JP2004269322A - Ceramic color composition, ceramic color paste, and manufacture method of glass plate with ceramic color layer - Google Patents

Ceramic color composition, ceramic color paste, and manufacture method of glass plate with ceramic color layer Download PDF

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Publication number
JP2004269322A
JP2004269322A JP2003063698A JP2003063698A JP2004269322A JP 2004269322 A JP2004269322 A JP 2004269322A JP 2003063698 A JP2003063698 A JP 2003063698A JP 2003063698 A JP2003063698 A JP 2003063698A JP 2004269322 A JP2004269322 A JP 2004269322A
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ceramic color
powder
color composition
glass plate
glass
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Inventor
Jiro Chiba
次郎 千葉
Susumu Otaguro
進 太田黒
Hiroshi Yamamoto
博志 山本
Eiji Ichikura
栄治 市倉
Nobuki Honda
伸樹 本田
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2003063698A priority Critical patent/JP2004269322A/en
Publication of JP2004269322A publication Critical patent/JP2004269322A/en
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    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • 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
    • 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
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • 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
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • 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
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ceramic color composition containing no lead, and excellent in both acid resistance and mold releasing property. <P>SOLUTION: This ceramic color composition essentially comprises 50-90 mass% silicate glass powder containing Bi<SB>2</SB>O<SB>3</SB>and TiO<SB>2</SB>, 0.01-10 mass% bismuth/titanium oxide powder, 9-40 mass% heat resistant pigment powder, and 0-30 mass% fire resistant filler. In this ceramic color composition, the bismuth/titanium oxide powder is at least a bismuth/titanium oxide powder selected from the group consisting of Bi<SB>2</SB>Ti<SB>4</SB>O<SB>11</SB>, Bi<SB>12</SB>TiO<SB>20</SB>, Bi<SB>2</SB>Ti<SB>2</SB>O<SB>7</SB>, and Bi<SB>4</SB>Ti<SB>3</SB>O<SB>12</SB>. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【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のに好適なセラミックカラー組成物およびセラミックカラーペーストに関する。また、自動車の窓ガラスに好適なセラミックカラー層付きガラス板の製造方法に関する。
【０００２】
【従来の技術】
自動車の窓ガラスの車内側周縁部には不透明着色層であるセラミックカラー層が形成されている。
セラミックカラー層は、窓ガラスと該窓ガラスをその周縁で車内側から保持するウレタンシーラントとの間に介在して該ウレタンシーラントの紫外線による劣化を防止し、また、窓ガラスの車内側周縁部に設けられた電熱線等の端子が車外側から見えないようにするために設けられる。
【０００３】
セラミックカラー層は、セラミックカラー組成物をペースト化し、ガラス板に塗布、乾燥後焼成することによりガラス板上に焼き付けて形成される。前記セラミックカラー組成物は、ガラス粉末、耐熱顔料粉末を必須成分として含有し、必要に応じて耐火物フィラーを含有する。なお、耐熱顔料粉末としては通常黒色のものが用いられる。
【０００４】
セラミックカラー組成物をガラス板上に焼き付けるときに同時にガラス板をプレス曲げ加工して曲面ガラス板を製造する場合には、該プレス曲げ加工に用いられるプレス型にセラミックカラー層が付着しないこと、すなわち型離れ性が良好であることが求められる。
【０００５】
このような型離れ性向上の課題を解決すべくケイ酸ビスマス種物質を含有するセラミックカラー組成物が提案されている（特許文献１参照）。
【０００６】
【特許文献１】
特開平９−１７５８３２号公報（第２−６頁）
【０００７】
【発明が解決しようとする課題】
近年雨水が酸性であることが問題となっており、セラミックカラー層がこの酸性雨水と接触すると白化等の変色が起る可能性がある。そのため、セラミックカラー層の耐酸性を向上させこの変色を防止することが求められる。
しかし、従来のセラミックカラー組成物によって前記型離れ性向上の課題に加えこの耐酸性向上の課題を解決することは困難であった。
本発明はこのような問題を解決できる、セラミックカラー組成物、セラミックカラーペースト、さらに、セラミックカラー層付きガラス板の製造方法の提供を目的とする。
【０００８】
【課題を解決するための手段】
本発明は、質量百分率表示で、Ｂｉ２Ｏ３およびＴｉＯ２を含有するケイ酸塩ガラス粉末５０〜９０％、ビスマスチタン酸化物粉末０．０１〜１０％、耐熱顔料粉末９〜４０％および耐火物フィラー０〜３０％、から本質的になるセラミックカラー組成物を提供する。
【０００９】
また、前記セラミックカラー組成物、バインダおよび有機溶剤から本質的になるセラミックカラーペーストを提供する。
また、前記セラミックカラーペーストが塗布されたガラス板を加熱し、該セラミックカラーペースト中のセラミックカラー組成物を前記ガラス板に焼き付けてセラミックカラー層とすることを特徴とするセラミックカラー層付きガラス板の製造方法を提供する。
【００１０】
【発明の実施の形態】
本発明のセラミックカラー組成物（以下、本発明の組成物という。）は、通常、エチルセルロース等のバインダおよびα−テルピネオール等の有機溶剤と混練してペースト化され、ソーダライムシリカガラス板等のガラス板に塗布して乾燥後焼成され、ガラス板上に焼き付けられたセラミックカラー層とされる。
【００１１】
軟化点が典型的には７３０℃であるソーダライムシリカガラス板上にセラミックカラー層を焼き付ける場合、たとえば、前記塗布はスクリーン印刷によって行われ、前記乾燥は８０〜１４０℃で、前記焼成は６００〜７５０℃でそれぞれ行われる。
【００１２】
なお、前記ペースト化されたものは本発明のセラミックカラーペースト（以下、本発明のペーストという。）であり、前記セラミックカラー層をガラス板に焼き付ける方法は本発明のセラミックカラー層付きガラス板の製造方法（以下、本発明の製造方法という。）である。
【００１３】
前記焼成によってガラス板上に本発明の組成物を焼き付けるときに同時に該ガラス板をプレス曲げ加工して曲面ガラス板としてもよく、このときの焼成温度すなわち曲げ加工温度は典型的には７００℃である。
【００１４】
次に、本発明の組成物の成分について質量百分率表示を用いて説明する。
Ｂｉ２Ｏ３およびＴｉＯ２を含有するケイ酸塩ガラス粉末（以下、本ガラス粉末という。）はセラミックカラー層をガラス板に焼き付ける成分であり必須である。５０％未満では焼き付けが不充分になる。好ましくは５５％以上である。また、その含有量は好ましくは８０％以下、より好ましくは７５％以下である。
【００１５】
本ガラス粉末の軟化点ＴＳは５００〜６００℃、５０〜３５０℃における平均線膨張係数αは５０×１０−７〜１３０×１０−７／℃であることがそれぞれ好ましい。ソーダライムシリカガラス板（典型的には、前記線膨張係数は８７×１０−７／℃。）に焼き付ける場合、ＴＳが上記範囲外では良好な焼き付けが困難になり、αが上記範囲外ではガラス板の強度の低下が大きくなる。
【００１６】
本ガラス粉末の質量平均粒径Ｄ５０は典型的には１〜６μｍである。
また、本ガラス粉末は、組成が１種類の、Ｂｉ２Ｏ３およびＴｉＯ２を含有するケイ酸塩ガラスの粉末であってもよいし、組成が２種類以上の同ガラスの混合粉末であってもよい。
前記ケイ酸塩ガラスは無鉛ガラスであることが好ましい。
【００１７】
本ガラス粉末は、下記成分基準のモル％表示で、ＳｉＯ２ ４０〜６５％、Ｂｉ２Ｏ３ １〜３０％、ＴｉＯ２ ０．５〜２０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ １〜２５％、Ｂ２Ｏ３ ０〜１０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ ０〜１０％、ＺｎＯ ０〜１０％、ＺｒＯ２＋ＳｎＯ２ ０〜１０％、Ａｌ２Ｏ３０〜５％、ＣｅＯ２ ０〜２％、Ｆ ０〜２％、から本質的になる無鉛ガラスの粉末である、または該無鉛ガラスの粉末を含有することが好ましい。
【００１８】
前記無鉛ガラスは上記成分から本質的になるが、その他の成分を本発明の目的を損なわない範囲で含有してもよい。その場合、当該その他の成分の含有量の合計は１０％以下であることが好ましい。
なお、たとえば「Ｂ２Ｏ３ ０〜１０％」は、Ｂ２Ｏ３は必須ではないが１０％まで含有してもよいことを示す。
【００１９】
前記無鉛ガラスは、同表示で、ＳｉＯ２ ５０〜６０％、Ｂｉ２Ｏ３ １０〜２０％、ＴｉＯ２ ５〜１５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ １０〜２０％、Ｂ２Ｏ３ ０〜５％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ ０〜５％、ＺｎＯ ０〜５％、ＺｒＯ２＋ＳｎＯ２ ０〜５％、Ａｌ２Ｏ３ ０〜３％、ＣｅＯ２ ０〜１％、Ｆ ０〜１％、から本質的になることがより好ましい。
【００２０】
本ガラス粉末は６７０℃に保持したときにビスマスチタン酸化物を析出するケイ酸塩ガラス粉末である、またはそのようなケイ酸塩ガラス粉末を含有していることが好ましい。そのようなものでないとソーダライムシリカガラス板に適用する場合等において型離れ性が低下するおそれがある。なお、前記６７０℃に保持する時間は典型的には５分間またはそれ以上である。
【００２１】
前記ビスマスチタン酸化物としては、Ｂｉ２Ｔｉ４Ｏ１１、Ｂｉ１２ＴｉＯ２０、Ｂｉ２Ｔｉ２Ｏ７およびＢｉ４Ｔｉ３Ｏ１２が例示される。
【００２２】
ビスマスチタン酸化物粉末は本ガラス粉末が焼成時に結晶、特にビスマスチタン酸化物を析出しやすくなるようにするための成分であり、必須である。０．０１％未満では結晶析出促進効果が小さい。好ましくは０．０５％以上、より好ましくは０．２％以上である。また、その含有量は好ましくは５％以下である。
【００２３】
ビスマスチタン酸化物粉末は、Ｂｉ２Ｔｉ４Ｏ１１、Ｂｉ１２ＴｉＯ２０、Ｂｉ２Ｔｉ２Ｏ７およびＢｉ４Ｔｉ３Ｏ１２からなる群から選ばれる１種以上のビスマスチタン酸化物の粉末であることが好ましい。
なお、ビスマスチタン酸化物粉末のＤ５０は典型的には０．１〜５μｍである。
【００２４】
耐熱顔料粉末は、紫外線を遮蔽し、または可視光も遮蔽する成分であり必須である。９％未満では紫外線遮蔽効果または可視光遮蔽効果が不充分になる。好ましくは１５％以上である。４０％超では焼き付けが不充分になる。好ましくは３０％以下である。
【００２５】
耐熱顔料粉末は銅クロムマンガン系複合酸化物、クロムコバルト系複合酸化物、鉄マンガン系複合酸化物、クロム鉄ニッケル系複合酸化物、クロム銅系複合酸化物、マグネタイトおよびチタニアからなる群から選ばれる１種以上の耐熱顔料の粉末であることがより好ましい。これらのうち、チタニアは白色顔料であり、その他のものは黒色顔料である。
耐熱顔料粉末のＤ５０は典型的には０．５〜２．５μｍである。
【００２６】
耐火物フィラーは必須ではないが、ガラス板の強度低下を抑制する、セラミックカラー層のαを小さくする、等のために３０％まで含有してもよい。３０％超では焼き付けが不充分になるおそれがある。好ましくは２５％以下である。
【００２７】
耐火物フィラーは典型的には、融点またはガラス転移点が７００℃以上である酸化物、ホウ化物、ケイ化物等の無機物の粉末である。α−アルミナ、α−石英、ジルコン、コーディエライト、β−ユークリプタイト、フォルステライト、ムライト、ジルコニア、ステアタイト、ホウ酸アルミニウムおよび石英ガラスからなる群から選ばれる１種以上の無機物の粉末であることが好ましい。
【００２８】
ガラス板の強度低下をより抑制したい場合、耐火物フィラーとしてホウ酸アルミニウムウィスカ等の耐熱ウィスカを含有することが好ましい。ここで耐熱ウィスカとは典型的には、融点またはガラス転移点が７００℃以上であり、繊維径が０．１〜１０μｍ、繊維長が０．５〜１００μｍ、繊維径／繊維長が０．００１〜２である無機ウィスカである。
【００２９】
本発明の組成物は本質的に上記成分からなるが、本発明の目的を損なわない範囲でその他の成分を含有してもよい。前記その他成分の含有量の合計は５％以下であることが好ましい。
【００３０】
本発明の組成物および本発明のペーストは、自動車用ガラス板に焼き付けてセラミックカラー層を形成するのに好適であるが、これに限定されず、たとえばガラスびん、ガラスコップ等へのセラミックカラー層形成にも適用できる。
【００３１】
本発明の製造方法においては、本発明のペーストしたがって本発明の組成物の使用が必須である。これにより、ガラス板に塗布された本発明の組成物をそのガラス板に焼き付けると同時にそのガラス板をプレス曲げ加工してもセラミックカラー層とプレス型の付着が起こらない、または起こりにくい。
前記ガラス板は典型的にはソーダライムシリカガラス板である。
【００３２】
【実施例】
モル％表示の組成が下記組成であり、Ｄ５０が１〜６μｍの範囲にあるガラス粉末Ａ、Ｂを次のようにして作製した。すなわち、下記組成となるように原料を調合、混合して白金ルツボに入れ、１０００〜１４００℃で１〜３時間溶解して溶融ガラスとした。この溶融ガラスを急冷してフレーク状ガラスとし、またはこの溶融ガラスを水砕して水砕ガラスとし、その後ボールミルで粉砕してガラス粉末を作製した。
【００３３】
ガラス粉末Ａ：ＳｉＯ２ ５５．８％、Ｂｉ２Ｏ３ １８．３％％、ＴｉＯ２８．５％、Ｌｉ２Ｏ １６．０％、Ｎａ２Ｏ １．０％、ＣｅＯ２ ０．４％。
ガラス粉末Ｂ：ＳｉＯ２ ５８．２％、Ｂｉ２Ｏ３ １５．０％％、ＴｉＯ２９．０％、Ｌｉ２Ｏ １５．０％、Ｋ２Ｏ ２．４％、ＣｅＯ２ ０．４％。
【００３４】
ガラス粉末Ａ、Ｂそれぞれについて６７０℃に５分間保持する焼成を行い、得られた焼成体についてＸ線回折測定を行った。その結果、ガラス粉末Ａの焼成体についてはＢｉ２ＳｉＯ５結晶が主として析出し、その他にビスマスチタン酸化物結晶も析出していることが、ガラス粉末Ｂの焼成体についてはＢｉ４Ｔｉ３Ｏ１２結晶が主として析出していることがそれぞれわかった。
また、ガラス粉末Ａ、ＢのＴＳはそれぞれ５４０℃、５６５℃、αはそれぞれ１１５×１０−７／℃、１１０×１０−７／℃であった。
【００３５】
ビスマスチタン酸化物粉末として、いずれも共立マテリアル社製のＢｉ２Ｔｉ４Ｏ１１粉末、Ｂｉ１２ＴｉＯ２０粉末、Ｂｉ２Ｔｉ２Ｏ７粉末およびＢｉ４Ｔｉ３Ｏ１２粉末を用意した。Ｄ５０は、Ｂｉ４Ｔｉ３Ｏ１２粉末（Ｄ５０＝０．８μｍ）を除き１．０〜３．０μｍである。また、同社製Ｂｉ４（ＳｉＯ４）３粉末（Ｄ５０＝１．８μｍ）も用意した。
【００３６】
耐熱顔料として、日本フェロー社製の銅クロムマンガン系複合酸化物黒色耐熱顔料（Ｄ５０＝０．９μｍ）および鉄マンガン系複合酸化物黒色耐熱顔料（Ｄ５０＝１．２μｍ）を用意した。表において前者は耐熱顔料Ｃｕ−Ｃｒ−Ｍｎ−Ｏ、後者は耐熱顔料Ｆｅ−Ｍｎ−Ｏとそれぞれ略記した。
【００３７】
耐火物フィラーとして、住友化学社製α−アルミナ粉末（Ｄ５０＝１．８μｍ）、白水化学社製ジルコン粉末（Ｄ５０＝２．０μｍ）、旭硝子社製コーディエライト粉末（Ｄ５０＝１．５μｍ）、四国化成社製ホウ酸アルミニウムウィスカＹＳ１０、龍森社製石英ガラス粉末（Ｄ５０＝１．０μｍ）を用意した。
【００３８】
これらを表のガラス粉末Ａから石英ガラスまでの欄に質量百分率表示で示す割合で混合してセラミックカラー組成物を作製した。例１〜９は実施例、例１０〜１２は比較例である。
【００３９】
次に、各セラミックカラー組成物８０質量部に対しビヒクルを２０質量部の割合で添加して混練し、三本ロールミルにより均質分散させてセラミックカラーペースト（以下、単にペーストという。）を作製した。なお、ビヒクルはα−テルピネオール溶液に質量百分率表示で１０％のエチルセルロースを溶解させて作製した。
【００４０】
得られたペーストを用いて、以下に述べるような焼結性、耐酸性、型離れ性の評価を行った。
ペーストを、厚さ３．５ｍｍ、大きさ１０ｃｍ×１０ｃｍのソーダライムシリカガラス板のほぼ全面にスクリーン印刷し、１００〜１２０℃で乾燥した。
ペーストが塗布された前記ガラス板を６７０℃に５分間保持して焼成した後、常温に冷却し、セラミックカラー層付ガラス板を得た。
【００４１】
このセラミックカラー層付ガラス板を割断し、セラミックカラー層（焼成体）の断面を走査型電子顕微鏡（ＳＥＭ）を用いて倍率＝２０００倍で観察して焼結性を評価した。
焼成体に空隙が少なく緻密性が良好であるものを○、空隙が多いものを×として表に示す。
【００４２】
また、前記セラミックカラー層付ガラス板を、ｐＨが１．０、温度が８０℃の硫酸溶液中に７２時間浸漬後取り出した。流水洗浄後、セラミックカラー層が焼き付けられていない面からガラス板を太陽光下で目視観察し、色調変化の程度を調べて耐酸性評価とした。色調変化が認められないものを◎、色調変化が若干認められたものを○、色調変化が若干とはいえないものを△、色調変化が若干とはいえないものであって顕著であるものを×として表に示す。
【００４３】
型離れ性については次のようにして評価した。
ペーストを、厚さ３．５ｍｍ、大きさ１０ｃｍ×１０ｃｍのソーダライムシリカガラス板のほぼ全面にスクリーン印刷し、乾燥した。
【００４４】
６７０℃に保持され、互いに対向する面にガラスクロスが張られた凸型プレス金型および凹型プレス金型の間に、ペーストが印刷され乾燥された前記ガラス板を挿入し、凸型プレス金型の上に１０ｋｇの重しを載せて５分間プレスしてセラミックカラー層付き曲面ガラス板を作製した。この曲面ガラス板の上から重しと凸方プレス金型を取り外し、凸方プレス金型表面へのセラミックカラー付着状況を調べ、これを型離れ性評価とした。セラミックカラーの付着が認められないまたは軽微であるものを○、付着が顕著であるものを×として表に示す。
【００４５】
【表１】

Figure 2004269322
【００４６】
【表２】
Figure 2004269322
【００４７】
例１２において耐酸性が良好でないことについては次のようなことが考えられる。すなわち、例１２の焼成体にはＸ線回折測定の結果ケイ酸ビスマス結晶が主として析出していることが判明した。このケイ酸ビスマス結晶析出にともない焼成体の残留ガラス相（マトリックス相）のＳｉＯ２分が減少し、その結果残留ガラス相の耐酸性が低下し、例１２の耐酸性が良好でなくなったと考えられる。
【００４８】
【発明の効果】
本発明によればセラミックカラー層がプレス型と付着することなくセラミックカラー層付き曲面ガラス板を製造でき、また、酸性雨水による当該セラミックカラー層の白化等の変色が起りにくく、かつ、当該セラミックカラー層が鉛を含有していないので環境面からも好ましい。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a ceramic color composition and a ceramic color paste suitable for baking on a glass plate for automobiles. Moreover, it is related with the manufacturing method of the glass plate with a ceramic color layer suitable for the window glass of a motor vehicle.
[0002]
[Prior art]
A ceramic color layer which is an opaque colored layer is formed on the inner peripheral edge of the window glass of the automobile.
The ceramic color layer is interposed between the window glass and a urethane sealant that holds the window glass at the periphery thereof from the inside of the vehicle to prevent deterioration of the urethane sealant due to ultraviolet rays. A terminal such as a heating wire provided is provided so that it cannot be seen from the outside of the vehicle.
[0003]
The ceramic color layer is formed by baking a ceramic color composition on a glass plate by pasting it, applying it to a glass plate, drying it and firing it. The ceramic color composition contains glass powder and heat-resistant pigment powder as essential components, and contains a refractory filler as necessary. The heat resistant pigment powder is usually black.
[0004]
When the ceramic color composition is baked on the glass plate and the glass plate is simultaneously press-bending to produce a curved glass plate, the ceramic color layer does not adhere to the press mold used for the press-bending process, that is, Good mold releasability is required.
[0005]
A ceramic color composition containing a bismuth silicate seed material has been proposed in order to solve the problem of improving mold release properties (see Patent Document 1).
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 9-175732 (page 2-6)
[0007]
[Problems to be solved by the invention]
In recent years, acidity of rainwater has become a problem, and discoloration such as whitening may occur when the ceramic color layer comes into contact with the acid rainwater. Therefore, it is required to improve the acid resistance of the ceramic color layer and prevent this discoloration.
However, it has been difficult to solve the problem of improving the acid resistance in addition to the problem of improving the mold releasability with the conventional ceramic color composition.
The object of the present invention is to provide a ceramic color composition, a ceramic color paste, and a method for producing a glass plate with a ceramic color layer, which can solve such problems.
[0008]
[Means for Solving the Problems]
The present invention is expressed in terms of mass percentage, silicate glass powder containing Bi 2 O 3 and TiO 2 50 to 90%, bismuth titanium oxide powder 0.01 to 10%, heat resistant pigment powder 9 to 40% and fire resistance A ceramic color composition consisting essentially of 0-30% of a filler is provided.
[0009]
Also provided is a ceramic color paste consisting essentially of the ceramic color composition, a binder and an organic solvent.
A glass plate with a ceramic color layer, wherein the glass plate coated with the ceramic color paste is heated, and the ceramic color composition in the ceramic color paste is baked on the glass plate to form a ceramic color layer. A manufacturing method is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The ceramic color composition of the present invention (hereinafter referred to as the composition of the present invention) is usually kneaded with a binder such as ethyl cellulose and an organic solvent such as α-terpineol to form a paste, and a glass such as a soda lime silica glass plate. The ceramic color layer is applied to a plate, dried, fired, and baked on a glass plate.
[0011]
When baking a ceramic color layer on a soda lime silica glass plate, typically having a softening point of 730 ° C., for example, the coating is performed by screen printing, the drying is 80-140 ° C., and the baking is 600- Each is performed at 750 ° C.
[0012]
The paste is the ceramic color paste of the present invention (hereinafter referred to as the paste of the present invention), and the method of baking the ceramic color layer on the glass plate is the production of the glass plate with the ceramic color layer of the present invention. This is a method (hereinafter referred to as the production method of the present invention).
[0013]
When the composition of the present invention is baked on the glass plate by the baking, the glass plate may be press-bent at the same time to form a curved glass plate, and the baking temperature, that is, the bending temperature is typically 700 ° C. is there.
[0014]
Next, the components of the composition of the present invention will be described using mass percentage display.
A silicate glass powder containing Bi 2 O 3 and TiO 2 (hereinafter referred to as the present glass powder) is a component for baking a ceramic color layer on a glass plate and is essential. If it is less than 50%, baking will be insufficient. Preferably it is 55% or more. Moreover, the content is preferably 80% or less, more preferably 75% or less.
[0015]
Softening point T S of the glass powder is 500 to 600 ° C., it is preferred that each of the average linear expansion coefficient α at 50 to 350 ° C. is 50 × 10 -7 ~130 × 10 -7 / ℃. Soda lime silica glass plate (typically, the linear expansion coefficient of 87 × 10 -7 / ℃.) When burn in, T S becomes difficult to ensure favorable baking outside the above range, alpha is outside the above range The decrease in strength of the glass plate is increased.
[0016]
Mass average particle diameter D 50 of the glass powder is typically in the 1 to 6 m.
Further, the present glass powder may be a silicate glass powder containing Bi 2 O 3 and TiO 2 with one composition, or a mixed powder of two or more compositions of the same glass. Also good.
The silicate glass is preferably lead-free glass.
[0017]
The present glass powder is expressed in terms of mol% based on the following component basis, SiO 2 40 to 65%, Bi 2 O 3 1 to 30%, TiO 2 0.5 to 20%, Li 2 O + Na 2 O + K 2 O 1 to 25%. , B 2 O 3 0-10%, MgO + CaO + SrO + BaO 0-10%, ZnO 0-10%, ZrO 2 + SnO 2 0-10%, Al 2 O 3 0-5%, CeO 2 0-2%, F 0 Preferably, the lead-free glass powder consists essentially of 2% or contains the lead-free glass powder.
[0018]
The lead-free glass consists essentially of the above components, but may contain other components as long as the object of the present invention is not impaired. In that case, the total content of the other components is preferably 10% or less.
For example, “B 2 O 3 0 to 10%” indicates that B 2 O 3 is not essential but may be contained up to 10%.
[0019]
The lead-free glass, in the same view, SiO 2 50~60%, Bi 2 O 3 10~20%, TiO 2 5~15%, Li 2 O + Na 2 O + K 2 O 10~20%, B 2 O 3 0~ Essentially from 5%, MgO + CaO + SrO + BaO 0-5%, ZnO 0-5%, ZrO 2 + SnO 2 0-5%, Al 2 O 3 0-3%, CeO 2 0-1%, F 0-1%. More preferably.
[0020]
The glass powder is preferably a silicate glass powder that deposits bismuth titanium oxide when held at 670 ° C. or contains such a silicate glass powder. Otherwise, the mold release property may be lowered when applied to a soda lime silica glass plate. The time for holding at 670 ° C. is typically 5 minutes or longer.
[0021]
Examples of the bismuth titanium oxide include Bi 2 Ti 4 O 11 , Bi 12 TiO 20 , Bi 2 Ti 2 O 7 and Bi 4 Ti 3 O 12 .
[0022]
The bismuth titanium oxide powder is an essential component for allowing the glass powder to easily precipitate crystals, particularly bismuth titanium oxide, during firing. If it is less than 0.01%, the crystal precipitation promoting effect is small. Preferably it is 0.05% or more, More preferably, it is 0.2% or more. Moreover, the content is preferably 5% or less.
[0023]
The bismuth titanium oxide powder is a powder of at least one bismuth titanium oxide selected from the group consisting of Bi 2 Ti 4 O 11 , Bi 12 TiO 20 , Bi 2 Ti 2 O 7 and Bi 4 Ti 3 O 12. It is preferable.
The D 50 of the bismuth titanium oxide powder is typically 0.1 to 5 μm.
[0024]
The heat-resistant pigment powder is a component that shields ultraviolet rays or visible light and is essential. If it is less than 9%, the ultraviolet ray shielding effect or the visible light shielding effect is insufficient. Preferably it is 15% or more. If it exceeds 40%, baking will be insufficient. Preferably it is 30% or less.
[0025]
The heat resistant pigment powder is selected from the group consisting of copper-chromium-manganese composite oxide, chromium-cobalt composite oxide, iron-manganese composite oxide, chromium-iron-nickel composite oxide, chromium-copper composite oxide, magnetite and titania. More preferably, it is a powder of one or more heat-resistant pigments. Of these, titania is a white pigment and the others are black pigments.
The D 50 of the heat resistant pigment powder is typically 0.5 to 2.5 μm.
[0026]
The refractory filler is not essential, but may be contained up to 30% in order to suppress the strength reduction of the glass plate, to reduce the α of the ceramic color layer, and the like. If it exceeds 30%, baking may be insufficient. Preferably it is 25% or less.
[0027]
The refractory filler is typically an inorganic powder such as an oxide, boride, or silicide having a melting point or glass transition point of 700 ° C. or higher. One or more inorganic powders selected from the group consisting of α-alumina, α-quartz, zircon, cordierite, β-eucryptite, forsterite, mullite, zirconia, steatite, aluminum borate and quartz glass Preferably there is.
[0028]
When it is desired to further suppress the strength reduction of the glass plate, it is preferable to contain a heat-resistant whisker such as an aluminum borate whisker as the refractory filler. Here, the heat-resistant whisker typically has a melting point or glass transition point of 700 ° C. or higher, a fiber diameter of 0.1 to 10 μm, a fiber length of 0.5 to 100 μm, and a fiber diameter / fiber length of 0.001. It is an inorganic whisker that is ~ 2.
[0029]
The composition of the present invention consists essentially of the above components, but may contain other components as long as the object of the present invention is not impaired. The total content of the other components is preferably 5% or less.
[0030]
The composition of the present invention and the paste of the present invention are suitable for baking on an automobile glass plate to form a ceramic color layer, but the present invention is not limited to this, for example, a ceramic color layer on glass bottles, glass cups and the like. It can also be applied to formation.
[0031]
In the production method of the present invention, it is essential to use the paste of the present invention and thus the composition of the present invention. Thereby, even if the composition of the present invention applied to the glass plate is baked on the glass plate and the glass plate is subjected to press bending, adhesion of the ceramic color layer and the press mold does not occur or hardly occurs.
The glass plate is typically a soda lime silica glass plate.
[0032]
【Example】
Glass powders A and B in which the composition in terms of mol% is the following composition and D 50 is in the range of 1 to 6 μm were prepared as follows. That is, the raw materials were prepared and mixed so as to have the following composition, put into a platinum crucible, and melted at 1000 to 1400 ° C. for 1 to 3 hours to obtain molten glass. The molten glass was rapidly cooled to form a flaky glass, or the molten glass was crushed to give a granulated glass, and then pulverized with a ball mill to produce a glass powder.
[0033]
Glass powder A: SiO 2 55.8%, Bi 2 O 3 18.3%, TiO 2 8.5%, Li 2 O 16.0%, Na 2 O 1.0%, CeO 2 0.4% .
Glass powder B: SiO 2 58.2%, Bi 2 O 3 15.0 %%, TiO 2 9.0%, Li 2 O 15.0%, K 2 O 2.4%, CeO 2 0.4% .
[0034]
The glass powder A and B were each fired at 670 ° C. for 5 minutes, and the obtained fired body was subjected to X-ray diffraction measurement. As a result, Bi 2 SiO 5 crystals are mainly precipitated for the fired body of glass powder A, and bismuth titanium oxide crystals are also precipitated. In addition, Bi 4 Ti 3 O 12 is used for the fired body of glass powder B. It was found that crystals were mainly precipitated.
The glass powder A, T S is the respective 540 ° C. in B, 565 ° C., alpha Each 115 × 10 -7 / ℃, was 110 × 10 -7 / ℃.
[0035]
As the bismuth titanium oxide powder, Bi 2 Ti 4 O 11 powder, Bi 12 TiO 20 powder, Bi 2 Ti 2 O 7 powder and Bi 4 Ti 3 O 12 powder manufactured by Kyoritsu Material Co., Ltd. were prepared. D 50 is 1.0 to 3.0 μm except for Bi 4 Ti 3 O 12 powder (D 50 = 0.8 μm). In addition, Bi 4 (SiO 4 ) 3 powder (D 50 = 1.8 μm) manufactured by the same company was also prepared.
[0036]
As heat-resistant pigments, a copper chrome-manganese complex oxide black heat-resistant pigment (D 50 = 0.9 μm) and an iron-manganese complex oxide black heat-resistant pigment (D 50 = 1.2 μm) manufactured by Nippon Fellow Co., Ltd. were prepared. In the table, the former is abbreviated as heat-resistant pigment Cu-Cr-Mn-O, and the latter is abbreviated as heat-resistant pigment Fe-Mn-O.
[0037]
As a refractory filler, α-alumina powder (D 50 = 1.8 μm) manufactured by Sumitomo Chemical Co., Ltd., zircon powder manufactured by Hakusui Chemical Co., Ltd. (D 50 = 2.0 μm), cordierite powder manufactured by Asahi Glass Co., Ltd. (D 50 = 1. 5 μm), aluminum borate whisker YS10 manufactured by Shikoku Kasei Co., Ltd., and quartz glass powder (D 50 = 1.0 μm) manufactured by Tatsumori Co., Ltd. were prepared.
[0038]
These were mixed at a ratio indicated by mass percentage in the column from glass powder A to quartz glass in the table to prepare a ceramic color composition. Examples 1 to 9 are examples, and examples 10 to 12 are comparative examples.
[0039]
Next, a vehicle was added at a ratio of 20 parts by mass to 80 parts by mass of each ceramic color composition, kneaded, and uniformly dispersed by a three-roll mill to prepare a ceramic color paste (hereinafter simply referred to as a paste). The vehicle was prepared by dissolving 10% ethyl cellulose by mass percentage display in an α-terpineol solution.
[0040]
Using the obtained paste, the sinterability, acid resistance, and mold release properties as described below were evaluated.
The paste was screen-printed on almost the whole surface of a soda lime silica glass plate having a thickness of 3.5 mm and a size of 10 cm × 10 cm, and dried at 100 to 120 ° C.
The glass plate coated with the paste was baked by holding at 670 ° C. for 5 minutes, and then cooled to room temperature to obtain a glass plate with a ceramic color layer.
[0041]
The glass plate with the ceramic color layer was cut, and the cross section of the ceramic color layer (fired body) was observed with a scanning electron microscope (SEM) at a magnification of 2000 times to evaluate the sinterability.
The sintered body with few voids and good denseness is shown in the table as ◯, and the one with many voids as x.
[0042]
The glass plate with a ceramic color layer was taken out after being immersed in a sulfuric acid solution having a pH of 1.0 and a temperature of 80 ° C. for 72 hours. After washing with running water, the glass plate was visually observed under sunlight from the surface where the ceramic color layer was not baked, and the degree of color tone change was examined to evaluate acid resistance. ◎ if there is no change in color tone, ◯ if there is a slight change in color tone, △ if there is no change in color tone, △, if the change in color tone is not so slight It shows in the table as x.
[0043]
The mold release property was evaluated as follows.
The paste was screen-printed on almost the whole surface of a soda lime silica glass plate having a thickness of 3.5 mm and a size of 10 cm × 10 cm, and dried.
[0044]
Between the convex press mold and the concave press mold held at 670 ° C. and having a glass cloth stretched on the surfaces facing each other, the glass plate on which the paste is printed and dried is inserted, and the convex press mold A curved surface glass plate with a ceramic color layer was prepared by placing a weight of 10 kg on top and pressing for 5 minutes. The weight and convex press mold were removed from the curved glass plate, and the state of ceramic color adhesion to the surface of the convex press mold was examined. In the table, the ceramic color adhesion is not recognized or slight, and the case where the adhesion is remarkable is marked as x.
[0045]
[Table 1]
Figure 2004269322
[0046]
[Table 2]
Figure 2004269322
[0047]
The following may be considered about the poor acid resistance in Example 12. That is, as a result of X-ray diffraction measurement, it was found that bismuth silicate crystals were mainly precipitated in the fired body of Example 12. With this bismuth silicate crystal precipitation, the SiO 2 content of the residual glass phase (matrix phase) of the fired body decreased, and as a result, the acid resistance of the residual glass phase was lowered, and the acid resistance of Example 12 was considered to be poor. .
[0048]
【The invention's effect】
According to the present invention, a curved glass plate with a ceramic color layer can be produced without the ceramic color layer adhering to the press mold, and the ceramic color layer is not easily discolored by acid rain water, and the ceramic color layer Since the layer does not contain lead, it is preferable from the viewpoint of environment.

Claims (9)

質量百分率表示で、Ｂｉ２Ｏ３およびＴｉＯ２を含有するケイ酸塩ガラス粉末５０〜９０％、ビスマスチタン酸化物粉末０．０１〜１０％、耐熱顔料粉末９〜４０％および耐火物フィラー０〜３０％、から本質的になるセラミックカラー組成物。Silicate glass powder containing Bi 2 O 3 and TiO 2 , 50 to 90%, bismuth titanium oxide powder 0.01 to 10%, heat resistant pigment powder 9 to 40%, and refractory filler 0 to 0 in terms of mass percentage A ceramic color composition consisting essentially of 30%. ビスマスチタン酸化物粉末が、Ｂｉ２Ｔｉ４Ｏ１１、Ｂｉ１２ＴｉＯ２０、Ｂｉ２Ｔｉ２Ｏ７およびＢｉ４Ｔｉ３Ｏ１２からなる群から選ばれる１種以上のビスマスチタン酸化物の粉末である請求項１に記載のセラミックカラー組成物。The bismuth titanium oxide powder is a powder of at least one bismuth titanium oxide selected from the group consisting of Bi 2 Ti 4 O 11 , Bi 12 TiO 20 , Bi 2 Ti 2 O 7 and Bi 4 Ti 3 O 12. The ceramic color composition according to claim 1. 前記ケイ酸塩ガラス粉末の軟化点が５００〜６００℃、５０〜３５０℃における平均線膨張係数が５０×１０−７〜１３０×１０−７／℃である請求項１または２に記載のセラミックカラー組成物。3. The ceramic color according to claim 1, wherein the silicate glass powder has a softening point of 500 to 600 ° C. and an average linear expansion coefficient of 50 × 10 −7 to 130 × 10 −7 / ° C. at 50 to 350 ° C. 4. Composition. 前記ケイ酸塩ガラス粉末が、６７０℃に保持したときにビスマスチタン酸化物を析出するケイ酸塩ガラス粉末である、または該ケイ酸塩ガラス粉末を含有している請求項１、２または３に記載のセラミックカラー組成物。The silicate glass powder is a silicate glass powder that deposits bismuth titanium oxide when held at 670 ° C, or contains the silicate glass powder. The ceramic color composition as described. 前記ケイ酸塩ガラス粉末が、下記成分基準のモル％表示で、ＳｉＯ２ ４０〜６５％、Ｂｉ２Ｏ３ １〜３０％、ＴｉＯ２ ０．５〜２０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ １〜２５％、Ｂ２Ｏ３ ０〜１０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ ０〜１０％、ＺｎＯ ０〜１０％、ＺｒＯ２＋ＳｎＯ２ ０〜１０％、Ａｌ２Ｏ３ ０〜５％、ＣｅＯ２ ０〜２％、Ｆ ０〜２％、から本質的になる無鉛ガラスの粉末である、または該無鉛ガラスの粉末を含有している請求項１、２、３または４に記載のセラミックカラー組成物。The silicate glass powder, as represented by mol% of the following component basis, SiO 2 40~65%, Bi 2 O 3 1~30%, TiO 2 0.5~20%, Li 2 O + Na 2 O + K 2 O 1 ~25%, B 2 O 3 0~10 %, MgO + CaO + SrO + BaO 0~10%, 0~10% ZnO, ZrO 2 + SnO 2 0~10%, Al 2 O 3 0~5%, CeO 2 0~2%, 5. The ceramic color composition according to claim 1, 2, 3, or 4, wherein the ceramic color composition is a lead-free glass powder consisting essentially of F 0 to 2% or contains the lead-free glass powder. 耐熱顔料粉末が、銅クロムマンガン系複合酸化物、クロムコバルト系複合酸化物、鉄マンガン系複合酸化物、クロム鉄ニッケル系複合酸化物、クロム銅系複合酸化物、マグネタイトおよびチタニアからなる群から選ばれる１種以上の耐熱顔料の粉末を含有する請求項１〜５のいずれかに記載のセラミックカラー組成物。The heat resistant pigment powder is selected from the group consisting of copper-chromium-manganese composite oxide, chromium-cobalt composite oxide, iron-manganese composite oxide, chromium-iron-nickel composite oxide, chromium-copper composite oxide, magnetite and titania. The ceramic color composition according to any one of claims 1 to 5, comprising a powder of one or more heat-resistant pigments. 耐火物フィラーが、α−アルミナ、α−石英、ジルコン、コーディエライト、β−ユークリプタイト、フォルステライト、ムライト、ステアタイト、ジルコニア、ホウ酸アルミニウムおよび石英ガラスからなる群から選ばれる１以上の耐火物の粉末である請求項１〜６のいずれかに記載のセラミックカラー組成物。The refractory filler is at least one selected from the group consisting of α-alumina, α-quartz, zircon, cordierite, β-eucryptite, forsterite, mullite, steatite, zirconia, aluminum borate and quartz glass. The ceramic color composition according to any one of claims 1 to 6, which is a refractory powder. 請求項１〜７のいずれかに記載のセラミックカラー組成物、バインダおよび有機溶剤から本質的になるセラミックカラーペースト。A ceramic color paste consisting essentially of the ceramic color composition according to any one of claims 1 to 7, a binder, and an organic solvent. 請求項８に記載のセラミックカラーペーストが塗布されたガラス板を加熱し、該セラミックカラーペースト中のセラミックカラー組成物を前記ガラス板に焼き付けてセラミックカラー層とすることを特徴とするセラミックカラー層付きガラス板の製造方法。A glass plate coated with the ceramic color paste according to claim 8 is heated, and the ceramic color composition in the ceramic color paste is baked on the glass plate to form a ceramic color layer. Manufacturing method of glass plate.
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