JPH09255359A - Composition for forming coating film - Google Patents

Composition for forming coating film

Info

Publication number
JPH09255359A
JPH09255359A JP7059996A JP7059996A JPH09255359A JP H09255359 A JPH09255359 A JP H09255359A JP 7059996 A JP7059996 A JP 7059996A JP 7059996 A JP7059996 A JP 7059996A JP H09255359 A JPH09255359 A JP H09255359A
Authority
JP
Japan
Prior art keywords
glass
composition
powder
film
coating film
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
JP7059996A
Other languages
Japanese (ja)
Inventor
Tsuneo Manabe
恒夫 真鍋
Kazuo Harada
和男 原田
Original Assignee
Asahi Glass Co Ltd
旭硝子株式会社
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, 旭硝子株式会社 filed Critical Asahi Glass Co Ltd
Priority to JP7059996A priority Critical patent/JPH09255359A/en
Publication of JPH09255359A publication Critical patent/JPH09255359A/en
Pending legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for forming coating film, which has excellent durability in the outdoors due to the extremely excellent sulfuric acid resistant and is easy to recycle a plate glass due to being readily soluble to nitric acid or hydrochloric acid, by using a specific low m.p. glass containing no lead. SOLUTION: The composition for forming coating film is a composition for forming a coating film by applying on a base material and firing. And the composition consists substantially of 50-100wt.% glass powder, 0-50wt.% colored heat resistant pigment powder and 0-50wt.% noncolored low expansion refractory filler power as inorganic components and the composition of the glass basing on oxide as a reference by wt.% is constituted substantially of 3-30 SiO2 , 6-45 B2 O3 , 38-63 CaO+SrO+BaO, 4-18 Li2 O+Na2 O+K2 O. In the case of applying to a ceramic color coating film, the inorganic component preferably consists substantially of the glass powder of 65-95, the colored heat resistant pigment powder of 5-35 and the noncolored lower expansion refractory filler powder of 0-35.

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、実質的に鉛を含ま
ず耐硫酸性の高い被膜形成用組成物、特にそれを用いた
セラミックカラー用の組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition containing substantially no lead and having high sulfuric acid resistance, and more particularly to a composition for a ceramic color using the same.
【0002】[0002]
【従来の技術】従来より、耐熱性基材にペースト化した
被膜形成用組成物を塗布し、焼成し焼き付けて被膜形成
し、装飾性に優れた材料を得る方法が知られている。
2. Description of the Related Art Heretofore, there has been known a method in which a paste-forming film-forming composition is applied to a heat-resistant base material, followed by baking and baking to form a film, thereby obtaining a material excellent in decorativeness.
【0003】特に、自動車の窓ガラス周辺部にペースト
化したセラミックカラー組成物を、スクリーン印刷し乾
燥した後、曲げ加工のためのガラス板加熱工程にて焼き
付けた自動車用セラミックカラーペーストが普及してい
る。このセラミックカラーペーストはガラス板周辺部に
焼き付けることにより、着色不透明層を形成し、ウレタ
ンシーラントの紫外線による劣化防止または電熱線の端
子等が車外から透視できないようにする目的で用いられ
ている。
In particular, a ceramic color paste for automobiles, which is obtained by screen-printing and drying a ceramic color composition pasted on the periphery of a window glass of an automobile and then baking it in a glass plate heating step for bending, has become popular. There is. This ceramic color paste is used for the purpose of forming a colored opaque layer by baking it on the periphery of a glass plate to prevent the urethane sealant from being deteriorated by ultraviolet rays or to prevent terminals of heating wires and the like from being seen through from outside the vehicle.
【0004】[0004]
【発明が解決しようとする課題】これらの用途の被膜形
成用組成物、特にソーダライムシリケートガラス等のガ
ラス板基材への焼き付けに用いられる組成物は、基材の
曲げ成形時や基材を物理強化する熱処理時に、同時に焼
き付けることが望ましいため、500〜700℃の温度
で焼き付けられる材料であることが望ましい。このよう
な用途には現在一般に鉛を主成分として含有する低融点
ガラスに種々の耐熱性着色顔料を混ぜたものが知られて
いる。しかし、これまで主として用いられてきた鉛を含
有する素材については、環境保護などの見地から代替物
の開発が望まれている。
The film forming composition for these uses, particularly the composition used for baking onto a glass plate substrate such as soda lime silicate glass, is used for bending the substrate or for forming the substrate. Since it is desirable to bake at the same time during the heat treatment for physical strengthening, it is desirable that the material be bake at a temperature of 500 to 700 ° C. For such applications, a mixture of low melting point glass containing lead as a main component and various heat resistant color pigments is generally known at present. However, for lead-containing materials that have been mainly used up to now, development of alternatives is desired from the viewpoint of environmental protection.
【0005】また、最近は環境汚染による酸性雨の影響
が顕著になってきており、被膜形成用組成物を焼き付け
て被膜形成した材料を屋外で使用すると、この被膜が酸
性雨により浸食され、変色を起こすという問題が顕在化
しつつある。酸性雨の主成分は硫酸であることから、耐
硫酸性に優れた被膜形成用組成物が強く望まれている。
しかし、比較的耐硫酸性に優れた低融点ガラスとして
は、前述の鉛含有ガラスしか知られていない。
Recently, the influence of acid rain due to environmental pollution has become remarkable, and when a film-formed composition by baking a film-forming composition is used outdoors, this film is eroded by acid rain and discolored. The problem of causing Since the main component of acid rain is sulfuric acid, a film-forming composition having excellent sulfuric acid resistance is strongly desired.
However, only the above-mentioned lead-containing glass is known as a low melting point glass having relatively excellent sulfuric acid resistance.
【0006】一方、板ガラス特に自動車用ガラスは、使
用後にリサイクルされ再度ガラス板原料として用いられ
ることが検討されている。しかし、上記のように鉛含有
ガラスを含む被膜形成用組成物で被膜形成、装飾した板
ガラスは、この被膜を化学的処理により板ガラスと分離
することが困難であるため、リサイクルが困難である場
合が多い。
On the other hand, it is considered that flat glass, especially glass for automobiles, is recycled after use and used again as a glass plate raw material. However, as described above, a plate glass formed with a film-forming composition containing a lead-containing glass and decorated is difficult to separate from the plate glass by a chemical treatment of this film, and thus it may be difficult to recycle. Many.
【0007】[0007]
【課題を解決するための手段】本発明者は鉛を含有しな
い特定組成の低融点ガラスを使用することにより、耐硫
酸性に非常に優れるために屋外での耐久性に優れ、しか
も硝酸、塩酸には容易に溶解することによりガラス板の
リサイクルを行うのに容易な被膜形成用組成物を見いだ
した。
The present inventor uses a low-melting-point glass having a specific composition containing no lead, so that it is excellent in sulfuric acid resistance and therefore excellent in outdoor durability, and further nitric acid and hydrochloric acid are used. As a result, they have found a composition for forming a film, which can be easily dissolved to recycle a glass plate.
【0008】すなわち、本発明は、基材上に塗布、焼成
することにより、被膜を形成するための組成物であっ
て、無機成分が実質的に、ガラス粉末50〜100重量
%、着色耐熱性顔料粉末0〜50重量%、非着色低膨張
耐火物フィラー粉末0〜50重量%からなり、前記ガラ
スの組成が、酸化物基準の重量%で、 SiO2 3〜30%、 B23 6〜45%、 CaO+SrO+BaO 38〜63%、 Li2 O+Na2 O+K2 O 4〜18%、 から実質的になる被膜形成用組成物である。
That is, the present invention is a composition for forming a film by coating and baking on a substrate, wherein the inorganic component is substantially 50 to 100% by weight of glass powder, and coloring heat resistance. It is composed of 0 to 50% by weight of a pigment powder and 0 to 50% by weight of a non-colored low expansion refractory filler powder, and the composition of the glass is SiO 2 3 to 30% and B 2 O 3 6 based on the oxide. ˜45%, CaO + SrO + BaO 38 to 63%, Li 2 O + Na 2 O + K 2 O 4 to 18%.
【0009】本発明の被膜形成用組成物は、500〜7
00℃の焼成で基材と強固に結合され、通常の窓等に使
用されるガラス板、すなわち、SiO2 :68〜74重
量%、Al23 :0.5〜2重量%、CaO:7〜1
2重量%、MgO:2〜5重量%、Na2 O:9〜15
重量%の組成を有するソーダライムシリケートガラス板
に焼き付けられるのに特に適する。
The film-forming composition of the present invention comprises 500 to 7
A glass plate that is firmly bonded to a base material by firing at 00 ° C. and is used for an ordinary window or the like, that is, SiO 2 : 68 to 74% by weight, Al 2 O 3 : 0.5 to 2% by weight, CaO: 7-1
2% by weight, MgO: 2 to 5% by weight, Na 2 O: 9 to 15
It is particularly suitable for being baked on soda-lime silicate glass plates having a composition of wt.
【0010】[0010]
【発明の実施の形態】本発明の被膜形成用組成物に用い
るガラスは、その組成が、酸化物基準の重量%で実質的
に、SiO2 :3〜30%、B23 :6〜45%、C
aO+SrO+BaO:38〜63%、Li2 O+Na
2 O+K2 O:4〜18%の範囲のものである。
BEST MODE FOR CARRYING OUT THE INVENTION The glass used in the composition for forming a coating film of the present invention is such that the composition is substantially SiO 2 : 3 to 30% and B 2 O 3 : 6 to 45%, C
aO + SrO + BaO: 38~63% , Li 2 O + Na
2 O + K 2 O: in the range of 4 to 18%.
【0011】SiO2 の含有量が3重量%(以下、単に
%という)に満たないとガラスの耐水性が低下し、30
%を超えると耐硫酸性が低下する。好ましくは、上記範
囲中6〜26%である。
If the content of SiO 2 is less than 3% by weight (hereinafter simply referred to as "%"), the water resistance of the glass is lowered and
If it exceeds%, the sulfuric acid resistance decreases. Preferably, it is 6 to 26% in the above range.
【0012】B23 の含有量が6%に満たないとガラ
ス化が困難になり、45%を超えるとガラス耐水性や耐
硫酸性が低下する。好ましくは、上記範囲中8〜38%
である。
If the B 2 O 3 content is less than 6%, vitrification becomes difficult, and if it exceeds 45%, the water resistance and sulfuric acid resistance of the glass deteriorate. Preferably 8 to 38% in the above range
It is.
【0013】CaO、SrO、BaOは、非常に高い耐
硫酸性を得るために、このうちの少なくとも1種の成分
が必須である。CaO、SrO、BaOの含有量が、合
量で、38%に満たないと耐硫酸性が低下する。63重
量%を超えると安定にガラスが製造できないおそれがあ
る。好ましくは、合量で、上記範囲中39〜56%であ
る。
CaO, SrO and BaO require at least one of these components in order to obtain very high sulfuric acid resistance. If the total content of CaO, SrO, and BaO is less than 38%, the sulfuric acid resistance decreases. If it exceeds 63% by weight, glass may not be stably produced. Preferably, the total amount is 39 to 56% in the above range.
【0014】また、焼成後の被膜に光沢を出すために
は、CaO、SrO、BaOのうち2種以上を併用する
ことが好ましく、艶消し状にするためにはCaO、Sr
O、BaOのどれか1成分を単独で用いることが好まし
い。
It is preferable to use two or more of CaO, SrO, and BaO in combination in order to give gloss to the coating after firing, and to make it matte, CaO and Sr.
It is preferable to use one of O and BaO alone.
【0015】Li2 O、Na2 O、K2 Oの含有量が、
合量で、4%に満たないとガラスの軟化温度が高くなっ
て、500〜700℃で焼き付けにくくなり、18%を
超えるとガラスの耐水性が低下するおそれがある。これ
ら成分は、耐水性を向上するために、2種以上併用する
ことが好ましい。より好ましくは、合量で、上記範囲中
5〜14%である。
The contents of Li 2 O, Na 2 O and K 2 O are
If the total amount is less than 4%, the softening temperature of the glass becomes high, making it difficult to bake at 500 to 700 ° C., and if it exceeds 18%, the water resistance of the glass may decrease. These components are preferably used in combination of two or more in order to improve water resistance. More preferably, the total amount is 5 to 14% in the above range.
【0016】このガラスには上記成分の他に、Al2
3 、La23 、TiO2 、ZrO2 、SnO2 、Mg
O、ZnO、Bi23 、P25 、CeO2 等の成分
を焼結温度、耐水性や熱膨張係数等の調整に、ガラスの
均質性を損なわない範囲で適宜含有させうる。
In addition to the above components, this glass contains Al 2 O.
3 , La 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , Mg
Ingredients such as O, ZnO, Bi 2 O 3 , P 2 O 5 , and CeO 2 may be appropriately contained in adjusting the sintering temperature, water resistance, thermal expansion coefficient, etc. within a range not impairing the homogeneity of the glass.
【0017】また、このガラスには鉛を実質的に含有し
ないので、環境汚染の防止やリサイクルなどの観点でも
有利である。
Further, since this glass does not substantially contain lead, it is advantageous from the viewpoint of preventing environmental pollution and recycling.
【0018】本発明の被膜形成用組成物では、以上説明
したような組成のガラスの粉末を必須成分とする。ガラ
ス粉末が、本発明の被膜形成用組成物の無機成分中で、
50%未満では500〜700℃でガラス板に組成物を
焼き付けることが難しくなるおそれがある。
In the film-forming composition of the present invention, glass powder having the above-described composition is an essential component. Glass powder, in the inorganic component of the film-forming composition of the present invention,
If it is less than 50%, it may be difficult to bake the composition on a glass plate at 500 to 700 ° C.
【0019】本発明の被膜形成用組成物において、着色
耐熱性顔料粉末は必須ではないが、装飾用として用いる
場合などの着色用に使用できる。ただし、50重量%を
超えるとガラスの量が少なくなりすぎ、500〜700
℃の温度で基材に焼き付けることが難しくなる。かかる
着色耐熱性顔料としては、焼き付け温度の500〜70
0℃の耐熱性を有していれば特に制限はなく、目的の色
調に応じて適宜選択される。たとえば、目的の色調が黒
色の場合、鉄マンガンの酸化物を主体とするもの、銅ク
ロムの酸化物を主体とするもの、コバルトクロムの酸化
物を主体とするものなどが選ばれる。
In the film-forming composition of the present invention, the colored heat-resistant pigment powder is not essential, but it can be used for coloring such as when used for decoration. However, when the amount exceeds 50% by weight, the amount of glass becomes too small, and 500 to 700
It becomes difficult to bake on a substrate at a temperature of ° C. Such colored heat-resistant pigment has a baking temperature of 500 to 70.
There is no particular limitation as long as it has a heat resistance of 0 ° C., and it is appropriately selected according to the intended color tone. For example, when the target color tone is black, those mainly containing an oxide of iron manganese, those mainly containing an oxide of copper chromium, those mainly containing an oxide of cobalt chromium are selected.
【0020】非着色低膨張耐火物フィラー粉末も、必須
ではないが、含有することにより、熱膨張係数の制御や
焼き付けた基材の強度低下の抑制を行うことができる。
ただし、その含有量が被膜形成用組成物中で50%を超
えるとガラス分が少なくなりすぎ、500〜700℃の
焼成温度で基材に焼き付けることが難しくなる。低膨張
耐火物フィラーとは、その室温〜350℃の熱膨張係数
が70×10-7/℃以下のものであり、具体的には、α
−アルミナ、ジルコン、コ−ディエライト、チタン酸ア
ルミニウム、ムライト、シリカ、β−ユークリプタイ
ト、β−スポジュメンおよびβ−石英固溶体が例示され
る。これらのうちの1種を単独で使用してもよく、また
は2種以上を併用してもよい。
The non-colored low expansion refractory filler powder is also not essential, but its inclusion can control the coefficient of thermal expansion and suppress the reduction in strength of the baked substrate.
However, if its content exceeds 50% in the film-forming composition, the glass content becomes too small, and it becomes difficult to bake it on the substrate at a firing temperature of 500 to 700 ° C. The low expansion refractory filler has a thermal expansion coefficient of 70 × 10 −7 / ° C. or less at room temperature to 350 ° C., and specifically, α
Examples are alumina, zircon, cordierite, aluminum titanate, mullite, silica, β-eucryptite, β-spodumene and β-quartz solid solution. One of these may be used alone, or two or more may be used in combination.
【0021】なお、前記着色耐熱性顔料の室温〜350
℃の線膨張係数が70×10-7/℃以下であれば、その
着色耐熱性顔料も低膨張耐火物フィラーの役割を同時に
果たすことができる。
The temperature of the colored heat-resistant pigment is from room temperature to 350.
When the coefficient of linear expansion at 70 ° C. is 70 × 10 −7 / ° C. or less, the colored heat-resistant pigment can also serve as a low expansion refractory filler.
【0022】本発明の被膜形成用組成物は、500〜7
00℃の焼成温度で基材に焼き付けることができ、これ
により形成された被膜は、耐硫酸性が高く、一方で、塩
酸に易溶である。
The film forming composition of the present invention comprises 500 to 7
It can be baked onto a substrate at a baking temperature of 00 ° C., and the coating film formed thereby has high sulfuric acid resistance while being easily soluble in hydrochloric acid.
【0023】本発明の被膜形成用組成物を、特に、車両
の窓ガラスの周縁部にセラミックカラー被膜として形成
して用いる場合、使用するガラス粉末は、前述の組成範
囲のものを使用できる。ただし、ガラスの曲げ成形を被
膜の焼成と同時に行う場合には、CaO、SrO、Ba
Oはいずれか1成分を単独で用いることが好ましい。こ
うすると、曲げ成形時の型との付着性が低く、曲げ成形
の生産性を高めうる。
When the composition for forming a coating film of the present invention is used by being formed as a ceramic color coating film on the peripheral portion of a window glass of a vehicle, the glass powder used may have the above composition range. However, if the glass is bent and formed at the same time as the firing of the coating, CaO, SrO, Ba
It is preferable to use any one component of O alone. In this case, the adhesiveness to the mold during bending is low, and the productivity of bending can be improved.
【0024】セラミックカラー被膜用途の被膜形成用組
成物としては、無機成分が実質的に、ガラス粉末65〜
95%、着色耐熱性顔料粉末5〜35%、非着色低膨張
耐火物フィラー粉末0〜35%からなるようにすること
が好ましい。
In the film-forming composition for use in the ceramic color film, the inorganic component is substantially contained in the glass powder 65-.
95%, colored heat resistant pigment powder 5 to 35%, and non-colored low expansion refractory filler powder 0 to 35% are preferable.
【0025】この場合、窓ガラスのウレタンシーラント
の劣化を防止するために透過光を遮蔽する必要があり、
着色耐熱性顔料粉末が必須となる。この着色耐熱性顔料
の含有量が組成物の無機成分中5%未満では所望の濃さ
が得られない。また、ガラス粉末は、500〜700℃
の温度で被膜形成用組成物を基材に強固に焼き付けるた
め、組成物中の無機成分の65%以上を占めることが好
ましい。
In this case, it is necessary to block the transmitted light in order to prevent the deterioration of the urethane sealant of the window glass,
Colored heat resistant pigment powder is essential. If the content of the colored heat resistant pigment is less than 5% in the inorganic component of the composition, the desired strength cannot be obtained. Further, the glass powder is 500 to 700 ° C.
Since the film-forming composition is strongly baked on the substrate at the temperature of, it is preferable that the composition occupy 65% or more of the inorganic components in the composition.
【0026】また、非着色低膨張耐火物フィラー粉末に
ついては、必須ではないが、5%以上含有すると、基材
の強度を向上させうるので好ましい。
The non-colored low expansion refractory filler powder is not essential, but it is preferable to contain it in an amount of 5% or more because the strength of the base material can be improved.
【0027】上記観点により、充分なセラミックカラー
被膜強度、基材強度、着色の程度を得るためには、被膜
形成用組成物の無機成分が実質的に、ガラス粉末65〜
88%、着色耐熱性顔料粉末7〜30%、非着色低膨張
耐火物フィラー粉末5〜28%からなるようにすること
が特に好ましい。
From the above viewpoint, in order to obtain sufficient ceramic color coating film strength, substrate strength, and degree of coloring, the inorganic component of the film-forming composition is substantially glass powder 65-.
It is particularly preferable that the composition comprises 88%, colored heat-resistant pigment powder 7 to 30%, and non-colored low expansion refractory filler powder 5 to 28%.
【0028】なお、セラミックカラー被膜形成用では、
本発明の被膜形成用組成物全量中に0〜10重量%の範
囲で金属またはホウ化物、ケイ化物を、着色剤またはガ
ラス曲げ型に対する離型材の目的で導入してもよい。1
0重量%を超えるとガラス板を曲げ加工する温度でガラ
ス板に焼き付けることが難しくなるおそれがある。こう
した金属、ホウ化物またはケイ化物を構成する金属とし
ては、Ni、Sn、Ti、Mn、Fe、Cu、Ag、L
a、Zr、Co、Mo、Cr、Ceが例示される。
For forming a ceramic color film,
A metal, a boride, or a silicide may be introduced in the range of 0 to 10% by weight in the total amount of the film-forming composition of the present invention for the purpose of a colorant or a release agent for a glass bending mold. 1
If it exceeds 0% by weight, it may be difficult to bake the glass plate at a temperature for bending the glass plate. Examples of such metals, metals forming borides or silicides include Ni, Sn, Ti, Mn, Fe, Cu, Ag and L.
Examples include a, Zr, Co, Mo, Cr, and Ce.
【0029】本発明の被膜形成用組成物について、各材
料の粉末の重量平均径については特に限定はないが、ス
クリーン印刷で塗布する場合には、0.1〜10μmの
範囲にすることが好ましい。重量平均径が0.1μmよ
り小さいものは実質的に生産性が悪く、高価となるた
め、一方、10μmより大きいと、ペーストの印刷性が
悪くなるのでいずれもスクリーン印刷には適さない。望
ましくは1〜6μmである。
In the composition for forming a film of the present invention, the weight average diameter of the powder of each material is not particularly limited, but when it is applied by screen printing, it is preferably in the range of 0.1 to 10 μm. . If the weight average diameter is smaller than 0.1 μm, the productivity is substantially low and the cost is high. On the other hand, if the weight average diameter is larger than 10 μm, the printability of the paste is deteriorated, and neither is suitable for screen printing. It is preferably 1 to 6 μm.
【0030】本発明の被膜形成用組成物を基材に塗布す
るためには、通常、上記被膜形成用組成物の無機成分に
有機ビヒクルを含有させペースト化する。有機ビヒクル
としては、通常使用されるエチルセルロース、アクリル
樹脂、スチレン樹脂、フェノール樹脂またはブチラール
樹脂等の高分子をα−テルピネオール、ブチルカルビト
ールアセテート、フタル酸エステル等の溶媒に溶解させ
たものが使用される。
In order to apply the coating film forming composition of the present invention to a substrate, an organic vehicle is usually added to the inorganic component of the coating film forming composition to form a paste. As the organic vehicle, those obtained by dissolving a commonly used polymer such as ethyl cellulose, acrylic resin, styrene resin, phenol resin or butyral resin in a solvent such as α-terpineol, butyl carbitol acetate, phthalate ester are used. It
【0031】次いで、ペースト化した被膜形成用組成物
を所定の基材の所望部位にスクリーン印刷等の塗布手段
により塗布する。基材としては、500〜700℃の耐
熱性を有するものであれば特に限定されず、通常のセラ
ミック、ガラス、金属に使用できるが、この焼成温度で
曲げ加工や物理強化を行うソーダライムシリケート系の
板ガラスに使用するのが経済的で特に適する。
Next, the pasted film-forming composition is applied to a desired portion of a predetermined substrate by an application means such as screen printing. The base material is not particularly limited as long as it has a heat resistance of 500 to 700 ° C., and it can be used for ordinary ceramics, glass, and metal, but is a soda lime silicate-based material that is bent and physically strengthened at this firing temperature. It is economical and particularly suitable for use in the plate glass of.
【0032】次いで、かかるペーストを塗布した基材
は、乾燥され、次いで加熱炉に搬入され加熱される。こ
の温度域は500〜700℃であり、この温度で被膜形
成用組成物の無機成分が基材に融着する。
Next, the base material coated with such paste is dried, then carried into a heating furnace and heated. This temperature range is 500 to 700 ° C., and at this temperature, the inorganic components of the film-forming composition fuse to the substrate.
【0033】自動車用ガラスのセラミックカラー被膜形
成に本発明の被膜形成用組成物が用いられる場合、ペー
ストが塗布されたガラス板は、500〜700℃の温度
に保持され、被膜形成用組成物の無機成分がガラス板に
焼き付けられ、ガラス板は常法により炉内に設けられた
プレス装置または真空吸着成形装置等の成形装置により
曲げ加工される。この際プレス装置、真空吸着成形装置
等の型は、通常ガラス繊維の布で覆われたステンレス鋼
が使用され、ガラス板はこの布を介して圧接される。
When the film-forming composition of the present invention is used to form a ceramic color film on automobile glass, the glass plate coated with the paste is kept at a temperature of 500 to 700 ° C. to form the film-forming composition. The inorganic component is baked on the glass plate, and the glass plate is bent by a forming device such as a press device or a vacuum adsorption forming device provided in the furnace by a conventional method. At this time, stainless steel covered with a cloth of glass fiber is usually used as a mold of a press machine, a vacuum adsorption molding machine, and the like, and a glass plate is pressure-welded through this cloth.
【0034】[0034]
【作用】本発明の被膜形成用組成物で用いるガラスは、
塩酸や硝酸への耐久性が低いにもかかわらず、硫酸に対
しては非常に耐久性が高いふるまいをする。この理由
は、このガラスが硫酸と接するとガラス表面に難溶性の
硫酸カルシウム、硫酸ストロンチウム、硫酸バリウムが
析出し、硫酸のガラスへの浸食を妨害するためと推測さ
れる。
The glass used in the film forming composition of the present invention is
Despite its low durability against hydrochloric acid and nitric acid, it behaves very durable against sulfuric acid. It is presumed that the reason for this is that when this glass comes into contact with sulfuric acid, the sparingly soluble calcium sulfate, strontium sulfate, and barium sulfate are deposited on the glass surface, which hinders the erosion of sulfuric acid into the glass.
【0035】[0035]
【実施例】表1に示すガラス組成(単位:重量%)とな
るように原料を調合・混合し、1200〜1500℃の
温度にて溶融しガラス化しガラスを得た。次いでこのガ
ラスを、ボールミルで粉砕し重量平均径約2.5μmの
ガラス粉末とした。次いで、このガラス粉末、耐熱性顔
料粉末(銅クロム系黒顔料)、および耐火物フィラー
(コージェライト)粉末を表1のペースト組成欄に示す
重量比率で混合した。なお、例6は従来の鉛含有ガラス
からなる組成物であり、比較例である。
[Examples] Raw materials were prepared and mixed so as to have the glass composition (unit: wt%) shown in Table 1, and melted at a temperature of 1200 to 1500 ° C to obtain vitrified glass. Next, this glass was crushed by a ball mill to obtain a glass powder having a weight average diameter of about 2.5 μm. Next, the glass powder, the heat resistant pigment powder (copper chrome-based black pigment), and the refractory filler (cordierite) powder were mixed in the weight ratios shown in the paste composition column of Table 1. In addition, Example 6 is a conventional composition containing lead-containing glass and is a comparative example.
【0036】次いで、この混合粉末80重量部に対し、
10重量%のエチルセルロースを溶解したα−テルピネ
オール溶液20重量部の割合で加えて混練し、3本ロー
ルミルにより均質分散を行い、所望のペースト粘度に調
整した。こうして得られたペーストを、ソーダライムシ
リケートガラス板(厚さ3.5mm、10cm角)の全
面にスクリーン印刷した後、乾燥した。
Next, with respect to 80 parts by weight of this mixed powder,
An α-terpineol solution in which 10% by weight of ethyl cellulose was dissolved was added at a ratio of 20 parts by weight, kneaded, and homogenously dispersed by a three-roll mill to adjust a desired paste viscosity. The paste thus obtained was screen-printed on the entire surface of a soda-lime silicate glass plate (thickness: 3.5 mm, 10 cm square) and then dried.
【0037】このガラス板を650℃に加熱し、焼成し
た後、常温に冷却し、試料を作製した。
This glass plate was heated to 650 ° C., baked, and then cooled to room temperature to prepare a sample.
【0038】この被膜を焼き付けたガラス板のガラス側
から見た色調、塗布面側から見た外観について、この板
ガラスを0.1N硫酸水溶液に24時間浸漬して、その
前後の変化を目視で観察した。例1〜5の組成物につい
ては、外観や色調変化は全く見られなかったが、例6の
組成物については、やや変色が見られた。
With respect to the color tone viewed from the glass side and the appearance viewed from the coating surface side of the glass plate on which this coating was baked, this plate glass was immersed in a 0.1N sulfuric acid aqueous solution for 24 hours, and the change before and after it was visually observed. did. No change in appearance or color tone was observed for the compositions of Examples 1-5, but a slight discoloration was observed for the compositions of Example 6.
【0039】また、これらの板ガラスを0.1N塩酸水
溶液に4時間浸漬したところ、例1〜例5の組成物につ
いては、被膜を軽くふき取ることができたが、例6につ
いては、ふき取ることができず、被膜の外観も、塩酸水
溶液に浸漬する前と変化が見られなかった。
When these plate glasses were dipped in a 0.1N hydrochloric acid aqueous solution for 4 hours, the coatings of the compositions of Examples 1 to 5 could be wiped off lightly, but those of Example 6 could be wiped off. It was not possible, and the appearance of the film was not changed from that before the immersion in the hydrochloric acid aqueous solution.
【0040】表1から明かなように、本発明によるセラ
ミックカラー組成物は鉛を含有せず、耐硫酸性にきわめ
て優れ、さらに塩酸等で容易に除去できる。
As can be seen from Table 1, the ceramic color composition according to the present invention does not contain lead, has an excellent resistance to sulfuric acid, and can be easily removed with hydrochloric acid or the like.
【0041】[0041]
【表1】 [Table 1]
【0042】[0042]
【発明の効果】本発明の被膜形成用組成物は、鉛を実質
的に含有せず、酸性雨への耐久性が優れるとともに、塩
酸等で容易に除去でき基材のリサイクルに有効である。
The film-forming composition of the present invention contains substantially no lead, has excellent durability to acid rain, and can be easily removed with hydrochloric acid or the like, and is effective for recycling a substrate.

Claims (2)

    【特許請求の範囲】[Claims]
  1. 【請求項1】基材上に塗布、焼成することにより、被膜
    を形成するための組成物であって、無機成分が実質的
    に、ガラス粉末50〜100重量%、着色耐熱性顔料粉
    末0〜50重量%、非着色低膨張耐火物フィラー粉末0
    〜50重量%からなり、前記ガラスの組成が、酸化物基
    準の重量%で、 SiO2 3〜30%、 B23 6〜45%、 CaO+SrO+BaO 38〜63%、 Li2 O+Na2 O+K2 O 4〜18%、 から実質的になる被膜形成用組成物。
    1. A composition for forming a film by coating and baking on a substrate, wherein the inorganic component is substantially from 50 to 100% by weight of glass powder, and from 0 to 0 of colored heat resistant pigment powder. 50% by weight, non-pigmented low expansion refractory filler powder 0
    .About.50 wt%, and the composition of the glass is wt% on an oxide basis: SiO 2 3 to 30%, B 2 O 3 6 to 45%, CaO + SrO + BaO 38 to 63%, Li 2 O + Na 2 O + K 2 O. A film-forming composition consisting essentially of 4 to 18%.
  2. 【請求項2】無機成分が実質的に、ガラス粉末65〜9
    5重量%、着色耐熱性顔料粉末5〜35重量%、非着色
    低膨張耐火物フィラー粉末0〜35重量%からなるセラ
    ミックカラー用の請求項1の被膜形成用組成物。
    2. An inorganic component is substantially glass powder 65-9.
    The film-forming composition according to claim 1, which comprises 5% by weight, 5 to 35% by weight of colored heat-resistant pigment powder, and 0 to 35% by weight of non-colored low expansion refractory filler powder.
JP7059996A 1996-03-26 1996-03-26 Composition for forming coating film Pending JPH09255359A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7059996A JPH09255359A (en) 1996-03-26 1996-03-26 Composition for forming coating film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7059996A JPH09255359A (en) 1996-03-26 1996-03-26 Composition for forming coating film

Publications (1)

Publication Number Publication Date
JPH09255359A true JPH09255359A (en) 1997-09-30

Family

ID=13436201

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7059996A Pending JPH09255359A (en) 1996-03-26 1996-03-26 Composition for forming coating film

Country Status (1)

Country Link
JP (1) JPH09255359A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001058849A (en) * 1999-06-09 2001-03-06 Asahi Glass Co Ltd Barium borosilicate glass and glass ceramic composition
WO2015108013A1 (en) * 2014-01-14 2015-07-23 日本電気硝子株式会社 Composite powder and paste of composite powder

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001058849A (en) * 1999-06-09 2001-03-06 Asahi Glass Co Ltd Barium borosilicate glass and glass ceramic composition
WO2015108013A1 (en) * 2014-01-14 2015-07-23 日本電気硝子株式会社 Composite powder and paste of composite powder

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