JP2000302480A - Low-melting glass composition - Google Patents
Low-melting glass compositionInfo
- Publication number
- JP2000302480A JP2000302480A JP11109741A JP10974199A JP2000302480A JP 2000302480 A JP2000302480 A JP 2000302480A JP 11109741 A JP11109741 A JP 11109741A JP 10974199 A JP10974199 A JP 10974199A JP 2000302480 A JP2000302480 A JP 2000302480A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic color
- glass
- glass composition
- low
- color paste
- 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- Withdrawn
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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、自動車用ガラス板
に焼き付けるセラミックカラーペーストに好適な低融点
ガラス組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-melting glass composition suitable for a ceramic color paste to be baked on an automotive glass plate.
【０００２】[0002]
【従来の技術】従来より、自動車用ガラス板の周縁部ま
たは中央部に、低融点ガラスを含有するセラミックカラ
ーペーストを塗布し乾燥した後、該ガラス板の曲げ加工
・加熱工程において該ガラス板に焼き付けることが行わ
れている。2. Description of the Related Art Conventionally, a ceramic color paste containing a low-melting glass is applied to the periphery or the center of a glass plate for an automobile, dried and then applied to the glass plate in a bending and heating step of the glass plate. Baking is done.
【０００３】このセラミックカラーペーストには、いわ
ゆる型離れ性がよいことと優れた耐酸性が求められてい
る。ここで、型離れ性がよい、とは、ガラス板に塗布さ
れたセラミックカラーペーストが前記曲げ加工時にプレ
ス型または曲げ用吸着型に付着しにくいことをいう。[0003] The ceramic color paste is required to have good mold release properties and to have excellent acid resistance. Here, the phrase “the mold releasability is good” means that the ceramic color paste applied to the glass plate does not easily adhere to the press mold or the bending suction mold during the bending.
【０００４】また、耐酸性は、近年問題となっている酸
性雨に関連してその向上が求められている。すなわち、
従来のセラミックカラーペーストをガラス板に焼き付け
て形成されたセラミックカラー層が酸性雨に長時間さら
されると、その色調が変化する、セラミックカラー層が
はがれる、等の問題があった。さらに前記低融点ガラス
には鉛およびカドミウムが含まれないことが求められて
いる。[0004] Further, acid resistance is required to be improved in relation to acid rain, which has recently become a problem. That is,
When a ceramic color layer formed by baking a conventional ceramic color paste on a glass plate is exposed to acid rain for a long time, the color tone changes, and the ceramic color layer peels off. Further, it is required that the low melting point glass does not contain lead and cadmium.
【０００５】[0005]
【発明が解決しようとする課題】特開平６−２３４５４
７には、このようなセラミックカラーペーストに用いら
れる低融点ガラスが開示されている。その実施例のガラ
ス組成の範囲は、重量％表示で、 ＳｉＯ2 １６．０〜３３．３、 Ｂｉ2Ｏ3 ５１．７〜６９．３、 ＴｉＯ2 ４．２〜９．０、 Ｌｉ2Ｏ ０〜２．３、 Ｎａ2Ｏ ０〜９．１、 Ｋ2Ｏ ０〜１１．６、 Ｂ2Ｏ3 ０〜２．３、 Ａｌ2Ｏ3 ０〜３．３、 である。Problems to be Solved by the Invention
No. 7 discloses a low melting point glass used for such a ceramic color paste. Range of the glass composition of the embodiment, in weight percentages, SiO 2 16.0~33.3, Bi 2 O 3 51.7~69.3, TiO 2 4.2~9.0, Li 2 O 0 to 2.3, Na 2 O 0 to 9.1, K 2 O 0 to 11.6, B 2 O 3 0 to 2.3, and Al 2 O 3 0 to 3.3.
【０００６】本発明は、上記組成範囲のガラスよりも耐
酸性に優れ、かつ、型離れ性のよいセラミックカラーペ
ーストを提供でき、かつ、鉛またはカドミウムを含まな
い低融点ガラス組成物の提供を目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a ceramic color paste which is more excellent in acid resistance than glass having the above composition range and has good mold release property, and provides a low melting point glass composition containing no lead or cadmium. And
【０００７】[0007]
【課題を解決するための手段】本発明は、実質的に重量
％表示で、 ＳｉＯ2 １０〜３６、 Ｂｉ2Ｏ3 ５６〜７５、 ＴｉＯ2 ３〜７、 Ｌｉ2Ｏ ３〜５、 Ｎａ2Ｏ ０〜２、 Ｋ2Ｏ ０〜３、 からなる低融点ガラス組成物を提供する。SUMMARY OF THE INVENTION The present invention is a substantially weight percentages, SiO 2 10~36, Bi 2 O 3 56~75, TiO 2 3~7, Li 2 O 3~5, Na 2 Provided is a low-melting glass composition comprising O 0-2 and K 2 O 0-3.
【０００８】[0008]
【発明の実施の形態】本発明の低融点ガラス組成物は、
自動車用ガラス板が曲げ加工される温度、すなわち５０
０〜７００℃において結晶を析出する。この結晶析出量
の多寡は前記型離れ性の良否を左右する。BEST MODE FOR CARRYING OUT THE INVENTION The low melting glass composition of the present invention comprises:
The temperature at which the automotive glass sheet is bent, ie, 50
Crystals precipitate at 0-700 ° C. The amount of the crystal precipitation affects the quality of the mold releasability.
【０００９】本発明の低融点ガラス組成物は、実質的に
重量％表示で、 ＳｉＯ2 ２０〜３３、 Ｂｉ2Ｏ3 ５８〜７０、 ＴｉＯ2 ４〜７、 Ｌｉ2Ｏ ３〜５、 Ｎａ2Ｏ ０〜２、 Ｋ2Ｏ ０〜３、 からなることが好ましい。The low-melting glass composition of the present invention is substantially represented by weight%, SiO 2 20-33, Bi 2 O 3 58-70, TiO 2 4-7, Li 2 O 3-5, Na 2 It is preferably composed of O 0-2 and K 2 O 0-3.
【００１０】より好ましくは、実質的に重量％表示で、 ＳｉＯ2 ２５〜３０、 Ｂｉ2Ｏ3 ５９〜６６、 ＴｉＯ2 ５〜６、 Ｌｉ2Ｏ ３〜５、 Ｎａ2Ｏ ０〜２、 Ｋ2Ｏ ０〜２、 からなることである。More preferably, substantially in terms of% by weight, SiO 2 25-30, Bi 2 O 3 59-66, TiO 2 5-6, Li 2 O 3-5, Na 2 O 0-2, K 2 O 0-2.
【００１１】組成限定理由を、重量％を単に％と表記し
て以下に説明する。ＳｉＯ2はネットワークフォーマで
あり、また結晶析出のための必須成分である。１０％未
満では、結晶析出量が不足し、また、Ｂｉ2Ｏ3含有量が
増加し耐酸性が低下する。好ましくは２０％以上、より
好ましくは２５％以上である。３６％超では、軟化点が
高くなりすぎ自動車用ガラス板の曲げ加工時にセラミッ
クカラーペーストを同時に焼き付けることが困難にな
る、また、Ｂｉ2Ｏ3含有量が減少しすぎ結晶析出量が不
足する。好ましくは３３％以下、より好ましくは３０％
以下である。The reasons for limiting the composition will be described below by simply expressing weight% as%. SiO 2 is a network former and is an essential component for crystal precipitation. If it is less than 10%, the amount of precipitated crystals will be insufficient, and the content of Bi 2 O 3 will increase, and the acid resistance will decrease. It is preferably at least 20%, more preferably at least 25%. If it exceeds 36%, the softening point will be too high, making it difficult to simultaneously bake the ceramic color paste during bending of the glass sheet for automobiles, and the content of Bi 2 O 3 will be too small, and the amount of crystal precipitation will be insufficient. Preferably not more than 33%, more preferably 30%
It is as follows.
【００１２】Ｂｉ2Ｏ3は軟化点を下げ、また結晶析出の
ための必須成分である。５６％未満では軟化点が高くな
りすぎ焼き付け不良となり、また、結晶析出量が不足す
る。好ましくは５８％以上、より好ましくは５９％以上
である。７５％超では耐酸性が低下する。好ましくは７
０％以下、より好ましくは６６％以下である。Bi 2 O 3 lowers the softening point and is an essential component for crystal precipitation. If it is less than 56%, the softening point becomes too high, resulting in poor baking, and the amount of crystal precipitation is insufficient. It is preferably at least 58%, more preferably at least 59%. If it exceeds 75%, the acid resistance decreases. Preferably 7
0% or less, more preferably 66% or less.
【００１３】ＴｉＯ2は必須成分であり、耐酸性を向上
させる。３％未満では耐酸性が低下する。好ましくは４
％以上、より好ましくは５％以上である。７％超では、
軟化点が高くなりすぎる。好ましくは６％以下である。TiO 2 is an essential component and improves the acid resistance. If it is less than 3%, the acid resistance decreases. Preferably 4
% Or more, more preferably 5% or more. With more than 7%
The softening point is too high. It is preferably at most 6%.
【００１４】Ｌｉ2Ｏは必須成分であり、耐酸性および
溶解性を向上させる。３％未満では、Ｎａ2Ｏおよび／
またはＫ2Ｏの含有量が増大して耐酸性が低下し、また
結晶析出量が不足する。５％超では結晶析出量が多くな
りすぎ流動性が低下する。好ましくは４．５％以下であ
る。Li 2 O is an essential component and improves acid resistance and solubility. If it is less than 3%, Na 2 O and / or
Alternatively, the content of K 2 O increases and the acid resistance decreases, and the amount of precipitated crystals is insufficient. If it exceeds 5%, the amount of crystal precipitation becomes too large and the fluidity decreases. Preferably it is 4.5% or less.
【００１５】Ｎａ2Ｏ、Ｋ2Ｏは必須ではないが、流動性
および溶解性の向上のためにそれぞれ２％、３％まで含
有してもよい。これを超えて含有すると耐酸性が低下す
るおそれがある。Ｋ2Ｏの含有量は、より好ましくは２
％以下である。Although Na 2 O and K 2 O are not essential, they may be contained up to 2% and 3%, respectively, for improving fluidity and solubility. If the content exceeds this, the acid resistance may be reduced. The content of K 2 O is more preferably 2
% Or less.
【００１６】本発明の低融点ガラス組成物は実質的に上
記成分からなるが、この他に、Ａｌ 2Ｏ3、ＭｇＯ、Ｃａ
Ｏ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｌａ2Ｏ3、ＺｒＯ2、Ｓ
ｎＯ2、Ｐ2Ｏ5、ＣｅＯ2、等を、軟化点、熱膨張係数、
等の調整のために、ガラスの均質性を損なわない範囲で
合量で３％まで適宜含有させてもよい。特にＢａＯは、
溶解性向上のために２％までの範囲で含有させてもよ
い。なおＢ2Ｏ3は、耐酸性を低下させるおそれがあるの
で実質的に含有しないことが好ましい。また、鉛および
カドミウムはいずれも実質的に含有しない。The low melting glass composition of the present invention is substantially
Consisting of the above-mentioned components. TwoOThree, MgO, Ca
O, SrO, BaO, ZnO, LaTwoOThree, ZrOTwo, S
nOTwo, PTwoOFive, CeOTwo, Etc., the softening point, the coefficient of thermal expansion,
For the adjustment of etc., within the range that does not impair the homogeneity of the glass
You may make it contain suitably 3% in total amount. In particular, BaO
May be included up to 2% to improve solubility
No. Note that BTwoOThreeMay reduce acid resistance
Is preferably not substantially contained. Also lead and
Cadmium is substantially free of any.
【００１７】本発明の低融点ガラス組成物は、プレス成
形等によりガラス板を曲げ加工する際に同時に該ガラス
板に焼き付けられるセラミックカラーペーストに好適に
使用される。The low melting point glass composition of the present invention is suitably used for a ceramic color paste which is simultaneously baked on a glass plate when the glass plate is bent by press molding or the like.
【００１８】[0018]
【実施例】表のＳｉＯ2〜Ｋ2Ｏの欄に示すガラス組成
（単位：重量％）となるように原料を調合、混合し、１
２５０〜１３５０℃の温度にて溶融してガラス化し低融
点ガラスを得た。この低融点ガラスをボールミルで粉砕
し、重量平均径が３μｍの低融点ガラス粉末とした。EXAMPLES Raw materials were mixed and mixed so that the glass composition (unit: wt%) shown in the column of SiO 2 to K 2 O in the table was obtained.
It was melted and vitrified at a temperature of 250 to 1350 ° C. to obtain a low-melting glass. This low melting point glass was pulverized with a ball mill to obtain a low melting point glass powder having a weight average diameter of 3 μm.
【００１９】この低融点ガラス粉末７０重量部と、Ｃｕ
−Ｃｒ−Ｏ系黒色耐熱性顔料粉末（日本フェロー株式会
社製、製品番号４２−３０２Ａ）３０重量部を調合、混
合して混合粉末とした。次いで、この混合粉末８５重量
部に、１０重量％のエチルセルロースを溶解したα−テ
ルピネオール溶液を１５重量部を加えて混練し、３本ロ
ールミルを３回通すことにより均質分散を行って所望の
ペースト粘度に調整し、セラミックカラーペーストを得
た。70 parts by weight of the low melting point glass powder and Cu
30 parts by weight of a Cr-O-based black heat-resistant pigment powder (manufactured by Nippon Fellow Co., Ltd., product number 42-302A) were mixed and mixed to obtain a mixed powder. Then, to 85 parts by weight of the mixed powder, 15 parts by weight of an α-terpineol solution in which 10% by weight of ethyl cellulose was dissolved was added and kneaded, and the mixture was homogenized by passing through a three-roll mill three times to obtain a desired paste viscosity. To obtain a ceramic color paste.
【００２０】このようにして得られたセラミックカラー
ペーストの型離れ性および耐酸性を以下のようにして評
価した。例１〜７は実施例、例８〜１３は比較例であ
る。 （１）型離れ性 セラミックカラーペーストをソーダライムシリカガラス
板（厚さ３．５ｍｍ、１０ｃｍ角）の全面にスクリーン
印刷して乾燥後、加熱炉に入れ、６７０℃に４分間保持
してプレス法により曲げ加工した。常温まで冷却後この
ガラス板を取り出し、ガラス板上に焼き付けられたセラ
ミックカラー層のプレス型への付着状況を調べた。結果
を表に示す。◎はまったく付着が認められなかったも
の、○はほとんど付着が認められなかったもの、×は付
着が認められたものである。The mold releasability and the acid resistance of the thus obtained ceramic color paste were evaluated as follows. Examples 1 to 7 are Examples and Examples 8 to 13 are Comparative Examples. (1) Mold releasability A ceramic color paste was screen-printed on the entire surface of a soda lime silica glass plate (3.5 mm thick, 10 cm square), dried, placed in a heating furnace, and held at 670 ° C. for 4 minutes to press. By bending. After cooling to room temperature, the glass plate was taken out, and the state of adhesion of the ceramic color layer baked on the glass plate to the press mold was examined. The results are shown in the table. ◎ indicates that no adhesion was observed, ○ indicates that almost no adhesion was observed, and X indicates that adhesion was observed.
【００２１】（２）耐酸性 セラミックカラーペーストをソーダライムシリカガラス
板（厚さ３．５ｍｍ、１０ｃｍ角）の全面にスクリーン
印刷して乾燥後、６７０℃に４分間保持して前記ガラス
板に焼き付け、セラミックカラー層付ガラス板を作製し
た。(2) Acid-resistant ceramic color paste is screen-printed on the entire surface of a soda lime silica glass plate (3.5 mm thick, 10 cm square), dried, held at 670 ° C. for 4 minutes, and baked on the glass plate. A glass plate with a ceramic color layer was produced.
【００２２】このセラミックカラー層付ガラス板を８０
℃の０．１Ｎ硫酸に１４０時間浸漬した後取り出し、ス
クリーン印刷をしていないガラス面側からの色度を、色
彩色差計（ミノルタ株式会社製、製品番号ＣＲ−２０
０）を用いて測定して耐酸性を評価した。浸漬前後の色
差△Ｅを表に示す。△Ｅが１．５以下であることが好ま
しい。The glass plate with the ceramic color layer is 80
After being immersed in 0.1N sulfuric acid at 140 ° C. for 140 hours, it was taken out, and the chromaticity from the glass surface side not subjected to screen printing was measured using a colorimeter (manufactured by Minolta, product number CR-20).
0) was used to evaluate the acid resistance. The color difference ΔE before and after immersion is shown in the table. ΔE is preferably 1.5 or less.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【発明の効果】本発明の低融点ガラスを含有するセラミ
ックカラーペーストを用いることにより、耐酸性および
型離れ性に優れたセラミックカラー層を得ることができ
る。また、本発明の低融点ガラスは鉛またはカドミウム
を含有せず、環境に負荷をかけるおそれがない。By using the ceramic color paste containing the low melting point glass of the present invention, a ceramic color layer excellent in acid resistance and mold release properties can be obtained. Further, the low-melting glass of the present invention does not contain lead or cadmium, and there is no possibility of imposing a load on the environment.
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Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11109741A JP2000302480A (en) | 1999-04-16 | 1999-04-16 | Low-melting glass composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11109741A JP2000302480A (en) | 1999-04-16 | 1999-04-16 | Low-melting glass composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000302480A true JP2000302480A (en) | 2000-10-31 |
| JP2000302480A5 JP2000302480A5 (en) | 2005-03-17 |
Family
ID=14518081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11109741A Withdrawn JP2000302480A (en) | 1999-04-16 | 1999-04-16 | Low-melting glass composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000302480A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010116913A1 (en) * | 2009-03-29 | 2010-10-14 | 日本山村硝子株式会社 | Lead-free glass composition |
| US7884547B2 (en) | 2007-02-06 | 2011-02-08 | Noritake Co., Limited | Lead-free acid-resistant glass composition and glass paste comprised of the same |
| CN103771702A (en) * | 2014-01-21 | 2014-05-07 | 江苏奥蓝工程玻璃有限公司 | Bending-resistant impact-resistant glass material and preparation method thereof |
| US20160185650A1 (en) * | 2013-08-09 | 2016-06-30 | Nippon Electric Glass Co. Ltd. | Bismuth-based glass composition, powder material, and powder material paste |
| CN110683764A (en) * | 2019-11-15 | 2020-01-14 | 黄山市晶特美新材料有限公司 | Glass powder for environment-friendly high-acid-resistance automobile glass slurry and preparation method thereof |
-
1999
- 1999-04-16 JP JP11109741A patent/JP2000302480A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7884547B2 (en) | 2007-02-06 | 2011-02-08 | Noritake Co., Limited | Lead-free acid-resistant glass composition and glass paste comprised of the same |
| WO2010116913A1 (en) * | 2009-03-29 | 2010-10-14 | 日本山村硝子株式会社 | Lead-free glass composition |
| US20160185650A1 (en) * | 2013-08-09 | 2016-06-30 | Nippon Electric Glass Co. Ltd. | Bismuth-based glass composition, powder material, and powder material paste |
| US10011519B2 (en) * | 2013-08-09 | 2018-07-03 | Nippon Electric Glass Co., Ltd. | Bismuth-based glass composition, powder material, and powder material paste |
| CN103771702A (en) * | 2014-01-21 | 2014-05-07 | 江苏奥蓝工程玻璃有限公司 | Bending-resistant impact-resistant glass material and preparation method thereof |
| CN110683764A (en) * | 2019-11-15 | 2020-01-14 | 黄山市晶特美新材料有限公司 | Glass powder for environment-friendly high-acid-resistance automobile glass slurry and preparation method thereof |
| CN110683764B (en) * | 2019-11-15 | 2022-05-03 | 黄山市晶特美新材料有限公司 | Glass powder for environment-friendly high-acid-resistance automobile glass slurry and preparation method thereof |
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