JPH0892822A - Method for producing tin oxide fiber - Google Patents

Abstract

(57) [Summary] [Structure] In a solution in which a tin halide compound such as stannous chloride and an alcohol-soluble polymer compound and, if necessary, a Group V compound such as antimony trichloride are dissolved in alcohol such as methanol The halogen content is controlled to form a spinning solution, the gel fiber spun from the spinning solution is brought into contact with an ammonia atmosphere, and then heat-treated to produce a tin oxide fiber. [Effect] The ratio of tin and halogen in the spinning solution is controlled,
Further, since it is treated in an ammonia atmosphere, it is possible to prevent the fiber shape from collapsing due to cutting or softening of the fiber even if the fiber is left to stand after spinning in a high humidity atmosphere. As a result, it will be possible to smoothly transition to the heat treatment process,
Productivity improved. Furthermore, since an alcohol-soluble polymer is mixed in the spinning solution, high-speed spinning is possible.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing tin oxide fibers and conductive tin oxide fibers.

[0002]

2. Description of the Related Art Tin oxide has excellent chemical resistance and heat resistance,
Moreover, it is an excellent material whose conductivity can be controlled over a wide range, and is used for various purposes. Recently, research is also progressing as a third-order nonlinear optical material.

In a gas sensor, it has been strongly desired to provide tin oxide in a fiber shape from the viewpoint of improving sensitivity and response speed. Further, carbon fibers and the like have been added for the purpose of imparting conductivity to polymer materials,
When carbon is used, there are problems that the material itself cannot be brightened because it is black and that it is very light and easily scattered. For this reason, it has been practiced to add powders of metal fibers and metal oxides. Although metal fibers have high conductivity, they have the drawback that their surface is oxidized or corroded over a long period of time to lower their conductivity. In addition, the conductivity of conventional metal oxide powders is not as high as that of metal fibers, so in order to impart conductivity to polymer materials, a relatively large amount must be added, and the physical properties inherent in polymer materials deteriorate. There was a drawback that caused it. Even tin oxide, which has excellent chemical resistance and heat resistance, has been attempted to be added in the form of powder that imparts conductivity.

By the way, it is known that the effect of imparting conductivity increases as the aspect ratio of the conductivity imparting material increases. For this reason, it has been required to make tin oxide having conductivity into a fiber. However, it has been difficult to manufacture a fiber by the conventional solid-phase reaction method. For this reason, JP-A-60-5997 and JP-A-60-161.
No. 337 and JP-A-60-158199 propose a method for producing tin oxide by a melt precipitation method. However, since these methods require a high temperature of 1000 ° C. or more and a reaction time of many days, it is possible to produce a very small amount on a laboratory scale, but it has not been industrially produced yet. . Moreover, the shape of the obtained tin oxide fiber is 1 μm or less in diameter and 3 in length.
When it is used as a composite material, there is a problem that its function cannot be sufficiently exerted and its application is limited because the aspect ratio is small when it is less than or equal to mm and the cross section is often rectangular. Furthermore, since the major axis is too small, it is difficult to produce a paper-like material. Further, in order to enhance the reproducibility of physical properties such as conductivity of the obtained composite material, it is important to control the shape and size of the tin oxide whiskers to be added with good reproducibility. However, since it is actually difficult to control the shape of tin oxide whiskers, if the fiber diameter and length of the added tin oxide were to be made uniform, it was only possible to classify what was accidentally produced. Therefore, the whiskers produced by such an inefficient method are extremely expensive and practically unusable.

The present inventors are surprised to find that a solution containing a tin compound and an alcohol as a main component is used without using a tin alkoxide as a raw material, which is unstable and difficult to handle because it is expensive and has a high reaction rate. The spinnability appears in
It was found that a tin oxide fiber can be easily and extremely inexpensively obtained by spinning and heating this, and it has already been proposed (JP-A-4-35287, JP-A-5-117906, JP-A-5-179512).

[0006]

However, in the case of spinning using the above spinning solution, when the gel fiber is exposed to a high humidity atmosphere between the spinning and the heat treatment, the thread shape is not retained and softens. There are cases where the phenomenon of collapse occurs. Therefore, earnest studies were conducted on a method for producing a fiber in which the yarn shape is not destroyed by the humidity in the atmosphere during spinning and / or after spinning.

[0007]

As a result, it was found that controlling the amount of halogen in the spinning solution and contacting the spun gel fiber with an ammonia atmosphere increases the moisture resistance of the gel fiber. It came to completion.

That is, according to the present invention, a tin halide compound and an alcohol-soluble polymer compound are dissolved in alcohol and the ratio of the number of halogen atoms to tin atoms (X / Sn) in the solution is 1.55. In the method for producing tin oxide fiber, the gel fiber spun from the spinning solution having a ratio of less than 1.80 is contacted with an ammonia atmosphere and then heat-treated.

Another invention comprises a tin halide compound, a Group V element compound of the periodic table and an alcohol-soluble polymer compound dissolved in alcohol, and the halogen, tin and the Group V element of the periodic table in the solution. The method for producing a tin oxide fiber is characterized in that the gel fiber spun from the spinning solution in which the respective numbers of atoms have the relationship of the following formula is brought into contact with an ammonia atmosphere and then heat-treated.

[0010]

[Equation 2]

[Here, N _Sn is the ratio of the number of tin atoms to the total number of tin atoms in the solution and the group V elements in the periodic table, and Nv is the tin in the solution and the group V elements in the periodic table. It is the ratio of the number of atoms of the Group V element of the periodic table to the total number of atoms of the elements, and X, Sn and V are each halogen in the solution,
Represents the number of atoms of tin and Group V elements of the periodic table. Next, the present invention will be described more specifically.

The alcohol used in the present invention is not limited as long as it dissolves the tin halide compound described below. When these alcohols are represented by the general formula ROH, R
Is an unsubstituted alkyl group such as methyl group, ethyl group, propyl group, butyl group, octyl group, 2-methoxyethyl group, 2
-Ethoxyethyl group, 2-hydroxyethyl group, 1-methoxy-2-propyl group, methoxyethoxyethyl group,
Examples thereof include substituted alkyl groups such as 2-phenylethyl group and phenylmethyl group, unsubstituted alkenyl groups such as allyl group, and substituted alkenyl groups such as 2-methyl-2-propenyl group and 3-methyl-3-butenyl group.

Specific examples of the substituent in the above-mentioned substituted alkyl group, substituted alkenyl group or substituted aryl group include alkoxy groups such as methoxy group and ethoxy group, hydroxyl group, phenyl group and the like found in the above-mentioned specific examples of R. In addition to the aryl group, the alkyl group such as a methyl group and an ethyl group, a halogen atom such as an amino group, a cyano group, a Cl atom, a Br atom, an I atom and an F atom.

Specific examples of the alcohol used in the present invention include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol,
2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, 1-methoxy-2-propyl alcohol, methoxyethoxyethanol, 2-phenylethyl alcohol, benzyl alcohol, allyl alcohol, 2-methyl-2-propen-1-ol, 3-methyl-3-butene-1 -I can mention all, etc.
In particular, methyl alcohol and ethyl alcohol are preferable because of high solubility of the tin halide compound. The above alcohols are usually used alone, but a mixture of two or more kinds of alcohols may be used in order to control the reactivity with the tin halide compound, the solubility of the tin halide compound and the like.

The halogen of the tin halide compound used in the present invention is Cl, Br, I or F atom. Among these tin halide compounds, tin chloride and tin bromide are preferable in terms of price and stability. Specifically, SnC
l ₂ , SnCl ₂ .2H ₂ 0, SnBr ₂ , SnI ₂ , Sn
F _{2 and the} like, and particularly SnCl ₂ , SnBr ₂ , Sn
Cl ₂ · 2H ₂ O is preferably used. Further, the tin halide compound modified with an organic compound such as Sn (CH ₃ ) ₂ Cl ₂ can also be used.

The mixing ratio of the above tin halide compound and alcohol is not particularly limited as long as the tin halide compound is uniformly dissolved in the alcohol. However,
If the proportion of the tin halide compound is too low, it does not show spinnability, so it is necessary to concentrate it considerably.
Is wasted. If the tin halide compound concentration is too high, precipitation will occur and a uniform spinning solution cannot be obtained. Therefore, the tin halide compound used and the alcohol
The mixing ratio varies depending on the kind of the alcohol, but generally, the molar ratio of the tin halide compound to the alcohol is preferably 0.02 to 0.5. After blending in this ratio to form a transparent and uniform solution, alcohol is further evaporated to concentrate the solution to obtain a spinning solution having a desired viscosity.

In the present invention, it is important to add an alcohol-soluble polymer compound to the spinning solution in order to carry out spinning at a high speed. As such a polymer compound, any polymer compound soluble in alcohol can be used without any limitation. Specific examples include celluloses such as ethyl cellulose, cellulose acetate, cellulose nitrate, cellulose propionate, cellulose triacetate, acetyl butyl cellulose, and hydroxyl propyl cellulose, polyvinyl butyral, polymethylene oxide, polyethylene oxide, polypropylene oxide, polyacetic acid. Vinyl etc. are mentioned.

By adding these alcohol-soluble polymer compounds, spinning can be performed at a higher speed in addition to being able to be spun almost without being affected by the humidity in the atmosphere. That is, for example, when a method of extruding the spinning solution from a nozzle is adopted, in order to perform stable spinning without adding an alcohol-soluble polymer compound, the viscosity of the spinning solution is about 500 by evaporating and concentrating the alcohol. ~ 1000 poise or more is required. Generally, the spinning speed tends to increase as the viscosity of the spinning solution is lowered, but if the viscosity is low, yarn breakage occurs and stable spinning, particularly high-speed spinning becomes difficult. However, when the above alcohol-soluble polymer compound is added to the spinning solution, spinning can be performed even at a low viscosity of about 50 to 500 poise, and high-speed spinning is possible. Further, since the viscosity can be lowered, the pressure applied to the solution is likely to be uniform, and spinning can be effectively performed from almost all of the plurality of spinning nozzles used.

The amount of the alcohol-soluble polymer compound added is preferably 0.01 to 20% by weight with respect to the tin compound. If the amount of the alcohol-soluble polymer compound added is less than 0.01% by weight, a sufficient effect cannot be obtained. On the other hand, if the amount exceeds 20% by weight, the effect is not only saturated, but also when the spun fiber is heat-treated, the amount of carbon and carbon dioxide gas generated increases, making it difficult to remove, and the resulting fiber has pores. Are generated, which is not preferable.

In order to obtain a highly conductive tin oxide fiber in the present invention, a compound of group V element of the periodic table (hereinafter referred to as a compound of group V) can be contained if necessary. The group V compound is finally converted into an oxide by the heat treatment described below and is solid-dissolved in tin oxide.

Examples of the Group V compound include compounds of Group V elements such as vanadium compounds, niobium compounds, tantalum compounds, antimony compounds, and bismuth compounds.

Specifically, as the vanadium compound, V
Br ₃ , VCl ₂ , VCl ₃ , VCl ₄ , VOBr ₂ , VO
_{Br 3, VOCl 3, VF 3} , VF 4, VF 5, VI 3 · 6H
₂ O, vanadium alkoxide, and niobium compounds such as NbCl ₅ , NbBr ₅ , NbF ₅ , and NbO.
Cl ₃ and alkoxides of niobium can be cited. As a tantalum compound, TaBr ₅ , TaCl ₅ , and an alkoxide of tantalum, and as an antimony compound, SbCl ₃ and Sb.
Cl ₅ , SbBr ₃ , antimony oxychloride, or an alkoxide of antimony, and examples of the bismuth compound include BiCl ₃ , BiI ₂ , and bismuth alkoxide.

When it is desired to impart conductivity to the tin oxide fiber, the compounding ratio of the Group V compound is preferably 0.1 to 25 mol% based on tin oxide in terms of oxide. If the ratio is too low, the tin oxide fiber obtained will have low conductivity, and if it is too high, the effect of imparting conductivity will be low.

The method for dissolving the tin halide compound, the alcohol-soluble polymer compound, the Group V compound and the alcohol is not particularly limited. A method in which alcohol is added dropwise to a mixture of a tin halide compound, an alcohol-soluble polymer compound and a Group V compound under stirring, or a tin halide compound, an alcohol-soluble polymer compound, a Group V compound in alcohol under stirring Can be used simultaneously or sequentially.

In the present invention, a solution containing the above-mentioned alcohol, a tin halide compound, an alcohol-soluble polymer compound and a Group V compound is used.
When the group V compound is not contained, the ratio of the number of atoms of halogen and tin, that is, X / Sn is 1.6 or more and less than 1.8, and when the group V compound is contained, halogen, tin and V group are used. The relationship between the numbers of atoms of each group element is

[0026]

[Equation 3]

It is important to make adjustments so as to satisfy

Here, N _Sn is the ratio of the number of tin atoms to the total number of atoms of tin and Group V elements in the solution, and Nv
Is the ratio of the number of atoms of the group V element to the total number of atoms of tin and the group V element in the solution, and X, Sn and V are the numbers of atoms of halogen, tin and the group V element in the solution, respectively. Represent.

The atomic number ratio X / Sn of halogen and tin,
Alternatively, stable spinning can be carried out by spinning from a spinning solution in which the relation X / (Sn + V) in the number of atoms of halogen, tin, and Group V elements is within the above range, and the spun gel fiber is under high humidity atmosphere. Also, the shape is easy to maintain and handling is extremely easy. When a Group V compound containing halogen is added, the halogen must be prepared in consideration of the halogen derived from the Group V compound in addition to the halogen derived from the tin halide compound.

The atomic ratio X / Sn of halogen and tin,
Alternatively, gel fibers can be spun even when the relationship X / (Sn + V) in the number of atoms of halogen, tin, and Group V elements is larger than the above range, but the obtained fibers are softened in a high-humidity atmosphere and have a shape. Since it easily collapses, it is necessary to control the humidity. Further, when the above-mentioned halogen / tin atomic number ratio X / Sn or the relationship between the number of halogen / tin and group V element atoms X / (Sn + V) is smaller than the above range, the spun gel fiber is produced even under high humidity. Although it is stable, there is a problem that the spinning solution becomes unstable, such as precipitation easily occurring in the spinning solution.
Therefore, the ratio of the number of atoms of halogen to tin X / Sn, or the relationship of the number of atoms of halogen to tin and Group V elements X / Sn
It is important to control (Sn + V) within the above range.

The method for controlling the above-mentioned atomic ratio of halogen and tin, or the relationship between the number of halogen and the number of atoms of tin and Group V elements is not particularly limited, and known methods can be used without any limitation. For example, a conventional method such as a method of removing halogen ions with an anion exchange resin, a method of precipitating and removing halogen ions as a halide, or a method of removing halogen by heat evaporation can be used. In the case of this heating evaporation, it is presumed that the halogen is evaporated as hydrogen halide. Further, when a spinning solution is prepared, a tin halide compound having a small ratio X / Sn of the number of atoms of halogen and tin from the beginning, such as SnCl ₂ , SnCl ₂ ·.
It is effective to use a compound in which tin is divalent such as 2H ₂ O and SnBr ₂ because the above range can be easily controlled.

The halogen, tin and Group V elements in the spinning solution may be quantified by any method, but the inductively coupled plasma emission spectrometry (ICP emission spectrometry) is used for the determination of tin and Group V elements. A precipitation titration method is preferably adopted for the determination of halogen.

In order to improve the stability of the spinning solution of the present invention, a compound having two or more carboxyl groups such as acetylacetone, ethyl acetoacetate and diethyl malonate may be appropriately contained as a tin complexing agent. The spinning method is not particularly limited, and a conventional spinning method can be used.
For example, a method of extruding a spinning solution from a spinning nozzle can be used. The major axis, the diameter, etc. of the obtained fiber can be arbitrarily controlled by adjusting the viscosity of the spinning solution, the nozzle diameter, the speed at which the spinning solution is extruded from the spinning nozzle, and the like. The fiber before heat treatment spun from the spinning solution is called gel fiber.

In the present invention, in order to further improve the stability of the gel fiber against humidity, it is important to contact the gel fiber with an ammonia atmosphere. Atom ratio X / Sn between halogen and tin in the spinning solution, or a relationship X / Sn between halogen and the number of atoms of tin and Group V elements X /
By controlling (Sn + V) within the above range, the stability of the gel fiber after spinning to humidity was improved, but it became clear that the stability to humidity was further increased by contacting with an ammonia atmosphere. That is, by treating the gel fiber in an ammonia atmosphere, the shape of the fiber is stably maintained even if the gel fiber is brought into contact with a high-humidity atmosphere until the heat treatment described later, so that the handling becomes extremely easy, and from the spinning step It enables smooth transition to the heat treatment process.

The method of contacting with the ammonia atmosphere is not particularly limited. For example, a method of contacting with an ammonia atmosphere immediately after spinning by spinning in an ammonia atmosphere, or a method of contacting with an ammonia atmosphere after spinning in air with low humidity, such as a method of not contacting with high humidity before contacting with an ammonia atmosphere If so, it can be used without any limitation.

As the ammonia atmosphere, pure ammonia gas, diluted ammonia gas obtained by diluting the ammonia gas with air, nitrogen, oxygen gas or the like, or ammonia gas evaporated from aqueous ammonia is appropriately adopted.
The ammonia concentration in the ammonia atmosphere is not particularly limited. When the ammonia concentration is low, the contact may be for a long time, and when the ammonia concentration is high, the contact may be for a short time. Generally, an ammonia atmosphere with a concentration of 0.02% to 5% is used.

Although the present inventors cannot fully explain why the moisture resistance of the gel fiber is improved by bringing it into contact with an ammonia atmosphere, the halogen contained in the gel fiber is trapped by the reaction with ammonia. It is presumed that it is because the hygroscopicity is lowered by being removed or removed.

The heat treatment of the gel fiber obtained by the ammonia atmosphere treatment is carried out at a temperature at which the organic solvent such as alcohol or water is removed from the gel fiber to strengthen the skeleton of the fiber and, in some cases, further crystallize. Be seen. The gel fiber as spun from the spinning solution does not show sufficient mechanical strength as it is. The mechanical strength is developed by heating the gel fiber. The heat treatment temperature is not particularly limited as long as it is within a temperature range capable of imparting mechanical strength to the obtained fiber. When the heat treatment temperature is low, alcohol, water, etc. remain in the fiber, so that sufficient mechanical strength does not occur. Also,
If the heat treatment temperature is too high, the decomposition of tin oxide will proceed, or the crystal grains in the fiber will grow too much and the strength will decrease. For the above reason, the heat treatment temperature is preferably in the range of 250 to 1550 ° C. More preferably, heat treatment at a temperature of 300 to 1500 ° C. is preferable.

When it is desired to add a Group V compound to improve the conductivity of the obtained fiber, the heat treatment is also necessary. The gel fiber as it is spun from the spinning solution is an insulator as it is, and conductivity is exhibited by heating the gel fiber. The heat treatment temperature is not particularly limited as long as it is within a temperature range capable of imparting conductivity to the obtained fiber. Generally, when the heat treatment temperature is low, organic substances such as alcohol, water, etc. remain in the fiber, and the Group V compound does not form an oxide and does not form a solid solution with tin oxide, resulting in poor conductivity. Does not happen. If the heat treatment temperature is too high, the group V compound in the fiber is volatilized to lower the conductivity, the decomposition of tin oxide proceeds, the crystal grains in the fiber grow too much, and the strength decreases. Occurs. Therefore, the heat treatment temperature is 2
A temperature range of 50 ° C to 1550 ° C is preferred. More preferably, the heat treatment is preferably performed at a temperature of 300 ° C to 1500 ° C.

The heat treatment is usually carried out in air, but when it is desired to obtain a fiber having particularly high conductivity, the heat treatment is carried out in a reducing atmosphere such as nitrogen, argon, hydrogen, or a mixed gas of argon and hydrogen, or in vacuum. Processing can be performed.

Further, in the heat treatment, it is desirable to remove volatile components such as water and alcohol present in the gel fiber by drying in order to obtain a good tin oxide fiber. Such drying may be performed at the same time as the heat treatment, but it is preferable to perform the drying before the heat treatment in order to obtain a good fiber. In these cases, the drying temperature is preferably as low as possible in order to prevent the resulting fiber from cracking,
When an alcohol having a high boiling point is used as the solvent, if it is too low, it takes a long time to dry and is not effective. Generally, the drying temperature is preferably in the range of room temperature to 300 ° C.

The specific resistance value of the conductive tin oxide fiber obtained from the spinning solution containing the Group V compound of the present invention is
Although it varies greatly depending on the type of the Group V compound, the amount added, the firing atmosphere, the firing temperature, etc., it is usually 10 ³ to 10 ^-1 Ω.
It can take the value of cm. The (conductive) tin oxide fiber obtained by the present invention may be crystalline or amorphous, but crystalline is preferable from the viewpoint of conductivity.

[0043]

According to the method of the present invention, even if the gel fiber is brought into contact with a high humidity atmosphere before the heat treatment, the gel fiber does not soften and lose its shape, so that the next heating step can be moved extremely smoothly. Became. As a result,
Industrially stable operation became possible and productivity improved.
Furthermore, the mechanical strength of the obtained fiber was improved.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 10 g (0.05 mol) of stannous chloride (SnCl ₂ ),
And polyethylene oxide having an average molecular weight of 500,000 0.0
6 g was dissolved in 100 ml (2.47 mol) of methanol to give a uniform and transparent solution. After that, concentration by an evaporator and addition of methanol were repeated to obtain a spinning solution having a viscosity of 200 poise with a chlorine / tin atom number relationship Cl / Sn of 1.62. The spinning solution was extruded from the spinning nozzle by applying pressure and continuously wound on a drum in an atmosphere having an ammonia concentration of 5000 ppm.
Stable spinning could be performed at a speed of 0 m / min.
It was also possible to spin from all 10 holes of the nozzle. After leaving the obtained fiber at room temperature for 1 day, 2 ° C
The temperature was raised to 120 ° C. at a speed of / min and the temperature was maintained for 30 minutes. Then, the temperature was raised to 500 ° C. at a rate of 10 ° C./min, and the temperature was maintained for 30 minutes to perform heat treatment. The obtained fibers had an average diameter of 15 μm, and X-ray diffraction confirmed that the fibers were tin oxide. The specific resistance of the obtained fiber is about 8 × 10 ⁴ Ω · c.
It was m. 85% relative humidity of gel fiber after spinning
Although it was left for 2.5 hours in the atmosphere, the fiber shape was maintained without softening.

Example 2 Stannous chloride (SnCl 2₂) 10 g (0.05 mol),
Antimony trichloride (SbCl₃) 1 g (0.004 m
And polyethylene oxide having an average molecular weight of 500,000
0.06 g to 100 ml (2.47 mol) of methanol
Dissolved into a uniform, transparent solution. After that, evaporation
Repeated concentration and addition of methanol with chlorine and tin
And the number of antimony atoms Cl / (Sn + Sb)
Was 1.62 and the viscosity was 200 poise.
Where 1.55N_Sn+ 1.60N _V= 1.55
1.80N_Sn+ 2.70N_V= 1.87. This
The spinning solution is pushed out from the spinning nozzle by applying pressure.
Continuously on the drum under an atmosphere with a near concentration of 2000 ppm
It was wound on a spinning reel at a spinning speed of 20 m / min.
Stable spinning was possible. Also the 10 nozzles
I was able to spin from all the holes. Obtained fa
After leaving the aver at room temperature for 1 day, the aver 12 at a rate of 2 ° C / min
The temperature was raised to 0 ° C. and the temperature was maintained for 30 minutes. Then 1
The temperature is raised to 500 ° C at a rate of 0 ° C / min and the temperature is increased to 3
A heat treatment was carried out by holding for 0 minute. Obtained phi
The bars have an average diameter of 15 μm and are analyzed by fluorescence X-ray analysis.
The antimony is present in the fiber according to the composition
Was confirmed. In addition, as a result of X-ray diffraction,
Has a peak of antimony, antimony is its oxide, etc.
No peak is observed and it is confirmed that the solid solution is present in tin oxide.
It has been certified. The specific resistance of the obtained fiber is about 8 × 10.^{ー 1}
It was Ω · cm. Relative humidity of gel fiber after spinning
Softened after being left in an atmosphere of 85% for 2.5 hours
Retained the fiber shape.

Example 3 The spinning solution was adjusted in the same manner as in Example 1 except that Cl / Sn = 1.78 and the ammonia concentration was 5%, and then spinning was carried out at a speed of 20 m / min. It could be spun continuously without dropping or breaking the yarn. It was also possible to spin from all 10 holes of the nozzle. As a result of X-ray diffraction of the obtained fiber, it was confirmed to be crystalline tin oxide. The specific resistance of the obtained fiber was 8 × 10 ⁴ Ω · cm on average. Further, the gel fiber immediately after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was retained. Example 4 The spinning solution was adjusted in the same manner as in Example 1 except that Cl / Sn = 1.55 and the ammonia concentration was 1%, and then spinning was performed at a speed of 20 m / min. The yarn could be spun continuously without causing yarn breakage. It was also possible to spin from all 10 holes of the nozzle. As a result of X-ray diffraction of the obtained fiber, it was confirmed to be crystalline tin oxide. The specific resistance of the obtained fiber was 8 × 10 ⁴ Ω · cm on average. Further, the gel fiber immediately after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was retained. This spinning solution did not precipitate even if left for 10 hours,
After standing for 24 hours, a part of the precipitate was precipitated in the spinning solution. Example 5 Stannous bromide (SnBr ₂ ) 13.9 g (0.05 mol), antimony trichloride (SbCl ₃ ) 1 g (0.00
(4 mol) was dissolved in 100 ml (2.47 mol) of methanol to form a uniform and transparent solution, which was then repeatedly concentrated by an evaporator and added with methanol. Then, 0.07 g of polyethylene oxide having a weight average molecular weight of 500,000 was added to 1
A solution dissolved in 0 ml of methanol was added to obtain a uniform solution. This solution is concentrated and the relationship between the numbers of atoms of bromine, chlorine, tin and antimony (Br + Cl) / (Sn + S
A spinning solution consisting of a sol having a viscosity of 200 poise and having a b) of 1.70 was prepared. Here, 1.55N _Sn +1.60
N _V = 1.55 and 1.80N _{S n} + 2.70N _V =
It is 1.87. When this spinning solution was extruded from a nozzle by applying pressure and continuously wound around a drum in an atmosphere having an ammonia concentration of 200 ppm, a spinning speed of 20 m /
When spinning was carried out at a speed of min, it was possible to carry out continuous spinning without causing drop of droplets and breakage of yarn. It was also possible to spin from all 10 holes of the nozzle. After leaving the obtained fiber at room temperature for 1 day, 2 ° C / m
The temperature was raised to 120 ° C. at a rate of in and the temperature was maintained for 30 minutes. Then, the temperature was raised to 500 ° C. at a rate of 10 ° C./min, and the temperature was maintained for 30 minutes to perform heat treatment. The fibers obtained have an average diameter of 15 μm,
By fluorescent X-ray analysis, it was confirmed that antimony was present in the fiber according to the charged composition. Further, as a result of X-ray diffraction, it was confirmed that it had a peak of tin oxide, and that the peak of antimony was not found in the oxide thereof and was dissolved in tin oxide. The specific resistance of the obtained fiber was 8 × 10 ⁻¹ Ω · cm on average. The gel fiber immediately after spinning was left for 2.5 hours in an atmosphere of relative humidity of 85%, but the fiber shape was maintained without softening.

Example 6 The procedure of Example 2 was repeated except that Cl / (Sn + Sb) was changed to 1.78 and the ammonia concentration was changed to 3%, and then spinning was performed at a speed of 20 m / min. It was possible to spin continuously without dropping or breaking the yarn. At this time, 1.55N _Sn + 1.60Nv = 1.55
And 1.80N _Sn + 2.70Nv = 1.87. It was also possible to spin from all 10 holes of the nozzle. As a result of analyzing the obtained fiber by fluorescent X-ray and X-ray diffraction, it was confirmed to be crystalline tin oxide in which antimony was solid-dissolved. Fiber obtained
The average specific resistance was 8 × 10 ⁻¹ Ω · cm. Further, the gel fiber immediately after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was retained.

Example 7 Relationship between the number of atoms of chlorine and tin and antimony in the spinning solution The spinning solution was adjusted in the same manner as in Example 2 except that Cl / (Sn + Sb) was set to 1.55, and then 20 m / min.
When spinning was carried out at the speed of, the spinning could be continuously carried out without the drop of the droplet and the breakage of the yarn. At this time, 1.55N _Sn
+1.60 Nv = 1.55 and 1.80 N _Sn +2.
70Nv = 1.87. It was also possible to spin from all 10 holes of the nozzle. The obtained fibers had an average diameter of 15 μm, and it was confirmed by fluorescent X-ray analysis that antimony was present in the fibers according to the charged composition. Further, as a result of X-ray diffraction, it was confirmed that it had a peak of tin oxide, and that the peak of antimony was not found in the oxide thereof and was dissolved in tin oxide. The specific resistance of the obtained fiber is 8 × 10 on average.
It was ^-1 Ω · cm. The gel fiber immediately after spinning was left for 2.5 hours in an atmosphere of relative humidity of 85%, but the fiber shape was maintained without softening. This spinning solution is 1
No precipitation occurred even after standing for 0 hour, but after standing for 24 hours, a part of the precipitate was precipitated in the spinning solution.

Example 8 Stannous bromide (SnBr ₂ ) 13.9 g (0.05 mol), antimony trichloride (SbCl ₃ ) 1 g (0.00
(4 mol) was dissolved in 100 ml (2.47 mol) of methanol to form a uniform and transparent solution, which was then repeatedly concentrated by an evaporator and added with methanol. Then, add 0.07 g of polyethylene oxide having an average molecular weight of 500,000 to 10 m.
A solution dissolved in 1 of methanol was added to obtain a uniform solution. This solution is concentrated and the relationship between the numbers of atoms of bromine, chlorine, tin and antimony [(Br + Cl)] / (Sn + S
b) was 1.70 and the viscosity was 200 poise. When this spinning solution was extruded from a nozzle by applying pressure and continuously wound on a drum in an atmosphere having an ammonia concentration of 500 ppm, stable spinning was possible at a spinning speed of 20 m / min. It was also possible to spin from all 10 holes of the nozzle. After leaving the obtained fiber at room temperature for 1 day, the fiber was heated at a rate of 2 ° C./min for 12 hours.
The temperature was raised to 0 ° C. and the temperature was maintained for 30 minutes. Then 1
The temperature is raised to 500 ° C at a rate of 0 ° C / min and the temperature is increased to 3
A heat treatment was carried out by holding for 0 minute. The obtained fibers had an average diameter of 15 μm, and it was confirmed by fluorescent X-ray analysis that antimony was present in the fibers according to the charged composition. Further, as a result of X-ray diffraction, it was confirmed that it had a peak of tin oxide, and that the peak of antimony was not found in the oxide thereof and was dissolved in tin oxide. The specific resistance of the obtained fiber is about 8 × 10 ^-1
It was Ω · cm. The gel fiber after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was maintained without softening.

Example 9 10 g (0.05 mol) of stannous chloride (SnCl ₂ ),
1 g (0.004 mol) of antimony trichloride (SbCl ₃ ) and 0.06 g of polyethylene oxide having an average molecular weight of 2,000,000 were dissolved in 100 ml (2.47 mol) of methanol to form a uniform and transparent solution. After that, concentration with an evaporator and addition of methanol were repeated, and the relationship between the number of atoms of chlorine and tin and antimony Cl / (Sn + Sb)
Was 1.62 and the viscosity was 200 poise.
Here, 1.55N _Sn + 1.60N _V = 1.55 and 1.80N _Sn + 2.70N _V = 1.87. When this spinning solution was pressed out from the spinning nozzle and continuously wound on a drum in an air atmosphere with a relative humidity of 55%, stable spinning was possible at a spinning speed of 20 m / min. It was also possible to spin from all 10 holes of the nozzle. The obtained fiber was left at room temperature in an atmosphere having an ammonia concentration of 200 ppm, then heated to 120 ° C. at a rate of 2 ° C./min in air and kept at that temperature for 30 minutes. Then 5 at a rate of 10 ° C / min
The temperature was raised to 00 ° C., and the temperature was maintained for 30 minutes for heat treatment. The obtained fibers had an average diameter of 15 μm, and it was confirmed by fluorescent X-ray analysis that antimony was present in the fibers according to the charged composition.
Further, as a result of X-ray diffraction, it was confirmed that it had a peak of tin oxide, and that the peak of antimony was not found in the oxide thereof and was dissolved in tin oxide. The specific resistance of the obtained fiber was about 8 × 10 ⁻¹ Ω · cm. The gel fiber after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was maintained without softening.

Example 10 Instead of methanol, 100 ml of ethanol was added to SbC.
Example 1 except that 1.13 g of Sb (OC ₂ H ₅ ) ₃ was used instead of 1 g of l ₃ and the relation Cl / (Sn + Sb) between the numbers of atoms of chlorine, tin and antimony was 1.65. In the same manner, spinning could be continuously performed at a speed of 20 m / min. Here, 1.55N _Sn + 1.60N _V =
1.55 and 1.80N _Sn + 2.70N _V = 1.8.
7 It was also possible to spin from all 10 holes of the nozzle. The obtained fiber is a fluorescent X-ray,
As a result of X-ray diffraction analysis, it was confirmed to be crystalline tin oxide in which antimony was solid-dissolved. The specific resistance of the obtained fiber was about 8 × 10 ⁻¹ Ω · cm. Further, the gel fiber after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was retained.

Example 11 The same procedure as in Example 2 was repeated except that 2-ethoxyethanol was used instead of methanol, and continuous spinning was possible at a speed of 20 m / min. It was also possible to spin from all 10 holes of the nozzle. As a result of analyzing the obtained fiber by fluorescent X-ray and X-ray diffraction, it was confirmed to be crystalline tin oxide in which antimony was solid-dissolved. The specific resistance of the obtained fiber is about 8 × 10 ^-1 Ω · c
It was m. Further, the gel fiber after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was retained.

Example 12 Instead of 1 g (0.004 mol) of antimony trichloride (SbCl ₃ ), 0.945 g (0.004) of TaCl ₅ was used.
The same procedure as in Example 2 was carried out except that 26 mol) was used, and a spinning solution having Cl / (Sn + Ta) = 1.62 and a viscosity of 200 poise was prepared, and spinning could be continuously performed at a speed of 20 m / min. Here, 1.55N _Sn + 1.60N _V = 1.55
And 1.80N _Sn + 2.70N _V = 1.84. It was also possible to spin from all 10 holes of the nozzle. Fluorescence X-ray analysis of the obtained fiber, X
As a result of line diffraction, it was confirmed that tantalum was a crystalline tin oxide that was solid-soluted according to the charged composition. The specific resistance of the obtained fiber was about 8 × 10 ² Ω · cm. Further, the gel fiber after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was retained.

Example 13 In place of 1 g (0.004 mol) of antimony trichloride (SbCl ₃ ), 0.712 g (0.00) of NbCl _{5 was} used.
The same procedure as in Example 1 was carried out except that 26 mol) was used, and a spinning solution having Cl / (Sn + Nb) = 1.70 and a viscosity of 200 poise was prepared, and the spinning could be continuously performed at a speed of 20 m / min. Here, 1.55N _Sn + 1.60N _V = 1.55
And 1.80N _Sn + 2.70N _V = 1.84. It was also possible to spin from all 10 holes of the nozzle. Fluorescence X-ray analysis of the obtained fiber, X
As a result of line diffraction analysis, it was confirmed that niobium was a crystalline tin oxide that was solid-solved according to the charged composition. The specific resistance of the obtained fiber was about 8 × 10 ² Ω · cm. Further, the gel fiber after spinning was left in an atmosphere of relative humidity of 85% for 2.5 hours, but the fiber shape was retained.

Example 14 The procedure of Example 9 was repeated except that the ammonia concentration was set to 500 ppm.

The obtained fiber had an average diameter of 15 μm, and it was confirmed by fluorescent X-ray analysis that antimony was present in the fiber according to the charged composition. Also, as a result of X-ray diffraction, having a peak of tin oxide,
It was confirmed that antimony did not show peaks such as its oxide and was dissolved in tin oxide. The specific resistance of the obtained fiber was about 8 × 10 ⁻¹ Ω · cm. After spinning the gel fiber in an atmosphere of 85% relative humidity, 2.5
After leaving for a while, the fiber shape was maintained without softening.

Comparative Example 1 A spinning speed of 20 m / m was obtained by carrying out the same procedure as in Example 1 except that the spinning was carried out in the air instead of the ammonia atmosphere.
Stable spinning could be performed at a speed of in. It was also possible to spin from all 10 holes of the nozzle.
After leaving the obtained fiber at room temperature for 1 day, 2 ° C / min
The temperature was raised to 120 ° C. at the rate of, and the temperature was maintained for 30 minutes. Then, the temperature was raised to 500 ° C. at a rate of 10 ° C./min, and the temperature was maintained for 30 minutes to perform heat treatment. The obtained fibers had an average diameter of 15 μm, and X-ray diffraction confirmed that the fibers were tin oxide. The specific resistance of the obtained fiber was about 8 × 10 ⁴ Ω · cm.
When the gel fiber after spinning was left in an atmosphere of relative humidity of 85% for 2 hours, it was softened and the fiber shape was broken.

Comparative Example 2 The same procedure as in Example 2 was repeated except that the spinning was carried out in the air instead of the ammonia atmosphere. The spinning speed was 20 m / m.
Stable spinning could be performed at a speed of in. It was also possible to spin from all 10 holes of the nozzle.
After leaving the obtained fiber at room temperature for 1 day, 2 ° C / min
The temperature was raised to 120 ° C. at the rate of, and the temperature was maintained for 30 minutes. Then, the temperature was raised to 500 ° C. at a rate of 10 ° C./min, and the temperature was maintained for 30 minutes to perform heat treatment. The obtained fibers had an average diameter of 15 μm, and it was confirmed by fluorescent X-ray analysis that antimony was present in the fibers according to the charged composition. Further, as a result of X-ray diffraction, it was confirmed that it had a peak of tin oxide, and that the peak of antimony was not found in the oxide thereof and was dissolved in tin oxide. The specific resistance of the obtained fiber was about 8 × 10 ⁻¹ Ω · cm. When the gel fiber after spinning was left in an atmosphere of relative humidity of 85% for 2 hours, it was softened and the fiber shape was broken.

Comparative Example 3 The viscosity of the spinning solution was adjusted to 2 without adding polyethylene oxide.
The same procedure as in Example 9 was carried out except that the poise was set to 00 poise.
At this time, spinning was possible from all 10 of the 10 holes of the nozzle, and the speed was 20 m / min.
The droplets intermittently dropped onto the gel fiber that had been wound up until then, and homogeneous spinning was not possible.

Comparative Example 4 The same procedure as in Example 1 was carried out except that the chlorine / tin ratio Cl / Sn in the spinning solution was set to 1.50, but a large amount of precipitate was deposited in the spinning solution to spin gel fibers. Could not be done.

Comparative Example 5 The same procedure as in Example 2 was carried out except that the relation Cl / (Sn + Sb) between the chlorine atom number and the atom number of tin and antimony in the spinning solution was set to 1.50. Precipitates were formed, and the spinning of gel fibers could not be performed. Here, 1.55N _Sn + 1.60N _V = 1.55,
It is 1.80N _Sn + 2.70N _V = 1.87.

Comparative Example 6 A spinning solution was prepared in the same manner as in Example 1 except that the chlorine / tin ratio Cl / Sn in the spinning solution was 1.90. When this spinning solution was extruded from a spinning nozzle by applying pressure and continuously wound around a drum in an atmosphere having an ammonia concentration of 5000 ppm, stable spinning was possible at a spinning speed of 20 m / min. It was also possible to spin from all 10 holes of the nozzle. After leaving the obtained fiber at room temperature for 1 day, 120 at a rate of 2 ° C / min.
The temperature was raised to ℃ and kept at that temperature for 30 minutes. Then 10
The temperature is raised to 500 ° C at a rate of ° C / min and the temperature is raised to 30
The heat treatment was performed by holding for a minute. The obtained fibers had an average diameter of 15 μm, and X-ray diffraction confirmed that the fibers were tin oxide. The specific resistance of the obtained fiber was about 8 × 10 ⁴ Ω · cm. When the gel fiber after spinning was placed in an atmosphere of 85% relative humidity, 2
After a time, it was softened and the fiber shape was broken.

Comparative Example 7 A spinning solution was prepared in the same manner as in Example 2 except that the relation Cl / (Sn + Sb) between the chlorine atom number and the atom number of tin and antimony in the spinning solution was 1.90. Where 1.55N
_Sn + 1.60N _V = 1.55, 1.80N _Sn +
A 2.70N _V = 1.87. This spinning solution is extruded from the spinning nozzle by applying pressure and the ammonia concentration is 2000.
When continuously wound on a drum in a ppm atmosphere, stable spinning was possible at a spinning speed of 20 m / min. It was also possible to spin from all 10 holes of the nozzle. The obtained fiber is 1 at room temperature
After standing for a day, the temperature was raised to 120 ° C. at a rate of 2 ° C./min and the temperature was maintained for 30 minutes. Then, the temperature was raised to 500 ° C. at a rate of 10 ° C./min, and the temperature was maintained for 30 minutes to perform heat treatment. The average fiber size is 15μ
Fluorescence X-ray analysis confirmed that antimony was present in the fiber according to the charge composition. Further, as a result of X-ray diffraction, it was confirmed that it had a peak of tin oxide, and that the peak of antimony was not found in the oxide thereof and was dissolved in tin oxide. The specific resistance of the obtained fiber was about 8 × 10 ⁻¹ Ω · cm. When the gel fiber after spinning was left in an atmosphere of relative humidity of 85%, it softened after 2 hours and collapsed into a fiber shape.

Claims (2)

[Claims] 1. A tin halide compound and an alcohol-soluble polymer compound are dissolved in alcohol, and the ratio of the number of halogen atoms to tin atoms in the solution (X / Sn) is 1.55 or more and 1.80. A method for producing a tin oxide fiber, which comprises subjecting a gel fiber spun from a spinning solution of less than 1 to an ammonia atmosphere and then heat-treating the gel fiber. 2. A halogenated tin compound, an atom of a group V element of the periodic table and an alcohol-soluble polymer compound dissolved in alcohol, and each atom of halogen, tin and a group V element of the periodic table in the solution. A method for producing a tin oxide fiber, which comprises contacting gel fibers spun from a spinning solution having a number of the following formulas with an ammonia atmosphere and then heat-treating the gel fibers. [Equation 1] [Here, N _Sn is the ratio of the number of tin atoms to the total number of atoms of tin and Group V elements in the periodic table, and Nv
Is the ratio of the number of atoms of the group V element of the periodic table to the total number of atoms of tin and the group V element of the periodic table in the solution, and X, S
n and V respectively represent the number of atoms of halogen, tin and Group V element in the periodic table in the solution]