JPS63230537A - Enameled product - Google Patents
Enameled productInfo
- Publication number
- JPS63230537A JPS63230537A JP6211987A JP6211987A JPS63230537A JP S63230537 A JPS63230537 A JP S63230537A JP 6211987 A JP6211987 A JP 6211987A JP 6211987 A JP6211987 A JP 6211987A JP S63230537 A JPS63230537 A JP S63230537A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- enamel
- matte
- layer
- zno
- 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 210000003298 dental enamel Anatomy 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 229910011255 B2O3 Inorganic materials 0.000 abstract description 7
- 229910052681 coesite Inorganic materials 0.000 abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 abstract description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- 239000002253 acid Substances 0.000 description 17
- 238000010304 firing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000009193 crawling Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910000680 Aluminized steel Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004534 enameling Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 102200021395 rs3739168 Human genes 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940095676 wafer product Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） この発明はほうろう製品に関する。[Detailed description of the invention] (Industrial application field) This invention relates to enamel products.
（従来の技術）
従来、鉄、アルミ、ステンレス等の基材の表面を被覆す
るほうろう層としては、光沢を有するクロス質のものが
一般に用いられていたが、最近建材用はうろうパネルや
看板、表示板あるいは黒板やホワイトボード（マーカー
ボード）等として、光沢の少ないマット質のほうろう層
を有するほうろう製品が要求されることが多くなってき
た。(Prior art) In the past, a glossy cloth material was generally used as the enamel layer to coat the surface of base materials such as iron, aluminum, and stainless steel, but recently it has been used for building materials such as enamel panels and signboards. Enamel products having a matte enamel layer with low gloss are increasingly required for display boards, blackboards, whiteboards (marker boards), and the like.
この艶消し状態のマット質はうろう層を有するほうろう
製品を得る方法としては種々の方法が試みられているが
問題が多い。Various methods have been tried to obtain enamel products having a waxy layer with this matte state, but there are many problems.
すわわち、通常のほうろうフリットにＳｉＯ２゜ＡＩ＋
０３．ＴｉＯ：＋等の高融点材料を多量に添加し、これ
らの材料の融点以下で焼成する方法は、はうろう層の表
面がざらつき、耐汚染性および耐食性が劣るうえ、焼成
温度のばらつきにより光沢むらを生じるという問題があ
る。またアルミはうろうで使用する鉛の含有量の多い低
融点フリットにアルカリ又はほう酸を多聞に加えて、珪
ｗｉ塩等の結晶を析出させる方法は、はうろう層表面の
ざらつき、および熱膨張係数の差によるヘアラインやク
ラックの発生により外観が劣り、耐薬品性、耐汚染性、
耐水性、耐候性とも劣る製品しか得られない。さらに５
ｆＯ２，ＴｉＯ２，Ａｌ１０３ 。In other words, SiO2゜AI+ is added to ordinary enamel frit.
03. The method of adding a large amount of high-melting-point materials such as TiO:+ and firing below the melting point of these materials results in a rough surface of the wax layer, poor stain resistance and corrosion resistance, and a lack of gloss due to variations in firing temperature. There is a problem of unevenness. In addition, a method of precipitating crystals such as silica salt by adding a large amount of alkali or boric acid to a low melting point frit with a high lead content used in aluminum coating is a method that prevents roughness on the surface of the coating layer and thermal expansion. The appearance is poor due to the occurrence of hairlines and cracks due to the difference in coefficients, and the chemical resistance, stain resistance,
Only products with poor water resistance and weather resistance can be obtained. 5 more
fO2, TiO2, Al103.
２ｒ０２などの高融点材料をプラズマ溶射により通常の
光沢を有するクロス質のほうろう層上に溶射する方法も
あるが、表面のざらつきが発生しやすく、耐汚染性の点
で問題がある。There is also a method of plasma spraying a high melting point material such as 2r02 onto a cloth enamel layer with normal gloss, but this tends to cause surface roughness and has problems in terms of stain resistance.
（発明が解決しようとする問題点）
この発明は上記従来の問題点を解決するもので、表面の
平滑性、耐酸性、耐汚染性、耐候性、基材への密着性等
がすぐれ均質で良好な外観を有するマット質はうろう層
をそなえたほうろう製品を提供しようとするものである
。(Problems to be Solved by the Invention) This invention solves the above-mentioned conventional problems. The objective is to provide an enamel product with a matte waxy layer that has a good appearance.
（問題点を解決するための手段）
しかしてこの発明のほうろう製品は、金属基板上に形成
したほうろう層が、ＳｉＯ２とＴｉＯ２とＺｒＯ２の合
計を４０〜６５重分％、Ｎａ２Ｏ。(Means for Solving the Problems) However, in the enamel product of the present invention, the enamel layer formed on the metal substrate contains 40 to 65% by weight of the total of SiO2, TiO2, and ZrO2, and Na2O.
Ｋ２Ｏ，Ｌｉ２Ｏのうち少なくともＬｉ２Ｏを含む２種
以上を１０〜２５重量％、ＺｎＯ，Ｍｇｃ。10 to 25% by weight of two or more of K2O and Li2O containing at least Li2O, ZnO, and Mgc.
Ｂａｄ、ＣａＯのうち少なくともＢａＯとＺｎＯを含む
２種以上を４〜２６重茄％、Ｂ２０３ 。B203 contains 4 to 26% by weight of two or more of Bad and CaO, including at least BaO and ZnO.
Ａｌ１０３．８ｂ２０３のうち少なくとも・Ｂ２０３を
含む１種以上を５〜２０重量％、Ｐ２Ｏ５とＭ２Ｏ３の
うち少な（ともＰ２０Ｓを含む１種以上を０．５〜６．
５重量％含有して成る光沢度５０％以下のマット質のほ
うろう層であり、かつ前記各成分の含有割合は、ＳｉＯ
２が１８〜４２重開％、ＴｉＯ２が１４〜２８重世％、
ＺｒＯ２が１〜４ｔｆｆｉ％、Ｌｉ２Ｏが２〜６重量％
、Ｎａ２Ｏが０〜１１重量％、Ｋ２０ｔｆｉＯ〜１２重
量％、ＺｎＯが１．５〜１０重量％、ＢａＯが１．５〜
１０１ｆｆｔ％、ＭａＯがＯ〜５ｆ［％、ＣａＯが０〜
８重ω％、Ｂ２Ｏ３が５〜１３重固％、Ａｌ２Ｏ３がＯ
〜４重量％、５ｂ２０３が０〜３重ω％、Ｐ２０５が０
．５〜２．５重量％、Ｍ ＯＯ３が０〜４重量％である
とともに、ＳｉＯ２／ＴｉＯ２の値が６５／３５〜４０
／６０の範囲内にあることを特徴とするほうろう製品で
ある。5 to 20% by weight of one or more of Al103.8b203 containing at least B203, and 0.5 to 6% of one or more of P2O5 and M2O3 (both containing P20S).
It is a matte enamel layer with a gloss level of 50% or less, containing 5% by weight of SiO
2 is 18-42%, TiO2 is 14-28%,
ZrO2 1-4tffi%, Li2O 2-6% by weight
, Na2O is 0-11% by weight, K20tfiO is ~12% by weight, ZnO is 1.5-10% by weight, BaO is 1.5-10% by weight.
101fft%, MaO is O~5f[%, CaO is 0~
8 weight ω%, B2O3 is 5-13 weight%, Al2O3 is O
~4% by weight, 5b203 is 0-3% ω%, P205 is 0
．． 5 to 2.5% by weight, MOO3 is 0 to 4% by weight, and the value of SiO2/TiO2 is 65/35 to 40.
It is an enamel product characterized by being within the range of /60.
この発明においては、発明者が研究の結果ｌ！Ｉた知見
に基づき、はうろう層の各構成成分を限定しているが、
以下その限定理由を説明する。In this invention, the inventor has researched l! Based on our knowledge, we have limited the constituent components of the crawling layer.
The reason for this limitation will be explained below.
まずＳｉＯ２，ＴｉＯ２，ＺｒＯ２（以下Ｒ０２群と総
称する）は、結晶化およびほうろうの耐久性向上のため
の必須成分であり、ＲＯ２群の総聞がほうろうフリット
中に占める割合が４０％（重量％。以下同じ）未満であ
ると焼成後のほうろう層の耐久性、耐酸性および表面の
艶消状態が劣るものとなり、また６５％を越えると結晶
化によりマット質化する温度が高くなり、生産性および
製品品質を低下させる。また各成分別では、ＳｉＯ２が
１８％未満だとほうろう層の耐久性、耐酸性が低下し、
４２％を越えるとマット質化潟度が高くなりすぎる。ま
たＴｉＯ２が１４％未満だと結晶化が悪く、２８％を越
えると焼成温度が高くなり、密着性も低下する。このＳ
ｉＯ２とＴｉＯ２の相互比率３ｉ０２／ＴｉＯ２が６５
／３５よりも大きくなるとマット質化が困難であり、た
とえマット質化しても必要焼成温度が非常に高温度であ
ったり、マット質の均一性、表面平滑性、発色の均一性
などを欠くことになる。また上記相互比率が４０／６０
未満になると焼成時にほうろうとしてガラス化しにくく
なり、密着性の低下をきたすので好ましくない。さらに
ＺｒＯ２については、その含有率が１％未満だとほうろ
う層の耐久性、耐酸性が劣り、４％を越えると他の成分
との関係でフリット中に均一に溶けにくくなり、溶融に
時間を要し、かつ耐酸性の低下、マット質化温度の高騰
をきたし好ましくない。First, SiO2, TiO2, and ZrO2 (hereinafter collectively referred to as the R02 group) are essential components for crystallization and improving the durability of enamel, and the total proportion of the RO2 group in the enamel frit is 40% (by weight). If the content is less than 65%, the durability, acid resistance, and matte surface of the enamel layer after firing will be poor, and if it exceeds 65%, the temperature at which it becomes matte due to crystallization will be high, which will reduce productivity. and reduce product quality. Furthermore, for each component, if SiO2 is less than 18%, the durability and acid resistance of the enamel layer will decrease.
If it exceeds 42%, the degree of matte formation becomes too high. Furthermore, if TiO2 is less than 14%, crystallization will be poor, and if it exceeds 28%, the firing temperature will be high and the adhesion will be reduced. This S
Mutual ratio of iO2 and TiO2 3i02/TiO2 is 65
If it is larger than /35, it is difficult to make it matte, and even if it is made matte, the required firing temperature may be extremely high, and the matte quality, surface smoothness, uniformity of color development, etc. will be lacking. become. Also, the above mutual ratio is 40/60
If it is less than this, it becomes enameled during firing and becomes difficult to vitrify, resulting in a decrease in adhesion, which is not preferable. Furthermore, regarding ZrO2, if the content is less than 1%, the durability and acid resistance of the enamel layer will be poor, and if it exceeds 4%, it will be difficult to dissolve uniformly in the frit due to the relationship with other components, and it will take time to melt. This is undesirable because it causes a decrease in acid resistance and a rise in the matting temperature.
次にＮａ２Ｏ、Ｋ２Ｏ、Ｌｉ２０（以下Ｒ２０群と総称
する）の総量を１０〜２５重出％に限定するのは、熱膨
張係数の大きいアルミはうろう基板以外のほうろう基板
に適したほうろう層の熱膨張係数を１１するためであり
、１０％未満だと硼酸やフッ化物などの低融点物質の混
入が必要となり、この場合はうろう層の耐久性、耐酸性
の著しい低下をきたし、通常の焼成温度では発色均一で
滑らかなマット質の形成が困難であり、また２５％を越
えると熱膨張係数率が大きくなりすぎ、ヘアライン、微
泡、変色等の外観的欠陥および耐久性の低下が生じるこ
とになる。またＲ２０群中、Ｌｉ２Ｏを必須成分とする
のは、ＴｉＯ２より低温の焼成温度で均一な乳白色の結
晶化を助長するためであり、Ｌｉ２Ｏが２％未満だとほ
うろう層が青味を帯びかつ、むらのある乳白色となり、
耐酸性の低下もきたし、６％を越えるとマット質はうろ
う層の表面の荒れが進み、耐酸性、耐汚染性、耐候性の
低下をきたし、熱膨張係数が大きくなりすぎてほうろう
欠陥を発生しやすくなる。Next, the reason why the total amount of Na2O, K2O, and Li20 (hereinafter collectively referred to as R20 group) is limited to 10 to 25% is because aluminum, which has a large coefficient of thermal expansion, is suitable for enameled substrates other than hollow substrates. This is to increase the expansion coefficient to 11. If it is less than 10%, it will be necessary to mix in low-melting substances such as boric acid or fluoride. In this case, the durability and acid resistance of the wax layer will be significantly reduced, making it difficult to perform normal firing. At high temperatures, it is difficult to form a smooth matte texture with uniform color development, and if the temperature exceeds 25%, the coefficient of thermal expansion becomes too large, resulting in appearance defects such as hair lines, microbubbles, and discoloration, and a decrease in durability. become. In addition, the reason why Li2O is an essential component in the R20 group is to promote uniform milky crystallization at a lower firing temperature than TiO2.If Li2O is less than 2%, the enamel layer becomes bluish and It becomes an uneven milky white color,
Acid resistance also decreases, and if it exceeds 6%, the surface of the enamel layer in matte materials becomes rough, resulting in a decrease in acid resistance, stain resistance, and weather resistance, and the coefficient of thermal expansion becomes too large, causing enamel defects. It is more likely to occur.
またＺｎＯ，ＭｏＯ，Ｂａｄ、ＣａＯ（以下Ｒ０群と総
称する）の総量が４％未満だと耐酸性、耐候性の低下を
きたし、２６％を越えるとフリットが高融点化し、焼成
不足状態のマット質表面しか得られず、密着不良をおこ
し好ましくない。またＺｎＯおよび８ａＯをそれぞれ１
．５〜１０％に限定するのは、はうろうの耐酸性、耐久
性の維持と、より低温域における均一で乳白色のマット
質はうろう層の形成をはかるためである。一方ＭｇＯお
よびＣａＯは金属素地の熱膨張係数に合せて選択するも
のであり、各成分上限値を越えると高融点化するととも
に、はうろう層の外観が鮮かな乳白色を呈しなくなり、
ｆｖｌｏ過剰添加の場合は青味を帯び易く、ＣａＯ過剰
添加の場合は淡褐色状の乳濁マット質になり易いという
問題を生じる。Furthermore, if the total amount of ZnO, MoO, Bad, and CaO (hereinafter collectively referred to as the R0 group) is less than 4%, acid resistance and weather resistance will decrease, and if it exceeds 26%, the frit will have a high melting point, resulting in an insufficiently fired mat. Only a rough surface can be obtained, resulting in poor adhesion, which is undesirable. In addition, 1 each of ZnO and 8aO was added.
．． The reason why it is limited to 5 to 10% is to maintain the acid resistance and durability of the wax, and to form a uniform milky white matte layer at lower temperatures. On the other hand, MgO and CaO are selected according to the thermal expansion coefficient of the metal base, and when the upper limit of each component is exceeded, the melting point becomes high and the appearance of the waxy layer no longer takes on a bright milky white color.
When excessive fvlo is added, it tends to be bluish, and when excessive CaO is added, it tends to become a light brown milky matte.
次に８２０３ 、Ａｌ１０３．５ｂ２０３ （以下Ｒ
２０３群と総称する）の総ωを５〜２０％とするのは、
はうろう層とほうろう基板の熱膨張合せのためと、耐久
性、耐酸性の維持を目的とするものである。このうちの
必須成分Ｂ２０３が５％未満だとフリットの高融点化お
よび高熱膨張化とそれに伴うほうろう外観の劣化をきた
し、１３％を越えると耐酸性、耐候性、耐汚染性等の低
下が著しくなる。なおＡ Ｉ２０３．５ｂ２０３をＢ２
Ｏ３に併用添加すれば、はうろう外観の向上、耐酸性維
持の点で好ましい。Next, 8203, Al103.5b203 (hereinafter R
The total ω of the 203 group) is set to 5 to 20% because
The purpose is to match the thermal expansion of the enamel layer and the enamel substrate, and to maintain durability and acid resistance. If the essential component B203 is less than 5%, the frit will have a high melting point and high thermal expansion, and the appearance of the enamel will deteriorate accordingly, and if it exceeds 13%, acid resistance, weather resistance, stain resistance, etc. will be significantly reduced. Become. In addition, A I203.5b203 is B2
It is preferable to add it together with O3 in terms of improving the waxy appearance and maintaining acid resistance.
その他の成分として、Ｐ２Ｏ５は少量で乳濁色のマット
質表面を形成する作用を有するが、２．５％を越える過
剰添加の場合はほうろう層表面に微細な泡を形成しやす
く、また正常な焼付が困難とる。またＭｏＯ３の添加は
ほうろう層表面を平滑化し、耐酸性、耐久性、耐汚染性
を向上させるものであるが、４％を越える添加は逆にほ
うろうが高融点化し焼不足を生じて密着不良となるので
好ましくない。As for other ingredients, P2O5 has the effect of forming a milky matte surface in small amounts, but if it is added in excess of 2.5%, it tends to form fine bubbles on the surface of the enamel layer, and Seizing is difficult. Additionally, the addition of MoO3 smoothes the surface of the enamel layer and improves acid resistance, durability, and stain resistance, but addition of more than 4% causes the enamel to have a high melting point, resulting in insufficient firing and poor adhesion. This is not desirable.
この発明におけるほうろう層とは、最外層表面部分のほ
うろう層を指すものである。The enamel layer in this invention refers to the enamel layer on the surface of the outermost layer.
またこの発明においてほうろう層の前記各構成成分の含
有率の調整は、前記各含有率の成分を有するほうろうフ
リットを用いることによっておこなってもよいし、フリ
ットに後入れ添加材を加えて釉薬を調合する際に、この
釉薬の各構成成分を前記各含有率に調整することによっ
ておこなってもよい。Further, in this invention, the content of each of the constituent components of the enamel layer may be adjusted by using an enamel frit having the components with the respective content, or by adding post-additives to the frit and preparing the glaze. When doing so, it may be carried out by adjusting each constituent component of this glaze to each of the above-mentioned contents.
（作用）
この発明のほうろう製品においては、はうろう層を構成
する各成分比率の組合せにより、この成分比率を有する
釉薬の焼成時に、６２０〜７４０℃の温度で溶融してい
た溶融はうろう層が７００〜８５０℃の焼成温度で失沢
化し、均質で滑らかな表面の光沢度５０％以下のマット
質はうろう層が金属基板上に形成される。(Function) In the enamel product of this invention, due to the combination of the ratios of each component constituting the enamel layer, when the glaze having this component ratio is fired, the molten enamel that was melted at a temperature of 620 to 740°C is removed. The layer loses luster at a firing temperature of 700 to 850°C, and a matte, wavy layer with a homogeneous and smooth surface with a gloss level of 50% or less is formed on the metal substrate.
（実施例） 以下この発明の実施例および比較例を説明する。(Example) Examples and comparative examples of the present invention will be described below.
先ずほうろう層形成用のフリットとして第１表に示す組
成のフリット順１〜８を用い、比較例としてアルミ用有
鉛フリットＮα９と通常の鉄はうろう用のチタン釉フリ
ットＮＱ１０を用いた。First, frits 1 to 8 having the compositions shown in Table 1 were used as frits for forming the enamel layer, and as comparative examples, a leaded frit Nα9 for aluminum and a titanium glaze frit NQ10 for ordinary iron were used.
これらのフリット中、フリットＮ（１１〜９は、フリッ
ト１００部に対しミル添加剤として炭酸カリウム０．２
部、市販のカープレックス（高５ｉＣ）＋粉末）０．５
部、硼酸０．２部、顔料として酸化チタン白５部を加え
、ｌｌＱ１０のフリットは、フリット１００部に対し、
蛙目粘土５部、炭酸カリウム０．２部、炭酸マグネシウ
ム０．１部、塩化カリウム０．２部を加えて、それぞれ
３００ｇ用磁製ボットミルに投入し専用ミル架台で１０
０分間粉砕後１００メツシュふるいでオールパスしたも
のを、釉薬１１Ｑ１〜１，０とした。さらにフリットＮ
α１０に上記添加剤の他、微珪石粉３０部を添加し、そ
の他は上記と同じ処理をして釉薬ＮＱ１１とした。Among these frits, Frit N (11 to 9 contains 0.2 potassium carbonate as a mill additive per 100 parts of frit)
part, commercially available Carplex (high 5iC) + powder) 0.5
part, 0.2 part of boric acid, and 5 parts of titanium oxide white as a pigment.
Add 5 parts of frog's eye clay, 0.2 parts of potassium carbonate, 0.1 part of magnesium carbonate, and 0.2 parts of potassium chloride, put each into a 300g porcelain bot mill, and grind for 10 minutes on a special mill stand.
The glaze 11Q1-1,0 was obtained by pulverizing for 0 minutes and passing through a 100-mesh sieve. Furthermore, frit N
In addition to the above additives, 30 parts of fine silica powder was added to α10, and the other treatments were the same as above to obtain glaze NQ11.
次にこれらの釉薬を下記イ〜ハの３種類のテストピース
上に施釉し、第１表に示すグロス質およびマット質の各
焼成温度で（ただし釉薬Ｎα１０はグロス費用として８
２０℃で、釉薬１１Ｑ１１はマット質として８２０℃で
）焼成して、はうろう製品試料を得た。Next, these glazes were glazed on the following three types of test pieces A to C, at each firing temperature for gloss and matte textures shown in Table 1 (however, glaze Nα10 was glazed at 8 as gross cost).
At 20°C, glaze 11Q11 was fired as a matte material (at 820°C) to obtain a wafer product sample.
イ）板厚１．６ａＩＩのほうろう用鋼板に鉄用黒下釉を
焼付けたもの
口）板厚０．５ ｍのアルミメッキ鋼板を７５０’Ｃで
１０分間加熱してＡｌ−Ｆｅ合金化処理したもの
ハ）板厚１．０ ｔｎｔｓの５ＵＳ−４３０’：）、テ
＞レスｔＪ４板をサンドプラス処理したもの
得られたほうろう製品試料について特性試験をおこなっ
た結果を第２表に示す。各特性試験の内容は下記の通り
である。B) A steel plate for enameling with a thickness of 1.6aII, which is baked with a black underglaze for iron.) An aluminized steel plate with a thickness of 0.5 m was heated at 750'C for 10 minutes to undergo Al-Fe alloying treatment. Table 2 shows the results of characteristic tests on the obtained enamel product samples obtained by sand-plus treatment of 5US-430':), Teeless TJ4 plate with a plate thickness of 1.0 tnts. The contents of each characteristic test are as follows.
（ａ）光沢度
ＪＩＳＺ−８７４１ｒ光沢度測定方法」により７５部鏡
面光沢測定法にて測定した。５０（％）以下がマット質
である。(a) Glossiness Measured by 75 parts specular gloss measurement method according to JISZ-8741r glossiness measurement method. 50(%) or less is matte.
（ｂ）表面粗さ
Ｊ １８Ｂ−０６０１ｒ表面あらさ」により測定したＲ
ｍａｘ（単位＝μｍ）を示す。(b) Surface roughness J R measured by 18B-0601r surface roughness
max (unit=μm) is shown.
（ｃ）発色
目視により発色を観察した。乳白色のものが均一な結晶
性のマット質をつくる。(c) Color development Color development was observed visually. The milky white color creates a uniform crystalline matte texture.
（ｄ）耐酸性
ＪＩＳＲ−４３０１ｒはうろう製品の品質基準」により
判定した。(d) Acid resistance JISR-4301r was determined according to the quality standards for Uro products.
（ｅ）耐汚染性
はうろう白板（ホワイトボード）用の黒色のマーカで線
書きしたものを、乾布、湿布でこすって書味性および消
去性を下記により判定した。(e) Stain resistance was determined by writing on a whiteboard with a black marker and rubbing it with a dry cloth or compress, and evaluating the writing quality and erasability as described below.
［書味性１ ◎＝スムーズに書ける。[Writability 1 ◎＝Can write smoothly.
〇−やや音が出て滑りが悪い。〇 - Slightly noisy and slippery.
八−音が出て引掛かり気味。Eight sounds come out and I feel like I'm stuck.
×＝引掛かってにじむ。× = Caught and smeared.
［消去性］ ◎＝乾布で軽くこすって消える。[Erasability] ◎ = Disappears by rubbing lightly with a dry cloth.
○＝乾布で強くこすって消える。○ = Disappears by rubbing vigorously with a dry cloth.
Δ＝湿布でこすると消える。Δ = Disappears when rubbed with a compress.
×＝消えない。× = does not disappear.
（ｆ）耐候性
カーボンアーク式のウェザ−メータ試験機を用いて２０
００時間照射し、東京地区約１０年に相当する促進試験
をおこない、はうろう面を目視観察した。(f) Using a weather resistant carbon arc type weather meter tester.
00 hours of irradiation, an accelerated test equivalent to about 10 years in the Tokyo area was conducted, and the crawling surface was visually observed.
（ｇ）密着性
Ｊ ｌ５Ｒ−４３０１により１ｍからの鋼球落下試験を
おこない、その結果を下記基準で判定した。(g) Adhesion J A steel ball drop test from 1 m was conducted using J15R-4301, and the results were judged according to the following criteria.
◎＝剥離、ひび割れ等の異常がない。◎=No abnormality such as peeling or cracking.
○＝小さなほうろう欠は又はひび割れが認められる。○=Small enamel chips or cracks are observed.
Δ＝一部素地が露出する。Δ=Part of the substrate is exposed.
Ｘ＝素地が広範囲にわたって露出する。X = substrate is exposed over a wide area.
（以下余白）
第２表から明らかなように、比較例のほうろう製品のマ
ット質はうろう層は、表面粗さが大きく、この肌荒れに
より耐酸性、耐汚染性、耐候性、密着性等が、いずれも
劣る実用困難なものしか得られないのに対し、実施例の
ほうろう製品のマット質はうろう層は、表面粗さが小さ
く、耐酸性、耐汚染性、耐候性、密着性等がいずれもす
ぐれていることが判る。(Margins below) As is clear from Table 2, the matte enamel layer of the comparative example enamel product has a large surface roughness, and this rough surface deteriorates acid resistance, stain resistance, weather resistance, adhesion, etc. In contrast, the matte quality and enamel layer of the enamel products in the examples have low surface roughness, and have good acid resistance, stain resistance, weather resistance, adhesion, etc. It turns out that both are excellent.
（発明の効果）
以上説明したようにこの発明によれば、表面の平滑性、
耐酸性、耐汚染性、耐候性、基材への密着性等がすぐれ
、均質で良好な外観を有するマット質はうろう層をそな
えたほうろう製品が得られ、建材パネルや看板、表示板
、黒板やホワイトボード等、光沢が少なくかつ耐久性に
富むほうろう製品として利用価値が高いものである。(Effects of the Invention) As explained above, according to the present invention, surface smoothness,
It has excellent acid resistance, stain resistance, weather resistance, adhesion to base materials, etc., and has a homogeneous and good appearance. Enamel products with a matte and waxy layer can be obtained, and can be used for building panels, signboards, display boards, etc. It has high utility value as a low-gloss, highly durable enamel product such as blackboards and whiteboards.
Claims (1)
Ｏ＿２とＺｒＯ＿２の合計を４０〜６５重量％、Ｎａ＿
２Ｏ、Ｋ＿２Ｏ、Ｌｉ＿２Ｏのうち少なくともＬｉＯ＿
２を含む２種以上を１０〜２５重量％、ＺｎＯ、ＭｇＯ
、ＢａＯ、ＣａＯのうち少なくともＢａＯとＺｎＯを含
む２種以上を４〜２６重量％、Ｂ＿２Ｏ＿３、Ａｌ＿２
Ｏ＿３、Ｓｂ＿２Ｏ＿３のうち少なくともＢ＿２Ｏ＿３
を含む１種以上を５〜２０重量％、Ｐ＿２Ｏ＿５とＭｏ
Ｏ＿３のうち少なくともＰ＿２Ｏ＿５を含む１種以上を
０．５〜６．５重量％含有して成る光沢度５０％以下の
マット質のほうろう層であり、かつ前記各成分の含有割
合は、 ＳｉＯ＿２が１８〜４２重量％、ＴｉＯ＿２が１４〜２
８重量％、ＺｒＯ＿２が１〜４重量％、Ｌｉ＿２Ｏが２
〜６重量％、Ｎａ＿２Ｏが０〜１１重量％、Ｋ＿２Ｏが
０〜１２重量％、ＺｎＯが１．５〜１０重量％、ＢａＯ
が１．５〜１０重量％、ＭｇＯが０〜５重量％、ＣａＯ
が０〜８重量％、Ｂ＿２Ｏ＿３が５〜１３重量％、Ａｌ
＿２Ｏ＿３が０〜４重量％、Ｓｂ＿２Ｏ＿３が０〜３重
量％、Ｐ＿２Ｏ＿５が０．５〜２．５重量％、ＭｏＯ＿
３が０〜４重量％であるとともに、ＳｉＯ＿２／ＴｉＯ
＿２の値が６５／３５〜４０／６０の範囲内にあること
を特徴とするほうろう製品。[Claims] The enamel layer formed on the metal substrate contains SiO_2 and Ti.
The total of O_2 and ZrO_2 is 40 to 65% by weight, Na_
At least LiO_ among 2O, K_2O, and Li_2O
10 to 25% by weight of two or more types including 2, ZnO, MgO
, 4 to 26% by weight of two or more of BaO and CaO containing at least BaO and ZnO, B_2O_3, Al_2
At least B_2O_3 among O_3 and Sb_2O_3
5 to 20% by weight of one or more types including P_2O_5 and Mo
It is a matte enamel layer with a glossiness of 50% or less, containing 0.5 to 6.5% by weight of at least one type of O_3, including at least P_2O_5, and the content ratio of each component is as follows: SiO_2 is 18%. ~42 wt%, TiO_2 14-2
8% by weight, 1 to 4% by weight of ZrO_2, 2% of Li_2O
~6% by weight, 0-11% by weight of Na_2O, 0-12% by weight of K_2O, 1.5-10% by weight of ZnO, BaO
is 1.5-10% by weight, MgO is 0-5% by weight, CaO
is 0 to 8% by weight, B_2O_3 is 5 to 13% by weight, Al
_2O_3 is 0-4% by weight, Sb_2O_3 is 0-3% by weight, P_2O_5 is 0.5-2.5% by weight, MoO_
3 is 0 to 4% by weight, and SiO_2/TiO
An enamel product characterized in that the value of _2 is within the range of 65/35 to 40/60.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6211987A JPH0672031B2 (en) | 1987-03-17 | 1987-03-17 | Enamel products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6211987A JPH0672031B2 (en) | 1987-03-17 | 1987-03-17 | Enamel products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63230537A true JPS63230537A (en) | 1988-09-27 |
| JPH0672031B2 JPH0672031B2 (en) | 1994-09-14 |
Family
ID=13190850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6211987A Expired - Fee Related JPH0672031B2 (en) | 1987-03-17 | 1987-03-17 | Enamel products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0672031B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63233026A (en) * | 1987-03-23 | 1988-09-28 | Nippon Furitsuto Kk | Enamel frit powder good in fluidity |
| US11261124B2 (en) | 2018-10-31 | 2022-03-01 | Lg Electronics Inc. | Enamel composition and method of preparing the same |
| US11274060B2 (en) | 2019-02-22 | 2022-03-15 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
| US11292743B2 (en) * | 2018-11-09 | 2022-04-05 | Lg Electronics Inc. | Enamel composition, method of preparing same, and cooking appliance |
| US11401201B2 (en) | 2019-02-22 | 2022-08-02 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
| US11479500B2 (en) | 2019-02-22 | 2022-10-25 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
| US11773007B2 (en) | 2019-02-22 | 2023-10-03 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
| US11780766B2 (en) | 2019-02-22 | 2023-10-10 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
-
1987
- 1987-03-17 JP JP6211987A patent/JPH0672031B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63233026A (en) * | 1987-03-23 | 1988-09-28 | Nippon Furitsuto Kk | Enamel frit powder good in fluidity |
| US11261124B2 (en) | 2018-10-31 | 2022-03-01 | Lg Electronics Inc. | Enamel composition and method of preparing the same |
| US11292743B2 (en) * | 2018-11-09 | 2022-04-05 | Lg Electronics Inc. | Enamel composition, method of preparing same, and cooking appliance |
| US11274060B2 (en) | 2019-02-22 | 2022-03-15 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
| US11401201B2 (en) | 2019-02-22 | 2022-08-02 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
| US11479500B2 (en) | 2019-02-22 | 2022-10-25 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
| US11773007B2 (en) | 2019-02-22 | 2023-10-03 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
| US11780766B2 (en) | 2019-02-22 | 2023-10-10 | Lg Electronics Inc. | Enamel composition, method for preparing enamel composition, and cooking appliance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0672031B2 (en) | 1994-09-14 |
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