JPH05270860A - Lead-and cadmium-free glass composition for glazing, enameling and decorating and its use - Google Patents
Lead-and cadmium-free glass composition for glazing, enameling and decorating and its useInfo
- Publication number
- JPH05270860A JPH05270860A JP1918293A JP1918293A JPH05270860A JP H05270860 A JPH05270860 A JP H05270860A JP 1918293 A JP1918293 A JP 1918293A JP 1918293 A JP1918293 A JP 1918293A JP H05270860 A JPH05270860 A JP H05270860A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass
- glass composition
- bao
- zro
- 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
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]
【産業上の利用分野】本発明は、釉掛け、ほうろう引き
及び装飾用の鉛フリー及びカドミウムフリーのガラス組
成物、及び特にホウケイ酸ガラス並びにガラスセラミッ
クスなど低熱膨張率を有するガラス類に対するそのよう
な用途に関する。This invention relates to lead-free and cadmium-free glass compositions for glazes, enamels and decorations, and in particular for borosilicate glasses and glasses having a low coefficient of thermal expansion such as glass ceramics. Regarding use.
【０００２】[0002]
【従来の技術】このようなガラス又はガラスセラミック
スの用途の主たる領域は、温度変動に耐性のある実験室
用器具や調理具、あるいはまた特に例えば調理面などの
加熱プレートから構成されている。釉は、物理的又は化
学的な表面特性の保護、強化及び／又は変更のために、
また例えば電子製品における埋封用に、あるいはまた単
に種々のガラス製品、ガラスセラミック、セラミック又
は磁器の装飾用に利用される低融点のガラスである。釉
は、通常、微粉末形態で、例えばペーストの形態で常法
に従って例えばスクリーン印刷、はけ塗りなどにより製
品に塗布される透明もしくは半透明のガラス組成物から
成る。微粉砕ガラス粉末はまた一般にフリットと呼ばれ
ている。The main area of application of such glasses or glass-ceramics consists of laboratory utensils and cooking utensils which are resistant to temperature fluctuations, and also especially heating plates, for example cooking surfaces. Glaze is for protecting, strengthening and / or modifying physical or chemical surface properties,
It is also a low-melting glass which is used, for example, for embedding in electronic products or also simply for decorating various glass products, glass ceramics, ceramics or porcelain. The glaze usually consists of a transparent or translucent glass composition which is applied to the product in the form of a fine powder, for example in the form of a paste, in the usual way, for example by screen printing, brushing or the like. Finely ground glass powder is also commonly referred to as a frit.
【０００３】ほうろう（又はエナメル）は、顔料などの
着色成分を含有する釉であり、エナメル中の顔料の割合
は３０重量％まで上げることができる。顔料は、通常、
釉に対して耐性があり、その選択に応じて所望の色感を
与えることができる酸化物である。Enamel (or enamel) is a glaze containing coloring components such as pigments, and the proportion of pigment in the enamel can be increased up to 30% by weight. Pigments are usually
It is an oxide that is resistant to glaze and can give a desired color feeling depending on its selection.
【０００４】釉又はエナメルは、処理される製品の軟化
点以下の温度で焼成され、釉及び／又はエナメルのそれ
ぞれのガラス組成物が溶融し、製品表面と安定な結合を
形成する。焼成はまた、釉又はエナメルの塗布用助剤と
して用いる有機ビヒクルの揮化を助ける。The glaze or enamel is fired at a temperature below the softening point of the product to be treated and the respective glass composition of the glaze and / or enamel melts and forms a stable bond with the product surface. Baking also helps volatilize the organic vehicle used as a glaze or enamel coating aid.
【０００５】焼成後及びその後の実際の使用期間中、釉
又はエナメルの充分で長期間の接着を確実なものとする
ためには、従来の理論的考察に従って、特に装飾される
べき製品と釉又はエナメルの熱膨張率を互いに注意深く
適合させることが必要である。この点に関して、従来、
釉は釉掛けされる製品よりも低い熱膨張率を有すること
が望ましいと考えられてきた。これは、釉又はエナメル
は焼成後冷却中に引張り応力がかかり、従ってこれが基
材の特性にいかなるマイナスの作用、特に強度低減作用
を及ぼさないようにするためであると考えられたからで
ある。In order to ensure a sufficient and long-term adhesion of the glaze or enamel after firing and during the actual use afterwards, according to conventional theoretical considerations, the product to be specially decorated and the glaze or It is necessary to carefully match the coefficient of thermal expansion of the enamel with each other. In this regard,
It has been considered desirable for glazes to have a lower coefficient of thermal expansion than the products to be glazed. This is believed to be because the glaze or enamel is under tensile stress during cooling after firing, and thus it does not have any negative effect on the properties of the substrate, in particular the strength reducing effect.
【０００６】従来、ホウケイ酸ガラス、特にβ−ユーク
リプタイト又はｈ−石英の混晶に基づく低熱膨張率を有
するガラスセラミックスの釉又はエナメル装飾において
は、熱処理により適当な出発ガラスのいわゆるセラミッ
ク化（ｃｅｒａｍｉｎｇ）を生ずるという問題があっ
た。このようなガラスセラミックスは、２０〜７００℃
の温度範囲で０±１×１０-6／Ｋの熱膨張率を有するこ
とにより識別される。これらのタイプのガラスの熱安定
性を考慮すると、釉又はエナメルでのそれぞれの装飾は
１０００℃以下の温度で行われねばならない。ガラスセ
ラミックスにおいては、釉又はエナメルの焼成は、好ま
しくはいわゆる直接焼成工程のようにセラミック生成プ
ロセスと同時に行われる。Conventionally, in the glaze or enamel decoration of glass ceramics having a low coefficient of thermal expansion based on a mixed crystal of borosilicate glass, especially β-eucryptite or h-quartz, a suitable starting glass is so-called ceramicized by heat treatment ( There was a problem of causing cerming). Such glass-ceramics are 20 ~ 700 ℃
It is identified by having a coefficient of thermal expansion of 0 ± 1 × 10 −6 / K in the temperature range of. Given the thermal stability of these types of glass, the respective decoration with glaze or enamel must be carried out at temperatures below 1000 ° C. In glass ceramics, the firing of glaze or enamel is preferably performed simultaneously with the ceramic production process, such as the so-called direct firing step.
【０００７】低熱膨張率のガラス及びガラスセラミック
スを被覆及び／又は装飾するためにこれまで使用されて
きた釉及びエナメルは、殆どの場合、今日でさえも依然
として鉛を含有し、またそれに加えてしばしば依然とし
てカドミウムさえも含有している。釉に鉛及びカドミウ
ムを使用する理由は、溶融特性に対するそれらの積極的
な効果、即ち釉又はエナメルの溶融温度を顕著に低減す
ると同時に最適な粘度特性にする効果のためである。そ
れに加えて、これらの釉又はエナメルは、直接焼成後、
基材に対して充分な接着強度を示し、また過剰に長い使
用期間においてさえも、実用上の条件下で求められる要
求を充分に満足する。このことは、基材と釉又はエナメ
ルの熱膨張率がほぼ同じであるべきであるという理論的
要求と対比すると、これらの鉛及びカドミウム含有ガラ
ス組成物が５×１０-6／Ｋ、さらには１０×１０-6／Ｋ
さえまでの高い熱膨張率を有するためにさらに驚くべき
ことである。なぜこれら高熱膨張ガラス組成物が例えば
ガラスセラミックなどの実際上殆ど熱膨張を示さない基
材に対して充分な接着性を示すかという理由は、この現
象がこれまで理解されてきた限りでは、特にこれら鉛及
びさらにはカドミウムの添加に帰されている。The glazes and enamel which have hitherto been used for coating and / or decorating low-thermal-expansion glass and glass-ceramics, in most cases, still still contain lead, and in addition often It still contains cadmium. The reason for using lead and cadmium in the glaze is due to their positive effect on the melting properties, i.e. the effect of significantly reducing the melting temperature of the glaze or enamel while at the same time providing optimum viscosity properties. In addition, these glazes or enamel are
It exhibits sufficient adhesive strength to the substrate and sufficiently satisfies the requirements required under practical conditions even for an excessively long period of use. This contrasts with the theoretical requirement that the substrate and the glaze or enamel should have approximately the same coefficient of thermal expansion, and these lead- and cadmium-containing glass compositions have 5 × 10 −6 / K, and 10 x 10 -6 / K
What is even more surprising is that it has a high coefficient of thermal expansion up to even. The reason why these high thermal expansion glass compositions exhibit sufficient adhesion to substrates that exhibit practically little thermal expansion, such as glass ceramics, is, to the extent that this phenomenon has been understood so far, in particular. It is attributed to the addition of lead and also cadmium.
【０００８】しかしながら、一方では、これらの物質の
人及び環境に及ぼす好ましくない毒性作用の結果、装飾
被膜中へのこのような鉛又はカドミウム化合物の添加が
部分的に又は完全に禁止された。従って、このタイプの
数多くの鉛フリー及びカドミウムフリーの生成物が文献
において提案されてきた。例えば、ドイツ特許第３，４
０５，７０８号明細書には、Ａｌ2 Ｏ3 、Ｂ2 Ｏ3 、Ｓ
ｉＯ2 、Ｌｉ2 Ｏ、ＺｒＯ2 、ＳｎＯ2 の成分、及びさ
らにＬａ2 Ｏ3 、ＣａＯ、ＳｒＯ、ＢａＯ、Ｎａ2 Ｏ及
びＦから成る鉛フリー、カドミウムフリー及び亜鉛フリ
ーのガラスフリット組成物が記載されており、これをガ
ラス、ガラスセラミック及びセラミック製品を装飾する
ための着色エナメルとして用いることが提案されてい
る。これらガラスフリット組成物は、Ｂ2 Ｏ3 及び特に
またＳｎＯ2 及び／又はＬａ2 Ｏ3 の含有量が高い。こ
のような高いＢ2 Ｏ3 含有量と同時に低いＳｉＯ2 含有
量を有するガラスフリット組成物は、耐薬品性、特に耐
酸性に対する高い要求を満足することは困難である。On the one hand, however, as a result of the unfavorable toxic effects of these substances on humans and the environment, the addition of such lead or cadmium compounds in decorative coatings has been partially or completely prohibited. Therefore, numerous lead-free and cadmium-free products of this type have been proposed in the literature. For example, German Patent Nos. 3,4
No. 05,708 describes Al 2 O 3 , B 2 O 3 and S.
A lead-free, cadmium-free and zinc-free glass frit composition comprising iO 2 , Li 2 O, ZrO 2 , SnO 2 components and additionally La 2 O 3 , CaO, SrO, BaO, Na 2 O and F is described. It has been proposed to use it as a colored enamel for decorating glass, glass ceramics and ceramic products. These glass frit compositions have a high content of B 2 O 3 and especially also SnO 2 and / or La 2 O 3 . It is difficult for the glass frit composition having such a high B 2 O 3 content and a low SiO 2 content to satisfy high requirements for chemical resistance, particularly acid resistance.
【０００９】ヨーロッパ特許出願公開第０ ２６７ １
５４ Ａ１号には、Ｎａ2 Ｏ、ＺｎＯ、Ｂ2 Ｏ3 、Ｓｉ
Ｏ2 及び任意成分としてＫ2 Ｏ、Ｌｉ2 Ｏ、ＣａＯ、Ｓ
ｒＯ、ＢａＯ、Ｂｉ2 Ｏ3 、Ａｌ2 Ｏ3 、ＺｒＯ2 、Ｔ
ｉＯ2 及びＷＯ3 から成る鉛フリー及びカドミウムフリ
ーのガラスフリット組成物が記載されている。このガラ
スフリット組成物は、４．０〜３０．０モル％のＺｎＯ
を含有している。亜鉛化合物もまた、カドミウムの毒性
よりも低いけれども僅かの濃度においてさえも毒性があ
ると考えられており、従って、鉛の代替物としては問題
があり、それ故望ましくない。また、高いＺｎＯ含有量
のガラスの耐薬品性は実際の使用においてしばしば不充
分である。European Patent Application Publication No. 0 267 1
No. 54 A1 includes Na 2 O, ZnO, B 2 O 3 and Si.
O 2 and optionally K 2 O, Li 2 O, CaO, S
rO, BaO, Bi 2 O 3 , Al 2 O 3 , ZrO 2 , T
glass frit composition of lead-free and cadmium-free consisting iO 2 and WO 3 are described. This glass frit composition comprises 4.0 to 30.0 mol% ZnO.
Contains. Zinc compounds are also believed to be less toxic than cadmium, but even at small concentrations, and are therefore problematic and therefore undesirable as lead replacements. Also, the chemical resistance of glasses with a high ZnO content is often insufficient in practical use.
【００１０】国際公開公報ＷＯ９０／１５７８２号に
は、３０〜５１重量％のＳｉＯ2 、１９〜５０重量％の
Ｂ2 Ｏ3 、２〜２０重量％のＺｒＯ2 、１４重量％以下
のＮａ2 Ｏ、６重量％以下のＫ2 Ｏ、１９重量％以下の
ＺｎＯ、５重量％以下のＬｉ2Ｏ、及び組成物の他の成
分１００重量部当り２〜８重量部のフッ素を含有する鉛
フリーのガラス組成物が記載されている。ここでもま
た、鉛は主として亜鉛により置換されている。International publication WO 90/15782 discloses that 30 to 51% by weight of SiO 2 , 19 to 50% by weight of B 2 O 3 , 2 to 20% by weight of ZrO 2 and 14% by weight or less of Na 2 O. Lead-free containing 6 wt% or less K 2 O, 19 wt% or less ZnO, 5 wt% or less Li 2 O, and 2 to 8 parts by weight of fluorine per 100 parts by weight of the other components of the composition. Glass compositions are described. Again, lead is replaced primarily by zinc.
【００１１】ヨーロッパ特許出願公開第０ ４０２ ０
０７ Ａ１号には、３０〜７０重量％のＳｉＯ2 、１０
〜３０重量％のＣａＯ、０〜２０重量％のＺｎＯ、３〜
８重量％のＭｏＯ3 、０〜２０重量％のＢ2 Ｏ3 、０〜
２５重量％のＡｌ2 Ｏ3 、０〜１０重量％のＫ2 Ｏ、０
〜１０重量％のＮａ2 Ｏ、０〜１０重量％のＭｇＯ、０
〜１５重量％のＢａＯ、０〜７重量％のＬｉ2 Ｏ、０〜
１０重量％のＰｂＯ、０〜５重量％のＳｒＯ、０〜１０
重量％のＣｅＯ、０〜０．１重量％のＣｏＯ、及び０〜
５重量％のＰ2 Ｏ5 を含有するガラス組成物が記載され
ている。ここでもまた、組成物は２０重量％までのＺｎ
Ｏを含有し、さらになお必須的に少なくとも３重量％の
ＭｏＯ3 を含有しており、その耐アルカリ性はモリブデ
ン酸塩の形成の危険のために不充分である。さらにこの
組成物は１０００℃よりも著しく高い焼成範囲が必要と
なる。European Patent Application Publication No. 0 402 0
No. 07 A1 contains 30 to 70% by weight of SiO 2 , 10
-30 wt% CaO, 0-20 wt% ZnO, 3-
8 wt% MoO 3 , 0-20 wt% B 2 O 3 , 0
25 wt% Al 2 O 3 , 0-10 wt% K 2 O, 0
-10 wt% Na 2 O, 0-10 wt% MgO, 0
15wt% of BaO, 0 to 7 wt% of Li 2 O, 0 to
10 wt% PbO, 0-5 wt% SrO, 0-10
Wt% CeO, 0-0.1 wt% CoO, and 0
A glass composition containing 5 % by weight of P 2 O 5 is described. Again, the composition is up to 20% by weight Zn
It contains O, and still essentially contains at least 3% by weight of MoO 3 , its alkali resistance being insufficient due to the risk of molybdate formation. Furthermore, this composition requires a firing range significantly higher than 1000 ° C.
【００１２】米国特許第４，９７０，１７８号には、
５．０〜１４．０モル％のＮａ2 Ｏ、８．０〜２５．０
モル％のＺｎＯ、６．０〜１３．０モル％のＢ2 Ｏ3 、
４５．０〜６０．０モル％のＳｉＯ2 、０〜８．０モル
％のＫ2 Ｏ、０〜５．０モル％のＬｉ2 Ｏ、０〜８．０
モル％のＣａＯ、０〜８．０モル％のＳｒＯ、０〜９．
０モル％のＢａＯ、０〜１０．０モル％のＢｉ2 Ｏ3 、
０〜４．０モル％のＡｌ2 Ｏ3 、０〜６．０モル％のＺ
ｒＯ2 、０〜７．０モル％のＴｉＯ2 、０〜１．０モル
％のＷＯ3 の組成を有する鉛フリーのガラスフリットが
クレームされている。このガラスフリットもまた必須的
にＺｎＯを含有している。US Pat. No. 4,970,178 discloses
5.0 to 14.0 mol% of Na 2 O, 8.0 to 25.0
Mol% ZnO, 6.0-13.0 mol% B 2 O 3 ,
45.0 to 60.0 mol% of SiO 2, 0 to 8.0 mol% of K 2 O, 0 to 5.0 mol% of Li 2 O, 0 to 8.0
Mol% CaO, 0-8.0 mol% SrO, 0-9.
0 mol% BaO, 0 to 10.0 mol% Bi 2 O 3 ,
0 to 4.0 mol% of Al 2 O 3, 0~6.0 mole percent of Z
and rO 2, 0-7.0 mol% of TiO 2, lead-free glass frit having a composition of WO 3 0 to 1.0 mol% is claimed. This glass frit also contains essentially ZnO.
【００１３】ヨーロッパ特許出願公開第０ ４１２ ３
３６ Ａ１号には、３５〜６０重量％のＳｉＯ2 、１５
〜３５重量％のＢ2 Ｏ3 、３〜８重量％のＺｒＯ2 、２
〜８重量％のＡｌ2 Ｏ3 、１０〜１８重量％のＮａ2 Ｏ
及び／又はＫ2 Ｏ、２〜６重量％のＬｉ2 Ｏから成るガ
ラスフリット７０〜８５重量％と、オレンジ色顔料１５
〜３０重量％とから作成された汚染物質フリーのオレン
ジ色装飾ペイントが開示されている。このフリットはＣ
ａＯを全く含有しておらず、タイル上に１０００℃で焼
き付けられる。従来技術によるそれぞれのガラス組成物
は、種々の部分的に望ましい特性を有するが、高い要求
を充分に満たすものではない。European Patent Application Publication No. 0 412 3
No. 36 A1 contains 35 to 60% by weight of SiO 2 , 15
˜35 wt% B 2 O 3 , 3-8 wt% ZrO 2 , 2
8% by weight of Al 2 O 3, 10~18 wt% of Na 2 O
And / or K 2 O, 70 to 85% by weight of a glass frit consisting of 2 to 6% by weight of Li 2 O, and an orange pigment 15.
A pollutant-free orange decorative paint made from .about.30% by weight is disclosed. This frit is C
It contains no aO and is baked on the tile at 1000 ° C. Each glass composition according to the prior art has various partially desirable properties, but does not meet the high requirements sufficiently.
【００１４】[0014]
【発明が解決しようとする課題】従って、本発明の目的
は、鉛、カドミウム及び他の毒物学的に好ましくない成
分を含有せず、高い要求を満足し、即ち特に広範な比較
的低い温度範囲で何ら問題もなく加工でき、さらに、工
業的及び家庭的使用において接着強度、熱安定性、温度
変動に対する安定性、耐摩耗性、及び著しい摩耗、汚染
による斑点発生傾向に対する耐性、及び耐酸、耐アルカ
リ等の耐薬品性に関して非常に良好な特性を示す釉及び
エナメルをそれぞれ生成するガラス組成物を提供するこ
とにある。さらに本発明の目的は、特にホウケイ酸ガラ
ス並びにガラスセラミックスなどの５．０×１０-6／Ｋ
未満の熱膨張率を有するガラス類の釉掛け、ほうろう引
き及び装飾用に適し、上記のような非常に良好な特性を
示す釉及びエナメルを生成する鉛フリー及びカドミウム
フリーのガラス組成物及びそのような用途を提供するこ
とにある。SUMMARY OF THE INVENTION It is therefore an object of the present invention to be free of lead, cadmium and other toxicologically unfavorable constituents and to meet the high demands, that is to say in a particularly wide and relatively low temperature range. Can be processed without any problems, and further, in industrial and domestic use, it has adhesive strength, thermal stability, stability against temperature fluctuation, abrasion resistance, and significant abrasion, resistance to spotting tendency due to contamination, and acid resistance and resistance. It is an object of the present invention to provide a glass composition that produces glaze and enamel, each of which exhibits very good properties with respect to resistance to chemicals such as alkalis. Further, the object of the present invention is 5.0 × 10 −6 / K especially for borosilicate glass and glass ceramics.
Lead-free and cadmium-free glass compositions suitable for glazes, enamels and decorations of glasses having a coefficient of thermal expansion of less than and exhibiting very good properties as described above, and such. To provide various uses.
【００１５】[0015]
【課題を解決するための手段】本発明によれば、前記目
的を達成するために、下記の組成を有するガラス組成物
が提供される。Ｌｉ2 Ｏ：０〜１２重量％、ＭｇＯ：０
〜１０重量％、ＣａＯ：３〜１８重量％、Ｂ2 Ｏ3 ：５
〜２５重量％、Ａｌ2 Ｏ3 ：３〜１８重量％、Ｎａ2
Ｏ：３〜１８重量％、Ｋ2 Ｏ：３〜１８重量％、Ｂａ
Ｏ：０〜１２重量％、ＳｉＯ2 ：２５〜５５重量％、Ｔ
ｉＯ2 ：０〜５重量％、ＺｒＯ2 ：０〜＜３重量％。本
発明に係るガラス組成物を用いることにより、毒性物質
又は環境問題関連物質を使用することなく、実際上の使
用における前記した高い要求を充分に満足する釉及びエ
ナメルを製造できる。According to the present invention, in order to achieve the above object, a glass composition having the following composition is provided. Li 2 O: 0 to 12% by weight, MgO: 0
10 wt%, CaO: 3 to 18 wt%, B 2 O 3: 5
25 wt%, Al 2 O 3: 3~18 wt%, Na 2
O: 3-18% by weight, K 2 O: 3-18% by weight, Ba
O: 0 to 12% by weight, SiO 2 : 25 to 55% by weight, T
iO 2: 0 to 5 wt%, ZrO 2: 0~ <3 wt%. By using the glass composition according to the present invention, it is possible to produce glazes and enamel that sufficiently satisfy the above-mentioned high requirements in practical use, without using toxic substances or substances related to environmental problems.
【００１６】[0016]
【発明の作用及び効果】驚くべきことに、本発明に係る
ガラス組成物は、鉛、カドミウム、亜鉛、錫、及びフッ
素化合物を添加しないでも全ての所望の特性を有するこ
とが見い出された。従来の技術よりも著しく多く存在す
るＣａＯ含有量により、本発明に係る他の成分の選定及
び使用量と相俟って、焼成工程の間に基材ガラスと釉又
はエナメルとの間の強度のそして確実な相互作用を生
じ、従って実際的な使用における充分に長期間に亘って
応力を生ずることもなく堅固な接合を形成する。Surprisingly, it has been found that the glass composition according to the invention has all the desired properties without the addition of lead, cadmium, zinc, tin and fluorine compounds. Due to the significantly higher CaO content than in the prior art, coupled with the selection and usage of the other components according to the invention, the strength of the strength between the base glass and the glaze or enamel during the firing process is increased. And it forms a firm bond without causing a positive interaction and thus stresses for a sufficiently long period of time in practical use.
【００１７】本発明に係るガラス組成物を用いてこのよ
うに形成された釉は、焼成後、引き続いての急冷試験及
び６７０℃での連続作業において卓越した接着強度を示
すことが確認された。釉の比較的大きな層厚、例えば９
μｍまでの層厚の場合においてさえも、スポーリングや
剥れ傾向は基材ガラスに全く認められず、このことは非
常に変動する温度負荷においてさえも長期間に亘って維
持された。組成物の熱安定性は充分であり、６７０℃で
７５時間後においてさえも実際上色変化は示さなかっ
た。本発明に係る釉組成物は、酸及びアルカリに対する
良好な耐薬品性を示し、また高光沢を有し、摩耗が少な
く、実際上スクリーン塗装及び同様に平面（固体）塗装
において著しい摩耗を全く示さない。It has been confirmed that the glaze thus formed using the glass composition according to the present invention exhibits excellent adhesive strength after firing, in subsequent quenching tests and in continuous operation at 670 ° C. Relatively large layer thickness of glaze, eg 9
No spalling or flaking tendency was observed in the base glass even at layer thicknesses up to μm, which was maintained over a long period of time even at very variable temperature loads. The thermal stability of the composition was sufficient and showed virtually no color change even after 75 hours at 670 ° C. The glaze composition according to the invention exhibits good chemical resistance to acids and alkalis, also has a high gloss, a low abrasion and practically no significant abrasion in screen coating and also in flat (solid) coating. Absent.
【００１８】本発明の組成物による釉はまた、３０重量
％の割合までの顔料をいつでも、問題なく混合すること
ができ、それにより着色被膜及び／又は装飾の生成用に
使用することができる。使用される顔料は、焼成温度で
ガラス組成物に耐性のある通常の酸化物材料などであ
る。しかしながら、釉はまた同様に本来備わった色に着
色されることもでき、例えば着色性の酸化物の制御され
た添加によって本質的に着色される。Glazes according to the compositions according to the invention can also be mixed with pigments up to 30% by weight at any time without problems, and can be used for producing pigmented coatings and / or decorations. The pigments used are, for example, the usual oxide materials which are resistant to glass compositions at the firing temperature. However, the glaze can likewise be colored in its own color, for example essentially by the controlled addition of coloring oxides.
【００１９】釉掛けガラス組成物は、まず最初に均質に
溶融され、このように形成されたガラスから次いで磨
砕、特に湿式磨砕によって１０μｍ未満、好ましくは１
〜３μｍの粒度を有するガラス粉末が製造される。この
粉末は、次いで標準的なスクリーン印刷油、例えばパイ
ン油をベースにした油によりペーストにされ、一般に知
られている技法に従って、例えばスクリーン印刷、転写
法、はけ塗りなどにより塗布される。低熱膨張のガラス
又はガラスセラミック上に焼き付けた後、２〜９μｍの
厚さの釉層が得られる。これらの層は、釉又はエナメル
と基材ガラスとの間の熱膨張差が非常に大きいにも拘ら
ず、優れた接着性及び温度変動に対する耐性を示す。The glaze glass composition is first homogeneously melted, and the glass thus formed is then ground, especially by wet grinding, to less than 10 μm, preferably 1
A glass powder with a particle size of ˜3 μm is produced. This powder is then pasted with a standard screen printing oil, for example an oil based on pine oil, and applied according to commonly known techniques, for example by screen printing, transfer methods, brushing and the like. After baking on low thermal expansion glass or glass-ceramic, a glaze layer with a thickness of 2-9 μm is obtained. These layers exhibit excellent adhesion and resistance to temperature fluctuations despite the very large thermal expansion difference between the glaze or enamel and the base glass.
【００２０】[0020]
【発明の態様】好適な態様においては、４〜１０重量％
のオーダーのＬｉ2 Ｏが本発明のガラス組成物に加えら
れ、またＣａＯの割合は上昇される。いずれの手段もガ
ラス組成物の溶融能力を著しく改善し、ＣａＯの割合を
増加することによりＬｉ2 Ｏ添加により引き起こされる
耐薬品性の僅かな低下が完全に補償される。この場合の
好適な組成範囲を示せば以下のとおりである。Ｌｉ2
Ｏ：４〜１０重量％、ＭｇＯ：０〜８重量％、ＣａＯ：
５〜１５重量％、Ｂ2 Ｏ3 ：１０〜２０重量％、Ａｌ2
Ｏ3 ：５〜１５重量％、Ｎａ2 Ｏ：５〜１５重量％、Ｋ
2 Ｏ：５〜１５重量％、ＢａＯ：０〜１０重量％、Ｓｉ
Ｏ2 ：３０〜５０重量％、ＴｉＯ2 ：０〜５重量％、Ｚ
ｒＯ2 ：０〜＜３重量％。In a preferred embodiment, 4-10% by weight
Li 2 O on the order of is added to the glass composition of the invention and the proportion of CaO is increased. Both measures significantly improve the melting ability of the glass composition, and by increasing the proportion of CaO, the slight decrease in chemical resistance caused by the addition of Li 2 O is completely compensated. The preferred composition range in this case is as follows. Li 2
O: 4 to 10% by weight, MgO: 0 to 8% by weight, CaO:
5 to 15% by weight, B 2 O 3 : 10 to 20% by weight, Al 2
O 3: 5 to 15 wt%, Na 2 O: 5~15 wt%, K
2 O: 5 to 15% by weight, BaO: 0 to 10% by weight, Si
O 2 : 30 to 50% by weight, TiO 2 : 0 to 5% by weight, Z
rO 2: 0~ <3% by weight.
【００２１】他の好適な態様においては、その後の使用
目的に応じて、同様に付加的に例えば８〜１０重量％の
ＢａＯ及び／又は例えば６〜１０重量％のＭｇＯを含有
する。この好適な態様の組成範囲としては、例えばＬｉ
2 Ｏ：８〜１２重量％、ＭｇＯ：０〜３重量％、Ｃａ
Ｏ：５〜１０重量％、Ｂ2 Ｏ3 ：５〜１３重量％、Ａｌ
2 Ｏ3 ：５〜１０重量％、Ｎａ2 Ｏ：５〜１０重量％、
Ｋ2 Ｏ：５〜１０重量％、ＢａＯ：８〜１２重量％、Ｓ
ｉＯ2 ：４５〜５５重量％、ＴｉＯ2 ：０〜５重量％、
ＺｒＯ2 ：０〜＜３重量％の組成を有するガラス組成
物、又はＬｉ2 Ｏ：８〜１２重量％、ＭｇＯ：６〜１０
重量％、ＣａＯ：５〜１０重量％、Ｂ2 Ｏ3：１５〜２
０重量％、Ａｌ2 Ｏ3 ：５〜１０重量％、Ｎａ2 Ｏ：５
〜１０重量％、Ｋ2 Ｏ：１０〜１５重量％、ＢａＯ：０
〜５重量％、ＳｉＯ2 ：３０〜４０重量％、ＴｉＯ2 ：
０〜５重量％、ＺｒＯ2 ：０〜＜３重量％の組成を有す
るガラス組成物を示すことができる。Other preferred embodiments likewise additionally contain, for example, 8 to 10% by weight of BaO and / or, for example, 6 to 10% by weight of MgO, depending on the intended use. The composition range of this preferred embodiment is, for example, Li
2 O: 8 to 12% by weight, MgO: 0 to 3% by weight, Ca
O: 5 to 10 wt%, B 2 O 3: 5~13 wt%, Al
2 O 3 : 5 to 10% by weight, Na 2 O: 5 to 10% by weight,
K 2 O: 5 to 10% by weight, BaO: 8 to 12% by weight, S
iO 2: 45 to 55 wt%, TiO 2: 0 to 5 wt%,
ZrO 2 : 0 to <3 wt% glass composition, or Li 2 O: 8 to 12 wt% MgO: 6 to 10
Wt%, CaO: 5 to 10 wt%, B 2 O 3: 15~2
0% by weight, Al 2 O 3 : 5 to 10% by weight, Na 2 O: 5
10 wt%, K 2 O: 10~15 wt%, BaO: 0
˜5 wt%, SiO 2 : 30-40 wt%, TiO 2 :
A glass composition having a composition of 0 to 5% by weight and ZrO 2 : 0 to <3% by weight can be shown.
【００２２】選択的な酸化物の添加は、ガラス組成物の
用途に応じて有利となり、例えば高いＬｉ2 Ｏ含有量は
一般に焼成温度を下降させる。ＢａＯはある割合までＣ
ａＯの代替物として供することができるが、一般には焼
成温度及び熱膨張率の上昇を引き起こす。ＴｉＯ2 の添
加により耐酸性が改善され、一方、ＺｒＯ2 はさらに耐
アルカリ性を改善することができる。このような点を考
慮して、本発明のガラス組成物の他の好適な態様の組成
範囲を示せば以下のとおりである。The selective addition of oxides is advantageous depending on the application of the glass composition, eg a high Li 2 O content generally lowers the firing temperature. BaO is C to some extent
It can serve as a substitute for aO, but generally causes an increase in firing temperature and coefficient of thermal expansion. The addition of TiO 2 improves the acid resistance, while ZrO 2 can further improve the alkali resistance. Considering such points, the composition ranges of other preferred embodiments of the glass composition of the present invention are as follows.
【００２３】ａ）下記の組成を有するガラス組成物 Ｌｉ2 Ｏ：８〜１２重量％、ＭｇＯ：０〜３重量％、Ｃ
ａＯ：５〜１０重量％、Ｂ2 Ｏ3 ：５〜１３重量％、Ａ
ｌ2 Ｏ3 ：１０〜１５重量％、Ｎａ2 Ｏ：５〜１０重量
％、Ｋ2 Ｏ：５〜１０重量％、ＢａＯ：０〜５重量％、
ＳｉＯ2 ：４５〜５５重量％、ＴｉＯ2 ：０〜５重量
％、ＺｒＯ2 ：０〜＜３重量％。 ｂ）下記の組成を有するガラス組成物 Ｌｉ2 Ｏ：８〜１２重量％、ＭｇＯ：０〜３重量％、Ｃ
ａＯ：１０〜１５重量％、Ｂ2 Ｏ3 ：５〜１３重量％、
Ａｌ2 Ｏ3 ：１０〜１５重量％、Ｎａ2 Ｏ：５〜１０重
量％、Ｋ2 Ｏ：５〜１０重量％、ＢａＯ：０〜５重量
％、ＳｉＯ2 ：３５〜４５重量％、ＴｉＯ2 ：０〜５重
量％、ＺｒＯ2 ：０〜＜３重量％。 ｃ）下記の組成を有するガラス組成物 Ｌｉ2 Ｏ：４〜８重量％、ＭｇＯ：０〜５重量％、Ｃａ
Ｏ：５〜１０重量％、Ｂ2 Ｏ3 ：５〜１３重量％、Ａｌ
2 Ｏ3 ：５〜１０重量％、Ｎａ2 Ｏ：５〜１０重量％、
Ｋ2 Ｏ：５〜１０重量％、ＢａＯ：８〜１２重量％、Ｓ
ｉＯ2 ：４０〜５０重量％、ＴｉＯ2 ：０〜５重量％、
ＺｒＯ2 ：０〜＜３重量％。 ｄ）下記の組成を有するガラス組成物 Ｌｉ2 Ｏ：４〜８重量％、ＭｇＯ：０〜３重量％、Ｃａ
Ｏ：１０〜１５重量％、Ｂ2 Ｏ3 ：１５〜２０重量％、
Ａｌ2 Ｏ3 ：５〜１０重量％、Ｎａ2 Ｏ：５〜１０重量
％、Ｋ2 Ｏ：５〜１０重量％、ＢａＯ：０〜５重量％、
ＳｉＯ2 ：４０〜５０重量％、ＴｉＯ2 ：０〜５重量
％、ＺｒＯ2 ：０〜＜３重量％。A) Glass composition having the following composition: Li 2 O: 8 to 12% by weight, MgO: 0 to 3% by weight, C
aO-: 5 to 10 wt%, B 2 O 3: 5~13 wt%, A
l 2 O 3 : 10 to 15% by weight, Na 2 O: 5 to 10% by weight, K 2 O: 5 to 10% by weight, BaO: 0 to 5% by weight,
SiO 2: 45 to 55 wt%, TiO 2: 0 to 5 wt%, ZrO 2: 0~ <3 wt%. b) Glass composition having the following composition: Li 2 O: 8 to 12% by weight, MgO: 0 to 3% by weight, C
aO-: 10 to 15 wt%, B 2 O 3: 5~13 wt%,
Al 2 O 3: 10~15 wt%, Na 2 O: 5~10 wt%, K 2 O: 5~10 wt%, BaO: 0 to 5 wt%, SiO 2: 35~45 wt%, TiO 2 : 0 to 5 wt%, ZrO 2: 0~ <3 wt%. c) Glass composition having the following composition: Li 2 O: 4 to 8% by weight, MgO: 0 to 5% by weight, Ca
O: 5 to 10 wt%, B 2 O 3: 5~13 wt%, Al
2 O 3 : 5 to 10% by weight, Na 2 O: 5 to 10% by weight,
K 2 O: 5 to 10% by weight, BaO: 8 to 12% by weight, S
iO 2: 40 to 50 wt%, TiO 2: 0 to 5 wt%,
ZrO 2 : 0- <3% by weight. d) Glass composition having the following composition: Li 2 O: 4 to 8% by weight, MgO: 0 to 3% by weight, Ca
O: 10 to 15 wt%, B 2 O 3: 15~20 wt%,
Al 2 O 3: 5~10 wt%, Na 2 O: 5 to 10 wt%, K 2 O: 5 to 10 wt%, BaO: 0 to 5 wt%,
SiO 2: 40 to 50 wt%, TiO 2: 0 to 5 wt%, ZrO 2: 0~ <3 wt%.
【００２４】[0024]
【実施例】以下、実施例を示して本発明についてさらに
詳しく説明する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００２５】実施例１〜１７ 表１及び表２に酸化物を基準として重量％で表わした本
発明の実施例１〜１７の釉組成物を示す。Examples 1 to 17 Tables 1 and 2 show the glaze compositions of Examples 1 to 17 of the present invention expressed in% by weight based on the oxide.
【表１】 [Table 1]
【００２６】[0026]
【表２】 [Table 2]
【００２７】表３に、表１及び表２に示す組成物Ｎｏ．
１〜１７について、それぞれの場合の℃単位の転移温度
（Ｔｇ）、℃単位の軟化温度（ＳＴ）、℃単位の加工温
度（ＰＴ）、並びに１０-6／Ｋ単位の２０〜３００℃で
の熱膨張率（ＣＴＥ）を示す。In Table 3, the composition Nos. Shown in Table 1 and Table 2 are shown.
1 to 17, in each case the transition temperature (Tg) in units of ° C, the softening temperature (ST) in units of ° C, the processing temperature (PT) in units of ° C, and in the range of 10 -6 / K at 20 to 300 ° C. The coefficient of thermal expansion (CTE) is shown.
【表３】 [Table 3]
【００２８】本発明に係るガラス組成物から形成された
釉は、表３に示す結果から明らかなように、約３００〜
５１０℃の転移温度、４００〜６１０℃の軟化温度、４
３０〜８４０℃の加工温度、及び９．２０〜１６．４０
×１０-6／Ｋの熱膨張率を有する。本発明による特に好
適な実施例は組成物Ｎｏ．１、１１、１５、１６及び１
７であり、約３８０〜４５０℃の範囲の転移温度、４５
０〜５７０℃の範囲の軟化温度、６３０〜７８０℃の加
工温度、及び１０．１８〜１３．１３×１０-6／Ｋの熱
膨張率を有する。これらの組成物はまた、慣用の従来の
標準的方法により行われた調査の間、並びに長期間試験
において、非常に良好な接着強度、高い耐熱性、耐薬品
性、及び優れた用途特性を示した。As can be seen from the results shown in Table 3, the glaze formed from the glass composition according to the present invention has a thickness of about 300-.
Transition temperature of 510 ° C., softening temperature of 400 to 610 ° C., 4
Processing temperature of 30-840 ° C, and 9.20-16.40.
It has a coefficient of thermal expansion of × 10 -6 / K. A particularly preferred embodiment according to the present invention is Composition No. 1, 11, 15, 16 and 1
7 and a transition temperature in the range of about 380 to 450 ° C., 45
It has a softening temperature in the range of 0 to 570 ° C., a processing temperature of 630 to 780 ° C., and a coefficient of thermal expansion of 10.18 to 13.13 × 10 −6 / K. These compositions also show very good bond strength, high heat resistance, chemical resistance, and excellent application properties during investigations carried out by conventional conventional standard methods and in long-term tests. It was
───────────────────────────────────────────────────── フロントページの続き (72)発明者 フリードリッヒ、ズィーベルス ドイツ連邦共和国、6500 マインツ １、 エメリッヒ−ヨーゼフシュトラーセ ３ ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Friedrich, Siebels, Federal Republic of Germany, 6500 Mainz 1, Emmerich-Josefstrasse 3
Claims (11)
し、特に５．０×１０-6／Ｋ未満の熱膨張率を有するガ
ラス類の釉掛け、ほうろう引き及び装飾用に適する鉛フ
リー及びカドミウムフリーのガラス組成物。1. The following composition: Li 2 O 0-12% by weight, MgO 0-10% by weight, CaO 3-18% by weight, B 2 O 3 5-25% by weight, Al 2 O 3 3-18% by weight. , Na 2 O 3-18% by weight, K 2 O 3-18% by weight, BaO 0-12% by weight, SiO 2 25-55% by weight, TiO 2 0-5% by weight, ZrO 2 0- <3% by weight. Lead-free, suitable for glazes, enamels, and decorations of glass, which contains 30% by weight or less of a pigment stable at the firing temperature and has a coefficient of thermal expansion of less than 5.0 × 10 −6 / K. And a cadmium-free glass composition.
４５０℃の転移温度、４００〜６１０℃、好ましくは４
５０〜５７０℃の軟化温度、及び４３０〜８４０℃、好
ましくは６３０〜７８０℃の加工温度を有する請求項１
乃至８のいずれか一項に記載のガラス組成物。9. 300 to 510 ° C., preferably 380 to
450 ° C. transition temperature, 400-610 ° C., preferably 4
A softening temperature of 50 to 570 ° C and a processing temperature of 430 to 840 ° C, preferably 630 to 780 ° C.
9. The glass composition according to any one of items 8 to 8.
１６．４０×１０-6／Ｋ、好ましくは１０．１８〜１
３．１３×１０-6／Ｋの熱膨張率を有する請求項１乃至
９のいずれか一項に記載のガラス組成物。10. A glaze formed from the composition is from 9.20.
16.40 × 10 −6 / K, preferably 10.18 to 1
The glass composition according to any one of claims 1 to 9, which has a coefficient of thermal expansion of 3.13 × 10 -6 / K.
ックスなどの５．０×１０-6／Ｋ未満の熱膨張率を有す
るガラス類の釉掛け、ほうろう引き及び装飾用に用いら
れる請求項１乃至１０のいずれか一項に記載のガラス組
成物の用途。11. The method according to claim 1, which is used for glaze, enamelling and decoration of glasses having a coefficient of thermal expansion of less than 5.0 × 10 −6 / K, such as borosilicate glass and glass ceramics. The use of the glass composition as described in 1 above.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924201286 DE4201286C2 (en) | 1992-01-20 | 1992-01-20 | Use of lead and cadmium-free glass compositions for glazing, enameling and decorating and their composition |
| DE4201286.4 | 1992-01-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05270860A true JPH05270860A (en) | 1993-10-19 |
Family
ID=6449807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1918293A Pending JPH05270860A (en) | 1992-01-20 | 1993-01-12 | Lead-and cadmium-free glass composition for glazing, enameling and decorating and its use |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH05270860A (en) |
| DE (1) | DE4201286C2 (en) |
| FR (1) | FR2686333B1 (en) |
| GB (1) | GB2263478B (en) |
| NL (1) | NL194123C (en) |
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| DE3926335C1 (en) * | 1989-08-09 | 1991-02-21 | Degussa Ag, 6000 Frankfurt, De |
-
1992
- 1992-01-20 DE DE19924201286 patent/DE4201286C2/en not_active Expired - Lifetime
- 1992-12-21 NL NL9202217A patent/NL194123C/en not_active IP Right Cessation
-
1993
- 1993-01-12 GB GB9300476A patent/GB2263478B/en not_active Expired - Fee Related
- 1993-01-12 JP JP1918293A patent/JPH05270860A/en active Pending
- 1993-01-18 FR FR9300388A patent/FR2686333B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| NL194123C (en) | 2001-07-03 |
| FR2686333A1 (en) | 1993-07-23 |
| GB2263478B (en) | 1995-06-07 |
| FR2686333B1 (en) | 1995-02-17 |
| GB9300476D0 (en) | 1993-03-03 |
| DE4201286C2 (en) | 1994-11-24 |
| DE4201286A1 (en) | 1993-07-22 |
| NL9202217A (en) | 1993-08-16 |
| NL194123B (en) | 2001-03-01 |
| GB2263478A (en) | 1993-07-28 |
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