JP3432399B2 - Conductive glass lining composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive glass lining for use in a glass lining machine using a low carbon steel plate or a stainless steel plate as a base material, which can withstand severe use conditions in the chemical industry, pharmaceutical industry, food industry and the like. It relates to a composition.

[0002]

[Prior Art / Problems] Conventional glass lining equipment
A low-carbon steel plate or a stainless steel plate is used as a base material, and a glaze glaze for strengthening the adhesion with the base metal is 0.2 to 0.4.
After baking for about mm, it is usually manufactured by baking over glaze having high corrosion resistance for about 0.8 to 2.0 mm.

Here, the glass lining material constituting the glass lining equipment has a volume resistivity of 1 × 10 ¹³ to 10 10.
^Since it is an insulating material of about ¹⁴ Ωcm, if the stirring operation is performed with a non-aqueous organic content liquid, the charge charge amount greatly exceeds the leak charge amount, and static electricity of tens or hundreds of thousands of volts is generated.
Even if the glass lining equipment is grounded, the glass lining material may be damaged or an explosion may occur.

Therefore, when a non-aqueous organic content is stirred and operated, the glass lining layer is preliminarily provided with Ta.
Although a metal chip is embedded or a Ta metal wire is wound around the surface of a baffle or the like, it is difficult to cover the entire glass lining surface with Ta metal, and it is not yet a countermeasure against static electricity. Further, when it is expected that a large amount of static electricity is generated, metal (for example, stainless steel) equipment is used instead of glass lining equipment.

Further, as a glass lining device equipped with an antistatic means, for example, Japanese Utility Model Laid-Open No. 7-28834 discloses an upper glass coating layer on the upper surface of a lower glass coating layer coated on the inner surface of a metal can. In a glass lining can body provided, the glass lining is characterized in that the upper glass is a conductive glass, and a platinum wire embedded in a conductive upper glass coating layer is connected to a metal can body base material. A can body is disclosed. However, in this glass-lined can, the antistatic effect cannot be expected so much in the part where the platinum wire is not embedded.

Further, Japanese Patent Publication No. 60-25380 discloses that a frit strip having a predetermined glass composition has a frit of 0.1-0.1%.
Disclosed is a method for producing a glass-lined product, which comprises blending 2 to 10% of an inorganic fiber having a length of 3 mm with 100% of an enamel frit and squeezing it with a spray gun or a dipping method. Here, the inorganic fibers exemplified in the publication are enamel glass, glass having a composition different from that of enamel glass, those obtained by fibrating commercially available glass, etc., rock fibers, natural mineral fibers such as kao wool, and zirconia. Artificially manufactured ceramic fibers such as alumina and chrome oxide, whiskers, etc., whose purpose is to reduce air bubbles in enamel products, prevent giant bubbles, color mottle resistance, anti-scratch resistance (prevention of cracks), thermal shock resistance. And improved mechanical shock resistance.

Further, Japanese Patent Publication No. 4-8390 discloses a glaze composition containing a frit, wherein an inorganic whisker having a diameter of 0.2 to 1 micron and a length / diameter shape ratio of 20 or more is added to 100 g of the frit. A whisker-containing glaze composition characterized by being contained in an amount of 20 to 100 parts by weight per part is disclosed. Here, the whiskers used in this publication are inorganic single crystal fibers selected from the group consisting of titania, potassium titanate, alumina, silicon carbide and silicon nitride, and the purpose of addition is cutting workability in glass lining. To improve wear resistance.

Further, as a conductive glass lining composition, the present applicant has disclosed in Japanese Patent Application No. 8-316460:
A glass lining composition containing a frit, the metal fiber having a diameter of 0.5 to 30 microns, a length of 1.5 to 10 mm and a length / diameter ratio of 50 or more based on 100 parts by weight of the frit. A patent application has already been filed for a conductive glass lining composition, which is characterized by containing 0.5 to 1.5 parts by weight.

Therefore, an object of the present invention is to provide a conductive glass lining composition which can provide a conductive glass lining exhibiting excellent volume resistivity.

[0010]

Means for Solving the Problems As a result of further research on the conductive glass lining composition, the present inventor found in the application that the fiberization was difficult at the time of filing of Japanese Patent Application No. 8-316460. We have succeeded in producing metal fibers with a diameter smaller than that of the metal fibers used, and by using this metal fiber, excellent conductivity can be achieved even if the amount of metal fiber added to the frit is reduced. They have found that they can be applied to glass linings and have completed the present invention.

That is, the conductive glass lining composition of the present invention is a glass lining composition containing a frit, having a diameter of 0.01 μm or more and less than 0.5 μm, a length of 0.5 to 1500 μm and a length. / Diameter shape ratio 50
Are the above noble metals and alloys of platinum and platinum group metals?
One or more metal fibers selected from the group consisting of 0.001 to 0.
It is characterized by containing 05 parts by weight.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The diameter of the metal fibers used in the conductive glass lining composition of the present invention is better as the diameter is smaller in relation to the amount of the metal fibers added to the glass lining composition and the sprayability of the composition. , 0.01 micron or more 0.5
It is less than μm, preferably in the range of 0.1 micron to less than 0.5 micron. Here, if the diameter of the metal fiber is less than 0.01 micron, it is difficult to process the metal fiber itself, and the metal fiber having a diameter of less than 0.01 micron cannot be obtained at present.

The length of the metal fiber is 0.5 to 150.
It is in the range of 0 micron, preferably 10 to 1000 microns. Here, it is less than 0.5 microns in length of the metal fibers, chips is difficult metal fiber itself, and if said length exceeds 1500 microns, 0.5 in maximum diameter
Metal fibers having a thickness of less than μm are not preferable because the slip viscosity as a glass lining composition is poor and the spraying workability is extremely poor.

Further, the shape ratio of the length / diameter of the metal fiber is
It is 50 or more. Metal fiber length / diameter ratio of 50
If it is less than the above range, the conductivity of the glass lining cannot be improved unless a large amount of metal fiber is blended, which is not preferable.

In the conductive glass lining composition of the present invention, the size of the metal fibers used is within the above range, but when mixed with the frit to be described later, the metal fibers are crushed and cut, and the conductive glass is used. When glazing the lining composition, a small amount of metal fibers smaller than the above range may be mixed, but even if such metal fibers are present, there is nothing in the conductivity of the conductive glass lining glazed layer obtained. It has no effect.

The conductive glass lining composition of the present invention is characterized by containing the above-mentioned metal fibers, but the same effect can be obtained by adding metal powder such as platinum powder to the frit. Obtainable. However, in order to obtain the same volume resistivity, an addition amount of about several tens of percent is required, and metal powder cannot be used from the viewpoint of cost and the like. In addition, if the metal powder is added in an amount of about several tens of percent, it is difficult to smooth the fired surface of the glass lining and a foaming phenomenon occurs, which is not desirable in terms of quality.

[0017] The metal fibers, noble metal-based metals, and Ru der one or more compounds selected from the group consisting of an alloy of platinum and platinum group metals. Here, as the noble metal-based metal fiber, for example, Ag fiber (volume resistivity: 1.6 × 10 ⁻⁶ Ωc
m), Au fiber (volume resistivity: 2.4 × 10 ⁻⁶ Ωc
m), Pt fiber (volume resistivity: 10.6 × 10 ⁻⁶ Ωc
m) and the like can be used. Further, as the alloy fiber of platinum and a platinum group metal, for example, Pt, Pd, Ir, R
Those made of alloys with h, Os or Ru can be used.

The electrically conductive glass lining composition of the present invention can be used as an undercoat or an overcoat, but it is not required to have a chemical oxidation resistance and is firmly adhered to the base metal. on drugs which are required to lower drug Yaka histological oxidation resistance which sex is required to use noble based metal fiber, an alloy fibers.

The amount of metal fiber added to the frit is
The amount is 0.001 to 0.05 parts by weight, preferably 0.01 to 0.05 parts by weight, based on 100 parts by weight of the frit. If the amount of the metal fiber added is less than 0.001 part by weight, the conductivity cannot be significantly improved. Although it is possible to add the metal fibers in an amount of more than 0.05 parts by weight, the improvement of the effect commensurate with the increase in the addition amount cannot be expected. If the amount of the metal fibers added is within the above range, good quality glass lining can be obtained without foaming or unevenness on the glass lining firing surface.

The frit used in the conductive glass lining composition of the present invention is not particularly limited, and any commonly used frit can be used. For example, the following (A) to
It is possible to use a frit having a composition consisting of (E): (A) SiO ₂ + TiO ₂ + ZrO ₂ : 46-67% by weight (4
0-75 mol%), however, SiO _2: 46~67 wt% (40 to 75 mol%) TiO _2: 0 to 18 wt% (0-20 mole%) ZrO _2: 0 to 12 wt% (0-12 Mol%) In addition, the weight% of the component (A) is a SiO ₂ conversion amount; (B) R ₂ O: 8 to 22 wt% (7 to 22 mol%), but Na ₂ O: 8 to 22 % By weight (7 to 22 mol%) K ₂ O: 0 to 16% by weight (0 to 15 mol%) Li ₂ O: 0 to 10% by weight (0 to 15 mol%) The weight of the component (B) % Is the Na ₂ O conversion amount; (C) RO: 0.9 to 7 wt% (1 to 7 mol%) However, CaO: 0.9 to 7 wt% (1 to 7 mol%) BaO: 0 to 6 wt% (0 to 6 mol%) ZnO: 0 to 6 wt% (0 to 6 mol%) MgO: 0 to 5 wt% (0 to 6 mol%) SnO: 0 to 5 wt% (0 to 6 mol%) SrO: 0 to 5 % (0-6 mol%) It should be noted that the component weight percentages of (C) is a CaO equivalent _{amount; (D) B 2 O 3} + Al 2 O 3: 0~22 wt% (0-20 mole%) However, B ₂ O _3: 0 to 22 wt% (0-20 mole%) Al ₂ O _3: 0~6 wt% (0-10 mole%) the weight percentages of the component (D) is B ₂ O ₃ is converted weight; (E) CoO + NiO + MnO 2: 0~5 wt% (0-4 mol%), however, CoO: 0 to 5 wt% (0-4 mol%) NiO: 0 to 5 wt% (0 ˜4 mol%) MnO ₂ : 0 to 5 wt% (0 to 4 mol%) In addition, the wt% display for the component (E) is a CoO equivalent amount.

Further, as a coloring component, Sb ₂ O ₅ , Cr
Frit composition of at least one of ₂ O ₃ and Fe ₂ O ₃
5% by weight (5 mol%) in terms of maximum Fe ₂ O ₃ equivalent to 0%
May be added up to. In order to accelerate frit melting, a fluoride may be used up to 5 mol% of the SiO ₂ , CaO and Na ₂ O components. For example, if SiO ₂ is Na ₂ S
iF ₆ , Na ₂ O is Na ₂ SiF ₆ , CaO is CaF ₂ , A
1 ₂ O ₃ is Na ₃ AlF ₆ . In addition, these components are
It is the one normally used for frits.

The conductive glass lining composition of the present invention can be glazed on a conventional substrate such as a low carbon steel plate or a stainless steel plate by a conventional method. Further, a conventional glass lining composition is used as the underpolish, the conductive glass lining composition of the present invention is used as the overpolish, or the conductive glass lining composition of the present invention is used as the underpolish, To use a conventional glass lining composition, or to use the conductive glass lining composition of the present invention for the lower and upper glazes, etc., to change various distribution patterns according to the application, and to change the number of glazes. It goes without saying that it can be changed and glazed.

[0023]

EXAMPLES The conductive glass lining composition of the present invention will be further described below with reference to examples and comparative examples. EXAMPLES The raw material composition (% by weight) and composition (mol%) of the under and over glazes used in the following invention products and comparative products are shown in Table 1 below.
Described in.

[0024]

[Table 1]

Next, using the above-mentioned lower and upper sandals,
The mill composition shown in Table 2 below (in addition to the metal fibers, 2 parts by weight of clay, 100 parts by weight of the lower or upper glaze, C
MC (0.05 parts by weight, barium chloride (0.3 parts by weight) and appropriate amount of water added) and firing conditions, thickness 1.0 mm, diameter 10
A 5 mm low carbon steel round plate was glazed. In addition, platinum fiber (P
The t fiber: 1) has a diameter of 0.4 μm and a length of 1500 μm manufactured by Tanaka Kikinzoku Co., Ltd., and the platinum fiber (Pt fiber: 2) has a diameter of 0.4 μm manufactured by Tanaka Kikinzoku Co., Ltd.
It has a length of 01 micron and a length of 0.5 micron. Further, the platinum powder (Pt powder) has a diameter of 1 to 10 microns manufactured by Kojundo Chemical Laboratory Co., Ltd.

[0026]

[Table 2]

Next, the volume resistivity of the obtained sample was obtained by the resistance measuring method by the three-terminal method shown in FIG. 1, and the obtained results are also shown in Table 2.

As is apparent from Table 2 above, the products 1 to 5 of the present invention in which the metal fibers were added to the lower and upper glazes were the comparative products 8 and 8 in which the metal fibers were not added to the lower and upper glazes. All of them had significantly smaller volume resistivity than that of No. 9, and showed good conductivity.

Comparative products 10 and 11 were prepared by adding 5 parts by weight and 20 parts by weight of platinum powder, respectively.
Its volume resistivity is 2.5 × 10 ¹⁴ Ωcm, 4.7 × 10 ³
It can be seen that the volume resistivity equivalent to that of the conductive glass lining composition of the present invention is exhibited by adding 20 parts by weight of platinum powder in Ωcm. But platinum powder is very expensive,
Economically cannot be used for glass lining.

Furthermore, 0.0005 was added to the upper surface of the platinum fiber.
The comparative product 6 added by weight and the comparative product 7 added by 0.0008 parts by weight over the platinum fiber did not show good conductivity because the amount of platinum fiber added was too small.

[0031]

According to the present invention, it is possible to provide a conductive glass lining composition capable of forming a glass lining having a low volume resistivity.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a resistance measuring method by a three-terminal method for measuring the volume resistivity of the product of the present invention and the comparative product.

Claims (2)

(57) [Claims] 1. A glass lining composition containing a frit, which is a noble metal-based metal having a diameter of 0.01 μm or more and less than 0.5 μm, a length of 0.5 to 1500 μm, and a length / diameter shape ratio of 50 or more. , And platinum and platinum group metals
One or more metal fibers selected from the group consisting of alloys are added in an amount of 0.001 with respect to 100 parts by weight of the frit.
The conductive glass lining composition is characterized by containing 0.05 to 0.05 parts by weight. 2. The conductive glass lining composition according to claim 1, wherein the frit has a composition consisting of the following (A) to (E): (A) SiO ₂ + TiO ₂ + ZrO ₂ : 46-67% by weight SiO _2: 46 to 67 wt% TiO _2: 0 to 18 wt% ZrO _2: 0 to 12 wt% Incidentally, the weight percentages of components (a) is a SiO ₂ equivalent amount; (B) R ₂ O: 8 to 22 wt%, however, Na ₂ O: 8-22 wt% K ₂ O: 0 to 16 wt% Li ₂ O: 0 wt% the weight percentages are terms of Na ₂ O of the component (B) (C) RO: 0.9 to 7% by weight However, CaO: 0.9 to 7% by weight BaO: 0 to 6% by weight ZnO: 0 to 6% by weight MgO: 0 to 5% by weight SnO: 0 to 5% by weight SrO: 0 to 5% by weight Note that the weight of the component (C) Display is CaO equivalent _{amount; (D) B 2 O 3} + Al 2 O 3: 0~22 wt%, however, B ₂ O _3: 0~22 wt% Al ₂ O _3: 0~6 wt% Incidentally, component The weight% display for (D) is the B ₂ O ₃ conversion amount; (E) CoO + NiO + MnO ₂ : 0 to 5 weight% However, CoO: 0 to 5 weight% NiO: 0 to 5 weight% MnO ₂ : 0 5% by weight It should be noted that the% by weight indication for the component (E) is a CoO equivalent amount.