JPH0761837A - Composition for decorating low expanding crystal glass and low expanding crystal glass plate decorated with the same - Google Patents
Composition for decorating low expanding crystal glass and low expanding crystal glass plate decorated with the sameInfo
- Publication number
- JPH0761837A JPH0761837A JP22214793A JP22214793A JPH0761837A JP H0761837 A JPH0761837 A JP H0761837A JP 22214793 A JP22214793 A JP 22214793A JP 22214793 A JP22214793 A JP 22214793A JP H0761837 A JPH0761837 A JP H0761837A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- glass
- crystallized glass
- weight
- coefficient
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 239000005355 lead glass Substances 0.000 title 2
- 239000011521 glass Substances 0.000 claims abstract description 92
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000049 pigment Substances 0.000 claims abstract description 21
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 10
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 10
- 238000005299 abrasion Methods 0.000 abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000009970 fire resistant effect Effects 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005034 decoration Methods 0.000 description 6
- 238000010422 painting Methods 0.000 description 5
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910018404 Al2 O3 Inorganic materials 0.000 description 1
- 229910011763 Li2 O Inorganic materials 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は低膨張結晶化ガラス装飾
用組成物に関し、特に調理器用トッププレート等の厨房
器具に利用される低膨張結晶化ガラスの装飾用組成物に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-expansion crystallized glass decorative composition, and more particularly to a low-expansion crystallized glass decorative composition used for kitchen appliances such as top plates for cooking appliances.
【０００２】[0002]
【従来の技術】調理器用トッププレート等の厨房器具と
して、３０〜７５０℃における熱膨張係数が約２０×１
０-7／℃以下であるような低膨張結晶化ガラスが使用さ
れているが、その表面を絵付けする場合は、低膨張ガラ
ス粉末と耐熱性顔料とからなる装飾用組成物が用いられ
ている。2. Description of the Related Art As a kitchen appliance such as a top plate for a cooker, the thermal expansion coefficient at 30 to 750 ° C. is about 20 × 1.
A low expansion crystallized glass having a temperature of 0 -7 / ° C or less is used, but when painting the surface thereof, a decorative composition comprising a low expansion glass powder and a heat resistant pigment is used. There is.
【０００３】[0003]
【発明が解決しようとする課題】この装飾用組成物に要
求される主な特性としては、結晶化ガラスと適合するよ
うな熱膨張係数を示すこと、ＰｂＯ等の有毒な成分を含
まないこと、８００〜８５０℃程度で熱処理できるこ
と、熱処理時に適度な流動性を示すこと、光沢があるこ
と、耐摩耗性が高いこと等である。The main characteristics required for this decorative composition are that it exhibits a coefficient of thermal expansion that is compatible with crystallized glass, and that it does not contain toxic components such as PbO. That is, it can be heat-treated at about 800 to 850 ° C., exhibits appropriate fluidity during heat treatment, has gloss, and has high abrasion resistance.
【０００４】このような装飾用組成物として、従来より
種々のものが提案されている。しかしながら、従来の装
飾用組成物の中で上記特性の全てを満足させるものはな
く、特に耐摩耗性の点について十分に満足させるものは
存在しないのが現状である。Various types of decorative compositions have been proposed in the past. However, none of the conventional decorative compositions satisfy all of the above characteristics, and none of them are particularly satisfactory in terms of wear resistance.
【０００５】本発明の目的は、先記した要求特性を全て
満足させ、特に耐摩耗性に優れた低膨張結晶化ガラス装
飾用組成物を提供することである。An object of the present invention is to provide a low expansion crystallized glass decorative composition which satisfies all the above-mentioned required properties and is particularly excellent in abrasion resistance.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、種々の実
験を行った結果、装飾用組成物にジルコン又はジルコニ
アを含有させることにより、耐摩耗性が改善されること
を見いだし、本発明として提案するものである。As a result of various experiments, the present inventors have found that the inclusion of zircon or zirconia in the decorative composition improves the wear resistance. Is proposed as.
【０００７】即ち、本発明の低膨張結晶化ガラス装飾用
組成物は、ガラス粉末５５〜９５重量部と、耐火性フィ
ラー０．１〜２０重量部と、耐熱性顔料３〜２５重量部
とからなり、該ガラス粉末が、重量百分率でＳｉＯ2 ５
０〜７５％、Ａｌ2 Ｏ3 ０．５〜１５％、Ｂ2 Ｏ3 ５〜
３０％、ＢａＯ ０〜７％、Ｌｉ2 Ｏ ０〜２％、Ｎａ
2 Ｏ ０〜５％、Ｋ2 Ｏ ０〜４％、Ｆ2 ０〜２％から
なり、且つ、該耐火性フィラーが、ジルコン及びジルコ
ニアから選ばれる１種以上であることを特徴とする。That is, the low expansion crystallized glass decorative composition of the present invention comprises 55 to 95 parts by weight of glass powder, 0.1 to 20 parts by weight of a refractory filler, and 3 to 25 parts by weight of a heat resistant pigment. And the glass powder contained SiO 2 5 in weight percentage.
0~75%, Al 2 O 3 0.5~15 %, B 2 O 3 5~
30%, BaO 0 to 7%, Li 2 O 0 to 2%, Na
2 O 0 to 5%, K 2 O 0 to 4%, F 2 0 to 2%, and the refractory filler is one or more selected from zircon and zirconia.
【０００８】[0008]
【作用】本発明の低膨張結晶化ガラス装飾用組成物にお
いて、使用するガラス粉末は、鉛等の有害物質を含有せ
ず、３０〜３８０℃における熱膨張係数が約４０〜５０
×１０-7／℃であり、また約６５０〜７５０℃の軟化点
を示すものである。In the low expansion crystallized glass decorative composition of the present invention, the glass powder used does not contain harmful substances such as lead and has a thermal expansion coefficient of about 40 to 50 at 30 to 380 ° C.
A × 10 -7 / ℃, also shows a softening point of about 650 to 750 ° C..
【０００９】本発明において、ガラス粉末の組成を限定
した理由を以下に述べる。The reason why the composition of the glass powder is limited in the present invention will be described below.
【００１０】ＳｉＯ2 の含有量は５０〜７５％、好まし
くは５５〜７０％である。ＳｉＯ2が５０％より少ない
と熱膨張係数が大きくなり、低膨張結晶化ガラスとの膨
張差が大きくなり過ぎて、形成される装飾被膜にクラッ
クが発生し易くなる。また７５％より多いとガラスの流
動性が悪くなって結晶化ガラスと強固に結合できず、絵
付け装飾が困難になる。The content of SiO 2 is 50 to 75%, preferably 55 to 70%. If SiO 2 is less than 50%, the coefficient of thermal expansion becomes large, the difference in expansion from the low expansion crystallized glass becomes too large, and cracks are easily generated in the formed decorative coating. On the other hand, if it is more than 75%, the fluidity of the glass is deteriorated so that the glass cannot be firmly bonded to the crystallized glass, which makes it difficult to decorate the glass.
【００１１】Ａｌ2 Ｏ3 の含有量は０．５〜１５％、好
ましくは０．７〜１５％である。Ａｌ2 Ｏ3 が０．５％
より少ない場合、及び１５％より多い場合は何れもガラ
スの流動性が悪くなる。The content of Al 2 O 3 is 0.5 to 15%, preferably 0.7 to 15%. Al 2 O 3 is 0.5%
When the amount is less than 15% or more than 15%, the fluidity of the glass is deteriorated.
【００１２】Ｂ2 Ｏ3 の含有量は５〜３０％、好ましく
は７〜２７％である。Ｂ2 Ｏ3 が５％より少ないとガラ
スの流動性が悪くなり、３０％より多いと熱膨張係数が
大きくなり過ぎる。The content of B 2 O 3 is 5 to 30%, preferably 7 to 27%. If B 2 O 3 is less than 5%, the fluidity of the glass will be poor, and if it is more than 30%, the coefficient of thermal expansion will be too large.
【００１３】ＢａＯは０〜７％、好ましくは０〜６％で
ある。ＢａＯが７％より多いと熱膨張係数が大きくなり
過ぎる。BaO is 0 to 7%, preferably 0 to 6%. When BaO is more than 7%, the coefficient of thermal expansion becomes too large.
【００１４】Ｌｉ2 Ｏの含有量は０〜２％、好ましくは
０．１〜１．５％である。Ｌｉ2 Ｏが２％より多いと熱
膨張係数が大きくなり過ぎる。The content of Li 2 O is 0 to 2%, preferably 0.1 to 1.5%. If the content of Li 2 O is more than 2%, the coefficient of thermal expansion becomes too large.
【００１５】Ｎａ2 Ｏの含有量は０〜５％、好ましくは
０〜４％である、Ｎａ2 Ｏが５％より多いと熱膨張係数
が大きくなり過ぎる。The content of Na 2 O is 0 to 5%, preferably 0 to 4%. When the content of Na 2 O is more than 5%, the coefficient of thermal expansion becomes too large.
【００１６】Ｋ2 Ｏの含有量は０〜４％、好ましくは０
〜３．５％である、Ｋ2 Ｏが４％より多いと熱膨張係数
が大きくなり過ぎる。The content of K 2 O is 0 to 4%, preferably 0.
When the content of K 2 O is more than 3.5%, the coefficient of thermal expansion becomes too large.
【００１７】Ｆ2 の含有量は０〜２％、好ましくは０〜
１．５％である。Ｆ2 が２％より多いと流動性が不安定
になり、絵付け装飾を行い難くなる。The content of F 2 is 0 to 2%, preferably 0 to
It is 1.5%. If F 2 is more than 2%, the fluidity becomes unstable, and it becomes difficult to decorate with decoration.
【００１８】本発明において、耐火性フィラーは耐摩耗
性を向上させるために添加するものであり、ジルコン及
びジルコニアから選ばれる１種以上を使用する。In the present invention, the refractory filler is added to improve wear resistance, and one or more kinds selected from zircon and zirconia are used.
【００１９】本発明において、使用する耐熱性顔料は特
に限定されず、例えば市販の陶磁器用顔料を使用するこ
とができる。In the present invention, the heat resistant pigment used is not particularly limited, and for example, commercially available pigments for ceramics can be used.
【００２０】また本発明の装飾用組成物において、ガラ
ス粉末、耐火性フィラー、及び耐熱性顔料の混合割合を
上記のように限定した理由は次の通りである。ガラス粉
末が５５重量部より少ないと流動性が不安定になって絵
付け装飾し難くなり、また９５重量部より多いと流動し
過ぎて所望のパターンを得難くなる。耐火性フィラーが
０．１重量部より少ないと十分な耐摩耗性が得られず、
２０重量部より多いと流動性が悪くなり、また耐摩耗性
も悪くなる。耐熱性顔料が３重量部より少ないと安定し
た色調が得られず２５重量部より多いと流動性が悪くな
る。The reason for limiting the mixing ratio of the glass powder, the refractory filler, and the heat-resistant pigment in the decorative composition of the present invention as described above is as follows. If the amount of the glass powder is less than 55 parts by weight, the fluidity becomes unstable and it becomes difficult to decorate it with decoration. If the amount of the glass powder is more than 95 parts by weight, the glass powder flows too much to obtain a desired pattern. If the refractory filler is less than 0.1 parts by weight, sufficient abrasion resistance cannot be obtained,
If it is more than 20 parts by weight, the fluidity will be poor and the abrasion resistance will be poor. If the heat-resistant pigment is less than 3 parts by weight, a stable color tone cannot be obtained, and if it is more than 25 parts by weight, the fluidity becomes poor.
【００２１】なおこのような装飾用組成物は、３０〜７
５０℃における熱膨張係数が約３０〜４０×１０-7／℃
であり、また約８００〜８５０℃で熱処理することが可
能なものである。Such a decorative composition has a composition of 30 to 7
Coefficient of thermal expansion at 50 ℃ is about 30-40 × 10 -7 / ℃
And can be heat-treated at about 800 to 850 ° C.
【００２２】次に本発明の装飾用組成物を用いて、低膨
張結晶化ガラスを絵付け装飾する方法を述べる。Next, a method for painting and decorating low expansion crystallized glass with the decorative composition of the present invention will be described.
【００２３】まず、上記した割合になるように、ガラス
粉末、耐火性フィラー、耐熱性顔料を混合し、さらにエ
チルセルロース、酢酸エチル等の溶媒と混練してペース
ト状にする。First, glass powder, a refractory filler and a heat resistant pigment are mixed in the above proportions and further kneaded with a solvent such as ethyl cellulose or ethyl acetate to form a paste.
【００２４】次にこのペーストをスクリーン印刷等の方
法を用いて低膨張結晶化ガラスの表面に塗布する。この
とき形成される装飾被膜の膜厚が１〜２０μｍとなるよ
うに塗布することが重要である。即ち、膜厚がこの範囲
から外れると、装飾被膜にクラックが発生し易くなるた
めである。Next, this paste is applied to the surface of the low expansion crystallized glass by using a method such as screen printing. It is important to apply so that the thickness of the decorative coating formed at this time is 1 to 20 μm. That is, if the film thickness deviates from this range, cracks are likely to occur in the decorative coating.
【００２５】その後、８００〜８５０℃程度の温度で熱
処理すると、ガラス、耐火性フィラー及び耐熱性顔料か
らなる装飾被膜が形成され、結晶化ガラス表面に絵付け
装飾が施される。Then, when heat-treated at a temperature of about 800 to 850 ° C., a decorative coating film composed of glass, a refractory filler and a heat-resistant pigment is formed, and the surface of the crystallized glass is decorated with painting.
【００２６】[0026]
【実施例】以下、実施例に基づいて本発明の低膨張結晶
化ガラス装飾用組成物を説明する。EXAMPLES Hereinafter, the low expansion crystallized glass decorative composition of the present invention will be described based on examples.
【００２７】表１は本発明の実施例（試料Ｎｏ．１〜
６）及び比較例（試料Ｎｏ．７）を示すものである。Table 1 shows examples of the present invention (Sample Nos. 1 to 1).
6) and a comparative example (sample No. 7).
【００２８】各試料は次のようにして調製した。まず、
表中の組成になるように調合したガラス原料を１４００
〜１５００℃の温度で１０〜１５時間溶融し、フィルム
状に成形した後、ボールミルにて微粉砕し、平均粒径５
μｍのガラス粉末を得た。さらにこのガラス粉末と、表
中に示した耐火性フィラーと、耐熱性顔料（日本フェロ
ー株式会社製ＮＦ−３１２９−Ｐ［ブラウン］）とを混
合して試料を得た。Each sample was prepared as follows. First,
1400 glass raw materials prepared to have the composition in the table
Melt at a temperature of ~ 1500 ° C for 10 to 15 hours, form into a film, and then finely pulverize with a ball mill to give an average particle size of 5
A glass powder of μm was obtained. Further, this glass powder, the refractory filler shown in the table, and a heat resistant pigment (NF-3129-P [Brown] manufactured by Nippon Fellow Co., Ltd.) were mixed to obtain a sample.
【００２９】続いて、各試料とエチルセルロースとを重
量比で２：１の割合で混練してペースト状にし、これを
スクリーン印刷法を用いて低膨張結晶化ガラス板に塗布
した。なお結晶化ガラス板は、重量％でＳｉＯ2 ６７
％、Ａｌ2 Ｏ3 ２３％、ＴｉＯ2 ２％、ＺｒＯ2 ３％、
Ｐ2 Ｏ5 １％、Ｌｉ2 Ｏ ４％の組成を有し、３０〜７
５０℃において約−３×１０-7／℃の熱膨張係数を示す
透明な結晶化ガラスを使用した。Subsequently, each sample and ethyl cellulose were kneaded in a weight ratio of 2: 1 to form a paste, which was applied to a low expansion crystallized glass plate by a screen printing method. The crystallized glass plate is made of SiO 2 67 by weight%.
%, Al 2 O 3 23%, TiO 2 2%, ZrO 2 3%,
P 2 O 5 1%, Li 2 O 4% composition, 30 to 7
A transparent crystallized glass having a coefficient of thermal expansion of about −3 × 10 −7 / ° C. at 50 ° C. was used.
【００３０】その後、８００〜８５０℃で熱処理するこ
とによって低膨張結晶化ガラス板を絵付け装飾した。な
お表面に形成された装飾被膜の膜厚は、１０〜１５μｍ
であった。Then, the low expansion crystallized glass plate was painted and decorated by heat treatment at 800 to 850.degree. The thickness of the decorative coating formed on the surface is 10 to 15 μm.
Met.
【００３１】次に、結晶化ガラス板上に形成された装飾
被膜の熱膨張係数、クラックの有無、光沢の有無、耐摩
耗性について評価した。結果を表１に示す。Next, the coefficient of thermal expansion, presence / absence of cracks, presence / absence of gloss, and abrasion resistance of the decorative coating formed on the crystallized glass plate were evaluated. The results are shown in Table 1.
【００３２】表から明らかなように、実施例である試料
Ｎｏ．１〜６を用いて絵付け装飾したものは、３０〜７
５０℃における熱膨張係数が３２〜３６×１０-7／℃で
あり、またクラックが認められず、光沢があり、しかも
良好な耐摩耗性を示した。これに対して、比較例である
試料Ｎｏ．７を用いたものは、熱膨張係数が３９×１０
-7／℃であり、またクラックがなく、光沢もあったが、
耐摩耗性が悪かった。As is apparent from the table, the sample No. What is decorated with 1 to 6 is 30 to 7
The coefficient of thermal expansion at 50 ° C. was 32 to 36 × 10 −7 / ° C., no crack was observed, the sample had gloss, and good abrasion resistance was exhibited. On the other hand, Sample No. which is a comparative example. The one using 7 has a thermal expansion coefficient of 39 × 10.
It was -7 / ° C, there was no crack, and it was glossy,
The wear resistance was poor.
【００３３】なお熱膨張係数は、各試料を角棒状にプレ
ス成形した後、８５０℃で焼成し、この焼成物を差動検
出式相対膨張計にて測定した。クラックの有無は、装飾
被膜表面を光学顕微鏡で観察して評価した。また耐摩耗
性は、＃１０００のサンドペーパー（１００φ）を用い
て、装飾被膜の表面を荷重３ｋｇ、片道１００ｍｍ／秒
の速度で１０００回往復した後、被膜の変化を目視で判
定し、全く変化のないものを良、少しでも変化したもの
を不良とした。The coefficient of thermal expansion was measured by press-molding each sample into a square rod shape, followed by firing at 850 ° C., and measuring the fired product with a differential detection relative dilatometer. The presence or absence of cracks was evaluated by observing the surface of the decorative coating with an optical microscope. In addition, abrasion resistance was measured by using # 1000 sandpaper (100φ) to reciprocate the surface of the decorative coating film 1000 times at a load of 3 kg and a speed of 100 mm / sec for one way, and then visually determine the change in the coating film, and it was completely changed. Those that did not exist were considered good, and those that changed even a little were considered defective.
【００３４】[0034]
【発明の効果】以上説明したように、本発明の装飾用組
成物は、要求される全ての特性を満足し、特に耐摩耗性
に優れているため、低膨張結晶化ガラスの装飾用として
好適なものである。Industrial Applicability As described above, the decorative composition of the present invention satisfies all the required properties and is particularly excellent in abrasion resistance, and is therefore suitable for decoration of low expansion crystallized glass. It is something.
【表１】 [Table 1]
【表２】 [Table 2]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年９月１３日[Submission date] September 13, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 低膨張結晶化ガラス装飾用組成物及び
これを用いて装飾した低膨張結晶化ガラス板Title: Low expansion crystallized glass decorative composition and low expansion crystallized glass plate decorated with the same
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は低膨張結晶化ガラス装飾
用組成物とこれを用いて装飾した低膨張結晶化ガラス板
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low expansion crystallized glass decorative composition and a low expansion crystallized glass plate decorated with the composition.
【０００２】[0002]
【従来の技術】調理器用トッププレート等の厨房器具と
して、３０〜７５０℃における熱膨張係数が約２０×１
０-7／℃以下であるような低膨張結晶化ガラスが使用さ
れているが、その表面を絵付けする場合は、低膨張ガラ
ス粉末と耐熱性顔料とからなる装飾用組成物が用いられ
ている。2. Description of the Related Art As a kitchen appliance such as a top plate for a cooker, the thermal expansion coefficient at 30 to 750 ° C. is about 20 × 1.
A low expansion crystallized glass having a temperature of 0 -7 / ° C or less is used, but when painting the surface thereof, a decorative composition comprising a low expansion glass powder and a heat resistant pigment is used. There is.
【０００３】[0003]
【発明が解決しようとする課題】この装飾用組成物に要
求される主な特性としては、結晶化ガラスと適合するよ
うな熱膨張係数を示すこと、ＰｂＯ等の有毒な成分を含
まないこと、８００〜８５０℃程度で熱処理できるこ
と、熱処理時に適度な流動性を示すこと、光沢があるこ
と、耐摩耗性が高いこと等である。The main characteristics required for this decorative composition are that it exhibits a coefficient of thermal expansion that is compatible with crystallized glass, and that it does not contain toxic components such as PbO. That is, it can be heat-treated at about 800 to 850 ° C., exhibits appropriate fluidity during heat treatment, has gloss, and has high abrasion resistance.
【０００４】このような装飾用組成物として、従来より
種々のものが提案されている。しかしながら、従来の装
飾用組成物の中で上記特性の全てを満足させるものはな
く、特に耐摩耗性の点について十分に満足させるものは
存在しないのが現状である。Various types of decorative compositions have been proposed in the past. However, none of the conventional decorative compositions satisfy all of the above characteristics, and none of them are particularly satisfactory in terms of wear resistance.
【０００５】本発明の目的は、先記した要求特性を全て
満足させ、特に耐摩耗性に優れた低膨張結晶化ガラス装
飾用組成物と、これを用いて装飾した低膨張結晶化ガラ
ス板を提供することである。An object of the present invention is to provide a low-expansion crystallized glass decorative composition which satisfies all the above-mentioned required characteristics and is particularly excellent in abrasion resistance, and a low-expansion crystallized glass plate decorated with the composition. Is to provide.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、種々の実
験を行った結果、装飾用組成物にジルコン又はジルコニ
アを含有させることにより、耐摩耗性が改善されること
を見いだし、本発明として提案するものである。As a result of various experiments, the present inventors have found that the inclusion of zircon or zirconia in the decorative composition improves the wear resistance. Is proposed as.
【０００７】即ち、本発明の低膨張結晶化ガラス装飾用
組成物は、ガラス粉末５５〜９５重量部と耐火性フィラ
ー０．１〜２０重量部と耐熱性顔料３〜２５重量部とか
らなり、該ガラス粉末が重量百分率でＳｉＯ2 ５０〜７
５％、Ａｌ2 Ｏ3 ０．５〜１５％、Ｂ2 Ｏ3 ５〜３０
％、ＢａＯ ０〜７％、Ｌｉ2 Ｏ ０〜２％、Ｎａ2 Ｏ
０〜５％、Ｋ2 Ｏ ０〜４％、Ｆ2 ０〜２％からなり、
且つ、該耐火性フィラーがジルコン及びジルコニアから
選ばれる１種以上であることを特徴とする。That is, the low expansion crystallized glass decorative composition of the present invention comprises 55 to 95 parts by weight of glass powder, 0.1 to 20 parts by weight of a refractory filler, and 3 to 25 parts by weight of a heat resistant pigment. The glass powder has a weight percentage of SiO 2 50-7.
5%, Al 2 O 3 0.5 to 15%, B 2 O 3 5 to 30
%, BaO 0 to 7%, Li 2 O 0 to 2%, Na 2 O
0-5%, K 2 O 0-4%, F 2 0-2%,
In addition, the refractory filler is one or more selected from zircon and zirconia.
【０００８】また本発明の低膨張結晶化ガラス板は、低
膨張結晶化ガラスの表面にガラス成分５５〜９５重量部
と耐火性フィラー成分０．１〜２０重量部と耐熱性顔料
成分３〜２５重量部とからなる装飾被膜が形成されてな
り、該ガラス成分が重量百分率でＳｉＯ2 ５０〜７５
％、Ａｌ2 Ｏ3 ０．５〜１５％、Ｂ2 Ｏ3 ５〜３０％、
ＢａＯ ０〜７％、Ｌｉ2 Ｏ ０〜２％、Ｎａ2 Ｏ ０
〜５％、Ｋ2 Ｏ ０〜４％、Ｆ2 ０〜２％からなり、且
つ、該耐火性フィラー成分がジルコン及びジルコニアか
ら選ばれる１種以上であることを特徴とする。The low expansion crystallized glass plate of the present invention comprises 55 to 95 parts by weight of a glass component, 0.1 to 20 parts by weight of a refractory filler component and 3 to 25 parts of a heat resistant pigment component on the surface of the low expansion crystallized glass. And the glass component is SiO 2 50-75 by weight percentage.
%, Al 2 O 3 0.5 to 15%, B 2 O 3 5 to 30%,
BaO 0 to 7%, Li 2 O 0 to 2%, Na 2 O 0
~5%, K 2 O 0~4% , consists F 2 0 to 2%, and, wherein the refractory filler component is one or more selected from zircon and zirconia.
【０００９】[0009]
【作用】本発明の低膨張結晶化ガラス装飾用組成物にお
いて、使用するガラス粉末は、鉛等の有害物質を含有せ
ず、３０〜３８０℃における熱膨張係数が約３０〜５０
×１０-7／℃であり、また約６５０〜７５０℃の軟化点
を示すものである。In the low expansion crystallized glass decorative composition of the present invention, the glass powder used does not contain harmful substances such as lead and has a thermal expansion coefficient of about 30 to 50 at 30 to 380 ° C.
A × 10 -7 / ℃, also shows a softening point of about 650 to 750 ° C..
【００１０】本発明において、ガラス粉末の組成を限定
した理由を以下に述べる。The reason why the composition of the glass powder is limited in the present invention will be described below.
【００１１】ＳｉＯ2 の含有量は５０〜７５％、好まし
くは５５〜７０％である。ＳｉＯ2が５０％より少ない
と熱膨張係数が大きくなり、低膨張結晶化ガラスとの膨
張差が大きくなり過ぎて、形成される装飾被膜にクラッ
クが発生し易くなる。また７５％より多いとガラスの流
動性が悪くなって結晶化ガラスと強固に結合できず、絵
付け装飾が困難になる。The content of SiO 2 is 50 to 75%, preferably 55 to 70%. If SiO 2 is less than 50%, the coefficient of thermal expansion becomes large, the difference in expansion from the low expansion crystallized glass becomes too large, and cracks are easily generated in the formed decorative coating. On the other hand, if it is more than 75%, the fluidity of the glass is deteriorated so that the glass cannot be firmly bonded to the crystallized glass, which makes it difficult to decorate the glass.
【００１２】Ａｌ2 Ｏ3 の含有量は０．５〜１５％、好
ましくは０．７〜１５％である。Ａｌ2 Ｏ3 が０．５％
より少ない場合、及び１５％より多い場合は何れもガラ
スの流動性が悪くなる。The content of Al 2 O 3 is 0.5 to 15%, preferably 0.7 to 15%. Al 2 O 3 is 0.5%
When the amount is less than 15% or more than 15%, the fluidity of the glass is deteriorated.
【００１３】Ｂ2 Ｏ3 の含有量は５〜３０％、好ましく
は７〜２７％である。Ｂ2 Ｏ3 が５％より少ないとガラ
スの流動性が悪くなり、３０％より多いと熱膨張係数が
大きくなり過ぎる。The content of B 2 O 3 is 5 to 30%, preferably 7 to 27%. If B 2 O 3 is less than 5%, the fluidity of the glass will be poor, and if it is more than 30%, the coefficient of thermal expansion will be too large.
【００１４】ＢａＯは０〜７％、好ましくは０〜６％で
ある。ＢａＯが７％より多いと熱膨張係数が大きくなり
過ぎる。BaO is 0 to 7%, preferably 0 to 6%. When BaO is more than 7%, the coefficient of thermal expansion becomes too large.
【００１５】Ｌｉ2 Ｏの含有量は０〜２％、好ましくは
０．１〜１．５％である。Ｌｉ2 Ｏが２％より多いと熱
膨張係数が大きくなり過ぎる。The content of Li 2 O is 0 to 2%, preferably 0.1 to 1.5%. If the content of Li 2 O is more than 2%, the coefficient of thermal expansion becomes too large.
【００１６】Ｎａ2 Ｏの含有量は０〜５％、好ましくは
０〜４％である、Ｎａ2 Ｏが５％より多いと熱膨張係数
が大きくなり過ぎる。The content of Na 2 O is 0 to 5%, preferably 0 to 4%. When the content of Na 2 O is more than 5%, the coefficient of thermal expansion becomes too large.
【００１７】Ｋ2 Ｏの含有量は０〜４％、好ましくは０
〜３．５％である、Ｋ2 Ｏが４％より多いと熱膨張係数
が大きくなり過ぎる。The content of K 2 O is 0 to 4%, preferably 0.
When the content of K 2 O is more than 3.5%, the coefficient of thermal expansion becomes too large.
【００１８】Ｆ2 の含有量は０〜２％、好ましくは０〜
１．５％である。Ｆ2 が２％より多いと流動性が不安定
になり、絵付け装飾を行い難くなる。The content of F 2 is 0 to 2%, preferably 0 to
It is 1.5%. If F 2 is more than 2%, the fluidity becomes unstable, and it becomes difficult to decorate with decoration.
【００１９】本発明において、耐火性フィラーは耐摩耗
性を向上させるために添加するものであり、ジルコン及
びジルコニアから選ばれる１種以上を使用する。In the present invention, the refractory filler is added to improve wear resistance, and one or more kinds selected from zircon and zirconia are used.
【００２０】本発明において、使用する耐熱性顔料は特
に限定されず、例えば市販の陶磁器用顔料を使用するこ
とができる。In the present invention, the heat resistant pigment to be used is not particularly limited, and for example, a commercially available pigment for ceramics can be used.
【００２１】また本発明の装飾用組成物において、ガラ
ス粉末、耐火性フィラー、及び耐熱性顔料の混合割合を
上記のように限定した理由は次の通りである。ガラス粉
末が５５重量部より少ないと流動性が不安定になって絵
付け装飾し難くなり、また９５重量部より多いと流動し
過ぎて所望のパターンを得難くなる。耐火性フィラーが
０．１重量部より少ないと十分な耐摩耗性が得られず、
２０重量部より多いと流動性が悪くなり、また耐摩耗性
も悪くなる。耐熱性顔料が３重量部より少ないと安定し
た色調が得られず２５重量部より多いと流動性が悪くな
る。The reason for limiting the mixing ratio of the glass powder, the refractory filler, and the heat-resistant pigment in the decorative composition of the present invention as described above is as follows. If the amount of the glass powder is less than 55 parts by weight, the fluidity becomes unstable and it becomes difficult to decorate it with decoration. If the amount of the glass powder is more than 95 parts by weight, the glass powder flows too much to obtain a desired pattern. If the refractory filler is less than 0.1 parts by weight, sufficient abrasion resistance cannot be obtained,
If it is more than 20 parts by weight, the fluidity will be poor and the abrasion resistance will be poor. If the heat-resistant pigment is less than 3 parts by weight, a stable color tone cannot be obtained, and if it is more than 25 parts by weight, the fluidity becomes poor.
【００２２】なおこのような装飾用組成物は、３０〜７
５０℃における熱膨張係数が約３０〜４０×１０-7／℃
であり、また約８００〜８５０℃で熱処理することが可
能なものである。Such a decorative composition has a composition of 30 to 7
Coefficient of thermal expansion at 50 ℃ is about 30-40 × 10 -7 / ℃
And can be heat-treated at about 800 to 850 ° C.
【００２３】次に本発明の装飾用組成物を用いて、低膨
張結晶化ガラスを絵付け装飾する方法を述べる。Next, a method for painting and decorating low expansion crystallized glass by using the decorative composition of the present invention will be described.
【００２４】まず、上記した割合になるように、ガラス
粉末、耐火性フィラー、耐熱性顔料を混合し、さらにエ
チルセルロース、酢酸エチル等の溶媒と混練してペース
ト状にする。First, glass powder, a refractory filler and a heat resistant pigment are mixed in the above proportions and further kneaded with a solvent such as ethyl cellulose or ethyl acetate to form a paste.
【００２５】次にこのペーストをスクリーン印刷等の方
法を用いて低膨張結晶化ガラスの表面に塗布する。この
とき形成される装飾被膜の膜厚が１〜２０μｍとなるよ
うに塗布することが重要である。即ち、膜厚がこの範囲
から外れると、装飾被膜にクラックが発生し易くなるた
めである。また使用する低膨張結晶化ガラスとしては、
３０〜７５０℃における熱膨張係数が２０×１０-7／℃
以下のものであり、このようなものとしてＬｉ2 Ｏ−Ａ
ｌ2 Ｏ3 −ＳｉＯ2 系の結晶化ガラスを使用することが
できる。Next, this paste is applied to the surface of the low expansion crystallized glass by using a method such as screen printing. It is important to apply so that the thickness of the decorative coating formed at this time is 1 to 20 μm. That is, if the film thickness deviates from this range, cracks are likely to occur in the decorative coating. As the low expansion crystallized glass used,
Coefficient of thermal expansion at 30 to 750 ℃ is 20 × 10 -7 / ℃
The following are such as Li 2 O-A
It is possible to use l 2 O 3 —SiO 2 -based crystallized glass.
【００２６】その後、８００〜８５０℃程度の温度で熱
処理すると、表面にガラス成分５５〜９５重量部と耐火
性フィラー成分０．１〜２０重量部と耐熱性顔料成分３
〜２５重量部とからなる装飾被膜が形成され、該ガラス
成分が重量百分率でＳｉＯ2５０〜７５％、Ａｌ2 Ｏ3
０．５〜１５％、Ｂ2 Ｏ3 ５〜３０％、ＢａＯ ０〜７
％、Ｌｉ2 Ｏ ０〜２％、Ｎａ2 Ｏ ０〜５％、Ｋ2 Ｏ
０〜４％、Ｆ2 ０〜２％からなり、また該耐火性フィ
ラー成分がジルコン及びジルコニアから選ばれる１種以
上である低膨張結晶化ガラス板を得ることができる。After that, when heat-treated at a temperature of about 800 to 850 ° C., 55 to 95 parts by weight of the glass component, 0.1 to 20 parts by weight of the refractory filler component and 3 of the heat resistant pigment component are formed on the surface.
Are formed enamel coating consisting of 25 parts by weight, the glass component is SiO 2 50 to 75% by weight percentage, Al 2 O 3
0.5~15%, B 2 O 3 5~30 %, BaO 0~7
%, Li 2 O 0 to 2%, Na 2 O 0 to 5%, K 2 O
It is possible to obtain a low expansion crystallized glass plate comprising 0 to 4% and F 2 0 to 2%, and the refractory filler component being one or more selected from zircon and zirconia.
【００２７】[0027]
【実施例】以下、実施例に基づいて本発明を説明する。EXAMPLES The present invention will be described below based on examples.
【００２８】表１は本発明の実施例（試料Ｎｏ．１〜
６）及び比較例（試料Ｎｏ．７）を示すものである。Table 1 shows examples of the present invention (Sample Nos. 1 to 1).
6) and a comparative example (sample No. 7).
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】各試料は次のようにして調製した。まず、
表中の組成になるように調合したガラス原料を１４００
〜１５００℃の温度で１０〜１５時間溶融し、フィルム
状に成形した後、ボールミルにて微粉砕し、平均粒径５
μｍのガラス粉末を得た。さらにこのガラス粉末と、表
中に示した耐火性フィラーと、耐熱性顔料（日本フェロ
ー株式会社製ＮＦ−３１２９−Ｐ［ブラウン］）とを混
合して試料を得た。Each sample was prepared as follows. First,
1400 glass raw materials prepared to have the composition in the table
Melt at a temperature of ~ 1500 ° C for 10 to 15 hours, form into a film, and then finely pulverize with a ball mill to give an average particle size of 5
A glass powder of μm was obtained. Further, this glass powder, the refractory filler shown in the table, and a heat resistant pigment (NF-3129-P [Brown] manufactured by Nippon Fellow Co., Ltd.) were mixed to obtain a sample.
【００３２】続いて、各試料とエチルセルロースとを重
量比で２：１の割合で混練してペースト状にし、これを
スクリーン印刷法を用いて低膨張結晶化ガラス板に塗布
した。なお結晶化ガラス板は、重量％でＳｉＯ2 ６７
％、Ａｌ2 Ｏ3 ２３％、ＴｉＯ 2 ２％、ＺｒＯ2 ３％、
Ｐ2 Ｏ5 １％、Ｌｉ2 Ｏ ４％の組成を有し、３０〜７
５０℃において約−３×１０-7／℃の熱膨張係数を示す
透明な結晶化ガラスを使用した。Subsequently, each sample and ethyl cellulose are weighed.
Knead in a ratio of 2: 1 to make a paste.
Apply to low expansion crystallized glass plate using screen printing method
did. The crystallized glass plate is made of SiO 2 by weight.2 67
%, Al2 O3 23%, TiO 2 2%, ZrO2 3%,
P2 OFive 1%, Li2 O 4% composition, 30-7
Approximately -3 x 10 at 50 ° C-7Indicates the coefficient of thermal expansion of / ° C
Clear crystallized glass was used.
【００３３】その後、８００〜８５０℃で熱処理するこ
とによって低膨張結晶化ガラス板を絵付け装飾した。な
お表面に形成された装飾被膜の膜厚は、１０〜１５μｍ
であった。Thereafter, the low expansion crystallized glass plate was painted and decorated by heat treatment at 800 to 850.degree. The thickness of the decorative coating formed on the surface is 10 to 15 μm.
Met.
【００３４】次に、結晶化ガラス板上に形成された装飾
被膜の熱膨張係数、クラックの有無、光沢の有無、耐摩
耗性について評価した。結果を表１に示す。Next, the coefficient of thermal expansion, presence / absence of cracks, presence / absence of gloss and abrasion resistance of the decorative coating formed on the crystallized glass plate were evaluated. The results are shown in Table 1.
【００３５】表から明らかなように、実施例である試料
Ｎｏ．１〜６を用いて絵付け装飾したものは、３０〜７
５０℃における熱膨張係数が３２〜３６×１０-7／℃で
あり、またクラックが認められず、光沢があり、しかも
良好な耐摩耗性を示した。これに対して、比較例である
試料Ｎｏ．７を用いたものは、熱膨張係数が３９×１０
-7／℃であり、またクラックがなく、光沢もあったが、
耐摩耗性が悪かった。As is apparent from the table, the sample No. What is decorated with 1 to 6 is 30 to 7
The coefficient of thermal expansion at 50 ° C. was 32 to 36 × 10 −7 / ° C., no crack was observed, the sample had gloss, and good abrasion resistance was exhibited. On the other hand, Sample No. which is a comparative example. The one using 7 has a thermal expansion coefficient of 39 × 10.
It was -7 / ° C, there was no crack, and it was glossy,
The wear resistance was poor.
【００３６】なお熱膨張係数は、各試料を角棒状にプレ
ス成形した後、８５０℃で焼成し、この焼成物を差動検
出式相対膨張計にて測定した。クラックの有無は、装飾
被膜表面を光学顕微鏡で観察して評価した。また耐摩耗
性は、＃１０００のサンドペーパー（１００φ）を用い
て、装飾被膜の表面を荷重３ｋｇ、片道１００ｍｍ／秒
の速度で１０００回往復した後、被膜の変化を目視で判
定し、全く変化のないものを良、少しでも変化したもの
を不良とした。The coefficient of thermal expansion was measured by press-molding each sample into a square rod shape, followed by firing at 850 ° C., and measuring the fired product with a differential detection relative dilatometer. The presence or absence of cracks was evaluated by observing the surface of the decorative coating with an optical microscope. In addition, abrasion resistance was measured by using # 1000 sandpaper (100φ) to reciprocate the surface of the decorative coating film 1000 times at a load of 3 kg and a speed of 100 mm / sec for one way, and then visually determine the change in the coating film, and it was completely changed. Those that did not exist were considered good, and those that changed even a little were considered defective.
【００３７】[0037]
【発明の効果】以上説明したように、本発明の装飾用組
成物は、要求される全ての特性を満足し、特に耐摩耗性
に優れているため、低膨張結晶化ガラスの装飾用として
好適なものである。Industrial Applicability As described above, the decorative composition of the present invention satisfies all the required properties and is particularly excellent in abrasion resistance, and is therefore suitable for decoration of low expansion crystallized glass. It is something.
【００３８】またこの装飾用組成物を用いて装飾した低
膨張結晶化ガラス板は、装飾被膜の耐摩耗性が高いため
に、調理器用トッププレート等の厨房器具用として好適
である。The low-expansion crystallized glass plate decorated with this decorative composition is suitable for kitchen appliances such as top plates for cookers because the decorative coating has high abrasion resistance.
Claims (1)
フィラー０．１〜２０重量部と、耐熱性顔料３〜２５重
量部とからなり、該ガラス粉末が、重量百分率でＳｉＯ
2 ５０〜７５％、Ａｌ2 Ｏ3 ０．５〜１５％、Ｂ2 Ｏ3
５〜３０％、ＢａＯ ０〜７％、Ｌｉ2 Ｏ ０〜２％、
Ｎａ2 Ｏ ０〜５％、Ｋ2 Ｏ ０〜４％、Ｆ2 ０〜２％
からなり、且つ、該耐火性フィラーが、ジルコン及びジ
ルコニアから選ばれる１種以上であることを特徴とする
低膨張結晶化ガラス装飾用組成物。1. 55 to 95 parts by weight of glass powder, 0.1 to 20 parts by weight of a refractory filler, and 3 to 25 parts by weight of a heat resistant pigment, wherein the glass powder is SiO 2 in weight percentage.
2 50-75%, Al 2 O 3 0.5-15%, B 2 O 3
5~30%, BaO 0~7%, Li 2 O 0~2%,
Na 2 O 0-5%, K 2 O 0-4%, F 2 0-2%
A low-expansion crystallized glass decorative composition, characterized in that the refractory filler is one or more selected from zircon and zirconia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22214793A JPH0761837A (en) | 1993-08-12 | 1993-08-12 | Composition for decorating low expanding crystal glass and low expanding crystal glass plate decorated with the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22214793A JPH0761837A (en) | 1993-08-12 | 1993-08-12 | Composition for decorating low expanding crystal glass and low expanding crystal glass plate decorated with the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0761837A true JPH0761837A (en) | 1995-03-07 |
Family
ID=16777922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22214793A Pending JPH0761837A (en) | 1993-08-12 | 1993-08-12 | Composition for decorating low expanding crystal glass and low expanding crystal glass plate decorated with the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761837A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0776867A1 (en) | 1995-11-30 | 1997-06-04 | Nippon Electric Glass Company., Ltd. | Enamel frit composition for a low-expansion crystallized glass and enamel-coated low-expansion crystallized glass plate using the same |
| EP0794158A1 (en) * | 1996-03-05 | 1997-09-10 | Nippon Electric Glass Company., Ltd. | Top plate having a first enamel coating in a heating portion and a second enamel coating in a non-heating portion on a surface of a low expansion crystallized glass |
| DE19834801A1 (en) * | 1998-08-01 | 2000-02-03 | Schott Glas | Lead- and cadmium-free glass composition for glazing, enamelling and decorating glasses or glass ceramics as well as processes for the production of a glass ceramic coated with them |
| US6525300B1 (en) | 1999-07-30 | 2003-02-25 | Schott Glas | Cooking surface for cooking food having a glass ceramic surface with a glass coating thereon |
| FR2862635A1 (en) * | 2003-11-26 | 2005-05-27 | Schott Ag | Transparent glass/vitroceramic plates coated with a colored opaque coating able to withstand high temperatures for cooker applications |
| EP1683767A1 (en) | 2005-01-24 | 2006-07-26 | Schott AG | Lead-free and cadmium-free glass for glazing, enameling and decoration of glasses or glass-ceramics |
| JP2006520309A (en) * | 2002-12-03 | 2006-09-07 | コーニング・インコーポレーテッド | Borosilicate glass composition and use thereof |
| DE102005040588B4 (en) * | 2004-08-20 | 2011-11-10 | Schott Ag | Use of a lead- and cadmium-free glass and method for glazing, enamelling and decorating of lithium aluminosilicate glass ceramics |
-
1993
- 1993-08-12 JP JP22214793A patent/JPH0761837A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0776867A1 (en) | 1995-11-30 | 1997-06-04 | Nippon Electric Glass Company., Ltd. | Enamel frit composition for a low-expansion crystallized glass and enamel-coated low-expansion crystallized glass plate using the same |
| US5691254A (en) * | 1995-11-30 | 1997-11-25 | Sakamoto; Akihiko | Enamel frit composition for a low-expansion crystallized glass and enamel-coated low-expansion crystallized glass plate using the same |
| EP0794158A1 (en) * | 1996-03-05 | 1997-09-10 | Nippon Electric Glass Company., Ltd. | Top plate having a first enamel coating in a heating portion and a second enamel coating in a non-heating portion on a surface of a low expansion crystallized glass |
| US5866239A (en) * | 1996-03-05 | 1999-02-02 | Nippon Electric Glass Co., Ltd. | Top plate having a first enamel coating in a heating portion and a second enamel coating in a non-heating portion on a surface of a low expansion crystallized glass |
| DE19834801A1 (en) * | 1998-08-01 | 2000-02-03 | Schott Glas | Lead- and cadmium-free glass composition for glazing, enamelling and decorating glasses or glass ceramics as well as processes for the production of a glass ceramic coated with them |
| DE19834801C2 (en) * | 1998-08-01 | 2002-08-08 | Schott Glas | Lead and cadmium-free glass composition for glazing, enamelling and decorating glasses or glass ceramics as well as processes for the production of a glass ceramic coated with them |
| US6525300B1 (en) | 1999-07-30 | 2003-02-25 | Schott Glas | Cooking surface for cooking food having a glass ceramic surface with a glass coating thereon |
| JP2006520309A (en) * | 2002-12-03 | 2006-09-07 | コーニング・インコーポレーテッド | Borosilicate glass composition and use thereof |
| JP4921713B2 (en) * | 2002-12-03 | 2012-04-25 | コーニング インコーポレイテッド | Borosilicate glass composition and use thereof |
| FR2862635A1 (en) * | 2003-11-26 | 2005-05-27 | Schott Ag | Transparent glass/vitroceramic plates coated with a colored opaque coating able to withstand high temperatures for cooker applications |
| DE102005040588B4 (en) * | 2004-08-20 | 2011-11-10 | Schott Ag | Use of a lead- and cadmium-free glass and method for glazing, enamelling and decorating of lithium aluminosilicate glass ceramics |
| DE102005040588B9 (en) * | 2004-08-20 | 2012-04-19 | Schott Ag | Use of a lead- and cadmium-free glass and method for glazing, enamelling and decorating of lithium aluminosilicate glass ceramics |
| EP1683767A1 (en) | 2005-01-24 | 2006-07-26 | Schott AG | Lead-free and cadmium-free glass for glazing, enameling and decoration of glasses or glass-ceramics |
| DE102005004068A1 (en) * | 2005-01-24 | 2006-07-27 | Schott Ag | Lead- and cadmium-free glass for glazing, enamelling and decorating glasses or glass ceramics |
| DE102005004068B4 (en) * | 2005-01-24 | 2008-01-17 | Schott Ag | Lead- and cadmium-free glass and process for glazing, enamelling and decorating of glasses or glass-ceramics as well as use of the glass |
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