JPH10139476A - Gray ground coat frit for enamel for steel plate - Google Patents
Gray ground coat frit for enamel for steel plateInfo
- Publication number
- JPH10139476A JPH10139476A JP30551996A JP30551996A JPH10139476A JP H10139476 A JPH10139476 A JP H10139476A JP 30551996 A JP30551996 A JP 30551996A JP 30551996 A JP30551996 A JP 30551996A JP H10139476 A JPH10139476 A JP H10139476A
- Authority
- JP
- Japan
- Prior art keywords
- frit
- adhesion
- enamel
- steel plate
- total amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 23
- 239000010959 steel Substances 0.000 title claims abstract description 23
- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 17
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000000049 pigment Substances 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004040 coloring Methods 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000002318 adhesion promoter Substances 0.000 abstract description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 2
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- 229910004865 K2 O Inorganic materials 0.000 abstract 1
- 229910011763 Li2 O Inorganic materials 0.000 abstract 1
- 229910004742 Na2 O Inorganic materials 0.000 abstract 1
- 229910017895 Sb2 O3 Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- 239000008267 milk Substances 0.000 description 6
- 210000004080 milk Anatomy 0.000 description 6
- 235000013336 milk Nutrition 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- -1 Na 2 O Chemical class 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- FYQZIUWOAGROCR-MRMRLACISA-N amotin Natural products CC(C)[C@]1(O)[C@@H]2OC(=O)[C@H]1[C@@H]3CC[C@]4(O)C(=O)O[C@H]2[C@]34C FYQZIUWOAGROCR-MRMRLACISA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000001058 brown pigment Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LPGWZGMPDKDHEP-NVDFJPPOSA-N vinleurosine Chemical compound C([C@]1([C@@H]2O1)CC)N(CCC=1C3=CC=CC=C3NC=11)C[C@@H]2C[C@]1(C(=O)OC)C1=CC([C@]23[C@H]([C@@]([C@H](OC(C)=O)[C@]4(CC)C=CCN([C@H]34)CC2)(O)C(=O)OC)N2C)=C2C=C1OC LPGWZGMPDKDHEP-NVDFJPPOSA-N 0.000 description 1
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
- 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
- C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
- C03C2207/04—Compositions specially applicable for the manufacture of vitreous enamels for steel
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)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鋼板にほうろう掛
けする下ぐすりとして好適なフリットに関する。更に詳
しくは、鋼板に焼き付けたうわぐすり層が灰白色でかつ
優れた密着性を有する、鋼板ほうろう用の下ぐすりに使
用するフリットに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a frit which is suitable as an underhang for enamelling a steel plate. More specifically, the present invention relates to a frit used for a bottom enamel for steel sheet enamel, wherein the glaze layer baked on the steel sheet is grayish white and has excellent adhesion.
【０００２】[0002]
【従来の技術】ほうろう製品の大部分を占めるほうろう
鉄器は、本発明の目的とする鋼板ほうろうと鋳鉄ほうろ
うに分けられる。一般に、鋼板ほうろう用下ぐすりには
鋼板との密着性を高めるためＣ0Ｏ、ＮｉＯ、ＭnＯ2、
ＣｕＯ、ＦｅＯ等の酸化物が添加されているので、焼成
後の色調は暗色（暗青色、暗褐色、暗灰色）のものしか
得られなかった。そのため、下ぐすりの着色をカバーす
るため、ＴｉＯ2、ＺｒＯ、Ｓｂ2Ｏ3などの乳白剤を用
いた上ぐすりの施釉が必要であった。また、チタン乳白
ぐすり、アンチモン乳白ぐすり、ジルコン乳白ぐすり等
の白色または灰白色を呈するこのような従来の上ぐすり
は、鋼板に直接焼き付けることはできず、鋼板に下ぐす
りを施すか又は特別な前処理（一般にニッケル処理）を
施すかしなければ、鋼板と密着ができなかった。BACKGROUND OF THE INVENTION Enamelled ironware, which accounts for the majority of enameled products, is divided into steel sheet enamel and cast iron enamel, which are the objects of the present invention. In general, C 0 O, NiO, M n O 2 for the lower steel plate enamel agents enhance the adhesion between the steel sheet,
Since oxides such as CuO and FeO were added, only dark colors (dark blue, dark brown, dark gray) were obtained after firing. For this reason, in order to cover coloring of the lower medicine, glaze of an upper medicine using an opacifying agent such as TiO 2 , ZrO, or Sb 2 O 3 was required. In addition, such conventional gums exhibiting white or gray white, such as titanium milk whitening, antimony milk whitening, and zircon milk whitening, cannot be directly baked on a steel sheet. Or, unless a special pre-treatment (generally nickel treatment) was performed, the steel sheet could not adhere to the steel sheet.
【０００３】更に、モリブデンを多量に含むうわぐすり
は鋼板に直接密着するが、焼成表面が悪い上、うわぐす
りのコストが非常に高価となる欠点があった。また従来
の下ぐすりは顔料を添加しても鮮やかな発色が得られな
かった。[0003] Furthermore, glazes containing a large amount of molybdenum adhere directly to steel sheets, but have the disadvantage that the fired surface is poor and the cost of glazes becomes extremely high. In addition, a vivid coloration could not be obtained with the conventional under-gum even if a pigment was added.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上述の様な鋼
板ほうろうの問題点を改善しようとするものである。即
ち、密着促進剤として、ＣｏＯ、ＮｉＯ等の着色性の強
い酸化物を添加しないため、焼成色が灰白色を呈すると
同時に焼成面が良好な平滑性をもちしかも鋼板との十分
な密着性を有する下ぐすりフリットを提供するものであ
る。また本発明の下ぐすりフリットは、鋼板に特別な前
処理を施さなくても、十分な密着を得ることができ、更
に本発明の下ぐすりフリットに顔料を添加したものは、
鮮やかな色調のうわぐすりを形成できる。SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems of the steel enamel. That is, since an oxide having strong coloring properties such as CoO and NiO is not added as an adhesion promoter, the sintering color has an off-white color and the sintering surface has good smoothness and has sufficient adhesion to a steel sheet. It provides a lower frit. In addition, the underground frit of the present invention can obtain sufficient adhesion without performing a special pretreatment on the steel sheet, and the underground frit of the present invention to which a pigment is added,
A glaze of vivid colors can be formed.
【０００５】[0005]
【課題を解決するための手段】本発明の要旨は、以上の
とおりの鋼板ほうろう用灰色下ぐすりフリットである。
重量％で、Ｓｂ2Ｏ3 ８〜２０％、Ｍ0Ｏ3 ３％以下、
Ｐ2Ｏ5 ３〜１５％、ＳｉＯ2 ２０〜３５％、Ａｌ2Ｏ
3 ５〜１５％、Ｂ2Ｏ3 １３〜２０％、Ｒ2Ｏ（Ｎａ2
Ｏ、Ｋ2Ｏ、Ｌｉ2Ｏの合計量） １３〜２０％、ＲＯ
（ＣａＯ、ＢａＯ、ＺｎＯなどのアルカリ土類金属酸化
物の合計量） ３〜１０％、Ｆ2 ５％未満を必須成分
とすることを特徴とする鋼板ほうろう用灰色下ぐすりフ
リット。本発明においてフリット中の各構成成分の添加
量を限定した理由は、以下のとおりである。まずＳｂ2
Ｏ3は乳白性及び密着性のための重要な成分で、８％未
満では十分な密着と良好な焼成面が得られない。また、
２０％を越えると結晶化が起こりやすく良好な焼成面が
得られない。次にＭｏＯ3は密着助剤として使用するも
ので、３％を越える添加は焼成面の平滑性を阻害するた
め好ましくない。またＰ2Ｏ5はフリットの結晶化を防ぐ
ために重要で、３％未満では結晶化が起こりやすくなり
焼成面の平滑性がなくなる。１５％を超える添加は乳白
の低下とフリットの老化性の点で好ましくない。ＳｉＯ
2以下の各成分は、下ぐすりフリットの一般的な構成成
分である。ＳｉＯ2は２０％未満であるとガラス構成が
軟らかくなりすぎ焼成後の表面が皺肌となる、また３５
％を越えると硬くなり密着を阻害する。Ａｌ2Ｏ3はガラ
ス構造の安定化と乳白性に関係しており、５％未満では
結晶化し易くなる、また１５％を越えると硬くなり密着
が悪くなる。Ｂ2Ｏ3は１３％未満ではガラス構造が軟ら
かすぎ焼成面が皺肌となり、２０％を越えると密着が阻
害される。またＮａ2Ｏ、Ｋ2Ｏ、Ｌｉ2Ｏ（以下Ｒ2Ｏと
総称する）も下ぐすりフリットの必須成分であり、その
総量が１３％未満では密着が阻害され、２０％を越える
とガラス構造が軟らかすぎ焼成面が皺肌となる。Ｃａ
ｏ、ＢａＯ、ＺｎＯなどのアルカリ土類金属酸化物（以
下ＲＯ群と総称する）はフリットの安定化及び乳白性に
関係し、その総量が３％未満では乳白は低下し、１０％
を越えると密着の点で好ましくない。Ｆ2は乳白性に関
係し、乳白のためには多い方が良いが、結晶化の防止及
びフリットの安定化のために５％未満の添加が好まし
い。本発明の下ぐすりフリットは、鋼板に焼成後、灰白
色を呈すると共に十分な密着が得られるうわぐすりを提
供する。また本発明の下ぐすりフリットに一般にほうろ
うに使用される顔料を添加して焼成すると、鮮やかな発
色が得られる。顔料の添加量に特に規定は無いが、一般
に５％を越える添加の場合密着性の低下が見られる。そ
の際は鋼板の前処理として酸洗及び軽いニッケル処理を
することで、十分な密着を得ることができる。The gist of the present invention is a gray underground frit for steel sheet enamel as described above.
In weight%, Sb 2 O 3 8~20% , M 0 O 3 3% or less,
P 2 O 5 3 to 15%, SiO 2 20 to 35%, Al 2 O
3 5~15%, B 2 O 3 13~20%, R 2 O (Na 2
O, the total amount of K 2 O, Li 2 O) 13~20%, RO
(Total amount of alkaline earth metal oxides such as CaO, BaO, ZnO, etc.) 3 to 10% and less than 5% of F 2 as essential components. The reason for limiting the amount of each component in the frit in the present invention is as follows. First, Sb 2
O 3 is an important component for milkiness and adhesion. If it is less than 8%, sufficient adhesion and a good fired surface cannot be obtained. Also,
If it exceeds 20%, crystallization is likely to occur and a good fired surface cannot be obtained. Next, MoO 3 is used as an adhesion assistant. Addition of more than 3% is not preferable because it impairs the smoothness of the fired surface. P 2 O 5 is important for preventing crystallization of the frit, and if it is less than 3%, crystallization is likely to occur, and the fired surface loses smoothness. Addition of more than 15% is not preferred in terms of milky white reduction and frit aging. SiO
Each component below 2 is a general component of a down-fill frit. If the content of SiO 2 is less than 20%, the glass composition becomes too soft and the surface after firing becomes wrinkled.
%, It becomes hard and hinders adhesion. Al 2 O 3 is related to the stabilization of the glass structure and the milkiness, and if it is less than 5%, it tends to crystallize, and if it exceeds 15%, it becomes hard and the adhesion becomes poor. If the content of B 2 O 3 is less than 13%, the glass structure is too soft and the fired surface becomes wrinkled, and if it exceeds 20%, the adhesion is hindered. Na 2 O, K 2 O, and Li 2 O (hereinafter collectively referred to as R 2 O) are also essential components of the lower frit. If the total amount is less than 13%, the adhesion is hindered. The structure is too soft and the fired surface becomes wrinkled. Ca
Alkaline earth metal oxides (hereinafter collectively referred to as RO group) such as o, BaO and ZnO are related to the stabilization of the frit and the milkiness, and if the total amount is less than 3%, the milky white is reduced and 10%
Is not preferable in terms of adhesion. F 2 is related to opalescent properties, but better large for milk white, addition of less than 5% in order to stabilize the prevention of crystallization and the frit are preferred. The underfill frit of the present invention provides a glaze that, after firing on a steel sheet, has an off-white appearance and provides sufficient adhesion. When a pigment generally used for enamel is added to the underfrit frit of the present invention and baked, a vivid color is obtained. Although there is no particular limitation on the amount of the pigment to be added, generally, when the amount exceeds 5%, a decrease in adhesion is observed. In this case, sufficient adhesion can be obtained by performing pickling and light nickel treatment as a pretreatment of the steel sheet.
【０００６】[0006]
【発明の実施の形態】所望の構成成分となるように調合
した原料を溶解炉にて溶解後、水冷ロールにより急冷
し、次いで乾燥して、下ぐすりフリットを得る。溶解の
温度は１２００〜１２５０℃が好ましい。次に、フリッ
ト１００部に対し、ミル添加原料として、粘土６部、珪
石５部、含水硼砂０．５部、亜硝酸ソーダ０．２部の割
合で配合し、湿式で粉砕し下ぐすり釉薬とする。釉薬は
２００メッシュふるい残渣が釉薬５０ｃｃ当たり１〜１
０ｇとなるよう粒度を調整するのが好ましい。この下ぐ
すり釉薬を脱脂又は酸洗した鋼板にスプレー又はたらし
掛けで施釉する。施釉量はウエットの状態で片面４〜６
ｇ／１０×１５ｃｍが基準で、焼成後の膜厚が８０〜１
４０μｍとなる。施釉された鋼板は乾燥器で乾燥後、焼
成炉で焼成する。焼成温度は８２０℃を基準とし、焼成
時間は鋼板の板厚によって調整が必要で、０．８ｍｍ板
の場合２．５〜３．０分が好ましく、板厚が薄い場合は
短く、厚い場合は長くする必要がある。上記の工程によ
り表面状態が平滑で、灰白色を呈し、密着性の良好なほ
うろう製品が得られる。更に上記で得られる下ぐすりフ
リット１００部に対しミル添加原料として、粘土１〜６
部、珪石０〜５部、含水硼砂０．５部、亜硝酸ソーダ
０．２部、更に顔料適当量を配合し得られる下ぐすり釉
薬は、１度のうわぐすり焼き付けで焼成色が鮮やかなほ
うろう製品となる。BEST MODE FOR CARRYING OUT THE INVENTION A raw material prepared to have desired components is melted in a melting furnace, quenched by a water-cooled roll, and then dried to obtain a frit. The melting temperature is preferably from 1200 to 1250 ° C. Next, with respect to 100 parts of the frit, 6 parts of clay, 5 parts of silica stone, 0.5 parts of hydrated borax and 0.2 parts of sodium nitrite were blended as a mill-added raw material, pulverized by a wet method, and ground glaze. And For glaze, 200 mesh sieve residue is 1-1 for every 50cc of glaze
It is preferable to adjust the particle size to be 0 g. The glaze is sprayed or glazed on the degreased or pickled steel plate. The amount of glaze is 4 to 6 on one side in wet condition
g / 10 × 15 cm, and the film thickness after firing is 80 to 1
It becomes 40 μm. The glazed steel sheet is dried in a dryer and fired in a firing furnace. The calcination temperature is based on 820 ° C., and the calcination time needs to be adjusted depending on the thickness of the steel sheet. It needs to be longer. According to the above process, an enamel product having a smooth surface state, exhibiting a grayish white color, and having good adhesion can be obtained. Further, as a mill addition raw material for 100 parts of the underfrit frit obtained above, clay 1-6
Parts, 0 to 5 parts of silica stone, 0.5 parts of hydrated borax, 0.2 parts of sodium nitrite, and a glaze glaze obtained by blending an appropriate amount of a pigment. It becomes a product.
【０００７】[0007]
【実施例】以下、本発明の実施例及び比較例を説明す
る。まず表１に、本発明を代表する組成比をもつうわぐ
すりの実施例１〜４を示す。次に表２に、組成比が本発
明の限定範囲を越える比較例１〜４のうわぐすりを示
す。また表３に比較例として、従来の下ぐすりの代表組
成、及び上ぐすりとしてチタン乳白フリット、アンモチ
ン乳白フリット、ジルコン乳白フリット、モリブデンフ
リットの組成を示す。但し、表中のＲ2Ｏはアルカリ金
属類のＮａ2Ｏ、Ｋ2Ｏ、Ｌｉ2Ｏの合計量、ＲＯはアル
カリ土類のＣａＯ、ＢａＯ、ＺｎＯなどの合計量を示
す。表１及び表２に示す８種類の組成比の下ぐすりフリ
ットを作成し、前記のミル配合比で湿式粉砕し８種類の
下ぐすり釉薬を得た。これらの釉薬を脱脂処理をした
０．８ｍｍ厚の鋼板に施釉、８２０℃の温度で２．５分
焼成し、厚さ約１００μｍのほうろう層を有するほうろ
う掛け試料を得た。得られた試料については、ほうろう
層の外観を目視観察し、ほうろう面の乳白度の測定及び
密着性判定試験を行った。これらの観察あるいは試験結
果は表１及び表２に示す通りであり、また試験及び評価
の内容は下記の通りである。 ａ）乳白度 測色計を用い明度指数（Ｌ＊値）を測定した。表中の各
符号の内容は次の通りである。 Ｌ＊値 ○＝５１以上 △＝４５〜５０ ×＝４５未満 ｂ）密着性 ＰＥＩ密着試験法に準じ、ハンドプレスで圧力を加え試
験体に所定の凹面変形を与えた後、密着度計で密着指数
を測定した。表中の各符号の内容は次の通りである。 密着指数 ○＝７１以上 △＝４０〜７０ ×＝４０未満 ｃ）外観 目視によりほうろう層の状態を観察した。表中の各符号
の内容は次の通りである。 ○＝表面が平滑であり、ぶつ、へこみが目立たない △＝表面が平滑であり、ぶつ、へこみが多少目立つ ×＝表面が平滑性がない又はぶつ、へこみが目立つ表１
実施例 （組成成分の単位は重量％） EXAMPLES Examples and comparative examples of the present invention will be described below. First, Tables 1 to 4 show Examples 1 to 4 of glazes having composition ratios representative of the present invention. Next, Table 2 shows glazes of Comparative Examples 1 to 4 in which the composition ratio exceeds the limited range of the present invention. In addition, Table 3 shows, as comparative examples, typical compositions of a conventional underdrug and compositions of a titanium milk frit, an amotin milk frit, a zircon milk frit, and a molybdenum frit as an upper medicine. In the table, R 2 O represents the total amount of alkali metals such as Na 2 O, K 2 O and Li 2 O, and RO represents the total amount of alkaline earth materials such as CaO, BaO and ZnO. Eight types of underground frit were prepared as shown in Tables 1 and 2 and wet-pulverized at the above-mentioned mill mixing ratio to obtain eight underground glazes. These glazes were glazed on a degreased 0.8 mm thick steel plate and baked at a temperature of 820 ° C. for 2.5 minutes to obtain an enamelled sample having an enamel layer having a thickness of about 100 μm. About the obtained sample, the appearance of the enamel layer was visually observed, and the measurement of the degree of opacity of the enamel surface and the test for judging the adhesion were performed. The observations and test results are as shown in Tables 1 and 2, and the contents of the tests and evaluations are as follows. a) Opacity The lightness index (L * value) was measured using a colorimeter. The contents of each code in the table are as follows. L * value ○ = 51 or more △ = 45-50 × = less than 45 b) Adhesion According to the PEI adhesion test method, apply pressure with a hand press to give a prescribed concave surface deformation to the specimen, and then adhere with an adhesion meter. The index was measured. The contents of each code in the table are as follows. Adhesion index ＝= 71 or more Δ = 40 to 70 × = less than 40 c) Appearance The state of the enamel layer was visually observed. The contents of each code in the table are as follows. ○ = Smooth surface, bumps and dents are not noticeable △ = Smooth surface, bumps and dents are somewhat noticeable × = Surface is not smooth or bumps and dents are noticeable
Example (The unit of composition is weight%)
【０００８】 （組成成分の単位は重量％） [0008] (The unit of composition is weight%)
【０００９】 １、表２及び表３から明らかなように、比較例のものは
乳白度、外観は良いが密着性が劣る、また密着性、外観
は良いが乳白度が劣る、あるいは密着性、乳白度は良い
が外観が劣ると言うもので実用には供し得ない物であ
る。特に従来の下ぐすりの明度指数（Ｌ＊値）は３０前
後の値しか得られない。一方、実施例のものは密着性、
外観、乳白度とも優れ灰白色の下ぐすりとして実用上十
分な性能を有することが判る。次に上記実施例の下ぐす
りフリットに顔料添加した場合と従来の下ぐすりフリッ
トに顔料を添加した時の色の違いについて表４にそれぞ
れのミル配合を、表５に焼成後の色調の違いを色差計の
測色値で示す。[0009] 1. As is clear from Tables 2 and 3, the comparative examples had good opacity and good appearance but poor adhesion, and also had good adhesion and good appearance but poor opacity, or adhesion and opacity. It is good but has poor appearance and cannot be put to practical use. In particular, the lightness index (L * value) of the conventional undergassing can be obtained only around 30. On the other hand, in the case of the embodiment,
It can be seen that both the appearance and the milkiness are excellent and practically sufficient performance as an off-white undergarment. Next, Table 4 shows the respective mill formulations for the difference in color between the case where the pigment was added to the bottom frit and the case where the pigment was added to the conventional bottom frit. The difference is indicated by the colorimetric value of the color difference meter.
【００１０】 但し、青色顔料は日本フェロー製４１−２０７Ｃ、茶色
顔料は同じく４１−１０４Ｃを使用した。[0010] However, 41-207C manufactured by Nippon Fellow was used for the blue pigment, and 41-104C was also used for the brown pigment.
【００１１】 表に示されるＬ＊、ａ＊、ｂ＊、Ｃ＊はＪＩＳ Ｚ ８
７２２に定義されるＤ−ｎ法に準拠し刺激値直読方法に
より測定された値で、Ｌ＊は明度指数、ａ＊、ｂ＊は色
度（色相、彩度）を表す単位で、ａ＊値は赤−緑方向、
ｂ＊は黄−青方向を表し、彩度（Ｃ＊）は次の式で求め
られる値を表す。 Ｃ＊＝√ａ＊2＋ｂ＊2 表５より明らかなように、本発明の下ぐすりを使用した
ものは明度（Ｌ＊値）も高く、彩度（Ｃ＊値）も高くな
っていることが判る。本発明は上記実施例に限定される
ものではなく、例えば釉薬の組成数値は上記以外のもの
としてよく、また基本成分以外の補助成分として例え
ば、ＴｉＯ2、ＺｒＯ2、ＳｎＯ2、ＣｅＯ2のような酸化
物の添加も可能である。[0011] L *, a *, b * and C * shown in the table are JIS Z 8
L * is a value measured by a stimulus value direct reading method according to the Dn method defined in 722, L * is a lightness index, a * and b * are units representing chromaticity (hue, saturation), and a * Value is red-green direction,
b * indicates a yellow-blue direction, and chroma (C *) indicates a value obtained by the following equation. C * = √a * 2 + b * 2 As is clear from Table 5, those using the underpour according to the present invention have high lightness (L * value) and high chroma (C * value). You can see that. The present invention is not limited to the above embodiments. For example, the composition values of the glaze may be other than those described above, and as auxiliary components other than the basic components, for example, TiO 2 , ZrO 2 , SnO 2 , and CeO 2 Addition of a suitable oxide is also possible.
【００１２】[0012]
【発明の効果】以上説明したように本発明によれば、灰
白色を有する密着性の優れた下ぐすりフリットを、また
顔料添加により鮮やかな色調の焼成面を呈するほうろう
釉薬が得られる。As described above, according to the present invention, an underglaze frit having an off-white color and excellent adhesion can be obtained, and an enamel glaze exhibiting a fired surface of a vivid color tone by adding a pigment can be obtained.
Claims (1)
Ｏ3 ３％以下、Ｐ2Ｏ5 ３〜１５％、ＳｉＯ2 ２０〜
３５％、Ａｌ2Ｏ3 ５〜１５％、Ｂ2Ｏ3 １３〜２０
％、Ｒ2Ｏ（Ｎａ2Ｏ、Ｋ2Ｏ、Ｌｉ2Ｏの合計量） １３
〜２０％、ＲＯ（ＣａＯ、ＢａＯ、ＺｎＯなどのアルカ
リ土類金属酸化物の合計量） ３〜１０％、Ｆ2 ５％
未満を必須成分とすることを特徴とする鋼板ほうろう用
灰色下ぐすりフリット。1. Sb 2 O 3 8-20% by weight, M 0
O 3 3% or less, P 2 O 5 3 to 15%, SiO 2 20 to
35%, Al 2 O 3 5 to 15%, B 2 O 3 13 to 20
%, R 2 O (total amount of Na 2 O, K 2 O, and Li 2 O) 13
~20%, RO (CaO, BaO , the total amount of alkaline earth metal oxides such as ZnO) 3~10%, F 2 5 %
A gray bottom frit for steel enamels, characterized in that less than is an essential component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30551996A JPH10139476A (en) | 1996-11-01 | 1996-11-01 | Gray ground coat frit for enamel for steel plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30551996A JPH10139476A (en) | 1996-11-01 | 1996-11-01 | Gray ground coat frit for enamel for steel plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10139476A true JPH10139476A (en) | 1998-05-26 |
Family
ID=17946134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30551996A Pending JPH10139476A (en) | 1996-11-01 | 1996-11-01 | Gray ground coat frit for enamel for steel plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10139476A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001092177A1 (en) * | 2000-05-31 | 2001-12-06 | Corning Incorporated | DURABLE Sb-STABILIZED Mo+W PHOSPHATE GLASSES |
| WO2017016952A1 (en) * | 2015-07-24 | 2017-02-02 | Onderzoekscentrum Voor Aanwending Van Staal N.V. | Method for providing a co- and ni-free vitreous enamelled metal coated steel substrate and a primer composition therefor |
-
1996
- 1996-11-01 JP JP30551996A patent/JPH10139476A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001092177A1 (en) * | 2000-05-31 | 2001-12-06 | Corning Incorporated | DURABLE Sb-STABILIZED Mo+W PHOSPHATE GLASSES |
| US6432851B1 (en) * | 2000-05-31 | 2002-08-13 | Corning Incorporated | Durable Sb-stabilized Mo+W phosphate glasses |
| WO2017016952A1 (en) * | 2015-07-24 | 2017-02-02 | Onderzoekscentrum Voor Aanwending Van Staal N.V. | Method for providing a co- and ni-free vitreous enamelled metal coated steel substrate and a primer composition therefor |
| CN108025947A (en) * | 2015-07-24 | 2018-05-11 | 范斯塔尔股份有限公司应用研究中心 | The method of the steel substrate coated for providing the nature of glass enamel metal without Co and Ni and the paint base composition for this method |
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