JP5460367B2 - Glass lining composition - Google Patents
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- JP5460367B2 JP5460367B2 JP2010030382A JP2010030382A JP5460367B2 JP 5460367 B2 JP5460367 B2 JP 5460367B2 JP 2010030382 A JP2010030382 A JP 2010030382A JP 2010030382 A JP2010030382 A JP 2010030382A JP 5460367 B2 JP5460367 B2 JP 5460367B2
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- 239000011521 glass Substances 0.000 title claims description 91
- 239000000203 mixture Substances 0.000 title claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000006103 coloring component Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000000156 glass melt Substances 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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Description
本発明は、グラスライニング組成物に関し、更に詳細には、微細気泡を有し、保温性及び断熱性に優れたグラスライニング施釉層を形成することができるグラスライニング組成物に関する。 The present invention relates to a glass lining composition, and more particularly, to a glass lining composition that has fine bubbles and can form a glass lining glazed layer having excellent heat retention and heat insulation.
従来からグラスライニング機器は、低炭素鋼板あるいはステンレス系鋼板を素地とし、この素地金属と密着を強固にする下ぐすり用グラスライニング組成物を０．２〜０．４ｍｍ位焼き付けた後、高耐食性能を有する上ぐすり用グラスライニング組成物を通常０．６〜２．５ｍｍ位焼き付けることにより製造されている。 Conventionally, glass lining equipment is based on a low-carbon steel plate or stainless steel plate, and after being baked about 0.2 to 0.4 mm in a glass lining composition for lowering to strengthen the adhesion to the base metal, it has high corrosion resistance. It is manufactured by baking a glass lining composition having a function of about 0.6 to 2.5 mm.
従来のグラスライニング機器に使用されている下ぐすり用グラスライニング組成物及び上ぐすり用グラスライニング組成物は、下記の組成を有するフリット（ガラス溶融物粉末）から構成されている：
（Ａ）ＳｉＯ２＋ＴｉＯ２＋ＺｒＯ２：４６〜６７質量％
ただし、
ＳｉＯ２：４６〜６７質量％
ＴｉＯ２：０〜１８質量％
ＺｒＯ２：０〜１２質量％
（Ｂ）Ｒ２Ｏ（ＲはＮａ、ＫまたはＬｉを表す）：８〜２２質量％
ただし、
Ｎａ２Ｏ：８〜２２質量％
Ｋ２Ｏ：０〜１６質量％
Ｌｉ２Ｏ：０〜１０質量％
（Ｃ）Ｒ’Ｏ（Ｒ’はＣａ、Ｂａ、ＺｎまたはＭｇを表す）：０．９〜７質量％
ただし、
ＣａＯ：０．９〜７質量％
ＢａＯ：０〜６質量％
ＺｎＯ：０〜６質量％
ＭｇＯ：０〜５質量％
（Ｄ）Ｂ２Ｏ３＋Ａｌ２Ｏ３：１．２〜２２質量％
ただし、
Ｂ２Ｏ３：１．２〜２２質量％
Ａｌ２Ｏ３：０〜６質量％
（Ｅ）ＣｏＯ＋ＮｉＯ＋ＭｎＯ２：０〜５質量％
ただし、
ＣｏＯ：０〜５質量％
ＮｉＯ：０〜５質量％
ＭｎＯ２：０〜５質量％
The glass lining composition for the undercoat and the glass lining composition for the topcoat used in conventional glass lining equipment are composed of a frit (glass melt powder) having the following composition:
(A) SiO 2 + TiO 2 + ZrO 2 : 46 to 67% by mass
However,
SiO 2: 46~67 mass%
TiO 2: 0 to 18 wt%
ZrO 2 : 0 to 12% by mass
(B) R 2 O (R represents Na, K or Li): 8 to 22 wt%
However,
Na 2 O: 8 to 22 wt%
K 2 O: 0 to 16% by mass
Li 2 O: 0 to 10% by mass
(C) R′O (R ′ represents Ca, Ba, Zn or Mg): 0.9 to 7% by mass
However,
CaO: 0.9-7 mass%
BaO: 0 to 6% by mass
ZnO: 0 to 6% by mass
MgO: 0 to 5% by mass
(D) B 2 O 3 + Al 2 O 3: 1.2~22 wt%
However,
B 2 O 3: 1.2~22 wt%
Al 2 O 3 : 0 to 6% by mass
(E) CoO + NiO + MnO 2 : 0 to 5% by mass
However,
CoO: 0 to 5% by mass
NiO: 0 to 5% by mass
MnO 2 : 0 to 5% by mass
また、着色成分としてＳｂ２Ｏ５、Ｃｒ２Ｏ３、Ｆｅ２Ｏ３、ＳｎＯ２の少なくとも１種を上記フリット組成１００％に対して最大Ｆｅ２Ｏ３換算量で５質量％まで添加されたフリットもある。更に、フリットの溶融を促進するために、前記ＳｉＯ２、ＣａＯ、Ｎａ２Ｏ成分のうち５質量％を限度にフッ化物も使用されている。フッ化物としては例えばＮａ２ＳｉＦ６、ＣａＦ２、Ｎａ３ＡｌＦ６が使用されている。 Further, as a coloring component, at least one of Sb 2 O 5 , Cr 2 O 3 , Fe 2 O 3 , and SnO 2 was added up to 5% by mass in terms of the maximum Fe 2 O 3 conversion amount with respect to 100% of the frit composition. There is also a frit. Furthermore, in order to promote melting of the frit, fluoride is also used up to 5% by mass of the SiO 2 , CaO, and Na 2 O components. For example, Na 2 SiF 6 , CaF 2 , or Na 3 AlF 6 is used as the fluoride.
また、グラスライニング施釉層の導電性を改善するために、例えば特許文献１には、フリットを含むグラスライニング組成物であって、直径０．５〜３０ミクロン、長さ１．５〜１０ｍｍ、長さ／直径の形状比５０以上の金属繊維を前記フリット１００重量部（質量部）に対して０．０５〜１．５重量部（質量部）含有してなることを特徴とする導電性グラスライニング組成物（請求項１）；金属繊維がステンレス系金属、貴金属系金属、及び白金と白金族金属との合金からなる群から選択される１種または２種以上である請求項１記載の導電性グラスライニング組成物（請求項２）が開示されている。 In order to improve the conductivity of the glass lining layer, for example, Patent Document 1 discloses a glass lining composition containing a frit having a diameter of 0.5 to 30 microns, a length of 1.5 to 10 mm, and a length. Conductive glass lining comprising 0.05 to 1.5 parts by weight (parts by mass) of metal fiber having a thickness / diameter shape ratio of 50 or more with respect to 100 parts by weight (parts by mass) of the frit The composition according to claim 1, wherein the metal fiber is one or more selected from the group consisting of a stainless steel metal, a noble metal metal, and an alloy of platinum and a platinum group metal. A glass lining composition (claim 2) is disclosed.
更に、特許文献２には、フリットを含むグラスライニング組成物であって、直径０．０１ミクロン以上０．５ミクロン未満、長さ０．５〜１５００ミクロン、長さ／直径の形状比５０以上の金属繊維を前記フリット１００重量部（質量部）に対して０．００１〜０．０５重量部（質量部）含有してなることを特徴とする導電性グラスライニング組成物（請求項１）が開示されている。 Furthermore, Patent Document 2 discloses a glass lining composition containing a frit having a diameter of 0.01 to less than 0.5 microns, a length of 0.5 to 1500 microns, and a length / diameter shape ratio of 50 or more. Disclosed is a conductive glass lining composition comprising metal fibers in an amount of 0.001 to 0.05 parts by weight (parts by weight) with respect to 100 parts by weight (parts by weight) of the frit. Has been.
また、特許文献３には、フリットを含むグラスライニング組成物であって、直径０．１〜３０ミクロン、長さ０．００５〜３ｍｍ、長さ／直径の形状比５０以上のセラミックス繊維を前記フリット１００重量部（質量部）に対して０．０５〜１．５重量部（質量部）含有してなることを特徴とする導電性グラスライニング組成物（請求項１）；セラミックス繊維が炭化物系繊維及び／または炭素繊維である、請求項１記載の導電性グラスライニング組成物（請求項２）；更に、直径０．０１〜３０ミクロン、長さ０．５ミクロン〜３ｍｍ、長さ／直径の形状比５０以上の金属繊維をフリット１００重量部（質量部）に対して０．００１〜１．４５重量部（質量部）含有してなる、請求項１または２記載の導電性グラスライニング組成物（請求項３）が開示されている。 Patent Document 3 discloses a glass lining composition containing a frit, wherein ceramic fibers having a diameter of 0.1 to 30 microns, a length of 0.005 to 3 mm, and a length / diameter shape ratio of 50 or more are included in the frit. The conductive glass lining composition comprising 0.05 to 1.5 parts by weight (parts by mass) with respect to 100 parts by weight (parts by mass) (Claim 1); 2. A conductive glass lining composition according to claim 1 which is and / or carbon fiber (claim 2); further, a shape of diameter 0.01-30 microns, length 0.5 microns-3 mm, length / diameter The conductive glass lining composition according to claim 1 or 2, comprising 0.001 to 1.45 parts by weight (parts by mass) of metal fibers having a ratio of 50 or more per 100 parts by weight (parts by mass) of the frit. Claim 3) is disclosed.
ここで、従来、グラスライニング機器におけるグラスライニング施釉層の厚みは、ＪＩＳ Ｒ４２０１規格により０．６〜２．５ｍｍと定められているが、実際のグラスライニング機器におけるグラスライニング施釉層の厚みは、焼成過程におけるピンホール発生、修正、手直し焼成等の反復により、１．３〜２．０ｍｍ程度で製品化されている。即ち、グラスライニング組成物の施釉は、１回当り０．２〜０．３ｍｍ位で、下ぐすり用グラスライニング組成物の施釉を１〜２回、上ぐすり用グラスライニング組成物の施釉を４〜６回行い、その都度、焼成炉内で溶融、焼き付けを行っている。 Here, conventionally, the thickness of the glass lining glazing layer in the glass lining equipment is defined as 0.6 to 2.5 mm according to the JIS R4201 standard, but the thickness of the glass lining glazing layer in the actual glass lining equipment is fired. It has been commercialized with a thickness of about 1.3 to 2.0 mm by repeating pinhole generation, correction, reworking firing, etc. in the process. That is, the glazing of the glass lining composition is about 0.2 to 0.3 mm per time, the glazing of the glass lining composition for the undercoat is applied once or twice, and the glazing of the glass lining composition for the upper lining is applied. It is performed 4 to 6 times, and each time melting and baking are performed in a baking furnace.
これまでのグラスライニング機器、グラスライニング施釉層に係る研究・開発は、グラスライニング施釉層の基体となる金属基体、例えば低炭素鋼板、ステンレス系鋼板等へのグラスライニング施釉層の密着性の向上、グラスライニング施釉層の薄肉化、グラスライニング施釉層からの汚染防止や、グラスライニング施釉層の帯電防止などに向けられており、グラスライニング施釉層の保温性や断熱性の向上については検討されていないのが現状である。 Research and development related to glass lining equipment and glass lining glazing layers so far have improved the adhesion of glass lining glazing layers to metal substrates such as low carbon steel plates and stainless steel plates, etc. It is aimed at reducing the thickness of the glass-lined glazed layer, preventing contamination from the glass-lined glazed layer, and preventing the anti-static property of the glass-lined glazed layer. is the current situation.
従って、本発明の目的は、微細気泡を有し、保温性及び断熱性に優れたグラスライニング施釉層を形成することができるグラスライニング組成物を提供することにある。 Accordingly, an object of the present invention is to provide a glass lining composition capable of forming a glass lining glazed layer having fine bubbles and having excellent heat retaining properties and heat insulating properties.
本発明者らは、上記課題を解消すべく鋭意検討した結果、これまでグラスライニング施釉層の諸特性を悪化させる、特に、ピンホールや剥離の原因となるとして嫌われていた多孔質材料を使用してグラスライニング施釉層に気泡を存在させ、且つ気泡寸法をナノメートルオーダーで制御することにより、グラスライニング施釉層の諸特性を飛躍的に向上することができると共に保温性及び断熱性を有するグラスライニング施釉層を形成することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have deteriorated various characteristics of the glass-lined glazed layer, and in particular, use a porous material that has been disliked as a cause of pinholes and peeling. The glass-lined glazed layer allows air bubbles to exist and the bubble size to be controlled on the order of nanometers, so that various properties of the glass-lined glazed layer can be drastically improved and the glass has heat retaining properties and heat insulation properties. The inventors have found that a lining glazed layer can be formed, and have completed the present invention.
即ち、本発明のグラスライニング組成物は、グラスライニング用フリット１００質量部に対してナノメートルオーダーの気泡を有するナノ多孔質（nanoporous）セラミック粒子を１〜５０質量部を含むことを特徴とする。 That is, the glass lining composition of the present invention includes 1 to 50 parts by mass of nanoporous ceramic particles having nanometer-order air bubbles with respect to 100 parts by mass of the glass lining frit.
本発明のグラスラスニング組成物によれは、微細気泡を有し、保温性及び断熱性に優れたグラスライニング施釉層を形成することができるグラスライニング組成物を提供することができるという効果を奏する。 According to the glass lining composition of the present invention, there is an effect that it is possible to provide a glass lining composition that has fine bubbles and can form a glass lining glazed layer that is excellent in heat retention and heat insulation. .
本発明のグラスライニング組成物は、グラスライニング用フリット（ガラス溶融物粉末）に、ナノメートルオーダーの気泡を有するナノ多孔質セラミック粒子を配合することに特徴がある。ナノメートルオーダーの気泡を有するナノ多孔質セラミック粒子を配合するによりより、微細気泡を有するグラスライニング施釉層を形成することができ、微細気泡の存在により、グラスライニング施釉層に保温性並びに断熱性を付与することができるものである。 The glass lining composition of the present invention is characterized in that nanoporous ceramic particles having nanometer order bubbles are blended with a glass lining frit (glass melt powder). By blending nanoporous ceramic particles with bubbles on the order of nanometers, it is possible to form a glass-lined glazed layer with fine bubbles, and the presence of fine bubbles makes the glass-lined glazed layer have heat retention and heat insulation. It can be granted.
ここで、グラスライニング用フリットへのナノメートルオーダーの気泡を有するナノ多孔質セラミック粒子の配合割合は、フリット１００質量部に対して１〜５０質量部、好ましくは１０〜３０質量部の範囲内である。ナノ多孔質セラミック粒子の配合割合が１質量部未満であると、その添加効果が発現しないために好ましくなく、また、５０質量部を超えると、耐火性が高くなりすぎ、平滑性に劣るために好ましくない。なお、ナノ多孔質セラミックス粒子に存在する「気泡」とは、粒子内に封止された形態で存在する気泡と、粒子表面に存在する開放気孔を総称するものとする。 Here, the compounding ratio of the nanoporous ceramic particles having nanometer-order bubbles to the glass lining frit is 1 to 50 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the frit. is there. If the blending ratio of the nanoporous ceramic particles is less than 1 part by mass, the addition effect is not manifested, and if it exceeds 50 parts by mass, the fire resistance becomes too high and the smoothness is poor. It is not preferable. The “bubbles” present in the nanoporous ceramic particles are generically referred to as bubbles present in a form sealed in the particles and open pores existing on the particle surface.
次に、本発明のグラスライニング組成物に使用できるナノメートルオーダーの気泡を有するナノ多孔質セラミック粒子としては、例えば粒子径１〜１５μｍ、好ましくは１〜１０μｍ、粒子内の気泡径１〜３００ｎｍ、好ましくは１〜１００ｎｍ、気孔率４５〜６５％、好ましくは５０〜６０％を有するナノ多孔質シリカ粒子を例示することができる。 Next, as nanoporous ceramic particles having nanometer-order bubbles that can be used in the glass lining composition of the present invention, for example, a particle diameter of 1 to 15 μm, preferably 1 to 10 μm, a bubble diameter of 1 to 300 nm in the particles, Nanoporous silica particles having preferably 1 to 100 nm and a porosity of 45 to 65%, preferably 50 to 60% can be exemplified.
このようなナノ多孔質シリカ粒子は、例えば水ガラスを油性溶媒及び界面活性剤と共に攪拌混合してコロイド状態にした後、沈澱、乾燥させて水成分を除去し、粒度調整することにより製造することができる。 Such nanoporous silica particles are produced by, for example, mixing water glass with an oily solvent and a surfactant into a colloidal state, then precipitating and drying to remove water components and adjusting the particle size. Can do.
次に、本発明のグラスライニング組成物に使用可能なグラスライニング用フリット（ガラス溶融物粉末）は、下記の（Ａ）〜（Ｄ）からなるものである：
（Ａ）ＳｉＯ２＋ＴｉＯ２＋ＺｒＯ２：４６〜７２質量％
ただし、ＳｉＯ２：４６〜７０質量％
ＴｉＯ２：０．１〜５質量％
ＺｒＯ２：２〜１５質量％
（Ｂ）Ｒ２Ｏ（ＲはＮａ、Ｋ、Ｌｉ、Ｃｓを示す）：８〜２２質量％
ただし、Ｎａ２Ｏ：６〜２０質量％
Ｋ２Ｏ：０〜１６質量％
Ｌｉ２Ｏ：２〜２０質量％
Ｃｓ２Ｏ：０〜１６質量％
（Ｃ）Ｒ’Ｏ（Ｒ’はＣａ、Ｍｇ、Ｂａ、Ｓｒ、Ｚｎを示す）：１〜８質量％
ただし、ＣａＯ：１〜８質量％
ＭｇＯ：０〜５質量％
ＢａＯ：０〜５質量％
ＳｒＯ：０〜５質量％
ＺｎＯ：０〜５質量％
（Ｄ）Ｂ２Ｏ３＋Ａｌ２Ｏ３：１〜１８質量％
ただし、Ｂ２Ｏ３：１〜１８質量％
Ａｌ２Ｏ３：０〜６質量％
Next, the glass lining frit (glass melt powder) that can be used in the glass lining composition of the present invention comprises the following (A) to (D):
(A) SiO 2 + TiO 2 + ZrO 2 : 46 to 72% by mass
However, SiO 2: 46~70 mass%
TiO 2 : 0.1 to 5% by mass
ZrO 2 : 2 to 15% by mass
(B) R 2 O (R represents Na, K, Li, Cs): 8 to 22% by mass
However, Na 2 O: 6~20 wt%
K 2 O: 0 to 16% by mass
Li 2 O: 2 to 20% by mass
Cs 2 O: 0 to 16% by mass
(C) R′O (R ′ represents Ca, Mg, Ba, Sr, Zn): 1 to 8% by mass
However, CaO: 1-8 mass%
MgO: 0 to 5% by mass
BaO: 0 to 5% by mass
SrO: 0 to 5% by mass
ZnO: 0 to 5% by mass
(D) B 2 O 3 + Al 2 O 3: 1~18 wt%
However, B 2 O 3: 1~18 wt%
Al 2 O 3 : 0 to 6% by mass
ここで、成分（Ａ）の含有量が、４６質量％未満であると、フリット自体の強度が低下するために好ましくなく、また、７２質量％を超えると、フリットの溶融粘性が高くなり、グラスライニング組成物の溶融点が上昇するために好ましくない。 Here, if the content of the component (A) is less than 46% by mass, the strength of the frit itself is not preferable, and if it exceeds 72% by mass, the melt viscosity of the frit increases, and the glass This is not preferable because the melting point of the lining composition is increased.
また、成分（Ｂ）の含有量が、８質量％未満であると、フリットの溶融性が悪くなるために好ましくなく、また、２２質量％を超えると、フリットの線熱膨張係数が上昇し、物性バランスが崩れるために好ましくない。 Further, if the content of the component (B) is less than 8% by mass, the frit meltability is deteriorated, which is not preferable. If the content exceeds 22% by mass, the linear thermal expansion coefficient of the frit increases. This is not preferable because the balance of physical properties is lost.
更に、成分（Ｃ）の含有量が、１質量％未満であると、フリットの耐アルカリ性能を向上させるためには不充分であり、また、８質量％を超えると、フリットの溶融粘性が高くなり、グラスライニング組成物の溶融点が上昇するために好ましくない。 Further, if the content of the component (C) is less than 1% by mass, it is insufficient for improving the alkali resistance performance of the frit. If it exceeds 8% by mass, the melt viscosity of the frit is high. This is not preferable because the melting point of the glass lining composition is increased.
また、成分（Ｄ）の含有量が、１質量％未満であると、フリットの溶融性を低下させる効果と、失透防止効果が減少するために好ましくなく、また、１８質量％を超えると、焼成中の発泡現象が著しくなるために好ましくない。 Further, if the content of the component (D) is less than 1% by mass, the effect of lowering the frit meltability and the devitrification preventing effect are not preferable, and if it exceeds 18% by mass, This is not preferable because the foaming phenomenon during firing becomes significant.
なお、グラスライニング用フリットは、ＳｉＯ２、Ａｌ２Ｏ３及びＣａＯのうち５質量％までをフッ化物の形態で使用することもできる。 Incidentally, the frit for glass lining may also be used up to 5% by weight of SiO 2, Al 2 O 3 and CaO in the form of fluoride.
更に、本発明のグラスライニング組成物に使用するグラスライニング用フリットは、ＭｎＯ２、ＮｉＯ、ＣｏＯ、Ｓｂ２Ｏ３、Ｃｒ２Ｏ３、Ｆｅ２Ｏ３、ＲｕＯ２及びＣｅＯ２からなる群から選択される１種または２種以上の着色成分を含有することができる。着色成分の配合量は、３質量％まで、好ましくは２質量％までである。ここで、着色成分の配合量が、３質量％を超えると、焼成中の発泡現象が著しくなるために好ましくない。 Further, the glass lining frit used in the glass lining composition of the present invention is selected from the group consisting of MnO 2 , NiO, CoO, Sb 2 O 3 , Cr 2 O 3 , Fe 2 O 3 , RuO 2 and CeO 2. One or two or more coloring components can be contained. The blending amount of the coloring component is up to 3% by mass, preferably up to 2% by mass. Here, if the blending amount of the coloring component exceeds 3% by mass, the foaming phenomenon during firing becomes remarkable, which is not preferable.
また、本発明のグラスライニング組成物は、更に、直径０．１〜３０ミクロン、好ましくは０．３〜２ミクロン、長さ０．００５〜３ｍｍミクロン、好ましくは０．０５〜１ｍｍ、長さ／直径の形状比５０以上、好ましくは１００以上の金属繊維を含有することができる。本発明のグラスライニング組成物に金属繊維を併用することにより、グラスライニング施釉層の耐火性と熱伝導性を向上させることができると共に施釉層に導電性を付与することもできる。ここで、金属繊維の直径が０．１ミクロン未満では、金属繊維自体の加工が難しく、現状では使用することができない。また、該直径が３０ミクロンを超えると、スリップ粘性が乏しくなるために好ましくない。また、金属繊維の長さが０．００５ｍｍ未満では、その添加効果が発現しないために好ましくなく、また、該長さが３ｍｍを超えると、グラスライニング組成物としてのスリップ粘性が乏しくなり、スプレー施工性が著しく劣り、グラスライニング施釉層を薄肉化することができないために好ましくない。更に、無機繊維の長さ／直径の形状比が５０未満であると、グラスライニング施釉層の耐火性や熱伝導性を向上させることができないために好ましくない。 The glass lining composition of the present invention further has a diameter of 0.1 to 30 microns, preferably 0.3 to 2 microns, a length of 0.005 to 3 mm, preferably 0.05 to 1 mm, length / Metal fibers having a diameter shape ratio of 50 or more, preferably 100 or more can be contained. By using a metal fiber in combination with the glass lining composition of the present invention, it is possible to improve the fire resistance and thermal conductivity of the glass lining glazed layer and to impart conductivity to the glazed layer. Here, if the diameter of the metal fiber is less than 0.1 microns, it is difficult to process the metal fiber itself, and it cannot be used at present. On the other hand, if the diameter exceeds 30 microns, the slip viscosity becomes poor, such being undesirable. Further, if the length of the metal fiber is less than 0.005 mm, the effect of addition is not exhibited, which is not preferable. If the length exceeds 3 mm, the slip viscosity as the glass lining composition becomes poor, and the spray construction is performed. This is not preferable because the glass lining glazed layer cannot be thinned. Furthermore, when the length / diameter shape ratio of the inorganic fibers is less than 50, the fire resistance and thermal conductivity of the glass-lined glazed layer cannot be improved.
なお、金属繊維の配合量は、グラスライニング用フリット１００質量部に対して外割で０．０１〜１．５質量部、好ましくは０．１〜０．５質量部の範囲内である。ここで、金属繊維の含有量が、０．０１質量％未満であると、その含有効果が発現しないために好ましくなく、また、１．５質量％を超えると、スリップ粘性が乏しくなり、スプレー施工性が著しく劣るために好ましくない。なお、金属繊維の含有量が上記範囲内であれば、グラスライニング焼成面での発泡や、凹凸現象がなく、良好な品質のグラスライニング施釉層を得ることができる。 In addition, the compounding quantity of a metal fiber is 0.01-1.5 mass parts by the outer division with respect to 100 mass parts of glass frit for glass lining, Preferably it exists in the range of 0.1-0.5 mass part. Here, if the content of the metal fiber is less than 0.01% by mass, the content effect is not manifested, and if it exceeds 1.5% by mass, the slip viscosity becomes poor and spraying is performed. This is not preferable because the property is extremely inferior. In addition, if content of a metal fiber is in the said range, there will be no foaming and an uneven | corrugated phenomenon in a glass lining baking surface, and a glass lining glazing layer of favorable quality can be obtained.
金属繊維としては、例えば貴金属系金属、及び白金と白金族金属との合金を使用することができる。 As the metal fiber, for example, a noble metal metal and an alloy of platinum and a platinum group metal can be used.
本発明のグラスライニング組成物は、上ぐすり用組成物または１回掛け用組成物として慣用の基材例えば鋼板あるいはステンレス系鋼板等へ慣用の方法により施釉することができる。例えばグラスライニング組成物には、グラスライニング用フリット１００質量％に対して粘土を外割で０〜５質量％、好ましくは２〜４質量％、セルロースを外割で０．０１〜０．０８質量％、好ましくは０．０３〜０．０６質量％、塩化バリウムを外割で０．０５〜０．３質量％、好ましくは０．１〜０．２質量％、及び水、アルコールのようなミル添加物を添加したスリップとして使用することができる。 The glass lining composition of the present invention can be applied to a conventional base material such as a steel plate or a stainless steel plate by a conventional method as a topping composition or a one-time composition. For example, in the glass lining composition, the clay is 0 to 5% by mass, preferably 2 to 4% by mass, and the cellulose is 0.01 to 0.08% by mass based on 100% by mass of the glass lining frit. %, Preferably 0.03 to 0.06% by mass, barium chloride is 0.05 to 0.3% by mass, preferably 0.1 to 0.2% by mass, and a mill such as water and alcohol It can be used as a slip with added additives.
なお、本発明のグラスライニング組成物のスリップの施釉操作、焼成温度等の操作は特に限定されるものではなく、慣用、公知の操作を使用することができる。 In addition, operation of slip glazing operation, baking temperature, etc. of the glass lining composition of the present invention is not particularly limited, and conventional and known operations can be used.
本発明のグラスライニング組成物は、施工性、密着性及び耐剥離性に優れ、更に、保温性及び断熱性に優れるので、例えば太陽熱収集装置の集熱部等に使用することもできる。太陽熱収集装置の集熱部が例えばパイプ状の場合、パラボラ型集光板の焦点部分に集熱部を設置することにより、太陽熱を集熱部に高密に集めることが可能となる。集熱部に使用されるパイプは、通常４〜６ｍの定尺長さを有する金属パイプから構成される。これより長い長尺パイプから構成される集熱体は、パイプ間のシール部分が少なく、接続部からの漏れによる太陽熱収集装置の運定停止が少なくなるために好ましい。この長尺パイプの製造方法としては、金属パイプの溶接部、サンドブラスト施工部、グラスライニング組成物をサンドブラスト処理部に施釉する施釉部、前記施釉部を焼成する加熱部を連続的に構成したトンネル状の装置を設けることにより製造することができる。このような製造装置を太陽熱収集装置を設置する現場に設置することにより、現場で連続した太陽熱収集装置を製造することが可能となる。また、集熱部はパイプ形状以外に平板形状でもよく、更に、平板形状の施釉される面を太陽面に向かって突出した複数のエンボス形状とすることにより、太陽光の光軸と平板の面がずれても、エンボス形状のいずれかの場所が太陽光のｉ光軸に直角に対峙することになり、太陽熱を高密に集めることが可能となる。 Since the glass lining composition of the present invention is excellent in workability, adhesion and peel resistance, and further excellent in heat retention and heat insulation, it can also be used, for example, in a heat collecting part of a solar heat collecting device. When the heat collecting part of the solar heat collecting apparatus is, for example, a pipe shape, it is possible to collect solar heat with high density in the heat collecting part by installing the heat collecting part at the focal part of the parabolic light collector. The pipe used for a heat collecting part is normally comprised from the metal pipe which has a fixed length of 4-6m. A heat collector composed of a long pipe longer than this is preferable because there are few sealing portions between the pipes and the operation stoppage of the solar heat collecting device due to leakage from the connection portion is reduced. As a manufacturing method of this long pipe, a welded part of a metal pipe, a sandblasting part, a glazing part for applying a glass lining composition to a sandblasting part, and a heating part for continuously firing the glazing part It can manufacture by providing this apparatus. By installing such a manufacturing apparatus at the site where the solar heat collecting device is installed, it becomes possible to manufacture a continuous solar heat collecting device at the site. Further, the heat collecting part may be a flat plate shape in addition to the pipe shape, and further, the surface of the flat plate shape is formed into a plurality of embossed shapes protruding toward the solar surface, so that the optical axis of sunlight and the flat plate surface Even if the deviation occurs, any part of the embossed shape faces the i optical axis of sunlight at right angles, so that solar heat can be collected with high density.
また、本発明のグラスライニング組成物から得られた施釉層を備えた構造体は、炉などからの排熱回収装置の集熱体にも使用でき、この場合の集熱体はパイプ形状あるいは平板形状のいずれでもよく、グラスライニング施釉層の微細気泡の気泡径、気孔率は、排熱を構成する赤外線などの線源に対応して適宜決定することができる。 Further, the structure provided with the glazed layer obtained from the glass lining composition of the present invention can also be used as a heat collector of an exhaust heat recovery apparatus from a furnace or the like. In this case, the heat collector is a pipe shape or a flat plate. Any of the shapes may be used, and the bubble diameter and porosity of the fine bubbles in the glass-lined glazed layer can be appropriately determined according to the radiation source such as infrared rays constituting the exhaust heat.
以下、実施例により、本発明のグラスライニング組成物を更に説明する。
実施例１
以下の表１に記載する配合割合にて本発明品及び比較品のグラスライニング組成物のスリップを調製した：
Hereinafter, the glass lining composition of the present invention will be further described with reference to examples.
Example 1
The slips of the inventive and comparative glass lining compositions were prepared at the compounding ratios listed in Table 1 below:
なお、表１中、フリットの組成は以下の通りである：
ＳｉＯ２＋ＴｉＯ２＋ＺｒＯ２：７０質量％
ＳｉＯ２：６７質量％
ＴｉＯ２：１質量％
ＺｒＯ２：２質量％
Ｒ２Ｏ：１７質量％
Ｎａ２Ｏ：１５質量％
Ｋ２Ｏ：０．５質量％
Ｌｉ２Ｏ：１．５質量％
Ｒ’Ｏ：５質量％
ＣａＯ：４．５質量％
ＢａＯ：０．５質量％
Ｂ２Ｏ３＋Ａｌ２Ｏ３：５．５質量％
Ｂ２Ｏ３：５質量％
Ａｌ２Ｏ３：０．５質量％
ＣｏＯ＋ＮｉＯ＋ＭｎＯ２
ＣｏＯ：１質量％
ＮｉＯ：０．５質量％
ＭｎＯ２：１質量％
また、ナノ多孔質シリカ粒子は、粒子径１〜１５μｍ、平均粒子径５μｍ、気泡径１〜３００ｎｍ、気孔率５５％のものである。
In Table 1, the composition of the frit is as follows:
SiO 2 + TiO 2 + ZrO 2 : 70% by mass
SiO 2 : 67% by mass
TiO 2 : 1% by mass
ZrO 2 : 2% by mass
R 2 O: 17% by mass
Na 2 O: 15% by mass
K 2 O: 0.5% by mass
Li 2 O: 1.5% by mass
R'O: 5% by mass
CaO: 4.5 mass%
BaO: 0.5 mass%
B 2 O 3 + Al 2 O 3 : 5.5% by mass
B 2 O 3 : 5% by mass
Al 2 O 3 : 0.5% by mass
CoO + NiO + MnO 2
CoO: 1% by mass
NiO: 0.5% by mass
MnO 2 : 1% by mass
The nanoporous silica particles have a particle diameter of 1 to 15 μm, an average particle diameter of 5 μm, a bubble diameter of 1 to 300 nm, and a porosity of 55%.
厚さ９ｍｍ、６０ｍｍ２の低炭素鋼板に、本発明品Ａ及びＢ並びに比較品のスリップを施釉し、８３０℃で２５分間焼成することにより、熱衝撃性テスト、機械衝撃性テスト並びに切削性テスト用の試料を作製した。
また、図１に示す４Ｒ、６Ｒ、８Ｒ、１２Ｒの曲面を有する小Ｒ形状の鋼製テストピースに、本発明品Ａ及びＢ並びに比較品のストリップを施釉し、８２０℃で４０分間焼成することにより、凸Ｒを変数とするグラスライニング性テスト用の試料を作製した。
A low carbon steel sheet with a thickness of 9 mm and 60 mm 2 is coated with the slips of the products A and B of the present invention and a comparative product, and fired at 830 ° C. for 25 minutes, so that a thermal shock test, a mechanical shock test and a machinability test are performed. A sample was prepared.
In addition, the small R-shaped steel test pieces having 4R, 6R, 8R, and 12R curved surfaces shown in FIG. 1 are coated with the strips of the products A and B of the present invention and the comparative product and fired at 820 ° C. for 40 minutes. Thus, a sample for a glass lining test with the convex R as a variable was prepared.
次に、下記の方法に従って熱衝撃性テスト、機械衝撃性テスト、切削性テスト及びグラスライニング性テストを行った：
熱衝撃性テストは、恒温器内で２２５℃に試料を加熱し、１時間保持した後、１５℃の水をグラスライニング施釉層表面に掛けることによる熱衝撃温度差ΔＴ２１０℃の操作を３回反復することによって行ったものである。なお、ピンホールの有無は、２０，０００ＶのＡＣピンホールテストの結果である。
機械衝撃性テストは４０ｍｍφ×２６０ｇの鋼球を１ｍの高さから自然落下させ、垂直にグラスライニング施釉層表面に衝撃を与えることによって行なったものである。
切削性テストは、三菱マテリアル社製ＳＴＩの鋼バイトを用いて、旋盤で２９０ｒｐｍの回転数でグラスライニング施釉層表面を０．３ｍｍ切削することによって行なったものである。なお、○は変化なし、△はクラック発生、×は剥離をそれぞれ示す。
グラスライニング性テストは、試料を９５℃熱水に２０分間浸漬後、１５℃の水中へ急冷することによる温度差Δ８０℃冷熱テストによるものである。なお、○は変化なし、△はクラック発生、×は剥離をそれぞれ示す。
得られた結果を表２に記載する。
Next, a thermal shock test, a mechanical impact test, a machinability test, and a glass lining test were performed according to the following methods:
In the thermal shock test, the sample was heated to 225 ° C. in a thermostatic chamber, held for 1 hour, and then subjected to a thermal shock temperature difference ΔT 210 ° C. of 3 times by applying 15 ° C. water to the surface of the glass lining layer. It was done by doing. The presence or absence of a pinhole is the result of an AC pinhole test of 20,000V.
The mechanical impact test was conducted by dropping a steel ball of 40 mmφ × 260 g from a height of 1 m and giving an impact to the surface of the glass lining glazed layer vertically.
The machinability test was performed by cutting 0.3 mm of the surface of the glass-lined glazed layer with a lathe using a STI steel tool manufactured by Mitsubishi Materials Corporation at a rotational speed of 290 rpm. In addition, (circle) shows no change, (triangle | delta) shows crack generation | occurrence | production and x shows peeling.
The glass lining property test is based on a temperature difference Δ80 ° C. cold heat test in which a sample is immersed in hot water at 95 ° C. for 20 minutes and then rapidly cooled to 15 ° C. water. In addition, (circle) shows no change, (triangle | delta) shows crack generation | occurrence | production and x shows peeling.
The results obtained are listed in Table 2.
本発明品Ａ及びＢから得られたグラスライニング施釉層は、熱衝撃性テスト及び機械衝撃性テストにおいて、施釉層表面にクラックが発生しただけであったのに対し、比較品のグラスライニング施釉層は剥離し、２０，０００ＶのＡＣピンホールテストで、ピンホールが発生するに至った。
また、切削性テストにおいて、本発明品Ａ及びＢから得られたグラスライニング施釉層は、変化なく優れた切削性を有するものであったが、比較品のグラスライニング施釉層では、クラックが発生した。
更に、グラスライニング性テストにおいて、本発明品Ａ及びＢから得られたグラスライニング施釉層を有する小Ｒ形状の鋼製テストピースでは、４Ｒ、６Ｒ、８Ｒ、１２Ｒの全てで、剥離やクラックの発生がなく良好であったのに対し、比較品のグラスライニング施釉層を有する小Ｒ形状の鋼製テストピースでは、４Ｒ、６Ｒの凸部で剥離し、８Ｒでクラックを発生し、焼成残留歪の緩和に劣ることが判る。
The glass-lined glazed layer obtained from the products A and B of the present invention had only cracks on the surface of the glazed layer in the thermal shock test and mechanical impact test, whereas the glass-lined glazed layer of the comparative product Peeled off, and a pinhole was generated in an AC pinhole test of 20,000 V.
Further, in the machinability test, the glass-lined glazed layer obtained from the products A and B of the present invention had excellent machinability without change, but cracks occurred in the comparative glass-lined glazed layer. .
Further, in the glass lining test, in the small R-shaped steel test pieces having the glass lining glazed layer obtained from the products A and B of the present invention, peeling and cracking occurred in all of 4R, 6R, 8R and 12R. In contrast, the small R-shaped steel test piece having the glass-lined glazed layer of the comparative product peeled off at the 4R and 6R protrusions, and cracked at 8R, resulting in a residual firing strain. It turns out that it is inferior to relaxation.
実施例２
以下の表３に示す本発明品Ｃ、Ｄ及びＥ並びに比較品のスリップを、パイプ母材（２２ｍｍφ×１８０ｍｍ×２．５ｍｍ厚；材質：ＳＴＰＧ炭素鋼管）の外面に施釉して８３０℃で２０分間焼成する工程を３回反復して厚さ１．０〜１．１ｍｍのグラスライニング施釉層を得た。なお、フリットの組成は実施例１に使用したフリットと同様である。
Example 2
The products C, D and E of the present invention shown in Table 3 below and the slips of the comparative product are applied to the outer surface of the pipe base material (22 mmφ × 180 mm × 2.5 mm thickness; material: STPG carbon steel pipe) and 20 ° C. at 830 ° C. The step of baking for 3 minutes was repeated 3 times to obtain a glass-lined glazed layer having a thickness of 1.0 to 1.1 mm. The composition of the frit is the same as that of the frit used in Example 1.
このパイプ試料の内部にラジエーター用不凍液を装填し、ガラス棒状温度計をゴム栓を介して挿入し、太陽熱吸収テストとして朝から夕方まで太陽光に暴露してパイプ試料内の温度変化を記録した。なお、対照として、グラスライニングを施釉していないパイプ試料並びに比較品のグラスライニング施釉層を備えたパイプ試料を使用した。得られた結果を表４に記載する。 The pipe sample was loaded with a radiator antifreeze, a glass rod thermometer was inserted through a rubber plug, and exposed to sunlight from morning to evening as a solar heat absorption test, and the temperature change in the pipe sample was recorded. In addition, as a control, a pipe sample not subjected to glass lining and a pipe sample provided with a comparative glass lining glazed layer were used. The results obtained are listed in Table 4.
ナノ多孔質シリカ粒子の配合量が多くなると、パイプ試料内の温度上昇が高く、温度降下も少ない結果を示し、これはナノ多孔質シリカ粒子が太陽光の最少波長０．３μｍ以下の１〜３００ｎｍの気孔により太陽光を透過するが、一方、ナノ多孔質シリカ粒子を含有したグラスライニング施釉層は断熱作用を有するためと思われる。 When the compounding amount of the nanoporous silica particles is increased, the temperature rise in the pipe sample is high and the temperature drop is small. This indicates that the nanoporous silica particles have a wavelength of 1 to 300 nm which is a minimum wavelength of 0.3 μm or less of sunlight. Sunlight is transmitted through the pores, but on the other hand, the glass-lined glazed layer containing nanoporous silica particles seems to have a heat insulating action.
本発明のグラスライニング組成物は、施工性、密着性並びに耐剥離性等に優れたグラスライニング施釉層を形成することができるので、従来公知のグラスライニングの用途は勿論のこと、更に、保温性及び断熱性に優れることから、例えば太陽熱収集装置や排熱回収装置等の保温及び断熱部材用グラスライニングとして好適に使用することができる。 Since the glass lining composition of the present invention can form a glass lining glazed layer having excellent workability, adhesion, and peel resistance, it can be used not only for conventionally known glass lining, but also for heat retention. And since it is excellent in heat insulation, it can be suitably used as a heat insulation and glass lining for a heat insulation member, for example, for a solar heat collection device or a waste heat recovery device.
Claims (7)
（Ａ）ＳｉＯ２＋ＴｉＯ２＋ＺｒＯ２：４６〜７２質量％
ただし、ＳｉＯ２：４６〜７０質量％
ＴｉＯ２：０．１〜５質量％
ＺｒＯ２：２〜１５質量％
（Ｂ）Ｒ２Ｏ（ＲはＮａ、Ｋ、Ｌｉ、Ｃｓを示す）：８〜２２質量％
ただし、Ｎａ２Ｏ：６〜２０質量％
Ｋ２Ｏ：０〜１６質量％
Ｌｉ２Ｏ：２〜２０質量％
Ｃｓ２Ｏ：０〜１６質量％
（Ｃ）Ｒ’Ｏ（Ｒ’はＣａ、Ｍｇ、Ｂａ、Ｓｒ、Ｚｎを示す）：１〜８質量％
ただし、ＣａＯ：１〜８質量％
ＭｇＯ：０〜５質量％
ＢａＯ：０〜５質量％
ＳｒＯ：０〜５質量％
ＺｎＯ：０〜５質量％
（Ｄ）Ｂ２Ｏ３＋Ａｌ２Ｏ３：１〜１８質量％
ただし、Ｂ２Ｏ３：１〜１８質量％
Ａｌ２Ｏ３：０〜６質量％ The glass lining composition according to claim 1 or 2, wherein the glass lining frit has a composition comprising the following (A) to (D):
(A) SiO 2 + TiO 2 + ZrO 2 : 46 to 72% by mass
However, SiO 2: 46~70 mass%
TiO 2 : 0.1 to 5% by mass
ZrO 2 : 2 to 15% by mass
(B) R 2 O (R represents Na, K, Li, Cs): 8 to 22% by mass
However, Na 2 O: 6~20 wt%
K 2 O: 0 to 16% by mass
Li 2 O: 2 to 20% by mass
Cs 2 O: 0 to 16% by mass
(C) R′O (R ′ represents Ca, Mg, Ba, Sr, Zn): 1 to 8% by mass
However, CaO: 1-8 mass%
MgO: 0 to 5% by mass
BaO: 0 to 5% by mass
SrO: 0 to 5% by mass
ZnO: 0 to 5% by mass
(D) B 2 O 3 + Al 2 O 3: 1~18 wt%
However, B 2 O 3: 1~18 wt%
Al 2 O 3 : 0 to 6% by mass
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