JP4473642B2 - Lining and lining method - Google Patents

Description

The present invention relates to a lining and a lining method for coating the inside of a reaction vessel, a transport pipe, and the like for manufacturing processes of pharmaceuticals, chemical products, foods, semiconductor materials, polymer materials and the like.

Conventionally, in reaction vessels and transport pipes for manufacturing processes such as pharmaceuticals, chemical products, foods, semiconductor materials, polymer materials, etc., metal substrates such as carbon steel materials or stainless steel materials such as reaction vessels and transport pipes are used. A frit soot is sprayed and fired to coat the inside of a reaction vessel, a transport pipe or the like. In general, a metal base is coated with a lower collar for improving adhesion at a thickness of about 0.3 mm, and then a chemically stable upper collar is coated at a thickness of about 0.8 to 2.3 mm. Manufactured.
In general, glass, which is the main component of the frit bottles that make up the lining, has a large specific resistance (is an insulator). Therefore, organic liquids and solids with high specific resistance are stirred in a reaction vessel or transported through a transport pipe. Even if the metal base is grounded, the amount of charge generated by rubbing the lining against liquid etc. exceeds the amount of leakage charge, and static electricity of tens of thousands to hundreds of thousands of volts is generated. There is a risk of damage such as destruction or fire. In addition, the liquid or the like may adhere to the lining surface due to the static electricity, and the liquid may be prevented from flowing.

Therefore, in the case of reaction vessels and transport pipes that use organic liquids or solids with high specific resistance as the contents, the lining and metal are used to prevent electrostatic charging between the contents and the lining. Attempts have been made to improve conduction with the substrate.
For example, what employ | adopted measures, such as embedding a high-corrosion-resistant metal in a lining beforehand, or winding the wire of a high-corrosion-resistant metal around a stirring blade and a baffle, and reducing those specific resistance, is known.
However, since the conductivity of the lining itself is low, the effect is limited to only the portion in contact with the metal, and there is still a problem that there is a possibility that the lining may be broken or a fire accident may occur.
Thus, attempts have been made to provide conductivity to the lining itself. As such a technique, for example, (Patent Document 1) describes “a glass lining a glass or ceramic powder surface coated with a chemically stable metal (for example, platinum) and a glass lining slurry”. A "lining composition" is disclosed.
(Patent Document 2) and (Patent Document 3) disclose “a glass lining composition imparted with conductivity by adding a noble metal fiber to a frit”.
(Patent Document 4) discloses “a glass lining composition imparted with conductivity by adding carbon or carbide fibers to a frit”.
(Patent Document 5) discloses “a conductive glass composition containing vanadium pentoxide”.
JP 2000-72476 A Japanese Patent Publication No. 10-81544 Japanese Patent Publication No. 11-116273 Japanese Patent Publication No. 11-189431 JP 2004-2181 A

However, the above conventional techniques have the following problems.
(1) The technique disclosed in (Patent Document 1) requires a step of coating a noble metal on glass by vapor deposition or the like, and has a problem of low productivity and high cost.
(2) The techniques disclosed in (Patent Document 2) and (Patent Document 3) have a problem that the cost is high because noble metal is used, and the technique cannot be used in an environment where the noble metal is corroded. .
(3) Since the technique disclosed in (Patent Document 4) uses carbon or carbide-based fibers, the firing needs to be performed in a nitrogen gas atmosphere so that the carbon is not oxidized. The product firing furnace has an internal volume of about 50 to 60 m ³ , and has a problem that a large amount of equipment is required to maintain the nitrogen gas atmosphere in the furnace.
(4) The technology disclosed in (Patent Document 5) attempts to impart conductivity by changing the glass composition itself of the frit, and is not applicable to any general frit used conventionally. There was a problem of lack of applicability.
(5) Although vanadium pentoxide is indispensable as a raw material, vanadium pentoxide is a harmful substance (a specific chemical substance stipulated in the Industrial Safety and Health Act), and thus has a problem of lack of handleability.

The present invention solves the above-described conventional problems, and imparts conductivity to all the conventional frit bottles to reliably reduce the amount of charge of the lining, so that it has excellent applicability and excellent safety. In addition, the conventional pulverization equipment can be used as it is, and it is excellent in versatility. In addition, a special firing furnace such as a nitrogen gas atmosphere is unnecessary, and the equipment and running costs can be reduced and the lining and the lining method with excellent productivity can be achieved . The purpose is to provide.

In order to solve the above conventional problems, the lining and the lining method of the present invention have the following configurations.
The lining according to claim 1 of the present invention has a frit of 100 parts by weight, a major axis average particle size of 0.05 to 5 μm, a minor axis average particle size of 0.003 to 0.3 μm, an average aspect ratio of 5 to 100, and Sb / A lining composition containing 3-6 parts by weight of acicular antimony-containing tin oxide powder as a conductive oxide ceramic powder formed in a needle shape with an atomic ratio of Sn of 0.3 / 100 to 5/100 It has a structure in which both the lower heel layer and the upper heel layer are formed.
With this configuration, the following effects can be obtained.
(1) Since it contains a frit and a conductive oxide ceramic powder, it has been conventionally used if a conductive oxide ceramic powder is blended together with the frit and wet pulverized when producing a glaze. In addition to providing conductivity to any frit soot, the amount of static charge caused by static electricity on the lining can be reduced reliably, so that it is highly applicable and safe. In addition, conventional grinding equipment can be used as is. Excellent.
(2) Since conductive oxide ceramic powder is used, the lining can be fired in a general firing furnace in the air atmosphere, and a special firing furnace such as a nitrogen gas atmosphere is unnecessary, reducing the equipment cost and running cost. It can be reduced, and it is excellent in versatility and productivity.
(3) Since it contains 100 parts by weight of frit and 1 to 15 parts by weight of conductive oxide ceramic powder, preferably 1 to 10 parts by weight, more preferably 3 to 6 parts by weight, acid resistance and surface gloss Further, it is possible to suppress the lining from being charged by imparting conductivity while maintaining smoothness.
(4) Depending on the type of conductive oxide ceramic powder, the base resistance, thermal shock resistance, and abrasion resistance can be improved, and the lining can be colored.
(5) Since the conductive oxide ceramic powder is a needle-like conductive antimony-containing tin oxide powder, it has excellent conductivity and excellent base resistance, and by adding a small amount to the frit, it increases conductivity and suppresses charging of the lining. Base resistance can be increased. Therefore, charging of the lining can be suppressed while maintaining the corrosion resistance of the lining and the gloss of the surface.
(6) Since the conductive oxide ceramic powder is a needle-like conductive antimony-containing tin oxide powder, it becomes a reinforcing material and can improve the thermal shock resistance of the lining.
(7) Since the conductive oxide ceramic powder is formed in a needle shape having a major axis average particle diameter of 0.05 to 5 μm and an average aspect ratio of 5 to 100, the substrate is coated with the substrate. Since the contact area between the powders increases in a layered manner along the surface of the powder, the conductivity can be reliably increased.
(8) Since the conductive oxide ceramic powder is in the form of fine needles, it has transparency, excellent surface smoothness and gloss when coated on the base material, and the arithmetic average roughness of the lining surface is 0.05-0. .15 μm can be made extremely smooth, the friction between the lining and the contents is small, and the generation of static electricity can be suppressed.

Here, the conductive oxide ceramic powder includes conductive zinc oxide, tin oxide, titanium oxide, zirconium oxide, potassium titanate, indium oxide, ITO (indium tin oxide), ruthenium oxide, bismuth-ruthenium series. Oxides (Bi ₂ Ru ₂ O ₇ ), indium-bismuth-ruthenium oxides (InBiRu ₂ O ₇ ), bismuth-iridium oxides (Bi ₂ Ir ₂ O ₇ ), gadolinium-bismuth-ruthenium oxides ( Oxide ceramic powders such as pyrochlore type oxides such as GdBiRu ₂ O ₇ ) and perovskite type oxides such as barium titanate are used. Conductive oxide ceramic powders can be used in the form of fibers, columns, rods, needles, spheres, irregular shapes, etc., but in particular, they are formed in fibers, columns, rods, needles. Those are preferred. When the lining coats the substrate, the conductive oxide ceramic powder is arranged in layers along the surface of the substrate, increasing the contact area between the powders, so that the conductivity can be reliably increased and the lining This is because the surface can be smoothed.
These conductive oxide ceramic powders are, for example, those in which tin oxide doped with antimony is coated on the surface of titanium oxide, those in which zinc oxide is doped with aluminum or bismuth, and the surface of fibrous potassium titanate is tin oxide A material provided with conductivity by means such as partially replacing a predetermined site of a perovskite oxide such as tin oxide containing antimony or barium titanate containing antimony can be used.

  As the frit, glass which is a main component of glaze and is crushed by being cooled rapidly after being put into water, flakes rapidly cooled by a roll, or the like is used.

As the amount of the conductive oxide ceramic powder with respect to 100 parts by weight of the frit becomes less than 3 parts by weight, the tendency to decrease the charge-suppressing effect is observed, and as the amount exceeds 6 parts by weight, the acid resistance of the lining tends to decrease. It is done. As the amount exceeds 10 parts by weight, in addition to the decrease in acid resistance of the lining, the gloss and smoothness of the surface of the lining decrease and the content tends to adhere to the surface of the lining. In particular, when the amount is less than 1 part by weight or more than 15 parts by weight, these tendencies are remarkable, so that neither is preferable.
As the acicular conductive antimony-containing tin oxide powder, a powder produced by firing a starting material containing a tin component and an antimony component in the presence of an alkali metal halide is used. In addition, those having an antimony component amount of 0.1 / 100 to 8/100, preferably 0.3 / 100 to 5/100, as the atomic ratio of Sb / Sn are used. As the antimony component amount becomes smaller than 0.3 / 100, the conductivity tends to decrease, and as it becomes larger than 5/100, the transparency tends to decrease. In particular, when the ratio is smaller than 0.1 / 100 or larger than 8/100, these tendencies are remarkable, so that neither is preferable.

The specific resistance of the conductive oxide ceramic powder is preferably 1~1000Ω · cm is preferably 1~400Ω · cm.
Thereby, the following actions are obtained.
(1) Since the specific resistance of the conductive oxide ceramic powder is 1-1000 Ω · cm, if a predetermined amount of the conductive oxide ceramic powder and frit are mixed, conductivity can be imparted to the lining and charging can be suppressed.

Here, as the specific resistance of the conductive oxide ceramic powder, a voltage is applied to the conductive oxide ceramic powder filled between the electrodes under a pressure of 100 kg / cm ² and the current flowing through the conductive oxide ceramic powder is expressed as follows. What was measured and calculated was used.
As the specific resistance of the conductive oxide ceramic powder becomes lower than 1 Ω · cm, the conductive oxide ceramic powder tends to scatter due to electrostatic repulsion, and the handling property tends to be lowered, which is not preferable. As the specific resistance is higher than 400 Ω · cm, the conductivity of the lining does not increase and the effect of suppressing the charging becomes difficult to occur. If a large amount of conductive ceramic powder is added to increase the effect of suppressing the charging, the acid resistance tends to decrease. It is done. In particular, if it is higher than 1000 Ω · cm, this tendency becomes remarkable, which is not preferable.

  Here, the long axis average particle diameter is obtained by observing an electron micrograph to determine the long axis average diameter of the conductive oxide ceramic powder. The average aspect ratio is obtained by observing an electron micrograph and calculating an average value obtained by dividing the length of the major axis by the length of the minor axis.

When the average particle diameter of the major axis of the conductive oxide ceramic powder is shorter than 0.05 μm, it tends to aggregate and it becomes difficult to uniformly disperse, and the conductivity tends to be difficult to increase. However, it is difficult to bend and be easily entangled with each other and uniform dispersion is difficult, and the conductivity is not improved.Although it depends on the type of conductive oxide ceramic powder, the acid resistance of the lining tends to decrease. Is also not preferable.
When the average aspect ratio of the conductive oxide ceramic powder is smaller than 5, when the substrate is coated, it is difficult for the conductive oxide ceramic powder to be arranged in layers along the surface of the substrate, and the contact area between the powders Tends to be difficult to increase and the conductivity is difficult to increase, and as it becomes larger than 100, the fluidity of the frit bottle decreases, and it is difficult to cause problems such as difficulty in being sprayed from a spray gun when coating a metal substrate. In addition, since the conductive oxide ceramic powder tends to be difficult to arrange in layers and the conductivity is difficult to improve, neither is preferable.

The short axis average particle size of the conductive oxide ceramic powder is preferably 0.003 to 0.3 μm. This is because the conductive oxide ceramic powder is fine so that it has transparency and is particularly excellent in surface smoothness and gloss when coated on a substrate.
The minor axis average particle diameter is obtained by observing an electron micrograph to obtain the minor axis average diameter of the conductive oxide ceramic powder.
As the minor axis average particle diameter of the conductive oxide ceramic powder becomes thinner than 0.003 μm, it tends to agglomerate and uniform dispersion becomes difficult, and the conductivity tends to be difficult to increase. As the conductive oxide ceramic powder becomes thicker than 0.3 μm, it becomes a base material. Since the surface gloss of the lining when coated is lowered, the surface smoothness is lowered, the friction between the lining and the contents is increased, and static electricity tends to be generated.

The lining according to claim 2 of the present invention has a frit of 100 parts by weight, a major axis average particle size of 0.05 to 5 μm, a minor axis average particle size of 0.003 to 0.3 μm, an average aspect ratio of 5 to 100, and Sb / Lining composition containing 5 to 6 parts by weight of acicular antimony-containing tin oxide powder as a conductive oxide ceramic powder formed in a needle shape with an atomic ratio of Sn of 0.3 / 100 to 5/100 It has a configuration in which both the upper heel layer and the lower heel layer are formed.

Invention of Claim 3 of this invention is lining of Claim 1 or 2 , Comprising: Other than the said acicular conductive antimony containing tin oxide powder and the said acicular conductive antimony containing tin oxide powder And a conductive oxide ceramic powder.
With this configuration, in addition to the operation obtained in the first or second aspect , the following operation can be obtained.
(1) Depending on the amount of needle-shaped conductive antimony-containing tin oxide powder, the amount of charge of the lining can be reduced by containing other conductive oxide ceramic powder, and the type and use of the contents Depending on the type, various conductive oxide ceramic powders can be blended, and the application range can be expanded.

Here, as the other conductive oxide ceramic powder, the conductive zinc oxide, tin oxide, titanium oxide, zirconium oxide, potassium titanate and the like described in claim 1 are used.
For example, by using zirconium oxide, the base resistance and abrasion resistance of the lining can be improved. In addition, the lining can be colored white by using titanium oxide or tin oxide. Further, by using zinc oxide, the fluidity of the frit soot can be adjusted, the covering property can be improved, and the workability can be enhanced.

Invention of Claim 4 of this invention is lining of any one of Claim 1 thru | or 3 , Comprising: 0.5-2 weight part of corrosion-resistant metal powder is contained with respect to 100 weight part of said frit. It has the structure.
According to this configuration, in addition to the action obtained in any one of claims 1 to 3 , the following action is obtained.
(1) The amount of electrification of the lining can also be reduced by containing a corrosion-resistant metal powder, and various corrosion-resistant metal powders can be blended depending on the type and use of the contents, thereby expanding the application range. it can.

  Here, as the corrosion-resistant metal powder, a noble metal powder such as gold, silver, platinum or palladium, a corrosion-resistant alloy powder such as tantalum or SUS, or the like is used.

As the content of the corrosion-resistant metal powder with respect to 100 parts by weight of the frit becomes less than 0.5 parts by weight, the effect of suppressing the charge amount due to the addition tends to disappear, and as the content exceeds 2 parts by weight, the corrosion-resistant metal powder Depending on the type, the corrosion resistance decreases and the gloss of the surface of the lining tends to decrease.
As an average particle diameter of the corrosion-resistant metal powder, 0.1 to 50 μm is preferably used. As the average particle size becomes smaller than 0.1 μm, it tends to agglomerate and tends to be difficult to uniformly disperse. As the average particle size becomes larger than 50 μm, the surface smoothness and glossiness of the lining coated with the substrate decrease and the inside of the frit bottle On the other hand, since the corrosion-resistant metal powder tends to settle and tends to be difficult to disperse uniformly in the frit bottle, neither is preferable.

In the lining method according to claim 5 of the present invention, the frit is 100 parts by weight, the major axis average particle size is 0.05 to 5 μm, the minor axis average particle size is 0.003 to 0.3 μm, and the average aspect ratio is 5 to 100. Lining containing 3-6 parts by weight of acicular conductive antimony-containing tin oxide powder as a conductive oxide ceramic powder formed into a needle shape having an atomic ratio of / Sn of 0.3 / 100 to 5/100 The composition has a configuration in which an upper collar layer is formed on the upper surface of the lower collar layer with the lining composition after a lower collar layer is formed on a metal substrate.
With this configuration, the following effects can be obtained.
(1) When manufacturing a glaze, if conductive oxide ceramic powder is blended with the frit and wet pulverized, conductivity is imparted to all the conventionally used frit glazes and the charge amount of the lining is increased. It can be reliably reduced, has excellent applicability, is excellent in safety, and can be used as it is with conventional pulverization equipment, and is excellent in versatility.
(2) Since conductive oxide ceramic powder is used, the lining can be fired in a general firing furnace in the air atmosphere, and a special firing furnace such as a nitrogen gas atmosphere is unnecessary, reducing the equipment cost and running cost. It can be reduced, and it is excellent in versatility and productivity.
(3) While maintaining acid resistance, surface gloss, and smoothness, it is possible to produce a lining excellent in antistatic property capable of imparting conductivity and suppressing lining from being charged.
(4) Depending on the type of the conductive oxide ceramic powder, the base resistance, thermal shock resistance, and abrasion resistance can be improved, and the lining can be colored to produce a high value-added lining.
(5) Excellent conductivity and base resistance. Addition of a small amount to the frit increases conductivity and suppresses lining charge, while increasing base resistance, maintaining lining corrosion resistance and surface gloss. Thus, it is possible to manufacture a lining that can suppress charging of the lining.
(6) Needle-like conductive antimony-containing tin oxide powder serves as a reinforcing material and can produce a lining having high thermal shock properties.

As described above, according to the lining and the lining method of the present invention, the following advantageous effects can be obtained.
According to the invention described in claim 1 or 2,
(1) When manufacturing a glaze, if conductive oxide ceramic powder is blended with the frit and wet pulverized, conductivity is imparted to all the conventionally used frit glazes and the charge amount of the lining is increased. It can be surely reduced, has excellent applicability, is excellent in safety, and can use conventional pulverization equipment as it is, thereby providing a versatile lining.
(2) Since conductive oxide ceramic powder is used, the lining can be fired in a general firing furnace in the air atmosphere, and a special firing furnace such as a nitrogen gas atmosphere is unnecessary, reducing the equipment cost and running cost. Therefore, it is possible to provide a lining having excellent versatility and excellent productivity.
(3) It is possible to provide a lining excellent in antistatic property capable of imparting conductivity and suppressing the lining from being charged while maintaining acid resistance, surface gloss and smoothness.
(4) Depending on the type of conductive oxide ceramic powder, the base resistance, thermal shock resistance, and abrasion resistance can be improved, and the lining can be colored to provide a highly valued lining. it can.
(5) Excellent conductivity and base resistance. Addition of a small amount to the frit increases conductivity and suppresses lining charge, while increasing base resistance, maintaining lining corrosion resistance and surface gloss. Thus, it is possible to provide a lining that can suppress charging of the lining.
(6) Needle-like conductive antimony-containing tin oxide powder serves as a reinforcing material and can provide a lining that can improve the thermal shock resistance of the lining.
(7) When the substrate is coated, it is arranged in layers along the surface of the substrate and the contact area between the powders increases, so that the conductivity can be reliably increased and a lining with excellent antistatic properties is provided. be able to.
(8) It is possible to provide a lining that has transparency and is excellent in surface smoothness and gloss when coated on a substrate, and can suppress the generation of static electricity.

According to invention of Claim 3, in addition to the effect of Claim 1 or 2,
(1) When a base material is coated, it is arranged in layers along the surface of the base material, and the contact area between the powders increases, so that the conductivity can be reliably increased and a lining excellent in antistatic property is provided. be able to.
(2) It is possible to provide a lining that has transparency and is excellent in surface smoothness and gloss when coated on a substrate, and can suppress the generation of static electricity.
(3) It is possible to provide a lining in which the conductive oxide ceramic powder becomes a reinforcing material and can improve thermal shock resistance.

According to invention of Claim 3 , in addition to the effect of Claim 1 or 2 ,
(1) Depending on the amount of needle-shaped conductive antimony-containing tin oxide powder, the amount of charge of the lining can be reduced by containing other conductive oxide ceramic powder, and the type and use of the contents Accordingly, various conductive oxide ceramic powders can be blended, and a lining excellent in applicability that can expand the application range can be provided.

According to the invention of claim 4 , in addition to the effect of any one of claims 1 to 3 ,
(1) The amount of electrification of the lining can also be reduced by containing a corrosion-resistant metal powder, and various corrosion-resistant metal powders can be blended depending on the type and use of the contents, thereby expanding the application range. It is possible to provide a lining excellent in applicability.

According to the invention of claim 5 ,
(1) When manufacturing a glaze, if conductive oxide ceramic powder is blended with the frit and wet pulverized, conductivity is imparted to all the conventionally used frit glazes and the charge amount of the lining is increased. It is possible to provide a lining method that can be surely reduced, is excellent in applicability, is excellent in safety, is excellent in safety, and can be used as it is, and has excellent versatility.
(2) Since conductive oxide ceramic powder is used, the lining can be fired in a general firing furnace in the air atmosphere, and a special firing furnace such as a nitrogen gas atmosphere is unnecessary, reducing the equipment cost and running cost. Therefore, it is possible to provide a lining method that is excellent in versatility and productivity.
(3) It is possible to provide a lining method excellent in antistatic property capable of imparting conductivity and suppressing lining from being charged while maintaining acid resistance, surface gloss and smoothness.
(4) To provide a lining method with high added value that can improve base resistance, thermal shock resistance, and abrasion resistance depending on the type of conductive oxide ceramic powder, and can color the lining. Can do.
(5) Excellent conductivity and base resistance. Addition of a small amount to the frit increases conductivity and suppresses lining charge, while increasing base resistance, maintaining lining corrosion resistance and surface gloss. Thus, it is possible to provide a lining method that can suppress charging of the lining.
(6) Needle-like conductive antimony-containing tin oxide powder serves as a reinforcing material and can provide a lining method capable of improving the thermal shock resistance of the lining.

Hereinafter, the present invention will be specifically described by experimental examples. The present invention is not limited to these experimental examples.
First, the frit 1-4 of the composition shown in (Table 1) was mix | blended and prepared. These compositions are those conventionally used as frit bottles.

  Using these frits 1 to 4, frit baskets were produced by the method shown below, and specimens of Experimental Examples 1 to 15 and Comparative Examples 1 to 3 were obtained. What is shown in (Table 2) and (Table 3) is the compounding quantity of the frit cake used for the test body of Experimental Examples 1-15 and Comparative Examples 1-3, and each numerical value represents a weight part.

(Experimental example 1)
100 parts by weight of frit 1, 7 parts by weight of clay (Kameme clay, manufactured by Fuji Mining), 0.4 parts by weight of electrolyte (sodium sulfite, manufactured by Mitsubishi Chemical), 50 parts by weight of silica powder (special grade of quartzite, manufactured by Iwatsuki Kasei) Part, 1 part by weight of an adhesive (nickel oxide, manufactured by Nippon Kagaku Sangyo), acicular conductive antimony-containing tin oxide powder (FS-10P, manufactured by Ishihara Sangyo, specific resistance 46.4 Ω · cm, minor axis average particle size 0. 1 μm, major axis average particle diameter 1.2 μm, average aspect ratio 12, represented by SnO ₂ in the table.) 5 parts by weight, appropriate amount of water added and wet pulverized; A slurry was obtained.
In addition, 100 parts by weight of frit 2, inorganic thickener (Kunigel VA, manufactured by Kunimine Industries) 2 parts by weight, organic thickener (CMC, manufactured by Nichirin Chemical Industries) 0.2 parts by weight, electrolyte (calcium chloride, Jun Hayashi) Medicinal) 0.2 parts by weight, acicular antimony-containing tin oxide powder (FS-10P, manufactured by Ishihara Sangyo Co., Ltd., characteristics such as specific resistance are the same as described above) 1 part by weight, wet with an appropriate amount of water By crushing, a slurry for the upper shell of Experimental Example 1 in the form of a slurry was obtained.
The above-mentioned slurry for underlay was sprayed on one side of a steel plate having a thickness of 6 mm and a diameter of 200 mm, dried and then fired in the atmosphere at 900 ° C. to form an undercoat layer having a thickness of about 0.2 mm. Next, the above-described upper iron slurry was sprayed on the upper surface of the lower iron, and after drying, the operation of firing in the atmosphere at 850 ° C. was repeated to form an upper iron layer having a thickness of about 1.3 mm. Thereby, the test body of Experimental Example 1 coated with a total thickness of 1.5 mm was obtained.

(Experimental example 2)
A test specimen of Experimental Example 2 was obtained in the same manner as in Experimental Example 1, except that the amount of the needle-like conductive antimony-containing tin oxide powder was 3 parts by weight.

(Experimental example 3)
A test specimen of Experimental Example 3 was obtained in the same manner as in Experimental Example 1, except that the amount of the needle-like conductive antimony-containing tin oxide powder was changed to 5 parts by weight.

(Experimental example 4)
A test body of Experimental Example 4 was obtained in the same manner as in Experimental Example 1, except that the amount of tin oxide powder containing acicular conductive antimony was changed to 6 parts by weight in the slurry for the upper eyelid.

(Experimental example 5)
In the slurry for the upper bran, the blending amount of the acicular conductive antimony-containing tin oxide powder is 3 parts by weight, and further the acicular titanium oxide powder (FT-3000, manufactured by Ishihara Sangyo Co., Ltd., specific resistance 50Ω · cm, minor axis average particle diameter) 0.27 μm, major axis average particle size 5.15 μm, average aspect ratio 19, represented by TiO ₂ in the table.) The test body of Experimental Example 5 was prepared in the same manner as in Experimental Example 1 except that 5 parts by weight were added. Obtained.

(Experimental example 6)
In the upper bran slurry, the amount of acicular conductive antimony-containing tin oxide powder is 3 parts by weight, and acicular zinc oxide powder (Panatetra, manufactured by Matsushita Amtec, specific resistance 10 Ω · cm, minor axis average particle diameter 0. (2 to 3 μm, long axis average particle diameter of 2 to 50 μm, average aspect ratio of 10, represented by ZnO in the table) Except for adding 5 parts by weight, a test body of Experimental Example 6 was obtained in the same manner as Experimental Example 1 It was.

(Experimental example 7)
In the slurry for upper bran, the blending amount of the acicular conductive antimony-containing tin oxide powder is 3 parts by weight, and further the acicular zirconium oxide powder (NZ, manufactured by Shinagawa White Brick, short axis average particle diameter of 6 to 20 μm, long axis average) A particle size of 20 to 500 μm, an average aspect ratio of 9, and represented by ZnO ₂ in the table.) A test body of Experimental Example 7 was obtained in the same manner as Experimental Example 1 except that 5 parts by weight was added.

(Experimental example 8)
In the slurry for the upper bran, the amount of the acicular conductive antimony-containing tin oxide powder is 3 parts by weight, and further silver powder as a corrosion-resistant metal powder (manufactured by Kanto Chemical Co., Ltd., reagent grade, 45 μm or less, represented by Ag in the table). A test body of Experimental Example 8 was obtained in the same manner as Experimental Example 1 except that 1 part by weight was added.

(Experimental example 9)
A test specimen of Experimental Example 9 was obtained in the same manner as in Experimental Example 1 except that 5 parts by weight of acicular titanium oxide powder was added in place of the acicular conductive antimony-containing tin oxide powder in the upper iron slurry. .

(Experimental example 10)
A test specimen of Experimental Example 10 was obtained in the same manner as in Experimental Example 1 except that 5 parts by weight of acicular zinc oxide powder was added instead of the acicular conductive antimony-containing tin oxide powder in the upper iron slurry. .

(Experimental example 11)
A test specimen of Experimental Example 11 was obtained in the same manner as in Experimental Example 1 except that 5 parts by weight of acicular zirconium oxide powder was added instead of the acicular conductive antimony-containing tin oxide powder in the upper iron slurry. .

(Experimental example 12)
A test body of Experimental Example 12 was obtained in the same manner as in Experimental Example 1 except that 1 part by weight of silver oxide powder was added to the upper slurry in place of the acicular conductive antimony-containing tin oxide powder.

(Experimental example 13)
In the lower slurry, a lower slurry for Experimental Example 13 was obtained in the same manner as in Experimental Example 1 except that the acicular conductive antimony-containing tin oxide powder was not blended.
A slurry for the upper eyelid of Experimental Example 13 was obtained in the same manner as in Experimental Example 1, except that the amount of the needle-like conductive antimony-containing tin oxide powder was 1 part by weight.
Next, a test body of Experimental Example 13 was obtained in the same manner as in Experimental Example 1 except that the lower arm slurry for Experimental Example 13 and the upper arm slurry for Experimental Example 13 were used.

(Experimental example 14)
The test of Experimental Example 14 was performed in the same manner as in Experimental Example 1, except that the frit 3 was used instead of the frit 2 in the upper bran slurry, and the blending amount of the acicular conductive antimony-containing tin oxide powder was 3 parts by weight. Got the body.

(Experimental example 15)
The test of Experimental Example 15 was carried out in the same manner as in Experimental Example 1, except that the frit 4 was used in place of the frit 2 and the blending amount of the acicular conductive antimony-containing tin oxide powder was 5 parts by weight. Got the body.

(Comparative Example 1)
A slurry for the lower arm of Comparative Example 1 was obtained in the same manner as in Experimental Example 1 except that the needle-shaped conductive antimony-containing tin oxide powder was not blended in the lower arm slurry.
A slurry for the upper eyelid of Comparative Example 1 was obtained in the same manner as in Experimental Example 1 except that the needle-like conductive antimony-containing tin oxide powder was not blended in the upper eyelid slurry.
Next, a test body of Comparative Example 1 was obtained in the same manner as in Experimental Example 1 except that the lower arm slurry for Comparative Example 1 and the upper arm slurry for Comparative Example 1 were used.

(Comparative Example 2)
A test specimen of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that the frit 3 was used in place of the frit 2 in the upper iron slurry.

(Comparative Example 3)
A test specimen of Comparative Example 3 was obtained in the same manner as in Comparative Example 1 except that the frit 4 was used in place of the frit 2 in the upper iron slurry.

(Measurement of charge amount)
After the specimens of Experimental Examples 1 to 15 and Comparative Examples 1 to 3 were charged by -20 kV corona discharge, the surface potential (charge amount) of the specimens was measured.
FIG. 1 is a schematic diagram of a surface potential measuring apparatus used in the experiment.
In the figure, 1 is a surface potential measuring device, 2 is a turntable rotating in a predetermined direction, 3 is a test body placed on the upper surface of the turntable 2, and 4 is a test placed above a predetermined position of the turntable 2. A corona discharge device 5 for discharging and charging the body 3 is a surface potential measuring device which is disposed above a predetermined position of the turntable 2 and measures the surface potential of the charged test body 3. In this experiment, the corona discharge device 3 used was JPK-3 manufactured by Kasuga Electric, and the surface potential measuring device 4 used was KSD-1010 manufactured by Kasuga Electric.
In addition, the measurement of the potential in this experiment is based on the technical document 2.2 “Measurement of the surface potential” of the Technical Guidelines “Static Safety Guidelines (1998): RIIS-TR-87-1” of the Ministry of Labor, Industrial Safety Institute. It is.
The measured charge amounts are shown in (Table 2) and (Table 3).

(Acid resistance test)
Condensed hydrochloric acid vapor test based on JIS R 4301 (1999) is performed on the test specimens of Experimental Examples 1 to 5 and Comparative Example 1, and the weight loss is calculated by subtracting the weight after the test from the weight before the test of the test specimen. The relative values of the weight loss of Experimental Examples 1 to 5 when the weight loss of Comparative Example 1 was set to 100 were obtained. The results are shown in (Table 4).

As can be seen from (Table 2) and (Table 3), Experimental Examples 1 to 4 in which the needle-shaped conductive antimony-containing tin oxide powder was added to both the lower iron slurry and the upper iron slurry were compared with Comparative Example 1. The amount of charge was low, and the amount of charge decreased as the amount of tin oxide powder containing acicular conductive antimony increased, and the amount of charge was 0 kV when the amount was 6 parts by weight (Experimental Example 4).
On the other hand, as can be seen from (Table 4), the weight loss in the condensed hydrochloric acid vapor test increases as the addition amount of the acicular conductive antimony-containing tin oxide powder increases. It gradually increased as the amount of tin powder added exceeded 3 parts by weight. Further, the total amount of the conductive oxide ceramic powder exceeded 6 parts by weight and 8 parts by weight (Experimental Example 5) was about 1.5 times the weight loss of Comparative Example 1.
From the above, a lining composition containing 100 parts by weight of a frit and 1 to 15 parts by weight of a conductive oxide ceramic powder containing a needle-like conductive antimony-containing tin oxide powder clearly shows the charge amount of the lining. It was confirmed that it was reduced. In particular, a lining composition containing 100 parts by weight of a frit and 1 to 10 parts by weight of a conductive oxide ceramic powder has excellent acid resistance, and in particular, a lining having 3 to 6 parts by weight of a conductive oxide ceramic powder. It has been revealed that the composition has a particularly excellent antistatic effect and corrosion resistance similar to that of the prior art, which has no practical problem.
In addition, since the specific resistance of the conductive oxide ceramic powder is 1-1000 Ω · cm, preferably 1-400 Ω · cm, if 100 parts by weight of the frit and 1-15 parts by weight of the conductive oxide ceramic powder are mixed, the conductive lining becomes conductive. It was revealed that charging can be suppressed by imparting properties.

In Experimental Example 13 in which the needle-like conductive antimony-containing tin oxide powder was added only to the upper iron slurry and not to the lower iron slurry, the charge amount decreased slightly compared to Comparative Example 1. all right. As a result, the amount of electrification can be reduced even if the conductive oxide ceramic powder is added only to the slurry for the upper iron, and it seems that it depends on the use conditions such as the type and contents of the contents. It has been found that the conductive oxide ceramic powder may be added to either the slurry or the upper slurry.
In Experimental Examples 9 to 11 in which the conductive oxide ceramic powder other than the acicular conductive antimony-containing tin oxide powder was added to the slurry for the upper eyelid, the charge amount was lower than that of Comparative Example 1, but the acicular conductive property was reduced. The effect as in Experimental Example 3 in which the same amount of the antimony-containing tin oxide powder was added was not obtained.
Also, in Experimental Example 12 in which the corrosion-resistant metal powder was added to the upper iron slurry, it became clear that the charge amount could be made lower than that in Comparative Example 1. As a result, even when a strongly acidic liquid or the like is used as the content, the conductive oxide ceramic powder is not added or added in a very small amount to the upper iron slurry to form a highly acid-resistant lining. Add a larger amount of conductive oxide ceramic powder to the sludge slurry than the lower slurry, and laminate the lining composition prepared by blending different amounts of conductive oxide ceramic powder. It has become clear that it can form a lining that balances with the above and is excellent in applicability.

Further, in addition to the acicular conductive antimony-containing tin oxide powder, Experimental Examples 5 to 7 in which other conductive oxide ceramic powders were added to the slurry for the upper eyelid only had the same amount of acicular conductive antimony-containing tin oxide powder. The amount of charge is lower than that of the experimental example 2 added, and depending on the type of contents and use conditions, the amount of charge is reduced. Therefore, the acicular antimony-containing tin oxide powder and other conductive oxide ceramics are used. It has been found that the powder may be added to the slurry simultaneously.
Similarly, Experimental Example 8 in which acicular conductive antimony-containing tin oxide powder and corrosion-resistant metal powder were added to the upper iron slurry was more charged than Experimental Example 2 in which only the same amount of acicular conductive antimony-containing tin oxide was added. Depending on the type of contents and use conditions, etc., the amount of charge may be reduced, so that the acicular antimony-containing tin oxide powder and the corrosion-resistant metal powder may be added simultaneously to the slurry. all right.
Moreover, also in Experimental Examples 14 and 15 in which the type of frit is different from that of Experimental Examples 1 to 13, by using the slurry to which the acicular conductive antimony-containing tin oxide powder was added, compared to the corresponding Comparative Examples 2 and 3, respectively. The amount of electrification decreased, and it was confirmed that it was effective to add conductive oxide ceramic powder to the slurry regardless of the type of frit.
Moreover, when the arithmetic mean roughness of the surface was measured by the stylus method, it was 0.05 μm in Comparative Example 1 and 0.08 μm in Experimental Example 3. This is a range that does not cause a problem in practical use, has excellent surface smoothness, and it is clear that the friction between the lining and the contents such as the powder and solution inside can be suppressed and the generation of static electricity can be suppressed. is there.
As described above, according to the present embodiment, conductivity can be imparted to all the conventional frit soots to reduce the charge amount of the lining reliably, so that it has excellent applicability and safety. It became clear that conventional pulverization equipment and the like can be used as they are and have excellent versatility.

In addition, in place of ZrO ₂ in Experimental Example 7, in the test body to which any one of ruthenium oxide, ITO, bismuth-ruthenium oxide (Bi ₂ Ru ₂ O ₇ ), and barium titanate was added, Nearly identical results were obtained.
Moreover, in place of the silver powder in Experimental Example 8, the same results as in Experimental Example 8 were obtained in the test specimen to which any one of gold, platinum, palladium, tantalum, and SUS was added.

The present invention relates to a lining and a lining method for coating reaction vessels and transport pipes for manufacturing processes of pharmaceuticals, chemical products, foods, semiconductor materials, polymer materials, etc. The amount of electrification of the lining can be surely reduced, and it has excellent applicability and safety, and can be used as it is with conventional pulverization equipment. A special firing furnace is not required, and equipment costs and running costs can be reduced, and a lining and a lining method excellent in productivity can be provided.

Schematic diagram of surface potential measuring device

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Surface potential measuring device 2 Turntable 3 Specimen 4 Corona discharge device 5 Surface potential measuring device

Claims (5)

100 parts by weight of frit, major axis average particle diameter 0.05 to 5 μm minor axis average particle diameter 0.003 to 0.3 μm average aspect ratio 5 to 100, and Sb / Sn atomic ratio 0.3 / 100 to 5 / 100 needle-shaped conductive antimony-containing tin oxide powder containing 3 to 6 parts by weight of conductive oxide ceramic powder, and any one of the lower layer and the upper layer A lining characterized in that it is also formed. 100 parts by weight of frit, major axis average particle diameter 0.05 to 5 μm minor axis average particle diameter 0.003 to 0.3 μm average aspect ratio 5 to 100, and Sb / Sn atomic ratio 0.3 / 100 to 5 / 100 needle-shaped conductive antimony-containing tin oxide powder containing 5 to 6 parts by weight of conductive oxide ceramic powder, and any one of the lower layer and the upper layer A lining characterized in that it is also formed. 3. The acicular conductive antimony-containing tin oxide powder and a conductive oxide ceramic powder other than the acicular conductive antimony-containing tin oxide powder, according to claim 1 or 2 . The lining described. The lining according to any one of claims 1 to 3 , wherein 0.5 to 2 parts by weight of a corrosion-resistant metal powder is contained with respect to 100 parts by weight of the frit. 100 parts by weight of frit, major axis average particle diameter 0.05 to 5 μm minor axis average particle diameter 0.003 to 0.3 μm average aspect ratio 5 to 100, and Sb / Sn atomic ratio 0.3 / 100 to 5 A lining composition containing needle conductive antimony-containing tin oxide powder 3 to 6 parts by weight as a conductive oxide ceramic powder formed into a / 100 needle shape, and a lower base layer on a metal substrate A lining method comprising forming an upper collar layer on the upper surface of the lower collar layer with the lining composition after the formation.

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