JP2003026444A - Ceramic color composition, ceramic color paste and method for producing glass board fitted with ceramic color layer - Google Patents

Ceramic color composition, ceramic color paste and method for producing glass board fitted with ceramic color layer

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Publication number
JP2003026444A
JP2003026444A JP2001210999A JP2001210999A JP2003026444A JP 2003026444 A JP2003026444 A JP 2003026444A JP 2001210999 A JP2001210999 A JP 2001210999A JP 2001210999 A JP2001210999 A JP 2001210999A JP 2003026444 A JP2003026444 A JP 2003026444A
Authority
JP
Japan
Prior art keywords
ceramic color
color composition
glass
powder
ceramic
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
Application number
JP2001210999A
Other languages
Japanese (ja)
Inventor
Jiro Chiba
次郎 千葉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2001210999A priority Critical patent/JP2003026444A/en
Publication of JP2003026444A publication Critical patent/JP2003026444A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing 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
    • 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
    • C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
    • 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
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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

Landscapes

  • 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)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a ceramic color composition by which a ceramic color layer containing no lead and having excellent oxidation resistance can be obtained. SOLUTION: The ceramic color composition essentially consists of, by mass, 40 to 90% lead-free glass powder, 1 to 60% heat resisting pigment powder and a 0 to 59% refractory filler. The lead-free glass powder consists essentially of, by mass based on the following components, 1 to 50% SiO2 , 1 to 30% B2 O3 , 1 to 25% Bi2 O3 , 1 to 20% Al2 O3 , 1 to 20% TiO2 +ZrO2 , 0.3 to 20% Li2 O+Na2 O+ K2 O, 0.1 to 10% P2 O5 +V2 O5 +SnO2 , 0 to 10% ZnO, 0 to 10% Fe2 O3 +CuO, 0 to 10% CeO2 , 0 to 10% La2 O3 and 0 to 5% F.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、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、自動車の窓ガラス等に用いられるセラミックカラー
層付きガラス板の製造方法に関する。TECHNICAL FIELD The present invention relates to a ceramic color composition and a ceramic color paste. The present invention also relates to a method for manufacturing a glass plate with a ceramic color layer used for automobile window glass and the like.

【０００２】[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。該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、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。2. Description of the Related Art A ceramic color layer, which is an opaque coloring layer, is formed on the inner peripheral edge of a window glass of an automobile. The ceramic color layer is interposed between the window glass and a urethane sealant that holds the window glass from the inside of the vehicle at the peripheral edge thereof to prevent deterioration of the urethane sealant due to ultraviolet rays, and also to protect the window glass from the inside edge of the vehicle. The terminals such as heating wires provided on the vehicle are provided so as not to be seen from the outside of the vehicle.

【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、ガラス粉末としては従来、鉛含有ガ
ラスの粉末が、また耐熱顔料粉末としては通常黒色のも
のが用いられている。The ceramic color layer is formed by baking the ceramic color composition into a paste, applying the composition to a glass plate, drying and baking the composition. The ceramic color composition contains glass powder and heat resistant pigment powder as essential components, and optionally a refractory filler. Incidentally, lead-containing glass powder has been conventionally used as the glass powder, and black powder is usually used as the heat-resistant pigment powder.

【０００４】[0004]

【発明が解決しようとする課題】近年、鉛を含有しない
セラミックカラー組成物が求めらている。また、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。この変色を防止するためにセラミックカ
ラー層の耐酸性が高いことが求められる。本発明は、上
記課題を解決するセラミックカラー組成物、セラミック
カラーペーストの提供、および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。In recent years, a lead-free ceramic color composition has been sought. Further, in recent years, it has been a problem that rainwater is acidic, and when the ceramic color layer comes into contact with the acidic rainwater, discoloration such as whitening may occur. In order to prevent this discoloration, the ceramic color layer is required to have high acid resistance. It is an object of the present invention to provide a ceramic color composition, a ceramic color paste, and a method for producing a glass plate with a ceramic color layer, which solve the above problems.

【０００５】[0005]

【課題を解決するための手段】本発明は、質量百分率表
示で本質的に、無鉛ガラス粉末 ４０〜９０％、耐熱顔
料粉末 １〜６０％、耐火物フィラー ０〜５９％、か
らなるセラミックカラー組成物であって、無鉛ガラス粉
末が、下記成分基準の質量百分率表示で本質的に、 ＳｉＯ２ １〜５０％、 Ｂ２Ｏ３ １〜３０％、 Ｂｉ２Ｏ３ １〜２５％、 Ａｌ２Ｏ３ １〜２０％、 ＴｉＯ２＋ＺｒＯ２ １〜２０％、 Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０．３〜２０％、 Ｐ２Ｏ５＋Ｖ２Ｏ５＋ＳｎＯ２ ０．１〜１０％、 ＺｎＯ ０〜１０％、 Ｆｅ２Ｏ３＋ＣｕＯ ０〜１０％、 ＣｅＯ２ ０〜１０％、 Ｌａ２Ｏ３ ０〜１０％、 Ｆ ０〜５％、 からなるセラミックカラー組成物を提供する。DISCLOSURE OF THE INVENTION The present invention is, in terms of mass percentage, essentially a ceramic color composition consisting of 40 to 90% of lead-free glass powder, 1 to 60% of heat-resistant pigment powder, and 0 to 59% of refractory filler. The lead-free glass powder is essentially the following component-based mass percentage display: SiO 2 1-50%, B 2 O 3 1-30%, Bi 2 O 3 1-25%, Al 2 O 3 1 to 20%, TiO 2 + ZrO 2 1 to 20%, Li 2 O + Na 2 O + K 2 O 0.3 to 20%, P 2 O 5 + V 2 O 5 + SnO 2 0.1 to 10%, ZnO 0 to 10% %, Fe 2 O 3 + CuO 0-10%, CeO 2 0-10%, La 2 O 3 0-10%, F 0-5%, and a ceramic color composition.

【０００６】また、バインダ、有機溶剤および前記セラ
ミックカラー組成物を含有す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を
ガラス板に塗布し、焼成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。A ceramic color paste containing a binder, an organic solvent and the ceramic color composition is also provided. Further, the present invention provides a method for producing a glass plate with a ceramic color layer, which comprises applying the ceramic color paste to a glass plate and baking the glass plate.

【０００７】[0007]

【発明の実施の形態】本発明のセラミックカラー組成物
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、
ガラス板に塗布後、乾燥、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。典型的には、
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℃で行われ、前記焼成は６００〜７００℃
で行われる。また、前記ガラス板は通常はソーダライム
シリカガラス板（軟化点は典型的には７３０℃）であ
る。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であり、前記セラミックカラー層が
焼き付けられたガラス板の製造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である。BEST MODE FOR CARRYING OUT THE INVENTION The ceramic color 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,
After being applied to a glass plate, it is dried and fired to form a ceramic color layer baked on the glass plate. Typically,
The coating is performed by screen printing, the drying is performed at 80 to 140 ° C, and the baking is performed at 600 to 700 ° C.
Done in. The glass plate is usually a soda lime silica glass plate (softening point is typically 730 ° C.). The paste is the ceramic color paste of the present invention, and the method for producing a glass plate on which the ceramic color layer is baked is the method for producing a glass plate with a ceramic color layer of the present invention.

【０００８】本発明のセラミックカラー組成物を焼成し
て得られる焼成体の５０〜３５０℃における平均線膨張
係数αは７０×１０−７〜９０×１０−７／℃であるこ
とが好ましい。この範囲外ではソーダライムシリカガラ
ス板（αは典型的には８７×１０−７／℃）との膨張係
数マッチングが困難になるおそれがある。The average linear expansion coefficient α at 50 to 350 ° C. of the fired body obtained by firing the ceramic color composition of the present invention is preferably 70 × 10 −7 to 90 × 10 −7 / ° C. Outside this range, it may be difficult to match the expansion coefficient with a soda lime silica glass plate (α is typically 87 × 10 −7 / ° C.).

【０００９】また、前記焼成体の軟化点ＴＳは５５０〜
６５０℃であることが好ましい。５５０℃未満では焼成
時の流動性が大きくなりすぎ、また、６５０℃超では焼
結性が低下するおそれがある。ここで、ＴＳは示差熱分
析（ＤＴＡ）によって測定される。The softening point T S of the fired body is 550 to
It is preferably 650 ° C. If it is less than 550 ° C, the fluidity during firing becomes too large, and if it exceeds 650 ° C, the sinterability may decrease. Here, T S is measured by differential thermal analysis (DTA).

【００１０】次に、本発明のセラミックカラー組成物の
各成分について、質量百分率表示を用いて説明する。無
鉛ガラス粉末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。４０％未満では焼き付けが
不充分になる。好ましくは５０％以上である。９０％超
では他の成分、特に耐熱顔料の含有量が小さくなる。好
ましくは８０％以下である。Next, each component of the ceramic color composition of the present invention will be described using the mass percentage display. The lead-free glass powder is a component for baking the ceramic color layer on the glass plate and is essential. If it is less than 40%, the baking will be insufficient. It is preferably 50% or more. If it exceeds 90%, the content of other components, particularly the heat resistant pigment, becomes small. It is preferably 80% or less.

【００１１】この無鉛ガラス粉末の組成について、質量
百分率表示を用いて以下に説明する。ＳｉＯ２はネット
ワークフォーマであり必須である。１％未満ではガラス
溶解時に失透するおそれがある。好ましくは５％以上で
ある。５０％超では軟化点が高くなり焼き付けが不充分
になる。好ましくは４５％以下である。The composition of the lead-free glass powder will be described below using the mass percentage display. SiO 2 is a network former and is essential. If it is less than 1%, the glass may be devitrified during melting. It is preferably at least 5%. If it exceeds 50%, the softening point becomes high and the baking becomes insufficient. It is preferably 45% or less.

【００１２】Ｂ２Ｏ３は軟化点を低下させ、またガラス
溶解時の失透を防止する成分であり必須である。１％未
満では軟化点が高くなり焼き付けが不充分になる。好ま
しくは５％以上である。３０％超では耐水性等の化学的
耐久性が低下する。好ましくは２５％以下である。B 2 O 3 is a component that lowers the softening point and prevents devitrification during glass melting, and is essential. If it is less than 1%, the softening point becomes high and the baking becomes insufficient. It is preferably at least 5%. If it exceeds 30%, the chemical durability such as water resistance is lowered. It is preferably 25% or less.

【００１３】Ｂｉ２Ｏ３は軟化点を低下させる成分であ
り必須である。１％未満では軟化点が高くなり焼き付け
が不充分になる。好ましくは３％以上である。２５％超
では膨張係数が大きくなる。また、白金るつぼ等の白金
含有容器を用いて溶解する場合、該白金含有容器が侵食
されやすくなる。好ましくは２３％以下である。Bi 2 O 3 is a component that lowers the softening point and is essential. If it is less than 1%, the softening point becomes high and the baking becomes insufficient. It is preferably at least 3%. If it exceeds 25%, the expansion coefficient becomes large. In addition, when a platinum-containing container such as a platinum crucible is used for melting, the platinum-containing container is easily corroded. It is preferably 23% or less.

【００１４】Ａｌ２Ｏ３は耐水性および耐酸性を向上さ
せる成分であり必須である。１％未満では耐水性または
耐酸性が低下する。２０％超では軟化点が高くなり焼き
付けが不充分になる。好ましくは１５％以下である。Al 2 O 3 is a component that improves water resistance and acid resistance and is essential. If it is less than 1%, water resistance or acid resistance is lowered. If it exceeds 20%, the softening point becomes high and the baking becomes insufficient. It is preferably 15% or less.

【００１５】ＴｉＯ２およびＺｒＯ２は耐酸性を向上さ
せる成分であり、少なくともいずれか１種を含有しなけ
ればならず、特にＴｉＯ２を含有することが好ましい。
ＴｉＯ２およびＺｒＯ２の合計が１％未満では耐酸性が
低下する。２０％超では軟化点が高くなり焼き付けが不
充分になる。好ましくは１７％以下である。TiO 2 and ZrO 2 are components that improve the acid resistance and must contain at least one of them, and particularly preferably contain TiO 2 .
If the total amount of TiO 2 and ZrO 2 is less than 1%, the acid resistance decreases. If it exceeds 20%, the softening point becomes high and the baking becomes insufficient. It is preferably 17% or less.

【００１６】Ｌｉ２Ｏ、Ｎａ２ＯおよびＫ２Ｏは軟化点
を低下させる成分であり、少なくともいずれか１種を含
有しなければならない。Ｌｉ２Ｏ、Ｎａ２ＯおよびＫ２
Ｏの含有量の合計が０．３％未満では軟化点が高くなり
焼き付けが不充分になる。好ましくは０．５％以上であ
る。２０％超では膨張係数が大きくなる。好ましくは１
５％以下である。Ｎａ２Ｏを含有する場合、その含有量
は、好ましくは０．１〜１５％、より好ましくは０．３
〜１３％である。Li 2 O, Na 2 O and K 2 O are components that lower the softening point and must contain at least one of them. Li 2 O, Na 2 O and K 2
If the total content of O is less than 0.3%, the softening point becomes high and the baking becomes insufficient. It is preferably at least 0.5%. If it exceeds 20%, the expansion coefficient becomes large. Preferably 1
It is 5% or less. When Na 2 O is contained, its content is preferably 0.1 to 15%, more preferably 0.3.
~ 13%.

【００１７】Ｐ２Ｏ５、Ｖ２Ｏ５およびＳｎＯ２は耐酸
性を向上させる成分であり、少なくともいずれか１種を
含有しなければならない。Ｐ２Ｏ５、Ｖ２Ｏ５およびＳ
ｎＯ ２の含有量の合計が０．１％未満では耐酸性が低下
する。好ましくは０．５％以上である。１０％超ではガ
ラス溶解時に失透するおそれがある。好ましくは５％以
下である。PTwoO5, VTwoO5And SnOTwoIs acid resistant
It is a component that improves the property, and at least one of
Must be included. PTwoO5, VTwoO5And S
nO TwoIf the total content of is less than 0.1%, the acid resistance decreases
To do. It is preferably at least 0.5%. If it exceeds 10%
May devitrify when lath is dissolved. Preferably 5% or more
Below.

【００１８】ＺｎＯは必須ではないが軟化点を低下させ
るために１０％まで含有してもよい。１０％超ではガラ
ス溶解時に失透するおそれがある。Ｆｅ２Ｏ３およびＣ
ｕＯはいずれも必須ではないがガラスを着色するために
合計で１０％まで含有してもよい。１０％超ではガラス
溶解時に失透するおそれがある。好ましくは５％以下で
ある。ZnO is not essential, but may be contained up to 10% in order to lower the softening point. If it exceeds 10%, the glass may be devitrified during melting. Fe 2 O 3 and C
uO is not essential, but may be contained up to 10% in total for coloring the glass. If it exceeds 10%, the glass may be devitrified during melting. It is preferably 5% or less.

【００１９】ＣｅＯ２は必須ではないが、白金含有容器
を用いて溶解する場合に該白金含有容器が侵食されるの
を防止するために１０％まで含有してもよい。１０％超
ではガラス溶解時に失透するおそれがある。好ましくは
５％以下である。Ｌａ２Ｏ３は必須ではないが耐水性ま
たは耐酸性を向上させるために１０％まで含有してもよ
い。１０％超ではガラス溶解時に失透するおそれがあ
る。好ましくは５％以下である。Ｆは必須ではないが軟
化点を低下させるために５％まで含有してもよい。５％
超ではガラス溶解時に失透するおそれがある。CeO 2 is not essential, but may be contained up to 10% in order to prevent corrosion of the platinum-containing container when it is dissolved using the platinum-containing container. If it exceeds 10%, the glass may be devitrified during melting. It is preferably 5% or less. La 2 O 3 is not essential, but may be contained up to 10% in order to improve water resistance or acid resistance. If it exceeds 10%, the glass may be devitrified during melting. It is preferably 5% or less. F is not essential, but may be contained up to 5% in order to lower the softening point. 5%
If it exceeds the above range, the glass may be devitrified during melting.

【００２０】無鉛ガラス粉末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。前記その他の成分の含有量の合計は１
０％以下であることが好ましい。The lead-free glass powder 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 1
It is preferably 0% or less.

【００２１】たとえば、前記その他の成分として、Ｍｇ
Ｏ、ＣａＯ、ＳｒＯ、ＢａＯ等をガラス溶融時の粘度を
低下させるために９％までの範囲で、好ましくは５％ま
での範囲で含有してもよい。また、ＣｏＯ、Ｃｒ
２Ｏ３、ＮｉＯ、ＭｎＯ、Ａｇ２Ｏ等の着色成分、Ｃｌ
等の軟化点を低下させる成分を必要に応じて含有しても
よい。なお、鉛は含有しない。For example, as the other component, Mg
O, CaO, SrO, BaO, etc. may be contained in the range of up to 9%, preferably up to 5% in order to reduce the viscosity when melting the glass. Also, CoO, Cr
2 O 3 , NiO, MnO, Ag 2 O and other coloring components, Cl
If necessary, a component that lowers the softening point may be contained. It does not contain lead.

【００２２】次に、無鉛ガラス粉末以外の成分について
説明する。耐熱顔料粉末は、紫外線を遮蔽し、また可視
光も遮蔽する成分であり必須である。１％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。６０
％超では焼き付けが不充分になる。耐熱顔料粉末とし
て、銅−クロム−マンガン複合酸化物、鉄−マンガン複
合酸化物、マグネタイト等の粉末を主成分とする黒色顔
料粉末、チタニア粉末等の白色顔料粉末、が例示され
る。Next, the components other than the lead-free glass powder will be described. The heat-resistant pigment powder is a component that shields ultraviolet rays and also visible light, and is essential. If it is less than 1%, the ultraviolet shielding effect or the visible light shielding effect becomes insufficient. 60
If it exceeds%, the baking becomes insufficient. Examples of the heat-resistant pigment powder include a black pigment powder containing copper-chromium-manganese composite oxide, iron-manganese composite oxide, magnetite and the like as a main component, and white pigment powder such as titania powder.

【００２３】耐火物フィラーは必須ではないが、前記焼
成体の強度を向上させるため、またはαを低下させるた
めに５９％まで含有してもよい。５９％超では焼き付け
が不充分になる。好ましくは５０％以下である。また、
耐火物フィラーを含有する場合、その含有量は、好まし
くは１０％以上、より好ましくは２０％以上である。The refractory filler is not essential, but may be contained up to 59% in order to improve the strength of the fired body or to reduce α. If it exceeds 59%, the baking will be insufficient. It is preferably 50% or less. Also,
When the refractory filler is contained, its content is preferably 10% or more, more preferably 20% or more.

【００２４】なお、耐火物フィラー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り、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、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
種以上の酸化物の粉末であることが好ましい。The refractory filler is a powder of an inorganic material such as oxides, borides and silicides having a melting point or glass transition point of 700 ° C. or higher, and α-alumina, α-quartz,
Zircon, cordierite, β-eucryptite,
Selected from the group consisting of forsterite, mullite, steatite, aluminum borate and quartz glass 1
It is preferably a powder of at least one oxide.

【００２５】本発明のセラミックカラー組成物は本質的
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、たとえばＳｉ粉末等を含有してもよ
い。なお、前記その他成分の含有量の合計は、好ましく
は５％以下である。The ceramic color composition of the present invention consists essentially of the above-mentioned components, but may contain other components, such as Si powder, as long as the object of the present invention is not impaired. The total content of the other components is preferably 5% or less.

【００２６】本発明の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は自動車の窓ガラスのセラミッ
クカラー層形成に好適であるがこれに限定されず、たと
えば、ガラスびん、ガラスコップ等のセラミックカラー
層形成にも使用できる。The ceramic color composition and the ceramic color paste of the present invention are suitable for forming a ceramic color layer on a window glass of an automobile, but are not limited thereto. For example, for forming a ceramic color layer on a glass bottle, a glass cup or the like. Can be used.

【００２７】[0027]

【実施例】表のＳｉＯ２からＦまでの欄に質量百分率表
示で示す組成となるように原料を調合、混合し、１２０
０〜１４００℃で白金るつぼを用いて１〜３時間溶解し
て溶融ガラスとし、該溶融ガラスを急冷してフレーク状
ガラスを得た、または該溶融ガラスを水砕して水砕ガラ
スを得た。次に、該フレーク状ガラスまたは該水砕ガラ
スをボールミルで粉砕して、質量平均粒径が１〜６μｍ
のガラス粉末を得た。[Examples] Raw materials were mixed and mixed so that the compositions shown in the mass percentages in the columns from SiO 2 to F in the table were mixed and mixed.
Molten glass was melted for 1 to 3 hours using a platinum crucible at 0 to 1400 ° C. to obtain molten glass, and the molten glass was rapidly cooled to obtain flaky glass, or the molten glass was water granulated to obtain granulated glass. . Next, the flaky glass or the water-crushed glass is crushed by a ball mill to have a mass average particle diameter of 1 to 6 μm.
Of glass powder was obtained.

【００２８】得られたガラス粉末、耐熱顔料、耐火物フ
ィラーを表に質量百分率表示で示すように調合、混合し
てセラミックカラー組成物を得た。例１〜８は実施例、
例９、１０は比較例である。耐熱顔料として、例１、
２、４、８、９、１０においては銅−クロム−マンガン
複合酸化物を主成分とする黒色顔料を、例３、５、６、
７においては鉄−マンガン複合酸化物を主成分とする黒
色顔料をそれぞれ使用した。The obtained glass powder, heat resistant pigment, and refractory filler were blended and mixed as shown in the table by the percentage by mass to obtain a ceramic color composition. Examples 1-8 are examples,
Examples 9 and 10 are comparative examples. Examples of heat-resistant pigments include
In Examples 2, 5, 8, and 6, black pigments containing copper-chromium-manganese composite oxide as a main component were used.
In No. 7, black pigments containing iron-manganese composite oxide as a main component were used.

【００２９】また、耐火物フィラーとして、例１におい
てはα−アルミナ粉末およびホウ酸アルミニウム粉末を
５０：５０の質量割合で混合したものを、例２、７にお
いてはコーディエライト粉末を、例３、８においてはジ
ルコン粉末を、例４、５においては石英ガラス粉末を、
例６、９においてはホウ酸アルミニウム粉末を、例１０
においてはα−アルミナ粉末をそれぞれ使用した。As the refractory filler, a mixture of α-alumina powder and aluminum borate powder in a mass ratio of 50:50 was used in Example 1, cordierite powder was used in Examples 2 and 7, and Example 3 was used. , 8 is zircon powder, Examples 4 and 5 are quartz glass powders,
In Examples 6 and 9, aluminum borate powder was used, and in Example 10
In the above, α-alumina powder was used.

【００３０】前記セラミックカラー組成物について、昇
温速度１０℃／分の条件でＤＴＡによりガラス転移点Ｔ
Ｇ（単位：℃）、軟化点ＴＳ（単位：℃）および結晶化
ピーク温度（単位：℃）を測定した。結果を表に示す。With respect to the above ceramic color composition, the glass transition point T was measured by DTA at a temperature rising rate of 10 ° C./min.
G (unit: ° C), softening point T S (unit: ° C) and crystallization peak temperature (unit: ° C) were measured. The results are shown in the table.

【００３１】また、前記セラミックカラー組成物をドラ
イプレス後７００℃に１５分間保持して焼成して得られ
た焼成体について、５０〜３５０℃における平均線膨張
係数α（単位：１０−７／℃）を測定した。結果を表に
示す。The average linear expansion coefficient α (unit: 10 −7 / ° C.) at 50 to 350 ° C. was obtained for the fired body obtained by holding the ceramic color composition at 700 ° C. for 15 minutes and firing it after dry pressing. ) Was measured. The results are shown in the table.

【００３２】また、前記焼成体の焼結性を次のようにし
て評価した。すなわち、焼成体を赤インクに５分間浸漬
後流水中に１分間保持して赤インクを除去し、赤インク
の焼成体への浸透の有無を目視観察によって調べた。例
１〜９については赤インクの浸透が認められず焼結性は
良好であったが、例１０については赤インクの焼成体表
面部分への残留すなわち浸透が認められ焼結性は不良で
あった。The sinterability of the fired body was evaluated as follows. That is, the fired body was immersed in the red ink for 5 minutes and then held in running water for 1 minute to remove the red ink, and the presence or absence of permeation of the red ink into the fired body was examined by visual observation. In Examples 1 to 9, the penetration of the red ink was not observed and the sinterability was good, but in Example 10, the red ink remained or penetrated to the surface portion of the fired body and the sinterability was poor. It was

【００３３】次に、前記セラミックカラー組成物８０質
量部に、質量百分率表示で１０％のエチルセルロースを
溶解したα−テルピネオール溶液２０質量部を加えて混
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。）とした。
このようにして得られたペーストを、厚さ３．５ｍｍ、
大きさ１０ｃｍ×１０ｃｍのソーダライムシリカガラス
板の全面にスクリーン印刷し、乾燥した。Next, to 80 parts by mass of the above ceramic color composition, 20 parts by mass of an α-terpineol solution in which 10% of ethyl cellulose in terms of mass percentage is dissolved is added and kneaded. The paste (hereinafter simply referred to as paste) was used.
The paste thus obtained has a thickness of 3.5 mm,
A soda lime silica glass plate having a size of 10 cm × 10 cm was screen-printed on the entire surface and dried.

【００３４】ペーストが塗布された前記ガラス板を７０
０℃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。The glass plate coated with the paste 70
After holding at 0 ° C. for 5 minutes for firing, it was cooled to room temperature to obtain a glass plate with a ceramic color layer.

【００３５】このセラミックカラー層付ガラス板から大
きさ２ｃｍ×２ｃｍのガラス板を切り出し、耐硫酸性お
よび耐硫酸銅性（質量減少率）を次のようにして評価・
測定した。 耐硫酸性：温度が約２０℃、質量百分率表示の濃度が１
０％である硫酸中に前記セラミックカラー層付ガラス板
を５時間浸漬後取り出し、流水で洗浄した。次に、セラ
ミックカラー層が焼き付けられていない面から当該ガラ
ス板を目視観察し、前記硫酸への浸漬による色調変化の
有無を調べた。例１〜９については色調変化は認められ
ず耐硫酸性は良好であったが、例１０については色調変
化が認められ耐硫酸性は良好ではなかった。A glass plate having a size of 2 cm × 2 cm was cut out from this glass plate provided with a ceramic color layer, and sulfuric acid resistance and copper sulfate resistance (mass reduction rate) were evaluated as follows.
It was measured. Sulfuric acid resistance: Temperature is about 20 ° C, concentration in mass percentage display is 1
The glass plate with the ceramic color layer was immersed in 0% sulfuric acid for 5 hours, then taken out and washed with running water. Next, the glass plate was visually observed from the surface on which the ceramic color layer was not baked, and examined for a change in color tone due to the immersion in the sulfuric acid. In Examples 1 to 9, no change in color tone was observed and the sulfuric acid resistance was good, but in Example 10, a change in color tone was observed and the sulfuric acid resistance was not good.

【００３６】耐硫酸銅性（質量減少率）：前記セラミッ
クカラー層付ガラス板の質量Ｗ１を測定後、温度が６０
℃、質量百分率表示の濃度が１０％である硫酸銅水溶液
中に３時間浸漬し、取り出した。該取り出したガラス板
の質量Ｗ２と前記Ｗ１とから質量減少率（単位：％）を
次式により算出した。結果を表に示す。 質量減少率＝１００×（Ｗ１−Ｗ２）／Ｗ１ 質量減少率は０．１％以下であることが好ましい。Copper sulfate resistance (mass reduction rate): After measuring the mass W 1 of the glass plate with the ceramic color layer, the temperature was 60.
It was immersed in an aqueous solution of copper sulfate having a concentration of 10% at 10 ° C. for 10 minutes, and then taken out. A mass reduction rate (unit:%) was calculated from the mass W 2 of the taken-out glass plate and the W 1 by the following formula. The results are shown in the table. Mass reduction rate = 100 × (W 1 −W 2 ) / W 1 The mass reduction rate is preferably 0.1% or less.

【００３７】[0037]

【表１】 [Table 1]

【００３８】[0038]

【発明の効果】本発明によれば、耐酸性が優れており酸
性雨水によるセラミックカラー層の白化等の変色が起り
にくく、かつ、鉛を含有していないセラミックカラー層
が形成されたガラス板が得られる。According to the present invention, a glass plate having excellent acid resistance, hardly causing discoloration such as whitening of the ceramic color layer due to acid rainwater, and having a ceramic color layer containing no lead is provided. can get.

フロントページの続き Ｆターム(参考） 4G059 AA01 AB05 AC08 CA01 CA08 CB09 4G062 AA09 BB01 DA03 DA04 DA05 DB03 DB04 DC03 DC04 DD01 DD02 DD03 DE01 DE02 DE03 DF01 EA01 EA02 EA03 EA04 EA10 EB01 EB02 EB03 EB04 EC01 EC02 EC03 EC04 ED01 EE01 EF01 EG01 FA01 FA10 FB01 FB02 FB03 FB04 FC01 FC02 FC03 FC04 FD01 FE01 FE02 FE03 FF01 FF02 FF03 FG01 FH01 FJ01 FK01 FK02 FK03 FL01 FL02 FL03 GA03 GA04 GB01 GC01 GD01 GE01 GE02 GE03 HH01 HH03 HH04 HH05 HH07 HH09 HH11 HH12 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM01 MM07 NN05 NN34 PP01 PP02 PP03 PP06 PP18 Continued front page    F-term (reference) 4G059 AA01 AB05 AC08 CA01 CA08                       CB09                 4G062 AA09 BB01 DA03 DA04 DA05                       DB03 DB04 DC03 DC04 DD01                       DD02 DD03 DE01 DE02 DE03                       DF01 EA01 EA02 EA03 EA04                       EA10 EB01 EB02 EB03 EB04                       EC01 EC02 EC03 EC04 ED01                       EE01 EF01 EG01 FA01 FA10                       FB01 FB02 FB03 FB04 FC01                       FC02 FC03 FC04 FD01 FE01                       FE02 FE03 FF01 FF02 FF03                       FG01 FH01 FJ01 FK01 FK02                       FK03 FL01 FL02 FL03 GA03                       GA04 GB01 GC01 GD01 GE01                       GE02 GE03 HH01 HH03 HH04                       HH05 HH07 HH09 HH11 HH12                       HH13 HH15 HH17 HH20 JJ01                       JJ03 JJ05 JJ07 JJ10 KK01                       KK03 KK05 KK07 KK10 MM01                       MM07 NN05 NN34 PP01 PP02                       PP03 PP06 PP18

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】質量百分率表示で本質的に、無鉛ガラス粉
末 ４０〜９０％、耐熱顔料粉末１〜６０％、耐火物フ
ィラー ０〜５９％、からなるセラミックカラー組成物
であって、無鉛ガラス粉末が、下記成分基準の質量百分
率表示で本質的に、 ＳｉＯ２ １〜５０％、 Ｂ２Ｏ３ １〜３０％、 Ｂｉ２Ｏ３ １〜２５％、 Ａｌ２Ｏ３ １〜２０％、 ＴｉＯ２＋ＺｒＯ２ １〜２０％、 Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０．３〜２０％、 Ｐ２Ｏ５＋Ｖ２Ｏ５＋ＳｎＯ２ ０．１〜１０％、 ＺｎＯ ０〜１０％、 Ｆｅ２Ｏ３＋ＣｕＯ ０〜１０％、 ＣｅＯ２ ０〜１０％、 Ｌａ２Ｏ３ ０〜１０％、 Ｆ ０〜５％、 からなるセラミックカラー組成物。1. A ceramic color composition essentially consisting of 40 to 90% of lead-free glass powder, 1 to 60% of heat-resistant pigment powder, and 0 to 59% of refractory filler, which is a lead-free glass powder. However, essentially, in terms of mass percentages based on the following components, SiO 2 1 to 50%, B 2 O 3 1 to 30%, Bi 2 O 3 1 to 25%, Al 2 O 3 1 to 20%, TiO 2 + ZrO 2 1 to 20%, Li 2 O + Na 2 O + K 2 O 0.3 to 20%, P 2 O 5 + V 2 O 5 + SnO 2 0.1 to 10%, ZnO 0 to 10%, Fe 2 O 3 + CuO 0. ~10%, CeO 2 0~10%, La 2 O 3 0~10%, F 0~5%, the ceramic color composition comprising. 【請求項２】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、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。2. The refractory filler is selected from the group consisting of α-alumina, α-quartz, zircon, cordierite, β-eucryptite, forsterite, mullite, steatite, aluminum borate and quartz glass. The ceramic color composition according to claim 1, which is a powder of one or more oxides. 【請求項３】請求項１または２に記載のセラミックカラ
ー組成物であって、該セラミックカラー組成物を焼成し
て得られる焼成体の５０〜３５０℃における平均線膨張
係数が７０×１０−７〜９０×１０−７／℃であること
を特徴とするセラミックカラー組成物。3. The ceramic color composition according to claim 1, wherein the fired body obtained by firing the ceramic color composition has an average linear expansion coefficient at 50 to 350 ° C. of 70 × 10 −7. The ceramic color composition is characterized in that it is 90 × 10 −7 / ° C. 【請求項４】バインダ、有機溶剤および請求項１、２ま
たは３に記載のセラミックカラー組成物を含有するセラ
ミックカラーペースト。4. A ceramic color paste containing a binder, an organic solvent and the ceramic color composition according to claim 1, 2 or 3. 【請求項５】請求項４に記載のセラミックカラーペース
トをガラス板に塗布し、焼成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。5. A method for producing a glass plate with a ceramic color layer, which comprises applying the ceramic color paste according to claim 4 to a glass plate and baking the glass plate.
JP2001210999A 2001-07-11 2001-07-11 Ceramic color composition, ceramic color paste and method for producing glass board fitted with ceramic color layer Pending JP2003026444A (en)

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JP2009078955A (en) * 2007-09-27 2009-04-16 Okuno Chem Ind Co Ltd Lead-free ceramic color composition
US7585798B2 (en) 2003-06-27 2009-09-08 Yamato Electronic Co., Ltd. Lead-free glass material for use in sealing and, sealed article and method for sealing using the same
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WO2011132753A1 (en) * 2010-04-21 2011-10-27 旭硝子株式会社 Method for producing glass member, and planar lens and glass paste
JP2011230973A (en) * 2010-04-30 2011-11-17 Nippon Electric Glass Co Ltd Bismuth-based non-lead glass and composite material
CN103011605A (en) * 2012-12-10 2013-04-03 彩虹集团公司 Lead-free glass powder for automobile glass printing ink and preparation method of lead-free glass powder
CN110627368A (en) * 2019-08-15 2019-12-31 中国科学院西安光学精密机械研究所 Beta-eucryptite/mullite fiber/glass-based composite material and preparation method thereof
CN116606074A (en) * 2023-04-28 2023-08-18 乾宇微纳技术(深圳)有限公司 Glass powder applied to medium slurry and preparation method thereof

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US7425518B2 (en) * 2003-02-19 2008-09-16 Yamato Electronic Co., Ltd. Lead-free glass material for use in sealing and, sealed article and method for sealing using the same
US7585798B2 (en) 2003-06-27 2009-09-08 Yamato Electronic Co., Ltd. Lead-free glass material for use in sealing and, sealed article and method for sealing using the same
EP2045218A1 (en) * 2007-09-13 2009-04-08 Denseo GmbH Glaze for coating of surfaces
US7846858B2 (en) 2007-09-13 2010-12-07 Denseo Gmbh Glaze for annealing surfaces
JP2009078955A (en) * 2007-09-27 2009-04-16 Okuno Chem Ind Co Ltd Lead-free ceramic color composition
JP2011084461A (en) * 2009-09-15 2011-04-28 Nippon Electric Glass Co Ltd Glass composition for forming resistor
WO2011132753A1 (en) * 2010-04-21 2011-10-27 旭硝子株式会社 Method for producing glass member, and planar lens and glass paste
JP2011230973A (en) * 2010-04-30 2011-11-17 Nippon Electric Glass Co Ltd Bismuth-based non-lead glass and composite material
CN103011605A (en) * 2012-12-10 2013-04-03 彩虹集团公司 Lead-free glass powder for automobile glass printing ink and preparation method of lead-free glass powder
CN110627368A (en) * 2019-08-15 2019-12-31 中国科学院西安光学精密机械研究所 Beta-eucryptite/mullite fiber/glass-based composite material and preparation method thereof
CN116606074A (en) * 2023-04-28 2023-08-18 乾宇微纳技术(深圳)有限公司 Glass powder applied to medium slurry and preparation method thereof

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