
遠い炉の底でも、素地をフリーズさせないための特別な
工夫が必要になると考えられる。Japanese Patent Application Laid-Open No. 4-275943 (corresponding to US Pat. No. 5,393,593) contains 1.0 to 1.7% by weight of total iron in terms of Fe 2 O 3 , and Se and CoO. Glasses containing no nickel or chromium are disclosed. However, since this glass contains a large amount of iron, its thermal efficiency during melting is poor. Therefore, it is considered that special measures are required to prevent the substrate from freezing even at the bottom of the furnace far from the heating source.

【０００５】また、特開平５−３３０８４７には、Ｆｅ
2 Ｏ3 換算で１．４〜４重量％の全鉄および必要に応じ
てＣｏＯ、Ｓｅ、Ｃｒ2 Ｏ3 を含有するガラスが開示さ
れている。このガラスも、全鉄量が多く、熔融が容易で
ない。Japanese Patent Application Laid-Open No. Hei 5-330847 discloses Fe
Disclosed is a glass containing 1.4 to 4% by weight of total iron in terms of 2 O 3 and optionally CoO, Se, and Cr 2 O 3 . This glass also has a large amount of total iron and is not easily melted.

【０００６】また、米国特許明細書第５４１１９２２号
には、Ｆｅ2 Ｏ3 を０．９０〜１．９０％含有する、Ｆ
ｅ2 Ｏ3 、ＣｏＯ、Ｓｅ、ＴｉＯ2 の組み合わせによる
濃グレー色ガラスが開示されている。Further, US Pat. No. 5,411,922 discloses that F 2 O 3 containing 0.90 to 1.90% of Fe 2 O 3.
Disclosed is a dark gray glass made of a combination of e 2 O 3 , CoO, Se, and TiO 2 .

【０００７】さらに、特開平８−１５７２３２には、Ｆ
ｅ2 Ｏ3 、ＴｉＯ2 、Ｓｅ、ＣｏＯの組み合わせによる
濃グレー色ガラスが、また、特開平９−３１５８３５に
は、Ｆｅ2 Ｏ3 、ＴｉＯ2 、Ｓｅ、ＣｏＯ、Ｃｒ2 Ｏ3
の組み合わせによる濃グレー色ガラスが開示されてい
る。Further, JP-A-8-157232 discloses that F
e 2 O 3, TiO 2, Se, dark gray colored glass according to the combination of CoO are also in the JP-A 9-315835, Fe 2 O 3, TiO 2, Se, CoO, Cr 2 O 3
Are disclosed.

【０００８】[0008]

【発明が解決しようとする課題】前述のように、米国特
許明細書第５４１１９２２号、特開平８−１５７２３２
および特開平９−３１５８３５には、Ｆｅ2 Ｏ3 、Ｃｏ
Ｏ、Ｓｅ、ＴｉＯ2 の組み合わせからなる着色剤を使用
した濃グレー色ガラスが開示されている。As described above, as described above, U.S. Pat. No. 5,411,922 and JP-A-8-157232.
And JP-A-9-315835 describe Fe 2 O 3 , Co
A dark gray glass using a colorant comprising a combination of O, Se, and TiO 2 is disclosed.

【０００９】このうち、Ｓｅは可視光透過率を低くする
ための成分として知られているが、Ｓｅを含むガラスを
熔解するときには、揮散したＳｅの処理が必須であり、
充分な除害を行なう必要がある。この観点では、低い透
過率のガラスを得るためには、Ｓｅの発色効率を良く
し、かつ熔解時の揮散率を抑制するとともに、ガラス中
のＳｅの含有量は多くとも３５ｐｐｍに抑制すべきであ
る。[0009] Of these, Se is known as a component for lowering the visible light transmittance, but when melting glass containing Se, it is necessary to treat the volatilized Se.
It is necessary to perform sufficient abatement. From this viewpoint, in order to obtain a glass having a low transmittance, while improving the coloring efficiency of Se and suppressing the volatilization rate at the time of melting, the content of Se in the glass should be suppressed to at most 35 ppm. is there.

【００１０】ところが、Ｓｅの発色効率と熔解時のＳｅ
の揮散率とは、いずれも、溶融ガラスの還元比に依存し
ており、相反する因子である。すなわち、熔融ガラスが
還元状態にある方がＳｅの発色効率が高いが、揮散率も
増大する。特に、コークスなどの還元剤をガラスの熔解
時に添加して、熔融ガラスが強制的に還元状態になるよ
うに制御すると、Ｓｅの揮散率は著しく高くなる。However, the coloring efficiency of Se and the Se
Are all dependent on the reduction ratio of the molten glass and are contradictory factors. In other words, when the molten glass is in the reduced state, the coloring efficiency of Se is higher, but the volatilization rate also increases. In particular, when a reducing agent such as coke is added during melting of the glass to control the molten glass to be in a reduced state, the volatilization rate of Se is significantly increased.

【００１１】この観点で、効率よくＳｅを使用するため
には、熔融ガラスを特定の還元比にする必要がある。具
体的には、鉄の還元比で表現して、Ｆｅ2 Ｏ3 に換算し
た全鉄中のＦｅ2 Ｏ3 に換算した２価の鉄の割合（以
下、この割合をＲＥＤＯＸともいう）が２２〜３０％に
なるように調整すべきである。From this viewpoint, in order to use Se efficiently, the molten glass needs to have a specific reduction ratio. Specifically, expressed in reduction ratio of iron, the percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 (hereinafter also referred to as REDOX this percentage) is 22 It should be adjusted to ~ 30%.

【００１２】一方、２価の鉄をある程度以上含有したガ
ラスは、熔解が困難になる場合がある。２価の鉄は、熔
融ガラスの熱伝導率を著しく低下させるので、これをあ
る程度以上含有したガラスは、通常のフロートガラスな
どに用いる熔解炉で熔解することが難しい。この観点
で、ガラス中のＦｅＯの含有量は０．２３重量％以下と
することが好ましい。On the other hand, glass containing a certain amount of divalent iron may be difficult to melt. Since divalent iron significantly lowers the thermal conductivity of the molten glass, it is difficult to melt glass containing a certain amount or more of it in a melting furnace used for ordinary float glass or the like. From this viewpoint, the content of FeO in the glass is preferably set to 0.23% by weight or less.

【００１３】以上のように、効率の良いＳｅの使用、お
よびガラスの熔解の容易性の２つの観点を考慮すると、
最終的に含有できる全鉄の量には一定の制限が生じる。
すなわち、全鉄の含有量が最大になるのは、ＦｅＯに換
算した２価の鉄（以下、単にＦｅＯという）の含有量が
０．２３重量％以下で、ＲＥＤＯＸが２２％の場合であ
り、生産の安定性を考慮すると、全鉄量の上限はほぼ
０．９重量％になる。As described above, in consideration of the two viewpoints of efficient use of Se and easy melting of glass,
There are certain restrictions on the amount of total iron that can ultimately be contained.
That is, the total iron content is maximized when the content of divalent iron (hereinafter, simply referred to as FeO) converted to FeO is 0.23% by weight or less and REDOX is 22%, Considering the stability of production, the upper limit of the total iron amount is almost 0.9% by weight.

【００１４】しかし、前述の公知例（米国特許明細書第
５４１１９２２号、特開平８−１５７２３２および特開
平９−３１５８３５）には、具体的に、全鉄が０．９重
量％以下、Ｓｅが３５ｐｐｍ以下で、標準Ａ光源を用い
て測定した４ｍｍ厚換算の可視光透過率が３０％以下の
濃グレー色ガラス板を得た例は記載されていない。However, the above-mentioned known examples (US Pat. No. 5,411,922, JP-A-8-157232 and JP-A-9-315835) specifically show that total iron is 0.9% by weight or less and Se is 35 ppm or less. Hereinafter, there is no description of an example of obtaining a dark gray glass plate having a visible light transmittance of 30% or less in terms of a thickness of 4 mm measured using a standard A light source.

【００１５】本発明の目的は、従来技術の上記課題を解
消し、熔解がきわめて容易で揮発したＳｅの処理にさほ
どの大規模の施設を必要とせず、通常のフロートガラス
製造法により製造でき、可視光透過率を低く制御し、紫
外線透過率を大幅に低くし、刺激純度が低く、容易に中
性色が得られるような濃グレー色を呈するガラスを得よ
うとするものである。An object of the present invention is to solve the above-mentioned problems of the prior art, and it is very easy to melt and does not require a large-scale facility for the treatment of volatilized Se, and can be manufactured by a normal float glass manufacturing method. An object of the present invention is to obtain a glass having a low visible light transmittance, a significantly low ultraviolet transmittance, a low stimulus purity, and a dark gray color that can easily obtain a neutral color.

【００１６】[0016]

【課題を解決するための手段】本発明者らは、Ｆｅ2 Ｏ
3 、ＣｏＯ、Ｓｅ、ＴｉＯ2 の組み合わせによる濃グレ
ー色ガラスにおいて、全鉄がほぼ０．９重量％以下、Ｓ
ｅがほぼ３５ｐｐｍ以下で、標準Ａ光源を用いて測定し
た４ｍｍ厚換算の可視光透過率が３０％以下になる濃グ
レー色ガラスが得られることを知見して、本発明に至っ
た。Means for Solving the Problems The present inventors have proposed Fe 2 O
3 , in a dark gray glass made of a combination of CoO, Se and TiO 2 , the total iron
The inventors have found that a dark gray glass having a visible light transmittance of 30% or less in terms of a thickness of 4 mm measured using a standard A light source when e is approximately 35 ppm or less was obtained, and the present invention was achieved.

【００１７】本発明は、ソーダライムシリケートガラス
からなる母成分１００重量部に対し、着色成分として、 Ｆｅ2 Ｏ3 で表した全鉄 ０．７〜０．９ 重量部、 ＴｉＯ2 ０．８〜３．０ 重量部、 Ｓｅ ０．００１〜０．００３５重量部、 ＣｏＯ ０．０１〜０．０３５ 重量部、 Ｃｒ2 Ｏ3 ０〜０．０５ 重量部、 ＣｅＯ2 ０〜０．５ 重量部、 Ｖ2 Ｏ5 ０〜０．５ 重量部、 を含有し、Ｆｅ2 Ｏ3 に換算した全鉄中のＦｅ2 Ｏ3 に
換算した２価の鉄の割合が２２〜３０％であり、４ｍｍ
の厚さに換算して、標準Ａ光源を用いて測定した可視光
透過率が３０％以下である濃グレー色ガラスである。According to the present invention, 0.7 to 0.9 parts by weight of total iron expressed as Fe 2 O 3 and TiO 2 0.8 to 0.8 parts by weight are used as coloring components with respect to 100 parts by weight of a mother component made of soda lime silicate glass. 3.0 parts by weight, Se from 0.001 to 0.0035 parts by weight, CoO .01 to 0.035 parts by weight, Cr 2 O 3 0 to 0.05 parts by weight, CeO 2 0 to 0.5 parts by weight, V 2 O 5 0 to 0.5 parts by weight, contains, the percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 is 22 to 30%, 4 mm
Is a dark gray glass having a visible light transmittance of 30% or less measured using a standard A light source.

【００１８】[0018]

【発明の実施の形態】上記着色成分について以下に説明
する。Ｆｅ2 Ｏ3 で表した全鉄の含有量が母成分１００
重量部に対して０．７重量部より少ないと可視光透過率
Ｔvaが大きくなりすぎる。好ましくは０．７５重量部以
上である。一方、０．９重量部より多いとガラスの熔融
が困難になる。ガラスを熔融しやすくするためには、清
澄剤を必要とするので、その量の調整を安定に行うのは
容易でない。また、このためにＳｅの揮散量が多くなる
不都合が生じるおそれがある。より好ましい全鉄の範囲
は母成分１００重量部に対して０．８７重量部以下であ
る。BEST MODE FOR CARRYING OUT THE INVENTION The coloring components will be described below. The total iron content, expressed as Fe 2 O 3 , is 100
If the amount is less than 0.7 parts by weight, the visible light transmittance T va becomes too large. It is preferably at least 0.75 parts by weight. On the other hand, if it is more than 0.9 parts by weight, melting of the glass becomes difficult. In order to easily melt the glass, a fining agent is required, so that it is not easy to stably adjust the amount. In addition, there is a possibility that the volatilization amount of Se may increase. A more preferable range of the total iron is 0.87 parts by weight or less based on 100 parts by weight of the mother component.

【００１９】この全鉄のうち、Ｆｅ2 Ｏ3 で換算した２
価の鉄の含有量がＦｅ2 Ｏ3 で換算した全鉄の２２〜３
０％である。２価の鉄の含有量が２２％より少ないとＳ
ｅの発色が悪くなり、Ｓｅの使用量を低減できない。好
ましくは２４％以上である。一方、３０％より多いと清
澄剤の使用になり、Ｓｅの揮散量が著しく多くなる。好
ましくは２９％以下である。Of the total iron, 2 converted to Fe 2 O 3
The content of iron with a valence of 22 to 3 of the total iron in terms of Fe 2 O 3
0%. If the content of divalent iron is less than 22%, S
The color development of e deteriorates, and the amount of Se used cannot be reduced. It is preferably at least 24%. On the other hand, if it is more than 30%, a fining agent is used, and the amount of Se volatilized significantly increases. Preferably it is 29% or less.

【００２０】ＴｉＯ2 は紫外線透過率Ｔuvを小さくする
とともに、鉄の存在とあいまって、Ｔvaを低くするため
に含有させる成分である。母成分１００重量部に対して
０．８重量部以上ＴｉＯ2 を含有することにより、Ｔuv
を低くするとともに、比較的少ない鉄含有量で、低いＴ
vaを得ることができる。一方、ＴｉＯ2 は母成分１００
重量部に対して３．０重量部までとされる。これを超え
ると、ガラスの諸物性（特に粘性）に悪影響が生じるお
それがある。TiO 2 is a component contained to reduce the UV transmittance T uv and to reduce T va in combination with the presence of iron. By containing 0.8 parts by weight or more of TiO 2 with respect to 100 parts by weight of the mother component, T uv
With a relatively low iron content and a low T
You can get va . On the other hand, TiO 2 contains 100
3.0 parts by weight with respect to parts by weight. Exceeding this may adversely affect various physical properties (particularly viscosity) of the glass.

【００２１】Ｓｅの含有量が母成分１００重量部に対し
て０．００１重量部より少ないと低いＴvaを得にくくな
る。好ましくは、０．００１２重量部以上である。一
方、０．００３５重量部より多いとガラス熔融時のＳｅ
の揮散量が多くなり、大規模な除害設備が必要になるお
それがある。好ましくは０．００３重量部以下である。If the content of Se is less than 0.001 part by weight based on 100 parts by weight of the mother component, it becomes difficult to obtain a low Tva . Preferably, it is 0.0012 parts by weight or more. On the other hand, if the content is more than 0.0035 parts by weight, the glass melts Se
The amount of volatilization of waste may increase, and large-scale abatement equipment may be required. Preferably it is 0.003 parts by weight or less.

【００２２】ＣｏＯは、Ｓｅとバランスして、中性色が
得られる程度の量が含有される。具体的には、重量比で
Ｓｅの５〜２０倍含有されることが好ましく、より好ま
しくは７〜１８倍である。ＣｏＯの含有量が母成分１０
０重量部に対して０．０１重量部より少ないとＴvaが大
きくなりすぎるおそれがある。好ましくは、０．０１２
重量部以上である。一方、母成分１００重量部に対して
０．０３５重量部より多いとガラスの色調が青みを帯
び、グレー色調のガラスが得られにくい。好ましくは、
０．０３重量部以下である。CoO is contained in such an amount that a neutral color can be obtained in balance with Se. Specifically, Se is preferably contained 5 to 20 times the weight of Se, more preferably 7 to 18 times. CoO content is the parent component 10
If the amount is less than 0.01 part by weight with respect to 0 part by weight, T va may be too large. Preferably, 0.012
It is more than weight part. On the other hand, if the amount is more than 0.035 parts by weight with respect to 100 parts by weight of the mother component, the color tone of the glass becomes bluish, and it is difficult to obtain glass having a gray color tone. Preferably,
0.03 parts by weight or less.

【００２３】Ｃｒ2 Ｏ3 は必須ではないが、本発明のガ
ラスにおいて、さほど刺激純度Ｐeを高めないで、Ｔva
を低減させうる成分であるので含有させることができ
る。Ｃｒ2 Ｏ3 の含有量が母成分１００重量部に対して
０．０５重量部より多いとＴvaは低下するが、Ｃｒ2 Ｏ
3 自身の吸収によりＰe が大きくなるおそれがある。ま
た、Ｃｒ2 Ｏ3 自身が強酸化剤として働くため、共存金
属イオンの価数変化を起こすおそれがある。[0023] Although Cr 2 O 3 is not essential, in the glass of the present invention, not less enhanced excitation purity P e, T va
Can be contained because it is a component that can reduce If the content of Cr 2 O 3 is more than 0.05 part by weight with respect to 100 parts by weight of the mother component, T va is reduced, but Cr 2 O 3 is reduced.
(3) Pe may increase due to absorption by itself. Further, since Cr 2 O 3 itself acts as a strong oxidizing agent, the valence of coexisting metal ions may change.

【００２４】ＣｅＯ2 およびＶ2 Ｏ5 はいずれも必須で
はないが、Ｔuvをより低くするために含有させることが
できる。しかし、それぞれ母成分１００重量部に対して
０．５重量部より多いと、これらの成分自身の吸収によ
り着色するおそれがある。Both CeO 2 and V 2 O 5 are not essential, but can be included to lower T uv . However, if the amount is more than 0.5 part by weight with respect to 100 parts by weight of the respective mother components, there is a possibility that these components themselves may be colored by absorption.

【００２５】母成分であるソーダライムシリケートガラ
スは、実質的に重量％で、以下のような組成であること
が好ましい。 ＳｉＯ2 ６５〜 ７５％、 Ａｌ2 Ｏ3 ０．１〜 ５％、 Ｎａ2 Ｏ＋Ｋ2 Ｏ １０〜 １８％、 ＣａＯ ５〜 １５％、 ＭｇＯ １〜 ６％。The soda lime silicate glass, which is the mother component, preferably has the following composition by weight%. SiO 2 65-75%, Al 2 O 3 0.1-5%, Na 2 O + K 2 O 10-18%, CaO 5-15%, MgO 1-6%.

【００２６】ＳｉＯ2 の含有量が６５重量％（以下、母
成分であるソーダライムシリケートガラスの成分につい
ては、％と記載）より少ないと耐候性が悪くなり、７５
％より多いと粘度が高くなり、熔融が困難になる。Ａｌ
2 Ｏ3 の含有量が０．１％より少ないと耐水性が低下
し、５％より多いと熔融性が低下する。If the content of SiO 2 is less than 65% by weight (hereinafter, the component of soda lime silicate glass which is a parent component is described as%), the weather resistance becomes poor, and
%, The viscosity increases and melting becomes difficult. Al
When the content of 2 O 3 is less than 0.1%, the water resistance decreases, and when it exceeds 5%, the meltability decreases.

【００２７】Ｎａ2 Ｏ、Ｋ2 Ｏは原料の熔融を促進する
成分である。両者の含有量が合量で１０％より少ないと
その効果が小さく、１８％より多いと耐候性が悪くな
る。ＣａＯ、ＭｇＯは原料の熔融を促進し耐候性を改善
する成分である。ＣａＯの含有量が５％より少ないと上
述の効果が小さく、１５％より多いと失透しやすくな
る。ＭｇＯの含有量が１％より少ないと上記効果が少な
く、６％より多いと失透しやすくなる。なお、実生産に
おいては、清澄剤として芒硝が用いられるため、その痕
跡として、０．０５〜１．０％程度のＳＯ3 がガラス中
に残存するのが通常である。Na 2 O and K 2 O are components that promote the melting of the raw materials. If the total content of both is less than 10%, the effect is small, and if it is more than 18%, the weather resistance is deteriorated. CaO and MgO are components that promote the melting of the raw materials and improve the weather resistance. If the content of CaO is less than 5%, the above-mentioned effects are small, and if it is more than 15%, devitrification tends to occur. If the content of MgO is less than 1%, the above effect is small, and if it is more than 6%, devitrification tends to occur. In actual production, since sodium sulfate is used as a fining agent, about 0.05 to 1.0% of SO 3 usually remains in the glass as a trace thereof.

【００２８】本発明のガラスは、４ｍｍの厚さに換算し
て、Ｔvaは３０％以下であり、２５％以下が好ましい。
典型的には、４ｍｍの厚さに換算したＴvaは１０〜３０
％、特に１０〜２５％になる。本発明のガラスは、自動
車用のほか建築用にも用いることができるが、自動車の
サンルーフやリヤガラスとして用いる場合、以下のよう
な光学特性を有することが好ましい。The glass of the present invention has a Tva of 30% or less, preferably 25% or less, when converted to a thickness of 4 mm.
Typically, T va converted to a thickness of 4 mm is 10 to 30.
%, Especially 10 to 25%. The glass of the present invention can be used not only for automobiles but also for architectural purposes. However, when used as an automobile sunroof or rear glass, the glass preferably has the following optical characteristics.

【００２９】まず、４ｍｍの厚さに換算して、日射透過
率Ｔe は３０％以下であることが好ましく、特に好まし
くは２５％以下である。さらに、４ｍｍの厚さに換算し
て、Ｔuvは１０％以下であることが好ましく、特に好ま
しくは７％以下である。また、４ｍｍの厚さに換算し
て、主波長Ｄw が４９０〜５８０ｎｍであることが好ま
しい。さらに、４ｍｍの厚さに換算して、Ｐe が７％以
下であることが好ましく、特に好ましくは５％以下であ
る。Firstly, in terms of the thickness of 4 mm, it is preferred that the solar transmittance T e is less than or equal to 30%, particularly preferably 25% or less. Further, T uv is preferably 10% or less, particularly preferably 7% or less, when converted to a thickness of 4 mm. Also, in terms of thickness of 4 mm, it is preferable dominant wavelength D w is 490～580Nm. Furthermore, in terms of the thickness of 4 mm, it is preferable that P e is equal to or less than 7%, particularly preferably 5% or less.

【００３０】本明細書を通じて、Ｔe 、ＴvaはＪＩＳ−
Ｒ３１０６により、ＴuvはＩＳＯ−９０５０により、そ
れぞれ求めたものである。また、Ｔvaは標準Ａ光源を、
ＤwとＰe は標準Ｃ光源を、それぞれ用いて測定したも
のである。[0030] Throughout this specification, T e, T va is JIS-
T uv is determined by R3106 and ISO-9050, respectively. T va is a standard A light source,
Dw and Pe are measured using a standard C light source, respectively.

【００３１】本発明のガラスは車両用としては、通常、
２．５〜５ｍｍ厚で用いられる。また、合わせガラスと
して用いる場合、合わせガラス素板の厚みは通常１．８
〜２．３ｍｍ程度であり、２枚の素板を合わせた状態で
のガラス部分の厚みは３．６〜４．６ｍｍ程度となる。The glass of the present invention is generally used for vehicles.
Used in a thickness of 2.5 to 5 mm. When used as a laminated glass, the thickness of the laminated glass plate is usually 1.8.
The thickness of the glass portion in a state where the two base plates are combined is about 3.6 to 4.6 mm.

【００３２】本発明のガラスの製造法は、特に限定され
ないが、たとえば、次のようにして製造できる。調合し
た原料を連続的に熔融炉に供給し、重油等により約１５
００℃に加熱してガラス化する。次いで、この熔融ガラ
スを清澄した後、フロート法等により所定の厚さのガラ
ス板に成形する。次いで、このガラス板を所定の形状に
切断することにより、本発明のガラスが製造される。そ
の後、必要に応じて、切断したガラスを強化処理し、合
わせガラスに加工し、または複層ガラスに加工すること
ができる。Although the method for producing the glass of the present invention is not particularly limited, it can be produced, for example, as follows. The blended raw material is continuously supplied to the melting furnace, and about 15
Heat to 00 ° C to vitrify. Next, after clarifying the molten glass, it is formed into a glass plate having a predetermined thickness by a float method or the like. Next, the glass of the present invention is manufactured by cutting the glass plate into a predetermined shape. Thereafter, if necessary, the cut glass can be tempered, processed into a laminated glass, or processed into a double glazing.

【００３３】[0033]

【実施例】原料としてケイ砂、長石、苦灰石、ソーダ
灰、芒硝、酸化第二鉄、酸化チタン、酸化コバルト、酸
化セレン、酸化セリウムおよび酸化クロムを用い、母成
分についは、ＳｉＯ2 ：７１．４、Ａｌ2 Ｏ3 ：１．
８、ＣａＯ：８．５、ＭｇＯ：４．５、Ｎａ2 Ｏ：１
２．８、Ｋ2 Ｏ：０．７およびＳＯ3 ：０．３（単位：
重量％）からなるソーダライムシリケートガラスとなる
ように、かつ、着色成分については、表１、表２に示す
目標組成が得られるように調合したバッチを、通常のタ
イプの熔融槽で熔融（Ｏ2 濃度２％程度の雰囲気）し、
その熔融槽に接続された小型フロート試験設備に熔融ガ
ラスを供給し４ｍｍ厚のグレー色の板ガラスを製造し
た。EXAMPLES silica sand as raw material, feldspar, using dolomite, soda ash, salt cake, ferric oxide, titanium oxide, cobalt oxide, selenium oxide, cerium oxide and chromium oxide, is attached to the base component, SiO 2: 71.4, Al 2 O 3 : 1.
8, CaO: 8.5, MgO: 4.5, Na 2 O: 1
2.8, K 2 O: 0.7 and SO 3 : 0.3 (unit:
(% By weight) and a batch prepared so as to obtain the target composition shown in Tables 1 and 2 with respect to the coloring component. 2 Atmosphere with a concentration of about 2%)
The molten glass was supplied to a small float test facility connected to the melting tank to produce a gray plate glass having a thickness of 4 mm.

【００３４】表１、表２は、母成分１００重量部に着色
成分として加えるｔ−Ｆｅ2 Ｏ3 （Ｆｅ2 Ｏ3 に換算し
た全鉄）、ＦｅＯ、ＣｏＯ、Ｓｅ、ＴｉＯ2 、ＣｅＯ2
およびＣｒ2 Ｏ3 の量（単位：母成分の合量１００重量
部に対する外掛けの重量部）、ＲＥＤＯＸ（単位：％）
を示す。Tables 1 and 2 show that t-Fe 2 O 3 (total iron in terms of Fe 2 O 3 ), FeO, CoO, Se, TiO 2 , CeO 2 added as a coloring component to 100 parts by weight of the mother component.
And amount of Cr 2 O 3 (unit: outer part by weight based on 100 parts by weight of the total amount of the mother component), REDOX (unit:%)
Is shown.

【００３５】これらの板ガラスについて、Ｔe （％）、
Ｔva（％）、Ｔuv（％）、Ｄw （ｎｍ）およびＰe
（％）を求めた結果を表１、表２に併記した。これらの
値はいずれも４ｍｍ厚さにおけるものである。なお、例
７、例８は本発明の範囲外の例である。本発明の実施例
において、Ｔvaが低く、Ｔe およびＴuvが大幅に低く、
かつ、Ｐe が低い濃グレー色ガラスが得られている。For these sheet glasses, T e (%),
T va (%), T uv (%), D w (nm) and Pe
(%) Are shown in Tables 1 and 2. These values are all at a thickness of 4 mm. Examples 7 and 8 are examples outside the scope of the present invention. In an embodiment of the present invention, T va is low, T e and T uv is significantly lower,
And, P e is lower dark gray glass is obtained.

【００３６】[0036]

【表１】 [Table 1]

【００３７】[0037]

【表２】 [Table 2]

【００３８】[0038]

【発明の効果】このように、本発明による濃グレー色ガ
ラスは、Ｔvaが低く、Ｔe およびＴuvを大幅に低下させ
たものであり、かつＰe が低いものである。さらに、Ｓ
ｅの使用量が少なく、熔融性に優れるため、通常のタイ
プの熔融槽により容易に熔融でき、また、生産性に優れ
たフロート法により製造できる。[Effect of the Invention] Thus, dark gray colored glass according to the present invention, T va is low, but was significantly reduced the T e and T uv, and those low P e. Furthermore, S
Since e is used in a small amount and is excellent in meltability, it can be easily melted in a usual type of melting tank, and can be manufactured by a float method excellent in productivity.

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】ソーダライムシリケートガラスからなる母
成分１００重量部に対し、着色成分として、 Ｆｅ2 Ｏ3 で表した全鉄 ０．７〜０．９ 重量部、 ＴｉＯ2 ０．８〜３．０ 重量部、 Ｓｅ ０．００１〜０．００３５重量部、 ＣｏＯ ０．０１〜０．０３５ 重量部、 Ｃｒ2 Ｏ3 ０〜０．０５ 重量部、 ＣｅＯ2 ０〜０．５ 重量部、 Ｖ2 Ｏ5 ０〜０．５ 重量部、 を含有し、Ｆｅ2 Ｏ3 に換算した全鉄中のＦｅ2 Ｏ3 に
換算した２価の鉄の割合が２２〜３０％であり、４ｍｍ
の厚さに換算して、標準Ａ光源を用いて測定した可視光
透過率が３０％以下である濃グレー色ガラス。1. As a coloring component, 0.7 to 0.9 parts by weight of total iron represented by Fe 2 O 3 , and 0.8 to 3 parts by weight of TiO 2 with respect to 100 parts by weight of a base component composed of soda lime silicate glass. 0 parts by weight, Se 0.001 to 0.0035 parts by weight, CoO 0.01 to 0.035 parts by weight, Cr 2 O 3 0 to 0.05 parts by weight, CeO 2 0 to 0.5 parts by weight, V 2 O 5 0 to 0.5 parts by weight, contains, the percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 is 22 to 30%, 4 mm
A dark gray colored glass having a visible light transmittance of 30% or less measured using a standard A light source in terms of thickness. 【請求項２】４ｍｍの厚さに換算して、ＩＳＯ−９０５
０にしたがって求めた紫外線透過率が１０％以下である
請求項１記載の濃グレー色ガラス。2. Converted to a thickness of 4 mm, ISO-905
2. The dark gray glass according to claim 1, wherein the ultraviolet transmittance determined according to 0 is 10% or less. 【請求項３】４ｍｍの厚さに換算して、標準Ｃ光源を用
いて測定した主波長が４９０〜５８０ｎｍであり、標準
Ｃ光源を用いて測定した刺激純度が７％以下である請求
項１または２記載の濃グレー色ガラス。3. The thickness of 4 mm, the dominant wavelength measured using a standard C light source is 490 to 580 nm, and the stimulus purity measured using a standard C light source is 7% or less. Or a dark gray colored glass according to 2. 【請求項４】ソーダライムシリケートガラスは、実質的
に重量％で、 ＳｉＯ2 ６５〜 ７５％、 Ａｌ2 Ｏ3 ０．１〜 ５％、 Ｎａ2 Ｏ＋Ｋ2 Ｏ １０〜 １８％、 ＣａＯ ５〜 １５％、 ＭｇＯ １〜 ６％、 からなることを特徴とする請求項１、２または３記載の
濃グレー色ガラス。4. The soda lime silicate glass is substantially 65% to 75% by weight of SiO 2 , 0.1 to 5% of Al 2 O 3, 10 to 18% of Na 2 O + K 2 O, and 5 to 15% of CaO. %, MgO 1 to 6%, The dark gray color glass according to claim 1, 2 or 3.
JP1975598A 1998-01-30 1998-01-30 Deep gray color glass Withdrawn JPH11217234A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1975598A JPH11217234A (en) 1998-01-30 1998-01-30 Deep gray color glass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1975598A JPH11217234A (en) 1998-01-30 1998-01-30 Deep gray color glass

Publications (1)

Publication Number Publication Date
JPH11217234A true JPH11217234A (en) 1999-08-10

Family

ID=12008175

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Link
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US10011520B2 (en) 2014-09-08 2018-07-03 Asahi Glass Company, Limited Ultraviolet-absorbing glass article
JP2016199457A (en) * 2015-04-08 2016-12-01 旭硝子株式会社 Laminate sheet
US10626044B2 (en) 2015-09-11 2020-04-21 AGC Inc. Ultraviolet-radiation absorbing glass product
US11498864B2 (en) 2015-09-11 2022-11-15 AGC Inc. Ultraviolet-radiation absorbing glass product
WO2017150684A1 (en) * 2016-03-03 2017-09-08 旭硝子株式会社 Ultraviolet absorbing glass

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