JPH0424299B2 - - Google Patents
Info
- Publication number
- JPH0424299B2 JPH0424299B2 JP1571885A JP1571885A JPH0424299B2 JP H0424299 B2 JPH0424299 B2 JP H0424299B2 JP 1571885 A JP1571885 A JP 1571885A JP 1571885 A JP1571885 A JP 1571885A JP H0424299 B2 JPH0424299 B2 JP H0424299B2
- Authority
- JP
- Japan
- Prior art keywords
- frit
- less
- powder coating
- resistance
- hot water
- 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.)
- Expired
Links
- 239000000843 powder Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000006103 coloring component Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 210000003298 dental enamel Anatomy 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004534 enameling Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010494 opalescence Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-LZFNBGRKSA-N Potassium-45 Chemical group [45K] ZLMJMSJWJFRBEC-LZFNBGRKSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Description
（産業上の利用分野）
本発明は耐薬品性、耐熱水性に優れたパウダー
コーテイング用乳白フリツトに関するものであ
る。
（従来の技術）
従来のほうろうフリツトは粘土とともに湿式粉
砕して釉薬となし、これを金属表面にデイツピン
グ、スプレー掛等の方法により施釉し焼成するも
のが普通であるが、数年前からフリツト粒子を静
電圧を利用して金属表面に付着させるパウダーコ
ーテイングが脚光を浴びている。この技法におい
てはフリツト粒子の付着性を向上させるために電
気抵抗値の高いフリツトが用いられ、表面にアル
コキシシランやオルガノポリシロキサン等の電気
抵抗値の高い有機物質を被覆したパウダーコーテ
イング用のフリツトが用いられている。（例えば、
特開昭52−98721号公報、特開昭51−7005号公報）
（発明が解決しようとする問題点）
ところがこのような従来のパウダーコーテイン
グ用のフリツトは施釉面を鏡面としやすい反面耐
薬品性及び耐熱水性が著しく劣るため、煮沸器
物、浴槽、流し台のような過酷な条件下で使用さ
れる器物には不適当とされていた。本発明は上記
のような従来の問題点を解決し、パウダーコーテ
イングに適する高い付着性を持ち、しかも、耐薬
品性及び耐熱水性に優れたパウダーコーテイング
用乳白フリツトを目的として完成されたものであ
る。
（問題点を解決するための手段）
本発明は3.1〜12.0％（重量％、以下同じ）の
Al2O3及び５〜25％のB2O3を必須的に含有する
R2O3成分と、12.5％以下のNa2Ｏを含有するR2O
成分と、TiO210〜25％かつSb2O34〜15％又は
TiO2＋ZrO2＋Sb2O34〜35％のいずれかの条件を
満足する乳白成分と、35〜55％のSiO2と、10％
以下のＦと、10％以下のP2O5と、10％以下のRO
成分と、３％以下のMoO3と、必要に応じて添加
される着色成分とから成ることを特徴とするもの
である。
本発明において必須的に含有されるAl2O3はフ
リツトの耐薬品性及び耐熱水性を増加させる成分
であり、3.1％以下では目的とする効果が得られ
ず、12.0％を越えると耐酸性の劣化を生ずるので
3.1〜12.0％の範囲とする必要がある。B2O3は５
％未満ではフリツトの溶融性、乳白性が不十分で
あり、25％を越すと耐熱水性の劣化を生ずるので
５〜25％の範囲とする必要がある。Na2O、
K2O、Li2O等のR2O成分はフリツトの溶融を容易
化し、低融点化を図るための成分であり、総量を
0.5〜30％の範囲とすることが好ましい。また
R2O成分中、特にNa2Oはフリツトの電気的特性
を左右する成分であり、フリツトにパウダーコー
テイング用フリツトとして好適な安定した帯電
性、付着性を持たせるためには12.5％以下とする
ことが好ましい。フリツトを乳白化させるために
はTiO210〜25％、Sb2O34〜15％又はTiO2＋ZrO2
＋Sb2O34〜35％のいずれかの条件を満足する乳
白成分を含有させる。Sb2O3はSb2O5の形で添加
してもよい。これらの乳白成分はいずれも上記含
有率未満では十分な乳白化を行わせることができ
ず、逆に上記含有率を越えると耐熱水性、耐薬品
性が劣化する。SiO2は主要なガラス形成酸化物
であり、35％未満では耐熱水性、耐酸性の劣化が
認められ、55％を越えるとフリツトが難溶性とな
るので35〜55％の範囲とすることが好ましい。
MgO、CaO、ZnO、BaO、SrO等のRO成分は総
量が10％を越えると耐熱水性、耐薬品性、乳白性
が低下する傾向を示すので10％以下とすることが
好ましい。このほか本発明のフリツト中には10％
以下のＦ、10％以下のP2O5、３％以下のMoO3等
が含有される。Ｆはフリツトの溶解性を向上させ
るうえに有効であるが、10％を越えると耐熱水
性、耐酸性の劣化を招く。P2O5は低融点化に効
果があり、しかも高温における粘性低下が少ない
ので低温焼成が可能で焼き切れしにくいフリツト
を得るために好ましい成分であるが、10％を越え
ると耐薬品性、耐熱水性の劣化を招く。MoO3は
耐酸性を向上させる成分であるが、３％を越える
と表面に異物結晶が発生するので３％以下とする
ことが望ましい。このほかフリツトに各種の色彩
を与えるための着色成分として、CoO、NiO、
Cr2O3、Fe2O3、CuO、V2O5等のうちの一種又は
二種以上を総量12％以下の範囲で外配添加しても
よい。
以上の組成を持つ本発明のパウダーコーテイン
グ用乳白フリツトは後述する実施例からも明らか
なようにパウダーコーテイングされた際に優れた
付着力を示し、しかも耐薬品性、耐熱水性に優れ
たものであるから、これを粉体化したうえ金属素
地表面に静電的に付着させれば過酷な使用条件に
も耐える優れた乳白色のほうろう製品を得ること
ができる。
（実施例）
第１表の実施例１〜13及び比較例14〜28の組成
となるように原料を調合し、1200〜1300℃で溶
融、急冷して乳白フリツトを製造した。これらの
乳白フリツトを実施例１〜13及び比較例14〜18の
ものはカプリング剤で処理してパウダーコーテイ
ング用乳白フリツトとし、予め下釉が焼付けられ
た鋼板に静電粉体用ガンを用いて−100kVの静電
圧を印加して施釉し焼成した。一方、比較例19〜
28のフリツトはフリツト100重量部に粘土６部、
塩化カリ0.2部、水45部を加えてミル粉砕し、200
メツシユ篩に５ｇ残るように調整したスリツプを
スプレー、デイツピング等の方法で同様の鋼板に
施釉し、乾燥、焼成した。このようにして得られ
た各試験片について耐酸スポツトテスト、質量減
耐酸試験、質量減耐アルカリ試験、質量減耐熱水
性試験、付着力評価を行つたところ、第２表に示
すように実施例１〜13のフリツトは優れた特性を
示し、またいずれも優れた乳白色を呈した。な
お、各試験方法は次のとおりである。
(Field of Industrial Application) The present invention relates to a milky white frit for powder coating that has excellent chemical resistance and hot water resistance. (Prior art) Conventional enamel frits are usually wet-pulverized together with clay to form a glaze, which is applied to the metal surface by dipping, spraying, etc., and then fired. Powder coating, which uses electrostatic voltage to attach metal to metal surfaces, is attracting attention. In this technique, a frit with a high electrical resistance value is used to improve the adhesion of the frit particles, and a powder coating frit whose surface is coated with an organic material with a high electrical resistance value such as alkoxysilane or organopolysiloxane is used. It is used. (for example,
JP-A No. 52-98721, JP-A No. 51-7005) (Problem to be solved by the invention) However, although such conventional powder coating frits tend to have a mirror-like glazed surface, they do not have chemical resistance. Also, because of its extremely poor hot water resistance, it was considered unsuitable for appliances used under harsh conditions, such as boilers, bathtubs, and sinks. The present invention was completed with the aim of solving the above-mentioned conventional problems and producing a milky white frit for powder coating that has high adhesion suitable for powder coating and has excellent chemical resistance and hot water resistance. . (Means for Solving the Problems) The present invention provides 3.1 to 12.0% (weight%, same hereinafter)
Essentially contains Al 2 O 3 and 5-25% B 2 O 3
R 2 O containing 3 components and 12.5% or less of N a2 O
Ingredients and TiO 2 10-25% and Sb 2 O 3 4-15% or
TiO 2 + ZrO 2 + Sb 2 O 3 A milky white component that satisfies any of the conditions of 4 to 35%, 35 to 55% SiO 2 , and 10%
less than F, less than 10% P 2 O 5 , and less than 10% RO
3% or less of MoO 3 , and a coloring component added as necessary. Al 2 O 3 , which is essential in the present invention, is a component that increases the chemical resistance and hot water resistance of the frit. If it is less than 3.1%, the desired effect cannot be obtained, and if it exceeds 12.0%, the acid resistance will be reduced. Because it causes deterioration
It needs to be in the range of 3.1 to 12.0%. B 2 O 3 is 5
If it is less than 25%, the meltability and opalescence of the frit will be insufficient, and if it exceeds 25%, the hot water resistance will deteriorate, so it is necessary to keep it in the range of 5 to 25%. Na2O ,
R 2 O components such as K 2 O and Li 2 O are components that facilitate the melting of the frit and lower the melting point.
It is preferably in the range of 0.5 to 30%. Also
Among the R 2 O components, Na 2 O in particular is a component that affects the electrical properties of the frit, and should be kept at 12.5% or less in order to give the frit stable chargeability and adhesion suitable for use as a powder coating frit. It is preferable. To opacify the frit, use TiO 2 10-25%, Sb 2 O 3 4-15% or TiO 2 + ZrO 2
+Sb 2 O 3 A milky white component satisfying any one of 4 to 35% is contained. Sb 2 O 3 may be added in the form of Sb 2 O 5 . If the content of any of these opalescent components is less than the above, sufficient opacification cannot be achieved, and if the content exceeds the above, hot water resistance and chemical resistance deteriorate. SiO 2 is the main glass-forming oxide, and if it is less than 35%, the hot water resistance and acid resistance will deteriorate, and if it exceeds 55%, the frit will become poorly soluble, so it is preferably in the range of 35 to 55%. .
If the total amount of RO components such as MgO, CaO, ZnO, BaO, and SrO exceeds 10%, hot water resistance, chemical resistance, and opalescence tend to decrease, so it is preferable to limit the amount to 10% or less. In addition, the frit of the present invention contains 10%
The following F, 10% or less P 2 O 5 , 3% or less MoO 3 , etc. are contained. F is effective in improving the solubility of frit, but if it exceeds 10%, it causes deterioration of hot water resistance and acid resistance. P 2 O 5 is effective in lowering the melting point and has little viscosity drop at high temperatures, so it is a preferred component in order to obtain a frit that can be fired at low temperatures and is difficult to burn out. However, if it exceeds 10%, chemical resistance and This leads to deterioration of hot water resistance. MoO 3 is a component that improves acid resistance, but if it exceeds 3%, foreign crystals will occur on the surface, so it is desirable to keep it at 3% or less. In addition, CoO, NiO,
One or more of Cr 2 O 3 , Fe 2 O 3 , CuO, V 2 O 5 and the like may be externally added in a total amount of 12% or less. The milky white frit for powder coating of the present invention having the above composition exhibits excellent adhesion when powder coated, as is clear from the examples described below, and has excellent chemical resistance and hot water resistance. By pulverizing this and electrostatically adhering it to the surface of a metal substrate, it is possible to obtain an excellent milky white enamel product that can withstand harsh usage conditions. (Example) Raw materials were prepared to have the compositions of Examples 1 to 13 and Comparative Examples 14 to 28 in Table 1, melted at 1200 to 1300°C, and rapidly cooled to produce milky white frits. These opalescent frits of Examples 1 to 13 and Comparative Examples 14 to 18 were treated with a coupling agent to obtain opalescent frits for powder coating, and then applied to a steel plate on which a lower glaze had been baked using an electrostatic powder gun. It was glazed and fired by applying an electrostatic voltage of -100kV. On the other hand, Comparative Example 19~
Frit 28 is 100 parts by weight of frit and 6 parts clay.
Add 0.2 parts of potassium chloride and 45 parts of water and grind to 200
A similar steel plate was glazed with a slip adjusted to leave 5 g on the mesh sieve by spraying, dipping, etc., dried, and fired. The acid resistance spot test, weight loss acid resistance test, weight loss resistance alkali test, weight loss hot water resistance test, and adhesion evaluation were conducted on each test piece thus obtained. As shown in Table 2, Example 1 -13 frits showed excellent properties and all exhibited excellent opalescent color. In addition, each test method is as follows.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
(1) 耐酸スポツトテスト
JIS Ｒ 4301 ５・９・１のクエン酸による
常温スポツト試験法に準ずる方法で、10％クエ
ン酸溶液を試験片上に置かれた３×３cmの３枚
重ねの濾紙の上からスポイトで滴下し、濾紙を
十分に湿らせた後常温で15分間放置し、その表
面光沢の変化を評価する。
(2) 質量減耐酸性試験
ISO−2733に準ずる試験装置を用いて６％ク
エン酸溶液450ml中に試験片を入れ沸騰状態で
６時間保持した後にほうろう層（液相試験片）
の減量値を測定する。測定値は３試験片の平均
値を取りｇ／m2の単位で示す。
(3) 質量減耐熱水性試験
(2)と同じ試験装置を用い、純水450ml中に試
験片を入れ沸騰状態で48時間保持した後に液相
試験片及び気相試験片のほうろう層の減量値を
測定する。測定値は３試験片の平均値を取り
ｇ／m2／dayの単位で示す。なお分子は液相試
験片のデータ、分母は気相試験片のデータであ
る。
(4) 質量減耐アルカリ性試験
ISO−2734に準ずる試験装置を用いて５％ピ
ロリン酸ナトリウム溶液中に試験片を入れ、90
℃±１℃の恒温槽中に６時間保持した後にほう
ろう層（液相試験片）の減量値を測定する。測
定値は３試験片の平均値を取り、ｇ／m2の単位
で示す。
(5) 付着力評価
粉体化されたフリツトを100mm×100mm×1.2t
mmのほうろう用鋼板に静電的に付着させ、焼成
することなく0.28Kg／cm2の衝撃を与えてフリツ
トの落下量を測定し、落下しなかつた割合を％
で示した。
（発明の効果）
本発明のパウダーコーテイング用乳白フリツト
は以上の実施例による説明からも明らかなよう
に、パウダーコーテイングに適する優れた付着力
を有し、しかも耐薬品性と耐熱水性に優れたもの
であるから、この乳白フリツトを用いたパウダー
コーテイング方法によれば耐薬品性と耐熱水性に
優れた乳白ほうろう層を持つほうろう製品を製造
することができる。従つて本発明によれば従来は
パウダーコーテイング方法を用いることができな
かつた煮沸器物、浴槽、流し台等に対してもパウ
ダーコーテイング方法によつて容易に乳白色のほ
うろう掛けができることとなる。よつて本発明は
従来の問題点を一掃したものとして、産業の発展
に寄与するところは極めて大なものである。[Table] (1) Acid resistance spot test A 10% citric acid solution was applied to a 3 x 3 cm stack of three sheets placed on a test piece using a method similar to the room temperature spot test method using citric acid in JIS R 4301 5.9.1. Drop the solution onto the filter paper with a dropper to sufficiently moisten the filter paper, then leave it at room temperature for 15 minutes and evaluate the change in surface gloss. (2) Mass loss acid resistance test Using a test device conforming to ISO-2733, the test piece was placed in 450 ml of 6% citric acid solution and kept in a boiling state for 6 hours, followed by an enamel layer (liquid phase test piece).
Measure the weight loss value. The measured value is the average value of three test pieces and is expressed in units of g/m 2 . (3) Mass loss hot water resistance test Using the same test equipment as in (2), the test piece was placed in 450 ml of pure water and kept in a boiling state for 48 hours, then the weight loss value of the enamel layer of the liquid phase test piece and the gas phase test piece was determined. Measure. The measured value is the average value of three test pieces and is expressed in units of g/m 2 /day. The numerator is the data for the liquid phase test piece, and the denominator is the data for the gas phase test piece. (4) Alkali resistance test for weight loss Using a test device based on ISO-2734, place the test piece in a 5% sodium pyrophosphate solution and
The weight loss value of the enamel layer (liquid phase test piece) is measured after being kept in a constant temperature bath at ±1°C for 6 hours. The measured value is the average value of three test pieces and is expressed in units of g/m 2 . (5) Adhesion evaluation Powdered frit is 100mm x 100mm x 1.2t
The frit was electrostatically attached to a steel plate for enameling with a diameter of 1 mm, and the amount of the frit falling was measured by applying an impact of 0.28 kg/cm 2 without firing, and the percentage of frits that did not fall was calculated as %.
It was shown in (Effects of the Invention) As is clear from the above examples, the milky white frit for powder coating of the present invention has excellent adhesion suitable for powder coating, and has excellent chemical resistance and hot water resistance. Therefore, according to the powder coating method using this opalescent frit, it is possible to produce an enamel product having an opalescent enamel layer with excellent chemical resistance and hot water resistance. Therefore, according to the present invention, milky white enameling can be easily applied to boilers, bathtubs, sinks, etc., to which powder coating methods could not be used in the past, by using powder coating methods. Therefore, the present invention eliminates the problems of the prior art and greatly contributes to the development of industry.
Claims (1)
B2O3を必須的に含有するR2O3成分と、12.5％以
下のNa2Ｏを含有するR2O成分と、TiO210〜25％
かつSb2O34〜15％又はTiO2＋ZrO2＋Sb2O34〜35
％のいずれかの条件を満足する乳白成分と、35〜
55％のSiO2と、10％以下のＦと、10％以下の
P2O5と、10％以下のRO成分と、３％以下の
MoO3と、必要に応じて添加される着色成分とか
ら成ることを特徴とするパウダーコーテイング用
乳白フリツト。 ２ 着色成分がCoO、NiO、MnO2、Cr2O3、
Fe2O3、CuO、V2O5のグループから選択された
１種又は２種以上のものである特許請求の範囲第
１項記載のパウダーコーテイング用乳白フリツ
ト。[Claims] 1. 3.1 to 12.0% Al 2 O 3 and 5 to 25% by weight
An R2O3 component that essentially contains B2O3 , an R2O component that contains 12.5% or less of N a2O , and 10 to 25 % TiO2
and Sb2O3 4-15 % or TiO2 + ZrO2 + Sb2O3 4-35
A milky white component that satisfies any of the conditions of 35 to 35%
55% SiO2 , 10% or less F, and 10% or less
P 2 O 5 , RO content of 10% or less, and 3% or less
A milky white frit for powder coating, characterized by comprising MoO 3 and a coloring component added as necessary. 2 Coloring components are CoO, NiO, MnO 2 , Cr 2 O 3 ,
The milky white frit for powder coating according to claim 1, which is one or more selected from the group of Fe 2 O 3 , CuO, and V 2 O 5 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1571885A JPS61178441A (en) | 1985-01-30 | 1985-01-30 | Powder coating opaque frit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1571885A JPS61178441A (en) | 1985-01-30 | 1985-01-30 | Powder coating opaque frit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61178441A JPS61178441A (en) | 1986-08-11 |
| JPH0424299B2 true JPH0424299B2 (en) | 1992-04-24 |
Family
ID=11896540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1571885A Granted JPS61178441A (en) | 1985-01-30 | 1985-01-30 | Powder coating opaque frit |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61178441A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2626291B1 (en) * | 1988-01-22 | 1991-05-03 | Mitsubishi Metal Corp | ZIRCONIUM-BASED ALLOY FOR USE AS A FUEL ASSEMBLY IN A NUCLEAR REACTOR |
-
1985
- 1985-01-30 JP JP1571885A patent/JPS61178441A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61178441A (en) | 1986-08-11 |
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